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Sample records for 5d transition metal

  1. Frontiers of 4d- and 5d-transition metal oxides

    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

  2. Correlation between the spin Hall angle and the structural phases of early 5d transition metals

    Liu, Jun; Ohkubo, Tadakatsu; Mitani, Seiji; Hono, Kazuhiro; Hayashi, Masamitsu, E-mail: hayashi.masamitsu@nimsgo.jp [National Institute for Materials Science, Tsukuba 305-0047 (Japan)

    2015-12-07

    We have studied the relationship between the structure and the spin Hall angle of the early 5d transition metals in X/CoFeB/MgO (X = Hf, Ta, W, and Re) heterostructures. Spin Hall magnetoresistance (SMR) is used to characterize the spin Hall angle of the heavy metals. Transmission electron microscopy images show that all underlayers are amorphous-like when their thicknesses are small, however, crystalline phases emerge as the thickness is increased for certain elements. We find that the heavy metal layer thickness dependence of the SMR reflects these changes in structure. The largest spin Hall angle |θ{sub SH}| of Hf, Ta, W, and Re (∼0.11, 0.10, 0.23, and 0.07, respectively) is found when the dominant phase is amorphous-like. We find that the amorphous-like phase not only possesses large resistivity but also exhibits sizeable spin Hall conductivity, which both contribute to the emergence of the large spin Hall angle.

  3. Correlation between the spin Hall angle and the structural phases of early 5d transition metals

    We have studied the relationship between the structure and the spin Hall angle of the early 5d transition metals in X/CoFeB/MgO (X = Hf, Ta, W, and Re) heterostructures. Spin Hall magnetoresistance (SMR) is used to characterize the spin Hall angle of the heavy metals. Transmission electron microscopy images show that all underlayers are amorphous-like when their thicknesses are small, however, crystalline phases emerge as the thickness is increased for certain elements. We find that the heavy metal layer thickness dependence of the SMR reflects these changes in structure. The largest spin Hall angle |θSH| of Hf, Ta, W, and Re (∼0.11, 0.10, 0.23, and 0.07, respectively) is found when the dominant phase is amorphous-like. We find that the amorphous-like phase not only possesses large resistivity but also exhibits sizeable spin Hall conductivity, which both contribute to the emergence of the large spin Hall angle

  4. Spin-correlations and magnetic structure in an Fe monolayer on 5d transition metal surfaces

    We present a detailed first principles study on the magnetic structure of an Fe monolayer on different surfaces of 5d transition metals. We use the spin-cluster expansion technique to obtain parameters of a spin model, and predict the possible magnetic ground state of the studied systems by employing the mean field approach and, in certain cases, by spin dynamics calculations. We point out that the number of shells considered for the isotropic exchange interactions plays a crucial role in the determination of the magnetic ground state. In the case of Ta substrate we demonstrate that the out-of-plane relaxation of the Fe monolayer causes a transition from ferromagnetic to antiferromagnetic ground state. We examine the relative magnitude of nearest neighbour Dzyaloshinskii–Moriya (D) and isotropic (J) exchange interactions in order to get insight into the nature of magnetic pattern formations. For the Fe/Os(0 0 0 1) system we calculate a very large D/J ratio, correspondingly, a spin spiral ground state. We find that, mainly through the leading isotropic exchange and Dzyaloshinskii–Moriya interactions, the inward layer relaxation substantially influences the magnetic ordering of the Fe monolayer. For the Fe/Re(0 0 0 1) system characterized by large antiferromagnetic interactions we also determine the chirality of the 120° Néel-type ground state. (paper)

  5. Vacancy properties in 5d bcc transition metals: Ab initio study at finite electron temperature

    The self-diffusion constants for the monovacancy mechanism in the 5d transition-metals with bcc structure (β-Hf, Ta and W) are investigated by first-principles pseudopotential calculations within the framework of the Local Density Functional Theory. The formation and migration energies, calculated for relaxed configurations using supercells containing 27 and 54 atomic sites, are in quite good agreement with experimental data in Ta and W, with a discrepancy lower than 10%. Preliminary results in β-Hf using smaller supercells suggest very large and relaxation energies. The effects of finite electron-temperature is shown to be quite important, and very different from one element to the other: the electron contribution to the activation entropy is negative in Ta and positive in W, reaching respectively -2 kB and 2 kB at the melting temperature. Using simple estimates for the attempt frequencies and the vibrational formation entropies, the calculated self-diffusion coefficient is in exceptional agreement with experiments in W, and clearly reproduces an accelerated diffusivity in Ta

  6. Electronic and magnetic behaviors of graphene with 5d series transition metal atom substitutions: A first-principles study

    Sun, Minglei; Tang, Wencheng; Ren, Qingqiang; Zhao, Yiming; Wang, Sake; Yu, Jin; Du, Yanhui; Hao, Yitong

    2016-06-01

    The electronic structures and magnetic behaviors of graphene with 5d series transition metal atom substitutions are investigated by performing first-principles calculations. All the impurities are tightly bonded to single vacancy in a graphene sheet. The substitutions of La and Ta lead to Fermi level shifting to valence and conduction band, respectively. Both the two substitutions result in metallic properties. Moreover, the Hf, Os and Pt-substituted systems exhibit semiconductor properties, while the Re and Ir-substituted ones exhibit robust half-metallic properties. Interestingly, W-substituted system shows dilute magnetic semiconductor property. On the other hand, the substitution of Ta, W, Re and Ir induce 0.86 μB, 2 μB, 1 μB and 0.99 μB magnetic moment, respectively. Our studies demonstrate that the 5d series transition metal substituted graphene have potential applications in nanoelectronics, spintronics and magnetic storage devices.

  7. On the R 5d band polarization in rare-earth-transition metal compounds.

    Burzo, E; Chioncel, L; Tetean, R; Isnard, O

    2011-01-19

    Magnetic measurements and band structure calculations were performed on RT(2) and RT(5) compounds, where R is a heavy rare-earth and T = Fe, Co, Ni, Al, as well as on pseudobinary compounds GdCo(2 - x)A(x) (A = Ni, Cu, Si), YFe(2 - x)V(x) and YCo(4 - x)Ni(x)B. The calculated moments per formula unit described well the experimentally determined magnetizations. By considering the 4f-5d-3d exchange interactions, we evaluate the contributions of local 4f-5d and short range 5d-3d interactions to R 5d and Y 4d band polarizations. The 4f-5d induced polarizations are proportional to the De Gennes factor and are the same for a given R and a similar type structure. The R 5d and Y 4d band polarizations induced by R 5d-T3d or Y 4d-T3d hybridizations are proportional to the number of neighbouring T atoms, to a given R, and their magnetic moments. Previous results on the matter are also discussed. PMID:21406851

  8. Trends in elasticity and electronic structure of 5d transition metal diborides: first-principles calculations

    We investigate the cohesive energy, heat of formation, elastic constant and electronic band structure of transition metal diborides TMB2 (TM = Hf, Ta, W, Re, Os and Ir, Pt) in the Pmmn space group using the ab initio pseudopotential total energy method. Our calculations indicate that there is a relationship between elastic constant and valence electron concentration (VEC): the bulk modulus and shear modulus achieve their maximum when the VEC is in the range of 6.8-7.2. In addition, trends in the elastic constant are well explained in terms of electronic band structure analysis, e.g., occupation of valence electrons in states near the Fermi level, which determines the cohesive energy and elastic properties. The maximum in bulk modulus and shear modulus is attributed to the nearly complete filling of TM d-B p bonding states without filling the antibonding states. On the basis of the observed relationship, we predict that alloying W and Re in the orthorhombic structure OsB2 might be harder than alloying the Ir element. Indeed, the further calculations confirmed this expectation

  9. Magnetocrystalline anisotropy of 4d/5d transition metals on a Co(0001) surface: A first-principles study

    Taivansaikhan, P.; Odkhuu, D.; Rhim, S. H.; Hong, S. C.

    2015-05-01

    Magnetism and magnetocrystalline anisotropy (MCA) of 4d and 5d transition metal monolayers have been investigated in the presence of a Co(0001) substrate using first-principles electronic structure calculations. Magnetization of Co-group elements undergoes a transition from an in-plane to perpendicular MCA on Co(0001), whose energies (EMCA) are +0.75 meV/cell and +3.67 meV/cell for Rh/Co(0001) and Ir/Co(0001), respectively. On the other hand, the Fe-group Ru/Co(0001) and Os/Co(0001) exhibit the in-plane MCA with antiparallel spin moments to that of the Co substrate. From band analysis, enhancement of MCA in the Ir/Co(0001) is mainly due to the Ir atom by ⟨ m = 0 | l x | m = ± 1 ⟩ matrix in the ↑↓-channel, where negative MCA found in Os/Co(0001) is due to Co with dominant contribution from ⟨ m = 0 | l x | m = ± 1 ⟩ and ⟨ m = ± 2 | l x | m = ± 1 ⟩ matrices in the ↓↓- and ↑↓-channel, respectively. The significant enhancement of EMCA in Rh/ and Ir/ Co(0001) is ascribed to larger spin-orbit coupling of 4d and 5d orbitals, mainly by coupling between m = 0 and m = ±1 states.

  10. Localized spin fluctuations in 4d and 5d transition metals with iron impurities

    The superconducting transition temperatures of TcMn, TcFe, and TcCo alloys have been measured. The rapid depression of the transition temperature of Tc by Fe impurities can be understood in terms of Roessler and Kiwi's theory for localized spin fluctuations in superconducting alloys. The magnetic character of Fe impurities in Tc, Ru, and Ir hosts has also been studied by Moessbauer experiments in the temperature region of 1.4 - 290 K and in external fields up to 50 kOe. Saturation hyperfine fields in 50 kOe are -7.3 +- 1 kOe for TcFe, -1 +- 1 kOe for RuFe, and -9.3 +- 1 kOe for IrFe, being much smaller than those of usual Kondo alloys. A qualitative explanation of these small hyperfine fields is attempted by a stochastic model based on the LSF concept. (author)

  11. Cluster Decay Half-Lives of 5d Transition Metal Nuclei Using the Coulomb and Proximity Potential Model

    Mageed, K E Abd El; Gado, K A; Shalaby, Asmaa G

    2016-01-01

    We have applied the Coulomb and proximity potential model,CPPM to calculate the half lives for various clusters decay of the selected even-even isotopes of the chosen nuclei. These nuclei are Hf, W, Os, Pt, and Hg in the 5d transition metal region in the periodic table with atomic number 72 greater or equal Z less than or equal 80. Furthermore, the half-lives are calculated using the universal formula for cluster decay. The calculated half-lives of alpha decay for the chosen isotopes are in good agreement with the experimental data, especially with the CPPM results. The alpha and cluster decays are more probable from the parents in the heavier mass number A equal 168,180 than from the parents in the lighter mass number A equal 156, 166.

  12. Magnetocrystalline anisotropy of 4d/5d transition metals on a Co(0001) surface: A first-principles study

    Taivansaikhan, P.; Rhim, S. H., E-mail: sonny@ulsan.ac.kr, E-mail: schong@ulsan.ac.kr; Hong, S. C., E-mail: sonny@ulsan.ac.kr, E-mail: schong@ulsan.ac.kr [Department of Physics and Energy Harvest Storage Research Center, University of Ulsan, Ulsan 680-749 (Korea, Republic of); Odkhuu, D. [Department of Physics, Incheon National University, Incheon 406-772 (Korea, Republic of)

    2015-05-07

    Magnetism and magnetocrystalline anisotropy (MCA) of 4d and 5d transition metal monolayers have been investigated in the presence of a Co(0001) substrate using first-principles electronic structure calculations. Magnetization of Co-group elements undergoes a transition from an in-plane to perpendicular MCA on Co(0001), whose energies (E{sub MCA}) are +0.75 meV/cell and +3.67 meV/cell for Rh/Co(0001) and Ir/Co(0001), respectively. On the other hand, the Fe-group Ru/Co(0001) and Os/Co(0001) exhibit the in-plane MCA with antiparallel spin moments to that of the Co substrate. From band analysis, enhancement of MCA in the Ir/Co(0001) is mainly due to the Ir atom by 〈m=0| l{sub x} |m=±1〉 matrix in the ↑↓-channel, where negative MCA found in Os/Co(0001) is due to Co with dominant contribution from 〈m=0| l{sub x} |m=±1〉 and 〈m=±2| l{sub x} |m=±1〉 matrices in the ↓↓- and ↑↓-channel, respectively. The significant enhancement of E{sub MCA} in Rh/ and Ir/ Co(0001) is ascribed to larger spin-orbit coupling of 4d and 5d orbitals, mainly by coupling between m = 0 and m = ±1 states.

  13. Vacuum Referred Binding Energy of the Single 3d, 4d, or 5d Electron in Transition Metal and Lanthanide Impurities in Compounds

    Rogers, E.G.; Dorenbos, P.

    2014-01-01

    The vacuum referred binding energy (VRBE) of the single electron in the lowest energy 3d level of Sc2 +, V4 +, Cr5 +, the lowest 4d level of Y2 +, Zr3 +, Nb4 +, Mo5 + and the lowest 5d level of Ta4 +, and W5 + in various compounds are determined by means of the chemical shift model. They will be compared with the VRBE in the already established lowest 3d level of Ti3 + and the lowest 5d level of Eu2 + and Ce3 +. Clear trends with changing charge of the transition metal (TM) cation and with ch...

  14. Relationships between the surface electronic and chemical properties of doped 4d and 5d late transition metal dioxides

    Xu, Zhongnan; Kitchin, John R., E-mail: jkitchin@andrew.cmu.edu [Department of Chemical Engineering, Carnegie Mellon University, 5000 Forbes Ave, Pittsburgh, Pennsylvania 15213 (United States)

    2015-03-14

    Density functional theory calculations were performed to elucidate the underlying physics describing the adsorption energies on doped late transition metal dioxide rutiles. Adsorption energies of atomic oxygen on doped rutiles M{sup D}-M{sup H}O{sub 2}, where transition metal M{sup D} is doped into M{sup H}O{sub 2}, were expressed in terms of a contribution from adsorption on the pure oxide of the dopant M{sup D} and perturbations to this adsorption energy caused by changing its neighboring metal cations and lattice parameters to that of the host oxide M{sup H}O{sub 2}, which we call the ligand and strain effects, respectively. Our analysis of atom projected density of states revealed that the t{sub 2g}-band center had the strongest correlation with adsorption energies. We show that charge transfer mediated shifts to the t{sub 2g}-band center describe the ligand effect, and the radii of the atomic orbitals of metal cations can predict the magnitude and direction of this charge transfer. Strain produces systematic shifts to all features of the atom projected density of states, but correlations between the strain effect and the electronic structure were dependent on the chemical identity of the metal cation. The slope of these correlations can be related to the idealized d-band filling. This work elucidates the underlying physics describing adsorption on doped late transition metal oxides and establishes a foundation for models that use known chemical properties for the prediction of reactivity.

  15. Extremely large perpendicular magnetic anisotropy of an Fe(001) surface capped by 5d transition metal monolayers: A density functional study

    Odkhuu, D.; Rhim, S. H.; Park, N.; Hong, S. C.

    2013-11-01

    Significant enhancement of the magnetocrystalline anisotropy (MCA) of an Fe(001) surface capped by 4d and 5d transition metal monolayers is presented in this study using first principles density functional calculations. In particular, an extremely large perpendicular MCA of +10 meV/Ir was found in Ir-capped Fe(001), which originates not from the Fe but from the large spin-orbit coupling of the Ir atoms. From the spin-channel decomposition of the MCA matrix and electronic structure analyses, we find that strong 3d-5d band hybridization in the minority spin state is responsible for the sign changes of the MCA from parallel to perpendicular.

  16. Optical Spectroscopic Studies of the Metal-Insulator Transition Driven by All-In-All-Out Magnetic Ordering in 5 d Pyrochlore Cd2 Os2 O7

    Sohn, C. H.; Jeong, Hogyun; Jin, Hosub; Kim, Soyeon; Sandilands, L. J.; Park, H. J.; Kim, K. W.; Moon, S. J.; Cho, Deok-Yong; Yamaura, J.; Hiroi, Z.; Noh, T. W.

    2015-12-01

    We investigated the metal-insulator transition (MIT) driven by all-in-all-out (AIAO) antiferromagnetic ordering in the 5 d pyrochlore Cd2 Os2 O7 using optical spectroscopy and first-principles calculations. We showed that the temperature evolution in the band-gap edge and free carrier density were consistent with rigid upward (downward) shifts of electron (hole) bands, similar to the case of Lifshitz transitions. The delicate relationship between the band gap and free carrier density provides experimental evidence for the presence of an AIAO metallic phase, a natural consequence of such MITs. The associated spectral weight change at high energy and first-principles calculations further support the origin of the MIT from the band shift near the Fermi level. Our data consistently support that the MIT induced by AIAO ordering in Cd2 Os2 O7 is not close to a Slater type but instead to a Lifshitz type.

  17. First-principles study of site occupancy of dilute 3d, 4d and 5d transition metal solutes in L10 TiAl

    Using a statistical-mechanical Wagner-Schottky model parametrized by first-principles density-functional (DFT-GGA) calculations on 32-atom supercells, we predict the lattice site occupancy of 3d (Ti-Cu), 4d (Zr-Ag) and 5d (Hf-Au) transition-metal elements in L10 TiAl intermetallic compound as a function of both alloy composition and temperature. The effects of local atomic relaxations, anisotropic lattice distortions, as well as magnetism on point defect energetics are fully taken into account. Our calculations show that, at all alloy compositions and temperatures, Zr and Hf consistently show a preference for the Ti sublattice, while Co, Ru, Rh, Pd, Ag, Re, Os, Ir, Pt and Au consistently show a preference for the Al sublattice. In contrast, the site preference of V, Cr, Mn, Fe, Ni, Cu, Nb, Mo, Tc, Ta and W strongly depend on both alloy stoichiometry and temperature. Our calculated results compare favorably with the existing theoretical and experimental studies in the literature

  18. Superconductivity, magnetism and metal-insulator transitions in some ternary and pseudoternary 3d-, 4d- and 5d-metal oxides

    Electron conduction effects have been found to be particularly important in the metallic compounds LiV2O4 and possibly Sr2Ir1-xRuxO4 (x > 0.7), but not in metallic Sr1-xLaxVO3 (x 2IrO4 and ZnV2O4 to be (Mott-Hubbard) insulators. The LiV2O4 spinel compound is especially interesting, because the V ions exhibit rather clear local moment (S = 1/2) behavior even though the compound is a metal

  19. Analysis of the (5d8+5d76s)-5d76p transition arrays of four times ionized mercury (Hg V)

    The spectrum of mercury was photographed in the 800-2000 A region on a 3-m normal incidence spectrograph (plate factor 1.385 A/mm). A low inductance triggered spark was used as an excitation source. The analysis of the 5d76s-5d76p transition array has lead to the confirmation of all levels of the 5d76p configuration established earlier, to adding of 35 levels to the 5d76p configuration and to establishing of 32 out of 38 levels of the 5d76s configuration. Three hundred and thirty lines have been classified in the 5d76s-5d76p transition array and 36 additional lines have been classified in the 5d8-5d76p transition array. In this transition array the 5d81S0 level, which is unknown in the sequence, has been established. The least squares fitted calculations describe the spectrum satisfactorily. (orig.)

  20. Analysis of the (5d[sup 8]+5d[sup 7]6s)-5d[sup 7]6p transition arrays of four times ionized mercury (Hg V)

    Wyart, J.F. (Lab. Aime Cotton, Bat 505, Centre Univ., 91 - Orsay (France)); Raassen, A.J.J. (Van der Waals-Zeeman Lab. Amsterdam (Netherlands)); Hof, G.J. van het (Physics Dept. St. Francis Xavier Univ., Antigonish, Nova Scotia (Canada)); Joshi, Y.N. (Physics Dept. St. Francis Xavier Univ., Antigonish, Nova Scotia (Canada))

    1993-06-01

    The spectrum of mercury was photographed in the 800-2000 A region on a 3-m normal incidence spectrograph (plate factor 1.385 A/mm). A low inductance triggered spark was used as an excitation source. The analysis of the 5d[sup 7]6s-5d[sup 7]6p transition array has lead to the confirmation of all levels of the 5d[sup 7]6p configuration established earlier, to adding of 35 levels to the 5d[sup 7]6p configuration and to establishing of 32 out of 38 levels of the 5d[sup 7]6s configuration. Three hundred and thirty lines have been classified in the 5d[sup 7]6s-5d[sup 7]6p transition array and 36 additional lines have been classified in the 5d[sup 8]-5d[sup 7]6p transition array. In this transition array the 5d[sup 8] [sup 1]S[sub 0] level, which is unknown in the sequence, has been established. The least squares fitted calculations describe the spectrum satisfactorily. (orig.).

  1. Oligocyclopentadienyl transition metal complexes

    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.

