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Sample records for bcc transition metals

  1. Cascade morphology transition in bcc metals.

    Science.gov (United States)

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

    2015-06-10

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

  2. Melting of bcc Transition Metals and Icosahedral Clustering

    Energy Technology Data Exchange (ETDEWEB)

    Ross, M; Boehler, R; Japel, S

    2006-05-26

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

  3. Calculated Pressure Induced BCC-FCC Phase Transitions in Alkali Metals

    OpenAIRE

    DAĞISTANLI, Hamdi; MUTLU, R. Haluk

    2008-01-01

    The partial occupation numbers and density of states (DOS), and the total DOS at the Fermi level are calculated as a function of reduced atomic volume for bcc and fcc alkali metals employing the linear-muffin-tin-orbital (LMTO) method. By means of the abrupt changes obtained in the partial and total DOS values at the Fermi level, good agreement with regard to experiment were found in predicting the bcc-fcc transition volumes of the alkali metals.

  4. Optical properties of bcc transition metals in the range 0-40 eV

    NARCIS (Netherlands)

    Romaniello, P; de Boeij, PL; Carbone, F; van der Marel, D

    2006-01-01

    We present a systematic analysis of the optical properties of bcc transition metals in the groups VB: V, Nb, and Ta, and VIB: paramagnetic Cr, Mo, and W. For this we use our formulation of time-dependent current-density-functional theory for the linear response of metals. The calculated dielectric a

  5. Optical properties of bcc transition metals in the range 0–40 eV

    NARCIS (Netherlands)

    Romaniello, P.; Boeij, P.L. de; Carbone, F.; Marel, D. van der

    2006-01-01

    We present a systematic analysis of the optical properties of bcc transition metals in the groups VB: V, Nb, and Ta, and VIB: paramagnetic Cr, Mo, and W. For this we use our formulation of time-dependent current-density-functional theory for the linear response of metals. The calculated dielectric a

  6. Magnetic coupling in 3d transition-metal monolayers and bilayers on bcc (100) iron

    DEFF Research Database (Denmark)

    Mirbt, S.; Eriksson, O.; Johansson, B.;

    1995-01-01

    We have calculated the magnetization profile in the (100) surface of bcc Fe covered by a monolayer or a bilayer of 3d transition metals. The calculated trends are explained in terms of the hybridization between the 3d states of the overlayer and the Fe substrate.......We have calculated the magnetization profile in the (100) surface of bcc Fe covered by a monolayer or a bilayer of 3d transition metals. The calculated trends are explained in terms of the hybridization between the 3d states of the overlayer and the Fe substrate....

  7. Divacancy binding energy, formation energy and surface energy of BCC transition metals using MEAM potentials

    Science.gov (United States)

    Uniyal, Shweta; Chand, Manesh; Joshi, Subodh; Semalty, P. D.

    2016-05-01

    The modified embedded atom method (MEAM) potential parameters have been employed to calculate the unrelaxed divacancy formation energy, binding energy and surface energies for low index planes in bcc transition metals. The calculated results of divacancy binding energy and vacancy formation energy compare well with experimental and other available calculated results.

  8. 18-Electron Resonance Structures in the BCC Transition Metals and Their CsCl-type Derivatives.

    Science.gov (United States)

    Vinokur, Anastasiya I; Fredrickson, Daniel C

    2017-02-20

    Bonding in elemental metals and simple alloys has long been thought of as involving intense delocalization, with little connection to the localized bonds of covalent systems. In this Article, we show that the bonding in body-centered cubic (bcc) structures of the group 6 transition metals can in fact be represented, via the concepts of the 18-n rule and isolobal bonding, in terms of two balanced resonance structures. We begin with a reversed approximation Molecular Orbital (raMO) analysis of elemental Mo in its bcc structure. The raMO analysis indicates that, despite the low electron count (six valence electrons per Mo atom), nine electron pairs can be associated with any given Mo atom, corresponding to a filled 18-electron configuration. Six of these electron pairs take part in isolobal bonds along the second-nearest neighbor contacts, with the remaining three (based on the t2g d orbitals) interacting almost exclusively with first-nearest neighbors. In this way, each primitive cubic network defined by the second-nearest neighbor contacts comprises an 18-n electron system with n = 6, which essentially describes the full electronic structure of the phase. Of course, either of the two interpenetrating primitive cubic frameworks of the bcc structure can act as a basis for this discussion, leading us to write two resonance structures with equal weights for bcc-Mo. The electronic structures of CsCl-type variants with the same electron count can then be interpreted in terms of changing the relative weights of these two resonance structures, as is qualitatively confirmed with raMO analysis. This combination of raMO analysis with the resonance concept offers an avenue to extend the 18-n rule into other transition metal-rich structures.

  9. Vibrational properties of vacancy in bcc transition metals using embedded atom method potentials

    Indian Academy of Sciences (India)

    Vandana Gairola; P D Semalty; P N Ram

    2013-06-01

    The embedded atom method (EAM) potentials, with the universal form of the embedding function along with the Morse form of pair potential, have been employed to determine the potential parameters for three bcc transition metals: Fe, Mo, and W, by fitting to Cauchy pressure $(C_{12} − C_{44})/2$, shear constants $G_{v} = (C_{11} − C_{12} + 3C_{44})/5$ and 44, cohesive energy and the vacancy formation energy. The obtained potential parameters are used to calculate the phonon dispersion spectra of these metals. Large discrepancies are found between the calculated results of phonon dispersion using the EAM and the experimental phonon dispersion results. Therefore, to overcome this inadequacy of the EAM model, we employ the modified embedded atom method (MEAM) in which a modified term along with the pair potential and embedding function is added in the total energy. The phonon dispersions calculated using potential parameters obtained from the MEAM show good agreement with experimental results compared to those obtained from the EAM. Using the calculated phonons, we evaluate the local density of states of the neighbours of vacancy using the Green’s function method. The local frequency spectrum of first neighbours of vacancy in Mo shows an increase at higher frequencies and a shift towards the lower frequencies whereas in Fe and W, the frequency spectrum shows a small decrease towards higher frequency and small shift towards lower frequency. For the second neighbours of vacancy in all the three metals, the local frequency spectrum is not much different from that of the host atom. The local density of states of the neighbours of the vacancy has been used to calculate the mean square displacements and the formation entropy of vacancy. The calculated mean square displacements of the first neighbours of vacancy are found to be higher than that of the host atom, whereas it is lower for the second neighbours. The calculated results of the formation entropy of the vacancy

  10. Simulation of He embrittlement at grain boundaries in bcc transition metals

    Science.gov (United States)

    Suzudo, Tomoaki; Yamaguchi, Masatake

    2015-10-01

    To investigate what atomic properties largely determine vulnerability to He embrittlement at grain boundaries (GB) of bcc metals, we introduce a computational model composed of first principles density functional theory and a He segregation rate theory model. Predictive calculations of He embrittlement at the first wall of the future DEMO fusion concept reactor indicate that variation in the He embrittlement originated not only from He production rate related to neutron irradiation, but also from the He segregation energy at the GB that has a systematic trend in the periodic table.

  11. Dissolving, trapping and detrapping mechanisms of hydrogen in bcc and fcc transition metals

    Directory of Open Access Journals (Sweden)

    Yu-Wei You

    2013-01-01

    Full Text Available First-principles calculations are performed to investigate the dissolving, trapping and detrapping of H in six bcc (V, Nb, Ta, Cr, Mo, W and six fcc (Ni, Pd, Pt, Cu, Ag, Au metals. We find that the zero-point vibrations do not change the site-preference order of H at interstitial sites in these metals except Pt. One vacancy could trap a maximum of 4 H atoms in Au and Pt, 6 H atoms in V, Nb, Ta, Cr, Ni, Pd, Cu and Ag, and 12 H atoms in Mo and W. The zero-point vibrations never change the maximum number of H atoms trapped in a single vacancy in these metals. By calculating the formation energy of vacancy-H (Vac-Hn complex, the superabundant vacancy in V, Nb, Ta, Pd and Ni is demonstrated to be much more easily formed than in the other metals, which has been found in many metals including Pd, Ni and Nb experimentally. Besides, we find that it is most energetically favorable to form Vac-H1 complex in Pt, Cu, Ag and Au, Vac-H4 in Cr, Mo and W, and Vac-H6 in V, Nb, Ta, Pd and Ni. At last, we examine the detrapping behaviors of H atoms in a single vacancy and find that with the heating rate of 10 K/min a vacancy could accommodate 4, 5 and 6 H atoms in Cr, Mo and W at room temperature, respectively. The detrapping temperatures of all H atoms in a single vacancy in V, Nb, Ta, Ni, Pd, Cu and Ag are below room temperature.

  12. Electronic structure and magnetism of strained bcc phases across the fcc to bcc transition in ultrathin Fe films

    Science.gov (United States)

    Calloni, Alberto; Berti, Giulia; Bussetti, Gianlorenzo; Fratesi, Guido; Finazzi, Marco; Ciccacci, Franco; Duò, Lamberto

    2016-11-01

    We investigated the electronic structure of the bcc metastable phases involved in the fcc to bcc transition of Fe. Ultrathin Fe films were grown on a 2-monolayer (ML) Ni/W(110) substrate, where a fcc lattice is stabilized at low Fe coverages and the transition proceeds through the formation of bcc nuclei showing a specific "Kurdjumov-Sachs" orientation with the substrate. A comprehensive description of the electronic structure evolution is achieved by combining spin-resolved UV photoemission spectroscopy and ab initio calculations. According to our results, an exchange-split band structure is observed starting from 2 ML of Fe, concomitant with the formation of ferromagnetic bcc nuclei. Continuous modifications are observed in the spin-resolved photoemission spectra for increasing Fe coverage, especially for what concerns the minority states, possibly indicative of the progressive relaxation of the strained bcc phase starting from the bcc/fcc interface.

  13. Fcc-bcc transition for Yukawa interactions determined by applied strain deformation

    OpenAIRE

    Hoy, Robert S.; Robbins, Mark O.

    2004-01-01

    Calculations of the work required to transform between bcc and fcc phases yield a high-precision bcc-fcc transition line for monodisperse point Yukawa (screened-Couloumb) systems. Our results agree qualitatively but not quantitatively with previously published simulations and phenomenological criteria for the bcc-fcc transition. In particular, the bcc-fcc-fluid triple point lies at a higher inverse screening length than previously reported.

  14. Angular distortive matrices of phase transitions in the fcc-bcc-hcp system

    OpenAIRE

    Cayron, Cyril

    2016-01-01

    This work generalizes the one-step model previously developed on fcc-bcc martensitic transformations to the larger family of phase transitions in the fcc-bcc-hcp system. The angular distortive matrices are calculated for the bcc-fcc, bcc-hcp and fcc-hcp transitions, and for fcc-fcc mechanical twinning. The analytical expressions of the continuous atomic displacements, lattice distortion and lattice correspondence matrices result directly from the orientation relationships; the unique assumpti...

  15. Metastable bcc phase formation in 3d ferromagnetic transition metal thin films sputter-deposited on GaAs(100) substrates

    Energy Technology Data Exchange (ETDEWEB)

    Minakawa, Shigeyuki, E-mail: s-minakawa@futamoto.elect.chuo-u.ac.jp; Ohtake, Mitsuru; Futamoto, Masaaki [Faculty of Science and Engineering, Chuo University, Bunkyo-ku, Tokyo 112-8551 (Japan); Kirino, Fumiyoshi [Graduate School of Fine Arts, Tokyo University of the Arts, Taito-ku, Tokyo 110-8714 (Japan); Inaba, Nobuyuki [Faculty of Engineering, Yamagata University, Yonezawa, Yamagata 992-8510 (Japan)

    2015-05-07

    Co{sub 100−x}Fe{sub x} and Ni{sub 100−y}Fe{sub y} (at. %, x = 0–30, y = 0–60) films of 10 nm thickness are prepared on GaAs(100) substrates at room temperature by using a radio-frequency magnetron sputtering system. The detailed growth behavior is investigated by in-situ reflection high-energy electron diffraction. (100)-oriented Co and Ni single-crystals with metastable bcc structure are formed in the early stage of film growth, where the metastable structure is stabilized through hetero-epitaxial growth. With increasing the thickness up to 2 nm, the Co and the Ni films start to transform into more stable hcp and fcc structures through atomic displacements parallel to bcc(110) slide planes, respectively. The stability of bcc phase is improved by adding a small volume of Fe atoms into a Co film. The critical thickness of bcc phase formation is thicker than 10 nm for Co{sub 100−x}Fe{sub x} films with x ≥ 10. On the contrary, the stability of bcc phase for Ni-Fe system is less than that for Co-Fe system. The critical thicknesses for Ni{sub 100−y}Fe{sub y} films with y = 20, 40, and 60 are 1, 3, and 5 nm, respectively. The Co{sub 100−x}Fe{sub x} single-crystal films with metastable bcc structure formed on GaAs(100) substrates show in-plane uniaxial magnetic anisotropies with the easy direction along GaAs[011], similar to the case of Fe film epitaxially grown on GaAs(100) substrate. A Co{sub 100−x}Fe{sub x} film with higher Fe content shows a higher saturation magnetization and a lower coercivity.

  16. Perturbation theory of solid-liquid interfacial free energies of bcc metals.

    Science.gov (United States)

    Warshavsky, Vadim B; Song, Xueyu

    2012-09-01

    A perturbation theory is used to calculate bcc solid-liquid interfacial free energies of metallic systems with embedded-atom model potentials. As a reference system for bcc crystals we used a single-occupancy cell, hard-sphere bcc system. Good agreements between the perturbation theory results and the corresponding results from simulations are found. The strategy to extract hard-sphere bcc solid-liquid interfacial free energies may have broader applications for other crystal lattices.

  17. Plastic anisotropy and dislocation trajectory in BCC metals

    Science.gov (United States)

    Dezerald, Lucile; Rodney, David; Clouet, Emmanuel; Ventelon, Lisa; Willaime, François

    2016-05-01

    Plasticity in body-centred cubic (BCC) metals at low temperatures is atypical, marked in particular by an anisotropic elastic limit in clear violation of the famous Schmid law applicable to most other metals. This effect is known to originate from the behaviour of the screw dislocations; however, the underlying physics has so far remained insufficiently understood to predict plastic anisotropy without adjustable parameters. Here we show that deviations from the Schmid law can be quantified from the deviations of the screw dislocation trajectory away from a straight path between equilibrium configurations, a consequence of the asymmetrical and metal-dependent potential energy landscape of the dislocation. We propose a modified parameter-free Schmid law, based on a projection of the applied stress on the curved trajectory, which compares well with experimental variations and first-principles calculations of the dislocation Peierls stress as a function of crystal orientation.

  18. Melting of Transition Metals

    Energy Technology Data Exchange (ETDEWEB)

    Ross, M; Japel, S; Boehler, R

    2005-04-11

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

  19. Slip Model Used for Prediction of r Value of BCC Metal Sheets from ODF Coefficients

    Institute of Scientific and Technical Information of China (English)

    2000-01-01

    Different slip models were used for prediction of rvalue of BCC metal sheets from ODF coefficients. According to the maximum plastic work theory developed by Bishop and Hill, it is expected that the higher of Taylor factors given by a slip model, the better predictio nobtained based on the model. From this point of view, a composed slip model of BCC metals was presented. Based on the model, the agreement of predicted rvalues for deep drawing steels with experimental ones is excellent.

  20. Kinetics study of crystallization with the disorder-bcc-fcc phase transition of charged colloidal dispersions.

    Science.gov (United States)

    Zhou, Hongwei; Xu, Shenghua; Sun, Zhiwei; Du, Xuan; Liu, Lixia

    2011-06-21

    Structure transformation (disorder-bcc-fcc) in charged colloidal dispersions, as a manifestation of the Ostwald's step rule, was confirmed by means of reflection spectrum (RS) measurements in our previous study. By taking advantage of a reflection spectrum containing plenty of information about the crystallization behaviors, time-dependent changes of parameters associated with the crystal structure and composition during the disorder-bcc-fcc transition are reported by treating the data from RS in this article. In addition, Avrami's model is adopted to analyze the transition process and investigate the transition rate. On the basis of the above investigations, associated kinetic features of crystallization with the disorder-bcc-fcc transition are described.

  1. Solid-liquid interface free energies of pure bcc metals and B2 phases.

    Science.gov (United States)

    Wilson, S R; Gunawardana, K G S H; Mendelev, M I

    2015-04-07

    The solid-liquid interface (SLI) free energy was determined from molecular dynamics (MD) simulation for several body centered cubic (bcc) metals and B2 metallic compounds (space group: Pm3̄m; prototype: CsCl). In order to include a bcc metal with a low melting temperature in our study, a semi-empirical potential was developed for Na. Two additional synthetic "Na" potentials were also developed to explore the effect of liquid structure and latent heat on the SLI free energy. The obtained MD data were compared with the empirical Turnbull, Laird, and Ewing relations. All three relations are found to predict the general trend observed in the MD data for bcc metals obtained within the present study. However, only the Laird and Ewing relations are able to predict the trend obtained within the sequence of "Na" potentials. The Laird relation provides the best prediction for our MD data and other MD data for bcc metals taken from the literature. Overall, the Laird relation also agrees well with our B2 data but requires a proportionality constant that is substantially different from the bcc case. It also fails to explain a considerable difference between the SLI free energies of some B2 phases which have nearly the same melting temperature. In contrast, this difference is satisfactorily described by the Ewing relation. Moreover, the Ewing relation obtained from the bcc dataset also provides a reasonable description of the B2 data.

  2. Effect of Crystal Quality on HCP-BCC Phase Transition in Solid 4He

    CERN Document Server

    Mikhin, N; Rudavskii, E; Vekhov, Y; Mikhin, Nikolay; Polev, Andrey; Rudavskii, Eduard; Vekhov, Yegor

    2006-01-01

    The kinetics of HCP-BCC structure phase transition is studied by precise pressure measurement technique in 4He crystals of different quality. An anomalous pressure behavior in bad quality crystals under constant volume conditions is detected just after HCP-BCC structure phase transition. A sharp pressure drop of 0.2 bar was observed at constant temperature. The subsequent pressure kinetics is a non-monotonic temperature function. The effect observed can be explained if we suppose that microscopic liquid droplets appear on the HCP-BCC interphase region in bad quality crystals. After the interphase region disappearance, these droplets are crystallized with pressure reduction. It is shown that this effect is absent in high quality thermal-treated crystals.

  3. On the stability of rhenium up to 1 TPa pressure against transition to the bcc structure

    Indian Academy of Sciences (India)

    A K Verma; P Ravindran; R S Rao; B K Godwal; R Jeanloz

    2003-01-01

    We have carried out electronic structure total energy calculations on rhenium in the hexagonal close packed (hcp) and body centred cubic (bcc) phases, by the full potential linear muffin–tin orbital method, in order to verify the stability of the ambient pressure hcp phase against transition to the bcc structure at high pressures. As per our results, no hcp to bcc structural transition can occur up to 1 TPa pressures. Moreover, our Bain path calculations show that face centred cubic and body centred tetragonal structures are also not energetically preferred over hcp in this pressure range. The axial ratio (/) of Re changes by less than 0.33% in the pressure range studied.

  4. Atomistic simulation of fcc-bcc phase transition in single crystal A1 under uniform compression

    Institute of Scientific and Technical Information of China (English)

    Li Li; Shao Jian-Li; Li Yan-Fang; Duan Su-Qing; [ Liang Jiu-Qing

    2012-01-01

    By molecular dynamics simulations employing an embedded atom model potential,we investigate the fcc-to-bcc phase transition in single crystal Al,caused by uniform compression.Results show that the fec structure is unstable when the pressure is over 250 GPa,in reasonable agreement with the calculated value through the density functional theory.The morphology evolution of the structural transition and the corresponding transition mechanism are analysed in detail.The bec (011) planes are transited from the fcc (11(1)) plane and the (1(1)1) plane.We suggest that the transition mechanism consists mainly of compression,shear,slid and rotation of the lattice.In addition,our radial distribution function analysis explicitly indicates the phase transition of A1 from fcc phase to bcc structure.

  5. Crystallization pathways of liquid-bcc transition for a model iron by fast quenching.

    Science.gov (United States)

    Pan, Shao-Peng; Feng, Shi-Dong; Qiao, Jun-Wei; Wang, Wei-Min; Qin, Jing-Yu

    2015-11-19

    We report simulations on the local structural evolution in the liquid-bcc transition of a model iron. Fourteen main Voronoi polyhedra are chosen as the representatives of short-range orders (SROs) and their transformations during crystallization are also investigated. Thus, the crystallization pathways for the main SROs are drawn. Our results also show that the transformations between two SROs in the crystallization pathways can be classified into two categories, first the enlargement of coordination number, second the transformation of local symmetry from five-fold to four-fold. The former reduces the potential energy while the latter increases it. It is found that the potential energy cannot decease monotonously whatever crystallization pathway is chosen to transform the icosahedral SRO to bcc SRO. Therefore, the latter transformation might provide the energy barrier of crystallization. We propose two transformation styles among SROs. All the transformations in the crystallization pathways can be achieved according to the styles. Moreover, the two transformation styles indicates that the bcc structure is more similar to liquid than other crystals. That might be the reason why the first phase nucleated during a rapid cooling process should be bcc crystal.

  6. Similarity and Difference of Phase Transition FCC – BCC in Calcium and Strontium

    Directory of Open Access Journals (Sweden)

    V.V. Pozhivatenko

    2016-11-01

    Full Text Available Features of polymorphism in calcium and strontium from the point of view of similarity of physical processes which occur at change of pressure and temperatures are researched. The known experimental facts are added calculated (first principal and fit by results which illustrate both similarity, and difference of structural phase transitions FCC – BCC in calcium and strontium. The increase in similarity of the effects connected with polymorphism is shown, at increase both pressure, and temperatures.

  7. Yield Functions and Plastic Potentials for BCC Metals and Possibly Other Materials

    Energy Technology Data Exchange (ETDEWEB)

    Christensen, R M

    2005-09-29

    Yield functions and plastic potentials are expressed in terms of the invariants of the stress tensor for polycrystalline metals and other isotropic materials. The plastic volume change data of Richmond is used to evaluate the embedded materials properties for some bcc metals and one polymer. A general form for the plastic potential is found that is intended to represent and cover a wide range of materials types.

  8. Grain Size Dependence of Uniform Elongation in Single-Phase FCC/BCC Metals

    Science.gov (United States)

    Liu, Haiting; Shen, Yao; Ma, Jiawei; Zheng, Pengfei; Zhang, Lei

    2016-09-01

    We studied the dependence of uniform elongation on grain size in the range of submicron to millimeter for single-phase FCC/BCC metals by reviewing recent experimental results and applying crystal plasticity finite element method simulation. In the order of increasing grain size, uniform elongation can be divided into three stages, namely low elongation stage, nearly constant elongation stage, and decreased elongation with large scatters stage. Low elongation stage features a dramatic increase near the critical grain size at the end of the stage, which is primarily attributed to the emergence of dislocation cell size transition from ultrafine to mid-size grain. Other factors can be neglected due to their negligible influence on overall variation trend. In nearly constant elongation stage, uniform elongation remains unchanged at a high level in general. As grain size keeps growing, uniform elongation starts decreasing and becomes scattered upon a certain grain size, indicating the initiation of decreased elongation with large scatters stage. It is shown that the increase is not linear or smooth but rather sharp at the end of low elongation stage, leading to a wider range in nearly constant elongation stage. The grain size dependence of uniform elongation can serve as a guiding principle for designing small uniaxial tensile specimens for mechanical testing, where size effect matters in most cases.

  9. Influence of reaction stresses induced by dislocation slips on the orientation evolution in bcc metals

    Institute of Scientific and Technical Information of China (English)

    2003-01-01

    A plastic deformation model for bcc metals is proposed in consideration of reaction stresses. The shear strains and the corresponding reaction stresses induced by the activation of dislocations are calculated in the model, which will influence the following dislocation activation. The rolling texture in bcc metals is simulated up to 80% reduction, while the ratio of critical resolved shear stresses between the dislocations slipping on the {110} and {112} planes is chosen as 0.95. The corresponding calculation is also conducted with the activation of second dislocation, if the difference between the orientation factor of the two dislocations with maximal orientation factors is lower than 5%. It is shown that the simulated texture is closer to that of the 80% rolled interstitial free steels than other modeling. It is believed that the new model can give more attention to both of the strain and stress continuities during the plastic deformation of polycrystalline metals, and therefore approaches closer to the real deformation process in bcc metals.

  10. Anisotropic strain enhanced hydrogen solubility in bcc metals: the independence on the sign of strain.

    Science.gov (United States)

    Zhou, Hong-Bo; Jin, Shuo; Zhang, Ying; Lu, Guang-Hong; Liu, Feng

    2012-09-28

    When an impurity is doped in a solid, it inevitably induces a local stress, tending to expand or contract the lattice. Consequently, strain can be applied to change the solubility of impurity in a solid. Generally, the solubility responds to strain "monotonically," increasing (decreasing) with the tensile (compressive) strain if the impurity induces a compressive stress or vice versa. Using first-principles calculations, however, we discovered that the H solubility can be enhanced by anisotropic strain in some bcc metals, almost independent of the sign of strain. This anomalous behavior is found to be caused by a continuous change of H location induced by anisotropic strain. Our finding suggests a cascading effect of H bubble formation in bcc metals: the H solution leads to H bubble formation that induces anisotropic strain that in turn enhances H solubility to further facilitate bubble growth.

  11. Superstructures formed by orientationally ordered tetrahedra in the bcc lattice: new diffusionless order-disorder transition in solids.

    Science.gov (United States)

    Tamura, Ryuji

    2015-03-04

    We investigated and clarified the superstructures formed by tetrahedra in the bcc lattice within the framework of second-order transitions. Compliance with both the Landau and Lifshitz conditions was investigated for all possible superstructures and, based on this, we demonstrate that bcc crystals that contain tetrahedra at an inversion center can exhibit a variety of second-order transitions, which are regarded as a new type of diffusionless order-disorder transition with antiferroic orientational orders. Finally, we show that the transition gives rise to a new glassy state. Breaking of the local inversion symmetry may lead to a new orientational glass, which is reminiscent of spin glasses in magnetism.

  12. Heats of Segregation and Segregation Profiles of BCC Metals

    Science.gov (United States)

    Good, Brian S.; Bozzolo, Guillermo

    2002-01-01

    The composition of metal alloy surfaces is often different from that of the bulk. Some alloys exhibit surface segregation, where one or more species reside preferentially at or near the surface. A detailed understanding of this behavior is necessary to correctly model such phenomena as adhesion or catalysis. Several phenomenological approaches to the problem have been put forward, falling into two broad categories: Thermodynamic approaches, where the equilibrium distribution of chemical species is computed. Atomistic approaches, where the tendency of a species to segregate is determined by computation of the energies of single atoms of that species in bulk and surface environments.

  13. Analytic bond-order potentials for the bcc refractory metals Nb, Ta, Mo and W.

    Science.gov (United States)

    Čák, M; Hammerschmidt, T; Rogal, J; Vitek, V; Drautz, R

    2014-05-14

    Bond-order potentials (BOPs) are based on the tight-binding approximation for determining the energy of a system of interacting atoms. The bond energy and forces are computed analytically within the formalism of the analytic BOPs. Here we present parametrizations of the analytic BOPs for the bcc refractory metals Nb, Ta, Mo and W. The parametrizations are optimized for the equilibrium bcc structure and tested for atomic environments far from equilibrium that had not been included in the fitting procedure. These tests include structural energy differences for competing crystal structures; tetragonal, trigonal, hexagonal and orthorhombic deformation paths; formation energies of point defects as well as phonon dispersion relations. Our tests show good agreement with available experimental and theoretical data. In practice, we obtain the energetic ordering of vacancy, [1 1 1], [1 1 0], and [1 0 0] self-interstitial atom in agreement with density functional theory calculations.

  14. 氦在bcc和fcc过渡金属中稳定性的理论研究%Theoretical Study on the Stability of Helium in bcc and fcc Transition Metals

    Institute of Scientific and Technical Information of China (English)

    杨莉; 祖小涛; 王小英; 刘柯钊; 王治国

    2008-01-01

    采用基于密度泛函理论的从头算对bcc和fcc过渡金属中氯原子的稳定性进行了研究.计算结果表明,除了V和Nb外,不管是bcc还是fcc,氦都是在替换位置最稳定,对于间隙位置,在bcc过渡金属中,氦在四面体位置比八面体位置更稳定,而在fcc过渡金属中,间隙氮的稳定位置没有规律可循.对有磁性的bccFe和fcc Ni进行自旋和非自旋极化研究,发现金属的磁性对间隙氦的稳定位置没有直接的影响.

  15. Observations on the deformation-induced beta internal friction peak in bcc metals

    Science.gov (United States)

    Dicarlo, J. A.

    1974-01-01

    During a study of the effects of electron irradiation on the tungsten alpha mechanism, internal friction data were obtained. The data indicate that the mechanism underlying the beta peak does not possess the relaxation parameters generally associated with a simple dislocation process. The significance of the experimental results in the light of beta observations in other metals is discussed. It is suggested that the beta peaks in deformed bcc metals are the anelastic result of the thermally-activated relaxation of deformation-induced imperfections.

  16. Modelling plastic deformation in BCC metals: Dynamic recovery and cell formation effects

    Energy Technology Data Exchange (ETDEWEB)

    Galindo-Nava, E.I. [Department of Materials Science and Metallurgy, Pembroke Street, CB2 3QZ, University of Cambridge, Cambridge (United Kingdom); Department of Materials Science and Engineering, Mekelweg 2 2628 CD, Delft University of Technology, Delft (Netherlands); Rivera-Diaz-del-Castillo, P.E.J., E-mail: pejr2@cam.ac.uk [Department of Materials Science and Metallurgy, Pembroke Street, CB2 3QZ, University of Cambridge, Cambridge (United Kingdom)

    2012-12-15

    A recently developed model for describing plasticity in FCC metals (E.I., Galindo-Nava, P.E.J., Rivera-Diaz-del-Castillo, Mater. Sci. Eng. A 543 (2012) 110-116; E.I. Galindo-Nava, P.E.J. Rivera-Diaz-del-Castillo, Acta Mater. 60 (2012) 4370-4378) has now been applied to BCC. The core of the theory is the thermostatistical description of dislocation annihilation paths, which determines the dynamic recovery rate of the material. Input to this is the energy for the formation, migration and ordering of dislocation paths; the latter term corresponds to the statistical entropy which features strongly on the solution. The distinctions between FCC and BCC stem primarily from the possible directions and planes for dislocation slip and cross-slip, as well as from the presence of the kink-pair mechanism for dislocation migration in BCC, which are incorporated to the mathematical formulation of the model. The theory is unique in describing the stress-strain response for pure iron, molybdenum, tantalum, vanadium and tungsten employing physical parameters as input; the description is made for wide ranges of temperature and strain rate. Additionally, succinct equations to predict dislocation cell size variation with strain, strain rate and temperature are provided and validated for pure iron.

  17. Effects of low-temperature neutron irradiation on the mechanical properties of BCC metals

    Science.gov (United States)

    Kitajima, K.; Abe, H.; Aono, Y.; Kuramoto, E.; Takamura, S.

    1982-08-01

    Tensile properties, together with the effects of point-irradiation annealings on them, were measured on single crystals of pure iron, iron containing 200 at. ppm carbon, and pure molybdenum, which were irradiated at 5 K in reactor JRR-3 and stored at 77 K, at the test temperatures of 4.2-800 K. Their measurements were compared with those irradiated by 2.5 and 28 MeV electrons at 77 K to elucidate the characteristics of neutron irradiation. Interpretations were then presented for the mechanisms of softening and hardening based on the interactions of defects and defect clusters formed in various annealing stages with screw dislocation in bcc metals.

  18. Properties of FeNiB-based metallic glasses with primary BCC and FCC crystallisation products

    Energy Technology Data Exchange (ETDEWEB)

    Uriarte, J.L. E-mail: euronano@ltpcm.inpg.fr; Yavari, A.R.; Surinach, S.; Rizzi, P.; Heunen, G.; Baricco, M.; Baro, M.D.; Kvick, A

    2003-01-01

    FeSiB tapes have long been commercialised for their excellent soft-magnetic properties but do not manifest a glass transition temperature T{sub g} as crystallisation intervenes. In this work, we present the crystallisation and properties of two Fe-based glasses, which show a glass transition before crystallisation. Using Ni and Co substitution, we can design glasses that form primary FCC or BCC FeNiCo solutions in their first stage of crystallisation followed by the formation of the metastable (FeNiCo){sub 4}B (C{sub 6}Cr{sub 23}-type cF116) intermetallic phase. Thermal and structural and magnetic properties were compared during heat treatment.

  19. Indium-defect interactions in FCC and BCC metals studied using the modified embedded atom method

    Science.gov (United States)

    Zacate, M. O.

    2016-12-01

    With the aim of developing a transferable potential set capable of predicting defect formation, defect association, and diffusion properties in a wide range of intermetallic compounds, the present study was undertaken to test parameterization strategies for determining empirical pair-wise interaction parameters in the modified embedded atom method (MEAM) developed by Baskes and coworkers. This report focuses on indium-solute and indium-vacancy interactions in FCC and BCC metals, for which a large set of experimental data obtained from perturbed angular correlation measurements is available for comparison. Simulation results were found to be in good agreement with experimental values after model parameters had been adjusted to reproduce as best as possible the following two sets of quantities: (1) lattice parameters, formation enthalpies, and bulk moduli of hypothetical equiatomic compounds with the NaCl crystal structure determined using density functional theory and (2) dilute solution enthalpies in metals as predicted by Miedema's semi-empirical model.

  20. Oligocyclopentadienyl transition metal complexes

    Energy Technology Data Exchange (ETDEWEB)

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

    2002-01-18

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

  1. A unified relation for the solid-liquid interface free energy of pure FCC, BCC, and HCP metals

    Science.gov (United States)

    Wilson, S. R.; Mendelev, M. I.

    2016-04-01

    We study correlations between the solid-liquid interface (SLI) free energy and bulk material properties (melting temperature, latent heat, and liquid structure) through the determination of SLI free energies for bcc and hcp metals from molecular dynamics (MD) simulation. Values obtained for the bcc metals in this study were compared to values predicted by the Turnbull, Laird, and Ewing relations on the basis of previously published MD simulation data. We found that of these three empirical relations, the Ewing relation better describes the MD simulation data. Moreover, whereas the original Ewing relation contains two constants for a particular crystal structure, we found that the first coefficient in the Ewing relation does not depend on crystal structure, taking a common value for all three phases, at least for the class of the systems described by embedded-atom method potentials (which are considered to provide a reasonable approximation for metals).

  2. A unified relation for the solid-liquid interface free energy of pure FCC, BCC, and HCP metals.

    Science.gov (United States)

    Wilson, S R; Mendelev, M I

    2016-04-14

    We study correlations between the solid-liquid interface (SLI) free energy and bulk material properties (melting temperature, latent heat, and liquid structure) through the determination of SLI free energies for bcc and hcp metals from molecular dynamics (MD) simulation. Values obtained for the bcc metals in this study were compared to values predicted by the Turnbull, Laird, and Ewing relations on the basis of previously published MD simulation data. We found that of these three empirical relations, the Ewing relation better describes the MD simulation data. Moreover, whereas the original Ewing relation contains two constants for a particular crystal structure, we found that the first coefficient in the Ewing relation does not depend on crystal structure, taking a common value for all three phases, at least for the class of the systems described by embedded-atom method potentials (which are considered to provide a reasonable approximation for metals).

  3. Superconductivity in transition metals.

    Science.gov (United States)

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

    2015-03-13

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

  4. Heats of Segregation of BCC Metals Using Ab Initio and Quantum Approximate Methods

    Science.gov (United States)

    Good, Brian; Chaka, Anne; Bozzolo, Guillermo

    2003-01-01

    Many multicomponent alloys exhibit surface segregation, in which the composition at or near a surface may be substantially different from that of the bulk. A number of phenomenological explanations for this tendency have been suggested, involving, among other things, differences among the components' surface energies, molar volumes, and heats of solution. From a theoretical standpoint, the complexity of the problem has precluded a simple, unified explanation, thus preventing the development of computational tools that would enable the identification of the driving mechanisms for segregation. In that context, we investigate the problem of surface segregation in a variety of bcc metal alloys by computing dilute-limit heats of segregation using both the quantum-approximate energy method of Bozzolo, Ferrante and Smith (BFS), and all-electron density functional theory. In addition, the composition dependence of the heats of segregation is investigated using a BFS-based Monte Carlo procedure, and, for selected cases of interest, density functional calculations. Results are discussed in the context of a simple picture that describes segregation behavior as the result of a competition between size mismatch and alloying effects

  5. The Snoek relaxation in bcc metals-From steel wire to meteorites

    Energy Technology Data Exchange (ETDEWEB)

    Weller, M. [Max-Planck-Institut fuer Metallforschung, Heisenbergstr. 3, D-70569 Stuttgart (Germany)]. E-mail: weller@mf.mpg.de

    2006-12-20

    Heavy interstitial atoms, such as O, N, or C, when dissolved in bcc metals (Fe, Nb, Ta, V), induce elastic dipoles with tetragonal symmetry. The stress induced reorientation produces anelastic relaxation and is the elementary step of interstitial diffusion. Mechanical loss spectra indicate the presence of interstitial atoms by Snoek peaks at distinct, characteristic temperatures. The magnitude of the peaks is proportional to the concentration of interstitial atoms in solution. The atomic model and theory of the Snoek relaxation for ideal interstitial solutions are presented. Experiments with single crystals allow determination of the tensor components of the dipoles. Measurements of the peak position over a wide range of frequencies (6 decades) allow determination of the interstitial diffusion coefficient as a function of temperature. Nonlinearitities in the Arrhenius plots are discussed. In concentrated alloys a broadening of the Snoek peaks is observed, which can be described by a random cooperative strain interaction (RCSI) model. Measurements of the Snoek peak height can be applied as a non-destructive analytical method. This is demonstrated for O-doped Nb wires with a wide range of concentrations (20 up to 10,000 at. ppm O) and for Ta and Nb single crystals doped with O and N. Finally various experimental studies of the carbon Snoek peak in iron are presented. These include measurements of a low carbon steel wire, a Fe-Ni meteorite, and a recently (April 2002) fallen meteorite named Neuschwanstein.

  6. Beyond chemical accuracy: The pseudopotential approximation in diffusion Monte Carlo calculations of the HCP to BCC phase transition in beryllium

    CERN Document Server

    Shulenburger, Luke; Desjarlais, M P

    2015-01-01

    Motivated by the disagreement between recent diffusion Monte Carlo calculations and experiments on the phase transition pressure between the ambient and beta-Sn phases of silicon, we present a study of the HCP to BCC phase transition in beryllium. This lighter element provides an oppor- tunity for directly testing many of the approximations required for calculations on silicon and may suggest a path towards increasing the practical accuracy of diffusion Monte Carlo calculations of solids in general. We demonstrate that the single largest approximation in these calculations is the pseudopotential approximation. After removing this we find excellent agreement with experiment for the ambient HCP phase and results similar to careful calculations using density functional theory for the phase transition pressure.

  7. Structural transition metal chemistry

    CERN Document Server

    Anderson, K M

    2002-01-01

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

  8. Transition metals in carbohydrate chemistry

    DEFF Research Database (Denmark)

    Madsen, Robert

    1997-01-01

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

  9. An ordered bcc CuPd nanoalloy synthesised via the thermal decomposition of Pd nanoparticles covered with a metal-organic framework under hydrogen gas.

    Science.gov (United States)

    Li, Guangqin; Kobayashi, Hirokazu; Kusada, Kohei; Taylor, Jared M; Kubota, Yoshiki; Kato, Kenichi; Takata, Masaki; Yamamoto, Tomokazu; Matsumura, Syo; Kitagawa, Hiroshi

    2014-11-18

    Presented here is the synthesis of an ordered bcc copper-palladium nanoalloy, via the decomposition of a Pd nanoparticle@metal-organic framework composite material. In situ XRD measurements were performed in order to understand the mechanism of the decomposition process. This result gives a further perspective into the synthesis of new nanomaterials via metal-organic framework decomposition.

  10. Transition Metal Compounds Towards Holography

    Directory of Open Access Journals (Sweden)

    Volker Dieckmann

    2012-06-01

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

  11. Shear moduli in bcc-fcc structure transition of colloidal crystals.

    Science.gov (United States)

    Zhou, Hongwei; Xu, Shenghua; Sun, Zhiwei; Zhu, Ruzeng

    2015-10-14

    Shear moduli variation in the metastable-stable structure transition of charged colloidal crystals was investigated by the combination techniques of torsional resonance spectroscopy and reflection spectrometer. Modulus of the system increases with the proceeding of the transition process and it finally reaches the maximum value at the end of the transition. For colloidal crystals in stable state, the experimental moduli show good consistence with theoretical expectations. However, in the transition process, the moduli are much smaller than theoretical ones and this can be chalked up to crystalline imperfection in the transition state.

  12. Shear moduli in bcc-fcc structure transition of colloidal crystals

    Science.gov (United States)

    Zhou, Hongwei; Xu, Shenghua; Sun, Zhiwei; Zhu, Ruzeng

    2015-10-01

    Shear moduli variation in the metastable-stable structure transition of charged colloidal crystals was investigated by the combination techniques of torsional resonance spectroscopy and reflection spectrometer. Modulus of the system increases with the proceeding of the transition process and it finally reaches the maximum value at the end of the transition. For colloidal crystals in stable state, the experimental moduli show good consistence with theoretical expectations. However, in the transition process, the moduli are much smaller than theoretical ones and this can be chalked up to crystalline imperfection in the transition state.

