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Sample records for mixed-valence dodecanuclear polyoxovanadate

  1. Inelastic neutron scattering on a mixed-valence dodecanuclear polyoxovanadate cluster

    CERN Document Server

    Basler, R; Andrés, H; Güdel, H U; Koegerler, P; Krickemeier, E; Bögge, H; Müller, A; Mutka, H

    2002-01-01

    The magnetic exchange interactions in the mixed-valence dodecanuclear polyoxovanadate cluster compound (NHEt sub 3) sub 4 [V sub 1 sub 2 As sub 8 O sub 4 sub 0 (H sub 2 O)] x H sub 2 O were investigated by a detailed inelastic neutron scattering study using cold neutrons. The data show clear evidence for the presence of a magnetic anisotropy within the cluster. Exchange parameters are accurately determined. (orig.)

  2. Role of the electron transfer and magnetic exchange interactions in the magnetic properties of mixed-valence polyoxovanadate complexes.

    Science.gov (United States)

    Calzado, Carmen J; Clemente-Juan, Juan M; Coronado, Eugenio; Gaita-Arino, Alejandro; Suaud, Nicolas

    2008-07-01

    Modeling the properties of high-nuclearity, high-electron-population, mixed-valence (MV) magnetic systems remains one of the open challenges in molecular magnetism. In this work, we analyze the magnetic properties of a series of polyoxovananadate clusters of formula [V 18O 42] (12-) and [V 18O 42] (4-). The first compound is a fully localized spin cluster that contains 18 unpaired electrons located at the metal sites, while the second one is a MV cluster with 10 unpaired electrons largely delocalized over the 18 metal sites. A theoretical model that takes into account the interplay between electron transfer and magnetic exchange interactions is developed to explain the unexpected enhancement of the antiferromagnetic coupling when the number of unpaired electrons is reduced from 18 to 10 in these clusters. In the MV area, these systems represent the most complex magnetic clusters studied theoretically so far. Because of the high complexity of the systems, the number of relevant parameters is too large for a conventional model Hamiltonian approach. We therefore perform a theoretical study that combines ab initio calculations with the model Hamiltonian. In this way, we use ab initio calculations performed on small fragments of the cluster to lower the degrees of freedom of the parameter set of the model Hamiltonian that operates in the whole MV cluster. This approach shows the usefulness of combining ab initio calculations with model Hamiltonians in order to explore the magnetic properties of large and complex molecular systems, emphasizing the key role played by the electron transfer in these model magnetic materials.

  3. Stark spectroscopy of mixed-valence systems.

    Science.gov (United States)

    Silverman, Lisa N; Kanchanawong, Pakorn; Treynor, Thomas P; Boxer, Steven G

    2008-01-13

    Many mixed-valence systems involve two or more states with different electric dipole moments whose magnitudes depend upon the charge transfer distance and the degree of delocalization; these systems can be interconverted by excitation of an intervalence charge transfer transition. Stark spectroscopy involves the interaction between the change in dipole moment of a transition and an electric field, so the Stark spectra of mixed-valence systems are expected to provide quantitative information on the degree of delocalization. In limiting cases, a classical Stark analysis can be used, but in intermediate cases the analysis is much more complex because the field affects not only the band position but also the intrinsic bandshape. Such non-classical Stark effects lead to widely different bandshapes. Several examples of both classes are discussed. Because electric fields are applied to immobilized samples, complications arise from inhomogeneous broadening, along with other effects that limit our ability to extract unique parameters in some cases. In the case of the radical cation of the special pair in photosynthetic reaction centres, where the mixed-valence system is in a very complex but structurally well-defined environment, a detailed analysis can be performed.

  4. [V16O38(CN)]9–: a soluble mixed-valence redox-active building block with strong antiferromagnetic coupling.

    Science.gov (United States)

    Keene, Tony D; D'Alessandro, Deanna M; Krämer, Karl W; Price, Jason R; Price, David J; Decurtins, Silvio; Kepert, Cameron J

    2012-09-03

    A new discrete [V(16)O(38)(CN)](9-) cluster, which displays the hitherto unknown 8- charge on the cluster shell and is the first to encapsulate the cyanide anion, has been synthesized and characterized by IR and UV/vis/near-IR spectroscopy, electrochemistry, and magnetic susceptibility measurements. Bond valence sum calculations conducted on the basis of the crystal structure analysis of K(9)[V(16)O(38)(CN)]·13H(2)O confirm that this new member of the polyoxovanadate series is a mixed-valence complex. The intervalence charge transfer bands arising from intrametal interactions reveal that a localized (class II) assignment is appropriate for the cluster; however, a small degree of electronic delocalization is present. Interesting possibilities exist for the incorporation of this unit into higher dimensionality framework structures, where the redox, optical, and magnetic properties can be exploited and tuned.

  5. Spin Dynamics and Magnetic Ordering in Mixed Valence Systems

    DEFF Research Database (Denmark)

    Shapiro, S. M.; Bjerrum Møller, Hans; Axe, J. D.

    1978-01-01

    Neutron scattering measurements are reported on the mixed valence compounds Ce//1// minus //xTh//x and TmSe. The chi double prime (Q, omega ) as derived from the inelastic spectra of Ce//0//. //7//4Th//0//. //2//6 shows a peak in the gamma phase near 20. 0 meV and shifts abruptly to greater than 70...

  6. Neutron scattering studies of mixed-valence semiconductors

    Energy Technology Data Exchange (ETDEWEB)

    Mignot, J.M. [Laboratoire Leon Brillouin (LLB) - Centre d`Etudes de Saclay, 91 - Gif-sur-Yvette (France); Alekseev, P.A. [Kurchatov Institute, Moscow (Russian Federation)

    1994-12-31

    Neutron scattering experiments on the mixed-valence (MV) compounds SmB{sub 6} are reported. The inelastic magnetic response of SmB{sub 6} at T = 2 K, measured on a double-isotope single crystal,displays a strongly damped peak at 35 meV corresponding to the inter multiplet transition of Sm{sup 2+}. At lower energies ( h.{omega} {approx_equal} 14 meV), a narrow magnetic excitation is observed, with remarkable scattering-vector and temperature dependences of its intensity. This novel feature is discussed in terms of recent theoretical works describing the formation of an anisotropic local bound state in semiconducting MV materials. If the average samarium valence is decreased by substituting La for Sm, a peak is found to appear at high energies. The elastic magnetic form factor of SmB{sub 6} was determined using polarised neutrons and no significant difference is observed in its Q-dependence with respect to that of pure divalent samarium. This surprising behaviour is constant with previous measurements on the gold (high-pressure) phase of SmS. The above results are compared to those already reported for other MV materials. In particular existing information for TmSe is supplemented by recent inelastic scattering measurements carried out on a large stoichiometric single crystal. (author). 44 refs., 7 figs.

  7. Two new polyoxovanadate clusters templated through cysteamine

    Indian Academy of Sciences (India)

    K Pavani; S Upreti; A Ramanan

    2006-03-01

    Two new fully oxidized polyoxovanadate cluster-based solids (C4N2S2H14)2[H2V10O28]$\\cdot$4H2O, 1 and (C4N2S2H14)5[H4V15O42]2.10H2O, 2 are crystallized under self-assembly process in the presence of cysteamine. In both 1 and 2, cysteamines are oxidized forming disulphide linkages and occur as counter cations. The organic cations assemble around V10O28 cluster anions in 1 whereas they aggregate around V15O42 clusters in 2. pH appears to be the structure determinant in the occurrence of decavanadate cluster in 1 and pentadecavanadate in 2, with the same counter cation.

  8. Delocalized mixed-valence bi- and trinuclear complexes with short Cu-Cu bonds.

    Science.gov (United States)

    Yang, Lei; Powell, Douglas R; Klein, Eric L; Grohmann, Andreas; Houser, Robert P

    2007-08-20

    Two mixed-valence copper complexes were synthesized with ligands N-(2-pyridylmethyl)acetamide (Hpmac) and N,N'-(2-methyl-2-pyridylpropan-1,3-diyl)bis(acetamide) (H2pp(ac)2). Dimer [Cu2(pmac)2]OTf and trimer [Cu3(pp(ac)2)2].NaOTf both contain fully delocalized, mixed-valence Cu(1.5)Cu(1.5) moieties.

  9. Mixed-Valence Porphyrin π-Cation Radical Derivatives: Electrochemical Investigations.

    Science.gov (United States)

    Scheidt, W Robert; Buentello, Kristin E; Ehlinger, Noelle; Cinquantini, Arnaldo; Fontani, Marco; Laschi, Franco

    2008-05-05

    The electrochemistry of [Cu(OEP)] and [Ni(OEP)] are compared with the mixed-valence π-cations [Cu(OEP•/2)]2+and[Ni(OEP•/2)]2+. These electrochemical studies, carried out with cyclic voltametry and hydrodynamic voltametry, show that the mixed valence π-cations have distinct electrochemical properties, although the differences between the [M(OEP)](+/0) and [M(OEP•/2)]2+/0 processes are subtle.

  10. Stabilization of Th 3+ ions into mixed-valence thorium fluoride

    Science.gov (United States)

    Dubois, Marc; Dieudonné, Belto; Mesbah, Adel; Bonnet, Pierre; El-Ghozzi, Malika; Renaudin, Guillaume; Avignant, Daniel

    2011-01-01

    The unusual oxidation state +3 of the thorium has been stabilized into a lithium containing non-stoichiometric mixed-valence (III/IV) thorium fluorinated phase with formula Li 2+ xTh 12F 50 (0afore mentioned single phase may be considered as an insertion compound. The Li + insertion is accompanied by the simultaneous reduction of a part of the Th 4+ ions, resulting in a mixed-valence III/IV thorium fluoride. The electrochemical insertion of Li + ions into the open channels of the host matrix has been carried out at 60 °C, using an alkylcarbonate PC-LiClO 4 1 M electrolyte. The Li + and Th 3+ contents, both in the starting composition and the Li + inserted ones, were investigated by high resolution solid state 7Li NMR and EPR, respectively.

  11. Epitaxial growth and electronic properties of mixed valence YbAl3 thin films

    Science.gov (United States)

    Chatterjee, Shouvik; Sung, Suk Hyun; Baek, David J.; Kourkoutis, Lena F.; Schlom, Darrell G.; Shen, Kyle M.

    2016-07-01

    We report the growth of thin films of the mixed valence compound YbAl3 on MgO using molecular-beam epitaxy. Employing an aluminum buffer layer, epitaxial (001) films can be grown with sub-nm surface roughness. Using x-ray diffraction, in situ low-energy electron diffraction, and aberration-corrected scanning transmission electron microscopy, we establish that the films are ordered in the bulk as well as at the surface. Our films show a coherence temperature of 37 K, comparable to that reported for bulk single crystals. Photoelectron spectroscopy reveals contributions from both f13 and f12 final states establishing that YbAl3 is a mixed valence compound and shows the presence of a Kondo Resonance peak near the Fermi-level.

  12. Solvent effect on intramolecular electron transfer rates of mixed-valence biferrocene monocation derivatives.

    Science.gov (United States)

    Masuda, Y; Shimizu, C

    2006-06-01

    Intramolecular electron transfer (ET) rates in various solvents of mixed-valence biferrocene monocation (Fe(II), Fe(III)) and the 1',1' ''-diiodo and 1',1' ''-diethyl derivatives (respectively abbreviated as BFC(+), I(2)BFC(+), and Et(2)BFC(+)) were determined by means of the spin-lattice relaxation times of the protons, taking into account the local magnetic field fluctuation caused by the electron hopping between the two ferrocene units. We also determined the ET rates of a mixed-valence diferrocenylacetylene monocation (DFA(+)) in order to examine the effect of the insertion of an acetylene bridge between the two ferrocene units. The insertion of the bridge decreased the ET rate, while the effect of substitution on the cyclopentadienyl rings on the rate was minor. The observed rates for each mixed-valence monocation in various solvents did not correlate with the reorganization energies, but we did find a significant contribution of the solvent dynamics. The observed rates were considerably higher than those expected on the basis of the Sumi-Marcus-Nalder model in which the solvents were regarded as dielectric continua. The slope of the logarithm plot of the pre-exponential factors in various solvents for each mixed-valence monocation versus the inverse of the longitudinal dielectric relaxation times of the solvents was significantly smaller than unity, and the slope for DFA(+) was larger than those for BFC(+), I(2)BFC(+), and Et(2)BFC(+). These results were ascribed to a partial contribution of the dielectric friction to the dynamics along the solvent coordinate; the extent of the contribution decreased with a reduction in the ET distance. For the dynamics along the solvent coordinate of the ET reactions in methanol, the observed rates indicated an important contribution by the minor dielectric relaxation components with faster relaxation times, rather than the major component with an extraordinarily long relaxation time.

  13. Di- and Trinuclear Mixed-Valence Copper Amidinate Complexes from Reduction of Iodine.

    Science.gov (United States)

    Lane, Andrew C; Barnes, Charles L; Antholine, William E; Wang, Denan; Fiedler, Adam T; Walensky, Justin R

    2015-09-08

    Molecular examples of mixed-valence copper complexes through chemical oxidation are rare but invoked in the mechanism of substrate activation, especially oxygen, in copper-containing enzymes. To examine the cooperative chemistry between two metals in close proximity to each other we began studying the reactivity of a dinuclear Cu(I) amidinate complex. The reaction of [(2,6-Me2C6H3N)2C(H)]2Cu2, 1, with I2 in tetrahydrofuran (THF), CH3CN, and toluene affords three new mixed-valence copper complexes [(2,6-Me2C6H3N)2C(H)]2Cu2(μ2-I3)(THF)2, 2, [(2,6-Me2C6H3N)2C(H)]2Cu2(μ2-I) (NCMe)2, 3, and [(2,6-Me2C6H3N)2C(H)]3Cu3(μ3-I)2, 4, respectively. The first two compounds were characterized by UV-vis and electron paramagnetic resonance spectroscopies, and their molecular structure was determined by X-ray crystallography. Both di- and trinuclear mixed-valence intermediates were characterized for the reaction of compound 1 to compound 4, and the molecular structure of 4 was determined by X-ray crystallography. The electronic structure of each of these complexes was also investigated using density functional theory.

  14. Self-doping of molecular quantum-dot cellular automata: mixed valence zwitterions.

    Science.gov (United States)

    Lu, Yuhui; Lent, Craig

    2011-09-07

    Molecular quantum-dot cellular automata (QCA) is a promising paradigm for realizing molecular electronics. In molecular QCA, binary information is encoded in the distribution of intramolecular charge, and Coulomb interactions between neighboring molecules combine to create long-range correlations in charge distribution that can be exploited for signal transfer and computation. Appropriate mixed-valence species are promising candidates for single-molecule device operation. A complication arises because many mixed-valence compounds are ions and the associated counterions can potentially disrupt the correct flow of information through the circuit. We suggest a self-doping mechanism which incorporates the counterion covalently into the structure of a neutral molecular cell, thus producing a zwitterionic mixed-valence complex. The counterion is located at the geometrical center of the QCA molecule and bound to the working dots via covalent bonds, thus avoiding counterion effects that bias the system toward one binary information state or the other. We investigate the feasibility of using multiply charged anion (MCA) boron clusters, specifically closo-borate dianion, as building blocks. A first principle calculation shows that neutral, bistable, and switchable QCA molecules are possible. The self-doping mechanism is confirmed by molecular orbital analysis, which shows that MCA counterions can be stabilized by the electrostatic interaction between negatively charged counterions and positively charged working dots. This journal is © the Owner Societies 2011

  15. The Total Position Spread in mixed-valence compounds: A study on the H4+ model system.

    Science.gov (United States)

    Bendazzoli, Gian Luigi; El Khatib, Muammar; Evangelisti, Stefano; Leininger, Thierry

    2014-04-15

    The behavior of the Total Position Spread (TPS) tensor, which is the second moment cumulant of the total position operator, is investigated in the case of a mixed-valence model system. The system consists of two H2 molecules placed at a distance D. If D is larger than about 4 bohr, the singly ionized system shows a mixed-valence character. It is shown that the magnitude of the TPS has a strong peak in the region of the avoided crossing. We believe that the TPS can be a powerful tool to characterize the behavior of the electrons in realistic mixed-valence compounds.

  16. Photoinduced mixed valency in zinc porphyrin dimer of triruthenium cluster dyads.

    Science.gov (United States)

    Henderson, Jane; Kubiak, Clifford P

    2014-10-20

    The preparation, electrochemistry, and spectroscopic characterization of three new species, (ZnTPPpy)Ru3O(OAc)6(CO)-pz-Ru3O(OAc)6(CO)L, where ZnTPPpy = zinc(II) 5-(4-pyridyl)-10,15,20-triphenylporphyin, L = pyridyl ligand, and pz = pyrazine, are reported. These porphyrin-coordinated Ru3O–BL–Ru3O (BL = bridging ligand) dyads are capable of undergoing intramolecular electron transfer from the photoexcited Zn porphyrin to Ru3O donor–bridge–acceptor dimer systems. Seven reversible redox processes are observed in the cyclic voltammograms of the newly synthesized dyads, showing no significant electrochemical interaction between the redox active porphyrin and the pyrazine-bridged ruthenium dimer of Ru3O trimers. From the electrochemical behavior of the dyads, large comproportionation constants (Kc = 6.0 × 10(7) for L = dmap) were calculated from the reduction potentials of the Ru(III)Ru(III)Ru(II) clusters, indicating a stable mixed-valence state. Electronic absorption spectra of the singly reduced mixed-valence species show two intervalence charge transfer (IVCT) bands assigned within the Brunschwig–Creutz–Sutin semiclassical three-state model as metal-to-bridge and metal-to-metal in character. The progression from most to least delocalized mixed-valence dimer ions, as determined by the divergence of the IVCT bands and in agreement with electrochemical data, follows the order of L = 4-dimethylaminopyridine (dmap) > pyridine (py) > 4-cyanopyridine (cpy). These systems show dynamic coalescence of the infrared spectra in the ν(CO) region of the singly reduced state. This sets the time scale of electron exchange at dimer is predicted to be thermodynamically favorable, with ΔGFET(0) ranging from −0.54 eV for L = dmap to −0.62 eV for L = cpy. Observation of IVCT band growth under continual photolysis (λexc = 568 nm) confirms a phototriggered intramolecular electron transfer process resulting in a strongly coupled singly reduced mixed-valence species.

  17. Charge transfer and mixed-valence behavior in phtalocyanine-dimer cations.

    Science.gov (United States)

    Monari, Antonio; Evangelisti, Stefano; Leininger, Thierry

    2010-09-28

    Phtalocyanine compounds deserved a considerable interest in recent times, particularly because of their possible use in the field of nanoelectronics. In particular, the charge mobility (of both electrons and holes) in phtalocyanine stacked arrangements has been recently extensively investigated. The present work focuses on the study of the hole-transfer mechanism between two phtalocyanine monomers. For an interdisk distance larger than 4.5 bohrs, the eclipsed dimer exhibits a mixed-valence behavior, with a saddle point transition state separating two equivalent minima. This behavior, however, is strongly dependent on the relative angle between the disks. In particular, the mixed-valence character of the compound is strongly enhanced for arrangements that are far from the eclipsed geometry. Moreover, for values of the angle close to π/8 and 3π/8, the ground and excited transition states have exactly the same energy, thus implying the presence of a conical intersection. These results can have deep implication in the charge transfer along phtalocyanine chains.

  18. NATO Advanced Study Institute on Mixed-Valence Compounds : Theory and Applications in Chemistry, Physics, Geology, and Biology

    CERN Document Server

    1980-01-01

    It has been a decade since two seminal reviews demonstrated that mixed-valence compounds share many unique and fascinating features. The insight pro­ vided by those early works has promoted a great deal of both experimental and theoretical study. As a result of extensive efforts, our understanding of the bonding and properties of mixed-valence compounds has advanced substantially. There has been no compre­ hensive treatment of mixed-valence compounds since 1967, and the meeting convened at Oxford in September, 1979, provided a unique opportunity to examine the subject and its many ramifications. Mixed-valence compounds play an important role in many fields. Although the major impact of the subject has been in chemistry, its importance has become increasingly clear in solid state physics, geology, and biology. Extensive interest and effort in the field of molecular metals has demonstrated that mixed-valency is a prerequisite for high elec­ trical conductivity. The intense colors of many minerals have been s...

  19. Introducing Students to Inner Sphere Electron Transfer Concepts through Electrochemistry Studies in Diferrocene Mixed-Valence Systems

    Science.gov (United States)

    Ventura, Karen; Smith, Mark B.; Prat, Jacob R.; Echegoyen, Lourdes E.; Villagran´, Dino

    2017-01-01

    We have designed a 4 h physical chemistry laboratory to introduce upper division students to electrochemistry concepts, including mixed valency and electron transfer (ET), using cyclic and differential pulse voltammetries. In this laboratory practice, students use a ferrocene dimer consisting of two ferrocene centers covalently bonded through a…

  20. The chemical response of main-group extended solids to formal mixed valency: the case of LixBC.

    Science.gov (United States)

    Fogg, A M; Darling, G R; Claridge, J B; Meldrum, J; Rosseinsky, M J

    2008-01-13

    The introduction of mixed valency into extended main-group solids is discussed using the example of hole-doped LiBC, where a combination of experimental measurements and density functional theory calculations is used to understand the observed electronic properties in terms of deviation from the expected rigid-band electronic structure behaviour.

  1. Synthesis of a mixed valence state Ce-MOF as an oxidase mimetic for the colorimetric detection of biothiols.

    Science.gov (United States)

    Xiong, Yuhao; Chen, Siheng; Ye, Fanggui; Su, Lingjing; Zhang, Cong; Shen, Shufen; Zhao, Shulin

    2015-03-18

    We demonstrate a facile and rapid in situ partial oxidation synthetic strategy for the fabrication of a mixed valence state Ce-MOF (MVCM) which exhibits intrinsic oxidase-like activity. Furthermore, on the basis of the excellent catalytic activity of the MCVM, a colorimetric approach for the high-throughput detection of biothiols in serum samples was established.

  2. Crystal structure of a mixed-valence μ-oxide Sn12 cluster

    Directory of Open Access Journals (Sweden)

    Marina M. Kireenko

    2014-11-01

    Full Text Available The mixed-valence μ-oxide Sn12 cluster, decacarbonyltetra-μ4-oxido-hexa-μ3-oxido-tetrakis[μ-2,2′-(pyridine-2,6-diylbis(1,1-diphenylethanolato]decatin(IIditin(IVdimolybdenum(O(2 Mo—Sn toluene heptasolvate, [Mo2Sn12(C33H27NO24O10(CO10]·7C7H8, has a crystallographically imposed inversion centre. The asymmetric unit also contains three and a half toluene solvent molecules, one of which is disordered about a centre of symmetry. The complex molecule comprises six distinct Sn atom species with four different coordination numbers, namely 3, 4, 5, and 6. The SnII atoms forming the central Sn10O10 core adopt distorted trigonal–pyramidal, square-pyramidal and octahedral coordination geometries provided by the μ-oxide atoms and by the O- and N-donor atoms of two pyridinediethanolate ligands. The terminal SnIV atoms have distorted trigonal–bipyramidal coordination geometries, with a μ4-oxide atom and the N atom of a pyridinediethanolate ligand occupying the axial positions, and the Mo atom of a Mo(CO5 group and the alkoxy O atoms of a ligand forming the equatorial plane. In the crystal, weak intra- and intermolecular C—H...O hydrogen bonds are observed.

  3. Mixed valence character of anionic linear beryllium chains: a CAS-SCF and MR-CI study.

    Science.gov (United States)

    Pastore, Mariachiara; Monari, Antonio; Evangelisti, Stefano; Leininger, Thierry

    2009-12-31

    A theoretical investigation on the mixed valence behavior, or bistability, of a series of anionic linear chains composed of beryllium atoms is presented. Calculations on Be(N)- (with N = 7, ..., 13) were performed at CAS-SCF and MR-CI levels by using an ANO basis set containing 6s4p3d2f contracted orbitals for each atom. Our results show a consistent gradual shift between different classes of mixed valence compounds as the number of beryllium atoms increases, from strong coupling (class III) toward valence-trapped (class II). Indeed, in the largest cases (N > 10), the anionic chains were found to become asymptotically closer to class I, where the coupling vanishes. The intramolecular electron-transfer parameters V(ab), E(barr), and E(opt) were calculated for each atomic chain. It is shown that the decrease of V(ab) with increasing N follows an exponential pattern.

  4. Phase transitions in mixed-valence potassium manganese hexacyanoferrate Prussian blue analogue: Heat capacity calorimetric study

    Energy Technology Data Exchange (ETDEWEB)

    Bhattacharjee, A. [Department of Physics, Visva-Bharati, Santiniketan 731235 (India)]. E-mail: ashis@vbphysics.net.in; Saha, S. [Department of Chemistry, Jadavpur University, Kolkata 700032 (India); Koner, S. [Department of Chemistry, Jadavpur University, Kolkata 700032 (India); Miyazaki, Y. [Research Center for Molecular Thermodynamics, Graduate School of Science, Osaka University, Toyonaka, Osaka 560-0043 (Japan)]. E-mail: miyazaki@chem.sci.osaka-u.ac.jp

    2007-05-15

    Phase transitions in K{sub 0.2}Mn{sub 0.66}{sup II}Mn{sub 1.44}{sup III}[Fe{sub 0.2}{sup II}Fe{sub 0.8}{sup III}(CN){sub 6}]O{sub 0.6}= {sub 6}(CH{sub 3}COO){sub 1.32}].7.6H{sub 2}O-a mixed valence PB analogue have been investigated with the help of heat capacity calorimetry under 0-90kOe magnetic fields in the 1.8-300K temperature range. Two heat capacity anomalies at 2.1 and 7.5K have been detected, which correspond to ferromagnetic and ferrimagnetic transitions, respectively. The magnitudes as well as the position of these thermal anomalies have varied with changing magnetic field. The estimated zero-field magnetic entropy amounted to 29.2JK{sup -1}mol{sup -1}, which is close to the expected value (33.7JK{sup -1}mol{sup -1}). The uniaxial zero-field splitting parameter is estimated to be D/k{sub B}=14.7K. A comparatively stronger antiferromagnetic interaction seems to lead to the magnetic transition around 7.3K, whereas a weaker ferromagnetic interaction gives rise to the thermal anomaly at 2.1K. The present results on magnetic phase transitions are in complete agreement with the earlier observations made through magnetic studies. Additionally, a glass transition at 194K has been observed in the heat capacity study presumably due to freezing of the orientational motion of the H{sub 2}O molecules present in the material. This phenomenon is reflected into the temperature dependence of the estimated Fe{sup III} and Fe{sup II} concentrations in the present material obtained earlier through Mossbauer spectroscopy.

  5. Synthesis and spectral characterization of trinuclear, oxo-centered, carboxylate-bridged, mixed-valence iron complexes with Schiff bases.

    Science.gov (United States)

    Singh, Atresh Kumar; Singh, Alok Kumar

    2012-10-01

    Some novel trinuclear, oxo-centered, carboxylate-bridged, mixed-valence iron complexes of the general formula [Fe(3)O(OOCR)(3)(SB)(3)L(3)] (where R=C(13)H(27), C(15)H(31) or C(17)H(35,) HSB=Schiff bases and L=Ethanol) have been synthesized by the stepwise substitutions of acetate ions from μ(3)-oxo-hexa(acetato)tri(aqua)iron(II)diiron(III), first with straight chain carboxylic acids and then with Schiff bases. The complexes were characterized by elemental analyses, molecular weight determinations and spectral (electronic, infrared, FAB mass, Mössbauer and powder XRD) studies. Molar conductance measurements indicated the complexes to be non-electrolytes in nitrobenzene. Bridging nature of carboxylate and Schiff base anions in the complexes was established by their infrared spectra. Mössbauer spectroscopic studies indicated two quadrupole-split doublets due to Fe(II) and Fe(III) ions at 80, 200 and 295K, confirming the complexes are mixed-valence species. This was also supported by the observed electronic spectra of the complexes. Magnetic susceptibility measurements displayed octahedral geometry around iron in mixed-valence state and a net antiferromagnetic exchange coupling via μ-oxo atom. Trinuclear nature of the complexes was confirmed by their molecular weight determination and FAB mass spectra. A plausible structure for these complexes has been established on the basis of spectral and magnetic moment data.

  6. Dodecanuclear [Cu(II)6Gd(III)6] nanoclusters as magnetic refrigerants.

    Science.gov (United States)

    Dinca, Alina S; Ghirri, Alberto; Madalan, Augustin M; Affronte, Marco; Andruh, Marius

    2012-04-02

    A novel dodecanuclear complex, [{(HL)(L)(DMF)Cu(II)Gd(III)(DMF)(H(2)O)}(6)]·6DMF (1; DMF = N,N-dimethylformamide), has been obtained using the ligand resulting from the condensation of 3-formylsalicylic acid with hydroxylamine (H(3)L). The exchange interaction between the phenoxo-bridged Cu(II) and Gd(III) ions is weak ferromagnetic (J = +1.01 cm(-1)). The combination of a high-spin ground state with small anisotropy leads to a significant magnetocaloric effect [-ΔS(m)(0-7 T) = 23.5 J K g(-1) K(-1) at ∼2 K].

  7. Benzoxazole-based heterometallic dodecanuclear complex [Dy(III)4Cu(II)8] with single-molecule-magnet behavior.

    Science.gov (United States)

    Iasco, Olga; Novitchi, Ghenadie; Jeanneau, Erwann; Wernsdorfer, Wolfgang; Luneau, Dominique

    2011-08-15

    Three Cu-Ln (Ln = Dy, Gd, Y) dodecanuclear clusters assembled by a novel ligand of the benzoxazole type are reported. The dysprosium cluster exhibits a frequency dependence of the alternating-current susceptibility and hysteresis loop at low temperature, indicating single-molecule-magnet behavior.

  8. Crystal structures of two mixed-valence copper cyanide complexes with N-methyl-ethylenedi-amine.

    Science.gov (United States)

    Corfield, Peter W R; Sabatino, Alexander

    2017-02-01

    The crystal structures of two mixed-valence copper cyanide compounds involving N-methyl-ethylenedi-amine (meen), are described. In compound (I), poly[bis(μ3-cyanido-κ3C:C:N)tris(μ2-cyanido-κ2C:N)bis(N-methylethane-1,2-di-amine-κ2N,N')tricopper(I)copper(II)], [Cu4(CN)5(C3H10N2)2] or Cu4(CN)5meen2, cyanide groups link Cu(I) atoms into a three-dimensional network containing open channels parallel to the b axis. In the network, two tetra-hedrally bound Cu(I) atoms are bonded by the C atoms of two end-on bridging CN groups to form Cu2(CN)6 moieties with the Cu atoms in close contact at 2.560 (1) Å. Other trigonally bound Cu(I) atoms link these units together to form the network. The Cu(II) atoms, coordinated by two meen units, are covalently linked to the network via a cyanide bridge, and project into the open network channels. In the mol-ecular compound (II), [(N-methylethylenediamine-κ(2)N,N')copper(II)]-μ(2)-cyanido-κ(2)C:N-[bis(cyanido-κC)copper(I)] monohydrate, [Cu2(CN)3(C3H10N2)2]·H2O or Cu2(CN)3meen2·H2O, a CN group connects a Cu(II) atom coordinated by two meen groups with a trigonal-planar Cu(I) atom coordinated by CN groups. The mol-ecules are linked into centrosymmetric dimers via hydrogen bonds to two water mol-ecules. In both compounds, the bridging cyanide between the Cu(II) and Cu(I) atoms has the N atom bonded to Cu(II) and the C atom bonded to Cu(I), and the Cu(II) atoms are in a square-pyramidal coordination.

  9. Determining the Extent of Delocalization in Mixed-Valence Iron Dimers using X-ray Absorption Spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Hoyt, Alison; /Yale U. /SLAC

    2007-11-07

    This study examines the extent of charge delocalization in mixed valence compounds. Understanding the structure of charge delocalization is the first step in understanding the local dynamics of charge transfer. This insight has diverse applications such as the ability to mimic biological reactions and to enhance solar technology. Because of its fast time scale, synchrotron radiation was used to probe the iron K-edge for three organometallic systems. In these complexes, two bridged metal atoms share an effective charge of 5+. In a Robin-Day Class II compound, charge is localized and the two iron atoms have effective oxidation states of 2+ and 3+ respectively. For Class III delocalized compounds each metal center has an effective charge of 2.5+. Class II/III compounds exhibit characteristics of both localized and delocalized systems according to various optical spectroscopies. Synchrotron radiation was used to study charge distribution in these poorly-understood Class II/III intermediate systems. In the limit of absolute localization, spectra of the mixed valence species were expected to be a linear combination of the reduced and oxidized species. For the delocalized case, a linear combination was not expected. These two cases were used as calibration limits to determine the extent of delocalization in the unknown Class II/III compound. Results showed that synchrotron radiation classifies the Class II/III compound as localized. However, data also demonstrated that the linear combination model did not hold as expected and a revised model is necessary to better understand this phenomenon.

  10. A mixed-valence metallogrid [CoCo] with an unusual electronic structure and single-ion-magnet characterization.

    Science.gov (United States)

    Huang, Wei; Pan, Feifei; Wang, Zhenxing; Bai, Yan; Feng, Xuejun; Gu, Jiande; Ouyang, Zhong-Wen; Wu, Dayu

    2017-04-11

    The reaction of the multisite coordination ligand (H2L) with Co(Ac)2·4H2O in the absence of any base affords a homometallic tetranuclear mixed-valence complex, [Co4(L)4(CH3CO2)2(CH3OH)2]·Et2O (1). This mixed-valence metallogrid [Co4(L)4(CH3CO2)2 (CH3OH)2]·Et2O (1) has been theoretically and experimentally analyzed to assign the valence and spin state in the form of trans-[Co-Co-Co-Co]. HF-EPR reveals the presence of axial anisotropy (D = -34.4 cm(-1)) with a significant transverse component (E = 9.5 cm(-1)) in the local high spin cobalt centers. Slow magnetic relaxation effects were observed in the presence of a dc field, demonstrating field-induced single ion magnetic behavior, which is associated with the unusual electronic structure of Co(ii) within the metallogrid.

  11. Mixed valency and site-preference chemistry for cerium and its compounds: A predictive density-functional theory study

    Energy Technology Data Exchange (ETDEWEB)

    Alam, Aftab [Ames Laboratory; Johnson, Duane D. [Ames Laboratory

    2014-06-01

    Cerium and its technologically relevant compounds are examples of anomalous mixed valency, originating from two competing oxidation states—itinerant Ce4+ and localized Ce3+. Under applied stress, anomalous transitions are observed but not well understood. Here we treat mixed valency as an “alloy” problem involving two valences with competing and numerous site-occupancy configurations. We use density-functional theory with Hubbard U (i.e., DFT+U) to evaluate the effective valence and predict properties, including controlling the valence by pseudoternary alloying. For Ce and its compounds, such as (Ce,La)2(Fe,Co)14B permanent magnets, we find a stable mixed-valent α state near the spectroscopic value of νs=3.53. Ce valency in compounds depends on its steric volume and local chemistry. For La doping, Ce valency shifts towards γ-like Ce3+, as expected from steric volume; for Co doping, valency depends on local Ce-site chemistry and steric volume. Our approach captures the key origins of anomalous valency and site-preference chemistry in complex compounds.

  12. Hybrid organic-inorganic polyoxometalates : synthesis and characterisation of organoarsonate and organophosphonate functionalised polyoxovanadate clusters

    OpenAIRE

    Breen, John Michael

    2010-01-01

    This thesis presents a significant contribution of research to the field of hybrid inorganic- organic polyoxometalates. Herein the functionalisation of polyoxovanadate clusters with aryl arsonates and aryl phosphonates is described and the structural and physiochemical properties of the product materials are discussed. Chapter 1 introduces the reader to the field of research, highlights recent significant achievements and puts accomplishments into a broader context. TARA (Trinity’s Access ...

  13. Mixed-valence iron minerals on Venus: Fe(2+)-Fe(3+) oxides and oxy-silicates formed by surface-atmosphere interactions

    Science.gov (United States)

    Burns, Roger G.; Straub, Darcy W.

    1992-01-01

    Inferences from these investigations are that Fe(3+)-bearing minerals such as hematite magnesioferrite, acmite, and epidote are thermodynamically unstable, and that magnetite is the predominant mixed-valence iron oxide mineral on venus. Recently, the Fe(2+)-Fe(3+) silicate mineral laihunite was proposed to be a reaction product of olivine with the venusian atmosphere. This possibility is discussed further here. We suggest that other mixed-valence Fe(2+)-Fe(3+)-Oz-OH(-) silicates could also result from surface-atmosphere interactions on Venus. Topics discussed include the following: (1) conversion of hematite to magnetite; (2) stability of laihunite; (3) the possible existence of oxy-amphiboles and oxy-micas on Venus; and (4) other mixed-valence Fe(2+)-Fe(3+) silicates likely to exist on Venus.

  14. EOMCC, MRPT, and TDDFT Studies of Charge Transfer Processes in Mixed-Valence Compounds: Application to the Spiro Molecule

    Energy Technology Data Exchange (ETDEWEB)

    Glaesemann, Kurt R.; Govind, Niranjan; Krishnamoorthy, Sriram; Kowalski, Karol

    2010-08-25

    The proper description of electron transfer (ET) processes in mixed-valence compounds poses a significant challenge for commonly used theoretical approaches. In this paper we analyze the 12A2 and 22A2 potential energy surfaces of the Spiro cation which is a frequently used model to study ET processes. We compare and contrast the results obtained with three different methods: Multireference Perturbation Theory, Equation-of-Motion Coupled Cluster Theory, Time-Dependent Density Functional Theory. We demonstrate that the proper inclusion of dynamical correlation effects plays a crucial role in the description of an avoided crossing between potential energy surfaces. We also find that proper balancing of the ground- and excited-state correlation effects is especially challenging in the vicinity of the 12A2 and 22A2 avoided crossing region.

  15. Structural and Electronic Properties of Polyoxovanadoborates Containing the [V12B18O60] Core in Different Mixed Valence States

    Directory of Open Access Journals (Sweden)

    Patricio Hermosilla-Ibáñez

    2015-07-01

    Full Text Available This review summarizes all published data until April 2015 related to crystalline lattices formed by the [V12B18O60] core, which generates polyanionic clusters with different degrees of protonation and mixed-valence ratios. The negative charge of this cluster is counterbalanced by different cations such as protonated amines, hydronium, and alkaline, and transition metal ions. The cluster is shown to form extended 1D, 2D, or 3D frameworks by forming covalent bonds or presenting hydrogen bond interactions with the present secondary cations. These cations have little influence on the solid state reflectance UV-visible spectra of the polyanionic cluster, but are shown to modify the FT-IR spectra and the magnetic behavior of the different reported species.

  16. Single-Nanoparticle Resolved Biomimetic Long-Range Electron Transfer and Electrocatalysis of Mixed-Valence Nanoparticles

    DEFF Research Database (Denmark)

    Zhu, Nan; Hao, Xian; Ulstrup, Jens

    2016-01-01

    stability in vitro. Development of robust biomimetic nanostructures is therefore highly desirable. Here, with Prussian blue nanoparticles (PBNPs) as an example we have demonstrated the preparation of highly stable and water-soluble mixed-valence nanoparticles under mild conditions. We have mapped...... their enzyme-mimicking catalytic properties and controlled LRET to single-nanoparticle resolution. PBNPs show high substrate binding affinity and tunable electrocatalytic efficiency toward hydrogen peroxide reduction, resembling the patterns for similar size redox metalloenzymes. We have further disclosed...... a correlation between electrocatalytic efficiency and distance-dependent interfacial ET kinetics. Given their high stability and low cost, such enzyme-mimicking nanoparticles could offer new perspectives in the fields of catalysis, sensors, and electrochemical energy conversion....

  17. A THIOLATO-BRIDGED OCTANUCLEAR COPPER(I,II MIXED- VALENCE COMPLEX WITH N,N,S-TRIDENTATE LIGAND

    Directory of Open Access Journals (Sweden)

    Takanori Kotera

    2007-06-01

    Full Text Available Thiolato-bridged complex [CuI4CuII4(peampt4Cl8]·2H2O (Hpeampt = 1-(2-pyridylethylamino methylpropane-2-thiol has been synthesized and characterized by the elemental analysis, IR and UV-vis spectroscopies and magnetic susceptibility measurement. The X-ray crystal structure analysis of this complex shows a localized mixed-valence octanuclear cage structure made up of four trigonal-bipyramidal CuIIN2SCl2, two trigonal CuIS2Cl, and two tetrahedral CuIS2Cl2 coordination sites. Temperature dependence of magnetic susceptibility (4.5— 300 K shows that a fairly strong antiferromagnetic interaction is operating between the four CuII ions.

  18. Mixed-valence copper coordination polymers based on CuSCN or CuN3 as bridging motifs

    Institute of Scientific and Technical Information of China (English)

    FAN Guang; GAO Shengli; CHEN Sanping; ZENG Minghua; XIE Gang

    2005-01-01

    Two novel mixed valence copper coordination polymers, [Cu(2-pac)2(CuN3)(H2O)]n (1) and [Cu(2-pac)2(CuSCN)2]n (2), have been prepared through hydrothermal synthesis and analyzed for structure determination, which exhibit two- and three-dimensional structures respectively. In complex (1), zigzag chains of [CuN3]n running parallel to the c direction are interconnected by Cu(2pac)2 to form a two-dimensional layer structure. In complex (2), the arrangement of μ-1,1,3 bridging thiocyanate ligand leads to the formation of ten-membered Cu-SCN- Cu-S-Cu-NCS rings, and each Cu atom is further linked by Cu(2-pac)2 to afford a three-dimensional configuration.

  19. Mulliken-Hush analysis of a bis(triarylamine) mixed-valence system with a N...N distance of 28.7 A.

    Science.gov (United States)

    Heckmann, Alexander; Amthor, Stephan; Lambert, Christoph

    2006-07-28

    An organic mixed valence compound with a spacer length of 25 unsaturated bonds separating two amine redox centres was synthesised and the electron transfer behaviour was investigated in the context of a Mulliken-Hush analysis in order to estimate the longest redox centre separation for which an intervalence charge transfer band can be observed.

  20. Theoretical and experimental study of high-magnetic-field XMCD spectra at the L2,3 absorption edges of mixed-valence rare-earth compounds

    Science.gov (United States)

    Kotani, Akio; Matsuda, Yasuhiro H.; Nojiri, Hiroyuki

    2009-11-01

    X-ray magnetic circular dichroism(XMCD) spectra at the L2,3 edges of mixed-valence rare-earth compounds in high magnetic fields are studied both theoretically and experimentally. The theoretical study is based on a new framework proposed recently by Kotani. The Zeeman splitting of 4f states, the mixed-valence character of 4f states, and the 4f-5d exchange interaction are incorporated into a single impurity Anderson model. New XMCD experiments in high magnetic fields up to 40 T are carried out for the mixed-valence compounds EuNi2(Si0.18Ge0.82)2 and YbInCu4 by using a miniature pulsed magnet, which was developed recently by Matsuda et al. The XMCD data are taken at 5 K by transmission measurements for incident X-rays with ± helicities at BL39XU in SPring-8. After giving a survey on recent developments in the theory of XMCD spectra for mixed-valence Ce and Yb compounds, we calculate the XMCD spectra of YbInCu4 at the field-induced valence transition around 32 T by applying the recent theoretical framework and by newly introducing at 32 T a discontinuous change in the Yb 4f level and that in the hybridization strength between the Yb 4f and conduction electrons. The calculated results are compared with the experimental ones.

  1. New nanostructured materials: synthesis of dodecanuclear Ni(II) complexes and surface deposition studies.

    Science.gov (United States)

    Pons-Balagué, Alba; Piligkos, Stergios; Teat, Simon J; Sánchez Costa, Jose; Shiddiq, Muhandis; Hill, Stephen; Castro, German R; Ferrer-Escorihuela, Pilar; Sañudo, E Carolina

    2013-07-01

    Microwave-assisted synthesis has been used to obtain the family of dodecanuclear Ni(II) complexes [Ni12(NO3)(MeO)12(MeC6H4CO2)9(MeOH)10(H2O)2][ClO4]2 (1), [Ni12(NO3)(MeO)12(BrC6H4CO2)9(MeOH)10(H2O)2][ClO4]2 (2), [Ni12(CO3)(MeO)12(MeC6H4CO2)9(MeOH)10(H2O)2]2[SO4] (3) and [Ni12(NO3)(MeO)12(MeC6H4CO2)9(MeOH)8(H2O)7][NO3]2 (4). They contain three {Ni4O4} cubane units which template around a central μ6 anion, either NO3(-) or CO3(2-). Their magnetic properties have been studied by superconducting quantum interference device (SQUID) magnetometry and high-field EPR measurements. The nanostructuration of the Ni12 species on mica surfaces is studied by AFM and grazing-incidence X-ray diffraction, which reveal the formation of polycrystalline thin layers.

  2. The mixed-valence state of Ce in the hexagonal CeNi sub 4 B compound

    CERN Document Server

    Tolinski, T; Pugaczowa-Michalska, M; Chelkowska, G

    2003-01-01

    Measurements of the magnetic susceptibility chi, x-ray photoemission spectra (XPS), electrical resistivity rho and electronic structure calculations for CeNi sub 4 B are reported. In the paramagnetic region, CeNi sub 4 B follows the Curie-Weiss law with mu sub e sub f sub f = 0.52 mu sub B /fu and theta -10.7 K. The effective magnetic moment is lower than the free Ce sup 3 sup + -ion value. The Ce(3d) XPS spectra have confirmed the mixed-valence state of Ce ions in CeNi sub 4 B. The f occupancy, n sub f , and the coupling DELTA between the f level and the conduction states were derived to be about 0.83 and 85 meV, respectively. Both susceptibility data and XPS spectra show that Ce ions in CeNi sub 4 B are in the intermediate-valence state. At low temperatures (below 12 K), the magnetic contribution to the electrical resistivity reveals a logarithmic slope characteristic of Kondo-like systems.

  3. Nanosheets of Two-Dimensional Magnetic and Conducting Fe(II)/Fe(III) Mixed-Valence Metal-Organic Frameworks.

    Science.gov (United States)

    Benmansour, Samia; Abhervé, Alexandre; Gómez-Claramunt, Patricia; Vallés-García, Cristina; Gómez-García, Carlos J

    2017-08-09

    We report the synthesis, magnetic properties, electrical conductivity, and delamination into thin nanosheets of two anilato-based Fe(II)/Fe(III) mixed-valence two-dimensional metal-organic frameworks (MOFs). Compounds [(H3O)(H2O)(phenazine)3][Fe(II)Fe(III)(C6O4X2)3]·12H2O [X = Cl (1) and Br (2)] present a honeycomb layered structure with an eclipsed packing that generates hexagonal channels containing the water molecules. Both compounds show ferrimagnetic ordering at ca. 2 K coexisting with electrical conductivity (with room temperature conductivities of 0.03 and 0.003 S/cm). Changing the X group from Cl to Br leads to a decrease in the ordering temperature and room temperature conductivity that is correlated with the decrease of the electronegativity of X. Despite the ionic charge of the anilato-based layers, these MOFs can be easily delaminated in thin nanosheets with the thickness of a few monolayers.

  4. Mixed valence as a necessary criteria for quasi-two dimensional electron gas in oxide hetero-interfaces

    Science.gov (United States)

    Singh, Vijeta; Pulikkotil, J. J.

    2017-02-01

    The origin of quasi-two dimensional electron gas at the interface of polar-nonpolar oxide hetero-structure, such as LaAlO3/SrTiO3, is debated over electronic reconstruction and defects/disorder models. Common to these models is the partial valence transformation of substrate Ti ions from its equilibrium 4 + state to an itinerant 3 + state. Given that the Hf ions have a lower ionization potential than Ti due to the 4 f orbital screening, one would expect a hetero-interface conductivity in the polar-nonpolar LaAlO3/SrHfO3 system as well. However, our first principles calculations show the converse. Unlike the Ti3+ -Ti4+ valence transition which occur at a nominal energy cost, the barrier energy associated with its isoelectronic Hf3+ -Hf4+ counterpart is very high, hence suppressing the formation of quasi-two dimensional electron gas at LaAlO3/SrHfO3 hetero-interface. These calculations, therefore, emphasize on the propensity of mixed valence at the interface as a necessary condition for an oxide hetero-structure to exihibit quasi two-dimensional electron gas.

  5. From discrete [Mn4] cluster to 1D complex: Two new mixed-valence manganese complexes with slow magnetization relaxation

    Institute of Scientific and Technical Information of China (English)

    2009-01-01

    A tetranuclear manganese complex [Mn4(HL)4(MeOH)4(SCN)2]·3MeOH (1) and a one-dimensional assembly of [Mn4] units, [Mn4(HL)4(MeOH)4(N(CN)2)2]·2.5MeOH (2) (H3L = 2,6-bis(hydroxymethyl)-4-methyl-phenol), have been synthesized and studied. Complexes 1 and 2 crystallize in the triclinic space group P 1and monoclinic space group P21/n, respectively. Complex 1 possesses a mixed-valence tetranuclear dicubane unit, which comprises two MnⅡ and two MnⅢ ions. Complex 2 is built from the similar tetranuclear [Mn4] units connected through two N(CN)2-anions into a 1-D chain. The temperature dependence of the magnetic susceptibilities of 1 and 2 indicates ferromagnetic interactions between the manganese ions. Frequency-dependent out-of-phase signals of alternating current magnetic susceptibilities are observed in the low temperature range for both complexes, indicating a slow magnetic relaxation.

  6. Intramolecular electronic couplings in class II/III organic mixed-valence systems of bis(1,4-dimethoxybenzene).

    Science.gov (United States)

    Yang, Juanhua; Zhang, Weiwei; Si, Yubing; Zhao, Yi

    2012-12-06

    The intramolecular electronic couplings in organic mixed-valence systems [D-(ph)(n)-D](•+) (D = 2,5-dimethoxy-4-methylphenyl, n = 0, 1, and 2) are calculated by dominantly using density functional theory to investigate their dependence of functionals. Since these systems have the property that the charge is from localization to delocalization, the optimized structures are sensitive to the functionals. The geometric optimizations show that CAM-B3LYP and ωB97X-D functionals are good choices for delocalized systems and LC-ωPBE and M06HF are suitable for the systems from charge almost localization to localization. The calculations of electronic couplings demonstrate that the pure functional generally underestimates the electronic couplings whereas the pure HF overestimates them. Furthermore, the electronic couplings from the conventional generalized Mulliken-Hush method are very sensitive to the HF component in functionals, which makes it a challenge to accurately estimate the values. A new reduced two-state method is thus proposed to overcome the deficiency, and the obtained electronic couplings are less sensitive to the ω value in LC-ω PBE functional and they are also consistent with the experimental data.

  7. Magnetic and thermoelectric properties of a heterogeneous mixed-valence system, Yb sub 2 Pt sub 3 Sn sub 5

    CERN Document Server

    Muro, Y; Kim, M S; Takabatake, T; Godart, C; Rogl, P

    2003-01-01

    We have studied the valence states and thermoelectric properties of Yb sub 2 T sub 3 Sn sub 5 (T=Pt and Pd) with two inequivalent Yb sites. For Yb sub 2 Pt sub 3 Sn sub 5 , the 4 f-hole occupation number n sub f is estimated to be 0.4 at 300 K from the magnetic susceptibility and L sub I sub I sub I -edge absorption spectrum. Intermediate-valence behaviors manifest themselves in a largely negative value of the paramagnetic Curie temperature, -216 K, a broad peak at 300 K in the magnetic part of the resistivity, and a large minimum in the thermopower, -38 mu V/K at 60 K. The specific heat shows no transition down to 0.6 K. These results are explained by a model in which Yb ions in one site are divalent and those in the other site are in a valence fluctuating state with a Kondo temperature of 200 K. Thus, Yb sub 2 Pt sub 3 Sn sub 5 is a rare example of the heterogeneous mixed-valence system. An isostructural compound Yb sub 2 Pd sub 3 Sn sub 5 has a larger unit-cell volume by 2.4%, which allows the Yb ions in b...

  8. Manganese L-edge X-ray absorption spectroscopy of manganese catalase from Lactobacillus plantarum and mixed valence manganese complexes

    Energy Technology Data Exchange (ETDEWEB)

    Grush, M.M.; Chen, J.; George, S.J. [Univ. of California, Davis, CA (United States)] [and others

    1996-01-10

    The first Mn L-edge absorption spectra of a Mn metalloprotein are presented in this paper. Both reduced and superoxidized Mn catalase have been examined by fluorescence-detected soft X-ray absorption spectroscopy, and their Mn L-edge spectra are dramatically different. The spectrum of reduced Mn(II)Mn(II) catalase has been interpreted by ligand field atomic multiplet calculations and by comparison to model compound spectra. The analysis finds a 10 Dq value of nearly 1.1 eV, consistent with coordination by predominately nitrogen and oxygen donor ligands. For interpretation of mixed valence Mn spectra, an empirical simulation procedure based on the addition of homovalent model compound spectra has been developed and was tested on a variety of Mn complexes and superoxidized Mn catalase. This routine was also used to determine the oxidation state composition of the Mn in [Ba{sub 8}Na{sub 2}ClMn{sub 16}(OH){sub 8}(CO{sub 3}){sub 4}L{sub 8}] .53 H{sub 2}O (L=1,3-diamino-2-hydroxypropane-N,N,N`N`-tetraacetic acid). 27 refs., 6 figs.

  9. Dodecanuclear 3d/4f-metal clusters with a 'Star of David' topology: single-molecule magnetism and magnetocaloric properties.

    Science.gov (United States)

    Alexandropoulos, Dimitris I; Cunha-Silva, Luís; Lorusso, Giulia; Evangelisti, Marco; Tang, Jinkui; Stamatatos, Theocharis C

    2016-01-28

    A family of interwoven molecular inorganic knots, shaped like the 'Star of David', was prepared by the employment of naphthalene-2,3-diol in 3d/4f-metal cluster chemistry; the isoskeletal dodecanuclear compounds exhibit slow relaxation of the magnetization and magnetocaloric properties, depending on the metal ion.

  10. Self-assembly of a chiral carbonate- and cytidine-containing dodecanuclear copper(II) complex: a multiarm-supplied globular capsule.

    Science.gov (United States)

    Armentano, Donatella; Marino, Nadia; Mastropietro, Teresa F; Martínez-Lillo, José; Cano, Joan; Julve, Miguel; Lloret, Francesc; De Munno, Giovanni

    2008-11-17

    A dodecanuclear copper(II) globular-shaped structure has been obtained with the cytidine nucleoside and the templating carbonate anion. It shows receptor properties through anion-cation and multiple anion-pi interactions toward ClO 4 (-) as well as an overall antiferromagnetic coupling.

  11. PT L 3 near edge structure of halogen-bridged mixed-valence pt complexes and pd-pt mixed-metal complexes

    Science.gov (United States)

    Tanino, H.; Oyanagi, H.; Yamashita, M.; Kobayashi, K.

    1985-03-01

    X-ray absorption near edge structure (XANES) of halogen-bridged mixed-valence Pt complexes and halogen-bridged Pd-Pt mixed-metal complexes have been measured using synchrotron radiation with a high energy resolution. In Pd-Pt mixed metal complexes, we demonstrate that the degree of the valence is estimated from the intensity of the white line at the Pt L 3 edge. In the mixed-valence complexes, the electron system is proved to be the Peierls insulator with a charge density wave of renormalized d electrons of Pt, where the total valence of Pt IV- and Pt 11 is conserved without excess electrons from ligands or anions.

  12. Formation of high nuclearity mixed-valent polyoxovanadates in the presence of copper amine complexes

    Indian Academy of Sciences (India)

    Jency Thomas; Sanjeev Sharma; S E Lofland; K V Ramanujachary; A Ramanana

    2006-01-01

    Two new Müller-type clusters, a one-dimensional solid {Cu()2}4[Cl ⊂ V15O36]$\\cdot$12H2O 1, and a three-dimensional solid {Cu()2}4[Cl ⊂ V18O42]$\\cdot$12H2O 2, have been synthesised by employing identical hydrothermal conditions except varying the nature of organic diamine. 1 crystallised in a chiral space group 212121 with = 12.757(1), = 18.927(2) and = 28.590(3) Å, and = 4. 2 crystallised in a tetragonal system with space group 4/, = 15.113(1) and = 18.542(3) Å, and = 2. Mixed-valent vanadium ions in structures 1 and 2 have been established both by magnetisation and bond-length bondvalence measurements. Chemistry of formation of high nuclearity polyoxovanadate clusters is discussed.

  13. Hexa- and dodecanuclear polyoxomolybdate cyclic compounds: application toward the facile synthesis of nanoparticles and film electrodeposition.

    Science.gov (United States)

    Dolbecq, Anne; Compain, Jean-Daniel; Mialane, Pierre; Marrot, Jérôme; Sécheresse, Francis; Keita, Bineta; Holzle, Luis Roberto Brudna; Miserque, Frédéric; Nadjo, Louis

    2009-01-01

    Two new compounds based on O(3)PCH(2)PO(3)(4-) ligands and {Mo(V)(2)O(4)} dimeric units have been synthesized and structurally characterized. The dodecanuclear Mo(V) polyoxomolybdate species in (NH(4))(18)[(Mo(V)(2)O(4))(6)(OH)(6)(O(3)PCH(2)PO(3))(6)] x 33 H(2)O (1) is a cyclohexane-like ring in a chair conformation with pseudo S(6) symmetry. In the solid state, the wheels align side by side, thus delimiting large rectangular voids. The hexanuclear anion in Na(8)[(Mo(V)(2)O(4))(3)(O(3)PCH(2)PO(3))(3)(CH(3)AsO(3))] x 19 H(2)O (2) has a triangular framework and encapsulates a methylarsenato ligand. (31)P NMR spectroscopic analysis revealed the stability of 2 in various aqueous media, whereas the stability of 1 depends on the nature of the cations present in solution. It has been evidenced that the transformation of 1 into 2 occurs in the presence of CH(3)AsO(3)(2-) ions. This behavior shows that 1 can be used as a new precursor for the synthesis of Mo(V)/diphosphonate systems. The two complexes were very efficient both as reductants of Pt and Pd metallic salts and as capping agents for the resulting Pt(0) and Pd(0) nanoparticles. The size of the obtained nanoparticles depends both on the nature of the polyoxometalate (POM; i.e., 1 or 2) and on the [metallic salt]/[POM] ratio. In all cases, X-ray photoelectron spectroscopy (XPS) measurements have revealed the presence of Mo(VI) species that stabilize the nanoparticles and the absence of Mo(V) moieties. Diffuse-reflectance FTIR spectra of the Pt nanoparticles show that the capping Mo(VI) POMs are identical for both systems and contain the diphosphonato ligand. The colloidal solutions do not show any precipitate and the nanoparticles remain well-dispersed for several months. The electrochemical reduction of Mo(V) species was studied for 2. Cyclic voltammetry alone and electrochemical quartz crystal microbalance coupled with cyclic voltammetry show the deposition of a film on the electrode surface during this reduction.

  14. Charge transfer phase transition with reversed thermal hysteresis loop in the mixed-valence Fe9[W(CN)8]6·xMeOH cluster.

    Science.gov (United States)

    Chorazy, Szymon; Podgajny, Robert; Nogaś, Wojciech; Nitek, Wojciech; Kozieł, Marcin; Rams, Michał; Juszyńska-Gałązka, Ewa; Żukrowski, Jan; Kapusta, Czesław; Nakabayashi, Koji; Fujimoto, Takashi; Ohkoshi, Shin-ichi; Sieklucka, Barbara

    2014-04-04

    A bimetallic pentadecanuclear cyanido-bridged {Fe9[W(CN)8]6 (MeOH)24}·xMeOH cluster of an Fe(II/III)-W(IV/V) mixed valence nature, reveals a reversible single-crystal-to-single-crystal transformation, concomitant with metal-to-metal charge transfer between Fe and W ions. The dominance of (HS)Fe(II)-NC-W(V) units at a high temperature, and (HS)Fe(III)-NC-W(IV) units at a low temperature, leads to an unprecedented reversed thermal hysteresis loop in magnetic measurements.

  15. Intervalence charge transfer transition in mixed valence complexes synthesised from RuIII(edta)- and FeII(CN)5-cores

    Indian Academy of Sciences (India)

    H C Bajaj; Atindra D Shukla; Amitava Das

    2002-08-01

    Intervalence charge transfer properties were studied for a set of mixed valence complexes incorporating Ru(III) and Fe(II)-centres linked by various saturated and unsaturated bridging ligands (BL). Studies reveal that degree of ground state electronic interaction and coupling between Ru(III) and Fe(II)-centres can be attenuated by changing the nature of the bridging ligand. Further, inclusion of the bridging ligand with interrupted -electron system in a -CD cavity initiate an optical electron transfer from Fe(II) to Ru(III) which is otherwise not observed.

  16. A Transition from Localized to Strongly Correlated Electron Behavior and Mixed Valence Driven by Physical or Chemical Pressure in ACo2As2 (A = Eu and Ca)

    Energy Technology Data Exchange (ETDEWEB)

    Tan, Xiaoyan; Fabbris, Gilberto; Haskel, Daniel; Yaroslavtsev, Alexander A.; Cao, H.; Thompson, Corey M.; Kovnir, Kirill; Menushenkov, Alexey P.; Chernikov, Roman V.; Garlea, V. Ovidiu; Shatruk, Michael

    2016-03-02

    We demonstrate that the action of physical pressure, chemical compression, or aliovalent substitution in ACo(2)As(2) (A = Eu and Ca) has a general consequence of causing these antiferromagnetic materials to become ferromagnets. In all cases, the mixed valence triggered at the electropositive A site results in the increase of the Co 3d density of states at the Fermi level. Remarkably, the dramatic alteration of magnetic behavior results from the very minor (<0.15 eleetron) change in the population of the 3d orbitals. The mixed valence state of En observed in the high-pressure (HP) form of EuCo2As2 exhibits a remarkable stability, achieving the average oxidation state of +2.25 at 12.6 GPa. In the case of CaCo2As2, substituting even 10% of Eu or La into the Ca site causes ferromagnetic ordering of Co moments. Similar to HP-EuCo2As2, the itinerant 3d ferromagnetism emerges from electronic doping into the Co layer because of chemical compression of Eu sites in Ca0.9Eu0.1Co1.91As2 or direct electron doping in Ca0.85La0.15Co1.89As2. The results reported herein demonstrate the general possibility of amplifying minor localized electronic effects to achieve major changes in material's properties via involvement of strongly correlated electrons.

  17. Hybrid Langmuir and Langmuir-Blodgett films of a viologen derivative and TCNQ in a mixed valence state: preparation route and characterization

    Science.gov (United States)

    Martín, Santiago; Cea, Pilar; Lafuente, Carlos; Royo, Félix M.; López, María. C.

    2004-08-01

    Hybrid Langmuir and Langmuir-Blodgett (LB) films containing two moieties of great chemical and electrochemical interest, namely a viologen derivative and tetracyanoquinodimethane (TCNQ) in a mixed valence state, were fabricated. To do so, positively ionized monolayers of 1,1 '-dioctadecyl 4,4 '-bipyridilium were prepared onto aqueous solutions of tetracyanoquinodimethane in a mixed valence state. Surface pressure vs. area ( π- A), surface potential vs. area (Δ V- A), and Brewster angle microscope (BAM) images were recorded and interpreted in terms of molecular interactions as well as the incorporation of the hydrophobic anions into the monolayer. After a comprehensive study, a 10 -6 M TCNQ aqueous solution was chosen as the best one to build hybrid LB films. Thus, the floating films were transferred onto solid substrates that were characterized using several techniques including ultraviolet-visible (UV-vis), infrared (IR), scanning electron microscopy (SEM), and atomic force microscopy (AFM) proving the incorporation of the TCNQ onto the film. These films show a good optical conductivity as well as a high degree of order and layers with a constant architecture.

  18. New route to the mixed valence semiquinone-catecholate based mononuclear FeIII and catecholate based dinuclear MnIII complexes: first experimental evidence of valence tautomerism in an iron complex.

    Science.gov (United States)

    Shaikh, Nizamuddin; Goswami, Sanchita; Panja, Anangamohan; Wang, Xin-Yi; Gao, Song; Butcher, Ray J; Banerjee, Pradyot

    2004-09-20

    The semiquinone-catecholate based mixed valence complex, [FeIII(bispicen)(Cl4Cat)(Cl4SQ)] x DMF (1), and catecholate based (H2bispictn)[Mn2III(Cl4Cat)4(DMF)2] (2) (bispicen = N,N'-bis(2-pyridylmethyl)-1,2-ethanediamine, bispictn = N,N'-bis(2-pyridylmethyl)-1,3-propanediamine, Cl4Cat = tetrachlorocatecholate dianion, and Cl4SQ = tetrachlorosemiquinone radical anion) were synthesized directly utilizing a facile route. Both the complexes have been characterized by single crystal X-ray diffraction study. The electronic structures have been elucidated by UV-vis-NIR absorption spectroscopy, cyclic voltammetry, EPR, and magnetic properties. The structural as well as spectroscopic features support the mixed valence tetrachlorosemiquinone-tetrachlorocatecholate charge distribution in 1. The ligand based mixed valence state was further confirmed by the presence of an intervalence charge transfer (IVCT) band in the 1900 nm region both in solution and in the solid. The intramolecular electron transfer, a phenomenon known as valence tautomerism (VT), has been followed by electronic absorption spectroscopy. For 1, the isomeric form [FeIII(bispicen)(Cl4Cat)(Cl4SQ)] is favored at low temperature, while at an elevated temperature, the [FeII(bispicen)(Cl4SQ)2] redox isomer dominates. Infrared as well as UV-vis-NIR spectral characterization for 2 suggest that the MnIII(Cat)2- moiety is admixed with its mixed valence semiquinone-catecholate isomer MnII(SQ)(Cat)-, and the electronic absorption spectrum is dominated by the mixed charged species. The origin of the intervalence charge transfer band in the 1900 nm range is associated with the mixed valence form, MnII(Cl4Cat)(Cl4SQ)-. The observation of VT in complex 1 is the first example where a mixed valence semiquinone-catecholate iron(III) complex undergoes intramolecular electron transfer similar to manganese and cobalt complexes.

  19. Mixed-valence copper(I,II) complexes with 4-(1H-pyrazol-1-yl)-6-R-pyrimidines: from ionic structures to coordination polymers.

    Science.gov (United States)

    Vinogradova, Katerina A; Krivopalov, Viktor P; Nikolaenkova, Elena B; Pervukhina, Natalia V; Naumov, Dmitrii Yu; Boguslavsky, Evgenii G; Bushuev, Mark B

    2016-01-14

    Two pyrimidine-based ligands, 4-(3,5-diphenyl-1H-pyrazol-1-yl)-6-(morpholino)pyrimidine () and 4-(3,5-diphenyl-1H-pyrazol-1-yl)-6-phenoxypyrimidine (), and a series of mixed-valence copper(i,ii) halide complexes, [Cu(L(2))2Br]2[Cu2Br4] (), [Cu(L(2))2Cl][CuCl2] (), and [Cu2L(3)Br3]n (), have been synthesized. The complex [Cu(L(2))2Br]2[Cu2Br4] was prepared by the reaction of with CuBr2 in a 1 : 1 molar ratio in MeCN. Its chlorido-analogue, the complex [Cu(L(2))2Cl][CuCl2], was synthesized by the reaction between , CuCl2 and CuCl in a 2 : 1 : 1 molar ratio in MeCN. The ligand acts as a chelating one. In the structures of the complexes [Cu(L(2))2Br]2[Cu2Br4] and [Cu(L(2))2Cl][CuCl2] the Cu(2+) ion is in the cationic part of the complex whereas the Cu(+) ion is located in the anionic part. The best way to synthesize the mixed-valence 1D coordination polymer [Cu2L(3)Br3]n is to react CuBr2 with in a 2 : 1 molar ratio in the MeCN/CHCl3 mixture on heating. In the structure of [Cu2L(3)Br3]n the ligand shows chelating/bridging tridentate coordination. This is the first example of the tridentate coordination of 4-(1H-pyrazol-1-yl)-6-R-pyrimidines. The striking difference between the coordination behavior of and (chelating bidentate vs. chelating/bridging coordination) is related with the possibility of rotation of the 6-phenoxy group around the C-O bond which makes the N(1) pyrimidine atom less sterically hindered, enabling it to participate in metal ion binding. Importantly, all copper ions in [Cu2L(3)Br3]n show similar tetrahedral environments, CuNBr3 and CuN2Br2, which is extremely rare for mixed-valence copper(i,ii) compounds. The ligands and show blue emission which is quenched upon their coordination to copper ions. The 1D coordination polymer [Cu2L(3)Br3]n shows high thermal stability and unusual solvent-occlusion properties. The role of the substituents favoring the formation of the mixed-valence copper(i,ii) complexes with 4-(1H-pyrazol-1-yl)-6-R

  20. The microstructure and electrical conductivity of mixed-valence TlIn(4)S(5)Cl quaternary compound micro- and nanowires.

    Science.gov (United States)

    Jiang, Xin; Deiseroth, Hans-Jörg; Gu, Changzhi; Xhaxhiu, Kledi; Huang, Yang; Li, Junjie; Che, Renchao; Wang, Zongli

    2008-05-21

    Quaternary mixed-valence compound TlIn(4)S(5)Cl micro- and nanowires are prepared by partial substitution of chalcogen with halogen starting from a stoichiometric mixture of TlCl, In and S. Their electrical conductivity and gas sensitivity properties are investigated by using standard four-terminal systems. The specific nanowire resistivity is about 10(7) Ω cm and corresponds to the value of a typical undoped semiconductor in air. This resistivity is, however, extremely sensitive to NO(2) (sensitivity about 150) or NH(3), with a rapid response of about 2 s and recovery times. This phenomenon is supposed to be particularly important for future nanodevice applications.

  1. Nonlinear lattice relaxation of photogenerated charge-transfer excitation in halogen-bridged mixed-valence metal complexes. II. Polaron channel

    Science.gov (United States)

    Mishima, A.; Nasu, K.

    1989-03-01

    The one-dimensional extended Peierls-Hubbard model with half-filled-band electrons is studied in order to clarify the lattice relaxation path of the photogenerated charge-transfer excitation in halogen-bridged mixed-valence metal complexes. The ground and excited states are calculated within mean-field theory for electrons and the adiabatic approximation for phonons. It is concluded that the main origin of the photoinduced absorption is a distant pair of the hole-polaron and the electron-polaron. This distant pair is created not from the ground state of the self-trapped exciton (STE), but from the excited states of the STE through their autodissociation. This is consistent with the experiment on the excitation energy dependence of the photoinduced absorption yield.

  2. Synthesis, Crystal Structure, and Electroconducting Properties of a 1D Mixed-Valence Cu(I–Cu(II Coordination Polymer with a Dicyclohexyl Dithiocarbamate Ligand

    Directory of Open Access Journals (Sweden)

    Kenji Nakatani

    2015-04-01

    Full Text Available A new mixed-valence Cu(I–Cu(II 1D coordination polymer, [CuI4CuIIBr4(Cy2dtc2]n, with an infinite chain structure is synthesized by the reaction of Cu(Cy2dtc2 (Cy2dtc− = dicyclohexyl dithiocarbamate, C13H22NS2 with CuBr·S(CH32. The as-synthesized polymer consists of mononuclear copper(II units of CuII(Cy2dtc2 and tetranuclear copper(I cluster units, CuI4Br4. In the cluster unit, all the CuI ions have distorted trigonal pyramidal coordination geometries, and the CuI–CuI or CuI–CuII distances between the nearest copper ions are shorter than the sum of van der Waals radii for Cu–Cu.

  3. Europium mixed-valence, long-range magnetic order, and dynamic magnetic response in EuCu2(SixGe1 -x)2

    Science.gov (United States)

    Nemkovski, K. S.; Kozlenko, D. P.; Alekseev, P. A.; Mignot, J.-M.; Menushenkov, A. P.; Yaroslavtsev, A. A.; Clementyev, E. S.; Ivanov, A. S.; Rols, S.; Klobes, B.; Hermann, R. P.; Gribanov, A. V.

    2016-11-01

    In mixed-valence or heavy-fermion systems, the hybridization between local f orbitals and conduction band states can cause the suppression of long-range magnetic order, which competes with strong spin fluctuations. Ce- and Yb-based systems have been found to exhibit fascinating physical properties (heavy-fermion superconductivity, non-Fermi-liquid states, etc.) when tuned to the vicinity of magnetic quantum critical points by use of various external control parameters (temperature, magnetic field, chemical composition). Recently, similar effects (mixed-valence, Kondo fluctuations, heavy Fermi liquid) have been reported to exist in some Eu-based compounds. Unlike Ce (Yb), Eu has a multiple electron (hole) occupancy of its 4 f shell, and the magnetic Eu2 + state (4 f7 ) has no orbital component in the usual L S coupling scheme, which can lead to a quite different and interesting physics. In the EuCu2(SixGe1 -x)2 series, where the valence can be tuned by varying the Si/Ge ratio, it has been reported that a significant valence fluctuation can exist even in the magnetic order regime. This paper presents a detailed study of the latter material using different microscopic probes (XANES, Mössbauer spectroscopy, elastic and inelastic neutron scattering), in which the composition dependence of the magnetic order and dynamics across the series is traced back to the change in the Eu valence state. In particular, the results support the persistence of valence fluctuations into the antiferromagnetic state over a sizable composition range below the critical Si concentration xc≈0.65 . The sequence of magnetic ground states in the series is shown to reflect the evolution of the magnetic spectral response.

  4. Versatile Reactivity and Theoretical Evaluation of Mono- and Dinuclear Oxidovanadium(V) Compounds of Aroylazines: Electrogeneration of Mixed-Valence Divanadium(IV,V) Complexes.

    Science.gov (United States)

    Dash, Subhashree P; Roy, Satabdi; Mohanty, Monalisa; Carvalho, M Fernanda N N; Kuznetsov, Maxim L; Pessoa, João Costa; Kumar, Amit; Patil, Yogesh P; Crochet, Aurélien; Dinda, Rupam

    2016-09-06

    The substituted hydrazones H2L(1-4) (L(1-4) = dibasic tridentate ONO(2-) donor ligands) obtained by the condensation of 2-hydroxy-1-naphthaldehyde and 2-aminobenzoylhydrazine (H2hnal-abhz) (H2L(1)) , 2-hydroxy-1-naphthaldehyde and 2-hydroxybenzoylhydrazine (H2hnal-hbhz) (H2L(2)), 2-hydroxy-1-acetonaphthone and benzoylhydrazine (H2han-bhz) (H2L(3)), or 2-hydroxy-1-acetonaphthone and 2-aminobenzoylhydrazine (H2han-abhz) (H2L(4)) are prepared and characterized. Reaction of ammonium vanadate with the appropriate H2L(1-4) results in the formation of oxidoethoxidovanadium(V) [V(V)O(OEt)(L(1-4))] (1-4) complexes. All compounds are characterized in the solid state and in solution by spectroscopic techniques (IR, UV-vis, (1)H, (13)C, and (51)V NMR, and electrospray ionization mass spectrometry). Single-crystal X-ray diffraction analysis of 1, 3, and 4 confirms the coordination of the corresponding ligands in the dianionic (ONO(2-)) enolate tautomeric form. In solution, the structurally characterized [V(V)O(OEt)(L)] compounds transform into the monooxido-bridged divanadium(V,V) [(V(V)OL)2-μ-O] complexes, with the processes being studied by IR and (1)H, (13)C, and (51)V NMR. The density functional theory (DFT) calculated Gibbs free energy of reaction 2[V(V)O(OEt)(L(4))] + H2O ⇆ [(V(V)OL(4))2-μ-O] + 2EtOH is only 2-3 kcal mol(-1), indicating that the dinuclear complexes may form in a significant amount. The electrochemical behavior of the complexes is investigated by cyclic voltammetry, with the V(V)-V(IV) E1/2(red) values being in the range 0.27-0.44 V (vs SCE). Upon controlled potential electrolysis, the corresponding (L)(O)V(IV)-O-V(V)(O)(L) mixed-valence species are obtained upon partial reduction of the [(V(V)OL)2-μ-O] complexes formed in solution, and some spectroscopic characteristics of these dinuclear mixed-valence complexes are investigated using DFT calculations and by electron paramagnetic resonance (EPR), with the formation of V(IV)-O-V(V) species being

  5. Charge, orbital and spin ordering phenomena in the mixed valence manganite (NaMn3+3)(Mn3+2Mn4+2)O12

    Science.gov (United States)

    Prodi, A.; Gilioli, E.; Gauzzi, A.; Licci, F.; Marezio, M.; Bolzoni, F.; Huang, Q.; Santoro, A.; Lynn, J. W.

    2004-01-01

    Mixed-valence manganites with the ABO3 perovskite structure display a variety of magnetic and structural transitions, dramatic changes of electrical conductivity and magnetoresistance effects. The physical properties vary with the relative concentration of Mn3+ and Mn4+ in the octahedral corner-sharing network, and the proportion of these two cations is usually changed by doping the trivalent large A cation (for example, La3+) with divalent cations. As the dopant and the original cation have, in general, different sizes, and as they are distributed randomly in the structure, such systems are characterized by local distortions that make it difficult to obtain direct information about their crystallographic and physical properties. On the other hand, the double oxides of formula AA'3Mn4O12 contain a perovskite-like network of oxygen octahedra centred on the Mn cations, coupled with an ordered arrangement of the A and A' cations, whose valences control the proportion of Mn3+ and Mn4+ in the structure. The compound investigated in this work, (NaMn3+3)(Mn3+2Mn4+2)O12, contains an equal number of Mn3+ and Mn4+ in the octahedral sites. We show that the absence of disorder enables the unambiguous determination of symmetry, the direct observation of full, or nearly full, charge ordering of Mn3+ and Mn4+ in distinct crystallographic sites, and a nearly perfect orbital ordering of the Mn3+ octahedra.

  6. Frustrated spin-1/2 molecular magnetism in the mixed-valence antiferromagnets Ba3M Ru2O9 (M =In , Y, Lu)

    Science.gov (United States)

    Ziat, D.; Aczel, A. A.; Sinclair, R.; Chen, Q.; Zhou, H. D.; Williams, T. J.; Stone, M. B.; Verrier, A.; Quilliam, J. A.

    2017-05-01

    We have performed magnetic susceptibility, heat capacity, muon spin relaxation, and neutron-scattering measurements on three members of the family Ba3M Ru2O9 , where M =In , Y, and Lu. These systems consist of mixed-valence Ru dimers on a triangular lattice with antiferromagnetic interdimer exchange. Although previous work has argued that charge order within the dimers or intradimer double exchange plays an important role in determining the magnetic properties, our results suggest that the dimers are better described as molecular units due to significant orbital hybridization, resulting in one spin-1/2 moment distributed equally over the two Ru sites. These molecular building blocks form a frustrated, quasi-two-dimensional triangular lattice. Our zero- and longitudinal-field μ SR results indicate that the molecular moments develop a collective, static magnetic ground state, with oscillations of the zero-field muon spin polarization indicative of long-range magnetic order in the Lu sample. The static magnetism is much more disordered in the Y and In samples, but they do not appear to be conventional spin glasses.

  7. Valence-delocalization of the mixed-valence oxo-centered trinuclear iron propionates [Fe{2/III}FeIIO(C2H5CO2)6(py)3] npy; n=0, 1.5

    Science.gov (United States)

    Nakamoto, Tadahiro; Katada, Motomi; Kawata, Satoshi; Kitagawa, Susumu; Sano, Hirotoshi; Konno, Michiko

    1994-12-01

    Mixed-valence trinuclear iron propionates [Fe{2/III}FeIIO(C2H5CO2)6(py)3]npy, where n=0, 1.5, were synthesized and the structure of the pyridine-solvated complex was determined by single-crystal X-ray diffraction. Mössbauer spectra of the solvated propionate complex showed a temperature-dependent mixed-valence state related to phase transitions, reaching an almost delocalized valence state at room temperature. On the other hand, the non-solvated propionate showed a remarkable change of the spectral shape related to a phase transition, remaining in a localized valence state at higher temperatures up to room temperature.

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

    Energy Technology Data Exchange (ETDEWEB)

    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.

  9. [2.2]paracyclophane-bridged mixed-valence compounds: application of a generalized Mulliken-Hush three-level model.

    Science.gov (United States)

    Amthor, Stephan; Lambert, Christoph

    2006-01-26

    A series of [2.2]paracylophane-bridged bis-triarylamine mixed-valence (MV) radical cations were analyzed by a generalized Mulliken-Hush (GMH) three-level model which takes two transitions into account: the intervalence charge transfer (IV-CT) band which is assigned to an optically induced hole transfer (HT) from one triarylamine unit to the second one and a second band associated with a triarylamine radical cation to bridge (in particular, the [2.2]paracyclophane bridge) hole transfer. From the GMH analysis, we conclude that the [2.2]paracyclophane moiety is not the limiting factor which governs the intramolecular charge transfer. AM1-CISD calculations reveal that both through-bond as well as through-space interactions of the [2.2]paracyclophane bridge play an important role for hole transfer processes. These electronic interactions are of course smaller than direct pi-conjugation, but from the order of magnitude of the couplings of the [2.2]paracyclophane MV species, we assume that this bridge is able to mediate significant through-space and through-bond interactions and that the cyclophane bridge acts more like an unsaturated spacer rather than a saturated one. From the exponential dependence of the electronic coupling V between the two triarylamine localized states on the distance r between the two redox centers, we infer that the hole transfer occurs via a superexchange mechanism. Our analysis reveals that even significantly longer pi-conjugated bridges should still mediate significant electronic interactions because the decay constant beta of a series of pi-conjugated MV species is small.