  2. Density functional theory investigation of 3d, 4d, and 5d 13-atom metal clusters

    The knowledge of the atomic structure of clusters composed by few atoms is a basic prerequisite to obtain insights into the mechanisms that determine their chemical and physical properties as a function of diameter, shape, surface termination, as well as to understand the mechanism of bulk formation. Due to the wide use of metal systems in our modern life, the accurate determination of the properties of 3d, 4d, and 5d metal clusters poses a huge problem for nanoscience. In this work, we report a density functional theory study of the atomic structure, binding energies, effective coordination numbers, average bond lengths, and magnetic properties of the 3d, 4d, and 5d metal (30 elements) clusters containing 13 atoms, M13. First, a set of lowest-energy local minimum structures (as supported by vibrational analysis) were obtained by combining high-temperature first-principles molecular-dynamics simulation, structure crossover, and the selection of five well-known M13 structures. Several new lower energy configurations were identified, e.g., Pd13, W13, Pt13, etc., and previous known structures were confirmed by our calculations. Furthermore, the following trends were identified: (i) compact icosahedral-like forms at the beginning of each metal series, more opened structures such as hexagonal bilayerlike and double simple-cubic layers at the middle of each metal series, and structures with an increasing effective coordination number occur for large d states occupation. (ii) For Au13, we found that spin-orbit coupling favors the three-dimensional (3D) structures, i.e., a 3D structure is about 0.10 eV lower in energy than the lowest energy known two-dimensional configuration. (iii) The magnetic exchange interactions play an important role for particular systems such as Fe, Cr, and Mn. (iv) The analysis of the binding energy and average bond lengths show a paraboliclike shape as a function of the occupation of the d states and hence, most of the properties can be explained

  3. The 7F0 → 5D0 Two-photon transition: a test of theoretical models

    Measurements of the polarization dependence of the 7F0 → 5D0 two-photon transition for the Sm2+ ion in BaClF are reported. The standard second-order Axe theory is shown to fail in interpreting the obtained data. A phenomenological approach taking account of higher-order contributions is then followed. It turns out to reproduce the experimental results in a very satisfactory way. It is pointed out that the scalar term responsible for the isotropic contribution to the 7F0 → 5D0 two-photon transition intensity is not the only one to be operative in this material

  4. First-principles relativistic calculation for 4f-5d transition energy of Ce3+ in various fluoride hosts

    In this paper, we investigated the 4f-5d transition energy of Ce3+ in various fluoride hosts based on the first-principles discrete-variational Dirac-Slater (DV-DS) calculations using Slater's transition-state theory. Especially, we focused on the lowest energy peak (1st peak) of 4f-5d transition for Ce3+ impurities. As the host crystals, we adopted the 15 fluorides, for which the experimental data of the lowest energy peak (1st peak) in 4f-5d transitions were available from literature except for NaMgF3 and BaMgF4. A high correlation between the experimental 1st peak energies and the theoretical ones was obtained which suggests a possibility to predict the 4f-5d transition energy of Ce3+ in various fluoride hosts using the first-principles calculation. - Graphical abstract: Correlation diagram between the experimental 1st peak energy and the theoretical 1st peak energy. The left figure (A) shows the results without the lattice relaxation by correction of bond length and right one (B) shows the results with the lattice relaxation by correction of bond length. The corresponding coefficients of correlation R are 0.78 and 0.98, respectively

  5. Melting of Transition Metals

    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.

  6. Semiconducting transition metal oxides

    Open shell transition metal oxides are usually described as Mott or charge transfer insulators, which are often viewed as being disparate from semiconductors. Based on the premise that the presence of a correlated gap and semiconductivity are not mutually exclusive, this work reviews electronic structure calculations on the binary 3d oxides, so to distill trends and design principles for semiconducting transition metal oxides. This class of materials possesses the potential for discovery, design, and development of novel functional semiconducting compounds, e.g. for energy applications. In order to place the 3d orbitals and the sp bands into an integrated picture, band structure calculations should treat both contributions on the same footing and, at the same time, account fully for electron correlation in the 3d shell. Fundamentally, this is a rather daunting task for electronic structure calculations, but quasi-particle energy calculations in GW approximation offer a viable approach for band structure predictions in these materials. Compared to conventional semiconductors, the inherent multivalent nature of transition metal cations is more likely to cause undesirable localization of electron or hole carriers. Therefore, a quantitative prediction of the carrier self-trapping energy is essential for the assessing the semiconducting properties and to determine whether the transport mechanism is a band-like large-polaron conduction or a small-polaron hopping conduction. An overview is given for the binary 3d oxides on how the hybridization between the 3d crystal field symmetries with the O-p orbitals of the ligands affects the effective masses and the likelihood of electron and hole self-trapping, identifying those situations where small masses and band-like conduction are more likely to be expected. The review concludes with an illustration of the implications of the increased electronic complexity of transition metal cations on the defect physics and doping, using

  7. Critical points and phase transitions in 5d compactifications of M-theory

    We study critical points of the BPS mass Z, the BPS string tension Zm, the black hole potential V and the gauged central charge potential P for M-theory compactified on Calabi-Yau three-folds. We first show that the stabilization equations for Z (determining the black hole entropy) take an extremely simple form in five dimensions as opposed to four dimensions. The stabilization equations for Zm are also very simple and determine the size of the infinite adS3throat of the string. The black hole potential in general exhibits two classes of critical points: supersymmetric critical points which coincide with those of the central charge and non-supersymmetric critical points. We then generalize the discussion to the entire extended Kaehler cone encompassing topologically different but birationally equivalent Calabi-Yau three-folds that are connected via flop transitions. We examine behavior of the four potentials to probe the nature of these phase transitions. We find that V and P are continuous but not smooth across the flop transition, while Z and its first two derivatives, as well as Zm and its first derivative, are continuous. This in turn implies that supersymmetric stabilization of Z and Zm for a given configuration takes place in at most one point throughout the entire extended Kaehler cone. The corresponding black holes (or string states) interpolate between different Calabi-Yau three-folds. At the boundaries of the extended Kaehler cone we observe that electric states become massless and/or magnetic strings become tensionless. (orig.)

  8. Transition metals in carbohydrate chemistry

    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. Electrical Conductivity in Transition Metals

    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…

  10. Pillared layered transition metal oxides

    2003-01-01

    This paper reviews the recent progress in the synthesis and application of pillared transition metal oxides during the last decade, mainly concerning the synthetic methods, structures, physical properties and catalytic applications of the layered transition metal oxides pillared by inorganic oxides. The factors and their affecting regularity in the process of preparation, and some important results obtained in the catalytic application studies are summarized. Finally, a prospect on the potential new directions in this research area is also presented.

  11. Merging transition-metal activation and aminocatalysis

    Rios, Ramon; Meazza, Marta

    2015-01-01

    In this review the principal enantioselective methodologies merging transition-metal catalysis and aminocatalysis are disclosed. 1 Introduction 2 Transition-Metal and Enamine Catalysis 3 Transition-Metal and Iminium Catalysis 4 Transition-Metal Catalysis and Organocascade (Iminium/Enamine) Activation 5 Conclusions and Perspectives

  12. Alkali and transition metal phospholides

    Major tendencies in modern chemistry of alkali and transition metal phospholides (phosphacyclopentadienides) are systematized, analyzed and generalized. Basic methods of synthesis of these compounds are presented. Their chemical properties are considered with a special focus on their complexing ability. Potential applications of phospholides and their derivatives are discussed. The bibliography includes 184 references

  13. Fluence-dependent dynamics of the 5d6s exchange splitting in Gd metal after femtosecond laser excitation

    Frietsch, Björn; Carley, Robert; Gleich, Markus; Teichmann, Martin; Bowlan, John; Weinelt, Martin

    2016-07-01

    We investigate the fluence-dependent dynamics of the exchange-split 5d6s valence bands of Gd metal after femtosecond, near-infrared (IR) laser excitation. Time- and angle-resolved photoelectron spectroscopy (tr-ARPES) with extreme ultraviolet (XUV) probe pulses is used to simultaneously map the transient binding energies of the minority and majority spin valence bands. The decay constant of the exchange splitting increases with fluence. This reflects the slower response of the occupied majority-spin component, which we attribute to Elliot–Yafet spin-flip scattering in accordance with the microscopic three-temperature model (M3TM). In contrast, the time constant of the partly unoccupied minority-spin band stays unaffected by a change in pump fluence. Here, we introduce as an alternative to superdiffusive spin transport exchange scattering, which is an ultrafast electronic mechanism explaining the observed dynamics. Exchange scattering can reduce the spin polarization in the partially unoccupied minority-spin band and thus its energetic position without effective demagnetization.

  14. Doppler-free approach to optical pumping dynamics in the 6S1/2-5D5/2 electric quadrupole transition of cesium vapor.

    Chan, Eng Aik; Aljunid, Syed Abdullah; Zheludev, Nikolay I; Wilkowski, David; Ducloy, Martial

    2016-05-01

    The 6S1/2-5D5/2 electric quadrupole transition is investigated in cesium vapor at room temperature via nonlinear Doppler-free 6P-6S-5D three-level spectroscopy. Frequency-resolved studies of individual E2 hyperfine lines allow one to analyze the optical pumping dynamics, polarization selection rules, and line intensities. It opens the way to studies of transfer of light orbital angular momentum to atoms and the influence of metamaterials on E2 line spectra. PMID:27128060

  15. Doppler-free approach to optical pumping dynamics in the $6S_{1/2}- 5D_{5/2}$ electric quadrupole transition of Cesium vapor

    Chan, Eng Aik; Zheludev, Nikolay I; Wilkowski, David; Ducloy, Martial

    2016-01-01

    The $6S_{1/2}-5D_{5/2}$ electric quadrupole transition is investigated in Cesium vapor at room temperature via nonlinear Doppler-free 6P-6S-5D three-level spectroscopy. Frequency-resolved studies of individual E2 hyperfine lines allow one to analyze optical pumping dynamics, polarization selection rules and line intensities. It opens the way to studies of transfer of light orbital angular momentum to atoms, and the influence of metamaterials on E2 line spectra.

  16. Engineering skyrmions in transition-metal multilayers for spintronics

    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.

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

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

    2016-01-01

    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. PMID:27257020

  18. Atomic transition probabilities in refractory metals

    Accurate transition probabilities for a large number of spectral lines in the first and second spectra of 3d, 4d and 5d metals are being measured. Radiative lifetimes of hundreds of levels in TaI, WI, MoI, NbI, HfI, ReI, RhI, RuI, NbII, CoII++, and other atoms and ions are measured using time-resolved laser-induced fluorescence on an atom or ion beam. The atom or ion beam is produced by a versatile hollow cathode discharge source. Branching ratios of levels in WI, NbI, HfI, and ReI are measured from calibrated spectra recorded on the Kitt Peak one-meter Fourier Transform Spectrometer. The transition probability measurements are used in solar and stellar elemental abundance determination. Some of the elements mentioned above are commonly used as electrodes in discharge devices. Accurate transition probabilities are also useful in studying concentrations and the effects of sputtered electrode material on laboratory discharges

  19. Approximating Metal-Insulator Transitions

    Danieli, C.; Rayanov, K.; Pavlov, B.; Martin, G.; Flach, S

    2014-01-01

    We consider quantum wave propagation in one-dimensional quasiperiodic lattices. We propose an iterative construction of quasiperiodic potentials from sequences of potentials with increasing spatial period. At each finite iteration step the eigenstates reflect the properties of the limiting quasiperiodic potential properties up to a controlled maximum system size. We then observe approximate metal-insulator transitions (MIT) at the finite iteration steps. We also report evidence on mobility ed...

  20. Metal-to-nonmetal transitions

    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...

  1. Direct NO decomposition over stepped transition-metal surfaces

    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 of...... diatomic molecules over stepped transition- and noble-metal surfaces. The potential energy diagram directly points to why Pd and Pt are the best direct NO decomposition catalysts among the 3d, 4d, and 5d metals. We analyze the NO decomposition reaction in terms of a Sabatier-Gibbs-type analysis, and we...... demonstrate that this type of analysis yields results that to within a surprisingly small margin of error are directly proportional to the measured direct NO decomposition over Ru, Rh, Pt, Pd, Ag, and An. We suggest that Pd, which is a better catalyst than Pt under the employed reaction conditions, is a...

  2. Synthesis of transition metal carbonitrides

    Munir, Zuhair A. R. (Davis, CA); Eslamloo-Grami, Maryam (Davis, CA)

    1994-01-01

    Transition metal carbonitrides (in particular, titanium carbonitride, TiC.sub.0.5 N.sub.0.5) are synthesized by a self-propagating reaction between the metal (e.g., titanium) and carbon in a nitrogen atmosphere. Complete conversion to the carbonitride phase is achieved with the addition of TiN as diluent and with a nitrogen pressure .gtoreq.0.6 MPa. Thermodynamic phase-stability calculations and experimental characterizations of quenched samples provided revealed that the mechanism of formation of the carbonitride is a two-step process. The first step involves the formation of the nonstoichiometric carbide, TiC.sub.0.5, and is followed by the formation of the product by the incorporation of nitrogen in the defect-structure carbide.

  3. Approximating metal-insulator transitions

    Danieli, Carlo; Rayanov, Kristian; Pavlov, Boris; Martin, Gaven; Flach, Sergej

    2015-12-01

    We consider quantum wave propagation in one-dimensional quasiperiodic lattices. We propose an iterative construction of quasiperiodic potentials from sequences of potentials with increasing spatial period. At each finite iteration step, the eigenstates reflect the properties of the limiting quasiperiodic potential properties up to a controlled maximum system size. We then observe approximate Metal-Insulator Transitions (MIT) at the finite iteration steps. We also report evidence on mobility edges, which are at variance to the celebrated Aubry-André model. The dynamics near the MIT shows a critical slowing down of the ballistic group velocity in the metallic phase, similar to the divergence of the localization length in the insulating phase.

  4. Heterostructures of transition metal dichalcogenides

    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.

  5. Energy transfer and non-linear optical properties at near ultraviolet wavelengths: Rare earth 4f yields 5d transitions in crystals and glasses

    Hamilton, D. S.

    1992-08-01

    The following topics were studied: two-photon transitions from 4f ground state to 5d excited states in Ce(3+):CaF2; optical absorption and photoionization measurements from excited state of Ce(3+):Y3Al5O12; excited state photoionization of Ce(3+) ions in Ce(3+):CaF2; optical gain and loss studies in Ce(3+):LiYF4; Gd yields Cr energy transfer in Cr(3+):GSGG, Cr(3+):GSAG, and Cr(3+):GGG crystals; nonradiative relaxation in Ce(3+) doped crystals and glasses; and grating formation in impurity doped crystals.

  6. Lattice Dynamics of Transition Metals

    The frequency versus wave-vector v(q) dispersion relations for the normal modes of vibration of several body-centred cubic transition metal, crystals have been measured recently at room temperature. The dispersion curves for niobium, measured by Nakagawa and Woods, displayed some very unusual features, and the results could only be fitted by means of a Born-von Kármán model if interactions out to very distant neighbours (beyond eighth) were included. Subsequent measurements on tantalum by Woods showed very similar results. This is not surprising since niobium and tantalum are in column V of the periodic table and many of their electronic properties are similar. Measurements of the dispersion curves of molybdenum by Woods and Chen and of tungsten by Chen and Brockhouse showed that although these metals, which are in column VI of the periodic table, had dispersion relations which were similar to each other, these dispersion relations were very different from those of the column V metals, niobium and tantalum. The gross features of the v(q) for molybdenum and tungsten were very nearly describable by a third neighbour axially-symmetric Born-von Kármán force model, although several important features were not reproduced by this model. One of these features is a striking anomaly in the [ζζζ] longitudinal (L) branch for molybdenum where the frequency changes from v = 6.3 x 1012 c/s at ζ = 0.92 to v= 5.5 x 1012 c/s at ζ = 1.0. If this and other observed features are Kohn anomalies, their positions are consistent with the dimensions of the Fermi suríace of the column V metals proposed by Lomer. Thus it is suggested that the striking differences between the dispersion relation for niobium and that for molybdenum (metals which are believed to have quite similar band structures) reflect differences in the Fermi energies and hence the Fermi surfaces for these materials. (author)

  7. Piperazine pivoted transition metal dithiocarbamates

    Khan, Sadaf; Nami, Shahab A. A.; Siddiqi, K. S.

    2008-03-01

    A quadridentate ligand disodium bis(2,2'-dithiopiperazinato-2,2'-diamino diethylamine) Na 2L 2 and its self assembled transition metal complexes of the type, M 2(L 2) 2 {M = Mn(II), Fe(II), Co(II), Ni(II), Cu(II), Zn(II), Cd(II) and Hg(II)} have been reported. The piperazine pivoted homodinuclear complexes have been characterized by a range of spectral, thermal, microanalytical and conductometric techniques. On the basis of IR and 1HNMR data a symmetrical bidentate coordination of the dithiocarbamato moiety has been observed in all the cases. The TGA profile of the ligand exhibits two stage thermolytic pattern although the complexes decompose in three steps, respectively. Metal sulfide is found to be the end product. The formation of homodinuclear complexes has been ascertained on the basis of FAB mass spectral data and a probable fragmentation pattern has been proposed. On the basis of UV-visible spectroscopic results and room temperature magnetic moment data a tetrahedral geometry has been proposed for all the complexes except for the Ni(II) and Cu(II) which are found to be square-planar.

  8. Superconducting Metallic Glass Transition-Edge-Sensors

    Hays, Charles C. (Inventor)

    2013-01-01

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

  9. Electronic and thermodynamic properties of transition metal elements and compounds

    This thesis focuses on the use of band-structure calculations for studying thermodynamic properties of solids. We discuss 3d-, 4d- and 5d-transition metal carbides and nitrides. Through a detailed comparison between theoretical and experimental results, we draw conclusions on the character of the atomic bonds in these materials. We show how electronic structure calculations can be used to give accurate predictions for bonding energies. Part of the thesis is devoted to the application of the generalized gradient approximation in electronic structure calculations on transition metals. For structures with vibrational disorder, we present a method for calculating averaged phonon frequencies without using empirical information. For magnetic excitations, we show how a combined use of theoretical results and experimental data can yield information on magnetic fluctuations at high temperatures. The main results in the thesis are: Apart for an almost constant shift, theoretically calculated bonding energies for transition metal carbides and nitrides agree with experimental data or with values from analysis of thermochemical information. The electronic spectrum of transition metal carbides and nitrides can be separated into bonding, antibonding and nonbonding electronic states. The lowest enthalpy of formation for substoichiometric vanadium carbide VC1-X at zero temperature and pressure occurs for a structure containing vacancies (x not equal to 0). The generalized gradient approximation improves theoretical calculated cohesive energies for 3d-transition metals. Magnetic phase transitions are sensitive to the description of exchange-correlation effects in electronic structure calculations. Trends in Debye temperatures can be successfully analysed in electronic structure calculations on disordered lattices. For the elements, there is a clear dependence on the crystal structure (e.g., bcc, fcc or hcp). Chromium has fluctuating local magnetic moments at temperatures well above

  10. Experimental transition probabilities for several spectral lines arising from the 5d10 6s{8s, 7p, 5f, 5g} electronic configurations of Pb III

    Transition probabilities for 30 spectral lines, arising from the 5d10 6s{8s, 7p, 5f, 5g} electronic configurations of Pb III (20 measured for the first time), have been experimentally determined from measurements of emission line intensities in a plasma lead induced by ablation with a Nd:YAG laser. The line intensities were obtained with the target placed in molecular argon at 6 Torr, recorded at a 400 ns delay from the laser pulse, which provides appropriate measurement conditions, and analysed between 200 and 700 nm. They are measured when the plasma reaches local thermodynamic equilibrium (LTE). The plasma under study had an electron temperature (T) of 21,400 K and an electron number density (Ne) of 7x1016 cm-3. The influence of self-absorption has been estimated for every line, and plasma homogeneity has been checked. The values obtained were compared with previous experimental values and theoretical estimates where possible.

  11. Energy transfer and non-linear optical properties at near ultraviolet wavelengths: Rare earth 4f yields 5d transitions in crystals and glasses

    Hamilton, D.S.

    1992-08-01

    The following topics were studied: two-photon transitions from 4f ground state to 5d excited states in Ce{sup 3+}:CaF{sub 2}; optical absorption and photoionization measurements from excited state of Ce{sup 3+}:Y{sub 3}Al{sub 5}O{sub 12}; excited state photoionization of Ce{sup 3+} ions in Ce{sub 3+}:CaF{sub 2}; optical gain and loss studies in Ce{sup 3+}:LiYF{sub 4}; Gd {yields}Cr energy transfer in Cr{sup 3+}:GSGG, Cr{sup 3+}:GSAG and Cr{sup 3+}:GGG crystals; nonradiative relaxation in Ce{sup 3+} doped crystals and glasses; and grating formation in impurity doped crystals.

  12. Electronic doping of transition metal oxide perovskites

    Cammarata, Antonio; Rondinelli, James M.

    2016-05-01

    CaFeO3 is a prototypical negative charge transfer oxide that undergoes electronic metal-insulator transition concomitant with a dilation and contraction of nearly rigid octahedra. Altering the charge neutrality of the bulk system destroys the electronic transition, while the structure is significantly modified at high charge content. Using density functional theory simulations, we predict an alternative avenue to modulate the structure and the electronic transition in CaFeO3. Charge distribution can be modulated using strain-rotation coupling and thin film engineering strategies, proposing themselves as a promising avenue for fine tuning electronic features in transition metal-oxide perovskites.

  13. Electronic spectroscopy of transition metal dimer

    Qian, Yue; 钱玥

    2013-01-01

    This thesis reports laser spectroscopic studies of gas-phase transition metal dimers using laser ablation/reaction with free jet expansion and laser-induced fluorescence (LIF) spectroscopy technique. Themolecules studied in this work are palladium dimer (Pd2) and vanadium dimer (V2). Many compounds formed from these transition metals are important and functional catalysts in chemical reactions. Therefore, it is of great significance to start from the fundamental level to understand the prope...