  13. Electrical Conductivity in Transition Metals

    Science.gov (United States)

    Talbot, Christopher; Vickneson, Kishanda

    2013-01-01

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

  14. Formation of Superlattices of Gold Nanoparticles Using Ostwald Ripening in Emulsions: Transition from fcc to bcc Structure.

    Science.gov (United States)

    Schmitt, Julien; Hajiw, Stéphanie; Lecchi, Amélie; Degrouard, Jéril; Salonen, Anniina; Impéror-Clerc, Marianne; Pansu, Brigitte

    2016-06-30

    An efficient method to form 3D superlattices of gold nanoparticles inside oil emulsion droplets is presented. We demonstrate that this method relies on Ostwald ripening, a well-known phenomenon occurring during the aging of emulsions. The key point is that the nanoparticle concentration inside the smaller droplets is increasing very slowly with time, thus inducing the crystallization of the nanoparticles into superlattices. Using oil-in-water emulsions doped with hydrophobic gold nanoparticles, we demonstrate that this method is efficient for different types of oils (toluene, cyclohexane, dodecane, and hexadecane). 3D superlattices of the nanoparticles are obtained, with dimensions reaching a hundred nanometers. The kinetics of the crystallization depends on the solubility of the oil in water but also on the initial concentration of the gold nanoparticles in oil. This method also provides an innovative way to obtain the complete phase diagram of nanoparticle suspensions with concentration. Indeed, during this slow crystallization process, a transition from a disordered suspension to a fcc structure is observed, followed by a transition toward a bcc structure. This evolution with time provides key results to understand the role played by the ligands located at the surface of the nanoparticles in order to control the type of superlattices which are formed.

  15. Quantum-based Atomistic Simulation of Transition Metals

    Energy Technology Data Exchange (ETDEWEB)

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

    2005-08-29

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

  16. Interface magnetism of 3d transition metals

    DEFF Research Database (Denmark)

    Niklasson, A. M. N.; Johansson, B.; Skriver, Hans Lomholt

    1999-01-01

    The layered resolved magnetic spin moments of the magnetic 3d bilayer interfaces Fe/V bcc, Fe/Co bcc, Fe/Cu bcc, Co/V bcc, Co/Ni fee, Co/Cu fee, Ni/V fee, Ni/Cr fcc, Ni/Cu fee and the magnetic surfaces Fe bcc, Co bcc, Co fee, and Ni fee are calculated for the (001), (011), and (111) orientations...

  17. Photochemistry of Transition Metal Hydrides.

    Science.gov (United States)

    Perutz, Robin N; Procacci, Barbara

    2016-08-10

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

  18. Microstructural Characterization of Dislocation Networks During Harper-Dorn Creep of fcc, bcc, and hcp Metals and Alloys

    Energy Technology Data Exchange (ETDEWEB)

    Przystupa, Marek A.

    2007-12-13

    Harper-Dorn (H-D) creep is observed in metals and geological materials exposed to very low stresses at temperatures close to the melting point. It is one of several types of creep processes wherein the steady-state strain rate is proportional to the applied stress, Nabarro-Herring creep and Coble creep being two other important processes. H-D creep can be somewhat insidious because the creep rates are much larger than those expected for Nabarro-Herring or Coble creep. Since the working conditions of structural components of power plants and propulsion systems, as well as the motion of the earth’s mantle all involve very low stresses, an understanding of the factors controlling H-D creep is critical in preventing failures associated with those higher-than-expected creep rates. The purpose of this investigation was to obtain missing microstructural information on the evolution of the dislocation structures during static annealing of materials with fcc, bcc and hcp structure and use obtained results to test predictive capabilities of the dislocation network theory of H-D creep. In our view the evolutionary processes during static annealing and during Harper-Dorn creep are intimately related. The materials used in this study were fcc aluminum, hcp zinc and bcc tin. All characterizations of dislocation structures, densities and dislocation link length distributions were carried out using the etch pit method. To obtain quantitative information on the evolution of the dislocation networks during annealing the pure fcc aluminum samples were pre-deformed by creep at 913 and 620 K and then annealed. The higher deformation temperature was selected to generate starting dislocation networks similar to those forming during Harper-Dorn creep and the lower, to obtain higher dislocation densities suitable for reliable estimates of the parameters of the network growth law. The measured experimental link length distribution were, after scaling, (1) the same for all annealing

  19. Atomic displacements in bcc dilute alloys

    Indian Academy of Sciences (India)

    Hitesh Sharma; S Prakash

    2007-04-01

    We present here a systematic investigation of the atomic displacements in bcc transition metal (TM) dilute alloys. We have calculated the atomic displacements in bcc (V, Cr, Fe, Nb, Mo, Ta and W) transition metals (TMs) due to 3d, 4d and 5d TMs at the substitutional site using the Kanzaki lattice static method. Wills and Harrison interatomic potential is used to calculate the atomic force constants, the dynamical matrix and the impurity-induced forces. We have thoroughly investigated the atomic displacements using impurities from 3d, 4d and 5d series in the same host metal and the same impurity in different hosts. We have observed a systematic pattern in the atomic displacements for Cr-, Fe-, Nb-, Mo-, Ta- and W-based dilute alloys. The atomic displacements are found to increase with increase in the number of d electrons for all alloys considered except for V dilute alloys. The 3d impurities are found to be more easily dissolved in the 3d host metals than 4d or 5d TMs whereas 4d and 5d impurities show more solubility in 4d and 5d TMs. In general, the relaxation energy calculation suggests that impurities may be easily solvable in 5d TM hosts when compared to 3d or 4d TMs.

  20. Simulation of the diffusion features of point defects in bcc metals

    NARCIS (Netherlands)

    Chirkov, AS; Nazarov, AV; Bokstein, BS; Straumal, BB

    2006-01-01

    This work is devoted to simulation of the diffusion features of point defects in bee metals. The properties of point defects have been investigated with the usage of many-body interatomic potentials. This approach, based on the density-functional theory, permitted us to derive more adequate diffusio

  1. Density functional theory studies of screw dislocation core structures in bcc metals

    DEFF Research Database (Denmark)

    Frederiksen, Søren Lund; Jacobsen, Karsten Wedel

    2003-01-01

    The core structures of (I 11) screw dislocations in bee metals are studied using density functional theory in the local-density approximation. For Mo and Fe, direct calculations of the core structures show the cores to be symmetric with respect to 180degrees rotations around an axis perpendicular...

  2. A composite dislocation cell model to describe strain path change effects in BCC metals

    NARCIS (Netherlands)

    Yalcinkaya, T.; Brekelmans, W.A.M.; Geers, M.G.D.

    2009-01-01

    Sheet metal forming processes are within the core of many modern manufacturing technologies, as applied in, e.g., automotive and packaging industries. Initially flat sheet material is forced to transform plastically into a three-dimensional shape through complex loading modes. Deviation from a propo

  3. Metal-to-nonmetal transitions

    CERN Document Server

    Hensel, Friedrich; Holst, Bastian

    2010-01-01

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

  4. Modified analytical embedded-atom method simulation of the mono-vacancy at three low-index surfaces of BCC transition metals%体心立方过渡金属低指数表面单空位的改进分析型嵌入原子法模拟

    Institute of Scientific and Technical Information of China (English)

    文艳妮; 张建民

    2007-01-01

    应用改进分析型嵌入原子法(modified analytical embedded-atom method,MAEAM),计算了7种体心立方(body-centered cubic,BCC)过渡金属Fe、W、Mo、Cr、Ta、Nb和V等低指数(100)、(110)和(111)表面前9层上的单空位形成能.结果表明,对每一种金属,单空位形成能在同一低指数表面层中的第1层最低,且在表面第1层和第2层(Nb除外)随表面原子密度的减小而降低,即E(111),11f<E(100),11f<E(110),11f,E(111),21f<E(100),21f<E(110),21f.这说明BCC过渡金属表面第1层比其他层更容易形成空位,尤其在(111)表面.

  5. Microstructural Characterization of Dislocation Networks During Harper-Dorn Creep of fcc, bcc, and hcp Metals and Alloys

    Energy Technology Data Exchange (ETDEWEB)

    Przystupa, Marek A.

    2007-12-13

    Harper-Dorn (H-D) creep is observed in metals and geological materials exposed to very low stresses at temperatures close to the melting point. It is one of several types of creep processes wherein the steady-state strain rate is proportional to the applied stress, Nabarro-Herring creep and Coble creep being two other important processes. H-D creep can be somewhat insidious because the creep rates are much larger than those expected for Nabarro-Herring or Coble creep. Since the working conditions of structural components of power plants and propulsion systems, as well as the motion of the earth’s mantle all involve very low stresses, an understanding of the factors controlling H-D creep is critical in preventing failures associated with those higher-than-expected creep rates. The purpose of this investigation was to obtain missing microstructural information on the evolution of the dislocation structures during static annealing of materials with fcc, bcc and hcp structure and use obtained results to test predictive capabilities of the dislocation network theory of H-D creep. In our view the evolutionary processes during static annealing and during Harper-Dorn creep are intimately related. The materials used in this study were fcc aluminum, hcp zinc and bcc tin. All characterizations of dislocation structures, densities and dislocation link length distributions were carried out using the etch pit method. To obtain quantitative information on the evolution of the dislocation networks during annealing the pure fcc aluminum samples were pre-deformed by creep at 913 and 620 K and then annealed. The higher deformation temperature was selected to generate starting dislocation networks similar to those forming during Harper-Dorn creep and the lower, to obtain higher dislocation densities suitable for reliable estimates of the parameters of the network growth law. The measured experimental link length distribution were, after scaling, (1) the same for all annealing

  6. The formation energy for steps and kinks on cubic transition metal surfaces

    DEFF Research Database (Denmark)

    Vitos, Levente; Skriver, Hans Lomholt; Kollàr, Janos

    1999-01-01

    We have used our first-principles database of surface energies for metals in conjunction with the concept of vicinal surfaces to derive the energies of formation of monoatomic steps and corresponding kinks on close-packed surface facets of bcc and fee transition metals. The entries in the database...... allow for a direct calculation of the energies of a number of important steps. For the remaining steps and for all the kinks the energies of formation have been estimated from pair potential expansions of the entries in the database. (C) 1999 Elsevier Science B.V. All rights reserved....

  7. Heterostructures of transition metal dichalcogenides

    KAUST Repository

    Amin, Bin

    2015-08-24

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

  8. ALLOYING-DRIVEN PHASE STABILITY IN GROUP-VB TRANSITION METALS UNDER COMPRESSION

    Energy Technology Data Exchange (ETDEWEB)

    Landa, A; Soderlind, P

    2011-04-11

    The change in phase stability of Group-VB (V, Nb, and Ta) transition metals due to pressure and alloying is explored by means of first-principles electronic-structure calculations. It is shown that under compression stabilization or destabilization of the ground-state body-centered cubic (bcc) phase of the metal is mainly dictated by the band-structure energy that correlates well with the position of the Kohn anomaly in the transverse acoustic phonon mode. The predicted position of the Kohn anomaly in V, Nb, and Ta is found to be in a good agreement with data from the inelastic x-ray or neutron scattering measurements. In the case of alloying the change in phase stability is defined by the interplay between the band-structure and Madelung energies. We show that band-structure effects determine phase stability when a particular Group-VB metal is alloyed with its nearest neighbors within the same d-transition series: the neighbor with less and more d electrons destabilize and stabilize the bcc phase, respectively. When V is alloyed with neighbors of a higher (4d- or 5d-) transition series, both electrostatic Madelung and band-structure energies stabilize the body-centered-cubic phase. The opposite effect (destabilization) happens when Nb or Ta is alloyed with neighbors of the 3d-transition series.

  9. Molecular precursor routes to transition metal sulfides

    Science.gov (United States)

    Dinnage, Christopher Walker

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

  10. Adsorbate Diffusion on Transition Metal Nanoparticles

    Science.gov (United States)

    2015-01-01

    catalysis . KEYWORDS: Heterogeneous catalysis , diffusion, edge barrier, transition metal nanoparticles, DFT calculations 2 Diffusion of adsorbed...species on transition metal surfaces is an important process for thin-film and nanostructure growth and for heterogeneous catalysis , among others.1-4 In...process for heterogeneously catalyzed reactions, and as a result, an atomistic understanding of the diffusion mechanism is very important. We

  11. Non-linear modelling of the effects of strain on transition metal surfaces

    Science.gov (United States)

    Shuttleworth, I. G.

    2016-12-01

    A sequence of polynomial expressions have been shown to describe the strained surface energy of low-index hexagonal and square transition metal surfaces. Distinguishable functions describe the hexagonal FCC (1 1 1) and HCP (0 0 0 1) surfaces, but a single function describes the FCC (1 0 0) and BCC (1 0 0) surfaces. A far weaker dependence exists between the strained surface energy and the electronic state of the surface, and the competition between geometric and electronic states across is discussed.

  12. Spinning around in Transition-Metal Chemistry

    OpenAIRE

    Swart, Marcel; Gruden-Pavlović, Maja

    2016-01-01

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

  13. Structure analysis of Ni thin films epitaxially grown on bcc metal underlayers formed on MgO(100 substrates

    Directory of Open Access Journals (Sweden)

    Futamoto Masaaki

    2013-01-01

    Full Text Available Ni thin films are prepared on Cr, V, and Nb underlayers with bcc structure formed on MgO(100 single-crystal substrates by molecular beam epitaxy. The growth behavior and the crystallographic properties are investigated by in-situ reflection high-energy electron diffraction and pole-figure X-ray diffraction. Cr(100 and V(100 single-crystal underlayers grow epitaxially on the substrates, whereas an Nb epitaxial_underlayer consisting of two bcc(110 variants is formed on the MgO(100 substrate. Metastable crystals nucleate on the Cr and the V underlayers, where the metastable hcp structure is stabilized through heteroepitaxial growth. With increasing the film thickness, the hcp structure starts to transform into more stable fcc structure by atomic displacement parallel to the hcp(0001 close-packed plane. The resulting films are consisting of mixtures of hcp and fcc crystals. On the other hand, only the formation of fcc crystal is recognized for the Ni film grown on Nb(110 underlayer.

  14. Layer texture of hot-rolled BCC metals and its significance for stress-corrosion cracking of main gas pipelines

    Science.gov (United States)

    Perlovich, Yu. A.; Isaenkova, M. G.; Krymskaya, O. A.; Morozov, N. S.

    2016-10-01

    Based on data of X-ray texture analysis of hot-rolled BCC materials it was shown that the layerwise texture inhomogeneity of products is formed during their manufacturing. The effect can be explained by saturation with interstitial impurities of the surface layer, resulting in dynamical deformation aging (DDA). DDA prevents the dislocation slip under rolling and leads to an increase of lattice parameters in the external layer. The degree of arising inhomogeneity correlates with the tendency of hot-rolled sheets and obtained therefrom tubes to stress-corrosion cracking under exploitation, since internal layers have a compressive effect on external layers, and prevents opening of corrosion cracks at the tube surface.

  15. Phase transition from fcc to bcc structure of the Cu-clusters during nanocrystallization of Fe{sub 85.2}Si{sub 1}B{sub 9}P{sub 4}Cu{sub 0.8} soft magnetic alloy

    Energy Technology Data Exchange (ETDEWEB)

    Nishijima, Masahiko; Matsuura, Makoto; Takenaka, Kana; Takeuchi, Akira; Makino, Akihiro [Research and Development Center for Ultra High Efficiency Nano-crystalline Soft Magnetic Material, Institute for Materials Research, Tohoku University, Sendai, Miyagi, 980 (Japan); Ofuchi, Hironori [Industrial Application Division, Japan Synchrotron Radiation Research Institute (JASRI) Kouto, Sayo, Hyogo 679-5198 (Japan)

    2014-05-15

    A role of Cu on the nanocrystallization of an Fe{sub 85.2}Si{sub 1}B{sub 9}P{sub 4}Cu{sub 0.8} alloy was investigated by X-ray absorption fine structure (XAFS) and transmission electron microscopy (TEM). The Cu K-edge XAFS results show that local structure around Cu is disordered for the as-quenched sample whereas it changes to fcc-like structure at 613 K. The fcc Cu-clusters are, however, thermodynamically unstable and begin to transform into bcc structure at 638 K. An explicit bcc structure is observed for the sample annealed at 693 K for 600 s in which TEM observation shows that precipitated bcc-Fe crystallites with ∼12 nm are homogeneously distributed. The bcc structure of the Cu-clusters transforms into the fcc-type again at 973 K, which can be explained by the TEM observations; Cu segregates at grain boundaries between bcc-Fe crystallites and Fe{sub 3}(B,P) compounds. Combining the XAFS results with the TEM observations, the structure transition of the Cu-clusters from fcc to bcc is highly correlated with the preliminary precipitation of the bcc-Fe which takes place prior to the onset of the first crystallization temperature, T{sub x1} = 707 K. Thermodynamic analysis suggests that an interfacial energy density γ between an fcc-Cu cluster and bcc-Fe matrix dominates at a certain case over the structural energy between fcc and bcc Cu, ΔG{sub fcc} {sub −} {sub bcc}, which causes phase transition of the Cu clusters from fcc to bcc structure.

  16. Plasmons in metallic monolayer and bilayer transition metal dichalcogenides

    DEFF Research Database (Denmark)

    Andersen, Kirsten; Thygesen, Kristian S.

    2013-01-01

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

  17. Transition metal catalysis in confined spaces.

    Science.gov (United States)

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

    2015-01-21

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

  18. Transition metal contacts to graphene

    Energy Technology Data Exchange (ETDEWEB)

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

    2015-10-12

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

  19. Microwave-assisted synthesis of transition metal phosphide

    Science.gov (United States)

    Viswanathan, Tito

    2014-12-30

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

  20. On hyper BCC-algebras

    Directory of Open Access Journals (Sweden)

    R. A. Borzooei

    2006-01-01

    Full Text Available We study hyper BCC-algebras which are a common generalization of BCC-algebras and hyper BCK-algebras. In particular, we investigate different types of hyper BCC-ideals and describe the relationship among them. Next, we calculate all nonisomorphic 22 hyper BCC-algebras of order 3 of which only three are not hyper BCK-algebras.

  1. On hyper BCC-algebras

    OpenAIRE

    Borzooei, R. A.; Dudek, W. A.; Koohestani, N.

    2006-01-01

    We study hyper BCC-algebras which are a common generalization of BCC-algebras and hyper BCK-algebras. In particular, we investigate different types of hyper BCC-ideals and describe the relationship among them. Next, we calculate all nonisomorphic 22 hyper BCC-algebras of order 3 of which only three are not hyper BCK-algebras.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2003-11-18

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

  3. Alkane Soluble Transition Metal Complexes.

    Science.gov (United States)

    1983-10-01

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

  4. Transition metal-catalyzed functionalization of pyrazines

    NARCIS (Netherlands)

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

    2013-01-01

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

  5. Fluid metals the liquid-vapor transition of metals

    CERN Document Server

    Hensel, Friedrich

    2014-01-01

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

  6. Mesoporous Transition Metal Oxides for Supercapacitors

    Science.gov (United States)

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

    2015-01-01

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

  7. Mesoporous Transition Metal Oxides for Supercapacitors

    Directory of Open Access Journals (Sweden)

    Yan Wang

    2015-10-01

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

  8. Transition metal based borohydrides for hydrogen storage

    Science.gov (United States)

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

    2010-03-01

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

  9. First principles study on the charge density and the bulk modulus of the transition metals and their carbides and nitrides

    Institute of Scientific and Technical Information of China (English)

    Li Cheng-Bin; Li Ming-Kai; Yin Dong; Liu Fu-Qing; Fan Xiang-Jun

    2005-01-01

    A first principles study of the electronic properties and bulk modulus (B0) of the fcc and bcc transition metals,transition metal carbides and nitrides is presented. The calculations were performed by plane-wave pseudopotential method in the framework of the density functional theory with local density approximation. The density of states and the valence charge densities of these solids are plotted. The results show that B0 does not vary monotonically when the number of the valence d electrons increases. B0 reaches a maximum and then decreases for each of the four sorts of solids. It is related to the occupation of the bonding and anti-bonding states in the solid. The value of the valence charge density at the midpoint between the two nearest metal atoms tends to be proportional to B0.

  10. Spin doping using transition metal phthalocyanine molecules

    Science.gov (United States)

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

    2016-12-01

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

  11. Insulator to Metal Transition in Fluid Hydrogen

    Energy Technology Data Exchange (ETDEWEB)

    Hood, R Q; Galli, G

    2003-06-15

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

  12. Bulk Properties of Transition Metals: A Challenge for the Design of Universal Density Functionals.

    Science.gov (United States)

    Janthon, Patanachai; Luo, Sijie Andy; Kozlov, Sergey M; Viñes, Francesc; Limtrakul, Jumras; Truhlar, Donald G; Illas, Francesc

    2014-09-09

    Systematic evaluation of the accuracy of exchange-correlation functionals is essential to guide scientists in their choice of an optimal method for a given problem when using density functional theory. In this work, accuracy of one Generalized Gradient Approximation (GGA) functional, three meta-GGA functionals, one Nonseparable Gradient Approximation (NGA) functional, one meta-NGA, and three hybrid GGA functionals was evaluated for calculations of the closest interatomic distances, cohesive energies, and bulk moduli of all 3d, 4d, and 5d bulk transition metals that have face centered cubic (fcc), hexagonal closed packed (hcp), or body centered cubic (bcc) structures (a total of 27 cases). Our results show that including the extra elements of kinetic energy density and Hartree-Fock exchange energy density into gradient approximation density functionals does not usually improve them. Nevertheless, the accuracies of the Tao-Perdew-Staroverov-Scuseria (TPSS) and M06-L meta-GGAs and the MN12-L meta-NGA approach the accuracy of the Perdew-Burke-Ernzerhof (PBE) GGA, so usage of these functionals may be advisable for systems containing both solid-state transition metals and molecular species. The N12 NGA functional is also shown to be almost as accurate as PBE for bulk transition metals, and thus it could be a good choice for studies of catalysis given its proven good performance for molecular species.

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

    Energy Technology Data Exchange (ETDEWEB)

    1992-01-01

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

  14. Lattice Location of Transition Metals in Semiconductors

    CERN Multimedia

    2002-01-01

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

  15. Magnetic Ground State Properties of Transition Metals

    DEFF Research Database (Denmark)

    Andersen, O. K.; Madsen, J.; Poulsen, U. K.;

    1977-01-01

    approximations, be reduced to the Stoner model. Results for the volume dependence of the ferromagnetic moment and the electronic pressure of bcc, fcc and hcp Fe are presented, together with theoretical values for the equilibrium atomic volume, the bulk modulus, the ferromagnetic moment, the spin susceptibility...

  16. Thermodynamic Hydricity of Transition Metal Hydrides.

    Science.gov (United States)

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

    2016-08-10

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

  17. Defect-Tolerant Monolayer Transition Metal Dichalcogenides

    DEFF Research Database (Denmark)

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

    2016-01-01

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

  18. Electronic structure of hcp transition metals

    DEFF Research Database (Denmark)

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

    1975-01-01

    Using the linear muffin-tin-orbital method described in the previous paper, we have calculated the electronic structures of the hcp transition metals, Zr, Hf, Ru, and Os. We show how the band structures of these metals may be synthesized from the sp and d bands, and illustrate the effects...... of hybridization, relativistic band shifts, and spin-orbit coupling by the example of Os. By making use of parameters derived from the muffin-tin potential, we discuss trends in the positions and widths of the energy bands, especially the d bands, as a function of the location in the periodic table. The densities...... of states of the four metals are presented, and the calculated heat capacities compared with experiment. The Fermi surfaces of both Ru and Os are found to be in excellent quantitative agreement with de Haas-van Alphen measurements, indicating that the calculated d-band position is misplaced by less than 10...

  19. Spinning around in Transition-Metal Chemistry.

    Science.gov (United States)

    Swart, Marcel; Gruden, Maja

    2016-12-20

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

  20. Smarandache hyper BCC-algebra

    OpenAIRE

    A. Ahadpanah; Borumand Saeid, A.

    2011-01-01

    In this paper, we define the Smarandache hyper BCC-algebra, and Smarandache hyper BCC-ideals of type 1, 2, 3 and 4. We state and prove some theorems in Smarandache hyper BCC -algebras, and then we determine the relationships between these hyper ideals.

  1. Laser materials based on transition metal ions

    Science.gov (United States)

    Moncorgé, Richard

    2017-01-01

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

  2. Electrical conduction in transition-metal salts

    Energy Technology Data Exchange (ETDEWEB)

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

    2016-08-01

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

  3. Catabolism of hyaluronan: involvement of transition metals

    OpenAIRE

    Šoltés, Ladislav; Kogan, Grigorij

    2009-01-01

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

  4. Crystal-Structure Contribution to the Solid Solubility in Transition Metal Alloys

    DEFF Research Database (Denmark)

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

    1998-01-01

    The solution energies of 4d metals in other 4d metals as well as the bcc-hcp structural energy differences in random 4d alloys are calculated by density functional theory. It is shown that the crystal structure of the host plays a crucial role in the solid solubility. A local virtual bond...

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

    Energy Technology Data Exchange (ETDEWEB)

    Richard T. Scalettar; Warren E. Pickett

    2005-08-02

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

  6. Methyl Complexes of the Transition Metals.

    Science.gov (United States)

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

    2016-05-01

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

  7. Tunable magnetocaloric effect in transition metal alloys.

    Science.gov (United States)

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

    2015-10-28

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

  8. Tunable magnetocaloric effect in transition metal alloys

    Science.gov (United States)

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

    2015-10-01

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

  9. Coordination chemistry of 1,4-bis-carboxymethylcyclam, H(2)(1,4-bcc).

    Science.gov (United States)

    Tonei, Deborah M; Ware, David C; Brothers, Penelope J; Plieger, Paul G; Clark, George R

    2006-01-07

    Zinc metal reduction of the cobalt(III) complex [Co(1,4-bcc)](+) (1,4-bcc = 1,4-bis-carboxymethylcyclam) produces the corresponding cobalt(II) complex which crystallises as the coordination polymer {[Co(1,4-bcc)]ZnCl(2)}(n). A method has been developed for removal of the cobalt(III) ion from [Co(1,4-bcc)](+) and isolation of the free ligand as its hydrochloride salt, H(2)(1,4-bcc).4HCl. This has been used for the preparation of new metal complexes, and the syntheses and characterisation of the copper(ii), nickel(ii), zinc(ii) and chromium(iii) complexes containing the 1,4-bcc ligand are described. X-Ray crystal structures of {[Co(1,4-bcc)]ZnCl(2)}(n).2.5H(2)O, {[Cu(1,4-bcc)]CuCl(2)}(n).0.25MeOH.H(2)O and [Cu(1,4-bcc)H]ClO(4) show the complexes to have the trans(O) geometry of the 1,4-bcc ligand, while the structure of [Cr(1,4-bcc)H(0.5)](ClO(4))(1.5).EtOH exhibits the cis(O) configuration.

  10. Electronic entanglement in late transition metal oxides.

    Science.gov (United States)

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

    2012-11-01

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

  11. Trends in Ionization Energy of Transition-Metal Elements

    Science.gov (United States)

    Matsumoto, Paul S.

    2005-01-01

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

  12. Nanostructured transition metal oxides useful for water oxidation catalysis

    Science.gov (United States)

    Frei, Heinz M; Jiao, Feng

    2013-12-24

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

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

    Science.gov (United States)

    Hood, M Indriati; Skaar, Eric P

    2012-07-16

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

  14. Critical behavior in the hydrogen insulator-metal transition

    Science.gov (United States)

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

    1990-01-01

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

  15. Heats of Segregation of BCC Binaries from ab Initio and Quantum Approximate Calculations

    Science.gov (United States)

    Good, Brian S.

    2004-01-01

    We compare dilute-limit heats of segregation for selected BCC transition metal binaries computed using ab initio and quantum approximate energy methods. Ab initio calculations are carried out using the CASTEP plane-wave pseudopotential computer code, while quantum approximate results are computed using the Bozzolo-Ferrante-Smith (BFS) method with the most recent LMTO-based parameters. Quantum approximate segregation energies are computed with and without atomistic relaxation, while the ab initio calculations are performed without relaxation. Results are discussed within the context of a segregation model driven by strain and bond-breaking effects. We compare our results with full-potential quantum calculations and with available experimental results.

  16. Properties of Transition Metal Doped Alumina

    Science.gov (United States)

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

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

  17. Transition metal-free olefin polymerization catalyst

    Science.gov (United States)

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

    2001-01-01

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

  18. Energetic characteristics of transition metal complexes.

    Science.gov (United States)

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

    2009-11-15

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

  19. 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.

  20. Transition-Metal Hydride Radical Cations.

    Science.gov (United States)

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

    2016-08-10

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

  1. Solid-solid phase transitions via melting in metals

    Science.gov (United States)

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

    2016-04-01

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

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2010-03-03

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

  3. Effect of the coupling between electronic structure and crystalline structure on some properties of transition metals; Couplage entre structure electronique et structure cristalline: effet sur quelques proprietes des metaux de transition

    Energy Technology Data Exchange (ETDEWEB)

    Nastar, M.

    1994-10-14

    The elastic constants, energetic stabilities and vacancy formation energies in transition metals are calculated within a Tight Binding model. In order to outline the effect of the electronic structure, these properties are represented as functions of band filling. The variation of the shear elastic constants of hexagonal close packed (HCP), body centered cubic (BCC) and face centered cubic (FCC) structures, is in contrast with the roughly parabolic behavior of bulk modulus. The general trends are in very good agreement with available experimental and `ab initio` data. The vacancy formation energy in the BCC structure shows strong deviations from bell shape behavior with a maximum corresponding approximately to the band filling of group 6. This band filling effect contributes to the noticeable decrease of the self diffusion rate between group 4 and group 6. We demonstrate that the abrupt increase of the C` elastic constant, the NT{sub 1} (0.-1.1) phonon frequency, the energy differences between BCC and HCP and between FCC and HCP as well as the vacancy formation energy, that occurs when going from Zr to Mo, is related to the presence of a pseudo-gap in the density of states of the BCC structure. Using the recursion method, we show that the general trends of these properties are correctly reproduced when considering only a few moments of the density of states (about 6). On the other hand, details such as the elastic constant singularities, are displayed only with an exact calculation of the density of states. (Author). 173 refs., 84 figs., 5 tabs.

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

    KAUST Repository

    Takanabe, Kazuhiro

    2015-03-05

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

  5. The metallicities of stars with and without transiting planets

    DEFF Research Database (Denmark)

    Buchhave, Lars A.; Latham, David W.

    2015-01-01

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

  6. Mechanisms of transition-metal gettering in silicon

    Energy Technology Data Exchange (ETDEWEB)

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

    2000-03-23

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

  7. On metal-insulator transition in cubic fullerides

    Science.gov (United States)

    Iwahara, Naoya; Chibotaru, Liviu

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

  8. Trends in catalytic NO decomposition over transition metal surfaces

    DEFF Research Database (Denmark)

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

    2007-01-01

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

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

    Science.gov (United States)

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

    2016-09-01

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

  10. Direct NO decomposition over stepped transition-metal surfaces

    DEFF Research Database (Denmark)

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

    2007-01-01

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

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

    Science.gov (United States)

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

    2015-11-21

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

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

    OpenAIRE

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

    2012-01-01

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

  13. T-fuzzy multiply positive implicative BCC-ideals of BCC-algebras

    OpenAIRE

    Jianming Zhan; Zhisong Tan

    2003-01-01

    The concept of fuzzy multiply positive BCC-ideals of BCC-algebras is introduced, and then some related results are obtained. Moreover, we introduce the concept of T-fuzzy multiply positive implicative BCC-ideals of BCC-algebras and investigate T-product of T-fuzzy multiply positive implicative BCC-ideals of BCC-algebras, examining its properties. Using a t-norm T, the direct product and T-product of T-fuzzy multiply positive implicative BCC-ideals of BCC-algebras are discussed and their...

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

    Science.gov (United States)

    1987-05-01

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

  15. Metal-Insulator Transition in C60-Polymers

    CERN Document Server

    Harigaya, K

    1995-01-01

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

  16. Maximum solid solubility of transition metals in vanadium solvent

    Institute of Scientific and Technical Information of China (English)

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

    2005-01-01

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

  17. High-resolution structural studies of ultra-thin magnetic, transition metal overlayers and two-dimensional transition metal oxides using synchrotron radiation

    Energy Technology Data Exchange (ETDEWEB)

    Kellar, S.A. [Univ. of California, Berkeley, CA (United States). Dept. of Chemistry]|[Lawrence Berkeley National Lab., CA (United States). Advanced Light Source Div.

    1997-05-01

    This thesis report the surface-structure determination of three, ultra-thin magnetic transition-metal films, Fe/Au(100), Mn/Ni(100), and Mn/Cu(100) using Angle-Resolved Photoemission Extended Fine Structure (ARPEFS) and photoelectron holography. These structural studies are the first to use non-s initial states in the ARPEFS procedure. This thesis also reports an ARPEFS surface-structure determination of a two-dimensional transition-metal oxide, [(1 x 1)O/W(110)] x 12. The authors have analyzed the ARPFES signal from the Au 4f{sub 7/5} core level of the Au(1 ML)/Fe(15 ML)/Au(100) system. The analysis shows that the Fe grows layer by layer with one monolayer of gold, acting as a surfactant, remaining on top of the growing Fe layers. These surface gold atoms sit in the four-fold hollow site, 1.67 {+-} 0.02 A above the iron surface. The grown Fe layer is very much like the bulk, bcc iron, with an interlayer spacing of 1.43 {+-} 0.03 A. Analysis of the Mn 3p ARPEFS signals from c(2 x 2)Mn/Ni(100) and c(2 x 2)Mn/Cu(100) shows that the Mn forms highly corrugated surface alloys. The corrugation of the Mn/Ni(100) and Mn/Cu(100) systems are 0.24 {+-} 0.02 A and 0.30 {+-} 0.04 A respectively. In both cases the Mn is sticking above the plane of the surface substrate atoms. For the Mn/Ni(100) system the first layer Ni is contracted 4% from the bulk value. The Mn/Cu(100) system shows bulk spacing for the substrate Cu. Photoelectron holography shows that the Mn/Ni interface is very abrupt with very little Mn leaking into the second layer, while the Mn/Cu(100) case has a significant amount of Mn leaking into the second layer. A new, five-element electrostatic electron lens was developed for hemispherical electron-energy analyzers. This lens system can be operated at constant transverse or constants angular magnification, and has been optimized for use with the very small photon-spot sizes. Improvements to the hemispherical electron-energy analyzer are also discussed.

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

    Science.gov (United States)

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

    2012-01-27

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

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

    Science.gov (United States)

    Bullen, Tomas D.; Baskaran, Mark

    2011-01-01

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

  20. Hyperfine interactions on iron nuclei in the BCC and fractally decomposed BCC/FCC mixed phase iron-gold alloys

    Energy Technology Data Exchange (ETDEWEB)

    Blachowski, A. [Moessbauer Spectroscopy Division, Institute of Physics, Pedagogical University, PL-30-084 Krakow, ul. Podchorazych 2 (Poland); Ruebenbauer, K. [Moessbauer Spectroscopy Division, Institute of Physics, Pedagogical University, PL-30-084 Krakow, ul. Podchorazych 2 (Poland)], E-mail: sfrueben@cyf-kr.edu.pl; Przewoznik, J.; Zukrowski, J. [Solid State Physics Department, Faculty of Physics and Applied Computer Science, AGH University of Science and Technology, PL-30-059 Krakow, Al. Mickiewicza 30 (Poland)

    2008-06-30

    Iron-gold alloys for the gold concentration ranging from 1 at.% till 70 at.% were investigated by means of the {sup 57}Fe-14.4 keV Moessbauer spectroscopy, X-ray diffraction and scanning electron microscopy. Samples were prepared by arc melting of the elements, and investigated as cast and after annealing. A single BCC phase is obtained for the gold concentration up to about 3 at.%, while for the higher gold concentration one obtains mixed phase samples containing BCC and FCC phases both. The BCC phase is ferromagnetically ordered at room temperature. Contributions to the charge and spin density on iron atoms in the BCC phase due to the gold impurities were determined up to the second neighbors. The FCC phase is either magnetically ordered at room temperature or it is paramagnetic at the above temperature depending upon iron concentration, as the magnetic transition temperature is increasing with the increasing iron concentration. BCC/FCC mixed phase samples are characterized by very small crystallites (nanoparticles) of both phases. These nanoparticles form hierarchical fractal structures on the scale ranging from more than 1 mm till less than 30 nm.

  1. Elastic phase transitions in metals at high pressures.

    Science.gov (United States)

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

    2012-04-19

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

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

    Science.gov (United States)

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

    2013-03-01

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

  3. On some generalizations of BCC-algebras

    CERN Document Server

    Dudek, Wieslaw A

    2012-01-01

    We describe weak BCC-algebras (also called BZ-algebras) in which the condition $(xy)z=(xz)y$ is satisfied only in the case when elements $x,y$ belong to the same branch. We also characterize branchwise commutative and branchwise implicative weak BCC-algebras satisfying this condition. We also describe connections between various types of implicative weak BCC-algebras.

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

    Institute of Scientific and Technical Information of China (English)

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

    2011-01-01

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

  5. Integrating Transition Metals into Nanomaterials: Strategies and Applications

    KAUST Repository

    Fhayli, Karim

    2016-04-14

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

  6. Volume variation of Gruneisen parameters of fcc transition metals

    Indian Academy of Sciences (India)

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

    2002-02-01

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

  7. Microstructure of N—Picolylpolyurethane Transition Metal Complexes

    Institute of Scientific and Technical Information of China (English)

    Qun-DongShen; Tian-DouHu; 等

    1999-01-01

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

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

    OpenAIRE

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

    2015-01-01

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

  9. Spheroidization behavior of dendritic b.c.c. phase in Zr-based モ-phase composite

    Directory of Open Access Journals (Sweden)

    Sun Guoyuan

    2013-03-01

    Full Text Available The spheroidization behavior of the dendritic b.c.c. phase dispersed in a bulk metallic glass (BMG matrix was investigated through applying semi-solid isothermal processing and a subsequent rapid quenching procedure to a Zr-based モ-phase composite. The Zr-based composite with the composition of Zr56.2Ti13.8Nb5.0Cu6.9Ni5.6Be12.5 was prefabricated by a water-cooled copper mold-casting method and characterized by X-ray diffraction (XRD and scanning electron microscope (SEM. The results show that the composite consists of a glassy matrix and uniformly distributed fine dendrites of the モ-Zr solid solution with the body-centered-cubic (b.c.c. structure. Based on the differential scanning calorimeter (DSC examination results, and in view of the b.c.c. モ-Zr to h.c.p. メ-Zr phase transition temperature, a semi-solid holding temperature of 900 ìC was determined. After reheating the prefabricated composite to the semi-solid temperature, followed by an isothermal holding process at this temperature for 5 min, and then quenching the semi-solid mixture into iced-water; the two-phase microstructure composed of a BMG matrix and uniformly dispersed spherical b.c.c. モ-Zr particles with a high degree of sphericity was achieved. The present spheroidization transition is a thermodynamically autonomic behavior, and essentially a diffusion process controlled by kinetic factors; and the formation of the BMG matrix should be attributed to the rapid quenching of the semi-solid mixture as well as the large glass-forming ability of the remaining melt in the semi-solid mixture.

  10. The Metallicities of Stars With and Without Transiting Planets

    CERN Document Server

    Buchhave, Lars A

    2015-01-01

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

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

    Science.gov (United States)

    Dias, Ranga P.; Silvera, Isaac F.

    2017-02-01

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

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

    Science.gov (United States)

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

    2016-10-01

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

  13. Cooperative catalysis with first-row late transition metals

    NARCIS (Netherlands)

    J.I. van der Vlugt

    2012-01-01

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

  14. The Electrochemical Synthesis of Transition-Metal Acetylacetonates

    Science.gov (United States)

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

    2008-01-01

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

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

    Institute of Scientific and Technical Information of China (English)

    Qi Fu; Bin Xiang

    2016-01-01

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

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

    NARCIS (Netherlands)

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

    1997-01-01

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

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

    Science.gov (United States)

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

    2011-03-21

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

  18. Superconductivity Series in Transition Metal Dichalcogenides by Ionic Gating

    NARCIS (Netherlands)

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

    2015-01-01

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

  19. Biomass transition metal hydrogen-evolution electrocatalysts and electrodes

    Energy Technology Data Exchange (ETDEWEB)

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

    2017-02-28

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

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

    Science.gov (United States)

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

    2005-01-01

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

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

    Science.gov (United States)

    Larionov, Evgeny; Li, Houhua; Mazet, Clément

    2014-09-07

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

  2. Electrocatalysis using transition metal carbide and oxide nanocrystals

    Science.gov (United States)

    Regmi, Yagya N.