  10. Synthesis of an S T = 7 [Mn 3 ] Mixed-Valence Complex Based on 1,3-Propanediol Ligand Derivatives and Its One-Dimensional Assemblies

    KAUST Repository

    Huang, Jian

    2013-10-07

    Controlled organization of high-spin complexes and single-molecule magnets is a great challenge in molecular magnetism in order to study the effect of the intercomplex magnetic interactions on the intrinsic properties of a given magnetic object. In this work, a new ST = 7 trinuclear mixed-valence Mn complex, [MnIIIMnII 2(LA) 2(Br)4(CH3OH)6] ·Br· (CH3OH)1.5·(H2O)0.5 (1), is reported using a pyridinium-functionalized 1,3-propanediol ligand (H 2LABr = 1-(3-bromo-2,2-bis(hydroxymethyl)propyl)pyridinium bromide). Using azido anions as bridging ligands and different pyridinium-functionalized 1,3-propanediol ligands (H2LBBr = 1-(3-bromo-2,2-bis(hydroxymethyl)propyl)-4-picolinium bromide; H 2LCBr = 1-(3-bromo-2,2-bis(hydroxymethyl)propyl)-3,5- lutidinium bromide), the linear [MnIIIMnII 2L2X4]+ building block has been assembled into one-dimensional coordination networks: [MnIIIMn II 2(LA)2(Br)4(CH 3OH)4(N3)]·((C2H 5)2O)1.25 (2∞), [MnIIIMn II 2(LB)2(Br)4(C 2H5OH)(CH3OH)(H2O) 2(N3)]·(H2O)0.25 (3∞), and [MnIIIMnII 2(LC) 2(Cl)3.8(Br)0.2(C2H 5OH)3(CH3OH)(N3)] (4∞). The syntheses, characterization, crystal structures, and magnetic properties of these new [Mn3]-based materials are reported. © 2013 American Chemical Society.

  11. Pseudotetragonal structure of Li(2+x)Ce(x)(3+)Ce(12-x)(4+)F(50): the first mixed valence cerium fluoride.

    Science.gov (United States)

    Renaudin, Guillaume; Dieudonné, Belto; Avignant, Daniel; Mapemba, Elise; El-Ghozzi, Malika; Fleutot, Solène; Martinez, Hervé; Cerný, Radovan; Dubois, Marc

    2010-01-18

    The crystal structure of the new Li(5.5)Ce(12)F(50) compound has been fully characterized by single-crystal and synchrotron powder X-ray diffraction. An accurate pseudotetragonal structure was described in the monoclinic P2(1) space group with 68 independent crystallographic sites. The Li(5.5)Ce(12)F(50) composition belongs to the Li(2+x)Ce(x)(3+)Ce(12-x)(4+)F(50) solid solution. Its structure consists of an opened fluorine framework where a channel network allows the intercalation of relatively mobile lithium cations, inducing the formation of the mixed-valence cerium (the intercalation of Li(+) leads to the reduction of a part of Ce(4+) to Ce(3+)). One part of the lithium ions, necessary for the electroneutrality of the tetravalent equivalent cerium fluoride (Li(2)Ce(12)F(50) composition), is in a locked fluorine polyhedron. Only the supplementary x amount of lithium is able to be exchanged in Li(2+x)Ce(x)(3+)Ce(12-x)(4+)F(50). The structure of Li(2+x)Ce(x)(3+)Ce(12-x)(4+)F(50) is a rearrangement, due to lithium intercalation, of the base CeF(4) structure. Bond valence calculation on Ce sites, Ce coordination polyhedra volumes, and a calculated Ce cationic radius give the indication of a partial long-range ordering of trivalent and tetravalent cerium cations in specific slabs of the structure. (7)Li NMR spectroscopy and XPS analyses have confirmed all of the structure details.

  12. Coordination and metalation bifunctionality of Cu with 5,10,15,20-tetra(4-pyridyl)porphyrin: toward a mixed-valence two-dimensional coordination network.

    Science.gov (United States)

    Li, Yang; Xiao, Jie; Shubina, Tatyana E; Chen, Min; Shi, Ziliang; Schmid, Martin; Steinrück, Hans-Peter; Gottfried, J Michael; Lin, Nian

    2012-04-11

    We investigated the coordination self-assembly and metalation reaction of Cu with 5,10,15,20-tetra(4-pyridyl)porphyrin (2HTPyP) on a Au(111) surface by means of scanning tunneling microscopy, X-ray photoelectron spectroscopy, and density functional theory calculations. 2HTPyP was found to interact with Cu through both the peripheral pyridyl groups and the porphyrin core. Pairs of pyridyl groups from neighboring molecules coordinate Cu(0) atoms, which leads to the formation of a supramolecular metal-organic coordination network. The network formation occurs at room temperature; annealing at 450 K enhances the process. The interaction of Cu with the porphyrin core is more complex. At room temperature, formation of an initial complex Cu(0)-2HTPyP is observed. Annealing at 450 K activates an intramolecular redox reaction, by which the coordinated Cu(0) is oxidized to Cu(II) and the complex Cu(II)TPyP is formed. The coordination network consists then of Cu(II) complexes linked by Cu(0) atoms; that is, it represents a mixed-valence two-dimensional coordination network consisting of an ordered array of Cu(II) and Cu(0) centers. Above 520 K, the network degrades and the Cu atoms in the linking positions diffuse into the substrate, while the Cu(II)TPyP complexes form a close-packed structure that is stabilized by weak intermolecular interactions. Density functional theory investigations show that the reaction with Cu(0) proceeds via formation of an initial complex between metal atom and porphyrin followed by formation of Cu(II) porphyrin within the course of the reaction. The activation barrier of the rate limiting step was found to be 24-37 kcal mol(-1) depending on the method used. In addition, linear coordination of a Cu atom by two CuTPyP molecules is favorable according to gas-phase calculations. © 2012 American Chemical Society

  13. Analysis of the excitation profiles of Raman bands of linear-chain mixed-valence complexes. The geometry of [Pt(en) 2][Pt(en) 2Br 2]Br 4 in the intervalence state

    Science.gov (United States)

    Clark, Robin J. H.; Dines, Trevor J.

    1991-10-01

    Calculations of the resonance Raman excitation profiles for the ν 1 band and its overtones have been performed for the linear- chain mixed-valence platinum complex [Pt(en) 2Br 2]Br 4. It is found that the Pt IV length increases by 0.075 Å in the intervalence state. A satisfactory fit to the excitation profiles requires the inclusion of a second excited state at 16500 cm -1, which we have assigned to Br→Pt IV charge transfer.

  14. P-T PHASE DIAGRAM AND GOLD VALENCE STATE OF NEW GOLD MIXED-VALENCE COMPLEXES, Cs2[AuIX2][AuIIIY4](X, Y = Cl, Br, I; X ¹ Y

    Directory of Open Access Journals (Sweden)

    K. Ikeda

    2004-12-01

    Full Text Available Cs2[AuIX2][AuIIIX4](X = Cl, Br, and I is well known for the perovskite-type gold mixed-valence system. This system undergoes pressure-induced and photo-induced Au valence transition from the mixed valence state of AuI,III to the single valence state of AuII. Recently, we have succeeded in synthesizing new gold mixed-valence complexes having perovskite-type structure, Cs2[AuIX2][AuIIIY4](X, Y = halogen, X ¹ Y, in organic solvent by using a new method. This hetero-halogen bridged gold mixed-valence system was confirmed by means of Raman spectroscopy. From the analysis of 197Au Mössbauer spectra, it was elucidated that the charge transfer interaction between AuI(5dx2-y2 and AuIII(5dx2-y2in the a-b plane becomes dominant for the AuI-AuIII interaction in Cs2[AuIX2][AuIIIY4] (X, Y = Cl, Br, and I in the order of X = Cl < Br < I, where Y is fixed. In order to elucidate the Au valence transition for Cs2[AuIX2][AuIIIY4], we have investigated the X-ray diffraction and Raman spectra under high pressure. Moreover, we have synthesized TlAuX3(X = Cl and Br having cubic perovskite structure and highly conducting behavior. The Au valence state in TlAuX3 is considered to be AuII at ambient pressure.

  15. Structure, magnetism, and theoretical study of a mixed-valence Co(II)3Co(III)4 heptanuclear wheel: lack of SMM behavior despite negative magnetic anisotropy.

    Science.gov (United States)

    Chibotaru, Liviu F; Ungur, Liviu; Aronica, Christophe; Elmoll, Hani; Pilet, Guillaume; Luneau, Dominique

    2008-09-17

    A mixed-valence Co(II)/Co(III) heptanuclear wheel [Co(II)3Co(III)4(L)6(MeO)6] (LH2 = 1,1,1-trifluoro-7-hydroxy-4-methyl-5-aza-hept-3-en-2-one) has been synthesized and its crystal structure determined using single-crystal X-ray diffraction. The valence state of each cobalt ion was established by bond valence sum calculations. Studies of the temperature dependence of the magnetic susceptibility and the field dependence of the magnetization evidence ferromagnetic interactions within the compound. In order to understand the magnetic properties of this Co7 wheel, we performed ab initio calculations for each cobalt fragment at the CASSCF/CASPT2 level, including spin-orbit coupling effects within the SO-RASSI approach. The four Co(III) ions were found to be diamagnetic and to give a significant temperature-independent paramagnetic contribution to the susceptibility. The spin-orbit coupling on the three Co(II) sites leads to separations of approximately 200 cm(-1) between the ground and excited Kramers doublets, placing the Co7 wheel into a weak-exchange limit in which the lowest electronic states are adequately described by the anisotropic exchange interaction between the lowest Kramers doublets on Co(II) sites. Simulation of the exchange interaction was done within the Lines model, keeping the fully ab initio treatment of magnetic anisotropy effects on individual cobalt fragments using a recently developed methodology. A good description of the susceptibility and magnetization was obtained for nearest-neighbor (J1) and next-nearest-neighbor (J2) exchange parameters (1.5 and 5.5 cm(-1), respectively). The strong ferromagnetic interaction between distant cobalt ions arises as a result of low electron-promotion energies in the exchange bridges containing Co(III) ions. The calculations showed a large value of the magnetization along the main magnetic axis (10.1 mu(B)), which is a combined effect of the ferromagnetic exchange interaction and negative magnetic anisotropy on

  16. Composition-induced structural, electrical, and magnetic phase transitions in AX-type mixed-valence cobalt oxynitride epitaxial thin films

    Energy Technology Data Exchange (ETDEWEB)

    Takahashi, Jumpei; Oka, Daichi [Department of Chemistry, School of Science, The University of Tokyo, 7-3-1 Hongo, Bunkyo, Tokyo 113-0033 (Japan); Kanagawa Academy of Science and Technology (KAST), 3-2-1 Sakado, Takatsu, Kawasaki 213-0012 (Japan); Hirose, Yasushi, E-mail: hirose@chem.s.u-tokyo.ac.jp; Yang, Chang; Fukumura, Tomoteru; Hasegawa, Tetsuya [Department of Chemistry, School of Science, The University of Tokyo, 7-3-1 Hongo, Bunkyo, Tokyo 113-0033 (Japan); Kanagawa Academy of Science and Technology (KAST), 3-2-1 Sakado, Takatsu, Kawasaki 213-0012 (Japan); CREST, Japan Science and Technology Agency, 7-3-1 Hongo, Bunkyo, Tokyo 113-0033 (Japan); Nakao, Shoichiro [Kanagawa Academy of Science and Technology (KAST), 3-2-1 Sakado, Takatsu, Kawasaki 213-0012 (Japan); CREST, Japan Science and Technology Agency, 7-3-1 Hongo, Bunkyo, Tokyo 113-0033 (Japan); Harayama, Isao; Sekiba, Daiichiro [University of Tsukuba Tandem Accelerator Complex (UTTAC), 1-1-1 Tennoudai, Tsukuba, Ibaraki 305-8577 (Japan)

    2015-12-07

    Synthesis of mid- to late-transition metal oxynitrides is generally difficult by conventional thermal ammonolysis because of thermal instability. In this letter, we synthesized epitaxial thin films of AX-type phase-pure cobalt oxynitrides (CoO{sub x}N{sub y}) by using nitrogen-plasma-assisted pulsed laser deposition and investigated their structural, electrical, and magnetic properties. The CoO{sub x}N{sub y} thin films with 0 ≤ y/(x + y) ≤ 0.63 grown on MgO (100) substrates showed a structural phase transition from rock salt (RS) to zinc blend at the nitrogen content y/(x + y) ∼ 0.5. As the nitrogen content increased, the room-temperature electrical resistivity of the CoO{sub x}N{sub y} thin films monotonically decreased from the order of 10{sup 5} Ω cm to 10{sup −4} Ω cm. Furthermore, we observed an insulator-to-metal transition at y/(x + y) ∼ 0.34 in the RS-CoO{sub x}N{sub y} phase, which has not yet been reported in Co{sup 2+}/Co{sup 3+} mixed-valence cobalt oxides with octahedral coordination. The low resistivity in the RS-CoO{sub x}N{sub y} phase, on the 10{sup −3} Ω cm order, may have originated from the intermediate spin state of Co{sup 3+} stabilized by the lowered crystal field symmetry of the CoO{sub 6−n}N{sub n} octahedra (n = 1, 2,…5). Magnetization measurements suggested that a magnetic phase transition occurred in the RS-CoO{sub x}N{sub y} films during the insulator-to-metal transition. These results demonstrate that low-temperature epitaxial growth is a promising approach for exploring novel electronic functionalities in oxynitrides.

  17. Mixed-Valence Molecular Unit for Quantum Cellular Automata: Beyond the Born-Oppenheimer Paradigm through the Symmetry-Assisted Vibronic Approach.

    Science.gov (United States)

    Clemente-Juan, Juan Modesto; Palii, Andrew; Coronado, Eugenio; Tsukerblat, Boris

    2016-08-09

    In this article, we focus on the electron-vibrational problem of the tetrameric mixed-valence (MV) complexes proposed for implementation as four-dot molecular quantum cellular automata (mQCA).1 Although the adiabatic approximation explored in ref 2 is an appropriate tool for the qualitative analysis of the basic characteristics of mQCA, like vibronic trapping of the electrons encoding binary information and cell-cell response, it loses its accuracy providing moderate vibronic coupling and fails in the description of the discrete pattern of the vibronic levels. Therefore, a precise solution of the quantum-mechanical vibronic problem is of primary importance for the evaluation of the shapes of the electron transfer optical absorption bands and quantitative analysis of the main parameters of tetrameric quantum cells. Here, we go beyond the Born-Oppenheimer paradigm and present a solution of the quantum-mechanical pseudo Jahn-Teller (JT) vibronic problem in bielectronic MV species (exemplified by the tetra-ruthenium complexes) based on the recently developed symmetry-assisted approach.3,4 The mathematical approach to the vibronic eigenproblem takes into consideration the point symmetry basis, and therefore, the total matrix of the JT Hamiltonian is blocked to the maximum extent. The submatrices correspond to the irreducible representations (irreps) of the point group. With this tool, we also extend the theory of the mQCA cell beyond the limit of prevailing Coulomb repulsion in the electronic pair (adopted in ref 2), and therefore, the general pseudo-JT problems for spin-singlet ((1)B1g, 2(1)A1g, (1)B2g, (1)Eu) ⊗ (b1g + eu) and spin-triplet states ((3)A2g, (3)B1g, 2(3)Eu) ⊗ (b1g + eu) in a square-planar bielectronic system are solved. The obtained symmetry-adapted electron-vibrational functions are employed for the calculation of the profiles (shape functions) of the charge transfer absorption bands in the tetrameric MV complexes and for the discussion of the

  18. EXAFS, XANES, and DFT study of the mixed-valence compound YMn2O5 : Site-selective substitution of Fe for Mn

    Science.gov (United States)

    Wunderlich, F.; Leisegang, T.; Weißbach, T.; Zschornak, M.; Stöcker, H.; Dshemuchadse, J.; Lubk, A.; Führlich, T.; Welter, E.; Souptel, D.; Gemming, S.; Seifert, G.; Meyer, D. C.

    2010-07-01

    In YMn2O5 , the Mn atoms occupy two nonequivalent Wyckoff sites within the unit cell exhibiting different oxygen coordinations, i.e., the system can be characterized as a mixed-valence compound. For the formation of the orthorhombic crystal structure, Jahn-Teller distortions are assumed to play an important role. In this study, we aimed at the investigation of the crystal structure changes upon the substitution of Mn by the non-Jahn-Teller cation Fe3+ . Therefore, we synthesized a series of YMn2-xFexO5 powder samples with x=0 , 0.5, and 1 by a citrate technique. We utilized extended x-ray absorption fine structure (EXAFS) and x-ray absorption near-edge structure (XANES) analysis as well as density-functional theory (DFT) to investigate the two nonequivalent Wyckoff sites within the orthorhombic crystal structure (confirmed for all compositions) occupied by transition-metal atoms. For quantitative determination of structural short-range order, all plausible options of substitution of Fe for Mn are discussed. On the basis of these evaluations, the EXAFS and XANES behavior is analyzed and appropriate crystallographic weights are assigned to the subset of structural models in accordance with the experimental data. From EXAFS analysis, using multiple-scattering theory, we conclude only the 4h Wyckoff site to be occupied by Fe [occupancy refined is (100±3)% in case of x=1 ]. Furthermore, taking the XANES spectra into account, we are able to verify the EXAFS results and additionally explain the differences in the MnK XANES spectra in dependence on x to be caused by changes in the dipole transitions to 4p final states. From quantitative pre-edge analysis an oxidation number of +4 for the Mn atom for x=1 is determined whereas the Fe valence is shown to be unchanged. Since the substitution process only involves one Wyckoff site, the experimentally observed limit to a maximum amount of x=1 is explained. Additionally, a possible disorder, discussed in the literature, is not

  19. Mixed-valence molecular four-dot unit for quantum cellular automata: Vibronic self-trapping and cell-cell response

    Energy Technology Data Exchange (ETDEWEB)

    Tsukerblat, Boris, E-mail: tsuker@bgu.ac.il, E-mail: andrew.palii@uv.es [Ben-Gurion University of the Negev, Beer-Sheva (Israel); Palii, Andrew, E-mail: tsuker@bgu.ac.il, E-mail: andrew.palii@uv.es [Institute of Applied Physics, Academy of Sciences of Moldova, Kishinev (Moldova, Republic of); Clemente-Juan, Juan Modesto; Coronado, Eugenio [Instituto de Ciencia Molecular (ICMol), Universidad de Valencia, Paterna (Spain)

    2015-10-07

    Our interest in this article is prompted by the vibronic problem of charge polarized states in the four-dot molecular quantum cellular automata (mQCA), a paradigm for nanoelectronics, in which binary information is encoded in charge configuration of the mQCA cell. Here, we report the evaluation of the electronic levels and adiabatic potentials of mixed-valence (MV) tetra-ruthenium (2Ru(II) + 2Ru(III)) derivatives (assembled as two coupled Creutz-Taube complexes) for which molecular implementations of quantum cellular automata (QCA) was proposed. The cell based on this molecule includes two holes shared among four spinless sites and correspondingly we employ the model which takes into account the two relevant electron transfer processes (through the side and through the diagonal of the square) as well as the difference in Coulomb energies for different instant positions of localization of the hole pair. The combined Jahn-Teller (JT) and pseudo JT vibronic coupling is treated within the conventional Piepho-Krauzs-Schatz model adapted to a bi-electronic MV species with the square-planar topology. The adiabatic potentials are evaluated for the low lying Coulomb levels in which the antipodal sites are occupied, the case just actual for utilization in mQCA. The conditions for the vibronic self-trapping in spin-singlet and spin-triplet states are revealed in terms of the two actual transfer pathways parameters and the strength of the vibronic coupling. Spin related effects in degrees of the localization which are found for spin-singlet and spin-triplet states are discussed. The polarization of the cell is evaluated and we demonstrate how the partial delocalization caused by the joint action of the vibronic coupling and electron transfer processes influences polarization of a four-dot cell. The results obtained within the adiabatic approach are compared with those based on the numerical solution of the dynamic vibronic problem. Finally, the Coulomb interaction between

  20. Influence of extrinsic factors on electron transfer in a mixed-valence Fe(2+)/Fe(3+) complex: experimental results and theoretical considerations.

    Science.gov (United States)

    Achim, C; Bominaar, E L; Staples, R J; Münck, E; Holm, R H

    2001-08-13

    The crystal structure of the mixed-valence complex (NEt(4))[Fe(2)(salmp)(2)].xMeCN(crystal) (x = 2,3) [1].xMeCN(crystal) was determined at temperatures between 153 and 293 K. The complex shows distinct Fe(2+) and Fe(3+) sites over this temperature interval. Variable temperature Mössbauer spectra confirm the valence-localized character of the complex. In contrast, spectroscopic investigation of powder samples generated from [1].xMeCN(crystal) indicate the presence of a valence-averaged component at temperatures above 150 K. To elucidate this apparent contradiction we have conducted a variable-temperature Mössbauer investigation of different forms of 1, including [1].xMeCN(crystal), [1].2DMF(crystal), [1].yMeCN(powder), and solution samples of 1 in acetonitrile. The low-temperature Mössbauer spectra of all forms are virtually identical and confirm the valence-localized nature of the S = (9)/(2) ground state. The high-temperature spectra reveal a subtle control of electron hopping by the environment of the complexes. Thus, [1].xMeCN(crystal) has valence-localized spectra at all explored temperatures, [1].2DMF(crystal) exhibits a complete collapse into a valence-averaged spectrum over a narrow temperature range, the powder exhibits partial valence averaging over a broad temperature interval, and the solution sample shows at 210 K the presence of a valence-averaged component in a minor proportion. The spectral transformations are characterized by a coexistence of valence-localized and valence-averaged spectral components. This phenomenon cannot be explained by intramolecular electron hopping between the valence-localized states Fe(A)(2+)Fe(B)(3+) and Fe(A)(3+)Fe(B)(2+) in a homogeneous ensemble of complexes, but requires relaxation processes involving at least three distinguishable states of the molecular anion. Hopping rates for [1].2DMF(crystal) and [1].yMeCN(powder) have been determined from spectral simulations, based on stochastic line shape theory. Analysis of

  1. Heterogeneous mixed valence in YbPd sub 3 S sub 4 : evidence from sup 1 sup 7 sup 0 Yb Moessbauer and x-ray L sub I sub I sub I -edge absorption measurements

    CERN Document Server

    Bonville, P; Alleno, E; Takahashi, F; Matsuoka, E; Ishikawa, M

    2003-01-01

    The intermetallic bronze YbPd sub 3 S sub 4 is shown to be a heterogeneous mixed-valence system, by means of sup 1 sup 7 sup 0 Yb Moessbauer spectroscopy and x-ray L sub I sub I sub I -edge absorption and magnetic measurements. Two valence states coexist in this compound: Yb sup 3 sup + and close-to-divalent Yb. The trivalent fraction (about 50%) undergoes a transition to magnetic ordering at about 2 K, with the GAMMA sub 7 doublet as the ground crystal field state. The possibility of charge (or valence) ordering is discussed. (letter to the editor)

  2. Crystal Structure and Characterization of a New Mixed-valence Manganese(Ⅲ/Ⅳ) Complex: [Mn2(cyclen)2(μ-O)2](ClO4)3-4H2O

    Institute of Scientific and Technical Information of China (English)

    任颜卫; 李珺; 张逢星; 张金花; 郭惠

    2005-01-01

    The mixed-valence manganese(Ⅲ/Ⅳ) complex [Mn2(cyclen)2(μ-O)2](ClO4)3-4H2O (1) (cyclen=1,4,7,10-tetraazacyclododecan) with chemical formula C16H48Cl3Mn2N8O18 has been synthesized and characterized by single crystal X-ray diffraction analysis, elemental analysis, IR and electronic spectra. The results showed that the manganese(Ⅲ/Ⅳ) ions were six-coordinated by four nitrogen atoms from cyclen and two oxygen atoms from the oxygen bridge, forming a distorted octahedron geometry. There were two very strong peaks in the range of 400-700 nm in electronic spectrum, which was similar to Mn catalase and Mn ribonucleotide reductase extracted from organisms.Electrochemical study indicated that the complex underwent a quasi-reversible one-electron reduction and oxidation at E1/2=0.827 V in acetonitrile.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2013-05-30

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

  4. Synthesis and Structure of a Novel Organic-Inorganic Hybrid Polyoxovanadate,[Ni(bpp)2]2(V4O12)(bpp=1,3-bi-4-pyridylpropane)

    Institute of Scientific and Technical Information of China (English)

    ZHANG,Li-Juan; HU,Zheng-Jun; ZHANG,Zhuo; GUO,Hong-You

    2007-01-01

    A novel organic-inorganic hybrid polyoxovanadate,[Ni(bpp)2]2(V4O12)(bpp=1,3-bi-4-pyridylpropane),was hydrothermally synthesized from a mixture of NiCl2·6H2O,NH4VO3,bpp,EtOH and H2O.The crystal structure consists of2∞[Ni(bpp)2+,two-dimensional networks interpenetrating perpendicularly with each other,and (V4O12)4-,cyclic tetranuclear clusters linking the 2∞[Ni(bpp)2]2+ networks to form a three-dimensional coordination framework.The crystal belongs to tetragonal space group I41/a with unit cell parameters,a=2.14705 nm,c=1.29293 nm.UV-Vis-NIR reflectance spectroscopy study revealed insulator nature for the crystal with an optical energy gap of 2.70 eV.

  5. Lanthanide complexes of macrocyclic polyoxovanadates by VO4 units: synthesis, characterization, and structure elucidation by X-ray crystallography and EXAFS spectroscopy.

    Science.gov (United States)

    Nishio, Masaki; Inami, Shinnosuke; Katayama, Misaki; Ozutsumi, Kazuhiko; Hayashi, Yoshihito

    2012-01-16

    Reactions of a tetravanadate anion, [V(4)O(12)](4-), with a series of lanthanide(III) salts yield three types of lanthanide complexes of macrocyclic polyoxovanadates: (Et(4)N)(6)[Ln(III)V(9)O(27)] [Ln = Nd (1), Sm (2), Eu (3), Gd (4), Tb (5), Dy (6)], (Et(4)N)(5)[(H(2)O)Ho(III)(V(4)O(12))(2)] (7), and (Et(4)N)(7)[Ln(III)V(10)O(30)] [Ln = Er (8), Tm (9), Yb (10), Lu (11)]. Lanthanide complexes 1-11 are isolated and characterized by IR, elemental analysis, single-crystal X-ray diffraction, and extended X-ray absorption fine structure spectroscopy (EXAFS). Lanthanide complexes 1-6 are composed of a square-antiprism eight-coordinated Ln(III) center with a macrocyclic polyoxovanadate that is constructed from nine VO(4) tetrahedra through vertex sharing. The structure of 7 is composed of a seven-coordinated Ho(III) center, which exhibits a capped trigonal-prism coordination environment by the sandwiching of two cyclic tetravanadates with a capping H(2)O ligand. Lanthanide complexes 8-11 have a six-coordinated Ln(III) center with a 10-membered vanadate ligand. The structural trend to adopt a larger coordination number for a larger lanthanide ion among the three types of structures is accompanied by a change in the vanadate ring sizes. These lanthanide complexes are examined by EXAFS spectroscopies on lanthanide L(III) absorption edges, and the EXAFS oscillations of each of the samples in the solid state and in acetonitrile are identical. The Ln-O and Ln···V bond lengths obtained from fits of the EXAFS data are consistent with the data from the single-crystal X-ray studies, reflecting retention of the structures in acetonitrile.

  6. Localized and mixed valence state of Ce 4 f in superconducting and ferromagnetic CeO1 -xFxBiS2 revealed by x-ray absorption and photoemission spectroscopy

    Science.gov (United States)

    Sugimoto, T.; Ootsuki, D.; Paris, E.; Iadecola, A.; Salome, M.; Schwier, E. F.; Iwasawa, H.; Shimada, K.; Asano, T.; Higashinaka, R.; Matsuda, T. D.; Aoki, Y.; Saini, N. L.; Mizokawa, T.

    2016-08-01

    We have performed Ce L3-edge x-ray absorption spectroscopy (XAS) and Ce 4 d -4 f resonant photoemission spectroscopy (PES) on single crystals of CeO1 -xFxBiS2 for x =0.0 and 0.5 in order to investigate the Ce 4 f electronic states. In Ce L3-edge XAS, a mixed valence of Ce was found in the x =0.0 sample, and F doping suppressed it, which is consistent with the results on polycrystalline samples. As for resonant PES, we found that the Ce 4 f electrons in both x =0.0 and 0.5 systems respectively formed a flat band at 1.0 and 1.4 eV below the Fermi level and there was no contribution to the Fermi surfaces. Interestingly, Ce valence in CeOBiS2 deviates from Ce3 + even though Ce 4 f electrons are localized, indicating the Ce valence is not in a typical valence fluctuation regime. We assume that localized Ce 4 f in CeOBiS2 is mixed with unoccupied Bi 6 pz , which is consistent with a previous local structural study. Based on the analysis of the Ce L3-edge XAS spectra using Anderson's impurity model calculation, we found that the transfer integral becomes smaller, increasing the number of Ce 4 f electrons upon the F substitution for O.

  7. Novel Co(III)/Co(II) mixed valence compound [Co(bapen)Br2]2[CoBr4] (bapen = N,N‧-bis(3-aminopropyl)ethane-1,2-diamine): Synthesis, crystal structure and magnetic properties

    Science.gov (United States)

    Smolko, Lukáš; Černák, Juraj; Kuchár, Juraj; Miklovič, Jozef; Boča, Roman

    2016-09-01

    Green crystals of Co(III)/Co(II) mixed valence compound [Co(bapen)Br2]2[CoBr4] (bapen = N,N‧-bis(3-aminopropyl)ethane-1,2-diamine) were isolated from the aqueous system CoBr2 - bapen - HBr, crystallographically studied and characterized by elemental analysis and IR spectroscopy. Its ionic crystal structure is built up of [Co(bapen)Br2]+ cations and [CoBr4]2- anions. The Co(III) central atoms within the complex cations are hexacoordinated (donor set trans-N4Br2) with bromido ligands placed in the axial positions. The Co(II) atoms exhibit distorted tetrahedral coordination. Beside ionic forces weak Nsbnd H⋯Br intermolecular hydrogen bonding interactions contribute to the stability of the structure. Temperature variable magnetic measurements confirm the S = 3/2 behavior with the zero-field splitting of an intermediate strength: D/hc = 8.7 cm-1.

  8. Density functional investigation of metal-metal interactions in mixed-valence d2d3 (Cr, Mo, W) and d3d4 (Mn, Tc, Re) face-shared [M2Cl9]2- systems.

    Science.gov (United States)

    Cavigliasso, Germán; Comba, Peter; Stranger, Robert

    2004-10-18

    The molecular and electronic structures of mixed-valence face-shared (Cr, Mo, W) d(2)d(3) and (Mn, Tc, Re) d(3)d(4) [M(2)Cl(9)](2-) dimers have been calculated by density functional methods in order to investigate metal-metal bonding in this series. The electronic structures of these systems have been analyzed using potential energy curves for the broken-symmetry and other spin states arising from the d(2)d(3) and d(3)d(4) coupling modes. In (d(2)d(3)) [Mo(2)Cl(9)](2-) and [W(2)Cl(9)](2-), the global minimum has been found to be a spin-doublet state characterized by delocalization of the metal-based electrons in a multiple metal-metal bond (with a formal bond order of 2.5). In contrast, weak coupling between the metal centers and electron localization are favored in (d(2)d(3)) [Cr(2)Cl(9)](2-), the global minimum for this species being a ferromagnetic S = 5/2 state with a relatively long Cr-Cr separation. The (d(3)d(4)) [Re(2)Cl(9)](2-) system also exhibits a global minimum corresponding to a metal-metal bonded spin-doublet state with a formal bond order of 2.5, reflecting the electron-hole equivalence between d(2)d(3) and d(3)d(4) configurations. Double minima behavior is predicted for (d(3)d(4)) [Tc(2)Cl(9)](2-) and [Mn(2)Cl(9)](2-) due to two energetically close low-lying states (these being S = 3/2 and S = 5/2 states for the former, and S = 5/2 and S = 7/2 states for the latter). A comparison of computational results for the d(2)d(2), d(2)d(3), and d(3)d(3) [W(2)Cl(9)](z-) series and the d(3)d(3), d(3)d(4), and d(4)d(4) [Re(2)Cl(9)](z-) series indicates that the observed trends in metal-metal distances can only be rationalized if changes in both the strength of sigma bonding and metal-metal bond order are taken into consideration. These two factors act conjointly in the W series but in opposition to one another in the Re series. In the case of the [Cr(2)Cl(9)](z-) and [Mn(2)Cl(9)](z-) dimers, the metal-metal bond lengths are significantly shorter for mixed-valence

  9. A C2-symmetric antimonato polyoxovanadate cluster [V16Sb4O42(H2O)](8-) derived from the {V18O42} archetype.

    Science.gov (United States)

    Antonova, Elena; Näther, Christian; Kögerler, Paul; Bensch, Wolfgang

    2012-06-21

    The new antimonato polyoxovanadate [V(IV)(16)Sb(III)(4)O(42)(H(2)O)](8-) cluster (1a) is the main structural motif of the solvothermally obtained compound {(trenH(2))Zn(tren)}(2)[V(16)Sb(4)O(42)(H(2)O)]·xH(2)O (x = 6-10) (1) (tren = tris(2-aminoethyl)amine). The C(2)-symmetric cluster structure is closely related to the {V(18)O(42)} archetype. 1 crystallizes in the monoclinic space group C2/c with a = 30.7070(19) Å, b = 13.9512(5) Å, c = 23.1435(14) Å, β = 128.076(6)°, and V = 7804.8(7) Å(3). The orientation of the [Sb(III)(2)O(5)](4-) groups in each cluster leads to intermolecular Sb···O contacts and the formation of channels between the clusters. [Zn(tren)(trenH(2))] complexes with trigonal bipyramidal coordination environments are located between the [V(16)Sb(4)O(42)(H(2)O)](8-) anions, and form a three dimensional network with them via strong N-H···O hydrogen bonds. Up to 250 °C crystal water molecules are emitted, which are reversibly incorporated in humid air.

  10. Reactivity of ammonia ligands of the antitumor agent cisplatin: a unique dodecanuclear Pt4,Pd4,Ag4 platform for four cytosine model nucleobases.

    Science.gov (United States)

    Kampf, Gunnar; Sanz Miguel, Pablo J; Morell Cerdà, Marta; Willermann, Michael; Schneider, Alexandra; Lippert, Bernhard

    2008-01-01

    The reaction of a potential mono(nucleobase) model adduct of cisplatin, cis-[Pt(NH(3))(2)(1-MeC-N3)(H(2)O)](2+) (6; 1-MeC: 1-methylcytosine), with the electrophile [Pd(en)(H(2)O)(2)](2+) (en: ethylenediamine) at pH approximately 6 yields a kinetic product X which is likely to be a dinuclear Pt,Pd complex containing 1-MeC(-)-N3,N4 and OH bridges, namely cis-[Pt(NH(3))(2)(1-MeC(-)-N3,N4)(OH)Pd(en)](2+). Upon addition of excess Ag(+) ions, conversion takes place to form a thermodynamic product, which, according to (1)H NMR spectroscopy and X-ray crystallography, is dominated by a mu-NH(2) bridge between the Pt(II) and Pd(II) centers. X-ray crystallography reveals that the compound crystallizes out of solution as a dodecanuclear complex containing four Pt(II), four Pd(II), and four Ag(+) entities: [{Pt(2)(1-MeC(-)-N3,N4)(2)(NH(3))(2)(NH(2))(2)(OH)Pd(2)(en)(2)Ag}(2){Ag(H(2)O)}(2)](NO(3))(10) 6 H(2)O (10) is composed of a roughly planar array of the 12 metal ions, in which the metal ions are interconnected by mu-NH(2) groups (between Pt and Pd centers), mu-OH groups (between pairs of Pt atoms), and metal-metal donor bonds (Pt-->Ag, Pd-->Ag). The four 1-methylcytosinato ligands, which are stacked pairwise, as well as the four NH(3) ligands and parts of the en rings, are approximately perpendicular to the metal plane. Two of the four Ag ions (Ag2, Ag2') of 10 are labile in solution and show the expected behavior of Ag(+) ions in water, that is, they are readily precipitated as AgCl by Cl(-) ions. The resulting pentanuclear complex [Pt(2)Pd(2)Ag(1-MeC(-))(2)(NH(2))(2)(OH)(NH(3))(2)(en)(2)](NO(3))(4)7 H(2)O (11) largely maintains the structural features of one half of 10. The other two Ag(+) ions (Ag1, Ag1') of 10 are remarkably unreactive toward excess NaCl. In fact, the pentanuclear complex [Pt(2)Pd(2)AgCl(1-MeC(-))(2)(NH(2))(2)(OH)(NH(3))(2)(en)(2)](NO(3))(3)4.5 H(2)O (12), obtained from 10 with excess NaCl, displays a Cl(-) anion bound to the Ag center (2.459(3) A) and

  11. Dithiolate complexes of manganese and rhenium: X-ray structure and properties of an unusual mixed valence cluster Mn3(CO)6(mu-eta2-SCH2CH2CH2S)3.

    Science.gov (United States)

    Begum, Noorjahan; Hyder, Md Iqbal; Kabir, Shariff E; Hossain, G M Golzar; Nordlander, Ebbe; Rokhsana, Dalia; Rosenberg, Edward

    2005-12-26

    Treatment of Mn(2)(CO)(10) with 3,4-toluenedithiol and 1,2-ethanedithiol in the presence of Me(3)NO.2H(2)O in CH(2)Cl(2) at room temperature afforded the dinuclear complexes Mn(2)(CO)(6)(mu-eta(4)-SC(6)H(3)(CH(3))S-SC(6)H(3)(CH(3))S) (1), and Mn(2)(CO)(6)(mu-eta(4)-SCH(2)CH(2)S-SCH(2)CH(2)S) (2), respectively. Similar reactions of Re(2)(CO)(10) with 3,4-toluenedithiol, 1,2-benzenedithiol, and 1,2-ethanedithiol yielded the dirhenium complexes Re(2)(CO)(6)(mu-eta(4)-SC(6)H(3)(CH(3))S-SC(6)H(3)(CH(3))S) (3), Re(2)(CO)(6)(mu-eta(4)-SC(6)H(4)S-SC(6)H(4)S) (4), and Re(2)(CO)(6)(SCH(2)CH(2)S-SCH(2)CH(2)S) (5), respectively. In contrast, treatment of Mn(2)(CO)(10) with 1,3-propanedithiol afforded the trimanganese compound Mn(3)(CO)(6)(mu-eta(2)-SCH(2)CH(2)CH(2)S)(3) (6), whereas Re(2)(CO)(10) gave only intractable materials. The molecular structures of 1, 3, and 6 have been determined by single-crystal X-ray diffraction studies. The dimanganese and dirhenium carbonyl compounds 1-5contain a binucleating disulfide ligand, formed by interligand disulfide bond formation between two dithiolate ligands identical in structure to that of the previously reported dimanganese complex Mn(2)(CO)(6)(mu-eta(4)-SC(6)H(4)S-SC(6)H(4)S). Complex 6, on the other hand, forms a unique example of a mixed-valence trimangenese carbonyl compound containing three bridging 1,3-propanedithiolate ligands. The solution properties of 6 have been investigated by UV-vis and EPR spectroscopies as well as electrochemical techniques.

  12. High Nuclearity Antimonato-Polyoxovanadate Cluster {V15 Sb6 O42 } as a Synthon for the Solvothermal in situ Generation of α- and β-{V14 Sb8 O42 } Isomers.

    Science.gov (United States)

    Wendt, Michael; Näther, Christian; Bensch, Wolfgang

    2016-06-01

    New heteroatom polyoxovanadates (POVs) were synthesized by applying a water-soluble high-nuclearity cluster as new synthon. The [V15 Sb6 O42 ](6-) cluster shell exhibiting D3 symmetry was in situ transformed into completely different cluster shells, namely, the α-[V14 Sb8 O42 ](4-) isomer with D2d and the β-[V14 Sb8 O42 ](4-) isomer with D2h symmetry. The solvothermal reaction of {Ni(en)3 }3 [V15 Sb6 O42 (H2 O)x ]⋅15 H2 O (x=0 or 1; en=ethylenediamine) in water led to the crystallization of [{Ni(en)2 }2 V14 Sb8 O42 ]⋅5.5 H2 O containing the β-isomer. The addition of [Ni(phen)3 ](ClO4 )2 ⋅0.5 H2 O (phen=1,10-phenanthroline) to the reaction slurry gave the new compound {Ni(phen)3 }2 [V14 Sb8 O42 ]⋅phen⋅12 H2 O with the α-isomer. Both transformation reactions are complex due the change of symmetry, the chemical composition, and rearrangement of the VO5 square pyramids and Sb2 O5 handle-like moieties.

  13. Mixed valence nanostructured Mn3O4 for supercapacitor applications

    Indian Academy of Sciences (India)

    Vipin C Bose; V Biju

    2015-08-01

    Nanostructured Mn3O4 with an average crystallite size of ∼19 nm was synthesized through a microwave-assisted chemical route. Structural characterization was carried out using X-ray diffraction analysis and transmission electron microscopy. Observed change in the ratio of lattice constants, / for the sample compared with single-crystalline Mn3O4 points to the presence of Mn4+ ions at the octahedral sites. This is attributed to the presence of cation vacancies. X-ray photoelectron spectroscopic studies confirm the presence of Mn4+ ions. Specific capacitance value of 665.08 F g−1 was obtained for symmetric supercapacitor with Mn3O4 active material at slow scan rate. Reasonably high power and energy density values, viz., 4.27 kW kg−1 and 4.36 × 10−2 Wh kg−1, respectively, were obtained for charge–discharge cycles at a constant current of 12.74 mA cm−2.

  14. Preparation, Characterization, and Selectivity Study of Mixed-Valence Sulfites

    Science.gov (United States)

    Silva, Luciana A.; de Andrade, Jailson B.

    2010-01-01

    A project involving the synthesis of an isomorphic double sulfite series and characterization by classical inorganic chemical analyses is described. The project is performed by upper-level undergraduate students in the laboratory. This compound series is suitable for examining several chemical concepts and analytical techniques in inorganic…

  15. Electrical conductivity in two mixed-valence liquids.

    Science.gov (United States)

    Yao, Wenzhi; Kelley, Steven P; Rogers, Robin D; Vaid, Thomas P

    2015-06-01

    Two different room-temperature liquid systems were investigated, both of which conduct a DC electrical current without decomposition or net chemical transformation. DC electrical conductivity is possible in both cases because of the presence of two different oxidation states of a redox-active species. One system is a 1 : 1 molar mixture of n-butylferrocene (BuFc) and its cation bis(trifluoromethane)sulfonimide salt, [BuFc(+)][NTf2(-)], while the other is a 1 : 1 molar mixture of TEMPO and its cation bis(trifluoromethane)sulfonimide salt, [TEMPO(+)][NTf2(-)]. The TEMPO-[TEMPO(+)][NTf2(-)] system is notable in that it is an electrically conducting liquid in which the conductivity originates from an organic molecule in two different oxidation states, with no metals present. Single-crystal X-ray diffraction of [TEMPO(+)][NTf2(-)] revealed a complex structure with structurally different cation-anion interactions for cis- and trans [NTf2(-)] conformers. The electron transfer self-exchange rate constant for BuFc/BuFc(+) in CD3CN was determined by (1)H NMR spectroscopy to be 5.4 × 10(6) M(-1) s(-1). The rate constant allowed calculation of an estimated electrical conductivity of 7.6 × 10(-5)Ω(-1) cm(-1) for BuFc-[BuFc(+)][NTf2(-)], twice the measured value of 3.8 × 10(-5)Ω(-1) cm(-1). Similarly, a previously reported self-exchange rate constant for TEMPO/TEMPO(+) in CH3CN led to an estimated conductivity of 1.3 × 10(-4)Ω(-1) cm(-1) for TEMPO-[TEMPO(+)][NTf2(-)], a factor of about 3 higher than the measured value of 4.3 × 10(-5)Ω(-1) cm(-1).

  16. Role of correlated hopping in mixed valence phenomena

    Indian Academy of Sciences (India)

    N K Ghosh; S K Bhowmick; N S Mondal

    2011-01-01

    Role of correlated hopping is studied using extended Falicov–Kimball model in a small cluster. A discontinuous insulator-to-metal transition is observed at a critical -level energy. Transition is sharper for larger correlated hopping. In the specific heat curves a two-peak structure consisting of a sharp peak followed by a Schottky-type broad peak is exhibited. In a limited parameter region, some heavy-fermion like characteristics have been observed

  17. Preparation, Characterization, and Selectivity Study of Mixed-Valence Sulfites

    Science.gov (United States)

    Silva, Luciana A.; de Andrade, Jailson B.

    2010-01-01

    A project involving the synthesis of an isomorphic double sulfite series and characterization by classical inorganic chemical analyses is described. The project is performed by upper-level undergraduate students in the laboratory. This compound series is suitable for examining several chemical concepts and analytical techniques in inorganic…

  18. Mixed valency of Cu, electron-mass enhancement, and three-dimensional arrangement of magnetic sites in the organic conductors (R1,R2-N,N'-dicyanoquinonediimine)2Cu (where R1,R2=CH3,CH3O,Cl,Br)

    Science.gov (United States)

    Kobayashi, H.; Miyamoto, A.; Kato, R.; Sakai, F.; Kobayashi, A.; Yamakita, Y.; Furukawa, Y.; Tasumi, M.; Watanabe, T.

    1993-02-01

    The unique molecular conductors with pπ-d mixing band structures (R1,R2-N,N'-dicyanoquinonediimine)2Cu [(R1,R2-DCNQI)2Cu] (R1,R2=CH3,CH3O,Cl,Br) were examined. General features of the phase diagram of the DCNQI-Cu system were depicted. A region that is related to the existence of anomalously heavy-metal electrons has been found. The T2 dependence of the low-temperature resistivity of the alloyed system (DMe1-xMeBrx-DCNQI)2Cu (where Me=CH3) suggests a large enhancement of the electron mass at the critical situation where the system begins to exhibit a characteristic metal instability. The mixed valency of Cu (Cu+1.3) in (DMe-DCNQI)2Cu was confirmed by ir experiments performed on neutral DMe-DCNQI crystals and (DMe-DCNQI)2M (M=Li, Ba, Cu). The same conclusion was also derived from a low-temperature x-ray-diffraction experiment. The gradual temperature dependences of the ir absorption intensities of totally symmetric modes of (DBr-DCNQI)2Cu observed below the metal-insulator transition temperature (TMI) are in contrast with the discontinuous resistivity and susceptibility changes at TMI. This may be attributable to the existence of two driving forces characterizing the M-I transition. One is the sharp charge ordering in Cu sites and the other is the continuous development of charge-density waves on DCNQI stacks. The arrangement of Cu2+ and Cu+ below TMI was determined by an x-ray crystal-structure analysis of the threefold insulating phase of (MeBr-DCNQI)2Cu at 110 K. The nearest-neighbor Cu2+ ions interact with each other via two DCNQI molecules. A plausible spin structure of the antiferromagnetic ground state was proposed. According to this spin-structure model, the magnetic moments of Cu2+ along the crystallographic c axis will be arranged ferromagnetically.

  19. Syntheses, crystal structures, and magnetic properties of the oxalato-bridged mixed-valence complexes (FeII(bpm)3]2[FeIII2(ox)5].8H2O and FeII(bpm)3Na(H2O)2Fe(ox)(3).4H2O (bpm = 2,2'-bipyrimidine).

    Science.gov (United States)

    Armentano, D; De Munno, G; Faus, J; Lloret, F; Julve, M

    2001-02-12

    The preparation and crystal structures of two oxalato-bridged FeII-FeIII mixed-valence compounds, [FeII(bpm)3]2[FeIII2(ox)5].8H2O (1) and FeII(bpm)3Na(H2O)2FeIII(ox)(3).4H2O (2) (bpm = 2,2'-bipyrimidine; ox = oxalate dianion) are reported here. Complex 1 crystallizes in the triclinic system, space group P1, with a = 10.998(2) A, b = 13.073(3) A, c = 13.308(3) A, alpha = 101.95(2) degrees, beta = 109.20(2) degrees, gamma = 99.89(2) degrees, and Z = 1. Complex 2 crystallizes in the monoclinic system, space group P2(1)/c, with a = 12.609(2) A, b = 19.670(5) A, c = 15.843(3) A, beta = 99.46(1) degrees, and Z = 4. The structure of complex 1 consists of centrosymmetric oxalato-bridged dinuclear high-spin iron(III) [Fe2(ox)5]2- anions, tris-chelated low-spin iron(II) [Fe(bpm)3]2+ cations, and lattice water molecules. The iron atoms are hexacoordinated: six oxygen atoms (iron(III)) from two bidentate and one bisbidentate oxalato ligands and six nitrogen atoms (iron(II)) from three bidentate bpm groups. The Fe(III)-O(ox) and Fe(II)-N(bpm) bond distances vary in the ranges 1.967(3)-2.099(3) and 1.967(4)-1.995(3) A, respectively. The iron(III)-iron(III) separation across the bridging oxalato is 5.449(2) A, whereas the shortest intermolecular iron(III)-iron(II) distance is 6.841(2) A. The structure of complex 2 consists of neutral heterotrinuclear Fe(bpm)2Na(H2O)2Fe(ox)3 units and water molecules of crystallization. The tris-chelated low-spin iron(II) ([Fe(bpm)3]2+) and high-spin iron(III) ([Fe(ox)3]3-) entities act as bidentate ligands (through two bpm-nitrogen and two oxalato-oxygen atoms, respectively) toward the univalent sodium cation, yielding the trinuclear (bpm)2Fe(II)-bpm-Na(I)-ox-Fe(III)(ox)2 complex. Two cis-coordinated water molecules complete the distorted octahedral surrounding of the sodium atom. The ranges of the Fe(II)-N(bpm) and Fe(III)-O(ox) bond distances [1.968(6)-1.993(5) and 1.992(6)-2.024(6) A, respectively] compare well with those observed in 1. The Na

  20. Porous layered and open-framework mixed-valence copper tellurites

    Science.gov (United States)

    Markovski, Mishel R.; Siidra, Oleg I.; Kayukov, Roman A.; Nazarchuk, Evgeni W.

    2016-11-01

    |Cu+Cl3|[Cu2+2(TeO3)] (1), |Cu+1.7Cl3.8|[Cu2+4O(TeO3)2] (2) and Tl+2[Cu2+2Te6+Te4+6O18] (3) were obtained by CVT and hydrothermal methods in CuCl-CuCl2-TeO2 and Tl2CO3-CuO-TeO2 systems. 1 demonstrates layered topology with pores (1×0.65 nm), whereas 2 has open-framework structural architecture with two-dimensional system of channels (1.16×0.74 nm). Channels in open-framework of 3 are occupied by Tl+ cations. 'Host-guest' structural organization of 1 and 2 with host Cu2+-tellurite units of different dimensionality formed by oxocentered OCu4 tetrahedra and OCu2Te triangles and guest Cu+-chloride species is the result of formation from gases in CVT reactions. Oxocentered units determine basic topologies of the structures of 1 and 2 and influence their stability and properties. [Te6+Te4+6O18]6- polytellurite-tellurate framework in 3 can be represented as consisting of Kagome-like layers.

  1. Mixed valence transition metal 2D-oxides: Comparison between delafossite and crednerite compounds

    Science.gov (United States)

    Martin, Christine; Poienar, Maria

    2017-08-01

    Transition metal oxides offer large opportunities to study relationships between structures and properties. Indeed these compounds crystallize in numerous frameworks corresponding to different dimensionalities and, accordingly, show a huge variety of properties (as high Tc superconductivity, colossal magnetoresistivity, multiferroicity..). The control of the oxidation state of the transition metal, via the monitoring of the oxygen content, is of prime importance to understand and optimize the properties, due to the strong coupling that exists between the lattice and the charges and spins of the transition metals. In this large playground for chemists, we reinvestigated several 2D-compounds derived from delafossite structure. Considering this paper as a very short review, we report here the results obtained on CuMO2 compounds (with M = Cr, Mn or Mn+Cu) by using a combination of techniques, as X-ray, neutrons and/or electrons diffraction on poly-crystals for structural characterisations that are correlated with electrical and/or magnetic properties. The complementarity of studies is also addressed by the synthesis and characterization of single crystals in addition to poly-crystals. Moreover the comparison of the structures of similar Cr and Mn based oxides highlights the crucial role of the Jahn-Teller effect of trivalent manganese to lift the degeneracy, which is responsible of the magnetic frustration in CuCrO2.

  2. Luminescent Gold Nanoparticles with Mixed Valence States Generated from Dissociation of Polymeric Au (I) Thiolates

    OpenAIRE

    Zhou, Chen; Sun, Ce; Yu, Mengxiao; Qin, Yanping; Wang, Jinguo; Kim, Moon; Zheng, Jie

    2010-01-01

    Dissociation process of glutathione-gold(I) polymers in aqueous solution resulted in the formation of a class of ~2 nm gold nanoparticles. Different from the same sized but NaBH4 reduced gold nanoparticles, these nanoparticles exhibit strong luminescence but no surface plasmon absorption. Luminescence lifetimes of the nanoparticles were found strongly dependent on excitation wavelengths, and singlet and triplet excited states involving the emission were found degenerate in energy. X-ray photo...

  3. Mechanically induced intramolecular electron transfer in a mixed-valence molecular shuttle

    Science.gov (United States)

    Barnes, Jonathan C.; Fahrenbach, Albert C.; Dyar, Scott M.; Frasconi, Marco; Giesener, Marc A.; Zhu, Zhixue; Liu, Zhichang; Hartlieb, Karel J.; Carmieli, Ranaan; Wasielewski, Michael R.; Stoddart, J. Fraser

    2012-01-01

    The kinetics and thermodynamics of intramolecular electron transfer (IET) can be subjected to redox control in a bistable [2]rotaxane comprised of a dumbbell component containing an electron-rich 1,5-dioxynaphthalene (DNP) unit and an electron-poor phenylene-bridged bipyridinium (P-BIPY2+) unit and a cyclobis (paraquat-p-phenylene) (CBPQT4+) ring component. The [2]rotaxane exists in the ground-state co-conformation (GSCC) wherein the CBPQT4+ ring encircles the DNP unit. Reduction of the CBPQT4+ leads to the CBPQT2(•+) diradical dication while the P-BIPY2+ unit is reduced to its P-BIPY•+ radical cation. A radical-state co-conformation (RSCC) results from movement of the CBPQT2(•+) ring along the dumbbell to surround the P-BIPY•+ unit. This shuttling event induces IET to occur between the pyridinium redox centers of the P-BIPY•+ unit, a property which is absent between these redox centers in the free dumbbell and in the 1∶1 complex formed between the CBPQT2(•+) ring and the radical cation of methyl-phenylene-viologen (MPV•+). Using electron paramagnetic resonance (EPR) spectroscopy, the process of IET was investigated by monitoring the line broadening at varying temperatures and determining the rate constant (kET = 1.33 × 107 s-1) and activation energy (ΔG‡ = 1.01 kcal mol-1) for electron transfer. These values were compared to the corresponding values predicted, using the optical absorption spectra and Marcus–Hush theory. PMID:22685213

  4. Computational study of topological effects on intramolecular electron transfer in mixed-valence compounds

    Institute of Scientific and Technical Information of China (English)

    Yinxi YU; Haobin WANG

    2011-01-01

    The constrained density functional theory (CDFT) was used to investigate the topological effects on intramolecular electron transfer processes that have been reported in previous experimental work [Inorg.Chem.,1997,36 (22),pp 5037-50491.The computation mainly focused on three isomers of diferrocenylbenzenes (ortho,para,and meta) and 5-substituted derivatives of m-diferrocencylbenzenes with R =NH2,Cl,CH3,CN,NO2,N(CH3)3+3,and N+2.The influence of a third group R' (R' =NH2 and N+2) was introduced to the ortho and para isomers.The calculations were compared with the experimental results.The relation between the substituted functional groups and the effectiveness of intramolecular electron transfer was discussed on the basis of CDFT computational results.

  5. Effect of Tb3+ doping in mixed-valence manganites and cobaltites

    Science.gov (United States)

    Knížek, K.; Jirák, Z.; Kaman, O.; Maryško, M.; Damay, F.

    2017-10-01

    The magnetic ordering of four Tb3+-doped manganites and cobaltites, La0.7Tb0.1Sr0.2MnO3, La0.7Tb0.1Ca0.2MnO3, La0.7Tb0.1Sr0.2CoO3 and La0.7Tb0.1Ca0.2CoO3, have been studied by means of neutron diffraction and SQUID magnetometry. All the samples were prepared by sintering of sol-gel precursors and their orthorhombic or rhombohedral perovskite structures at room and low temperatures were refined. A long-range ferromagnetic (FM) order was detected at the Mn and Co sites. In addition, a small but significant ordered moment was observed at A sites of studied cobaltites, which was attributed to local Tb3+ moments, aligned by exchange interactions due to FM ordered Co sublattice. No or minor Tb3+ contribution was detected in studied manganites.

  6. Nanophase mixed-valence iron minerals in meteorites identified by cryogenic Moessbauer spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Burns, R.G. [Massachusetts Inst. of Tech., Cambridge, MA (United States). Dept. of Earth, Atmospheric and Planetary Sciences; Fisher, D.S. [Massachusetts Inst. of Tech., Cambridge, MA (United States). Dept. of Earth, Atmospheric and Planetary Sciences

    1994-11-01

    Determination of oxidation states and the crystal chemistry of iron-bearing minerals in carbonaceous chondrites by Moessbauer spectroscopy is complicated by thermally-induced electron-hopping in cronstedtite, superparamagnetism of hydrous ferric oxides and ill-defined contributions from an incommensurate layered iron sulfide phase believed to be tochilinite. Moessbauer spectra measurements at 30 K of several terrestrial cronstedtite and tochilinite specimens have enables modal proportions of these minerals, as well as Fe{sup 3+}/Fe{sup 2+} ratios, to be determined quantitatively in a suite of CM-type meteorites. (orig.)

  7. Amperometric Biosensors Based on Carbon Paste Electrodes Modified with Nanostructured Mixed-valence Manganese Oxides and Glucose Oxidase

    Energy Technology Data Exchange (ETDEWEB)

    Cui, Xiaoli; Liu, Guodong; Lin, Yuehe

    2005-06-01

    Nanostructured multivalent manganese oxides octahedral molecular sieve (OMS), including cryptomelane-type manganese oxides and todorokite-type manganese oxides, were synthesized and evaluated for chemical sensing and biosensing at low operating potential. Both cryptomelane-type manganese oxides and todorokite-type manganese oxides are nanofibrous crystals with sub-nanometer open tunnels that provide a unique property for sensing applications. The electrochemical and electrocatalytic performance of OMS for the oxidation of H2O2 have been compared. Both cryptomelane-type manganese oxides and todorokite-type manganese oxides can be used to fabricate sensitive H2O2 sensors. Amperometric glucose biosensors are constructed by bulk modification of carbon paste electrodes (CPEs) with glucose oxidase as a biocomponent and nanostructured OMS as a mediator. A Nafion thin film was applied as an immobilization/encapsulation and protective layer. The biosensors were evaluated as an amperometric glucose detector at phosphate buffer solution with a pH 7.4 at an operating potential of 0.3 V (vs. Ag/AgCl). The biosensor is characterized by a well-reproducible amperometric response, linear signal-to-glucose concentration range up to 3.5 mM and 1.75 mM, and detection limits (S/N = 3) of 0.1 mM and 0.05 mM for todorokite-type manganese oxide and cryptomelane-type manganese oxide modified electrodes, respectively. The biosensors based on OMS exhibit considerable good reproducibility and stability, and the construction and renewal are simple and inexpensive.

  8. Amperometric biosensors based on carbon paste electrodes modified with nanostructured mixed-valence manganese oxides and glucose oxidase.

    Science.gov (United States)

    Cui, Xiaoli; Liu, Guodong; Lin, Yuehe

    2005-06-01

    Nanostructured, multivalent, manganese-oxide octahedral molecular sieves (OMS), including cryptomelane-type manganese oxides and todorokite-type manganese oxides, were synthesized and evaluated for chemical sensing and biosensing at low operating potential. Both cryptomelane-type manganese oxides and todorokite-type manganese oxides are nanofibrous crystals with subnanometer open tunnels that provide a unique property for sensing applications. The electrochemical and electrocatalytic performance of OMS for the oxidation of H2O2 have been compared. Both cryptomelane-type manganese oxides and todorokite-type manganese oxides can be used to fabricate sensitive H2O2 sensors. With glucose oxidase (GOx) as an enzyme model, amperometric glucose biosensors are constructed by bulk modification of carbon paste electrodes with GOx as a biocomponent and nanostructured OMS as a mediator. A Nafion thin film was applied as an immobilization/encapsulation and protective layer. The biosensors were evaluated as an amperometric glucose detector at phosphate buffer solution with a pH 7.4 at an operating potential of 0.3 V (vs Ag/AgCl). The biosensor is characterized by a well-reproducible amperometric response, linear signal-to-glucose concentration range up to 3.5 mmol/L and 1.75 mmol/L, and detection limits (S/N = 3) of 0.1 mmol/L and 0.05 mmol/L for todorokite-type manganese oxide and cryptomelane-type manganese oxide-modified electrodes, respectively. The biosensors based on OMS exhibit considerable good reproducibility and stability, and the construction and renewal are simple and inexpensive.

  9. Novel Countercation in MMX-Type Mixed-Valence Chain Compound: Coexistence of Neutral and Protonated Amino Substituents

    Directory of Open Access Journals (Sweden)

    Hiroaki Iguchi

    2011-10-01

    Full Text Available The first MMX-type quasi-one-dimensional (Q1D Pt chain complex (MMX chain that contains a mono-protonated diamine as countercation, {o-(H3NC6H4NH2}4[Pt2(pop4I]·H2O (pop = P2H2O52–, was synthesized. According to the crystal structural analysis, –NH2 group was hydrogen-bonded to either lattice H2O molecule or –NH3+ group in addition to typical hydrogen bond between –NH3+ group and pop ligand. To control the partial deprotonation of the countercation will be an important method for achieving the high-conductive MMX-chain polymer by the hole doping.

  10. Crystalline, mixed-valence manganese analogue of prussian blue: magnetic, spectroscopic, X-ray and neutron diffraction studies.

    Science.gov (United States)

    Franz, Patrick; Ambrus, Christina; Hauser, Andreas; Chernyshov, Dmitry; Hostettler, Marc; Hauser, Jürg; Keller, Lukas; Krämer, Karl; Stoeckli-Evans, Helen; Pattison, Philip; Bürgi, Hans-Beat; Decurtins, Silvio

    2004-12-22

    The compound of stoichiometry Mn(II)3[Mn(III)(CN)6]2.zH2O (z = 12-16) (1) forms air-stable, transparent red crystals. Low-temperature single crystal optical spectroscopy and single crystal X-ray diffraction provide compelling evidence for N-bonded high-spin manganese(II), and C-bonded low-spin manganese(III) ions arranged in a disordered, face-centered cubic lattice analogous to that of Prussian Blue. X-ray and neutron diffraction show structured diffuse scattering indicative of partially correlated (rather than random) substitutions of [Mn(III)(CN)6] ions by (H2O)6 clusters. Magnetic susceptibility measurements and elastic neutron scattering experiments indicate a ferrimagnetic structure below the critical temperature Tc = 35.5 K.

  11. THE STRUCTURE OF LICU2O2 WITH MIXED-VALENCE COPPER FROM TWIN-CRYSTAL DATA

    NARCIS (Netherlands)

    Berger, R; Meetsma, A; van Smaalen, S; Sundberg, M

    1991-01-01

    The structure of LiCu2O2 was solved using two sets of X-ray diffraction twin-crystal data. Extended twinning creates virtual tetragonal symmetry. The compound crystallizes in Pnma (62) with unit-cell parameters a = 5.72 angstrom, b = 2.86 angstrom and c = 12.4 angstrom with a certain homogeneity ran

  12. Novel composite material polyoxovanadate@MIL-101(Cr): a highly efficient electrocatalyst for ascorbic acid oxidation.

    Science.gov (United States)

    Fernandes, Diana M; Barbosa, André D S; Pires, João; Balula, Salete S; Cunha-Silva, Luís; Freire, Cristina

    2013-12-26

    A novel hybrid composite material, PMo10V2@MIL-101 was prepared by the encapsulation of the tetra-butylammonium (TBA) salt of the vanadium-substituted phosphomolybdate [PMo10V2O40](5-) (PMo10V2) into the porous metal-organic framework (MOF) MIL-101(Cr). The materials characterization by powder X-ray diffraction, Fourier transform infrared spectra and scanning electron microscopy confirmed the preparation of the composite material without disruption of the MOF porous structure. Pyrolytic graphite electrodes modified with the original components (MIL-101(Cr), PMo10V2), and the composite material PMo10V2@MIL-101 were prepared and their electrochemical responses were studied by cyclic voltammetry. Surface confined redox processes were observed for all the immobilized materials. MIL-101(Cr) showed one-electron reduction process due to chromium centers (Cr(III) → Cr(II)), while PMo10V2 presented five reduction processes: the peak at more positive potentials is attributed to two superimposed 1-electron vanadium reduction processes (V(V) → V(IV)) and the other four peaks to Mo-centred two-electron reduction processes (Mo(VI) → Mo(V)). The electrochemical behavior of the composite material PMo10V2@MIL-101 showed both MIL-101(Cr) and PMo10V2 redox features, although with the splitting of the two vanadium processes and the shift of the Mo- and Cr- centered processes to more negative potentials. Finally, PMo10V2@MIL-101 modified electrode showed outstanding enhanced vanadium-based electrocatalytic properties towards ascorbic acid oxidation, in comparison with the free PMo10V2, as a result of its immobilization into the porous structure of the MOF. Furthermore, PMo10V2@MIL-101 modified electrode showed successful simultaneous detection of ascorbic acid and dopamine.

  13. Polyoxometalates from heteropoly "brown" precursors. A new structural class of mixed valence heteropolytungstates, [(XO4)W3IVW17VIO 62Hx]n-

    Science.gov (United States)

    Dickman, M.H.; Ozeki, T.; Evans, H.T.; Rong, C.; Jameson, G.B.; Pope, M.T.

    2000-01-01

    Reduction of the ??-Keggin anion [Xn+O4W12O36][8-n]- (X = H22+, B3+, Si4+) by six electrons results in the known tungsten "brown" species [Xn+O4(H2O)3WIV3WVI9O33][8-n]- in which three W atoms have been reduced from WVI to WIV, forming a metal-metal bonded triad. The WIV atoms have terminal water coordinated in place of terminal oxo groups. Additional tungstate can condense onto these water molecules in aqueous solution between pH = 4 and 6.5 to form the species reported here, [(XO4)WIV3WVI17O 62Hx]y-. The boron derivative (X = B3+) is more stable than the metatungstate (X = H22+), both of which have been characterized by elemental analysis, 183W NMR and X-ray crystal structure analysis. Eight additional tungstate groups condense in the form of a partial Keggin structure containing two triads and one dyad which is rotated 60?? relative to a hypothetical ??-isomer. ?? The Royal Society of Chemistry 2000.

  14. Topological Properties and the Dynamical Crossover from Mixed-Valence to Kondo-Lattice Behavior in the Golden Phase of SmS.

    Science.gov (United States)

    Kang, Chang-Jong; Choi, Hong Chul; Kim, Kyoo; Min, B I

    2015-04-24

    We have investigated temperature-dependent behaviors of electronic structure and resistivity in a mixed-valent golden phase of SmS, based on the dynamical mean-field-theory band-structure calculations. Upon cooling, the coherent Sm 4f bands are formed to produce the hybridization-induced pseudogap near the Fermi level, and accordingly the topology of the Fermi surface is changed to exhibit a Lifshitz-like transition. The surface states emerging in the bulk gap region are found to be not topologically protected states but just typical Rashba spin-polarized states, indicating that SmS is not a topological Kondo semimetal. From the analysis of anomalous resistivity behavior in SmS, we have identified universal energy scales, which characterize the Kondo-mixed-valent semimetallic systems.

  15. Metal Dependence of Signal Transmission through MolecularQuantum-Dot Cellular Automata (QCA: A Theoretical Studyon Fe, Ru, and Os Mixed-Valence Complexes

    Directory of Open Access Journals (Sweden)

    Ken Tokunaga

    2010-08-01

    Full Text Available Dynamic behavior of signal transmission through metal complexes [L5M-BL-ML5]5+ (M=Fe, Ru, Os, BL=pyrazine (py, 4,4’-bipyridine (bpy, L=NH3, which are simplified models of the molecular quantum-dot cellular automata (molecular QCA, is discussed from the viewpoint of one-electron theory, density functional theory. It is found that for py complexes, the signal transmission time (tst is Fe(0.6 fs < Os(0.7 fs < Ru(1.1 fs and the signal amplitude (A is Fe(0.05 e < Os(0.06 e < Ru(0.10 e. For bpy complexes, tst and A are Fe(1.4 fs < Os(1.7 fs < Ru(2.5 fs and Os(0.11 e < Ru(0.12 e

  16. Magnetic properties of mixed valence La2/3Sr1/3Mn1−TO3 (T = Fe,Cr) manganites obtained by Pechini method

    Indian Academy of Sciences (India)

    I Betancourt; A Morales-Hernández

    2013-05-01

    Polycrystalline manganites of composition La2/3Sr1/3Mn1−TO3 (T = Cr3+ or Fe3+, x = 0.0-0.10) were obtained by the Pechini method. Their magnetic properties exhibited a marked dependence on Fe/Cr content, with significant reduction of the magnetic moment per formula unit and their Curie temperatures. In addition, the magnetocaloric effect, determined by isothermal magnetization measurements, displayed a decreasing tendency with increasing Fe/Cr concentration. Results were interpreted on the basis of a deleterious effect on the double exchange interaction provoked by the presence of Fe3+ and Cr3+ ions within the crystal structure.

  17. Electrochemistry and Spectroelectrochemistry of 1,8-Naphthalene and 1,8- Anthracene-Linked Cofacial Binuclear Metallophthalocynanines. New Mixed Valence Metallopthalocyanines

    Science.gov (United States)

    1990-05-10

    cyclic voltametry at 200, 100, 50 and 20 mV/s, Average data being E : (Eps + Epc)/2 are reported. Data in parenthesis are estimated from overlapping...Perkin-Elmer Hitachi Model 340 microprocessor spectrometer. Cyclic and differential pulse voltammetry were performed with a Princeton Applied Research...and dried under reduced pressure. Judging from the cyclic voltammetric curve under argon at the prepared electrode, the surface concentration of the

  18. Characterization of the pressure-induced second-order phase transition in the mixed-valence vanadate BaV{sub 6}O{sub 11}

    Energy Technology Data Exchange (ETDEWEB)

    Friese, Karen; Grzechnik, Andrzej [Universidad del Pais Vasco, Bilbao (Spain). Dept. de Fisica Materia Condensada; Kanke, Yasushi [National Inst. for Mateials Science, Tsukuba, Ibaraki (Japan). Advanced Nano Materials Lab.

    2009-06-15

    The pressure dependence of the structure of the mixedvalence vanadate BaV{sub 6}O{sub 11} was studied with single-crystal Xray diffraction in a diamond-anvil cell. The compressibility data could be fitted with a Murnaghan equation of state with the zero-pressure bulk modulus B{sub 0}=161(7) GPa and the unitcell volume at ambient pressure=387.1(3) A{sup 3} (B'=4.00). A phase transition involving a symmetry reduction from P6{sub 3}/mmc to P6{sub 3}mc can be reliably detected in the high-pressure data. The estimated transition pressure lies in the range 1.18

  19. (I,0) Mixed-valence state of a diiron complex with pertinence to the [FeFe]-hydrogenase active site: an IR, EPR, and computational study.

    Science.gov (United States)

    Singh, Pradyumna S; Rudbeck, Hans Christian; Huang, Ping; Ezzaher, Salah; Eriksson, Lars; Stein, Matthias; Ott, Sascha; Lomoth, Reiner

    2009-12-01

    Biphenyl-2,2'-dithiolate (bpdt) bridged Fe(2)(bpdt)(CO)(6) (1) undergoes two sequential electrochemically quasi-reversible reductions. The one-electron reduction product 1(-) is unusually stable against irreversible structural changes and could be characterized by IR and EPR spectroscopy supported by computational methods. Reduction to the (I,0) state does not trigger bridging coordination of CO but partial deligation of the dithiolate in 1(-) that ultimately forms a diamagnetic dimerization product.

  20. A new mixed-valence lead(II manganese(II/III phosphate(V: PbMnII2MnIII(PO43

    Directory of Open Access Journals (Sweden)

    Ghaleb Alhakmi

    2013-07-01

    Full Text Available The title compound, lead trimanganese tris(orthophosphate, has been synthesized by hydrothermal methods. In this structure, only two O atoms are in general positions and all others atoms are in the special positions of the Imma space group. Indeed, the atoms in the Wyckoff positions are namely: Pb1 and P1 on 4e (mm2; Mn1 on 4b (2/m; Mn2 and P2 on 8g (2; O1 on 8h (m; O2 on 8i (m. The crystal structure can be viewed as a three-dimensional network of corner- and edge-sharing PO4 tetrahedra and MnO6 octahedra, building two types of chains running along the b axis. The first is an infinite linear chain, formed by alternating MnIIIO6 octahedra and PO4 tetrahedra which share one vertex. The second chain is built up from two adjacent edge-sharing octahedra (MnII2O10 dimers whose ends are linked to two PO4 tetrahedra by a common edge. These chains are linked together by common vertices of polyhedra in such a way as to form porous layers parallel to (001. These sheets are bonded by the first linear chains, leading to the appearance of two types of tunnels, one propagating along the a axis and the other along b. The PbII ions are located within the intersections of the tunnels with eight neighbouring O atoms in form of a trigonal prism that is capped by two O atoms on one side. The three-dimensional framework of this structure is compared with similar phosphates such as Ag2Co3(HPO4(PO42 and Ag2Ni3(HPO4(PO42.

  1. Electrochemical synthesis and structural characterization of a novel mixed-valence copper(I)-copper(II) complex: {[bis(ethylenediamine)copper(II)] bis[diiodocuprate(I)]}.

    Science.gov (United States)

    Fotouhi, Lida; Dehghanpour, Saeed; Heravi, Majid M; Ardakani, Mahboobeh Dashti

    2007-07-12

    A novel, mixed-valent copper(I)-copper(II) complex, {[bis(ethylene-diamine)copper(II)] bis[diiodocuprate(I)]} (1), has been prepared by electrochemical dissolution of a sacrificial copper anode in a solution of ethylenediamine (en), I2 and tetraethylammoniumperchlorate (TEAP) as supporting electrolyte in acetonitrile (AcN)and characterized by single-crystal X-ray structure determination. The crystal structure of the complex 1 shows that it consists of a CuI2 polymer formed from I- ligands bridging Cu(I) ions, with a nearly square planar geometry of bivalent Cu(II) atoms chelated by two ethylenediamine ligands. The results also show that direct electrosynthesis of the complex had high current efficiency, purity and electrolysis yield.

  2. Electrochemical Synthesis and Structural Characterization of a Novel Mixed-valence Copper (I)-copper (II) Complex: {[Bis(ethylenediamine) Copper (II)] Bis[diiodocuprate (I)]}

    OpenAIRE

    Mahboobeh Dashti Ardakani; Majid M. Heravi; Saeed Dehghanpour; Lida Fotouhi

    2007-01-01

    A novel, mixed-valent copper(I)-copper(II) complex, {[bis(ethylene-diamine)copper(II)] bis[diiodocuprate(I)]} (1), has been prepared by electrochemicaldissolution of a sacrificial copper anode in a solution of ethylenediamine (en), I2 andtetraethylammoniumperchlorate (TEAP) as supporting electrolyte in acetonitrile (AcN)and characterized by single-crystal X-ray structure determination. The crystal structure ofthe complex 1 shows that it consists of a CuI2 polymer formed from I- ligands bridgi...

  3. Electrochemical Synthesis and Structural Characterization of a Novel Mixed-valence Copper (I-copper (II Complex: {[Bis(ethylenediamine Copper (II] Bis[diiodocuprate (I]}

    Directory of Open Access Journals (Sweden)

    Mahboobeh Dashti Ardakani

    2007-07-01

    Full Text Available A novel, mixed-valent copper(I-copper(II complex, {[bis(ethylene-diaminecopper(II] bis[diiodocuprate(I]} (1, has been prepared by electrochemicaldissolution of a sacrificial copper anode in a solution of ethylenediamine (en, I2 andtetraethylammoniumperchlorate (TEAP as supporting electrolyte in acetonitrile (AcNand characterized by single-crystal X-ray structure determination. The crystal structure ofthe complex 1 shows that it consists of a CuI2 polymer formed from I- ligands bridgingCu(I ions, with a nearly square planar geometry of bivalente Cu(II atoms chelated by twoethylenediamine ligands. The results also show that direct electrosynthesis of the complexhad high current efficiency, purity and electrolysis yield.

  4. Accuracy of embedded fragment calculation for evaluating electron interactions in mixed valence magnetic systems: study of 2e-reduced lindqvist polyoxometalates.

    Science.gov (United States)

    Suaud, Nicolas; López, Xavier; Ben Amor, Nadia; Bandeira, Nuno A G; de Graaf, Coen; Poblet, Josep M

    2015-02-10

    Accurate quantum chemical calculations on real-world magnetic systems are challenging, the inclusion of electron correlation being the bottleneck of such task. One method proposed to overcome this difficulty is the embedded fragment approach. It tackles a chemical problem by dividing it into small fragments, which are treated in a highly accurate way, surrounded by an embedding included at an approximate level. For the vast family of medium-to-large sized polyoxometalates, two-electron-reduced systems are habitual and their magnetic properties are interesting. In this paper, we aim at assessing the quality of embedded fragment calculations by checking their ability to reproduce the electronic spectra of a complete system, here the mixed-metal series [MoxW6-xO19](4-) (x = 0-6). The microscopic parameters extracted from fragment calculations (electron hopping, intersite electrostatic repulsion, local orbital energy, etc.) have been used to reproduce the spectra through model Hamiltonian calculations. These energies are compared to the results of the highly accurate ab initio difference dedicated configuration interaction (DDCI) method on the complete system. In general, the model Hamiltonian calculations using parameters extracted from embedded fragments nearly exactly reproduce the DDCI spectra. This is quite an important result since it can be generalized to any inorganic magnetic system. Finally, the occurrence of singlet or triplet ground states in the series of molecules studied is rationalized upon the interplay of the parameters extracted.

  5. Hydrothermal Synthesis and Properties of Open-Framework Mixed-valence Iron Phosphates FeIII2FeII1.5(PO4)3 with Three-dimensional Structure

    Institute of Scientific and Technical Information of China (English)

    DUAN,Li-Ying(段丽颖); LIU,Fu-Chen(刘福臣); WANG,En-Bo(王恩波); LI,Yang-Guang(李阳光); HU,Chang-Wen(胡长文); XU,Lin(许林)

    2004-01-01

    The open-framework iron phosphate FeIII2FeII1.5(PO4)3 was hydrothermally synthesized and characterized by elemental analysis, IR, EPR, XPS and single crystal X-ray diffraction analysis. The title compound crystallized in the triclinic, space group P1 with a=0.64724(4) nm, b=0.79651(6) nm, c=0.94229(5) nm, α=104.447(2)°, β=108.919(4)°, γ=101.741(4)°, V=0.42302(5) nm3, Z=1 and R1 (wR2)=0.0307 (0.0793). Crystal data were collected on a Rigaku R-AXIS RAPID IP diffractometer with Mo Kα (λ=0.071073 nm) at 293(2) K in the range of 2.43°<θ<27.46°. The structure of 1 consists of 19 non-hydrogen atoms including three and a half crystallographically independent Fe and three P atoms. Fe(1) connects its symmetrical Fe(1A) through bridging oxygen forming a dimer and the dimers are connected by Fe(4) forming an infinite staircase-like chain. Fe(2) and Fe(3) connect the infinite chains into a layer with bridging oxygen. Layers are interconnected via Fe(4) forming the six-membered and eight-membered channel systems.

  6. A three-dimensional mixed-valence Cu(II)/Cu(I) coordination polymer constructed from biphenyl-3,4',5-tricarboxylate and 1,4-bis(1H-imidazol-1-yl)benzene ligands.

    Science.gov (United States)

    Liu, Ya Hui; Lu, Li Ping; Zhu, Miao Li; Su, Feng

    2016-04-01

    Coordination polymers (CPs) built by coordination bonds between metal ions/clusters and multidentate organic ligands exhibit fascinating structural topologies and potential applications as functional solid materials. The title coordination polymer, poly[diaquabis(μ4-biphenyl-3,4',5-tricarboxylato-κ(4)O(3):O(3'):O(4'):O(5))tris[μ2-1,4-bis(1H-imidazol-1-yl)benzene-κ(2)N(3):N(3')]dicopper(II)dicopper(I)], [Cu(II)2Cu(I)2(C15H7O6)2(C12H10N4)3(H2O)2]n, was crystallized from a mixture of biphenyl-3,4',5-tricarboxylic acid (H3bpt), 1,4-bis(1H-imidazol-1-yl)benzene (1,4-bib) and copper(II) chloride in a water-CH3CN mixture under solvothermal reaction conditions. The asymmetric unit consists of two crystallographically independent Cu atoms, one of which is Cu(II), while the other has been reduced to the Cu(I) ion. The Cu(II) centre is pentacoordinated by three O atoms from three bpt(3-) ligands, one N atom from a 1,4-bib ligand and one O atom from a coordinated water molecule, and the coordination geometry can be described as distorted trigonal bipyramidal. The Cu(I) atom exhibits a T-shaped geometry (CuN2O) coordinated by one O atom from a bpt(3-) ligand and two N atoms from two 1,4-bib ligands. The Cu(II) atoms are extended by bpt(3-) and 1,4-bib linkers to generate a two-dimensional network, while the Cu(I) atoms are linked by 1,4-bib ligands, forming one-dimensional chains along the [20-1] direction. In addition, the completely deprotonated μ4-η(1):η(1):η(1):η(1) bpt(3-) ligands bridge one Cu(I) and three Cu(II) cations along the a (or [100]) direction to form a three-dimensional framework with a (10(3))2(10)2(4(2).6.10(2).12)2(4(2).6.8(2).10)2(8) topology via a 2,2,3,4,4-connected net. An investigation of the magnetic properties indicated a very weak ferromagnetic behaviour.

  7. Unusual Mixed Valence of Eu in Two Materials-EuSr2Bi2S4F4 and Eu2SrBi2S4F4: Mössbauer and X-ray Photoemission Spectroscopy Investigations.