  14. Doping dependent plasmon dispersion in 2 H -transition metal dichalcogenides

    Müller, Eric; Büchner, Bernd; Habenicht, Carsten; König, Andreas; Knupfer, Martin; Berger, Helmuth; Huotari, Simo

    2016-07-01

    We report the behavior of the charge carrier plasmon of 2 H -transition metal dichalcogenides (TMDs) as a function of intercalation with alkali metals. Intercalation and concurrent doping of the TMD layers have a substantial impact on plasmon energy and dispersion. While the plasmon energy shifts are related to the intercalation level as expected within a simple homogeneous electron gas picture, the plasmon dispersion changes in a peculiar manner independent of the intercalant and the TMD materials. Starting from a negative dispersion, the slope of the plasmon dispersion changes sign and grows monotonously upon doping. Quantitatively, the increase of this slope depends on the orbital character (4 d or 5 d ) of the conduction bands, which indicates a decisive role of band structure effects on the plasmon behavior.

  15. Nitrogen-rich transition metal nitrides

    Salamat, Ashkan; Hector, Andrew L.; Kroll, Peter; McMillan, Paul F.

    2013-01-01

    The solid state chemistry leading to the synthesis and characterization of metal nitrides with N:M ratios >1 is summarized. Studies of these compounds represent an emerging area of research. Most transition metal nitrides have much lower nitrogen contents, and they often form with non- or sub-stoichiometric compositions. These materials are typically metallic with often superconducting properties, and they provide highly refractory, high hardness materials with many technological applications...

  16. Electronic structure of hcp transition metals

    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...... bands. This gives rise to a Fermi surface which is topologically equivalent to that recently found in Ti, and which does not support open orbits when the magnetic field is sufficiently great that breakdown is complete. It is suggested that the Fermi surface of Hf is probably similar, although very...... majority of the transition metals....

  17. Transition metal contacts to graphene

    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.

  18. Plasmons in metallic monolayer and bilayer transition metal dichalcogenides

    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...

  19. Transition Metal Catalyzed Synthesis of Aryl Sulfides

    Chad C. Eichman

    2011-01-01

    Full Text Available The presence of aryl sulfides in biologically active compounds has resulted in the development of new methods to form carbon-sulfur bonds. The synthesis of aryl sulfides via metal catalysis has significantly increased in recent years. Historically, thiolates and sulfides have been thought to plague catalyst activity in the presence of transition metals. Indeed, strong coordination of thiolates and thioethers to transition metals can often hinder catalytic activity; however, various catalysts are able to withstand catalyst deactivation and form aryl carbon-sulfur bonds in high-yielding transformations. This review discusses the metal-catalyzed arylation of thiols and the use of disulfides as metal-thiolate precursors for the formation of C-S bonds.

  20. Chemical vapour deposition: Transition metal carbides go 2D

    Gogotsi, Yury

    2015-11-01

    The unique properties of 2D materials, such as graphene or transition metal dichalcogenides, have been attracting much attention in the past decade. Now, metallically conductive and even superconducting transition metal carbides are entering the game.

  1. Nuclear Scattering from Transition Metals

    Hira, Ajit; McKeough, James; Valerio, Mario; Cathey, Tommy

    2016-03-01

    In view of the continued interest in the scattering of light projectiles by metallic nuclei, we present a computational study of the interactions between different nuclear species of atoms such as H through F (Z neutron scattering can be used to record holographic images of materials. We have developed a FORTRAN computer program to compute stopping cross sections and scattering angles in Ag and other metals for the small nuclear projectiles, using Monte Carlo calculation. This code allows for different angles of incidence. Next, simulations were done in the energy interval from 50 to 210 keV. The computational results thus obtained are compared with relevant experimental data. The data are further analyzed to identify periodic trends in terms of the atomic number of the projectile. Such studies also have potential applications in nuclear physics and in nuclear medicine. Funding from National Science Foundation.

  2. The effect of pressure on the position and fluorescence lifetime for the 5D0→7F2 transition in Y1.9Eu0.1O3

    The aim of this study was to assess the effect of pressure on the position and fluorescence lifetime for the 5D0→7F2 transition in Y1.9Eu0.1O3 within the 0-104 kbar range. The relationship between the pressure and the line position is given by linear regression: λ(nm)=611.29+0.011P (kbar). The change of the fluorescence lifetime for the 5D0→7F2 transition with pressure can be expressed by an exponential decay: τ (ms)=1.175+0.818[1+0.006(P-16.796)2]-1. (author)

  3. Mesoporous Transition Metal Oxides for Supercapacitors

    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.

  4. Fluid metals the liquid-vapor transition of metals

    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

  5. Transition-metal dichalcogenides for spintronic applications

    Zibouche, Nourdine; Kuc, Agnieszka; Heine, Thomas [School of Engineering and Science, Jacobs University Bremen (Germany); Musfeldt, Janice [Department of Chemistry, University of Tennessee, Knoxville, TN (United States)

    2014-10-15

    Spin-orbit splitting in transition-metal dichalcogenide monolayers is investigated on the basis of density-functional theory within explicit two-dimensional periodic boundary conditions. The spin-orbit splitting reaches few hundred meV and increases with the size of the metal and chalcogen atoms, resulting in nearly 500 meV for WTe{sub 2}. Furthermore, we find that similar to the band gap, spin-orbit splitting changes drastically under tensile strain. In centrosymmetric transition metal dichalcogenide bilayers, spin-orbit splitting is suppressed by the inversion symmetry. However, it could be induced if the inversion symmetry is explicitly broken, e.g. by a potential gradient normal to the plane, as it is present in heterobilayers (Rashba-splitting). In such systems, the spin-orbit splitting could be as large as for the heavier monolayer that forms heterobilayer. These properties of transition metal dichalcogenide materials suggest them for potential applications in opto-, spin- and straintronics. (copyright 2014 by WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  6. Transition-metal dichalcogenides for spintronic applications

    Spin-orbit splitting in transition-metal dichalcogenide monolayers is investigated on the basis of density-functional theory within explicit two-dimensional periodic boundary conditions. The spin-orbit splitting reaches few hundred meV and increases with the size of the metal and chalcogen atoms, resulting in nearly 500 meV for WTe2. Furthermore, we find that similar to the band gap, spin-orbit splitting changes drastically under tensile strain. In centrosymmetric transition metal dichalcogenide bilayers, spin-orbit splitting is suppressed by the inversion symmetry. However, it could be induced if the inversion symmetry is explicitly broken, e.g. by a potential gradient normal to the plane, as it is present in heterobilayers (Rashba-splitting). In such systems, the spin-orbit splitting could be as large as for the heavier monolayer that forms heterobilayer. These properties of transition metal dichalcogenide materials suggest them for potential applications in opto-, spin- and straintronics. (copyright 2014 by WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  7. Quantum spin Hall effect in a transition metal oxide Na2IrO3

    Shitade, Atsuo; Katsura, Hosho; Kunes, Jan; Qi, Xiao-Liang; Zhang, Shou-Cheng; Nagaosa, Naoto

    2008-01-01

    We study theoretically the electronic states in a $5d$ transition metal oxide Na$_2$IrO$_3$, in which both the spin-orbit interaction and the electron correlation play crucial roles. Tight-binding model analysis together with the fisrt-principles band structure calculation predicts that this material is a layered quantum spin Hall system. Due to the electron correlation, an antiferromagnetic order first develops at the edge, and later inside the bulk at low temperatures.

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

    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.

  9. Lattice Location of Transition Metals in Semiconductors

    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...

  10. The phosphorus and the transition metals chemistry

    The 1988 progress report, concerning the Polytechnic School unit (France), which studies the phosphorus and the transition metals chemistry, is presented. The laboratory activities are related to the following topics: the phosporus heterocyclic chemistry, the phosphorus-carbon double bonds chemistry, the new transition metals phosphorus compounds, the phosphonates and their uses. Some practical applications of homogeneous catalysis and new materials synthesis are investigated. The main results obtained are: the discovery of the tetra-phosphafulvalenes, the utilization of a new synthesis method of the phosphorus-carbon double bonds and the stabilization of the α-phosphonyled carbanions by the lithium diisopropylamidourea. The papers, the congress communications and the thesis are also shown

  11. Transformation paths in transition-metal disilicides

    Káňa, Tomáš; Šob, Mojmír; Vitek, V.

    2011-01-01

    Roč. 465, - (2011), s. 61-64. ISSN 1662-9795. [MSMF /6./ Materials Structure and Micromechanics of Fracture. Brno, 28.06.2010-30.06.2010] R&D Projects: GA AV ČR IAA100100920; GA MŠk(CZ) OC10008 Institutional research plan: CEZ:AV0Z20410507 Keywords : transition-metal disilicides * transformation path * structural stability * electronic structure Subject RIV: BM - Solid Matter Physics ; Magnetism

  12. Covalent bonding and bandgap formation in transition-metal aluminides: di-aluminides of group VIII transition metals

    In this paper we study the electronic structure, electron density distribution and bonding mechanism in transition-metal (TM) di-aluminides Al2TM formed by metals of group VIII (TM=Fe,Ru,Os) and crystal structures of TM di-silicides C11b (MoSi2), C40 (CrSi2) and C54 (TiSi2). A peculiar feature of the electronic structure of these TM di-aluminides is the existence of a semiconducting gap at the Fermi level. A substitution of a 3d TM by 4d or 5d metal enhances the width of the gap. From the analysis of the charge-density distribution and the crystal-orbital overlap population we conclude that the bonding between atoms has strong covalent character. This is confirmed not only from the enhanced charge density halfway between atoms, but also by a clear bonding-antibonding splitting of the electronic states. Groups of bonding and antibonding states corresponding to a particular bonding configuration of atoms are separated by a gap. As such a gap is observed in all bonding configurations among atoms in the unit cell it results in a gap in the total density of states. The bandgap exists at a certain electron per atom ratio e/A∼4.67 and also occurs in TM di-aluminides of groups VII and IX. For group VIII TM di-aluminides the Fermi level falls just in the gap. (author)

  13. Ferroelectric control of metal-insulator transition

    He, Xu; Jin, Kui-juan; Ge, Chen; Ma, Zhong-shui; Yang, Guo-zhen

    2016-03-01

    We propose a method of controlling the metal-insulator transition of one perovskite material at its interface with another ferroelectric material based on first principle calculations. The operating principle is that the rotation of oxygen octahedra tuned by the ferroelectric polarization can modulate the superexchange interaction in this perovskite. We designed a tri-color superlattice of (BiFeO3)N/LaNiO3/LaTiO3, in which the BiFeO3 layers are ferroelectric, the LaNiO3 layer is the layer of which the electronic structure is to be tuned, and LaTiO3 layer is inserted to enhance the inversion asymmetry. By reversing the ferroelectric polarization in this structure, there is a metal-insulator transition of the LaNiO3 layer because of the changes of crystal field splitting of the Ni eg orbitals and the bandwidth of the Ni in-plane eg orbital. It is highly expected that a metal-transition can be realized by designing the structures at the interfaces for more materials.

  14. Aging of Transition Metal Dichalcogenide Monolayers.

    Gao, Jian; Li, Baichang; Tan, Jiawei; Chow, Phil; Lu, Toh-Ming; Koratkar, Nikhil

    2016-02-23

    Two-dimensional sheets of transition metal dichalcogenides are an emerging class of atomically thin semiconductors that are considered to be "air-stable", similar to graphene. Here we report that, contrary to current understanding, chemical vapor deposited transition metal dichalcogenide monolayers exhibit poor long-term stability in air. After room-temperature exposure to the environment for several months, monolayers of molybdenum disulfide and tungsten disulfide undergo dramatic aging effects including extensive cracking, changes in morphology, and severe quenching of the direct gap photoluminescence. X-ray photoelectron and Auger electron spectroscopy reveal that this effect is related to gradual oxidation along the grain boundaries and the adsorption of organic contaminants. These results highlight important challenges associated with the utilization of transition metal dichalcogenide monolayers in electronic and optoelectronic devices. We also demonstrate a potential solution to this problem, featuring encapsulation of the monolayer sheet by a 10-20 nm thick optically transparent polymer (parylene C). This strategy is shown to successfully prevent the degradation of the monolayer material under accelerated aging (i.e., high-temperature, oxygen-rich) conditions. PMID:26808328

  15. Ab initio calculation of molecular field interactions in rare-earth transition-metal intermetallics (invited)

    Brooks, M. S. S.; Gasche, T.; Auluck, S.; Nordström, L.; Severin, L.; Trygg, J.; Johansson, B.

    1991-11-01

    The interaction, KRM, between the rare-earth 4f moment and the transition-metal 3d moments in rare-earth transition-metal intermetallics is shown to depend upon the R-5d moment, which is due to 3d-5d hybridization, and local 4f-5d exchange integrals. Both the R-5d moment and KRM may be calculated ab initio from the local spin-density approximation to density functional theory in self-consistent energy-band calculations with the localized 4f-moments fixed at their Russel-Saunders values. Detailed examples are given for the RFe2 (R=Gd-Yb) series. The exchange integrals are similar to those entering into the density functional version of Stoner theory and their energy dependence must be treated carefully. The calculated local exchange integrals are shown to be related to the molecular fields derived from spin Hamiltonians, hence to the spin-wave spectra. Reasonable agreement with values of the molecular fields extracted from inelastic neutron scattering and high field susceptibility measurements is obtained.

  16. Polarization matrices in simple and transition metals

    Full text: The polarization of an inhomogeneous electron gas within a metal due to electron-electron correlations is fundamental for the prediction of inelastic electron scattering experiments such as energy-lose measurements and Compton profile studies. Moreover, the polarization matrix serves as starting point for many advanced theoretical topics as quasiparticle band structures, self energies and realistic electron momentum densities. For this contribution, we calculated polarization matrices for alkali metals, as well as for the complete serves from potassium (atomic number 19) to zinc (30) including all 3d transition metals. The main topic of our work is to study how the polarization is influenced by the fast that the correlating particles are 'Bloch electrons'. These influences become visible in the polarization matrices by (i) deviations of their diagonal elements with respect to the 'homogeneous case', and by (ii) the appearance of non-diagonal elements. We obtained an excellent agreement for the simple metals Na, K and Rb with 'jellium results', and found remarkable deviations for Li and Cs. Moreover, our results show that the non-uniform character of the 3d transition elements depends sensitively on the number of d-electrons and the energetic position of the d-bands with respect to the Fermi energy. (author)

  17. Hydrodenitrogenation of pyridine over transition metal nitrides

    Milad, I.K.; Smith, K.J. [British Columbia Univ., Vancouver, BC (Canada). Dept. of Chemical Engineering

    1997-11-01

    The use of transition metal nitrides (TMN) as catalysts for hydrodenitrogenation (HDN) was discussed. A study was conducted in which a series of unsupported and supported Mo, Fe, W, Co, Nb, Cr, V and Ti nitrides were examined as catalysts for the HDN of pyridine at atmospheric pressure and 350 degrees C. The catalysts were prepared by temperature programmed nitridation of the metal oxide with NH{sub 3}. It was shown that a single nitride phase was present in each of the catalysts. The Mo nitride showed the greatest activity per gram of catalyst. Co and Fe nitrides showed the highest activities per surface area of the unsupported catalyst. Metal nitrides with lower heats of formation showed higher HDN activity. 1 tab.

  18. Defect-Tolerant Monolayer Transition Metal Dichalcogenides

    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...

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

    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.

  20. Raman spectroscopy of transition metal dichalcogenides.

    Saito, R; Tatsumi, Y; Huang, S; Ling, X; Dresselhaus, M S

    2016-09-01

    Raman spectroscopy of transition metal dichalcogenides (TMDs) is reviewed based on our recent theoretical and experimental works. First, we discuss the semi-classical and quantum mechanical description for the polarization dependence of Raman spectra of TMDs in which the optical dipole transition matrix elements as a function of laser excitation energy are important for understanding the polarization dependence of the Raman intensity and Raman tensor. Overviewing the symmetry of TMDs, we discuss the dependence of the Raman spectra of TMDs on layer thickness, polarization, laser energy and the structural phase. Furthermore, we discuss the Raman spectra of twisted bilayer and heterostructures of TMDs. Finally, we give our perspectives on the Raman spectroscopy of TMDs. PMID:27388703

  1. Electrical conduction in transition-metal salts

    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.

  2. Magnetic correlations in doped transition metal oxides

    The authors review recent reactor- and spallation-source-based neutron scattering experiments on the magnetic fluctuations and order in a variety of doped transition metal oxides. In particular, data are shown for the NiO chain compound, Y2-xCaxBaNiO5, the two-dimensional cuprate superconductors La2-xSrxCuO4 and YBa2Cu3 O6+x, and the classical three-dimensional ''Mott-Hubbard'' system V2-yO3

  3. Catabolism of hyaluronan: involvement of transition metals

    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. Electrical conduction in transition-metal salts

    We predict that a given transition-metal salt as, for example, a K2CuCl4.2H2O-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.

  5. Strain Engineering of Transition Metal Dichalcogenides

    Dadgar, Ali; Pasupathy, Abhay; Herman, Irving; Wang, Dennis; Kang, Kyungnam; Yang, Eui-Hyeok

    The application of strain to materials can cause changes to bandwidth, effective masses, degeneracies and even structural phases. In the case of the transition metal dichalcogenide (TMD) semiconductors, small strain (around 1 percent) is expected to change band gaps and mobilities, while larger strains are expected to cause phase changes from the triangular 2H phase to orthorhombic 1T' phases. We will describe experimental techniques to apply small and large (around 10 percent) strains to one or few layer samples of the TMD semiconductors, and describe the effect of the strain using optical (Raman, photoluminescence) and cryogenic transport techniques.

  6. Branching fractions and oscillator strengths for FeII transitions from the 3d6(5D)4p subconfiguration

    New experimental branching fractions and transition probabilities are reported for 56 transitions in FeII. The branching fractions are measured with a Fourier transform spectrometer and also with a high-resolution grating spectrometer on an optically thin hollow cathode discharge. Highly accurate experimental radiative lifetimes from the recent literature provide the normalization required to convert our branching fractions into absolute transition probabilities. Results are compared with experimental and theoretical values in the literature. Our new transition probabilities will establish the absolute scale for relative absorption oscillator strengths of vacuum ultraviolet lines measured using a new high-sensitivity absorption experiment at the University of Wisconsin. copyright 1996 The American Astronomical Society

  7. Tunable magnetocaloric effect in transition metal alloys

    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.

  8. Methyl Complexes of the Transition Metals.

    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. PMID:26991740

  9. Transition Metal Nitrides: A First Principles Study

    Pathak, Ashish; Singh, A. K.

    2016-04-01

    The present work describes the structural stability and electronic and mechanical properties of transition metal nitrides (TmNs: B1 cubic structure (cF8, Fm ‾ overline 3 m)) using first principles density functional theory (DFT) within generalized gradient approximation (GGA). The lattice constant of TmNs increases with increasing the atomic radii of the transition metals. Stability of the TmNs decreases from IVB to VIB groups due to increase in formation energy/atom. The bonding characteristics of these nitrides have been explained based on electronic density of states and charge density. All the TmNs satisfy Born stability criteria in terms of elastic constants except CrN and MoN that do not exist in equilibrium binary phase diagrams. The groups IVB and V-VIB nitrides are associated with brittle and ductile behaviour based on G/B ratios, respectively. The estimated melting temperatures of these nitrides exhibit reasonably good agreement with calculated with B than those of the C11 for all nitrides.

  10. Study of concentrated metal-ammonia solutions: magnetic properties and non metal-metal transition

    The magnetic susceptibility of alkali metal-liquid ammonia solutions has been measured in the concentration range where the solutions show a progressive passage toward the metallic state. The Knight shift of the metal nuclei and the nitrogen nucleus have been determined as a function of concentration and temperature, in Na-NH3 and Cs-NH3 solutions. A phenomenological analysis of the transport properties of metal-ammonia solutions is also presented. This analysis permits the presentation of a model for the mechanism of the transition to the metallic state. (author)

  11. New Layered Ternary Transition-Metal Tellurides

    Mar, Arthur

    Several new ternary transition-metal tellurides, a class of compounds hitherto largely unexplored, have been synthesized and characterized. These are layered materials whose structures have been determined by single -crystal X-ray diffraction methods. The successful preparation of the compound TaPtTe_5 was crucial in developing an understanding of the MM'Te_5 (M = Nb, Ta; M' = Ni, Pd, Pt) series of compounds, which adopt either of two possible closely-related layered structures. Interestingly, the compound TaPdTe _5 remains unknown. Instead, the compound Ta_4Pd_3Te _{16} has been prepared. Its structure is closely related to that of the previously prepared compound Ta_3Pd _3Te_{14}. The physical properties of these compounds have been measured and correlated with the metal substitutions and interlayer separations. A new series of compounds, MM'Te _4 (M = Nb, Ta; M' = Ru, Os, Rh, Ir), has been discovered. The structure of NbIrTe_4 serves as a prototype: it is an ordered variant of the binary telluride WTe_2. Electronic band-structure calculations have been performed in order to rationalize the trends in metal-metal and tellurium -tellurium bonding observed in WTe_2 and the MM'Te_4 phases. Extension of these studies to include main-group metals has resulted in the synthesis of the new layered ternary germanium tellurides TiGeTe_6, ZrGeTe_4 , and HfGeTe_4. Because germanium can behave ambiguously in its role as a metalloid element, it serves as an anion by capping the metal-centered trigonal prisms and also as a cation in being coordinated in turn by other tellurium atoms in a trigonal pyramidal fashion. Structural relationships among these compounds are illustrated through the use of bicapped trigonal prisms and trigonal pyramids as the basic structural building blocks. The electrical and magnetic properties of these compounds have been measured. Insight into the unusual bonding and physical properties of these germanium-containing compounds has been gained through

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

    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...