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

  3. On the thermodynamics of phase transitions in metal hydrides

    Science.gov (United States)

    Vita, Andrea

    2012-02-01

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

  4. Covalent bonds against magnetism in transition metal compounds.

    Science.gov (United States)

    Streltsov, Sergey V; Khomskii, Daniel I

    2016-09-20

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

  5. Phase transition from fcc to bcc structure of the Cu-clusters during nanocrystallization of Fe85.2Si1B9P4Cu0.8 soft magnetic alloy

    OpenAIRE

    Masahiko Nishijima; Makoto Matsuura; Kana Takenaka; Akira Takeuchi; Hironori Ofuchi; Akihiro Makino

    2014-01-01

    A role of Cu on the nanocrystallization of an Fe85.2Si1B9P4Cu0.8 alloy was investigated by X-ray absorption fine structure (XAFS) and transmission electron microscopy (TEM). The Cu K-edge XAFS results show that local structure around Cu is disordered for the as-quenched sample whereas it changes to fcc-like structure at 613 K. The fcc Cu-clusters are, however, thermodynamically unstable and begin to transform into bcc structure at 638 K. An explicit bcc structure is observed for the sample an...

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

    Science.gov (United States)

    Xie, Junfeng; Xie, Yi

    2016-03-07

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

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

    Science.gov (United States)

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

    2017-01-01

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

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

    Science.gov (United States)

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

    2016-03-01

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

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2015-11-21

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

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

    Science.gov (United States)

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

    2016-05-20

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

  11. Evaluation of the Bilingual Curriculum Content (BCC) Pilot Project: A Three-Year Study. First Interim Report.

    Science.gov (United States)

    Rothfarb, Sylvia H.; And Others

    Bilingual Curriculum Content (BCC) is an instructional component of the Transitional Bilingual Basic Skills program offered to students with limited English proficiency (LEP) in the Dade County Public Schools, Florida. In BCC instruction, students learn mathematics and combined instruction (science, social studies, and health/safety) in their…

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

    Science.gov (United States)

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

    2013-07-22

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

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

    Science.gov (United States)

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

    2015-01-21

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

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2004-07-15

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

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

    Science.gov (United States)

    Hathaway, Brian

    1979-01-01

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

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

    Science.gov (United States)

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

    2004-10-07

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

  17. Synthesis of heterocycles through transition-metal-catalyzed isomerization reactions

    DEFF Research Database (Denmark)

    Ishøy, Mette; Nielsen, Thomas Eiland

    2014-01-01

    of structurally complex and diverse heterocycles. In this Concept article, we attempt to cover this area of research through a selection of recent versatile examples. A sea of opportunities! Transition-metal-catalyzed isomerization of N- and O-allylic compounds provides a mild, selective and synthetically......Metal-catalyzed isomerization of N- and O-allylic systems is emerging as an effective method to form synthetically useful iminium and oxocarbenium intermediates. In the presence of tethered nucleophiles, several recent examples illuminate this approach as a powerful strategy for the synthesis...

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

    Science.gov (United States)

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

    2016-12-01

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

  19. Engineering skyrmions in transition-metal multilayers for spintronics

    Science.gov (United States)

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

    2016-06-01

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

  20. Laser Assisted Additively Manufactured Transition Metal Coating on Aluminum

    Science.gov (United States)

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

    2016-07-01

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

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

    Science.gov (United States)

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

    2016-06-03

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

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

    Science.gov (United States)

    Singh, Sujay Kumar

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

  3. Microscopic Origin of Heisenberg and Non-Heisenberg Exchange Interactions in Ferromagnetic bcc Fe.

    Science.gov (United States)

    Kvashnin, Y O; Cardias, R; Szilva, A; Di Marco, I; Katsnelson, M I; Lichtenstein, A I; Nordström, L; Klautau, A B; Eriksson, O

    2016-05-27

    By means of first principles calculations, we investigate the nature of exchange coupling in ferromagnetic bcc Fe on a microscopic level. Analyzing the basic electronic structure reveals a drastic difference between the 3d orbitals of E_{g} and T_{2g} symmetries. The latter ones define the shape of the Fermi surface, while the former ones form weakly interacting impurity levels. We demonstrate that, as a result of this, in Fe the T_{2g} orbitals participate in exchange interactions, which are only weakly dependent on the configuration of the spin moments and thus can be classified as Heisenberg-like. These couplings are shown to be driven by Fermi surface nesting. In contrast, for the E_{g} states, the Heisenberg picture breaks down since the corresponding contribution to the exchange interactions is shown to strongly depend on the reference state they are extracted from. Our analysis of the nearest-neighbor coupling indicates that the interactions among E_{g} states are mainly proportional to the corresponding hopping integral and thus can be attributed to be of double-exchange origin. By making a comparison to other magnetic transition metals, we put the results of bcc Fe into context and argue that iron has a unique behavior when it comes to magnetic exchange interactions.

  4. Preparation of nanocomposites containing nanoclusters of transition metals

    Energy Technology Data Exchange (ETDEWEB)

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

    1996-10-01

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

  5. Unique reactivity of fluorinated molecules with transition metals.

    Science.gov (United States)

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

    2014-01-01

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

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

    Energy Technology Data Exchange (ETDEWEB)

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

    1992-01-01

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

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

    Energy Technology Data Exchange (ETDEWEB)

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

    1992-10-01

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

  8. Cointercalation of titanium dichalcogenides with transition metals and copper

    Science.gov (United States)

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

    2017-01-01

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

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

    Science.gov (United States)

    Bazan, Guillermo C.; Chen, Yaofeng

    2011-10-25

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

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

    Energy Technology Data Exchange (ETDEWEB)

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

    1996-04-01

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

  11. Applications of Transition Metals in Organic Synthesis and Polymerization

    Institute of Scientific and Technical Information of China (English)

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

    2007-01-01

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

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

    DEFF Research Database (Denmark)

    Tritsaris, G. A.; Rossmeisl, J.

    2012-01-01

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

  13. Exciton ionization in multilayer transition-metal dichalcogenides

    DEFF Research Database (Denmark)

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

    2016-01-01

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

  14. Current noise in some transition-metal compounds

    NARCIS (Netherlands)

    Kleinpenning, Th.G.M.

    1972-01-01

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

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

    Institute of Scientific and Technical Information of China (English)

    周自强; 方守狮; 冯锋

    2003-01-01

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

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

    Directory of Open Access Journals (Sweden)

    Jeremy Isler

    2016-06-01

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

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

    Science.gov (United States)

    Melton, Kim R.

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

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

    Science.gov (United States)

    Sachdev, Subir

    2009-03-01

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

  19. COMPUTER SIMULATION OF THE STRUCTURE OF bcc/hcp AND bcc/9R MARTENSITE INTERFACES

    OpenAIRE

    Barcelo, G.; Crocker, A.

    1982-01-01

    The structures of two interfaces of martensitic transformations in Cu Zn based alloys have been investigated using computer simulation techniques. A new interatomic potential has been developed which is assumed to represent all interactions between atoms in the parent bcc phase and the product hcp and 9R phases. Stable relaxed structures of bcc/hcp and bcc/9R interfaces have been found. In both cases the interface migrates into the bcc phase during the relaxation process. The boundary in the ...

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

    Directory of Open Access Journals (Sweden)

    R. C. Aggarwal

    1975-10-01

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

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

    CERN Document Server

    Pergament, A

    2003-01-01

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

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

    Directory of Open Access Journals (Sweden)

    Huixuan Li

    2015-07-01

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

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

    Science.gov (United States)

    Hodak, Miroslav; Bernholc, Jerry

    2012-02-01

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

  4. Thermophysical Property Measurements of Silicon-Transition Metal Alloys

    Science.gov (United States)

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

    2014-01-01

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

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

    DEFF Research Database (Denmark)

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

    2013-01-01

    Periodic Density Functional Theory calculations are capable of providing powerful insights into the structural, energetics, and electronic phenomena that underlie heterogeneous catalysis on transition metal nanoparticles. Such calculations are now routinely applied to single crystal metal surfaces...... and to subnanometer metal clusters. Descriptions of catalysis on truly nanosized structures, however, are generally not as well developed. In this talk, I will illustrate different approaches to analyzing nanocatalytic phenomena with DFT calculations. I will describe case studies from heterogeneous catalysis...... and electrocatalysis, in which single crystal models are combined with Wulff construction-based ideas to produce descriptions of average nanocatalyst behavior. Then, I will proceed to describe explicitly DFT-based descriptions of catalysis on truly nanosized particles (

  6. Method for treating rare earth-transition metal scrap

    Science.gov (United States)

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

    1992-12-29

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

  7. T-fuzzy multiply positive implicative BCC-ideals of BCC-algebras

    Directory of Open Access Journals (Sweden)

    Jianming Zhan

    2003-01-01

    of BCC-algebras, examining its properties. Using a t-norm T, the direct product and T-product of T-fuzzy multiply positive implicative BCC-ideals of BCC-algebras are discussed and their properties are investigated.

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

    Science.gov (United States)

    Silvera, Isaac; Zaghoo, Mohamed; Salamat, Ashkan

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

  9. Polaronic Transport in Phosphate Glasses Containing Transition Metal Ions

    Science.gov (United States)

    Henderson, Mark

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

  10. Prediction of a stable half-metal ferromagnetic BaCl solid

    Science.gov (United States)

    Greschner, Michael J.; Klug, Dennis D.; Yao, Yansun

    2016-03-01

    The modification of Ba in BaCl compounds from alkaline-metal to transition- and half-metal behavior is explored. High-pressure structural changes in BaCl are predicted using an ab initio structure search method. Dynamically stable bcc and R -3 m forms of BaCl are predicted at 15 and 10 GPa, respectively. The BaCl forms are more stable than elemental Ba plus BaC l2 above ˜10 GPa. Ba in stable BaCl adopts transition-metal properties via an s -d transition. At ambient pressure the fcc structure is ferromagnetic, and the bcc structure is half metallic and ferromagnetic. The transition-metal electronic structure found is sufficient to support superconductivity, with Tc as high as 3.4 K near ambient pressure.

  11. Disorder and metal-insulator transitions in Weyl semimetals

    Science.gov (United States)

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

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

  12. Annihilators on weakly standard BCC-algebras

    OpenAIRE

    R. Halaš; L. Plojhar

    2005-01-01

    In a recent paper the authors presented a new construction of BCC-algebras derived from posets with the top element 1. Resulting BCC-algebras, called weakly standard, are those for which every 4-element subset containing 1 is a subalgebra. In this paper we continue our investigations focusing on the properties of their lattices of congruence kernels.

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

    Science.gov (United States)

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

    2015-02-01

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

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2015-02-07

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

  15. Electronic structures and magnetic properties of 3d and 4d transition-metal impurities in ferromagnetic Fe

    CERN Document Server

    Park, J H; Min, B I; Cho, H S

    2000-01-01

    Employing the self-consistent local approach, the tight-binding linear-muffin-tin orbital recursion method, we have investigated the electronic structures and the magnetic properties of 3d and 4d transition-metal (TM) impurities in ferromagnetic bcc Fe. In both 3d and 4d TM impurities, virtual bound states appear and are characterized by a high density of states in the energy spectrum. The characters of the states are studied by calculating the bond order between interaction orbitals. For early TM impurities, the states at the impurity sites have more antibonding characters, while the states at neighboring Fe sites have more bonding characters. For late TM impurities, the situation is reversed. late TM impurities of both the 3d and the 4d TM series have the same magnetic ordering as the host Fe atoms whereas early TM impurities have magnetic moments antiparallel to that of the host. As for the Mn impurity, an inward relaxation of neighboring Fe atoms stabilizes the antiferromagnetic ordering with respect to t...

  16. Vismodegib in the treatment of advanced BCC.

    Science.gov (United States)

    O'Kane, G M; Lyons, T; McDonald, I; Mulligan, N; Moloney, F J; Murray, D; Kelly, C M

    2014-01-01

    Basal-cell carcinoma (BCC) is the most commonly diagnosed malignancy, comprising over 80 per thousand of non-melanoma skin cancers. Surgical excision is adequate treatment for most BCC's. Options are however limited for the minority of patients presenting with locally advanced inoperable or metastatic BCC. The Hedgehog signalling pathway is a critical driver in the pathogenesis of both sporadic and hereditary BCC. On 31st January 2012, based on a phase II clinical trial the US Food and Drug Administration approved Vismodegib (Erivedge, Roche) a first-in-class, small-molecule oral Hedgehog-inhibitor for the treatment of locally advanced inoperable and metastatic BCC. We present our experience treating the first Irish patient with this agent.

  17. PREDICTION OF YIELD FUNCTIONS ON BCC POLYCRYSTALS

    Institute of Scientific and Technical Information of China (English)

    Huang Mojia; Fu Mingfu; Zheng Chaomei

    2006-01-01

    By the nonlinear optimization theory, we predict the yield function of single BCC crystals in Hill's criterion form. Then we give a formula on the macroscopic yield function of a BCC polycrystal Ω under Sachs' model, where the volume average of the yield functions of all BCC crystallites in Ω is taken as the macroscopic yield function of the BCC polycrystal. In constructing the formula, we try to find the relationship among the macroscopic yield function, the orientation distribution function (ODF), and the single BCC crystal's plasticity. An expression for the yield stress of a uniaxial tensile problem is derived under Taylor's model in order to compare the expression with that of the macroscopic yield function.

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

    Science.gov (United States)

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

    2016-06-01

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

  19. The Holographic Disorder-Driven Supeconductor-Metal Transition

    CERN Document Server

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

    2015-01-01

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

  20. Holographic metal-insulator transition in higher derivative gravity

    Science.gov (United States)

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

    2017-03-01

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

  1. Holographic Metal-Insulator Transition in Higher Derivative Gravity

    CERN Document Server

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

    2016-01-01

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

  2. Holographic metal-insulator transition in higher derivative gravity

    Directory of Open Access Journals (Sweden)

    Yi Ling

    2017-03-01

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

  3. Transition metal catalysis in the mitochondria of living cells

    Science.gov (United States)

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

    2016-09-01

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

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

    Science.gov (United States)

    Okuyama, Rin; Izumida, Wataru; Eto, Mikio

    2017-01-01

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

  5. Surface entropy of liquid transition and noble metals

    Science.gov (United States)

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

    2015-07-01

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

  6. Transistor-like behavior of transition metal complexes

    DEFF Research Database (Denmark)

    Albrecht, Tim; Guckian, A; Ulstrup, Jens

    2005-01-01

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

  7. Efficient photocarrier injection in a transition metal oxide heterostructure

    CERN Document Server

    Muraoka, Y; Ueda, Y; Hiroi, Z

    2002-01-01

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

  8. Nanoparticle plasmonics: going practical with transition metal nitrides

    Directory of Open Access Journals (Sweden)

    Urcan Guler

    2015-05-01

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

  9. Novel synthetic routes to nanocomposites of transition metal phosphides

    Energy Technology Data Exchange (ETDEWEB)

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

    1996-10-01

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

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

    CERN Document Server

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

    2010-01-01

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

  11. Magnetism in 3d transition metal doped SnO

    KAUST Repository

    Albar, Arwa

    2016-09-12

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

  12. First-principles study of transition metal carbides

    Science.gov (United States)

    Connétable, Damien

    2016-12-01

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

  13. CVD-graphene growth on different polycrystalline transition metals

    Directory of Open Access Journals (Sweden)

    M. P. Lavin-Lopez

    2017-01-01

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

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

    Science.gov (United States)

    Naumov, Ivan I.; Hemley, Russell J.

    2015-04-01

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

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

    Science.gov (United States)

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

    2013-06-01

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

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

    NARCIS (Netherlands)

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

    2013-01-01

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

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

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

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

  18. Defects and ferromagnetism in transition metal doped zinc oxide

    Science.gov (United States)

    Thapa, Sunil

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

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

    Science.gov (United States)

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

    2013-08-14

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

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

    Science.gov (United States)

    Farley, Katie Elizabeth

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

  1. Polynuclear transition metal complexes with thiocarbohydrazide and dithiocarbamates

    Science.gov (United States)

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

    2007-07-01

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

  2. High pressure behavior of 3d transition metal carbonates

    Science.gov (United States)

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

    2012-12-01

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

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

    Science.gov (United States)

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

    2012-06-07

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

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

    Science.gov (United States)

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

    2016-01-14

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

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

    Science.gov (United States)

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

    2017-03-01

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

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

    Science.gov (United States)

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

    2016-12-01

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

  7. The Role of Ligand Packing Frustration in Body-Centered Cubic (bcc) Superlattices of Colloidal Nanocrystals.

    Science.gov (United States)

    Goodfellow, Brian W; Yu, Yixuan; Bosoy, Christian A; Smilgies, Detlef-M; Korgel, Brian A

    2015-07-02

    This paper addresses the assembly of body centered-cubic (bcc) superlattices of organic ligand-coated nanocrystals. First, examples of bcc superlattices of dodecanethiol-capped Au nanocrystals and oleic acid-capped PbS and PbSe nanocrystals are presented and examined by transmission electron microscopy (TEM) and grazing incidence small-angle X-ray scattering (GISAXS). These superlattices tend to orient on their densest (110) superlattice planes and exhibit a significant amount of {112} twinning. The same nanocrystals deposit as monolayers with hexagonal packing, and these thin films can coexist with thicker bcc superlattice layers, even though there is no hexagonal plane in a bcc lattice. Both the preference of bcc in bulk films over the denser face-centered cubic (fcc) superlattice structure and the transition to hexagonal monolayers can be rationalized in terms of packing frustration of the ligands. A model is presented to calculate the difference in entropy associated with capping ligand packing frustration in bcc and fcc superlattices.

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

    Energy Technology Data Exchange (ETDEWEB)

    Smith, Kjell-Tore

    1996-08-01

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

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

    Energy Technology Data Exchange (ETDEWEB)

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

    1995-01-01

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

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

    Institute of Scientific and Technical Information of China (English)

    丁建文; 颜晓红; 刘超平; 唐娜斯

    2004-01-01

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

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

    Science.gov (United States)

    Maksoed, Wh-

    2016-11-01

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

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

    DEFF Research Database (Denmark)

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

    1997-01-01

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

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

    Science.gov (United States)

    Heine, Thomas

    2015-01-20

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

  14. Chiral topological excitons in the monolayer transition metal dichalcogenides

    Science.gov (United States)

    Gong, Z. R.; Luo, W. Z.; Jiang, Z. F.; Fu, H. C.

    2017-02-01

    We theoretically investigate the chiral topological excitons emerging in the monolayer transition metal dichalcogenides, where a bulk energy gap of valley excitons is opened up by a position dependent external magnetic field. We find two emerging chiral topological nontrivial excitons states, which exactly connects to the bulk topological properties, i.e., Chern number = 2. The dependence of the spectrum of the chiral topological excitons on the width of the magnetic field domain wall as well as the magnetic filed strength is numerically revealed. The chiral topological valley excitons are not only important to the excitonic transport due to prevention of the backscattering, but also give rise to the quantum coherent control in the optoelectronic applications.

  15. On holographic disorder-driven metal-insulator transitions

    CERN Document Server

    Baggioli, Matteo

    2016-01-01

    We give a minimal holographic model of a disorder-driven metal-insulator transition. It consists in a CFT with a charge sector and a translation-breaking sector that interact in the most generic way allowed by the symmetries and by dynamical consistency. In the gravity dual, it reduces to a Massive Gravity-Maxwell model with new direct couplings between the Maxwell and metric that are allowed when gravity is massive. We show that, generically, the effect of disorder is to decrease the DC electrical conductivity. This happens to such an extent that the conductivity does not obey any lower bound and can be very small in the insulating phase. In some cases, the large disorder limit produces gradient instabilities that hint at the formation of modulated phases.

  16. Mechanism of Transition-Metal Nanoparticle Catalytic Graphene Cutting.

    Science.gov (United States)

    Ma, Liang; Wang, Jinlan; Yip, Joanne; Ding, Feng

    2014-04-03

    Catalytic cutting by transition-metal (TM) particles is a promising method for the synthesizing of high-quality graphene quantum dots and nanoribbons with smooth edges. Experimentally, it is observed that the cutting always results in channels with zigzag (ZZ) or armchair (AC) edges. However, the driving force that is responsible for such a cutting behavior remains a puzzle. Here, by calculating the interfacial formation energies of the TM-graphene edges with ab initio method, we show that the surface of a catalyst particle tends to be aligned along either AC or ZZ direction of the graphene lattice, and thus the cutting of graphene is guided as such. The different cutting behaviors of various catalysts are well-explained based on the competition between TM-passivated graphene edges and the etching-agent-terminated ones. Furthermore, the kinetics of graphene catalytic cutting along ZZ and AC directions, respectively, are explored at the atomic level.

  17. Ab initio study of the transition-metal carbene cations

    Institute of Scientific and Technical Information of China (English)

    李吉海; 冯大诚; 冯圣玉

    1999-01-01

    The geometries and bonding characteristics of the first-row transition-metal carbene cations MCH2+ were investigated by ab initio molecular orbital theory (HF/LANL2DZ). All of MCH2+ are coplanar. In the closed shell structures the C bonds to M with double bonds; while in the open shell structures the partial double bonds are formed, because one of the σ and π orbitals is singly occupied. It is mainly the π-type overlap between the 2px orbital of C and 4px, 3dxz, orbitals of M+ that forms the π orbitals. The dissociation energies of C—M bond appear in periodic trend from Sc to Cu. Most of the calculated bond dissociation energies are close to the experimental ones.

  18. Extrinsic Spin Hall Effect Due to Transition-Metal Impurities

    Science.gov (United States)

    Tanaka, T.; Kontani, H.

    2012-11-01

    We investigate the extrinsic spin Hall effect in the electron gas model due to transition-metal impurities based on the single-impurity Anderson model with orbital degrees of freedom. Both the skew scattering and side jump mechanisms are analyzed in a unified way, and the significant role of orbital degrees of freedom are clarified. The obtained spin Hall conductivities are in proportion to the spin-orbit polarization at the Fermi level _{μ} as is the case with the intrinsic spin Hall effect: skew scattering term {SH}^{ss} ∝ _{μ} δ_1 σ_{xx}, and side jump term σ_{SH}^{sj} ∝ _{μ}, where δ_1 is the phase shift for p (l = 1) partial wave. Furthermore, the present study indicates the existence of a nontrivial close relationship between the intrinsic term σ_{SH}^{int} and the extrinsic side jump term σ_{SH}^{sj}.

  19. Ferromagnetic semiconductor-metal transition in europium monoxide

    Energy Technology Data Exchange (ETDEWEB)

    Arnold, M.

    2007-10-15

    We present a microscopical model to describe the simultaneous para-to-ferromagnetic and semiconductor-to-metal transition in electron-doped EuO. The physical properties of the model are systematically studied, whereas the main remark is on the interplay between magnetic order and the transport properties. The theory correctly describes detailed experimental features of the conductivity and of the magnetization, obtained for EuO{sub 1-x} or Gd-doped Gd{sub x}Eu{sub 1-x}0. In particular the doping dependence of the Curie temperature is reproduced The existence of correlation-induced local moments on the impurity sites is essential for this description. (orig.)

  20. Noncollinear exchange interaction in transition metal dichalcogenide edges

    Science.gov (United States)

    Ávalos-Ovando, Oscar; Mastrogiuseppe, Diego; Ulloa, Sergio E.

    2016-04-01

    We study the Ruderman-Kittel-Kasuya-Yosida effective exchange interaction between magnetic impurities embedded on the edges of transition metal dichalcogenide flakes, using a three-orbital tight-binding model. Electronic states lying midgap of the bulk structure have a strong one-dimensional (1D) character, localized on the edges of the crystallite. This results in exchange interactions with 1 /r (or slower) decay with distance r , similar to other 1D systems. Most interestingly, however, the strong spin-orbit interaction in these materials results in sizable noncollinear Dzyaloshinskii-Moriya interactions between impurities, comparable in size to the usual Ising and in-plane components. Varying the relevant Fermi energy by doping or gating may allow one to modulate the effective interactions, controlling the possible helical ground state configurations of multiple impurities.

  1. Induced magnetism in transition metal intercalated graphitic systems

    KAUST Repository

    Kaloni, Thaneshwor P.

    2011-10-26

    We investigate the structure, chemical bonding, electronic properties, and magnetic behavior of a three-dimensional graphitic network in aba and aaa stacking with intercalated transition metal atoms (Mn, Fe, Co, Ni, and Cu). Using density functional theory, we find induced spin-polarization of the C atoms both when the graphene sheets are aba stacked (forming graphite) and aaa stacked (resembling bi-layer graphene). The magnetic moment induced by Mn, Fe, and Co turns out to vary from 1.38 μB to 4.10 μB, whereas intercalation of Ni and Cu does not lead to a magnetic state. The selective induction of spin-polarization can be utilized in spintronic and nanoelectronic applications.

  2. Transition Metal Carbides and Nitrides in Energy Storage and Conversion.

    Science.gov (United States)

    Zhong, Yu; Xia, Xinhui; Shi, Fan; Zhan, Jiye; Tu, Jiangping; Fan, Hong Jin

    2016-05-01

    High-performance electrode materials are the key to advances in the areas of energy conversion and storage (e.g., fuel cells and batteries). In this Review, recent progress in the synthesis and electrochemical application of transition metal carbides (TMCs) and nitrides (TMNs) for energy storage and conversion is summarized. Their electrochemical properties in Li-ion and Na-ion batteries as well as in supercapacitors, and electrocatalytic reactions (oxygen evolution and reduction reactions, and hydrogen evolution reaction) are discussed in association with their crystal structure/morphology/composition. Advantages and benefits of nanostructuring (e.g., 2D MXenes) are highlighted. Prospects of future research trends in rational design of high-performance TMCs and TMNs electrodes are provided at the end.

  3. Transition metal dichalcogenides based saturable absorbers for pulsed laser technology

    Science.gov (United States)

    Mohanraj, J.; Velmurugan, V.; Sivabalan, S.

    2016-10-01

    Ultrashort pulsed laser is an indispensable tool for the evolution of photonic technology in the present and future. This laser has been progressing tremendously with new pulse regimes and incorporating novel devices inside its cavity. Recently, a nanomaterial based saturable absorber (SA) was used in ultrafast laser that has improved the lasing performance and caused a reduction in the physical dimension when compared to conventional SAs. To date, the nanomaterials that are exploited for the development of SA devices are carbon nanotubes, graphene, topological insulators, transition metal dichalcogenides (TMDs) and black phosphorous. These materials have unique advantages such as high nonlinear optical response, fiber compatibility and ease of fabrication. In these, TMDs are prominent and an emerging two-dimensional nanomaterial for photonics and optoelectronics applications. Therefore, we review the reports of Q-switched and mode-locked pulsed lasers using TMDs (specifically MoS2, MoSe2, WS2 and WSe2) based SAs.

  4. Optical limiting of layered transition metal dichalcogenide semiconductors

    CERN Document Server

    Dong, Ningning; Feng, Yanyan; Zhang, Saifeng; Zhang, Xiaoyan; Chang, Chunxia; Fan, Jintai; Zhang, Long; Wang, Jun

    2015-01-01

    Nonlinear optical property of transition metal dichalcogenide (TMDC) nanosheet dispersions, including MoS2, MoSe2, WS2, and WSe2, was performed by using Z-scan technique with ns pulsed laser at 1064 nm and 532 nm. The results demonstrate that the TMDC dispersions exhibit significant optical limiting response at 1064 nm due to nonlinear scattering, in contrast to the combined effect of both saturable absorption and nonlinear scattering at 532 nm. Selenium compounds show better optical limiting performance than that of the sulfides in the near infrared. A liquid dispersion system based theoretical modelling is proposed to estimate the number density of the nanosheet dispersions, the relationship between incident laser fluence and the size of the laser generated micro-bubbles, and hence the Mie scattering-induced broadband optical limiting behavior in the TMDC dispersions.

  5. Electronics and optoelectronics of two-dimensional transition metal dichalcogenides.

    Science.gov (United States)

    Wang, Qing Hua; Kalantar-Zadeh, Kourosh; Kis, Andras; Coleman, Jonathan N; Strano, Michael S

    2012-11-01

    The remarkable properties of graphene have renewed interest in inorganic, two-dimensional materials with unique electronic and optical attributes. Transition metal dichalcogenides (TMDCs) are layered materials with strong in-plane bonding and weak out-of-plane interactions enabling exfoliation into two-dimensional layers of single unit cell thickness. Although TMDCs have been studied for decades, recent advances in nanoscale materials characterization and device fabrication have opened up new opportunities for two-dimensional layers of thin TMDCs in nanoelectronics and optoelectronics. TMDCs such as MoS(2), MoSe(2), WS(2) and WSe(2) have sizable bandgaps that change from indirect to direct in single layers, allowing applications such as transistors, photodetectors and electroluminescent devices. We review the historical development of TMDCs, methods for preparing atomically thin layers, their electronic and optical properties, and prospects for future advances in electronics and optoelectronics.

  6. Liquid Exfoliation of Layered Transition Metal Dichalcogenides for Biological Applications.

    Science.gov (United States)

    Nguyen, Emily P; Daeneke, Torben; Zhuiykov, Serge; Kalantar-Zadeh, Kourosh

    2016-06-02

    Known to possess distinctive properties that differ greatly from their bulk form, layered two-dimensional materials have been extensively studied and incorporated into many versatile applications ranging from optoelectronics to sensors. For biomedical research, two-dimensional transition metal dichalcogenides (2D TMDs) have garnered much interest as they have been shown to exhibit relatively low toxicity, high stability in aqueous environments, and the ability to adhere to biological materials such as proteins. These materials are promising candidates, demonstrating potential applications in biosensing, cell imaging, diagnostics, and therapeutics. Preparation and exfoliation of 2D TMDs play an important part in these various applications as their properties are heavily dependent on the number of layers and lateral size. Described in this article are protocols for the liquid exfoliation of 2D TMDs from their bulk materials. Additional protocols are also provided for functionalizing or modifying the surface of the exfoliated 2D TMDs. © 2016 by John Wiley & Sons, Inc.

  7. Superconductor to Quantum Metal Transitions in Ultra Thin Films

    Science.gov (United States)

    Lin, Yen-Hsiang; Goldman, Allen M.

    2009-03-01

    Homogeneous films of amorphous bismuth have been continuously tuned from the superconducting state by increasing a perpendicular magnetic field. Electrical transport and Hall measurements show that the non-superconducting states of the films are quantum-corrected metals. In the vicinity of transition field, the resistance can be fit by an Arrhenius type of conduction at high temperatures but this form fails at lower temperatures where the resistance is a non-monotonic function of temperature. This suggests that a two-phase regime develops near criticality. Theories suggest that this is in the form of superconducting puddles embedded in a normal matrix^1,2. ^1B. Spivak, P. Oreto, and S. A. Kivelson, Phys. Rev. B 77, 214523 (2008) ^2Y. Dubi, Y. Meir, and Y. Avishai, Nature 449, 876-880 (2007)

  8. Nonequilibrium carrier dynamics in transition metal dichalcogenide semiconductors

    Science.gov (United States)

    Steinhoff, A.; Florian, M.; Rösner, M.; Lorke, M.; Wehling, T. O.; Gies, C.; Jahnke, F.

    2016-09-01

    When exploring new materials for their potential in (opto)electronic device applications, it is important to understand the role of various carrier interaction and scattering processes. In atomically thin transition metal dichalcogenide semiconductors, the Coulomb interaction is known to be much stronger than in quantum wells of conventional semiconductors like GaAs, as witnessed by the 50 times larger exciton binding energy. The question arises, whether this directly translates into equivalently faster carrier-carrier Coulomb scattering of excited carriers. Here we show that a combination of ab initio band-structure and many-body theory predicts Coulomb-mediated carrier relaxation on a sub-100 fs time scale for a wide range of excitation densities, which is less than an order of magnitude faster than in quantum wells.

  9. BCC and Childhood Low Dose Radiation

    Directory of Open Access Journals (Sweden)

    Arash Beiraghi Toosi

    2014-10-01

    Full Text Available Skin cancer is a late complication of ionizing radiation. Two skin neoplasms prominent Basal Cell Carcinoma (BCC and Squamous Cell Carcinoma (SCC are the most famous complications of radiotherapy. Basal Cell Carcinoma (BCC is the most common human malignant neoplasm. Many genetic and environmental factors are involved in its onset. BCC is observed in sun-exposed areas of skin. Some patients with scalp BCC have had a history of scalp radiation for the treatment of tinea capitis in childhood. Evidence that ionizing radiation is carcinogenic first came from past reports of nonmelanoma skin cancers on the hands of workers using radiation devices. The total dose of radiation and irradiated site exposed to sunlight can lead to a short incubation period. It is not clear whether BCC in these cases has a more aggressive nature and requires a more aggressive resection of the lesion. The aim of this review was to evaluate the differences between BCC specification and treatment results between irradiated and nonirradiated patients.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2014-11-15

    Comproportionation reactions of rare-earth metal trihalides (RX{sub 3}) with the respective rare-earth metals (R) and transition metals (T) led to the formation of 22 oligomeric R cluster halides encapsulating T, in 19 cases for the first time. The structures of these compounds were determined by single-crystal X-ray diffraction and are composed of trimers ((T{sub 3}R{sub 11})X{sub 15}-type, P6{sub 3}/m), tetramers ((T{sub 4}R{sub 16})X{sub 28}(R{sub 4}) (P-43m), (T{sub 4}R{sub 16})X{sub 20} (P4{sub 2}/nnm), (T{sub 4}R{sub 16})X{sub 24}(RX{sub 3}){sub 4} (I4{sub 1}/a) and (T{sub 4}R{sub 16})X{sub 23} (C2/m) types of structure) and pentamers ((Ru{sub 5}La{sub 14}){sub 2}Br{sub 39}, Cc) of (TR{sub r}){sub n} (n=2–5) clusters. These oligomers are further enveloped by inner (X{sup i}) as well as outer (X{sup a}) halido ligands, which possess diverse functionalities and interconnect like oligomers through i–i, i–a and/or a–i bridges. The general features of the crystal structures for these new compounds are discussed and compared to literature entries as well as different structure types with oligomeric T centered R clusters. Dimers and tetramers originating from the aggregation of (TR{sub 6}) octahedra via common edges are more frequent than trimers and pentamers, in which the (TR{sub r}) clusters share common faces. - Graphical abstract: Rare earth-metal cluster complexes with endohedral transition metal atoms (TR{sub 6}) may connect via common edges or faces to form dimers, trimers, tetramers and pentamers of which the tetramers are the most prolific. Packing effects and electron counts play an important role. - Highlights: • Rare-earth metal cluster complexes encapsulate transition metal atoms. • Oligomers are built via connection of octahedral clusters via common edges or faces. • Dimers through pentamers with closed structures are known. • Tetramers including a tetrahedron of endohedral atoms are the most prolific.

  11. Probing Magnetism in 2D Molecular Networks after in Situ Metalation by Transition Metal Atoms.

    Science.gov (United States)

    Schouteden, K; Ivanova, Ts; Li, Z; Iancu, V; Janssens, E; Van Haesendonck, C

    2015-03-19

    Metalated molecules are the ideal building blocks for the bottom-up fabrication of, e.g., two-dimensional arrays of magnetic particles for spintronics applications. Compared to chemical synthesis, metalation after network formation by an atom beam can yield a higher degree of control and flexibility and allows for mixing of different types of magnetic atoms. We report on successful metalation of tetrapyridyl-porphyrins (TPyP) by Co and Cr atoms, as demonstrated by scanning tunneling microscopy experiments. For the metalation, large periodic networks formed by the TPyP molecules on a Ag(111) substrate are exposed in situ to an atom beam. Voltage-induced dehydrogenation experiments support the conclusion that the porphyrin macrocycle of the TPyP molecule incorporates one transition metal atom. The newly synthesized Co-TPyP and Cr-TPyP complexes exhibit striking differences in their electronic behavior, leading to a magnetic character for Cr-TPyP only as evidenced by Kondo resonance measurements.

  12. Preparation and magnetic properties of phthalocyanine-based carbon materials containing transition metals

    Science.gov (United States)

    Honda, Z.; Sato, S.; Hagiwara, M.; Kida, T.; Sakai, M.; Fukuda, T.; Kamata, N.

    2016-07-01

    A simple method for the preparation of bulk quantities of magnetic carbon materials, which contain uniformly dispersed transition metals (M = Fe, Co, Ni, and Cu) as the magnetic components, is presented. By using highly chlorinated metal phthalocyanine as the building block and potassium as the coupling reagent, phthalocyanine-based carbon materials (PBCMs) containing transition metals were obtained. Our experiments demonstrate the structure of these PBCMs consists of transition metals embedded in graphitic carbon that includes a square planar MN4 magnetic core and the Fe and Co-PBCM possess spontaneous magnetization at room temperature. In addition, carbon-coated transition metal particles were obtained by the Wurtz-type reaction with excess amount of potassium coupling agent. The large transition metal surface area and magnetization of these M-PBCMs are useful for spintronic and catalytic applications.

  13. Plasmonic percolation: Plasmon-manifested dielectric-to-metal transition

    KAUST Repository

    Chen, Huanjun

    2012-08-28

    Percolation generally refers to the phenomenon of abrupt variations in electrical, magnetic, or optical properties caused by gradual volume fraction changes of one component across a threshold in bicomponent systems. Percolation behaviors have usually been observed in macroscopic systems, with most studies devoted to electrical percolation. We report on our observation of plasmonic percolation in Au nanorod core-Pd shell nanostructures. When the Pd volume fraction in the shell consisting of palladium and water approaches the plasmonic percolation threshold, ∼70%, the plasmon of the nanostructure transits from red to blue shifts with respect to that of the unshelled Au nanorod. This plasmonic percolation behavior is also confirmed by the scattering measurements on the individual core-shell nanostructures. Quasistatic theory and numerical simulations show that the plasmonic percolation originates from a positive-to-negative transition in the real part of the dielectric function of the shell as the Pd volume fraction is increased. The observed plasmonic percolation is found to be independent of the metal type in the shell. Moreover, compared to the unshelled Au nanorods with similar plasmon wavelengths, the Au nanorod core-Pd shell nanostructures exhibit larger refractive index sensitivities, which is ascribed to the expulsion of the electric field intensity from the Au nanorod core by the adsorbed Pd nanoparticles. © 2012 American Chemical Society.

  14. Transistor-like behavior of transition metal complexes.

    Science.gov (United States)

    Albrecht, Tim; Guckian, Adrian; Ulstrup, Jens; Vos, Johannes G

    2005-07-01

    Electron transport through semiconductor and metallic nanoscale structures, molecular monolayers, and single molecules connected to external electrodes display rectification, switch, and staircase functionality of potential importance in future miniaturization of electronic devices. Common to most reported systems is, however, ultrahigh vacuum and/or cryogenic working conditions. Here we introduce a single-molecule device concept based on a class of robust redox active transition metal (Os(II)/(III)) complexes inserted between the working electrode and tip in an electrochemical scanning tunneling microscope (in situ STM). This configuration resembles a single-molecule transistor, where the reference electrode corresponds to the gate electrode. It operates at room temperature in a condensed matter (here aqueous) environment. Amplification on-off ratios up to 50 are found when the redox level is brought into the energy window between the Fermi levels of the electrodes by the overpotential ("gate voltage"). The current-voltage characteristics for two Os(II)/(III) complexes have been characterized systematically and supported by theoretical frames based on molecular charge transport theory.

  15. Photoinduced energy transfer in transition metal complex oligomers

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    1997-04-01

    The work we have done over the past three years has been directed toward the preparation, characterization and photophysical examination of mono- and bimetallic diimine complexes. The work is part of a broader project directed toward the development of stable, efficient, light harvesting arrays of transition metal complex chromophores. One focus has been the synthesis of rigid bis-bidentate and bis-tridentate bridging ligands. We have managed to make the ligand bphb in multigram quantities from inexpensive starting materials. The synthetic approach used has allowed us prepare a variety of other ligands which may have unique applications (vide infra). We have prepared, characterized and examined the photophysical behavior of Ru(II) and Re(I) complexes of the ligands. Energy donor/acceptor complexes of bphb have been prepared which exhibit nearly activationless energy transfer. Complexes of Ru(II) and Re(I) have also been prepared with other polyunsaturated ligands in which two different long lived ( > 50 ns) excited states exist; results of luminescence and transient absorbance measurements suggest the two states are metal-to-ligand charge transfer and ligand localized {pi}{r_arrow}{pi}* triplets. Finally, we have developed methods to prepare polymetallic complexes which are covalently bound to various surfaces. The long term objective of this work is to make light harvesting arrays for the sensitization of large band gap semiconductors. Details of this work are provided in the body of the report.

  16. Photoinduced energy transfer in transition metal complex oligomers

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    1997-06-01

    The work done over the past three years has been directed toward the preparation, characterization and photophysical examination of mono- and bimetallic diimine complexes. The work is part of a broader project directed toward the development of stable, efficient, light harvesting arrays of transition metal complex chromophores. One focus has been the synthesis of rigid bis-bidentate and bis-tridentate bridging ligands. The authors have managed to make the ligand bphb in multigram quantities from inexpensive starting materials. The synthetic approach used has allowed them to prepare a variety of other ligands which may have unique applications (vide infra). They have prepared, characterized and examined the photophysical behavior of Ru(II) and Re(I) complexes of the ligands. Energy donor/acceptor complexes of bphb have been prepared which exhibit nearly activationless energy transfer. Complexes of Ru(II) and Re(I) have also been prepared with other polyunsaturated ligands in which two different long lived (> 50 ns) excited states exist; results of luminescence and transient absorbance measurements suggest the two states are metal-to-ligand charge transfer and ligand localized {pi}{r_arrow}{pi}* triplets. Finally, the authors have developed methods to prepare polymetallic complexes which are covalently bound to various surfaces. The long term objective of this work is to make light harvesting arrays for the sensitization of large band gap semiconductors. Details of this work are provided in the body of the report.