    Science.gov (United States)

    Haque, Zeba; Thakur, Gohil Singh; Parthasarathy, Rangasamy; Gerke, Birgit; Block, Theresa; Heletta, Lukas; Pöttgen, Rainer; Joshi, Amish G; Selvan, Ganesan Kalai; Arumugam, Sonachalam; Gupta, Laxmi Chand; Ganguli, Ashok Kumar

    2017-02-28

    We have synthesized two new Eu-based compounds, EuSr2Bi2S4F4 and Eu2SrBi2S4F4, which are derivatives of Eu3Bi2S4F4, an intrinsic superconductor with Tc = 1.5 K. They belong to a tetragonal structure (SG: I4/mmm, Z = 2), similar to the parent compound Eu3Bi2S4F4. Our structural and (151)Eu Mössbauer spectroscopy studies show that, in EuSr2Bi2S4F4, Eu-atoms exclusively occupy the crystallographic 2a-sites. In Eu2SrBi2S4F4, 2a-sites are fully occupied by Eu-atoms and the other half of Eu-atoms and Sr-atoms together fully occupy 4e-sites in a statistical distribution. In both compounds Eu atoms occupying the crystallographic 2a-sites are in a homogeneous mixed valent state ∼2.6-2.7. From our magnetization studies in an applied H ≤ 9 T, we infer that the valence of Eu-atoms in Eu2SrBi2S4F4 at the 2a-sites exhibits a shift toward 2+. Our XPS studies corroborate the occurrence of valence fluctuations of Eu and after Ar-ion sputtering show evidence of enhanced population of Eu(2+)-states. Resistivity measurements, down to 2 K, suggest a semimetallic nature for both compounds.

  8. Hydrothermal Synthesis and Structure of a Mixed-valence Polyoxotungstate Decorated by Copper(I) Coordination Group, [Cu(en)2H2O]2[{Cu(en)2}HPW12O40]·2H2O

    Institute of Scientific and Technical Information of China (English)

    LI Zhen; LIN Bi-Zhou; HAN Guo-Hua; GENG Feng; LIU Pei-De

    2005-01-01

    A complex [Cu(en)2H2O]2[{Cu(en)2}HPW12O40]·2H2O (C12H57Cu3N12O44PW12, Mr = 3501.49) has been synthesized under hydrothermal conditions and its crystal structure was determined by X-ray diffraction.It crystallizes in the orthorhombic system, space group Pbca with a = 21.680(4), b = 20.680(4), c = 26.120(5) (A), V = 11711(4) (A)3, Dc = 3.972 g/cm3, Z = 8, μ(MoKa) = 24.661 mm-1, F(000) = 12440, the final R = 0.0527 and wR = 0.1416 for 11527 observed reflec- tions with I > 2σ(I).The crystal structure is composed of [{Cu(en)2}HPW12O40]2- anions, discrete [Cu(en)2H2O]+ complex cations and crystal water molecules, which are held together into a three- dimensional network through hydrogen-bonding interactions.The anionic [{Cu(en)2}HPW12O40]2- is formed by the mixed valance {HPWVI11WVO40}3- Keggin unit covalently linked by a {Cu(en)2}+ group.

  9. Mixed-valence, layered, cation radical salts of the ethane-bridged dimeric tetrathiafulvalene [(EDT-TTF-CH2-)2#centre dot#+] [X-][THF]0.5, X-=FeCl4-, GaCl4-

    DEFF Research Database (Denmark)

    Mézière, C.; Fourmigué, M.; Canadell, E.

    2000-01-01

    The synthesis and X-ray crystal structure of the ethane-linked dimeric tetrathiafulvalene [(EDT-TTF-CH2)(2)], 1,2-bis(ethylenedithiotetrathiafulvalenyl)ethane (1), is reported. It oxidizes reversibly at 0.45 and 0.90 V vs SCE. Electrocrystallization in the presence of [n-Bu4N][FeCl4] or [n-Bu4N...

  10. The first example of metallocene-like coordination mode of THBQ(4-): a mixed-valence heptanucler palladium complex [Pd7(THBQ)2(tben)6](PF6)4.

    Science.gov (United States)

    Asato, Eiji; Kyan, Ayano; Madanbashi, Tomokura; Tamura, Toshihide; Tadokoro, Makoto; Mizuno, Motohiro

    2010-02-28

    The title compound adopts a structure reminiscent of metallocene analogues, in which two disk-like units [Pd(II)(3)(THBQ)(tben)(3)](2+) bind to one naked Pd(0) metal in a sandwich form through each C(6)O(6)(4-) (THBQ(4-)) ring with an eta(6)-binding fashion.

  11. [V16Sb4O42(H2O){VO(C6H14N2)2}4]: a terminal expansion to a polyoxovanadate archetype.

    Science.gov (United States)

    Wutkowski, Adam; Näther, Christian; Kögerler, Paul; Bensch, Wolfgang

    2008-03-17

    The charge-neutral antimonatopolyoxovanadium(IV) cluster [V(IV)16Sb(III)4O42(H2O){V(IV)O(C6H14N2)2}4].10H2O.C6H14N2 was obtained under solvothermal conditions. The central cluster fragment, [V(IV) 16Sb(III)4O42], is a derivative of the [V18O42] archetype and is formed by replacing two VO5 polyhedra by two Sb2O5 units. The {V20Sb4} structure expands the {V16Sb4} motif by the addition of four square-pyramidal, terminal VO(1,2-diaminocyclohexane)2 groups. At low temperatures, the magnetic ground state is characterized by four independent S = 1/2 sites.

  12. 密度泛函理论在分子磁学中的应用——混合价三核锰配合物磁性的理论研究%Application of Density Functional Theory to Molecular Magnetism——Theoretical Study on Magnetic Properties of Mixed-valence Trinuclear Manganese Compounds

    Institute of Scientific and Technical Information of China (English)

    任杰; 王炳武; 陈志达; 徐光宪

    2008-01-01

    在对混合价化合物分类的基础上,将双核耦合模型推广到三核磁耦合体系,重点研究定域与离域两类混合价化合物的磁学性质.以混合价三核锰为例,应用密度泛函理论方法计算了定域与离域[Mn3O(O2CH)6L3]z+(L=pyridine;z=0)化合物的电子结构,得到与实验可比较的磁耦合常数J.结果表明,密度泛函理论(DFT)结合对称性破损(BS)方法可用于此三核混合价体系;对于完全离域的混合价Mn3ⅡⅢⅢ体系,必须考虑电子的离域作用对磁耦合的影响,其Hamiltonian量应该包含双交换参数B.为便于比较,同时计算了等价三核锰化合物[Mn3O(O2CH)6L3]z+(L=pyridine;z=1)的磁学性质.

  13. 1,1,1-Tris(hydroxymethyl)propane in manganese carboxylate chemistry: synthesis, structure and magnetic properties of a mixed-valence [MnIII4MnII4] cluster featuring the novel [MnIII4MnII4(mu3-OR)6(mu2-OR)8]6+ core.

    Science.gov (United States)

    Milios, Constantinos J; Fabbiani, Francesca P A; Parsons, Simon; Murugesu, Muralee; Christou, George; Brechin, Euan K

    2006-01-14

    The reaction between MnBr(2).4H(2)O with H(3)tmp (1,1,1-tris(hydroxymethyl)propane) in MeCN in the presence of Na(O(2)CCMe(3)) and NBu(4)Br produces the complex [Mn(8)(O(2)CCMe(3))(2)(tmp)(2)(Htmp)(4)Br(4)(H(2)O)(2)].2MeCN (1.2MeCN) in good yield. The centrosymmetric octanuclear molecule consists of four Mn(III) and four Mn(II) ions assembled together by fourteen alkoxo bridges to give a [Mn(III)(4)Mn(II)(4)(mu(3)-OR)(6)(mu(2)-OR)(8)](6+) rod-like core in which the metal centres are arranged in a planar zigzag fashion. Peripheral ligation is provided by a combination of bridging pivalate ions, terminal bromides and water molecules. Dc magnetic susceptibility measurements reveal the presence of dominant antiferromagnetic interactions leading to a spin ground state of S = 0. A rationalization of this result is attempted by structural comparison with previously reported tetranuclear manganese complexes containing the [Mn(III)(2)Mn(II)(2)(mu(3)-OR)(2)(mu(2)-OR)(4)] core in which the magnetic interactions are ferromagnetic.

  14. Study on the ferromagnetic state in iron mixed-valence complexes, A[Fe{sup II}Fe{sup III}(dto){sub 3}] (A = (n-C{sub n}H{sub 2n + 1}){sub 4}N; dto = C{sub 2}S{sub 2}O{sub 2}) by means of Moessbauer spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Ono, Yuki; Okazawa, Atsushi, E-mail: cokazawa@mail.ecc.u-tokyo.ac.jp [University of Tokyo, Graduate School of Arts and Sciences (Japan); Enomoto, Masaya [Tokyo University of Science, Department of Chemistry, Faculty of Science Division I (Japan); Kojima, Norimichi, E-mail: cnori@mail.ecc.u-tokyo.ac.jp [University of Tokyo, Graduate School of Arts and Sciences (Japan)

    2012-03-15

    We have investigated the ferromagnetic states for (n-C{sub n}H{sub 2n + 1}){sub 4}N[Fe{sup II}Fe{sup III}(dto){sub 3}] (n = 3-6; dto C{sub 2}O{sub 2}S{sub 2}) by means of {sup 57}Fe Moessbauer spectroscopy. The major component of the spin configuration in the ferromagnetic states for n = 3 and 4 is the low-temperature phase (LTP) with the Fe{sup III} (S = 5/2) and Fe{sup II} (S = 0) states. The high-temperature phase (HTP) of n = 4 remains by more than 20%, which is consistent with two ferromagnetic transitions (T{sub C} = 7 and 13 K). Moreover, it was revealed that the Moessbauer spectra in the ferromagnetic states for n = 5 and 6 correspond to the HTP consisting of the Fe{sup II} (S = 2) and Fe{sup III} (S = 1/2) states.

  15. Synthesis and characterization of the Bis- Cyclometalating Ligand 3,3',5,5'-tetrakis[(dimethylamino)methyl]biphenyl and its use in the preparation of bimetallic M(II), M(IV) (M = Pt, Pd) and mixed-valence Pt(II)-Pt(IV) complexes via a dilithio-derivative. Crystal structure of the Pd dimer [ClPd{2,6-(Me2NCH2)2C6H2}]2,

    NARCIS (Netherlands)

    Koten, G. van; Lagunas, M.C.; Gossage, R.A.; Spek, A.L.

    1998-01-01

    The potentially bis-cyclometalating ligand 3,3',5,5'-tetrakis[(dimethylamino)methyl]biphenyl, was prepared from 3,5-(Me2NCH2)2C6H3Br in a one-pot synthesis involving lithium-halogen exchange, transmetalation, and reductive-elimination reactions. This ligand undergoes selective dilithiation in the 4

  16. Synthesis and characterization of the Bis- Cyclometalating Ligand 3,3',5,5'-tetrakis[(dimethylamino)methyl]biphenyl and its use in the preparation of bimetallic M(II), M(IV) (M = Pt, Pd) and mixed-valence Pt(II)-Pt(IV) complexes via a dilithio-derivative. Crystal structure of the Pd dimer [ClPd{2,6-(Me2NCH2)2C6H2}]2,

    NARCIS (Netherlands)

    Koten, G. van; Lagunas, M.C.; Gossage, R.A.; Spek, A.L.

    1998-01-01

    The potentially bis-cyclometalating ligand 3,3',5,5'-tetrakis[(dimethylamino)methyl]biphenyl, was prepared from 3,5-(Me2NCH2)2C6H3Br in a one-pot synthesis involving lithium-halogen exchange, transmetalation, and reductive-elimination reactions. This ligand undergoes selective dilithiation in the 4

  17. Synthesis, structure and magnetic properties of the polyoxovanadate cluster [Zn2(NH2(CH2)2NH2)5][{Zn(NH2(CH2)2NH2)2}2{V18O42(H2O)}]$\\cdot x$H2O ( ∼ 12), possessing a layered structure

    Indian Academy of Sciences (India)

    Srinivasan Natarajan; K S Narayan; Swapan K Pati

    2006-01-01

    A hydrothermal reaction of a mixture of ZnCl2, V2O5, ethylenediamine and water gave rise to a layered poly oxovanadate material [Zn2(NH2(CH2)2NH2)5][{Zn(NH2(CH2)2NH2)2}2{V18O42(H2O)}]$\\cdot x$H2O ( = 12) (I) consisting of [V18O42]12- clusters. These clusters, with all the vanadium ions in the +4 state, are connected together through Zn(NH2(CH2)2NH2)2 linkers forming a two-dimensional structure. The layers are also separated by distorted trigonal bipyramidal [Zn2(NH2(CH2)2NH2)5] complexes. The structure, thus, presents a dual role for the Zn-ethylenediamine complex. The magnetic susceptibility studies indicate that the interactions between the V centres in I are predominantly antiferromagnetic in nature and the compound shows highly frustrated behaviour. The magnetic properties are compared to the theoretical calculations based on the Heisenberg model, in addition to correlating to the structure. Crystal data for the complexes are presented.

  18. A temperature induced ferrocene–ferrocenium interconversion in a ferrocene functionalized μ{sub 3}-O chromium carboxylate

    Energy Technology Data Exchange (ETDEWEB)

    Mereacre, Valeriu, E-mail: valeriu.mereacre@kit.edu [Institut für Anorganische Chemie, Karlsruher Institut für Technologie, D-76131 Karlsruhe (Germany); Schlageter, Martin [Institut für Nanotechnologie, Karlsruher Institut für Technologie, D-76344 Eggenstein-Leopoldshafen (Germany); Powell, Annie K., E-mail: annie.powell@kit.edu [Institut für Anorganische Chemie, Karlsruher Institut für Technologie, D-76131 Karlsruhe (Germany); Institut für Nanotechnologie, Karlsruher Institut für Technologie, D-76344 Eggenstein-Leopoldshafen (Germany)

    2015-05-01

    The infrared spectra and {sup 57}Fe Mössbauer measurements of a ferrocenecarboxylate functionalized {Cr_3O} complex in solid state are reported. It was established that conjugation of ferrocene Cp orbitals with the π orbitals of the adjacent carboxylic group stabilizes the trapped mixed-valence state leading to an intriguing coexistence of ferrocene and ferrocenium species giving rise to a new type of compound showing valence tautomerism in the solid state. - Highlights: • A stabilized ferrocene trapped mixed-valence state is reported. • New type of compound showing valence tautomerism in solid state. • A thermally induced electron transfer and a mixed-valence state near room temperature.

  19. Bulk superconductivity in Tl 2Ba 2CaCu 2O 8 and TlBa 2Ca 2Cu 3O 9 phases

    Science.gov (United States)

    Sulpice, A.; Giordanengo, B.; Tournier, R.; Hervieu, M.; Maignan, A.; Martin, C.; Michel, C.; Provost, J.

    1988-09-01

    Well-crystallized Tl 2Ba 2CaCu 2O 8 phases have been observed superconducting or normal below 108 K depending on their stoichiometry. This observation is an evidence that a (Cu IL&.zbnd;O -) mixed valence induced by vacancies or substitution on different sites gives rise to superconductivity in this phase. The new phase TlBa 2Ca 2CuO 9 which intrinsically contains a mixed valence has been observed as having a sharp transition to bulk superconductivity in the Meissner effect at a critical temperature of 120 K. This temperature is much higher than the recently observed one.

  20. Superconductivity below 120 K of new thallium compounds

    Energy Technology Data Exchange (ETDEWEB)

    Giordanengo, B.; Sulpice, A.; Tournier, R.; Hervieu, M.; Maignan, A.; Martin, C.; Michel, C.; Provost, J.; Raveau, B.

    1989-05-01

    Well-cristallized Tl/sub 2/Ba/sub 2/CaCu/sub 2/0/sub 8/ phases have been observed superconducting or normal below 108 K depending on their stoichiometry. This observation is an evidence that a (Cu/sup ii/-0/sup -/) mixed valence induced by vacancies or substitutions on different sites gives rise to superconductivity in this phase. The new phase TlBa/sub 2/Ca/sub 2/Cu/sub 3/O/sub 9/ which intrinsically contains a mixed valence has been observed as having a sharp transition to bulk superconductivity in the Meissner effect at a critical temperature of 120 K.

  1. Theoretical Studies of Magnetic Systems. Final Report, August 1, 1994 - November 30, 1997

    Science.gov (United States)

    Gor`kov, L. P.; Novotny, M. A.; Schrieffer, J. R.

    1997-01-01

    During the grant period the authors have studied five areas of research: (1) low dimensional ferrimagnets; (2) lattice effects in the mixed valence problem; (3) spin compensation in the one dimensional Kondo lattice; (4) the interaction of quasi particles in short coherence length superconductors; and (5) novel effects in angle resolved photoemission spectra from nearly antiferromagnetic materials. Progress in each area is summarized.

  2. Molecular orbital (SCF-Xα-SW) theory of metal-metal charge transfer processes in minerals

    Science.gov (United States)

    Sherman, David M.

    1987-01-01

    A number of mixed valence iron oxides and silicates (e.g., magnetite, ilvaite) exhibit thermally induced electron delocalization between adjacent Fe2+ and Fe3+ ions and optically induced electronic transitions which are assigned to Fe2+→Fe3+ intervalence charge transfer.

  3. Synchrotron Studies of Narrow Band and Low-Dimensional Materials. Final Report for July 1, 1990---December 31, 2002

    Energy Technology Data Exchange (ETDEWEB)

    Allen, J. W.

    2003-05-13

    This report summarizes a 12-year program of various kinds of synchrotron spectroscopies directed at the electronic structures of narrow band and low-dimensional materials that display correlated electron behaviors such as metal-insulator transitions, mixed valence, superconductivity, Kondo moment quenching, heavy Fermions, and non-Fermi liquid properties.

  4. Concerning the electronic coupling of MoMo quadruple bonds linked by 4,4'-azodibenzoate and comparison with t2g 6-Ru(II) centers by 4,4'-azodiphenylcyanamido ligands.

    Science.gov (United States)

    Chisholm, Malcolm H; D'Acchioli, Jason S; Hadad, Christopher M; Patmore, Nathan J

    2006-12-25

    From the reactions between Mo2(O2CtBu)4 and each of terephthalic acid and 4,4'-azodibenzoic acid, the compounds [Mo2(O2CtBu)3]2(mu-O2CC6H4CO2) (1) and [Mo2(O2CtBu)3]2(mu-O2CC6H4N2C6H4CO2) (2) have been made and characterized by spectroscopic and electrochemical methods. Their electronic structures have been examined by computations employing density functional theory on model compounds where HCO2 substitutes for tBuCO2. On the basis of these studies, the two Mo2 units are shown to be only weakly coupled and the mixed-valence ions 1+ and 2+ to be valence-trapped and Class II and I, respectively, on the Robin-Day classification scheme for mixed-valence compounds. These results are compared to t2g6-Ru centers linked by 1,4-dicyanamidobenzene and azo-4,4'-diphenylcyanamido bridges for which the mixed-valence ions [Ru-bridge-Ru]5+ have been previously classified as fully delocalized, Class III [Crutchley et al. Inorg. Chem. 2001, 40, 1189; Inorg. Chem. 2004, 43, 1770], and on the basis of results described herein, it is proposed that the latter complex ion is more likely a mixed-valence organic radical where the bridge is oxidized and not the Ru(2+) centers.

  5. Prussian Blue Analogues of Reduced Dimensionality

    NARCIS (Netherlands)

    Gengler, Regis Y. N.; Toma, Luminita M.; Pardo, Emilio; Lloret, Francesc; Ke, Xiaoxing; Van Tendeloo, Gustaaf; Gournis, Dimitrios; Rudolf, Petra

    2012-01-01

    Mixed-valence polycyanides (Prussian Blue analogues) possess a rich palette of properties spanning from room-temperature ferromagnetism to zero thermal expansion, which can be tuned by chemical modifications or the application of external stimuli (temperature, pressure, light irradiation). While mol

  6. The met axial ligand determines the redox potential in Cu-A sites

    DEFF Research Database (Denmark)

    Ledesma, G.N.; Murgida, D.H.; Ly, H.K.;

    2007-01-01

    The replacement of the axial methionine ligand in a native Cu-A protein rendered a series of stable mutants with spectroscopic features of a mixed valence center. The mutations resulted in minor perturbations of the electronic structure of this site but led to significant changes in the redox pot...

  7. The met axial ligand determines the redox potential in Cu-A sites

    DEFF Research Database (Denmark)

    Ledesma, G.N.; Murgida, D.H.; Ly, H.K.

    2007-01-01

    The replacement of the axial methionine ligand in a native Cu-A protein rendered a series of stable mutants with spectroscopic features of a mixed valence center. The mutations resulted in minor perturbations of the electronic structure of this site but led to significant changes in the redox pot...

  8. A redox-active tri-star molecule: merging of TTF and HAT chemistry.

    Science.gov (United States)

    Jia, Chunyang; Liu, Shi-Xia; Tanner, Christian; Leiggener, Claudia; Sanguinet, Lionel; Levillain, Eric; Leutwyler, Samuel; Hauser, Andreas; Decurtins, Silvio

    2006-05-07

    A planar pi-conjugated heteroaromatic molecule 1 has been synthesized and fully characterized; it combines two characteristics, a charge-transfer transition originating from its inherent donor-acceptor nature in its neutral state and an intervalence charge-transfer transition in its 1(2+) mixed-valence state.

  9. Prussian Blue Analogues of Reduced Dimensionality

    NARCIS (Netherlands)

    Gengler, Regis Y. N.; Toma, Luminita M.; Pardo, Emilio; Lloret, Francesc; Ke, Xiaoxing; Van Tendeloo, Gustaaf; Gournis, Dimitrios; Rudolf, Petra

    2012-01-01

    Mixed-valence polycyanides (Prussian Blue analogues) possess a rich palette of properties spanning from room-temperature ferromagnetism to zero thermal expansion, which can be tuned by chemical modifications or the application of external stimuli (temperature, pressure, light irradiation). While

  10. Electronic bistability in linear beryllium chains.

    Science.gov (United States)

    Helal, Wissam; Monari, Antonio; Evangelisti, Stefano; Leininger, Thierry

    2009-04-30

    A theoretical investigation on the mixed-valence behavior (bistability) of a series of cationic linear chains composed of beryllium atoms, Be(N)(+) (with N = 6,..., 12), is presented. The calculations were performed at CAS-SCF and MR-CI levels by using an ANO basis set containing 6s4p3d2f orbitals for each atom. Our results show a consistent gradual shift between different classes of mixed-valence compounds as the number of beryllium atoms increases, from class III strong coupling toward class II valence trapped. Indeed, in the largest cases (N > 10), the cationic chains were found to be closer to class I, where the coupling vanishes. The intramolecular electron transfer parameters V(ab), E(a), and E(opt) were calculated for each atomic chain. It is shown that the decrease of V(ab) with increasing N follows an exponential pattern.

  11. Isomorphic series of double sulfites of the Cu2SO3.MSO3.2H2O (M = Cu, Fe, Mn, and Cd Type: a review

    Directory of Open Access Journals (Sweden)

    Silva Luciana A. da

    2004-01-01

    Full Text Available Although the first mixed valence double sulfite, Cu2SO3.CuSO3.2H2O, was prepared in the early 19th century by M. Chevreul, interest in this type of compound was only rekindled in the mid-1960s, when the crystalline structure of Chevreul's salt was determined and its infrared spectrum characterized. Studies of this type of compound have been intensified in recent years, especially after the discovery that the isomorphic Cu(II in Chrevreul's salt could be replaced by a divalent metal ion, forming an isomorphic series whose properties are strongly dependent on the nature of the M(II cation. Because of their interesting properties, these mixed valence systems can be used as models to identify intermediates in atmospheric corrosion processes, and to evaluate the role of transition metals as catalysts of S(IV autoxidation in the conversion of SO2 in the atmosphere.

  12. Comparative study of photochromic ferrocene-conjugated dimethyldihydropyrene derivatives.

    Science.gov (United States)

    Muratsugu, Satoshi; Kishida, Masa-aki; Sakamoto, Ryota; Nishihara, Hiroshi

    2013-12-16

    The photochemical properties and the mixed-valence state of bis(ferrocenylethynyl)benzodimethyldihydropyrene (1) and other benzodimethyldihydropyrene (BzDHP) derivatives were investigated to understand the reversible photoswitching in the electronic communication of 1. Absorption spectra of 1 were characterized by UV/Vis spectroscopy and calculated by using time-dependent density functional theory (TD-DFT), and the d orbitals of the ferrocene (Fc) moieties were shown to contribute to the occupied valence orbitals that were responsible for the photochromic behavior. 1 exhibited reversible photoisomerization in THF; however, photochromic behavior was not observed in dichloromethane. Analysis of redox potentials showed that the mixed-valence state of 1 was more stable in dichloromethane than in THF. This is consistent with the observation that chemical oxidation led to an intervalence charge-transfer (IVCT) band between the Fc moieties in the mixed-valence state of 1 in dichloromethane, whereas such a band was not observed for one-electron-oxidized 1 in THF. Bis(pentamethylferrocenylethynyl)benzodimethyldihydropyrene (2) did not show photochromic behavior even in THF. The mixed-valence state of 2 was much less stable than that of 1 in dichloromethane, and no obvious IVCT band was observed for one-electron-oxidized 2 in dichloromethane. The difference in the redox contribution of Fc and pentamethylferrocene (Me5Fc) to BzDHP played an important role for these redox and photochromic behaviors; this was supported by analysis of valence orbital energies from DFT calculations. Designing molecules that connect redox centers through the use of a photochromic linker with a redox potential close to that of the redox centers could constitute a useful approach for the production of photochromic redox-active metal complexes with strong electronic communication.

  13. Polynuclear hafnium polyhydrides with a 1,3-butadiene-1,4-diyl fragment from hydrogenolysis of a butadiene alkyl complex

    NARCIS (Netherlands)

    Visser, Cindy; Hende, Johannes R. van den; Meetsma, Auke; Hessen, Bart

    2003-01-01

    Hydrogenolysis of (eta(5)-C5Me5)Hf(2,3-dimethyl-1,3-butadiene)CH2SiMe3 leads to the formation of the mixed-valence tetranuclear polyhydride (eta(5)-C5Me5)(4)Hf-4-(sigma(1):sigma(1):eta(4):eta(4)C(6)H(8)(mu-H)(6) , with a central 2,3-dimethyl-1,3-butadiene-1,4-diyl fragment. The same reaction in the

  14. Label-Free THz-Optoelectronic Sensing of Ultra-Low Concentration of Genetic Sequences: Theoretical Treatment

    Science.gov (United States)

    2009-12-15

    Single or A Few Bio-Molecular Architectures, Peiji Zhao, Dwight Woolard, Jorge M. Seminario , Robert Trew, Journal of High Speed Electronics and...Woolard, and Jorge M. Seminario , Journal of High Speed Electronics and Systems 16, 705(2006). Figure 7 Methodology for Design of Substrate 15 4...Mixed-Valence Transition Metal Complexes for Molecular Computing, Peiji Zhao, Dwight Woolard, and Jorge M. Seminario , 4th IEEE Conference on

  15. Spontaneous Tl(I)-to-Tl(III) oxidation in dynamic heterobimetallic Hg(II)/Tl(I) porphyrin complexes.

    Science.gov (United States)

    Ndoyom, Victoria; Fusaro, Luca; Roisnel, Thierry; Le Gac, Stéphane; Boitrel, Bernard

    2016-01-11

    Strapped heterobimetallic Hg(II)/Tl(I) porphyrin complexes, with both metal ions bridged by the N-core in a dynamic way, undergo spontaneous Tl(I)-to-Tl(III) oxidation leading to a mono-Tl(III) complex and a mixed valence Tl(I)/Tl(III) bimetallic complex. It provides a new opportunity to tune metal ion translocations in bimetallic porphyrin systems.

  16. Multifunctional redox polymers: electrochrome, polyelectrolyte, sensor, electrode modifier, nanoparticle stabilizer, and catalyst template.

    Science.gov (United States)

    Deraedt, Christophe; Rapakousiou, Amalia; Wang, Yanlan; Salmon, Lionel; Bousquet, Melanie; Astruc, Didier

    2014-08-04

    Simple "click" polycondensation metallopolymers of redox-robust bis(ethynyl)biferrocene (biFc) and di(azido) poly(ethylene glycol) (PEG400 and PEG1000) were designed for multiple functions including improvement of water solubility and biocompatibility, the introduction of mixed valency and sensing capabilities, and as nanoparticle stabilizers for catalysis. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Synthesis of [MoOS3Cu3U(3,5-diMePy)4]·CH3CN and(Et4N)4[Mo4Cu8O4S12{(Ph2PS)2N}4]from Solid State Product[Et4N]4[Mo2O2S6Cu6I4Br2]%从固相反应产物[NEt4]4[Mo2O2S6Cu6I4Br2]合成原子簇[MoOS3Cu3I(3,5-diMePy)4]·CH3CN和(EtN)4[Mo4Cu8O4S12{(Ph2PS)2}4](英文)

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    @@ Treatment of iodide-bridged dimer [NEt4] 4[Mo2O2S6Cu6I4Br2] 1 with 3, 5-bimethylpyridine or with K[(Ph2PS) 2N] in CH3CN afforded the tetranuclear cluster [MoOS3Cu3I(3,5-diMePy)4]·CH3CN 2 and dodecanuclear cluster (Et4N)4[Mo4Cu8O4S12{(Ph2PS)2N}4] 3. Monomeric 2 possess a nest-shaped skeleton.The structure of oligomeric 3 can be regarded as a tetramer of nest-shaped MoCu3OS3[(Ph2PS)aN]groups co-polymerized by sharing the limbic Cu atoms.

  18. Synthesis, crystal structure and magnetic properties of Li{sub 0.44}Eu{sub 3}[B{sub 3}N{sub 6}

    Energy Technology Data Exchange (ETDEWEB)

    Kokal, I. [Koç University, Rumelifeneri Yolu, Sariyer, Istanbul 34450 (Turkey); Aydemir, U., E-mail: uaydemir@ku.edu.tr [Koç University, Rumelifeneri Yolu, Sariyer, Istanbul 34450 (Turkey); Max-Planck-Institut für Chemische Physik fester Stoffe, Nöthnitzer Str.40, Dresden 01187 (Germany); Prots, Yu.; Förster, T.; Sichelschmidt, J. [Max-Planck-Institut für Chemische Physik fester Stoffe, Nöthnitzer Str.40, Dresden 01187 (Germany); Yahyaoglu, M. [Koç University, Rumelifeneri Yolu, Sariyer, Istanbul 34450 (Turkey); Auffermann, G.; Schnelle, W. [Max-Planck-Institut für Chemische Physik fester Stoffe, Nöthnitzer Str.40, Dresden 01187 (Germany); Schappacher, F.; Pöttgen, R. [Institut für Anorganische und Analytische Chemie, Universität Münster, Corrensstraße 30, Münster 48149 (Germany); Somer, M., E-mail: msomer@ku.edu.tr [Koç University, Rumelifeneri Yolu, Sariyer, Istanbul 34450 (Turkey)

    2014-02-15

    Li{sub 0.44}Eu{sub 3}[B{sub 3}N{sub 6}] was synthesized from the metathesis reaction of Li{sub 3}[BN{sub 2}] and EuCl{sub 3} at 850 °C. Li{sub 0.44}Eu{sub 3}[B{sub 3}N{sub 6}] crystallizes in the trigonal space group R3{sup ¯}c (No. 167) with a=12.0225(2) Å, c=6.8556(2) Å and Z=6. In the crystal structure, isolated, planar cyclic [B{sub 3}N{sub 6}]{sup 9−} units are charge-balanced by the mixed-valence Eu{sup 3+}/Eu{sup 2+} and Li{sup +} cations. Li{sup +} occupies partially (44%) the Wyckoff site 6b and is sandwiched between the [B{sub 3}N{sub 6}]{sup 9−} anions. Mössbauer spectroscopy results show the resonance lines of Eu{sup 2+} and Eu{sup 3+}, respectively, indicating the heterogeneous mixed valency of the Eu atoms. X-Band ESR investigations between 5 and 300 K reveal an intense signal over the whole temperature range originating from Eu{sup 2+}. Magnetic susceptibility measurements indicate a Curie–Weiss behavior with an experimental effective magnetic moment of μ{sub eff}=8.28 μ{sub B} per formula unit. - Graphical abstract: Single crystals of Li{sub 0.44}Eu{sub 3}[B{sub 3}N{sub 6}] was obtained from the metathesis reaction of Li{sub 3}[BN{sub 2}] and EuCl{sub 3.}{sup 151}Eu Mössbauer, ESR and magnetic susceptibility measurements reveal the heterogeneous mixed valency of the Eu atoms. Display Omitted - Highlights: • Single crystals of Li{sub 0.44}Eu{sub 3}[B{sub 3}N{sub 6}] was obtained from the metathesis reaction of Li{sub 3}[BN{sub 2}] and EuCl{sub 3} at 850 °C. • Crystal structure is built up by isolated, planar cyclic [B{sub 3}N{sub 6}]{sup 9−} units which are surrounded by mixed valence Eu{sup 3+}/Eu{sup 2+}. • Li{sup +} occupies partially (44%) the site 6b and is sandwiched between the [B{sub 3}N{sub 6}]{sup 9−} anions. • The {sup 151}Eu Mössbauer spectroscopy, electron spin resonance spectroscopy and magnetic susceptibility measurements confirm the heterogeneous mixed valency of Eu.

  19. Non-adiabatic Landau-Zener transitions in low-spin molecular magnet V sub 1 sub 5

    CERN Document Server

    Chiorescu, I; Müller, A; Bögge, H; Barbara, B

    2000-01-01

    The V sub 1 sub 5 polyoxovanadate molecule is made of 15 spins ((1)/(2)) with antiferromagnetic couplings. It belongs to the class of molecules with very large Hilbert space dimension (2 sup 1 sup 5 in V sub 1 sub 5 , 10 sup 8 in Mn sub 1 sub 2 -AC). It is a low spin/large molecule with spin S=((1)/(2)). Contrary to large spins/large molecules of the Mn sub 1 sub 2 -AC type, V sub 1 sub 5 has no energy barrier against spin rotation. Magnetization measurements have been performed and despite the absence of a barrier, magnetic hysteresis is observed over a timescale of several seconds. This new phenomenon characterized by a 'butterfly' hysteresis loop is due to the effect of the environment on the quantum rotation of the entangled 15 spins of the molecule, in which the phonon density of states is not at its equilibrium (phonon bottleneck).

  20. Large exchange bias effect in LaCr0.9Ru0.1O3

    Science.gov (United States)

    Sarkar, Babusona; Dalal, Biswajit; De, S. K.

    2016-11-01

    The incorporation of tetravalent Ru (10%) into antiferromagnetic spin structure of LaCrO3 leads to mixed valence states of Cr (Cr2+ and Cr3+). Highly delocalized 4d orbital of Ru induces prominent ferromagnetic (FM) component in antiferromagnetic (AFM) matrix of parent compound. The complex magnetic interaction across the interface of FM and AFM regions gives rise to large exchange bias field (HEB) of about 10 kOe. The inverse and normal magnetocaloric effect for magnetic field up to 50 kOe coexists in a single material due to multiple magnetic phase transitions with temperature.

  1. Transient Process of Transport Through a Quantum Dot in a Stepped Bias: a Numerical Approach

    Institute of Scientific and Technical Information of China (English)

    熊永建; 熊诗杰

    2001-01-01

    The time evolution of the current though a quantum dot responding to a stepped bias voltage is studied by a numerical approach in the mixed-valence regime and the Kondo regime. Our numerical results show the quasiperiodic oscillations of the current with a short damping time. When the deviation of the Fermi energy from the resonant dot level is increased by changing the gate voltage, the frequency of the oscillations is increased, but the average current decreases. The results also show a relatively slow oscillation in the Kondo regime.

  2. Basic Aspects of the Quantum Theory of Solids

    Science.gov (United States)

    Khomskii, Daniel I.

    2010-09-01

    1. Some basic notions of the classical and quantum statistical physics; 2. General theory of phase transitions; 3. Bose- and Fermi-statistics; 4. Phonons in crystals; 5. General Bose-systems: Bose-condensation; 6. Magnetism; 7. Electrons in metals; 8. Interacting electrons: Green functions and Feynman diagrams (methods of the field theory in many-particle physics); 9. Electrons with Coulomb interaction; 10. Fermi-liquid theory and its possible generalizations; 11. Instabilities and phase transitions in electronic systems; 12. Strongly correlated electrons; 13. Magnetic impurities in metals, Kondo effect, heavy fermions and mixed valence; References; Index.

  3. Effect of growth temperature on the terahertz-frequency conductivity of the epitaxial transparent conducting spinel NiCo2O4 films

    Science.gov (United States)

    Silwal, Punam; La-o-vorakiat, Chan; Chia, Elbert E. M.; Kim, Dae Ho; Talbayev, Diyar

    2013-09-01

    We have measured the terahertz-frequency optical conductivity of the epitaxial inverse spinel NiCo2O4 films grown at different temperatures. The low-temperature-grown film exhibits a metallic behavior with ferrimagnetic ordering, while the high-temperature-grown film shows greatly suppressed magnetization and insulating behavior. Both films exhibit band-like coherent conduction at intermediate temperatures, albeit with very different carrier densities consistent with the proposed models of cation valencies in this mixed-valence material. Both films also display a crossover to incoherent transport at low temperatures, indicating a disorder-induced tendency toward localization.

  4. Effect of growth temperature on the terahertz-frequency conductivity of the epitaxial transparent conducting spinel NiCo2O4 films

    Directory of Open Access Journals (Sweden)

    Punam Silwal

    2013-09-01

    Full Text Available We have measured the terahertz-frequency optical conductivity of the epitaxial inverse spinel NiCo2O4 films grown at different temperatures. The low-temperature-grown film exhibits a metallic behavior with ferrimagnetic ordering, while the high-temperature-grown film shows greatly suppressed magnetization and insulating behavior. Both films exhibit band-like coherent conduction at intermediate temperatures, albeit with very different carrier densities consistent with the proposed models of cation valencies in this mixed-valence material. Both films also display a crossover to incoherent transport at low temperatures, indicating a disorder-induced tendency toward localization.

  5. Inter-layer charge disproportionation in the dual-layer organic metal (tTTF-I)2ClO4 with unsymmetrical I***O halogen bond interactions.

    OpenAIRE

    Shin, Kyoung-Soon; Jeannin, Olivier; Brezgunova, Mariya; Dahaoui, Slimane; Aubert, Emmanuel; Espinosa, Enrique; Auban-Senzier, Pascale; Świetlik, Roman; Frąckowiak, Arkadiusz; Fourmigué, Marc

    2014-01-01

    Accepted 19 Nov 2013; International audience; A mixed-valence salt of tTTF-I with ClO4(-), formulated as (tTTF-I)2ClO4, is characterized by the presence of two crystallographically independent donor molecules, segregated in different layers and linked together through I***O interactions with the ClO4(-) anion disordered at room temperature. The tTTF-I donor molecule was prepared by metallation of tTTF (trimethylene tetrathiafulvalene) followed by reaction with iodine to afford the mono and di...

  6. Chemical Information revealed by Mössbauer spectroscopy and DFT calculations

    Energy Technology Data Exchange (ETDEWEB)

    Nakashima, Satoru, E-mail: snaka@hiroshima-u.ac.jp [Hiroshima University, Natural Science Center for Basic Research and Development (Japan)

    2017-11-15

    Mixed-valence state of binuclear metallocene derivatives and spin-crossover (SCO) phenomena of the assembled Fe(II) complexes have been studied by using Mössbauer spectroscopy. The understanding of the results obtained by Mössbauer spectra is well supported by means of X-ray structural analysis and density functional theory (DFT) calculation. Benchmark study of relativisitic DFT calculation by using Mössbauer isomer shifts of Eu, Np complexes reveals the validity of the calculation. Such study sheds light on the bonding character of 4f and 5f electron. These results are reviewed.

  7. Generalized oscillator strengths for some higher valence-shell excitations of krypton atom

    Institute of Scientific and Technical Information of China (English)

    2007-01-01

    The valence-shell excitations of krypton atom have been investigated by fast electron impact with an angle-resolved electron-energy-loss spectrometer. The generalized oscillator strengths for some higher mixed valence-shell excitations in 4d, 4f, 5p, 5d, 6s, 6p, 7s ← 4p of krypton atom have been determined. Their profiles are discussed, and the generalized oscillator strengths for the electric monopole and quadrupole excitations in 5p ← 4p are compared with the calculations of Amusia et al. (Phys. Rev. A 67 022703 (2003)). The differences between the experimental results and theoretical calculations show that more studies are needed.

  8. Orbital-occupancy versus charge ordering and the strength of electron correlations in electron-doped CaMnO3.

    Science.gov (United States)

    Luo, Weidong; Franceschetti, Alberto; Varela, Maria; Tao, Jing; Pennycook, Stephen J; Pantelides, Sokrates T

    2007-07-20

    The structural, electronic, and magnetic properties of mixed-valence compounds are believed to be governed by strong electron correlations. Here we report benchmark density-functional calculations in the spin-polarized generalized-gradient approximation (GGA) for the ground-state properties of doped CaMnO(3). We find excellent agreement with all available data, while inclusion of strong correlations in the GGA+U scheme impairs this agreement. We demonstrate that formal oxidation states reflect only orbital occupancies, not charge transfer, and resolve outstanding controversies about charge ordering.

  9. Electronic State of Bismuth in BaBiO3 up to 9 Gpa Investigated by Optical Spectroscopy

    Institute of Scientific and Technical Information of China (English)

    刘晓峻; 守友浩

    2003-01-01

    Effects of hydrostatic pressure on the mixed-valence(MV)bismuth complex BaBiOa have been investigated up to ~9 GPa by means of high-pressure Raman scattering and absorption spectra at 300K.The pressure-induced hardening behaviour of the Bi-O stretching mode suggests that the predicted pressure-induced MV to the singlevalence(SV)phase change cannot occur.Investigation of absorption spectra with pressure shows the enhanced optical gap Egap,which further indicates the remained MV state of Bi ions.

  10. 2D atomic mapping of oxidation states in transition metal oxides by scanning transmission electron microscopy and electron energy-loss spectroscopy

    OpenAIRE

    Tan, H.; Turner, S.; Yücelen, E.; Verbeeck, J.; Van Tendeloo, G.

    2011-01-01

    Abstract: Using a combination of high-angle annular dark-field scanning transmission electron microscopy and atomically resolved electron energy-loss spectroscopy in an aberration-corrected transmission electron microscope we demonstrate the possibility of 2D atom by atom valence mapping in the mixed valence compound Mn3O4. The Mn L2,3 energy-loss near-edge structures from Mn2+ and Mn3+ cation sites are similar to those of MnO and Mn2O3 references. Comparison with simulations shows that even ...

  11. Entanglement in Anderson Nanoclusters

    CERN Document Server

    Samuelsson, Peter

    2007-01-01

    We investigate the two-particle spin entanglement in magnetic nanoclusters described by the periodic Anderson model. An entanglement phase diagram is obtained, providing a novel perspective on a central property of magnetic nanoclusters, namely the temperature dependent competition between local Kondo screening and nonlocal Ruderman-Kittel-Kasuya-Yoshida spin ordering. We find that multiparticle entangled states are present for finite magnetic field as well as in the mixed valence regime and away from half filling. Our results emphasize the role of charge fluctuations.

  12. Cobalt-based layered double hydroxides as oxygen evolving electrocatalysts in neutral electrolyte

    Science.gov (United States)

    Lin, Hong; Zhang, Ye; Wang, Gang; Li, Jian-Bao

    2012-06-01

    Co-M (M= Co, Ni, Fe, Mn) layered double hydroxides (LDHs) were successfully fabricated by a hexamethylenetetramine (HMT) pyrolysis method. Composite electrodes were made using a self-assembly fashion at inorganic/organic surface binder-free and were used to catalyze oxygen evolution reaction. Water oxidation can take place in neutral electrolyte operating with modest overpotential. The doping of other transitional metal cations affords mix valences and thus more intimate electronic interactions for reversible chemisorption of dioxygen molecules. The application of employing LDH materials in water oxidation process bodes well to facilitate future hydrogen utilization.

  13. Structural and magnetic properties of layered perovskite manganite LaCaBiMn2O7

    Directory of Open Access Journals (Sweden)

    Oubla M.

    2013-09-01

    Full Text Available The layered perovskite oxide, LaCaBiMn2O7, has been prepared by the conventional aqueous solution precipitation method. The powder X-ray diffraction studies suggest that the phase crystallizes with tetragonal unit cell in the space group I4/mmm. The magnetic properties suggest that the ferromagnetic interactions are dominant and manganese ion in the phase is present in mixed valence states Mn3+and Mn4+. The thermomagnetization curve is found to obey the Bloch law. Spin wave stiffness constant D and the approximate value for JMnMnexchange interaction were estimated from the experimental results.

  14. Artificial charge-modulationin atomic-scale perovskite titanate superlattices.

    Science.gov (United States)

    Ohtomo, A; Muller, D A; Grazul, J L; Hwang, H Y

    2002-09-26

    The nature and length scales of charge screening in complex oxides are fundamental to a wide range of systems, spanning ceramic voltage-dependent resistors (varistors), oxide tunnel junctions and charge ordering in mixed-valence compounds. There are wide variations in the degree of charge disproportionation, length scale, and orientation in the mixed-valence compounds: these have been the subject of intense theoretical study, but little is known about the microscopic electronic structure. Here we have fabricated an idealized structure to examine these issues by growing atomically abrupt layers of LaTi(3+)O(3) embedded in SrTi(4+)O(3). Using an atomic-scale electron beam, we have observed the spatial distribution of the extra electron on the titanium sites. This distribution results in metallic conductivity, even though the superlattice structure is based on two insulators. Despite the chemical abruptness of the interfaces, we find that a minimum thickness of five LaTiO(3) layers is required for the centre titanium site to recover bulk-like electronic properties. This represents a framework within which the short-length-scale electronic response can be probed and incorporated in thin-film oxide heterostructures.

  15. Multi-wavelength excitable europium-doped borosilicate glasses for orange-red emission: composition-induced structure and valence variation

    Institute of Scientific and Technical Information of China (English)

    QIU Kun; TIAN Hua; SONG Jun; MAO Zhiyong; WANG Dajian

    2012-01-01

    Europium-doped borosilicate glasses were prepared by melt-quenching procedure in the air.The mixed valence of Eu2+ and Eu3+was identified by photoluminescence spectrum and electron paramagnetic resonanoe (EPR).The existence of mixed valence was observed owing to the unequivalent substitution and de-polymerization network of the as-prepared borosilicate glasses.The variation of the glass composition in B2O3/BaO ratios changed the stability of the Eu3+ ions distinctly.In particular,as-prepared borosilicate glasses exhibited a tri-wavelength light excitable spectra centered at 397,466 and 534 nm to give the broadened orange-red emission at around 592 and 617 nm,due to supersensitive transitions of Eu3+ ions.This simultaneous tri-wavelength excitation happened to correspond with the emitting wavelength from near ultraviolet,blue AllnGaN chips and that from YAG:Ce3+.The total quantum yield (QY) of the Eu-doped glasses under 466nm excitation was evaluated to be 10%,potentially providing a versatile combination with the europium-doped borosilicate glasses for red component addition to improve the quality of white light.

  16. Intervalence Charge Transfer Luminescence: Interplay between anomalous and 5d-4f emissions in Yb-doped fluorite-type crystals

    CERN Document Server

    Barandiaran, Zoila

    2014-01-01

    We report the existence of intervalence charge transfer (IVCT) luminescence in Yb-doped fluorites associated with Yb2+-Yb3+ mixed valence pairs. We show that the very broad band, anomalous emission of Yb2+-doped CaF2 and SrF2, usually associated with impurity-trapped excitons, is, rather, an IVCT luminescence associated with Yb2+-Yb3+ mixed valence pairs. It is very efficiently excited by a two-photon upconversion mechanism. The IVCT vertical transition leaves the pair moieties very far from their equilibrium structures; this explains the unexpectedly large band width of the emission band and its low peak energy, because the large reorganization energies are substracted from the normal emission. The ab initio IVCT energy diagrams explain the different luminescent properties of Yb-doped CaF2, SrF2, BaF2, and SrCl2: the presence of IVCT luminescence in Yb-doped CaF2 and SrF2; its coexistence with regular 5d-4f emission in SrF2; its absence in BaF2 and SrCl2; the quenching of all emissions in BaF2; and the prese...

  17. Electrochemical properties of the hexacyanoferrate(II)–ruthenium(III) complex immobilized on silica gel surface chemically modified with zirconium(IV) oxide

    Energy Technology Data Exchange (ETDEWEB)

    Panice, Lucimara B.; Oliveira, Elisangela A. de; Filho, Ricardo A.D. Molin; Oliveira, Daniela P. de [Departamento de Química, Universidade Estadual de Maringá, Av. Colombo, 5790, 87020-900 Maringá, PR (Brazil); Lazarin, Angélica M., E-mail: amlazarin2@uem.br [Departamento de Química, Universidade Estadual de Maringá, Av. Colombo, 5790, 87020-900 Maringá, PR (Brazil); Andreotti, Elza I.S.; Sernaglia, Rosana L. [Departamento de Química, Universidade Estadual de Maringá, Av. Colombo, 5790, 87020-900 Maringá, PR (Brazil); Gushikem, Yoshitaka [Instituto de Química, Universidade Estadual de Campinas, Caixa Postal 6154, 13084-971 Campinas, São Paulo (Brazil)

    2014-10-15

    Highlights: • The cyano-bridged mixed valence ruthenium composite material was synthesized. • This newly synthesized compound was incorporated into a carbon paste electrode. • The electrode did not show significant changes in response after six months of use. • The modified electrode is very stable and reproducible. • The electrode sensor was successfully applied for ascorbic acid determination. - Abstract: The chemically modified silica gel with zirconium(IV) oxide was used to immobilize the [Fe(CN){sub 6}]{sup 4−} complex ion initially. The reaction of this material with [Ru(edta)H{sub 2}O]{sup −} complex ion formed the immobilized cyano-bridged mixed valence ruthenium complex, (≡Zr){sub 5}[(edta)RuNCFe(CN){sub 5}]. This material was incorporated into a carbon paste electrode and, its electrochemical properties were investigated. However, for an ascorbic acid solution, an enhancement of the anodic peak current was detected due to electrocatalytic oxidation. The electrode presented the same response for at least 150 successive measurements, with a good repeatability. The modified electrode is very stable and reproducible. The sensor was applied for ascorbic acid determination in pharmaceutical preparation with success.

  18. Reaction of Molybdenum Hexa-carbonyl with Mercapto-pyridine (PySH) or Mercapto-pyridine Oxide (PyS→O) and Crystal Structure of [Et4N][Mo2(PyS)3(CO)5

    Institute of Scientific and Technical Information of China (English)

    ZHUANG, Bo-Tao(庄伯涛); YU, Pei-Hua(余佩华); HUANG, Liang-Ren(黄梁仁); HE, Ling-Jie(何玲洁); ZHOU, Zhang-Feng(周张锋); WU, Ke-Chen(吴克琛)

    2004-01-01

    Mixed-valence dinuclear molybdenum complex [Et4N][Mo2(PyS)3(CO)5] (1) (PyS=C5H4NS) has been synthesized and characterized by crystallography. 1 crystallizes in monoclinic system with space group P21/c with a= 1.5769(11) nm, b= 1.3144(5) nm, c= 1.6935(10) nm; β= 111.20(4)°; V=3.2724 nm3; Z=4, Dc=1.61 g/cm3,μ=9.7 cm-1 and F(000)=1600. The final R=0.054 and wR=0.073, for 1811 observed reflection with I>3σ (I). In compound 1, one chelating PyS ligand and two bridging PyS ligands are 3-electron and 5-electron donors, respectively, and two molybdenum atoms are located in different coordination environments resulting in mixed-valence state. The reaction mechanism of Mo(CO)6 with PySH and PyS→O (C5H5SN→O) was investigated and two reaction pathways were proposed.

  19. Electronic structure, lattice dynamics and thermodynamic stability of paramelaconite Cu{sub 4}O{sub 3}

    Energy Technology Data Exchange (ETDEWEB)

    Debbichi, Lamjed, E-mail: debbichilamjed@yahoo.fr [Laboratoire Interdisciplinaire Carnot de Bourgogne, UMR 6303 Université de Bourgogne – CNRS, BP 47870, F-21078 Dijon (France); Marco de Lucas, Maria C., E-mail: delucas@u-bourgogne.fr [Laboratoire Interdisciplinaire Carnot de Bourgogne, UMR 6303 Université de Bourgogne – CNRS, BP 47870, F-21078 Dijon (France); Krüger, Peter, E-mail: pkruger@chiba-u.jp [Laboratoire Interdisciplinaire Carnot de Bourgogne, UMR 6303 Université de Bourgogne – CNRS, BP 47870, F-21078 Dijon (France); Nanomaterial Science Department, Chiba University, Chiba 263-8522 (Japan)

    2014-11-14

    An ab initio study of the electronic structure, lattice dynamic and thermodynamic properties of paramelaconite Cu{sub 4}O{sub 3} is reported. The insulating, mixed-valence character of Cu{sub 4}O{sub 3} is elucidated by analyzing the band structure and the spin-orbital symmetry of the Cu-3d hole states. Exchange coupling constants between Cu{sup 2+} ions are computed which confirm the frustrated antiferromagnetism of the spin lattice. The lattice dynamics is studied from first principles and main features of the vibrational spectrum are assigned to the different chemical species Cu{sup +}, Cu{sup 2+} and O. The thermodynamic stability of Cu{sub 4}O{sub 3} is investigated by calculating the free energy of the decomposition reaction into CuO and Cu{sub 2} O as a function of temperature. The results agree with the available experimental data and indicate that the vibrational entropy plays an essential role for the decomposition reaction, which occurs at elevated temperatures. - Highlights: • Antiferromagnetic frustration confirmed by calculating exchange coupling constants. • Mixed valency elucidated by analyzing spin-orbital character of hole states. • Main features of ab initio vibrational spectrum assigned to ionic species. • Vibrational entropy shown to be crucial for decomposition reaction of Cu{sub 4}O{sub 3}.

  20. Redox properties of an engineered purple Cu(A) azurin.

    Science.gov (United States)

    Sun, Dapeng; Wang, Xiaotang; Davidson, Victor L

    2002-08-01

    Purple Cu(A) centers are a class of binuclear, mixed-valence copper complexes found in cytochrome c oxidase and nitrous oxide reductase. An engineered Cu(A) protein was formed by replacing a portion of the amino acid sequence that contains three of the ligands to the native type I copper center of Pseudomonas aeruginosa azurin with the corresponding portion of sequence from the Cu(A) center of cytochrome c oxidase from Paracoccus denitrificans [Proc. Natl. Acad. Sci. USA 93 (1996) 461]. Oxidation-reduction midpoint potential (E(m)) values of the Cu(A) azurin of +399+/-10 and +380+/-2mV, respectively, were determined by cyclic voltammetry and spectrochemical titration. An n value of one was obtained, indicating that the redox reaction is cycling between the mixed valence and the fully reduced states. Whereas the E(m) value of native azurin is pH dependent, the E(m) value of Cu(A) azurin is not, as expected for the Cu(A) center. Similarities and differences in the redox properties are discussed in terms of the known crystal structures of Cu(A) centers in cytochrome c oxidase and Cu(A) azurin.

  1. An investigation into the use of novel organic materials in gas sensor devices

    CERN Document Server

    Bates, J

    1993-01-01

    oxidised it to the lower conductivity (10 sup - sup 3 S/cm) neutral (Ni(dmit) sub 2) species; the SO sub 2 was presumed to act upon the mixed valence phase and reduce it to the lower conductivity (10 sup - sup 3 S/cm) monoanion species. In order to identify the species responsible for the gas sensitivity various analytical techniques were used including X-Ray diffraction, C,H,N,S analysis, scanning electron microscopy and cyclic voltammetry experiments. The SEM studies showed the effect of solvent composition on the film morphology and indicated that the films were of a highly crystalline nature and this was confirmed by X-Ray diffraction. Single crystal analysis showed the species deposited on platinum wire electrodes at 1.1 V/SCE was the neutral Ni(dmit) sub 2 species. C,H,N,S analysis suggested the films were primarily the neutral Ni(dmit) sub 2 species with a small amount of the mixed valence phase present. Cyclic voltammetry experiments enabled identification of the various electrochemical processes invo...

  2. Metal-insulator transition of valence-controlled VO2 thin film prepared by RF magnetron sputtering using oxygen radical

    Science.gov (United States)

    Suetsugu, Takaaki; Shimazu, Yuichi; Tsuchiya, Takashi; Kobayashi, Masaki; Minohara, Makoto; Sakai, Enju; Horiba, Koji; Kumigashira, Hiroshi; Higuchi, Tohru

    2016-06-01

    We have prepared b-axis-oriented VO2 thin films by RF magnetron sputtering using oxygen radicals as the reactive gas. The VO2 thin films consist of a mixed-valence V3+/V4+ state formed by oxygen vacancies. The V3+ ratio strongly depends on the film thickness and the oxygen partial pressure of the radical gun during deposition. The lattice constant of the b-axis increases and the metal-insulator transition (MIT) temperature decreases with decreasing V3+ ratio, although the VO2 thin films with a high V3+ ratio of 42% do not exhibit MIT. The bandwidths and spectral weights of V 3d a1g and \\text{e}\\text{g}σ bands at around the Fermi level, which correspond to the insulating phase at 300 K, are smaller in the VO2 thin films with a low V3+ ratio. These results indicate that the control of the mixed-valence V3+/V4+ state is important for the MIT of b-axis-oriented VO2 thin films.

  3. Mn 3+ stabilization in complex phosphate-fluoride fluxes and its incorporation into langbeinite framework

    Science.gov (United States)

    Ogorodnyk, Ivan V.; Zatovsky, Igor V.; Baumer, Vyacheslav N.; Slobodyanik, Nikolay S.; Shishkin, Oleg V.; Vorona, Igor P.

    2007-10-01

    Two new mixed valence manganese-containing orthophosphates with a langbeinite structure have been obtained from the complex fluoride-phosphate melts using the high-temperature flux technique. MIVF 4 and K 2MIVF 6 ( MIV—Zr, Hf) were used as fluoride and polyvalent metal precursors. Obtained langbeinites were investigated using a single-crystal X-ray diffraction, FTIR-, UV-VIS- and electron paramagnetic resonance (EPR)-spectroscopy. Both compounds crystallize in a cubic system (sp. gr. P2 13) with cell parameters a=10.2106(12) and 10.1896(9) Å for K 1.96Mn 0.57Zr 1.43(PO 4) 3 and K 1.93Mn 0.53Hf 1.47(PO 4) 3, respectively. The rigid langbeinite-like framework is built up from the isolated [MO 6] octahedra and [PO 4] tetrahedra interlinked via oxygen vertices. Potassium cations occupy positions in the large closed cavities of the framework. Statistical distribution of manganese and tetravalent metal over two crystallographic positions in octahedral oxygen environment can be observed. The presence of the mixed valence manganese in the reported phosphates was confirmed using UV-VIS and EPR-spectroscopy.

  4. 12-Ring Network Coordination Polymer—— {[Cu(C4N2H10)4]2·H4V4O14 }n Formed by Linking cyclo-[H4V4O14]4- with Cu(C4N2H10)2+4 Cation Clusters

    Institute of Scientific and Technical Information of China (English)

    2006-01-01

    A novel 12-ring network coordination polymer, {2 H4V4O14}n(denoted as QUST-4), was hydrothermally synthesized and structurally determined by X-ray single-crystal diffraction analysis. QUST-4 was crystallized in a monoclinic system with space group P21/n. The parameters of the unit cell are a=1.0497(2) nm, b=1.6728(3) nm, c=1.2857(3) nm, β=94.14(3)°, V=2.2517(8) nm3, Z=4, Dcal = 1.841 Mg/m3, R1=0.1071, and wR3=0.2703. The largest difference peak and hole were2284 and -1040 e/nm3, respectively. The SBU(secondary building unit) of QUST-4 was a new cyclo- aggregate of polyoxovanadate cyclo-4-, different from cyclo-4-, which was condensed from two tetrahedral and two trigonal bipyramids via alternate arrangement. Cu(piper)4(piper=piperazine) group connected the cyclo-4- anions to form the 12-ring network. The adjacent layers were linked by van der Walls forces.

  5. Syntheses, structures and properties of two 2-D layered hybrid organic-inorganic materials based on different V4O12 building units.

    Science.gov (United States)

    Hou, Wentao; Guo, Jiuyu; Xu, Xiao; Wang, Zuoxiang; Zhang, Deng; Wan, Hongxiang; Song, You; Zhu, Dunru; Xu, Yan

    2014-01-14

    Two new layered hybrid organic-inorganic compounds [Zn(pyim)]2V4O12 () (pyim = 2-(2-pyridyl)imidazole) and [Cu(bim)2]2V4O12(H2O)·CH3CH2OH () (bim = bis(1-imidazolyl)methane) based on polyoxovanadates (POVs) and organic ligands decorated transition metal units have been synthesized by hydrothermal and solvothermal methods respectively. Single crystal XRD, fluorescence spectrum, magnetic measurement, IR spectra, powder XRD and thermogravimetric (TG) measurements were performed to analyze the structures and properties of and . The structural analysis reveals that compound features a two-dimensional {[Zn(pyim)]2V4O12}n layered structure, constructed by sine wave-like {V4O12}n(4n-) chains, Zn(2+) ions and pyim ligands. In the layered structure of , {V4O12}(4-) circles are connected by Cu(2+) ions to form {Cu(V4O12)}n(2n-) chains, which are further linked by {Cu(bim)4}(2+) subunits to generate a hybrid layer of . The magnetic susceptibility measurement indicates strong antiferromagnetic interactions between Cu(2+) ions in .

  6. Synthesis and electrochemical properties of nonstoichiometric composition Li2.7Ti2(PO4)3/C with orthorhombic structure

    Science.gov (United States)

    Yao, Xiang; Su, Zhi; Pan, Hui

    2016-08-01

    Carbon-coated Li2.7Ti2(PO4)3, a new mixed-valence titanium(III/IV) phosphate, is synthesized by the microwave-assisted sol-gel method using citric acid as both a chelating reagent and carbon source for the cathode material in lithium-ion batteries. The contents of Li, Ti and P are analyzed by inductively coupled plasma atomic emission spectrometry (ICP-AES) and ion chromatography (IC). The microstructure, composition, and electrochemical performance of Li2.7Ti2(PO4)3/C samples are characterized by X-ray Diffraction (XRD), X-ray photoelectron spectroscopy(XPS), scanning electron microscope (SEM) and cyclic voltammetry (CV). The Li2.7Ti2(PO4)3/C sample exhibits a high initial discharge capacity of 123.6 mA h g-1 at 0.1C and outstanding cycling ability.

  7. In situ TEM studies of oxygen vacancy migration for electrically induced resistance change effect in cerium oxides.

    Science.gov (United States)

    Gao, Peng; Wang, Zhenzhong; Fu, Wangyang; Liao, Zhaoliang; Liu, Kaihui; Wang, Wenlong; Bai, Xuedong; Wang, Enge

    2010-06-01

    Oxide materials with resistance hysteresis are very promising for next generation memory devices. However, the microscopic dynamic process of the resistance change is still elusive. Here, we use in situ transmission electron microscopy method to study the role of oxygen vacancies for the resistance switching effect in cerium oxides. The structure change during oxygen vacancy migration in CeO(2) induced by electric field was in situ imaged inside high-resolution transmission electron microscope, which gives a direct evidence for oxygen migration mechanism for the microscopic origin of resistance change effect in CeO(2). Our results have implications for understanding the nature of resistance change in metal oxides with mixed valence cations, such as fluorite, rutile and perovskite oxides. Copyright 2009 Elsevier Ltd. All rights reserved.

  8. Peculiarities of the valence state of Ce and Yb in RM{sub 4}Al{sub 8} (R=rare earth; M=Cr, Mn, Fe, Cu)

    Energy Technology Data Exchange (ETDEWEB)

    Shcherba, I.D. [L`vovskij Gosudarstvennyj Univ., Lvov (Ukraine); Koterlyn, M.D. [L`vovskij Gosudarstvennyj Univ., Lvov (Ukraine); Kushnir, A.P. [L`vovskij Gosudarstvennyj Univ., Lvov (Ukraine); Kutjanskyj, R.R. [L`vovskij Gosudarstvennyj Univ., Lvov (Ukraine); Synjushko, V.G. [L`vovskij Gosudarstvennyj Univ., Lvov (Ukraine); Tsybukh, Yu.D. [L`vovskij Gosudarstvennyj Univ., Lvov (Ukraine); Yatsyk, B.M. [L`vovskij Gosudarstvennyj Univ., Lvov (Ukraine); Margolych, I.I. [L`vovskij Gosudarstvennyj Univ., Lvov (Ukraine)

    1996-05-01

    L{sub III} X-ray absorption (77 and 300 K) and magnetic susceptibility measurements have been performed on RM{sub 4}Al{sub 8} compounds. The mixed valence state of Ce was observed in CeM{sub 4}Al{sub 8} with M=Cr,Mn,Fe. In the case of M=Cu the Ce{sup 3+} state is stabilized, but the Yb-based compound shows intermediate valence (V{sub Yb}{approx}2.5). In other Yb-based compounds, the Yb ion is mainly in the trivalent state. The temperature dependence of the magnetic susceptibility of RFe{sub 4}Al{sub 8} compounds fits the Curie-Weiss law over a wide temperature range. (orig.).

  9. The first observation of Mo5+ in the passivation layer of Mo2N

    Institute of Scientific and Technical Information of China (English)

    2000-01-01

    Molybdenum nitride powder with sg of 115 m2·g-1 (passivated) has been prepared by a temperature programmed reaction of MoO3 in H2/N2 mixture. It exhibited high catalytic activity in CO oxidation at low temperature. XPS, EPR and LRS studies have shown the existence of mixed valence states of Mo ions, especially Mo5+ ion (g⊥=1.932, g‖=1.892) observed for the first time, in the passivation layer of molybdenum nitride. A surface superoxide species, O-2(g = 2.001, Raman band 1 124 cm-1), was found to be produced accompanying the transformation of Mo5+/Mo4+ redox pair. Evidence has been given to suggest that this surface superoxide might be responsible for CO oxidation over Mo2N catalyst.

  10. Decomposition of monochlorogallane, [H2GaCl]n, and adducts with amine and phosphine bases: formation of cationic gallane derivatives.

    Science.gov (United States)

    Tang, Christina Y; Downs, Anthony J; Greene, Tim M; Marchant, Sarah; Parsons, Simon

    2005-10-03

    Thermal decomposition of monochlorogallane, [H2GaCl]n, at ambient temperatures results in the formation of subvalent gallium species. To Ga[HGaCl3], previously reported, has now been added a second mixed-valence solid, Ga4[HGaCl3]2[Ga2Cl6] (1), the crystal structure of which at 150 K shows a number of unusual features. Adducts of monochlorogallane, most readily prepared from the hydrochloride of the base and LiGaH4 in appropriate proportions, include not only the 1:1 molecular complex Me3P.GaH2Cl (2), but also 2:1 amine complexes which prove to be cationic gallane derivatives, [H2Ga(NH2R)2]+Cl-, where R = tBu (3a) or sBu (3b). All three of these complexes have been characterized crystallographically at 150 K.

  11. Synthesis, crystal structure, and photocatalytical properties of Ba3Ta5O14N

    Science.gov (United States)

    Anke, B.; Bredow, T.; Soldat, J.; Wark, M.; Lerch, M.

    2016-01-01

    Light yellow Ba3TaV5O14N was successfully synthesized as phase-pure material crystallizing isostructurally to well-known mixed-valence Ba3TaV4TaIVO15. The electronic structure of Ba3Ta5O14N was studied theoretically with a hybrid Hartree-Fock-DFT method. The most stable structure was obtained when nitrogen atoms were placed at 4 h sites having fourfold coordination. By incorporating nitrogen, the band gap decreases from ∼3.8 eV commonly known for barium tantalum(V) oxides to 2.8 eV for the oxide nitride, giving rise to an absorption band well in the visible-light region. Ba3Ta5O14N was also tested for photocatalytic hydrogen formation.

  12. Co–Fe Prussian Blue Analogue Intercalated into Diamagnetic Mg–Al Layered Double Hydroxides

    Directory of Open Access Journals (Sweden)

    Cuijuan Zhang

    2016-04-01

    Full Text Available A heterostructure of diamagnetic magnesium‒aluminium layered double hydroxides (Mg‒Al LDHs and photomag‐ netic cobalt‒iron Prussian Blue analogue (Co‒Fe PBA was designed, synthesized and then designated as LDH‒PB. The cyanide-bridged Co‒Fe PBA was two-dimensionally intercalated into the Mg‒Al LDH template by the stepwise anion exchange method. LDH‒PB showed ferrimagnetic properties with in-plane antiferromagnetic exchange interactions, as well as small photo-induced magnetization by visible light illumination due to the low dimensional structures and the characteristic photo-induced electronic states of the mixed valence of FeIII(low spin, S = 1/2‒CN‒ CoII(high spin, S = 3/2‒NC‒FeII (low spin, S = 0.

  13. The oxidation of chromium(III) by hydroxyl radical in alkaline solution. A stopped-flow and pre-mix pulse radiolysis study

    DEFF Research Database (Denmark)

    Zhao, Zhongwei; Rush, J.D.; Holcman, J.

    1995-01-01

    The pK(a) for the equilibrium Cr(III)(H2O)3(OH)3(OH)3 reversible Cr(III)(H2O)2(OH)4- + H+ was determined to be 12.8 at 25-degrees-C. The dimerization of the two monomeric forms was studied in alkaline solutions using the stopped-flow method: k2[Cr(III)(H2O)3(OH)3 + Cr(III)(H2O)3(OH)3] = (2.5 +/- ......(VI)-(O-Cr(III))n]. Furthermore, a second-order reaction between two Cr(IV) monomers to yield a species which may be either a (Cr)2IV,IV or a (Cr)2III,V mixed-valence dimer was observed. The corresponding spectra in both the UV and visible range were determined....

  14. Mesoporous cerium oxide nanospheres for the visible-light driven photocatalytic degradation of dyes

    Directory of Open Access Journals (Sweden)

    Subas K. Muduli

    2014-04-01

    Full Text Available A facile, solvothermal synthesis of mesoporous cerium oxide nanospheres is reported for the purpose of the photocatalytic degradation of organic dyes and future applications in sustainable energy research. The earth-abundant, relatively affordable, mixed valence cerium oxide sample, which consists of predominantly Ce7O12, has been characterized by powder X-ray diffraction, X-ray photoelectron and UV–vis spectroscopy, and transmission electron microscopy. Together with N2 sorption experiments, the data confirms that the new cerium oxide material is mesoporous and absorbs visible light. The photocatalytic degradation of rhodamin B is investigated with a series of radical scavengers, suggesting that the mechanism of photocatalytic activity under visible-light irradiation involves predominantly hydroxyl radicals as the active species.

  15. Copper-promoted methylene C-H oxidation to a ketone derivative by O2

    DEFF Research Database (Denmark)

    Deville, Claire; McKee, Vickie; McKenzie, Christine J.

    2017-01-01

    ) was characterized in the heteroleptic copper(ii) complex [Cu(bpca)(hidpe)](ClO4). The co-ligand in this complex, N-(2′-pyridylcarbonyl)pyridine-2-carboximidate (bpca−), is derived from a copper-promoted Beckmann rearrangement of hidpe. In the presence of bromide only [Cu(bpca)Br] is isolated. When significant water...... of C-H activation are produced from the dpeo-Cu/Mn systems and specifically O2. The metastable copper complexes [Cu(dpeo)2](ClO4)2 and [Cu(bpca)(hidpe)](ClO4), along with [NiX2(dpeo)2] (X = Cl, Br), [Ni(dpeo)3](ClO4)2, [Co(dpeo)3](ClO4)3 and the mixed valence complex [FeIIIFeII2(dpeo-H)3(dpeo)3](PF6...

  16. The oxidation of chromium(III) by hydroxyl radical in alkaline solution. A stopped-flow and pre-mix pulse radiolysis study

    DEFF Research Database (Denmark)

    Zhao, Zhongwei; Rush, J.D.; Holcman, J.

    1995-01-01

    The pK(a) for the equilibrium Cr(III)(H2O)3(OH)3(OH)3 reversible Cr(III)(H2O)2(OH)4- + H+ was determined to be 12.8 at 25-degrees-C. The dimerization of the two monomeric forms was studied in alkaline solutions using the stopped-flow method: k2[Cr(III)(H2O)3(OH)3 + Cr(III)(H2O)3(OH)3] = (2.5 +/- ......(VI)-(O-Cr(III))n]. Furthermore, a second-order reaction between two Cr(IV) monomers to yield a species which may be either a (Cr)2IV,IV or a (Cr)2III,V mixed-valence dimer was observed. The corresponding spectra in both the UV and visible range were determined....

  17. Resonance raman spectra of metal II/IV dimer chain complexes of platinum and palladium. Analysis of the component structure to the band assigned to the symmetric XMX chain stretching mode (X = Cl or Br)

    Science.gov (United States)

    Clark, Robin J. H.; Michael, David J.

    1988-10-01

    Resonance Raman spectra of the linear-chain, mixed-valence, halogen-bridged complexes [Pt(pn) 2] [Pt(pn) 2X 2] (ClO 4) 4, where X = Cl or Br, and [Pd(pn) 2] [Pd(pn) 2Br 2] (ClO 4) 4 have been obtained over the range of excitation wavelengths 457.9 to 647.1 nm. Of particular interest is the symmetric metal—halogen stretch, ν 1, which has several components. The relative intensities of these components change with variation of the wavenumber of excitation within the intervalence electronic absorption. This effect and the origin of the different components are discussed.

  18. Time-resolved photoluminescence study of excitonic relaxation in one-dimensional systems

    Science.gov (United States)

    Tanino, H.; Rühle, W. W.; Takahashi, K.

    1988-12-01

    Self-trapped exciton luminescence of quasi-one-dimensional (1D) halogen-bridged mixed-valence platinum complexes [Pt(II) (EA)4][Pt(IV)Cl2(EA)4] Cl4.4H2O (EA=ethylamine) and [Pt(II)(en)2] [Pt(IV)Cl2(en)2](ClO4)4 (en=1,2-diaminoethane) are studied by time-resolved photoluminescence experiments. The lifetimes of the luminescence of self-trapped exciton are exceptionally short, of the order of 100 psec. We interpret the short lifetime by a ``giant oscillator strength'' caused by a strong coupling between the electron and hole of the 1D charge transfer exciton and an extended polaronlike character of the 1D state. The lifetimes of the broad luminescence and of the resonant Raman lines during the barrier-free relaxation process are both faster than 7 psec.

  19. Solid-state reaction synthesis and characterization of PrB6 nanocrystals

    Science.gov (United States)

    Wei, Wei; Lihong, Bao; Yingjie, Li; Luomeng, Chao; Tegus, O.

    2015-04-01

    Crystalline PrB6 nanoparticles with the sizes ranging from 100~300 nm were synthesized by a solid-state reaction of Pr6O11/PrCl3 and NaBH4 in the temperature range of 1100~1200 °C. The crystal structure, component and morphology of the PrB6 nanoparticles were characterized by using X-ray diffraction, scanning electron microscopy and transmission electron microscopy. The results show that the particles crystallize in the CsCl structure type. The selected-area electron diffraction patterns reveal the particles have single-crystalline nature. XANES study shows that the Pr atoms in the PrB6 particles are in trivalent state even if the Pr atoms possess the mixed valence state in the raw material Pr6O11.

  20. A new metal exchanged zeolite for a present environmental problem. An in-situ XAS study

    Science.gov (United States)

    Alonso-Escobar, C.; Franch-Martí, C.; Palomares, A. E.; Rey, F.; Guilera, G.

    2013-04-01

    The medium pore zeolite, TNU-9, is prepared and studied for the selective catalytic reduction (SCR) of NO using C3H8 as the reducing agent. The catalytic activity of TNU-9 zeolites for the SCR is comparable to other known highly active zeolites but with the advantage of TNU-9 of having almost the same catalytic performance in the presence of H2O during reaction. The nature and behaviour of Cu and Co active sites contained in the TNU-9 catalysts have been studied under operation conditions using X-ray Absorption Spectroscopy (XAS) to understand the key parameters controlling the performance of this reaction.1 It was found that the well dispersed Cu and Co centres need to be in a mixed valence state to obtain good catalytic results for the SCR and that the catalytic performance is related to the topology of the TNU-9 itself.

  1. Green rust formation controls nutrient availability in a ferruginous water column

    DEFF Research Database (Denmark)

    Zegeye, Asfaw; Bonneville, Steeve; Benning, Liane G.

    2013-01-01

    Iron-rich (ferruginous) conditions were a prevalent feature of the ocean throughout much of Earth's history. The nature of elemental cycling in such settings is poorly understood, however, thus hampering reconstruction of paleoenvironmental conditions during key periods in Earth evolution...... a mechanism for reconstructing ancient ocean chemistry. Such reconstructions depend, however, on precise knowledge of the iron minerals formed in the water column. Here, we combine mineralogical and geochemical analyses to demonstrate formation of the mixed-valence iron mineral, green rust, in ferruginous....... This is particularly true regarding controls on nutrient bioavailability, which is intimately linked to Earth's oxygenation history. Elemental scavenging during precipitation of iron minerals exerts a major control on nutrient cycling in ferruginous basins, and the predictable nature of removal processes provides...

  2. Giant magnetoresistance of novel ferromagnets AMg4Mn6O15 (A=K, Rb, and Cs) with highly symmetric structure

    Science.gov (United States)

    Tanaka, Yudai; Sato, Hirohiko

    2017-04-01

    A novel family of cubic manganese oxides, AMg4Mn6O15 (A=K, Rb, and Cs), were discovered. In this type of structure, the MnO6 octahedra share edges, constructing a highly symmetric framework where Mn atoms form a three-dimensional network of truncated octahedra. The crystallographic site of Mn is unique and the average oxidation state of Mn is 3.5, indicating a mixed-valence electronic state where Mn3+ and Mn4+ sites are completely indistinguishable. These compounds become ferromagnetic with fully polarized magnetic moments of Mn ions. The ferromagnetic transition temperature TC is 170 K, that is considerably high for manganese oxides. The electric resistivity of KMg4Mn6O15 is about 105 Ωcm at 300 K and exhibits a non-metallic temperature dependence. It reveals a large negative magnetoresistance; about 40% of the resistivity is suppressed by 5 T of magnetic field at TC.

  3. Ginsparg-Wilson Pions Scattering on a Staggered Sea

    CERN Document Server

    Chen, J W; De van Water, R S; Walker-Loud, A; Chen, Jiunn-Wei; Connell, Donal O'; Water, Ruth S. Van de; Walker-Loud, Andre

    2006-01-01

    In this article, we calculate isospin 2 (I=2) pion-pion scattering in chiral perturbation theory for a partially quenched, mixed action theory with Ginsparg-Wilson valence quarks and staggered sea quarks. We determine the scattering length at threshold for both 2 sea quarks and 2+1 sea quarks in the isospin limit. The scattering length, expressed in terms of the pion mass and the decay constant measured on the lattice, has no contributions from mixed valence-sea mesons. Thus, it does not depend upon the parameter, C_Mix, that appears in the chiral Lagrangian of the mixed theory. This result holds for both 2 and 2+1 flavors of sea quarks. Finally, we take the continuum limit of our mixed action results and give expressions for the scattering length in continuum 2 and 2+1 flavor partially quenched chiral perturbation theory.

  4. Nature of the golden phase of samarium monosulfide

    Energy Technology Data Exchange (ETDEWEB)

    Kikoin, K.A.

    1983-09-01

    A theory of reconstruction of the ground state on transition to the golden phase under pressure is proposed on basis of an analysis of the problem of exciton states in the black (semiconductor) phase of SmS. According to the theory, SmS in the golden phase is a narrow-gap semiconductor with a valence band consisting of states with mixed valency; in the states one of the f-electrons of each Sm ion can be redistributed with a certain probability over lhe d-orbitals which encompass several coordination spheres. The kinetic, optical, thermodynamic and magnetic properties of the golden phase of SmS are explained within the framework of the model.

  5. Fabrication of pulsed-laser deposited V-W-Nd mixed-oxide films

    Energy Technology Data Exchange (ETDEWEB)

    Iida, Yusuke; Venkatachalam, S.; Kaneko, Yoshikazu [Interdisciplinary Graduate School of Medicine and Engineering, University of Yamanashi, 4-3-11 Takeda, Kofu 400-8511 (Japan); Kanno, Yoshinori [Interdisciplinary Graduate School of Medicine and Engineering, University of Yamanashi, 4-3-11 Takeda, Kofu 400-8511 (Japan)], E-mail: kanno@yamanashi.ac.jp

    2007-11-15

    V-W-Nd mixed-oxide films were prepared by pulse-laser deposition (PLD) technique from the targets sintered at different temperatures. X-ray photoelectron spectroscopy (XPS) data indicate that the films fabricated from the targets sintered at low temperature were composed of various mixed valences. Raman spectroscopy shows that V-W-Nd films were composed of the vanadates as NdVO{sub 4}, and the W{sup 6+} doping supplements the formation of vanadate. Atomic force microscopy (AFM) image of the films fabricated from the target sintered at 923 K reveals the average particle size is estimated around 86 nm. The surface morphology of the films roughness shows a dramatic change at 923-943 K.

  6. The MOF-driven synthesis of supported palladium clusters with catalytic activity for carbene-mediated chemistry

    Science.gov (United States)

    Fortea-Pérez, Francisco R.; Mon, Marta; Ferrando-Soria, Jesús; Boronat, Mercedes; Leyva-Pérez, Antonio; Corma, Avelino; Herrera, Juan Manuel; Osadchii, Dmitrii; Gascon, Jorge; Armentano, Donatella; Pardo, Emilio

    2017-07-01

    The development of catalysts able to assist industrially important chemical processes is a topic of high importance. In view of the catalytic capabilities of small metal clusters, research efforts are being focused on the synthesis of novel catalysts bearing such active sites. Here we report a heterogeneous catalyst consisting of Pd4 clusters with mixed-valence 0/+1 oxidation states, stabilized and homogeneously organized within the walls of a metal-organic framework (MOF). The resulting solid catalyst outperforms state-of-the-art metal catalysts in carbene-mediated reactions of diazoacetates, with high yields (>90%) and turnover numbers (up to 100,000). In addition, the MOF-supported Pd4 clusters retain their catalytic activity in repeated batch and flow reactions (>20 cycles). Our findings demonstrate how this synthetic approach may now instruct the future design of heterogeneous catalysts with advantageous reaction capabilities for other important processes.