  13. Phase transitions in strontium perovskites. Studies of SrOsO3 compared to other 4d and 5d perovksites

    Kennedy, Brendan J.; Avdeev, Maxim; Feng, Hai L.; Yamaura, Kazunari

    2016-05-01

    The structure of a polycrystalline sample of SrOsO3 has been investigated using powder neutron diffraction from 5 to 300 K, and powder synchrotron X-ray diffraction from 80 to 870 K. At low temperatures SrOsO3 is orthorhombic in Pbnm and heating results in a sequence of phase transition transitions Pbnm → Imma → I 4 / mcm → Pm 3 ̅ m . This behavior is compared to that of other Sr containing perovskites. Comparison of the transition temperatures in SrBO3 perovskites shows that the tolerance factor alone does not determine the temperature at which the cubic phase is stabilized but rather the electronic configuration of the B-site cation appears to be significant.

  14. Smoothing of ultrathin silver films by transition metal seeding

    Anders, André; Byon, Eungsun; Kim, Dong-Ho; Fukuda, Kentaro; Lim, Sunnie H. N.

    2006-11-01

    The nucleation and coalescence of silver islands on coated glass was investigated by in situ measurements of the sheet resistance. Sub-monolayer amounts of niobium and other transition metals were deposited prior to the deposition of silver. It was found that in some cases, the transition metals lead to coalescence of silver at nominally thinner films with smoother topology. The smoothing or roughening effects by the presence of the transition metal can be explained by kinetically limited transition metal islands growth and oxidation, followed by defect-dominated nucleation of silver.

  15. Radiation damage of transition metal carbides

    Dixon, G.

    1991-01-01

    In this grant period we have investigated electrical properties of transition metal carbides and radiation-induced defects produced by low-temperature electron irradiation in them. Special attention has been given to the composition VC[sub 0.88] in which the vacancies on the carbon sublattice of this fcc crystal order to produce a V[sub 8]C[sub 7] superlattice. The existence of this superlattice structure was found to make the crystal somewhat resistant to radiation damage at low doses and/or at ambient temperature. At larger doses significant changes in the resistivity are produced. Annealing effects were observed which we believe to be connected with the reconstitution of the superlattice structure.

  16. Catalytic and surface oxidation processes on transition metal surfaces

    Jaatinen, Sampsa

    2007-01-01

    Transition metals are technologically important catalytic materials. The transition metal catalysts are used for example in petroleum and fertilizer industry. In the car industry the catalytic materials are used in the catalytic converters. Because of the industrial importance the catalytic metals have been widely studied throughout the past decades. Nonetheless, the oxidation mechanisms of small molecules and the effect of alloying to catalytic properties of metals are not fully understood. ...

  17. Ordering in binary transition metal alloys

    Rusakov, G. [Institute for Metal Physics UB RAS, 18 Kovalevskoj St., 620990 Ekaterinburg (Russian Federation); Ural State Technical University - UPI, 19 Mira St., 620002 Ekaterinburg (Russian Federation); Son, L., E-mail: ldson@yandex.ru [Ural State Pedagogical University, 26 Cosmonavtov Ave, 620017 Ekaterinburg (Russian Federation); Efimova, E. [Institute for Metal Physics UB RAS, 18 Kovalevskoj St., 620990 Ekaterinburg (Russian Federation); Ural State Technical University - UPI, 19 Mira St., 620002 Ekaterinburg (Russian Federation); Dubinin, N. [Institute for Metallurgy UB RAS, 101 Amundsen St., 620016 Ekaterinburg (Russian Federation); Ural State Technical University - UPI, 19 Mira St., 620002 Ekaterinburg (Russian Federation)

    2012-03-20

    We present the phenomenological thermodynamic modeling of binary alloys which demonstrate solubility of the components at high temperatures, and form intermediate phase near equiatomic composition at lower ones (the so-called sigma-phase). Besides, the regular solution miscibility gap takes place also. The nonequilibrium thermodynamic potential is written out as a sum of the free energy of regular solution and polynomial term of scalar order parameter {phi}, which describes the {sigma}-phase ordering. There are four parameters in the model: the energy of regular solution mixing, the energy of {sigma}-phase formation at zero temperature, and the widths of temperature and concentration intervals of {sigma}-phase existence in the alloy with frozen-in random distribution of components. Up to now, both phase transitions which take place in a number of transition metals binary alloys (the {sigma}-phase formation and miscibility in the regular solution) have been treated separately. In present work, the standard technique of phase diagram calculation allows us to analyze all possible phase diagrams which may arise in the alloy.

  18. Transition-metal substitutions in iron chalcogenides

    Bezusyy, V. L.; Gawryluk, D. J.; Malinowski, A.; Cieplak, Marta Z.

    2015-03-01

    The a b -plane resistivity and Hall effect are studied in Fe1 -yMyTe0.65Se0.35 single crystals doped with two transition-metal elements, M = Co or Ni, over a wide doping range, 0 ≤y ≤0.2 . The superconducting transition temperature, Tc, reaches zero for Co at y ≃0.14 and for Ni at y ≃0.032 , while the resistivity at the Tc onset increases weakly with Co doping, and strongly with Ni doping. The Hall coefficient RH, positive for y =0 , remains so at high temperatures for all y , while it changes sign to negative at low T for y >0.135 (Co) and y >0.06 (Ni). The analysis based on a two-band model suggests that at high T residual hole pockets survive the doping, but holes get localized upon the lowering of T , so that the effect of the electron doping on the transport becomes evident. The suppression of the Tc by Co impurity is related to electron doping, while in the case of the Ni impurity strong electron localization most likely contributes to fast decrease of the Tc.

  19. Spectral hole burning in the 4f-5d transition of Ce3+ in LuPO4 and YPO4

    Persistent spectral holes in the inhomogeneously broadened 4f1-4f05d1 zero-phonon transitions in LuPO4:Ce3+ and YPO4:Ce3+ crystals were burned at T=2 K. The holes observed in absorption were deep (up to 50%) and could be observed at least minutes after they were burned. The burning process was very efficient and is due to a single photon process. The observed spectral holes are burned in a photochemical process of photoionization of Ce3+ ions involving electron tunneling from Ce3+ centers to traps

  20. Nanostructured transition metal oxides useful for water oxidation catalysis

    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.

  1. Trends in Ionization Energy of Transition-Metal Elements

    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…

  2. Strain field due to transition metal impurities in Ni and Pd

    Hitesh Sharma; S Prakash

    2003-01-01

    The strain field due to body centered substitutional transition metal impurities in Ni and Pd metals are investigated. The calculations are carried out in the discrete lattice model of the metal using Kanzaki lattice static method. The effective ion–ion interaction potential due to Wills and Harrison is used to evaluate dynamical matrix and the impurity-induced forces. The results for atomic displacements due to 3d, 4d and 5d impurities (Fe, Co, Cu, Nb, Mo, Pd, Pt and Au) in Ni and (Fe, Co, Cu, Ni, Nb, Mo, Pt and Au) impurities in Pd are given up to 25 NN’s of impurity and these are compared with the available experimental data. The maximum displacements of 4.6% and 3.8% of 1NN distance are found for NiNb and PdNb alloys respectively, while the minimum displacements of 0.63% and 0.23% of 1NN distance are found for NiFe and PdFe alloys respectively. Except for Cu, the atomic displacements are found to be proportional to the core radii and d state radius. The relaxation energies for 3d impurities are found less than those for 4d and 5d impurities in Ni and Pd metals. Therefore, 3d impurities may easily be solvable in these metals.

  3. Site preference of early transition metal elements in C15 NbCr2

    The site preference of early 3d (Ti, V), 4d (Zr, Mo) and 5d (Hf, Ta, W) transition metal elements in C15 NbCr2 Laves phase was studied using first-principles calculations. According to the present calculations, at T 0 K, Zr, Hf and Ta consistently have a preference for the Nb sites in Nb-rich, Cr-rich and stoichiometric NbCr2, while the site preference of Ti, V, Mo and W varies strongly with alloy composition. Using a statistical-mechanical Wagner-Schottky model based on the canonical ensemble, the finite temperature site occupancy behavior of those transition metal elements in NbCr2 was further predicted. It was found that the site preference of Ti, V, Mo and W also depends strongly on temperature. The calculated results compare favorably with the experimental measurements using ALCHEMI and synchrotron X-ray diffraction techniques

  4. First principles description of the insulator-metal transition in europium monoxide

    Wang, Hao

    2012-02-01

    Europium monoxide, EuO, is a ferromagnetic insulator. Its electronic structure under pressure and doping is investigated by means of density functional theory. We employ spin polarized electronic structure calculations including onsite electron-electron interaction for the localized Eu 4f and 5d electrons. Our results show that under pressure the ferromagnetism is stable, both for hydrostatic and uniaxial pressure, while the compound undergoes an insulator-metal transition. The insulator-metal transition in O deficient and Gd doped EuO is reproduced for an impurity concentration of 6.25%. A 10 monolayer thick EuO(1 0 0) thin film is predicted to be an insulator with a narrow band gap of 0.08 eV. © 2011 Elsevier B.V. All rights reserved.

  5. Quantum spin Hall effect in a transition metal oxide Na2IrO3

    Shitade, Atsuo

    2010-05-26

    We study theoretically the electronic states in a 5d transition metal oxide Na{sub 2}I{sub r}O{sub 3}, in which both the spin-orbit interaction and the electron correlation play crucial roles. Tight-binding model analysis together with the fisrt-principles band structure calculation predicts that this material is a layered quantum spin Hall system. Due to the electron correlation, an antiferromagnetic order first develops at the edge, and later inside the bulk at low temperatures.

  6. First-principles calculations of the vacancy formation energy in transition and noble metals

    Korzhavyi, P.A.; Abrikosov, Igor A.; Johansson, Börje; Ruban, Andrei; Skriver, Hans Lomholt

    1999-01-01

    Abstract: The vacancy formation energy and the vacancy formation volume of the 3d, 4d, and 5d transition and noble metals have been calculated within the local-density approximation. The calculations employ the order-N locally self-consistent Green's-function method in conjunction with a supercell...... approach and include electrostatic multipole corrections to the atomic sphere approximation. The results are in excellent agreement with available full-potential calculations and with the vacancy formation energies obtained in positron annihilation measurements. The variation of the vacancy formation...

  7. Transition metal oxofluorides comprising lone pair elements : Synthesis and Characterization

    Hu, Shichao

    2014-01-01

    Within the family of transition metal oxochlorides/bromides containing lone pair elements, the transition metal cations often adopt a low-dimensional arrangement such as 2D layers, 1D chains or 0D clusters. The reduced dimensionality is attributed to the presence of stereochemically active lone pairs which are positioned in the non-bonding orbital and will not participate in bond formation and instead act as structural spacers that help to separate coordination polyhedra around transition met...

  8. Patterning Superatom Dopants on Transition Metal Dichalcogenides.

    Yu, Jaeeun; Lee, Chul-Ho; Bouilly, Delphine; Han, Minyong; Kim, Philip; Steigerwald, Michael L; Roy, Xavier; Nuckolls, Colin

    2016-05-11

    This study describes a new and simple approach to dope two-dimensional transition metal dichalcogenides (TMDCs) using the superatom Co6Se8(PEt3)6 as the electron dopant. Semiconducting TMDCs are wired into field-effect transistor devices and then immersed into a solution of these superatoms. The degree of doping is determined by the concentration of the superatoms in solution and by the length of time the films are immersed in the dopant solution. Using this chemical approach, we are able to turn mono- and few-layer MoS2 samples from moderately to heavily electron-doped states. The same approach applied on WSe2 films changes their characteristics from hole transporting to electron transporting. Moreover, we show that the superatom doping can be patterned on specific areas of TMDC films. To illustrate the power of this technique, we demonstrate the fabrication of a lateral p-n junction by selectively doping only a portion of the channel in a WSe2 device. Finally, encapsulation of the doped films with crystalline hydrocarbon layers stabilizes their properties in an ambient environment. PMID:27082448

  9. Impact Electrochemistry of Layered Transition Metal Dichalcogenides.

    Lim, Chee Shan; Tan, Shu Min; Sofer, Zdeněk; Pumera, Martin

    2015-08-25

    Layered transition metal dichalcogenides (TMDs) exhibit paramount importance in the electrocatalysis of the hydrogen evolution reaction. It is crucial to determine the size of the electrocatalytic particles as well as to establish their electrocatalytic activity, which occurs at the edges of these particles. Here, we show that individual TMD (MoS2, MoSe2, WS2, or WSe2; in general MX2) nanoparticles impacting an electrode surface provide well-defined current "spikes" in both the cathodic and anodic regions. These spikes originate from direct oxidation of the nanoparticles (from M(4+) to M(6+)) at the anodic region and from the electrocatalytic currents generated upon hydrogen evolution in the cathodic region. The positive correlation between the frequency of the impacts and the concentration of TMD nanoparticles is also demonstrated here, enabling determination of the concentration of TMD nanoparticles in colloidal form. In addition, the size of individual TMD nanoparticles can be evaluated using the charge passed during every spike. The capability of detecting both the "indirect" catalytic effect of an impacting TMD nanoparticle as well as "direct" oxidation indicates that the frequency of impacts in both the "indirect" and "direct" scenarios are comparable. This suggests that all TMD nanoparticles, which are electrochemically oxidizable (thus capable of donating electrons to electrodes), are also capable of catalyzing the hydrogen reduction reaction. PMID:26241193

  10. Properties of Transition Metal Doped Alumina

    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.

  11. Transition metal-free olefin polymerization catalyst

    Sen, Ayusman (State College, PA); Wojcinski, II, Louis M. (State College, PA); Liu, Shengsheng (State College, PA)

    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).

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

    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.

  13. Hyperfine structure studies of transition metals

    This past year our studies of hyperfine structure (hfs) in metastable states of transition metals concentrated on the analysis of hfs in the four-valence electron system, Nb II. Earlier, we measured hfs intervals using the laser-rf double resonance and laser-induced fluorescence methods in a fast-ion beam of Nb+. The resulting experimental magnetic dipole and electric quadrupole interaction constants are compared to those calculated by a relativistic configuration interaction approach. These are the first hfs data on this refractory element. Theoretically, it is found that the most important contributions to the energy are the pair excitations, valence single excitations and core polarization from the shallow core. However, the inner core polarization is found to be crucial for hfs, albeit unimportant for energy. For the J=2 level at 12805 cm-1, 4d43F. the theoretical relativistic configuration A-value is in agreement with the experimental result to an accuracy of 4%. Other calculated A-values are expected to be of the same accuracy. A paper describing these results was accepted for publication. Experimental studies of the four-valence electron system V+ in the (4s+3d)4 manifold are complete. The theoretical difficulties for the 3d manifold, noted earlier for the three-valence electron Ti+, as compared to the 4d manifold appear to be repeated in the case of the four-valence electron systems (Nb+ and V+). Relativistic configuration interaction calculations are underway, after which a paper will be published

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

    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.

  15. The metallicities of stars with and without transiting planets

    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 the...

  16. Energy transfer and non-linear optical properties at near ultraviolet wavelengths: Rare earth 4f {yields} 5d transitions in crystals and glasses. Final report, June 1, 1984--May 31, 1992

    Hamilton, D.S.

    1992-08-01

    The following topics were studied: two-photon transitions from 4f ground state to 5d excited states in Ce{sup 3+}:CaF{sub 2}; optical absorption and photoionization measurements from excited state of Ce{sup 3+}:Y{sub 3}Al{sub 5}O{sub 12}; excited state photoionization of Ce{sup 3+} ions in Ce{sub 3+}:CaF{sub 2}; optical gain and loss studies in Ce{sup 3+}:LiYF{sub 4}; Gd {yields}Cr energy transfer in Cr{sup 3+}:GSGG, Cr{sup 3+}:GSAG and Cr{sup 3+}:GGG crystals; nonradiative relaxation in Ce{sup 3+} doped crystals and glasses; and grating formation in impurity doped crystals.

  17. Mechanisms of transition-metal gettering in silicon

    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.

  18. Trends in catalytic NO decomposition over transition metal surfaces

    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....

  19. Transition metal complexing with polymetric sulfur-containing fibrous ligand

    A study was made on interaction of Cr4, V5, Cu2 transition metals with thioamidated polymeric PVS-PAN-T ligand of fibrous structure. Sorption characteristics of PVS-PAN-T, depending on pH and temperature of solutions of copper, chromium and vanadium salts were determined. Parameters of ESR spectra of PVS-PAN-T compounds with transition metals enabled to determine the structure of formed coordination centers

  20. Excited states and transition metal compounds with quantum Monte Carlo

    Bande, Annika

    2007-01-01

    To the most challenging electron structure calculations belong weak interactions, excited state calculations, transition metals and properties. In this work the performance of variational (VMC) and fixed-node diffusion quantum Monte Carlo (FN-DMC) is tested for challenging electron structure problems using the quantum Monte Carlo amolqc code by Lüchow et al. The transition metal compounds under consideration are vanadium oxides. Here excitation, ionization, oxygen atom and molecule abstractio...

  1. Ternary transition metal phosphides: High-temperature superconductors

    Barz, H.; Ku, H. C.; Meisner, G. P.; Fisk, Z.; Matthias, B. T.

    1980-01-01

    Two systems of ternary transition metal phosphides with the ordered Fe2P-type hexagonal structure are reported. They have the general formula MRuP and MOsP, in which M can be Ti, Zr, or Hf. An onset of the superconducting transition temperature as high as 13.0 K is reported for the ZrRuP compound.

  2. Metal-insulator transitions of bulk and domain-wall states in pyrochlore iridates

    Ueda, Kentaro

    A family of pyrochlore iridates R2Ir2O7 offers an ideal platform to explore intriguing phases such as topological Mott insulator and Weyl semimetal. Here we report transport and spectroscopic studies on the metal-insulator transition (MIT) induced by the modulations of effective electron correlation and magnetic structures, which is finely tuned by external pressure, chemical substitutions (R = Nd1-x Prx and SmyNd1-y) , and magnetic field. A reentrant insulator-metal-insulator transition is observed near the paramagnetic insulator-metal phase boundary reminiscent of a first-order Mott transition for R = SmyNd1-y compounds (y~0.8). The metallic states on the magnetic domain walls (DWs), which are observed for R = Nd in real space as well as in transport properties, is simultaneously turned into the insulating one. These findings imply that the DW electronic state is intimately linked to the bulk states. For the mixed R = Nd1-x Prx compounds, the divergent behavior of resistivity with antiferromagnetic order is significantly suppressed by applying a magnetic field along [001] direction. It is attributed to the phase transition from the antiferromagnetic insulating state to the novel Weyl (semi-)metal state accompanied by the change of magnetic structure. The present study combined with experiment and theory suggests that there are abundant exotic phases with physical parameters such as electron correlation and Ir-5 d magnetic order pattern. Work performed in collaboration with J. Fujioka, B.-J. Yang, C. Terakura, N. Nagaosa, Y. Tokura (University of Tokyo, RIKEN CEMS), J. Shiogai, A. Tsukazaki, S. Nakamura, S. Awaji (Tohoku University). 1This work was supported by JSPS FIRST Program and Grant-in-Aid for Scientific Research (Grants No. 80609488 and No. 24224009).

  3. Transition metals and mitochondrial metabolism in the heart

    Rines, Amy K.; Ardehali, Hossein

    2012-01-01

    Transition metals are essential to many biological processes in almost all organisms from bacteria to humans. Their versatility, which arises from an ability to undergo reduction–oxidation chemistry, enables them to act as critical cofactors of enzymes throughout the cell. Accumulation of metals, however, can also lead to oxidative stress and cellular damage. The importance of metals to both enzymatic reactions and oxidative stress makes them key players in mitochondria. Mitochondria are the ...

  4. Theory of the transition temperature of superconducting amorphous transition metals

    In the present paper first the transition temperature Tsub(c) is shown to be a local quantity, which depends on the (average) short range order, and second it is demonstrated how to calculate local electronic properties in the framework of a short range order model and the transition temperature of amorphous systems based on accepted structure models of the amorphous state. In chapter I the theoretical basis of this work is presented in brief. The model used to study the role of short range order (in periodically ordered as well as in disordered system) is described in chapter II. The results of this model for the periodically ordered case are compared in chapter III with band structure calculations. In chapter IV it is shown how to establish short range order models for disordered systems and what kind of information can be obtained with respect to the electronic properties. Finally in chapter V it is discussed to what extend the interpretation of the transition temperature Tsub(c) as being determined by short range order effects can be supported by the electronic properties, which are calculated in the chapters III and IV. (orig.)

  5. Electronic and magnetic engineering of transition metal dichalcogenides

    Tang, Youjian; Crespi, Vincent; Vincent Crespi group Team

    Transition metal dichalcogenides (TMDs) have moderate bandgaps and great potential in electronic and optoelectronic applications. We show that by intercalation and compensated doping of transition metal ions, we could generate a ``half-semiconductor'', half-metal or doped magnetic semiconductor. We will also show that covalently connecting a single layer of WS2 to a small aromatic molecule with appropriate electronegativity, it is possible to align the molecular energy levels with the WS2 conduction band edge, yielding an electronic structure of potential interest for thermoelectric applications, and covalently connecting single-layer WS2 to magnetic coordination compounds could introduce magnetization into the WS2 layer.