  17. Nucleation of hcp and fcc phases in bcc iron under uniform compression: classical molecular dynamics simulations.

    Science.gov (United States)

    Wang, B T; Shao, J L; Zhang, G C; Li, W D; Zhang, P

    2010-11-03

    By classical molecular dynamics simulations employing an embedded atom method potential, we have simulated the bcc to hcp/fcc structural transition in single-crystal iron under uniform compression. Results showed that the transition pressure is different from uniaxial compression and shock loading. The transformation occurs on a picosecond timescale and the transition time decreases along with the increase of pressure. The nucleation and growth of the hcp and fcc phases under constant pressure and temperature are analyzed in detail. The nucleation planes, all belonging to the {110}(bcc) family and parallel to the three compression directions [100], [010], and [001], have been observed. About 20% bcc atoms have transformed to fcc phase under pressure just over the critical point, and under higher pressure the fraction of the fcc phase increases steadily to exceed that of the hcp phase. We have investigated the transition mechanism of iron from initial bcc to hcp/fcc and found that the transition mainly consists of compression, rotation, and shuffle.

  18. Strong electron correlations in biomimetic transition metal molecules

    Science.gov (United States)

    Labute, Montiago Xavier

    The first-row transition metals (Fe, Co, V,...) are key players in the active sites of proteins and enzymes responsible for diverse biological processes such as NO regulation and photosynthesis. Many small transition metal complexes possess chemical coordination environments in the vicinity of the metal atom that are reminiscent of these active sites. We have studied the electronic structure of these molecules and discussed the relevance for their biological analogues. The specific question on which we wish to focus is: Do strong correlations (resulting from the localized character of the TM 3d-orbitals) contribute significantly to the reaction energetics of these molecules and, if so, can these effects be observed by experiment? To accomplish these ends we focus on the cobalt valence tautomer molecules and the phenomenon of electron transfer in aqueous hexaammine cobalt ions. We utilize theoretical methods in order to study the cobalt valence tautomer molecules which undergo an interconversion with temperature that is reminiscent of the changes in structure and spin that the heme group experiences as the result of Fe-ligand interactions. We perform fully ab initio calculations using the GGA implementation of density functional theory with the computer code SIESTA. In addition, a simple Anderson Impurity Model has been employed that more properly accounts for the Coulomb interaction among the 3d electrons on the cobalt atom. The calculated Co K x-ray absorption near-edge spectra XANES agrees well with experimental data and a prediction for the Co L-edge XAS that could be tested in future experiments is also presented. We believe that there are structures in both spectra that may only be explained by a strong admixture of configurations. It is conjectured that strong electron correlations help explain the non-Arrhenius rate behavior observed in the high-spin to low-spin relaxation rate at low temperatures. Work on electron-transfer in CoNH32 +/3+6aq using these

  19. Ammonia and hydrazine. Transition-metal-catalyzed hydroamination and metal-free catalyzed functionalization

    Energy Technology Data Exchange (ETDEWEB)

    Bertrand, Guy [Univ. of California, San Diego, CA (United States)

    2012-06-29

    The efficient and selective preparation of organic molecules is critical for mankind. For the future, it is of paramount importance to find catalysts able to transform abundant and cheap feedstocks into useful compounds. Acyclic and heterocyclic nitrogen-containing derivatives are common components of naturally occurring compounds, agrochemicals, cosmetics, and pharmaceuticals; they are also useful intermediates in a number of industrial processes. One of the most widely used synthetic strategies, allowing the formation of an N-C bond, is the addition of an N-H bond across a carbon-carbon multiple bond, the so-called hydroamination reaction. This chemical transformation fulfills the principle of “green chemistry” since it ideally occurs with 100% atom economy. Various catalysts have been found to promote this reaction, although many limitations remain; one of the most prominent is the lack of methods that permit the use of NH3 and NH2NH2 as the amine partners. In fact, ammonia and hydrazine have rarely succumbed to homogeneous catalytic transformations. Considering the low cost and abundance of ammonia (136 million metric tons produced in 2011) and hydrazine, catalysts able to improve the reactivity and selectivity of the NH3- and NH2NH2-hydroamination reaction, and more broadly speaking the functionalization of these chemicals, are highly desirable. In the last funded period, we discovered the first homogeneous catalysts able to promote the hydroamination of alkynes and allenes with ammonia and the parent hydrazine. The key feature of our catalytic systems is that the formation of catalytically inactive Werner complexes is reversible, in marked contrast to most of the known ammonia and hydrazine transition metal complexes. This is due to the peculiar electronic properties of our neutral ancillary ligands, especially their strong donating capabilities. However, our catalysts currently require

  20. Solubility Behavior and Phase Stability of Transition Metal Oxides in Alkaline Hydrothermal Environments

    Energy Technology Data Exchange (ETDEWEB)

    S.E. Ziemniak

    2000-05-18

    The solubility behavior of transition metal oxides in high temperature water is interpreted by recognizing three types of chemical reaction equilibria: metal oxide hydration/dehydration, metal oxide dissolution and metal ion hydroxocomplex formation. The equilibria are quantified using thermodynamic concepts and the thermochemical properties of the metal oxides/ions representative of the most common constituents of construction metal alloys, i.e., element shaving atomic numbers between Z = 22 (Ti) and Z = 30 (Zn), are summarized on the basis of metal oxide solubility studies conducted in the laboratory. Particular attention is devoted to the uncharged metal ion hydrocomplex, M{sup Z}(OH){sub Z}(aq), since its thermochemical properties define minimum solubilities of the metal oxide at a given temperature. Experimentally-extracted values of standard partial molal entropy (S{sup 0}) for the transition metal ion neutral hydroxocomplex are shown to be influenced by ligand field stabilization energies and complex symmetry.

  1. Synthetic Fabrication of Nanoscale MoS2-Based Transition Metal Sulfides

    Directory of Open Access Journals (Sweden)

    Jikang Yuan

    2010-01-01

    Full Text Available Transition metal sulfides are scientifically and technologically important materials. This review summarizes recent progress on the synthetic fabrication of transition metal sulfides nanocrystals with controlled shape, size, and surface functionality. Special attention is paid to the case of MoS2 nanoparticles, where organic (surfactant, polymer, inorganic (support, promoter, doping compounds and intercalation chemistry are applied.

  2. Effect of transition metal ions on the conductivity and stability of stabilized zirconia

    DEFF Research Database (Denmark)

    Lybye, D.; Mogensen, Mogens Bjerg

    2007-01-01

    the effect of co-doping with smaller transition metal ions such as Ti-, Fe- and Mn-ions. Many of the ionic radii of the transition metal ions are too small compared to the host lattice ionic radius of zirconium. Here we explore the effect of a) the small ionic radii compared to the large ionic radii...

  3. Magnetic-field-induced superconductor-metal-insulator transitions in bismuth metal graphite

    Science.gov (United States)

    Suzuki, Masatsugu; Suzuki, Itsuko S.; Lee, Robert; Walter, Jürgen

    2002-07-01

    Bismuth metal graphite (MG) has a unique layered structure where Bi nanoparticles are encapsulated between adjacent sheets of nanographites. The superconductivity below Tc (=2.48 K) is due to Bi nanoparticles. The Curie-like susceptibility below 30 K is due to conduction electrons localized near zigzag edges of nanographites. A magnetic-field-induced transition from metallic to semiconductorlike phase is observed in the in-plane resistivity ρa around Hc (~25 kOe) for both H⊥c and H||c (c: c axis). A negative magnetoresistance in ρa for H⊥c (040 kOe) suggest the occurrence of a two-dimensional weak-localization effect.

  4. Mott metal-insulator transition in a metallic liquid - Gutzwiller molecular dynamics simulations

    Science.gov (United States)

    Barros, Kipton; Chern, Gia-Wei; Batista, Cristian D.; Kress, Joel D.; Kotliar, Gabriel

    2015-03-01

    Molecular dynamics (MD) simulations are crucial to modern computational physics, chemistry, and materials science, especially when combined with potentials derived from density-functional theory. However, even in state of the art MD codes, the on-site Coulomb repulsion is only treated at the self-consistent Hartree-Fock level. This standard approximation may miss important effects due to electron correlations. The Gutzwiller variational method captures essential correlated-electron physics yet is much faster than, e.g., the dynamical-mean field theory approach. We present our efficient Gutzwiller-MD implementation. With it, we investigate the Mott metal-insulator transition in a metallic fluid and uncover several surprising static and dynamic properties of this system.

  5. Ternary Amides Containing Transition Metals for Hydrogen Storage: A Case Study with Alkali Metal Amidozincates.

    Science.gov (United States)

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

    2015-11-01

    The alkali metal amidozincates Li4 [Zn(NH2)4](NH2)2 and K2[Zn(NH2)4] were, to the best of our knowledge, studied for the first time as hydrogen storage media. Compared with the LiNH2-2 LiH system, both Li4 [Zn(NH2)4](NH2)2-12 LiH and K2[Zn(NH2)4]-8 LiH systems showed improved rehydrogenation performance, especially K2[Zn(NH2)4]-8 LiH, which can be fully hydrogenated within 30 s at approximately 230 °C. The absorption properties are stable upon cycling. This work shows that ternary amides containing transition metals have great potential as hydrogen storage materials.

  6. Late transition metal m-or chemistry and D6 metal complex photoeliminations

    Energy Technology Data Exchange (ETDEWEB)

    Sharp, Paul [Univ. of Missouri, Columbia, MO (United States)

    2015-07-31

    With the goal of understanding and controlling photoreductive elimination reactions from d6 transition metal complexes as part of a solar energy storage cycle we have investigated the photochemistry of Pt(IV) bromo, chloro, hydroxo, and hydroperoxo complexes. Photoreductive elimination reactions occur for all of these complexes and appear to involve initial Pt-Br, Pt-Cl, or Pt-O bond fission. In the case of Pt-OH bond fission, the subsequent chemistry can be controlled through hydrogen bonding to the hydroxo group.

  7. Ligational behavior of Schiff bases towards transition metal ion and metalation effect on their antibacterial activity.

    Science.gov (United States)

    Devi, Jai; Batra, Nisha; Malhotra, Rajesh

    2012-11-01

    New Schiff bases pyrazine-2-carboxylicacid (phenyl-pyridin-2-yl-methylene)-hydrazide (Hpch-bp) HL(1) and pyrazine-2-carboxylicacid (pyridin-2-ylmethylene)-hydrazide (Hpch-pc) HL(2) derived from condensation of pyrazine carboxylic hydrazide (Hpch) with 2-benzoyl pyridine (bp) or pyridine 2-carbaldehyde (pc) and their transition metal complexes of type ML((1-2)2) have been synthesized, where M=Mn(II), Co(II), Ni(II), Cu(II) and Zn(II). Characterization of ligands and their metal complexes was carried out by elemental analysis, conductimetric studies, magnetic susceptibility, spectroscopic techniques (IR, UV-VIS, NMR, ESR, Mass) and thermogravimetric analysis. The physico-chemical studies revealed octahedral geometry or distorted octahedral geometry around metal ion. These azomethine Schiff base ligands acted as tridentate coordinating through carbonyl, azomethine and pyridine nitrogen present in the ligand. The thermodynamic and thermal properties of the complexes have been investigated and it was observed on the basis of these studies that thermal stability of complexes follows the order Mnantibacterial activity at different concentrations against bacteria viz. Gram positive Bacillus subtilis, Micrococcus luteus and Gram negative Pseudomonas aeruginosa, Pseudomonas mendocina. A marked enhancement in biocidal activity of the ligands under similar experimental conditions was observed as a consequence of coordination with metal ions. The trend of growth inhibition in the complexes was found to be in the order: Cu>Mn>Ni>Co>Zn.

  8. Ligational behavior of Schiff bases towards transition metal ion and metalation effect on their antibacterial activity

    Science.gov (United States)

    Devi, Jai; Batra, Nisha; Malhotra, Rajesh

    2012-11-01

    New Schiff bases pyrazine-2-carboxylicacid (phenyl-pyridin-2-yl-methylene)-hydrazide (Hpch-bp) HL1 and pyrazine-2-carboxylicacid (pyridin-2-ylmethylene)-hydrazide (Hpch-pc) HL2 derived from condensation of pyrazine carboxylic hydrazide (Hpch) with 2-benzoyl pyridine (bp) or pyridine 2-carbaldehyde (pc) and their transition metal complexes of type ML(1-2)2 have been synthesized, where M = Mn(II), Co(II), Ni(II), Cu(II) and Zn(II). Characterization of ligands and their metal complexes was carried out by elemental analysis, conductimetric studies, magnetic susceptibility, spectroscopic techniques (IR, UV-VIS, NMR, ESR, Mass) and thermogravimetric analysis. The physico-chemical studies revealed octahedral geometry or distorted octahedral geometry around metal ion. These azomethine Schiff base ligands acted as tridentate ? coordinating through carbonyl, azomethine and pyridine nitrogen present in the ligand. The thermodynamic and thermal properties of the complexes have been investigated and it was observed on the basis of these studies that thermal stability of complexes follows the order Mn complexes were tested for in vitro antibacterial activity at different concentrations against bacteria viz. Gram positive Bacillus subtilis, Micrococcus luteus and Gram negative Pseudomonas aeruginosa, Pseudomonas mendocina. A marked enhancement in biocidal activity of the ligands under similar experimental conditions was observed as a consequence of coordination with metal ions. The trend of growth inhibition in the complexes was found to be in the order: Cu > Mn > Ni > Co > Zn.

  9. The highly synergistic, broad spectrum, antibacterial activity of organic acids and transition metals

    Science.gov (United States)

    Zhitnitsky, Daniel; Rose, Jessica; Lewinson, Oded

    2017-01-01

    For millennia, transition metals have been exploited to inhibit bacterial growth. We report here the potentiation of the anti-bacterial activity of transition metals by organic acids. Strong synergy between low, non-toxic concentrations of transition metals and organic acids was observed with up to ~1000-fold higher inhibitory effect on bacterial growth. We show that organic acids shuttle transition metals through the permeability barrier of the bacterial membrane, leading to increased influx of transition metals into bacterial cells. We demonstrate that this synergy can be effectively used to inhibit the growth of a broad range of plant and human bacterial pathogens, and suggest that a revision of food preservation and crop protection strategies may be in order. These findings bear significant biomedical, agricultural, financial and environmental opportunities. PMID:28294164

  10. Electron Scattering at Surfaces and Interfaces of Transition Metals

    Science.gov (United States)

    Zheng, Pengyuan

    The effect of surfaces on the electron transport at reduced scales is attracting continuous interest due to its broad impact on both the understanding of materials properties and their application for nanoelectronics. The size dependence of for conductor's electrical resistivity rho due to electron surface scattering is most commonly described within the framework of Fuchs and Sondheimer (FS) and their various extensions, which uses a phenomenological scattering parameter p to define the probability of electrons being elastically (i.e. specularly) scattered by the surface without causing an increase of rho at reduced size. However, a basic understanding of what surface chemistry and structure parameters determine the specularity p is still lacking. In addition, the assumption of a spherical Fermi surface in the FS model is too simple for transition metals to give accurate account of the actual surface scattering effect. The goal of this study is to develop an understanding of the physics governing electron surface/interface scattering in transition metals and to study the significance of their Fermi surface shape on surface scattering. The advancement of the scientific knowledge in electron surface and interface scattering of transition metals can provide insights into how to design high-conductivity nanowires that will facilitate the viable development of advanced integrated circuits, thermoelectric power generation and spintronics. Sequential in situ and ex situ transport measurements as a function of surface chemistry demonstrate that electron surface/interface scattering can be engineered by surface doping, causing a decrease in the rho. For instance, the rho of 9.3-nm-thick epitaxial and polycrystalline Cu is reduced by 11--13% when coated with 0.75 nm Ni. This is due to electron surface scattering which exhibits a specularity p = 0.7 for the Cu-vacuum interface that transitions to completely diffuse (p = 0) when exposed to air. In contrast, Ni-coated surfaces

  11. Transition-metal embedded carbon nitride monolayers: high-temperature ferromagnetism and half-metallicity

    Science.gov (United States)

    Choudhuri, Indrani; Kumar, Sourabh; Mahata, Arup; Rawat, Kuber Singh; Pathak, Biswarup

    2016-07-01

    High-temperature ferromagnetic materials with planar surfaces are promising candidates for spintronics applications. Using state-of-the-art density functional theory (DFT) calculations, transition metal (TM = Cr, Mn, and Fe) incorporated graphitic carbon nitride (TM@gt-C3N4) systems are investigated as possible spintronics devices. Interestingly, ferromagnetism and half-metallicity were observed in all of the TM@gt-C3N4 systems. We find that Cr@gt-C3N4 is a nearly half-metallic ferromagnetic material with a Curie temperature of ~450 K. The calculated Curie temperature is noticeably higher than other planar 2D materials studied to date. Furthermore, it has a steel-like mechanical stability and also possesses remarkable dynamic and thermal (500 K) stability. The calculated magnetic anisotropy energy (MAE) in Cr@gt-C3N4 is as high as 137.26 μeV per Cr. Thereby, such material with a high Curie temperature can be operated at high temperatures for spintronics devices.High-temperature ferromagnetic materials with planar surfaces are promising candidates for spintronics applications. Using state-of-the-art density functional theory (DFT) calculations, transition metal (TM = Cr, Mn, and Fe) incorporated graphitic carbon nitride (TM@gt-C3N4) systems are investigated as possible spintronics devices. Interestingly, ferromagnetism and half-metallicity were observed in all of the TM@gt-C3N4 systems. We find that Cr@gt-C3N4 is a nearly half-metallic ferromagnetic material with a Curie temperature of ~450 K. The calculated Curie temperature is noticeably higher than other planar 2D materials studied to date. Furthermore, it has a steel-like mechanical stability and also possesses remarkable dynamic and thermal (500 K) stability. The calculated magnetic anisotropy energy (MAE) in Cr@gt-C3N4 is as high as 137.26 μeV per Cr. Thereby, such material with a high Curie temperature can be operated at high temperatures for spintronics devices. Electronic supplementary information (ESI

  12. Voltage controlled magnetism in 3d transitional metals

    Science.gov (United States)

    Wang, Weigang

    2015-03-01

    Despite having attracted much attention in multiferroic materials and diluted magnetic semiconductors, the impact of an electric field on the magnetic properties remains largely unknown in 3d transitional ferromagnets (FMs) until recent years. A great deal of effort has been focused on the voltage-controlled magnetic anisotropy (VCMA) effect where the modulation of anisotropy field is understood by the change of electron density among different d orbitals of FMs in the presence of an electric field. Here we demonstrate another approach to alter the magnetism by electrically controlling the oxidation state of the 3d FM at the FM/oxide interface. The thin FM film sandwiched between a heavy metal layer and a gate oxide can be reversibly changed from an optimally-oxidized state with a strong perpendicular magnetic anisotropy to a metallic state with an in-plane magnetic anisotropy, or to a fully-oxidized state with nearly zero magnetization, depending on the polarity and time duration of the applied electric fields. This is a voltage controlled magnetism (VCM) effect, where both the saturation magnetization and anisotropy field of the 3d FM layer can be simultaneously controlled by voltage in a non-volatile fashion. We will also discuss the impact of this VCM effect on magnetic tunnel junctions and spin Hall switching experiments. This work, in collaboration with C. Bi, Y.H. Liu, T. Newhouse-Illige, M. Xu, M. Rosales, J.W. Freeland, O. Mryasov, S. Zhang, and S.G.E. te Velthuis, was supported in part by NSF (ECCS-1310338) and by C-SPIN, one of six centers of STARnet, a Semiconductor Research Corporation program, sponsored by MARCO and DARPA.

  13. Liquid-Liquid Structure Transition in Metallic Melts: Experimental Evidence by Viscosity Measurement

    Institute of Scientific and Technical Information of China (English)

    WANG Yu-Qing; WU Yu-Qin; BIAN Xiu-Fang

    2007-01-01

    Temperature dependence of viscosity for more than ten kinds of metallic melts is analysed based on viscosity measurements. An obvious turning point is observed on the Arrhenius curves. Since viscosity is one of the physical properties sensitive to structure, its discontinuous change with temperature reveals the possible liquidliquid structure transition in the metallic melts. Furthermore, an integrated liquid structure transition diagram of the Sn-Bi system is presented. The universality of liquid-liquid structure transition is also discussed simply.

  14. Impact of d -band filling on the dislocation properties of bcc transition metals: The case of tantalum-tungsten alloys investigated by density-functional theory

    Science.gov (United States)

    Li, Hong; Draxl, Claudia; Wurster, Stefan; Pippan, Reinhard; Romaner, Lorenz

    2017-03-01

    We address the impact of tantalum alloying on dislocation properties of tungsten. To that aim, we calculate elastic constants, atomic-row displacement energy, dislocation core energy, and Peierls stress for different degrees of alloying within the framework of density-functional theory. We show that the elastic shear constants decrease monotonously with Ta content. Conversely, atomic-row displacement energy and, consequently, core energy and Peierls stress show a nonmonotonous behavior. These quantities peak at 25 at% Ta, indicating a tendency for embrittlement of W at such alloying concentrations. Our findings are in agreement with the experimental literature.

  15. Study of loop-loop and loop-edge dislocation interactions in bcc iron

    DEFF Research Database (Denmark)

    Osetsky, Y.N.; Bacon, D.J.; Gao, F.;

    2000-01-01

    that the evolution of heterogeneities such as dislocation decoration and rafts has serious impacts on the mechanical properties on neutron-irradiated metals. In the present work, atomic-scale computer modelling (ASCM) has been applied to study the mechanisms for the formation of such microstructure in bcc iron...

  16. Dissociation of N2, NO, and CO on transition metal surfaces

    DEFF Research Database (Denmark)

    Mavrikakis, Manos; Hansen, Lars Bruno; Mortensen, Jens Jørgen;

    1999-01-01

    Using density functional theory we study the dissociation of N2, NO, and CO on transition metal surfaces. We discuss an efficient method to locate the minimum energy path and the transition state, and review recent calculations using this method to determine the transition state for dissociation...

  17. Metamagnetism of η-carbide-type transition-metal carbides and nitrides

    Science.gov (United States)

    Waki, T.; Terazawa, S.; Umemoto, Y.; Tabata, Y.; Sato, K.; Kondo, A.; Kindo, K.; Nakamura, H.

    2011-09-01

    η-carbide-type transition-metal compounds include the frustrated stella quadran-gula lattice. Due to characteristics of the lattice, we expect subtle transitions between frustrated and non-frustrated states. Here, we report metamagnetic transitions newly found in η-carbide-type compounds Fe3W3C, Fe6W6C and Co6W6C.

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

    Science.gov (United States)

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

    2015-08-18

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

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2015-05-07

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

  20. Robust quantum anomalous Hall effect in ferromagnetic transition metal halides

    CERN Document Server

    Huang, Chengxi; Wu, Haiping; Deng, Kaiming; Jena, Puru; Kan, Erjun

    2016-01-01

    The quantum anomalous Hall (QAH) effect is a novel topological spintronic phenomenon arising from inherent magnetization and spin-orbit coupling. Various theoretical and experimental efforts have been devoted in search of robust intrinsic QAH insulators. However, up to now, it has only been observed in Cr or V doped (Bi,Sb)2Te3 film in experiments with very low working temperature. Based on the successful synthesis of transition metal halides, we use first-principles calculations to predict that RuI3 monolayer is an intrinsic ferromagnetic QAH insulator with a topologically nontrivial global band gap of 11 meV. This topologically nontrivial band gap at the Fermi level is due to its crystal symmetry, thus the QAH effect is robust. Its Curie temperature, estimated to be ~360 K using Monte-Carlo simulation, is above room temperature and higher than most of two-dimensional ferromagnetic thin films. We also discuss the manipulation of its exchange energy and nontrivial band gap by applying in-plane strain. Our wor...

  1. PNP-Pincer-Type Phosphaalkene Complexes of Late Transition Metals.

    Science.gov (United States)

    Ozawa, Fumiyuki; Nakajima, Yumiko

    2016-10-01

    This account summarizes our recent studies on PNP-pincer-type phosphaalkene complexes. Phosphaalkenes with a P=C bond possess an extremely low-lying π* orbital and have a marked tendency to engage in strong π back-bonding with transition metals. This particular ligand property provides PNP-pincer complexes with unique structures and reactivities. 2,6-Bis(phosphaethenyl)pyridine leads to the isolation of coordinatively unsaturated complexes of Fe(I) and Cu(I); the former adopts a trigonal monopyramidal configuration, whereas the latter has a strong affinity for PF6- and SbF6- as non-coordinating anions. Unsymmetrical PNP-pincer-type phosphaalkene complexes of Ir(I) bearing a dearomatized pyridine unit instantly cleave the N-H bond of NH3 and the C-H bond of MeCN at room temperature. The dearomatized iridium complexes catalyze the dehydrative coupling of amines with alcohols to afford N-alkylated amines and imines in high yields.

  2. Interactions between lasers and two-dimensional transition metal dichalcogenides.

    Science.gov (United States)

    Lu, Junpeng; Liu, Hongwei; Tok, Eng Soon; Sow, Chorng-Haur

    2016-05-03

    The recent increasing research interest in two-dimensional (2D) layered materials has led to an explosion of in the discovery of novel physical and chemical phenomena in these materials. Among the 2D family, group-VI transition metal dichalcogenides (TMDs), such as represented by MoS2 and WSe2, are remarkable semiconductors with sizable energy band gaps, which make the TMDs promising building blocks for new generation optoelectronics. On the other hand, the specificity and tunability of the band gaps can generate particularly strong light-matter interactions between TMD crystals and specific photons, which can trigger complex and interesting phenomena such as photo-scattering, photo-excitation, photo-destruction, photo-physical modification, photochemical reaction and photo-oxidation. Herein, we provide an overview of the phenomena explained by various interactions between lasers and the 2D TMDs. Characterizations of the optical fundamentals of the TMDs via laser spectroscopies are reviewed. Subsequently, photoelectric conversion devices enabled by laser excitation and the functionality extension and performance improvement of the TMDs materials via laser modification are comprehensively summarized. Finally, we conclude the review by discussing the prospects for further development in this research area.

  3. Coherent quantum dynamics of excitons in monolayer transition metal dichalcogenides

    KAUST Repository

    Moody, Galan

    2016-03-14

    Transition metal dichalcogenides (TMDs) have garnered considerable interest in recent years owing to their layer thickness-dependent optoelectronic properties. In monolayer TMDs, the large carrier effective masses, strong quantum confinement, and reduced dielectric screening lead to pronounced exciton resonances with remarkably large binding energies and coupled spin and valley degrees of freedom (valley excitons). Coherent control of valley excitons for atomically thin optoelectronics and valleytronics requires understanding and quantifying sources of exciton decoherence. In this work, we reveal how exciton-exciton and exciton-phonon scattering influence the coherent quantum dynamics of valley excitons in monolayer TMDs, specifically tungsten diselenide (WSe2), using two-dimensional coherent spectroscopy. Excitation-density and temperature dependent measurements of the homogeneous linewidth (inversely proportional to the optical coherence time) reveal that exciton-exciton and exciton-phonon interactions are significantly stronger compared to quasi-2D quantum wells and 3D bulk materials. The residual homogeneous linewidth extrapolated to zero excitation density and temperature is ~1:6 meV (equivalent to a coherence time of 0.4 ps), which is limited only by the population recombination lifetime in this sample. © (2016) COPYRIGHT Society of Photo-Optical Instrumentation Engineers (SPIE). Downloading of the abstract is permitted for personal use only.

  4. Band Alignment of 2D Transition Metal Dichalcogenide Heterojunctions

    KAUST Repository

    Chiu, Ming Hui

    2016-09-20

    It is critically important to characterize the band alignment in semiconductor heterojunctions (HJs) because it controls the electronic and optical properties. However, the well-known Anderson\\'s model usually fails to predict the band alignment in bulk HJ systems due to the presence of charge transfer at the interfacial bonding. Atomically thin 2D transition metal dichalcogenide materials have attracted much attention recently since the ultrathin HJs and devices can be easily built and they are promising for future electronics. The vertical HJs based on 2D materials can be constructed via van der Waals stacking regardless of the lattice mismatch between two materials. Despite the defect-free characteristics of the junction interface, experimental evidence is still lacking on whether the simple Anderson rule can predict the band alignment of HJs. Here, the validity of Anderson\\'s model is verified for the 2D heterojunction systems and the success of Anderson\\'s model is attributed to the absence of dangling bonds (i.e., interface dipoles) at the van der Waal interface. The results from the work set a foundation allowing the use of powerful Anderson\\'s rule to determine the band alignments of 2D HJs, which is beneficial to future electronic, photonic, and optoelectronic devices. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. Defect engineering of two-dimensional transition metal dichalcogenides

    Science.gov (United States)

    Lin, Zhong; Carvalho, Bruno R.; Kahn, Ethan; Lv, Ruitao; Rao, Rahul; Terrones, Humberto; Pimenta, Marcos A.; Terrones, Mauricio

    2016-06-01

    Two-dimensional transition metal dichalcogenides (TMDs), an emerging family of layered materials, have provided researchers a fertile ground for harvesting fundamental science and emergent applications. TMDs can contain a number of different structural defects in their crystal lattices which significantly alter their physico-chemical properties. Having structural defects can be either detrimental or beneficial, depending on the targeted application. Therefore, a comprehensive understanding of structural defects is required. Here we review different defects in semiconducting TMDs by summarizing: (i) the dimensionalities and atomic structures of defects; (ii) the pathways to generating structural defects during and after synthesis and, (iii) the effects of having defects on the physico-chemical properties and applications of TMDs. Thus far, significant progress has been made, although we are probably still witnessing the tip of the iceberg. A better understanding and control of defects is important in order to move forward the field of Defect Engineering in TMDs. Finally, we also provide our perspective on the challenges and opportunities in this emerging field.

  6. Nature of the Metallization Transition in Solid Hydrogen

    CERN Document Server

    Azadi, Sam; Foulkes, W M C

    2016-01-01

    We present an accurate study of the static-nucleus electronic energy band gap of solid molecular hydrogen at high pressure. The excitonic and quasiparticle gaps of the $C2/c$, $Pc$, $Pbcn$, and $P6_3/m$ structures at pressures of 250, 300, and 350~GPa are calculated using the fixed-node diffusion quantum Monte Carlo (DMC) method. The difference between the mean-field and many-body band gaps at the same density is found to be almost independent of system size and can therefore be applied as a scissor correction to the mean-field gap of an infinite system to obtain an estimate of the many-body gap in the thermodynamic limit. By comparing our static-nucleus DMC energy gaps with available experimental results, we demonstrate the important role played by nuclear quantum effects in the electronic structure of solid hydrogen. Our DMC results suggest that the metallization of high-pressure solid hydrogen occurs via a structural phase transition rather than band gap closure.

  7. Optoelectronics of Transition Metal Dichalcogenide Monolayers and Heterostructures

    Science.gov (United States)

    Schaibley, John

    2015-03-01

    Monolayer transition metal dichalcogenides (TMDs) contain 2D valley excitons which reside in two degenerate momentum space valleys at the edges of the Brillouin zone. It is crucially important to understand fundamental 2D exciton properties in TMD monolayers and van der Waals heterostructures. By performing coherent nonlinear optical spectroscopy with high spectral resolution, we observe nanosecond decay dynamics in single monolayers of MoSe2, implying the presence of a previously unreported long-lived state that appears to trap the exciton population. In MoSe2-WSe2 vertical heterostructures, we observe intralayer excitons, where the electron and hole are confined to different monolayers, and show evidence of strong exciton-exciton interaction effects and long lifetimes. Based on TMD monolayer excitons, we have also investigated a variety of fundamental quantum devices, including a nano-cavity laser and a second-harmonic generation transistor. Finally, we report a new type of single quantum emitter, based on single localized excitons spatially confined to defects in monolayers of WSe2. The photoluminescence from these localized excitons is spectrally narrow and shows strong anti-bunching, demonstrating the single photon nature of the emission.

  8. Fluorine substituent effects on dihydrogen bonding of transition metal hydrides.

    Science.gov (United States)

    Jacobsen, Heiko

    2009-09-07

    Hydrogen and dihydrogen bonding of the fluorinated alcohol (CF(3))(2)CHOH with the transition metal complex WH(CO)(2)(NO)(PMe(3))(2) has been explored by a set of four exemplary density functional theory methods that comprises the BP86, PBE, B3LYP and TPSS functionals. The hydride, nitrosyl and carbonyl ligands of the tungsten complex have been considered as sites of protonation. The main effect of fluorination is an increased dihydrogen bond strength by about 15 kJ mol(-1). The [see equation in text] dihydrogen bond is about 10 kJ mol(-1) stronger than the [W]-NOH-OR hydrogen bond. Of the four DFT methods investigated, the BP86 functional provides the most satisfying quantitative as well as qualitative agreement with experiment. The geometry of the [see equation in text] linkage is significantly influenced by secondary dispersive intermolecular bonding. Linear and bent dihydrogen bonds are separated in energy only by about 1 kJ mol(-1), and represent local minima on the corresponding energy hypersurface.

  9. Application of transition metal isotope tracers in global change research

    Institute of Scientific and Technical Information of China (English)

    SONG Jinming; Thomas F. Pedersen

    2005-01-01

    High-precision isotope composition determinations using multicollector, magnetic-sector inductively coupled plasma mass spectrometry (MC-ICPMS) have recently revealed that some transition metal isotopes such as those of Mo, Fe, Cu, Zn etc. can be used as biogeochemical tracers in global change research.The Mo isotope system may be useful in paleoredox investigations indicating that δ 97/95Mo in seawater may co-vary with changes in the relative proportions of anoxic and oxic sedimentation in the ocean, and that this variation may be recorded in δ 97/95Mo of anoxic sediments. The Mo continental flux into the oceans and the global Mo isotope budget can be estimated fromδ 97/95MO values. The Fe isotope composition in seawater is an important issue because Fe plays a controlling role in biological productivity in the oceans and its abundance in seawater may have substantial effect on climate changes. Iron isotope fractionations could result from bio- and abio-processes and have about 0.1% variation (δ 56/54Fe), so Fe isotopes considered alone cannot be used to distinguish the products of abiotic and biotic Fe processing in geological records. Cu and Zn isotopes are also used as biogeochemical tracers, but the researches are relatively less. This review mainly focuses on the methods for preparation, purification and determination of new isotope tracer samples, and on isotope applications in marine environmental changes.

  10. Quantum anomalous Hall effect in ferromagnetic transition metal halides

    Science.gov (United States)

    Huang, Chengxi; Zhou, Jian; Wu, Haiping; Deng, Kaiming; Jena, Puru; Kan, Erjun

    2017-01-01

    The quantum anomalous Hall (QAH) effect is a novel topological spintronic phenomenon arising from inherent magnetization and spin-orbit coupling. Various theoretical and experimental efforts have been devoted in search of intrinsic QAH insulators. However, up to now, it has only been observed in Cr or V doped (Bi,Sb ) 2T e3 film in experiments with very low working temperature. Based on the successful synthesis of transition metal halides, we use first-principles calculations to predict that the Ru I3 monolayer is an intrinsic ferromagnetic QAH insulator with a topologically nontrivial global band gap of 11 meV. This topologically nontrivial band gap at the Fermi level is due to its crystal symmetry, thus the QAH effect is robust. Its Curie temperature, estimated to be ˜360 K using Monte Carlo simulation, is above room temperature and higher than most two-dimensional ferromagnetic thin films. The inclusion of Hubbard U in the Ru-d electrons does not affect this result. We also discuss the manipulation of its exchange energy and nontrivial band gap by applying in-plane strain. Our work adds an experimentally feasible member to the QAH insulator family, which is expected to have broad applications in nanoelectronics and spintronics.

  11. Superconductivity Series in Transition Metal Dichalcogenides by Ionic Gating.

    Science.gov (United States)

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

    2015-08-03

    Functionalities of two-dimensional (2D) crystals based on semiconducting transition metal dichalcogenides (TMDs) have now stemmed from simple field effect transistors (FETs) to a variety of electronic and opto-valleytronic devices, and even to superconductivity. Among them, superconductivity is the least studied property in TMDs due to methodological difficulty accessing it in different TMD species. Here, we report the systematic study of superconductivity in MoSe2, MoTe2 and WS2 by ionic gating in different regimes. Electrostatic gating using ionic liquid was able to induce superconductivity in MoSe2 but not in MoTe2 because of inefficient electron accumulation limited by electronic band alignment. Alternative gating using KClO4/polyethylene glycol enabled a crossover from surface doping to bulk doping, which induced superconductivities in MoTe2 and WS2 electrochemically. These new varieties greatly enriched the TMD superconductor families and unveiled critical methodology to expand the capability of ionic gating to other materials.

  12. Transition metal dichalcogenide heterojunction PN diode toward ultimate photovoltaic benefits

    Science.gov (United States)

    Ahn, Jongtae; Jeon, Pyo Jin; Raza, Syed Raza Ali; Pezeshki, Atiye; Min, Sung-Wook; Hwang, Do Kyung; Im, Seongil

    2016-12-01

    Recently, two-dimensional (2D) transition metal dichalcogenide (TMDC) semiconductors as van der Waals (vdW) materials have attracted much attention from researchers. Among many 2D TMDC materials, a few layer-thin molybdenum disulfide (MoS2) and tungsten diselenide (WSe2) have been most intensively studied respectively as 2D n- and p-type semiconductors. Here, we have fabricated vertical vdW heterojunction n-MoS2/p-WSe2 diode with a few tens nm-thick layers by using vertically-sandwiched ohmic terminals, so that no quasi neutral region may exist between two terminals. As a result, we obtained high photo responsivity at zero volt without any electric power, and it appears comparable to those of commercially-optimized Si PN diode. Photo-voltage output of 0.3 V was easily obtained from our vdW PN diode as open circuit voltage, and can be doubled up to 0.6 V by using two PN diodes. These beneficial photovoltaic results from vdW PN diode were directly applied to PV switching dynamics and transistor photo gating, for the first time. We regard that our vdW n-MoS2/p-WSe2 heterojunction diode could maximize its photovoltaic energy benefits with optimized TMDC thicknesses.

  13. THE ELECTROCONDUCTIVITY OF THE LIQUID ALLOYS OF TRANSITION METALS

    Directory of Open Access Journals (Sweden)

    V.T.Shvets

    2004-01-01

    Full Text Available The concentration dependance of electroresistivity of the liquid binary alloys of transition metals Fe, Co and Ni is calculated. We considered the contribution to conductivity from the s-electrons, described within the model of nearly free electrons. The role of the partially occupied d-bands is reduced to resonance scattering of the s-electrons on d-states. The interaction of the s- and d-electrons is described by the hybridization potential of s- and d-states. The interaction with the ions, not including the partially occupied d-states, is described using the pseudopotential of the electron-ion interaction. The electroresistivity of the alloys is calculated in the second order of the perturbation theory in pseudopotential and hybridization potential. The concentration dependance of electroresistivity of the binary alloys approaches the linear regime as the resonance scattering of the s-electrons on d-states prevails over the scattering on the ions. The calculations exhibit good agreement with the experimental data.

  14. Arsenic poisoning of magnetism in bcc cobalt

    Science.gov (United States)

    Singh, David J.

    1992-04-01

    Highly converged local spin-density approximation calculations are used to determine the effectiveness of As as a poisoning agent for the magnetism of bcc Co films grown on GaAs. To do this, supercell calculations of the magnetization were performed using an extension of the general potential linearized augmented plane-wave method for Co7As, Co15As, and Co31As. The effect of the nearest-neighbor relaxation around As impurities, calculated using total energy techniques, was included. It is found that substitutional As is moderately effective as a poisoning agent, each As atom contributes a moment of -3.8μB, and this may be important in explaining the discrepancy of 0.2-0.3μB between the calculated magnetization of bcc Co and the measured magnetization of bcc Co films on GaAs.

  15. Magnetic-field induced superconductor-metal-insulator transitions in bismuth metal-graphite

    Science.gov (United States)

    Suzuki, Masatsugu; Suzuki, Itsuko S.; Lee, Robert; Walter, Jürgen

    2002-03-01

    Bismuth-metal graphite (MG) has a unique layered structure where Bi nanoparticles are encapsulated in nanographites. The size of nanographite is on the same order as that of Bi nanographite. The observed superconductivity below Tc (= 2.48 K) and the Curie-like Pauli paramagnetic susceptibility below 30 K are related to the high density of states at the Fermi energy arising from edge states of nanographites.^1 A magnetic-field induced transition from metallic to semiconductor-like phase is observed in the in-plane resistivity ρa around Hc (≈ 25 kOe) for both H⊥c and H‖c (c: c axis). The suppression of the metallic phase by H is independent of the directions of H (H‖c and H⊥c) for Bi-MG, suggesting that the spin related effect is significant compared to the orbital effect. The Zeemann energy gSμ_BH at 25 kOe corresponds to a thermal energy k_BTH with TH = 1.7 K, where g = 2 and S = 1/2. The temperature TH is slightly lower than T_c. A negative magnetoresistance in ρa for H⊥c (040 kOe) suggest the occurrence of two-dimensional weak localization effect. ^1K. Wakabayashi, M. Fujita, H. Ajiki, and M. Sigrist, Phys. Rev. 59, 8271 (1999).

  16. Electrocatalytic reduction of carbon dioxide on post-transition metal and metal oxide nanoparticles

    Science.gov (United States)

    White, James L.