  7. Mn K-edge XANES spectra of manganites measured by Kbeta emission.

    Science.gov (United States)

    García, J; Sánchez, M C; Subías, G; Blasco, J; Proietti, M G

    2001-03-01

    The electronic state of Mn atoms in mixed valence manganites has been studied by means of X-ray absorption spectroscopy at the Mn K-edge. Higher resolution than in conventional measurements has been achieved by measuring the Mn Kbeta fluorescence line. We have found a unique resonance at the edge in the XANES spectra of intermediate composition RE1-xCa(x)MnO3 samples. The features of these XANES spectra do not depend on small changes in the local structure around the Mn atom. However, the spectra of the intermediate composition samples can not be reproduced by a linear combination of REMnO3 and CaMnO3 spectra. Accordingly, the electronic state of Mn atoms in these compounds can not be considered as a mixture of Mn3+ and Mn4+ pure states.

  8. Structural and magnetic phase transitions of kagome-like compounds REBaCo{sub 4}O{sub 7} (RE=Dy, Ho, Er, Tm, Yb, Lu)

    Energy Technology Data Exchange (ETDEWEB)

    Markina, M., E-mail: markina@lt.phys.msu.r [Low Temperature Physics Department, Moscow State University, Moscow 119992 (Russian Federation); Vasiliev, A.N. [Low Temperature Physics Department, Moscow State University, Moscow 119992 (Russian Federation); Nakayama, N.; Mizota, T. [Department of Advanced Materials Science and Engineering, Faculty of Engineering, Yamaguchi University, Ube 755-8611 (Japan); Yeda, Y. [Materials Design and Characterization Laboratory, Institute for Solid State Physics, University of Tokyo, Kashiwa 277-8581 (Japan)

    2010-05-15

    In a temperature range 5-300 K the specific heat C(T) on a new mixed valence cobalt oxides REBaCo{sub 4}O{sub 7} (RE=Dy, Ho, Er, Tm, Yb, Lu) was investigated. The first-order structural phase transitions from hexagonal P6{sub 3}mc to orthorhombic Cmc{sub 2}1 phase was indicated by a peak-like anomaly in C(T) curves at T{sub S}approx160, 178, 224, and 280 K for RE=Lu, Yb, Tm, and Er correspondingly. The magnetic phase transitions was indicated as the changes of slope on the C(T) curves were found at corresponding temperatures: T{sub N}approx50, 74, 98, and 98 K for RE=Lu, Yb, Tm, and Er, correspondingly.

  9. Communication between remote moieties in linear Ru-Ru-Ru trimetallic cyanide-bridged complexes.

    Science.gov (United States)

    Pieslinger, German E; Albores, Pablo; Slep, Leonardo D; Coe, Benjamin J; Timpson, Cliff J; Baraldo, Luis M

    2013-03-18

    In this article, we report the structural, spectroscopic, and electrochemical properties of the cyanide-bridged complex salts trans-[(NC)Ru(II)(L)4(μ-CN)Ru(II)(py)4Cl]PF6 and trans-[Ru(II)(L)4{(μ-CN)Ru(II)(py)4Cl}2](PF6)2 (L = pyridine or 4-methoxypyridine). The mixed-valence forms of these compounds show a variety of metal-to-metal charge-transfer bands, including one arising from charge transfer between the remote ruthenium units. The latter is more intense when L = 4-methoxypyridine and points to the role of the bridging ruthenium unit in promoting mixing between the dπ orbitals of the terminal fragments.

  10. The Complex Core Level Spectra of CeO2: An Analysis in Terms of Atomic and Charge Transfer Effects

    Energy Technology Data Exchange (ETDEWEB)

    Bagus, Paul S; Nelin, Constance J; Ilton, Eugene S; Baron, Martin; Abbott, Heather; Primorac, Elena; Kuhlenbeck, Helmut; Shaikhutdinov, Shamil; Freund, Hans-Joachim

    2010-03-05

    We present a rigorous parameter-free theoretical treatment of the Ce 4s and 5s photoelectron spectra of CeO2. In the currently accepted model the satellite structure in the photoelectron spectra is explained in terms of a mixed valence (Ce 4f0 O 2p6, Ce 4f1 O 2p5, and Ce 4f2 O 2p4) configurations. We show that charge transfer (CT) into Ce 5d as well as configurations involving intra-atomic movement of charge must be considered in addition and compute their contributions to the spectra.

  11. Tunable electrical conductivity in oriented thin films of tetrathiafulvalene-based covalent organic framework

    Energy Technology Data Exchange (ETDEWEB)

    Cai, SL; Zhang, YB; Pun, AB; He, B; Yang, JH; Toma, FM; Sharp, ID; Yaghi, OM; Fan, J; Zheng, SR; Zhang, WG; Liu, Y

    2014-09-16

    Despite the high charge-carrier mobility in covalent organic frameworks (COFs), the low intrinsic conductivity and poor solution processability still impose a great challenge for their applications in flexible electronics. We report the growth of oriented thin films of a tetrathiafulvalene-based COF (TTF-COF) and its tunable doping. The porous structure of the crystalline TTF-COF thin film allows the diffusion of dopants such as I-2 and tetracyanoquinodimethane (TCNQ) for redox reactions, while the closely packed 2D grid sheets facilitate the cross-layer delocalization of thus-formed TTF radical cations to generate more conductive mixed-valence TTF species, as is verified by UV-vis-NIR and electron paramagnetic resonance spectra. Conductivity as high as 0.28 S m(-1) is observed for the doped COF thin films, which is three orders of magnitude higher than that of the pristine film and is among the highest for COF materials.

  12. Synthesis, structure and properties of the La{sub 0.7}K{sub 0.3}MnO{sub 3}

    Energy Technology Data Exchange (ETDEWEB)

    Jurado, J.F.; Sanchez, J.E. [Laboratorio de Propiedades Opticas de Materiales GTA-POM, Departamento de Fisica y Quimica, Universidad Nacional de Colombia, A.A 127, Manizales (Colombia); Vargas-Hernandez, C. [Laboratorio de Propiedades Opticas de Materiales GTA-POM, Departamento de Fisica y Quimica, Universidad Nacional de Colombia, A.A 127, Manizales (Colombia)], E-mail: cvargash@unal.edu.co

    2008-10-01

    The mixed-valence manganites La{sub 0.7}K{sub 0.3}MnO{sub 3} have been synthesized using the citrate route method. The appropriate stoichiometric quantities were dissolved in an aqueous nitric acid solution and the final composition was annealed at high temperature 700 deg. C . The crystalline structure of the samples was verified using X-ray diffraction (XRD), which showed that the polycrystalline compound has a rhombohedral structure. XRD pattern reveals that mixed polycrystalline oxide is attributed to La(OH){sub 3}. The presence of the precursor phase forces the formation of the manganite, along with impurities such as lanthanide hydroxide. The resistivity measurements below room temperature provided evidence of an insulating behavior, while the field-dependent magnetization measurements revealed a transition from a ferromagnetic to a paramagnetic phase.

  13. Understanding the differential performance of Rh2(esp)2 as a catalyst for C-H amination.

    Science.gov (United States)

    Zalatan, David N; Du Bois, J

    2009-06-10

    Catalytic amination of saturated C-H bonds is performed efficiently with the use of Rh(2)(esp)(2). Efforts to identify pathways for catalyst degradation and/or arrest have revealed a single-electron oxidation event that gives rise to a red-colored, mixed-valence dimer, [Rh(2)(esp)(2)](+). This species is fortuitously reduced by carboxylic acid, a byproduct generated in the reaction cycle with each turnover of the diacyloxyiodine oxidant. These findings have led to the conclusion that the high performance of Rh(2)(esp)(2) is due in part to the superior kinetic stability of its one-electron oxidized form relative to other dimeric Rh complexes.

  14. Influence of Dynamical Conditions on the Reduction of UVI at the Magnetite-Solution Interface

    Energy Technology Data Exchange (ETDEWEB)

    Ilton, Eugene S.; Boily, Jean F.; Buck, Edgar C.; Skomurski, Frances N.; Rosso, Kevin M.; Cahill, Christopher L.; Bargar, John R.; Felmy, Andrew R.

    2010-01-14

    The heterogeneous reduction of UVI to UIV by ferrous iron is a potentially key process influencing the fate and transport of U in the environment. The reactivity of both sorbed and structural FeII has been studied for numerous substrates, including magnetite. The results from UVI-magnetite experiments have been variable, ranging from no reduction to clear evidence for the formation of UIV. In this contribution, we used XAS and high resolution (+cryogenic) XPS to study the interaction of UVI with nano-particulate magnetite. The results indicated that UVI was partially reduced to UV with no evidence of UIV. However, thermodynamic calculations indicated that mixed-valence U phases with average oxidation states below (V) should have been stable, indicating that the system was not in redox equilibrium. A reaction pathway that involves incorporation of U and stabilization of UV and UVI in secondary phases is invoked to explain the observations.

  15. Similarities between Copper and Plutonium containing 'high T {sub c}' superconductors

    Energy Technology Data Exchange (ETDEWEB)

    Wachter, P. [Laboratorium fuer Festkoerperphysik, ETH Zuerich, 8093 Zuerich (Switzerland)]. E-mail: wachter@solid.phys.ethz.ch

    2007-09-13

    PuCoGa{sub 5} with 18.5 K has an extremely high T {sub c} for superconductivity compared with other actinide materials having T {sub c}s around 2-3 K. It appears to be a 'high T {sub c} superconductor' in the field of actinides. After nearly 20 years of research in high T {sub c} superconductors only Cu containing materials have T {sub c}s above about 30 K (exception MgB{sub 2}). BCS theory cannot explain such high transition temperatures, thus other or additional coupling mechanisms, like magnetic exchange are necessary. Mixed valence, spin holes in an antiferromagnetic lattice, small energy difference between the various valences and two-dimensionality are common features of Cu and Pu containing superconductors. It can be shown in this paper that the mechanism for superconductivity is the same for Cu and Pu containing materials.

  16. Similarities between Cu and Pu containing 'high T {sub c}' superconductors

    Energy Technology Data Exchange (ETDEWEB)

    Wachter, P. [Laboratorium fuer Festkoerperphysik, ETH Zuerich, 8093 Zurich (Switzerland)]. E-mail: wachter@solid.phys.ethz.ch

    2007-03-15

    PuCoGa{sub 5} has with 18.5 K an extremely high T {sub c} for superconductivity compared with other actinide materials having T{sub c}s around 2-3 K. It appears to be a 'high T {sub c} superconductor' in the field of actinides. After nearly 20 years of research in high T{sub c} superconductors, only Cu containing materials have T{sub c}s above about 30 K (exception MgB{sub 2}). BCS theory cannot explain such high transition temperatures, thus other or additional coupling mechanisms like magnetic exchange are necessary. Mixed valence, spin holes in an antiferromagnetic lattice, small energy difference between the various valences and two-dimensionality are common features of Cu and Pu containing superconductors. It can be shown in this paper that the mechanism for superconductivity is the same for Cu and Pu containing materials.

  17. Electronic and magnetic properties of a conductive metal-organic framework from first principles

    Science.gov (United States)

    Hamed, Samia M.; Reyes-Lillo, Sebastian E.; Neaton, Jeffrey B.

    Motivated by the recent synthesis of a mixed-valence metal-organic framework (MOF) displaying high electron mobilities upon reduction, we undertake a computational study of its electronic, structural, and magnetic properties, utilizing ab initio density functional theory. We model the reduced system through charge doping, and the local ligand environment through finite cluster calculations. Molecular orbitals near the Fermi level are found to display mixtures of localized iron d and delocalized ligand p states suggesting strong charge carrier delocalization. Furthermore, we extend our study to one dimensional and three dimensional periodic systems and discuss possible transport mechanisms. Finally, the static correlation effects due to the presence of partially filled iron d orbitals requires an especially careful choice of exchange correlation functional, and the consequence of this choice is demonstrated.

  18. Magnetic-Moment Fragmentation and Monopole Crystallization

    Directory of Open Access Journals (Sweden)

    M. E. Brooks-Bartlett

    2014-01-01

    Full Text Available The Coulomb phase, with its dipolar correlations and pinch-point–scattering patterns, is central to discussions of geometrically frustrated systems, from water ice to binary and mixed-valence alloys, as well as numerous examples of frustrated magnets. The emergent Coulomb phase of lattice-based systems has been associated with divergence-free fields and the absence of long-range order. Here, we go beyond this paradigm, demonstrating that a Coulomb phase can emerge naturally as a persistent fluctuating background in an otherwise ordered system. To explain this behavior, we introduce the concept of the fragmentation of the field of magnetic moments into two parts, one giving rise to a magnetic monopole crystal, the other a magnetic fluid with all the characteristics of an emergent Coulomb phase. Our theory is backed up by numerical simulations, and we discuss its importance with regard to the interpretation of a number of experimental results.

  19. Supramolecular Isomers of Metal-Organic Frameworks Derived from a Partially Flexible Ligand with Distinct Binding Motifs

    KAUST Repository

    Abdul Halim, Racha Ghassan

    2016-01-04

    Three novel metal-organic frameworks (MOFs) were isolated upon reacting a heterofunctional ligand 4 (pyrimidin-5 yl)benzoic acid (4,5-pmbc) with mixed valence Cu(I,II) under solvothermal conditions. X-ray crystal structural analysis reveals that the first compound is a layered structure composed of one type of inorganic building block, dinuclear paddlewheel [Cu2(O2C–)4], which are linked through 4,5-pmbc ligands. The two other supramolecular isomers are composed of the same Cu(II) dinuclear paddlewheel and a dinuclear Cu2I2 cluster, which are linked via the 4,5-pmbc linkers to yield two different 3-periodic frameworks with underlying topologies related to lvt and nbo. The observed structural diversity in these structures is due to the distinct coordination modes of the two coordinating moieties (the carboxylate group on the phenyl ring and the N-donor atoms from the pyrimidine moiety).

  20. Star-shaped tetrathiafulvalene oligomers towards the construction of conducting supramolecular assembly

    Science.gov (United States)

    Hasegawa, Masashi

    2015-01-01

    Summary The construction of redox-active supramolecular assemblies based on star-shaped and radially expanded tetrathiafulvalene (TTF) oligomers with divergent and extended conjugation is summarized. Star-shaped TTF oligomers easily self-aggregate with a nanophase separation to produce supramolecular structures, and their TTF units stack face-to-face to form columnar structures using the fastener effect. Based on redox-active self-organizing supramolecular structures, conducting nanoobjects are constructed by doping of TTF oligomers with oxidants after the formation of such nanostructures. Although radical cations derived from TTF oligomers strongly interact in solution to produce a mixed-valence dimer and π-dimer, it seems to be difficult to produce nanoobjects of radical cations different from those of neutral TTF oligomers. In some cases, however, radical cations form nanostructured fibers and rods by controlling the supramolecular assembly, oxidation states, and counter anions employed. PMID:26664579

  1. Coexistence of superconductivity and complex 4 f magnetism in Eu0.5Ce0.5BiS2F.

    Science.gov (United States)

    Zhai, Hui-Fei; Zhang, Pan; Tang, Zhang-Tu; Bao, Jin-Ke; Jiang, Hao; Feng, Chun-Mu; Xu, Zhu-An; Cao, Guang-Han

    2015-09-30

    EuBiS2F is a self-doped superconductor due to the mixed valence of Eu. Here we report that, with the Ce substitution for Eu by 50 at.%, the material exhibits ferromagnetic ordering at 8 K for the Ce-4 f moment, superconductivity at 2.2 K in the BiS2 layers and possibly antiferromagnetic ordering at 2.1 K for the Eu-4 f spins. The Eu valence is essentially divalent with the Ce incorporation. We tentatively interpret the coexistence of ferromagnetism and superconductivity by considering different Bi-6p orbitals that are responsible for the superconductivity itself and for mediating the ferromagnetic interaction, respectively. We argue that the antiferromagnetic ordering of the Eu-4 f spins is most likely due to a magnetic dipole-dipole interaction.

  2. Electron-mediating Cu(A) centers in proteins

    DEFF Research Database (Denmark)

    Epel, Boris; Slutter, Claire S; Neese, Frank

    2002-01-01

    High field (W-band, 95 GHz) pulsed electron-nuclear double resonance (ENDOR) measurements were carried out on a number of proteins that contain the mixed-valence, binuclear electron-mediating Cu(A) center. These include nitrous oxide reductase (N(2)OR), the recombinant water-soluble fragment...... of subunit II of Thermus thermophilus cytochrome c oxidase (COX) ba(3) (M160T9), its M160QT0 mutant, where the weak axial methionine ligand has been replaced by a glutamine, and the engineered "purple" azurin (purpAz). The three-dimensional (3-D) structures of these proteins, apart from the mutant, are known......-D structures and compared with the experimental spectra. It was found that the width of the powder patterns of the weakly coupled protons recorded at g(perpendicular) is mainly determined by the histidine H(epsilon)(1) protons. Furthermore, the splitting in the outer wings of these powder patterns...

  3. Bonding structure and morphology of chromium oxide films grown by pulsed-DC reactive magnetron sputter deposition

    Energy Technology Data Exchange (ETDEWEB)

    Gago, R., E-mail: rgago@icmm.csic.es [Instituto de Ciencia de Materiales de Madrid, Consejo Superior de Investigaciones Científicas, E-28049 Madrid (Spain); Vinnichenko, M. [Fraunhofer-Institut für Keramische Technologien und Systeme IKTS, D-01277 Dresden (Germany); Hübner, R. [Helmholtz-Zentrum Dresden – Rossendorf, Institute of Ion Beam Physics and Materials Research, Bautzner Landstraße 400, 01328 Dresden (Germany); Redondo-Cubero, A. [Departamento de Física Aplicada and Centro de Microanálisis de Materiales, Universidad Autónoma de Madrid, E-28049 Madrid (Spain)

    2016-07-05

    Chromium oxide (CrO{sub x}) thin films were grown by pulsed-DC reactive magnetron sputter deposition in an Ar/O{sub 2} discharge as a function of the O{sub 2} fraction in the gas mixture (ƒ) and for substrate temperatures, T{sub s}, up to 450 °C. The samples were analysed by Rutherford backscattering spectrometry (RBS), spectroscopic ellipsometry (SE), atomic force microscopy (AFM), scanning (SEM) and transmission (TEM) electron microscopy, X-ray diffraction (XRD), and X-ray absorption near-edge structure (XANES). On unheated substrates, by increasing ƒ the growth rate is higher and the O/Cr ratio (x) rises from ∼2 up to ∼2.5. Inversely, by increasing T{sub s} the atomic incorporation rate drops and x falls to ∼1.8. XRD shows that samples grown on unheated substrates are amorphous and that nanocrystalline Cr{sub 2}O{sub 3} (x = 1.5) is formed by increasing T{sub s}. In amorphous CrO{sub x}, XANES reveals the presence of multiple Cr environments that indicate the growth of mixed-valence oxides, with progressive promotion of hexavalent states with ƒ. XANES data also confirms the formation of single-phase nanocrystalline Cr{sub 2}O{sub 3} at elevated T{sub s}. These structural changes also reflect on the optical and morphological properties of the films. - Highlights: • XANES of CrO{sub x} thin films grown by pulsed-DC reactive magnetron sputtering. • Identification of mixed-valence amorphous CrO{sub x} oxides on unheated substrates. • Promotion of amorphous chromic acid (Cr{sup VI}) by increasing O{sub 2} partial pressure. • Production of single-phase Cr{sub 2}O{sub 3} films by increasing substrate temperature. • Correlation of bonding structure with morphological and optical properties.

  4. Pulse electron paramagnetic resonance studies of the interaction of methanol with the S2 state of the Mn4O5Ca cluster of photosystem II.

    Science.gov (United States)

    Oyala, Paul H; Stich, Troy A; Stull, Jamie A; Yu, Fangting; Pecoraro, Vincent L; Britt, R David

    2014-12-23

    The binding of the substrate analogue methanol to the catalytic Mn4CaO5 cluster of the water-oxidizing enzyme photosystem II is known to alter the electronic structure properties of the oxygen-evolving complex without retarding O2-evolution under steady-state illumination conditions. We report the binding mode of (13)C-labeled methanol determined using 9.4 GHz (X-band) hyperfine sublevel-correlation (HYSCORE) and 34 GHz (Q-band) electron spin-echo electron nuclear double resonance (ESE-ENDOR) spectroscopies. These results are compared to analogous experiments on a mixed-valence Mn(III)Mn(IV) complex (2-OH-3,5-Cl2-salpn)2Mn(III)Mn(IV) (salpn = N,N'-bis(3,5-dichlorosalicylidene)-1,3-diamino-2-hydroxypropane) in which methanol ligates to the Mn(III) ion ( Larson et al. (1992) J. Am. Chem. Soc. , 114 , 6263 ). In the mixed-valence Mn(III,IV) complex, the hyperfine coupling to the (13)C of the bound methanol (Aiso = 0.65 MHz, T = 1.25 MHz) is appreciably larger than that observed for (13)C methanol associated with the Mn4CaO5 cluster poised in the S2 state, where only a weak dipolar hyperfine interaction (Aiso = 0.05 MHz, T = 0.27 MHz) is observed. An evaluation of the (13)C hyperfine interaction using the X-ray structure coordinates of the Mn4CaO5 cluster indicates that methanol does not bind as a terminal ligand to any of the manganese ions in the oxygen-evolving complex. We favor methanol binding in place of a water ligand to the Ca(2+) in the Mn4CaO5 cluster or in place of one of the waters that form hydrogen bonds with the oxygen bridges of the cluster.

  5. Computational design of materials for solar hydrogen generation

    Science.gov (United States)

    Umezawa, Naoto

    Photocatalysis has a great potential for the production of hydrogen from aquerous solution under solar light. In this talk, two different approaches toward the computational materials desing for solar hydrogen generation will be presented. Tin (Sn), which has two major oxidation states, Sn2+ and Sn4+, is abundant on the earth's crust. Recently, visible-light responsive photocatalytc H2 evolution reaction was identified over a mixed valence tin oxide Sn3O4. We have carried out crystal structure prediction for mixed valence tin oxides in different atomic compositions under ambient pressure condition using advanced computational methods based on the evolutionary crystal-structure search and density-functional theory. The predicted novel crystal structures realize the desirable band gaps and band edge positions for H2 evolution under visible light irradiation. It is concluded that multivalent tin oxides have a great potential as an abundant, cheap and environmentally-benign solar-energy conversion photofunctional materials. Transition metal doping is effective for sensitizing SrTiO3 under visible light. We have theoretically investigated the roles of the doped Cr in STO based on hybrid density-functional calculations. Cr atoms are preferably substituting for Ti under any equilibrium growth conditions. The lower oxidation state Cr3+, which is stabilized under an n-type condition of STO, is found to be advantageous for the photocatalytic performance. It is firther predicted that lanthanum is the best codopant for stabilizing the favorable oxidation state, Cr3+. The prediction was validated by our experiments that La and Cr co-doped STO shows the best performance among examined samples. This work was supported by the Japan Science and Technology Agency (JST) Precursory Research for Embryonic Science and Technology (PRESTO) and International Research Fellow program of Japan Society for the Promotion of Science (JSPS) through project P14207.

  6. Interplay of Charge Transfer, Dimensionality, and Amide Hydrogen Bond Network Adaptability in TCNQF 4 Complexes of EDO-TTF-CONH 2 and EDT-TTF-CONH 2

    Science.gov (United States)

    Baudron, Stéphane A.; Mézière, Cécile; Heuzé, Karine; Fourmigué, Marc; Batail, Patrick; Molinié, Philippe; Auban-Senzier, Pascale

    2002-11-01

    [EDO-TTF-CONH 2][TCNQF 4], triclinic system, space group P-1, a=8.2479(12) Å, b=12.282(2) Å, c=12.6842(18) Å, α=113.850(17)°, β=106.420(17)°, γ=90.284(19)°, V=1116.8(4) Å 3; and [EDT-TTF-CONH 2] 2[TCNQF 4], triclinic system, space group P-1, a=6.5858(9) Å, b=11.699(2) Å, c=12.2281(18) Å, α=104.000(19)°, β=93.611(17)°, γ=98.279(19)°, V=899.9(3) Å 3, whose π-donor molecules, (ethylenedioxo)-carbamoyltetrathiafulvalene and (ethylenedithio)-carbamoyltetrathiafulvalene, respectively, differ solely by the nature of the chalcogen atoms in their outer ethylene dichalcogeno bridge, yet form very different charge-transfer complexes with the same π-acceptor. [EDO-TTF-CONH 2•+] 2 [TCNQF 4•-] 2 is a diamagnetic insulating ionic salt with a three-dimensional rock-salt-type structure based on discrete dimers while in the semi-conducting mixed-valence complex, [EDT-TTF-CONH 2] 2•+[TCNQF 4•-], the mixed-valence dimers aggregate into infinite chains interspersed within parallel rows of non-interacting radical anions. It is shown how the robust and adaptable supramolecular amide hydrogen bond tweezers-like motifs common to the two solids simply comply to the 3-to-1 dimensionality reduction upon substitution of O for S.

  7. UV excitations of halons

    Science.gov (United States)

    Stojanović, Ljiljana; Alyoubi, Abdulrahman O.; Aziz, Saadullah G.; Hilal, Rifaat H.; Barbatti, Mario

    2016-11-01

    In the present study, we examined the UV excitations of a newly introduced molecular set, Halons-9, composed of nine gaseous halon molecules. The performance of the density functional-based multi-reference configuration interaction method (DFT/MRCI) and time-dependent density functional theory with CAM-B3LYP functional (TD-CAM-B3LYP) in the computation of singlet and triplet excited states of this set was evaluated against coupled-cluster with singles and doubles (CCSD). Excited states up to the corresponding ionization limits, including both localized and delocalized excitations, have been benchmarked. TD-CAM-B3LYP significantly underestimates excitation energies of the higher mixed valence-Rydberg and Rydberg states, with computed mean absolute deviations from the equation of motion (EOM)-CCSD results 1.06 and 0.76 eV, respectively. DFT/MRCI gives a significantly better description of higher excited states, albeit still poor, compared to the TD-CAM-B3LYP. The mean absolute deviations of mixed valence-Rydberg and Rydberg states from the reference EOM-CCSD values are 0.66 and 0.47 eV, respectively. The performance of DFT/MRCI for description of strongly correlated states with valence-Rydberg mixing is still not satisfactory enough. On the other hand, oscillator strengths of most of singlet states obtained with both methods are close to the EOM-CCSD values. The largest deviations, occurring in the case of several high-lying multiconfigurational states, are of an order of magnitude.

  8. Syntheses, structures and photoluminescent properties of three d{sup 10} coordination architectures based on in-situ 1,3,5-triazine derivatives

    Energy Technology Data Exchange (ETDEWEB)

    Xiao, Changyu [Institute of Molecular and Crystal Engineering, College of Chemistry and Chemical Engineering, Henan University, Kaifeng, Henan 475004 (China); Li, Yamin, E-mail: liyamin@henu.edu.cn [Institute of Molecular and Crystal Engineering, College of Chemistry and Chemical Engineering, Henan University, Kaifeng, Henan 475004 (China); Lun, Huijie; Cui, Caiyan [Institute of Molecular and Crystal Engineering, College of Chemistry and Chemical Engineering, Henan University, Kaifeng, Henan 475004 (China); Xu, Yanqing [School of Chemistry, Key Laboratory of Cluster Science, Ministry of Education of China, Beijing Institute of Technology, Beijing 100081 (China)

    2013-12-15

    In the presence of aromatic carboxylic acids, three new d{sup 10} transition metal coordination polymers, [Ag(PAHT)]{sub n}(1), [Ag{sub 2}(HCA)]{sub n}(2) and [Cu{sub 6}(CA){sub 2}(H{sub 2}O)]{sub n}(3) (HPAHT=2-phenyl-4-amino-6-hydroxy-1,3,5-triazine, H{sub 3}CA=cyanuric acid) have been synthesized based on in-situ 1,3,5-triazine derivatives resulting from 2,4-diamino-6-phenyl-1,3,5-triazine, 2-chloro-4,6-diamino-1,3,5-triazine and melamine under hydrothermal conditions. Complexes 1–3 have been characterized by single-crystal X-ray diffraction, IR spectra, elemental analysis and thermogravimetric analysis (TGA). The compound 1 exhibits a uninodal three-connected 3D network with a rare lig LiGe type topology, which contains right-handed and left-handed [Ag(PAHT)]{sub n} helical chains. For compound 2, the 3D network is comprised of 2D sheet by strongly Ag–O and weakly Ag(I)…Ag(I) interactions. In compound 3, it is infrequently observed that dodecanuclear copper(I) units as secondary building units (SBUs) construct 3D network by the ligands CA{sup 3−} with a rare uninodal 10-connected bct topology (3{sup 12}.4{sup 28}.5{sup 5}). The photoluminescent properties of three compounds have also been measured. - Graphical abstract: Three d{sup 10} transition metal coordination polymers 1–3 have been hydrothermally synthesized and characterized by single-crystal X-ray diffraction, IR spectra, elemental analysis, photoluminescent spectra and thermogravimetric analysis (TGA). - Highlights: • The compound 1 exhibits a new 3D network with two kinds of single helical chains. • New 3D d{sup 10} transition metal coordination polymers. • The photoluminescent properties have been measured.

  9. Recent perspectives into biochemistry of decavanadate

    Institute of Scientific and Technical Information of China (English)

    Manuel; Aureliano

    2011-01-01

    The number of papers about decavanadate has doubled in the past decade. In the present review, new insights into decavanadate biochemistry, cell biology, and antidiabetic and antitumor activities are described. Decameric vanadate species (V10) clearly differs from monomeric vanadate (V1), and affects differently calcium pumps, and structure and function of myosin and actin. Only decavanadate inhibits calcium accumulation by calcium pump ATPase, and strongly inhibits actomyosin ATPase activity (IC50 = 1.4 μmol/L, V10), whereas no such ef- fects are detected with V1 up to 150 μmol/L; prevents actin polymerization (IC50 of 68 μmol/L, whereas no effects detected with up to 2 mmol/L V1); and interacts with actin in a way that induces cysteine oxidation and vanadate reduction to vanadyl. Moreover, in vivo decavanadate toxicity studies have revealed that acute exposure to polyoxovanadate induces different changes in antioxidant enzymes and oxidative stress parameters, in comparison with vanadate. In vitro studies have clearly demonstrated that mitochondrial oxygen consumption is strongly affected by decavanadate (IC50, 0.1 μmol/L); perhaps the most relevant biological effect. Finally, decavanadate (100 μmol/L) increases rat adipocyte glucose accumulation more potently than several vanadium complexes. Preliminary studies sug- gest that decavanadate does not have similar effects in human adipocytes. Although decavanadate can be a useful biochemical tool, further studies must be carried out before it can be conf irmed that decavanadate and its complexes can be used as anticancer or antidiabetic agents.

  10. Recent perspectives into biochemistry of decavanadate.

    Science.gov (United States)

    Aureliano, Manuel

    2011-10-26

    The number of papers about decavanadate has doubled in the past decade. In the present review, new insights into decavanadate biochemistry, cell biology, and antidiabetic and antitumor activities are described. Decameric vanadate species (V(10)) clearly differs from monomeric vanadate (V(1)), and affects differently calcium pumps, and structure and function of myosin and actin. Only decavanadate inhibits calcium accumulation by calcium pump ATPase, and strongly inhibits actomyosin ATPase activity (IC(50) = 1.4 μmol/L, V(10)), whereas no such effects are detected with V(1) up to 150 μmol/L; prevents actin polymerization (IC(50) of 68 μmol/L, whereas no effects detected with up to 2 mmol/L V(1)); and interacts with actin in a way that induces cysteine oxidation and vanadate reduction to vanadyl. Moreover, in vivo decavanadate toxicity studies have revealed that acute exposure to polyoxovanadate induces different changes in antioxidant enzymes and oxidative stress parameters, in comparison with vanadate. In vitro studies have clearly demonstrated that mitochondrial oxygen consumption is strongly affected by decavanadate (IC(50), 0.1 μmol/L); perhaps the most relevant biological effect. Finally, decavanadate (100 μmol/L) increases rat adipocyte glucose accumulation more potently than several vanadium complexes. Preliminary studies suggest that decavanadate does not have similar effects in human adipocytes. Although decavanadate can be a useful biochemical tool, further studies must be carried out before it can be confirmed that decavanadate and its complexes can be used as anticancer or antidiabetic agents.

  11. Spillover Phenomena and Its Striking Impacts in Electrocatalysis for Hydrogen and Oxygen Electrode Reactions

    Directory of Open Access Journals (Sweden)

    Georgios D. Papakonstantinou

    2011-01-01

    Full Text Available The core subject of the present paper represents the interrelated spillover (effusion phenomena both of the primary oxide and the H-adatoms, their theory and practice, causes, appearances and consequences, and evidences of existence, their specific properties, and their alterpolar equilibria and kinetic behavior, structural, and resulting catalytic, and double layer charging features. The aim is to introduce electron conductive and d-d interactive individual and composite (mixed valence hypo-d-oxide compounds, of increased altervalent capacity, or their suboxides (Magnéli phases, as the interactive catalytic supports and therefrom provide (i the strong metal-support interaction (SMSI catalytic effect and (ii dynamic spillover interactive transfer of primary oxides (M-OH and free effusional H-adatoms for further electrode reactions and thereby advance the overall electrocatalytic activity. Since hypo-d-oxides feature the exchange membrane properties, the higher the altervalent capacity, the higher the spillover effect. In fact, altervalent hypo-d-oxides impose spontaneous dissociative adsorption of water molecules and then spontaneously pronounced membrane spillover transferring properties instantaneously resulting with corresponding bronze type (Pt/HxWO3 under cathodic and/or its hydrated state (Pt/W(OH6, responsible for Pt-OH effusion, under anodic polarization, this way establishing instantaneous reversibly revertible alterpolar bronze features (Pt/H0.35WO3⇔ Pt/W(OH6 and substantially advanced electrocatalytic properties of these composite interactive electrocatalysts. Such nanostructured-type electrocatalysts, even of mixed-valence hypo-d-oxide structures (Pt/H0.35WO3/TiO2/C, Pt/HxNbO3/TiO2/C, have for the first time been synthesized by the sol-gel methods and shown rather high stability, electron conductivity, and nonexchanged initial pure monobronze spillover and catalytic properties. Such a unique electrocatalytic system, as the

  12. Oxidation control of fluxes for mixed-valent inorganic oxide materials synthesis

    Science.gov (United States)

    Schrier, Marc David

    This dissertation is concerned with controlling the flux synthesis and ensuing physical properties of mixed-valence metal oxides. Molten alkali metal nitrates and hydroxides have been explored to determine and exploit their variable redox chemistries for the synthesis of mixed-valent oxide materials. Cationic and anionic additives have been utilized in these molten salts to control the relative concentrations of the redox-active species present to effectively tune and cap the electrochemical potential of the flux. Atoms like bismuth, copper, and manganese are capable of providing different numbers of electrons for bonding. With appropriate doping near the metal-insulator transition, many of these mixed-valent inorganic metal oxides exhibit extraordinary electronic and magnetic properties. Traditionally, these materials have been prepared by classical high temperature solid state routes where microscopic homogeneity is hard to attain. In these routes, the starting composition dictates the doping level, and in turn, the formal oxidation state achieved. Molten flux syntheses developed in this work have provided the potential for preparing single-phase, homogeneous, and crystalline materials. The redox-active fluxes provide a medium for enhanced doping and mixed-valency control in which the electrochemical potential adjusts the formal oxidation state, and the doping takes place to maintain charge neutrality. The two superconductor systems investigated are: (1) the potassium-doped barium bismuth oxides, and (2) the alkali metal- and alkaline earth metal-doped lanthanum copper oxides. Controlled oxidative doping has been achieved in both systems by two different approaches. The superconducting properties of these materials have been assessed, and the materials have been characterized by powder X-ray diffraction and e-beam microprobe elemental analyses. In the course of these studies, several other materials have been identified. Analysis of these materials, and the

  13. Thermal expansion behaviour of a versatile monazite phase with simulated HLW: A high temperature x-ray diffraction study

    Energy Technology Data Exchange (ETDEWEB)

    Asuvathraman, R.; Kutty, K.V. Govindan, E-mail: kvg@igcar.gov.in

    2014-04-01

    Highlights: • The XPS characterization of the versatile monazite phase, Ce{sub 0.8}Ca{sub 0.2}PO{sub 4} (Ce{sub 0.6}{sup 3+}Ce{sub 0.2}{sup 4+}Ca{sub 0.2}{sup 2+}PO{sub 4}) confirms the mixed valence state of Ce. • The monoclinic lattice parameters all increase to nearly the same extent with temperature displaying the isotropic behaviour for the monazite phase. • The thermal expansion along the three crystallographic axes vary in the order b < a < c. - Abstract: Synthetic analogues of monazite are considered as an alternate ceramic host for the immobilization of high level waste (HLW) generated in the nuclear fuel cycle. The Ca doped CePO{sub 4} (Ce{sub 0.8}Ca{sub 0.2}PO{sub 4}) is expected to be a versatile monazite phase for this purpose due to the mixed valence state of cerium in this compound which assists in accommodating cations of any valence by initiating the internal redox reaction, viz., Ce{sup 3+} ⇌ Ce{sup 4+} + e{sup −}, as required by the incoming cation for charge neutrality of the lattice. The thermal expansion of this versatile monazite phase with 20 wt.% simulated HLW was measured using high temperature x-ray diffractometer (HTXRD) in the temperature range of 298–973 K and are reported here. The thermal expansion behaviour is found to be similar for CePO{sub 4}, Ce{sub 0.8}Ca{sub 0.2}PO{sub 4} and Ce{sub 0.8}Ca{sub 0.2}PO{sub 4} with 20 wt.% simulated HLW with the average volume expansion coefficient of 27.4, 26.5 and 24.1 × 10{sup −6} K{sup −1} respectively in the temperature range of 298–973 K.

  14. Polymer-mediated formation of polyoxomolybdate nanomaterials

    Science.gov (United States)

    Wan, Quan

    A polymer-mediated synthetic pathway to a polyoxomolybdate nanomaterial is investigated in this work. Block copolymers or homopolymers containing poly(ethylene oxide) (PEO) are mixed with a MoO2(OH)(OOH) aqueous solution to form a golden gel or viscous solution. As revealed by synchrotron X-ray scattering measurements, electron microscopy, and other characterization techniques, the final dark blue polyoxomolybdate product is a highly ordered simple cubic network similar to certain zeolite structure but with a much larger lattice constant of ˜5.2 nm. The average size of the cube-like single crystals is close to 1 mum. Based on its relatively low density (˜2.2 g/cm3), the nanomaterial can be highly porous if the amount of the residual polymer can be substantially reduced. The valence of molybdenum is ˜5.7 based on cerimetric titration, representing the mixed-valence nature of the polyoxomolybdate structure. The self-assembled structures (if any) of the polymer gel do not have any correlation with the final polyoxomolybdate nanostructure, excluding the possible role of polymers being a structure-directing template. On the other hand, the PEO polymer stabilizes the precursor molybdenum compound through coordination between its ether oxygen atoms and molybdenum atoms, and reduces the molybdenum (VI) precursor compound with its hydroxyl group being a reducing agent. The rare simple cubic ordering necessitates the existence of special affinities among the polyoxomolybdate nanosphere units resulted from the reduction reaction. Our mechanism study shows that the acidified condition is necessary for the synthesis of the mixed-valence polyoxomolybdate clusters, while H2O2 content modulates the rate of the reduction reaction. The polymer degradation is evidenced by the observation of a huge viscosity change, and is likely through a hydrolysis process catalyzed by molybdenum compounds. Cube-like polyoxomolybdate nanocrystals with size of ˜40 nm are obtained by means of

  15. Experimental investigation on the mechanism of chelation-assisted, copper(II) acetate-accelerated azide-alkyne cycloaddition.

    Science.gov (United States)

    Kuang, Gui-Chao; Guha, Pampa M; Brotherton, Wendy S; Simmons, J Tyler; Stankee, Lisa A; Nguyen, Brian T; Clark, Ronald J; Zhu, Lei

    2011-09-07

    A mechanistic model is formulated to account for the high reactivity of chelating azides (organic azides capable of chelation-assisted metal coordination at the alkylated azido nitrogen position) and copper(II) acetate (Cu(OAc)(2)) in copper(II)-mediated azide-alkyne cycloaddition (AAC) reactions. Fluorescence and (1)H NMR assays are developed for monitoring the reaction progress in two different solvents, methanol and acetonitrile. Solvent kinetic isotopic effect and premixing experiments give credence to the proposed different induction reactions for converting copper(II) to catalytic copper(I) species in methanol (methanol oxidation) and acetonitrile (alkyne oxidative homocoupling), respectively. The kinetic orders of individual components in a chelation-assisted, copper(II)-accelerated AAC reaction are determined in both methanol and acetonitrile. Key conclusions resulting from the kinetic studies include (1) the interaction between copper ion (either in +1 or +2 oxidation state) and a chelating azide occurs in a fast, pre-equilibrium step prior to the formation of the in-cycle copper(I)-acetylide, (2) alkyne deprotonation is involved in several kinetically significant steps, and (3) consistent with prior experimental and computational results by other groups, two copper centers are involved in the catalysis. The X-ray crystal structures of chelating azides with Cu(OAc)(2) suggest a mechanistic synergy between alkyne oxidative homocoupling and copper(II)-accelerated AAC reactions, in which both a bimetallic catalytic pathway and a base are involved. The different roles of the two copper centers (a Lewis acid to enhance the electrophilicity of the azido group and a two-electron reducing agent in oxidative metallacycle formation, respectively) in the proposed catalytic cycle suggest that a mixed valency (+2 and +1) dinuclear copper species be a highly efficient catalyst. This proposition is supported by the higher activity of the partially reduced Cu(OAc)(2) in

  16. Iron-Manganese Redox Processes and Synergism in the Mechanism for Manganese-Catalyzed Autoxidation of Hydrogen Sulfite.

    Science.gov (United States)

    Fronaeus, Sture; Berglund, Johan; Elding, Lars I.

    1998-09-21

    The mechanism for manganese-catalyzed aqueous autoxidation of hydrogen sulfite at pH 2.4 has been revised on the basis of previous comprehensive kinetic studies and thermodynamic data for iron-manganese redox processes and manganese(II) and -(III) protolysis equilibria. The catalytically active manganese species is concluded to be an oxo- (or hydroxo-) bridged mixed-valence complex of composition (OH)Mn(III)OMn(II)(aq) with a formation constant beta' of (3 +/- 1) x 10(4) M(-)(1) from kinetics or ca. 7 x 10(4) M(-)(1) from thermodynamics. It is formed via rapid reaction between Mn(H(2)O)(6)(2+) and hydrolyzed manganese(III) aqua hydroxo complexes, and it initiates the chain reaction via formation of a precursor complex with HSO(3)(-), within which fast bridged electron transfer from S(IV) to Mn(III) takes place, resulting in formation of chain propagating sulfite radicals, SO(3)(*)(-). The very high acidity of Mn(3+)(aq), indicating a strong bond Mn(III)-OH(2) in hydrolyzed manganese(III), makes an attack by HSO(3)(-) on substitution labile Mn(II) in the bridged complex more favorable than one directly on manganese(III). The synergistic effect observed in systems containing iron as well as manganese and the chain initiation by trace concentrations of iron(III) of ca. 5 x 10(-)(8) M can also be rationalized in terms of formation of this bridged mixed-valence dimanganese(II,III) complex. The presence of iron(III) in a Mn(II)/HSO(3)(-) system results in rapid establishment of an iron-manganese redox equilibrium, increasing the concentration of manganese(III) and of the catalytically active bridged complex. The bridged complex oxidizes HSO(3)(-) several orders of magnitude faster than does iron(III) itself. Comparison with some previous studies shows that the different experimental rate laws reported do not necessarily indicate different reaction mechanisms. Instead, they can be rationalized in terms of different rate-determining steps within the same complex chain

  17. Redox-controlled interaction of biferrocenyl-terminated dendrimers with beta-cyclodextrin molecular printboards.

    Science.gov (United States)

    Nijhuis, Christian A; Dolatowska, Karolina A; Ravoo, Bart Jan; Huskens, Jurriaan; Reinhoudt, David N

    2007-01-01

    This paper describes the synthesis and electrochemistry of biferrocenyl-terminated dendrimers and their beta-cyclodextrin (beta-CD) inclusion complexes in aqueous solution and at surfaces. Three generations of poly(propylene imine) (PPI) dendrimers, decorated with 4, 8, and 16 biferrocenyl (BFc) units, respectively, were synthesized. A water-soluble BFc derivative forms stable inclusion complexes with beta-CD. The intrinsic binding constant is K(i)=2.5 x 10(4) M(-1). The BFc dendrimers were solubilized in water by complexation of the end groups with beta-CD, resulting in large water-soluble supramolecular assemblies. Cyclic voltammetry (CV) and differential pulse voltammetry (DPV) showed that all the end groups are complexed to beta-CD. Adsorption of the dendrimers at self-assembled monolayers (SAMs) of heptathioether-functionalized beta-CD on gold ("molecular printboards") resulted in stable monolayers of the dendrimers due to the formation of multivalent host-guest interactions between the BFc end groups of the dendrimers and the immobilized beta-CD molecules. The number of interacting end groups is 3, 4, and 4 for dendrimer generations 1, 2, and 3, respectively. The complexation of BFc to beta-CD is sensitive to the oxidation state of the BFc unit. Oxidation of neutral BFc-Fe(2) ((II,II)) to the cationic, mixed-valence biferrocenium BFc-Fe(2) ((II,III)+) resulted in dissociation of the host-guest complexes. Scan-rate-dependent CV and DPV analyses of the dendrimer-beta-CD assemblies immobilized at the beta-CD host surface and in solution revealed that the dendrimers are oxidized in three steps. First, the surface-beta-CD-bound BFc moieties are oxidized to the mixed-valence state, Fe(2) ((II,III)+), followed by the oxidation of the non-surface-interacting BFc groups to the Fe(2) ((II,III)+) state. The third step involves the oxidation of all the BFc moieties to the Fe(2) ((III,III)2+) state.

  18. Magnetic, thermal and electronic properties of Ce{sub 11}Ni{sub 4}In{sub 9} and CeNi{sub 9}In{sub 2}

    Energy Technology Data Exchange (ETDEWEB)

    Szytuła, A., E-mail: andrzej.szytula@uj.edu.pl [Marian Smoluchowski Institute of Physics, Jagiellonian University, Reymonta 4, 30-059 Kraków (Poland); Baran, S.; Penc, B. [Marian Smoluchowski Institute of Physics, Jagiellonian University, Reymonta 4, 30-059 Kraków (Poland); Przewoźnik, J. [Department of Solid State Physics, Faculty of Physics and Applied Computer Science, AGH University of Science and Technology, Al. Mickiewicza 30, 30-059 Kraków (Poland); Winiarski, A. [August Chełkowski Institute of Physics, University of Silesia, Uniwersytecka 4, 40-007 Katowice (Poland); Tyvanchuk, Yu.; Kalychak, Ya.M. [Department of Analytical Chemistry, Ivan Franko National University of Lviv, Kyryla and Mephodiya 6, 79005 Lviv (Ukraine)

    2014-03-15

    Highlights: • Basis on the X-ray data the crystal structure of Ce{sub 11}Ni{sub 4}In{sub 9} and CeNi{sub 9}In{sub 2} compounds determined. • In Ce{sub 11}Ni{sub 4}In{sub 9} the Ce magnetic moments order at low temperatures, where in CeNi{sub 9}In{sub 2} not detected localized moment. • Magnetic and specific heat data of Ce{sub 11}Ni{sub 4}In{sub 9} indicate two phase transitions at 5 and 16.5 K. • XPS spectra indicate for both compounds sizable hybridization of the Ce4f electrons with conduction band. • For CeNi{sub 9}In{sub 2} the existence of Ce3d{sup 9}4f{sup 0} configuration indicates the mixed-valence state. -- Abstract: Crystal structure, magnetic, thermal and electronic properties of Ce{sub 11}Ni{sub 4}In{sub 9} and CeNi{sub 9}In{sub 2} compounds were investigated by means of X-ray diffraction, magnetic, calorimetric and X-ray photoelectron spectroscopy measurements. Ce{sub 11}Ni{sub 4}In{sub 9} crystallizes in the orthorhombic Nd{sub 11}Pd{sub 4}In{sub 9}-type structure (space group Cmmm) while CeNi{sub 9}In{sub 2} crystallizes in the YNi{sub 9}In{sub 2}-type structure (space group P4/mbm) (in which Ce atoms occupy only one Wyckoff position). Magnetic and specific heat measurements indicate that in Ce{sub 11}Ni{sub 4}In{sub 9} the Ce magnetic moment orders below 16.5 K, while in CeNi{sub 9}In{sub 2} it does not carry a localized moment. Our data indicate that Ni atoms are likely non-magnetic in both compounds. The XPS spectra of the valence band and the core-level are reported. The contributions to the density of states at E{sub F} are dominated by the Ni3d states. The XPS Ce3d data indicate sizable hybridization of the Ce-4f electrons with conduction band for both compounds. The existence in CeNi{sub 9}In{sub 2} of Ce3d{sup 9}4f{sup 0} configuration indicates a mixed-valence system. The core-level Ni2p{sub 3/2} spectra indicate incomplete Ni3d band filling in this compound.

  19. Redetermination of the crystal structure of catena-poly[[[bis(ethylenediamineplatinum(II]-μ-iodido-[bis(ethylenediamineplatinum(IV]-μ-iodido] tetrakis(octane-1-sulfonate dihydrate

    Directory of Open Access Journals (Sweden)

    Nobuyuki Matsushita

    2015-10-01

    Full Text Available The structure of the title compound, which represents a mixed-valence platinum(II,IV complex, {[PtIIPtIVI2(C2H8N24][CH3(CH27SO3]4·2H2O}n, has been redetermined in a different space group. In contrast to the previously reported determination in the space group P21cn [Matsushita & Taira (1999. Synth. Met. 102, 1787–1788], the current model was refined in the centrosymmetric space group Pmcn using the original diffraction data. The title compound has a linear chain structure composed of square-planar [Pt(en2]2+ and elongated octahedral trans-[PtI2(en2]2+ cations (en is ethylenediamine stacked alternately, bridged by the I atoms, parallel to the c axis. Inorganic layers aligned parallel to the bc plane, composed of the Pt-complex columns, the –SO3− part of the octane-1-sulfonate anion, and the water molecule of crystallization, are stacked alternately with organic layers composed of the long-chain alkyl groups along the a axis. The Pt and I sites are located on the same mirror plane whereby the I site is equally disordered over two positions. The Pt and I atoms form a slight zigzag ...I—PtIV—I...PtII... chain, with PtIV—I bond lengths of 2.6888 (17 and 2.7239 (17 Å, PtII...I contacts of 3.2065 (17 and 3.1732 (16 Å, and PtIV—I...PtII angles of 178.3 (3 and 176.7 (2°. The mixed-valence state of the Pt site is expressed by the structural parameter δ = (PtIV—I/(PtII...I, with values of 0.839 and 0.858 for the two independent I atoms. In the crystal, N—H...O hydrogen bonds involving the cationic chains, the sulfonate groups and water molecules of crystallization, stabilize the columnar structure.

  20. Insights into the Halogen Oxidative Addition Reaction to Dinuclear Gold(I) Di(NHC) Complexes

    KAUST Repository

    Baron, Marco

    2016-06-14

    Gold(I) dicarbene complexes [Au2(MeIm-Y-ImMe)2](PF6)2(Y=CH2(1), (CH2)2(2), (CH2)4(4), MeIm=1-methylimidazol-2-ylidene) react with iodine to give the mixed-valence complex [Au(MeIm-CH2-ImMe)2AuI2](PF6)2(1 aI) and the gold(III) complexes [Au2I4(MeIm-Y-ImMe)2](PF6)2(2 cIand 4 cI). Reaction of complexes 1 and 2 with an excess of ICl allows the isolation of the tetrachloro gold(III) complexes [Au2Cl4(MeIm-CH2-ImMe)2](PF6)2(1 cCl) and [Au2Cl4(MeIm-(CH2)2-ImMe)2](Cl)2(2 cCl-Cl) (as main product); remarkably in the case of complex 2, the X-ray molecular structure of the crystals also shows the presence of I-Au-Cl mixed-sphere coordination. The same type of coordination has been observed in the main product of the reaction of complexes 3 or 4 with ICl. The study of the reactivity towards the oxidative addition of halogens to a large series of dinuclear bis(dicarbene) gold(I) complexes has been extended and reviewed. The complexes react with Cl2, Br2and I2to give the successive formation of the mixed-valence gold(I)/gold(III) n aXand gold(III) n cX(excluding compound 1 cI) complexes. However, complex 3 affords with Cl2and Br2the gold(II) complex 3 bX[Au2X2(MeIm-(CH2)3-ImMe)2](PF6)2(X=Cl, Br), which is the predominant species over compound 3 cXeven in the presence of free halogen. The observed different relative stabilities of the oxidised complexes of compounds 1 and 3 have also been confirmed by DFT calculations. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. Magnetic ordering and conduction mechanism of different electroactive regions in Lu2NiMnO6

    Science.gov (United States)

    Chanda, Sadhan; Saha, Sujoy; Dutta, Alo; Krishna Murthy, J.; Venimadhav, A.; Shannigrahi, Santiranjan; Sinha, T. P.

    2016-10-01

    The magnetodielectric response of a double perovskite oxide Lu2NiMnO6 (LNMO) synthesised by the sol-gel process has been investigated. The Rietveld refinement of the X-ray diffraction data indicates that the room-temperature crystal structure of LNMO is monoclinic with the space group P21/n, which contains an ordered array of alternate MnO6 and NiO6 octahedra. X-ray photoelectron spectroscopy studies confirm the mix valence state of Mn (4+ and 3+) and Ni (2+ and 3+). The optical band gap (Eg = 1.56 eV) obtained from the UV-Visible absorption spectrum suggests that LNMO is a semiconductor. The field cooled and zero-field cooled measurements show the ferromagnetic behaviour of the sample with the transition temperature (Tc) = 45 K and a saturation magnetization of 5.2 μB/f.u. is observed at 2.5 K. The temperature and frequency dependent dielectric measurements reveal colossal values of the dielectric constant, which are interpreted by the Maxwell-Wagner interfacial polarization. The temperature dependence of the bulk dc conductivity indicates a variable-range-hopping mechanism. The saturation polarization value is estimated to be 232 μC/m2 from the pyroelectric current measurement. A negative magnetodielectric effect of 1% is observed at the paramagnetic to ferromagnetic transition temperature. The electronic structure calculations based on density functional theory have been performed to analyse the magnetic properties of LNMO.

  2. La0.67Pb0.33- x K x MnO3 perovskites synthesized by sol-gel method: the effect of potassium substitution on the magnetic and electrical properties

    Science.gov (United States)

    Zaidi, Asma; Alharbi, T.; Dhahri, J.; Alzobaidi, S.; Zaidi, M. A.; Hlil, E. K.

    2017-01-01

    The influence of the potassium substitution for Pb ions in the mixed valence perovskites La0.67Pb0.33- x K x MnO3 (0 ≤ x ≤ 0.15) was investigated by X-ray diffraction, magnetic and electric transport measurements. All the compositions were synthesized using the sol-gel technique. X-ray diffraction and structure refinement showed that they crystallize in the rhombohedral structure with R{bar{3}}c space group. Upon K doping on Pb sites, the lattice parameters, unit cell volume, and the Mn-O-Mn bond angle were reduced. All the samples exhibited a ferromagnetic-paramagnetic transition and metallic-semiconductor one with increasing temperature. The analysis of the electrical resistivity data concluded that the metallic (ferromagnetic) part of the resistivity (below T M-Sc) can be explained by the following equation ρ( T) = ρ 0 + ρ 2 T 2 + ρ 4.5 T 4.5, signifying the importance of the domain boundary/grain, combination of electron-magnon, electron-electron and electron-phonon scattering processes. At higher-temperature ( T > T M-Sc) paramagnetic semiconducting regime, the adiabatic small polarons hopping mechanism (ASPH) was found to fit well.

  3. Co{sub 3}O{sub 4}/TiO{sub 2} films obtained by laser ablation and sol-gel for the reaction of oxygen liberation in alkaline medium; Peliculas de Co{sub 3}O{sub 4}/TiO{sub 2} obtenidas por ablacion laser y sol-gel para la reaccion de desprendimiento de oxigeno en medio alcalino

    Energy Technology Data Exchange (ETDEWEB)

    Perez A, J.; Fernandez V, S. M.; Escobar A, L.; Jimenez B, J. [Departamento de Quimica, ININ, Carretera Mexico-Toluca s/n, Ocoyoacac, Estado de Mexico (Mexico)

    2008-07-01

    The laser ablation technique known as Pulsed Laser Deposition (PLD) is used for obtaining thin films of TiO{sub 2}/SnO{sub 2}, which was later modified with Co{sub 3}O{sub 4} by PLD or by sol-gel technique. The films were characterized by X-ray diffraction, ultraviolet Vis and Raman spectroscopies, scanning electron microscopy and energy analysis of the dispersed X-rays produced by Auger decay. The anatase phase with particles of nano metric size was obtained by depositing the titanium dioxide in argon atmosphere. The Co{sub 3}O{sub 4} films obtained by PLD on the TiO{sub 2} showed the same morphology. The electrocatalytic activity of the films that were used as photo anodes for the reaction of oxygen liberation was carried out in the darkness, with environment light and the light emitted by a xenon lamp. The current density was higher for films of Co{sub 3}O{sub 4}/TiO{sub 2}/SnO{sub 2} obtained by PLD that for cobalt dioxide of mixed valence obtained by sol-gel. (Author)

  4. XPS Studies of Yb14MnSb11 and Yb14ZnSb11

    Energy Technology Data Exchange (ETDEWEB)

    Holm, A P; Ozawa, T C; Kauzlarich, S M; Morton, S A; Waddill, G D; Pickett, W E; Tobin, J G

    2003-10-02

    Measurements of core and valence electronic states of single crystals of the rare earth transition metal Zintl phases Yb{sub 14}MnSb{sub 11} and Yb{sub 14}ZnSb{sub 11} were performed using the X-ray photoelectron spectroscopy station of Beamline 7 at the Advanced Light Source. Sample surfaces of Yb{sub 14}MnSb{sub 11} and Yb{sub 14}ZnSb{sub 11} were measured as received, after Ar{sup +} ion bombardment, and after cleaving in situ. Detailed analysis of the clean Mn and Zn analog sample surfaces reveal a significant contribution of both Yb{sup 3+} and Yb{sup 2+} 4f states in the valence band region for the Zn analog and no contribution of Yb{sup 3+} states to the valence band for the Mn analog. This result is predicted for the Zn analog by Zintl counting rules, and single crystal X-ray diffraction studies presented here also support the mixed valency of Yb for Yb{sub 14}ZnSb{sub 11}. Further detailed analysis of the core and valence band structure of both Yb{sub 14}MnSb{sub 11} and Yb{sub 14}ZnSb{sub 11} will be presented.

  5. Altering properties of cerium oxide thin films by Rh doping

    Energy Technology Data Exchange (ETDEWEB)

    Ševčíková, Klára, E-mail: klarak.sevcikova@seznam.cz [Faculty of Mathematics and Physics, Department of Surface and Plasma Science, Charles University in Prague, V Holešovičkách 2, 180 00 Prague 8 (Czech Republic); NIMS Beamline Station at SPring-8, National Institute for Materials Science, Sayo, Hyogo 679-5148 (Japan); Nehasil, Václav, E-mail: nehasil@mbox.troja.mff.cuni.cz [Faculty of Mathematics and Physics, Department of Surface and Plasma Science, Charles University in Prague, V Holešovičkách 2, 180 00 Prague 8 (Czech Republic); Vorokhta, Mykhailo, E-mail: vorohtam@gmail.com [Faculty of Mathematics and Physics, Department of Surface and Plasma Science, Charles University in Prague, V Holešovičkách 2, 180 00 Prague 8 (Czech Republic); Haviar, Stanislav, E-mail: stanislav.haviar@gmail.com [Faculty of Mathematics and Physics, Department of Surface and Plasma Science, Charles University in Prague, V Holešovičkách 2, 180 00 Prague 8 (Czech Republic); Matolín, Vladimír, E-mail: matolin@mbox.troja.mff.cuni.cz [Faculty of Mathematics and Physics, Department of Surface and Plasma Science, Charles University in Prague, V Holešovičkách 2, 180 00 Prague 8 (Czech Republic); and others

    2015-07-15

    Highlights: • Thin films of ceria doped by rhodium deposited by RF magnetron sputtering. • Concentration of rhodium has great impact on properties of Rh–CeO{sub x} thin films. • Intensive oxygen migration in films with low concentration of rhodium. • Oxygen migration suppressed in films with high amount of Rh dopants. - Abstract: Ceria containing highly dispersed ions of rhodium is a promising material for catalytic applications. The Rh–CeO{sub x} thin films with different concentrations of rhodium were deposited by RF magnetron sputtering and were studied by soft and hard X-ray photoelectron spectroscopies, Temperature programmed reaction and X-ray powder diffraction techniques. The sputtered films consist of rhodium–cerium mixed oxide where cerium exhibits a mixed valency of Ce{sup 4+} and Ce{sup 3+} and rhodium occurs in two oxidation states, Rh{sup 3+} and Rh{sup n+}. We show that the concentration of rhodium has a great influence on the chemical composition, structure and reducibility of the Rh–CeO{sub x} thin films. The films with low concentrations of rhodium are polycrystalline, while the films with higher amount of Rh dopants are amorphous. The morphology of the films strongly influences the mobility of oxygen in the material. Therefore, varying the concentration of rhodium in Rh–CeO{sub x} thin films leads to preparing materials with different properties.

  6. On the transport properties of the solid solution Sr 1- xLa xPbO 3- δ (0 ⩽ x ⩽ 0.15)

    Science.gov (United States)

    Hadjarab, B.; Bassaid, S.; Bouguelia, A.; Trari, M.

    2006-06-01

    Mixed valencies system Sr 1- xLa xPbO 3- δ (0 ⩽ x ⩽ 0.15) has been prepared by solid state reaction at 900 °C. All solutions crystallize in a distorted perovskite structure and were carefully examined by chemical analysis and X-ray diffraction. The La 3+-substitution was checked via the linear dependence of lattice constants on x-value, i.e. Vegard’s law. The expansion of the unit cell volume involves a simultaneous increase of all the parameters. The magnetic susceptibilities are slightly temperature dependent, dominated by core diamagnetism giving an effective mass m∗ of ∼9. The transport properties were investigated from 300 K down to liquid helium. The resistivity was found to change markedly with the rate substitution x and the oxides behave as degenerate semi-conductors with very weak activation energies. The insulating-metal transition can thus be considered of Anderson type attributed to random potential as lanthanum is substituted for strontium. The electric balance comes also from departure of oxygen and would imply a simultaneous reduction Pb 4+/2+. The electron mobility is thermally activated with a temperature independent carrier concentration.

  7. On the transport properties of the solid solution Sr{sub 1-x}La {sub x}PbO{sub 3-{delta}} (0 {<=} x {<=} 0.15)

    Energy Technology Data Exchange (ETDEWEB)

    Hadjarab, B. [Laboratoire des Solutions Solides Faculte de Physique, USTHB BP 32, 16111 Algiers (Algeria); Bassaid, S. [Laboratoire de Stockage et de Valorisation des Energies Renouvelables, Faculte de Chimie USTHB BP32, 16111 Algiers (Algeria); Bouguelia, A. [Laboratoire de Stockage et de Valorisation des Energies Renouvelables, Faculte de Chimie USTHB BP32, 16111 Algiers (Algeria); Trari, M. [Laboratoire de Stockage et de Valorisation des Energies Renouvelables, Faculte de Chimie USTHB BP32, 16111 Algiers (Algeria)]. E-mail: mtrari@caramail.com

    2006-06-15

    Mixed valencies system Sr{sub 1-x}La {sub x}PbO{sub 3-{delta}} (0 {<=} x {<=} 0.15) has been prepared by solid state reaction at 900 {sup o}C. All solutions crystallize in a distorted perovskite structure and were carefully examined by chemical analysis and X-ray diffraction. The La{sup 3+}-substitution was checked via the linear dependence of lattice constants on x-value, i.e. Vegard's law. The expansion of the unit cell volume involves a simultaneous increase of all the parameters. The magnetic susceptibilities are slightly temperature dependent, dominated by core diamagnetism giving an effective mass m * of {approx}9. The transport properties were investigated from 300 K down to liquid helium. The resistivity was found to change markedly with the rate substitution x and the oxides behave as degenerate semi-conductors with very weak activation energies. The insulating-metal transition can thus be considered of Anderson type attributed to random potential as lanthanum is substituted for strontium. The electric balance comes also from departure of oxygen and would imply a simultaneous reduction Pb{sup 4+/2+}. The electron mobility is thermally activated with a temperature independent carrier concentration.

  8. Eu valence and Fermi-surface development in EuX{sub 2}Si{sub 2} (X = Co, Rh, Ir) systems

    Energy Technology Data Exchange (ETDEWEB)

    Goetze, K. [Hochfeld-Magnetlabor Dresden, Helmholtz-Zentrum Dresden-Rossendorf (Germany); TU Dresden, Institut fuer Festkoerperphysik (Germany); Seiro, S.; Geibel, C.; Rosner, H.; Petzold, V. [MPI for Chemical Physics of Solids (Germany); Polyakov, A.; Wosnitza, J. [Hochfeld-Magnetlabor Dresden, Helmholtz-Zentrum Dresden-Rossendorf (Germany); Sheikin, I. [LNCMI-Grenoble (France); Suslov, A. [National High Magnetic Field Laboratory, Tallahassee (United States)

    2013-07-01

    The valence-fluctuating Eu systems EuX{sub 2}Si{sub 2}, with X being the transition metal Co, Ir, or Rh, show different types of ground states, strongly depending on X. The instability of the Eu 4f shell underlies this phenomenon and leads among other effects to different valence states ranging from Eu{sup 2+} over mixed valence and intermediate valence behavior to Eu{sup 3+}. Investigations on the structure and the magnetic behavior of EuCo{sub 2}Si{sub 2}, EuIr{sub 2}Si{sub 2}, and EuRh{sub 2}Si{sub 2} have revealed their Eu valence. Further experiments on specific heat and resistivity gave insights to magnetic ordering, electronic correlations, and possible valence fluctuations. We report about a systematic de Haas-van Alphen study on the Fermi-surface development of the EuX{sub 2}Si{sub 2} compounds in magnetic fields up to 35 T. High-quality single crystals were available for the first time. We focus on the Fermi-surface topology obtained by angle dependent measurements and discuss a comparison to band-structure calculations.

  9. Local electronic structure and ferromagnetic interaction in La(Co,Ni)O3

    Science.gov (United States)

    Huang, Meng-Jie; Nagel, Peter; Fuchs, Dirk; von Loehneysen, Hilbert; Merz, Michael; Schuppler, Stefan

    Perovskite-related transition-metal oxides exhibit a wide range of properties from insulating to superconducting as well as many peculiar magnetic phases, and cobaltites, in particular, have been known for their proximity to spin-state transitions. How this changes with partial substitution by Ni is the topic of the present study. The local electronic structure and the ferromagnetic interaction in La(Co1-xNix) O3 has been studied by x-ray absorption (XAS) and x-ray magnetic circular dichroism (XMCD). XAS clearly indicates a mixed-valence state for both Co and Ni, with both valences changing systematically with Ni content, x. While the gradual spin-state transition of Co3+ from low-spin (LS) to high-spin (HS) is preserved for low x it is suppressed in the high Ni-content samples. Regarding the spin configuration of Ni we find it stabilized in a ``mixed'' spin state, unlike the purely LS state of Ni in LaNiO3. XMCD identifies the element-specific contributions to the magnetic moment and interactions. In particular, we find that it must be the coexistence of the HS state in both Co3+ and Ni3 + that induces t2 g-based ferromagnetic interaction via the double-exchange mechanism.

  10. Theory of low energy excitations in resonant inelastic x-ray scattering for rare-earth systems: Yb compounds as typical examples

    Science.gov (United States)

    Kotani, A.

    2011-04-01

    Theoretical predictions are given for low energy excitations, such as crystal field excitations and Kondo resonance excitations, to be detected by high-resolution measurements of resonant inelastic x-ray scattering (RIXS) of rare-earth materials with Yb compounds as typical examples. Crystal field excitations in the Yb 3d RIXS of a Yb3+ ion in the cubic crystal field are formulated, and the calculation of RIXS spectra for YbN is done. Kondo resonance excitations revealed in the Yb 3d RIXS spectra are calculated for mixed-valence Yb compounds, Yb1-xLuxAl3, in the leading term approximation of the 1/Nf expansion method with a single impurity Anderson model. It is emphasized that the high-resolution RIXS with polarization dependence is a powerful tool to study the crystal field levels together with their symmetry and also the Kondo bound state in rare-earth compounds. Some in-depth discussions are given on the polarization effects of RIXS, including 4d and 2p RIXS spectra, the coherence effect of the Kondo bound states, and the importance of the high-resolution RIXS spectra for condensed matter physics under extreme conditions.

  11. Thermal and chemical decomposition of di(pyrazine)silver(II) peroxydisulfate and unusual crystal structure of a Ag(I) by-product.

    Science.gov (United States)

    Leszczyński, Piotr J; Budzianowski, Armand; Dobrzycki, Lukasz; Cyrański, Michał K; Derzsi, Mariana; Grochala, Wojciech

    2012-01-14

    High purity samples of a [Ag(pyrazine)(2)]S(2)O(8) complex were obtained using modified synthetic pathways. Di(pyrazine)silver(II) peroxydisulfate is sensitive to moisture forming [Ag(pyrazine)(2)](S(2)O(8))(H(2)O) hydrate which degrades over time yielding HSO(4)(-) derivatives and releasing oxygen. One polymorphic form of pyrazinium hydrogensulfate, β-(pyrazineH(+))(HSO(4)(-)), is found among the products of chemical decomposition together with unique [Ag(i)(pyrazine)](5)(H(2)O)(2)(HSO(4))(2)[H(SO(4))(2)]. Chemical degradation of [Ag(pyrazine)(2)]S(2)O(8) in the presence of trace amounts of moisture can explain the very low yield of wet synthesis (11-15%). Attempts have failed to obtain a mixed valence Ag(II)/Ag(I) pyrazine complex via partial chemical reduction of the [Ag(pyrazine)(2)]S(2)O(8) precursor with a variety of inorganic and organic reducing agents, or via controlled thermal decomposition. Thermal degradation of [Ag(pyrazine)(2)]S(2)O(8) containing occluded water proceeds at T > 90 °C via evolution of O(2); simultaneous release of pyrazine and SO(3) is observed during the next stages of thermal decomposition (120-285 °C), while Ag(2)SO(4) and Ag are obtained upon heating to 400-450 °C.

  12. The Intriguing Properties of Transition Metal Oxides

    Science.gov (United States)

    Hoch, Michael J. R.

    2007-05-01

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

  13. Mental Imagery-Based Training to Modify Mood and Cognitive Bias in Adolescents: Effects of Valence and Perspective.

    Science.gov (United States)

    Burnett Heyes, S; Pictet, A; Mitchell, H; Raeder, S M; Lau, J Y F; Holmes, E A; Blackwell, S E

    2017-01-01

    Mental imagery has a powerful impact on emotion and cognitive processing in adults, and is implicated in emotional disorders. Research suggests the perspective adopted in mental imagery modulates its emotional impact. However, little is known about the impact of mental imagery in adolescence, despite adolescence being the key time for the onset of emotional dysfunction. We administered computerised positive versus mixed valence picture-word mental imagery training to male adolescent participants (N = 60, aged 11-16 years) across separate field and observer perspective sessions. Positive mood increased more following positive than mixed imagery; pleasantness ratings of ambiguous pictures increased following positive versus mixed imagery generated from field but not observer perspective; negative interpretation bias on a novel scrambled sentences task was smaller following positive than mixed imagery particularly when imagery was generated from field perspective. These findings suggest positive mental imagery generation alters mood and cognition in male adolescents, with the latter moderated by imagery perspective. Identifying key components of such training, such as imagery perspective, extends understanding of the relationship between mental imagery, mood, and cognition in adolescence.

  14. Synthesis, crystal structure, and photocatalytical properties of Ba{sub 3}Ta{sub 5}O{sub 14}N

    Energy Technology Data Exchange (ETDEWEB)

    Anke, B. [Institut für Chemie, Technische Universität Berlin, Straße des 17. Juni 135, 10623 Berlin (Germany); Bredow, T. [Mulliken Center for Theoretical Chemistry, Institut für Physikalische und Theoretische Chemie, Universität Bonn, Beringstr. 4, 53115 Bonn (Germany); Soldat, J. [Lehrstuhl für Technische Chemie, Ruhr-Universität Bochum, Universitätsstr. 150, 44801 Bochum (Germany); Institut für Chemie, Carl von Ossietzky Universität Oldenburg, Carl-von-Ossietzky-Str. 9-11, 26129 Oldenburg (Germany); Wark, M. [Institut für Chemie, Carl von Ossietzky Universität Oldenburg, Carl-von-Ossietzky-Str. 9-11, 26129 Oldenburg (Germany); Lerch, M. [Institut für Chemie, Technische Universität Berlin, Straße des 17. Juni 135, 10623 Berlin (Germany)

    2016-01-15

    Light yellow Ba{sub 3}Ta{sup V}{sub 5}O{sub 14}N was successfully synthesized as phase-pure material crystallizing isostructurally to well-known mixed-valence Ba{sub 3}Ta{sup V}{sub 4}Ta{sup IV}O{sub 15}. The electronic structure of Ba{sub 3}Ta{sub 5}O{sub 14}N was studied theoretically with a hybrid Hartree–Fock-DFT method. The most stable structure was obtained when nitrogen atoms were placed at 4 h sites having fourfold coordination. By incorporating nitrogen, the band gap decreases from ∼3.8 eV commonly known for barium tantalum(V) oxides to 2.8 eV for the oxide nitride, giving rise to an absorption band well in the visible-light region. Ba{sub 3}Ta{sub 5}O{sub 14}N was also tested for photocatalytic hydrogen formation. - Graphical abstract: Ta(O/N){sub 6} octahedra in Ba{sub 3}Ta{sub 5}O{sub 14}N with the determined bond lengths (Å).

  15. Morphology-controlled synthesis and electrochemical performance of NiCo{sub 2}O{sub 4} as anode material in lithium-ion battery application

    Energy Technology Data Exchange (ETDEWEB)

    Xu, Shan; Lu, Lin; Zhang, Qing; Zheng, Hao; Liu, Lian; Yin, Shengyu; Wang, Shiquan, E-mail: wsqhao@126.com; Li, Guohua; Feng, Chuanqi [Hubei University, Hubei Collaborative Innovation Center for Advanced Organic Chemical Materials, Ministry-of-Education Key Laboratory for Synthesis and Applications of Organic Functional Molecules (China)

    2015-09-15

    Mixed-valence oxide precursors were synthesized by a solvothermal method using NiSO{sub 4}, CoSO{sub 4}, and NH{sub 4}HCO{sub 3} as raw materials. The precursors were heat-treated in a muffle furnace at 500 °C to obtain the products (NiCo{sub 2}O{sub 4}). The samples were characterized by X-ray diffractometer, thermogravimetric, energy-dispersive spectroscopy, scanning electron microscopy, and transmission electron microscopy. The results show that dumbbells, microspheres, and particle-like NiCo{sub 2}O{sub 4} were successfully synthesized by changing the volume of solvent and solvothermal temperature. The NiCo{sub 2}O{sub 4} microspheres (prepared at 180 °C with 30 ml solvent) as anode material for lithium-ion battery, exhibit a reversible discharge capacity of 1160 mAh g{sup −1} and good cycling stability (729 mAh g{sup −1} after 50 cycles) at a constant current of 100 mA g{sup −1} in the voltage range of 0.01–3.0 V due to its high crystallinity and uniform porous morphology. Hence, the synthetic method could be extended to other high-capacity ternary metal oxide materials for lithium-ion battery application.

  16. Intervalence Charge Transfer luminescence: The anomalous luminescence of Cerium-doped Cs2LiLuCl6 elpasolite

    CERN Document Server

    Seijo, Luis

    2014-01-01

    The existence of intervalence charge transfer (IVCT) luminescence is reported. It is shown that the so called anomalous luminescence of Ce-doped elpasolite Cs2LiLuCl6, which is characterized mainly by a very large Stokes shift and a very large band width, corresponds to an IVCT emission in Ce3+-Ce4+ pairs, from the 5deg orbital of Ce3+ to 4f orbitals of Ce4+. Its Stokes shift is the sum of the large reorganization energies of the Ce4+ and Ce3+ centers formed after the fixed-nuclei electron transfer and it is equal to the energy of the IVCT absorption commonly found in mixed-valence compounds, which is predicted to exist in this material and to be slightly larger than 10000 cm-1. The large band width is the consequence of the large offset between the minima of the Ce3+-Ce4+ and Ce4+-Ce3+ pairs along the electron transfer reaction coordinate. This offset is approximately 2*sqrt(3) times the difference of Ce-Cl equilibrium distances in the Ce3+ and Ce4+ centers. It is shown that the energies of the peaks and the...

  17. Moessbauer studies of perovskite Gd sub 0 sub . sub 5 Sr sub 0 sub . sub 5 FeO sub 3 sub - sub y

    CERN Document Server

    Kim, C S; Sur, J C

    2000-01-01

    Perovskite powder Gd sub 0 sub . sub 5 Sr sub 0 sub . sub 5 FeO sub 3 sub - sub y was studied by X-ray diffraction, Moessbauer spectroscopy, vibrating samples magnetometry, and Mohr's salt analysis. Gd sub 0 sub . sub 5 Sr sub 0 sub . sub 5 FeO sub 3 sub - sub y was synthesized by using the solid-solid reaction method. The crystal structure was found to be orthorhombic with lattice parameters, a sub 0 =5.531 A, b sub 0 =5.608 A and c sub 0 =7.724 A. Moessbauer spectra of Gd sub 0 sub . sub 5 Sr sub 0 sub . sub 5 FeO sub 3 sub - sub y have been taken at various temperatures ranging from 4.2 to 600 K. The spectrum pattern at 4.2 K consisted of four sets of six Lorentzians, and the magnetic hyperfine fields are found to be 275, 486, 514 and 540 kOe. The Neel temperature, T sub N , was found to be 478 K. Mohr's salt analysis for Gd sub 0 sub . sub 5 Sr sub 0 sub . sub 5 FeO sub 3 sub - sub y demonstrated the existence of the mixed valence states, Fe sup 3 sup + (73%) and Fe sup 4 sup + (27%), and y=0.11 at room t...

  18. Antisite disorder driven spontaneous exchange bias effect in La2-x Sr x CoMnO6 (0  ⩽  x  ⩽  1)

    Science.gov (United States)

    Krishna Murthy, J.; Chandrasekhar, K. D.; Wu, H. C.; Yang, H. D.; Lin, J. Y.; Venimadhav, A.

    2016-03-01

    Doping at the rare-earth site by divalent alkaline-earth ions in perovskite lattice has witnessed a variety of magnetic and electronic orders with spatially correlated charge, spin and orbital degrees of freedom. Here, we report an antisite disorder driven spontaneous exchange bias effect as a result of hole carrier (Sr2+) doping in La2-x Sr x CoMnO6 (0  x  perovskites. X-ray diffraction and Raman spectroscopy have evidenced an increase in disorder with the increase of Sr content up to x  =  0.5 and thereby a decrease from x  =  0.5 to 1. X-ray absorption spectroscopy has revealed that only Co is present in the mixed valence of Co2+ and Co3+ states with Sr doping to compensate the charge neutrality. Magnetotransport is strongly correlated with the increase of antisite disorder. The antisite disorder at the B-site interrupts the long-range ferromagnetic order by introducing various magnetic interactions and instigates reentrant glassy dynamics, phase separation and canted type antiferromagnetic behavior with the decrease of temperature. This leads to a novel magnetic microstructure with unidirectional anisotropy that causes a spontaneous exchange bias effect that can be tuned with the amount of antisite disorder.

  19. Structural and magnetic investigation of Ca2MnReO6 doped with Ce

    Directory of Open Access Journals (Sweden)

    J. B. Depianti

    2013-06-01

    Full Text Available We have studied the properties of Ce doping in Ca-site of Ca2MnReO6 double perovskite up to 10%. These compounds have presented a monoclinic cell with P2(1/n space group. A small increase of lattice parameters in doped sample were observed through Rietveld refinement of X-ray diffraction pattern. The spectra at the Mn K-edge and Re L3-edge showed a mixed valence for Mn and Re in both samples. We do not observed any variation on Mn K-edge valence in XANES measurements under pressure. However a change was observed for Re L3-edge as a function of applied pressure. The Ce-doped sample showed a magnetic geometric frustration and a small decrease of the temperature frustration as compared with Ca2MnReO6 sample. The decrease of temperature frustration can be related to the MnO6 and ReO6 octahedral distortion.

  20. Correlation between vacancies and magnetoresistance changes in FM manganites using the Monte Carlo method

    Science.gov (United States)

    Agudelo-Giraldo, J. D.; Restrepo-Parra, E.; Restrepo, J.