  6. Optical lifetime and linewidth studies of the 7F0→5D0 transition in EuCl3·6H2O: A potential material for quantum memory applications

    The effect of substituting deuterium for hydrogen in EuCl3·6H2O on the lifetime and homogeneous and inhomogeneous linewidths of the 7F0→5D0 transition at below 4 K are investigated. It is observed that the transition lifetime increases from 116μs to 2.6 ms and the homogeneous linewidth decreases from 4.1 kHz to 430 Hz. The sensitivity of the inhomogeneous broadening to the residual hydrogen concentration is estimated to be 91 MHz/atm%. The potential of utilizing this crystal for quantum memory applications is discussed. - Highlights: ► The optical lifetime of EuCl3·6H2O increases 20 times with full deuteration. ► An optical coherence time of 740μs was observed in EuCl3·6D2O. ► High D purity EuCl3·6H2O is a good candidate material for quantum memories.

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

    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.

  8. Probable metal-insulator transition in Ag4SSe

    Highlights: • New phase transition in Ag4SSe was discovered with scanning calorimetry and supported with X-ray powder diffraction. • The thermal effect relates to the anomaly in electrical and thermal conductivity of Ag4SSe. • Similar thermal and electrical effects in K3Cu8S6 are explained with the metal-insulator transition. - Abstract: New phase transition (285 K) in low-temperature monoclinic Ag4SSe was found out below the α-β transition (358 K) after the measurements with differential scanning calorimetry. The transition reveals significant hysteresis (over 30 K). X-ray powder diffraction shows that the superlattice with doubled a and b parameters of the unit cell exists below the new transition point. The signs of this new phase transition can be found in thermal and electrical conductivity of Ag4SSe published in literature. Elusive phase transition in Ag2Se shows similar properties. The new transition is likely related to the metal-insulator type transition, like K3Cu8S6

  9. Bonding effects in dilute transition-metal alloys

    The Moessbauer isomer-shift data of transition-metal nuclei as impurities in metals were considered in previous papers where it was shown that, once volume effects were suitably accounted for, the data fell on a ''universal'' curve. In this paper, the deviations from universality are examined in more detail in an attempt to better understand the alloying behavior. It is found that atom A as an impurity in metal B does not sustain a shift of the same magnitude as atom B does when it is an impurity in metal A. The results are discussed in terms of d-band hybridization and of the asymmetry in the solubility behavior in transition-metal-alloy phase diagrams

  10. Bonding effects in dilute transition-metal alloys

    Watson, R.E.; Swartzendruber, L.J.; Bennett, L.H.

    1981-12-01

    The Moessbauer isomer-shift data of transition-metal nuclei as impurities in metals were considered in previous papers where it was shown that, once volume effects were suitably accounted for, the data fell on a ''universal'' curve. In this paper, the deviations from universality are examined in more detail in an attempt to better understand the alloying behavior. It is found that atom A as an impurity in metal B does not sustain a shift of the same magnitude as atom B does when it is an impurity in metal A. The results are discussed in terms of d-band hybridization and of the asymmetry in the solubility behavior in transition-metal-alloy phase diagrams.

  11. Flexible metallic seal for transition duct in turbine system

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

    2014-04-22

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

  12. The metal-insulator transition in magnetite.

    Cullen, J. R.; Callen, E.

    1972-01-01

    We describe an electronic model for the low temperature transition in magnetite, in which the average number of electrons on a site is non-integral. The solution of the one-dimensional problem is reviewed, and the connection of the model with the Verwey ordering is discussed. Some of the implication of the three dimensional problem are discussed.

  13. Glutathione and Transition-Metal Homeostasis in Escherichia coli▿

    Helbig, Kerstin; Bleuel, Corinna; Krauss, Gerd J.; Nies, Dietrich H.

    2008-01-01

    Glutathione (GSH) and its derivative phytochelatin are important binding factors in transition-metal homeostasis in many eukaryotes. Here, we demonstrate that GSH is also involved in chromate, Zn(II), Cd(II), and Cu(II) homeostasis and resistance in Escherichia coli. While the loss of the ability to synthesize GSH influenced metal tolerance in wild-type cells only slightly, GSH was important for residual metal resistance in cells without metal efflux systems. In mutant cells without the P-typ...

  14. Electronic Transitions in f-electron Metals at High Pressures:

    This study was to investigate unusual phase transitions driven by electron correlation effects that occur in many f-band transition metals and are often accompanied by large volume changes: ∼20% at the (delta)-α transition in Pu and 5-15% for analogous transitions in Ce, Pr, and Gd. The exact nature of these transitions has not been well understood, including the short-range correlation effects themselves, their relation to long-range crystalline order, the possible existence of remnants of the transitions in the liquid, the role of magnetic moments and order, the critical behavior, and dynamics of the transitions, among other issues. Many of these questions represent forefront physics challenges central to Stockpile materials and are also important in understanding the high-pressure behavior of other f- and d-band transition metal compounds including 3d-magnetic transition monoxide (TMO, TM=Mn, Fe, Co, Ni). The overarching goal of this study was, therefore, to understand the relationships between crystal structure and electronic structure of transition metals at high pressures, by using the nation's brightest third-generation synchrotron x-ray at the Advanced Photon Source (APS). Significant progresses have been made, including new discoveries of the Mott transition in MnO at 105 GPa and Kondo-like 4f-electron dehybridization and new developments of high-pressure resonance inelastic x-ray spectroscopy and x-ray emission spectroscopy. These scientific discoveries and technology developments provide new insights and enabling tools to understand scientific challenges in stockpile materials. The project has broader impacts in training two SEGRF graduate students and developing an university collaboration (funded through SSAAP)

  15. Memristor using a transition metal nitride insulator

    Stevens, James E; Marinella, Matthew; Lohn, Andrew John

    2014-10-28

    Apparatus is disclosed in which at least one resistive switching element is interposed between at least a first and a second conducting electrode element. The resistive switching element comprises a metal oxynitride. A method for making such a resistive switching element is also disclosed.

  16. Metallization and charge-transfer gap closure of transition-metal iodides under pressure

    Chen, A. Li-Chung

    1993-05-01

    It is shown with resistivity and near-IR absorption measurements that NiI{sub 2}, CoI{sub 2}, and FeI{sub 2} metallize under pressure by closure of the charge-transfer energy gap at pressures of 17, 10, and 23 GPa, respectively, which is close to the antiferromagnetic-diamagnetic transition in NiI{sub 2} and CoI{sub 2}. Thus, the magnetic transitions probably are caused by the metallization; in NiI{sub 2} and CoI{sub 2}, the insulator-metal transitions are first order. Moessbauer and XRD data were also collected. Figs, 46 refs.

  17. Development of dissimilar metal transition joint by hot bond rolling

    Metallurgically bonded transition joints which enable to connect reprocessing equipments made of superior corrosion resistant valve metals (Ti-5Ta, Zr or Ti) to stainless steel piping are required for nuclear fuel reprocessing plants. The authors have developed dissimilar transition joints made of stainless steel and Ti-5Ta, Zr or Ti with an insert metal of Ta by the hot bond rolling process of clad bars and clad pipes, using a newly developed mill called 'rotary reduction mill'. This report presents the manufacturing process of dissimilar transition joints produced from the clad pipe with three layers by the hot bond rolling. First, the method of hot bond rolling of clad pipe is proposed. Then, the mechanical and corrosion properties of the dissimilar transition joints are evaluated in detail by carrying out various tests. Finally, the rolling properties in the clad pipe method are discussed. (author)

  18. Chemical compatibility between lithium oxide and transition metals

    The chemical reactions between Li2O and transition metals (Ti, V, Cr, Mn, Fe, Ni), particularly 316 steel, have been studied up to 1273 K in sealed systems under argon and also under vacuum. Pure Li2O is inherently inert towards transition metals except when such equilibria as 4Li2O + Fe = Li5FeO4 + 3Li 2Li2O + Cr = LiCrO2 + 3Li are disturbed by removal of Li by vacuum or chemical means. The results are rationalised with the known thermodynamics. LiOH impurity has a deleterious effect on the metals and accounts for some of the supposed reactivity of LI2O. It may be possible to inhibit the corrosive reaction of LiOH and LiOT towards steel, and facilitate the release of T2, by introducing metallic lithium. (orig.)

  19. Crystalfield symmetries of luminescent Eu{sup 3+} centers in GaN: The importance of the {sup 5}D{sub 0} to {sup 7}F{sub 1} transition

    O' Donnell, K. P., E-mail: k.p.odonnell@strath.ac.uk; Edwards, P. R. [SUPA Department of Physics, University of Strathclyde, 107 Rottenrow, Glasgow G4 0NG, Scotland (United Kingdom); Yamaga, M. [Department of Mathematical and Design Engineering, Gifu University, Gifu 501-1193 (Japan); Lorenz, K. [IPFN, Instituto Superior Técnico, Universidade de Lisboa, Campus Tecnológico e Nuclear, Estrada Nacional 10, 2695-066 Bobadela LRS (Portugal); Kappers, M. J. [Department of Materials Science and Metallurgy, University of Cambridge, 27 Charles Babbage Road, Cambridge CB3 0FS, England (United Kingdom); Boćkowski, M. [Institute of High Pressure Physics PAS, Sokolowska 29/37, 01-142 Warsaw (Poland)

    2016-01-11

    Eu-doped GaN is a promising material with potential application not only in optoelectronics but also in magneto-optical and quantum optical devices “beyond the light emitting diode.” Its interesting spectroscopy is unfortunately complicated by spectral overlaps due to “site multiplicity,” the existence in a given sample of multiple composite centers in which Eu ions associate with intrinsic or extrinsic defects. We show here that elementary crystalfield analysis of the {sup 5}D{sub 0} to {sup 7}F{sub 1} transition can critically distinguish such sites. Hence, we find that the center involved in the hysteretic photochromic switching observed in GaN(Mg):Eu, proposed as the basis of a solid state qubit material, is not in fact Eu1, as previously reported, but a related defect, Eu1(Mg). Furthermore, the decomposition of the crystalfield distortions of Eu0, Eu1(Mg), and Eu1 into axial and non-axial components strongly suggests reasonable microscopic models for the defects themselves.

  20. The nonmetal-metal transition in solutions of metals in molten salts

    Solutions of metals in molten salts present a rich phenomenology: localization of electrons in disordered ionic media, activated electron transport increasing with metal concentration towards a nonmetal-metal (NM-M) transition, and liquid-liquid phase separation. A brief review of progress in the study of these systems is given in this article, with main focus on the NM-M transition. After recalling the known NM-M behaviour of the component elements in the case of expanded fluid alkali metals and mercury and of solid halogens under pressure, the article focuses on liquid metal - molten salt solutions and traces the different NM-M behaviours of the alkalis in their halides and of metals added to polyvalent metal halides. (author). 51 refs, 2 figs

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

    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.

  2. An inverse scattering approach to the physics of transition metals

    A method is developed for the deduction of a transition metal ion potential from a knowledge of the phase-shift nl(k). The method used is based on the distorted plane-wave scattering approximation for the deduction of non-singular potentials from scattering phase-shifts in an inverse scattering approach. The resulting electron-ion potential obtained is a finite Dirichlet series sum of short range exponential functions. The Fourier transform of the potential is obtained for applications in the area of transition metal solid state physics. (author). 14 refs, 1 tab

  3. Estimating the acidity of transition metal hydride and dihydrogen complexes by adding ligand acidity constants.

    Morris, Robert H

    2014-02-01

    A simple equation (pKa(THF) = ∑AL + Ccharge + Cnd + Cd6) can be used to obtain an estimate of the pKa of diamagnetic transition metal hydride and dihydrogen complexes in tetrahydrofuran, and, by use of conversion equations, in other solvents. It involves adding acidity constants AL for each of the ligands in the 5-, 6-, 7-, or 8-coordinate conjugate base complex of the hydride or dihydrogen complex along with a correction for the charge (Ccharge = -15, 0 or 30 for x = +1, 0 or -1 charge, respectively) and the periodic row of the transition metal (Cnd = 0 for 3d or 4d metal, 2 for 5d metal) as well as a correction for d(6) octahedral acids (Cd6 = 6 for d(6) metal ion in the acid, 0 for others) that are not dihydrogen complexes. Constants AL are provided for 13 commonly occurring ligand types; of these, nine neutral ligands are correlated with Lever's electrochemical ligand parameters EL. This method gives good estimates of the over 170 literature pKa values that range from less than zero to 50 with a standard deviation of 3 pKa units for complexes of the metals chromium to nickel, molybdenum, ruthenium to palladium, and tungsten to platinum in the periodic table. This approach allows a quick assessment of the acidity of hydride complexes found in nature (e.g., hydrogenases) and in industry (e.g., catalysis and hydrogen energy applications). The pKa values calculated for acids that have bulky or large bite angle chelating ligands deviate the most from this correlation. The method also provides an estimate of the base strength of the deprotonated form of the complex. PMID:24410025

  4. Integrating Transition Metals into Nanomaterials: Strategies and Applications

    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.

  5. Volume variation of Gruneisen parameters of fcc transition metals

    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.

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

    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...

  7. Dimensional effects in a disordered system near metal-insulator transitions and superconductor-insulator transitions

    Low temperature transport in disordered conducting materials implies quantum interference, Coulomb repulsion, and superconducting fluctuations. Since 2-D is the lower critical dimension for the existence of metallic and superconducting states, we have studied two quantum phase transitions - the Superconductor-to-Insulator Transition (SIT) and the Metal-to-Insulator Transition (MIT) - when the thickness of a disordered system - here a-NbSi - is lowered. The underlying problem is the transition between the different states and the conditions for a 2-D metal to exist. We have studied the field and disorder-induced SIT. The principal characteristics we have observed (renormalization, role of the field orientation) are well explained by M.P.A. Fisher's theory. However, we do not find the critical exponents values and a universal resistance at the transition as predicted by this theory. Concerning the MIT, we have decreased the thickness of a metallic system to reach the dimension 2 and an insulating state. In both transitions, the passage to the insulating state clearly shows the existence of dissipative states at zero temperature that are not predicted by conventional theories. We propose an interpretation of all our results that implies the existence of a novel phase in 2-D, a Bose Metal, between the superconducting and the metallic states. This new state has been predicted by recent theories. We trace the corresponding phase diagram for the model system NbSi with respect to concentration and film thickness. In the second appendix it is shown how superconducting thin films of NbxSi1-x are used to make transition edge sensors used in the particle detection field. (author)

  8. The Metallicities of Stars With and Without Transiting Planets

    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...

  9. Transition metal bioconjugates with an organometallic link between the metal and the biomolecular scaffold

    Monney, Angèle; Albrecht, Martin

    2013-01-01

    This overview compiles recent advances in the synthesis and application of organometallic bioconjugates that comprise a metal–carbon linkage between the metal and the biomolecular scaffold. This specific area of bioorganometallic chemistry has been spurred by the discovery of naturally occurring bioorganometallic compounds and afforded organometallic bioconjugates from transition metals binding to amino acids, nucleic acids and other biomolecules. These artificial bioorganometallic compounds ...

  10. Chromospheric, transition layer and coronal emission of metal deficient stars

    Boehm-Vitense, E.

    1982-01-01

    It is shown that while MgII k line emission decreases for metal deficient stars, the Ly alpha emission increases. The sum of chromospheric hydrogen and metallic emission appears to be independent of metal abundances. The total chromospheric energy loss is estimated to be 0.0004 F sub bol. The chromospheric energy input does not seem to decrease for increasing age. The transition layer emission is reduced for metal deficient stars, but it is not known whether the reduction is larger than can be explained by curve of growth effects only. Coronal X-ray emission was measured for 4 metal deficient stars. Within a 12 limit it could still be consistent with the emission of solar abundance stars.

  11. Recipe for high-Tc transition-metal chalcogenide superconductors

    The conditions for the occurrence of superconductivity in cuprates are enumerated. There is a minimum of seven, which are discussed in some detail. They may be taken as a recipe in the search for superconductors at elevated temperature with other transition-metal chalcogenide compounds. (orig.)

  12. Reaction ability of nitrosyl group in transition metal complexes

    Transformations of the intraspheric nitrosyl group in complexes of transition metals are reviewed. All the reactions involving these groups are divided into two types: reactions associated with the electrophilic properties of the nitrosyl group; reactions associated with the nucleophilic properties of the nitrosyl group. Attempts to correlate the reactivity of the nitrosyl group with its structure and spectral characteristics are considered

  13. Transport properties of transition metal impurities on gold nanowires

    Pontes, Renato B.; da Silva, Edison Z.; Fazzio, Adalberto; da Silva, Antônio J. R.

    2009-03-01

    Performing first principles density functional theory (DFT) we calculated the electronic and transport properties of a Au thin nanowire with transition metal atoms (Mn, Fe, Ni or Co) bridging the two sides of the Au nanowire. We will show that these systems have strong spin dependent transport properties and that the local symmetry can dramatically change them, leading to a significant spin polarized conductance. This spin dependent transport is also associated with the transition metal in the nanowire, in particular with the d-level positioning. Using Co, for example [1], when the symmetry permits the mixing between the wire s-orbitals with the transition metal d-states, there are interference effects that resemble Fano-like resonances with an anisotropy of 0.07 at the Fermi level. On the other hand, if this symmetry decouples such states, we simply have a sum of independent transmission channels and the calculated anisotropy was 0.23. The anisotropies for the other transition metals, as well as calculated transmittances for two Co impurities will also be presented [1] R. B. Pontes, E. Z. da Silva, A. Fazzio and Antônio J. R. da Silva, J. Am. Chem. Soc. 130 (30), 9897-903, 2008

  14. The Electrochemical Synthesis of Transition-Metal Acetylacetonates

    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. Electron-Hole Liquids in Transition Metal Oxide Heterostructures

    Millis, Andrew J.; Schlom, Darrell G.

    2010-01-01

    Appropriately designed transition metal oxide heterostructures involving small band gap Mott insulators are argued to support spatially separated electron and hole gasses at equilibrium. Spatial separations and carrier densities favoring the formation of excitonic states are achievable. The excitonic states may exhibit potentially novel properties. Energetic estimates are given, candidate material systems are discussed, and the possibility of large photvoltaic effects is mentioned

  16. Reactions of transition metal complexes with cyclic ethers

    Three novel reactions of epoxides with homogeneous transition-metal catalysts have been explored: (a) the selective rearrangement of internal epoxides to ketones; (b) the cleavage of C-C bond in epoxides having electron-attracting substituents; (c) the transformation of terminal epoxides into esters. Based on an intensive kinetic study, a general mechanism for the transformations of epoxides is postulated

  17. Surface segregation energies in transition-metal alloys

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

    1999-01-01

    to the electrostatic potential and energy. We use the database to establish the major factors which govern surface segregation in transition metal alloys. We find that the calculated trends are well described by Friedel's rectangular state density model and that the few but significant deviations...

  18. Pressure-induced phase transitions and metallization in VO2

    Bai, Ligang; Li, Quan; Corr, Serena A.; Meng, Yue; Park, Changyong; Sinogeikin, Stanislav V.; Ko, Changhyun; Wu, Junqiao; Shen, Guoyin

    2015-03-01

    We report the results of pressure-induced phase transitions and metallization in VO2 based on synchrotron x-ray diffraction, electrical resistivity, and Raman spectroscopy. Our isothermal compression experiments at room temperature and 383 K show that the room temperature monoclinic phase (M 1 ,P 21/c ) and the high-temperature rutile phase (R ,P 42/m n m ) of VO2 undergo phase transitions to a distorted M 1 monoclinic phase (M 1' ,P 21/c ) above 13.0 GPa and to an orthorhombic phase (CaCl2-like, P n n m ) above 13.7 GPa, respectively. Upon further compression, both high-pressure phases transform into a new phase (phase X ) above 34.3 and 38.3 GPa at room temperature and 383 K, respectively. The room temperature M 1 -M 1' phase transition structurally resembles the R -CaCl2 phase transition at 383 K, suggesting a second-order displacive type of transition. Contrary to previous studies, our electrical resistivity results, Raman measurements, as well as ab initio calculations indicate that the new phase X , rather than the M 1' phase, is responsible for the metallization under pressure. The metallization mechanism is discussed based on the proposed crystal structure.

  19. Electrocatalysis using transition metal carbide and oxide nanocrystals

    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

  20. Semiconductor-metal transition in semiconductor melts with 3d metal admixtures

    Electrical conductivity and thermoelectric power measurements were performed for liquid semiconductor alloys Se0.5Te0.5 doped with 3d metals in a wide temperature range (up to 1600 K) under ambient pressures of argon gas (up to 30 MPa). Structure changes were studied by means of X-ray diffraction method. The 3d metal admixtures affect electrophysical properties and a temperature of the semiconductor-metal transition (SMT)

  1. Preparation of nanoporous metal foam from high nitrogen transition metal complexes

    Tappan, Bryce C.; Huynh, My Hang V.; Hiskey, Michael A.; Son, Steven F.; Oschwald, David M.; Chavez, David E.; Naud, Darren L.

    2006-11-28

    Nanoporous metal foams are prepared by ignition of high nitrogen transition metal complexes. The ammonium salts of iron(III) tris[bi(tetrazolato)-amine], cobalt(III) tris(bi(tetrazolato)amine), and high nitrogen compounds of copper and silver were prepared as loose powders, pressed into pellets and wafers, and ignited under an inert atmosphere to form nanoporous metal foam monoliths having very high surface area and very low density.