    The electroreduction of carbon dioxide to liquid products is an important component in the utilization of CO2 and in the high-density storage of intermittent renewable energy in the form of chemical bonds. Materials based on indium and tin, which yield predominantly formic acid, have been investigated in order to gain a greater understanding of the electrochemically active species and the mechanism of CO2 reduction on these heavy post-transition metals, since prior studies on the bulk metals did not provide thermodynamically sensible reaction pathways. Nanoparticles of the oxides and hydroxides of tin and indium have been prepared and characterized by transmission electron microscopy, X-ray diffractometry, X-ray photoelectron spectroscopy, and various electrochemical methods in order to obtain structural information and analyze the role of various surface species on the CO2 reduction pathway. On both indium and tin, metastable surface-bound hydroxides bound CO2 and formed metal carbonates, which can then be reduced electrochemically. The relevant oxidation state of tin was suggested to be SnII rather than SnIV, necessitating a pre reduction to generate the CO2-binding species. Metallic indium nanoparticles partially oxidized in air and became highly efficient CO2 reduction electrocatalysts. Unit Faradaic efficiencies for formate, much higher than on bulk indium, were achieved with only 300 mV of overpotential on these particles, which possessed an oxyhydroxide shell surrounding a conductive metallic core. Alloys and mixed-metal oxide and hydroxide particles of tin and indium have also been studied for their carbon dioxide electrocatalytic capabilities, especially in comparison to the pure metal species. Additionally, a solar-driven indium-based CO2 electrolyzer was developed to investigate the overall efficiency for intermittent energy storage. The three flow cells were powered by a commercial photovoltaic array and had a maximum conversion efficiency of incident

  17. Modeling of the magnetic free energy of self-diffusion in bcc Fe

    Science.gov (United States)

    Sandberg, N.; Chang, Z.; Messina, L.; Olsson, P.; Korzhavyi, P.

    2015-11-01

    A first-principles based approach to calculating self-diffusion rates in bcc Fe is discussed with particular focus on the magnetic free energy associated with diffusion activation. First, the enthalpies and entropies of vacancy formation and migration in ferromagnetic bcc Fe are calculated from standard density functional theory methods in combination with transition state theory. Next, the shift in diffusion activation energy when going from the ferromagnetic to the paramagnetic state is estimated by averaging over random spin states. Classical and quantum mechanical Monte Carlo simulations within the Heisenberg model are used to study the effect of spin disordering on the vacancy formation and migration free energy. Finally, a quasiempirical model of the magnetic contribution to the diffusion activation free energy is applied in order to connect the current first-principles results to experimental data. The importance of the zero-point magnon energy in modeling of diffusion in bcc Fe is stressed.

  18. Studies on the Transition Metal Ion Induced Fluorescence Enhancement of 1,8-Naphthalimide Derivatives

    Institute of Scientific and Technical Information of China (English)

    WEN,Guo-Tao; ZHU,Man-Zhou; WANG,Zhuo; MENG,Xiang-Ming; HU,Hui-Yuan; GUO,Qing-Xiang

    2006-01-01

    Two fluorosensor systems have been designed and synthesized with their photophysical properties and fluorescence responses toward the transition metal ions studied. The fluorosensor was composed of 1,8-naphthalimide and 4-chloro-1,8-naphthalimide as fluorophore respectively, an amino moiety as the receptor and a hydrocarbon chain as the spacer to link the fluorophore and receptor. Fluorescence intensity of these systems is very weak due to the process of the efficient intramolecular photoinduced electron transfer (PET) in the absence of metal ions. Titration of the transition metal ions can switch on the fluorescence immediately. The intensity of released fluorescence is even higher than the expected from the consideration of the PET in these systems. It may be rationalized that the receptor bound to transition metal ions and the solvation of the fluorophore by the water molecules from the hydrated transition metal salts, may significantly cause fluorescence enhancement.

  19. Porous nanoarchitectures of spinel-type transition metal oxides for electrochemical energy storage systems.

    Science.gov (United States)

    Park, Min-Sik; Kim, Jeonghun; Kim, Ki Jae; Lee, Jong-Won; Kim, Jung Ho; Yamauchi, Yusuke

    2015-12-14

    Transition metal oxides possessing two kinds of metals (denoted as AxB3-xO4, which is generally defined as a spinel structure; A, B = Co, Ni, Zn, Mn, Fe, etc.), with stoichiometric or even non-stoichiometric compositions, have recently attracted great interest in electrochemical energy storage systems (ESSs). The spinel-type transition metal oxides exhibit outstanding electrochemical activity and stability, and thus, they can play a key role in realising cost-effective and environmentally friendly ESSs. Moreover, porous nanoarchitectures can offer a large number of electrochemically active sites and, at the same time, facilitate transport of charge carriers (electrons and ions) during energy storage reactions. In the design of spinel-type transition metal oxides for energy storage applications, therefore, nanostructural engineering is one of the most essential approaches to achieving high electrochemical performance in ESSs. In this perspective, we introduce spinel-type transition metal oxides with various transition metals and present recent research advances in material design of spinel-type transition metal oxides with tunable architectures (shape, porosity, and size) and compositions on the micro- and nano-scale. Furthermore, their technological applications as electrode materials for next-generation ESSs, including metal-air batteries, lithium-ion batteries, and supercapacitors, are discussed.

  20. Comparing the structural stability of PbS nanocrystals assembled in fcc and bcc superlattice allotropes.

    Science.gov (United States)

    Bian, Kaifu; Wang, Zhongwu; Hanrath, Tobias

    2012-07-04

    We investigated the structural stability of colloidal PbS nanocrystals (NCs) self-assembled into superlattice (SL) allotropes of either face-centered cubic (fcc) or body-centered cubic (bcc) symmetry. Small-angle X-ray scattering analysis showed that the NC packing density is higher in the bcc than in the fcc SL; this is a manifestation of the cuboctahedral shape of the NC building block. Using the high-pressure rock-salt/orthorhombic phase transition as a stability indicator, we discovered that the transition pressure for NCs in a bcc SL occurs at 8.5 GPa, which is 1.5 GPa higher than the transition pressure (7.0 GPa) observed for a fcc SL. The higher structural stability in the bcc SL is attributed primarily to the effective absorption of loading force in specific SL symmetry and to a lesser extent to the surface energy of the NCs. The experimental results provide new insights into the fundamental relationship between the symmetry of the self-assembled SL and the structural stability of the constituent NCs.

  1. Laser surface alloying of aluminium-transition metal alloys

    Directory of Open Access Journals (Sweden)

    Almeida, A.

    1998-04-01

    Full Text Available Laser surface alloying has been used as a tool to produce hard and corrosion resistant Al-transition metal (TM alloys. Cr and Mo are particularly interesting alloying elements to produce stable highstrength alloys because they present low diffusion coefficients and solid solubility in Al. To produce Al-TM surface alloys a two-step laser process was developed: firstly, the material is alloyed using low scanning speed and secondly, the microstructure is modified by a refinement step. This process was used in the production of Al-Cr, Al-Mo and Al-Nb surface alloys by alloying Cr, Mo or Nb powder into an Al and 7175 Al alloy substrate using a CO2 laser. This paper presents a review of the work that has been developed at Instituto Superior Tecnico on laser alloying of Al-TM alloys, over the last years.

    En el presente trabajo se estudia la aleación superficial mediante láser de aluminio con metales de transición. El cromo y el molibdeno son particularmente interesantes porque producen aleaciones de alta resistencia y por el bajo coeficiente de difusión y solución sólida en aluminio. Para producir estas aleaciones se ha seguido un procedimiento desarrollado en dos partes. En primer lugar, el material se alea usando una baja velocidad de procesado y en segundo lugar la estructura se modifica mediante un refinamiento posterior. Este procedimiento se ha empleado en la producción de aleaciones Al-Cr, Al-Mo y Al-Nb mediante aleación con láser de CO2 de polvos de Cr, Mo o Nb en aluminio y la aleación 7175. Este trabajo es una revisión del desarrollado en el Instituto Superior Técnico de Lisboa en los últimos años.

  2. Rules for maximum solid solubility of transition metals in Ti, Zr and Hf solvents

    Institute of Scientific and Technical Information of China (English)

    周自强; 方守狮; 冯锋

    2003-01-01

    Based on the principle of energy change of alloy formation, the rules for the maximum solid solubility (Cmax) of various transition metals in the metals Ti, Zr and Hf were studied. It is deduced that the Cmax of transition metals in the metals Ti, Zr and Hf can be described as a semi-empirical equation using three atomic parameters, i.e., electronegativity difference, atomic diameter and electron concentration. From the equation analysis by using experimental data, it shows that atomic size parameter and electronegativity difference are the main factors that affect the Cmax of the transition metals in the metals Ti, Zr and Hf while electron concentration parameter has the smallest effect on Cmax.

  3. Scaling Relationships for Adsorption Energies of C2 Hydrocarbons on Transition Metal Surfaces

    Energy Technology Data Exchange (ETDEWEB)

    Jones, G

    2011-08-18

    Using density functional theory calculations we show that the adsorption energies for C{sub 2}H{sub x}-type adsorbates on transition metal surfaces scale with each other according to a simple bond order conservation model. This observation generalizes some recently recognized adsorption energy scaling laws for AH{sub x}-type adsorbates to unsaturated hydrocarbons and establishes a coherent simplified description of saturated as well as unsaturated hydrocarbons adsorbed on transition metal surfaces. A number of potential applications are discussed. We apply the model to the dehydrogenation of ethane over pure transition metal catalysts. Comparison with the corresponding full density functional theory calculations shows excellent agreement.

  4. Density functional theory optimized basis sets for gradient corrected functionals: 3d transition metal systems.

    Science.gov (United States)

    Calaminici, Patrizia; Janetzko, Florian; Köster, Andreas M; Mejia-Olvera, Roberto; Zuniga-Gutierrez, Bernardo

    2007-01-28

    Density functional theory optimized basis sets for gradient corrected functionals for 3d transition metal atoms are presented. Double zeta valence polarization and triple zeta valence polarization basis sets are optimized with the PW86 functional. The performance of the newly optimized basis sets is tested in atomic and molecular calculations. Excitation energies of 3d transition metal atoms, as well as electronic configurations, structural parameters, dissociation energies, and harmonic vibrational frequencies of a large number of molecules containing 3d transition metal elements, are presented. The obtained results are compared with available experimental data as well as with other theoretical data from the literature.

  5. Effect of transition-metal additives on hydrogen desorption kinetics of MgH2

    Science.gov (United States)

    Roy, Anindya; Janotti, Anderson; Van de Walle, Chris G.

    2013-01-01

    Using first-principles calculations, we study the effect of transition-metal additives (Ti, Fe, Co, and Ni) on the rate of hydrogen desorption in MgH2. The presence of large concentrations of transition-metal impurities causes the Fermi level to shift according to the position of the transition-metal acceptor/donor levels in the band gap. This shift can lower the formation energy of native defects and increase their concentration. The resulting higher rates of hydrogen desorption enhance the prospect of MgH2 as a solid-state hydrogen-storage material.

  6. Evaluating transition-metal catalysis in gas generation from the Permian Kupferschiefer by hydrous pyrolysis

    Science.gov (United States)

    Lewan, M.D.; Kotarba, M.J.; Wieclaw, D.; Piestrzynski, A.

    2008-01-01

    Transition metals in source rocks have been advocated as catalysts in determining extent, composition, and timing of natural gas generation (Mango, F. D. (1996) Transition metal catalysis in the generation of natural gas. Org. Geochem.24, 977–984). This controversial hypothesis may have important implications concerning gas generation in unconventional shale-gas accumulations. Although experiments have been conducted to test the metal-catalysis hypothesis, their approach and results remain equivocal in evaluating natural assemblages of transition metals and organic matter in shale. The Permian Kupferschiefer of Poland offers an excellent opportunity to test the hypothesis with immature to marginally mature shale rich in both transition metals and organic matter. Twelve subsurface samples containing similar Type-II kerogen with different amounts and types of transition metals were subjected to hydrous pyrolysis at 330° and 355 °C for 72 h. The gases generated in these experiments were quantitatively collected and analyzed for molecular composition and stable isotopes. Expelled immiscible oils, reacted waters, and spent rock were also quantitatively collected. The results show that transition metals have no effect on methane yields or enrichment. δ13C values of generated methane, ethane, propane and butanes show no systematic changes with increasing transition metals. The potential for transition metals to enhance gas generation and oil cracking was examined by looking at the ratio of the generated hydrocarbon gases to generated expelled immiscible oil (i.e., GOR), which showed no systematic change with increasing transition metals. Assuming maximum yields at 355 °C for 72 h and first-order reaction rates, pseudo-rate constants for methane generation at 330 °C were calculated. These rate constants showed no increase with increasing transition metals. The lack of a significant catalytic effect of transition metals on the extent, composition, and timing of

  7. Structural and Electrochemical Characterization of Lithium Transition Metal Phosphates

    Science.gov (United States)

    Hashambhoy, Ayesha Maria

    The lithium ion battery has emerged as one of the most promising hybrid vehicle energy storage systems of the future. Of the potential cathode chemistries explored, lithium transition metal phosphates have generated a significant amount of interest due to their low-cost precursors, potential ease of synthesis, stability, and their environmentally friendly nature. This is in contrast to layered oxide systems such as LiCoO2, which have long been considered state of the art, but are now being reevaluated due to their structural instability at elevated temperatures, and higher cost. In particular, LiFePO4 has an operating potential comparable to those batteries available on the market (˜3.5V vs. Li/Li+), and higher theoretical specific capacity (170mAh/g vs. that of LiCoO2 which is 140mAh/g). The manganese analog to LiFePO4, LiMnPO4, exhibits a higher operating potential (˜4.1V v Li/Li+), and the same theoretical capacity, however Li-ion diffusion through this structure is much more rate limited and its theoretical capacity cannot be realized at rates suitable for commercial applications. The purpose of this work was threefold: 1) To explore the impact of Fe substitution on Mn sites in LiMnPO 4. 2) To examine the effects of alterations to the particle/electrolyte interface on rate capability. 3) To explore a novel fabrication route for LiMnPO4 using microwaves, and determine an optimal power and time combination for best performance. The coexistence of Fe and Mn on the transition metal site M, of LiMPO 4 resulted in an improved apparent Li-ion diffusivity in both Fe and Mn regimes as compared to that observed for LiFePO4 and LiMnPO 4 respectively. Calculations made from two different analysis methods, cyclic voltammetry (CV) and galvanostatic intermittent titration (GITT) drew this same conclusion. The signature characteristics observed from the CVs pertaining to single and dual phase reactions led to a delithiation model of LiFe0.5Mn0.5PO4 proposing the localization

  8. Noncollinear magnetism in surfaces and interfaces of transition metals

    Energy Technology Data Exchange (ETDEWEB)

    Tan, Huahai

    2009-09-15

    Noncollinear (NC) magnetism is common in nature, especially when there exist geometrical frustration and chemical imparity in the system. In this work we studied the NC magnetism and the response to external magnetic fields in surfaces and interfaces of transition metals by using an semi-empirical tight-binding (TB) method that parameterized to the ab initio TB-LMTO calculations. We implemented this method to study two systems. The first one is the system of 6 Mn monolayers on Fe(001) substrate. Due to the complex structure and magnetic properties of Mn, we found 23 collinear magnetic configurations but only one NC configuration. The collinear ground state has a layered antiferromagnetic (AFM) coupling which agrees with previous experiments and calculations. In the NC configuration the local AFM coupling in the Mn layers is preserved, but the surface is 90 degree coupled to the substrate. Similar to the experiment in CdCr{sub 2}O{sub 4}, we obtained a collinear plateau in the NC evolution of the average magnetic moment in Mn slab under external magnetic fields. Another is the system of a Cr monolayer on a stepped Fe(001) substrate. As expected, the local AFM coupling in the interface of Cr and Fe are preserved. However, the edge Cr atoms is about 90 coupled to their nearest Fe neighbors. We also simulated the procedure of adding more Cr coverages gradually to a Cr bilayer coverage. As coverages increase, the magnetic moments in the Cr interface reduce, and the collinear plateau becomes wider as coverages increase. However, the saturation fields in both the two systems are extremely high, around 10 kT.We expect that when the effect of temperature is taken into account, and in some proper systems, the saturation fields could be largely reduced to the scale that can be implemented in experiment, and our study may shed light on information storage devices with ultrahigh storage density. (orig.)

  9. Metal-insulator transition in 3d transition-metal oxides with ABO 3 and A 2BO 4 type structures

    Science.gov (United States)

    Eisaki, H.; Ido, T.; Magoshi, K.; Mochizuki, M.; Yamatsu, H.; Ito, T.; Uchida, S.

    1991-12-01

    3d transition-metal oxides with perovskite and K 2NiF 4 crystal structures, (La,Sr)VO 3, (La,Sr)FeO 3, (La,Sr)CoO 3, LaNiO 3 and (La,Sr) 2NiO 4 systems are investigated focusing on the effect of carrier doping performed by the A-site ion substitution. Both (La,Sr)VO 3 and (La,Sr)CoO 3 systems show an insulator to metal transition by Sr substitution, however, the magnetic behavior differs drastically. The mid-infrared structure induced by Sr substitution is observed in the optical spectra of (La,Sr) 2NiO 4 system. Relation between the behavior of metal-insulator transition and the variation of the electronic and/or spin structure in these systems is discussed in comparison with the high-T c copper oxides.

  10. Lanthanide Single-Molecule Magnets Framed by Alkali Metals & Magnetic and Spectroscopic Studies of 3d Transition Metal Complexes

    DEFF Research Database (Denmark)

    Konstantatos, Andreas

    )imino)- methyl)benzene-1,2-diol]. Using this ligand, we were able to synthesize four different families of lanthanide complexes framed by alkali metals. Throughout the chapter we demonstrate how we can exploit the presence of the coordinated alkali metal ions in order to induce changes to the structure....... In Chapter 3 we present the results of our work with third row (3d) transition metal ions and their complexes. Specifically, in section 2.1 we report a series of complexes synthesized using a tripodal hexadentate Schiff-base ligand. The ligand demonstrates the ability to form mononuclear or trinuclear...... complexes of M3+ or M2+ metal ions (M: 3d transition metal) with the preference to either approximate octahedral or trigonal prismatic coordination geometry. A detailed magnetic characterization for most of the complexes is presented where a trinuclear Co2+ cluster stands out for its pronounced SMM...

  11. Infrared Spectroscopy of Transition Metal-Molecular interactions in the Gas Phase

    Energy Technology Data Exchange (ETDEWEB)

    Duncan, Michael A. [Univ. of Georgia, Athens, GA (United States)

    2008-11-14

    Transition metal-molecular complexes produced in a molecular beam are mass-selected and studied with infrared laser photodissociation spectroscopy. Metal complexes with carbon monoxide, carbon dioxide, nitrogen, water, acetylene or benzene are studied for a variety of metals. The number and intensity of infrared active bands are compared to the predictions of density functional theory calculations to derive structures, spin states and coordination numbers in these systems. These studied provide new insights into subtle details of metal-molecular interactions important in heterogeneous catalysis, metal-ligand bonding and metal ion solvation.

  12. k-asymmetric spin splitting at the interface between transition metal ferromagnets and heavy metals

    KAUST Repository

    Grytsyuk, Sergiy

    2016-05-23

    We systematically investigate the spin-orbit coupling-induced band splitting originating from inversion symmetry breaking at the interface between a Co monolayer and 4d (Tc, Ru, Rh, Pd, and Ag) or 5d (Re, Os, Ir, Pt, and Au) transition metals. In spite of the complex band structure of these systems, the odd-in-k spin splitting of the bands displays striking similarities with the much simpler Rashba spin-orbit coupling picture. We establish a clear connection between the overall strength of the odd-in-k spin splitting of the bands and the charge transfer between the d orbitals at the interface. Furthermore, we show that the spin splitting of the Fermi surface scales with the induced orbital moment, weighted by the spin-orbit coupling.

  13. CO adsorption on metal-oxide surfaces doped with transition-metal adatoms

    Energy Technology Data Exchange (ETDEWEB)

    Blomqvist, Janne; Lehman, Lauri; Salo, Petri [Department of Applied Physics, Aalto University, FI-00076 Aalto (Finland)

    2012-05-15

    Using first principles density functional theory calculations, we have studied the adsorption of carbon monoxide (CO) on clean, Ag and Pd doped MgO(001), TiO{sub 2}(110), and {alpha}-Al{sub 2}O{sub 3}(0001) surfaces. Our results show that adsorption of CO on the clean surfaces is generally weak. Ag doping improves the adsorption only weakly, except on the TiO{sub 2} surface. The presence of Pd, however, significantly improves adsorption on all the surfaces studied. On the doped surfaces, the best adsorption sites are always the sites on top of the transition metal adatom, and the interaction range is 3-4 Aa around an isolated adatom. (Copyright copyright 2012 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  14. On fuzzy BCC-ideals over a t-norm

    OpenAIRE

    Dudek, W. A.; JUN, Y. B.

    2000-01-01

    Using a t-norm T, the notion of T-fuzzy BCC-ideals of BCC-algebras is introduced, and some of their properties are investigated. Connections between different types of fuzzy BCC-ideals induced by t-norms are described.

  15. Metal-insulator phase transition in a VO2 thin film observed with terahertz spectroscopy

    DEFF Research Database (Denmark)

    Jepsen, Peter Uhd; Fischer, Bernd M.; Thoman, Andreas

    2006-01-01

    We investigate the dielectric properties of a thin VO2 film in the terahertz frequency range in the vicinity of the semiconductor-metal phase transition. Phase-sensitive broadband spectroscopy in the frequency region below the phonon bands of VO2 gives insight into the conductive properties...... of the film during the phase transition. We compare our experimental data with models proposed for the evolution of the phase transition. The experimental data show that the phase transition occurs via the gradual growth of metallic domains in the film, and that the dielectric properties of the film...

  16. Defect Studies in bcc and fcc Iron

    OpenAIRE

    Ghorai, A.; Arjun Das

    2012-01-01

    Variation of vacancy formation energy (EF1v) with rc of Ashcroft's empty core model potential (AECMP) model for different exchange and correlation functions (ECFs) show almost independent nature but slight variation with ECF for both bcc α iron and fcc γ iron.

  17. Systemic treatments for basal cell carcinoma (BCC): the advent of dermato-oncology in BCC.

    Science.gov (United States)

    Ali, F R; Lear, J T

    2013-07-01

    Basal cell carcinoma (BCC) is the most common cancer in the U.K. and its incidence is increasing. Vismodegib, a hedgehog pathway inhibitor, has recently been licensed by the U.S. Food and Drug Administration for treatment of advanced BCC. Phase 2 trials have demonstrated efficacy in cases of locally advanced and metastatic BCC, as well as cases of hereditary basal cell naevus (Gorlin) syndrome. Side-effects are frequent and considerable and include myalgia, taste disturbance, alopecia, weight loss and fatigue. Further research is needed to investigate means of circumventing these side-effects, and longitudinal data are required to assess the long-term benefits of, and the nature of resistance to, this novel class of agents. Alternative hedgehog inhibitors are currently in clinical development. We review the current data pertaining to this novel treatment modality and discuss its likely future role in the management of BCC.

  18. Prediction of spin-dependent electronic structure in 3d-transition-metal doped antimonene

    Science.gov (United States)

    Yang, L. F.; Song, Y.; Mi, W. B.; Wang, X. C.

    2016-07-01

    We investigate the geometric structure and electronic and magnetic properties of 3d-transition-metal atom doped antimonene using spin-polarized first-principles calculations. Strong orbital hybridization exhibits between 3d-transition-metal and Sb atoms, where covalent bonds form in antimonene. A spin-polarized semiconducting state appears in Cr-doped antimonene, while half-metallic states appear by doping Ti, V, and Mn. These findings indicate that once combined with doping states, the bands of antimonene systems offer a variety of features. Specific dopants lead to half-metallic characters with high spin polarization that has potential application in spintronics.

  19. 22 CFR 41.33 - Nonresident alien Canadian border crossing identification card (BCC).

    Science.gov (United States)

    2010-04-01

    ... identification card (BCC). 41.33 Section 41.33 Foreign Relations DEPARTMENT OF STATE VISAS VISAS: DOCUMENTATION... Nonresident alien Canadian border crossing identification card (BCC). (a) Validity of Canadian BCC. A Canadian BCC or the BCC portion of a Canadian B-1/B-2 Visa/BCC issued to a permanent resident of...

  20. Controlled synthesis of transition metal/conducting polymer nanocomposites

    Science.gov (United States)

    Liu, Zhen; Liu, Yang; Zhang, Lin; Poyraz, Selcuk; Lu, Ning; Kim, Moon; Smith, James; Wang, Xiaolong; Yu, Yajiao; Zhang, Xinyu

    2012-08-01

    A novel displacement reaction has been observed to occur between conducting polymers (CP) and metal salts which can be used to fabricate nanostructured CP-metal composites in a one-pot manner. Vanadium pentoxide (V 2O5) nanofiber is used during the synthesis as the reactive seeds to induce the nanofibril CP-metal network formation. The CP-metal nanocomposites exhibit excellent sensory properties for hydrogen peroxide (H2O2) detection, where both high sensitivity and a low detection limit can be obtained. The sensory performance of the CP-metal composite can be further enhanced by a facile microwave treatment. It is believed that the CP-metal nanofibril network can be converted to a carbon-metal network by a microwave-induced carbonization process and result in the sensory enhancement.

  1. Suppression of Structural Phase Transition in VO2 by Epitaxial Strain in Vicinity of Metal-insulator Transition

    Science.gov (United States)

    Yang, Mengmeng; Yang, Yuanjun; Bin Hong; Wang, Liangxin; Hu, Kai; Dong, Yongqi; Xu, Han; Huang, Haoliang; Zhao, Jiangtao; Chen, Haiping; Song, Li; Ju, Huanxin; Zhu, Junfa; Bao, Jun; Li, Xiaoguang; Gu, Yueliang; Yang, Tieying; Gao, Xingyu; Luo, Zhenlin; Gao, Chen

    2016-03-01

    Mechanism of metal-insulator transition (MIT) in strained VO2 thin films is very complicated and incompletely understood despite three scenarios with potential explanations including electronic correlation (Mott mechanism), structural transformation (Peierls theory) and collaborative Mott-Peierls transition. Herein, we have decoupled coactions of structural and electronic phase transitions across the MIT by implementing epitaxial strain on 13-nm-thick (001)-VO2 films in comparison to thicker films. The structural evolution during MIT characterized by temperature-dependent synchrotron radiation high-resolution X-ray diffraction reciprocal space mapping and Raman spectroscopy suggested that the structural phase transition in the temperature range of vicinity of the MIT is suppressed by epitaxial strain. Furthermore, temperature-dependent Ultraviolet Photoelectron Spectroscopy (UPS) revealed the changes in electron occupancy near the Fermi energy EF of V 3d orbital, implying that the electronic transition triggers the MIT in the strained films. Thus the MIT in the bi-axially strained VO2 thin films should be only driven by electronic transition without assistance of structural phase transition. Density functional theoretical calculations further confirmed that the tetragonal phase across the MIT can be both in insulating and metallic states in the strained (001)-VO2/TiO2 thin films. This work offers a better understanding of the mechanism of MIT in the strained VO2 films.

  2. Solving the puzzle of interstitial loop formation in bcc Iron.

    Science.gov (United States)

    Xu, Haixuan; Stoller, Roger E; Osetsky, Yury N; Terentyev, Dmitry

    2013-06-28

    The interstitial loop is a unique signature of radiation damage in structural materials for nuclear and other advanced energy systems. Unlike other bcc metals, two types of interstitial loops, 1/2 and , are formed in bcc iron and its alloys. However, the mechanism by which interstitial dislocation loops are formed has remained undetermined since they were first observed more than fifty years ago. We describe our atomistic simulations that have provided the first direct observation of loop formation. The process was initially observed using our self-evolving atomistic kinetic Monte Carlo method, and subsequently confirmed using molecular dynamics simulations. Formation of loops involves a distinctly atomistic interaction between two 1/2 loops, and does not follow the conventional assumption of dislocation theory, which is Burgers vector conservation between the reactants and the product. The process observed is different from all previously proposed mechanisms. Thus, our observations might provide a direct link between experiments and simulations and new insights into defect formation that may provide a basis to increase the radiation resistance of these strategic materials.

  3. Fuzzy Ideals and Congruences in BCC-algebras%BCC-代数的模糊理想与同余

    Institute of Scientific and Technical Information of China (English)

    彭家寅

    2010-01-01

    引入BCC-代数的一种新的模糊理想,并研究了它的性质,讨论了BCC-代数中模糊BCC-子代数、模糊BCK-子代数、模糊BCC-理想、模糊BCK-理想四者间的关系,给出了BCC-代数的模糊BCC-理想与BCC-代数的积代数的模糊BCC-理想二者间的关系,揭示了BCC-代数的模糊BCC-理想与同余之间的联系,讨论了由模糊BBC-理想诱导的商BCC-代数. 最后,研究了模糊BCC-理想与模糊BCK-子代数的同态象和同态逆象,建立了模糊同态基本定理.

  4. Volcano Relation for the Deacon Process over Transition-Metal Oxides

    DEFF Research Database (Denmark)

    Studt, Felix; Abild-Pedersen, Frank; Hansen, Heine Anton

    2010-01-01

    We establish an activity relation for the heterogeneous catalytic oxidation of HCI (the Deacon Process) over rutile transition-metal oxide catalysts by combining density functional theory calculations (DFT) with microkinetic modeling. Linear energy relations for the elementary reaction steps...

  5. Determination of mobility edge in presence of metal-to-insulator transition

    Science.gov (United States)

    Tito, M. A.; Pusep, Yu. A.

    2017-04-01

    Determination of mobility edge in presence of metal-to-insulator transition Recombination dynamics of excitons was studied in multiple narrow quantum well GaAs/AlGaAs heterostructures. Disorder generated by interface roughness considerably affects transport of the conduction band electrons and at appropriate quantum well width results in a metal-to insulator transition. Localization of the electrons was found to be responsible for the exciton recombination time measured in the vicinity of the metal-to-insulator transition. Measurement of the exciton recombination time as a function of the energy allowed for determination of the critical energy of the mobility edge attributed to the conduction band electrons. The mobility edge energy obtained in this way demonstrates intersection with the Fermi level energy at the critical disorder corresponding to the metal-to-insulator transition.

  6. Electron Spin Resonance of Tetrahedral Transition Metal Oxyanions (MO4n-) in Solids.

    Science.gov (United States)

    Greenblatt, M.

    1980-01-01

    Outlines general principles in observing sharp electron spin resonance (ESR) lines in the solid state by incorporating the transition metal ion of interest into an isostructural diamagnetic host material in small concentration. Examples of some recent studies are described. (CS)

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

    Science.gov (United States)

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

    2013-02-01

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

  8. Preparation of transition metal nanoparticles and surfaces modified with (co)polymers synthesized by RAFT

    Science.gov (United States)

    McCormick, III, Charles L.; Lowe, Andrew B.; Sumerlin, Brent S.

    2011-12-27

    A new, facile, general one-phase method of generating thiol-functionalized transition metal nanoparticles and surfaces modified by (co)polymers synthesized by the RAFT method is described. The method includes the steps of forming a (co)polymer in aqueous solution using the RAFT methodology, forming a colloidal transition metal precursor solution from an appropriate transition metal; adding the metal precursor solution or surface to the (co)polymer solution, adding a reducing agent into the solution to reduce the metal colloid in situ to produce the stabilized nanoparticles or surface, and isolating the stabilized nanoparticles or surface in a manner such that aggregation is minimized. The functionalized surfaces generated using these methods can further undergo planar surface modifications, such as functionalization with a variety of different chemical groups, expanding their utility and application.

  9. Structural and magnetic properties of a variety of transition metal incorporated DNA double helices.

    Science.gov (United States)

    Samanta, Pralok K; Pati, Swapan K

    2014-02-03

    By using density functional theory calculations, the structural, energetic, magnetic, and optical properties for a variety of transition metal (M = Mn, Fe, Co, Ni and Cu) ions incorporated modified-DNA (M-DNA) double helices has been investigated. The DNA is modified with either hydroxypyridone (H) or bis(salicylaldehyde)ethylenediamine (S-en) metalated bases. We find the formation of extended M-O network leading to the ferromagnetic interactions for the case of H-DNA for all the metal ions. More ordered stacking arrangement was found for S-en-DNA. We calculate the exchange coupling constant (J) considering Heisenberg Hamiltonian for quantitative description of magnetic interactions. The ferromagnetic and antiferromagnetic interactions are obtained by varying different transition metal ions. The extent of the magnetic interaction depends on the number of transition metal ions. Optical profiles show peaks below 2 eV, a clear signature of spin-spin coupling.

  10. Trends in oxygen reduction and methanol activation on transition metal chalcogenides

    DEFF Research Database (Denmark)

    Tritsaris, Georgios; Nørskov, Jens Kehlet; Rossmeisl, Jan

    2011-01-01

    We use density functional theory calculations to study the oxygen reduction reaction and methanol activation on selenium and sulfur-containing transition metal surfaces. With ruthenium selenium as a starting point, we study the effect of the chalcogen on the activity, selectivity and stability...... of the catalyst. Ruthenium surfaces with moderate content of selenium are calculated active for the oxygen reduction reaction, and insensitive to methanol. A significant upper limit for the activity of transition metal chalcogenides is estimated....

  11. A Ratiometric Luminescent Thermometer Co-doped with Lanthanide and Transition Metals.

    Science.gov (United States)

    Li, Zhiqiang; Hou, Zhaohui; Ha, Denghui; Li, Huanrong

    2015-12-01

    Herein, we report the fabrication of a sensitive ratiometric and colorimetric luminescent thermometer with a wide operating-temperature range, from cryogenic temperatures up to high temperatures, through the combination of lanthanide and transition metal complexes. Benefiting from the transition metal complex as a self-reference, the lanthanide content in the mixed-coordination complex, Eu0.05(Mebip-mim bromine)0.15Zn0.95(Mebip-mim bromine)1.9, was lowered to 5%.

  12. A general scheme for the estimation of oxygen binding energies on binary transition metal surface alloys

    DEFF Research Database (Denmark)

    Greeley, Jeffrey Philip; Nørskov, Jens Kehlet

    2005-01-01

    A simple scheme for the estimation of oxygen binding energies on transition metal surface alloys is presented. It is shown that a d-band center model of the alloy surfaces is a convenient and appropriate basis for this scheme; variations in chemical composition, strain effects, and ligand effects...... for the estimation of oxygen binding energies on a wide variety of transition metal alloys. (c) 2005 Elsevier B.V. All rights reserved....

  13. Polypyridyl transition metal complexes with application in water oxidation catalysis and dye-sensitised solar cells

    OpenAIRE

    Rudd, Jennifer A.

    2012-01-01

    This thesis contains complementary synthetic and computational studies of transition metal complexes with polypyridyl ligands for use either as water oxidation catalysts or for application in dye-sensitised solar cells (DSSCs). Chapter 1 introduces the reasons for researching water splitting catalysts and describes a number of current techniques used to do so; from photoelectrochemical cells to the use of transition metal polypyridyl complexes. It also introduces three commercially avail...

  14. PHASE ANALYSIS AND CRYSTAL STRUCTURE STUDIES ON BINARY ALLOYS OF ALUMINUM WITH TRANSITION METALS.

    Science.gov (United States)

    In order to provide the necessary background for detailed crystal-chemistry studies in the field of binary aluminum - transition metal systems, extensive investigations have been carried out on the phase relations of a large number of such systems. The results of these studies are briefly summarized, as are also the results of crystal structure determinations of a few alumi num - transition metal phases. (Author)

  15. The thermodynamics and transport properties of transition metals in critical point

    CERN Document Server

    Khomkin, Alexander L

    2016-01-01

    A new method for calculating the critical point parameters (density, temperature, pressure and electrical conductivity) and binodal of vapor-liquid (dielectric-metal) phase transition is proposed. It is based on the assumption that cohesion, which determines the main properties of solid state, also determines the properties in the vicinity of the critical point. Comparison with experimental and theoretical data available for transition metals is made.

  16. The transition metals copper and iron in neurodegenerative diseases.

    Science.gov (United States)

    Rivera-Mancía, Susana; Pérez-Neri, Iván; Ríos, Camilo; Tristán-López, Luis; Rivera-Espinosa, Liliana; Montes, Sergio

    2010-07-30

    Neurodegenerative diseases constitute a worldwide health problem. Metals like iron and copper are essential for life, but they are also involved in several neurodegenerative mechanisms such as protein aggregation, free radical generation and oxidative stress. The role of Fe and Cu, their pathogenic mechanisms and possible therapeutic relevance are discussed regarding four of the most common neurodegenerative diseases, Alzheimer's, Parkinson's and Huntington's diseases as well as amyotrophic lateral sclerosis. Metal-mediated oxidation by Fenton chemistry is a common feature for all those disorders and takes part of a self-amplifying damaging mechanism, leading to neurodegeneration. The interaction between metals and proteins in the nervous system seems to be a crucial factor for the development or absence of neurodegeneration. The present review also deals with the therapeutic strategies tested, mainly using metal chelating drugs. Metal accumulation within the nervous system observed in those diseases could be the result of compensatory mechanisms to improve metal availability for physiological processes.

  17. Theory of magnetic transition metal nanoclusters on surfaces

    Energy Technology Data Exchange (ETDEWEB)

    Lounis, S.

    2007-04-17

    This thesis is motivated by the quest for the understanding and the exploration of complex magnetism provided by atomic scale magnetic clusters deposited on surfaces or embedded in the bulk. Use is made of the density functional theory (DFT). Acting within this framework, we have developed and implemented the treatment of non-collinear magnetism into the Juelich version of the full-potential Korringa-Kohn-Rostoker Green Function (KKR-GF) method. Firstly, the method was applied to 3d transition-metal clusters on different ferromagnetic surfaces. Different types of magnetic clusters where selected. In order to investigate magnetic frustration due to competing interactions within the ad-cluster we considered a (001) oriented surface of fcc metals, a topology which usually does not lead to non-collinear magnetism. We tuned the strength of the magnetic coupling between the ad-clusters and the ferromagnetic surface by varying the substrate from the case of Ni(001) with a rather weak hybridization of the Ni d-states with the adatom d-states to the case of Fe{sub 3ML}/Cu(001) with a much stronger hybridization due to the larger extend of the Fe wavefunctions. On Ni(001), the interaction between the Cr- as well as the Mn-dimer adatoms is of antiferromagnetic nature, which is in competition with the interaction with the substrate atoms. After performing total energy calculations we find that for Cr-dimer the ground state is collinear whereas the Mn-dimer prefers the non-collinear configuration as ground state. Bigger clusters are found to be magnetically collinear. These calculations were extended to 3d multimers on Fe{sub 3ML}/Cu(001). All neighboring Cr(Mn) moments in the compact tetramer are antiferromagnetically aligned in-plane, with the directions slightly tilted towards (outwards from) the substrate to gain some exchange interaction energy. The second type of frustration was investigated employing a Ni(111) surface, a surface with a triangular lattice of atoms, were

  18. Surface analysis of transition metal oxalates: Damage aspects

    Energy Technology Data Exchange (ETDEWEB)

    Chenakin, S.P., E-mail: chenakin@imp.kiev.ua [Université Libre de Bruxelles (ULB), Chimie-Physique des Matériaux, B-1050 Bruxelles (Belgium); Institute of Metal Physics, Nat. Acad. Sci. of Ukraine, Akad. Vernadsky Blvd. 36, 03680 Kiev (Ukraine); Szukiewicz, R. [Université Libre de Bruxelles (ULB), Chimie-Physique des Matériaux, B-1050 Bruxelles (Belgium); Barbosa, R.; Kruse, N. [Université Libre de Bruxelles (ULB), Chimie-Physique des Matériaux, B-1050 Bruxelles (Belgium); Voiland School of Chemical Engineering and Bioengineering, Washington State University, 155 Wegner Hall, Pullman, WA 99164-6515 (United States)

    2016-05-15

    Highlights: • Gas evolution from the Mn, Co, Ni and Cu oxalate hydrates in vacuum, during exposure to X-rays and after termination of X-ray irradiation is studied. • A comparative study of the damage caused by X-rays in NiC{sub 2}O{sub 4} and CuC{sub 2}O{sub 4} is carried out. • Effect of Ar{sup +} bombardment on the structure and composition of CoC{sub 2}O{sub 4} is studied. - Abstract: The behavior of transition metal oxalates in vacuum, under X-ray irradiation and low-energy Ar{sup +} ion bombardment was studied. A comparative mass-spectrometric analysis was carried out of gas evolution from the surface of Mn, Co, Ni and Cu oxalate hydrates in vacuum, during exposure to X-rays and after termination of X-ray irradiation. The rates of H{sub 2}O and CO{sub 2} liberation from the oxalates were found to be in an inverse correlation with the temperatures of dehydration and decomposition, respectively. X-ray photoelectron spectroscopy (XPS) was employed to study the X-ray induced damage in NiC{sub 2}O{sub 4} and CuC{sub 2}O{sub 4} by measuring the various XP spectral characteristics and surface composition of the oxalates as a function of time of exposure to X-rays. It was shown that Cu oxalate underwent a significantly faster degradation than Ni oxalate and demonstrated a high degree of X-ray induced reduction from the Cu{sup 2+} to the Cu{sup 1+} chemical state. 500 eV Ar{sup +} sputter cleaning of CoC{sub 2}O{sub 4} for 10 min was found to cause a strong transformation of the oxalate structure which manifested itself in an appreciable alteration of the XP core-level and valence band spectra. The analysis of changes in stoichiometry and comparison of XP spectra of bombarded oxalate with respective spectra of a reference carbonate CoCO{sub 3} implied that the bombardment-induced decomposition of CoC{sub 2}O{sub 4} gave rise to the formation of CoO-like and disordered CoCO{sub 3}-like phases.