    2015-10-01

    The Metropolis algorithm and the classical Heisenberg approximation were implemented by the Monte Carlo method to design a computational approach to the magnetization and resistivity of La2/3Ca1/3MnO3, which depends on the Mn ion vacancies as the external magnetic field increases. This compound is ferromagnetic, and it exhibits the colossal magnetoresistance (CMR) effect. The monolayer was built with L×L×d dimensions, and it had L=30 umc (units of magnetic cells) for its dimension in the x-y plane and was d=12 umc in thickness. The Hamiltonian that was used contains interactions between first neighbors, the magnetocrystalline anisotropy effect and the external applied magnetic field response. The system that was considered contains mixed-valence bonds: Mn3+eg'-O-Mn3+eg, Mn3+eg-O-Mn4+d3 and Mn3+eg'-O-Mn4+d3. The vacancies were placed randomly in the sample, replacing any type of Mn ion. The main result shows that without vacancies, the transitions TC (Curie temperature) and TMI (metal-insulator temperature) are similar, whereas with the increase in the vacancy percentage, TMI presented lower values than TC. This situation is caused by the competition between the external magnetic field, the vacancy percentage and the magnetocrystalline anisotropy, which favors the magnetoresistive effect at temperatures below TMI. Resistivity loops were also observed, which shows a direct correlation with the hysteresis loops of magnetization at temperatures below TC.

  1. Self-assembly of novel hierarchical flowers-like Sn3O4 decorated on 2D graphene nanosheets hybrid as high-performance anode materials for LIBs

    Science.gov (United States)

    Chen, Xuefang; Huang, Ying; Li, Tianpeng; Wei, Chao; Yan, Jing; Feng, Xuansheng

    2017-05-01

    Novel hierarchical flower-like Sn3O4 assembled by thin Sn3O4 nanosheets, as a kind of mixed-valence tin oxide, decorated on two-dimensional graphene nanosheets has been synthesized via a hydrothermal route and a step solution deoxidization technique. More importantly, as the anode materials for lithium ion batteries, the flower-like Sn3O4/graphene composite has not been investigated in detail. Noticeably, the nanosheets stemming from flower-like Sn3O4 and graphene have been linked together to form a specials three dimensional structure, possessing high active surface area and large enough inner spaces, which is benefit to the diffusion of liquid electrolyte into the electrode materials. In addition, the special structure could provide sufficient free volume to buffer the volume expansion appeared in the process of discharging and charging. The as-prepared flowers-like Sn3O4/graphene displayed excellent electrochemical performance with high capacity and good cycling stability as anode materials for lithium ion batteries. The discharge capacity is 1727 mAh/g in the first cycle at the current density of 60 mA/g. The obtained reversible capacity is 631mAh/g with a coulomb efficiency of 97.04% after 50 cycles. With its better electrochemical properties, the as-prepared flowers-like Sn3O4/graphene has the potential to be the next generation materials as an environmentally benign, abundant, cheap anode materials for lithium ion batteries.

  2. Study on visible emission of Cu-ion-doped perovskite hafnate in view of excitation energy dependence

    Energy Technology Data Exchange (ETDEWEB)

    Lee, D. J.; Lee, Y. S. [Soongnsil University, Seoul (Korea, Republic of); Noh, H. J. [Chonnam National University, Gwangju (Korea, Republic of)

    2015-12-15

    We studied on the visible emission of Cu-ion-doped perovskite hafnate SrHfO{sub 3} (SHO:Cu) with the photo-excitation energy dependence. The polycrystalline SHO:Cu samples were newly synthesized in the solid state reaction method. From the X-ray diffraction measurement it was found that the crystalline structure of SHO:Cu is nearly identical to that of undoped SrHfO{sub 3}. Interestingly, the photoluminescence excitation (PLE) spectra change significantly with the emission energy, which is linked to the strong dependence of the visible emission on the photo-excitation energy. This unusual emission behavior is likely to be associated with the mixed valence states of the doped Cu ions, which were revealed by X-ray photoelectron spectroscopy. We compared our finding of tunable visible emission in the SHO:Cu compounds with the cases of similar materials, SrTiO{sub 3} and SrZrO{sub 3} with Cu-ion-doping.

  3. Preparation and characterization of a reduced chromium complex via vinyl oxidative coupling: formation of a self-activating catalyst for selective ethylene trimerization.

    Science.gov (United States)

    Albahily, Khalid; Fomitcheva, Valeria; Gambarotta, Sandro; Korobkov, Ilia; Murugesu, Muralee; Gorelsky, Serge I

    2011-04-27

    Reaction of the divalent [(t-Bu)NP(Ph)(2)N(t-Bu)]CrCl(2)Li(THF)(2) (1) with 1 equiv of vinyl Grignard (CH(2)=CH)MgCl reproducibly afforded the triangulo {π-[(t-Bu)N-P(Ph)(2)-N(t-Bu)]Cr}(2)(μ,μ',η(4),η(4)'-C(4)H(4)){σ-[(t-Bu)N-P(Ph)(2)-N(t-Bu)]Cr} (2) containing a σ-/π-bonded butadiene-diyl unit. The diene-diyl moiety was generated by an oxidative coupling and deprotonation of two vinyl anions. The crystal structure revealed that of the three chromium atoms, each bearing one NPN ligand, two are perpendicularly bonded to the two sides of the π-system of the butadiene-diyl residue in a sort of inverted sandwich type of structure. The third is instead coplanar with the doubly deprotonated C(4) unit and σ-bonded to the two terminal carbon atoms. Despite the appearance as a Cr(II)/Cr(I) mixed valence species, DFT calculations have revealed that the structure of 2 consists of three divalent chromium atoms, while the additional electron resides on the π-system of the bridging organic residue. Complex 2 behaves as a single component selective catalyst for ethylene trimerization.

  4. Synthesis, characterisation and computational studies on a novel one-dimensional arrangement of Schiff-base Mn3 single-molecule magnet.

    Science.gov (United States)

    Lin, Po-Heng; Gorelsky, Serge; Savard, Didier; Burchell, Tara J; Wernsdorfer, Wolfgang; Clérac, Rodolphe; Murugesu, Muralee

    2010-09-07

    The syntheses, structures and magnetic properties are reported for three new manganese complexes containing the Schiff-base ((2-hydroxy-3-methoxyphenyl)methylene)isonicotinohydrazine (H(2)hmi) ligand. Complex [Mn(II)(H(2)hmi)(2)(MeOH)(2)Cl(2)] (1) was obtained from the reaction of H(2)hmi with MnCl(2) in a MeOH-MeCN mixture. Addition of triethylamine to the previous reaction mixture followed by diethyl ether diffusion yielded a dinuclear manganese [Mn(III)(2)(hmi)(2)(OMe)(2)](infinity).2MeCN.2OEt(2) (2) compound. Upon increasing the MnCl(2)/H(2)hmi ratio, the mixed valence complex [Mn(III)(2)Mn(II)(hmi)(2)(OMe)(2)Cl(2)](infinity).MeOH (3) was obtained. Dc and ac magnetic measurements were carried out on all three samples. The ac susceptibility and field dependence of the magnetisation measurements confirmed that complex 3 exhibits a single-molecule magnet behaviour with an effective energy barrier of 8.1 K and an Arrhenius pre-exponential factor of 3 x 10(-9) s.

  5. Anisotropic imprint of amorphization and phase separation in manganite thin films via laser interference irradiation

    KAUST Repository

    Ding, Junfeng

    2014-09-16

    Materials with mesoscopic structural and electronic phase separation, either inherent from synthesis or created via external means, are known to exhibit functionalities absent in the homogeneous counterparts. One of the most notable examples is the colossal magnetoresistance discovered in mixed-valence manganites, where the coexistence of nano-to micrometer-sized phase-separated domains dictates the magnetotransport. However, it remains challenging to pattern and process such materials into predesigned structures and devices. In this work, a direct laser interference irradiation (LII) method is employed to produce periodic stripes in thin films of a prototypical phase-separated manganite Pr0.65(Ca0.75Sr0.25)0.35MnO3 (PCSMO). LII induces selective structural amorphization within the crystalline PCSMO matrix, forming arrays with dimensions commensurate with the laser wavelength. Furthermore, because the length scale of LII modification is compatible to that of phase separation in PCSMO, three orders of magnitude of increase in magnetoresistance and significant in-plane transport anisotropy are observed in treated PCSMO thin films. Our results show that LII is a rapid, cost-effective and contamination-free technique to tailor and improve the physical properties of manganite thin films, and it is promising to be generalized to other functional materials.

  6. Synthesis, structure and properties of oxalato and thio-oxalato molecule based magnets

    CERN Document Server

    Bradley, J M

    2001-01-01

    A number of techniques have been used to investigate the structure and magnetic properties of a range of materials based on transition metal complexes of the oxalate (C sub 2 O sub 4 sup 2 sup -) and dithio-oxalate (C sub 2 S sub 2 O sub 2 sup 2 sup -) ions. Structural studies were carried out using X ray and neutron diffraction. Magnetic properties were studied using DC magnetisation, neutron diffraction, muon spin relaxation and Mossbauer spectroscopy. Supporting evidence for structural studies was also gained from extended X ray absorption fine structure (EXAFS). The materials studied are all mixed valence transition metal compounds with general formula AM sup I sup I M sup I sup I sup I (L) sub 3 (A = NR sub 4 sup + , PPh sub 4 sup +), M sup I sup I = Cr,Mn,Fe,Ni,Co, M sup I sup I sup I = Cr,Fe and L C sub 2 O sub 4 sup 2 sup - , C sub 2 S sub 2 O sub 2 sup 2 sup - , in which the metals are linked by either the oxalate or dithio-oxalate ligand to give 2 dimensional honeycomb lattices. These sheets are sep...

  7. Barrier-free proton transfer in the valence anion of 2'-deoxyadenosine-5'-monophosphate. II. A computational study.

    Science.gov (United States)

    Kobyłecka, Monika; Gu, Jiande; Rak, Janusz; Leszczynski, Jerzy

    2008-01-28

    The propensity of four representative conformations of 2(')-deoxyadenosine-5(')-monophosphate (5(')-dAMPH) to bind an excess electron has been studied at the B3LYP6-31++G(d,p) level. While isolated canonical adenine does not support stable valence anions in the gas phase, all considered neutral conformations of 5(')-dAMPH form adiabatically stable anions. The type of an anionic 5(')-dAMPH state, i.e., the valence, dipole bound, or mixed (valence/dipole bound), depends on the internal hydrogen bond(s) pattern exhibited by a particular tautomer. The most stable anion results from an electron attachment to the neutral syn-south conformer. The formation of this anion is associated with a barrier-free proton transfer triggered by electron attachment and the internal rotation around the C4(')-C5(') bond. The adiabatic electron affinity of the a_south-syn anion is 1.19 eV, while its vertical detachment energy is 1.89 eV. Our results are compared with the photoelectron spectrum (PES) of 5(')-dAMPH(-) measured recently by Stokes et al., [J. Chem. Phys. 128, 044314 (2008)]. The computational VDE obtained for the most stable anionic structure matches well with the experimental electron binding energy region of maximum intensity. A further understanding of DNA damage might require experimental and computational studies on the systems in which purine nucleotides are engaged in hydrogen bonding.

  8. A temperature-induced absorption band centered in the region of 666 nm related to the configuration of the active site in frozen cytochrome oxidase.

    Science.gov (United States)

    Denis, M; Clore, G M

    1979-03-15

    The existence of a temperature-induced absorption band centred in the region of 666 nm is demonstrated for both membrane-bound and soluble cytochrome oxidase in the frozen state. The 666 nm band is generated solely by an increase in temperature of both fully reduced and mixed valence state cytochrome oxidase in the presence of CO or O2 within the 'pocket' containing the active site; it is not formed in the absence of both CO and O2 from the sample. The formation of the 666 nm band is entirely reversible when the temperature is decreased again and its formation is not dependent on the presence of liganded CO at the sixth coordination site of haem a3 in the low temperature range (below --120 degrees C) prior to photolysis. The shape and intensity of the 666 nm band are not affected by the extent of CO recombination following flash and photolysis and temperature increase and are not affected by changes in the valence states of the four metal centres when the O2 reaction is in progress.

  9. Magnetic interactions in La{sub 0.7}Sr{sub 0.3}Mn{sub 1−x}Me{sub x}O{sub 3} (Me=Ga, Fe, Cr) manganites

    Energy Technology Data Exchange (ETDEWEB)

    Troyanchuk, I.O., E-mail: troyan@physics.by [Scientific-Practical Materials Research Centre of NAS of Belarus, P. Brovki str. 19, 220072 Minsk (Belarus); Bushinsky, M.V.; Karpinsky, D.V.; Tereshko, N.V. [Scientific-Practical Materials Research Centre of NAS of Belarus, P. Brovki str. 19, 220072 Minsk (Belarus); Dobryansky, V.M. [Belarussian State Agrarian Technical University, Nezavisimosti av. 99, 220023 Minsk (Belarus); Többens, D.M. [Helmholt-Zentrum Berlin, Hahn-Meitner-Platz 1, 14109 Berlin (Germany); Sikolenko, V. [Helmholt-Zentrum Berlin, Hahn-Meitner-Platz 1, 14109 Berlin (Germany); Joint Institute for Nuclear Research, Joliot-Curie 6, 141980 Dubna (Russian Federation); Efimov, V. [Joint Institute for Nuclear Research, Joliot-Curie 6, 141980 Dubna (Russian Federation)

    2015-11-15

    Magnetic properties and crystal structure of La{sub 0.7}Sr{sub 0.3}Mn{sub 1−x}Me{sub x}O{sub 3} (Me=Ga, Fe, Cr; x≤0.3) have been studied by neutron powder diffraction and magnetization measurements. It is shown that substitution of manganese ions by chromium or gallium ions (x=0.3) leads to phase separation into antiferromagnetic and ferromagnetic phases whereas replacement by Fe ions stabilizes spin glass state (x=0.3). Ferromagnetic interactions in Cr-substituted compounds are much more pronounced than in Fe- and Ga-doped ones. Magnetic properties are discussed in the model assuming a dominance of superexchange interactions. It is considered that ferromagnetism in the Cr-substituted compositions is associated with nearly equal contributions from positive and negative components of the superexchange interaction between Mn{sup 3+} and Cr{sup 3+} ions as well as to mixed valence of chromium ions. The spin glass state observed for the Fe-doped sample (x=0.3) is associated with strong antiferromagnetic superexchange between Fe{sup 3+}–O–Fe{sup 3+} and Fe{sup 3+}–O–(Mn{sup 3+}, Mn{sup 4+}). - Highlights: • Magnetic structure of the compounds has been clarified by NPD. • Magnetic properties of the compounds has been explained using superexchange scenario. • Mn–O–Fe and Fe–O–Fe superexchange interactions are strongly antiferromagnetic.

  10. ARPES investigation on the surface vs bulk electronic structures of correlated topological insulators YbB6 and other rare earth hexaborides

    Science.gov (United States)

    Xu, Nan; Matt, C. E.; Pomjakushina, E.; Dil, J. H.; Landolt, G.; Ma, J. Z.; Shi, X.; Dhaka, R. S.; Plumb, N. C.; Radovic, M.; Rogalev, V.; Strocov, V.; Kim, T. K.; Hoesch, M.; Conder, K.; Mesot, J.; Ding, H.; Shi, Ming

    2015-03-01

    Using ARPES performed in wide photon energy range we systematically studied the bulk and surface electronic structures of a topological mixed- valence insulator candidate, YbB6. The bulk B-2p states are probed with bulk-sensitive soft X-ray ARPES, exhibiting strong three-dimensionality with the band top locating 80 meV below the EF at the X point. The measured bulk Yb-4f states are located at 1 and 2.3 eV below EF, which hybridize with the dispersive B-2p states. The bulk band structures obtained by experiments are substantially different from the first principle calculations, but it can be better described by adding a correlation parameter U = 7 eV, indicating YbB6 is a correlated system. Using surface-sensitive VUV ARPES, we revealed two-dimensional surface states which form three electron-like FSs with Dirac-cone-like dispersions. The odd number of surface FSs gives the first indication that the surface states are topological non-trivial. The spin-resolved ARPES measurements provide further evidence that these surface states are spin polarized with spin locked to the crystal momentum. Recent results on the TI phase in other rare earth hexaborides will also be shown.

  11. Epitaxial growth and magnetic properties of ultraviolet transparent Ga2O3/(Ga1-xFex)2O3 multilayer thin films

    Science.gov (United States)

    Guo, Daoyou; An, Yuehua; Cui, Wei; Zhi, Yusong; Zhao, Xiaolong; Lei, Ming; Li, Linghong; Li, Peigang; Wu, Zhenping; Tang, Weihua

    2016-04-01

    Multilayer thin films based on the ferromagnetic and ultraviolet transparent semiconductors may be interesting because their magnetic/electronic/photonic properties can be manipulated by the high energy photons. Herein, the Ga2O3/(Ga1-xFex)2O3 multilayer epitaxial thin films were obtained by alternating depositing of wide band gap Ga2O3 layer and Fe ultrathin layer due to inter diffusion between two layers at high temperature using the laser molecular beam epitaxy technique. The multilayer films exhibits a preferred growth orientation of crystal plane, and the crystal lattice expands as Fe replaces Ga site. Fe ions with a mixed valence of Fe2+ and Fe3+ are stratified distributed in the film and exhibit obvious agglomerated areas. The multilayer films only show a sharp absorption edge at about 250 nm, indicating a high transparency for ultraviolet light. What’s more, the Ga2O3/(Ga1-xFex)2O3 multilayer epitaxial thin films also exhibits room temperature ferromagnetism deriving from the Fe doping Ga2O3.

  12. Positive electrode materials for lithium batteries based on VOPO{sub 4}

    Energy Technology Data Exchange (ETDEWEB)

    Dupre, N.; Gaubicher, J.; Le Mercier, T.; Wallez, G.; Angenault, J.; Quarton, M. [Laboratoire de Cristallochimie du Solide, Universite Pierre et Marie Curie-Paris VI, Case 176, 4 place Jussieu, F-75252 Cedex 05 Paris (France)

    2001-04-01

    A detailed electrochemical study of Li insertion in the {alpha}-form of VOPO{sub 4} and the optimization of the cycling performance are presented. The redox process occurs in one step close to 3.76 V, along with a phase transition. In order to improve the intercalation kinetics, the electronic conductivity was optimized by introducing a mixed valency, and the ionic conductivity was favored by introducing 'pillaring' molecules or ions in the interlayer space. In this way, the electrochemical behaviors of {alpha}-VOPO{sub 4}{center_dot}2H{sub 2}O, {alpha}-Na{sub x}VOPO{sub 4}, {alpha}-K{sub x}VOPO{sub 4} and {alpha}-Mg{sub x}VOPO{sub 4} (0{<=}x{<=}1) have been studied: the hydrate compound shows a good specific capacity (100 mA h/g at a C/5 regime), but a poor cyclability was mainly because of water oxidation. The inserted large alkaline ions improved the cyclability up to 80 cycles (Na{sup +}) or over 100 cycles (K{sup +}). Enhancements of the VOPO{sub 4} specific capacity have been obtained as well by mechanical ball-millings.

  13. Extending the Family of V(4+) S=(1/2) Kagome Antiferromagnets.

    Science.gov (United States)

    Clark, Lucy; Aidoudi, Farida H; Black, Cameron; Arachchige, Kasun S A; Slawin, Alexandra M Z; Morris, Russell E; Lightfoot, Philip

    2015-12-14

    The ionothermal synthesis, structure, and magnetic susceptibility of a novel inorganic-organic hybrid material, imidazolium vanadium(III,IV) oxyfluoride [C3 H5 N2 ][V9 O6 F24 (H2 O)2 ] (ImVOF) are presented. The structure consists of inorganic vanadium oxyfluoride slabs with kagome layers of V(4+) S=${{ 1/2 }}$ ions separated by a mixed valence layer. These inorganic slabs are intercalated with imidazolium cations. Quinuclidinium (Q) and pyrazinium (Pyz) cations can also be incorporated into the hybrid structure type to give QVOF and PyzVOF analogues, respectively. The highly frustrated topology of the inorganic slabs, along with the quantum nature of the magnetism associated with V(4+) , means that these materials are excellent candidates to host exotic magnetic ground states, such as the highly sought quantum spin liquid. Magnetic susceptibility measurements of all samples suggest an absence of conventional long-range magnetic order down to 2 K despite considerable antiferromagnetic exchange.

  14. Possible magnetic phase separation in Ru-doped La{sub 0.67}Ca{sub 0.33}MnO{sub 3}

    Energy Technology Data Exchange (ETDEWEB)

    Seetha Lakshmi, L.; Sridharan, V. E-mail: varadu@igcar.ernet.insridh61@hotmail.com; Natarajan, D.V.; Chandra, Sharat; Sankara Sastry, V.; Radhakrishnan, T.S.; Pandian, Ponn; Justine Joseyphus, R.; Narayanasamy, A

    2003-02-01

    X-ray diffraction, resistivity, AC susceptibility and magnetization studies on La{sub 0.67}Ca{sub 0.33}Mn{sub 1-x}Ru{sub x}O{sub 3} (0{<=}x<0.085) were carried out. A significant increase in the lattice parameters indicated the presence of mixed valence state of Ru: Ru{sup 3+} and Ru{sup 4+}. The resistivity of the doped compounds exhibited two features: a broad hump and a relatively sharp peak. While a para- to ferromagnetic transition could be observed for the latter peak, no magnetic signal either in AC susceptibility or in magnetization measurements could be observed for the broad hump. The magnetic moment of Mn per unit cell decreases non-linearly from 3.55 to 3 {mu}{sub B} for the Ru compositions studied. Based on the results of the present studies and existing literature on Mn-site substituted systems, we argue that a magnetic phase separation occurs in the Ru-doped system. While the sharp peak in the resistivity corresponds to Ru{sup 4+}-enriched regions with ferromagnetic coupling of Ru with the neighboring Mn ions, the broad peak corresponds to Ru{sup 3+}-rich regions, with antiferromagnetic coupling of Ru with the neighboring Mn ions.

  15. Predicting Thin Film Stoichiometry In V-O2 Reactive Sputtering

    Directory of Open Access Journals (Sweden)

    He Yu

    2015-06-01

    Full Text Available The electrical, optical and mechanical properties of compound oxides film depend strongly on the composition of the film, especially for vanadium oxide thin films, since the vanadium-oxygen phase diagram includes mixed valence oxides with two or more oxidation states. Therefore, it is interesting to predict the film stoichiometry in VOx films. However, it has not, to any great extent yet, been possible to predict the composition of vanadium oxides films. In this article, we present a model that enables us to predict film composition of vanadium oxides prepared by reactive sputtering. Based on this model, the fraction ratio of V, V2O3, VO2 and V2O5 in the substrate surface as a function of oxygen flow is investigated. It is concluded that the presented theoretical model for the involved reactions and composition of VOx thin film during reactive sputtering process is in qualitative agreement with the XPS results from experiment and can be used to find optimum processing conditions for deposition of films of a desired composition.DOI: http://dx.doi.org/10.5755/j01.ms.21.2.6910

  16. Large exchange bias effect in LaCr{sub 0.9}Ru{sub 0.1}O{sub 3}

    Energy Technology Data Exchange (ETDEWEB)

    Sarkar, Babusona; Dalal, Biswajit; De, S.K., E-mail: msskd@iacs.res.in

    2016-11-01

    The incorporation of tetravalent Ru (10%) into antiferromagnetic spin structure of LaCrO{sub 3} leads to mixed valence states of Cr (Cr{sup 2+} and Cr{sup 3+}). Highly delocalized 4d orbital of Ru induces prominent ferromagnetic (FM) component in antiferromagnetic (AFM) matrix of parent compound. The complex magnetic interaction across the interface of FM and AFM regions gives rise to large exchange bias field (H{sub EB}) of about 10 kOe. The inverse and normal magnetocaloric effect for magnetic field up to 50 kOe coexists in a single material due to multiple magnetic phase transitions with temperature. - Graphical abstract: Highly delocalized 4d orbital of Ru induces prominent ferromagnetic (FM) component in antiferromagnetic (AFM) matrix of parent compound. - Highlights: • Incorporation of Ru{sup 4+} into the antiferromagnetic spin structure of LaCrO{sub 3}. • Large exchange bias has been observed for 10% Ru doped LaCrO{sub 3}. • Coexistence of normal and inverse magnetocaloric effect.

  17. Magnetic phase diagram of Ce(Mn1-xCux)2Si2

    Science.gov (United States)

    Liang, G.; Yen, F.

    2008-04-01

    The magnetic structure of mixed valence-Kondo-heavy fermion series Ce(Mn1-xCux)2Si2 (0⩽x ⩽1) is reported. The magnetic susceptibility results indicate that for 0⩽x⩽0.3, Mn moments are antiferromagnetically (AFM) ordered and the Neel temperature TN decreases rapidly with decreasing x. For 0.4⩽x⩽0.7, ferromagnetic (FM) phase is observed below 140K and both the ordering temperature Tc and Curie-Weiss temperature θp decrease with increasing x, showing the weakening of in-plane FM magnetic coupling between Mn moments due to the substitution of Mn by nonmagnetic Cu. For 0.8⩽x⩽1, samples exhibit only paramagnetic behavior. The types of magnetic order in this series are basically consistent with the criterion that FM (AFM) phase is favored when intralayer Mn-Mn spacing RMn-Mna is greater (smaller) than a critical value of 2.865Å. A magnetic phase diagram is constructed for this compound series.

  18. 基于二茂铁的多响应信号体系对不同类别客体的识别与传感%The Recognition and Sensing for Different Guests of A Multi-Signal Response System Based on Ferrocene

    Institute of Scientific and Technical Information of China (English)

    乔彬彬; 刘阳; 张丙广; 邓克俭

    2012-01-01

    The title compound with ferrocenyl and quinolinyl groups bridged by urea,was prepared and was characterized by 1 HNMR and elemental analysis. UV-Vis Titrations and electrochemical titrations indicated that the compound sensed redox active Cu( Ⅱ ) and Fe( Ⅲ) by the formation of mixed valence,sensed some high electronegative anions according to the cathodic shift of oxidation-reduction potential.%合成了一种通过脲基将喹啉基团连接到二茂铁上的双取代衍生物FcQL,采用1HNMR和元素分析对其进行了表征,研究了其对常见阴离子和阳离子的传感性质.结果发现,该化合物能通过产生混合价吸收而传感Cu(Ⅱ)和Fe(Ⅲ),通过氧化还原电位的变化传感高电负性的易形成氢键的阴离子.

  19. Mesoporous NiCo2O4 Nanoplates on Three-Dimensional Graphene Foam as an Efficient Electrocatalyst for the Oxygen Reduction Reaction.

    Science.gov (United States)

    Tong, Xili; Chen, Shuai; Guo, Congxiu; Xia, Xinhui; Guo, Xiang-Yun

    2016-01-21

    Catalysts for the oxygen reduction reaction (ORR) are highly important in fuel cells and metal-air batteries. Cheap ORR catalysts with ultrahigh electrochemical activity, selectivity, and stability are extremely desirable but still remain challenging. Herein, mesoporous NiCo2O4 nanoplate (NP) arrays on three-dimensional (3D) graphene foam are shown to be a highly economical ORR catalyst. This mesoporous mixed-valence oxide can provide more electrocatalytic active sites with increased accessible surface area. In addition, graphene-foam-supported NiCo2O4 NP arrays have a 3D hierarchical porous structure, which is of great benefit to ion diffusion and electron transfer. As a result, the mesoporous NiCo2O4 NP arrays/graphene foam catalyst exhibits outstanding ORR performance with the four-electron reduction of O2 to H2O in alkaline media. Furthermore, the mesoporous catalyst shows enhanced electrocatalytic activity with a half-wave potential of 0.86 V vs RHE and better stability compared with a commercial Pt/C catalyst.

  20. Carbon Supported Engineering NiCo2O4 Hybrid Nanofibers with Enhanced Electrocatalytic Activity for Oxygen Reduction Reaction

    Directory of Open Access Journals (Sweden)

    Diab Hassan

    2016-09-01

    Full Text Available The design of cheap and efficient oxygen reduction reaction (ORR electrocatalysts is of a significant importance in sustainable and renewable energy technologies. Therefore, ORR catalysts with superb electrocatalytic activity and durability are becoming a necessity but still remain challenging. Herein, we report C/NiCo2O4 nanocomposite fibers fabricated by a straightforward electrospinning technique followed by a simple sintering process as a promising ORR electrocatalyst in alkaline condition. The mixed-valence oxide can offer numerous accessible active sites. In addition, the as-obtained C/NiCo2O4 hybrid reveals significantly remarkable electrocatalytic performance with a highly positive onset potential of 0.65 V, which is only 50 mV lower than that of commercially available Pt/C catalysts. The analyses indicate that C/NiCo2O4 catalyst can catalyze O2-molecules via direct four electron pathway in a similar behavior as commercial Pt/C catalysts dose. Compared to single NiCo2O4 and carbon free NiCo2O4, the C/NiCo2O4 hybrid displays higher ORR current and more positive half-wave potential. The incorporated carbon matrices are beneficial for fast electron transfer and can significantly impose an outstanding contribution to the electrocatalytic activity. Results indicate that the synthetic strategy hold a potential as efficient route to fabricate highly active nanostructures for practical use in energy technologies.

  1. Rational Integration of Inbuilt Aperture with Mesoporous Framework in Unusual Asymmetrical Yolk-Shell Structures for Energy Storage and Conversion.

    Science.gov (United States)

    Zhu, Ting; Zhu, Liangliang; Wang, Jing; Ho, Ghim Wei

    2016-12-07

    Despite the attractive benefits of hollow structures as electrodes for advanced energy storage-conversion capabilities, one prevailing shortcoming is their compromised structural integrity and volumetric energy density due to the introduction of an ultrathin shell with an excessively underutilized large hollow cavity. Herein, we report a facile and template-free synthetic route to realize unusual asymmetrical yolk-shell (AYs) structures composed of mixed-valence NiCo2O4 material. Explicitly, this work highlights the unusual off-central core, an AYs structure that encompasses a hemispherical hollow interior, and a mesoporous solid counterpart. As such, it retains desirable hollow structural characteristics while favorably precludes the excessive unexploited hollow interior space for increased active material packing. Unlike the conventional symmetrical yolk-shell (SYs) which is composed of a porous shell framework radially throughout the structure, the mesoporous solid constitution of the AYs structure offers an inbuilt reinforced framework to support the partial porous shell and concurrently leaves sufficient void for volumetric buffering. Another unique structural feature of the AYs structure is the formation of a submicron aperture or opening on the shell that enhances accessibility of electrolyte diffusion. All of these synergistic structural features of NiCo2O4 AYs structures enhance the pseudocapacitive and electrocatalytic properties.

  2. Synthesis of hierarchical NiCo2O4 hollow nanorods via sacrificial-template accelerate hydrolysis for electrochemical glucose oxidation.

    Science.gov (United States)

    Yang, Jiao; Cho, Misuk; Lee, Youngkwan

    2016-01-15

    Hierarchical NiCo2O4 hollow nanorods (HR) were directly grown on stainless steel via a sacrificial template accelerated hydrolysis and post calcination using ZnO nanorod as a template. The composition of the NiCo2O4 HR electrode was determined using X-ray diffraction and X-ray photoelectron spectroscopy. The morphology of the NiCo2O4 HR is comprised of nanoflakes that were characterized with scanning electron microscopy and transmission electron microscopy. The mixed-valence metal oxide and hollow structure provided high chemical reactivity and a large surface area for glucose oxidation in an alkaline solution. Under an optimal applied potential of +0.6 V, the developed NiCo2O4 HR electrode showed a broad detection range of 0.0003–1.0 mM, a sensitivity of 1685.1 μA mM−1 cm−2, and a low detection limit of 0.16 μM. These results represent a significant improvement over both NiO and Co3O4 HR. The developed NiCo2O4 HR electrode not only demonstrated excellent selectivity in the presence of several electro-active species, but also exhibited high stability following a 200 cycles voltammetry test.

  3. Morphology-controlled synthesis and electrochemical performance of NiCo2O4 as anode material in lithium-ion battery application

    Science.gov (United States)

    Xu, Shan; Lu, Lin; Zhang, Qing; Zheng, Hao; Liu, Lian; Yin, Shengyu; Wang, Shiquan; Li, Guohua; Feng, Chuanqi

    2015-09-01

    Mixed-valence oxide precursors were synthesized by a solvothermal method using NiSO4, CoSO4, and NH4HCO3 as raw materials. The precursors were heat-treated in a muffle furnace at 500 °C to obtain the products (NiCo2O4). The samples were characterized by X-ray diffractometer, thermogravimetric, energy-dispersive spectroscopy, scanning electron microscopy, and transmission electron microscopy. The results show that dumbbells, microspheres, and particle-like NiCo2O4 were successfully synthesized by changing the volume of solvent and solvothermal temperature. The NiCo2O4 microspheres (prepared at 180 °C with 30 ml solvent) as anode material for lithium-ion battery, exhibit a reversible discharge capacity of 1160 mAh g-1 and good cycling stability (729 mAh g-1 after 50 cycles) at a constant current of 100 mA g-1 in the voltage range of 0.01-3.0 V due to its high crystallinity and uniform porous morphology. Hence, the synthetic method could be extended to other high-capacity ternary metal oxide materials for lithium-ion battery application.

  4. Single impurity Anderson model versus density functional theory for describing Ce L3 x-ray absorption spectra of CeFe2: resolution of a recent controversy.

    Science.gov (United States)

    Kotani, A; Kvashnina, K O; Glatzel, P; Parlebas, J C; Schmerber, G

    2012-01-20

    We resolved a recent controversy on the structure of the Ce L(3) x-ray absorption spectra (XAS) of CeFe(2); i.e., which of the single impurity Anderson model (SIAM) and the first-principles band calculations based on the density-functional theory (DFT) describes more appropriately the Ce 4f states and their contribution to the Ce L(3) XAS? For this purpose, we examined the core-hole effect in Ce L(3) XAS as an application of our new method taking advantage of resonant x-ray emission spectroscopy. Our result clearly shows that the Ce L(3) XAS structure is caused by the mixed valence 4f character revealed by the core-hole potential effect as indicated by SIAM, but denies the possibility that the L(3) XAS structure is caused by the 5d band structure with a very small core-hole effect as predicted by band calculations based on DFT. © 2012 American Physical Society

  5. Hydroxonium hydrate tris(2,4,6-triamino-1,3,5-triazin-1-ium bis[bis(pyridine-2,6-dicarboxylatocuprate(II] pyridine-2,6-dicarboxylic acid hexahydrate

    Directory of Open Access Journals (Sweden)

    Shabnam Hooshmand

    2009-02-01

    Full Text Available The reaction of copper(II nitrate hexahydrate with pyridine-2,6-dicarboxylic acid (pydcH2 and 2,4,6-triamino-1,3,5-triazine (melamine in aqueous solution in a 1:2:2 molar ratio gave the title compound, (H5O2(C3H7N63[Cu(C7H3NO42]2·C7H5NO4·6H2O. The hydroxonium hydrate (H5O2+, also known as the Zundel cation, resides on a twofold rotation axis. The O—H distance is 1.274 (14 Å, the O...O distance is 2.518 (5 Å, and the O—H—O angle is 162 (8°. One of the melamine H+ cations, the uncoordinated pydcH2, and two water molecules also reside on crystallographic twofold axes. The CuII atom has a tetragonally distorted octahedral coordination environment. The structure features extensive hydrogen bonding, with 21 distinct interactions. There is also a centrosymmetric C=O...π interaction with an O...centroid distance of 3.288 (3 Å. The structure is similar to a mixed-valence manganese(II/III structure but shows interesting differences in the metal-atom coordination. One of the water molecules is equally disordered with respect to a twofold axis.

  6. Discretization effects and the scalar meson correlator in mixed-action lattice simulations

    CERN Document Server

    Aubin, C; Van de Water, Ruth S

    2008-01-01

    We study discretization effects in a mixed-action lattice theory with domain-wall valence quarks and Asqtad-improved staggered sea quarks. At the level of the chiral effective Lagrangian, discretization effects in the mixed-action theory give rise to two new parameters as compared to the lowest order Lagrangian for staggered fermions -- the residual quark mass, m_res, and the mixed valence-sea meson mass-splitting, Delta_mix. We find that the size of m_res is approximately four times smaller than our lightest valence quark mass on our coarser lattice spacing, and comparable to that of simulations by RBC and UKQCD. We also find that the size of Delta_mix is comparable to the smallest of the staggered meson taste-splittings measured by MILC. Because lattice artifacts are different in the valence and sea sectors of the mixed-action theory, they give rise to unitarity-violating effects that disappear in the continuum limit. Such effects are expected to be mild for many quantities of interest, but are significant ...

  7. La0.9Sr0.1Ga0.8M0.2O3– (M = Mn, Co, Ni, Cu or Zn): Transition metal-substituted derivatives of lanthanum–strontium–gallium–magnesium (LSGM) perovskite oxide ion conductor

    Indian Academy of Sciences (India)

    Litty Sebastian; A K Shukla; J Gopalakrishnan

    2000-06-01

    Perovskite oxides of the general formula, La0.9Sr0.1Ga0.8M0.2O3– for M = Mn, Co, Ni, Cu and Zn, have been prepared and investigated. All the oxides exhibit high electrical conductivities ( ∼ 10–2 S/cm at 800°C) comparable to that of the best perovskite oxide ion conductor, La0.9Sr0.1Ga0.8Mg0.2O2.85 (LSGM) ( ∼ 8 × 10–2 S/cm at 800°C). While M = Mn, Co, Ni, Cu members appear to be mixed conductors with a variable electronic contribution to the conductivity, especially at high oxygen partial pressures (O2 \\geq 1 atm), arising from mixed-valency of the transition metals, the M = Zn(II) phase is a pure oxide ion conductor exhibiting a conductivity ( ∼ 1.5 × 10–2 S/cm at 800°C) that is slightly lower than that of LSGM. The lower conductivity of the M = Zn(II) derivative could be due to the preference of Zn(II) for a tetrahedral oxygen coordination.

  8. Glacial influence on the geochemistry of riverine iron fluxes to the Gulf of Alaska and effects of deglaciation

    Science.gov (United States)

    Schroth, A.W.; Crusius, J.; Chever, F.; Bostick, B.C.; Rouxel, O.J.

    2011-01-01

    Riverine iron (Fe) derived from glacial weathering is a critical micronutrient source to ecosystems of the Gulf of Alaska (GoA). Here we demonstrate that the source and chemical nature of riverine Fe input to the GoA could change dramatically due to the widespread watershed deglaciation that is underway. We examine Fe size partitioning, speciation, and isotopic composition in tributaries of the Copper River which exemplify a long-term GoA watershed evolution from one strongly influenced by glacial weathering to a boreal-forested watershed. Iron fluxes from glacierized tributaries bear high suspended sediment and colloidal Fe loads of mixed valence silicate species, with low concentrations of dissolved Fe and dissolved organic carbon (DOC). Iron isotopic composition is indicative of mechanical weathering as the Fe source. Conversely, Fe fluxes from boreal-forested systems have higher dissolved Fe concentrations corresponding to higher DOC concentrations. Iron colloids and suspended sediment consist of Fe (hydr)oxides and organic complexes. These watersheds have an iron isotopic composition indicative of an internal chemical processing source. We predict that as the GoA watershed evolves due to deglaciation, so will the source, flux, and chemical nature of riverine Fe loads, which could have significant ramifications for Alaskan marine and freshwater ecosystems.

  9. Crystal structure, electronic and magnetic properties of double perovskite Ba2FeWO6: A combined experimental-theoretical study

    Science.gov (United States)

    Saad, H.-E, M. Musa; Rammeh, N.

    2016-01-01

    Double perovskite oxide Ba2FeWO6 has been synthesized in polycrystalline form by the solid-state ceramic method at 950 °C. Structural characterization was performed by using the X-ray powder diffraction (XRD) and neutron powder diffraction (NPD) followed by Rietveld analysis of these patterns. The crystal structure of Ba2FeWO6 is cubic; space group Fm-3m with lattice parameter of a=8.1351 Å. Also, a density functional theory (DFT) study of the crystal structure, electronic and magnetic properties of Ba2FeWO6 has been carried out using full potential linear muffin-tin orbital (FP-LMTO). We showed that the obtained symmetry lattice parameter agree well with the experimental results. The influence of Fe element on the magnetic and electronic properties of double perovskite oxide Ba2FeWO6 is analyzed. Band structure calculations for cubic Ba2FeWO6 predict an energy-gap in both spin-up and spin-down. The semiconductor antiferromagnetic (AFM) phase is stabilized by the hybridization of nonmagnetic W6+ (5d°) site positioned in between the magnetic Fe2+ (3d6) sites through the O2- anions in a long range O-Fe-O-W-O arrangement. 57Fe Mössbaur spectrum and DFT calculations suggest that the AFM behavior arises since the mixed valence Fe2+-Fe3+ effect introduces in Fe2+-O2--W6+ anticoupling.

  10. Effect of Mn Substitution for Multiferroic BiFeO3 Probed by High-Resolution Soft-X-Ray Spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Higuchi, Tohru; Higuchi, T.; Hattori, T.; Sakamoto, W.; Itoh, N.; Shimura, T.; Yogo, T.; Yao, P.; Liu, Y.; Glans, P.; Chang, C.; Wu, Z.; Guo, Jinghua

    2008-07-11

    The electronic structures of BiFeO{sub 3} (BF) and Mn-doped BiFeO{sub 3} (BF(Mn)) have been studied by X-ray absorption spectroscopy (XAS) and soft-X-ray emission spectroscopy (SXES). The BF and BF(Mn) have the mixed valence state of Fe{sup 2+} and Fe{sup 3+}. The valence band is mainly composed of O 2p state hybridized with the majority-spin t{sub 2g} and e{sub g} orbitals of Fe 3d state. The conduction band is composed of the minority-spin t{sub 2g} and e{sub g} orbitals of Fe 3d. The band gaps of BF and BF(Mn) are estimated to be 1.3 eV and 2.7 eV, respectively. The increase of band gap with Mn substitution contributes to the change of bandwidth of valence band.

  11. Interlocked graphene-Prussian blue hybrid composites enable multifunctional electrochemical applications.

    Science.gov (United States)

    Zhang, Minwei; Hou, Chengyi; Halder, Arnab; Ulstrup, Jens; Chi, Qijin

    2017-03-15

    There has been increasing interest recently in mixed-valence inorganic nanostructure functionalized graphene composites, represented by Prussian blue, because they can cost-effectively apply to biosensors and energy devices. In this work, we present a one-pot green method to synthesize interlocked graphene-Prussian Blue hybrid composites as high-performance materials for biosensors and supercapacitor electrodes. Given the fact that graphene oxide (GO) can act as an electron acceptor, we used iron(II) and glucose as co-reducing agents to reduce GO under mild reaction conditions without introducing toxic agents. High quality Prussian blue nanocubes with no or little coordinated water were generated simultaneously. Reduced graphene oxide (rGO) was thus functionalized by Prussian blue nanocubes via chemical bonding to form a kind of interlocked microstructure with high stability and good conductivity. The as-synthesized composites were tested for biosensing of hydrogen peroxide (H2O2) and as supercapacitor electrode materials. The specific capacitance of the microcomposite based electrodes can reach 428Fg(-1), with good cycling stability. The microcomposite also displays high performance catalysis towards electroreduction of H2O2 with a high sensitivity of 1.5Acm(-2)M(-1).

  12. Electronic structures of Cu2O,Cu4O3 , and CuO: A joint experimental and theoretical study

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Y.; Lany, S.; Ghanbaja, J.; Fagot-Revurat, Y.; Chen, Y. P.; Soldera, F.; Horwat, D.; Mücklich, F.; Pierson, J. F.

    2016-12-01

    A joint experimental and theoretical study is presented for the electronic structures of copper oxides including Cu2O, CuO, and the metastable mixed-valence oxide Cu4O3. The optical band gap is determined by experimental optical absorption coefficient, and the electronic structure in valence and conduction bands is probed by photoemission and electron energy loss spectroscopies, respectively. The experimental results are compared with many-body GW calculations utilizing an additional on-site potential for d-orbital energies that facilitates tractable and predictive computations. The side-by-side comparison between the three oxides, including a band insulator (Cu2O) and two Mott/charge-transfer insulators (CuO, Cu4O3) leads to a consistent picture for the optical and band-structure properties of the Cu oxides, strongly supporting indirect band gaps of about 1.2 and 0.8 eV in CuO and Cu4O3, respectively. This comparison also points towards surface oxidation and reduction effects that can complicate the interpretation of the photoemission spectra.

  13. A new strategy for storage and transportation of sensitive high-energy materials: guest-dependent energy and sensitivity of 3D metal-organic-framework-based energetic compounds.

    Science.gov (United States)

    Zhang, Sheng; Liu, Xiangyu; Yang, Qi; Su, Zhiyong; Gao, Wenjuan; Wei, Qing; Xie, Gang; Chen, Sanping; Gao, Shengli

    2014-06-23

    Reaction of Co(II) with the nitrogen-rich ligand N,N-bis(1H-tetrazole-5-yl)-amine (H2bta) leads to a mixed-valence, 3D, porous, metal-organic framework (MOF)-based, energetic material with the nitrogen content of 51.78%, [Co9(bta)10(Hbta)2(H2O)10]n⋅(22 H2O)n (1). Compound 1 was thermohydrated to produce a new, stable, energetic material with the nitrogen content of 59.85% and heat of denotation of 4.537 kcal cm(-3), [Co9(bta)10(Hbta)2(H2O)10]n (2). Sensitivity tests show that 2 is more sensitivity to external stimuli than 1, reflecting guest-dependent energy and sensitivity of 3D, MOF-based, energetic materials. Less-sensitive 1 can be regarded as a more safe form for storage and transformation to sensitive 2. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. Adsorption of water on TiN (1 0 0), (1 1 0) and (1 1 1) surfaces: A first-principles study

    Science.gov (United States)

    Sanyal, Suchismita; Waghmare, Umesh V.; Ruud, James A.

    2011-05-01

    We use first-principles density functional theory-based calculations in the analysis of the interaction of H 2O with (1 0 0), (1 1 0) and (1 1 1) surfaces of TiN, and develop understanding in terms of surface energies, polarity of the surface and chemistry of the cation, through comparison with H 2O adsorption on ZrN. While water molecule physisorbs preferentially at Ti site of (1 0 0) and (1 1 1) surfaces, it adsorbs dissociatively on (1 1 0) surface of TiN with binding stronger than almost 1.32 eV/molecule. Our analysis reveals the following general trends: (a) surfaces with higher energies typically lead to stronger adsorption, (b) dissociative adsorption of H 2O necessarily occurs on a charge neutral high energy surface and (c) lower symmetry of the (1 1 0) plane results in many configurations of comparable stability, as opposed to the higher symmetry (1 0 0) and (1 1 1) surfaces, which also consistently explain the results of H 2O adsorption on MgO available in literature. Finally, weaker adsorption of H 2O on TiN than on ZrN can be rationalized in terms of greater chemical stability of Ti arising from its ability to be in mixed valence.

  15. A systematic approach to vertically excited states of ethylene using configuration interaction and coupled cluster techniques

    Energy Technology Data Exchange (ETDEWEB)

    Feller, David, E-mail: dfeller@owt.com; Peterson, Kirk A. [Department of Chemistry, Washington State University, Pullman, Washington 99164-4630 (United States); Davidson, Ernest R. [Department of Chemistry, University of Washington, Seattle, Washington 98195-1700 (United States)

    2014-09-14

    A systematic sequence of configuration interaction and coupled cluster calculations were used to describe selected low-lying singlet and triplet vertically excited states of ethylene with the goal of approaching the all electron, full configuration interaction/complete basis set limit. Included among these is the notoriously difficult, mixed valence/Rydberg {sup 1}B{sub 1u} V state. Techniques included complete active space and iterative natural orbital configuration interaction with large reference spaces which led to variational spaces of 1.8 × 10{sup 9} parameters. Care was taken to avoid unintentionally biasing the results due to the widely recognized sensitivity of the V state to the details of the calculation. The lowest vertical and adiabatic ionization potentials to the {sup 2}B{sub 3u} and {sup 2}B{sub 3} states were also determined. In addition, the heat of formation of twisted ethylene {sup 3}A{sub 1} was obtained from large basis set coupled cluster theory calculations including corrections for core/valence, scalar relativistic and higher order correlation recovery.

  16. Local states in one-dimensional CDW (charge density wave) materials: Spectral signatures for polarons and bipolarons in MX chains

    Energy Technology Data Exchange (ETDEWEB)

    Swanson, B. I.; Donohoe, R. J.; Worl, L. A.; Bulou, A. D.F.; Arrington, C. A.; Gammel, J. T.; Saxena, A.; Bishop, A. R.

    1990-01-01

    We have undertaken a combined theoretical and experimental effort directed toward the examination of both the ground and defect states in halide-bridged mixed-valence metal linear chains materials as they are tuned within and between broken symmetry phases. Novel low-dimensional highly correlated electronic materials offer a difficult theoretical challenge as we must span from a description of electronic structure on a molecular scale to the meso scale structure that is intrinsic to these solids. Our theoretical effort at Los Alamos combines quantum chemistry, band structure calculations, and many body modeling using Peierls-Hubbard Hamiltonians in order to model ground and local states. The experimental effort combines synthesis and a variety of microscopic structural and spectroscopic probes and macroscopic measurements in an effort to fully characterize both ground and local states as these materials are tuned in the phase boundary regions between broken symmetry states. The present article summarizes some of our recent research using optical spectroscopy to obtain signatures of photoexcited and intrinsic local states and compares these experimental results with Peierls-Hubbard calculations of the optical properties of these materials. Details concerning the theoretical and experimental approaches can be found elsewhere.

  17. Bose-Hubbard model on a kagome lattice with sextic ring-exchange terms

    Science.gov (United States)

    Rousseau, Valéry G.; Tam, Ka-Ming; Jarrell, Mark; Moreno, Juana

    2013-02-01

    High-order ring-exchange interactions are crucial for the study of quantum fluctuations on many highly frustrated systems. A versatile and efficient quantum Monte Carlo method, which can handle finite and essentially zero temperature and canonical and grand-canonical ensembles, has long been sought. In this paper, we present an exact quantum Monte Carlo study of a model of hard-core bosons with sixth-order ring-exchange interactions on a two-dimensional kagome lattice. By using the stochastic Green function algorithm with global space-time update, we show that the system becomes unstable in the limit of large ring-exchange interactions. It undergoes a phase separation at all fillings, except at (1)/(3) and (2)/(3) fillings for which the superfluid density vanishes and an unusual mixed valence bond and charge density ordered solid is formed. This explains the universal features seen in previous studies on various different models, such as the transverse-field Ising models, on a kagome lattice near the classical limit.

  18. Magnetic behavior of bulk and fine particles of RCr{sub 2}Si{sub 2}C (R = La, Ce) compounds: possible magnetic ordering from Cr

    Energy Technology Data Exchange (ETDEWEB)

    Mukherjee, K; Iyer, Kartik K; Sampathkumaran, E V, E-mail: sampath@mailhost.tifr.res.i [Tata Institute of Fundamental Research, Homi Bhabha Road, Colaba, Mumbai 400005 (India)

    2010-07-28

    The magnetic behavior of the quaternary compounds, RCr{sub 2}Si{sub 2}C (R = La, Ce), has been investigated by magnetization (M) and heat-capacity (C) measurements (1.8-300 K) in the bulk polycrystals and nano forms (<1 {mu}m) obtained by high-energy balling. Our finding is that Cr appears to exhibit magnetic ordering of an itinerant type at low temperatures (<20 K) in the bulk form, as inferred from a combined look at all the data. The magnetic ordering gets gradually suppressed with increasing milling time. Evidence for a mixed-valence state of Ce for the bulk form is obtained from the tendency of magnetic susceptibility to exhibit a maximum above 300 K. However, this feature vanishes in the nano form, which exhibits a Curie-Weiss behavior above 200 K as though Ce tends towards trivalency in these fine particles; in addition, there is a weak upturn in C/T below 10 K in the bulk, which becomes very prominent in the milled Ce-based specimens at lower temperatures, as though heavy-fermion behavior gets stronger in smaller particles.

  19. Charge Distribution and Local Structure and Speciation in the UO2+x and PuO2+x Binary Oxides for x <= 0.25

    Energy Technology Data Exchange (ETDEWEB)

    Conradson, Steven D.; Begg, Bruce D.; Clark, David L.; Den Auwer, Christophe J.; Ding, Mei; Dorhout, Peter K.; Espinosa-Faller, Francisco J.; Gordon, Pamela L.; Haire, Richard G.; Hess, Nancy J.; Hess, Ryan F.; Keogh, D. Webster; Lander, Gerard H.; Manara, Dario; Morales, Luis A.; Neu, Mary P.; Paviet-Hartmann, Patricia; Rebizant, Jean; Rondinella, Vincenzo V.; Runde, Wolfgang; Tait, C DREW.; Veirs, D. Kirk; Villella, Phillip M.; Wastin, Franck

    2005-02-01

    The local structure and chemical speciation of the mixed valence, fluorite-based oxides UO2+x (0.00pxp0.20) and PuO2+x/PuO2+x*y(OH)2y * zH2O have been determined by U/Pu LIII XAFS spectroscopy. The U spectra indicate (1) that the O atoms are incorporated as oxo groups at short (1.75A ? ) U?O distances consistent with U(VI) concomitant with a large range of U displacements that reduce the apparent number of U neighbors and (2) that the UO2 fraction remains intact implying that these O defects interact to form clusters and give the heterogeneous structure consistent with the diffraction patterns. The PuO2+x system, which does not show a separate phase at its x ? 0:25 endpoint, also displays (1) oxo groups at longer 1.9A ? distances consistent with Pu(V+d), (2) a multisite Pu?O distribution even when x is close to zero indicative of the formation of stable species with H2O and its hydrolysis products with O2*, and (3) a highly disordered, spectroscopically invisible Pu?Pu component. The structure and bonding in AnO2+x are therefore more complicated than have previously been assumed and show both similarities but also distinct differences among the different elements.

  20. Synthesis and measurement of structural and magnetic properties of K-doped LaCoO3 perovskite materials

    Institute of Scientific and Technical Information of China (English)

    Manjunath B.Bellakki; C.Madhu; Tobias Greindl; Sandeep Kohli; Patrick McCurdy; V.Manivannan

    2010-01-01

    Polycrystalline La1-xKxCoO3 (0≤x≤0.2) rare earth cobaltates have been synthesized by a solution combustion method using glycine as a fuel.The synthesized ceramic materials were characterized by powder X-ray diffraction (XRD),scanning electron microscopy (SEM),Fourier transform infrared spectroscopy (FTIR),and magnetic measurements and studied for physical properties,such as photocatalytic activity.FTIR measurements in conjunction with XRD showed that phases beyond 10% K doping are accompanied by small amounts of impurities.Chemical titrations show the presence of Co4+ and account for the Co3+ -Co4+ mixed-valency of the system.The parent LaCoO3 shows spin-glass transition at low temperatures,whereas doped samples show transition from spin-glass behavior to paramagnetic ordering on progressive doping of K."Mixed-conductor" nature of these ceramics positions them as viable candidates for solid oxide fuel cell (SOFC) applications.

  1. From Ba3Ta5O14N to LaBa2Ta5O13N2: Decreasing the optical band gap of a photocatalyst

    Science.gov (United States)

    Anke, B.; Bredow, T.; Pilarski, M.; Wark, M.; Lerch, M.

    2017-02-01

    Yellow LaBa2Ta5O13N2 was successfully synthesized as phase-pure material crystallizing isostructurally to previously reported Ba3Ta5O14N and mixed-valence Ba3TaV4TaIVO15. The electronic structure of LaBa2Ta5O13N2 was studied theoretically with the range-separated hybrid method HSE06. The most stable structure was obtained when lanthanum was placed on 2a and nitrogen on 4h sites confirming Pauling's second rule. By incorporating nitrogen, the measured band gap decreases from ∼3.8 eV for the oxide via 2.74 eV for Ba3Ta5O14N to 2.63 eV for the new oxide nitride, giving rise to an absorption band well in the visible-light region. Calculated fundamental band gaps confirm the experimental trend. The atom-projected density of states has large contributions from N2p orbitals close to the valence band edge. These are responsible for the observed band gap reduction. Photocatalytic hydrogen formation was investigated and compared with that of Ba3Ta5O14N revealing significantly higher activity for LaBa2Ta5O13N2 under UV-light.

  2. Synthesis, microstructure and EPR of CaMnO{sub 3} and Eu{sub x}Ca{sub 1-x}MnO{sub 3} manganite, obtained by coprecipitation

    Energy Technology Data Exchange (ETDEWEB)

    Santiago T, M.; Hernandez C, L.; Legorreta G, F. [Universidad Autonoma del Estado de Hidalgo, AACTyM, Carretera Pachuca-Tulancingo Km 4.5, 42074 Pachuca, Hidalgo (Mexico); Montiel S, H. [UNAM, Centro de Ciencias Aplicadas y Desarrollo Tecnologico, Departamento de Tecnociencias, Ciudad Universitaria, 04510 Mexico D. F. (Mexico); Alvarez L, G. [IPN, Escuela Superior de Fisica y Matematicas, Departamento de Fisica, U. P. Adolfo Lopez Mateos, Edif. 9, Col. Lindavista, 07738 Mexico D. F. (Mexico); Flores G, M. A., E-mail: mar200878@hotmail.com [Universidad Politecnica de Pachuca, Laboratorio de Nanotecnologia y Bioelectromagnetismo Aplicado, Carretera Pachuca-Cd. Sahagun Km 20, Ex-Hacienda de Santa Barbara, 43830 Zempoala, Hidalgo (Mexico)

    2011-07-01

    The synthesis of CaMnO{sub 3} and Eu{sub x}Ca{sub 1-x}MnO{sub 3} obtained by coprecipitation method is showed. The synthesized samples were characterized by X-ray diffraction and scanning electronic microscopy, the powders showed orthorhombic structure and pnma space group. When it was doped with Europium, their morphology tendency was spherical. Measurements were carried out on electron paramagnetic resonance (EPR) with constant frequency = 9.4 GHz (band X) and dc magnetic field (H dc) 0-0.8 T, measurements were at 300 K and 77 K. EPR spectra showed significant differences between both samples, indicating that the substitution of divalent alkaline earth cations by trivalent rare earth ions, allowing the formation of a mixed valence state of manganese, Mn{sup 3+} and Mn{sup 4+}. A 77 K, the manganite of concentration x = 0.30 had a magnetic ordering, noted by the presence of hysteresis. (Author)

  3. Electrochemical synthesis, structural characterization, and decomposition of rhenium oxoethoxide, Re4O4(OEt)12. Ligand influence on the structure and bonding in the high-valent tetranuclear planar rhenium alkoxide clusters.

    Science.gov (United States)

    Nikonova, Olesya A; Jansson, Kjell; Kessler, Vadim G; Sundberg, Margareta; Baranov, Alexei I; Shevelkov, Andrei V; Drobot, Dmitrii V; Seisenbaeva, Gulaim A

    2008-02-18

    Anodic oxidation of rhenium in ethanol in the presence of LiCl as a conductive additive results with high yield in formation of a new oxoethoxide cluster, Re(4)O(4)(OEt)(12). The structure of the planar centrosymmetric metal-oxygen core of this molecule is composed of four edge-sharing Re(V)O(6) octahedra. Eight electrons are available for the formation of metal-metal bonds indicated by five relatively short Re-Re distances within the Re 4-rhombus, a "planar butterfly" type cluster. The theoretical calculations are indicating relatively low contribution of metal-metal bonding in the stability of the core. The stability of the +V-oxidation state, unusual for rhenium alkoxides can be at least partially attributed to the size effects in the packing of ligands. The X-ray powder study indicates that treatment of Re(4)O(4)(OEt)(12). in ambient atmosphere rapidly transforms it into a mixed-valence derivative Re(4)O(6)(OEt)(10) with a structure related to the earlier investigated cluster Re(4)O(6)(O(i)Pr)(10). Thermal decomposition of the latter rhenium oxoethoxide results in reduction to rhenium metal at as low temperatures as 380 degrees C, producing aggregates of metal nanoparticles with the average size of 3 nm.

  4. Band description of materials with localizing orbitals

    Energy Technology Data Exchange (ETDEWEB)

    Koelling, D.D.

    1986-03-01

    Density functional theory is a form of many-body theory which maps the problem onto an equivalent single particle-like system by limiting to the ground state (or some limited ensemble). So it should be surprising that this ground state theory could have any relevance whatsoever to the excitation properties of a material - and yet it does when used carefully. However, the most interesting materials involve active orbitals which are at least partially localized in space and this has profound effects both on the ground state and the excitation spectrum. My long term interest is in Ce and actinide compounds such that the popular concerns are mixed valence, heavy fermions, and the various forms of magnetic transitions. Band structure calculations can give a great deal of information concerning the mechanisms and degree of the localization as shown by examples using the Ce and U Ll/sub 2/ structured materials and the Ce cubic Laves phase materials. There are some difficulties due to an incomplete knowledge of the functionals involved which causes an underestimate of the local character. This is illustrated and discussed.

  5. Comparative study of heterogeneous magnetic state above T{sub C} in La{sub 0.82}Sr{sub 0.18}CoO{sub 3} cobaltite and La{sub 0.83}Sr{sub 0.17}MnO{sub 3} manganite

    Energy Technology Data Exchange (ETDEWEB)

    Ryzhov, V.A., E-mail: ryzhov@omrb.pnpi.spb.ru [Petersburg Nuclear Physics Institute, Orlova Coppice, Gatchina, Leningrad Obl. 188300 (Russian Federation); Lazuta, A.V.; Molkanov, P.L.; Khavronin, V.P.; Kurbakov, A.I.; Runov, V.V. [Petersburg Nuclear Physics Institute, Orlova Coppice, Gatchina, Leningrad Obl. 188300 (Russian Federation); Mukovskii, Ya.M.; Pestun, A.E.; Privezentsev, R.V. [Moskow State Steel and Alloys Institute, Leninskii Prospekt 4, Moscow 119049 (Russian Federation)

    2012-10-15

    The magnetic, transport and structural properties are studied for La{sub 0.83}Sr{sub 0.17}MnO{sub 3} and La{sub 0.82}Sr{sub 0.18}CoO{sub 3} single crystals with nearly the same doping and the metallic ground state. Their comparisons have shown that ferromagnetic clusters originate in the paramagnetic matrix below T{sup Low-Asterisk }>T{sub C} in both samples and exhibit similar properties. This suggests the possible universality of such phenomena in doped mixed-valence oxides of transition metals with the perovskite-type structure. The cluster density increases on cooling and plays an important role on the physical properties of these systems. The differences in cluster evolutions and scenarios of their insulator-metal transitions are related to different magnetic behaviors of the matrixes in these crystals that is mainly due to distinct spin states of the Mn{sup 3+} and Co{sup 3+} ions.

  6. Charge delocalization in an organic mixed valent bithiophene is greater than in a structurally analogous biselenophene.

    Science.gov (United States)

    Jahnke, Ann Christin; Proppe, Jonny; Spulber, Mariana; Palivan, Cornelia G; Herrmann, Carmen; Wenger, Oliver S

    2014-11-26

    A series of selenophenes with redox-active amine end-capping groups was synthesized and investigated. A combination of cyclic voltammetry, optical absorption, EPR spectroscopy, and quantum-chemical calculations based on Kohn-Sham density functional theory was used to explore charge delocalization in the monocationic mixed-valence forms of these selenophenes, and the results were compared to those obtained from analogous studies of structurally identical thiophenes. The striking finding is that the comproportionation constant (Kc) for the experimentally investigated biselenophene is more than 2 orders of magnitude lower than for its bithiophene counterpart (in CH3CN with 0.1 M TBAPF6), and the electronic coupling between the two amine end-capping groups in the mixed-valent biselenophene monocation is only roughly half as strong as in the corresponding bithiophene monocation. These are surprisingly large differences given the structural similarity between the respective biselenophene and bithiophene molecules. However, the computationally determined comproportionation constants for biselenophene and bithiophene are almost identical, and the electronic coupling in the monocationic biselenophene is only slightly smaller than that in the monocationic bithiophene. We assume that the external electric field may be responsible for the differences in monocation stabilities between experiment and computation. Our findings indicate that charge delocalization across individual selenophenes tends to be less pronounced than across individual thiophenes, and this may have important implications for long-range charge transfer across selenophene oligomers or polymers.

  7. Electrical and structural properties of TiO2-δ thin film with oxygen vacancies prepared by RF magnetron sputtering using oxygen radical

    Science.gov (United States)

    Kawamura, Kinya; Suzuki, Naoya; Tsuchiya, Takashi; Shimazu, Yuichi; Minohara, Makoto; Kobayashi, Masaki; Horiba, Koji; Kumigashira, Hiroshi; Higuchi, Tohru

    2016-06-01

    Anatase TiO2-δ thin film was prepared by RF magnetron sputtering using oxygen radical and Ti-metal target. Degrees of the TiO2-δ crystal orientation in the thin film depends of the oxygen gas pressure (P\\text{O2}) in the radical gun. The (004)- and (112)-oriented TiO2-δ thin films crystallized without postannealing have the mixed valence Ti4+/Ti3+ state. The electrical conductivities, which corresponds to n-type oxide semiconductor, is higher in the case of (004)-oriented TiO2-δ thin film containing with high concentration of oxygen vacancy. The donor band of TiO2-δ thin film is observed at ˜1.0 eV from the Fermi level (E F). The density-of-state at E F is higher in (004)-oriented TiO2-δ thin film. The above results indicate that the oxygen vacancies can control by changing the P\\text{O2} of the oxygen radical.

  8. Controlled synthesis of rod-like LiVMoO6 nanocrystals for application in lithium-ion batteries

    Science.gov (United States)

    Liang, Yongguang; Han, Xiaoyan; Cong, Changjie; Yi, Zonghui; Zhou, Liqun; Sun, Jutang; Zhang, Keli; Zhou, Yunhong

    2007-04-01

    This paper reports a newly developed method for the shape and size control of transition metal composite oxides, such as LiVMoO6, to obtain significantly enhanced electrode properties for lithium-ion batteries. Rod-like LiVMoO6 nanocrystals were synthesized through a designed route of partial reduction, self-assembly and re-oxidation. V5+ and Mo6+ ions were used with low-grade starting materials to get a mixed valence of V and Mo. It is believed that ion pairs of V5+/V4+ or Mo6+/Mo5+ in the resultant mixture play an important role in the formation of a template precursor by self-assembly during a rheological phase reaction, although further explanation is required. The electrochemical performance of the LiVMoO6 obtained has been much improved due to the increased crystallinity and reduced particle size of this material. 176 mA h g-1 and 166 mA h g-1 capacity was delivered in the initial discharge with a reversible capacity retention of 94.8% and 95.3% after 100 cycles in the range of 3.6-1.80 V versus metallic Li at 1 and 3 C current rate, respectively.

  9. Synthesis of Bidimensional Prussian Blue Analogue Using an Inverted Langmuir-Schaefer Method.

    Science.gov (United States)

    Rossos, Andreas K; Gengler, Régis Y N; Badali, Daniel S; Miller, R J Dwayne

    2016-09-27

    One of the aspects of modern materials science that has been captivating scientific interest for the past decade is low-dimensional systems. This stems from the fact that the physical, chemical, and biological properties of such systems are often vastly different from their bulk counterparts. Additionally, low-dimensionality structures frequently serve as a convenient platform for device applications. However, such materials are typically constructed from building blocks that are inherently three-dimensional, and so, from a morphological point of view, these can still be categorized as bulk powders or crystals. To push the boundaries of reduced dimensionality, we synthesized truly two-dimensional films of Prussian blue analogues (mixed valence tetracyanides) by combining an air-water interface reaction and a novel inverted Langmuir-Schaefer technique. The methodology introduced in this study offers control and tailoring over the Prussian blue analogues' film characteristics, which is an important step toward their incorporation into tangible applications. Standard isotherms were collected as a function of the initial reactant volume, and a number of characterization techniques such as X-ray photoelectron spectroscopy (XPS), UV-visible spectroscopy (UV-vis), transmission electron microscopy (TEM), selected area electron diffraction (SAED), and atomic force microscopy (AFM) were performed on films transferred on various substrates. The results indicated a collection of single-crystalline and polycrystalline flakes possessing different thicknesses and having a structural coherence length of 11 ± 3 nm.

  10. Ab initio studies of [Fe4S4] ^2+/3+ clusters in metalloprotein MutY

    Science.gov (United States)

    Lin, Jong-Chin

    2005-03-01

    Iron sulfur clusters are present in the DNA repair protein MutY in a region highly homologous in species as diverse as E. Coli and Homo Sapiens, yet their function remains unknown. In MutY, this mixed valence cluster exists in two oxidation states, [Fe4S4]^2+/3+, with the stability depending upon the presence of DNA. We have studied the electronic structure and stability of these clusters using density functional theory, in particular the local orbital based SIESTA program. Our calculation shows that the energy difference between 2+ and 3+ forms is within the range of 0.1eV, which suggests that the redox process is reversible. We use this to propose a possible redox mechanism for modulating the rate for scanning for oxidized G-A mismatches in DNA by MutY ootnotetextM. Slutsky and L.A. Mirny, preprint q-bio.BM/0402005 at http://arxiv.org.. We note that this redox modulation mechanism for site recognition scanning may have broader generality.

  11. Atomic-Scale Study Of Complex Cobalt Oxide Using Scanning Transmission Electron Microscope

    Science.gov (United States)

    Gulec, Ahmet

    Cobalt oxides offer a rich ?eld for the formation of novel phases, including superconductors and exotic magnetic phases, involving a mixed valence state for cobalt and/or the presence of oxygen vacancies. Having spin states, such as, low spin (LS), high spin (HS), and intermediate spin (IS), cobalt oxides differ from other 3d metal oxides The presence of such spin states make the physics of the cobalt oxides so complicated that it has not yet been completely understood. In order to improve our understanding of the various phase transitions observed in Cobalt oxides and to comprehend the relationship between crystal and electronic structure, both high energy resolution and high spatial resolution are essential. Fortunately, transmission electron microscopy (TEM) is a technique which is capable of ful?lling both of these requirements. In this thesis, I have utilized unique techniques in a scanning transmission electron microscope (STEM) to analyze the atomic-scale structure-property relationship, both at room temperature and through insitu cooling to liquid nitrogen (LN2) temperature. In particular, by using correlated Z-contrast imaging, electron energy loss spectrum (EELS) and electron energy loss magnetic circular dichroism (EMCD), the structure, composition, bonding and magnetic behavior are characterized directly on the atomic scale.

  12. A 2D Semiquinone Radical-Containing Microporous Magnet with Solvent-Induced Switching from Tc = 26 to 80 K.

    Science.gov (United States)

    Jeon, Ie-Rang; Negru, Bogdan; Van Duyne, Richard P; Harris, T David

    2015-12-23

    The incorporation of tetraoxolene radical bridging ligands into a microporous magnetic solid is demonstrated. Metalation of the redox-active bridging ligand 2,5-dichloro-3,6-dihydroxy-1,4-benzoquinone (LH2) with Fe(II) affords the solid (Me2NH2)2[Fe2L3]·2H2O·6DMF. Analysis of X-ray diffraction, Raman spectra, and Mössbauer spectra confirm the presence of Fe(III) centers with mixed-valence ligands of the form (L3)(8-) that result from a spontaneous electron transfer from Fe(II) to L(2-). Upon removal of DMF and H2O solvent molecules, the compound undergoes a slight structural distortion to give the desolvated phase (Me2NH2)2[Fe2L3], and a fit to N2 adsorption data of this activated compound gives a BET surface area of 885(105) m(2)/g. Dc magnetic susceptibility measurements reveal a spontaneous magnetization below 80 and 26 K for the solvated and the activated solids, respectively, with magnetic hysteresis up to 60 and 20 K. These results highlight the ability of redox-active tetraoxolene ligands to support the formation of a microporous magnet and provide the first example of a structurally characterized extended solid that contains tetraoxolene radical ligands.

  13. X-ray spectroscopy of manganese clusters

    Energy Technology Data Exchange (ETDEWEB)

    Grush, M.M. [Univ. of California, Davis, CA (United States). Dept. of Applied Science]|[Lawrence Berkeley National Lab., CA (United States). Energy and Environment Div.

    1996-06-01

    Much of this thesis represents the groundwork necessary in order to probe Mn clusters more productively than with conventional Mn K-edge XAS and is presented in Part 1. Part 2 contains the application of x-ray techniques to Mn metalloproteins and includes a prognosis at the end of each chapter. Individual Mn oxidation states are more readily distinguishable in Mn L-edge spectra. An empirical mixed valence simulation routine for determining the average Mn oxidation state has been developed. The first Mn L-edge spectra of a metalloprotein were measured and interpreted. The energy of Mn K{beta} emission is strongly correlated with average Mn oxidation state. K{beta} results support oxidation states of Mn(III){sub 2}(IV){sub 2} for the S{sub 1} state of Photosystem II chemical chemically reduced preparations contain predominantly Mn(II). A strength and limitation of XAS is that it probes all of the species of a particular element in a sample. It would often be advantageous to selectively probe different forms of the same element. The first demonstration that chemical shifts in x-ray fluorescence energies can be used to obtain oxidation state-selective x-ray absorption spectra is presented. Spin-dependent spectra can also be used to obtain a more simplified picture of local structure. The first spin-polarized extended x-ray absorption fine structure using Mn K{beta} fluorescence detection is shown.

  14. Synthesis and Crystal Structure of a New Dinuclear Manganese(Ⅱ) Manganese(Ⅲ) Complex of a Macrocyclic Ligand

    Institute of Scientific and Technical Information of China (English)

    JIAN Fang-fang; XIAO Hai-lian; XU Liang-zhong; PANG Lei

    2004-01-01

    A mixed-valence dinuclear manganese complex, [MnⅡMnⅢL](ClO4)·1/2MeOH, where L is a macrocyclic ligand derived from the cyclocondensation of sodium 2,6-diformyl-4-methylphenolate with N,N-bis(2-aminoethyl)-2-hydroxybenzyl amine, was obtained and its structure was determined by X-ray diffraction. The orange crystal is a monoclinic system with space group P21/c and lattice parameters a=1.1617(4), b=1.4005(3), c=1.4641(3) nm, β=113.03(2)°, and Z=2. The crystal structure shows that each pendant-arm is bonded in a bidentate fashion to the adjacent metal atom and that both the arms are on the same side of the macrocycle. The two Mn atoms are bridged by two μ2-phenoxy oxygen atoms of the tetra-imine macrocycle, and each Mn atom, locating in a trigonal prismatic coordination environment(N3O3), is six-coordinated by the two imine nitrogen atoms, one tertiary nitrogen atom and a pendant phenol moiety apart from the two oxygen atoms.

  15. Europium ion as a probe for binding sites to carrageenans

    Energy Technology Data Exchange (ETDEWEB)

    Ramos, Ana P.; Goncalves, Rogeria R.; Serra, Osvaldo A. [Departamento de Quimica, Faculdade de Filosofia, Ciencias e Letras de Ribeirao Preto, Universidade de Sao Paulo, Ribeirao Preto, Sao Paulo 14040-901 (Brazil); Zaniquelli, Maria Elisabete D. [Departamento de Quimica, Faculdade de Filosofia, Ciencias e Letras de Ribeirao Preto, Universidade de Sao Paulo, Ribeirao Preto, Sao Paulo 14040-901 (Brazil)], E-mail: medzaniquelli@ffclrp.usp.br; Wong, Kenneth [Laboratorio de Fisico-Quimica, Centro de Pesquisas de Paulinia, Rhodia Brasil, Paulinia, Sao Paulo (Brazil)

    2007-12-15

    Carrageenans, sulfated polysaccharides extracted from red algae, present a coil-helix transition and helix aggregation dependence on the type and concentration of counterions. In this study, we focus attention on a mixed valence counterion system: Eu{sup 3+}/Na{sup +} or K{sup +} with different gel-forming carrageenans: kappa, iota, and kappa-2. Results of stationary and time-dependent luminescence showed to be a suitable tool to probe ion binding to both the negatively charged sulfate group and the hydroxyl groups present in the biopolymer. For lower europium ion concentrations, a single longer decay emission lifetime was detected, which was attributed to the binding of europium ion to the carrageenan sulfate groups. An additional decay ascribed to europium binding to hydroxyl groups was observed above a threshold concentration, and this decay was dependent on the carrageenan charge density. Symmetry of the europium ion microenvironment was estimated by the ratio between the intensities of its emission bands, which has been shown to depend on the concentration of europium ions and on the specificity of the monovalent counterion bound to the carrageenan.

  16. Model predictions of realgar precipitation by reaction of As(III) with synthetic mackinawite under anoxic conditions

    Science.gov (United States)

    Gallegos, T.J.; Han, Y.-S.; Hayes, K.F.

    2008-01-01

    This study investigates the removal of As(III) from solution using mackinawite, a nanoparticulate reduced iron sulfide. Mackinawite suspensions (0.1-40 g/L) effectively lower initial concentrations of 1.3 ?? 10 -5 M As(III) from pH 5-10, with maximum removal occurring under acidic conditions. Based on Eh measurements, it was found that the redox state of the system depended on the mackinawite solids concentration and pH. Higher initial mackinawite concentrations and alkaline pH resulted in a more reducing redox condition. Given this, the pH edge data were modeled thermodynamically using pe (-log[e-]) as a fitting parameter and linear pe-pH relationships within the range of measured Eh values as a function of pH and mackinawite concentration. The model predicts removal of As(III) from solution by precipitation of realgar with the formation of secondary oxidation products, greigite or a mixed-valence iron oxide phase, depending on pH. This study demonstrates that mackinawite is an effective sequestration agent for As(III) and highlights the importance of incorporating redox into models describing the As-Fe-S-H2O system. ?? 2008 American Chemical Society.

  17. Improved electronic structure and magnetic exchange interactions in transition metal oxides.

    Science.gov (United States)

    Gopal, Priya; De Gennaro, Riccardo; Silva Dos Santos Guzmao, Marta; Al Rahal Al Orabi, Rabih; Wang, Haihang; Curtarolo, Stefano; Fornari, Marco; Buongiorno Nardelli, Marco

    2017-08-15

    We discuss the application of the Agapito Curtarolo and Buongiorno Nardelli (ACBN0) pseudo-hybrid Hubbard density functional to several transition metal oxides. ACBN0 is a fast, accurate and parameter-free alternative to traditional DFT+U and hybrid exact exchange methods. In ACBN0, the Hubbard energy of DFT+U is calculated via the direct evaluation of the local Coulomb and exchange integrals in which the screening of the bare Coulomb potential is accounted for by a renormalization of the density matrix. We demonstrate the success of the ACBN0 approach for the electronic properties of a series technologically relevant mono-oxides (MnO, CoO, NiO, FeO, both at equilibrium and under pressure). We also present results on two mixed valence compounds, Co3O4 and Mn3O4. Our results, obtained at the computational cost of a standard LDA/PBE calculation, are in excellent agreement with hybrid functionals, the GW approximation and experimental measurements. © 2017 IOP Publishing Ltd.

  18. Magnetic States of the Co-ions in Ca and Y Doped (Bi,Pb2Sr2Co2O8 Thermoelectric Materials

    Directory of Open Access Journals (Sweden)

    Inge M. Sutjahja

    2012-11-01

    Full Text Available The magnetic states of Cobalt ions in magnetic thermoelectric materials of Bi1.5Pb0.5Ca2-zYzCo2O8 (z = 0, 0.1, 0.2, and 0.3 have been studied from the structural (X-ray diffraction and magnetic susceptibility data. The misfit structure was revealed from refinement of the XRD data, with reduction of the lattice parameters while increasing the Y doping content. Compared with the (Bi,Pb2Sr2Co2O8 parent compound system, the lattice parameter c was reduced significantly, while the misfit degree remained almost the same. The analysis of the magnetic data shows that the Cobalt ions are coupled antiferromagnetically within the CoO2 layers, with the existence of mixed valence states between Co3+ and Co4+ ions. Besides that, the effective magnetic moments of Cobalt ions are almost constant along the Y doping content. Assuming the orbital quenching as commonly found in most transition metal ions, the data are best fitted by taking the low-spin state of Co3+ ions and intermediate spin state of Co4+ ions. We argue qualitatively, that the spin-state transition across the gap are induced by the shrinkage of the charge transfer energy gaps between O 2p and Co levels due to reduction of the ionic spaces between Co and O ions.

  19. 5th International Conference on Valence Fluctuations

    CERN Document Server

    Malik, S

    1987-01-01

    During the Koln meeting (August 28-31, 1984), Irdia was chosen as the venue for the next International Conference on Valence Fluctuations. lhis was in recognition ard appreciation of the work done, both experimental ard theoretical, by the Irdian scientists in this area during the last decade. We decided to hold this Conference in the month of January, 1987 at Bangalore. lhe subject of Valence Fluctuations has kept itself alive ard active as it has provided many shocks ard suprises particularly among the Ce- ard U-based intermetallies. lhe richness of many interesting physical phenomena occurring in mixed valent materials, the flexibility of modifying their physical properties (by alloying, for example) ard the possibility of synthesizing a wide variety of new such materials seem to be the key factors in this regard. Barely six months before this Conference, an International Conference on Anomalous Rare Earths and Actinides (ICAREA) had been held at Grenoble (July, 1986) which also focussed on mixed valence a...

  20. On magnetic ordering in heavily sodium substituted hole doped lanthanum manganites

    Energy Technology Data Exchange (ETDEWEB)

    Sethulakshmi, N. [Department of Physics, Cochin University of Science and Technology, Cochin 682022, Kerala (India); Unnimaya, A.N. [Centre for Materials for Electronic Technology (CMET), Thrissur 680581, Kerala (India); Al-Omari, I.A.; Al-Harthi, Salim [Department of Physics, Sultan Qaboos University, PC 123 Muscat (Oman); Sagar, S. [Government College for Women, Thiruvananthapuram 695014, Kerala (India); Thomas, Senoy [Materials Science and Technology Division, National Institute for Interdisciplinary Science and Technology, Thiruvananthapuram 695019, Kerala (India); Srinivasan, G. [Department of Physics, Oakland University, Rochester (United States); Anantharaman, M.R., E-mail: mraiyer@yahoo.com [Department of Physics, Cochin University of Science and Technology, Cochin 682022, Kerala (India)

    2015-10-01

    Mixed valence manganite system with monovalent sodium substituted lanthanum manganites form the basis of the present work. Lanthanum manganites belonging to the series La{sub 1−x}Na{sub x}MnO{sub 3} with x=0.5–0.9 were synthesized using modified citrate gel method. Variation of lattice parameters and unit cell volume with Na concentration were analyzed and the magnetization measurements indicated ferromagnetic ordering in all samples at room temperature. Low temperature magnetization behavior indicated that all samples exhibit antiferromagnetism along with ferromagnetism and it has also been observed that antiferromagnetic ordering dominates ferromagnetic ordering as concentration is increased. Evidence for such a magnetic inhomogeneity in these samples has been confirmed from the variation in Mn{sup 3+}/Mn{sup 4+} ion ratio from X-ray Photoelectron Spectroscopy and from the absorption peak studies using Ferromagnetic Resonance Spectroscopy. - Highlights: • Higher substitution of more than 50 percent of monovalent ion, sodium for La sites in lanthanum manganites scarce in literature. • Structural studies using XRD and further structure refinement by Rietveld refinement confirmed orthorhombic pbnm spacegroup. • Ferromagnetic behavior at room temperature with saturation magnetization decreasing with increase in sodium concentration. • M vs T measurements using FC ZFC proved coexisting FM/AFM behavior arising from exchange interactions between different valence states of Mn ions. • Disparity in ratio of Mn valence ions indicated presence of vacancies providing the role of vacancies and oxygen stoichiometry in deciding magnetic inhomogeneity.