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

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

    2003-11-18

    -band occupancy, and are different from those of their 4d- and 5d-counter parts. This anomalous behavior has been interpreted in terms of the spin-polarized d-band altering the d-band occupancy [1]. At high pressures, however, the d-valence band is expected to broaden resulting in a suppression or even a complete loss of magnetism. Experimentally, ferromagnetic {alpha}(bcc)-Fe has been confirmed to transform to non-magnetic {var_epsilon}-Fe (hcp) at 10 GPa [2,3]. Recently, we have also observed a similar transition in Co from ferromagnetic {alpha}(hcp)-Co to likely nonmagnetic {beta}(fcc)-Co at 105 GPa[4]. A similar structural phase transition is expected in Ni, probably in the second-order fcc-fcc transition. However, there has been no directly measured change in magnetism associated with the structural phase transition in Co, nor has yet been confirmed such an iso-structural phase transition in Ni. Similar electronic transitions have been proposed in these 3d-transition metal oxides (FeO, CoO and NiO) from high spin (magnetic) to low spin (nonmagnetic) states [5]. In each of these systems, the magnetic transition is accompanied by a first-order structural transition involving large volume collapse (10% in FeO, for example). So far, there have been no electronic measurements under pressure confirming these significant theoretical predictions, although the predicted pressures for the volume collapse transitions are within the experimental pressure range (80-200GPa).

  3. Empirical prediction of optical transitions in metallic armchair SWCNTs

    G. R. Ahmed Jamal

    2015-12-01

    Full Text Available In this work, a quick and effective method to calculate the second and third optical transition energies of metallic armchair single-wall carbon nanotubes (SWCNT is presented. In this proposed method, the transition energy of any armchair SWCNT can be predicted directly by knowing its one chiral index as both of its chiral indices are same. The predicted results are compared with recent experimental data and found to be accurate over a wide diameter range from 2 to 4.8 nm. The empirical equation proposed here is also compared with that proposed in earlier works. The proposed way may help the research works or applications where information of optical transitions of armchair metallic nanotubes is needed.

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

    Xie, Junfeng; Xie, Yi

    2016-03-01

    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. PMID:26494184

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

    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.

  6. Transition Metal d-Orbital Splitting Diagrams: An Updated Educational Resource for Square Planar Transition Metal Complexes

    Bo¨rgel, Jonas; Campbell, Michael G.; Ritter, Tobias

    2016-01-01

    The presentation of d-orbital splitting diagrams for square planar transition metal complexes in textbooks and educational materials is often inconsistent and therefore confusing for students. Here we provide a concise summary of the key features of orbital splitting diagrams for square planar complexes, which we propose may be used as an updated…

  7. Adhesion and friction of transition metals in contact with non-metallic hard materials

    An investigation was conducted to examine the adhesion and friction behavior of transition metals in contact with various non-metallic hard materials and the nature of the metal transfer to the hard materials. Sliding friction experiments were conducted with the metals yttrium, titanium, tantalum, zirconium, vanadium, neodymium, iron, cobalt, nickel, tungsten, platinum, rhenium, ruthenium and rhodium in sliding contact with single-crystal diamond, silicon carbide, pyrolytic boron nitride and ferrite. All experiments were conducted under the following conditions: loads, 0.05-0.3 N; sliding velocities, 3 x 10-3 and 0.7 x 10-3 m min-1; in a vacuum of 10-8 Pa; at room temperature. Auger electron spectroscopy analysis was conducted with the metals and non-metals to determine the surface chemistry and the degree of surface cleanness. The results of the investigation indicate the adhesion and friction of the transition metals in contact with diamond, silicon carbide, boron nitride and ferrite are related to the relative chemical activity of the metals. The more chemically active the metal, the higher the coefficient of friction and the greater the amount of transfer to the non-metals. (Auth.)

  8. Transition-metal-catalyzed C-S bond coupling reaction.

    Lee, Chin-Fa; Liu, Yi-Chen; Badsara, Satpal Singh

    2014-03-01

    Sulfur-containing molecules such as thioethers are commonly found in chemical biology, organic synthesis, and materials chemistry. While many reliable methods have been developed for preparing these compounds, harsh reaction conditions are usually required in the traditional methods. The transition metals have been applied in this field, and the palladium-catalyzed coupling of thiols with aryl halides and pseudo halides is one of the most important methods in the synthesis of thioethers. Other metals have also been used for the same purpose. Here, we summarize recent efforts in metal-catalyzed C-S bond cross-coupling reactions, focusing especially on the coupling of thiols with aryl- and vinyl halides based on different metals. PMID:24443103

  9. The pressure-induced Mott Transition in transition-metal iodides

    Pasternak, M.P. (Tel Aviv Univ. (Israel). School of Physics and Astronomy); Taylor, R.D. (Los Alamos National Lab., NM (USA)); Jeanloz, R. (California Univ., Berkeley, CA (USA). Dept. of Geology and Geophysics)

    1991-01-01

    Many of the Transition Metal (TM) compounds, because of exchange and correlation interactions within the narrow and poorly overlapping d-bands, become antiferromagnetic insulators, the Mott Insulators (MI). The properties of the MI and their gradual transition into the non-correlated metallic state (the Mott Transition) are of crucial important for the elucidation of HTS materials features in particular and to magnetism in general. The transition of the MI into a metal can be achieved either by doping or by high pressure. To yield the definitive data on the Mott transition high pressure work on well characterized materials should be sought. The present studies provide for the first time extensive information on the Mott-Hubbard gap closure induced by high pressure. High pressure studies using Diamond Anvil Cells were conducted in several (TM)I{sub 2} compounds. They all have layered structures and other antiferromagnetically at ambient pressure. {sup 129}I Moessbauer Spectroscopy (MS) was used to study the properties of the (TM){sup 2+} sublattice magnetization as a function of pressure and temperature, and X-ray diffraction was used to look for possible crystallographic transitions and to obtain the equation of state. Results show that the high pressure transition at P{sub c} from a magnetic to a non-magnetic state is not accompanied by crystallographic changes. Previous studies{sup 1} with NiI{sub 2} have confirmed the presence of a metallic state at P > P{sub c}. Inherent to the pressure behavior of the magnetic state is the gradual increase of T{sub N} in all cases and a slight increase in the TM{sup 2+} moments with pressure increase. The collapse of the magnetic state is abrupt for some cases (NiI{sub 2}) and gradual for others (CoI{sub 2}), indicative of different band-overlap mechanisms. 2 refs., 5 figs.

  10. Structural relationships in complex hydrides of the late transition metals

    Literature data on complex hydrides of the late transition metals (groups 7-10), such as the hydrogen storage material Mg2NiH4, are reviewed with respect to order-disorder phase transitions and structural relationships. They are analysed in terms of crystallographic group-subgroup trees and their use in understanding the different crystal structures from a symmetry point of view is demonstrated. New data are presented on the low temperature behaviour of magnesium iridium hydrides and strontium rhodium hydrides studied by powder X-ray diffraction. (orig.)

  11. Pressure-induced phase transitions and metallization in VO2

    Bai, Ligang; Li, Quan; Corr, Serena A; Meng, Yue; Park, Changyong; Sinogeikin, Stanislav V.; Ko, Changhyun; Wu, Junqiao; Shen, Guoyin

    2015-01-01

    We report the results of pressure-induced phase transitions and metallization in VO2 based on synchrotron x-ray diffraction, electrical resistivity, and Raman spectroscopy. Our isothermal compression experiments at room temperature and 383 K show that the room temperature monoclinic phase (M1,P21/c) and the high-temperature rutile phase (R,P42/mnm) of VO2 undergo phase transitions to a distorted M1 monoclinic phase (M1′,P21/c) above 13.0 GPa and to an orthorhombic phase (CaCl2-like, Pnnm) abo...

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

    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)

  13. Nonlinear d10-ML2 Transition-Metal Complexes

    Wolters, Lando P.; Bickelhaupt, F. Matthias

    2013-01-01

    We have investigated the molecular geometries of a series of dicoordinated d10-transition-metal complexes ML2 (M=Co−, Rh−, Ir−, Ni, Pd, Pt, Cu+, Ag+, Au+; L=NH3, PH3, CO) using relativistic density functional theory (DFT) at ZORA-BLYP/TZ2P. Not all complexes have the expected linear ligand–metal–ligand (L–M–L) angle: this angle varies from 180° to 128.6° as a function of the metal as well as the ligands. Our main objective is to present a detailed explanation why ML2 complexes can become bent...

  14. Multireference Character for 4d Transition Metal-Containing Molecules.

    Wang, Jiaqi; Manivasagam, Sivabalan; Wilson, Angela K

    2015-12-01

    Four diagnostic criteria have been examined to identify the suitability of single-reference wave function-based quantum chemistry methods for a set of 118 4d transition metal species. These diagnostics include the weight of the leading configuration of the CASSCF wave function, C0(2); the Frobenius norm of the coupled cluster amplitude vector related to single excitations, T1; the matrix 2-norm of the coupled cluster T1 amplitude vector arising from coupled cluster calculations, D1; and the percent total atomization energy, %TAE, corresponding to a relationship between energies determined with CCSD and CCSD(T) calculations. New criteria, namely, T1 ≥ 0.045, D1 ≥ 0.120, and %TAE ≥ 10%, are herein proposed as a gauge for 4d transition metal-containing molecules to predict the possible need to employ multireference (MR) wave function-based methods to describe energetic and spectroscopic properties. PMID:26642991

  15. On thermal lattice dilatation of some transition metal compounds

    The report deals with the thermal lattice dilatation of cubic transition metal compounds. The thermal dilatation is determined through the variation of the lattice constants. The measurements are carried out 'in situ' by use of a high-temperature X-ray diffractometer chamber. The evaluation relates to both the linear thermal expansion coefficient α and, for some compounds, the specific heat at constant volume Csub(V) and the Grueneisen constant γ. In general a higher thermal dilatation is observed for nitrides than for carbides with the compounds formed by the transition metals belonging to the IVA and VA groups. The influence exerted by vacancies and by the oxygen dissolved in the lattice on the thermal dilatation of carbonitrides of zirconium, hafnium and tantalum is explained by the more pronounced anharmonic character of atomic vibrations in the crystal lattice. (orig.)

  16. Laser Assisted Additively Manufactured Transition Metal Coating on Aluminum

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

    2016-05-01

    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 (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.

  17. Quantum superconductor-metal transition in a proximity array

    Feigel' man, M V; Larkin, A I; Skvortsov, M A [L D Landau Institute for Theoretical Physics, Russian Academy of Sciences, ul. Kosygina 2, 117940 Moscow (Russian Federation)

    2001-10-01

    A theory of the zero-temperature superconductor-metal transition is developed for an array of superconductive islands (of size d) coupled via a disordered two-dimensional conductor with the dimensionless conductance g = h/e{sup 2} R{sub {open_square}} >> 1. At T = 0 macroscopically superconductive state of the array with lattice spacing b >> d is destroyed at g < g{sub c} {approx} 0.1 ln{sup 2} (b/d). At high temperatures the normal-state resistance between neighboring islands at b = b{sub c} is much smaller than R{sub Q} = h/4e{sup 2}. (5. superconductor-metal-insulator transitions)

  18. Laser Assisted Additively Manufactured Transition Metal Coating on Aluminum

    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 (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.

  19. Photonics and optoelectronics of 2D semiconductor transition metal dichalcogenides

    Mak, Kin Fai; Shan, Jie

    2016-04-01

    Recent advances in the development of atomically thin layers of van der Waals bonded solids have opened up new possibilities for the exploration of 2D physics as well as for materials for applications. Among them, semiconductor transition metal dichalcogenides, MX2 (M = Mo, W; X = S, Se), have bandgaps in the near-infrared to the visible region, in contrast to the zero bandgap of graphene. In the monolayer limit, these materials have been shown to possess direct bandgaps, a property well suited for photonics and optoelectronics applications. Here, we review the electronic and optical properties and the recent progress in applications of 2D semiconductor transition metal dichalcogenides with emphasis on strong excitonic effects, and spin- and valley-dependent properties.

  20. Structural models for amorphous transition metal binary alloys

    A dense random packing of 445 hard spheres with two different diameters in a concentration ratio of 3 : 1 was hand-built to simulate the structure of amorphous transition metal-metalloid alloys. By introducing appropriate pair potentials of the Lennard-Jones type, the structure is dynamically relaxed by minimizing the total energy. The radial distribution functions (RDF) for amorphous Fe0.75P0.25, Ni0.75P0.25, Co0.75P0.25 are obtained and compared with the experimental data. The calculated RDF's are resolved into their partial components. The results indicate that such dynamically constructed models are capable of accounting for some subtle features in the RDF of amorphous transition metal-metalloid alloys

  1. Laser Assisted Additively Manufactured Transition Metal Coating on Aluminum

    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 (engineering via a 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.

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

    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. Synthesis and Characterization of Few Layer Semiconducting Transition Metal Dichalcogenides

    Mann, John Calif

    2013-01-01

    The intense interest in graphene as the prototypical 2D electronic material has recently been accompanied by the investigation of layered transition metal dichalcogenides (TMDC), most notably MoS2 and MoSe2. Like graphene, they can be prepared in a stable form down to monolayer thickness. These materials provide favorable mechanical properties similar to graphene, but exhibit an intrinsic indirect band gap that crossovers to a direct band gap in the monolayer limit without the need for nanos...

  4. Ab initio calculations of temperature dependent resistivity for transition metals

    Wagenknecht, D.; Turek, Ilja; Carva, K.

    Praha : Matfyzpress, 2015 - (Šafránková, J.; Pavlů, J.), s. 42-47 ISBN 978-80-7378-311-2. [Week of Doctoral Students 2015. Praha (CZ), 02.06.2015-04.06.2015] R&D Projects: GA ČR GA15-13436S Institutional support: RVO:68081723 Keywords : electrical resistivity * temperature dependence * transition metals Subject RIV: BM - Solid Matter Physics ; Magnetism

  5. Metal - Insulator Transition in 3D Quantum Percolation

    Travenec, Igor

    2007-01-01

    We present the metal - insulator transition study of a quantum site percolation model on simple cubic lattice. Transfer matrix method is used to calculate transport properties - Landauer conductance - for the binary distribution of energies. We calculate the mobility edge in disorder (ratio of insulating sites) - energy plane in detail and we find the extremal critical disorder somewhat closer to the classical percolation threshold, than formerly reported. We calculate the critical exponent $...

  6. Applications of Transition Metals in Organic Synthesis and Polymerization

    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...

  7. Excitonic linewidth and coherence lifetime in monolayer transition metal dichalcogenides

    Selig, Malte; Berghäuser, Gunnar; Raja, Archana; Nagler, Philipp; Schüller, Christian; Heinz, Tony F.; Korn, Tobias; Chernikov, Alexey; Malic, Ermin; Knorr, Andreas

    2016-01-01

    Atomically thin transition metal dichalcogenides (TMDs) are direct-gap semiconductors with strong light-matter and Coulomb interaction. The latter accounts for tightly bound excitons, which dominate the optical properties of these technologically promising materials. Besides the optically accessible bright excitons, these systems exhibit a variety of dark excitonic states. They are not visible in optical spectra, but can strongly influence the coherence lifetime and the linewidth of the emiss...

  8. Two dimensional transition metal dichalcogenides grown by chemical vapor deposition

    Tsang, Ka-yi; 曾家懿

    2014-01-01

    An atomically thin film of semiconducting transition metal dichalcogenides (TMDCs) is emerging as a class of key materials in chemistry and physics due to their remarkable chemical and electronic properties. The TMDCs are layered materials with weak out-of-plane van der Waals (vdW) interaction and strong in-plane covalent bonding enabling scalable exfoliation into two-dimensional (2D) layers of atomic thickness. The growth techniques to prepare these 2D TMDC materials in high yield and large ...

  9. Planar defects and dislocations in transition metal disilicides

    Paidar, Václav

    Boston: John Wiley & Sons, 2013 - (Marquis, F.), s. 431-437 ISBN 978-1-63266-000-8. [Pacific Rim International Congress on Advanced Materials and Processing 2013 /8./ (PRICM-8). Waikoloa (US), 04.08.2013-09.08.2013] R&D Projects: GA AV ČR IAA100100920 Grant ostatní: AV ČR(CZ) M100411202 Institutional support: RVO:68378271 Keywords : transition metal disilicides * dislocation cores * stacking faults Subject RIV: BM - Solid Matter Physics ; Magnetism

  10. Superparamagnetism of transition metal nanoparticles in conducting polymer film

    Magnetic properties of transition metal (cobalt, iron, nickel, manganese, chromium) nanoparticles prepared by ion-exchange method in the perfluorinated sulfo-cation polymeric membrane (MF-4SK) have been investigated. While manganese and chromium in MF-4SK exhibited paramagnetic properties, cobalt, iron and nickel particles showed superparamagnetic behaviors. Our experimental evidence suggests that cobalt, iron and nickel nanoparticles in the polymer film obey a single-domain theory

  11. Exciton ionization in multilayer transition-metal dichalcogenides

    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....

  12. Organometallic compounds of the lanthanides, actinides and early transition metals

    This book provides a reference compilation of physical and biographical data on over 1500 of the most important and useful organometallic compounds of the lanthanides, actinides and early transition metals representing 38 different elements. The compounds are listed in molecular formula order in a series of entries in dictionary format. Details of structure, physical and chemical properties, reactions and key references are clearly set out. All the data is fully indexed and a structural index is provided. (U.K.)

  13. Surface-Induced Modification of Supported Late Transition Metal Complexes

    Snezhkova, Olesia

    2016-01-01

    The work presented in this thesis addresses the investigation of the electronic, magnetic, and structural properties of late transition metal complexes supported on various surfaces. The research is aimed at studying the interaction between the molecules and the support, together with the intermolecular interaction. This knowledge is essential e.g. for the development of organic molecule-based devices and the creation of active and stable catalysts. In this work, the modification of th...

  14. Synthesis of nanosized, electrochemically active lithium transition metal phosphates

    Stark, Michael Andreas

    2011-01-01

    The increasing interest to develop new types of Li-ion batteries is motivated by the amplified need of batteries with high charge and discharge rates. Lithium transition metal phosphates are promising candidates to challenge this need. Before LiMnPO4 can be used as active material, research has to challenge two different aspects. First of all, for this material a crystallite size reduction is very important to improve the rate performance. And second, the electronic conductivity has to be imp...

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

    Soni, Shubhangi; Kaurav, Netram; Jain, A.; Shah, S.; Choudhary, K. K.

    2015-06-01

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

  16. Thermodynamics of the structural transition in metal-organic frameworks.

    Rodriguez, J; Beurroies, I; Coulet, M-V; Fabry, P; Devic, T; Serre, C; Denoyel, R; Llewellyn, P L

    2016-03-01

    A thermodynamic study of the structural large-pore (LP) to narrow pore (NP) transition in various Metal Organic Frameworks (MOFs) is presented. First, the pressure induced transition at a constant temperature is investigated using a Tian-Calvet microcalorimeter set-up equipped with a high pressure cell. This device permits simultaneous measurements of the mechanical work and heat associated with the LP → NP transition. It is shown that MIL-53(Al) and MIL-53(Cr) have similar thermodynamic and mechanical behaviour whilst the MIL-47(V) system is characterized by much higher transition energy and mechanical work. Second, the temperature induced transition at ambient pressure is studied by means of differential scanning calorimetry (DSC) combined with X-ray absorption spectroscopy. This set-up enables one to follow simultaneously the structural changes associated with the phase transition detected by DSC. The MIL-53(Cr)-Br functionalized MOF is chosen here as a case study where both energetics and structural changes are discussed. PMID:26574728

  17. Discontinuous structural phase transition of liquid metal and alloys (2)

    The diameter (df) of diffusion fluid cluster before and after phase transition has been calculated in terms of the paper ''Discontinuous structural phase transition of liquid metal and alloy (1)'' Physics Letters. A 326 (2004) 429-435, to verify quantitatively the discontinuity of structural phase transition; the phenomena of thermal contraction and thermal expansion during the phase transition, together with the evolution model of discontinuous structural phase transition are also discussed in this Letter to explore further the nature of structural transition; In addition, based on the viscosity experimental result mentioned in paper [Y. Waseda, The Structure of Non-Crystalline Materials--Liquids and Amorphous Solids, McGraw-Hill, New York, 1980], we present an approach to draw an embryo of the liquid-liquid (L-L) phase diagram for binary alloys above liquidus in the paper, expecting to guide metallurgy process so as to improve the properties of alloys. The idea that controls amorphous structure and its properties by means of the L-L phase diagram for alloys and by the rapid cooling technique to form the amorphous alloy has been brought forward in the end

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

    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. Optical properties of transition metal oxide quantum wells

    Lin, Chungwei; Posadas, Agham; Choi, Miri; Demkov, Alexander A.

    2015-01-01

    Fabrication of a quantum well, a structure that confines the electron motion along one or more spatial directions, is a powerful method of controlling the electronic structure and corresponding optical response of a material. For example, semiconductor quantum wells are used to enhance optical properties of laser diodes. The ability to control the growth of transition metal oxide films to atomic precision opens an exciting opportunity of engineering quantum wells in these materials. The wide range of transition metal oxide band gaps offers unprecedented control of confinement while the strong correlation of d-electrons allows for various cooperative phenomena to come into play. Here, we combine density functional theory and tight-binding model Hamiltonian analysis to provide a simple physical picture of transition metal oxide quantum well states using a SrO/SrTiO3/SrO heterostructure as an example. The optical properties of the well are investigated by computing the frequency-dependent dielectric functions. The effect of an external electric field, which is essential for electro-optical devices, is also considered.