  19. Correlation between oxygen adsorption energy and electronic structure of transition metal macrocyclic complexes.

    Science.gov (United States)

    Liu, Kexi; Lei, Yinkai; Wang, Guofeng

    2013-11-28

    Oxygen adsorption energy is directly relevant to the catalytic activity of electrocatalysts for oxygen reduction reaction (ORR). In this study, we established the correlation between the O2 adsorption energy and the electronic structure of transition metal macrocyclic complexes which exhibit activity for ORR. To this end, we have predicted the molecular and electronic structures of a series of transition metal macrocyclic complexes with planar N4 chelation, as well as the molecular and electronic structures for the O2 adsorption on these macrocyclic molecules, using the density functional theory calculation method. We found that the calculated adsorption energy of O2 on the transition metal macrocyclic complexes was linearly related to the average position (relative to the lowest unoccupied molecular orbital of the macrocyclic complexes) of the non-bonding d orbitals (d(z(2)), d(xy), d(xz), and d(yz)) which belong to the central transition metal atom. Importantly, our results suggest that varying the energy level of the non-bonding d orbitals through changing the central transition metal atom and/or peripheral ligand groups could be an effective way to tuning their O2 adsorption energy for enhancing the ORR activity of transition metal macrocyclic complex catalysts.

  20. Investigation of Ternary Transition-Metal Nitride Systems by Reactive Cosputtering

    NARCIS (Netherlands)

    Dover, R.B. Van; Hessen, B.; Werder, D.; Chen, C.-H.; Felder, R.J.

    1993-01-01

    A reactive dc cosputtering technique has been used to evaluate compound formation in bimetallic transition-metal nitride systems. A wide range in M-M’ composition can be studied in a single deposition run, and the method is applicable to nonalloying metal combinations. Using this technique, it was f

  1. Structures of the dehydrogenation products of methane activation by 5d transition metal cations

    NARCIS (Netherlands)

    Lapoutre, V. J. F.; Redlich, B.; van der Meer, A. F. G.; Oomens, J.; Bakker, J. M.; Sweeney, A.; Mookherjee, A.; Armentrout, P. B.

    2013-01-01

    The activation of methane by gas-phase transition metal cations (M +) has been studied extensively, both experimentally and using density functional theory (DFT). Methane is exothermically dehydrogenated by several 5d metal ions to form [M,C,2H]+ and H2. However, the structure of the dehydrogenation

  2. Approaches for reducing the insulator-metal transition pressure in hydrogen

    Science.gov (United States)

    Carlsson, A. E.; Ashcroft, N. W.

    1983-01-01

    Two possible techniques for reducing the external pressure required to induce the insulator-metal transition in solid hydrogen are described. One uses impurities to lower the energy of the metallic phase relative to that of the insulating phase. The other utilizes a negative pressure induced in the insulating phase by electron-hole pairs, created either with laser irradiation or pulsed synchrotron sources.

  3. Transition metal functionalized photo- and redox-switchable diarylethene based molecular switches

    NARCIS (Netherlands)

    Harvey, Emma C.; Feringa, Ben L.; Vos, Johannes G.; Browne, Wesley R.; Pryce, Mary T.

    2015-01-01

    In this review recent progress in combining metal carbonyl and bipyridyl transition metal complexes with dithienylethene photochromic switches is discussed. A key challenge in designing such systems is to allow for interaction between the various components, but without loss in photochemical activit

  4. Reactivity of Dinitrogen Bound to Mid- and Late-Transition-Metal Centers

    NARCIS (Netherlands)

    Khoenkhoen, N.; de Bruin, B.; Reek, J.N.H.; Dzik, W.I.

    2015-01-01

    This review presents a comprehensive overview of the reactions of N-2 within the coordination sphere of transition metals of groups 6 to 9. Many of these metals mediate the reaction of N-2 with protons under reductive conditions, which can lead to the (catalytic) formation of ammonia or hydrazine, a

  5. Complex transition metal hydrides: linear correlation of countercation electronegativity versus T-D bond lengths.

    Science.gov (United States)

    Humphries, T D; Sheppard, D A; Buckley, C E

    2015-06-30

    For homoleptic 18-electron complex hydrides, an inverse linear correlation has been established between the T-deuterium bond length (T = Fe, Co, Ni) and the average electronegativity of the metal countercations. This relationship can be further employed towards aiding structural solutions and predicting physical properties of novel complex transition metal hydrides.

  6. Size Controlled Synthesis of Transition Metal Nanoparticles for Catalytic Applications

    KAUST Repository

    Esparza, Angel

    2011-07-07

    Catalysis offers cleaner and more efficient chemical reactions for environmental scientists. More than 90% of industrial processes are performed with a catalyst involved, however research it is still required to improve the catalyst materials. The purpose of this work is to contribute with the development of catalysts synthesis with two different approaches. First, the precise size control of non-noble metals nanoparticles. Second, a new one-pot synthesis method based on a microemulsion system was developed to synthesize size-controlled metal nanoparticles in oxide supports. The one-pot method represents a simple approach to synthesize both support and immobilized nanometer-sized non-noble metal nanoparticles in the same reaction system. Narrow size distribution nickel, cobalt, iron and cobalt-nickel nanoparticles were obtained. High metal dispersions are attainable regardless the metal or support used in the synthesis. Thus, the methodology is adaptable and robust. The sizecontrolled supported metal nanoparticles offer the opportunity to study size effects and metal-support interactions on different catalytic reactions with different sets of metals and supports.

  7. Transition Metal Ions at the Crossroads of Mucosal Immunity and Microbial Pathogenesis

    Directory of Open Access Journals (Sweden)

    Vladimir eDiaz-Ochoa

    2014-01-01

    Full Text Available Transition metal ions are essential micronutrients for all living organisms. In mammals, these ions are often protein-bound and sequestered within cells, limiting their availability to microbes. Moreover, in response to infection, mammalian hosts further reduce the availability of metal nutrients by activating epithelial cells and recruiting neutrophils, both of which release metal-binding proteins with antimicrobial function. Microorganisms, in turn, have evolved sophisticated systems to overcome these limitations and acquire the metal ions essential for their growth. Here we review some of the mechanisms employed by the host and by pathogenic microorganisms to compete for transition metal ions, with a discussion of how evading nutritional immunity benefits pathogens. Furthermore, we provide new insights on the mechanisms of host-microbe competition for metal ions in the mucosa, particularly in the inflamed gut.

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

    Science.gov (United States)

    Sahin, H.; Peeters, F. M.

    2013-02-01

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

  9. Heterobimetallic coordination polymers involving 3d metal complexes and heavier transition metals cyanometallates

    Energy Technology Data Exchange (ETDEWEB)

    Peresypkina, Eugenia V. [Nikolaev Institute of Inorganic Chemistry, SB RAS, Novosibirsk 630090 (Russian Federation); Samsonenko, Denis G. [Nikolaev Institute of Inorganic Chemistry, SB RAS, Novosibirsk 630090 (Russian Federation); Novosibirsk State University, Novosibirsk 630090 (Russian Federation); Vostrikova, Kira E., E-mail: vosk@niic.nsc.ru [Nikolaev Institute of Inorganic Chemistry, SB RAS, Novosibirsk 630090 (Russian Federation); LMI, Université Claude Bernard Lyon 1, 69622 Villeurbanne Cedex (France)

    2015-04-15

    The results of the first steps in the design of coordination polymers based on penta- and heptacyanometallates of heavier d transitions metals are presented. The 2D structure of the coordination polymers: [(Mn(acacen)){sub 2}Ru(NO)(CN){sub 5}]{sub n} and two complexes composed of different cyanorhenates, [Ni(cyclam)]{sub 2}[ReO(OH)(CN){sub 4}](ClO{sub 4}){sub 2}(H{sub 2}O){sub 1.25} and [Cu(cyclam)]{sub 2}[Re(CN){sub 7}](H{sub 2}O){sub 12}, was confirmed by single crystal XRD study, the rhenium oxidation state having been proved by the magnetic measurements. An amorphism of [M(cyclam)]{sub 3}[Re(CN){sub 7}]{sub 2} (M=Ni, Cu) polymers does not allow to define strictly their dimensionality and to model anisotropic magnetic behavior of the compounds. However, with high probability a honey-comb like layer structure could be expected for [M(cyclam)]{sub 3}[Re(CN){sub 7}]{sub 2} complexes, studied in this work, because such an arrangement is the most common among the bimetallic assemblies of hexa- and octacyanometallates with a ratio [M(cyclam)]/[M(CN){sub n}]=3/2. For the first time was prepared and fully characterized a precursor (n-Bu{sub 4}N){sub 2}[Ru(NO)(CN){sub 5}], soluble in organic media. - Graphical abstract: The very first results in the design of 2D coordination polymers based on penta- and heptacyanometallates of 4d and5d transitions metals are presented. - Highlights: • Design of coordination polymers based on penta- and heptacyanometallates. • New Ru and Re cyanide based heterobimetallic coordination complexes. • Hydrolysis and ox/red processes involving [Re(CN){sub 7}]{sup 3+} during crystallization. • High magnetic anisotropy of [M(cyclam)]{sub 3}[Re(CN){sub 7}]{sub 2}(H{sub 2}O){sub n}, M=Cu, Ni, complexes.

  10. BCC-代数的不分明化理想%On Fuzzifying Ideals in BCC-algebras

    Institute of Scientific and Technical Information of China (English)

    彭家寅

    2009-01-01

    通过一元谓词和采用格值逻辑语义方法推广了不分明化BCC-代数,引入了BCC代数的不分明化BCH-子代数、不分明化BCK-理想和不分明化BCC-理想的概念,讨论了它们的性质和它们间的关系.研究了BCC-代数的不分明化BCH-子代数(不分明化BCK-理想、不分明化BCC-理想)的同态象和同态原象,讨论了BCC-代数的不分明化BCH-子代数(不分明化BCK-理想、不分明化BCC-理想)的积代数的性质.%The fuzzifying BCC-algebra is extended by a unary predicate and by adopting the semantic method of lattice valued logic, and the concepts of fuzzifying subalgebras, fuzzifying BCK-ideals and fuzzifying BCC-ideais in BCC-algebras are defined, and their properties and relations among them are discussed. How to deal with the homomorphic images and inverse images of fuzzifying subalgebras, fuzzifying BCK-ideals and fuzzifying BCC-ideals are studied. Some properties of the product of two fuzzifying subalgebras (fuzzifying BCK-ideals, fuzzifying BCC-ideals)are investigated.

  11. Terahertz transport dynamics in the metal-insulator transition of V2O3 thin film

    Science.gov (United States)

    Luo, Y. Y.; Su, F. H.; Zhang, C.; Zhong, L.; Pan, S. S.; Xu, S. C.; Wang, H.; Dai, J. M.; Li, G. H.

    2017-03-01

    The dynamic behavior of thermally-induced metal-insulator transition of V2O3 thin film on Si substrate grown by reactive magnetron sputtering was investigated by the terahertz time-domain spectroscopy. It was found that the THz absorption and optical conductivity of the thin films are temperature-dependent, and the THz amplitude modulation can reach as high as 74.7%. The complex THz optical conductivity in the metallic state of the V2O3 thin films can be well-fitted by the Drude-Smith model, which offer the insight into the electron transport dynamic during the metal-insulator transition of the thin film.

  12. Direct measurement and modulation of single-molecule coordinative bonding forces in a transition metal complex

    DEFF Research Database (Denmark)

    Hao, Xian; Zhu, Nan; Gschneidtner, Tina

    2013-01-01

    Coordination chemistry has been a consistently active branch of chemistry since Werner's seminal theory of coordination compounds inaugurated in 1893, with the central focus on transition metal complexes. However, control and measurement of metal-ligand interactions at the single-molecule level...... remain a daunting challenge. Here we demonstrate an interdisciplinary and systematic approach that enables measurement and modulation of the coordinative bonding forces in a transition metal complex. Terpyridine is derived with a thiol linker, facilitating covalent attachment of this ligand on both gold...

  13. New trends in the optical and electronic applications of polymers containing transition-metal complexes.

    Science.gov (United States)

    Liu, Shu-Juan; Chen, Yang; Xu, Wen-Juan; Zhao, Qiang; Huang, Wei

    2012-04-13

    Polymers containing transition-metal complexes exhibit excellent optical and electronic properties, which are different from those of polymers with a pure organic skeleton and combine the advantages of both polymers and metal complexes. Hence, research about this class of polymers has attracted more and more interest in recent years. Up to now, a number of novel polymers containing transition-metal complexes have been exploited, and significant advances in their optical and electronic applications have been achieved. In this article, we summarize some new research trends in the applications of this important class of optoelectronic polymers, such as chemo/biosensors, electronic memory devices and photovoltaic devices.

  14. Control of metal-insulator transition in (EDO-TTF)2SbF6

    Science.gov (United States)

    Maesato, Mitsuhiko; Nakano, Yoshiaki; Shao, Xiangfeng; Yoshida, Yukihiro; Yamochi, Hideki; Saito, Gunzi; Moreac, Alain; Ameline, Jean-Claude; Collet, Eric; Uruichi, Mikio; Yakushi, Kyuya

    2009-02-01

    We have examined the temperature dependence of optical reflectance spectra of (EDO-TTF)2SbF6 salt, and succeeded to detect the thermal hysteresis by the reflectance spectra. In order to investigate high pressure effects on the metal-insulator transition of SbF6 salt, we have performed Raman experiments under pressures up to 6 kbar. Drastic changes in the frequencies of charge sensitive C=C stretching modes suggested the pressure-induced reentrant metal-insulator-metal transition at room temperature.

  15. Universal Quantum Criticality in the Metal-Insulator Transition of Two-Dimensional Interacting Dirac Electrons

    Science.gov (United States)

    Otsuka, Yuichi; Yunoki, Seiji; Sorella, Sandro

    2016-01-01

    The metal-insulator transition has been a subject of intense research since Mott first proposed that the metallic behavior of interacting electrons could turn to an insulating one as electron correlations increase. Here, we consider electrons with massless Dirac-like dispersion in two spatial dimensions, described by the Hubbard models on two geometrically different lattices, and perform numerically exact calculations on unprecedentedly large systems that, combined with a careful finite-size scaling analysis, allow us to explore the quantum critical behavior in the vicinity of the interaction-driven metal-insulator transition. Thereby, we find that the transition is continuous, and we determine the quantum criticality for the corresponding universality class, which is described in the continuous limit by the Gross-Neveu model, a model extensively studied in quantum field theory. Furthermore, we discuss a fluctuation-driven scenario for the metal-insulator transition in the interacting Dirac electrons: The metal-insulator transition is triggered only by the vanishing of the quasiparticle weight, not by the Dirac Fermi velocity, which instead remains finite near the transition. This important feature cannot be captured by a simple mean-field or Gutzwiller-type approximate picture but is rather consistent with the low-energy behavior of the Gross-Neveu model.

  16. Theory of quantum metal to superconductor transitions in highly conducting systems

    Energy Technology Data Exchange (ETDEWEB)

    Spivak, B.

    2010-04-06

    We derive the theory of the quantum (zero temperature) superconductor to metal transition in disordered materials when the resistance of the normal metal near criticality is small compared to the quantum of resistivity. This can occur most readily in situations in which 'Anderson's theorem' does not apply. We explicitly study the transition in superconductor-metal composites, in an swave superconducting film in the presence of a magnetic field, and in a low temperature disordered d-wave superconductor. Near the point of the transition, the distribution of the superconducting order parameter is highly inhomogeneous. To describe this situation we employ a procedure which is similar to that introduced by Mott for description of the temperature dependence of the variable range hopping conduction. As the system approaches the point of the transition from the metal to the superconductor, the conductivity of the system diverges, and the Wiedemann-Franz law is violated. In the case of d-wave (or other exotic) superconductors we predict the existence of (at least) two sequential transitions as a function of increasing disorder: a d-wave to s-wave, and then an s-wave to metal transition.

  17. Direct observation of an abrupt insulator-to-metal transition in dense liquid deuterium

    Science.gov (United States)

    Knudson, M. D.; Desjarlais, M. P.; Becker, A.; Lemke, R. W.; Cochrane, K. R.; Savage, M. E.; Bliss, D. E.; Mattsson, T. R.; Redmer, R.

    2015-06-01

    Eighty years ago, it was proposed that solid hydrogen would become metallic at sufficiently high density. Despite numerous investigations, this transition has not yet been experimentally observed. More recently, there has been much interest in the analog of this predicted metallic transition in the dense liquid, due to its relevance to planetary science. Here, we show direct observation of an abrupt insulator-to-metal transition in dense liquid deuterium. Experimental determination of the location of this transition provides a much-needed benchmark for theory and may constrain the region of hydrogen-helium immiscibility and the boundary-layer pressure in standard models of the internal structure of gas-giant planets.

  18. Sol-Gel Synthesis and Characterization of Selected Transition Metal Nano-Ferrites

    Directory of Open Access Journals (Sweden)

    Aurelija GATELYTĖ

    2011-09-01

    Full Text Available In the present work, the sinterability and formation of nanosized yttrium iron garnet (Y3Fe5O12, yttrium perovskite ferrite (YFeO3, cobalt, nickel and zinc iron spinel (CoFe2O4, NiFe2O4 and ZnFe2O4, respectively powders by an aqueous sol-gel processes are investigated. The metal ions, generated by dissolving starting materials of transition metals in the diluted acetic acid were complexed by 1,2-ethanediol to obtain the precursors for the transition metal ferrite ceramics. The phase purity of synthesized nano-compounds was characterized by infrared spectroscopy (IR and powder X-ray diffraction analysis (XRD. The microstructural evolution and morphological features of obtained transition metal ferrites were studied by scanning electron microscopy (SEM.http://dx.doi.org/10.5755/j01.ms.17.3.598

  19. Resolving the VO2 controversy: Mott mechanism dominates the insulator-to-metal transition

    Science.gov (United States)

    Nájera, O.; Civelli, M.; Dobrosavljević, V.; Rozenberg, M. J.

    2017-01-01

    We consider a minimal model to investigate the metal-insulator transition in VO2. We adopt a Hubbard model with two orbitals per unit cell, which captures the competition between Mott and singlet-dimer localization. We solve the model within dynamical mean-field theory, characterizing in detail the metal-insulator transition and finding new features in the electronic states. We compare our results with available experimental data, obtaining good agreement in the relevant model parameter range. Crucially, we can account for puzzling optical conductivity data obtained within the hysteresis region, which we associate with a metallic state characterized by a split heavy quasiparticle band. Our results show that the thermal-driven insulator-to-metal transition in VO2 is compatible with a Mott electronic mechanism, providing fresh insight to a long-standing "chicken-and-egg" debate and calling for further research of "Mottronics" applications of this system.

  20. Synthesis and Electronic Properties of Transition Metal Containing Polymers

    Institute of Scientific and Technical Information of China (English)

    Wai Kin Chan

    2000-01-01

    @@ 1. Introduction Since the discovery of the first organic light emitting polymer in 1991, research in this area has been mainly focused on conjugated organic polymers. The use of polymer metal complexes for electroluminescence applications has received relatively few attention.

  1. Differential tolerance of Sulfolobus strains to transition metals

    Science.gov (United States)

    Miller, K.W.; Sass, Risanico S.; Risatti, J.B.

    1992-01-01

    Sulfolobus acidocaldarius strains 98-3 and B12, and S. solfataricus ATCC 35091 were evaluated for tolerance to Cd, Co, Cu, Ni, Zn and Mg. The tolerance of strains 98-3 and ATCC 35091 to these metals was Mg > Zn > Cd > Cu ??? Co > Ni. For B12, however, the order of tolerance was Mg > Cd > Zn = Co > Ni > Cu. Tolerance to these metals is also presented as a potentially useful taxonomic indicator.

  2. Gastrointestinal transit of undigestible solids measured by metal detector EAS II.

    Science.gov (United States)

    Ewe, K; Press, A G; Dederer, W

    1989-06-01

    A new method was developed to measure gastrointestinal transit: a metal particle is followed on its way through the gastrointestinal tract by means of a portable metal detector. Deviation of measured localization of the metal particle from the exact site was 0.5-1.0 cm depending on its size and distance from the search probe. A metal sphere of 6 mm diameter can be located accurately in the body at a distance of 2-12 cm from the abdominal surface. Emptying of a metal particle from the stomach, its arrival at the caecal area and its passage through the colon into the rectum can be registered and hence, gastric residence time, small intestinal transit and transit through different parts of the colon were determined. Gastric residence time at the interdigestive phase was (mean +/- SD) 67 +/- 52 min in 20 persons with a range of 9-185 min. When gastric emptying was recorded by pH sensitive radiotelemetering capsule in 10 persons, correlation of both methods was r = 0.99. Small intestinal transit averaged 110 +/- 56 min in six healthy volunteers when breakfast was eaten after the marker had left the stomach. It was delayed to 218 +/- 34 min (P less than 0.01) when fasting was continued. Large intestinal transit of the metal marker was compared to whole body transit of radio-opaque ('Hinton') markers. In nine normal persons, 70% of the Hinton markers were excreted together with the metal particle. It is concluded that this new method is suitable for studying a large variety of physiological, pathophysiological and pharmacological questions concerning gastrointestinal transit.(ABSTRACT TRUNCATED AT 250 WORDS)

  3. Molecular dynamics simulations of hcp/fcc nucleation and growth in bcc iron driven by uniaxial compression.

    Science.gov (United States)

    Wang, B T; Shao, J L; Zhang, G C; Li, W D; Zhang, P

    2009-12-02

    Molecular dynamics simulations have been performed to study the structural transition in bcc iron under uniaxial strain loading. We found that the transition pressures are less dependent on the crystal orientations, ∼14 GPa for [001], [011], and [111] loadings. However, the pressure interval of a mixed phase for [011] loading is much shorter than loading along other orientations. In addition, the temperature increased amplitude for [001] loading is evidently lower than other orientations. The nucleation and growth of the hcp/fcc phases, and their crystal orientation dependence, were analyzed in detail, where the atom structure was presented by the topological medium-range-order analysis. For [001] compression, the hcp structure occurs first and grows into a laminar morphology in the (011)(bcc) plane with some fcc atoms as an intermediate structure. For loading along [011] and [111] directions, both hcp and fcc structure nucleation and growth along the {110}(bcc) planes are observed; their morphology is also discussed.

  4. Electronic spectroscopy and electronic structure of the smallest metal clusters: the diatomic 3D transition metal aluminides

    Science.gov (United States)

    Behm, Jane M.; Morse, Michael D.

    1994-06-01

    A systematic study of the electronic spectroscopy, electronic structure, and chemical bonding has been initiated for the 3d series of diatomic transition metal aluminides. This report provides a review of the progress to date, with specific emphasis on AlCa, AlV, AlCr, AlMn, AlCo, AlNi, AlCu, and AlZn.

  5. Transitions in Theory and Practice: Managing Metals in the Circular Economy

    Directory of Open Access Journals (Sweden)

    Melissa Jackson

    2014-07-01

    Full Text Available Transitioning from current resource management practice dominated by linear economic models of consumption and production, to circular models of resource use, will require insights into the stages and processes associated with socio-technical transitions. This paper is concerned with transitions in practice. It explores two frameworks within the transitions literature—the multi-level perspective and transition management theory—for practical guidance to inform a deliberate transition in practice. The critical futures literature is proposed as a source of tools and methods to be used in conjunction with the transition frameworks to influence and enable transitions in practice. This enhanced practical guidance for initiating action is applied to a specific context—transitioning the Australian metals sector towards a circular economy model. This particular transition case study is relevant because the vision of a circular economy model of resource management is gaining traction internationally, Australia is significant globally as a supplier of finite mineral resources and it will also be used in a collaborative research project on Wealth from Waste to investigate possibilities for the circular economy and metals recycling.

  6. Asymmetries in transition metal XPS spectra: metal nanoparticle structure, and interaction with the graphene-structured substrate surface.

    Science.gov (United States)

    Sacher, E

    2010-03-16

    Transition-metal XPS spectra have traditionally been considered to possess a natural asymmetry, extending to the high-binding-energy side. This is based on the fact that these spectra have generally been found experimentally to have such an asymmetry, as well as on the confirmation of asymmetry offered by the Doniach-Sunjić equation, an equation based on the proposal that the conduction electron scattering amplitude for interband absorption or emission in metals, at the Fermi level, is a singularity. Our discovery that metal nanoparticles, prepared under vacuum and characterized without exposure to air, have symmetric peaks, which become asymmetric with time, informed us that these peak asymmetries have other sources. On the basis of our belief that all metal spectra are composed of symmetric peaks, where the asymmetries are attributed to overlapping minor peaks that are consistent with known physical and chemical phenomena associated with that metal, we have shown that, for the metals that we have studied, these asymmetries contain much information, otherwise unavailable, on the structures, contaminants, oxidation, and interfacial interactions of nanoparticle surfaces. The existence of this information has been demonstrated for several metals, and its value is shown by its use in explaining the strong interfacial bonding of the nanoparticles with substrates having graphene structures. A possible future research direction is offered in the field of metal-metal interactions in nanoparticle alloys.

  7. Features of structure and phase transitions in pure uranium and U-Mo alloys: atomistic simulation

    Science.gov (United States)

    Kolotova, L. N.; Kuksin, A. Yu; Smirnova, D. E.; Starikov, S. V.; Tseplyaev, V. I.

    2016-11-01

    We study structural properties of cubic and tetragonal phases of U-Mo alloys using atomistic simulations: molecular dynamics and density functional theory. For pure uranium and U-Mo alloys at low temperatures we observe body-centered tetragonal (bct) structure, which is similar to the metastable γ°-phase found in the experiments. At higher temperatures bct structure transforms to a quasi body-centered cubic (q-bcc) phase that exhibits cubic symmetry just on the scale of several interatomic spacings or when averaged over time. Instantaneous pair distribution function (PDF) differs from PDF for the time-averaged atomic coordinates corresponding to the bcc lattice. The local positions of uranium atoms in q-bcc lattice correspond to the bct structure, which is energetically favourable due to formation of short U-U bonds. Transition from bct to q-bcc could be considered as ferro-to paraelastic transition of order-disorder type. The temperature of transition depends on Mo concentration. For pure uranium it is equal to about 700 K, which is well below than the upper boundary of the stability region of the α-U phase. Due to this reason, bct phase is observed only in uranium alloys containing metals with low solubility in α-U.

  8. First principles calculations and experimental insight into methane steam reforming over transition metal catalysts

    DEFF Research Database (Denmark)

    Jones, Glenn; Jakobsen, Jon Geest; Shim, Signe Sarah

    2008-01-01

    reforming. The reaction is found to be kinetically controlled by a methane dissociation step and a CO formation step, where the latter step is found to be dominant at lower temperatures. The particle size of the metal catalysts particles have been determined by transmission electron microscopy (TEM...... metal Surfaces to develop an overview of the steam reforming process catalyzed by a range of transition metal surfaces. By combining scaling relationships with thermodynamic and kinetic analysis, we show that it is possible to determine the reactivity trends of the pure metals for methane steam...... in situ TEM measurements under a hydrogen atmosphere. The overall agreement between theory and experiment (at 773 K, 1 bar pressure and 10% conversion) is found to be excellent with Ru and Rh being the most active pure transition metals for methane steam reforming, while Ni, Ir, Pt, and Pd...

  9. Transport studies in 2D transition metal dichalcogenides and black phosphorus

    Science.gov (United States)

    Du, Yuchen; Neal, Adam T.; Zhou, Hong; Ye, Peide D.

    2016-07-01

    Two-dimensional (2D) materials are a new family of materials with interesting physical properties, ranging from insulating hexagonal boron nitride, semiconducting or semi-metallic transition metal dichalcogenides, to gapless metallic graphene. In this review, we provide a brief discussion of transport studies in transition metal dichalcogenides, including both semiconducting and semi-metallic phases, as well as a discussion of the newly emerged narrow bandgap layered material, black phosphorus, in terms of its electrical and quantum transport properties at room and cryogenic temperatures. Ultra-thin layered channel materials with atomic layer thickness in the cross-plane direction, together with relatively high carrier mobility with appropriate passivation techniques, provide the promise for new scientific discoveries and broad device applications.

  10. Metal-insulator transition in Na{sub x}WO{sub 3}: Photoemission spectromicroscopy study

    Energy Technology Data Exchange (ETDEWEB)

    Paul, Sanhita, E-mail: raj@iiserkol.ac.in; Ghosh, Anirudha, E-mail: raj@iiserkol.ac.in; Raj, Satyabrata, E-mail: raj@iiserkol.ac.in [Department of Physical Sciences, Indian Institute of Science Education and Research - Kolkata, Mohanpur Campus, Nadia -741252, West Bengal (India)

    2014-04-24

    We have investigated the validity of percolation model, which is quite often invoked to explain the metal-insulator transition in sodium tungsten bronzes, Na{sub x}WO{sub 3} by photoelectron spectromicroscopy. The spatially resolved direct spectromicroscopic probing on both the insulating and metallic phases of high quality single crystals of Na{sub x}WO{sub 3} reveals the absence of any microscopic inhomogeneities embedded in the system within the experimental limit. Neither any metallic domains in the insulating host nor any insulating domains in the metallic host have been found to support the validity of percolation model to explain the metal-insulator transition in Na{sub x}WO{sub 3}.

  11. Extraction and Binding Efficiency of Calix[8]arene Derivative Toward Selected Transition Metals

    Directory of Open Access Journals (Sweden)

    Imdadullah Qureshi

    2008-12-01

    Full Text Available In this article we have explored the extraction efficiency as well as binding ability of calix[8]arene derivative (3 for selected transition metal ions (Co2+, Cd2+, Ni2+, Pb2+ and Cu2+. Picrate salt solutions of these metals were used in the liquid-liquid extraction experiments. It is apparent from the results that ligand 3 shows appreciable high extraction of transition metal cations, with the relative order Pb2+>Cu2+>Ni2+>Co2+>Cd2+ being observed. Highest extraction efficiency has been observed for Pb2+ and Cu2+ i.e. 95 and 91% respectively. The significant extraction and complexation ability for these metal ions may be attributed to the nature, size, structure and geometry of both ligand and metal ions.

  12. On the structure and bonding of first row transition metal ozone carbonyl hydrides.

    Science.gov (United States)

    Venter, Gerhard A; Raubenheimer, Helgard G; Dillen, Jan

    2007-08-23

    Model complexes of the general form M(CO)m(H)n(O3) (m = 1-5, n = 0 or 1) between ozone and the transition metals Ti to Cu were studied by density functional theory (DFT) calculations. The CDA charge decomposition method was used to analyze the interaction between the metal atom and the ozone ligand in terms of the traditional donation-back-donation mechanisms. Information about bond strengths was extracted from an analysis of the electron density in terms of the theory of atoms in molecules (AIM). The bonding in the ozone-metal complex was also studied within the NBO paradigm. Bond dissociation energies were calculated to be positive for all the complexes studied. Considering all the criteria employed in this study to analyze the interaction between the ozone and the transition metal, the Fe-complex is predicted to be the most stable, whereas the copper complex has the weakest metal-ozone interaction.

  13. A P-type ATPase importer that discriminates between essential and toxic transition metals.

    Science.gov (United States)

    Lewinson, Oded; Lee, Allen T; Rees, Douglas C

    2009-03-24

    Transition metals, although being essential cofactors in many physiological processes, are toxic at elevated concentrations. Among the membrane-embedded transport proteins that maintain appropriate intracellular levels of transition metals are ATP-driven pumps belonging to the P-type ATPase superfamily. These metal transporters may be differentiated according to their substrate specificities, where the majority of pumps can extrude either silver and copper or zinc, cadmium, and lead. In the present report, we have established the substrate specificities of nine previously uncharacterized prokaryotic transition-metal P-type ATPases. We find that all of the newly identified exporters indeed fall into one of the two above-mentioned categories. In addition to these exporters, one importer, Pseudomonas aeruginosa Q9I147, was also identified. This protein, designated HmtA (heavy metal transporter A), exhibited a different substrate recognition profile from the exporters. In vivo metal susceptibility assays, intracellular metal measurements, and transport experiments all suggest that HmtA mediates the uptake of copper and zinc but not of silver, mercury, or cadmium. The substrate selectivity of this importer ensures the high-affinity uptake of essential metals, while avoiding intracellular contamination by their toxic counterparts.

  14. Adhesion and friction of single-crystal diamond in contact with transition metals

    Science.gov (United States)

    Miyoshi, K.; Buckley, D. H.

    1980-01-01

    An investigation was conducted to examine the adhesion and friction of single-crystal diamond in contact with various transition metals and the nature of metal transfer to diamond. Sliding friction experiments were conducted with diamond in sliding contact with the metals yttrium, titanium, zirconium, vanadium, iron, cobalt, nickel, tungsten, platinum, rhenium and rhodium. All experiments were conducted with loads of 0.05 to 0.3 N, at a sliding velocity of 0.003 m per minute, in a vacuum of 10 to the -8th Pa, at room temperature, and on the (111) plane of diamond with sliding in the 110 line type direction. The results of the investigation indicate that the coefficient of friction for diamond in contact with various metals is related to the relative chemical activity of the metals in high vacuum. The more active the metal, the higher the coefficient of friction. All the metals examined transferred to the surface of diamond in sliding.

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

    Science.gov (United States)

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

    2015-09-01

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

  16. Nonlocal Coulomb Correlations in Metals Close to a Charge Order Insulator Transition

    Science.gov (United States)

    Merino, Jaime

    2007-07-01

    The charge ordering transition induced by the nearest-neighbor Coulomb repulsion V in the 1/4-filled extended Hubbard model is investigated using cellular dynamical mean-field theory. We find a transition to a strongly renormalized charge ordered Fermi liquid at VCO and a metal-to-insulator transition at VMI>VCO. Short range antiferromagnetism occurs concomitantly with the CO transition. Approaching the charge ordered insulator, V≲VMI, the Fermi surface deforms and the scattering rate of electrons develops momentum dependence on the Fermi surface.

  17. Correlation functions between specific volume and stoichiometry for transition metal nitrides

    Energy Technology Data Exchange (ETDEWEB)

    Soto, G. [Centro de Ciencias de la Materia Condensada, UNAM, Ap. Postal 2681, 22800 Ensenada B. C. (Mexico)]. E-mail: gerardo@ccmc.unam.mx; Aparicio, E. [Centro de Ciencias de la Materia Condensada, UNAM, Ap. Postal 2681, 22800 Ensenada B. C. (Mexico); Avalos-Borja, M. [Centro de Ciencias de la Materia Condensada, UNAM, Ap. Postal 2681, 22800 Ensenada B. C. (Mexico)

    2005-03-08

    A methodology is proposed to correlate the structural aspects of transition metal nitrides (TMN) to the stoichiometric ratio: x = [N]/[M]. The method is based on a numeric figure, {upsilon}, given by the difference between the atomic concentrations of nitride and parent metal normalized to the atomic concentration of parent metal. Numerical regression is used to construct interpolating functions for {upsilon}(x) using as input the available data for TMN in two well-recognized databases (ICDD and ICSD). In summary we obtain functions of x that describe the deformation caused in the parent metal lattice by the nitrogen assimilation. The results are attractive, since TMN show remarkable trends.

  18. A Review on the Synthesis and Applications of Mesostructured Transition Metal Phosphates

    Directory of Open Access Journals (Sweden)

    Ronghe Lin

    2013-01-01

    Full Text Available Considerable efforts have been devoted to extending the range of the elemental composition of mesoporous materials since the pioneering work of the M41S family of ordered mesoporous silica by Mobil researchers. The synthesis of transition metal-containing mesostructured materials with large surface area and high porosity has drawn great attention for its potential applications in acid and redox catalysis, photocatalysis, proton conducting devices, environmental restoration and so on. Thus, various transition metals-containing mesoporous materials, including transition metal-substituted mesoporous silicates, mesostructured transition metal oxides and transition metal phosphates (TMP, have been documented in the literature. Among these, mesostructured TMP materials are less studied, but possess some unique features, partly because of the easy and facile functionalization of PO4 and/or P–OH groups, rendering them interesting functional materials. This review first introduced the general synthesis strategies for manufacturing mesostructured TMP materials, as well as advantages and disadvantages of the respective method; then, we surveyed the ongoing developments of fabrication and application of the TMP materials in three groups on the basis of their components and application fields. Future perspectives on existing problems related to the present synthesis routes and further modifying of the functional groups for the purpose of tailoring special physical-chemical properties to meet wide application requirements were also provided in the last part.

  19. Semiconductor-to-metal transition in trans-polyacetylene (the role of correlated solitons

    Directory of Open Access Journals (Sweden)

    S. A. Ketabi

    2004-06-01

    Full Text Available  In this study the nature of transition to metallic regime in trans-polyacetylene (trans-PA is investigated. Based on Su-Schrieffer-Heeger (SSH model and the use of Continued - Fraction Representation (CFR as well as Lanczos algorithm procedure, we studied the effects of some selected soliton distributions on the semiconductor-to-metal transition in trans-PA.We found that,this transition occurs only when there exists a soliton sublattice in trans-PA, disordered soliton distributions and soliton clustering are the origin of the metallic transition in trans-PA, that is consistent with the experimental data. Our results show that in the presence of correlation between solitons, the disorder in accompanying single soliton distributions plays a crucial role in inducing the transition to metallic regime, so that in contrast to Anderson’s localization theorem, the electronic states near the Fermi level are extended, that is the most significant criteria for the metallic regime .

  20. MICROSTRUCTURE AND INFRARED EMISSIVITY AT NORMAL TEMPERATURE IN TRANSITIONAL METAL OXIDES SYSTEM CERAMICS

    Institute of Scientific and Technical Information of China (English)

    2000-01-01

    The fabrication of Fe2O3-MnO2-Co2O3-CuO system ceramics, and the composite system ceramics of transitional metal oxides-cordierite and transitional metal oxides-kaolinit are presented in this work. The research was carried out with the main attention to the infrared emissivity in the band of 8~14μm at room temperature,the microstructure of the ceramics and the relation between them. High infrared emissivities exceeding 0.9 in the band of 8~14μm at room temperature were gained in the transitional metal oxide ceramics and the composite system ceramics. It is suggested that the formation of inverse spinels and partially inverse spinels, such as Fe3O4, CoFe2O4, CuFe2O4 and CuMn2O4, is beneficial to the enhancement of the infrared emissivity of the transitional metal oxide ceramics. The transitional metal oxides play an important role in determining the infrared emissivity of the composite system ceramics.

  1. Transition metal complexes with Girard reagents and their hydrazones

    Directory of Open Access Journals (Sweden)

    Vojinović-Ješić Ljiljana S.

    2012-01-01

    Full Text Available This is the first review dealing with the coordination chemistry of metal complexes with Girard's reagents and their hydrazones. The short introduction points out to chemical properties and significance of these organic compounds. The next section briefly describes synthetic methods for preparing complexes with Girard's reagents, as well as modes of coordination of these ligands. The last two extensive sections review the preparation, stereochemistry and structural characteristics of metal complexes with Girard's hydrazones, including some newer non-hydrazonic derivatives of Girard's reagents, also.[Acknowledgments. Projekat Ministarstva nauke Republike Srbije, br. 172014

  2. Ab-initio study of transition metal hydrides

    Energy Technology Data Exchange (ETDEWEB)

    Sharma, Ramesh [Dept. of Physics, Feroze Gandhi Insititute of Engineering and Technology, Raebareli-229001 (India); Shukla, Seema, E-mail: sharma.yamini62@gmail.com; Dwivedi, Shalini, E-mail: sharma.yamini62@gmail.com; Sharma, Yamini, E-mail: sharma.yamini62@gmail.com [Theoretical Condensed Matter Physics Laboratory, Dept. of Physics Feroze Gandhi College, Raebareli-229001 (India)

    2014-04-24

    We have performed ab initio self consistent calculations based on Full potential linearized augmented plane wave (FP-LAPW) method to investigate the optical and thermal properties of yttrium hydrides. From the band structure and density of states, the optical absorption spectra and specific heats have been calculated. The band structure of Yttrium metal changes dramatically due to hybridization of Y sp orbitals with H s orbitals and there is a net charge transfer from metal to hydrogen site. The electrical resistivity and specific heats of yttrium hydrides are lowered but the thermal conductivity is slightly enhanced due to increase in scattering from hydrogen sites.