  1. Bismuth centred magnetic perovskite: A projected multiferroic

    Science.gov (United States)

    Kundu, Asish K.; Seikh, Md. Motin; Nautiyal, Pranjal

    2015-03-01

    In recent time substantial attention has been initiated to understand the physics behind multiferroism and to design new multiferroic materials. BiMnO3 and BiFeO3 are the well-studied Bi-centred multiferroic oxides. BiMnO3 is a ferromagnetic-ferroelectric (metastable) phase and require drastic conditions to synthesize. However, lanthanum substituted BiMnO3 phases stabilized at ambient pressure. It is thus of major importance to increase the number of ferromagnetic perovskites with Bi cations that could be designed under ambient conditions. In this article, we have presented an up to date report of investigations on Bi-centred magnetic perovskites, a prospective material for multiferroic application. Central focus is concentrated on La0.5Bi0.5MnO3 perovskite with various substitutions at different levels. A few of these perovskites are found to be of practical importance e.g. La0.5Bi0.5Mn0.67Co0.33O3 with high dielectric permittivity coupled with ferromagnetism. A comprehensive analysis of different physical functionalities and their interrelation for a wide range of compositions of these Bi-centred perovskites is presented. It has been found that the complex magnetic behaviour originates from mixed valence metal ions. The ferroelectricity is associated with the 6s2 lone pair of Bi3+ cations. The magnetic ground state influences the dielectric properties reflecting the multiferroism in a single material.

  2. Synthesis and characterization of mesoporous indium tin oxide possessing an electronically conductive framework.

    Science.gov (United States)

    Emons, Theo T; Li, Jianquan; Nazar, Linda F

    2002-07-24

    The new mesoporous transparent conducting oxide based on indium-tin-oxide, meso-ITO, has been synthesized by a modified sol-gel method, using CTAB as the surfactant. Critical was the employment of triethanolamine to control the rate of hydrolysis and inhibit deposition of the bulk oxides. Removal of the surfactant by calcination yielded a relatively well-ordered worm-hole motif arrangement of pores visible in the TEM and stable to 400 degrees C. BET measurements revealed no hysteresis in the absorption-desorption isotherm, consistent with a narrow pore-size distribution (between 20 and 40 A depending on the In:Sn ratio); surface areas ranged between 270 and 310 m2/g. This colorless material is the first mesoporous oxide exhibiting substantial framework conductivity, with a conductivity at 25 degrees C of 1.2 x 10-3 S/cm. This distinguishes it from mesoporous mixed-valence transition-metal oxides that exhibit weak hopping semiconductor behavior and much lower conductivity.

  3. Fluorine segregation in crystalline materials: structural control and solid-state [2+2] cycloaddition in CF(3)-substituted tetrathiafulvalene derivatives.

    Science.gov (United States)

    Jeannin, Olivier; Fourmigué, Marc

    2006-04-03

    The well-known influence of long perfluorinated chains on the structures and stability of amphiphilic molecules in liquid crystalline mesophases or mesoscopic micellar arrangements is evaluated here in the realm of crystalline materials based on rigid aromatic molecules bearing only a limited number of CF(3) moieties. Tetrathiafulvalene (TTF) derivatives bearing one or two CF(3) groups, that is, (Z)- and (E)-(CF(3))(2)TTF ((Z)-1, (E)-1), EDT-TTF-CF(3) (2), and EDT-TTF(CF(3))(2) (3) (EDT=ethylenedithio) are prepared from the 1,3-dipolar reaction of methyl 4,4,4-trifluorotetrolate with ethylenetrithiocarbonate. The structures of neutral (Z)-1, (E)-1, 2, and 3 as indicated by single-crystal X-ray diffraction measurements reveal the recurrent formation of layered structures with a strong segregation of the fluorinated moieties and formation of fluorous bilayers, attributed to the amphiphilic character of those TTF derivatives upon CF(3) functionalization, and without need for longer C(n)F(2n+1) (n>1) perfluorinated chains. The short intermolecular distance between outer C==C double bonds observed in the layered structure of (E)-1 allows a solid-state [2+2] photocyclization with formation of chiral dyads incorporating the characteristic cyclobutane ring. These dyads containing two dihydrotetrathiafulvalene moieties facing each other exhibit reversible oxidation to the mixed-valence radical cation state and organize in the solid-state into the same layered structures with fluorous bilayers.

  4. Photochromic hybrid organic-inorganic liquid-crystalline materials built from nonionic surfactants and polyoxometalates: elaboration and structural study.

    Science.gov (United States)

    Poulos, Andreas S; Constantin, Doru; Davidson, Patrick; Impéror, Marianne; Pansu, Brigitte; Panine, Pierre; Nicole, Lionel; Sanchez, Clément

    2008-06-17

    This work reports the elaboration and structural study of new hybrid organic-inorganic materials constructed via the coupling of liquid-crystalline nonionic surfactants and polyoxometalates (POMs). X-ray scattering and polarized light microscopy demonstrate that these hybrid materials, highly loaded with POMs (up to 18 wt %), are nanocomposites of liquid-crystalline lamellar structure (Lalpha), with viscoelastic properties close to those of gels. The interpretation of X-ray scattering data strongly suggests that the POMs are located close to the terminal -OH groups of the nonionic surfactants, within the aqueous sublayers. Moreover, these materials exhibit a reversible photochromism associated to the photoreduction of the polyanion. The photoinduced mixed-valence behavior has been characterized through ESR and UV-visible-near-IR spectroscopies that demonstrate the presence of W(V) metal cations and of the characteristic intervalence charge transfer band in the near-IR region, respectively. These hybrid nanocomposites exhibit optical properties that may be useful for applications involving UV-light-sensitive coatings or liquid-crystal-based photochromic switches. From a more fundamental point of view, these hybrid materials should be very helpful models for the study of both the static and dynamic properties of nano-objects confined within soft lamellar structures.

  5. Glycoluril–tetrathiafulvalene molecular clips: on the influence of electronic and spatial properties for binding neutral accepting guests

    Directory of Open Access Journals (Sweden)

    Yoann Cotelle

    2015-06-01

    Full Text Available Glycoluril-based molecular clips incorporating tetrathiafulvalene (TTF sidewalls have been synthesized through different strategies with the aim of investigating the effect of electrochemical and spatial properties for binding neutral accepting guests. We have in particular focused our study on the spacer extension in order to tune the intramolecular TTF···TTF distance within the clip and, consequently, the redox behavior of the receptor. Carried out at different concentrations in solution, electrochemical and spectroelectrochemical experiments provide evidence of mixed-valence and/or π-dimer intermolecular interactions between TTF units from two closed clips. The stepwise oxidation of each molecular clip involves an electrochemical mechanism with three one-electron processes and two charge-coupled chemical reactions, a scheme which is supported by electrochemical simulations. The fine-tunable π-donating ability of the TTF units and the cavity size allow to control binding interaction towards a strong electron acceptor such as tetrafluorotetracyanoquinodimethane (F4-TCNQ or a weaker electron acceptor such as 1,3-dinitrobenzene (m-DNB.

  6. Fermi energy 5f spectral weight variation in uranium alloys

    Energy Technology Data Exchange (ETDEWEB)

    Denlinger, J.D.; Clack, J.; Allen, J.W. [Univ. of Michigan, Ann Arbor, MI (United States)] [and others

    1997-04-01

    Uranium materials display a wide range of thermal, electrical and magnetic properties, often exotic. For more than a decade there have been efforts to use photoemission spectroscopy to develop a systematic and unified understanding of the 5f electron states giving rise to this behavior. These efforts have been hampered by a paucity of systems where changes in transport properties are accompanied by substantial spectral changes, so as to allow an attempt to correlate the two kinds of properties within some model. The authors have made resonant photoemission measurements to extract the 5f spectral weight in three systems which show varying degrees of promise of permitting such an attempt, Y{sub 1{minus}x}U{sub x}Pd{sub 3}, U(Pd{sub x}Pt{sub 1{minus}x}){sub 3} and U(Pd{sub x}Cu{sub 1{minus}x}){sub 5}. They have also measured U 4f core level spectra. The 4f spectra can be modeled with some success by the impurity Anderson model (IAM), and the 5f spectra are currently being analyzed in that framework. The IAM characterizes the 5f-electrons of a single site by an f binding energy {epsilon}{sub f}, an f Coulomb interaction and a hybridization V to conduction electrons. Latent in the model are the phenomena of 5f mixed valence and the Kondo effect.

  7. Synthesis, crystal structure and magnetic properties of single-molecule magnet: [Mn4(CF3COO)4(hmp)6

    Institute of Scientific and Technical Information of China (English)

    Liyan NA; Guiling NING; Fengjie ZHANG; Bing WANG

    2008-01-01

    The preparation, X-ray structure and magnetic properties are presented for a new mixed-valence tetra-nuclear manganese complex that functions as a single-molecule magnet (SMM): [Mn4(CF3COO)4(hmp)6], where hmp is the anion of 2-(hydroxymethyl) pyridine and is a N,O bidentate chelate. The compound crystallizes in a monoclinic system, space group P21/C (No. 14) with unit cell parameters a = 13.663(3) (A), b = 14.705(3) (A), c = 14.734(3) (A), β = 98.51(3)°, V= 2927.6 (A)3 and Z = 2. The structure of the complex shows a novel coordination of the trifluoroacetate (TFA) anions, with one anion acting as a monodentate ligand while the second one coordinating through both oxygens to the same Mn center. Direct current magnetic susceptibility measurement in the 2-300 K temperature range supports a high-spin ground state. The presence of a frequency-dependent alternating current susceptibility signal indicates that the individual molecule is acting as magnet.

  8. Tandem catalysis of ring-closing metathesis/atom transfer radical reactions with homobimetallic ruthenium–arene complexes

    Directory of Open Access Journals (Sweden)

    Yannick Borguet

    2010-12-01

    Full Text Available The tandem catalysis of ring-closing metathesis/atom transfer radical reactions was investigated with the homobimetallic ruthenium–indenylidene complex [(p-cymeneRu(μ-Cl3RuCl(3-phenyl-1-indenylidene(PCy3] (1 to generate active species in situ. The two catalytic processes were first carried out independently in a case study before the whole sequence was optimized and applied to the synthesis of several polyhalogenated bicyclic γ-lactams and lactones from α,ω-diene substrates bearing trihaloacetamide or trichloroacetate functionalities. The individual steps were carefully monitored by 1H and 31P NMR spectroscopies in order to understand the intimate details of the catalytic cycles. Polyhalogenated substrates and the ethylene released upon metathesis induced the clean transformation of catalyst precursor 1 into the Ru(II–Ru(III mixed-valence compound [(p-cymeneRu(μ-Cl3RuCl2(PCy3], which was found to be an efficient promoter for atom transfer radical reactions under the adopted experimental conditions.

  9. O2 insertion into group 9 metal-hydride bonds: evidence for oxygen activation through the hydrogen-atom-abstraction mechanism.

    Science.gov (United States)

    Keith, Jason M; Teets, Thomas S; Nocera, Daniel G

    2012-09-03

    A detailed density functional study was performed to examine the reaction of mixed-valence dirhodium and diiridium species [M(2)(0,II)(tfepma)(2)(CN(t)Bu)(2)(Cl)(2) (1, tfepma = MeN[P(OCH(2)CF(3))(2)](2), CN(t)Bu = tert-butyl isocyaninde)] with HCl and oxygen with an interest in examining the pathways for oxygen insertion into the intermediate metal hydride to form hydroperoxo species. The O(2) hydrogen atom abstraction mechanism for both the Rh and Ir was found to be feasible. This is the first time this mechanism has been applied to a Rh system and only the second time it has been examined for a system other than Pd. The competing trans HCl reductive elimination pathway was also examined and found to be greatly dependent on the stereochemistry of the starting hydride primarily due to the intermediate formed upon the loss of Cl(-). As a result, the reductive elimination pathway was more favorable by 11.5 kcal/mol for the experimentally observed Ir stereoisomer, while the two pathways were isoenergetic for the other stereoisomer of the Rh complex. All findings are consistent with the kinetics study previously performed.

  10. Spectral properties of actinide materials: Charge density self-consistent LDA+Hubbard I method in FP-LAPW basis

    Energy Technology Data Exchange (ETDEWEB)

    Kolorenc, Jindrich [Institute of Physics ASCR, Prague (Czech Republic); University of Hamburg, Hamburg (Germany); Shick, Alexander B. [Institute of Physics ASCR, Prague (Czech Republic); Havela, Ladislav [Charles University, Prague (Czech Republic); Lichtenstein, Alexander I. [University of Hamburg, Hamburg (Germany)

    2010-07-01

    We provide a numerically efficient procedure to perform LDA+Hubbard I calculations including self-consistency over the charge density in the FP-LAPW basis. The method is applied to Pu, Am, and PuAm and PuCe alloys. Our results for valence photoemission spectra (PES) agree with experimental data and with previous LDA+DMFT calculations. Analysis of the J=5/2 and J=7/2 contributions to the f-occupation supports the intermediate-coupling picture of f-states in heavy actinides. The electronic specific heat coefficient is calculated for PuAm and PuCe alloys in reasonable agreement with recent experiments. We show that Pu atoms keep their mixed-valence character in these alloys. Next, we study electronic and spectral properties of Pu-based superconductor PuCoGa{sub 5} and obtain good agreement with experimental PES. Finally, we analyze surface effects. In Pu monolayer, we find substantial modification of PES due to 5f-electron localization consistent with experimental observations.

  11. A study on transformation of some transition metal oxides in molten steelmaking slag to magnetically susceptible compounds

    Directory of Open Access Journals (Sweden)

    Shatokha V.

    2013-01-01

    Full Text Available Sustainable development of steelmaking requires solving a number of environmental problems. Economically feasible and environmentally friendly recycling of slag wastes is of special concern. Research of the team representing National Metallurgical Academy of Ukraine, Royal Institute of Technology, Carnegie Mellon University and URS Corp revealed a possibility of the controlled phase transformations in the liquid silicate melts followed by formation of the magnetically susceptible compounds. This approach enables selective recovery of metal values from slag. In this paper, the results obtained and further research directions are discussed. A possibility to exploit physical properties of the transition metals, typical for the metallurgical slags (such as Fe, Mn, V and others, and corresponding specific properties of their compounds, such as non-stoichiometry, mixed valency, pseudomorphosis, thermodynamic stability etc, in production of value-added materials from slag wastes is discussed. The results of the studies of thermodynamics and kinetics of oxidation in slags followed by phase transformation with binary, ternary and complex oxides under various physicochemical conditions are discussed in the view of their application for production of the materials with predefined physical properties. Peculiarities of precipitation in slags with various basicities are analysed and demonstrate capacity of the proposed approach in the production of the material with a given structure and size - for example, nano-sized crystals with structure of spinel. The approaches towards industrial realization of the developed method are also discussed.

  12. Ferrous Iron Binding Key to Mms6 Magnetite Biomineralisation: A Mechanistic Study to Understand Magnetite Formation Using pH Titration and NMR Spectroscopy.

    Science.gov (United States)

    Rawlings, Andrea E; Bramble, Jonathan P; Hounslow, Andrea M; Williamson, Michael P; Monnington, Amy E; Cooke, David J; Staniland, Sarah S

    2016-06-01

    Formation of magnetite nanocrystals by magnetotactic bacteria is controlled by specific proteins which regulate the particles' nucleation and growth. One such protein is Mms6. This small, amphiphilic protein can self-assemble and bind ferric ions to aid in magnetite formation. To understand the role of Mms6 during in vitro iron oxide precipitation we have performed in situ pH titrations. We find Mms6 has little effect during ferric salt precipitation, but exerts greatest influence during the incorporation of ferrous ions and conversion of this salt to mixed-valence iron minerals, suggesting Mms6 has a hitherto unrecorded ferrous iron interacting property which promotes the formation of magnetite in ferrous-rich solutions. We show ferrous binding to the DEEVE motif within the C-terminal region of Mms6 by NMR spectroscopy, and model these binding events using molecular simulations. We conclude that Mms6 functions as a magnetite nucleating protein under conditions where ferrous ions predominate. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. Magnetic and electrical transport properties of Pb1-xLaxTi1-xMnxO3 ceramics

    Directory of Open Access Journals (Sweden)

    Jie Xu

    2012-09-01

    Full Text Available Pb1-xLaxTi1-xMnxO3 (PLTM100x, x = 0.20, 0.40, 0.50, 0.60, and 0.80 ceramics have been prepared and investigated. X-ray diffractions show all ceramics are crystallized into perovskite structures with tetragonal symmetry for PLTMO20 and orthorhombic symmetry for the other compositions. X-ray photoelectron spectroscopy results confirm that the Mn cations in PLTMO20 and PLTMO40 have the valence state of +3, whereas in other compositions, the Mn cations have mixed valences states of +3 and +4. With increasing x from 0.20 to 0.80, the materials change from superparamagnetic to coexisting ferromagnetic and antiferromagnetic magnetic behaviour whereas all compositions persist insulating behaviour, as confirmed by the magnetization-magnetic field (M-H, the temperature dependent magnetization (M-T and transport measurements. Especially, the PLTMO80 has a large negative magnetoresistance of −41.5% at 10 K with the applied filed of 2 T. By considering the chemical states of Mn cations, these results are attributed to that the coexistence of metallic ferromagnetic and insulating non-ferromagnetic phases.

  14. The dynamics of the laser-induced metal-semiconductor phase transition of samarium sulfide (SmS); Die Dynamik des laserinduzierten Metall-Halbleiter-Phasenuebergangs von Samariumsulfid (SmS)

    Energy Technology Data Exchange (ETDEWEB)

    Kaempfer, Tino

    2009-12-15

    The present thesis is dedicated to the experimental study of the metal-semiconductor phase transition of samarium sulfide (SmS): Temperature- and time-resolved experiments on the characterization of the phase transition of mixed-valence SmS samples (M-SmS) are presented. The measurement of the dynamics of the laser-induced phase transition pursues via time-resolved ultrashort-time microscopy and by X-ray diffraction with sub-picosecond time resolution. The electronic and structural processes, which follow an excitation of M-SmS with infrared femtosecond laser pulses, are physically interpreted on the base of the results obtained in this thesis and model imaginations. [German] Die vorliegende Arbeit ist der experimentellen Untersuchung des Metall-Halbleiter-Phasenuebergangs von Samariumsulfid (SmS) gewidmet. Es werden temperatur- und zeitaufgeloeste Experimente zur Charakterisierung des Phasenuebergangs gemischt-valenter SmS Proben (M-SmS) vorgestellt. Die Messung der Dynamik des laserinduzierten Phasenuebergangs erfolgt ueber zeitaufgeloeste Ultrakurzzeit-Mikroskopie und durch Roentgenbeugung mit subpikosekunden Zeitaufloesung. Die elektronischen und strukturellen Prozesse, welche einer Anregung von M-SmS mit infraroten Femtosekunden-Laserpulsen folgen, werden auf der Basis der in dieser Arbeit gewonnenen Ergebnisse und Modellvorstellungen physikalisch interpretiert. (orig.)

  15. Monovalent plasmonic nanoparticles for biological applications

    Science.gov (United States)

    Seo, Daeha; Lee, Hyunjung; Lee, Jung-uk; Haas, Thomas J.; Jun, Young-wook

    2016-03-01

    The multivalent nature of commercial nanoparticle imaging agents and the difficulties associated with producing monovalent nanoparticles challenge their use in biology, where clustering of target biomolecules can perturb dynamics of biomolecular targets. Here, we report production and purification of monovalent gold and silver nanoparticles for their single molecule imaging application. We first synthesized DNA-conjugated 20 nm and 40 nm gold and silver nanoparticles via conventional metal-thiol chemistry, yielding nanoparticles with mixed valency. By employing an anion-exchange high performance liquid chromatography (AE-HPLC) method, we purified monovalent nanoparticles from the mixtures. To allow efficient peak-separation resolution while keeping the excellent colloidal stability of nanoparticles against harsh purification condition (e.g. high NaCl), we optimized surface properties of nanoparticles by modulating surface functional groups. We characterized the monovalent character of the purified nanoparticles by hybridizing two complementary conjugates, forming dimers. Finally, we demonstrate the use of the monovalent plasmonic nanoprobes as single molecule imaging probes by tracking single TrkA receptors diffusing on the cell membrane and compare to monovalent quantum dot probes.

  16. In situ study of the solid-state formation of U(1-x)Am(x)O(2±δ) solid solution.

    Science.gov (United States)

    Lebreton, Florent; Belin, Renaud C; Prieur, Damien; Delahaye, Thibaud; Blanchart, Philippe

    2012-09-03

    In order to reduce the nuclear waste inventory and radiotoxicity, U(1-x)Am(x)O(2±δ) materials are promising fuels for heterogeneous transmutation. In this context, they are generally fabricated from UO(2+δ) and AmO(2-δ) dioxide powders. In the subsequent solid solution, americium is assumed to be trivalent whereas uranium exhibits a mixed-valence (+IV/+V) state. However, no formation mechanisms were ever evidenced and, more particularly, it was not possible to know whether the reduction of Am(IV) to Am(III) occurs before the solid-solution formation, or only once it is established. In this study, we used high-temperature X-ray diffraction on a UO(2±δ)/AmO(2-δ) (15 mol %) mixture to observe in situ the formation of the U(1-x)Am(x)O(2±δ) solid solution. We show that UO(2+δ) is, at relatively low temperature (solid solution starts forming at 1740 K. The UO(2) fluorite phase vanishes after 4 h at 1970 K, indicating that the formation of the solid solution is completed, which proves that this solid solution is formed after the complete reduction of Am(IV) to Am(III).

  17. Metal-ion pillared clays as hydrocracking catalysts (II): effect of contact time on products from coal extracts and petroleum distillation residues

    Energy Technology Data Exchange (ETDEWEB)

    S.D. Bodman; W.R. McWhinnie; V. Begon; M. Millan; I. Suelves; M.-J. Lazaro; A.A. Herod; R. Kandiyoti [Aston University, Birmingham (United Kingdom). Department of Chemical Engineering and Applied Chemistry

    2003-11-01

    Novel catalysts have been prepared, based on montmorillonite (a natural clay) and laponite (a synthetic clay) pillared with tin, chromium and aluminium pillars as well as layered double hydroxides based on polyoxo-vanadate and -molybdate as previously described. These novel catalysts were compared initially with a standard Ni/Mo catalyst supported on alumina and a dispersed catalyst, Mo(CO){sub 6} in hydrocracking a coal extract for a short contact time of 10 min at 440{sup o}C in a microbomb reactor with tetralin solvent and hydrogen at a pressure of 190 bar. In the present work, the best of the novel catalysts, chromium montmorillonite calcined at 500{sup o}C and tin laponite, have been compared with the supported catalyst and a dispersed catalyst (Mo(CO){sub 6}) in the repeated hydrocracking of fresh coal extract over three sequential periods of 1 h. Also, the chromium montmorillonite calcined at 500{sup o}C has been used in the hydrocracking of primary coal extracts, prepared in the flowing solvent liquefaction rig from Pittsburgh No. 8 and Illinois No. 6 coals, for reaction times of 10 min and 2 h. Further, the chromium montmorillonite calcined at 500{sup o}C and tin laponite, have been compared with the supported catalyst and in the absence of a catalyst, in the hydrocracking of a petroleum distillation residue with 10 min and 2 h reaction times. Results were compared by size exclusion chromatography in NMP solvent and by UV-fluorescence and evaluated by the extent of the shift of the SEC profile to small molecules and by the shift of the synchronous UV-fluorescence profiles to shorter wavelengths. The performances of both catalysts at short, long or repeated reaction times are seen to be better than that of the conventional NiMo catalyst for the hydrocracking of coal-derived materials and a petroleum residue. Trials on a longer time scale are necessary in the next level of evaluation. 37 refs., 14 figs., 1 tab.

  18. Effect of calcination temperature on performance of Mn-Fe/CeO2-TiO2catalyst for selective catalytic reduction of NO by NH3 at low temperature%焙烧温度对Mn-Fe/CeO2-TiO2催化剂低温NH3选择性催化还原NO的影响

    Institute of Scientific and Technical Information of China (English)

    吴大旺; 张秋林; 林涛; 龚茂初; 陈耀强

    2012-01-01

    采用等体积浸渍法制备了Mn-Fe/CeO2-TiO2催化剂,考察了不同焙烧温度对其NH3选择性催化还原(SCR) NO活性及催化剂性能的影响.并用N2吸附-脱附,X射线衍射(XRD)和X射线光电子能谱(XPS)等手段对催化剂进行了表征.活性结果表明,随着焙烧温度的升高,Mn-Fe./CeO2-TiO2催化剂的催化活性先升高后降低.其中焙烧温度为500℃时Mn/CeO2-TiO2的NH3-SCR活性最佳,该催化剂在113 ~ 250℃之间表现出了良好NO去除效率.表征结果表明,500℃焙烧时,催化剂中Fe和Mn物种在CeO2-TiO2表面的分散效果最好.500℃焙烧时Mn-Fe/CeO2-TiO2表面Mn以+4价存在,Fe以+3、+2价存在,而Ce以+4、+3存在.%The Mn-Fe/CeO2-TiO2 catalyst was prepared by the incipient wetness method,the influence of calcination temperature on the property and catalytic activity of Mn-Fe/CeO2 -TiO2 was studied for selective catalytic reduction( SCR) of NO by NH3. The catalysts were characterized by N2-adsorption-desorption, X-ray diffraction and X-ray photoelectron spectroscopy. The performance results showed that the catalytic activities were fust increased and subsequently decreased with the increase of calcination temperature. The catalyst calcined at 500℃ showed the best activity for NO reduction by NH3, and this catalyst exhibited high NO conversion in a wide temperature range of 113-250℃. The characterization results revealed that the Mn-Fe/CeO2-TiO2 catalyst calcined at 500℃ promoted the dispersion of Mn and Fe species on CeO2-TiO2. The XPS results indicated that the Mn species was existed in a valence of +4. Fe species was existed as a mixed valence of +3 and+2 and Ce species was a mixed valence of existed as +4 and +3.

  19. Magnetocaloric materials

    Energy Technology Data Exchange (ETDEWEB)

    Jeppesen, Stinus

    2008-10-15

    New and improved magnetocaloric materials are one of the cornerstones in the development of room temperature magnetic refrigeration. Magnetic refrigeration has been used since the 1930ies in cryogenic applications, but has since the discovery of room temperature refrigerants received enormous attention. This Ph.D. work has been mainly concerned with developing a new technique to characterize the magnetocaloric effect (MCE) and using this technique in the investigations on new and improved magnetocaloric materials. For this purpose a novel differential scanning calorimeter (DSC) with applied magnetic fields was developed for measuring heat capacity as function of magnetic field. Measurements using the developed DSC demonstrate a very high sensitivity, fast measurements and good agreement with results obtained by other techniques. Furthermore, two material systems have been described in this work. Both systems take basis in the mixed-valence manganite system La{sub 1-x}Ca{sub x}MnO{sub 3} well known from research on colossal magnetoresistance (CMR). The mixed-valence manganite crystallizes in the perovskite structure of general formula ABO{sub 3}. The first material system is designed to investigate the influence of low level Cu doping on the B-site. Six different samples were prepared with over-stoichiometric compositions La{sub 0.67}Ca{sub 0.33}Mn{sub 1.05}Cu{sub x}O{sub 3}, x=0, 1, 2, 3, 4 and 5%. All compositions crystallized well in the same perovskite structure, but the morphology of the samples changed drastically with doping. Investigation on the magnetocaloric properties revealed that small levels of Cu up to around 3% could improve the magnetocaloric performance of the materials. Furthermore, Cu could be used to tune the temperature interval without deteriorating the MCE, which is a much desired characteristic for potential use in magnetic refrigerators. A less comprehensive part of the work has been concerned with the investigation of doping on the A

  20. Structure, optical and magnetic properties of (In{sub 1−x}Fe{sub x}){sub 2}O{sub 3} films by magnetron sputtering

    Energy Technology Data Exchange (ETDEWEB)

    Yang, Dongyan; Feng, Deqiang [Key Laboratory of Display Materials and Photoelectric Devices, Ministry of Education, Tianjin Key Laboratory for Photoelectric Materials and Devices, School of Material Science and Engineering, Tianjin University of Technology, Tianjin 300384 (China); Wu, Zhonghua [Beijing Synchrotron Radiation Facility (BSRF), Institute of High Energy Physics, Chinese Academy of Sciences, Beijing 100049 (China); Ma, Guanxiong, E-mail: ma_guanxiong@sina.com [College of Science, Shenyang Agricultural University, Shengyang 110866 (China); Liu, Jiwen [Key Laboratory of Display Materials and Photoelectric Devices, Ministry of Education, Tianjin Key Laboratory for Photoelectric Materials and Devices, School of Material Science and Engineering, Tianjin University of Technology, Tianjin 300384 (China); An, Yukai, E-mail: ykan@tjut.edu.cn [Key Laboratory of Display Materials and Photoelectric Devices, Ministry of Education, Tianjin Key Laboratory for Photoelectric Materials and Devices, School of Material Science and Engineering, Tianjin University of Technology, Tianjin 300384 (China)

    2015-01-15

    Highlights: • Structural, optical and magnetic properties of films were investigated. • Fe substitute for In sites of In{sub 2}O{sub 3} lattice with a mixed-valence (Fe{sup 2+}/Fe{sup 3+}). • Oxygen vacancies play an important role in activating RT ferromagnetism. - Abstract: Effect of Fe doping on structural, optical and magnetic properties of the (In{sub 1−x}Fe{sub x}){sub 2}O{sub 3} films (0 ⩽ x ⩽ 0.31) are investigated systematically by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), extended X-ray absorption fine structure (EXAFS), UV–Vis, Hall effect and magnetic measurements. Combining XRD, XPS and EXAFS measurements, it reveals that Fe dopant ions substitute for In{sup 3+} sites of In{sub 2}O{sub 3} lattice with a mixed-valence (Fe{sup 2+}/Fe{sup 3+}) in the (In{sub 1−x}Fe{sub x}){sub 2}O{sub 3} films with low Fe concentration (x ⩽ 0.16), while a part of Fe atoms form the precipitate of Fe metal clusters in the (In{sub 1−x}Fe{sub x}){sub 2}O{sub 3} films with high Fe concentration (x ⩾ 0.22). The decreased transmittance and optical band gap of films with Fe doping is ascribed to sp-d exchange interaction associated with the Fe dopants. Magnetic characterizations show that all the films display a clear room-temperature (RT) ferromagnetic behavior. The saturated magnetization (M{sub S}) increases monotonically with the increase of Fe concentration and reaches 85.5 emu/cm{sup 3} for the (In{sub 0.69}Fe{sub 0.31}){sub 2}O{sub 3} film. However, the Hall measurements show that the carrier concentration n{sub c} decreases monotonically with Fe doping, implying that the ferromagnetism is not mediated by carriers in the (In{sub 1−x}Fe{sub x}){sub 2}O{sub 3} films (x ⩽ 0.16). It can be concluded that oxygen vacancies play an important role in activating the observed intrinsic RT ferromagnetism in the (In{sub 1−x}Fe{sub x}){sub 2}O{sub 3} films (x ⩽ 0.16). However, the larger M{sub S} in the (In{sub 1−x}Fe{sub x}){sub 2

  1. Structural and Magnetothermal Properties of Compounds: Yb5SixGe4-x,Sm5SixGe4-x, EuO, and Eu3O4

    Energy Technology Data Exchange (ETDEWEB)

    Ahn, Kyunghan [Iowa State Univ., Ames, IA (United States)

    2007-01-01

    The family of R5SixGe4-x alloys demonstrates a variety of unique physical phenomena related to magneto-structural transitions associated with reversible breaking and reforming of specific bonds that can be controlled by numerous external parameters such as chemical composition, magnetic field, temperature, and pressure. Therefore, R5SixGe4-x systems have been extensively studied to uncover the mechanism of the extraordinary magneto-responsive properties including the giant magnetoresistance (GMR) and colossal magnetostriction, as well as giant magnetocaloric effect (GMCE). Until now, more than a half of possible R5SixGe4-x pseudobinary systems have been completely or partially investigated with respect to their crystallography and phase relationships (R = La, Pr, Nd, Gd, Tb, Dy, Er, Lu, Y). Still, there are other R5SixGe4-x systems (R = Ce, Sm, Ho, Tm, and Yb) that are not studied yet. Here, we report on phase relationships and structural, magnetic, and thermodynamic properties in the Yb5SixGe4-xand Sm5SixGe4-x pseudobinary systems, which may exhibit mixed valence states. The crystallography, phase relationships, and physical properties of Yb5SixGe4-x alloys with 0 ≤ x ≤ 4 have been examined by using single crystal and powder x-ray diffraction at room temperature, and dc magnetization and heat capacity measurements between 1.8 K and 400 K in magnetic fields ranging from 0 to 7 T. Unlike the majority of R5SixGe4-x systems studied to date, where R is the rare earth metal, all Yb-based germanide-silicides with the 5:4 stoichiometry crystallize in the same Gd5Si4-type structure. The magnetic properties of Yb5SixGe4-x materials are nearly composition

  2. Intervalence charge transfer luminescence: Interplay between anomalous and 5d − 4f emissions in Yb-doped fluorite-type crystals

    Energy Technology Data Exchange (ETDEWEB)

    Barandiarán, Zoila, E-mail: zoila.barandiaran@uam.es; Seijo, Luis [Departamento de Química, Universidad Autónoma de Madrid, 28049 Madrid (Spain); Instituto Universitario de Ciencia de Materiales Nicolás Cabrera, Universidad Autónoma de Madrid, 28049 Madrid (Spain)

    2014-12-21

    In this paper, we report the existence of intervalence charge transfer (IVCT) luminescence in Yb-doped fluorite-type crystals associated with Yb{sup 2+}–Yb{sup 3+} mixed valence pairs. By means of embedded cluster, wave function theory ab initio calculations, we show that the widely studied, very broad band, anomalous emission of Yb{sup 2+}-doped CaF{sub 2} and SrF{sub 2}, usually associated with impurity-trapped excitons, is, rather, an IVCT luminescence associated with Yb{sup 2+}–Yb{sup 3+} mixed valence pairs. The IVCT luminescence is very efficiently excited by a two-photon upconversion mechanism where each photon provokes the same strong 4f{sup 14}–1A{sub 1g}→ 4f{sup 13}({sup 2}F{sub 7/2})5de{sub g}–1T{sub 1u} absorption in the Yb{sup 2+} part of the pair: the first one, from the pair ground state; the second one, from an excited state of the pair whose Yb{sup 3+} moiety is in the higher 4f{sup 13}({sup 2}F{sub 5/2}) multiplet. The Yb{sup 2+}–Yb{sup 3+} → Yb{sup 3+}–Yb{sup 2+} IVCT emission consists of an Yb{sup 2+} 5de{sub g} → Yb{sup 3+} 4f{sub 7/2} charge transfer accompanied by a 4f{sub 7/2} → 4f{sub 5/2} deexcitation within the Yb{sup 2+} 4f{sup 13} subshell: [{sup 2}F{sub 5/2}5de{sub g},{sup 2}F{sub 7/2}] → [{sup 2}F{sub 7/2},4f{sup 14}]. The IVCT vertical transition leaves the oxidized and reduced moieties of the pair after electron transfer very far from their equilibrium structures; this explains the unexpectedly large band width of the emission band and its low peak energy, because the large reorganization energies are subtracted from the normal emission. The IVCT energy diagrams resulting from the quantum mechanical calculations explain the different luminescent properties of Yb-doped CaF{sub 2}, SrF{sub 2}, BaF{sub 2}, and SrCl{sub 2}: the presence of IVCT luminescence in Yb-doped CaF{sub 2} and SrF{sub 2}; its coexistence with regular 5d-4f emission in SrF{sub 2}; its absence in BaF{sub 2} and SrCl{sub 2}; the quenching of

  3. Soft X-ray Spectroscopy Study of the Electronic Structure of Oxidized and Partially Oxidized Magnetite Nanoparticles

    Energy Technology Data Exchange (ETDEWEB)

    Gilbert, Benjamin; Katz, Jordan E.; Denlinger, Jonathan D.; Yin, Yadong; Falcone, Roger; Waychunas, Glenn A.

    2010-10-24

    The crystal structure of magnetite nanoparticles may be transformed to maghemite by complete oxidation, but under many relevant conditions the oxidation is partial, creating a mixed-valence material with structural and electronic properties that are poorly characterized. We used X-ray diffraction, Fe K-edge extended X-ray absorption fine structure (EXAFS) spectroscopy, and soft X-ray absorption and emission spectroscopy to characterize the products of oxidizing uncoated and oleic acid-coated magnetite nanoparticles in air. The oxidization of uncoated magnetite nanoparticles creates a material that is structurally and electronically indistinguishable from maghemite. By contrast, while oxidized oleic acid-coated nanoparticles are also structurally indistinguishable from maghemite, Fe L-edge spectroscopy revealed the presence of interior reduced iron sites even after a 2-year period. We used X-ray emission spectroscopy at the O K-edge to study the valence bands (VB) of the iron oxide nanoparticles, using resonant excitation to remove the contributions from oxygen atoms in the ligands and from low-energy excitations that obscured the VB edge. The bonding in all nanoparticles was typical of maghemite, with no detectable VB states introduced by the long-lived, reduced-iron sites in the oleic acid-coated sample. However, O K-edge absorption spectroscopy observed a 0.2 eV shift in the position of the lowest unoccupied states in the coated sample, indicating an increase in the semiconductor band gap relative to bulk stoichiometric maghemite that was also observed by optical absorption spectroscopy. The results show that the ferrous iron sites within ferric iron oxide nanoparticles coated by an organic ligand can persist under ambient conditions with no evidence of a distinct interior phase and can exert an effect on the global electronic and optical properties of the material. This phenomenon resembles the band gap enlargement caused by electron accumulation in the

  4. Physical properties of hematite α-Fe2O3 thin films: application to photoelectrochemical solar cells

    Institute of Scientific and Technical Information of China (English)

    S. S. Shinde; R. A. Bansode; C. H. Bhosale; K. Y. Rajpure

    2011-01-01

    The physical properties and photoelectrochemical characterization of aluminium doped hematite α-Fe2O3, synthesized by spray pyrolysis, have been investigated in regard to solar energy conversion. Stable Al-doped iron (Ⅲ) oxide thin films synthesized by a spray pyrolysis technique reveals an oxygen deficiency, and the oxide exhibits n-type conductivity confirmed by anodic photocurrent generation. The preparative parameters have been optimized to obtain good quality thin films which are uniform and well adherent to the substrate. The deposited iron oxide thin films show the single hematite phase with polycrystalline rhombohedral crystal structure with crystallite size 20-40 nm. Optical analysis enabled to point out the increase in direct band-gap energy from 2.2 to 2.25 eV with doping concentration which is attributed to a blue shift. The dielectric constant and dielectric loss are studied as a function of frequency. To understand the conduction mechanism in the films, AC conductivity is measured. The conduction occurs by small polaron hopping through mixed valences Fe2+/3+ with an electron mobility 300 K of 1.08 cm2/(V.s). The α-Fe2O3 exhibits long term chemical stability in neutral solution and has been characterized photoelectrochemically to assess its activity as a photoanode for various electrolytes using white light to obtain Ⅰ- characteristics. The Al-doped hematite exhibited a higher photocurrent response when compared with undoped films achieving a power conversion efficiency of 2.37% at 10 at% Al:Fe2O3 thin films along with fill factor 0.38 in NaOH electrolyte. The flat band potential Vfb (-0.87 VSCE) is determined by extrapolating the linear part to C-2 = 0 and the slope of the Mott-Schottky plot.

  5. Origin of giant dielectric constant and magnetodielectric study in Ba(Fe{sub 0.5}Nb{sub 0.5})O{sub 3} nanoceramics

    Energy Technology Data Exchange (ETDEWEB)

    Patel, Piyush Kumar [Department of Physics, Indian Institute of Technology Roorkee, Roorkee 247667 (India); Yadav, K.L., E-mail: klyadav35@yahoo.com [Department of Physics, Indian Institute of Technology Roorkee, Roorkee 247667 (India); Singh, Harishchandra [Indus Synchrotrons Utilization Division, Raja Ramanna Center for Advanced Technology, Indore 452013 (India); Yadav, A.K. [Atomic and Molecular Physics Division, Bhabha Atomic Research Centre, Mumbai 400088 (India)

    2014-04-05

    Highlights: • High dielectric constant (∼33,000) with low loss (∼0.45) was found at room temperature. • Cole–Cole plot analysis confirmed the formation of barrier layers on grain–grain boundary interfaces. • XANES study confirms the mixed valence state of Fe ion. • Reporting first time about presence of magnetocapacitance (∼3.4%) in the system. -- Abstract: Lead free Ba(Fe{sub 0.5}Nb{sub 0.5})O{sub 3} (BFN) ceramics were synthesized by sol–gel method. X-ray diffraction pattern of the samples at room temperature shows a monoclinic structure. The influence of sintering temperature on microstructure and dielectric properties of BFN ceramics were analysed. Microstructure analysis shows well-grown and dense microstructure in 1200 °C sintered sample exhibiting enhanced dielectric and magnetodielectric properties. We report a very high dielectric constant (∼33,000) with low dielectric loss (∼0.45) at room temperature for 1200 °C sintered sample at 100 Hz frequency. Cole–Cole plot shows that the grain boundary effect (barrier layer formation) is responsible for such a high value of dielectric constant. The sample was also analyzed by Fe K-edge X-ray absorption near-edge structure spectroscopy to obtain the Fe oxidation state. This analysis confirms that Fe ions in BFN ceramics are in mixed valance state (Fe{sup 2+}/Fe{sup 3+}). Another interesting feature of BFN ceramics is the appearance of room temperature high magnetodielectric response (3.8%) at 7 kOe magnetic field and 100 Hz frequency.

  6. Synthesis, Structure, Optical, and Electrochemical Properties of Triple- and Quadruple-Decker Co-facial Tetrathiafulvalene Arrays.

    Science.gov (United States)

    Hasegawa, Masashi; Nakamura, Ken-Ichi; Tokunaga, Saki; Baba, Yumi; Shiba, Ryota; Shirahata, Takashi; Mazaki, Yasuhiro; Misaki, Yohji

    2016-07-11

    Understanding the details of the electronic structure in face-to-face arranged tetrathiafulvalenes (TTFs) is very important for the design of supramolecular functional materials and superior conductive organic materials. This article is a comprehensive study of the interactions among columnar stacked TTFs using trimeric (trimer) and tetrameric (tetramer) TTFs linked by alkylenedithio groups (-S(CH2 )n S-, n=1-4) as models of triple- and quadruple-decker TTF arrays. Single-crystal X-ray analyses of neutral trimeric TTFs revealed that the three TTF moieties are oriented in a zigzag arrangement. Cyclic voltammetry measurements (CV) reveal that the trimer and tetramer exhibited diverse reversible redox processes with multi-electron transfers, depending on the length of the -S(CH2 )n S- units and substituents. The electronic spectra of the radical cations, prepared by electrochemical oxidation, showed charge resonance (CR) bands in the NIR/IR region (1630-1850 nm), attributed to a mixed valence (MV) state of the triple- and quadruple-decker TTF arrays. In the trimeric systems, the dicationic state (+2; 0.66 cation per TTF unit) was found to be a stable state, whereas the monocationic state (+1) was not observed in the electronic spectra. In the tetrameric system, substituent-dependent redox processes were observed. Moreover, π-trimers and π-tetramers, which show a significant Davydov blueshift in the spectra, are formed in the tricationic (trimer) and tetracationic (tetramer) state. In addition, these attractive interactions are strongly dependent on the length of the linkage unit.

  7. Nuclear magnetic resonance study of the magnetic line phases in SrCoO x (2.5 ≤ × ≤ 3)

    Science.gov (United States)

    Hines, W. A.; Perry, D. M.; Xie, C. K.; Budnick, J. I.; Wells, B. O.; Dabrowski, B.

    2016-07-01

    A 59Co spin-echo nuclear magnetic resonance (NMR) study, along with complimentary magnetization and x-ray diffraction characterization, is reported for three of the four magnetic line phases which occur in the hole-doped perovskite system SrCoO x , 2.5 ≤ x ≤ 3. The magnetic line phases are the single-valence state end-member compounds SrCoO2.5 and SrCoO3, as well as the mixed-valence state compound SrCoO2.88. In this work, the Co valence was varied by changing the oxygen stoichiometry through electrochemical oxidation/reduction. Antiferromagnetic SrCoO2.5, with trivalent Co3+ (3d6), is characterized by a single strong, relatively narrow, 59Co NMR peak centered at 314 MHz. The 314 MHz peak frequency can be explained using a typical 3d hyperfine coupling constant and the Co moment value ≈3 μ B obtained from neutron diffraction measurements. Ferromagnetic SrCoO3 with tetravalent Co4+ (3d5), is characterized by a single strong, relatively narrow, 59Co NMR peak centered at 93 MHz. However, the 93 MHz peak frequency is considerably smaller than expected from the 2.1 μ B Co moment values obtained from the saturation magnetization indicating a significant orbital contribution. Ferromagnetic and mixed-valent (Co3+/Co4+) SrCoO2.88 is characterized by three broad 59Co peaks, centered at 47, 134, and 280 MHz, consistent with previous reports. Based on the NMR results from the end-member compounds, the 280 MHz peak is most likely due to Co3+ and not Co4+ as previously reported.

  8. An Excursion into the Intriguing World of Polymeric Tl(I and Ag(I Cyanoximates

    Directory of Open Access Journals (Sweden)

    Nikolay Gerasimchuk

    2011-09-01

    Full Text Available The reaction of hot (~95 °C aqueous solutions of Tl2CO3 with solid HL (HL = NC-C(=N-OH-R is a cyanoxime, and R is an electron-withdrawing group; 37 ligands are known up-to-date leads to crystalline yellow/orange TlL. Similarly, the reaction between AgNO3 and ML (M = K+, Na+; L = anion of the monodeprotonated cyanoxime this time at room temperature in mixed ethanol/aqueous solutions leads to sparingly soluble, colored AgL in high-yield. All synthesized monovalent Tl and Ag complexes were characterized using a variety of spectroscopic methods and X-ray analysis, which revealed the formation of primarily 2D coordination polymers of different complexity. In all cases cyanoxime mono-anions act as bridging ligands. Thallium(I cyanoximates adopt in most cases a double-stranded motif that is originated from centrosymmetric (TlL2 dimers in which two Tl2O2 rhombs are fused into infinite “ladder-type” structure. There are very short (3.65–3.85 Å intermetallic distances in (TlLn, which are close to that (3.46 Å in metallic thallium. This opens the possibility for the electrochemical or chemical generation of mixed valence Tl(I/Tl(III polymers that may exhibit electrical conductivity. Synthesized silver(I compounds demonstrate a very significant (for multiple years! stability towards visible light. There are three areas of potential practical applications of these unusual complexes: (1 battery-less detectors of UV-radiation, (2 non electrical sensors for gases of industrial importance, (3 antimicrobial additives to light-curable acrylate polymeric glues, fillers and adhesives used during introduction of indwelling medical devices. Chemical, structural, technological and biological aspects of application of Tl(I and Ag(I cyanoximes-based coordination polymers are reviewed.

  9. Eu-doped ZnO-HfO2 hybrid nanocrystal-embedded low-loss glass-ceramic waveguides.

    Science.gov (United States)

    Ghosh, Subhabrata; Bhaktha B N, Shivakiran

    2016-03-11

    We report on the sol-gel fabrication, using a dip-coating technique, of low-loss Eu-doped 70SiO2 -[Formula: see text] HfO2-xZnO (x = 2, 5, 7 and 10 mol%) ternary glass-ceramic planar waveguides. Transmission electron microscopy and grazing incident x-ray diffraction experiments confirm the controlled growth of hybrid nanocrystals with an average size of 3 nm-25 nm, composed of ZnO encapsulated by a thin layer of nanocrystalline HfO2, with an increase of ZnO concentration from x = 2 mol% to 10 mol%  in the SiO2-HfO2 composite matrix. The effect of crystallization on the local environment of Eu ions, doped in the ZnO-HfO2 hybrid nanocrystal-embedded glass-ceramic matrix, is studied using photoluminescence spectra, wherein an intense mixed-valence state (divalent as well as trivalent) emission of Eu ions is observed. The existence of Eu(2+) and Eu(3+) in the SiO2-HfO2-ZnO ternary matrix is confirmed by x-ray photoelectron spectroscopy. Importantly, the Eu[Formula: see text]-doped ternary waveguides exhibit low propagation losses (0.3 ± 0.2 dB cm(-1) at 632.8 nm) and optical transparency in the visible region of the electromagnetic spectrum, which makes ZnO-HfO2 nanocrystal-embedded SiO2-HfO2-ZnO waveguides a viable candidate for the development of on-chip, active, integrated optical devices.

  10. Characterization of proton coupled electron transfer in a biomimetic oxomanganese complex: Evaluation of the DFT B3LYP level of theory.

    Science.gov (United States)

    Wang, Ting; Brudvig, Gary; Batista, Victor S

    2010-01-29

    The capabilities and limitations of the Becke-3-Lee-Yang-Parr (B3LYP) density functional theory (DFT) for modeling proton coupled electron transfer (PCET) in the mixed-valence oxomanganese complex 1 [(bpy)(2)Mn(III)(mu-O)(2)Mn(IV)(bpy)(2)](3+) (bpy = 2,2'-bipyridyl) are analyzed. Complex 1 serves as a prototypical synthetic model for studies of redox processes analogous to those responsible for water oxidation in the oxygen-evolving complex (OEC) of photosystem II (PSII). DFT B3LYP free energy calculations of redox potentials and pKa's are obtained according to the thermodynamic cycle formalism applied in conjunction with a continuum solvation model. We find that the pKa's of the oxo-ligands depend strongly on the oxidation states of the complex, changing by approximately 10 pH units (i.e., from pH~2 to pH~12) upon III,IV-->III,III reduction of complex 1. These computational results are consistent with the experimental pKa's determined by solution magnetic susceptibility and near-IR spectroscopy as well as with the pH dependence of the redox potential reported by cyclic voltammogram measurements, suggesting that the III,IV-->III,III reduction of complex 1 is coupled to protonation of the di-mu-oxo bridge as follows: [(bpy)(2)Mn(III)(mu-O)(2) Mn(IV)(bpy)(2)](3+)+H(+)+e(-)-->[(bpy)(2)Mn(III)(mu-O)(mu-OH)Mn(III)(bpy)(2)](3+). It is thus natural to expect that analogous redox processes might strongly modulate the pKa's of oxo and hydroxo/water ligands in the OEC of PSII, leading to deprotonation of the OEC upon oxidation state transitions.

  11. Evolution of magnetic properties and exchange interactions in Ru doped YbCrO3

    Science.gov (United States)

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

    2016-10-01

    Magnetic properties of YbCr1-x Ru x O3 as a function of temperature and magnetic field have been investigated to explore the intriguing magnetic phenomena in rare-earth orthochromites. A quantitative analysis of x-ray photoelectron spectroscopy confirms the mixed valence state (Yb3+ and Yb2+) of Yb ions for the highest doped sample. Field-cooled magnetization reveals a broad peak around 75 K and then becomes zero at about 20-24 K, due to the antiparallel coupling between Cr3+ and Yb3+ moments. An increase of the Ru4+ ion concentration leads to a slight increase of compensation temperature T comp from 20 to 24 K, but the Néel temperature remains constant. A larger value of the magnetic moment of Yb ions gives rise to negative magnetization at low temperature. An external magnetic field significantly modifies the temperature dependent magnetization. Simulation of temperature dependent magnetization data, below T N, based on the three (two) magnetic sub-lattice model predicts stronger intra-sublattice exchange interaction than that of inter-sublattice. Thermal hysteresis and Arrot plots suggest first order magnetic phase transition. Random substitution of Ru4+ ion reduces the magnetic relaxation time. Weak ferromagnetic component in canted antiferromagnetic system and negative internal magnetic field cause zero-field-cooled exchange bias effect. Large magnetocrystalline anisotropy associated with Ru creates high coercivity in the Ru doped sample. A maximum value of magnetocaloric effect is found around the antiferromagnetic ordering of Yb3+ ions. Antiferromagnetic transition at about 120 K and temperature induced magnetization reversal lead to normal and inverse magnetocaloric effects in the same material.

  12. Magnetic, transport and electronic structure properties of U{sub 2}RuGa{sub 8}

    Energy Technology Data Exchange (ETDEWEB)

    Troc, R. [W. Trzebiatowski, Institute of Low Temperature and Structure Research, Polish Academy of Sciences, Lower Silesia, P.O. Box 1410, 50-950 WrocIaw (Poland)]. E-mail: troc@int.pan.wroc.pl; Bukowski, Z. [W. Trzebiatowski, Institute of Low Temperature and Structure Research, Polish Academy of Sciences, Lower Silesia, P.O. Box 1410, 50-950 WrocIaw (Poland); SuIkowski, C. [W. Trzebiatowski, Institute of Low Temperature and Structure Research, Polish Academy of Sciences, Lower Silesia, P.O. Box 1410, 50-950 WrocIaw (Poland); Morkowski, J.A. [W. Trzebiatowski, Institute of Low Temperature and Structure Research, Polish Academy of Sciences, Lower Silesia, P.O. Box 1410, 50-950 WrocIaw (Poland); Szajek, A. [W. Trzebiatowski, Institute of Low Temperature and Structure Research, Polish Academy of Sciences, Lower Silesia, P.O. Box 1410, 50-950 WrocIaw (Poland); CheIkowska, G. [W. Trzebiatowski, Institute of Low Temperature and Structure Research, Polish Academy of Sciences, Lower Silesia, P.O. Box 1410, 50-950 WrocIaw (Poland)

    2005-04-30

    A single crystal of uranium ternary intermetallic of U{sub 2}RuGa{sub 8} was grown by the Ga self-flux method. This compound crystallizes in the tetragonal unit cell of space group P4/mmm. Despite the fairly large U-U shortest distance of 4.22A, this compound shows no signs of any magnetic ordering down to 1.9K. Instead, the susceptibility measured along the a and c axes, goes through a broad maximum at T{sub max}=220K showing a distinct anisotropy. For j||a there is a weak temperature dependence of the electrical resistivity with a large value of {rho}{sub 0}=117{mu}{omega}cm, while for j||c the {rho}(T) curve goes through a maximum at about 130K. The magnetoresistivity measured along two crystallographic directions is small and positive. The thermopower S for the two directions studied is positive and larger along the a-axis. It goes through a broad maximum at 175K reaching a value of 45{mu}V/K. The electronic structure has been calculated by the tight-binding linear muffin-tin orbital method (TB-LMTO) and the results were used in calculation of the valence band near the Fermi level compared next to that found in photoemission experiment. The core 4f spectra are also presented. All the above properties are discussed in view of mixed valence behaviour of uranium atom in this compound.

  13. Dysprosium complexes with the tetraphenylporphyrin macrocyclic ligand; Complejos de disprosio con el ligante macrociclico tetrafenilporfirina

    Energy Technology Data Exchange (ETDEWEB)

    Martinez M, V.; Padilla, J.; Ramirez, F.M

    1992-04-15

    In this report, the results obtained on the synthesis, characterization and study of the chemical behavior of dysprosium complex with the acetylacetone chelating agent (Hacac) and the tetraphenylporphyrin macrocyclic ligand (H{sub 2}TFP) are given. Based on the literature but according to our necessities and interest, the appropriate methodology settled down from the synthesis of prime matters until the obtaining and characterization of the products. The acetyl acetonate complex was obtained of mono hydrated dysprosium [Dy(acac){sub 3}. H{sub 2}0] and trihydrated [Dy(acac){sub 3} .3 H{sub 2}0], the mono tetra phenyl porphyrinate [Dy(TFP)(acac). 2 ac] the double sandwich of the dysprosium porphyrinate [Dy(TFP){sub 2}] and the triple sandwich of the dysprosium porphyrinate [Dy(TFP){sub 3}. 2 TCB] (TCB = trichlorobenzene). Its were characterized by their melting points, solubility, IR, UV, TGA and DTA both first and besides the techniques already mentioned for NMR'H, RPE and Magnetic susceptibility the three last complexes. From the spectroscopic point of view, IR and RPE its suggested the existence of a complex of inverse mixed valence [Dy(TFP){sup 2-} (TFP) {sup 1-}] for the Dy(TFP){sub 2} as a result of the existence of the free radical (TFP' {sup 1-} and that it was not in none of the other porphyrin compounds. In the NMR'H spectra of the compounds were not observed signals in the region from 0 to 10 ppm that which shows that the dysprosium complexes in special those of the porphyrin type are highly paramagnetic and its could be used as displacement reagents, creators of images and contrast agents of great utility in these days in studies of NMR, technique today by today used in medical diagnoses. (Author)

  14. Novel optically active lead-free relaxor ferroelectric (Ba0.6Bi0.2Li0.2)TiO3

    Science.gov (United States)

    Borkar, Hitesh; Rao, Vaibhav; Dutta, Soma; Barvat, Arun; Pal, Prabir; Tomar, M.; Gupta, Vinay; Scott, J. F.; Kumar, Ashok

    2016-07-01

    We discovered a near-room-temperature lead-free relaxor-ferroelectric (Ba0.6Bi0.2Li0.2)TiO3 (BBLT) having A-site compositionally disordered ABO3 perovskite structure. Microstructure-property relations revealed that the chemical inhomogeneities and development of local polar nano-regions (PNRs) are responsible for dielectric dispersion as a function of probe frequencies and temperatures. Rietveld analysis indicates mixed crystal structure with 80% tetragonal structure (space group P4mm) and 20% orthorhombic structure (space group Amm2), which is confirmed by the high resolution transmission electron diffraction (HRTEM). Dielectric constant and tangent loss dispersion with and without illumination of light obey nonlinear Vogel-Fulcher (VF) relations. The material shows slim polarization-hysteresis (P-E) loops and excellent displacement coefficients (d 33 ~ 233 pm V-1) near room temperature, which gradually diminish near the maximum dielectric dispersion temperature (T m ). The underlying physics for light-sensitive dielectric dispersion was probed by x-ray photon spectroscopy (XPS), which strongly suggests that mixed valence of bismuth ions, especially Bi5+ ions, comprise most of the optically active centers. Ultraviolet photoemission measurements showed most of the Ti ions are in 4 +  states and sit at the centers of the TiO6 octahedra; along with asymmetric hybridization between O 2p and Bi 6s orbitals, this appears to be the main driving force for net polarization. This BBLT material may open a new path for environmental friendly lead-free relaxor-ferroelectric research.

  15. Investigation into the effect of molybdenum-site substitution on the performance of Sr2Fe1.5Mo0.5O6-δ for intermediate temperature solid oxide fuel cells

    Science.gov (United States)

    Hou, Mingyue; Sun, Wang; Li, Pengfa; Feng, Jie; Yang, Guoquan; Qiao, Jinshuo; Wang, Zhenhua; Rooney, David; Feng, Jinsheng; Sun, Kening

    2014-12-01

    In this paper, niobium doping is evaluated as a means of enhancing the electrochemical performance of a Sr2Fe1.5Mo0.5O6-δ (SFM) perovskite structure cathode material for intermediate temperature solid oxide fuel cells (IT-SOFCs) applications. As the radius of Nb approximates that of Mo and exhibits +4/+5 mixed valences, its substitution is expected to improve material performance. A series of Sr2Fe1.5Mo0.5-xNbxO6-δ (x = 0.05, 0.10, 0.15, 0.20) cathode materials are prepared and the phase structure, chemical compatibility, microstructure, electrical conductivity, polarization resistance and power generation are systematically characterized. Among the series of samples, Sr2Fe1.5Mo0.4Nb0.10O6-δ (SFMNb0.10) exhibits the highest conductivity value of 30 S cm-1 at 550 °C, and the lowest area specific resistance of 0.068 Ω cm2 at 800 °C. Furthermore, an anode-supported single cell incorporating a SFMNb0.10 cathode presents a maximum power density of 1102 mW cm-2 at 800 °C. Furthermore no obvious performance degradation is observed over 15 h at 750 °C with wet H2 (3% H2O) as fuel and ambient air as the oxidant. These results demonstrate that SFMNb shows great promise as a novel cathode material for IT-SOFCs.

  16. Crystal structure, electronic and magnetic properties of double perovskite Ba{sub 2}FeWO{sub 6}: A combined experimental–theoretical study

    Energy Technology Data Exchange (ETDEWEB)

    Musa Saad, H.-E., E-mail: musa.1964@gmail.com [Department of Physics, College of Science, Qassim University, P.O. 4466, Buraidah 51452 (Saudi Arabia); Rammeh, N. [Laboratoire de Physico-Chimie des Matériaux Minéraux et leurs Applications, Centre National de Recherches en Sciences des Matériaux, B. P. 95, Hammam-Lif 2050 (Tunisia)

    2016-01-15

    Double perovskite oxide Ba{sub 2}FeWO{sub 6} has been synthesized in polycrystalline form by the solid-state ceramic method at 950 °C. Structural characterization was performed by using the X-ray powder diffraction (XRD) and neutron powder diffraction (NPD) followed by Rietveld analysis of these patterns. The crystal structure of Ba{sub 2}FeWO{sub 6} is cubic; space group Fm-3m with lattice parameter of a=8.1351 Å. Also, a density functional theory (DFT) study of the crystal structure, electronic and magnetic properties of Ba{sub 2}FeWO{sub 6} has been carried out using full potential linear muffin-tin orbital (FP-LMTO). We showed that the obtained symmetry lattice parameter agree well with the experimental results. The influence of Fe element on the magnetic and electronic properties of double perovskite oxide Ba{sub 2}FeWO{sub 6} is analyzed. Band structure calculations for cubic Ba{sub 2}FeWO{sub 6} predict an energy-gap in both spin-up and spin-down. The semiconductor antiferromagnetic (AFM) phase is stabilized by the hybridization of nonmagnetic W{sup 6+} (5d°) site positioned in between the magnetic Fe{sup 2+} (3d{sup 6}) sites through the O{sup 2−} anions in a long range O–Fe–O–W–O arrangement. {sup 57}Fe Mössbaur spectrum and DFT calculations suggest that the AFM behavior arises since the mixed valence Fe{sup 2+}–Fe{sup 3+} effect introduces in Fe{sup 2+}–O{sup 2–}–W{sup 6+} anticoupling.

  17. Impact of Jahn-Teller active Mn3+ on strain effects and phase transitions in Sr0.65Pr0.35MnO3

    Science.gov (United States)

    Tan, Teck-Yee; Kennedy, Brendan J.; Zhou, Qingdi; Ling, Christopher D.; Miiller, Wojciech; Howard, Christopher J.; Carpenter, Michael A.; Knight, Kevin S.

    2012-03-01

    The mixed-valence manganite Sr0.65Pr0.35MnO3 has been prepared and its crystal and magnetic structure investigated between 7 and 1200 K using high-resolution powder neutron diffraction. The structural and lattice parameter data have been used to determine the octahedral tilting and spontaneous strains associated with the structural, electronic, and magnetic phase transitions. At room temperature, the structure is tetragonal and is characterized by cooperative out-of-phase tilts of the MnO6 octahedra about the c axis and a large Jahn-Teller-type distortion due to the presence of Mn3+. The sample exhibits a reversible phase transition from the cubic Pm3¯m perovskite to a tetragonal I4/mcm structure at 750 K. The Pm3¯m ↔ I4/mcm phase transition is continuous, and the tetragonal strain, which is dominated by the Jahn-Teller-type distortion of the MnO6 octahedra, exhibits an unusual et0.5 ∝ (Tc - T) temperature dependence. At low temperatures, a C-type antiferromagnetic structure develops with a Neel temperature TN of 250 K. The Mn magnetic moment at 7 K is 2.99(2) μB/Mn. The magnetic ordering introduces additional tetragonal strain, and this strain shows the expected quadratic dependence on the magnetic moment at low temperatures. An increase in the octahedral tilt angle at TN demonstrates an effective coupling between the magnetic ordering process and octahedral tilting.

  18. Structural and chemical evolution of Fe-Co-O based ceramics under reduction/oxidation--an in situ neutron diffraction study

    Energy Technology Data Exchange (ETDEWEB)

    Li Yaping; Maxey, Evan R.; Richardson, James W.; Ma Beihai

    2004-01-15

    Air-sintered ceramic samples in composition CoO{center_dot}nFe{sub 2}O{sub 3} (n=1 and 2) were prepared in solid-state reactions, resulting in a single spinel phase with composition CoFe{sub 2}O{sub 4}, and a two-phase mixture of identical spinel with {alpha}-Fe{sub 2}O{sub 3} for n=1 and 2, respectively. Their structural and chemical evolution over pO{sub 2} range of 10{sup -0.9} to 10{sup -19} atm was investigated using in situ neutron diffraction at isothermal condition ({approx}900 deg. C). Neutron diffraction data were analyzed through Rietveld refinements. The following sequences of structural transformation from {alpha}-Fe{sub 2}O{sub 3} hematite{yields}(Fe,Co)-spinel{yields}(Fe,Co){sub 1-x}O wustite{yields}(Fe,Co)O rocksalt{yields}{gamma}-(Fe,Co){yields}{alpha}-(Fe,Co){yields}({gamma}-(Fe,Co)) were observed on the reduction of Fe-Co-O based ceramics. With the development of reduction at pO{sub 2} down to 10{sup -15} atm, mixed valence (Fe{sup 2+} and Fe{sup 3+}) spinel was first formed in Fe-excess (Fe, Co) spinel phases. The intermediate phases were usually Co-rich compared with their parent mixed oxide phases. Particularly, the initial metallic precipitate is Co-rich {gamma}, independent of initial stoichiometry. Reduction kinetics at pO{sub 2} of {approx}10{sup -19} atm is extremely fast, but crystalline form and structural integrity are maintained. As crystal structures of the various involved phases are very similar, few structural blocks were disturbed as oxygen was released from the samples. In addition, re-oxidation behavior of reduced products was also studied, and phase composition and microstructure of post-neutron experiments were characterized by X-ray diffraction and scanning electron microscopy.

  19. Analogues of Cis- and Transplatin with a Rich Solution Chemistry: cis-[PtCl2 (NH3 )(1-MeC-N3)] and trans-[PtI2 (NH3 )(1-MeC-N3)].

    Science.gov (United States)

    Siebel, Sabine; Dammann, Claudia; Sanz Miguel, Pablo J; Drewello, Thomas; Kampf, Gunnar; Teubner, Natascha; Bednarski, Patrick J; Freisinger, Eva; Lippert, Bernhard

    2015-12-01

    Mono(nucleobase) complexes of the general composition cis-[PtCl2 (NH3 )L] with L=1-methylcytosine, 1-MeC (1 a) and L=1-ethyl-5-methylcytosine, as well as trans-[PtX2 (NH3 )(1-MeC)] with X=I (5 a) and X=Br (5 b) have been isolated and were characterized by X-ray crystallography. The Pt coordination occurs through the N3 atom of the cytosine in all cases. The diaqua complexes of compounds 1 a and 5 a, cis-[Pt(H2 O)2 (NH3 )(1-MeC)](2+) and trans-[Pt(H2 O)2 (NH3 )(1-MeC)](2+) , display a rich chemistry in aqueous solution, which is dominated by extensive condensation reactions leading to μ-OH- and μ-(1-MeC(-) -N3,N4)-bridged species and ready oxidation of Pt to mixed-valence state complexes as well as diplatinum(III) compounds, one of which was characterized by X-ray crystallography: h,t-[{Pt(NH3 )2 (OH)(1-MeC(-) -N3,N4)}2 ](NO3 )2 ⋅2 [NH4 ](NO3 )⋅2 H2 O. A combination of (1) H NMR spectroscopy and ESI mass spectrometry was applied to identify some of the various species present in solution and the gas phase, respectively. As it turned out, mass spectrometry did not permit an unambiguous assignment of the structures of +1 cations due to the possibilities of realizing multiple bridging patterns in isomeric species, the occurrence of different tautomers, and uncertainties regarding the Pt oxidation states. Additionally, compound 1 a was found to have selective and moderate antiproliferative activity for a human cervix cancer line (SISO) compared to six other human cancer cell lines.

  20. Rare-earth (R) and transition metals (d) based skutterudites RM4Sb12: new materials for thermoelectric power generation; Etude de skutterudites de terres-rares (R) et de metaux d (M) du type RM4Sb12: de nouveaux materiaux thermoelectriques pour la generation d'electricite

    Energy Technology Data Exchange (ETDEWEB)

    Berardan, D.

    2004-07-15

    This thesis presents the physical and thermoelectric properties of new skutterudite compounds, with general formula R{sub y-p}R'{sub p}Fe{sub 4-x}(Co/Ni){sub x}Sb{sub 12} (R and R' = Ce, Yb, Ba, La). It shows that Yb valence state decreases when Yb fraction increases. However, it does not depend on the temperature, which evidences a mixed valence state (two different valence states for two distinct crystallographic sites at a local point of view). Ce is always trivalent in these compounds. The character of the dominant interactions changes from antiferromagnetic to ferromagnetic when one goes from trivalent cerium or lanthanum to nearly divalent ytterbium or divalent barium. The effective paramagnetic moment has been separated into three contributions originating from Ce, Yb and [Fe{sub 4}Sb{sub 12}]. The last one does not depend on the nature or on the valence state or R and R' atoms, but it decreases when Ni substitutes Fe. A magnetic transition occurs at 6.5 K for R = Yb and Ba, possibly to a spin glass state. Electrical and thermal transport properties have been determined from 5 K to 800 K, and the materials properties of the materials have been discussed concerning thermoelectric power generation. The power factor, and the thermoelectric figure of merit ZT are increased in Ce{sub y}/2Yb{sub y}/2Fe{sub 4-x}(Co/Ni){sub x}Sb{sub 12} type skutterudites as compared to R{sub y}Fe{sub 4-x}(Co/Ni){sub x}Sb{sub 12} type skutterudites. (author)

  1. Inter-layer charge disproportionation in the dual-layer organic metal (tTTF-I)2ClO4 with unsymmetrical I···O halogen bond interactions.

    Science.gov (United States)

    Shin, Kyoung-Soon; Jeannin, Olivier; Brezgunova, Mariya; Dahaoui, Slimane; Aubert, Emmanuel; Espinosa, Enrique; Auban-Senzier, Pascale; Świetlik, Roman; Frąckowiak, Arkadiusz; Fourmigué, Marc

    2014-04-14

    A mixed-valence salt of tTTF-I with ClO4(-), formulated as (tTTF-I)2ClO4, is characterized by the presence of two crystallographically independent donor molecules, segregated in different layers and linked together through I···O interactions with the ClO4(-) anion disordered at room temperature. The tTTF-I donor molecule was prepared by metallation of tTTF (trimethylene tetrathiafulvalene) followed by reaction with iodine to afford the mono and diiodo derivatives tTTF-I and tTTFI2, respectively. The crystal structure of the latter neutral tTTFI2 shows the occurrence of strong type II, II halogen bond interactions. Band structure calculations of the dual-layer structure of the 2 : 1 salt (tTTF-I)2ClO4 show co-existence of both 1D open and 2D closed Fermi surfaces. The salt undergoes a metal-insulator phase transition at T(MI) = 90 K, associated with an electronic dimensionality decrease, since already at 100 K, the 2D part of the Fermi surface transforms into 1D corrugated planes. High resolution X-ray investigations performed at 100 K, combined with multipolar refinements, indicate an approximately equivalent +0.5e charge in both donor molecules, as also deduced from the intramolecular bond distances. On the other hand, Raman spectroscopic investigations show that at ambient temperature the charge is actually distributed non-uniformly in conducting layers of tTTF-I molecules, with the identification of molecules with charges +1, +0.5, 0e, while at low temperature the charge distribution becomes essentially uniform (+0.5e), as confirmed from the X-ray high resolution data. These apparently contradictory behaviors are actually a consequence of a partial electron transfer between the two independent slabs to reach a common Fermi level in the metallic phase.

  2. The role of deep acceptor centers in the oxidation of acceptor-doped wide-band-gap perovskites ABO3

    Science.gov (United States)

    Putilov, L. P.; Tsidilkovski, V. I.

    2017-03-01

    The impact of deep acceptor centers on defect thermodynamics and oxidation of wide-band-gap acceptor-doped perovskites without mixed-valence cations is studied. These deep centers are formed by the acceptor-bound small hole polarons whose stabilization energy can be high enough (significantly higher than the hole-acceptor Coulomb interaction energy). It is shown that the oxidation enthalpy ΔHox of oxide is determined by the energy εA of acceptor-bound states along with the formation energy EV of oxygen vacancies. The oxidation reaction is demonstrated to be either endothermic or exothermic, and the regions of εA and EV values corresponding to the positive or negative ΔHox are determined. The contribution of acceptor-bound holes to the defect thermodynamics strongly depends on the acceptor states depth εA: it becomes negligible at εA less than a certain value (at which the acceptor levels are still deep). With increasing εA, the concentration of acceptor-bound small hole polarons can reach the values comparable to the dopant content. The results are illustrated with the acceptor-doped BaZrO3 as an example. It is shown that the experimental data on the bulk hole conductivity of barium zirconate can be described both in the band transport model and in the model of hopping small polarons localized on oxygen ions away from the acceptor centers. Depending on the εA magnitude, the oxidation reaction can be either endothermic or exothermic for both mobility mechanisms.

  3. A quantitative description of the ground-state wave function of Cu(A) by X-ray absorption spectroscopy: comparison to plastocyanin and relevance to electron transfer.

    Science.gov (United States)

    DeBeer George, S; Metz, M; Szilagyi, R K; Wang, H; Cramer, S P; Lu, Y; Tolman, W B; Hedman, B; Hodgson, K O; Solomon, E I

    2001-06-20

    To evaluate the importance of the electronic structure of Cu(A) to its electron-transfer (ET) function, a quantitative description of the ground-state wave function of the mixed-valence (MV) binuclear Cu(A) center engineered into Pseudomonas aeruginosa azurin has been developed, using a combination of S K-edge and Cu L-edge X-ray absorption spectroscopies (XAS). Parallel descriptions have been developed for a binuclear thiolate-bridged MV reference model complex ([(L(i)(PrdacoS)Cu)(2)](+)) and a homovalent (II,II) analogue ([L(i)(Pr2tacnS)Cu)(2)](2+), where L(i)(PrdacoS) and L(i)(Pr2tacnS) are macrocyclic ligands with attached thiolates that bridge the Cu ions. Previous studies have qualitatively defined the ground-state wave function of Cu(A) in terms of ligand field effects on the orbital orientation and the presence of a metal--metal bond. The studies presented here provide further evidence for a direct Cu--Cu interaction and, importantly, experimentally quantify the covalency of the ground-state wave function. The experimental results are further supported by DFT calculations. The nature of the ground-state wave function of Cu(A) is compared to that of the well-defined blue copper site in plastocyanin, and the importance of this wave function to the lower reorganization energy and ET function of Cu(A) is discussed. This wave function incorporates anisotropic covalency into the intra- and intermolecular ET pathways in cytochrome c oxidase. Thus, the high covalency of the Cys--Cu bond allows a path through this ligand to become competitive with a shorter His path in the intramolecular ET from Cu(A) to heme a and is particularly important for activating the intermolecular ET path from heme c to Cu(A).

  4. Expression, purification and characterization of the soluble CUA domain of cytochrome c oxidase of Paracoccus versutus

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    The key subunit Ⅱ of cytochrome c oxidase (CcO) contains a soluble binuclear copper center (CuA) do main. The CuA domain of Paracoccus versutus was cloned,expressed, purified and characterized. The gene encoding the CuA domain in pET11d vector was expressed in E. coli BL21(DE3). The results showed that the CuA domain was ex pressed mostly in inclusion bodies and the CuA domain pro tein synthesized in E. coli cells represents approximately 10percent of the total cellular proteins. Dissolved in urea, dia lyzed and recombined with Cu+/Cu2+ and purified by the Q-sepharose fast flow anion-exchange column and Sephadex G-75 gel filtration column, the soluble purple-colored protein,which shows a single band in electrophoresis, was obtained.The UV-visible absorption spectrum of CuA domain showed that there are intense band at 478 mn and a shoulder peak at 530 nm, and two weak bands at 360 and 806 nm respectively,which can be assigned to the charge transfer and the interac tions of obitals of Cu-S and Cu-Cu in the mixed-valence binuclear metal center (Cu2S2R2). The far-UV CD spectrum indicated that this domain is predominantly in β-sheet structure. The fluorescence spectra showed that its maximal excitation wavelength and maximal emission wavelength are at 280 and 345 nm, respectively.

  5. Synthesis, structural and magnetic characterisation of iron(II/III), cobalt(II) and copper(II) cluster complexes of the polytopic ligand: N-(2-pyridyl)-3-carboxypropanamide.

    Science.gov (United States)

    Russell, Mark E; Hawes, Chris S; Ferguson, Alan; Polson, Matthew I J; Chilton, Nicholas F; Moubaraki, Boujemaa; Murray, Keith S; Kruger, Paul E

    2013-10-07

    Herein we describe the synthesis, structural and magnetic characterisation of three transition metal cluster complexes that feature the polytopic ligand N-(2-pyridyl)-3-carboxypropanamide (H2L): [Fe3(III)Fe2(II)(HL)6(O)(H2O)3][ClO4]5·3MeCN·4H2O, 1, [Co8(HL)8(O)(OH)4(MeOH)3(H2O)]-[ClO4]3·5MeOH·2H2O, 2, and [Cu6(L(ox))4(MeOH)(H2O)3]·MeOH, 3. Complex 1 is a mixed valence penta-nuclear iron cluster containing the archetypal {Fe3(III)O} triangular basic carboxylate cluster at its core, with two Fe(II) ions above and below the core coordinated to three bidentate pyridyl-amide groups. The structure of the octanuclear Co(II) complex, 2, is based upon a central Co4 square with the remaining four Co(II) centres at the 'wing-tips' of the complex. The cluster core is replete with bridging oxide, hydroxide and carboxylate groups. Cluster 3 contains an oxidised derivative of the ligand, L(ox), generated in situ through hydroxylation of an α-carbon atom. This hexanuclear cluster has a 'barrel-like' core and contains Cu(II) ions in both square planar and square-based pyramidal geometries. Bridging between Cu(II) centres is furnished by alkoxide and carboxylate groups. Magnetic studies on 1-3 reveals dominant antiferro-magnetic interactions for 1 and 2, leading to small non-zero spin ground states, while 3 shows ferro-magnetic exchange between the Cu(II) centres to give an S = 3 spin ground state.

  6. Valence Fluctuations in CeCo2 and Ti-Doped CeCo2

    Science.gov (United States)

    Öner, Yıldırhan

    2016-12-01

    We report on the magnetic measurements of polycrystalline samples of CeCo2 and CeCo(2-x)Ti x (x = 0.01, 0.02, 0.03, 0.04, and 0.05) which have been synthesized by an arc melting technique. All these compounds crystallize into the face-centered cubic (FCC) structure with the Fd bar{3} m space group. The lattice parameter decreases linearly with increasing Ti content from 7.15808(5) Å for x = 0 (CeCo2) to 7.15231(7) Å for x = 0.05. The magnetic behavior of these compounds has been investigated in the temperature range 5-400 K. The zero field-cooled (ZFC) and field-cooled magnetization (FC) curves show irreversibility below T = 400 K. This result indicates that an inhomogeneous, dynamic magnetic state exists over a wide temperature range. The magnetic susceptibility for both ZFC and FC cases initially decreases with Ti content and then increases with further Ti addition. This behavior is interpreted in terms of band magnetism in the presence of magnetic clusters. This result indicates that the magnetic inhomogeneity of these alloys becomes dominant over a wide temperature range. The observed temperature dependence of the magnetic susceptibility leads us to suggest that these compounds are in a mixed-valence state of the magnetic Ce3+ ions and non-magnetic Ce4+ ions. This fact allows us to successfully interpret the ZFC magnetic susceptibility data with the two-level ionic inter-configuration fluctuations model. We also observe that the magnetic susceptibility increases by the addition of Ti, as evidenced by the enhancement of the formation of magnetic Co clusters due to local disorder. Finally, the magnetic state below the Curie temperatures are discussed based on Griffiths-like behavior.

  7. Core-level magnetic circular dichroism in 3d and 4f magnetic systems (invited) (abstract)

    Science.gov (United States)

    Koide, T.

    1994-05-01

    With the recent availability of circulary polarized synchrotron radiation over a wide photon energy range from VUV to hard X rays, the magnetic circular dichroism (MCD) in core-level photoabsorption has rapidly attracted growing interest, both experimentally and theoretically. This novel technique can provide element-specific and site-selective information about the magnetic and the electronic states in various magnetic substances because the core-level MCD process involves optical transitions in which the one-electron initial states are well localized and have well-defined angular momenta. In order to get insight into the local magnetic states in 3d and 4f magnetic systems, we have studied MCD of ferrites, Fe1-xPtx alloys, and mixed-valence CeRh3B2 at the core-absorption edges in the VUV˜soft x-ray region. The experiments were performed by utilizing directly characterized, circularly polarized undulator radiation and off-plane synchrotron radiation1 in conjunction with an ultrahigh vacuum compatible superconducting magnet of special design.2 Clear MCD signals were observed for CeRh3B2 in the prethreshold region of the Ce 4d→4f (N4,5) edges. A comparison of the experimental MCD spectrum with theoretical ones3 for uniaxial crystal fields of Δc=0 and 0.2 eV shows that the experimental spectrum qualitatively agrees with the theoretical one for Δc=0 eV. Theory predicts that the MCD pattern for ΔcCeRh3B2. We will also present the MCD data in the M2,3 core-absorption region for ferrites (Fe3O4 and CoFe2O4) and Fe1-xPtx alloys, discussing the results.