  20. Optical properties of transition metal oxide quantum wells

    Lin, Chungwei; Posadas, Agham; Choi, Miri; Demkov, Alexander A. [Department of Physics, University of Texas at Austin, Austin, Texas 78712 (United States)

    2015-01-21

    Fabrication of a quantum well, a structure that confines the electron motion along one or more spatial directions, is a powerful method of controlling the electronic structure and corresponding optical response of a material. For example, semiconductor quantum wells are used to enhance optical properties of laser diodes. The ability to control the growth of transition metal oxide films to atomic precision opens an exciting opportunity of engineering quantum wells in these materials. The wide range of transition metal oxide band gaps offers unprecedented control of confinement while the strong correlation of d-electrons allows for various cooperative phenomena to come into play. Here, we combine density functional theory and tight-binding model Hamiltonian analysis to provide a simple physical picture of transition metal oxide quantum well states using a SrO/SrTiO{sub 3}/SrO heterostructure as an example. The optical properties of the well are investigated by computing the frequency-dependent dielectric functions. The effect of an external electric field, which is essential for electro-optical devices, is also considered.

  1. Optical properties of transition metal oxide quantum wells

    Fabrication of a quantum well, a structure that confines the electron motion along one or more spatial directions, is a powerful method of controlling the electronic structure and corresponding optical response of a material. For example, semiconductor quantum wells are used to enhance optical properties of laser diodes. The ability to control the growth of transition metal oxide films to atomic precision opens an exciting opportunity of engineering quantum wells in these materials. The wide range of transition metal oxide band gaps offers unprecedented control of confinement while the strong correlation of d-electrons allows for various cooperative phenomena to come into play. Here, we combine density functional theory and tight-binding model Hamiltonian analysis to provide a simple physical picture of transition metal oxide quantum well states using a SrO/SrTiO3/SrO heterostructure as an example. The optical properties of the well are investigated by computing the frequency-dependent dielectric functions. The effect of an external electric field, which is essential for electro-optical devices, is also considered

  2. Holographic metal/superconductor phase transitions with dark matter sector

    Peng, Yan

    2015-01-01

    In this paper, we investigate the holographic phase transitions with dark matter sector in the AdS black hole background away from the probe limit. We firstly detect the formation of the scalar hair by examining the behaviors of the superconducting solutions and the effective mass of the scalar field. Then we study the condensation of the scalar operator with respect to the Hawking temperature T. As a further step, we disclose the properties of the phase transitions from the holographic topological entanglement entropy of the system. The holographic topological entanglement entropy is proved to be very useful in characterizing the difference between various phases. At last, we also derive the qualitative properties through the analytical methods. In summary, we find that the model parameters can provide rich physics in the general holographic metal/superconductor phase transitions.

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

    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.

  4. Calculated electronic and magnetic properties of the half-metallic, transition metal based Heusler compounds

    Kandpal, Hem C.; FECHER, GERHARD H.; Felser, Claudia

    2006-01-01

    In this work, results of {\\it ab-initio} band structure calculations for $A_2BC$ Heusler compounds that have $A$ and $B$ sites occupied by transition metals and $C$ by a main group element are presented. This class of materials includes some interesting half-metallic and ferromagnetic properties. The calculations have been performed in order to understand the properties of the minority band gap and the peculiar magnetic behavior found in these materials. Among the interesting aspects of the e...

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

    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.

  6. Perspectives of Two-dimensional Transition Metal Dichalcogenide Monolayers

    Hui Pan

    2015-06-01

    Full Text Available The discovery of graphene, a novel two-dimensional (2D nanostructure, has triggered an extensive study on monolayers for diverse applications in Nano devices, optoelectronics, sensors, catalysts, and energy storage because of the easy fabrication, exceptional charge transport, thermal, optical, chemical, and mechanical properties [1]. As one of important members of 2D monolayers, 2D transition metal dichalcogenides (TMDs monolayers show a wide range of electronic, optical, mechanical, chemical, and thermal properties [2]. TMDs have a chemical formula of MX2, where M is a transition metal element from group IV, group V, or group VI, and X is a chalcogen (S, Se, or Te. They are layered materials with weakly van der Walls interaction holding together. Each layer is a sandwich structure (X–M–X, where a M-atom layer is enclosed within two X layers and the atoms in layers are hexagonally packed [3]. Depending to stacking orders and metal atom coordination, the overall symmetry of TMD can be hexagonal or rhombohedral, and the metal atoms have octahedral or trigonal prismatic coordination.

  7. Low energy 4f-5d transitions in lanthanide doped CaLaSiN3 with low degree of cross-linking between SiN4 tetrahedra

    CaLaSiN3 samples doped with Eu, Yb, Sm, Ce and Pr have been prepared via solid-state reaction synthesis and the optical properties have been studied. Both Yb and Sm were only observed in the trivalent state due to the fact that their Ln2+ ground states are located inside or very close to the conduction band of the CaLaSiN3 host lattice. Doping with Ce3+ or Eu2+ resulted in a very low energy Ce3+ or Eu2+ 4f-5d absorption band around 1.9 eV (650 nm) and 1.4 eV (885 nm), respectively. The Ce3+ 5d-4f emission appeared to be quenched, just as the Eu2+ 5d-4f emission, which can be explained as the result of auto-ionization. (paper)

  8. Method for treating rare earth-transition metal scrap

    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.

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

    Greeley, Jeffrey Philip; Rankin, Rees; Zeng, Zhenhua; Chun, Hee-Joon; Clayborne, Andre; Li, Lin; Abild-Pedersen, Frank; Nørskov, Jens Kehlet; Larsen, Ask Hjorth; Kleis, Jesper; Jacobsen, Karsten Wedel; Romero, Nichols

    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 (<~4 nm in diameter), and I...

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

    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.

  11. Mixed-Ligand Approach to Changing the Metal Ratio in Bismuth-Transition Metal Heterometallic Precursors.

    Lieberman, Craig M; Wei, Zheng; Filatov, Alexander S; Dikarev, Evgeny V

    2016-04-18

    A new series of heteroleptic bismuth-transition metal β-diketonates [BiM(hfac)3(thd)2] (M = Mn (1), Co (2), and Ni (3); hfac = hexafluoroacetylacetonate, thd = tetramethylheptanedionate) with Bi:M = 1:1 ratio have been synthesized by stoichiometric reactions between homometallic reagents [Bi(III)(hfac)3] and [M(II)(thd)2]. On the basis of analysis of the metal-ligand interactions in heterometallic structures, the title compounds were formulated as ion-pair {[Bi(III)(thd)2](+)[M(II)(hfac)3](-)} complexes. The direct reaction between homometallic reagents proceeds with a full ligand exchange between main group and transition metal centers, yielding dinuclear heterometallic molecules. In heteroleptic molecules 1-3, the Lewis acidic, coordinatively unsaturated Bi(III) centers are chelated by two bulky, electron-donating thd ligands and maintain bridging interactions with three oxygen atoms of small, electron-withdrawing hfac groups that chelate the neighboring divalent transition metals. Application of the mixed-ligand approach allows one to change the connectivity pattern within the heterometallic assembly and to isolate highly volatile precursors with the proper Bi:M = 1:1 ratio. The mixed-ligand approach employed in this work opens broad opportunities for the synthesis of heterometallic (main group-transition metal) molecular precursors with specific M:M' ratio in the case when homoleptic counterparts either do not exist or afford products with an incorrect metal:metal ratio for the target materials. Heteroleptic complexes obtained in the course of this study represent prospective single-source precursors for the low-temperature preparation of multiferroic perovskite-type oxides. PMID:27054922

  12. Effect of Transition Metals on Polysialic Acid Structure and Functions.

    Murthy, Raghavendra Vasudeva; Bharate, Priya; Gade, Madhuri; Sangabathuni, Sivakoti; Kikkeri, Raghavendra

    2016-04-01

    Polysialic acid (PSA) is one of the most abundant glycopolymer present in embryonic brain, and it is known to be involved in key roles such as plasticity in the central nervous system, cell adhesion, migration and localization of neurotrophins. However, in adult brain, its expression is quite low. The exception to this is in Alzheimer's disease (AD) brain, where significantly increased levels of polysilylated neural cell adhesion molecule (PSA-NCAM) have been reported. Here, we confirm the role of PSA as a metal chelator, allowing it to decrease cytotoxicity caused by high levels of transition metals, commonly found in AD brain, and as a regulator of cell behavior. UV-visible (UV-vis) and circular dichroism (CD) spectroscopy, atomic force microscopy (AFM), and isothermal titration calorimetry (ITC) techniques were used to investigate the assembly of PSA-metals complexes. These PSA-metal complexes exhibited less toxicity compared to free metal ions, and in particular, the PSA-Cu(2+) complex synergistically promoted neurite outgrowth in PC12 cells. PMID:26990355

  13. Bonding in transition-metal cluster compounds. 2. The metal cluster-borane analogy

    Following the detailed discussion of the transition-metal cluster moiety M6(μ3-X)8 in the preceding paper, a more general account of the importance of the d electrons in transition-metal cluster chemistry is presented. The putative analogy with borane clusters (and their derivatives) is examined critically. Although an isolobal relationship exists between, e.g., BH and appropriate ML/sub n/ fragments (e.g. conical Fe(CO)3), this does not imply that the BH and ML/sub n/ fragments behave in electronically similar ways when cluster formation occurs, even when structurally related clusters are formed. Nonidentical isolobal fragments have orbital differences that manifest themselves in interfragment resonance integrals and require a qualitative distinction to be drawn between the bonding modes and detailed electronic structures of (i) transition-metal cluster compounds and (ii) boranes, carboranes, and their metalla derivatives; an analysis developed in the electronic structure theory of transition-metal systems shows why this is the case. The isolobal principle and Wade's rule owe their generality and utility to being symmetry-based statements; the energetics and details of the electronic structure of cluster compounds however are a separate matter requiring appropriate methods of theoretical chemistry. 39 references, 3 figures

  14. Atomic structure of non-stoichiometric transition metal carbides

    Different kinds of experimental studies of the atomic arrangement in non-stoichiometric transition metal carbides are proposed: the ordering of carbon vacancies and the atomic static displacements are the main subjects studied. Powder neutron diffraction on TiCsub(1-x) allowed us to determine the order-disorder transition critical temperature -Tsub(c) approximately 7700C- in the TiCsub(0.52-0.67) range, and to analyze at 300 K the crystal structure of long-range ordered samples. A neutron diffuse scattering quantitative study at 300 K of short-range order in TiCsub(0.76), TiCsub(0.79) and NbCsub(0.73) single crystals is presented: as in Ti2Csub(1+x) and Nb6C5 superstructures, vacancies avoid to be on each side of a metal atom. Besides, the mean-square carbon atom displacements from their sites are small, whereas metal atoms move radially about 0.03 A away from vacancies. These results are in qualitative agreement with EXAFS measurements at titanium-K edge of TiCsub(1-x). An interpretation of ordering in term of short-range interaction pair potentials between vacancies is proposed

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

    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

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

    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. PMID:27143686

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

    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.

  18. Holographic Metal-Insulator Transition in Higher Derivative Gravity

    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).

  19. Compressibility of AlB2-type transition metal diborides

    The pressure behaviour of a series of transition metal borides has been studied both experimentally and by means of ab initio calculations. X-ray diffraction patterns measured up to ∼50 GPa for VB2 and ZrB2 show no obvious phase transition. Bulk moduli of 322 and 317 GPa, respectively, were obtained using a Murnaghan equation of state. Hartree-Fock LCCO (linear combination of crystal orbitals) calculations performed for TiB2 have allowed its compression behaviour to be studied. The bulk modulus obtained (292 GPa) and the proposed important contribution of the interlayer interaction to the elastic behaviour under high pressure are consistent with the experimental results for the other borides

  20. Luminescence of deep transition metal centres in solids

    The open-shell configuration of transition metal (TM) impurities greatly influences the carrier-binding properties of levels which they introduce into the band gap of a solid. Absorption and luminescence spectroscopy have proved invaluable in identifying deep TM centres and in giving insight into the nature of excited states involving interaction with carriers. Examples of transitions at associate centres and involving electron transfer between the lattice bands and the impurity are discussed. The effect which the open-shell configuration has on the characteristic recombination luminescence is illustrated for Cu impurities in II-VI compounds. Three different mechanisms for excitation of intracentre luminescence involving carrier relaxation at isolectronic TM impurities are outlined, based on spectroscopic measurements. (orig.)

  1. Stacking dependent electronic structures of transition metal dichalcogenides heterobilayer

    Lee, Yea-Lee; Park, Cheol-Hwan; Ihm, Jisoon

    The systematic study of the electronic structures and optical properties of the transition metal dichalcogenides (TMD) heterobilayers can significantly improve the designing of new electronic and optoelectronic devices. Here, we theoretically study the electronic structures and optical properties of TMD heterobilayers using the first-principles methods. The band structures of TMD heterobilayer are shown to be determined by the band alignments of the each layer, the weak interlayer interactions, and angle dependent stacking patterns. The photoluminescence spectra are investigated using the calculated band structures, and the optical absorption spectra are examined by the GW approximations including the electron-hole interaction through the solution of the Bethe-Salpeter equation. It is expected that the weak interlayer interaction gives rise to the substantial interlayer optical transition which will be corresponding to the interlayer exciton.

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

    Ishøy, Mette; Nielsen, Thomas Eiland

    2014-01-01

    versatile method to form iminium and oxocarbenium ions. Given the number of reactions involving these highly electrophilic intermediates, this concept provides a sea of opportunities for heterocycle synthesis, (see scheme; Nu=nucleophile). © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.......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. A sea of opportunities! Transition-metal-catalyzed isomerization of N- and O-allylic compounds provides a mild, selective and synthetically...

  3. Control of plasmonic nanoantennas by reversible metal-insulator transition.

    Abate, Yohannes; Marvel, Robert E; Ziegler, Jed I; Gamage, Sampath; Javani, Mohammad H; Stockman, Mark I; Haglund, Richard F

    2015-01-01

    We demonstrate dynamic reversible switching of VO2 insulator-to-metal transition (IMT) locally on the scale of 15 nm or less and control of nanoantennas, observed for the first time in the near-field. Using polarization-selective near-field imaging techniques, we simultaneously monitor the IMT in VO2 and the change of plasmons on gold infrared nanoantennas. Structured nanodomains of the metallic VO2 locally and reversibly transform infrared plasmonic dipole nanoantennas to monopole nanoantennas. Fundamentally, the IMT in VO2 can be triggered on femtosecond timescale to allow ultrafast nanoscale control of optical phenomena. These unique features open up promising novel applications in active nanophotonics. PMID:26358623

  4. New Transition metal assisted complex borohydrides for hydrogen storage

    High capacity hydrogen storage systems are indeed essential for the on-board vehicular application that leads to the pollution free environment. Apart from the various hydrogen storage systems explored in the past, complex hydrides involving light weight alkali/alkaline metals exhibits promising hydrogenation/ dehydrogenation characteristics. New transition metal assisted complex borohydrides [Zn(BH4)2] have been successfully synthesized by an inexpensive mechano-chemical process. These complex hydrides possesses gravimetric hydrogen storage capacity of ∼8.4 wt.% at around 120 C. We have determined the volumetric hydrogen absorption and desorption of these materials for a number of cycles. Another complex borohydride mixture LiBH4/MgH2 catalyzed with ZnCl2 has been synthesized and characterized using various analytical techniques. (authors)

  5. Nanoparticle plasmonics: going practical with transition metal nitrides

    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.

  6. Ising superconductivity and Majorana fermions in transition-metal dichalcogenides

    Zhou, Benjamin T.; Yuan, Noah F. Q.; Jiang, Hong-Liang; Law, K. T.

    2016-05-01

    In monolayer transition-metal dichalcogenides (TMDs), electrons in opposite K valleys are subject to opposite effective Zeeman fields, which are referred to as Ising spin-orbit coupling (SOC) fields. The Ising SOC, originating from in-plane mirror symmetry breaking, pins the electron spins to the out-of-plane directions, and results in Ising superconducting states with strongly enhanced upper critical fields. Here, we show that the Ising SOC generates equal-spin-triplet Cooper pairs with spin polarized in the in-plane directions. Importantly, the spin-triplet Cooper pairs can induce superconducting pairings in a half-metal wire placed on top of the TMD and result in a topological superconductor with Majorana end states. Direct ways to detect equal-spin triplet Cooper pairs and the differences between Ising superconductors and Rashba superconductors are discussed.

  7. Efficient photocarrier injection in a transition metal oxide heterostructure

    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. Structural and electronic properties of isostructural transition metal nitrides

    Sahnoun, M., E-mail: sahnoun_cum@yahoo.f [Faculte des Sciences et Technologie, Universite de Mascara, DZ-29000 Mascara (Algeria); Parlebas, J.C. [IPCMS, UMR 7504 CNRS-ULP, 23 Rue de Loess, 67034 Strasbourg Cedex 2 (France); Driz, M. [Applied Materials Laboratory, Universite de Sidi Bel Abbes, DZ-22000 Sidi Bel Abbes (Algeria); Daul, C. [Departement de Chimie, Universite de Fribourg, CH-1700 Fribourg (Switzerland)

    2010-09-15

    The structural and electronic properties of three isostructural transition metal nitrides VN, NbN and TaN have been calculated using the full-potential linearized augmented plane-wave method within a generalized gradient approximation scheme for the exchange-correlation potential. Perfect NaCl structures as well as lattices containing nitrogen vacancies (M{sub 4}N{sub 3}), and an hexagonal {epsilon}-M{sub 2}N structure are considered. The trends are discussed and compared with available experimental and other theoretical results.

  9. Correlated electron pseudopotentials for 3d-transition metals

    A recently published correlated electron pseudopotentials (CEPPs) method has been adapted for application to the 3d-transition metals, and to include relativistic effects. New CEPPs are reported for the atoms Sc − Fe, constructed from atomic quantum chemical calculations that include an accurate description of correlated electrons. Dissociation energies, molecular geometries, and zero-point vibrational energies of small molecules are compared with all electron results, with all quantities evaluated using coupled cluster singles doubles and triples calculations. The CEPPs give better results in the correlated-electron calculations than Hartree-Fock-based pseudopotentials available in the literature

  10. Correlated electron pseudopotentials for 3d-transition metals

    Trail, J. R.; Needs, R. J.

    2015-02-01

    A recently published correlated electron pseudopotentials (CEPPs) method has been adapted for application to the 3d-transition metals, and to include relativistic effects. New CEPPs are reported for the atoms Sc - Fe, constructed from atomic quantum chemical calculations that include an accurate description of correlated electrons. Dissociation energies, molecular geometries, and zero-point vibrational energies of small molecules are compared with all electron results, with all quantities evaluated using coupled cluster singles doubles and triples calculations. The CEPPs give better results in the correlated-electron calculations than Hartree-Fock-based pseudopotentials available in the literature.

  11. Correlated electron pseudopotentials for 3d-transition metals

    Trail, J. R., E-mail: jrt32@cam.ac.uk; Needs, R. J. [Theory of Condensed Matter Group, Cavendish Laboratory, J J Thomson Avenue, Cambridge CB3 0HE (United Kingdom)

    2015-02-14

    A recently published correlated electron pseudopotentials (CEPPs) method has been adapted for application to the 3d-transition metals, and to include relativistic effects. New CEPPs are reported for the atoms Sc − Fe, constructed from atomic quantum chemical calculations that include an accurate description of correlated electrons. Dissociation energies, molecular geometries, and zero-point vibrational energies of small molecules are compared with all electron results, with all quantities evaluated using coupled cluster singles doubles and triples calculations. The CEPPs give better results in the correlated-electron calculations than Hartree-Fock-based pseudopotentials available in the literature.

  12. Thermodynamic investigations of transition metal systems containing coabon and nitrogen

    Teng, Lidong

    2004-01-01

    In view of the important applications of carbides and carbo-nitrides of transition metals in the heat-resistant and hard materials industries, the thermodynamic activities of Cr and Mn in the Cr-C, Fe-Cr-C, Mn-Ni-C and Mn-Ni-C-N systems have been studied in the present work by the use of the galvanic cell technique. CaF2single crystals were used as the solid electrolyte. The phase relationships in selected regions of the systems in question were investigated by the use of the equilibration te...

  13. Transition Metal Catalyzed Polymerization of 1,3,5-Trioxane

    Henes, Michael

    2002-01-01

    We highlighted that transition metal complexes can serve as mediators for the cationic ROP of 1,3,5-trioxane. As examples cyclopentadienyl molybdenum complexes of different Lewis acidity were employed tolerating considerable more water than classical Lewis acid catalysts like BF3 · OEt2 or tBuClO4. They are less active than iridium or palladium catalysts, but [CpMo(CO)3OTf] (2a) was an excellent example to carry out time-dependent 1H NMR spectroscopic studies to follow the course of the polym...