  3. Metal-insulator transition and superconductivity in heavily boron-doped diamond and related materials

    Energy Technology Data Exchange (ETDEWEB)

    Achatz, Philipp

    2009-05-15

    During this PhD project, the metal-insulator transition and superconductivity of highly boron-doped single crystal diamond and related materials have been investigated. The critical boron concentration n{sub c} for the metal-insulator transition was found to be the same as for the normal-superconductor transition. All metallic samples have been found to be superconducting and we were able to link the occurence of superconductivity to the proximity to the metal-insulator transition. For this purpose, a scaling law approach based on low temperature transport was proposed. Furthermore, we tried to study the nature of the superconductivity in highly boron doped single crystal diamond. Raman spectroscopy measurements on the isotopically substituted series suggest that the feature occuring at low wavenumbers ({approx} 500 cm{sup -1}) is the A1g vibrational mode associated with boron dimers. Usual Hall effect measurements yielded a puzzling situation in metallic boron-doped diamond samples, leading to carrier concentrations up to a factor 10 higher than the boron concentration determined by secondary ion mass spectroscopy (SIMS). The low temperature transport follows the one expected for a granular metal or insulator, depending on the interplay of intergranular and intragranular (tunneling) conductance. The metal-insulator transition takes place at a critical conductance g{sub c}. The granularity also influences significantly the superconducting properties by introducing the superconducting gap {delta} in the grain and Josephson coupling J between superconducting grains. A peak in magnetoresistance is observed which can be explained by superconducting fluctuations and the granularity of the system. Additionally we studied the low temperature transport of boron-doped Si samples grown by gas immersion laser doping, some of which yielded a superconducting transition at very low temperatures. Furthermore, preliminary results on the LO-phonon-plasmon coupling are shown for the

  4. Main Group Lewis Acid-Mediated Transformations of Transition-Metal Hydride Complexes.

    Science.gov (United States)

    Maity, Ayan; Teets, Thomas S

    2016-08-10

    This Review highlights stoichiometric reactions and elementary steps of catalytic reactions involving cooperative participation of transition-metal hydrides and main group Lewis acids. Included are reactions where the transition-metal hydride acts as a reactant as well as transformations that form the metal hydride as a product. This Review is divided by reaction type, illustrating the diverse roles that Lewis acids can play in mediating transformations involving transition-metal hydrides as either reactants or products. We begin with a discussion of reactions where metal hydrides form direct adducts with Lewis acids, elaborating the structure and dynamics of the products of these reactions. The bulk of this Review focuses on reactions where the transition metal and Lewis acid act in cooperation, and includes sections on carbonyl reduction, H2 activation, and hydride elimination reactions, all of which can be promoted by Lewis acids. Also included is a section on Lewis acid-base secondary coordination sphere interactions, which can influence the reactivity of hydrides. Work from the past 50 years is included, but the majority of this Review focuses on research from the past decade, with the intent of showcasing the rapid emergence of this field and the potential for further development into the future.

  5. Enhancement of Platinum Cathode Catalysis by Addition of Transition Metals

    Science.gov (United States)

    Duong, Hung Tuan

    2009-01-01

    The sluggish kinetics of oxygen reduction reaction (ORR) contributes significantly to the loss of cathode overpotential in fuel cells, thus requiring high loadings of platinum (Pt), which is an expensive metal with limited supply. However, Pt and Pt-based alloys are still the best available electrocatalysts for ORR thus far. The research presented…

  6. On Transition Metal Catalyzed Reduction of N-nitrosodimethlamine

    CERN Document Server

    Zhou, Jun; Tian, Junhua; Zhao, Zhun

    2014-01-01

    This report provides a critical review on "Metal-Catalyzed Reduction of N-Nitrosodimethylamine with Hydrogen in Water", by Davie et al. N-nitrosodimethlamine (NDMA) is a contaminant in drinking and ground water which is difficult to remove by conventional physical methods, such as air stripping. Based on the reported robust capability of metal based powder shaped catalysts in hydrogen reduction, several monometallic and bimetallic catalyst are studied in this paper on the reduction of NDMA with hydrogen. Two kinds of kinetics, metal weight normalized and surface area normalized, are compared between each catalyst in terms of pseudo-first order reaction rate. Palladium, copper enhanced palladium and nickel are found to be very efficient in NDMA reduction, with half-lives on the order of hours per 10 mg/l catalyst metal. Preliminary LC-MS data and carbon balance showed no intermediates. Finally, a simple hydrogen and NMDA surface activated reaction mechanism is proposed by the author for palladium and nickel.

  7. Hydrogen evolution on nano-particulate transition metal sulfides

    DEFF Research Database (Denmark)

    Bonde, Jacob Lindner; Moses, Poul Georg; Jaramillo, Thomas F.;

    2008-01-01

    The hydrogen evolution reaction (HER) on carbon supported MoS2 nanoparticles is investigated and compared to findings with previously published work on Au(111) supported MoS2. An investigation into MoS2 oxidation is presented and used to quantify the surface concentration of MoS2. Other metal sul...

  8. Hydrogenation-controlled phase transition on two-dimensional transition metal dichalcogenides and their unique physical and catalytic properties

    Science.gov (United States)

    Qu, Yuanju; Pan, Hui; Kwok, Chi Tat

    2016-09-01

    Two-dimensional (2D) transition metal dichalcogenides (TMDs) have been widely used from nanodevices to energy harvesting/storage because of their tunable physical and chemical properties. In this work, we systematically investigate the effects of hydrogenation on the structural, electronic, magnetic, and catalytic properties of 33 TMDs based on first-principles calculations. We find that the stable phases of TMD monolayers can transit from 1T to 2H phase or vice versa upon the hydrogenation. We show that the hydrogenation can switch their magnetic and electronic states accompanying with the phase transition. The hydrogenation can tune the magnetic states of TMDs among non-, ferro, para-, and antiferro-magnetism and their electronic states among semiconductor, metal, and half-metal. We further show that, out of 33 TMD monolayers, 2H-TiS2 has impressive catalytic ability comparable to Pt in hydrogen evolution reaction in a wide range of hydrogen coverages. Our findings would shed the light on the multi-functional applications of TMDs.

  9. Transition Metal Transport in Plants and Associated Endosymbionts: Arbuscular Mycorrhizal Fungi and Rhizobia.

    Science.gov (United States)

    González-Guerrero, Manuel; Escudero, Viviana; Saéz, Ángela; Tejada-Jiménez, Manuel

    2016-01-01

    Transition metals such as iron, copper, zinc, or molybdenum are essential nutrients for plants. These elements are involved in almost every biological process, including photosynthesis, tolerance to biotic and abiotic stress, or symbiotic nitrogen fixation. However, plants often grow in soils with limiting metallic oligonutrient bioavailability. Consequently, to ensure the proper metal levels, plants have developed a complex metal uptake and distribution system, that not only involves the plant itself, but also its associated microorganisms. These microorganisms can simply increase metal solubility in soils and making them more accessible to the host plant, as well as induce the plant metal deficiency response, or directly deliver transition elements to cortical cells. Other, instead of providing metals, can act as metal sinks, such as endosymbiotic rhizobia in legume nodules that requires relatively large amounts to carry out nitrogen fixation. In this review, we propose to do an overview of metal transport mechanisms in the plant-microbe system, emphasizing the role of arbuscular mycorrhizal fungi and endosymbiotic rhizobia.

  10. TRANSITION METAL TRANSPORT IN PLANTS AND ASSOCIATED ENDOSYMBIONTS: ARBUSCULAR MYCORRHIZAL FUNGI AND RHIZOBIA

    Directory of Open Access Journals (Sweden)

    Manuel González-Guerrero

    2016-07-01

    Full Text Available Transition metals such as iron, copper, zinc, or molybdenum, are essential nutrients for plants. These elements are involved in almost every biological process, including photosynthesis, tolerance to biotic and abiotic stress, or symbiotic nitrogen fixation. However, plants often grow in soils with limiting metallic oligonutrient bioavailability. Consequently, to ensure the proper metal levels, plants have developed a complex metal uptake and distribution system, that not only involves the plant itself, but also its associated microorganisms. These microorganisms can simply increase metal solubility in soils and making them more accessible to the host plant, as well as induce the plant metal deficiency response, or deliver directly transition elements to cortical cells. Other, instead of providing metals can act as metal sinks, such as endosymbiotic rhizobia in legume nodules that requires relatively large amounts to carry out nitrogen fixation. In this review, we propose to do an overview of metal transport mechanisms in the plant-microbe system, emphasizing the role of arbuscular mycorrhizal fungi and endosymbiotic rhizobia.

  11. Corrosion behavior of some transition metals and 4340 steel metals exposed to sulfate-reducing bacteria

    Energy Technology Data Exchange (ETDEWEB)

    Natishan, P.M.; Jones-Meehan, J.; Loeb, G.I.; Little, B.J.; Ray, R.; Beard, M.

    1999-11-01

    Microbial colonization of metals (zirconium, chromium, niobium, tantalum, molybdenum, tungsten, and type 4340 steel [UNS G43400]) and susceptibility of these metals to microbiologically influenced corrosion by sulfate-reducing bacteria was investigated. Environmental scanning electron microscopy characterization after 12 months and 21 months showed patchy biofilms on all metals except tungsten. Weight loss after 24 months for zirconium and niobium were either nonexistent or negligible, indicating that these metals did not experience MIC under the test conditions.

  12. Reactivities of d~0 transition metal complexes toward oxygen:Synthetic and mechanistic studies

    Institute of Scientific and Technical Information of China (English)

    2009-01-01

    Transition metals such as Fe in porphyrin complexes are known to bind or react with O2,and such reactions are critical to many biological functions and catalytic oxidation using O2.The transition metals in these reactions often contain valence d electrons,and oxidation of metals is an important step.In recent years,reactions of O2 with d0 transition metal complexes such as Hf(NR2)4(R=alkyl) have been used to make metal oxide thin films as insulating gate materials in new microelectronic devices.This feature article discusses our recent studies of such reactions and the formation of TiO2 thin films.In contrast to the reactions of many dn complexes where metals are often oxidized,reactions of d0 complexes such as Hf(NMe2)4 and Ta(NMe2)4(SiR3) with O2 usually lead to the oxidation of ligands,forming,e.g.,-ONMe2 and -OSiR3 from-NMe2 and-SiR3 ligands,respectively.Mechanistic and theoretical studies of these reactions have revealed pathways in the formation of the metal oxide thin films as microelectronic materials.

  13. Reactivities of d~0 transition metal complexes toward oxygen:Synthetic and mechanistic studies

    Institute of Scientific and Technical Information of China (English)

    CHEN ShuJian; ZHANG XinHao; LIN ZhenYang; WU YunDong; XUE ZiLing

    2009-01-01

    Transition metals such as Fe in porphyrin complexes are known to bind or react with O_2,and such reactions are critical to many biological functions and catalytic oxidation using O_2.The transition metals in these reactions often contain valence d electrons,and oxidation of metals is an important step.In recent years,reactions of O_2 with d~0 transition metal complexes such as Hf(NR_2)_4 (R=alkyl) have been used to make metal oxide thin films as insulating gate materials in new microelectronic devices.This feature article discusses our recent studies of such reactions and the formation of TiO_2 thin films.In contrast to the reactions of many d~n complexes where metals are often oxidized,reactions of d~0 complexes such as Hf(Nme_2)_4 and Ta(Nme_2)_4(SiR_3) with O_2 usually lead to the oxidation of ligands,forming,e.g.,-ONMe_2 and-OSiR_3 from-Nme_2 and-SiR_3 ligands,respectively.Mechanistic and theoretical studies of these reactions have revealed pathways in the formation of the metal oxide thin films as microelectronic materials.

  14. Transition metal complexes supported on metal-organic frameworks for heterogeneous catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Farha, Omar K.; Hupp, Joseph T.; Delferro, Massimiliano; Klet, Rachel C.

    2017-02-07

    A robust mesoporous metal-organic framework comprising a hafnium-based metal-organic framework and a single-site zirconium-benzyl species is provided. The hafnium, zirconium-benzyl metal-organic framework is useful as a catalyst for the polymerization of an alkene.

  15. Global transcriptome and deletome profiles of yeast exposed to transition metals.

    Directory of Open Access Journals (Sweden)

    Yong Hwan Jin

    2008-04-01

    Full Text Available A variety of pathologies are associated with exposure to supraphysiological concentrations of essential metals and to non-essential metals and metalloids. The molecular mechanisms linking metal exposure to human pathologies have not been clearly defined. To address these gaps in our understanding of the molecular biology of transition metals, the genomic effects of exposure to Group IB (copper, silver, IIB (zinc, cadmium, mercury, VIA (chromium, and VB (arsenic elements on the yeast Saccharomyces cerevisiae were examined. Two comprehensive sets of metal-responsive genomic profiles were generated following exposure to equi-toxic concentrations of metal: one that provides information on the transcriptional changes associated with metal exposure (transcriptome, and a second that provides information on the relationship between the expression of approximately 4,700 non-essential genes and sensitivity to metal exposure (deletome. Approximately 22% of the genome was affected by exposure to at least one metal. Principal component and cluster analyses suggest that the chemical properties of the metal are major determinants in defining the expression profile. Furthermore, cells may have developed common or convergent regulatory mechanisms to accommodate metal exposure. The transcriptome and deletome had 22 genes in common, however, comparison between Gene Ontology biological processes for the two gene sets revealed that metal stress adaptation and detoxification categories were commonly enriched. Analysis of the transcriptome and deletome identified several evolutionarily conserved, signal transduction pathways that may be involved in regulating the responses to metal exposure. In this study, we identified genes and cognate signaling pathways that respond to exposure to essential and non-essential metals. In addition, genes that are essential for survival in the presence of these metals were identified. This information will contribute to our

  16. Prebiotic coordination chemistry: The potential role of transition-metal complexes in the chemical evolution

    Science.gov (United States)

    Beck, M.

    1979-01-01

    In approaching the extremely involved and complex problem of the origin of life, consideration of the coordination chemistry appeared not only as a possibility but as a necessity. The first model experiments appear to be promising because of prebiotic-type synthesis by means of transition-metal complexes. It is especially significant that in some instances various types of vitally important substances (nucleic bases, amino acids) are formed simultaneously. There is ground to hope that systematic studies in this field will clarify the role of transition-metal complexes in the organizatorial phase of chemical evolution. It is obvious that researchers working in the fields of the chemistry of cyano and carbonyl complexes, and of the catalytic effect of transition-metal complexes are best suited to study these aspects of the attractive and interesting problem of the origin of life.

  17. Development of dissimilar metal transition joint by hot roll bonding technique

    Energy Technology Data Exchange (ETDEWEB)

    Nagai, Takayuki; Takeda, Seiichiro; Tanaka, Yasumasa (Power Reactor and Nuclear Fuel Development Corp., Tokai, Ibaraki (Japan). Tokai Works); Ogawa, Kazuhiro; Nakasuji, Kazuyuki; Ikenaga, Yoshiaki

    1994-12-01

    Metallurgically bonded transition joints which enable to connect reprocessing equipments made of superior corrosion resistant valve metals (Ti-5Ta, Zr or Ti) with stainless steel piping is needed for nuclear fuel reprocessing plants. The authors have developed dissimilar metal transition joints between stainless steel and Ti-5Ta, Zr or Ti with an insert metal of Ta by the hot roll bonding process, using the newly developed mill called 'rotary reduction mill'. In the R and D program, appropriate bonding conditions in the manufacturing process of the joints were established. This report presents the structure of transition joints and the manufacturing process by the hot roll bonding technique. Then, the evaluation of mechanical and corrosion properties and the results of demonstration test of joints for practical use are described. (author).

  18. Development of dissimilar metal transition joint by hot roll bonding technique

    Energy Technology Data Exchange (ETDEWEB)

    Nagai, Takayuki; Takeuchi, Masayuki; Takeda, Seiichiro; Shikakura, Sakae [Power Reactor and Nuclear Fuel Development Corp., Tokai, Ibaraki (Japan). Tokai Works; Ogawa, Kazuhiro; Nakasuji, Kazuyuki; Kajimura, Haruhiko

    1995-12-01

    Metallurgically bonded transition joints which enable to connect reprocessing equipments made of superior corrosion resistant valve metals (Ti-5Ta, Zr or Ti) with stainless steel piping is needed for nuclear fuel reprocessing plants. The authors have developed dissimilar metal transition joints between stainless steel and Ti-5Ta, Zr or Ti with an insert metal of Ta by the hot roll bonding process, using the newly developed mill called `rotary reduction mill`. In the R and D program, appropriate bonding conditions in the manufacturing process of the joints were established. This report presents the structure of transition joints and the manufacturing process by hot roll bonding technique. Then, the evaluation of mechanical and corrosion properties and the results of demonstration test of joints for practical use are described. (author).

  19. Effective modification of MgO with surface transition metal oxides for NF3 decomposition

    Institute of Scientific and Technical Information of China (English)

    Yanan Wang; Xiufeng Xu; Pei Sheng; Hongguang Li; Tingting Wang; Youfen Huang; Fangshu Liu

    2011-01-01

    NF3 decomposition over transition metal oxides coated MgO reagents in the absence of water is investigated.The results show that NF3 can be decomposed completely over pure MgO but the time of NF3 steady full conversion kept as short as 80 min,while the reactivities of coated MgO reagents were remarkably enhanced by transition metal oxides,for example the time of NF3 complete conversion over 12%Fe/MgO extended to 380 min.It is suggested that not only an increase in surface area but also a significant enhancement in the fluorination of MgO substrate caused by the surface transition metal oxides result in an improved reactivity of coated MgO reagents for NF3 decomposition.

  20. Using a Semiconductor-to-Metal Transition to Control Optical Transmission through Subwavelength Hole Arrays

    Directory of Open Access Journals (Sweden)

    E. U. Donev

    2008-01-01

    Full Text Available We describe a simple configuration in which the extraordinary optical transmission effect through subwavelength hole arrays in noble-metal films can be switched by the semiconductor-to-metal transition in an underlying thin film of vanadium dioxide. In these experiments, the transition is brought about by thermal heating of the bilayer film. The surprising reverse hysteretic behavior of the transmission through the subwavelength holes in the vanadium oxide suggest that this modulation is accomplished by a dielectric-matching condition rather than plasmon coupling through the bilayer film. The results of this switching, including the wavelength dependence, are qualitatively reproduced by a transfer matrix model. The prospects for effecting a similar modulation on a much faster time scale by using ultrafast laser pulses to trigger the semiconductor-to-metal transition are also discussed.

  1. Moderate bending strain induced semiconductor to metal transition in Si nanowires

    Science.gov (United States)

    Rabbani, M. Golam; Patil, Sunil R.; Anantram, M. P.

    2016-12-01

    A moderate amount of bending strains, ∼3% is found to be enough to induce the semiconductor-metal transition in Si nanowires of ∼4 nm diameter. The influence of bending on silicon nanowires of 1 nm to 4.3 nm diameter is investigated using molecular dynamics and quantum transport simulations. Local strains in nanowires are analyzed along with the effect of bending strain and nanowire diameter on electronic transport and the transmission energy gap. Interestingly, relatively wider nanowires are found to undergo semiconductor-metal transition at relatively lower bending strains. The effect of bending strain on electronic properties is then compared with the conventional way of straining, i.e. uniaxial, which shows that bending is a much more efficient way of straining to enhance the electronic transport and also to induce the semiconductor-metal transition in experimentally realizable Si nanowires.

  2. Analysis on insulator–metal transition in yttrium doped LSMO from electron density distribution

    Indian Academy of Sciences (India)

    S Israel; S Saravana Kumar; R Renuretson; R A J R Sheeba; R Saravanan

    2012-02-01

    Yttrium doped LSMO (La1−SrMnO3) was prepared using sol–gel technique and analysed for the insulator–metal transition fromcharge density variation in the unit cell with respect to different stoichiometric inclusion of yttrium. X-ray powder diffraction profiles of the samples were obtained and the well known Rietveld method and a versatile tool called maximum entropy method (MEM) were used for structural and profile refinement. The charge density in the unit cell was constructed using refined structure factors and was analysed. The charge ordering taking place in the insulator–metal transition was investigated and quantified. The insulator–metal transition was found to occur when 20% of La/Sr atoms were replaced by yttrium. The changes in the charge environment have also been analysed.

  3. Probing Critical Point Energies of Transition Metal Dichalcogenides: Surprising Indirect Gap of Single Layer WSe 2

    KAUST Repository

    Zhang, Chendong

    2015-09-21

    By using a comprehensive form of scanning tunneling spectroscopy, we have revealed detailed quasi-particle electronic structures in transition metal dichalcogenides, including the quasi-particle gaps, critical point energy locations, and their origins in the Brillouin zones. We show that single layer WSe surprisingly has an indirect quasi-particle gap with the conduction band minimum located at the Q-point (instead of K), albeit the two states are nearly degenerate. We have further observed rich quasi-particle electronic structures of transition metal dichalcogenides as a function of atomic structures and spin-orbit couplings. Such a local probe for detailed electronic structures in conduction and valence bands will be ideal to investigate how electronic structures of transition metal dichalcogenides are influenced by variations of local environment.

  4. Probing Critical Point Energies of Transition Metal Dichalcogenides: Surprising Indirect Gap of Single Layer WSe2.

    Science.gov (United States)

    Zhang, Chendong; Chen, Yuxuan; Johnson, Amber; Li, Ming-Yang; Li, Lain-Jong; Mende, Patrick C; Feenstra, Randall M; Shih, Chih-Kang

    2015-10-14

    By using a comprehensive form of scanning tunneling spectroscopy, we have revealed detailed quasi-particle electronic structures in transition metal dichalcogenides, including the quasi-particle gaps, critical point energy locations, and their origins in the Brillouin zones. We show that single layer WSe2 surprisingly has an indirect quasi-particle gap with the conduction band minimum located at the Q-point (instead of K), albeit the two states are nearly degenerate. We have further observed rich quasi-particle electronic structures of transition metal dichalcogenides as a function of atomic structures and spin-orbit couplings. Such a local probe for detailed electronic structures in conduction and valence bands will be ideal to investigate how electronic structures of transition metal dichalcogenides are influenced by variations of local environment.

  5. Theoretical Investigation of Nonlinear Optical Properties of Organic and Transition Metal Hybrid Azobenzene Dendrimers

    Institute of Scientific and Technical Information of China (English)

    LIU Cai-Ping; LIU Ping; WU Ke-Chen

    2008-01-01

    In this work, we report a theoretical exploration of the responses of organic azo-benzene dendrimers. The polarizabilities, the first and second hyperpolarizabilities of the azobenzene monomers (GO), and the first, second and third generation (G1, G2 and G3, respectively) are investigated by semi-empirical methods. The calculated results show that the nonlinear optical (NLO)properties of these organic dendrimers are mainly determined by the azobenzene chromospheres.Additionally, the values of β and γ increase almost in proportion to the number of chromophores. On the other hand, two types of transition metal hybrid azobenzene dendrimers (core-hybrid and branch-end hybrid according to the sites combined with transition metals) are simulated and discussed in detail in the framework of time-dependent density functional theory (TDDFT). The calculated results reveal that the NLO responses of these metal dendrimers distinctly varied as a result of altering the charge transfer transition scale and the excitation energies.

  6. Magnetic engineering in 3d transition metals on phosphorene by strain

    Science.gov (United States)

    Cai, Xiaolin; Niu, Chunyao; Wang, Jianjun; Yu, Weiyang; Ren, XiaoYan; Zhu, Zhili

    2017-04-01

    Using first-principles density functional theory (DFT) calculations, we systematically investigate the strain effects on the adsorption energies, magnetic ordering and electronic properties of 3d transition metal (TM) atoms (from Sc to Co) adsorbed on phosphorene (P). We find that the adsorption energy of TM can be enhanced by compressive strain whereas weakened by tensile strain. Our results show that strain plays a decisive role in the magnetic moments as well as the magnetic coupling states of TM adatoms. Importantly, the transitions from antiferromagnetic (AFM) state to ferromagnetic (FM) state or to another different AFM ordering can be induced by strain effect. In addition, we observe the semiconductor to metal or half-metal transitions in some TM@P systems by applying strain. Our findings shed a new light on precisely engineering the magnetic properties and electronic properties of the TM@P systems, which will have great potential applications in spin electronics and other related fields.

  7. Identifying patients at risk for recurrent or advanced BCC.

    Science.gov (United States)

    Hamid, Omid; Goldenberg, Gary

    2013-11-01

    Basal cell carcinoma (BCC) is a common skin cancer and its incidence is on the rise worldwide. Clinical presentation and histologic examination are used for diagnosis and to stratify BCCs as either low- or high-risk for recurrence or development of advanced disease. A number of surgical and nonsurgical options are available for BCC. BCC is most often managed with a surgical approach, but not all tumors and patients are suitable for surgery. Vismodegib is a recently approved first-in-class hedgehog pathway inhibitor that has expanded options for patients who have locally advanced or metastatic BCC.

  8. Polyporphyrin Complexes of Some Transition Metals. Synthesis and Catalytic Properties

    Directory of Open Access Journals (Sweden)

    A.V. Shakhvorostov

    2016-10-01

    Full Text Available The paper presents the results of synthesis of polyporphyrin structures and metal complex catalyzers at their basis. Porphyrin to be derived from the addition reaction of pyrrole and formaldehyde. Metal complex catalyzers to be derived at the reaction of complex formation of ions of Mn2+, Co2+, Ni2+ and Fe3+ with porphyrin. The structure, physical and chemical properties of derived materials to be examined with IR spectroscopy, differential thermal analysis, thermogravimetric analysis, scanning electron microscopy investigation. Catalytic activity of synthesized catalytic systems to be established at the reaction of decompounding of hydrogen peroxide and alkylaromatics oxidation by hydrogen peroxide. The processes have been conducted under soft conditions, and also at different organic solvents.

  9. Electromagnetic interference shielding with 2D transition metal carbides (MXenes)

    Science.gov (United States)

    Shahzad, Faisal; Alhabeb, Mohamed; Hatter, Christine B.; Anasori, Babak; Man Hong, Soon; Koo, Chong Min; Gogotsi, Yury

    2016-09-01

    Materials with good flexibility and high conductivity that can provide electromagnetic interference (EMI) shielding with minimal thickness are highly desirable, especially if they can be easily processed into films. Two-dimensional metal carbides and nitrides, known as MXenes, combine metallic conductivity and hydrophilic surfaces. Here, we demonstrate the potential of several MXenes and their polymer composites for EMI shielding. A 45-micrometer-thick Ti3C2Tx film exhibited EMI shielding effectiveness of 92 decibels (>50 decibels for a 2.5-micrometer film), which is the highest among synthetic materials of comparable thickness produced to date. This performance originates from the excellent electrical conductivity of Ti3C2Tx films (4600 Siemens per centimeter) and multiple internal reflections from Ti3C2Tx flakes in free-standing films. The mechanical flexibility and easy coating capability offered by MXenes and their composites enable them to shield surfaces of any shape while providing high EMI shielding efficiency.

  10. Oxygen Intercalation of Graphene on Transition Metal Substrate: An Edge-Limited Mechanism.

    Science.gov (United States)

    Ma, Liang; Zeng, Xiao Cheng; Wang, Jinlan

    2015-10-15

    Oxygen intercalation has been proven to be an efficient experimental approach to decouple chemical vapor deposition grown graphene from metal substrate with mild damage, thereby enabling graphene transfer. However, the mechanism of oxygen intercalation and associated rate-limiting step are still unclear on the molecular level. Here, by using density functional theory, we evaluate the thermodynamics stability of graphene edge on transition metal surface in the context of oxygen and explore various reaction pathways and energy barriers, from which we can identify the key steps as well as the roles of metal passivated graphene edges during the oxygen intercalation. Our calculations suggest that in well-controlled experimental conditions, oxygen atoms can be easily intercalated through either zigzag or armchair graphene edges on metal surface, whereas the unwanted graphene oxidation etching can be suppressed. Oxygen intercalation is, thus, an efficient and low-damage way to decouple graphene from a metal substrate while it allows reusing metal substrate for graphene growth.

  11. Synthesis of heterocycles through transition-metal-catalyzed isomerization reactions.

    Science.gov (United States)

    Ishoey, Mette; Nielsen, Thomas E

    2014-07-14

    Metal-catalyzed isomerization of N- and O-allylic systems is emerging as an effective method to form synthetically useful iminium and oxocarbenium intermediates. In the presence of tethered nucleophiles, several recent examples illuminate this approach as a powerful strategy for the synthesis of structurally complex and diverse heterocycles. In this Concept article, we attempt to cover this area of research through a selection of recent versatile examples.

  12. Raman scattering in transition metal compounds: Titanium and compounds of titanium

    Energy Technology Data Exchange (ETDEWEB)

    Jimenez, J.; Ederer, D.L.; Shu, T. [Tulane Univ., New Orleans, LA (United States)] [and others

    1997-04-01

    The transition metal compounds form a very interesting and important set of materials. The diversity arises from the many states of ionization the transition elements may take when forming compounds. This variety provides ample opportunity for a large class of materials to have a vast range of electronic and magnetic properties. The x-ray spectroscopy of the transition elements is especially interesting because they have unfilled d bands that are at the bottom of the conduction band with atomic like structure. This group embarked on the systematic study of transition metal sulfides and oxides. As an example of the type of spectra observed in some of these compounds they have chosen to showcase the L{sub II, III} emission and Raman scattering in some titanium compounds obtained by photon excitation.

  13. On the behavior of Bronsted-Evans-Polanyi Relations for Transition Metal Oxides

    Energy Technology Data Exchange (ETDEWEB)

    Vojvodic, Aleksandra

    2011-08-22

    Versatile Broensted-Evans-Polanyi (BEP) relations are found from density functional theory for a wide range of transition metal oxides including rutiles and perovskites. For oxides, the relation depends on the type of oxide, the active site and the dissociating molecule. The slope of the BEP relation is strongly coupled to the adsorbate geometry in the transition state. If it is final state-like the dissociative chemisorption energy can be considered as a descriptor for the dissociation. If it is initial state-like, on the other hand, the dissociative chemisorption energy is not suitable as descriptor for the dissociation. Dissociation of molecules with strong intramolecular bonds belong to the former and molecules with weak intramolecular bonds to the latter group. We show, for the prototype system La-perovskites, that there is a 'cyclic' behavior in the transition state characteristics upon change of the active transition metal of the oxide.

  14. Loss-induced transition of the Goos-Hänchen effect for metals and dielectrics.

    Science.gov (United States)

    Götte, J B; Aiello, A; Woerdman, J P

    2008-03-17

    We report a unifying approach to the Goos-Hänchen (GH) shifts on external optical reflection for metals and dielectrics in particular for the case of high losses, that is for a large imaginary part of the dielectric constant. In this regime metals and dielectrics have a similar GH shift which is in contrast to the low-loss regime where the metallic and dielectric forms of the GH shift are very different. When going from the low-loss to the high-loss regime we find that metals show a much more prominent transition; we present a condition on the dielectric constant which characterizes this transition. We illustrate our theoretical analysis with a realistic example of seven lossy materials.

  15. The N-heterocyclic carbene chemistry of transition-metal carbonyl clusters.

    Science.gov (United States)

    Cabeza, Javier A; García-Álvarez, Pablo

    2011-11-01

    In the last decade, chemists have dedicated many efforts to investigate the coordination chemistry of N-heterocyclic carbenes (NHCs). Although most of that research activity has been devoted to mononuclear complexes, transition-metal carbonyl clusters have not escaped from these investigations. This critical review, which is focussed on the reactivity of NHCs (or their precursors) with transition-metal carbonyl clusters (mostly are of ruthenium and osmium) and on the transformations underwent by the NHC-containing species initially formed in those reactions, shows that the polynuclear character of these metallic compounds or, more precisely, the close proximity of one or more metal atoms to that which is or can be attached to the NHC ligand, is responsible for reactivity patterns that have no parallel in the NHC chemistry of mononuclear complexes (74 references).

  16. Phomalactone optimization and production of entomopathogenic fungi by Ophiocordyceps communis BCC 1842 and BCC 2763.

    Science.gov (United States)

    Prathumpai, W; Kocharin, K

    2016-01-01

    Phomalactone, an antibacterial, insecticidal, and herbicidal compound, was produced by insect pathogenic fungi, Ophiocordyceps communis BCC 1842 and BCC 2763, in bioreactors using different carbon and nitrogen sources. Glucose and fructose were preferable for growth and phomalactone production. The highest specific growth rate (μ) of 0.012 hr(-1), the highest biomass yield (Ysx) of 0.38 g DW g(-1) sugar, the highest volumetric sugar consumption rate (qs) of 0.036 g (L hr)(-1), the maximum phomalactone concentration ([Formula: see text]) of 93.30 mg L(-1) at 127 hr, and the highest volumetric production rate of phomalactone (qp) of 0.46 ± 0.12 mg (L d)(-1) were obtained on glucose and sodium nitrate as the sole carbon and nitrogen sources, respectively, by O. communis BCC 1842. In contrast, O. communis BCC 2763 gave lower phomalactone production. This mass phomalactone production is useful for the biological synthesis of a precursor for more broad-range potent analogs such as antitumor, antifungal, and others and for its further biological studies.

  17. Chromatographic separation studies of penicillins, cephalosporins and carbapenems on transition-metal silicate modified silica layers.

    Science.gov (United States)

    Singh, Dhruv K; Maheshwari, Gunjan

    2012-01-01

    The chromatographic behavior of penicillins, cephalosporins and carbapenems has been studied on the thin layers of transition-metal ion (viz. Ni(2+)/Zn(2+)/Cu(2+)/Co(2+)) silicate modified silica. Transition-metal silicate (3.92%) and silica (96.08%) were found to be optimum and resulted in spherical-compact spots and improved resolution of the analytes. The effect of various mobile phases was also investigated. The chromatograms were visualized as yellow spots by placing in an I(2)-chamber. The method has been found to be reproducible and convenient for routine analysis.

  18. Electron spectroscopic investigation of metal-insulator transition in Ce1-SrTiO3

    Indian Academy of Sciences (India)

    U Manju; S R Krishnakumar; Sugata Ray; S Raj; M Onoda; C Carbone; D D Sarma

    2003-10-01

    We have carried out detailed electron spectroscopic investigation of Ce1-SrTiO3 exhibiting insulator-metal transition with . Core level X-ray photoelectron spectra of Ce 3 as well as resonant photoemission spectra obtained at the Ce 4 → 4 resonant absorption threshold establish Ce as being in the trivalent state throughout the series. Using the `off-resonance’ condition for Ce 4 states, we obtain the Ti 3 dominated spectral features close to , exhibiting clear signatures of coherent and incoherent peaks. We discuss the implications of our findings in relation to the metal-insulator transition observed in this series of compounds.

  19. Metal-insulator transition of fermions on a kagome lattice at 1/3 filling.

    Science.gov (United States)

    Nishimoto, Satoshi; Nakamura, Masaaki; O'Brien, Aroon; Fulde, Peter

    2010-05-14

    We discuss the metal-insulator transition of the spinless fermion model on a kagome lattice at 1/3 filling. The system is analyzed by using exact diagonalization, density-matrix renormalization group methods, and random-phase approximation. In the strong-coupling region, the charge-ordered ground state is consistent with the predictions of an effective model, i.e., plaquette order. We find that the qualitative properties of the metal-insulator transition are totally different depending on the sign of the hopping matrix elements, reflecting the difference in the band structure near the Fermi level.

  20. Frontiers of 4d- and 5d-transition metal oxides

    CERN Document Server

    Cao, Gang

    2013-01-01

    This book is aimed at advanced undergraduates, graduate students and other researchers who possess an introductory background in materials physics and/or chemistry, and an interest in the physical and chemical properties of novel materials, especially transition metal oxides.New materials often exhibit novel phenomena of great fundamental and technological importance. Contributing authors review the structural, physical and chemical properties of notable 4d- and 5d-transition metal oxides discovered over the last 10 years. These materials exhibit extraordinary physical properties that differ s

  1. Density functional studies of functionalized graphitic materials with late transition metals for oxygen reduction reactions

    DEFF Research Database (Denmark)

    Vallejo, Federico Calle; Martinez, Jose Ignacio; Rossmeisl, Jan

    2011-01-01

    Reaction (OER). Spin analyses suggest that the oxidation state of those elements in the active sites should in general be +2. Moreover, our results verify that the adsorption behavior of transition metals is not intrinsic, since it can be severely altered by changes in the local geometry of the active site......) at the cathode. In this contribution, on the basis of Density Functional Theory (DFT) calculations, we show that graphitic materials with active sites composed of 4 nitrogen atoms and transition metal atoms belonging to groups 7 to 9 in the periodic table are active towards ORR, and also towards Oxygen Evolution...

  2. Characterization of Transition Metal Carbide Layers Synthesized by Thermo-reactive Diffusion Processes

    DEFF Research Database (Denmark)

    Laursen, Mads Brink; Fernandes, Frederico Augusto Pires; Christiansen, Thomas Lundin

    2015-01-01

    Hard wear resistant surface layers of transition metal carbides can be produced by thermo-reactive diffusion processes where interstitial elements from a steel substrate together with external sources of transition metals (Ti, V, Cr etc.) form hard carbide and/or nitride layers at the steel surface...... electron microscopy, X-ray diffraction and Vickers hardness testing. The study shows that porosityfree, homogenous and very hard surface layers can be produced by thermo-reactive diffusion processes. The carbon availability of the substrate influences thickness of obtained layers, as Vanadis 6 tool steel...

  3. Laplace DLTS investigation of transition metal-hydrogen complexes in germanium

    Science.gov (United States)

    Gurimskaya, Y.; Mesli, A.

    2014-02-01

    High-resolution Laplace DLTS technique has been used to examine fine structures in the carrier emission processes hidden in the broad conventional DLTS peaks recorded in germanium samples, doped by several transition metals - Ni, Cr and Fe. These structures are found to be correlated with the acceptors, related to mentioned impurities, and also with possible presence of hydrogen-related defects. A link explaining interaction of transition metals with hydrogen due to the applied chemical treatment during sample preparation process is revealed and compared to what is known in silicon.

  4. Protonation of transition-metal hydrides: a not so simple process.

    Science.gov (United States)

    Besora, Maria; Lledós, Agustí; Maseras, Feliu

    2009-04-01

    The protonation of a transition-metal hydride is a formally simple process between a proton donor and a proton acceptor with several potential basic centres. The detailed mechanism is however quite subtle, with multistep reactions and involvement of different intermediates. The process is furthermore very sensitive to the nature of both the proton donor and the transition-metal complex, as well as to the solvent and to the presence and identity of eventual counteranions. This tutorial review summarizes the recent progress in the understanding of the reaction, obtained through the joint application of a number of computational and experimental techniques.

  5. Transition absorption as a mechanism of surface photoelectron emission from metals

    DEFF Research Database (Denmark)

    Zhukovsky, Sergei; Protsenko, Igor E.; Ikhsanov, Renat Sh;

    2015-01-01

    Transition absorption of a photon by an electron passingthrough a boundary between two media with different permit-tivities is described both classically and quantum mechani-cally. Transition absorption is shown to make a substantialcontribution to photoelectron emission at a metal/semicon-ductor....../semicon-ductor interface in nanoplasmonic systems, and is put forth asa possible microscopic mechanism of the surface photoelec-tric effect in photodetectors and solar cells containing plas-monic nanoparticles....

  6. Transition absorption as a mechanism of surface photoelectron emission from metals

    DEFF Research Database (Denmark)

    Zhukovsky, Sergei; Protsenko, Igor E.; Ikhsanov, Renat Sh

    2015-01-01

    Transition absorption of a photon by an electron passingthrough a boundary between two media with different permit-tivities is described both classically and quantum mechani-cally. Transition absorption is shown to make a substantialcontribution to photoelectron emission at a metal....../semicon-ductor interface in nanoplasmonic systems, and is put forth asa possible microscopic mechanism of the surface photoelec-tric effect in photodetectors and solar cells containing plas-monic nanoparticles....

  7. d-Wave to s-wave to normal metal transitions in disordered superconductors

    Energy Technology Data Exchange (ETDEWEB)

    Spivak, B. [Department of Physics, University of Washington, Seattle, WA 98195 (United States)], E-mail: spivak@u.washington.edu; Oreto, P.; Kivelson, S.A. [Department of Physics, Stanford University, Stanford, CA 94305 (United States)

    2009-03-01

    We study suppression of superconductivity by disorder in d-wave superconductors, and predict the existence of (at least) two sequential low-temperature transitions as a function of increasing disorder: a d-wave to s-wave, and then an s-wave to metal transition. This is a universal property of the system which is independent of the sign of the interaction constant in the s-channel.

  8. True boundary for the formation of homoleptic transition-metal hydride complexes.

    Science.gov (United States)

    Takagi, Shigeyuki; Iijima, Yuki; Sato, Toyoto; Saitoh, Hiroyuki; Ikeda, Kazutaka; Otomo, Toshiya; Miwa, Kazutoshi; Ikeshoji, Tamio; Aoki, Katsutoshi; Orimo, Shin-ichi

    2015-05-04

    Despite many exploratory studies over the past several decades, the presently known transition metals that form homoleptic transition-metal hydride complexes are limited to the Groups 7-12. Here we present evidence for the formation of Mg3 CrH8 , containing the first Group 6 hydride complex [CrH7 ](5-) . Our theoretical calculations reveal that pentagonal-bipyramidal H coordination allows the formation of σ-bonds between H and Cr. The results are strongly supported by neutron diffraction and IR spectroscopic measurements. Given that the Group 3-5 elements favor ionic/metallic bonding with H, along with the current results, the true boundary for the formation of homoleptic transition-metal hydride complexes should be between Group 5 and 6. As the H coordination number generally tends to increase with decreasing atomic number of transition metals, the revised boundary suggests high potential for further discovery of hydrogen-rich materials that are of both technological and fundamental interest.

  9. Regularities of formation of ternary alloy phases between non-transition metals

    Institute of Scientific and Technical Information of China (English)

    姚莉秀; 陈瑞亮; 钦佩; 陈念贻; 陆文聪

    2000-01-01

    Using a four-parameter model based on extended Miedema’ s cellular model of alloy phases and pattern recognition methods, the regularities of formation of ternary intermetallic compounds between non-transition metals have been investigated. The criterion of formation can be expressed as some empirical functions of Φ (electronegativity), nws1/3( valence electron density in Wagn-er-Seitz cell), R (Pauling’s metallic radius) and Z (number of valence electrons in atom).

  10. Regularities of formation of ternary alloy phases between non-transition metals

    Institute of Scientific and Technical Information of China (English)

    2000-01-01

    Using a four-parameter model based on extended Miedema's cellular model of alloy phases and pattern recognition methods, the regularities of formation of ternary intermetallic compounds between non-transition metals have been investigated. The criterion of formation can be expressed as some empirical functions of Ф (electronegativity), n1/3WS (valence electron density in Wagner-Seitz cell), R (Pauling's metallic radius) and Z (number of valence electrons in atom).