  8. Common Building Motifs in Ba2Fe3(PO4)4·2H2O, BaFe3(PO4)3, and Na3Fe3(PO4)4: Labile Fe(2+)/Fe(3+) Ordering and Charge-Dependent Magnetism.

    Science.gov (United States)

    David, Rénald; Pautrat, Alain; Kabbour, Houria; Mentré, Olivier

    2016-05-02

    Two new mixed-valence Fe(2/3+) barium phosphates have been synthesized in hydrothermal conditions and characterized: Ba2Fe(2.66+)3(PO4)4·2H2O (compound 1, ratio Fe(3+)/Fe(2+) = 2:1, orthorhombic space group Pbca, a = 6.71240(10) Å, b = 10.6077(2) Å, c = 20.9975(5) Å, R1 = 3.39%) and BaFe(2.33+)3(PO4)3 (compound 2, ratio Fe(3+)/Fe(2+) = 1:2, orthorhombic, space group Imma with a = 10.5236(3) Å, b = 13.4454(4) Å, c = 6.6411(2) Å, R1 = 1.63%). 1 has a two-dimensional crystal structure built of [Fe(2.5+)2Fe(3+)1(PO4)4](4-) layers with charge segregation on two individual Fe crystal sites, in contrast to the single valence on these two sites found in similar layers of Na3Fe(3+)3(PO4)4. The crystal structure of 2 is formed of the same layers but condensed into a 3D [Fe(2+)2Fe(3+)1(PO4)3](2-) framework. The complete Fe(2+) vs Fe(3+) charge ordering on the two available sites differs from what was found in the two previous cases and denotes a remarkable charge adaptability of the common elementary units. Compared to the antiferromagnetic Na3Fe(3+)3(PO4)4 the partial iron reduction into Fe(2+) is responsible for strong ferromagnetic components along the c-easy axis for both 1 and 2. Additionally 1 shows multiple magnetization steps in the perpendicular direction, giving raise to atypical anisotropic magnetism into a complex magnetic phase diagram.

  9. Axial ligand modulation of the electronic structures of binuclear copper sites: analysis of paramagnetic 1H NMR spectra of Met160Gln Cu(A).

    Science.gov (United States)

    Fernández, C O; Cricco, J A; Slutter, C E; Richards, J H; Gray, H B; Vila, A J

    2001-11-28

    Cu(A) is an electron-transfer copper center present in heme-copper oxidases and N2O reductases. The center is a binuclear unit, with two cysteine ligands bridging the metal ions and two terminal histidine residues. A Met residue and a peptide carbonyl group are located on opposite sides of the Cu2S2 plane; these weaker ligands are fully conserved in all known Cu(A) sites. The Met160Gln mutant of the soluble subunit II of Thermus thermophilus ba3 oxidase has been studied by NMR spectroscopy. In its oxidized form, the binuclear copper is a fully delocalized mixed-valence pair, as are all natural Cu(A) centers. The faster nuclear relaxation in this mutant suggests that a low-lying excited state has shifted to higher energies compared to that of the wild-type protein. The introduction of the Gln residue alters the coordination mode of His114 but does not affect His157, thereby confirming the proposal that the axial ligand-to-copper distances influence the copper-His interactions (Robinson, H.; Ang, M. C.; Gao, Y. G.; Hay, M. T.; Lu, Y.; Wang, A. H. Biochemistry 1999, 38, 5677). Changes in the hyperfine coupling constants of the Cys beta-CH2 groups are attributed to minor geometrical changes that affect the Cu-S-C(beta)-H(beta) dihedral angles. These changes, in addition, shift the thermally accessible excited states, thus influencing the spectral position of the Cys beta-CH2 resonances. The Cu-Cys bonds are not substantially altered by the Cu-Gln160 interaction, in contrast to the situation found in the evolutionarily related blue copper proteins. It is possible that regulatory subunits in the mitochondrial oxidases fix the relative positions of thermally accessible Cu(A) excited states by tuning axial ligand interactions.

  10. Gutzwiller wave-function solution for Anderson lattice model: Emerging universal regimes of heavy quasiparticle states

    Science.gov (United States)

    Wysokiński, Marcin M.; Kaczmarczyk, Jan; Spałek, Jozef

    2015-09-01

    The recently proposed diagrammatic expansion (DE) technique for the full Gutzwiller wave function (GWF) is applied to the Anderson lattice model. This approach allows for a systematic evaluation of the expectation values with full Gutzwiller wave function in finite-dimensional systems. It introduces results extending in an essential manner those obtained by means of the standard Gutzwiller approximation (GA), which is variationally exact only in infinite dimensions. Within the DE-GWF approach we discuss the principal paramagnetic properties and their relevance to heavy-fermion systems. We demonstrate the formation of an effective, narrow f band originating from atomic f -electron states and subsequently interpret this behavior as a direct itineracy of f electrons; it represents a combined effect of both the hybridization and the correlations induced by the Coulomb repulsive interaction. Such a feature is absent on the level of GA, which is equivalent to the zeroth order of our expansion. Formation of the hybridization- and electron-concentration-dependent narrow f band rationalizes the common assumption of such dispersion of f levels in the phenomenological modeling of the band structure of CeCoIn5. Moreover, it is shown that the emerging f -electron direct itineracy leads in a natural manner to three physically distinct regimes within a single model that are frequently discussed for 4 f - or 5 f -electron compounds as separate model situations. We identify these regimes as (i) the mixed-valence regime, (ii) Kondo/almost-Kondo insulating regime, and (iii) the Kondo-lattice limit when the f -electron occupancy is very close to the f -state half filling, →1 . The nonstandard features of the emerging correlated quantum liquid state are stressed.

  11. Dense ceramic membranes: A review of the state of the art

    Directory of Open Access Journals (Sweden)

    Kozhukharov, V.

    1999-02-01

    Full Text Available During the past several years the concepts of oxygen permeation through mixed valency ceramic membranes possess special interest. In this context, a classification and brief review of the major membrane ceramic materials will be presented. The focus will be on dense ceramic membranes as elements for advanced application. A discussion will be proposed for mixed conductor ceramics as perovskite ABO3 compounds. Dense membranes on perovskite base are the object of the present review and some details about processing and characterization of double (A- and B-site substituted La1-x Sr(BaxCo0.8Fe0.2O3-d perovskites will be presented.

    El concepto de permeación de oxígeno a través de membranas cerámicas de valencia mixta, ha venido adquiriendo especial relevancia a lo largo de los últimos años. En este contexto se hace se efectúa una clasificación y breve revisión de los materiales cerámicos más relevantes utilizados como membranas. En particular se orienta la descripción hacia las membranas cerámicas densas para aplicaciones avanzadas. Se propone un análisis de los conductores cerámicos mixtos, como los compuestos de tipo perovskita ABO3. Se realiza una revisión de los materiales de este tipo existentes, así como se describen algunos aspectos sobre el procesamiento y caracterización de las perovskitas tipo La1-x Sr(BaxCo0.8Fe0.2O3-d doblemente sustituidas (lugares A- y B-.

  12. Wigner-Mott insulator-to-insulator transition at pressure in charge-ordered Fe2OBO3

    Science.gov (United States)

    Diguet, G.; Hearne, G. R.; Sibanda, W. N.; Carleschi, E.; Musyimi, P.; Pischedda, V.; Attfield, J. P.

    2014-01-01

    Magnetic-electronic studies of mixed-valence Fe2OBO3 have shown that ionic charge order (CO) is disrupted at ˜16 GPa. The pertinent minority-spin carrier exhibits persistent intersite electron exchange Fe2+ ⇔ Fe3+ to well beyond this pressure. Temperature-dependent electrical transport measurements over an extended pressure range presented here demonstrate that the electronic structure remains gapped to well beyond 16 GPa. Extrapolation of data to higher pressure suggests that metallization will only prevail at P>50 GPa. Both the persistent gapped electronic state across the CO instability and signature of carrier confinement to Fe-Fe dimers in the Fe2+ ⇔ Fe3+ electron exchange are rationalized as crossover from a Wigner crystal (site centered) insulator to a dimer Mott (bond centered type) insulator—"Wigner-Mott transition" at ˜16 GPa. The dimer insulating state is a consequence of modulation of the relevant hopping parameter t in quasi-low-dimensional features in the structure (ribbons and chains). Complementary structural studies suggest that the a axis is appreciably more compressible than other crystallographic directions of the original monoclinic unit cell. Therefore, such a modulation in t may arise from Peierls type distortions along the a axis or else stems from intrinsic modulation in the c axis direction of the unit cell. This is aided by a monoclinic (P21/c) → orthorhombic (Pmcn) structural adjustment that is concurrent across the electronic transition. Pressure tuning of relative values of on-site U/t and intersite V/t Coulomb interaction parameters of the quasi-low-dimensional features evolve the system from site-centered to dimer-centered electron localization.

  13. Rate and extent of aqueous perchlorate removal by iron surfaces.

    Science.gov (United States)

    Moore, Angela M; De Leon, Corinne H; Young, Thomas M

    2003-07-15

    The rate and extent of perchlorate reduction on several types of iron metal was studied in batch and column reactors. Mass balances performed on the batch experiments indicate that perchlorate is initially sorbed to the iron surface, followed by a reduction to chloride. Perchlorate removal was proportional to the iron dosage in the batch reactors, with up to 66% removal in 336 h in the highest dosage system (1.25 g mL(-1)). Surface-normalized reaction rates among three commercial sources of iron filings were similar for acid-washed samples. The most significant perchlorate removal occurred in solutions with slightly acidic or near-neutral initial pH values. Surface mediation of the reaction is supported by the absence of reduction in batch experiments with soluble Fe2+ and also by the similarity in specific reaction rate constants (kSA) determined for three different iron types. Elevated soluble chloride concentrations significantly inhibited perchlorate reduction, and lower removal rates were observed for iron samples with higher amounts of background chloride contamination. Perchlorate reduction was not observed on electrolytic sources of iron or on a mixed-phase oxide (Fe3O4), suggesting that the reactive iron phase is neither pure zerovalent iron nor the mixed oxide alone. A mixed valence iron hydr(oxide) coating or a sorbed Fe2+ surface complex represent the most likely sites for the reaction. The observed reaction rates are too slow for immediate use in remediation system design, but the findings may provide a basis for future development of cost-effective abiotic perchlorate removal techniques.

  14. Chemical Doping Induced Ferro- and Antiferro-magnetic States in non-Magnetic Insulating FeGa3

    Science.gov (United States)

    Haldolaarachchige, N.; Prestigiacomo, J.; Xiong, Y.; Phelan, A.; Chan, J.; Sheehy, D.; Adams, P.; Ditusa, J.; Stadler, S.; Young, D.

    2013-03-01

    A ferromagnetic quantum critical point (FM-QCP) in Ge-doped FeGa3 was reported very recently (Umeo et al. PRB 86 (14), 144421, 2012). We have simultaneously observed the FM-QCP in this system. Furthermore, we analyzed the magnetic properties of FeGa3 in the context of a unique structural feature, where the four Fe atoms in the unit cell exist as two Fe-Fe dimers (Yin and Picket, PRB 82 (15), 155202, 2010). We propose a phenomenological model where the extrinsic electrons from the Ge doping creates a mixed valence Fe-dimer with a net effective spin. Such a model provides a novel mechanism for the (FM-QCP) and is consistent with the system's magnetic and thermal properties. In addition to Ge doping, we have investigated effects of Ru/Mn substitution on the Fe site. Ru substitution produces an unexpected ferromagnetic (FM) insulating phase that develops immediately, and it disappears above an intermediate doping level. This behavior agrees well with our model of spin creation on the transition-metal dimers via conduction electrons, and the enhanced insulating behavior in the electrical resistivity suggests the Ru acquires a 2 + state. Interestingly, Mn-doped FeGa3 shows an apparent antiferromagnetic (AFM) insulating phase, where the magnetic data is consistent with the effective moment coming from Mn(3 +) . These results provide further evidence of the important role of the Fe-Fe dimer structure in FeGa3in determining its unique magnetic properties.

  15. Tuning the electronic coupling in Mo2-Mo2 systems by variation of the coordinating atoms of the bridging ligands.

    Science.gov (United States)

    Shu, Yao; Lei, Hao; Tan, Ying Ning; Meng, Miao; Zhang, Xiao Chun; Liu, Chun Y

    2014-10-21

    Three novel [Mo2]-bridge-[Mo2] complexes were synthesized by a convergent assembling reaction of the dimetal precursor Mo2(DAniF)3(O2CCH3) (DAniF = N,N'-di(p-anisyl)formamidinate) with the bridging ligands terephthalamidine, terephthalamide and dithioterephthalamide. The structures of these compounds, [Mo2(DAniF)3]2[μ-1,4-{C(E)NH}2-C6H4] (E = NH (), O () or S ()), were determined, either by X-ray crystallography or (1)H NMR spectroscopy, to be the analogues of the terephthalate bridged dimolybdenum dimer. These compounds are structurally and electronically closely related by having the same structural skeleton and similar bonding parameters, which allowed us to analyze the differences between N, O and S atoms on the bridging ligand in promoting electronic interaction between the two [Mo2] units. In the electronic spectra, the metal to ligand charge transfer absorption bands, attributed to the HOMO (dδ) → LUMO (pπ*) transition, was red shifted as the variable atoms change from N to O to S. The mixed-valence species (+), (+) and (+), generated by one-electron oxidation of the neutral precursors and measured in situ, exhibited characteristic intervalence absorption bands, for which the energy and half-height bandwidth decreased from (+) to (+). Therefore, in comparison to O atoms, S atoms are capable of enhancing the electronic coupling between the two [Mo2] units, and the incorporation of N atoms to the bridging ligands slightly diminished the metal-metal interaction. The molecular structures and spectroscopic properties of these compounds were simulated by theoretical calculations at DFT level on the simplified models, which gave results consistent with the experimental observations.

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

    Science.gov (United States)

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

    2007-04-02

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

  17. Structure, optical properties and thermal stability of HfErO films deposited by simultaneous RF and VHF magnetron sputtering

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, H.Y. [Soochow University, College of Physics, Optoelectronics and Energy and Collaborative Innovation Center of Suzhou Nano Science and Technology, Suzhou (China); Nanjing University of Posts and Telecommunications, School of Tongda, Nanjing (China); Soochow University, Key Lab of Advanced Optical Manufacturing Technologies of Jiangsu Province and Key Lab of Modern Optical Technologies of Education Ministry of China, Suzhou (China); He, H.J.; Zhang, Z.; Jin, C.G.; Yang, Y.; Wang, Y.Y.; Ye, C. [Soochow University, College of Physics, Optoelectronics and Energy and Collaborative Innovation Center of Suzhou Nano Science and Technology, Suzhou (China); Soochow University, Key Lab of Advanced Optical Manufacturing Technologies of Jiangsu Province and Key Lab of Modern Optical Technologies of Education Ministry of China, Suzhou (China); Zhuge, L.J. [Soochow University, Key Lab of Advanced Optical Manufacturing Technologies of Jiangsu Province and Key Lab of Modern Optical Technologies of Education Ministry of China, Suzhou (China); Soochow University, Analysis and Testing Center, Suzhou (China); Wu, X.M. [Soochow University, College of Physics, Optoelectronics and Energy and Collaborative Innovation Center of Suzhou Nano Science and Technology, Suzhou (China); Soochow University, Key Lab of Advanced Optical Manufacturing Technologies of Jiangsu Province and Key Lab of Modern Optical Technologies of Education Ministry of China, Suzhou (China); Chinese Academy of Sciences, State Key Laboratory of Functional Materials for Informatics, Shanghai Institute of Microsystem and Information Technology, Shanghai (China)

    2015-01-23

    HfErO films are deposited on Si substrates by simultaneous radio frequency (RF) and very high frequency (VHF) magnetron sputtering technique. The content of the doped ingredient of Er and the body composition of HfO{sub x} are, respectively, controlled through the VHF and RF powers. Low content of Er doping in the HfErO films can be achieved, because the VHF source of 27.12 MHz has higher ion energy and lower ion flux than the RF source resulting in low sputtering rate in the magnetron sputtering system. The structure, optical properties and thermal stability of the HfErO films are investigated in this work. Results show that the doped content of Er is independently controlled by the VHF power. The oxygen vacancies are created by the Er incorporation. The hafnium in the HfErO films forms mixed valence of Hf{sup 2+} and Hf{sup 4+}. The HfErO films are composed with the structures of HfO{sub 2}, HfO and ErO{sub x}, which can be optimized through the VHF power. At high VHF power, the Hf-Er-O bonds are formed, which demonstrates that the Er atoms are doped into the lattice of HfO{sub 2} in the HfErO films. The HfErO films have bad thermal stability as the crystallization temperature decreases from 900 to 800 C. After thermal annealing, cubic phase of HfO{sub 2} are stabilized, which is ascribed to the oxygen vacancies creation by the Er incorporation. The optical properties such as the refractive index and the optical band gap of the HfErO films are optimized by the VHF power. (orig.)

  18. Bismuth centred magnetic perovskite: A projected multiferroic

    Energy Technology Data Exchange (ETDEWEB)

    Kundu, Asish K., E-mail: asish.k@gmail.com [Discipline of Physics, Indian Institute of Information Technology, Design and Manufacturing, Dumna Airport Road, Jabalpur 482005 (India); Seikh, Md. Motin [Department of Chemistry, Visva-Bharati University, Santiniketan, West Bengal 731235 (India); Nautiyal, Pranjal [Discipline of Mechanical Engineering, Indian Institute of Information Technology, Design and Manufacturing, Dumna Airport Road, Jabalpur 482005 (India)

    2015-03-15

    In recent time substantial attention has been initiated to understand the physics behind multiferroism and to design new multiferroic materials. BiMnO{sub 3} and BiFeO{sub 3} are the well-studied Bi-centred multiferroic oxides. BiMnO{sub 3} is a ferromagnetic–ferroelectric (metastable) phase and require drastic conditions to synthesize. However, lanthanum substituted BiMnO{sub 3} phases stabilized at ambient pressure. It is thus of major importance to increase the number of ferromagnetic perovskites with Bi cations that could be designed under ambient conditions. In this article, we have presented an up to date report of investigations on Bi-centred magnetic perovskites, a prospective material for multiferroic application. Central focus is concentrated on La{sub 0.5}Bi{sub 0.5}MnO{sub 3} perovskite with various substitutions at different levels. A few of these perovskites are found to be of practical importance e.g. La{sub 0.5}Bi{sub 0.5}Mn{sub 0.67}Co{sub 0.33}O{sub 3} with high dielectric permittivity coupled with ferromagnetism. A comprehensive analysis of different physical functionalities and their interrelation for a wide range of compositions of these Bi-centred perovskites is presented. It has been found that the complex magnetic behaviour originates from mixed valence metal ions. The ferroelectricity is associated with the 6s{sup 2} lone pair of Bi{sup 3+} cations. The magnetic ground state influences the dielectric properties reflecting the multiferroism in a single material. - Highlights: • Multiferroics have attracted increasing attention due to their possible device applications. • Bismuth centred magnetic perovskite is one kind of such promising multiferroic materials. • Ferromagnetic Bi-perovskites, which are synthesized at ambient conditions, have been discussed.

  19. Reduction of V{sub 2}O{sub 5} thin films deposited by aqueous sol–gel method to VO{sub 2}(B) and investigation of its photocatalytic activity

    Energy Technology Data Exchange (ETDEWEB)

    Monfort, Olivier [Department of Inorganic Chemistry, Faculty of Natural Sciences, Comenius University, 842 15 Bratislava (Slovakia); Roch, Tomas; Satrapinskyy, Leonid; Gregor, Maros; Plecenik, Tomas; Plecenik, Andrej [Department of Experimental Physics, Faculty of Mathematics, Physics and Informatics, Comenius University, 842 48 Bratislava (Slovakia); Plesch, Gustav, E-mail: plesch@fns.uniba.sk [Department of Inorganic Chemistry, Faculty of Natural Sciences, Comenius University, 842 15 Bratislava (Slovakia)

    2014-12-15

    Graphical abstract: - Highlights: • Preparation of VO{sub 2}(B) films by aqueous sol–gel method and their characterization. • Influence of annealing conditions on the mechanism of V{sub 2}O{sub 5} film reduction. • The VO{sub 2}(B) films with energy gap of 2.8 eV show photocatalytic activity. • The films with higher roughness exhibit increased photoactivity. - Abstract: A way of preparation of VO{sub 2}(B) thin films by reduction of V{sub 2}O{sub 5} films synthesized from an aqueous sol–gel system has been developed and photocatalytic properties of the obtained films were studied. The reduction was performed by annealing of the V{sub 2}O{sub 5} film in vacuum as well as in H{sub 2}/Ar atmosphere, which was followed by temperature dependent XRD. It has been shown that the reduction is influenced by the layered-structure of the vanadium oxides. It is a two-step process, where the mixed-valence vanadium oxide V{sub 4}O{sub 9} is first formed before reaching the VO{sub 2}(B) phase. The film microstructure was characterized by SEM and AFM and the valence states of vanadium in VO{sub 2}(B) films were evaluated by XPS. The VO{sub 2}(B) polymorph shows an energy band-gap around 2.8 eV and it exhibits photocatalytic properties. It was measured by following the degradation of rhodamine B under UVA as well as metalhalogenide lamp irradiation, which has similar spectral distribution as natural sunlight. The VO{sub 2}(B) films show distinct photoactivities under both lamps, although they were found to be more active under the UVA irradiation. The film annealed under reducing hydrogen atmosphere, which exhibits higher granularity and surface roughness, shows higher photoactivity than the vacuum-annealed film.

  20. Structure and properties of α-AgFe 2(MoO 4) 3

    Science.gov (United States)

    Balsanova, L.; Mikhailova, D.; Senyshyn, A.; Trots, D.; Fuess, H.; Lottermoser, W.; Ehrenberg, H.

    2009-06-01

    Silver diiron tris(oxomolybdate), α-AgFe 2(MoO 4) 3, was synthesized in sealed silica tubes at 1050 K and is isostructural to α-NaFe 2(MoO 4) 3, determined by single-crystal X-ray diffraction (space group P-1, a = 6.9320(7) Å, b = 6.9266(6) Å, c = 10.9732(13) Å, α = 81.197(8)°, β = 83.456(9)°, γ = 81.352(8)° at 300 K, Z = 2). The crystal structure is built up from both monomers and edge-sharing dimers of [FeO 6]-octahedra, which are linked with each other by isolated [MoO 4]-tetrahedra to a three-dimensional network. Ag ions are situated on a site with four near oxygen neighbours. Thermal expansion is most pronounced along the c-axis, while the angle α decreases with increasing temperature. Antiferromagnetic ordering is indicated by a sharp maximum in the temperature dependence of magnetization at 21.5(5) K, and a magnetic moment of 5.36(1) μ B per Fe-ion was derived from the Curie constant in the paramagnetic region. The collinear antiferromagnetic structure with propagation vector k = (0,½,½) and an ordered magnetic moment of 4.62(9) μ B per Fe-ion were deduced from neutron powder diffraction data and give evidence for an underlying magnetic interaction mechanism, resulting in rather strong and long-ranged couplings. Mössbauer spectroscopy shows a change in the electronic configuration on the two distinct Fe sites between room temperature and 150 K, accompanied by an increase of the average Fe-O distance for one site and a shrinking one for the other as expected for charge ordering in a mixed valence compound with Fe(II) and Fe(III).

  1. Synthesis, structure, magnetic, electrical and electrochemical properties of Al, Cu and Mg doped MnO{sub 2}

    Energy Technology Data Exchange (ETDEWEB)

    Hashem, Ahmed M., E-mail: ahmedh242@yahoo.com [National Research Centre, Inorganic Chemistry Department, Behoes St., Dokki, Cairo (Egypt); Institute for Complex Materials, IFW Dresden, Helmholtzstr. 20, D-01069 Dresden (Germany); Abuzeid, Hanaa M. [National Research Centre, Inorganic Chemistry Department, Behoes St., Dokki, Cairo (Egypt); Narayanan, N. [Institute for Complex Materials, IFW Dresden, Helmholtzstr. 20, D-01069 Dresden (Germany); Ehrenberg, Helmut [Institute for Complex Materials, IFW Dresden, Helmholtzstr. 20, D-01069 Dresden (Germany); Materials Science, Technische Universitaet Darmstadt, Petersenstr. 23, D-64287 Darmstadt (Germany); Julien, C.M. [Universite Pierre et Marie Curie, Physicochimie des Electrolytes, Colloides et Sciences Analytiques (PECSA), 4 place Jussieu, 75005 Paris (France)

    2011-10-17

    Highlights: {yields} Al, Mg and Cu doped MnO{sub 2} as cathode in Li-ion batteries. {yields} Pure phase MnO{sub 2} for virgin and doped MnO{sub 2} were obtained. {yields} Doping elements improve the electrical conductivity of MnO{sub 2}. {yields} Electrochemical behaviour of MnO{sub 2} improved after doping by Al, Mg and Cu. - Abstract: Pure and doped manganese dioxides were prepared by wet-chemical method using fumaric acid and potassium permanganate as raw materials. X-ray diffraction patterns show that pure and Al, Cu and Mg doped manganese dioxides (d-MnO{sub 2}) crystallized in the cryptomelane-MnO{sub 2} structure. Thermal analysis show that, with the assistance of potassium ions inside the 2 x 2 tunnel, the presence of Al, Cu and Mg doping elements increases the thermal stability of d-MnO{sub 2}. The electrical conductivity of d-MnO{sub 2} increases in comparison with pure MnO{sub 2}, while Al-doped MnO{sub 2} exhibits the lower resistivity. As shown in the magnetic measurements, the value of the experimental effective magnetic moment of Mn ions decreases with introduction of dopants, which is attributed to the presence of a mixed valency of high-spin state Mn{sup 4+}/Mn{sup 3+}. Doped MnO{sub 2} materials show good capacity retention in comparison with virgin MnO{sub 2}. Al-doped MnO{sub 2} shows the best electrochemical results in terms of capacity retention and recharge efficiency.

  2. Composition-dependent charge transfer and phase separation in the V1-xRexO2 solid solution.

    Science.gov (United States)

    Mikhailova, D; Kuratieva, N N; Utsumi, Y; Tsirlin, A A; Abakumov, A M; Schmidt, M; Oswald, S; Fuess, H; Ehrenberg, H

    2017-01-31

    The substitution of vanadium in vanadium dioxide VO2 influences the critical temperatures of structural and metal-to-insulator transitions in different ways depending on the valence of the dopant. Rhenium adopts valence states between +4 and +7 in an octahedral oxygen surrounding and is particularly interesting in this context. Structural investigation of V1-xRexO2 solid solutions (0.01 ≤ x ≤ 0.30) between 80 and 1200 K using synchrotron X-ray powder diffraction revealed only two polymorphs that resemble VO2: the low-temperature monoclinic MoO2-type form (space group P21/c), and the tetragonal rutile-like form (space group P42/mnm). However, for compositions with 0.03 < x ≤ 0.15 a phase separation in the solid solution was observed below 1000 K upon cooling down from 1200 K, giving rise to two isostructural phases with slightly different lattice parameters. This is reflected in the appearance of two metal-to-insulator transition temperatures detected by magnetization and specific heat measurements. Comprehensive X-ray photoelectron spectroscopy studies showed that an increased amount of Re leads to a change in the Re valence state from solely Re(6+) at a low doping level (≤3 at% Re) via mixed-valence states Re(4+)/Re(6+) for at least 0.03 < x ≤ 0.10, up to nearly pure Re(4+) in V0.70Re0.30O2. Thus, compositions V1-xRexO2 with only one valence state of Re in the material (Re(6+) or Re(4+)) can be obtained as a single phase, while intermediate compositions are subjected to a phase separation, presumably due to different valence states of Re.

  3. Tungsten Incorporation into Gallium Oxide: Crystal Structure, Surface and Interface Chemistry, Thermal Stability and Interdiffusion

    Energy Technology Data Exchange (ETDEWEB)

    Rubio, E. J.; Mates, T. E.; Manandhar, S.; Nandasiri, M.; Shutthanandan, V.; Ramana, C. V.

    2016-12-01

    Tungsten (W) incorporated gallium oxide (Ga2O3) (GWO) thin films were deposited by radio-frequency magnetron co-sputtering of W-metal and Ga2O3-ceramic targets. Films were produced by varying sputtering power applied to the W-target in order to achieve variable W-content (0-12 at%) into Ga2O3 while substrate temperature was kept constant at 500 °C. Chemical composition, chemical valence states, microstructure and crystal structure of as-deposited and annealed GWO films were evaluated as a function of W-content. The structural and chemical analyses indicate that the samples deposited without any W-incorporation are stoichiometric, nanocrystalline Ga2O3 films, which crystallize in β-phase monoclinic structure. While GWO films also crystallize in monoclinic β-Ga2O3 phase, W-incorporation induces surface amorphization as revealed by structural studies. The chemical valence state of Ga ions probed by X-ray photoelectron spectroscopic (XPS) analyses is characterized by the highest oxidation state i.e., Ga3+. No changes in Ga chemical state are noted for variable W-incorporation in the range of 0-12 at%. Rutherford backscattering spectrometry (RBS) analyses indicate the uniform distribution of W-content in the GWO films. However, XPS analyses indicate the formation of mixed valence states for W ions, which may be responsible for surface amorphization in GWO films. GWO films were stable up to 900 oC, at which point thermally induced secondary phase (W-oxide) formation was observed. A transition to mesoporous structure coupled with W interdiffusion occurs due to thermal annealing as derived from the chemical analyses at the GWO films’ surface as well as depth-profiling towards the GWO-Si interface. A model has been formulated to account for the mechanism of W-incorporation, thermal stability and interdiffusion via pore formation in GWO films.

  4. From iron coordination compounds to metal oxide nanoparticles

    Directory of Open Access Journals (Sweden)

    Mihail Iacob

    2016-12-01

    Full Text Available Various types, shapes and sizes of iron oxide nanoparticles were obtained depending on the nature of the precursor, preparation method and reaction conditions. The mixed valence trinuclear iron acetate, [Fe2IIIFeIIO(CH3COO6(H2O3]·2H2O (FeAc1, μ3-oxo trinuclear iron(III acetate, [Fe3O(CH3COO6(H2O3]NO3∙4H2O (FeAc2, iron furoate, [Fe3O(C4H3OCOO6(CH3OH3]NO3∙2CH3OH (FeF, iron chromium furoate, FeCr2O(C4H3OCOO6(CH3OH3]NO3∙2CH3OH (FeCrF, and an iron complex with an original macromolecular ligand (FePAZ were used as precursors for the corresponding oxide nanoparticles. Five series of nanoparticle samples were prepared employing either a classical thermal pathway (i.e., thermal decomposition in solution, solvothermal method, dry thermal decomposition/calcination or using a nonconventional energy source (i.e., microwave or ultrasonic treatment to convert precursors into iron oxides. The resulting materials were structurally characterized by wide-angle X-ray diffraction and Fourier transform infrared, Raman, energy-dispersive X-ray, and X-ray fluorescence spectroscopies, as well as thermogravimetric analysis. The morphology was characterized by transmission electron microscopy, atomic force microscopy and dynamic light scattering. The parameters were varied within each route to fine tune the size and shape of the formed nanoparticles.

  5. Iron-reducing bacteria accumulate ferric oxyhydroxide nanoparticle aggregates that may support planktonic growth.

    Science.gov (United States)

    Luef, Birgit; Fakra, Sirine C; Csencsits, Roseann; Wrighton, Kelly C; Williams, Kenneth H; Wilkins, Michael J; Downing, Kenneth H; Long, Philip E; Comolli, Luis R; Banfield, Jillian F

    2013-02-01

    Iron-reducing bacteria (FeRB) play key roles in anaerobic metal and carbon cycling and carry out biogeochemical transformations that can be harnessed for environmental bioremediation. A subset of FeRB require direct contact with Fe(III)-bearing minerals for dissimilatory growth, yet these bacteria must move between mineral particles. Furthermore, they proliferate in planktonic consortia during biostimulation experiments. Thus, a key question is how such organisms can sustain growth under these conditions. Here we characterized planktonic microbial communities sampled from an aquifer in Rifle, Colorado, USA, close to the peak of iron reduction following in situ acetate amendment. Samples were cryo-plunged on site and subsequently examined using correlated two- and three-dimensional cryogenic transmission electron microscopy (cryo-TEM) and scanning transmission X-ray microscopy (STXM). The outer membranes of most cells were decorated with aggregates up to 150 nm in diameter composed of ∼3 nm wide amorphous, Fe-rich nanoparticles. Fluorescent in situ hybridization of lineage-specific probes applied to rRNA of cells subsequently imaged via cryo-TEM identified Geobacter spp., a well-studied group of FeRB. STXM results at the Fe L(2,3) absorption edges indicate that nanoparticle aggregates contain a variable mixture of Fe(II)-Fe(III), and are generally enriched in Fe(III). Geobacter bemidjiensis cultivated anaerobically in the laboratory on acetate and hydrous ferric oxyhydroxides also accumulated mixed-valence nanoparticle aggregates. In field-collected samples, FeRB with a wide variety of morphologies were associated with nano-aggregates, indicating that cell surface Fe(III) accumulation may be a general mechanism by which FeRB can grow while in planktonic suspension.

  6. Iron-reducing bacteria accumulate ferric oxyhydroxide nanoparticle aggregates that may support planktonic growth

    Energy Technology Data Exchange (ETDEWEB)

    Luef, Birgit; Fakra, Sirine C.; Csencsits, Roseann; Wrighton, Kelly C.; Williams, Kenneth H.; Wilkins, Michael J.; Downing, Kenneth H.; Long, Philip E.; Comolli, Luis R.; Banfield, Jillian F.

    2013-02-04

    Iron-reducing bacteria (FeRB) play key roles in anaerobic metal and carbon cycling and carry out biogeochemical transformations that can be harnessed for environmental bioremediation. A subset of FeRB require direct contact with Fe(III) bearing minerals for dissimilatory growth, yet these bacteria must move between mineral particles. Further, they proliferate in planktonic consortia during biostimulation experiments. Thus, a key question is how such organisms can sustain growth under these conditions. Here we characterized planktonic microbial communities sampled from an aquifer in Rifle, Colorado, USA close to the peak of iron reduction following in situ acetate amendment. Samples were cryo-plunged on site and subsequently examined using correlated 2- and 3- dimensional cryogenic transmission electron microscopy (cryo-TEM) and scanning transmission X-ray microscopy (STXM). Most cells had their outer membranes decorated with up to 150 nm diameter aggregates composed of a few nm wide amorphous, Fe-rich nanoparticles. Fluorescent in situ hybridization of lineage-specific probes applied to rRNA of cells subsequently imaged via cryo-TEM identified Geobacter spp., a well studied group of FeRB. STXM results at the Fe L2,3 absorption edges indicate that nanoparticle aggregates contain a variable mixture of Fe(II)-Fe(III), and are generally enriched in Fe(III). Geobacter bemidjiensis cultivated anaerobically in the laboratory on acetate and hydrous ferric oxyhydroxides also accumulated mixed valence nanoparticle aggregates. In field-collected samples, FeRB with a wide variety of morphologies were associated with nano-aggregates, indicating that cell-surface Fe(III) accumulation may be a general mechanism by which FeRB can grow while in planktonic suspension.

  7. Synthesis and characterization of homo- and heterovalent tetra- hexa- hepta- and decanuclear manganese clusters using pyridyl functionalized beta-diketone, carboxylate and triethanolamine ligands.

    Science.gov (United States)

    Langley, Stuart K; Chilton, Nicholas F; Massi, Massimiliano; Moubaraki, Boujemaa; Berry, Kevin J; Murray, Keith S

    2010-08-21

    The syntheses and characterizations are reported for six new homo- and heterovalent manganese clusters, utilizing pyridyl functionalized beta-diketones ligands. The reaction of the trinuclear complex [Mn3O(O2CPh)6(H2O)(Py)2] with 1,3-di(pyridine-2-yl)propane-1,3-dione (dppdH) in CH2Cl2 resulted in a mixed-valence Mn3(II)Mn6(III)Mn(IV) decanuclear cluster of formula [Mn10O7(dppd)3(O2CPh)11] x 4 CH2Cl2 (1). The structure of the core of 1 is based upon a centred tricapped trigonal prism. Reacting Mn(BF4)2 x xH2O with dppdH and triethylamine (NEt3) in CH2Cl2-MeOH gave a rare, homoleptic hexanuclear cluster of formula [Mn(II)6(dppd)8][BF4]4 (2) which has a triangular based core. Reaction of Mn(Y)2 x xH2O, Y = NO3(-) or BF4(-), with dppdH or 1-phenyl-3-(2-pyridyl)propane-1,3-dione (pppdH) in the presence of triethanolamine (teaH3) and NEt3 gave a heptanuclear 'disc' like manganese core of general formula [Mn(II)7(X)6(tea)(OH)3][Y]2 x solv (3) X = pppd- or dppd- and Y = NO3(-) or BF4(-). The addition of N-(2-pyridinyl)acetoacetamide (paaH) to Mn(Y)2 x 4 H2O Y = NO3(-) or ClO4(-) in MeOH gave a second divalent heptanuclear cluster with a 'disc'-like core of general formula [Mn7(paa)6(OMe)6][X]2 x solv (4) (X = NO3(-) or ClO4(-)), whilst the addition of paaH to a mixture of Mn(NO3)2 x 4 H2O, teaH3 and NEt3 in CH2Cl2-MeOH resulted in the formation of a mixed-valence Mn2(II)Mn2(III) tetranuclear 'butterfly' complex of formula [Mn4(paa)4(teaH)2][NO3]2 x 2 MeOH x 2 CH2Cl2 (5). Compound 5 displays the rare Mn(II/III) oxidation state distribution of the body positions being Mn(II) while the wing tips are Mn(III). The in situ formation of the tetranuclear [Mn4(teaH)2(teaH2)2(O2C(CH3)3)2][O2C(CH3)3]2 'butterfly' complex followed by the addition of Mn(O2CMe)2 x 4 H2O resulted in a mixed-valence Mn4(II)Mn(III)Mn(IV) hexanuclear species of formula [Mn6O2(teaH2)4(O2CMe)4][NO3]2[O2CMe] x CH2Cl2 x MeOH x 2 H2O (6). The core of 6 displays a face sharing dicubane topology. Compounds 1 and

  8. Transport and dielectric studies of metallic, semiconducting, and magnetic materials and devices

    Science.gov (United States)

    Vasic, Relja

    Several organic and inorganic systems of importance for fundamental physics and applications have been studied by magnetotransport, dielectric constant, and Raman spectroscopy techniques. At the beginning of my thesis work, I investigated three carbon based organic systems: carbon fibers, pentacene derivatives, and a nanomagnetic material ("V15"). In the latter stages of my dissertation, I used the techniques I had developed to explore the properties of two inorganic systems: NiFe nanopillars in a silicon matrix, and spin systems in multiferroic rare earth-transition metal oxides. The main activities and achievements of my thesis work are as follows: The carbon fibers were characterized by magnetotransport and Raman spectroscopy studies. I found that carbon fibers are promising as wires in molecular electronics and compatible with organic films. Preliminary results on simple films of melted pentacene derivatives connected with carbon fiber wires were a first step in the fabrication and characterization of pentacene field effect transistors (FET's). The work on the pentacene system resulted in a series of successful logic circuits based on field-effect transistors such as NOT (inverter), NOR, and NAND. The temperature-dependent mobility was described as thermally activated at low gate voltages, but at high gate voltages the mobility was enhanced due to shallow traps. The second system investigated was the organic nanomagnetic material, polyoxovanadate, K6[V15As6O42(H 2O)]˙8H2O (i.e. V15). The conductivity and the dielectric measurements at high and low temperatures respectively were used to determine electrical properties of this single magnet molecule system. The main accomplishments were the determination of the energy gap (0.2eV) and the identification of multiple dipole relaxation modes. Raman vibrational spectroscopy was used to correlate dielectric relaxation with the Raman intramolecular vibrations. An investigation was then carried out on NiFe nanopillars

  9. Electrocatalysis of oxygen reduction on Cu{sub x}Mn{sub 3-x}O{sub 4} (1.0 {<=} x {<=} 1.4) spinel particles/polypyrrole composite electrodes

    Energy Technology Data Exchange (ETDEWEB)

    Rios, E.; Abarca, S.; Daccarett, P.; Gautier, J.L. [Laboratorio de Fisicoquimica y Electroquimica de Solidos, Departamento de Quimica de los Materiales, Facultad de Quimica y Biologia, Universidad de Santiago de Chile, Av. L. B. O' Higgins 3363, Santiago (Chile); Nguyen Cong, H.; Martel, D. [Laboratoire commun au CNRS et a l' Universite Louis Pasteur, LC 3, UMR 7177,1-4 rue Blaise Pascal, 67000 Strasbourg (France); Marco, J.F.; Gancedo, J.R. [Instituto de Quimica-Fisica ' ' Rocasolano' ' , CSIC, c/Serrano, 119, 28006 Madrid (Spain)

    2008-10-15

    Spinel-type binary transition metal oxides of copper and manganese with composition Cu{sub x}Mn{sub 3-x}O{sub 4} (with x = 1.0; 1.1; 1.2; 1.3 and 1.4) were prepared in powder forms by thermal decomposition of nitrate precursors at different temperatures. Their structural properties have been examined by X-ray powder diffraction (XRD), oxidation power and X-ray Photoelectron Spectroscopy (XPS) measurements. To study the effects of solid state properties of the spinel-type compounds on their electrocatalytic activity for the oxygen reduction reaction (orr) in aqueous KCl-KOH solutions, the cathodic polarization characteristics were investigated on composite electrodes of copper and manganese spinel-type oxides nanoparticles embedded in an electrically conductive polymer. These electrodes consisted of multilayered composite electrodes on conductive glass (CG), having the structure CG/PPy/PPy (Ox)/PPy, where PPy is the polypyrrole and Ox is a mixed valence oxide with the general composition Cu{sub x}Mn{sub 3-x}O{sub 4} (1.0 {<=} x {<=} 1.4). The data have shown that the substitution of Mn by Cu increases the catalytic activity, the maximum being that exhibited by Cu{sub 1.4}Mn{sub 1.6}O{sub 4}. Correlations between solid state chemistry and electrocatalytical reactivities towards the oxygen reduction reaction in alkaline media were also investigated on the composite powder electrodes of Cu{sub x}Mn{sub 3-x}O{sub 4} (1.0 {<=} x {<=} 1.4). The results have indicated that the copper content promotes not only the Mn{sup 4+} formation but also the increase of the Mn{sup 4+}/Mn{sup 3+} relation. The change of the Mn{sup 4+}/Mn{sup 3+} ratio as a function of x has been correlated to the electrocatalytical parameters of the orr. The enhanced activity that is observed is related to the higher occurrence of the Mn{sup 4+}/Mn{sup 3+} solid state redox couple in octahedral sites. (author)

  10. The transport and photo electrochemical properties of La-doped stannate BaSnO{sub 3}

    Energy Technology Data Exchange (ETDEWEB)

    Hadjarab, B. [Laboratoire des Solutions Solides (Faculty of Physic), USTHB, BP 32, 16111 Algiers (Algeria); Bouguelia, A. [Laboratoire de Stockage et de Valorisation des Energies Renouvelables (Faculty of Chemistry), USTHB, BP 32, 16111 Algiers (Algeria); Benchettara, A. [Laboratoire Electrochimie-Corrosion, Metallurgie et Chimie Minerale (Faculty of Chemistry), USTHB, BP 32, 16111 Algiers (Algeria); Trari, M. [Laboratoire de Stockage et de Valorisation des Energies Renouvelables (Faculty of Chemistry), USTHB, BP 32, 16111 Algiers (Algeria)], E-mail: mtrari@caramail.com

    2008-08-11

    The electrical conductivity and thermoelectric power of polycrystalline Ba{sub 0.98}La{sub 0.02}SnO{sub 3-{delta}}, prepared under O{sub 2}-free atmosphere, have been measured between 4.2 and 300 K. The existence of onsite bipolaron is due to the tendency to Sn{sup 3+} ions to disproportionate into mixed valences Sn{sup 2+} and Sn{sup 4+} in equivalent sites. The data indicates electron degeneracy like conduction with polaron conductivity and a finite density of states at the Fermi level. The thermal evolution of the conductivity follows an Arrhenius type law with activation energy of 1 meV and electron mobility thermally activated. The conduction mechanism changes to a variable range hopping at low temperatures. From photo electrochemical measurements, the band gap E{sub g} was found to be 3.26 eV and the transition is directly allowed; further indirect interband transition occurs at 2.82 eV. The valence band edge, located at 7.4 eV below vacuum, is made up from O:2p orbital typical of perovskite oxides. The respective values of the slopes (231 and 1104 mV dec{sup -1}) and the exchange current density J (0.339 mA cm{sup -2}) in the semi-logarithmic plot predict long-lived material. As expected, the title oxide exhibits a pH-dependent flat band potential V{sub fb} and at pH 13.60 (KOH 1 M), the current-potential characteristic gave a V{sub fb}-value of -0.03 V{sub SCE}, close to that obtained from the capacitance measurement (+0.05 V{sub SCE}). The C{sup -2}-potential plot displays a straight linear part with a positive slope confirming the n-type conductivity and a uniform doping density (N{sub d} = 7.24 x 10{sup 20} cm{sup -3}). The utilization of BaSnO{sub 3} as coating for PEC electrode is suggested.

  11. Physical properties and photoelectrochemical characterization of SrPbO{sub 3}

    Energy Technology Data Exchange (ETDEWEB)

    Hadjarab, B. [Laboratoire des Solutions Solides, Faculty of Physic (USTHB), BP 32, 16111 Algiers (Algeria); Saadi, S.; Bouguelia, A.; Trari, M. [Laboratoire de Stockage et de Valorisation des Energies Renouvelables, Faculty of Chemistry (USTHB), BP 32, 16111 Algiers (Algeria)

    2007-07-15

    SrPbO{sub 3-{delta}} is n-type, narrow-bandgap semiconductor crystallizing in a distorted perovskite structure. The electrical conductivity varies with temperature but in a nonmonotonic manner. At high temperatures, the thermal evolution of the conductivity follows an Arrhenius-type law with an activation energy of 0.11 eV attributed to mixed valency states Pb{sup 4+/2+} and leading to a dielectric constant of 13.6. The sign of thermopower S is negative, indicating that the mobile carriers are electrons, which is ascribed to oxygen extraction. The electron hopping occurs between similar electronic localized states in the vicinity of the mobility edge with an electron mobility of {proportional_to}10{sup -2} m{sup 2} V{sup -1} s{sup -1} that is thermally activated. The variation S (T) suggests a finite density of states at the Fermi level. At low temperatures, the conduction mechanism changes to a variable-range hopping. The weak hybridization of the Pb-O bond, due to the tilting of PbO{sub 6} octahedra, lowers the energy of the antibonding conduction band resulting in a small optical gap E{sub g}. The E{sub g} value was found to be 1.76 eV and the transition is directly allowed; a further indirect transition occurs at 0.79 eV. The flat potential V{sub fb} measured from the Mott-Schottky plot was equal to -0.38 V{sub SCE}. The upper valence-band edge, located at 6.8 eV below vacuum, is made from mainly the O:2p orbital, whereas the conduction band consists of empty 6s levels. The linear plot log real capacitance-log frequency indicates a capacitive behavior. The relevance of 6s conduction band to the performance of semiconducting photoelectrodes is discussed. (copyright 2007 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim) (orig.)

  12. Physical and photoelectrochemical characterizations of hematite {alpha}-Fe{sub 2}O{sub 3}: Application to photocatalytic oxygen evolution

    Energy Technology Data Exchange (ETDEWEB)

    Boumaza, S.; Boudjemaa, A. [Technical and Scientific Research Centre of Physical Analysis (CRAPC), BP 248, RP 16004 Algiers (Algeria); Laboratory of Chemistry of Natural Gas, Faculty of Chemistry (USTHB), BP 32, 16111 Algiers (Algeria); Omeiri, S. [Technical and Scientific Research Centre of Physical Analysis (CRAPC), BP 248, RP 16004 Algiers (Algeria); Laboratory of Storage and Valorization of Renewable Energies, Faculty of Chemistry (USTHB), BP 32, 16111 Algiers (Algeria); Bouarab, R. [Technical and Scientific Research Centre of Physical Analysis (CRAPC), BP 248, RP 16004 Algiers (Algeria); Bouguelia, A.; Trari, M. [Laboratory of Storage and Valorization of Renewable Energies, Faculty of Chemistry (USTHB), BP 32, 16111 Algiers (Algeria)

    2010-04-15

    The physical properties and photoelectrochemical characterization of {alpha}-Fe{sub 2}O{sub 3}, synthesized by co-precipitation, have been investigated in regard to solar energy conversion. The optical gap is found to be 1.94 eV and the transition is indirectly allowed. The chemical analysis reveals an oxygen deficiency and the oxide exhibits n-type conductivity, confirmed by a negative thermopower. The plot log {sigma} vs 1/T shows linearity in the range (400-670 K) with the donor levels at 0.14 eV below the conduction band and a break at {proportional_to}590 K, attributed to the ionization of the donors. The conduction occurs by small polaron hopping through mixed valences Fe{sup 2+/3+} with an electron mobility {mu}{sub 400} {sub K} of 10{sup -3} V cm{sup 2} s{sup -1}. {alpha}-Fe{sub 2}O{sub 3} exhibits long term chemical stability in neutral solution and has been characterized photoelectrochemically to assess its activity as bias-free O{sub 2}-photoanode. The flat band potential V{sub fb} (-0.45V{sub SCE}) and the electron density N{sub D} (1.63 x 10{sup 18} cm{sup -3}) were determined, respectively, by extrapolating the linear part to C{sup -2} = 0 and the slope of the Mott Schottky plot. At pH 6.5, the valence band (+1.35V{sub SCE}) is suitably positioned with respect to the O{sub 2}/H{sub 2}O level (+0.62 V) and {alpha}-Fe{sub 2}O{sub 3} has been evaluated for the chemical energy storage through the photocatalytic reaction: (2SO{sub 3}{sup 2-}+2 H{sup +}{yields} S{sub 2} O{sub 3}{sup 2-}+ O{sub 2}+ H{sub 2} O, {delta}G = 213.36 kJ mol{sup -1}). The best photoactivity occurs in SO{sub 3}{sup 2-} solution (0.025 M, pH 8) with an oxygen rate evolution of 7.8 cm{sup 3} (g catalyst){sup -1} h{sup -1}. (author)

  13. Optical and transport properties of lanthanum-doped stannate BaSnO3

    Science.gov (United States)

    Hadjarab, B.; Bouguelia, A.; Trari, M.

    2007-10-01

    BaSnO3 crystallizes in a cubic perovskite structure and exhibits insulating behaviour. It can be made conducting by reducing a small fraction of Sn4+ into Sn2+ under an O2-free atmosphere. This can be achieved through the solid solution Ba1-xLaxSnO3-δ which is a mixed phase for x > 0.02, behaviour readily understood in terms of the lone pair cation Sn2+. The magnetic susceptibility was measured down to 4.2 K and is less than 1.7 × 10-5 emu cgs mol-1 consistent with collective electron behaviour. The Mössbauer spectrum exhibits a wide unsplit peak with a quadrupole doublet of 3.18 mm s-1 and an isomer shift of 0.12 mm s-1 characteristic of Sn4+and corroborating the delocalization of the stereo chemical pair 5s2. The band gap Eg was found to be 3.12 eV; further indirectly allowed inter-band transition occurs at 2.85 eV. The transport properties of Ba0.98La0.02SnO3-δ indicate n-type conductivity (σ300 K = 4.03 Ω-1 cm-1), little temperature dependence, with an activation energy ΔE of ~1 meV and an electron mobility μ300 K ~ 0.1 cm2 V-1 s-1, thermally activated. The conduction occurs by small polaron hopping between mixed valence Sn4+/2+ ions. The observed conductivity is greater than that coming from La-substitution with one-electron doping implying the existence of oxygen vacancies. The electrons are believed to travel in the Sn-5s conduction band with an effective mass of 3.7 mo. The non-linear dependence of Ln σ versus T-1 at low temperatures could result from a predominant variable range hopping as suggested by the linear variation of log σ versus T-0.25. The electron localization may be attributed to the random distribution of lanthanum as well as oxygen vacancies.

  14. Optical and transport properties of lanthanum-doped stannate BaSnO{sub 3}

    Energy Technology Data Exchange (ETDEWEB)

    Hadjarab, B [Laboratoire des Solutions Solides (Faculty of Physics), BP 32, Algiers 16111 (Algeria); Bouguelia, A [Laboratoire de Stockage et de Valorisation des Energies Renouvelables (Faculty of Chemistry), BP 32, Algiers 16111 (Algeria); Trari, M [Laboratoire de Stockage et de Valorisation des Energies Renouvelables (Faculty of Chemistry), BP 32, Algiers 16111 (Algeria)

    2007-10-07

    BaSnO{sub 3} crystallizes in a cubic perovskite structure and exhibits insulating behaviour. It can be made conducting by reducing a small fraction of Sn{sup 4+} into Sn{sup 2+} under an O{sub 2}-free atmosphere. This can be achieved through the solid solution Ba{sub 1-x}La{sub x}SnO{sub 3-{delta}} which is a mixed phase for x > 0.02, behaviour readily understood in terms of the lone pair cation Sn{sup 2+}. The magnetic susceptibility was measured down to 4.2 K and is less than 1.7 x 10{sup -5} emu cgs mol{sup -1} consistent with collective electron behaviour. The Moessbauer spectrum exhibits a wide unsplit peak with a quadrupole doublet of 3.18 mm s{sup -1} and an isomer shift of 0.12 mm s{sup -1} characteristic of Sn{sup 4+}and corroborating the delocalization of the stereo chemical pair 5s{sup 2}. The band gap E{sub g} was found to be 3.12 eV; further indirectly allowed inter-band transition occurs at 2.85 eV. The transport properties of Ba{sub 0.98}La{sub 0.02}SnO{sub 3-{delta}} indicate n-type conductivity ({sigma}{sub 300K} = 4.03 {omega}{sup -1} cm{sup -1}), little temperature dependence, with an activation energy {delta}E of {approx}1 meV and an electron mobility {mu}{sub 300K} {approx} 0.1 cm{sup 2} V{sup -1} s{sup -1}, thermally activated. The conduction occurs by small polaron hopping between mixed valence Sn{sup 4+/2+} ions. The observed conductivity is greater than that coming from La-substitution with one-electron doping implying the existence of oxygen vacancies. The electrons are believed to travel in the Sn-5s conduction band with an effective mass of 3.7 m{sub o}. The non-linear dependence of Ln {sigma} versus T{sup -1} at low temperatures could result from a predominant variable range hopping as suggested by the linear variation of log {sigma} versus T{sup -0.25}. The electron localization may be attributed to the random distribution of lanthanum as well as oxygen vacancies.

  15. Hydrogen photo-evolution over the spinel CuCr{sub 2}O{sub 4}

    Energy Technology Data Exchange (ETDEWEB)

    Boumaza, Souhila [Laboratoire de Chimie de Gaz Naturel, USTHB, BP 32 16111 Algiers (Algeria); Centre de Recherche Scientifique et Technique en Analyses Physico-Chimiques (C.R.A.P.C) BP248 Algiers RP, 16004 (Algeria); Bouarab, Rabah [Laboratoire de Chimie de Gaz Naturel, USTHB, BP 32 16111 Algiers (Algeria); Trari, Mohamed; Bouguelia, Aissa [Laboratoire de Stockage et de Valorisation des Energies Renouvelables, Faculte de Chimie, USTHB, BP 32 Bab Ezzouar, 16111 Algiers (Algeria)

    2009-01-15

    The photocatalytic H{sub 2} evolution over CuCr{sub 2}O{sub 4} has been studied in connection with some physical properties. The black oxide is classified as a narrow band gap semiconductor crystallizing in the normal spinel structure. The photoactivity is dependent on the preparative conditions through the surface area of the powder and CuCr{sub 2}O{sub 4} has been synthesized by nitrate route. The conductivity varies exponentially with temperature indicating an extrinsic conductivity between mixed valences states Cr{sup 3+/4+} located in octahedra sharing common corners. The oxide exhibits p-type conductivity with an activation energy of 0.20 eV and a hole mobility of 2.14 x 10{sup -8} cm{sup 2}/V s thermally activated. CuCr{sub 2}O{sub 4} shows an excellent chemical stability, a corrosion potential of -0.775 V{sub SCE} and an exchange current density of 16 {mu}A cm{sup -2} have been determined from the semilogarithm plot. The capacitance measurement (C{sup -2}-V), performed in basic electrolyte, exhibits a linear behavior from which a flat band potential of 0.48 V{sub SCE} was obtained. CuCr{sub 2}O{sub 4} is photoelectrochemically stable by hole consumption reactions involving X{sup 2-} (=SO{sub 3}{sup 2-} and S{sub 2} O{sub 3}{sup 2-}) as hole scavengers. The best catalytic performance for H{sub 2}-photoproduction was obtained in (NaOH 0.5 M, Na{sub 2}S{sub 2}O{sub 3} 0.025 M) with an average rate of 0.013 cm{sup 3} h{sup -1} (mg catalyst){sup -1} and a quantum efficiency of 0.2% under polychromatic light. S{sub 2} O{sub 3}{sup 2-} is oxidized to SO{sub 3}{sup 2-} and subsequently to SO{sub 4}{sup 2-} as proven by the dual slopes in the Tafel plot. The system shows a tendency towards saturation whose deceleration is the result of the competitive reductions of the end products namely S{sub 2} O{sub 6}{sup 2-} and S{sub 2} O{sub 4}{sup 2-} with the water discharge. (author)

  16. Calix[4]arene Based Single-Molecule Magnets

    Energy Technology Data Exchange (ETDEWEB)

    Karotsis, Georgios; Teat, Simon J.; Wernsdorfer, Wolfgang; Piligkos, Stergios; Dalgarno, Scott J.; Brechin, Euan K.

    2009-06-04

    n = 4-8) also suggests they should be excellent candidates as ligands for the isolation of molecular magnets, but to date their use in the isolation of paramagnetic cluster compounds is rather limited. Herein we present the first Mn cluster and the first SMM to be isolated using any methylene bridged calix[n]arene - a ferromagnetically coupled mixed-valence [Mn{sub 2}{sup III}Mn{sub 2}{sup II}] complex housed between either two TBC4s or two C4s.

  17. Copper(I)- and copper(0)-promoted homocoupling and homocoupling-hydrodehalogenation reactions of dihalogenoclathrochelate precursors for C-C conjugated iron(II) bis-cage complexes.

    Science.gov (United States)

    Varzatskii, Oleg A; Shul'ga, Sergey V; Belov, Alexander S; Novikov, Valentin V; Dolganov, Alexander V; Vologzhanina, Anna V; Voloshin, Yan Z

    2014-12-28

    . As follows from CV data, the C-C conjugated iron(II) bis-clathrochelates undergo stepwise electrochemical reduction and oxidation giving mixed-valence Fe(II)Fe(I) and Fe(II)Fe(III) bis-cage intermediates.

  18. Characterization of natural titanomagnetites (Fe3-xTixO4) for studying heterogeneous electron transfer to Tc(VII) in the Hanford subsurface

    Science.gov (United States)

    Pearce, C. I.; Liu, J.; Baer, D. R.; Qafoku, O.; Heald, S. M.; Arenholz, E.; Grosz, A. E.; McKinley, J. P.; Resch, C. T.; Bowden, M. E.; Engelhard, M. H.; Rosso, K. M.

    2014-03-01

    Sediments with basaltic provenance, such as those at the Hanford nuclear reservation, Washington, USA, are rich in Fe-bearing minerals of mixed valence. These minerals are redox reactive with aqueous O2 or Fe(II), and have the potential to react with important environmental contaminants including Tc. Here we isolate, identify and characterize natural Fe(II)/Fe(III)-bearing microparticles from Hanford sediments, develop synthetic analogues and investigate their batch redox reactivity with aqueous Tc(VII). Natural Fe-rich mineral samples were isolated by magnetic separation from sediments collected at several locations on Hanford’s central plateau. This magnetic mineral fraction was found to represent up to 1 wt% of the total sediment, and be composed of 90% magnetite with minor ilmenite and hematite, as determined by X-ray diffraction. The magnetite contained variable amounts of transition metals consistent with alio- and isovalent metal substitutions for Fe. X-ray microprobe analysis showed that Ti was the most significant substituent, and that these grains could be described with the titanomagnetite formula Fe3-xTixO4, which falls between endmember magnetite (x = 0) and ulvöspinel (x = 1). The dominant composition was determined to be x = 0.15 by chemical analysis and electron probe microanalysis in the bulk, and by L-edge X-ray absorption spectroscopy and X-ray photoelectron spectroscopy at the surface. Site-level characterization of the titanomagnetites by X-ray magnetic circular dichroism showed that despite native oxidation, octahedral Fe(II) was detectable within 5 nm of the mineral surface. By testing the effect of contact with oxic Hanford and Ringold groundwaters to reduced Ringold groundwater, it was found that the concentration of this near-surface structural Fe(II) was strongly dependent on aqueous redox condition. This highlights the potential for restoring reducing equivalents and thus reduction capacity to oxidized Fe-mineral surfaces through

  19. Cationic disorder and Mn{sup 3+}/Mn{sup 4+} charge ordering in the B′ and B″ sites of Ca{sub 3}Mn{sub 2}NbO{sub 9} perovskite: a comparison with Ca{sub 3}Mn{sub 2}WO{sub 9}

    Energy Technology Data Exchange (ETDEWEB)

    López, C.A., E-mail: calopez@unsl.edu.ar [INTEQUI-Área de Química General e Inorgánica “Dr. G. F. Puelles”, Facultad de Química, Bioquímica y Farmacia, Universidad Nacional de San Luis, Chacabuco y Pedernera, 5700 San Luis (Argentina); Centro Atómico Bariloche, Comisión Nacional de Energía Atómica and Instituto Balseiro, Universidad Nacional de Cuyo, 8400S.C. de Bariloche, Río Negro (Argentina); Saleta, M.E. [Centro Atómico Bariloche, Comisión Nacional de Energía Atómica and Instituto Balseiro, Universidad Nacional de Cuyo, 8400S.C. de Bariloche, Río Negro (Argentina); Pedregosa, J.C. [INTEQUI-Área de Química General e Inorgánica “Dr. G. F. Puelles”, Facultad de Química, Bioquímica y Farmacia, Universidad Nacional de San Luis, Chacabuco y Pedernera, 5700 San Luis (Argentina); Sánchez, R.D. [Centro Atómico Bariloche, Comisión Nacional de Energía Atómica and Instituto Balseiro, Universidad Nacional de Cuyo, 8400S.C. de Bariloche, Río Negro (Argentina); Alonso, J.A. [Instituto de Ciencia de Materiales de Madrid, CSIC, Cantoblanco, E-28049 Madrid (Spain); and others

    2014-02-15

    We describe the preparation, crystal structure determination, magnetic and transport properties of two novel Mn-containing perovskites, with a different electronic configuration for Mn atoms located in B site. Ca{sub 3}Mn{sup 3+}{sub 2}WO{sub 9} and Ca{sub 3}Mn{sup 3+/4+}{sub 2}NbO{sub 9} were synthesized by standard ceramic procedures; the crystallographic structure was studied from X-ray powder diffraction (XRPD) and neutron powder diffraction (NPD). Both phases exhibit a monoclinic symmetry (S.G.: P2{sub 1}/n); Ca{sub 3}Mn{sub 2}WO{sub 9} presents a long-range ordering over the B sites, whereas Ca{sub 3}Mn{sub 2}NbO{sub 9} is strongly disordered. By “in-situ” NPD, the temperature evolution of the structure study presents an interesting evolution in the octahedral size (〈Mn–O〉) for Ca{sub 3}Mn{sub 2}NbO{sub 9}, driven by a charge ordering effect between Mn{sup 3+} and Mn{sup 4+} atoms, related to the anomaly observed in the transport measurements at T≈160 K. Both materials present a magnetic order below T{sub C}=30 K and 40 K for W and Nb materials, respectively. The magneto-transport measurements display non-negligible magnetoresistance properties in the paramagnetic regime. - Graphical abstract: Comparison between the octahedron size and the magnetic behaviour for Ca{sub 3}Mn{sub 2}NbO{sub 9} in the temperature region where the charge and magnetic order occur. Display Omitted - Highlights: • Two novel Mn-containing double perovskites were obtained by solid-state reactions. • Both double perovskites are monoclinic (P2{sub 1}/n) determined by XRPD and NPD. • Ca{sub 3}Mn{sub 2}WO{sub 9} contains Mn{sup 3+} while Ca{sub 3}Mn{sub 2}NbO{sub 9} includes mixed-valence cations Mn{sup 3+}/Mn{sup 4+}. • Ca{sub 3}Mn{sub 2}NbO{sub 9} presents a charge-ordering effect between Mn{sup 3+} and Mn{sup 4+} evidenced by NPD. • The magnetic and transport studies evidenced the charge ordering in Ca{sub 3}Mn{sub 2}NbO{sub 9}.

  20. 含席夫碱桥联配体的双核金属钌配合物的合成及其性能研究%Synthesis and Properties of Dinuclear Ruthenium Complexes with Schiff Base Bridging Ligands

    Institute of Scientific and Technical Information of China (English)

    张燕; 熊碧; 蔡苹; 程功臻

    2012-01-01

    合成了3种双核钌配合物[Ru(bpy)2]2{[(PyCHN)-Ph-O-C6H4-]2R}(ClO4)4,bpy=2,2′-联吡啶,PyCHN=N-2-吡啶亚甲基,R=无(1),-C(CH3)2(2),-SO2(3)并进行了有关表征.电化学研究表明:配合物3的△E和K值最大,说明苯环和硫原子之间存在着较强的(p(π)-dπ相互作用,有助于获得较强的金属-金属相互作用.配合物1,2,3都有混合价,通过Hush方程可以得到Vab的值大概为320~420 cm-1.这些结果表明:Schiff碱作为桥配体对于调配金属-金属相互作用并将其作为分子导线起着特殊的作用.%Binuclear ruthenium complexes [Ru (bpy)2]2 {[(PyCHN)-Ph-O-C6H4-]2R} (ClO4)4 where bpy =2,2′-bipyridine,PyCHN=N-2-pyridylmethylene,R=none for 1,-C(CH3)2 for 2 and-SO2 for 3,have been prepared and characterized.Electrochemical studies reveal that the ΔE and Kc for complexes 1,2 and 3 are surprisingly and unprecedentedly large.However,the complex 3 gives larger ΔE and Kc.It is suggested that the strong (p(π)-d)π interactions between the phenyl rings and the sulfur atom should be helpful to achieve stronger metal-metal interaction.For mixed-valence species of complexes 1,2 and 3,Vab can be obtained by Hush equation with a value of 320~420 cm-1.These results indicate that the Schiff base bridging ligands show particular efficiency for mediating the metal-metal interactions and for using as molecular wires.

  1. Structure-activity relationships in cytotoxic Au(I)/Au(III) complexes derived from 2-(2'-pyridyl)benzimidazole.

    Science.gov (United States)

    Maiore, Laura; Aragoni, Maria Carla; Deiana, Carlo; Cinellu, Maria Agostina; Isaia, Francesco; Lippolis, Vito; Pintus, Anna; Serratrice, Maria; Arca, Massimiliano

    2014-04-21

    Gold(I) and gold(III) complexes derived from 2-(2'-pyridyl)benzimidazole (pbiH) were proven to be a promising class of in vitro antitumor agents against A2780 human ovarian cancer cells. In this paper, a comparative electrochemical, UV-vis absorption, and emission spectroscopic investigation is reported on pbiH, the two mononuclear Au(III) complexes [(pbi)AuX2] (X = Cl (1), AcO (2)), the four mononuclear Au(I) derivatives [(pbiH)AuCl] (3), [(pbiH)Au(PPh3)]PF6 ((4(+))(PF6(-))), [(pbi)Au(PPh3)] (5), and [(pbi)Au(TPA)] (6), the three mixed-valence Au(III)/Au(I) complexes [(μ-pbi)Au2Cl3] (7), [(Ph3P)Au(μ-pbi)AuX2]PF6 (X = Cl ((8(+))(PF6(-))), AcO ((9(+))(PF6(-)))), and the binuclear Au(I)-Au(I) compound [(μ-pbi)Au2(PPh3)2]PF6 ((10(+))(PF6(-))). All complexes feature irreversible reduction processes related to the Au(III)/Au(I) or Au(I)/Au(0) processes and peculiar luminescent emission at about 360-370 nm in CH2Cl2, with quantum yields that are remarkably lower ((0.7-14.5) × 10(-2)) in comparison to that determined for the free pbiH ligand (31.5 × 10(-2)) in the same solvent. The spectroscopic and electrochemical properties of all complexes were interpreted on the grounds of time-dependent PBE0/DFT calculations carried out both in the gas phase and in CH2Cl2 implicitly considered within the IEF-PCM SCRF approach. The electronic structure of the complexes, and in particular the energy and composition of the Kohn-Sham LUMOs, can be related to the antiproliferative properties against the A2780 ovarian carcinoma cell line, providing sound quantitative structure-activity relationships and shedding a light on the role played by the global charge and nature of ancillary ligands in the effectiveness of Au-based antitumor drugs.

  2. Large Mn25 single-molecule magnet with spin S = 51/2: magnetic and high-frequency electron paramagnetic resonance spectroscopic characterization of a giant spin state.

    Science.gov (United States)

    Murugesu, Muralee; Takahashi, Susumu; Wilson, Anthony; Abboud, Khalil A; Wernsdorfer, Wolfgang; Hill, Stephen; Christou, George

    2008-10-20

    The synthesis and structural, spectroscopic, and magnetic characterization of a Mn25 coordination cluster with a large ground-state spin of S = 51/2 are reported. Reaction of MnCl2 with pyridine-2,6-dimethanol (pdmH2) and NaN3 in MeCN/MeOH gives the mixed valence cluster [Mn25O18(OH)2(N3)12(pdm)6(pdmH)6]Cl2 (1; 6Mn(II), 18Mn(III), Mn(IV)), which has a barrel-like cage structure. Variable temperature direct current (dc) magnetic susceptibility data were collected in the 1.8-300 K temperature range in a 0.1 T field. Variable-temperature and -field magnetization (M) data were collected in the 1.8-4.0 K and 0.1-7 T ranges and fit by matrix diagonalization assuming only the ground state is occupied at these temperatures. The fit parameters were S = 51/2, D = -0.020(2) cm(-1), and g = 1.87(3), where D is the axial zero-field splitting parameter. Alternating current (ac) susceptibility measurements in the 1.8-8.0 K range and a 3.5 G ac field oscillating at frequencies in the 50-1500 Hz range revealed a frequency-dependent out-of-phase (chi(M)'') signal below 3 K, suggesting 1 to be a single-molecule magnet (SMM). This was confirmed by magnetization vs dc field sweeps, which exhibited hysteresis loops but with no clear steps characteristic of resonant quantum tunneling of magnetization (QTM). However, magnetization decay data below 1 K were collected and used to construct an Arrhenius plot, and the fit of the thermally activated region above approximately 0.5 K gave U(eff)/k = 12 K, where U(eff) is the effective relaxation barrier. The g value and the magnitude and sign of the D value were independently confirmed by detailed high-frequency electron paramagnetic resonance (HFEPR) spectroscopy on polycrystalline samples. The combined studies confirm both the high ground-state spin S = 51/2 of complex 1 and that it is a SMM that, in addition, exhibits QTM.

  3. 1,5-Diamido-9,10-anthraquinone, a Centrosymmetric Redox-Active Bridge with Two Coupled β-Ketiminato Chelate Functions: Symmetric and Asymmetric Diruthenium Complexes.

    Science.gov (United States)

    Ansari, Mohd Asif; Mandal, Abhishek; Paretzki, Alexa; Beyer, Katharina; Fiedler, Jan; Kaim, Wolfgang; Lahiri, Goutam Kumar

    2016-06-01

    The dinuclear complexes {(μ-H2L)[Ru(bpy)2]2}(ClO4)2 ([3](ClO4)2), {(μ-H2L)[Ru(pap)2]2}(ClO4)2 ([4](ClO4)2), and the asymmetric [(bpy)2Ru(μ-H2L)Ru(pap)2](ClO4)2 ([5](ClO4)2) were synthesized via the mononuclear species [Ru(H3L)(bpy)2]ClO4 ([1]ClO4) and [Ru(H3L)(pap)2]ClO4 ([2]ClO4), where H4L is the centrosymmetric 1,5-diamino-9,10-anthraquinone, bpy is 2,2'-bipyridine, and pap is 2-phenylazopyridine. Electrochemistry of the structurally characterized [1]ClO4, [2]ClO4, [3](ClO4)2, [4](ClO4)2, and [5](ClO4)2 reveals multistep oxidation and reduction processes, which were analyzed by electron paramagnetic resonance (EPR) of paramagnetic intermediates and by UV-vis-NIR spectro-electrochemistry. With support by time-dependent density functional theory (DFT) calculations the redox processes could be assigned. Significant results include the dimetal/bridging ligand mixed spin distribution in 3(3+) versus largely bridge-centered spin in 4(3+)-a result of the presence of Ru(II)-stabilizig pap coligands. In addition to the metal/ligand alternative for electron transfer and spin location, the dinuclear systems allow for the observation of ligand/ligand and metal/metal site differentiation within the multistep redox series. DFT-supported EPR and NIR absorption spectroscopy of the latter case revealed class II mixed-valence behavior of the oxidized asymmetric system 5(3+) with about equal contributions from a radical bridge formulation. In comparison to the analogues with the deprotonated 1,4-diaminoanthraquinone isomer the centrosymmetric H2L(2-) bridge shows anodically shifted redox potentials and weaker electronic coupling between the chelate sites.

  4. Modular construction of oxide structures--compositional control of transition metal coordination environments.

    Science.gov (United States)

    Tenailleau, Christophe; Allix, Mathieu; Claridge, John B; Hervieu, Maryvonne; Thomas, Michael F; Hirst, James P; Rosseinsky, Matthew J

    2008-06-18

    The effects of reaction temperature and pO2 were investigated on a series of (Ba,Ca,Nd)FeO3-delta perovskite systems in order to isolate phases containing ordered arrangements of the distinct vacancy and cation ordering patterns identified in less compositionally complex iron oxide systems. Initial synthesis in air at high temperature yields cubic perovskite phases (I) with average iron oxidation states higher than 3; selected area electron diffraction together with diffuse features observed in the synchrotron X-ray diffraction (SXRD) patterns of these materials show evidence of small domains of short-range cation and vacancy order. Annealing these materials in nitrogen or in a sealed tube in the presence of an NiO/Ni buffer yielded the Fe(3+) phase Ca2Ba2Nd2Fe6O16 (II), closely related to Sr2LaFe3O8 but with partial cation order as well as anion order present the larger Ba cations are largely present in the 12-coordinate site between the octahedral iron layers, and Ca is largely present in 10-coordinate sites between octahedral and tetrahedral sites. Further reduction of Ca2Ba2Nd2Fe6O16 using a Zr getter yields the mixed-valence phase Ca2Ba2Nd2Fe6O15.6 (III). The structure of III was solved by maximum entropy analysis of XRD data coupled with analysis of high-temperature neutron diffraction data and refined against combined SXRD and high-Q ambient-temperature neutron data. This material crystallizes in a 20-fold perovskite super cell (Imma, a approximately square root(2 x a(p), b approximately 10 x a(p), c approximately square root(x 2a(p)) and can be visualized as an intergrowth between brownmillerite (Ca2Fe2O5) and the YBa2Fe3O8 structure. There are three distinct iron coordination environments, octahedral (O), square-pyramidal (Sp), and trigonal planar (Tp, formed by distorting the tetrahedral site in brownmillerite), which form a Sp-O-Tp-O-Sp repeat. Bond valence calculations indicate that Tp is an Fe(2+) site, while the O and Sp sites are Fe(3+). The A

  5. Mineral Bionization - Surface Chemical Modeling of the Emergence of Life

    Science.gov (United States)

    Arrhenius, G.

    2001-12-01

    The earliest stages in entering an RNA-world require natural mechanisms that are capable of selective concentration of simple aldehydes from dilute solution in the environment (4), furthermore phosphorylation of the sequestered aldehydes (2) and their catalytic condensation to form, selectively, tetrose- (threose) or pentose- (ribose) phosphate (3); the latter representing the R in RNA. A variety of common positively charged sheet structure minerals (mixed valence double layer metal hydroxide minerals such as hydrotalcite and green rust) have proven to be remarkably capable of performing these crucial tasks under simplified natural conditions (1). These prebiotic model reactions have demonstrated plausible closure of the gap, previously thought to preclude the natural formation of nucleoside phosphates, the backbone components of the information carrying genetic material. Pioneering research by other workers (5) has demonstrated the feasibility of necessary further steps in the chain toward functional RNA; mineral (montmorillonite) catalyzed oligomerization of nucleotides, the formation of complementary RNA strands (6) and the enzymatic activity of RNA (ribozymes). These contributions have placed the initially conjectural concept of an initial RNA-world on an experimental footing. Remaining problems include the initial transfer of information to spontaneously forming RNA, sufficient to convey biofunctionallity (7). Also in this central problem mineral surface interactions may be speculated to play a natural role; a question that is open to experimental verification. References. 1. Pitsch, S.; Eschenmoser, A.; Gedulin, B.; Hui, S. and Arrhenius, G. Origins Life Evol. Biosphere, 1994, 24 (5), 389. 2. Kolb, V.; Zhang, S.; Xu, Y.; Arrhenius, G. Origins Life Evol. Biosphere, 1997, 27, 485. 3. Krishnamurthy, R.; Pitsch, S.; Arrhenius, G. Origins Life Evol. Biosphere, Origins Life Evol. Biosphere 1999, 29, 139 4. Pitsch, S.; Krishnamurthy, R.; Arrhenius, G. Helv. Chim

  6. Enhancement of magnetoresistance and ferromagnetic coupling in the complex perovskites CaCu{sub 3}(Mn{sub 4−x}Al{sub x})O{sub 12} (x = 0, 0.2, 0.4, and 0.6): A neutron diffraction study

    Energy Technology Data Exchange (ETDEWEB)

    Ben Hassine, R.; Cherif, W. [Faculty of Sciences, Sfax University, Sfax, B.P. 1171-3000 (Tunisia); Sánchez-Benítez, J. [Departamento de Química Física I, Facultad de Ciencias Químicas, Universidad Complutense de Madrid, E-28040 Madrid (Spain); Mompean, F. J.; Alonso, J. A., E-mail: ja.alonso@icmm.csic.es [Instituto de Ciencia de Materiales de Madrid, Consejo Superior de Investigaciones Científicas, Cantoblanco, E-28049 Madrid (Spain); Fernández-Díaz, M. T. [Institut Laue-Langevin, B.P. 156, F-38042 Grenoble Cedex 9 (France); Elhalouani, F. [National School of Engineers, Sfax University, Sfax, B.P. W 3038 (Tunisia)

    2015-09-14

    New compounds of the series CaCu{sub 3}(Mn{sub 4−x}Al{sub x})O{sub 12} have been prepared under high pressure conditions (2 GPa), in the presence of KClO{sub 4} as oxidizing agent to stabilize Mn{sup 3+,4+} mixed valence. The polycrystalline samples have been characterized by x-ray diffraction, neutron powder diffraction (NPD), magnetic, and magnetotransport measurements. All the samples are cubic, space group Im-3. These oxides adopt a superstructure of ABO{sub 3} perovskite given by the long-range 1:3 ordering of Ca{sup 2+} and Cu{sup 2+} ions at the A sublattice. The NPD study for x = 0.4 shows that Al{sup 3+} ions are statistically distributed at the octahedral positions, being the (Mn,Al)O{sub 6} octahedra strongly tilted, with superexchange (Mn,Al)-O-(Mn,Al) angles of 142.1°. Also, neutron data clearly show that some Mn{sup 3+} ions (0.65(2) per formula) are located together with Cu{sup 2+} at the square-planar 6b positions. Regarding the magnetic properties, all the compounds present a spontaneous increase of the magnetization below T{sub C}, typical of ferro-or ferrimagnetic materials, with T{sub C} decreasing upon Al introduction. The magnetic structure determined from low-temperature NPD data unveils a ferromagnetic coupling between (Cu{sup 2+}, Mn{sup 3+}){sub 6b} spins and Mn{sub 8c} spins at octahedral positions; this is in contrast with the ferrimagnetic structure observed for RCu{sub 3}Mn{sub 4}O{sub 12} and CaCu{sub 3}Mn{sub 4}O{sub 12}, where an AFM coupling is observed between both magnetic sublattices. Interestingly, an enhancement of the magnetoresistance effect is observed for x = 0.2, well beyond that found for the parent compound. This effect, in materials subtly doped with non-magnetic elements at the Mn positions, may be of interest for applications.

  7. Synthesis and Electronic Structure of Ru2(Xap)4(Y-gem-DEE) Type Compounds: Effect of Cross-Conjugation.

    Science.gov (United States)

    Forrest, William P; Choudhuri, Mohommad M R; Kilyanek, Stefan M; Natoli, Sean N; Prentice, Boone M; Fanwick, Phillip E; Crutchley, Robert J; Ren, Tong

    2015-08-03

    Reported in this Article are the preparation and characterization of a series of new Ru2(II,III) compounds bearing one cross-conjugated σ-geminal-diethynylethene ligand (gem-DEE), namely, Ru2(Xap)4(Y-gem-DEE) (Xap = N,N'-anilinopyridinate (ap) or 2-(3,5-dimethoxy)anilinopyridinate (DiMeOap), and Y = Si(i)Pr3 (1) or H (2)) and [Ru2(ap)4]2(μ-gem-DEE) (3). Compounds 1-3 were characterized by spectroscopic and voltammetric techniques as well as the single crystal X-ray diffraction study of 2a. The X-ray structural data of 2a and the spectroscopic/voltammetric data of compounds 1 and 2 indicate that the gem-DEE ligands are similar to simple alkynyls in their effects on the molecular and electronic structures of the Ru2(Xap)4 moiety. Similar to the previously studied [Ru2(ap)4]2(μ-C2n) type compounds, dimer 3 exhibits pairwise 1e(-) oxidations and reductions, albeit the potential splits within the pair (ΔE1/2) are significantly smaller than those of [Ru2(ap)4]2(μ-C4). The electronic absorption spectra of the reduced and oxidized derivatives of 1a and 3 were determined using spectroelectrochemistry methods. No discernible intervalence charge transfer transition (IVCT) was detected in the near-IR spectrum for either 3(-) or 3(+), suggesting that the Ru2-Ru2 coupling in these mixed-valence states is weak. DFT calculations on a model compound of 3 yielded six singly occupied molecular orbitals (SOMOs), which have Ru2 contributions similar to those previously calculated for the [Ru2(ap)4]2(μ-C2n) type compounds. Among six SOMOs, SOMO-2 is the only one containing substantial dπ-π(gem-DEE) character across the entire Ru2-μ-gem-DEE-Ru2 linkage, which explains the weakened Ru2-Ru2 coupling.

  8. Correlation between vacancies and magnetoresistance changes in FM manganites using the Monte Carlo method

    Energy Technology Data Exchange (ETDEWEB)

    Agudelo-Giraldo, J.D. [PCM Computational Applications, Universidad Nacional de Colombia-Sede Manizales, Km. 9 vía al aeropuerto, Manizales (Colombia); Restrepo-Parra, E., E-mail: erestrepopa@unal.edu.co [PCM Computational Applications, Universidad Nacional de Colombia-Sede Manizales, Km. 9 vía al aeropuerto, Manizales (Colombia); Restrepo, J. [Grupo de Magnetismo y Simulación, Instituto de Física, Universidad de Antioquia, A.A. 1226, Medellín (Colombia)

    2015-10-01

    The Metropolis algorithm and the classical Heisenberg approximation were implemented by the Monte Carlo method to design a computational approach to the magnetization and resistivity of La{sub 2/3}Ca{sub 1/3}MnO{sub 3}, which depends on the Mn ion vacancies as the external magnetic field increases. This compound is ferromagnetic, and it exhibits the colossal magnetoresistance (CMR) effect. The monolayer was built with L×L×d dimensions, and it had L=30 umc (units of magnetic cells) for its dimension in the x–y plane and was d=12 umc in thickness. The Hamiltonian that was used contains interactions between first neighbors, the magnetocrystalline anisotropy effect and the external applied magnetic field response. The system that was considered contains mixed-valence bonds: Mn{sup 3+eg’}–O–Mn{sup 3+eg}, Mn{sup 3+eg}–O–Mn{sup 4+d3} and Mn{sup 3+eg’}–O–Mn{sup 4+d3}. The vacancies were placed randomly in the sample, replacing any type of Mn ion. The main result shows that without vacancies, the transitions T{sub C} (Curie temperature) and T{sub MI} (metal–insulator temperature) are similar, whereas with the increase in the vacancy percentage, T{sub MI} presented lower values than T{sub C}. This situation is caused by the competition between the external magnetic field, the vacancy percentage and the magnetocrystalline anisotropy, which favors the magnetoresistive effect at temperatures below T{sub MI}. Resistivity loops were also observed, which shows a direct correlation with the hysteresis loops of magnetization at temperatures below T{sub C}. - Highlights: • Changes in the resistivity of FM materials as a function of the temperature and external magnetic field can be obtained by the Monte Carlo method, Metropolis algorithm, classical Heisenberg and Kronig–Penney approximation for magnetic clusters. • Increases in the magnetoresistive effect were observed at temperatures below T{sub MI} by the vacancies effect. • The resistive hysteresis

  9. Cooperative magnetic behaviour in the new valence fluctuating compound Ce2Rh3Ge

    Science.gov (United States)

    Falkowski, M.; Strydom, A. M.

    2015-10-01

    In this study we report the physical properties of the new ternary compound Ce2Rh3Ge that crystallizes in the rhombohedral, triple hexagonal MgCu2-type of structure. The electronic ground state properties of Ce2Rh3Ge were characterized by magnetic susceptibility, specific heat, electrical resistivity and thermal transport measurements. The results indicate the presence of short range magnetic interaction, probably of ferromagnetic origin below T C  =  4 K. The shape of χ -1(T) deviates from the Curie-Weiss behavior with a broad minimum at about T\\min{{χ-1}}   =  450 K reminiscent of valence fluctuating cerium systems. At T  =  10 K, the magnetic part of the resistivity ρ 4 f (T) exhibits a shallow minimum followed by increase of resistivity ρ(T) \\propto   -lnT, which hints at a substantial Kondo screening effect. Ce2Rh3Ge belongs to a small group of strongly correlated cerium compounds in which the two competing effects of Kondo and RKKY interactions produce long-range magnetic order from strongly hybridized and intermediate-valent 4 f spins. At sufficiently low temperatures Ce2Rh3Ge scales well with the Kadowaki-Woods ratio A/γ 2 and the value of the Wilson ratio χ(T  →  0)/γ found for this compound classifies it as a mixed-valence compound. The presence of valence fluctuation and magnetic order it is rare for these attributes to be found simultaneously in same compound, in same temperature range. In our opinion a novelty of presented results of Ce2Rh3Ge is that this compound adds a new member to a small but growing class of systems bearing a strongly mixed- or intermediate-valent 4 f magnetic moment, but in which the lattice of spins nevertheless end up finding it possible to order magnetically.

  10. Microbial and hydrothermal aspects of ferric oxyhydroxides and ferrosic hydroxides: the example of Franklin Seamount, Western Woodlark Basin, Papua New Guinea

    Directory of Open Access Journals (Sweden)

    Boyd TD

    2001-09-01

    Full Text Available Deposits of Fe-Si-Mn oxyhydroxides are commonly found on the seafloor on seamounts and mid-ocean spreading centers. At Franklin Seamount located near the western extremity of Woodlark Basin, Papua New Guinea, Fe-Si-Mn oxyhydroxides are being precipitated as chimneys and mounds upon a substrate of mafic lava. Previous studies have shown that the vent fluids have a low temperature (20–30°C and are characterized by a total dissolved iron concentration of 0.038 mM kg-1, neutral pH (6.26 and no measurable H2S. The chimneys have a yellowish appearance with mottled red–orange patches when observed in situ from a submersible, but collected samples become redder within a few hours of being removed from the sea. The amorphous iron oxyhydroxides, obtained from active and inactive vents, commonly possess filamentous textures similar in appearance to sheaths and stalks excreted by the iron-oxidizing bacteria Leptothrix and Gallionella; however, formless agglomerates are also common. Textural relationships between apparent bacterial and non-bacterial iron suggest that the filaments are coeval with and/or growing outwards from the agglomerates. The amorphous iron oxyhydroxides are suggested to precipitate hydrothermally as ferrosic hydroxide, a mixed-valence (Fe2+-Fe3+ green–yellow iron hydroxide compound. Consideration of the thermodynamics and kinetics of iron in the vent fluid, suggest that the precipitation is largely pH controlled and that large amounts of amorphous iron oxyhydroxides are capable of being precipitated by a combination of abiotic hydrothermal processes. Some biologically induced precipitation of primary ferric oxyhydroxides (two-XRD-line ferrihydrite may have occurred directly from the fluid, but most of the filamentous iron micro-textures in the samples appear to have a diagenetic origin. They may have formed as a result of the interaction between the iron-oxidizing bacteria and the initially precipitated ferrosic hydroxide that

  11. Room temperature relaxor ferroelectricity and spin glass behavior in Sr{sub 2}FeTiO{sub 6} double perovskite

    Energy Technology Data Exchange (ETDEWEB)

    Neenu Lekshmi, P.; Savitha Pillai, S. [Materials Science and Technology Division, National Institute for Interdisciplinary Science and Technology NIIST, CSIR, Trivandrum 695 019 (India); Suresh, K.G. [Department of Physics, Indian Institute of Technology Bombay, Mumbai 400 076 (India); Santhosh, P.N. [Department of Physics, Indian Institute of Technology Madras, Chennai 600 036 (India); Varma, Manoj Raama, E-mail: manojraamavarma@yahoo.co.uk [Materials Science and Technology Division, National Institute for Interdisciplinary Science and Technology NIIST, CSIR, Trivandrum 695 019 (India)

    2012-05-05

    Highlights: Black-Right-Pointing-Pointer Studied the structure, dielectric and magnetic properties of Sr{sub 2}FeTiO{sub 6} complex double perovskite. Black-Right-Pointing-Pointer The thermal evolution of the lattice parameter and volume shows no structural phase transition. Black-Right-Pointing-Pointer Dielectric data analysis shows a diffuse phase transition characteristics. Black-Right-Pointing-Pointer The diffusion-assisted small-polaron hopping conduction evidences an intermediate-valence state and semiconductor like behaviour. Black-Right-Pointing-Pointer The magnetic characterisation exhibits a non-metallic spin-glass-like state below 16 K. - Abstract: The structure, dielectric and magnetic properties of complex Sr{sub 2}FeTiO{sub 6} double perovskite have been investigated. Reitveld analysis of X-ray powder diffraction pattern reveals that the material is stabilized in a cubic perovskite phase with Pm3{sup Macron }m space group without the B-site cations ordering. The temperature evolution of crystal structural studies indicates the absence of structural changes with temperature. The scanning electron micrograph exhibits heterogeneous grain distribution with average grain size of 1-7.5 {mu}m. The bond valence sum calculations and diffusion-assisted small-polaron hopping conduction mechanism confirm the mixed valence state of Fe/Ti ions. Dielectric spectra show a broad dielectric anomaly coupled with a shift in dielectric maxima towards higher temperature with frequency, exhibiting a typical relaxor ferroelectric behavior. The relaxor behavior has been quantitatively characterized based on the phenomenological parameters (T{sub m}, T{sub B}, {gamma}, {Delta}T{sub relax}). The agreement of dielectric relaxation with non-linear Vogel Fulcher relation indicates that the system is indeed a relaxor exhibiting glassy characteristics. The transport studies show a semiconductor like behavior and a negligible magnetoresistance. Furthermore, the magnetic

  12. Self-assembly, redox activity, and charge transport of functional surface nano-architectures by molecular design

    Science.gov (United States)

    Skomski, Daniel

    Surface-assisted molecular self-assembly is a promising strategy to program the structure and chemical state of atoms and molecules in nano-architectures to achieve a specific function. The experiments described in this thesis demonstrate that the design and programming of basic organic components leads to desired characteristics by self-assembly. The fabrication of uniform single-site metal centers at surfaces, important for high selectivity in next-generation catalysts, was accomplished by coordination to redox non-innocent phenanthroline and tetrazine-based ligands. These examples were the first demonstrating tuning of the metal oxidation state in surface coordination architectures through rational ligand design. The molecular-scale coordination architectures were the first formed from chromium and vanadium, and the first from platinum in a non-porphyrin system. The first mixed valence metal-ligand surface structure was fabricated that attained the same ligand coordination number for all metal sites. A new surface reaction method was demonstrated between an inexpensive sodium chloride reagent and carboxylate ligands. High-temperature, molecular-resolution microscopy and spectroscopy of the ordered metal-organic structures demonstrated thermal stability up to 300 °C, the highest molecular-level thermal stability in organic surface nanostructures yet achieved, making such systems potential candidates for moderate-temperature catalytic reactions. Molecular self-assembly was expanded into organic semiconductor thin films. In a two-component, bi-layered system, hydrogen bonding between carboxylates and carboxylic acid-substituted thiophenes was utilized, yielding the first real-space images of phenyl-thiophene stacking. In a one-component system, multiple donor-acceptor pi-pi contacts between phenyltriazole building blocks accomplished assembly of flat-lying molecules from a surface with molecular-scale precision through more than twenty molecular layers. Sufficient

  13. Respective role of Fe and Mn oxide contents for arsenic sorption in iron and manganese binary oxide: an X-ray absorption spectroscopy investigation.

    Science.gov (United States)

    Zhang, Gaosheng; Liu, Fudong; Liu, Huijuan; Qu, Jiuhui; Liu, Ruiping

    2014-09-02

    In our previous studies, a synthesized Fe-Mn binary oxide was found to be very effective for both As(V) and As(III) removal in aqueous phase, because As(III) could be easily oxidized to As(V). As(III) oxidation and As(V) sorption by the Fe-Mn binary oxide may also play an important role in the natural cycling of As, because of its common occurrence in the environment. In the present study, the respective role of Fe and Mn contents present in the Fe-Mn binary oxide on As(III) removal was investigated via a direct in situ determination of arsenic speciation using X-ray absorption spectroscopy. X-ray absorption near edge structure results indicate that Mn atoms exist in a mixed valence state of +3 and +4 and further confirm that MnOx (1.5 oxidizing As(III) to As(V) through a two-step pathway [reduction of Mn(IV) to Mn(III) and subsequent Mn(III) to Mn(II)] and FeOOH content is dominant for adsorbing the formed As(V). No significant As(III) oxidation by pure FeOOH had been observed during its sorption, when the system was exposed to air. The extended X-ray absorption fine structure results reveal that the As surface complex on both the As(V)- and As(III)-treated sample surfaces is an inner-sphere bidentate binuclear corner-sharing complex with an As-M (M = Fe or Mn) interatomic distance of 3.22-3.24 Å. In addition, the MnOx and FeOOH contents exist only as a mixture, and no solid solution is formed. Because of its high effectiveness, low cost, and environmental friendliness, the Fe-Mn binary oxide would play a beneficial role as both an efficient oxidant of As(III) and a sorbent for As(V) in drinking water treatment and environmental remediation.

  14. Investigation into the effect of Si doping on the performance of Sr(1-y)Ca(y)MnO(3-δ) SOFC cathode materials.

    Science.gov (United States)

    Porras-Vazquez, Jose M; Losilla, Enrique R; Keenan, Philip J; Hancock, Cathryn A; Kemp, Thomas F; Hanna, John V; Slater, Peter R

    2013-04-21

    In this paper we report the successful incorporation of silicon into Sr1-yCayMnO3-δ perovskite materials for potential applications in cathodes for solid oxide fuel cells. The Si substitution onto the B site of a (29)Si enriched Sr1-yCayMn1-xSixO3-δ perovskite system is confirmed by (29)Si MAS NMR measurements at low B0 field. The very large paramagnetic shift (~3000-3500 ppm) and anisotropy (span ~4000 ppm) suggests that the Si(4+) species experiences both Fermi contact and electron-nuclear dipolar contributions to the paramagnetic interaction with the Mn(3+/4+) centres. An improvement in the conductivity is observed for low level Si doping, which can be attributed to two factors. The first of these is attributed to the tetrahedral coordination preference of Si leading to the introduction of oxide ion vacancies, and hence a partial reduction of Mn(4+) to give mixed valence Mn. Secondly, for samples with high Sr levels, the undoped systems adopt a hexagonal perovskite structure containing face sharing of MnO6 octahedra, while Si doping is shown to help to stabilise the more highly conducting cubic perovskite containing corner linked octahedra. The level of Si, x, required to stabilise the cubic Sr1-yCayMn1-xSixO3-δ perovskite in these cases is shown to decrease with increasing Ca content; thus cubic symmetry is achieved at x = 0.05 for the Sr0.5Ca0.5Mn1-xSixO3-δ series; x = 0.075 for Sr0.7Ca0.3Mn1-xSixO3-δ; x = 0.10 for Sr0.8Ca0.2Mn1-xSixO3-δ; and x = 0.15 for SrMn1-xSixO3-δ. Composites with 50% Ce0.9Gd0.1O1.95 were examined on dense Ce0.9Gd0.1O1.95 pellets. For all series an improvement in the area specific resistances (ASR) values is observed for the Si-doped samples. Thus these preliminary results show that silicon can be incorporated into perovskite cathode materials and can have a beneficial effect on the performance.

  15. Organic electronic materials: Recent advances in the dft description of the ground and excited states using tuned range-separated hybrid functionals

    KAUST Repository

    Körzdörfer, Thomas

    2014-11-18

    Density functional theory (DFT) and its time-dependent extension (TD-DFT) are powerful tools enabling the theoretical prediction of the ground- and excited-state properties of organic electronic materials with reasonable accuracy at affordable computational costs. Due to their excellent accuracy-to-numerical-costs ratio, semilocal and global hybrid functionals such as B3LYP have become the workhorse for geometry optimizations and the prediction of vibrational spectra in modern theoretical organic chemistry. Despite the overwhelming success of these out-of-the-box functionals for such applications, the computational treatment of electronic and structural properties that are of particular interest in organic electronic materials sometimes reveals severe and qualitative failures of such functionals. Important examples include the overestimation of conjugation, torsional barriers, and electronic coupling as well as the underestimation of bond-length alternations or excited-state energies in low-band-gap polymers.In this Account, we highlight how these failures can be traced back to the delocalization error inherent to semilocal and global hybrid functionals, which leads to the spurious delocalization of electron densities and an overestimation of conjugation. The delocalization error for systems and functionals of interest can be quantified by allowing for fractional occupation of the highest occupied molecular orbital. It can be minimized by using long-range corrected hybrid functionals and a nonempirical tuning procedure for the range-separation parameter.We then review the benefits and drawbacks of using tuned long-range corrected hybrid functionals for the description of the ground and excited states of π-conjugated systems. In particular, we show that this approach provides for robust and efficient means of characterizing the electronic couplings in organic mixed-valence systems, for the calculation of accurate torsional barriers at the polymer limit, and for the

  16. Local structure of Fe-doped In{sub 2}O{sub 3} films investigated by X-ray absorption fine structure spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    An, Yukai; Wang, Shiqi; Feng, Deqiang; Liu, Jiwen [Key Laboratory of Display Materials and Photoelectric Devices, Ministry of Education, Tianjin (China); Tianjin Key Laboratory for Photoelectric Materials and Devices, Tianjin (China); Tianjin University of Technology, School of Material Science and Engineering, Tianjin (China); Wu, Zhonghua [Chinese Academy of Sciences, Beijing Synchrotron Radiation Facility (BSRF), Institute of High Energy Physics, Beijing (China)

    2014-06-15

    (In{sub 1-x}Fe{sub x}){sub 2}O{sub 3} (x = 0.07, 0.09, 0.16, 0.22, 0.31) films were deposited on Si(100) substrates by RF-magnetron sputtering technique. The influence of Fe doping on the local structure of films was investigated by X-ray absorption spectroscopy (XAS) at Fe K-edge and L-edge. For the (In{sub 1-x}Fe{sub x}){sub 2}O{sub 3} films with x = 0.07, 0.09 and 0.16, Fe ions dissolve into In{sub 2}O{sub 3} and substitute for In{sup 3+} sites with a mixed-valence state (Fe{sup 2+}/Fe{sup 3+}) of Fe ions. However, a secondary phase of Fe metal clusters is formed in the (In{sub 1-x}Fe{sub x}){sub 2}O{sub 3} films with x = 0.22 and 0.31. The qualitative analyses of Fe-K edge extended X-ray absorption fine structure (EXAFS) reveal that the Fe-O bond length shortens and the corresponding Debye-Waller factor (α{sup 2}) increases with the increase of Fe concentration, indicating the relaxation of oxygen environment of Fe ions upon substitution. The anomalously large structural disorder and very short Fe-O distance are also observed in the films with high Fe concentration. Linear combination fittings at Fe L-edge further confirm the coexistence of Fe{sup 2+} and Fe{sup 3+} with a ratio of ∝3:2 (Fe{sup 2+}: Fe{sup 3+}) for the (In{sub 1-x}Fe{sub x}){sub 2}O{sub 3} film with x = 0.16. However, a significant fraction (∝40 at%) of the Fe metal clusters is found in the (In{sub 1-x}Fe{sub x}){sub 2}O{sub 3} film with x = 0.31. (orig.)

  17. Calix[4]arene Based Single-Molecule Magnets

    Energy Technology Data Exchange (ETDEWEB)

    Karotsis, Georgios; Teat, Simon J.; Wernsdorfer, Wolfgang; Piligkos, Stergios; Dalgarno, Scott J.; Brechin, Euan K.

    2009-06-04

    n = 4-8) also suggests they should be excellent candidates as ligands for the isolation of molecular magnets, but to date their use in the isolation of paramagnetic cluster compounds is rather limited. Herein we present the first Mn cluster and the first SMM to be isolated using any methylene bridged calix[n]arene - a ferromagnetically coupled mixed-valence [Mn{sub 2}{sup III}Mn{sub 2}{sup II}] complex housed between either two TBC4s or two C4s.

  18. Comparative study of rare earth hexaborides using high resolution angle-resolved photoemission

    Energy Technology Data Exchange (ETDEWEB)

    Ramankutty, S.V., E-mail: s.v.ramankutty@uva.nl [Van der Waals-Zeeman Institute, Institute of Physics (IoP), University of Amsterdam, Science Park 904, 1098 XH Amsterdam (Netherlands); Jong, N. de; Huang, Y.K.; Zwartsenberg, B. [Van der Waals-Zeeman Institute, Institute of Physics (IoP), University of Amsterdam, Science Park 904, 1098 XH Amsterdam (Netherlands); Massee, F. [Laboratory of Atomic and Solid State Physics, Department of Physics, Cornell University, Ithaca, NY 14853 (United States); Bay, T.V. [Van der Waals-Zeeman Institute, Institute of Physics (IoP), University of Amsterdam, Science Park 904, 1098 XH Amsterdam (Netherlands); Golden, M.S., E-mail: m.s.golden@uva.nl [Van der Waals-Zeeman Institute, Institute of Physics (IoP), University of Amsterdam, Science Park 904, 1098 XH Amsterdam (Netherlands); Frantzeskakis, E., E-mail: e.frantzeskakis@uva.nl [Van der Waals-Zeeman Institute, Institute of Physics (IoP), University of Amsterdam, Science Park 904, 1098 XH Amsterdam (Netherlands)

    2016-04-15

    Highlights: • ARPES electronic structure study of rare-earth (RE) hexaborides SmB{sub 6}, CeB{sub 6} and YbB{sub 6}. • Increasing RE valence Yb[II], Sm[II/III], Ce[III] increases d-band occupancy. • YbB{sub 6} and SmB{sub 6} posses 2D states at E{sub F}, whereas the Fermi surface of CeB{sub 6} is 3D. • ARPES, LEED and STM data prove structural relaxation of the SmB{sub 6}(001) surface. - Abstract: Strong electron correlations in rare earth hexaborides can give rise to a variety of interesting phenomena like ferromagnetism, Kondo hybridization, mixed valence, superconductivity and possibly topological characteristics. The theoretical prediction of topological properties in SmB{sub 6} and YbB{sub 6} has rekindled the scientific interest in the rare earth hexaborides, and high-resolution ARPES has been playing a major role in the debate. The electronic band structure of the hexaborides contains the key to understand the origin of the different phenomena observed, and much can be learned by comparing the experimental data from different rare earth hexaborides. We have performed high-resolution ARPES on the (001) surfaces of YbB{sub 6}, CeB{sub 6} and SmB{sub 6}. On the most basic level, the data show that the differences in the valence of the rare earth element are reflected in the experimental electronic band structure primarily as a rigid shift of the energy position of the metal 5d states with respect to the Fermi level. Although the overall shape of the d-derived Fermi surface contours remains the same, we report differences in the dimensionality of these states between the compounds studied. Moreover, the spectroscopic fingerprint of the 4f states also reveals considerable differences that are related to their coherence and the strength of the d–f hybridization. For the SmB{sub 6} case, we use ARPES in combination with STM imaging and electron diffraction to reveal time dependent changes in the structural symmetry of the highly debated SmB{sub 6

  19. Group 4 Half-Sandwich Tris(trimethylsilylmethyl) Complexes: Thermal Decomposition and Reactivity with N,N-Dimethylamine-Borane.

    Science.gov (United States)

    Greño, Maider; Horno, Estefanía Del; Mena, Miguel; Pérez-Redondo, Adrián; Varela-Izquierdo, Víctor; Yélamos, Carlos

    2017-08-29

    The thermal decomposition of group 4 trimethylsilylmethyl derivatives [M(η(5)-C5Me5)(CH2SiMe3)3] (M = Ti (1), Zr (2), Hf (3)) in solution and their reactivity with N,N-dimethylamine-borane were investigated. Heating of hydrocarbon solutions of compounds 2 and 3 at 130-200 °C results in the elimination of SiMe4 and the clean formation of the singular alkylidene-alkylidyne zirconium and hafnium compounds [{M(η(5)-C5Me5)}3{(μ-CH)3SiMe}(μ3-CSiMe3)] (M = Zr (4), Hf (5)). The reaction of 2 and 3 with NHMe2BH3 (≥1 equiv) at room temperature affords the dialkyl(dimethylamidoborane) complexes [M(η(5)-C5Me5)(CH2SiMe3)2(NMe2BH3)] (M = Zr (6), Hf (7)). Compounds 6 and 7 are unstable in solution and decompose with formation of the alkyl(dimethylamino)borane [B(CH2SiMe3)H(NMe2)] (8), SiMe4, and other minor byproducts, including the tetranuclear zirconium(III) octahydride complex [{Zr(η(5)-C5Me5)}4(μ-H)8] (9) in the decomposition of 6. Addition of NHMe2BH3 to the titanium tris(trimethylsilylmethyl) derivative 1 gives the trinuclear mixed valence Ti(II)/Ti(III) tetrahydride complex [{Ti(η(5)-C5Me5)(μ-H)}3(μ3-H)(μ3-NMe2BH2)] (10) at 45-65 °C. While the complete conversion of 1 under argon atmosphere requires excess NHMe2BH3 (up to 15 equiv), complex 10 is readily prepared with 3 equiv of NHMe2BH3 under a hydrogen atmosphere indicating that the formation of 10 involves hydrogenolysis of 1 in the presence of (NMe2BH2)2. In absence of amine-borane, the reaction of 1 with H2 leads to the tetranuclear titanium(III) octahydride [{Ti(η(5)-C5Me5)}4(μ-H)8] (11), which upon addition of NHMe2BH3 and subsequent heating at 65 °C affords complex 10. The X-ray crystal structures of 2, 4, 5, 10, and 11 were determined.

  20. Mono- and Dinuclear Manganese Carbonyls Supported by 1,8-Disubstituted (L = Py, SMe, SH) Anthracene Ligand Scaffolds.

    Science.gov (United States)

    Manes, Taylor A; Rose, Michael J

    2016-06-06

    Presented herein is a synthetic scheme to generate symmetric and asymmetric ligands based on a 1,8-disubstituted anthracene scaffold. The metal-binding scaffolds were prepared by aryl chloride activation of 1,8-dichloroanthracene using Suzuki-type couplings facilitated by [Pd(dba)2] as a Pd source; the choice of cocatalyst (XPhos or SPhos) yielded symmetrically or asymmetrically substituted scaffolds (respectively): namely, Anth-SMe2 (3), Anth-N2 (4), and Anth-NSMe (6). The ligands exhibit a nonplanar geometry in the solid state (X-ray), owing to steric hindrance between the anthracene scaffold and the coupled aryl units. To determine the flexibility and binding characteristics of the anthracene-based ligands, the symmetric scaffolds were complexed with [Mn(CO)5Br] to afford the mononuclear species [(Anth-SMe2)Mn(CO)3Br] (8) and [(Anth-N2)Mn(CO)3Br] (9), in which the donor moieties chelate the Mn center in a cis fashion. The asymmetric ligand Anth-NSMe (6) binds preferentially through the py moieties, affording the bis-ligated complex [(Anth-NSMe)2Mn(CO)3Br] (10), wherein the thioether-S donors remain unbound. Alternatively, deprotection of the thioether in 6 affords the free thiol ligand Anth-NSH (7), which more readily binds the Mn center. Complexation of 7 ultimately affords the mixed-valence Mn(I)/Mn(II) dimer of formula [(Anth-NS)3Mn2(CO)3] (11), which exhibits a fac-{Mn(CO)3} unit supported by a triad of bridging thiolates, which are in turn ligated to a supporting Mn(II) center (EPR: |D| = 0.053 cm(-1), E/|D| = 0.3, Aiso = -150 MHz). All of the metal complexes have been characterized by single-crystal X-ray diffraction, IR spectroscopy and NMR/EPR measurements-all of which demonstrate that the meta-linked, anthracene-based ligand scaffold is a viable approach for the coordination of metal carbonyls.

  1. Single crystalline monoclinic La0.7Sr0.3MnO3 nanowires with high temperature ferromagnetism

    Energy Technology Data Exchange (ETDEWEB)

    Carretero-Genevrier, Adrian [ICMAB, Barcelona, Spain; Gazquez Alabart, Jaume [ORNL; Idrobo Tapia, Juan C [ORNL; Oro, Judith [ICMAB, Barcelona, Spain; Arbiol, Jordi [ICMAB, Barcelona, Spain; Varela del Arco, Maria [ORNL; Ferain, Etienne [Universite catholique de Louvain, Belgium (UCL); Rodriguez-Carvajal, Juan [Institut Laue-Langevin (ILL); Puig, Teresa [ICMAB, Barcelona, Spain; Mestres, Narcis [ICMAB, Barcelona, Spain; Obradors, Xavier [ICMAB, Barcelona, Spain

    2011-01-01

    Porous mixed-valent manganese oxides are a group of multifunctional materials that can be used as molecular sieves, catalysts, battery materials, and gas sensors. However, material properties and thus activity can vary significantly with different synthesis methods or process conditions, such as temperature and time. Here, we report on a new synthesis route for MnO{sub 2} and LaSr-doped molecular sieve single crystalline nanowires based on a solution chemistry methodology combined with the use of nanoporous polymer templates supported on top of single crystalline substrates. Because of the confined nucleation in high aspect ratio nanopores and of the high temperatures attained, new structures with novel physical properties have been produced. During the calcination process, the nucleation and crystallization of {var_epsilon}-MnO{sub 2} nanoparticles with a new hexagonal structure is promoted. These nanoparticles generated up to 30 {mu}m long and flexible hexagonal nanowires at mild growth temperatures (T{sub g} = 700 C) as a consequence of the large crystallographic anisotropy of {var_epsilon}-MnO{sub 2}. The nanocrystallites of MnO{sub 2} formed at low temperatures serve as seeds for the growth of La{sub 0.7}Sr{sub 0.3}MnO{sub 3} nanowires at growth temperatures above 800 C, through the diffusion of La and Sr into the empty 1D-channels of {var_epsilon}-MnO{sub 2}. Our particular growth method has allowed the synthesis of single crystalline molecular sieve (LaSr-2 x 4) monoclinic nanowires with composition La{sub 0.7}Sr{sub 0.3}MnO{sub 3} and with ordered arrangement of La{sup 3+} and Sr{sup 2+} cations inside the 1D-channels. These nanowires exhibit ferromagnetic ordering with strongly enhanced Curie temperature (T{sub c} > 500 K) that probably results from the new crystallographic order and from the mixed valence of manganese.

  2. Water-soluble, recombinant CuA-domain of the cytochrome ba3 subunit II from Thermus thermophilus.

    Science.gov (United States)

    Slutter, C E; Sanders, D; Wittung, P; Malmström, B G; Aasa, R; Richards, J H; Gray, H B; Fee, J A

    1996-03-19

    Recently, the genes of cytochrome ba3 from thermus thermophilus [Keightley, J.A., et al. (1995) J. Biol. Chem. 270, 20345-20358], a homolog of the heme-copper oxidase family, have been cloned. We report here expression of a truncated gene, encoding the copper A (CuA) domain of cytochrome ba3, that is regulated by a T7 RNA polymerase promoter in Escherichia coli. The CuA-containing domain is purified in high yields as a water-soluble, thermostable, purple-colored protein. Copper analysis by chemical assay, mass spectrometry, X-ray fluorescence, and EPR spin quantification show that this protein contains two copper ions bound in a mixed-valence state, indicating that the CuA site in cytochrome ba3, is a binuclear center. The absorption spectrum of the CuA site, free of the heme interference in cytochrome ba3, is similar to the spectra of other soluble fragments from the aa3-type oxidase of Parachccus denitrificans [Lappalainen, P., et al. (1993) J. Biol Chem. 268, 26416-26421] and the caa3-type oxidase of Bacillus subtilis [von Wachenfeldt, C. et al. (1994) FEBS Lett. 340, 109-113]. There are intense bands at 480 nm (3100 M(-1) cm(-1)) and 530 nm (3200 M(-1) cm(-1)), a band in the near -IR centered at 790 nm (1900 M(-1) cn(-1)), and a weaker band at 363 nm (1300M(-1) cm(-1)). The visible CD spectrum shows a positive-going band at 460 nm and a negative-going band at 527 nm, the opposite signs of which may result from the binuclear nature of the site. The secondary structure prediction from the far-UV CD spectrum indicates that this domain is predominantly beta-sheet, in agreement with the recent X-ray structure reported for the complete P. denitrificans cytochrome aa3 molecule [Iwata, S., et al. (1995) Nature 376, 660-669] and the engineered, purple CyoA protein [Wilmanns, M., et al. (1996) Proc. Natl Acad. Sci. U.S.A. 92, 11955-11959]. However, the thermostability of the fragment described here (Tm approximately 80 degrees C) and the stable binding of copper over a

  3. Resistivity, Specific Heat, and Susceptibility of the Intermediate Valence System Cerium ((RHODIUM(X)PALLADIUM(1 -X))(3))

    Science.gov (United States)

    Scoboria, Clarence Preston, III

    In the mixed valent system Ce(Rh(,x)Pd(,1-x))(,3), the dependence of resistivity, magnetic susceptibility, and specific heat on the rhodium concentration x has been experimentally studied. Ce(Rh(,x)Pd(,1-x))(,3) is tetravalent from x = .216 to 1.00, and mixed valent from x = .216 to x = 0. Based on Vegard's rule and lattice constant data, n(,f) is considered to vary linearly with x, ranging from n(,f) = 0 at x = .216 to n(,f) (TURNEQ) .55 at x = 0. The resistivity was measured from 1.5K to 300K for x from 0 to 1. In the tetravalent range the temperature dependence was independent of x. In the mixed valent region (rho) at all temperatures increased rapidly with n(,f). (rho) (T = 0) was found to be proportional to n(,f)('2) in the mixed valent range. Application of pressures up to seven kilobars were found to produce very little change in resistivity in the mixed valent range. The specific heat was measured from 2K to 15K in the mixed valent range and for CeRh(,3). C/T versus T('2) plots were well-fitted by a straight line at low temperature except for a bump at 6K, which is not understood. The mixed valence component of the electronic specific heat coefficient (gamma) is found to be proportional to n(,f)('2). Magnetic susceptibility was measured from 2K to 300K in the mixed valent range. For each x, (chi) (T) was approximately independent of temperature below (TURN) 150K, except for an impurity tail below 40K. (chi)(,0) (the plateau value) was found to be approximately proportional to n(,f) in the mixed valent range. All three quantities (rho), (gamma), and (chi) are compared to the theories of Yosida and Sakurai, and Newns and Hewson. The best fits indicate that the f level density of states is well represented by a lorentzian which can accommodate six electrons.

  4. Magnetic susceptibility as a proxy for the hydrobiogeochemical cycling of iron within the water table fluctuation zone at hydrocarbon contaminated sites

    Science.gov (United States)

    Atekwana, E. A.; Enright, A.; Atekwana, E. A.; Beaver, C. L.; Rossbach, S.; Slater, L. D.; Ntarlagiannis, D.

    2016-12-01

    Sharp redox gradients are indicative of enhanced biogeochemical activity and occur at or near the water table. Hydrologic forcing drives changes in redox state and oxygen levels, enhancing the elemental cycling of metals, and coupling different biogeochemical cycles. These coupled hydrobiogeochemical cycles are often difficult to study in the field using geochemical and microbial proxies because of direct sampling limitations, the costs associated with these techniques, and because the dynamic nature of these processes complicates the interpretation of single time point measurements, which may not give accurate representations of prevailing conditions. Geophysical techniques can provide both the spatial and temporal resolution needed to elucidate these processes. Here we investigated the use of magnetic susceptibility (c) as a viable proxy for understanding the biogeochemical cycling of iron at several hydrocarbon contaminated sites where active intrinsic bioremediation is occurring. We performed borehole c logging using a Bartington c probe in the field as well as made c measurements on core samples retrieved from the field sites. Our results show the following: (1) in both sulfate-rich and sulfate-poor aquifers, excursions in c are coincident with zones of free product contamination and are limited to the water table fluctuation (smear) zone; (2) c values within the free product plume and contamination source zones are higher compared to values within the dissolved product plume; (3) high c coincides with zones of elevated Fe (II) and Fe (III) concentrations extracted from aquifer solids; and (4) the mixed valence magnetite and greigite were the dominant magnetic minerals. The c excursions are limited to the water table fluctuation zones because fluctuating water level conditions are hot beds for microbial activity due to the steep hydrocarbon and nutrients and consequently redox gradients. High water levels during periods of recharge favor anaerobic conditions

  5. High Magnetic Susceptibility in a Highly Saline Sulfate-Rich Aquifer Undergoing Biodegradation of Hydrocarbon Results from Sulfate Reduction.

    Science.gov (United States)

    Atekwana, E. A.; Enright, A.; Ntarlagiannis, D.; Slater, L. D.; Bernier, R.; Beaver, C. L.; Rossbach, S.

    2016-12-01

    We investigated the chemical and stable carbon isotope composition of groundwater in a highly saline aquifer contaminated with hydrocarbon. Our aim to evaluate hydrocarbon degradation and to constrain the geochemical conditions that generated high anomalous magnetic susceptibility (MS) signatures observed at the water table interface. The occurrence of high MS in the water table fluctuating zone has been attributed to microbial iron reduction, suggesting the use of MS as a proxy for iron cycling. The highly saline aquifer had total dissolved solids concentrations of 3.7 to 29.3 g/L and sulfate concentrations of 787 to 37,100 mg/L. We compared our results for groundwater locations with high hydrocarbon contamination (total petroleum hydrocarbon (TPH) >10 mg/L), at lightly contaminated (TPH contaminations. Our results for the terminal electron acceptors (TEAs) dissolved oxygen (DO), nitrate (NO3-), dissolved iron (Fe2+) , dissolved manganese (Mn2+), sulfate (SO42-) and methane (CH4) suggest a chemically heterogeneous aquifer, probably controlled by heterogeneous distribution of TEAs and contamination (type of hydrocarbon, phase and age of contamination). The concentrations of dissolved inorganic carbon (DIC) ranged from 67 to 648 mg C/L and the stable carbon isotope (δ13CDIC) ranged from -30.0‰ to 1.0 ‰ and DIC-δ13CDIC modeling indicates that the carbon in the DIC is derived primarily from hydrocarbon degradation. The concentrations of Fe2+ in the aquifer ranged from 0.1 to 55.8 mg/L, but was mostly low, averaging 2.7+10.9 mg/L. Given the low Fe2+ [AE1] in the aqueous phase and the high MS at contaminated locations, we suggest that the high MS observed does not arise from iron reduction but rather from sulfate reduction. Sulfate reduction produces H2S which reacts with Fe2+ to produce ferrous sulfide (Fe2+S) or the mixed valence greigite (Fe2+Fe3+2S4). We conclude that in highly saline aquifers with high concentrations of sulfate and contaminated with

  6. Progress of Multi Functional Properties of Organic-Inorganic Hybrid System, A[FeIIFeIIIX3] (A = (n-CnH2n+14N, Spiropyran; X = C2O2S2, C2OS3, C2O3S

    Directory of Open Access Journals (Sweden)

    Norimichi Kojima

    2010-05-01

    Full Text Available In the case of mixed-valence systems whose spin states are situated in the spin crossover region, new types of conjugated phenomena coupled with spin and charge are expected. From this viewpoint, we have investigated the multifunctional properties coupled with spin, charge and photon for the organic-inorganic hybrid system, A[FeIIFeIIIX3](A = (n-CnH2n+14N, spiropyran; X = dto(C2O2S2, tto(C2OS3, mto(C2O3S. A[FeIIFeIII(dto3] and A[FeIIFeIII(tto3] undergo the ferromagnetic phase transitions, while A[FeIIFeIII(mto3] undergoes a ferrimagnetic transition. In (n-CnH2n+14N [FeIIFeIII(dto3](n = 3,4, a new type of phase transition called charge transfer phase transition (CTPT takes place around 120 K, where the thermally induced charge transfer between FeII and FeIII occurs reversibly. At the CTPT, the iron valence state dynamically fluctuated with a frequency of about 0.1 MHz, which was confirmed by means of muon spin relaxation. The charge transfer phase transition and the ferromagnetic transition for (n-CnH2n+14N[FeIIFeIII(dto3] remarkably depend on the size of intercalated cation. In the case of (SP[FeIIFeIII(dto3](SP = spiropyran, the photoinduced isomerization of SP under UV irradiation induces the charge transfer phase transition in the [FeIIFeIII(dto3] layer and the remarkable change of the ferromagnetic transition temperature. In the case of (n-CnH2n+14N[FeIIFeIII(mto3](mto = C2O3S, a rapid spin equilibrium between the high-spin state (S = 5/2 and the low-spin state (S = 1/2 at the FeIIIO3S3 site takes place in a wide temperature range, which induces the valence fluctuation of the FeS3O3 and FeO6 sites through the ferromagnetic coupling between the low spin state (S = 1/2 of the FeIIIS3O3 site and the high spin state (S = 2 of the FeIIO6 site.

  7. Redox-active organometallics: magnetic and electronic couplings through carbon-silicon hybrid molecular connectors.

    Science.gov (United States)

    Hamon, Paul; Justaud, Frederic; Cador, Olivier; Hapiot, Philippe; Rigaut, Stéphane; Toupet, Loïc; Ouahab, Lahcène; Stueger, Harald; Hamon, Jean-René; Lapinte, Claude

    2008-12-24

    Treatment of the triflate complex Cp*(dppe)FeOTf [12; Cp* = eta(5)-C(5)(CH(3))(5), dppe = 1,2-bis(diphenylphosphino)ethane, OTf = CF(3)SO(3)] with an excess of HC[triple bond]C-(Si(CH(3))(2))(x)-C[triple bond]CH (x = 2-4) in diethyl ether provides the binuclear bis(vinylidene) derivatives [Cp*(dppe)Fe=C=CH(Si(CH(3))(2))(x)CH=C=Fe(dppe)Cp*][OTf](2) (x = 2, 13; x = 3, 14; x = 4, 15), which were isolated as ochre solids and rapidly characterized by FT-IR, (1)H, (31)P, and (13)C NMR spectroscopies. The complexes 13-15 were reacted with potassium tert-butoxide to afford the bis(alkynediyl) complexes [Cp*(dppe)Fe-C[triple bond]C(Si(CH(3))(2))(x)C[triple bond]C-Fe(dppe)Cp*] (x = 2, 1; x = 3, 2; x = 4, 3), which were isolated as orange powders in yields ranging from 76 to 91%. The IR, cyclic voltammetry, and UV-vis data obtained for 1-3 and the X-ray crystal structures determined for 1 and 3 reveal the importance of the sigma-pi conjugation (hyperconjugation) between the Si-Si sigma bond and the adjacent C[triple bond]C pi-symmetric orbitals in the description of the electronic structure of the ground state of these complexes. When reacted at low temperature with 2 equiv of [(C(5)H(5))(2)Fe]X or AgX [X = BPh(4), B(3,5-(CF(3))(2)C(6)H(3))(4))], compounds 1-3 provide 1[X](2), 2[X](2), and 3[X](2), which can be isolated and stored below -20 degrees C. EPR spectroscopy and magnetization measurements established that the superexchange interaction propagates through the Si-Si bonds (J = -0.97(2) cm(-1) for 3[X](2)). UV-vis-near-IR spectra were obtained with an optically transparent thin-layer electrosynthetic (OTTLE) cell for 1-3[OTf](n) (n = 0-2). A band with a maximum that increases from 6400 cm(-1) (1[OTf]) to 8500 cm(-1) (3[OTf]) observed for the mixed-valence species was ascribed to intervalence charge transfer evidencing photodriven electron transfer through the carbon-silicon hybrid connectors with H(ab) parameters ranging from 64 to 285 cm(-1).

  8. Functional Metal Oxide Nanostructures: Their Synthesis, Characterization, and Energy Applications

    Science.gov (United States)

    Iyer, Aparna

    This research focuses on studying metal oxides (MnO 2, Co3O4, MgO, Y2O3) for various applications including water oxidation and photocatalytic oxidation, developing different synthesis methodologies, and presenting detailed characterization studies of these metal oxides. This research consists of three major parts. The first part is studying novel applications and developing a synthesis method for manganese oxide nanomaterials. Manganese oxide materials were studied for renewable energy applications by using them as catalysts for water oxidation reactions. In this study, various crystallographic forms of manganese oxides (amorphous, 2D layered, 1D 2 x 2 tunnel structures) were evaluated for water oxidation catalysis. Amorphous manganese oxides (AMO) were found to be catalytically active for chemical and photochemical water oxidation compared to cryptomelane type tunnel manganese oxides (2 x 2 tunnels; OMS2) or layered birnessite (OL-1) materials. Detailed characterization was done to establish a correlation between the properties of the manganese oxide materials and their catalytic activities in water oxidation. The gas phase photocatalytic oxidation of 2-propanol under visible light was studied using manganese oxide 2 x 2 tunnel structures (OMS-2) as catalysts (Chapter 3). The reaction is 100% selective to acetone. As suggested by the photocatalytic and characterization data, important factors for the design of active OMS-2 photocatalysts are synthesis methodology, morphology, mixed valency and the release of oxygen from the OMS-2 structure. Manganese oxide octahedral molecular sieves (2 x 2 tunnels; OMS-2) with self-assembled dense or hollow sphere morphologies were fabricated via a room temperature ultrasonic atomization assisted synthesis (Chapter 4). The properties and catalytic activities of these newly developed materials were compared with that of OMS-2 synthesized by conventional reflux route. These materials exhibit exceptionally high catalytic activities

  9. The electronic structure and magnetic interactions in the mixed transition-metal oxide La(Co,Ni)O{sub 3} studied by X-ray absorption spectroscopies

    Energy Technology Data Exchange (ETDEWEB)

    Huang, Meng-Jie

    2016-11-11

    Transition-metal oxides have attracted a lot of attention because they exhibit a variety of intriguing physical properties. Among the transition-metal oxides, LaCoO{sub 3} is a very special compound which shows different spin states and spin-state transitions. Further, the physical properties can be controlled by changing temperature, replacement of rare-earth element, electron- or hole-doping, or by applying strain. The ground state of LaCoO{sub 3} is a non-magnetic insulator because the lowest energy configuration is t{sub 2g}{sup 6}e{sub g}{sup 0} (S = 0). However, the partial substitution of Co by Ni in La(Co,Ni)O{sub 3} (LCNO) will induce a ferromagnetic behavior. A number of models have been proposed for explaining the nature of the magnetic behavior in the past decades, but it is still a puzzle. In order to understand the origin of the ferromagnetism in La(Co,Ni)O{sub 3}, I have studied the electronic structure and magnetic interaction in this compound in a very direct way: by using X-ray absorption (XAS) and X-ray magnetic circular dichroism (XMCD) along with multiplet simulations. Samples were synthesized by the sol-gel method and structurally and magnetically characterized by XRD and SQUID. XAS clearly indicates a mixed-valence state for both Co and Ni, with both valences increasing monotonously with Ni content, x. While the gradual spin-state transition of Co{sup 3+} from low-spin (LS) to high-spin (HS) is preserved for low x it is suppressed in the high Ni-content samples. Regarding the spin configuration of Ni we find it stabilized in a ''mixed'' spin state, unlike the purely LS state of Ni in LaNiO{sub 3}. XMCD identifies the element-specific contributions to the magnetic moment and interactions. In particular, we find that it must be the coexistence of the HS state in both Co{sup 3+} and Ni{sup 3+} that induces t{sub 2g}-based ferromagnetic interaction via a ''double-exchange-like'' mechanism. Other species

  10. Study of the electron transfer in analog compounds of the Prussia blue; Estudio de transferencia electronica en compuestos analogos del azul de Prusia

    Energy Technology Data Exchange (ETDEWEB)

    Romero V, S.; Damaso C, L.F. [ESFM-IPN, 07738 Mexico D.F. (Mexico); Reguera R, E.; Yee M, H.T. [CICATA-IPN, 11500 Mexico D.F. (Mexico)

    2006-07-01

    As answer to the necessity of the search of new nano structured materials, the present work was carried out that it studies the electron transfer in compound similar of the Prussia blue (CAAP), which are representative molecular materials, because its chromophore, magnetic, and electric properties, depend mainly on the processes that are made in their levels or orbital energy. It is known that these made up with octahedra symmetry that its are presented in form of powders, suffer processes of electron transfer when its are exposed to external stimulation by means of light (embracing the regions from the ultraviolet one until the infrared in the electromagnetic spectrum), because they are made up of mixed valency. To know that types of electronic transfers are those that are made in the study materials, 4 series of CAAP its were synthesized by the method of mixtures of aqueous solutions: M[Fe{sup +3}CN){sub 6}]{sub 2}nH{sub 2}O, M[Cr{sup +3}(CN){sub 6}]{sub 2}nH{sub 2}O, M[Mn{sup +3}(CN){sub 6}]{sub 3}nH{sub 2}O y M[Co{sup +3}(CN){sub 6}]{sub 3}nH{sub 2}O, and later on studied by means of the electron spectroscopy technique with a UV-SENSE spectrophotometer (Perkin-Elmer) in or n range of work of 250 to 1100 nm. Because to discuss the electronic structures of any compound, it is required the calculation of the energy levels, they took like reference the data tabulated by John Alexander and Harry Gray calculated by the modified theoretical approach of Wolfsberg-Helmhoz. When comparing the obtained spectra with the theoretical data, it was concludes that in the CAAP, its are carried out electronic transfers among orbital molecular metallic of the type d {yields} d, and load transfer (TC) among orbital molecular of the ligand and metal. When being carried out a load transfer in the CAAP that initially are made up of under-spin these its are photoinduced to an excited state of high spin. In consequence it is possible to vary the interactions among the metals of

  11. Uranium and thorium based phosphate matrix: synthesis, characterizations and lixiviation; Matrices a base de phosphate d'uranium et de thorium: syntheses, caracterisations et lixiviation

    Energy Technology Data Exchange (ETDEWEB)

    Dacheux, N

    1995-03-01

    In the framework of the search for a ceramic material usable in the radioactive waste storage, uranium and thorium phosphates have been investigated. Their experimental synthesis conditions have been entirely reviewed, they lead to the preparation of four new compounds: U(UO{sub 2})(PO{sub 4}){sub 2}, U{sub 2}O(PO{sub 4}){sub 2}, UCIPO{sub 4}, 4H{sub 2}O, and Th{sub 4}(PO{sub 4}){sub 4}P{sub 2}O{sub 7}. Experimental evidenced are advanced for non existent compounds such as: U{sub 3}(PO{sub 4}){sub 4}, U{sub 2}O{sub 3}P{sub 2}O{sub 7} and Th{sub 3} (PO{sub 4}){sub 4}. Characterization by several techniques (X-rays and neutron powder diffractions, UV-Visible and Infra-red spectroscopies, XPS,...) were performed. The ab initio structure determination of U(UO{sub 2})(PO{sub 4}){sub 2} has been achieved by X-rays and refined by neutron diffractions. Through its physico-chemical analysis, we found that this compound was a new mixed valence uranium phosphate in which U{sup 4+} and UO{sub 2}{sup 2+} ions are ordered in pairs along parallel chains according to a new type of arrangement. Reaction mechanism, starting from UCIPO{sub 4}, 4H{sub 2}O and based on redox processes of uranium in solid state was set up. From two main matrices U(UO{sub 2})(PO{sub 4}){sub 2} and Th{sub 4}(PO{sub 4}){sub 4}P{sub 2}O{sub 7}, solid solutions were studied. They consist of replacement of U(IV) by Th(IV) and reversely. The leaching tests on pure, loaded and doped matrices were performed in terms of storage time, pH of solutions, and determined by the use of solids labelled with {sup 230}U or by the measurement of uranyl concentration by Laser-Induced Time-Resolved Spectro-fluorimetry. Average concentration of uranium in the liquid phase is around 10{sup -4} M to 10{sup -6} M. Taking into account the very low solubilities of the studied phosphate ceramics, we estimated their chemical performances promising as an answer to the important nuclear waste problem, if we compare them to the glasses

  12. 钒电解液的制备及其电化学和热力学分析%Preparation,Thermodynamic and Electrochemical Properties of Vanadium Solution

    Institute of Scientific and Technical Information of China (English)

    吴雄伟; 李厦; 黄可龙; 丁正平; 姜志成; 刘素琴; 李晓刚

    2011-01-01

    The vanadium solution was prepared by heating the mixture of vanadium trioxide and vanadium pentoxide in sulfuric acid solution,which utilized the autocatalytic effect of vanadium with mixed valence,to intensify the dissolving of the mixture of vanadium trioxide and vanadium pentoxide.The formations of vanadium ions were theoretically determined.Moreover,negative ΔrGm and ΔrHm of the reactions were calculated by thermomechanical analysis.The reactions was proved to be a spontaneous process(ΔrGm0).The results were confirmed by the UV-Vis analysis for the formation of ions.Its electrochemical performance was characterized by cyclic voltammetry and charge-discharge.The results showed that the prepared vanadium solution had an excellent electrochemical behavior,which indicated that the method was suitable for the industrial application.Our work may serve as the theoretical basis for industrial production of the electrolyte of vanadium redox-flow batteries.%以冶金级V2O3和V2O5为原料,采用混合加热和自催化强化溶解相结合的方法制备钒电解液.通过热力学分析,从理论上计算并确定了V2O5和V2O3溶解过程中在硫酸溶液中的离子存在形式,从而计算了钒电解液VOSO4过程的吉布斯自由能变化?rGm,以及相应的反应生成焓?rHm.结果表明:反应为放热反应,且为自发过程(?rGm〈0).同时通过UV-Vis光谱对所制备的电解液存在形式进行表征,证实了理论分析的正确性;使用循环伏安和充放电对其电化学性能予以分析,所得钒电解液具有很好的电化学性能.

  13. Crystal growth and first crystallographic characterization of mixed uranium(IV)-plutonium(III) oxalates.

    Science.gov (United States)

    Tamain, Christelle; Arab Chapelet, Bénédicte; Rivenet, Murielle; Abraham, Francis; Caraballo, Richard; Grandjean, Stéphane

    2013-05-06

    The mixed-actinide uranium(IV)-plutonium(III) oxalate single crystals (NH4)0.5[Pu(III)0.5U(IV)0.5(C2O4)2·H2O]·nH2O (1) and (NH4)2.7Pu(III)0.7U(IV)1.3(C2O4)5·nH2O (2) have been prepared by the diffusion of different ions through membranes separating compartments of a triple cell. UV-vis, Raman, and thermal ionization mass spectrometry analyses demonstrate the presence of both uranium and plutonium metal cations with conservation of the initial oxidation state, U(IV) and Pu(III), and the formation of mixed-valence, mixed-actinide oxalate compounds. The structure of 1 and an average structure of 2 were determined by single-crystal X-ray diffraction and were solved by direct methods and Fourier difference techniques. Compounds 1 and 2 are the first mixed uranium(IV)-plutonium(III) compounds to be structurally characterized by single-crystal X-ray diffraction. The structure of 1, space group P4/n, a = 8.8558(3) Å, b = 7.8963(2) Å, Z = 2, consists of layers formed by four-membered rings of the two actinide metals occupying the same crystallographic site connected through oxalate ions. The actinide atoms are nine-coordinated by oxygen atoms from four bidentate oxalate ligands and one water molecule, which alternates up and down the layer. The single-charged cations and nonbonded water molecules are disordered in the same crystallographic site. For compound 2, an average structure has been determined in space group P6/mmm with a = 11.158(2) Å and c = 6.400(1) Å. The honeycomb-like framework [Pu(III)0.7U(IV)1.3(C2O4)5](2.7-) results from a three-dimensional arrangement of mixed (U0.65Pu0.35)O10 polyhedra connected by five bis-bidentate μ(2)-oxalate ions in a trigonal-bipyramidal configuration.

  14. Intervalence charge transfer luminescence: The anomalous luminescence of cerium-doped Cs{sub 2}LiLuCl{sub 6} elpasolite

    Energy Technology Data Exchange (ETDEWEB)

    Seijo, Luis [Departamento de Química, Universidad Autónoma de Madrid, 28049 Madrid (Spain); Instituto Universitario de Ciencia de Materiales Nicolás Cabrera, Universidad Autónoma de Madrid, 28049 Madrid (Spain); Barandiarán, Zoila [Instituto Universitario de Ciencia de Materiales Nicolás Cabrera, Universidad Autónoma de Madrid, 28049 Madrid (Spain)

    2014-12-07

    The existence of intervalence charge transfer (IVCT) luminescence is reported. It is shown that the so called anomalous luminescence of Ce-doped elpasolite Cs{sub 2}LiLuCl{sub 6}, which is characterized mainly by a very large Stokes shift and a very large band width, corresponds to an IVCT emission that takes place in Ce{sup 3+}–Ce{sup 4+} pairs, from the 5de{sub g} orbital of Ce{sup 3+} to 4f orbitals of Ce{sup 4+}. Its Stokes shift is the sum of the large reorganization energies of the Ce{sup 4+} and Ce{sup 3+} centers formed after the fixed-nuclei electron transfer and it is equal to the energy of the IVCT absorption commonly found in mixed-valence compounds, which is predicted to exist in this material and to be slightly larger than 10 000 cm{sup −1}. The large band width is the consequence of the large offset between the minima of the Ce{sup 3+}–Ce{sup 4+} and Ce{sup 4+}–Ce{sup 3+} pairs along the electron transfer reaction coordinate. This offset is approximately 2√(3) times the difference of Ce–Cl equilibrium distances in the Ce{sup 3+} and Ce{sup 4+} centers. It is shown that the energies of the peaks and the widths of IVCT absorption and emission bands can be calculated ab initio with reasonable accuracy from diabatic energy surfaces of the ground and excited states and that these can be obtained, in turn, from independent calculations on the donor and acceptor active centers. We obtained the energies of the Ce{sup 3+} and Ce{sup 4+} active centers of Ce-doped Cs{sub 2}LiLuCl{sub 6} by means of state-of-the-art wave-function-theory spin-orbit coupling relativistic calculations on the donor cluster (CeCl{sub 6}Li{sub 6}Cs{sub 8}){sup 11+} and the acceptor cluster (CeCl{sub 6}Li{sub 6}Cs{sub 8}){sup 12+} embedded in a quantum mechanical embedding potential of the host. The calculations provide interpretations of unexplained experimental observations as due to higher energy IVCT absorptions, and allow to reinterpret others. The existence of

  15. Phenomena and significance of intermediate spillover in electrocatalysis of oxygen and hydrogen electrode reactions

    Directory of Open Access Journals (Sweden)

    Jakšić Jelena M.

    2012-01-01

    Full Text Available Altervalent hypo-d-oxides of transition metal series impose spontaneous dissociative adsorption of water molecules and pronounced membrane spillover transferring properties instantaneously resulting with corresponding bronze type (Pt/HxWO3 under cathodic, and/or its hydrated state (Pt/W(OH6 responsible for the primary oxide (Pt-OH effusion, under anodic polarization, this way establishing instantaneous reversibly revertible alterpolar bronze features (Pt/H0.35WO3 Pt/W(OH6, and substantially advanced electrocatalytic properties of these composite interactive electrocatalysts. As the consequence, the new striking and unpredictable prospects both in law and medium temperature proton exchange membrane fuell cell (L&MT PEMFC and water electrolysis (WE have been opened by the interactive supported individual (Pt, Pd, Ni or prevailing hyper-d-electronic nanostructured intermetallic phase clusters (WPt3, NbPt3, HfPd3, ZrNi3, grafted upon and within high altervalent capacity hypo-d-oxides (WO3, Nb2O5, Ta2O5, TiO2 and their proper mixed valence compounds, to create a novel type of alterpolar interchangeable composite electrocatalysts for hydrogen and oxygen electrode reactions. Whereas in aqueous media Pt (Pt/C features either chemisorbed catalytic surface properties of H-adatoms (Pt-H, or surface oxide (Pt=O, missing any effusion of other interacting species, new generation and selection of composite and interactive strong metal-support interaction (SMSI electrocatalysts in condensed wet state primarily characterizes interchangeable extremely fast reversible spillover of either H-adatoms, or the primary oxides (Pt-OH, Au-OH, or the invertible bronze type behavior of these significant interactive electrocatalytic ingredients. Such nanostructured type electrocatalysts, even of mixed hypo-d-oxide structure (Pt/H0.35WO3/TiO2/C, Pt/HxNbO3/TiO2/C, have for the first time been synthesized by the sol-gel methods and shown rather high stability, electron

  16. Interfacial functionalization and engineering of nanoparticles

    Science.gov (United States)

    Song, Yang

    nanoparticles in the formation of functional nanocomposites. Part of the dissertation research was also devoted to graphene quantum dots (GQDs)-supported platinum (Pt/G) nanoparticles and their electrocatalytic activity in oxygen reduction reaction. These Pt/G nanocomposites were prepared by a hydrothermal procedure at controlled temperatures. Spectroscopic measurements based on FTIR, Raman and XPS confirmed the formation of various oxygenated structural defects on GQDs and the variation of their concentrations with the hydrothermal conditions. Interestingly, electrocatalytic activity of GQD/Pt composites exhibited a volcano-shaped variation with the GQD structural defects, with the best identified as the samples prepared at 160 °C for 6 h where the mass activity was found to meet the DOE target for 2015. This remarkable performance was accounted for by the deliberate manipulation of the adsorption of oxygen and reaction intermediates on platinum by the GQD structural defects through partial charge transfer. The strategy presented herein may offer a new paradigm in the design and engineering of nanoparticle catalysts for fuel cell electrochemistry. In addition, studies were also carried out to study intervalence charge transfer between ferrocenyl moieties bonded on carbon nanoparticle surfaces by diazonium reaction. Electrochemical studies exhibited two pairs of voltammetric waves with a difference of their formal potentials at about 78 mV, suggesting nanoparticle-mediated intraparticle charge delocalization at mixed valence as a result of the strong core-ligand covalent bonds and the conductive sp 2 carbon matrix of the graphitic cores. Consistent behaviors were observed in near-infrared measurements, indicating that the particles behaved analogously to a Class I/II mixed-valence compound.

  17. Social Annotation Valence: The Impact on Online Informed Consent Beliefs and Behavior.

    Science.gov (United States)

    Balestra, Martina; Shaer, Orit; Okerlund, Johanna; Westendorf, Lauren; Ball, Madeleine; Nov, Oded

    2016-07-20

    Social media, mobile and wearable technology, and connected devices have significantly expanded the opportunities for conducting biomedical research online. Electronic consent to collecting such data, however, poses new challenges when contrasted to traditional consent processes. It reduces the participant-researcher dialogue but provides an opportunity for the consent deliberation process to move from solitary to social settings. In this research, we propose that social annotations, embedded in the consent form, can help prospective participants deliberate on the research and the organization behind it in ways that traditional consent forms cannot. Furthermore, we examine the role of the comments' valence on prospective participants' beliefs and behavior. This study focuses specifically on the influence of annotations' valence on participants' perceptions and behaviors surrounding online consent for biomedical research. We hope to shed light on how social annotation can be incorporated into digitally mediated consent forms responsibly and effectively. In this controlled between-subjects experiment, participants were presented with an online consent form for a personal genomics study that contained social annotations embedded in its margins. Individuals were randomly assigned to view the consent form with positive-, negative-, or mixed-valence comments beside the text of the consent form. We compared participants' perceptions of being informed and having understood the material, their trust in the organization seeking the consent, and their actual consent across conditions. We find that comment valence has a marginally significant main effect on participants' perception of being informed (F2=2.40, P=.07); specifically, participants in the positive condition (mean 4.17, SD 0.94) felt less informed than those in the mixed condition (mean 4.50, SD 0.69, P=.09). Comment valence also had a marginal main effect on the extent to which participants reported trusting the

  18. Sterically congested uranyl complexes with seven-coordination of the UO{sub 2} unit: the peculiar ligation mode of nitrate in [UO{sub 2}(NO{sub 3}){sub 2}(Rbtp)] complexes

    Energy Technology Data Exchange (ETDEWEB)

    Berthet, J. C.; Thuery, P.; Dognon, J. P.; Ephritikhine, M. [CEA Saclay, DSM, Serv Chim Mol, CNRS, URA 331, F-91191 Gif Sur Yvette, (France); Guillaneux, D. [CEA VALRHO, DEN/VRH/DRCP/SCPS/LCAM, F-30207 Bagnols Sur Ceze, (France)

    2008-07-01

    Addition of 1 or 2 molar equiv of Rbtp [Rbtp 2,6-bis(5,6-dialkyl-1,2,4-triazin-3-yl)pyridine; R = Me, Pr{sup n} to UO{sub 2}(OTf){sub 2} in anhydrous acetonitrile gave the neutral compounds [UO{sub 2}(OTf){sub 2}(Rbtp)] [RMe (1), {sup n}Pr (2)] and the cationic complexes [UO{sub 2}(Rbtp){sub 2}][OTf]{sub 2} [R = Me (3), Pr{sup n} (4)], respectively. No equilibrium between the mono and bis(Rbtp) complexes or between [UO{sub 2}(Rbtp){sub 2}][OTf]{sub 2} and free Rbtp in acetonitrile was detected by NMR spectroscopy. The crystal structures of 1 and 3 resemble those of their ter-pyridine analogues, and 3 is another example of a uranyl complex with the uranium atom in the unusual rhombohedral environment. In the presence of 1 molar equiv of Rbtp in acetonitrile, UO{sub 2}(NO{sub 3}){sub 2} was in equilibrium with [UO{sub 2}(NO{sub 3}){sub 2}(Rbtp)] and the formation of the bis adduct was not observed, even with an excess of Rbtp. The X-ray crystal structures of [UO{sub 2}(NO{sub 3}){sub 2}(Rbtp)] [R = Me (5), Pr{sup n} (6)] reveal a particular coordination geometry with seven coordinating atoms around the UO{sub 2} fragment. The large steric crowding in the equatorial girdle forces the bidentate nitrate ligands to be almost perpendicular to the mean equatorial plane, inducing bending of the UO{sub 2} fragment. The dinuclear oxo compound [U(CyMe{sub 4}btbp){sub 2}({mu}-O)UO{sub 2}(NO{sub 3}){sub 3}][OTf] (7), which was obtained fortuitously from a 1:21 mixture of U(OTf){sub 4}, CyMe{sub 4}btbp, and UO{sub 2}(NO{sub 3}){sub 2} [CyMe{sub 4}btbp6,6'-bis-(3,3,6,6-tetramethyl-cyclohexane-1,2,4-triazin-3-yl)-2,2 = '-bipyridine] is a very rare example of a mixed valence complex involving covalently bound U(IV) and U(VI) ions; its crystal structure also exhibits a seven coordinate uranyl moiety, with one bidentate nitrate group almost parallel to the UO{sub 2} fragment. The distinct structural features of [UO{sub 2}(k{sup 2}-NO{sub 3}){sub 2}(Mebtp)], with its high

  19. Mixed-valent metals bridged by a radical ligand: fact or fiction based on structure-oxidation state correlations.

    Science.gov (United States)

    Sarkar, Biprajit; Patra, Srikanta; Fiedler, Jan; Sunoj, Raghavan B; Janardanan, Deepa; Lahiri, Goutam Kumar; Kaim, Wolfgang

    2008-03-19

    Electron-rich Ru(acac)2 (acac- = 2,4-pentanedionato) binds to the pi electron-deficient bis-chelate ligands L, L = 2,2'-azobispyridine (abpy) or azobis(5-chloropyrimidine) (abcp), with considerable transfer of negative charge. The compounds studied, (abpy)Ru(acac)2 (1), meso-(mu-abpy)[Ru(acac)2]2 (2), rac-(mu-abpy)[Ru(acac)2]2 (3), and (mu-abcp)[Ru(acac)2]2 (4), were calculated by DFT to assess the degree of this metal-to-ligand electron shift. The calculated and experimental structures of 2 and 3 both yield about 1.35 A for the length of the central N-N bond which suggests a monoanion character of the bridging ligand. The NBO analysis confirms this interpretation, and TD-DFT calculations reproduce the observed intense long-wavelength absorptions. While mononuclear 1 is calculated with a lower net ruthenium-to-abpy charge shift as illustrated by the computed 1.30 A for d(N-N), compound 4 with the stronger pi accepting abcp bridge is calculated with a slightly lengthened N-N distance relative to that of 2. The formulation of the dinuclear systems with monoanionic bridging ligands implies an obviously valence-averaged Ru(III)Ru(II) mixed-valent state for the neutral molecules. Mixed valency in conjunction with an anion radical bridging ligand had been discussed before in the discussion of MLCT excited states of symmetrically dinuclear coordination compounds. Whereas 1 still exhibits a conventional electrochemical and spectroelectrochemical behavior with metal centered oxidation and two ligand-based one-electron reduction waves, the two one-electron oxidation and two one-electron reduction processes for each of the dinuclear compounds Ru2.5(L*-)Ru2.5 reveal more unusual features via EPR and UV-vis-NIR spectroelectrochemistry. In spite of intense near-infrared absorptions, the EPR results show that the first reduction leads to Ru(II)(L*-)Ru(II) species, with an increased metal contribution for system 4*-. The second reduction to Ru(II)(L2-)Ru(II) causes the

  20. Fabrication of functional transition metal oxide and hydroxide used as catalysts and battery materials

    Science.gov (United States)

    Xu, Linping

    My research is focused on developing metal oxide and hydroxide nanomaterials which can be used as battery materials, organic transformation catalysts, and photocatalysts. This research involves studying ZnO with different morphologies as photocatalysts for phenol degradation, producing CuO as olefin epoxidation catalysts, developing V and Cu incorporated manganese oxides as cathode materials for Li-ion batteries, and fabricating alpha-nickel hydroxide for Li-air battery materials. The first part includes producing ZnO as a photocatalyst for phenol degradation. The goal of this study is the synthesis of ZnO with different morphologies using the solvothermal method. The influence of solvents has been studied in detail. Their properties and photocatalytic performances have been explored as well. The second part of the research is concerned with developing novel urchin-like CuO as an olefin epoxidation catalyst. The purpose of this study is to develop a new catalyst, CuO, for olefin epoxidation. The copper source and precipitators were optimized, and the possible self-assembly mechanism of the urchin-like morphology was proposed. The catalytic activity of CuO for olefin epoxidation was studied. The third part of this work includes developing V, Cu incorporated manganese oxide (V-Cu-OMS-2) as cathode materials for Li-ion batteries. The purpose of this project is to develop a new material with enhanced battery performance. V and Cu incorporated manganese oxide were developed using hydrothermal methods. Octahedral molecular sieve (OMS) materials show mixed valences of Mn 3+ and Mn4+, which produces novel properties in battery applications. Inexpensive starting materials make OMS materials more promising for commercial applications. How the incorporation of V and Cu affected OMS-2 materials was investigated in terms of their crystal structure, morphologies, and surface areas. The battery performance of the incorporated OMS-2 materials with different loading amounts of V

  1. Electron-mediating Cu(A) centers in proteins: a comparative high field (1)H ENDOR study.

    Science.gov (United States)

    Epel, Boris; Slutter, Claire S; Neese, Frank; Kroneck, Peter M H; Zumft, Walter G; Pecht, Israel; Farver, Ole; Lu, Yi; Goldfarb, Daniella

    2002-07-10

    High field (W-band, 95 GHz) pulsed electron-nuclear double resonance (ENDOR) measurements were carried out on a number of proteins that contain the mixed-valence, binuclear electron-mediating Cu(A) center. These include nitrous oxide reductase (N(2)OR), the recombinant water-soluble fragment of subunit II of Thermus thermophilus cytochrome c oxidase (COX) ba(3) (M160T9), its M160QT0 mutant, where the weak axial methionine ligand has been replaced by a glutamine, and the engineered "purple" azurin (purpAz). The three-dimensional (3-D) structures of these proteins, apart from the mutant, are known. The EPR spectra of all samples showed the presence of a mononuclear Cu(II) impurity with EPR characteristics of a type II copper. At W-band, the g( perpendicular) features of this center and of Cu(A) are well resolved, thus allowing us to obtain a clean Cu(A) ENDOR spectrum. The latter consists of two types of ENDOR signals. The first includes the signals of the four strongly coupled cysteine beta-protons, with isotropic hyperfine couplings, A(iso), in the 7-15 MHz range. The second group consists of weakly coupled protons with a primarily anisotropic character with A(zz) < 3 MHz. Orientation selective ENDOR spectra were collected for N(2)OR, M160QT0, and purpAz, and simulations of the cysteine beta-protons signals provided their isotropic and anisotropic hyperfine interactions. A linear correlation with a negative slope was found between the maximum A(iso) value of the beta-protons and the copper hyperfine interaction. Comparison of the best-fit anisotropic hyperfine parameters with those calculated from dipolar interactions extracted from the available 3-D structures sets limit to the sulfur spin densities. Similarly, the small coupling spectral region was simulated on the basis of the 3-D structures and compared with the experimental spectra. It was found that the width of the powder patterns of the weakly coupled protons recorded at g(perpendicular) is mainly

  2. Photo- and electro-chromic organometallics with dithienylethene (DTE) linker, L2CpM-DTE-MCpL2: dually stimuli-responsive molecular switch.

    Science.gov (United States)

    Motoyama, Keiko; Li, Huifang; Koike, Takashi; Hatakeyama, Makoto; Yokojima, Satoshi; Nakamura, Shinichiro; Akita, Munetaka

    2011-10-28

    Photochromic dithienylethene (DTE) derivatives, M-DTE-M (M: M(η(5)-C(5)R(5))L(2); M = Fe, Ru; R = H, Me; L = CO, phosphine), with direct σ-bonded, redox-active organometallic attachments are prepared and their response to photo- and electro-chemical stimuli as well as wire-like and switching performance has been investigated. These properties turn out to be dependent on the metal and the auxiliary ligands. The DTE complexes with the MCp(CO)(2) and RuCp(CO)(PPh(3)) fragments undergo reversible photochemical ring-closing and -opening of the DTE moiety upon UV and visible-light irradiation, respectively, whereas the other FeCp(CO)(PPh(3)) and Fe(η(5)-C(5)R(5))(dppe) derivatives are virtually inert with respect to the photochemical ring closing process. Electrochemical analysis of the DTE complexes reveals that 2e-oxidation of the open isomer O also brings about the ring closure of the DTE moiety to afford the Fischer-carbene-type, dicationic closed derivatives C(2+) with the π-conjugated system different from that in the neutral ones C obtained photochemically. Subsequent reduction of C(2+) furnishes the neutral closed species C. Thus the ring closure is mediated not only by the conventional photochemical process but also by the sequential oxidation-reduction process, i.e. the organometallic DTE complexes are found to be dually photo- and electro-chromic. It is notable that the oxidative procedures are viable for the photochemically inert derivatives. Wire-like and switching performance has been evaluated on the basis of the comproportionation constant K(C) for the 1e-oxidized mixed valence monocationic species obtained by the electrochemical analysis and the switching factor SF (K(C)(C)/K(C)(O)), respectively. The K(C)(C) (7.5 × 10(4)) and SF values (5.4 × 10(3)) for phosphine-substituted derivatives are significantly large, as a result of the distinct π-conjugated systems of the DTE moieties involved in the O- (with cross-conjugation) and C-forms (fully

  3. Sandwich and half-sandwich metal complexes derived from cross-conjugated 3-methylene-penta-1,4-diynes.

    Science.gov (United States)

    Vincent, Kevin B; Gluyas, Josef B G; Zeng, Qiang; Yufit, Dmitry S; Howard, Judith A K; Hartl, František; Low, Paul J

    2017-05-02

    ferrocenyl moieties are enhanced in solutions of the weakly ion-pairing electrolyte n-Bu4N[B{C6H3(CF3)2-3,5}4], leading to better resolution of the individual electrochemical processes. The comparative IR spectroelectrochemical response of 6a and 6b suggest the vinyl ferrocene moiety in 6b undergoes oxidation before the ethynyl ferrocene fragments. There is no evidence of electronic coupling between the metallocene moieties and [6a](+), [6b](n+) (n = 1, 2) are best described as Class I mixed-valence compounds.

  4. Social Annotation Valence: The Impact on Online Informed Consent Beliefs and Behavior

    Science.gov (United States)

    Shaer, Orit; Okerlund, Johanna; Westendorf, Lauren; Ball, Madeleine; Nov, Oded

    2016-01-01

    Background Social media, mobile and wearable technology, and connected devices have significantly expanded the opportunities for conducting biomedical research online. Electronic consent to collecting such data, however, poses new challenges when contrasted to traditional consent processes. It reduces the participant-researcher dialogue but provides an opportunity for the consent deliberation process to move from solitary to social settings. In this research, we propose that social annotations, embedded in the consent form, can help prospective participants deliberate on the research and the organization behind it in ways that traditional consent forms cannot. Furthermore, we examine the role of the comments’ valence on prospective participants’ beliefs and behavior. Objective This study focuses specifically on the influence of annotations’ valence on participants’ perceptions and behaviors surrounding online consent for biomedical research. We hope to shed light on how social annotation can be incorporated into digitally mediated consent forms responsibly and effectively. Methods In this controlled between-subjects experiment, participants were presented with an online consent form for a personal genomics study that contained social annotations embedded in its margins. Individuals were randomly assigned to view the consent form with positive-, negative-, or mixed-valence comments beside the text of the consent form. We compared participants’ perceptions of being informed and having understood the material, their trust in the organization seeking the consent, and their actual consent across conditions. Results We find that comment valence has a marginally significant main effect on participants’ perception of being informed (F2=2.40, P=.07); specifically, participants in the positive condition (mean 4.17, SD 0.94) felt less informed than those in the mixed condition (mean 4.50, SD 0.69, P=.09). Comment valence also had a marginal main effect on the

  5. Synthesis and structural characterization of the Ca2MnReO6 double perovskite Síntese e caracterização estrutural da dupla perovsquita Ca2MnReO6

    Directory of Open Access Journals (Sweden)

    H. P. S Corrêa

    2010-06-01

    Full Text Available The Ca2Mn1Re1O6 double perovskite has been prepared in polycrystalline form by using the encapsulated quartz tube method. The partial oxygen pressure inside the quartz tube revealed this to be a crucial synthesis parameter for the production of a single structural phase sample. This parameter was controlled using the ratio between ReO2 and ReO3 content and the filling factor parameter (ratio between mass and total inner volume of the quartz tube. The morphology and chemical composition was investigated by scanning electron microscopy and energy dispersive X-ray spectroscopy. The crystal structure parameters were determined by analysis of the synchrotron high-resolution X-ray powder diffraction pattern. The analysis indicates that the sample is an ideal single-phase compound with a monoclinic crystal structure (space group P2(1/n with a = 5.44445(2 Å; b = 5.63957(3 Å; c = 7.77524(3 Å; and β = 90.18(1º. Computer simulations were performed considering two cation valence configurations, namely, (i Mn2+Re6+ or (ii Mn3+Re5+, for the Ca2Mn1Re1O6 compound. XANES analysis measurements indicated +2.3 for the average valence of Mn (a mixture of Mn2+ and Mn3+ and +5.7 for the effective valence of Re (an intermediate valence between Re4+ (ReO2 and Re6+ (ReO3. As a summary, we concluded there is a mixed valence configuration for Mn and Re in Ca2Mn1Re1O6 , taken into account the oxygen content of 6.0±0.1.A dupla perovsquita Ca2MnReO6 na forma policristalina foi preparada utilizando o método do tubo de quartzo encapsulado. A pressão parcial de oxigênio dentro do tubo de quartzo mostrou-se ser um parâmetro crucial para a produção de uma amostra estrutural monofásica. Esse parâmetro foi controlado usando a relação entre o conteúdo dos precursores ReO2 e ReO3 e o parâmetro fator de preenchimento (razão entre a massa e o volume interno total do tubo de quartzo.A morfologia e a composição química foi investigada através da microscopia eletr

  6. Hydrologic Resources Management Program and Underground Test Area Project FY 2001-2002 Progress Report

    Energy Technology Data Exchange (ETDEWEB)

    Rose, T P; Kersting, A B; Harris, L J; Hudson, G B; Smith, D K; Williams, R W; Loewen, D R; Nelson, E J; Allen, P G; Ryerson, F J; Pawloski, G A; Laue, C A; Moran, J E

    2003-08-15

    and abundance of actinides in a nuclear test cavity and chimney. This work demonstrates that early-time processes can widely disperse actinides at low concentrations outside the melt glass, implying that melt glass dissolution may not be the sole mechanism for the release of actinides to groundwater. The study also provides evidence for the isotopic fractionation of plutonium under the extreme conditions accompanying nuclear explosions. In Chapter 4, X-ray absorption spectroscopy measurements were used to determine the redox state of Fe and U in nuclear melt glass samples from the NTS. Both elements were found to occur in mixed valence states (Fe{sup 2+}/Fe{sup 3+} and U{sup 5+}/U{sup 6+}) in all samples. Comparison of the Fe and U redox states with published redox studies of synthetic glasses suggests that plutonium is predominantly in the Pu{sup 4+} oxidation state in the melt glasses. In Chapter 5, alpha autoradiography is used in a NTS field study to investigate the spatial distribution and transport of actinides in soils, and to help identify the size distribution and morphology of the actinide particles. It was found that {alpha}-emitting radionuclides have moved to at least 39 cm depth in the soil profile, far deeper than expected. The methodology that was developed could easily be applied to other field locations where actinides are dispersed in the soil zone. Chapter 6 summarizes the development of a method for measuring environmental levels of {sup 241}Am on the multi-collector inductively coupled plasma mass spectrometer. The method detection limit of 0.017 pCi/L is about two times lower than the best analyses possible by alpha spectrometry. Chapter 7 describes a chlorine-36 study of vertical groundwater transport processes in Frenchman Flat. Mass balance calculations developed from a {sup 36}Cl mixing model at well ER-5-3 No.2 are used to estimate vertical transport fluxes and average vertical flow velocities through the thick volcanic section underlying