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

    Institute of Scientific and Technical Information of China (English)

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

    2004-01-01

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

  12. Steam Reforming on Transition-metal Carbides from Density-functional Theory

    Energy Technology Data Exchange (ETDEWEB)

    Vojvodic, Aleksandra

    2012-05-11

    A screening study of the steam reforming reaction on clean and oxygen covered early transition-metal carbides surfaces is performed by means of density-functional theory calculations. It is found that carbides provide a wide spectrum of reactivities, from too reactive via suitable to too inert. Several molybdenum-based systems are identified as possible steam reforming catalysts. The findings suggest that carbides provide a playground for reactivity tuning, comparable to the one for pure metals.

  13. Percolation metal-insullator transition in BiSrCaCuO films

    Science.gov (United States)

    Okunev, V. D.; Pafomov, N. N.; Svistunov, V. M.; Lewandowski, S. J.; Gierlowski, P.; Kula, W.

    1996-02-01

    An experimental investigation of the metal-insulator trnasition in BiSrCaCuO (BSCCO) films is reported. We performed resistivity, optical-absorption and critical-temperature measurements on several samples obtained by different technological methods. The results agree well with the percolation mechanism of the metal-insulator transition and show interesting correlations between room-temperature conductivity and superconducting properties of the investigated films.

  14. Origin of nonlinear transport across the magnetically induced superconductor-metal-insulator transition in two dimensions.

    Science.gov (United States)

    Seo, Y; Qin, Y; Vicente, C L; Choi, K S; Yoon, Jongsoo

    2006-08-04

    We have studied the effect of perpendicular magnetic fields and temperatures on nonlinear electronic transport in amorphous Ta superconducting thin films. The films exhibit a magnetic field-induced metallic behavior intervening the superconductor-insulator transition in the zero temperature limit. We show that the phase-identifying nonlinear transport in the superconducting and metallic phases arises from an intrinsic origin, not from an electron heating effect. The nonlinear transport is found to accompany an extraordinarily long voltage response time.

  15. Studies of high temperature ternary phases in mixed-metal-rich early transition metal sulfide and phosphide systems

    Energy Technology Data Exchange (ETDEWEB)

    Marking, G.A.

    1994-01-04

    Investigations of ternary mixed early transition metal-rich sulfide and phosphide systems resulted in the discovery of new structures and new phases. A new series of Zr and Hf - group V transition metal - sulfur K-phases was synthesized and crystallographically characterized. When the group V transition metal was Nb or Ta, the unit cell volume was larger than any previously reported K-phase. The presence of adventitious oxygen was determined in two K-phases through a combination of neutron scattering and X-ray diffraction experiments. A compound Hf{sub 10}Ta{sub 3}S{sub 3} was found to crystallize in a new-structure type similar to the known gamma brasses. This structure is unique in that it is the only reported {open_quotes}stuffed{close_quotes} gamma-brass type structure. The metal components, Hf and Ta, are larger in size and more electropositive than the metals found in normal gamma brasses (e.g. Cu and Zn) and because of the larger metallic radii, sulfur can be incorporated into the structure where it plays an integral role in stabilizing this phase relative to others. X-ray single-crystal, X-ray powder and neutron powder refinements were performed on this structure. A new structure was found in the ternary Nb-Zr-P system which has characteristics in common with many known early transition metal-rich sulfides, selenides, and phosphides. This structure has the simplest known interconnection of the basic building blocks known for this structural class. Anomalous scattering was a powerful tool for differentiating between Zr and Nb when using Mo K{alpha} X-radiation. The compounds ZrNbP and HfNbP formed in the space group Prima with the simple Co{sub 2}Si structure which is among the most common structures found for crystalline solid materials. Solid solution compounds in the Ta-Nb-P, Ta-Zr-P, Nb-Zr-P, Hf-Nb-P, and Hf-Zr-S systems were crystallographically characterized. The structural information corroborated ideas about bonding in metal-rich compounds.

  16. Ab-initio study of high temperature lattice dynamics of BCC zirconium (β-Zr) and uranium (γ-U)

    Energy Technology Data Exchange (ETDEWEB)

    Ghosh, Partha S., E-mail: parthasarathi13@gmail.com; Arya, A., E-mail: parthasarathi13@gmail.com; Dey, G. K., E-mail: parthasarathi13@gmail.com [Materials Science Division, Bhabha Atomic Research Centre, Mumbai-400085 (India)

    2014-04-24

    Using self consistent ab-initio lattice dynamics calculations, we show that bcc structures of Zr and U phases become stable at high temperature by phonon-phonon interactions. The calculated temperature dependent phonon dispersion curve (PDC) of β-Zr match excellently with experimental PDC. But the calculated PDC for γ-U shows negative phonon frequencies even at solid to liquid transition temperature. We show that this discrepancy is due to an overestimation of instability depth of bcc U phase which is removed by incorporation of spin-orbit coupling in the electronic structure calculations.

  17. Heterocyclic ring based colorimetric and fluorescent chemosensor for transition metal ions in an aqueous medium

    Energy Technology Data Exchange (ETDEWEB)

    Udhayakumari, Duraisamy [Department of Chemistry, Organic and Polymer Synthesis Laboratory, National Institute of Technology, Tiruchirappalli 620015 (India); Velmathi, Sivan, E-mail: velmathis@nitt.edu [Department of Chemistry, Organic and Polymer Synthesis Laboratory, National Institute of Technology, Tiruchirappalli 620015 (India); Boobalan, Maria susai [Department of Chemistry, St. Joseph' s College (Autonomous), Tiruchirappalli 620002 (India); Venkatesan, Parthiban; Wu, Shu-Pao [Department of Applied Chemistry, National Chiao Tung University, Hsinchu 300, Taiwan, ROC (China)

    2015-02-15

    Heterocyclic ring based R1–R3 have been synthesized from the simple condensation method. R1–R3 exhibit highly selective and sensitive recognition towards transition metal ions in an aqueous medium via visual color change and were further confirmed by UV–vis and fluorescent spectroscopic methods. Fluorescent turn on and turn off behavior was observed for receptors tested with transition metal ions. The interaction of transition metal ions and receptors R1–R3 was confirmed to adopt 1:1 binding stoichiometry. Micromolar detection limit was found for R1–R3 with metal ions. DFT theoretical calculations were employed to understand the sensing mechanism of the sensors towards the metal ions. R1 and R2 were also successfully demonstrated as a fluorescent probe for detecting Cu{sup 2+} ions in living cells. - highlights: • R1–R3 act as colorimetric and fluorescent sensors for metal ions. • Receptors (R1–R3) detect Cu{sup 2+} ions in aqueous solution at nanomolar levels. • R1 and R2 act as a fluorescent probe for detecting Cu{sup 2+} ions in living cells.

  18. Matrix infrared spectra and density functional calculations of transition metal hydrides and dihydrogen complexes.

    Science.gov (United States)

    Andrews, Lester

    2004-02-20

    Metal hydrides are of considerable importance in chemical synthesis as intermediates in catalytic hydrogenation reactions. Transition metal atoms react with dihydrogen to produce metal dihydrides or dihydrogen complexes and these may be trapped in solid matrix samples for infrared spectroscopic study. The MH(2) or M(H(2)) molecules so formed react further to form higher MH(4), (H(2))MH(2), or M(H(2))(2), and MH(6), (H(2))(2)MH(2), or M(H(2))(3) hydrides or complexes depending on the metal. In this critical review these transition metal and dihydrogen reaction products are surveyed for Groups 3 though 12 and the contrasting behaviour in Groups 6 and 10 is discussed. Minimum energy structures and vibrational frequencies predicted by Density Functional Theory agree with the experimental results, strongly supporting the identification of novel binary transition metal hydride species, which the matrix-isolation method is well-suited to investigate. 104 references are cited.

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

    Science.gov (United States)

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

    2014-07-21

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

  20. Atomistic Simulation of Fcc-bcc Phase Transition in Single Crystal Al Under Uniform Deformation Compression%等变形压加载下单晶铝fcc-bcc相变的分子动力学模拟

    Institute of Scientific and Technical Information of China (English)

    郭钰; 何凯; 李莉; 梁九卿

    2012-01-01

    By molecular dynamics simulations employing an embedded atom method potential, we simulate structural transformations in single crystal Al caused by high rate uniform strain loading. The simulations show that the phase transition takes place at about 270 GPa, corresponding to the reduced volume of 0. 55V0,in reasonable agreement with the calculated value through density functional theory.%采用EAM势,利用分子动力学方法模拟了单晶铝在高速率等变形压加载条件下的fcc-bcc的结构相变.模拟结果表明,在等变形压加载条件下,单晶铝在加压至270 GPa左右,体积缩小至0.55V0时,由面心立方结构转变为体心立方结构.这一结果与第一原理计算的结果大致符合.

  1. Chemical Reactions of Metal-Metal Bonded Compounds of the Transition Elements.

    Science.gov (United States)

    1981-05-18

    methanol, has led to the isolation ot solvento complexes , e.g. Mo2 Cl4 (PPh3 )2 (MeOH)2, in which onc ot the ligands L in XLI is replaced by a solvent...Hexa- and Other Polynuclear Complexes .... 8 2. Formation of Metal-Metal Bonds.................... .................... 11 2.1. From Mononuclear...17 2.3. By Addition of a Metal Complex or Fragment Across an M-X Multiple Bond

  2. The Influence of Oxygen in Transition Metal Oxides

    Science.gov (United States)

    Bach, P. L.; Leboran, V.; Rivadulla, F.

    2012-02-01

    The existence of a 2D metallic state at the interface between LaAlO3 and SrTiO3 (LAO/STO) has generated much excitement. Its origin has been attributed to charge redistribution to avoid a dielectric catastrophe; however, oxygen vacancies in TiO2-terminated STO can play a significant role in the electronic properties of the interface. In order to determine the nature and origin of the metallic phase, we have induced vacancies in TiO2-terminated STO single crystal substrates by annealing under controlled vacuum conditions. We report resistivity, Hall effect, and thermopower measurements on these materials and discuss their implications for the nature of the 2D electron gas at the STO surface. We have explored the possibility of gate-tuning these systems in order to fabricate single-oxide based devices. This work was supported by the Ministerio de Ciencia e Innovaci'on (Spain), grant MAT2010-16157, and the European Research Council, grant ERC-2010-StG 259082 2D THERMS.

  3. Rotational frequencies of transition metal hydrides for astrophysical searches in the far-infrared

    Science.gov (United States)

    Brown, John M.; Beaton, Stuart P.; Evenson, Kenneth M.

    1993-01-01

    Accurate frequencies for the lowest rotational transitions of five transition metal hydrides (CrH, FeH, CoH, NiH, and CuH) in their ground electronic states are reported to help the identification of these species in astrophysical sources from their far-infrared spectra. Accurate frequencies are determined in two ways: for CuH, by calculation from rotational constants determined from higher J transitions with an accuracy of 190 kHz; for the other species, by extrapolation to zero magnetic field from laser magnetic resonance spectra with an accuracy of 0.7 MHz.

  4. Oxygen vacancy induced metal-insulator transition in LaNiO3

    Science.gov (United States)

    Misra, Debolina; Kundu, Tarun Kumar

    2016-01-01

    First principle calculations were carried out to examine the metal-insulator transition in LaNiO3 due to changes in oxygen content and consequent alteration of valence state of nickel. The optical properties of all the oxygen deficient LaNiO3-x compounds were calculated to illustrate the electronic structures of the compounds and the change they undergo during the metal-insulator transition. The metallic nature of LaNiO3 is characterized by the Drude peak in the optical conductivity spectra and the high reflectivity it exhibits in the low frequency region. The complex dielectric function and the optical conductivity spectra clearly show that, for x = 0.25, i.e., LaNiO2.75 becomes a semiconductor. As x increases further to 0.5, a gap in the optical spectra appears, indicating the insulating nature of LaNiO2.5. The insulating state of LaNiO2.5 is best described by the GW+HSE method which gives a good estimation of the optical gap of the material. The absorption spectra of LaNiO2.5 clearly reveal that this material is transparent in the low frequency region. This metal-insulator transition is followed by another insulator to semiconductor transition, as x is increased further to 1 i.e., in case of LaNiO2. The metal-insulator transition is then explained on the basis of electron localization function calculations, which show the increase in the covalent bonding in the system as the transition to the insulating state sets in.

  5. Inhomogeneous electronic state near the insulator-to-metal transition in the correlated oxide VO2

    Science.gov (United States)

    Frenzel, A.; Qazilbash, M. M.; Brehm, M.; Chae, Byung-Gyu; Kim, Bong-Jun; Kim, Hyun-Tak; Balatsky, A. V.; Keilmann, F.; Basov, D. N.

    2009-09-01

    We investigate the percolative insulator-to-metal transition (IMT) in films of the correlated material vanadium dioxide (VO2) . Scattering-type scanning near-field infrared microscopy and atomic force microscopy were used to explore the relationship between the nucleation of metallic regions and the topography in insulating VO2 . We demonstrate that the IMT begins within 10 nm from grain boundaries and crevices by using mean curvature and statistical analysis. We also observe coexistence of insulating and metallic domains in a single crystalline grain that points to intrinsic inhomogeneity in VO2 due to competing electronic phases in the IMT regime.

  6. Extremely bulky amido first row transition metal(II) halide complexes: potential precursors to low coordinate metal-metal bonded systems.

    Science.gov (United States)

    Hicks, Jamie; Jones, Cameron

    2013-04-01

    Reactions of the extremely bulky potassium amide complexes, [KL'(η(6)-toluene)] or [KL"] (L'/L" = N(Ar*)(SiR3), Ar* = C6H2{C(H)Ph2}2Me-2,6,4; R = Me (L') or Ph (L")), with a series of first row transition metal(II) halides have yielded 10 rare examples of monodentate amido first row transition metal(II) halide complexes, all of which were crystallographically characterized. They encompass the dimeric, square-planar chromium complexes, [{CrL'(THF)(μ-Cl)}2] and [{CrL"(μ-Cl)}2], the latter of which displays intramolecular η(2)-Ph···Cr interactions; the dimeric tetrahedral complexes, [{ML'(THF)(μ-Br)}2] (M = Mn or Fe), [{ML"(THF)(μ-X)}2] (M = Mn, Fe or Co; X = Cl or Br) and [{CoL"(μ-Cl)}2] (which displays intramolecular η(2)-Ph···Co interactions); and the monomeric zinc amides, [L'ZnBr(THF)] (three-coordinate) and [L"ZnBr] (two-coordinate). Solution state magnetic moment determinations on all but one of the paramagnetic compounds show them to be high-spin systems. Throughout, comparisons are made with related bulky terphenyl transition metal(II) halide complexes, and the potential for the use of the prepared complexes as precursors to low-valent transition metal systems is discussed.

  7. Negative ion photoelectron spectroscopic studies of transition metal cluster

    Science.gov (United States)

    Marcy, Timothy Paul

    The studies reported in this thesis were performed using a negative ion photoelectron spectrometer consisting of a cold cathode DC discharge ion source, a flowing afterglow ion-molecule reactor, a magnetic sector mass analyzer, an argon ion laser for photodetachment and a hemispherical electron kinetic energy analyzer and microchannel plate detector for photoelectron spectrum generation. The 476.5 nm (2.601 eV), 488.0 nm (2.540 eV) and 514.5 nm (2.410 eV) negative ion photoelectron spectra of VMn are reported and compared to the previously studied spectra of isoelectronic Cr2.1 The photoelectron spectra are remarkably similar to those of Cr2 in electron affinity and vibrational frequencies. The 488.0 nm photoelectron spectra and electron affinities of Nb n- (n = 1 - 9) are reported with discussion of observed vibrational structure. There are transitions to several electronic states of Nb2 in the reported spectra with overlapping vibrational progressions. The spectra of Nb3, Nb4 and Nb6 show partially resolved vibrational structure in the transitions to the lowest observed electronic state of each cluster. There is a single distinct active vibrational mode in the transition to the ground state of Nb8. Spin-orbit energies of Nb- are also reported. The 488.0 nm negative ion photoelectron spectra of Nb3H(D) are reported and compared to those of Nb3. There is a single vibrational mode active in the spectra of Nb3H(D) which is very similar to the most distinct mode active in the spectrum of Nb3. The 488.0 nm photoelectron spectra of the NbxCyH(D) y- (x = 1, 2, 3, y = 2, 4, 6) dehydrogenated products of the reactions of ethylene with niobium cluster anions are reported. Temperature studies of some of these species give evidence for the presence of multiple isomers of each molecule in the ion beam. The spectra of NbC6H(D) 6 are identical to those obtained from the reactions of benzene with niobium clusters and indicate that benzene is being formed from ethylene in the flow

  8. Nucleation of the BCC phase from disorder in a diblock copolymer melt: Testing approximate theories through simulation

    Science.gov (United States)

    Spencer, Russell K. W.; Curry, Paul F.; Wickham, Robert A.

    2016-10-01

    We examine nucleation of the stable body-centred-cubic (BCC) phase from the metastable uniform disordered phase in an asymmetric diblock copolymer melt. Our comprehensive, large-scale simulations of the time-dependent, mean-field Landau-Brazovskii model find that spherical droplets of the BCC phase nucleate directly from disorder. Near the order-disorder transition, the critical nucleus is large and has a classical profile, attaining the bulk BCC phase in an interior that is separated from disorder by a sharp interface. At greater undercooling, the amplitude of BCC order in the interior decreases and the nucleus interface broadens, leading to a diffuse critical nucleus. This diffuse nucleus becomes large as the simulation approaches the disordered phase spinodal. We show that our simulation follows the same nucleation pathway that Cahn and Hilliard found for an incompressible two-component fluid, across the entire metastable region. In contrast, a classical nucleation theory calculation based on the free energy of a planar interface between coexisting BCC and disordered phases agrees with simulation only in the limit of very small undercooling; we can expand this region of validity somewhat by accounting for the curvature of the droplet interface. A nucleation pathway involving a classical droplet persists, however, to deep undercooling in our simulation, but this pathway is energetically unfavourable. As a droplet grows in the simulation, its interface moves with a constant speed, and this speed is approximately proportional to the undercooling.

  9. Non-local Coulomb correlations in metals close to a charge order insulator transition

    Science.gov (United States)

    Merino, Jaime

    2008-03-01

    Recent extensions of dynamical mean-field theory (DMFT) to clusters either in its real space (CDMFT) or momentum space versions (DCA) have become important tools for the description of electronic properties of low dimensional strongly correlated systems. In contrast to single site DMFT, short range correlation effects on electronic properties of systems close to the Mott transition can be analyzed. We have investigated the charge ordering transition induced by the nearest-neighbor Coulomb repulsion V in the 1/4-filled extended Hubbard model using CDMFT. We find a transition to a strongly renormalized charge ordered Fermi liquid at VCO and a metal-to- insulator transition at VMI>VCO. Short range antiferromagnetism occurs concomitantly with the CO transition. Approaching the charge ordered insulator, V

  10. Reactivity patterns of transition metal hydrides and alkyls

    Energy Technology Data Exchange (ETDEWEB)

    Jones, W.D. II

    1979-05-01

    The complex PPN/sup +/ CpV(CO)/sub 3/H/sup -/ (Cp=eta/sup 5/-C/sub 5/H/sub 5/ and PPN = (Ph/sub 3/P)/sub 2/) was prepared in 70% yield and its physical properties and chemical reactions investigated. PPN/sup +/ CpV(CO)/sub 3/H/sup -/ reacts with a wide range of organic halides. The organometallic products of these reactions are the vanadium halides PPN/sup +/(CpV(C)/sub 3/X)/sup -/ and in some cases the binuclear bridging hydride PPN/sup +/ (CpV(CO)/sub 3/)/sub 2/H/sup -/. The borohydride salt PPN/sup +/(CpV(CO)/sub 3/BH/sub 4/)/sup -/ has also been prepared. The reaction between CpV(CO)/sub 3/H/sup -/ and organic halides was investigated and compared with halide reductions carried out using tri-n-butyltin hydride. Results demonstrate that in almost all cases, the reduction reaction proceeds via free radical intermediates which are generated in a chain process, and are trapped by hydrogen transfer from CpV(CO)/sub 3/H/sup -/. Sodium amalgam reduction of CpRh(CO)/sub 2/ or a mixture of CpRh(CO)/sub 2/ and CpCo(CO)/sub 2/ affords two new anions, PPN/sup +/ (Cp/sub 2/Rh/sub 3/(CO)/sub 4/)/sup -/ and PPN/sup +/(Cp/sub 2/RhCo(CO)/sub 2/)/sup -/. CpMo(CO)/sub 3/H reacts with CpMo(CO)/sub 3/R (R=CH/sub 3/,C/sub 2/H/sub 5/, CH/sub 2/C/sub 6/H/sub 5/) at 25 to 50/sup 0/C to produce aldehyde RCHO and the dimers (CpMo(CO)/sub 3/)/sub 2/ and (CpMo(CO)/sub 2/)/sub 2/. In general, CpV(CO)/sub 3/H/sup -/ appears to transfer a hydrogen atom to the metal radical anion formed in an electron transfer process, whereas CpMo(CO)/sub 3/H transfers hydride in a 2-electron process to a vacant coordination site. The chemical consequences are that CpV(CO)/sub 3/H/sup -/ generally reacts with metal alkyls to give alkanes via intermediate alkyl hydride species whereas CpMo(CO)/sub 3/H reacts with metal alkyls to produce aldehyde, via an intermediate acyl hydride species.

  11. 18-Electron rule inspired Zintl-like ions composed of all transition metals.

    Science.gov (United States)

    Zhou, Jian; Giri, Santanab; Jena, Purusottam

    2014-10-07

    Zintl phase compounds constitute a unique class of compounds composed of metal cations and covalently bonded multiply charged cluster anions. Potential applications of these materials in solution chemistry and thermoelectric materials have given rise to renewed interest in the search for new Zintl ions. Up to now these ions have been mostly composed of group 13, 14, and 15 post-transition metal elements and no Zintl ions composed of all transition metal elements are known. Using gradient corrected density functional theory we show that the 18-electron rule can be applied to design a new class of Zintl-like ions composed of all transition metal atoms. We demonstrate this possibility by using Ti@Au12(2-) and Ni@Au6(2-) di-anions as examples of Zintl-like ions. Predictive capability of our approach is demonstrated by showing that FeH6(4-) in an already synthesized complex metal hydride, Mg2FeH6, is a Zintl-like ion, satisfying the 18-electron rule. We also show that novel Zintl phase compounds can be formed by using all transition metal Zintl-like ions as building blocks. For example, a two-dimensional periodic structure of Na2[Ti@Au12] is semiconducting and nonmagnetic while a one-dimensional periodic structure of Mg[Ti@Au12] is metallic and ferromagnetic. Our results open the door to the design and synthesis of a new class of Zintl-like ions and compounds with potential for applications.

  12. Ultramicrosensors based on transition metal hexacyanoferrates for scanning electrochemical microscopy

    Directory of Open Access Journals (Sweden)

    Maria A. Komkova

    2013-10-01

    Full Text Available We report here a way for improving the stability of ultramicroelectrodes (UME based on hexacyanoferrate-modified metals for the detection of hydrogen peroxide. The most stable sensors were obtained by electrochemical deposition of six layers of hexacyanoferrates (HCF, more specifically, an alternating pattern of three layers of Prussian Blue and three layers of Ni–HCF. The microelectrodes modified with mixed layers were continuously monitored in 1 mM hydrogen peroxide and proved to be stable for more than 5 h under these conditions. The mixed layer microelectrodes exhibited a stability which is five times as high as the stability of conventional Prussian Blue-modified UMEs. The sensitivity of the mixed layer sensor was 0.32 A·M−1·cm−2, and the detection limit was 10 µM. The mixed layer-based UMEs were used as sensors in scanning electrochemical microscopy (SECM experiments for imaging of hydrogen peroxide evolution.

  13. Two-Dimensional Hexagonal Transition-Metal Oxide for Spintronics.

    Science.gov (United States)

    Kan, Erjun; Li, Ming; Hu, Shuanglin; Xiao, Chuanyun; Xiang, Hongjun; Deng, Kaiming

    2013-04-04

    Two-dimensional materials have been the hot subject of studies due to their great potential in applications. However, their applications in spintronics have been blocked by the difficulty in producing ordered spin structures in 2D structures. Here we demonstrated that the ultrathin films of recently experimentally realized wurtzite MnO can automatically transform into a stable graphitic structure with ordered spin arrangement via density functional calculation, and the stability of graphitic structure can be enhanced by external strain. Moreover, the antiferromagnetic ordering of graphitic MnO single layer can be switched into half-metallic ferromagnetism by small hole-doping, and the estimated Curie temperature is higher than 300 K. Thus, our results highlight a promising way toward 2D magnetic materials.

  14. Coherent/incoherent metal transition in a holographic model

    CERN Document Server

    Kim, Keun-Yong; Seo, Yunseok; Sin, Sang-Jin

    2014-01-01

    We study AC electric($\\sigma$), thermoelectric($\\alpha$), and thermal($\\bar{\\kappa}$) conductivities in a holographic model, which is based on 3+1 dimensional Einstein-Maxwell-scalar action. There is momentum relaxation due to massless scalar fields linear to spatial coordinate. The model has three field theory parameters: temperature($T$), chemical potential($\\mu$), and effective impurity($\\beta$). At low frequencies, if $\\beta \\mu$ the shape of peak deviates from the Drude form(incoherent metal). At intermediate frequencies($T<\\omega<\\mu$), we have analysed numerical data of three conductivities($\\sigma, \\alpha, \\bar{\\kappa}$) for a wide variety of parameters, searching for scaling laws, which are expected from either experimental results on cuprates superconductors or some holographic models. In the model we study, we find no clear signs of scaling behaviour.

  15. Short-to-Medium-Range Order and Atomic Packing in Zr48Cu36Ag8Al8 Bulk Metallic Glass

    Directory of Open Access Journals (Sweden)

    Yong Xu

    2016-10-01

    Full Text Available Due to its excellent glass-forming ability (GFA, the Zr48Cu36Al8Ag8 bulk metallic glass (BMG is of great importance in glass transition investigations and new materials development. However, due to the lack of detailed structural information, the local structure and atomic packing of this alloy is still unknown. In this work, synchrotron measurement and reverse Monte Carlo simulation are performed on the atomic configuration of a Zr-based bulk metallic glass. The local structure is characterized in terms of bond pairs and Voronoi tessellation. It is found that there are mainly two types of bond pairs in the configuration, as the body-centered cubic (bcc-type and icosahedral (ico-type bond pairs. On the other hand, the main polyhedra in the configuration are icosahedra and the bcc structure. That is, the bcc-type bond pairs, together with the ico-type bond pairs, form the bcc polyhedra, introducing the distortion in bcc clusters in short range. However, in the medium range, the atoms formed linear or planar structures, other than the tridimensional clusters. That is, the medium-range order in glass is of 1D or 2D structure, suggesting the imperfect ordered packing feature.

  16. Role of transition metal exporters in virulence: the example of Neisseria meningitidis.

    Science.gov (United States)

    Guilhen, Cyril; Taha, Muhamed-Kheir; Veyrier, Frédéric J

    2013-01-01

    Transition metals such as iron, manganese, and zinc are essential micronutrients for bacteria. However, at high concentration, they can generate non-functional proteins or toxic compounds. Metal metabolism is therefore regulated to prevent shortage or overload, both of which can impair cell survival. In addition, equilibrium among these metals has to be tightly controlled to avoid molecular replacement in the active site of enzymes. Bacteria must actively maintain intracellular metal concentrations to meet physiological needs within the context of the local environment. When intracellular buffering capacity is reached, they rely primarily on membrane-localized exporters to maintain metal homeostasis. Recently, several groups have characterized new export systems and emphasized their importance in the virulence of several pathogens. This article discusses the role of export systems as general virulence determinants. Furthermore, it highlights the contribution of these exporters in pathogens emergence with emphasis on the human nasopharyngeal colonizer Neisseria meningitidis.

  17. Synthesis, Structure and Characterization of a Series of Transition Metal Complexes with Tripodal Polyimidazole Ligand

    Institute of Scientific and Technical Information of China (English)

    任颜卫; 吴爱芝; 李珺; 张逢星; 张金花

    2005-01-01

    Five new metal transition metal complexes formed with tripodal polyimidazole ligand tri{2-[2-(1-methyl)imidazoly](methylimino)ethyl}amine ((min)3tren), [Zn(min)3tren](ClO4)2 (1) [Cu(min)3tren](ClO4)2 (2), [Ni(min)3tren]-(ClO4)2 (3), [Co(min)3tren](ClO4)2 (4), and [Mn(min)3tren](ClO4)2·CH3CN (5) were synthesized and characterized by elemental analysis, molar conductances, IR and electronic spectra. Analytical results show 1 : 1 metal-ligand stoichiometry and 2 : 1 type of electrolyte in all metal complexes. The crystal structures of 4 and 5 have been determined. The metal atoms in 4 and 5, being in distorted [MN6] octahedra, are coordinated with three imine nitrogen atoms and three imidazole nitrogen atoms.

  18. Trends in the chemical properties in early transition metal carbide surfaces: A density functional study

    DEFF Research Database (Denmark)

    Kitchin, J.R.; Nørskov, Jens Kehlet; Barteau, M.A.;

    2005-01-01

    In this paper we present density functional theory (DFT) investigations of the physical, chemical and electronic structure properties of several close-packed surfaces of early transition metal carbides, including beta-Mo2C(0 0 0 1), and the (1 1 1) surfaces of TiC, VC, NbC, and TaC. The results...

  19. Catalytic Ring Hydrogenation of Benzoic Acid with Supported Transition Metal Catalysts in scCO2

    Directory of Open Access Journals (Sweden)

    Fengyu Zhao

    2007-07-01

    Full Text Available The ring hydrogenation of benzoic acid to cyclohexanecarboxylic acid overcharcoal-supported transition metal catalysts in supercritical CO2 medium has been studiedin the present work. The cyclohexanecarboxylic acid can be produced efficiently insupercritical CO2 at the low reaction temperature of 323 K. The presence of CO2 increasesthe reaction rate and several parameters have been discussed.

  20. Scaling relationships for adsorption energies of C2 hydrocarbons on transition metal surfaces

    DEFF Research Database (Denmark)

    Jones, Glenn; Studt, Felix; Abild-Pedersen, Frank;

    2011-01-01

    Using density functional theory calculations we show that the adsorption energies for C2Hx-type adsorbates on transition metal surfaces scale with each other according to a simple bond order conservation model. This observation generalizes some recently recognized adsorption energy scaling laws f...

  1. Disorder-driven metal-insulator transitions from dirty black holes

    CERN Document Server

    Fadafan, Kazem Bitaghsir

    2016-01-01

    In this paper we study disorder-driven metal-insulator transition in the holographic disordered Einstein-Maxwell-dilaton theories. We study analytically the DC conductivity of such holographic models in terms of black hole horizon data. As it is expected, the electrical conductivity does not obey the lower bound.

  2. Photoinduced Coherent Spin Fluctuation in Primary Dynamics of Insulator to Metal Transition in Perovskite Cobalt Oxide

    Directory of Open Access Journals (Sweden)

    Arima T.

    2013-03-01

    Full Text Available Coherent spin fluctuation was detected in the photoinduced Mott insulator-metal transition in perovskite cobalt oxide by using 3 optical-cycle infrared pulse. Such coherent spin fluctuation is driven by the perovskite distortion changing orbital gap.

  3. Bandgap Control via Structural and Chemical Tuning of Transition Metal Perovskite Chalcogenides.

    Science.gov (United States)

    Niu, Shanyuan; Huyan, Huaixun; Liu, Yang; Yeung, Matthew; Ye, Kevin; Blankemeier, Louis; Orvis, Thomas; Sarkar, Debarghya; Singh, David J; Kapadia, Rehan; Ravichandran, Jayakanth

    2017-03-01

    Transition metal perovskite chalcogenides are a new class of versatile semiconductors with high absorption coefficient and luminescence efficiency. Polycrystalline materials synthesized by an iodine-catalyzed solid-state reaction show distinctive optical colors and tunable bandgaps across the visible range in photoluminescence, with one of the materials' external efficiency approaching the level of single-crystal InP and CdSe.

  4. Insulator-to-metal transition in (R,Ca)VO(3)

    NARCIS (Netherlands)

    Sage, M. H.; Blake, G. R.; Palstra, T. T. M.

    2008-01-01

    We have carried out a comprehensive study of the transport and thermodynamic properties of R(1-x)Ca(x)VO(3) (R=Pr, Sm, and Y), obtaining detailed information on the nature of the insulator-metal transition induced by Ca doping. The behavior of the electronic term of the specific heat as a function o

  5. Continuous-wave broadband emitter based on a transition-metal-ion-doped waveguide

    NARCIS (Netherlands)

    Pollnau, M.; Salathé, R.P.; Bhutta, T.; Shepherd, D.P.; Eason, R.W.

    2001-01-01

    We demonstrate the suitability of a simple continuous-wave-pumped transition-metal-ion-doped waveguide as a broadband light source in the wavelength region 600–1000 nm for interferometric applications. Spatially coherent (single mode in the confined direction), spectrally broadband (~130-nm FWHM) lu

  6. Trends in the Hydrodeoxygenation Activity and Selectivity of Transition Metal Surfaces

    DEFF Research Database (Denmark)

    Lausche, Adam C.; Falsig, Hanne; Jensen, Anker Degn

    2014-01-01

    This paper reports the use of a combination of density functional theory and microkinetic modelling to establish trends in the hydrodeoxygenation rates and selectivites of transition metal surfaces. Biomass and biomass-derived chemicals often contain large fractions of oxygenates. Removal of the ...

  7. Catalytic Ring Hydrogenation of Benzoic Acid with Supported Transition Metal Catalysts in scCO2

    OpenAIRE

    2007-01-01

    The ring hydrogenation of benzoic acid to cyclohexanecarboxylic acid over charcoal-supported transition metal catalysts in supercritical CO2 medium has been studied in the present work. The cyclohexanecarboxylic acid can be produced efficiently in supercritical CO2 at the low reaction temperature of 323 K. The presence of CO2 increases the reaction rate and several parameters have been discussed.

  8. Crossover of angular dependent magnetoresistance with the metal-insulator transition in colossal magnetoresistive manganite films

    DEFF Research Database (Denmark)

    Chen, Yunzhong; Sun, J.R.; Zhao, T.Y.;

    2009-01-01

    directions was observed with the appearance of magnetic-field-induced metal-insulator transition, which further led to a sign crossover in the AMR effect. The AMR crossover may give a direct evidence of the drastic modification of electronic structure or possible orbital reconstruction with the magnetic...

  9. Molecular recognition in homogeneous transition metal catalysis: a biomimetic strategy for high selectivity.

    Science.gov (United States)

    Das, Siddartha; Brudvig, Gary W; Crabtree, Robert H

    2008-01-28

    Traditional methods for selectivity control in homogeneous transition metal catalysis either employ steric effects in a binding pocket or chelate control. In a supramolecular strategy, encapsulation of the substrate can provide useful shape and size selectivity. A fully developed molecular recognition strategy involving hydrogen bonding or solvophobic forces has given almost completely regioselective functionalization of remote, unactivated C-H bonds.

  10. Synthesis of 2-substituted tetraphenylenes via transition-metal-catalyzed derivatization of tetraphenylene

    Directory of Open Access Journals (Sweden)

    Shulei Pan

    2016-06-01

    Full Text Available A new strategy for the synthesis of 2-substituted tetraphenylenes through a transition-metal-catalyzed derivatization has been developed. Three types of functionalities, including OAc, X (Cl, Br, I and carbonyl, were introduced onto tetraphenylene, which allows the easy access to a variety of monosubstituted tetraphenylenes. These reactions could accelerate research on the properties and application of tetraphenylene derivatives.

  11. Atomically Thin Ordered Alloys of Transition Metal Dichalcogenides: Stability and Band Structures

    DEFF Research Database (Denmark)

    Pandey, Mohnish; Jacobsen, Karsten Wedel; Thygesen, Kristian Sommer

    2016-01-01

    We explore the possibility of modulating the electronic band edges of the transition metal dichalcogenides (TMD) via alloying of different semiconductors within the same group (intra-group alloying). The stability of the ordered alloys is assessed from the calculated mixing enthalpy which is found...

  12. Lattice-Inversion Embedded-Atom-Method Interatomic Potentials for Group-VA Transition Metals

    Institute of Scientific and Technical Information of China (English)

    袁晓俭; 陈难先; 申江

    2011-01-01

    The lattice-inversion embedded-atom-method (LI-EAM) interatomic potential we developed previously [J. Phys.: Condens. Matter 22 (2010) 375503] is extended to group- VA transition metals (V, Nb and Ta). It is found that considering interatomic interactions up to appropriate-distance-neighbor atoms is crucial to constructing accurate EAM potentials, especially for the prediction of surface energy. The LI-EAM interatomic potentials for group-VA transition metals are successfully built by considering interatomic interactions up to the fifth neighbor atoms. These angular-independent potentials drastically promote the accuracy of the predicted surface energies, which match the experimental resuits well.%The lattice-inversion embedded-atom-method(LI-EAM)interatomic potential we developed previously[J.Phys.:Condens.Matter 22(2010)375503]is extended to group-VA transition metals(V,Nb and Ta).It is found that considering interatomic interactions up to appropriate-distance-neighbor atoms is crucial to constructing accurate EAM potentials,especially for the prediction of surface energy.The LI-EAM interatomic potentials for group-VA transition metals are successfully built by considering interatomic interactions up to the fifth neighbor atoms.These angular-independent potentials drastically promote the accuracy of the predicted surface energies,which match the experimental results well.

  13. Group 4 Transition-Metal Complexes of an Aniline–Carbene–Phenol Ligand

    KAUST Repository

    Despagnet-Ayoub, Emmanuelle

    2013-05-24

    Attempts to install a tridentate aniline-NHC-phenol (NCO) ligand on titanium and zirconium led instead to complexes resulting from unexpected rearrangement pathways that illustrate common behavior in carbene-early- transition-metal chemistry. © 2013 American Chemical Society.

  14. Filtrates & Residues: Hemoglobinometry--A Biochemistry Experiment that Utilizes the Principles of Transition Metal Chemistry.

    Science.gov (United States)

    Giuliano, Vincenzo; Rieck, John Paul

    1987-01-01

    Describes a chemistry experiment dealing with hemoglobinometry that can apply to transition metal chemistry, colorimetry, and biochemistry. Provides a detailed description of the experimental procedure, including discussions of the preparation of the cyanide reagent, colorimetric measurements, and waste disposal and treatment. (TW)

  15. A New Fluorescent Sensor for Transition Metal Ions in Aqueous Solution

    Institute of Scientific and Technical Information of China (English)

    2000-01-01

    A new fluorescent sensor consisted of fluorenyl and dioxotetraaza unit, namely, 2,10-dimethyl-6-(9-fluorenyl)-1,4,8,11-tetraazaundencane-5,7-dione (L), was synthesized. It is a fluorescent sensor for transition metal ions in aqueous solution.

  16. On the behavior of Brønsted-Evans-Polanyi relations for transition metal oxides

    DEFF Research Database (Denmark)

    Vojvodic, Aleksandra; Vallejo, Federico Calle; Guo, Wei

    2011-01-01

    Versatile Brønsted-Evans-Polanyi (BEP) relations are found from density functional theory for a wide range of transition metal oxides including rutiles and perovskites. For oxides, the relation depends on the type of oxide, the active site, and the dissociating molecule. The slope of the BEP...

  17. Reflection symmetry at a B=0 metal-insulator transition in two dimensions

    OpenAIRE

    Simonian, D.; Kravchenko, S. V.; Sarachik, M. P.

    1996-01-01

    We report a remarkable symmetry between the resistivity and conductivity on opposite sides of the B=0 metal-insulator transition in a two-dimensional electron gas in high-mobility silicon MOSFET's. This symmetry implies that the transport mechanisms on the two sides are related.

  18. Metal insulator transition and Froehlich conductivity in the Su-Schrieffer-Heeger model

    NARCIS (Netherlands)

    Michielsen, Kristel; Raedt, Hans De

    1996-01-01

    A quantum molecular dynamics technique is used to study the single-particle density of states, Drude weight, optical conductivity and flux quantization in the Su-Schrieffer-Heeger (SSH) model. Our simulation data show that the SSH model has a metal-insulator transition away from half-filling. In the

  19. Metal-insulator transition and Frohlich conductivity in the Su-Schrieffer-Heeger model

    NARCIS (Netherlands)

    Michielsen, K.F L; de Raedt, H.A.

    1996-01-01

    A quantum molecular dynamics technique is used to study the single-particle density of states, Drude weight, optical conductivity and flux quantization in the Su-Schrieffer-Heeger (SSH) model. Our simulation data show that the SSH model has a metal-insulator transition away from half-filling. In the

  20. Synthesis of 2-substituted tetraphenylenes via transition-metal-catalyzed derivatization of tetraphenylene

    Science.gov (United States)

    Pan, Shulei; Jiang, Hang; Zhang, Yu; Chen, Dushen

    2016-01-01

    Summary A new strategy for the synthesis of 2-substituted tetraphenylenes through a transition-metal-catalyzed derivatization has been developed. Three types of functionalities, including OAc, X (Cl, Br, I) and carbonyl, were introduced onto tetraphenylene, which allows the easy access to a variety of monosubstituted tetraphenylenes. These reactions could accelerate research on the properties and application of tetraphenylene derivatives. PMID:27559378