  14. The metal-to-insulator transition in disordered lithium titanate

    Fazileh, Farhad

    The electronic and magnetic properties of the superconducting spinel lithium titanate have attracted substantial interest during the last three decades. This compound is one of the four spinel systems among more than 300 known spinel compounds that exhibit superconducting properties at low temperatures. It is still an open question whether electronic correlations have any significant role in the electronic and superconducting properties of this material. In this thesis, we provide some supporting evidence for the presence and importance of strong electronic correlations in this compound by studying the composition-induced metal-insulator transitions in Li1+ xTi2-xO4 and LiAlyTi2-yO 4 systems. In this study, first we introduce a one electron model for the conducting electrons, a so-called quantum site percolation (QSP) model. Experimentally, the non-stoichiometric compounds of lithium titanate, Li1+xTi2-x O4 and LiAlyTi 2-yO4, show metal-to-insulator transitions at critical doping concentrations of xc = 0.15 and yc = 0.33. We performed systematic numerical calculations based on the above-mentioned quantum site percolation model on a corner-sharing tetrahedral lattice, and our numerical results led to predictions for the critical doping concentrations of xc = 0.32 and yc = 0.83, more than twice the experimental values. Thus, this discrepancy indirectly supports the idea that perhaps electronic correlations are important, and their omission is the source of this discrepancy. The hypothesis that the screened Coulomb potentials of the doping cations could explain this disagreement was also rejected by our detailed study of this effect. We showed that this effect can only slightly change the critical doping concentrations of the metal-to-insulator transition. In the final part of our study we take into account the electronic interactions in a real-space Hartree-Fock approximation. In this model the QSP disorder is treated exactly, but the interactions are included in a

  15. Metal-insulator transition in three-band Hubbard model

    We describe a transition from a metal to an antiferromagnetic (AF) insulator in the three-band Hubbard Hamiltonian for the undoped CuO2 planes of high-temperature superconductors, including local hole correlations. If the realistic parameters are used, one finds the AF ground states with magnetic moment of ≅0.47μB and ≅0.56μB for La2CuO4 and YBa2Cu2O6, respectively. Correlations and the interoxygen hopping reduce drastically the region of the AF long-range order which disappears for the doping of 0.06 hole per unit cell. (orig.)

  16. Hydrogen induced deformational effects in some transition metals

    Investigation into regularities and nature of acceleration of creep, relaxation of stress ete under hydrogen absortion of (Fe, Pd, Nb, Ta, V) transition metals is carried out. It is shown, that under combined effect of internal or external fields of stress one can observe manifold acceleration of microplastic deformation of mechanical aftereffect (MAE). Mechanisms responsible for MAE initiated by hydrogen absorption are suggested on the ground of observation of elastic constants, internal friction and electrical conductivity and of data obtained by means of X-ray diffraction, metallographic and fractographic analyses

  17. Transition Metal Silicide Nanowires Growth and Electrical Characterization

    PENG Zu-Lin; LIANG S.; DENG Luo-Gen

    2009-01-01

    We report the characterization of self-assembled epitaxially grown transition metal,Fe,Co,Ni,silicide nanowires(TM-NW)growth and electrical transport properties.NWs grown by reactive deposition epitaxy on various silicon surfaces show a dimension of 10nm by 5nm,and several micrometers in length.NW orientations strongly depend on substrate crystal orientation,and follow the substrate symmetry.By using conductive-AFM(c-AFM),the electron transport properties of one single NW were measured,the resistivity of crystalline nickel silicide NW was estimated to be 2×10~(-2) Ω·cm.

  18. Ferromagnetic semiconductor-metal transition in europium monoxide

    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 EuO1-x or Gd-doped GdxEu1-x0. 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.)

  19. Electronic Doping and Scattering by Transition Metals on Graphene

    Pi, K.; McCreary, K. M.; Bao, W.; Han, Wei; Chiang, Y. F.; Li, Yan; Tsai, S. -W.; Lau, C. N.; Kawakami, R. K.

    2009-01-01

    We investigate the effects of transition metals (TM) on the electronic doping and scattering in graphene using molecular beam epitaxy combined with in situ transport measurements. The room temperature deposition of TM onto graphene produces clusters that dope n-type for all TM investigated (Ti, Fe, Pt). We also find that the scattering by TM clusters exhibits different behavior compared to 1/r Coulomb scattering. At high coverage, Pt films are able to produce doping that is either n-type or w...

  20. LCAO-Xα calculations of transition metal clusters

    The electronic structure of some transition metal clusters (V6, Cr6, Cu6, Ag6) is studied by an approximate LCAO-Xα scheme. Energy level spectra are discussed with respect to other theoretical investigations. The density-of-states curves are represented and compared with those from band-structure calculations. The correlation between binding energies of clusters and the corresponding cohesive energies of the bulk material is shown. Furthermore, the binding energies in copper clusters versus cluster size are discussed. Finally, some experimental results according beams of copper clusters and ESR studies of matrix isolated copper clusters are explained briefly. (author)

  1. Band engineering in transition metal dichalcogenides: Stacked versus lateral heterostructures

    Guo, Yuzheng; Robertson, John

    2016-06-01

    We calculate a large difference in the band alignments for transition metal dichalcogenide (TMD) heterojunctions when arranged in the stacked layer or lateral (in-plane) geometries, using direct supercell calculations. The stacked case follows the unpinned limit of the electron affinity rule, whereas the lateral geometry follows the strongly pinned limit of alignment of charge neutrality levels. TMDs therefore provide one of the few clear tests of band alignment models, whereas three-dimensional semiconductors give less stringent tests because of accidental chemical trends in their properties.

  2. Functionalization of Two-Dimensional Transition-Metal Dichalcogenides.

    Chen, Xin; McDonald, Aidan R

    2016-07-01

    Two-dimensional (2D) layered transition-metal dichalcogenides (TMDs) are a fascinating class of nanomaterials that have the potential for application in catalysis, electronics, photonics, energy storage, and sensing. TMDs are rather inert, and thus pose problems for chemical derivatization. However, to further modify the properties of TMDs and fully harness their capabilities, routes towards their chemical functionalization must be identified. Herein, recent efforts toward the chemical (bond-forming) functionalization of 2D TMDs are critically reviewed. Recent successes are highlighted, along with areas where further detailed analyses and experimentation are required. This burgeoning field is very much in its infancy but has already provided several important breakthroughs. PMID:26848815

  3. Transition metal borides. Synthesis, characterization and superconducting properties

    A systematic study was done on the synthesis and superconducting properties of metal rich transition metal borides. Five different binary systems were investigated including the boride systems of niobium, tantalum, molybdenum, tungsten and rhenium. High temperature solid state methods were used in order to synthesize samples of different transition metal borides of the composition M2B, MB, M3B2, MB2, and M2B4. The reactions were carried out in three different furnaces with different sample containers: the electric arc (copper crucible), the high frequency induction furnace (boron nitride, tantalum or glassy carbon crucibles), and the conventional tube furnace (sealed evacuated quartz ampoules). The products obtained were characterized with X-ray powder diffractometry, scanning electron microscopy and energy-dispersive X-ray spectroscopy. Phase analyses and crystal structure refinements using the Rietveld method and based on structure models known from literature were performed. A neutron diffraction measurement was done for W2B4 to allow for a complete crystal structure determination, because of the presence of a heavy element like tungsten and a light element like boron that made it difficult to determine the accurate determination of the boron atom positions and occupancies from X-ray data. A new structure model for W2B4 was proposed. Magnetic measurements in a SQUID magnetometer down to temperatures as low as 1.8 K were performed to several of the products in order to see if the transition metal borides become superconducting at low temperatures, and the results were compared with data from literature. Superconducting properties were found for the following compounds: NbB2 (TC = 3.5 K), β-MoB (TC = 2.4 K), β-WB (TC = 2.0 K), α-WB (TC = 4.3 K), W2B4 (TC = 5.4 K), Re7B3 (TC = 2.4 K). A relationship between the superconducting properties and the compositional and structural features was discussed for metal diborides. Also it was found that there is an influence

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

    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).

  5. Nucleation and growth of noble metals on transition-metal di-tellurides

    Hla, S. W.; Marinković, V.; Prodan, A.

    1997-04-01

    Transition-metal di-tellurides (α- and β-MoTe 2 and WTe 2) were used as substrates for nucleation and growth studies of noble metals. They represent a group of chemically closely related compounds with different surface topographies. Nucleation and growth of Ag and Au at room temperature were studied by means of UHV-STM, AFM and TEM. The results revealed that the growth and orientation of these metals are influenced by the topography of the substrate surfaces. Contrary to the growth on atomically flat α-MoTe 2, there is an enhanced diffusion and nucleation along the periodic surface troughs on β-MoTe 2 and WTe 2. The topography of their (001) surfaces is responsible for the orientation of metal (112) planes being parallel to the substrate surface.)

  6. First-principles study of structural stabilities, elastic and electronic properties of transition metal monocarbides (TMCs) and mononitrides (TMNs)

    Rached, H.; Rached, D.; Benalia, S. [Laboratoire des Matériaux Magnétiques, Faculté des Sciences, Université Djillali Liabès de Sidi Bel-Abbès, Sidi Bel-Abbès 22000 (Algeria); Reshak, A.H., E-mail: maalidph@yahoo.co.uk [Institute of Complex Systems, FFPW, CENAKVA, University of South Bohemia in CB, Nove Hrady 37333 (Czech Republic); Center of Excellence Geopolymer and Green Technology, School of Material Engineering, University Malaysia Perlis, 01007 Kangar, Perlis (Malaysia); Rabah, M. [Laboratoire des Matériaux Magnétiques, Faculté des Sciences, Université Djillali Liabès de Sidi Bel-Abbès, Sidi Bel-Abbès 22000 (Algeria); Khenata, R. [Laboratoire de Physique Quantique et de Modélisation Mathématique de la Matière (LPQ3M), université de Mascara, Mascara 29000 (Algeria); Bin Omran, S. [Department of Physics and Astronomy, Faculty of Science, King Saud University, Riyadh 11451 (Saudi Arabia)

    2013-12-16

    The structural stabilities, elastic and electronic properties of 5d transition metal mononitrides (TMNs) XN with (X = Ir, Os, Re, W and Ta) and 5d transition metal monocarbides (TMCs) XC with (X = Ir, Os, Re and Ta) were investigated using the full-potential linear muffin-tin orbital (FP-LMTO) method, in the framework of the density functional theory (DFT) within the local density approximation (LDA) for the exchange correlation functional. The ground state quantities such as the lattice parameter, bulks modulus and its pressure derivatives for the six considered crystal structures, Rock-salt (B1), CsCl (B2), zinc-blend (B3), Wurtzite (B4), NiAs (B8{sub 1}) and the tungsten carbides (B{sub h}) are calculated. The elastic constants of TMNs and TMCs compounds in its different stable phases are determined by using the total energy variation with strain technique. The elastic modulus for polycrystalline materials, shear modulus (G), Young's modulus (E), and Poisson's ratio (ν) are calculated. The Debye temperature (θ{sub D}) and sound velocities (v{sub m}) were also derived from the obtained elastic modulus. The analysis of the hardness of the herein studied compounds classifies OsN – (B4 et B8{sub 1}), ReN – (B8{sub 1}), WN – (B8{sub 1}) and OsC – (B8{sub 1}) as superhard materials. Our results for the band structure and densities of states (DOS), show that TMNs and TMCs compounds in theirs energetically and mechanically stable phase has metallic characteristic with strong covalent nature Metal–Nonmetal elements. - Highlights: • Structural stabilities, elastic, electronic properties of 5d TMNs XN are investigated. • 5d TMCs XC with (X = Ir, Os, Re and Ta) were investigated. • The ground state properties for the six considered crystal structure are calculated. • The elastic constants of TMNs and TMCs in its different stable phases are determined. • The elastic modulus for polycrystalline materials, G, E, and ν are calculated.

  7. Magnetic properties of 4d transition-metal clusters

    We analyze the stability of magnetic states obtained within the tight-binding model solved by molecular dynamics for cubo-octahedral (fcc) and icosahedral clusters of 3d (Ni and Co) and 4d (Pd, Rh, and Ru) transition metals. The magnetic states are stabilized by the Hund close-quote s rule exchange interaction between the d orbitals. Taking realistic parameters deduced from band structure calculations and spectroscopic data, we obtained saturated ferromagnetism for Ni13, Co13, and Pd13 clusters, while Rh13 fcc and Ru13 clusters are partially magnetic, with an antiferromagnetic orientation of the moments on the central atoms in Ru clusters. Our results for 4d transition-metal clusters agree qualitatively with the recent experimental data and with other calculations. Metastable magnetic clusters were identified in several situations. We found a dependence of the equilibrium lattice constant on the magnetization in the considered clusters which may be explained by the character of wave functions in the cluster electronic structure. copyright 1996 The American Physical Society

  8. Electron-energy-loss spectroscopy of transition-metal carbides

    Electron-energy-loss spectroscopy (EELS) was applied to several problems dealing with the transition-metal carbides. First, narrow (200A) precipitates of TiC were identified in a single crystal of titanium diboride. Second, the carbon concentration in individual stacking faults of TaC was determined to be less than in the surrounding matrix, and the implications of this finding for crystal structure and mechanical properties were discussed. Next, thin films of amorphous carbon and TiO were studied with EELS. Experimental cross sections for C and Ti were obtained from these spectra and used for quantitative analysis of a material of known stoichiometry, V6C5 (by assuming V and Ti cross sections equal), and one of unknown stoichiometry, a cemented carbide composed of 1 to 5 μm grains of TiC/sub x/ embedded in a Ni-Mo binder. These experimental cross sections gave a C/V ratio of 0.84, very close to the expected value of 0.833, and a C/Ti ratio of 0.81 for a grain of TiC/sub x/, a reasonable value of x in these materials. Two other methods of determining cross sections were applied: calculated cross sections based on a hydrogenic model gave inaccurate results, perhaps due to the inadequacy of the model for these transition metals; and efficiency factors applied to the Bethe cross section gave reasonable results, but inferior to those from the experimental cross sections

  9. Anderson metal-insulator transitions with classical magnetic impurities

    Jung, Daniel; Kettemann, Stefan; Slevin, Keith

    2016-04-01

    We study numerically the effects of classical magnetic impurities on the Anderson metal-insulator transition. We find that a small concentration of Heisenberg impurities enhances the critical disorder amplitude Wc with increasing exchange coupling strength J . The resulting scaling with J is analyzed which supports an anomalous scaling prediction by Wegner due to the combined breaking of time-reversal and spin-rotational symmetry. Moreover, we find that the presence of magnetic impurities lowers the critical correlation length exponent ν and enhances the multifractality parameter α0. The new value of ν improves the agreement with the value measured in experiments on the metal-insulator transition (MIT) in doped semiconductors like phosphor-doped silicon, where a finite density of magnetic moments is known to exist in the vicinity of the MIT. The results are obtained by a finite-size scaling analysis of the geometric mean of the local density of states which is calculated by means of the kernel polynomial method. We establish this combination of numerical techniques as a method to obtain critical properties of disordered systems quantitatively.

  10. Isothermal compression of bcc transition metals to 100 kbar

    Pressure-volume relationships for the bcc transition metals in the groups VB (V, Nb, and Ta) and VIB (Cr, Mo, and W) were determined under hydrostatic pressure to 100 kbar at room temperature by means of x-ray diffraction, employing diamond-anvil pressure cell and the ruby (R1 line) fluorescence calibration technique. Using the measured ultrasonic K'0 values, where K0 is the bulk modulus at ambient pressure, for five metals and the deduced shock-wave K'0 value for Cr, the values of K0 for V, Nb, Ta, Mo, W, and Cr are calculated to be 1.54, 1.71, 1.94, 2.67, 3.07, and 1.93 Mbar, respectively, by least-squares fit of the experimental P-V data to the Birch-Murnaghan equation. The K0 values thus determined are in good agreement with the ultrasonic and shock-wave values for V, Nb, Ta, Mo, and W. For Cr, the K0 value (1.93 Mbar) is in agreement with the shock-wave value (1.92 Mbar) but not with the ultrasonic value (1.65 Mbar). This discrepancy can be explained in view of the paramagnetic→antiferromagnetic transition in Cr in the temperature proximity of the ultrasonic measurements (Neel temperature T/sub N/approx.311 0K at 1 bar) and by the negative pressure dependence of T/sub N/

  11. Polynuclear transition metal complexes with thiocarbohydrazide and dithiocarbamates

    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.

  12. Electronic self-energy in simple and transition metals

    Full text: In state-of-the art quasi-particle calculations of electrons in crystalline media like metals, semiconductors, and insulators, the dynamical self-energy function of the electrons Σ(r, r'; ω) plays a fundamental role. Beyond this aspect, the self-energy can also be used to calculate the Green's function (G) of the interacting electrons, and the knowledge of G directly leads to such important quantities like occupation number or momentum density distributions. For these reasons, a profound knowledge of Σ is of vital importance for many theoretical purposes. In this contribution, we present and discuss the self-energy function in the GW approximation for simple metals like Na and Al, and transition metals as Cr, Ni, and Cu. A main topic of our work is to investigate if and to what extent our results are influenced by approximations which are frequently described in the literature, namely (i) the neglect of non-diagonal elements of the self-energy and the polarisation matrix, and (ii) the use of the so-called plasmon-pole model for the inverse of the dielectric matrix. (author)

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

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

    2015-12-01

    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.

  14. On the interactions between carbon monoxide and transition metals

    The sticking of carbon monoxide on surface atoms of transition metals is a collective phenomenon: according to the adsorption process period which is considered, this phenomenon may be formally described either by the Elovich equation or essentially from a steric point of view. The process rate depends upon the nature of the metal, the carbon monoxide pressure the temperature and the population densities of the induced and fundamental energy levels of the gas-solid bond. At least one of these induced levels tends to disappear with increasing time. For a localised adsorption and taking into account the surface Rayleigh waves, the analysis of the surface entropy yields the so-called iso-kinetic temperature for thermal desorption. This temperature is correlated with the cohesive energy of the metal surface atoms. Finally, it is shown that the interactions of a low energy electron bean with adsorbed molecules - reflection and energy exchange, desorption, ionization or dissociative ionization are strongly dependent on the energy levels of the gas-solid bond and the relative populations of these levels. (author)

  15. Surface stacking faults in close-packed transition metals

    The deposition of a metallic monolayer on a close-packed surface of FCC and HCP metals can induce a surface stacking fault. The energy of such stacking faults on FCC (111) and HCP (0001) surfaces of transition metals is evaluated at 0 K with a tight-binding scheme using a continued fraction technique. Perturbative potentials near the surface are calculated using a zero charge approximation. Both homo and heteroepitaxy are considered. In the case of homoepitaxy a systematic study with the d-band filling of the substrate is carried out. It is proved that a FCC (111) surface is always in perfect registry with the substrate at 0 K. The same trend is also found for the HCP (0001) surface except for the range of d-band filling which could correspond to the elements of the IIIB column. Surface stacking fault energies are of the same order of magnitude as in the bulk. In the case of heteroepitaxy, the possibility of occurrence of surface stacking fault is discussed as a function of the d-band filling of the overlayer for a given substrate. Our conclusions are in agreement with existing experimental data. (orig.)

  16. Catalytic mechanism of transition-metal compounds on Mg hydrogen sorption reaction.

    Barkhordarian, Gagik; Klassen, Thomas; Bormann, Rüdiger

    2006-06-01

    The catalytic mechanisms of transition-metal compounds during the hydrogen sorption reaction of magnesium-based hydrides were investigated through relevant experiments. Catalytic activity was found to be influenced by four distinct physico-thermodynamic properties of the transition-metal compound: a high number of structural defects, a low stability of the compound, which however has to be high enough to avoid complete reduction of the transition metal under operating conditions, a high valence state of the transition-metal ion within the compound, and a high affinity of the transition-metal ion to hydrogen. On the basis of these results, further optimization of the selection of catalysts for improving sorption properties of magnesium-based hydrides is possible. In addition, utilization of transition-metal compounds as catalysts for other hydrogen storage materials is considered. PMID:16771356

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

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

    2014-06-01

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

  18. Functionalization of transition metal dichalcogenides with metallic nanoparticles: implications for doping and gas-sensing.

    Sarkar, Deblina; Xie, Xuejun; Kang, Jiahao; Zhang, Haojun; Liu, Wei; Navarrete, Jose; Moskovits, Martin; Banerjee, Kaustav

    2015-05-13

    Transition metal dichalcogenides (TMDs), belonging to the class of two-dimensional (2D) layered materials, have instigated a lot of interest in diverse application fields due to their unique electrical, mechanical, magnetic, and optical properties. Tuning the electrical properties of TMDs through charge transfer or doping is necessary for various optoelectronic applications. This paper presents the experimental investigation of the doping effect on TMDs, mainly focusing on molybdenum disulfide (MoS2), by metallic nanoparticles (NPs), exploring noble metals such as silver (Ag), palladium (Pd), and platinum (Pt) as well as the low workfunction metals such as scandium (Sc) and yttrium (Y) for the first time. The dependence of the doping behavior of MoS2 on the metal workfunction is demonstrated and it is shown that Pt nanoparticles can lead to as large as 137 V shift in threshold voltage of a back-gated monolayered MoS2 FET. Variation of the MoS2 FET transfer curves with the increase in the dose of NPs as well as the effect of the number of MoS2 layers on the doping characteristics are also discussed for the first time. Moreover, the doping effect on WSe2 is studied with the first demonstration of p-type doping using Pt NPs. Apart from doping, the use of metallic NP functionalized TMDs for gas sensing application is also demonstrated. PMID:25723363

  19. Quantum Spin Hall Effect and Topological Phase Transition in Two-Dimensional Square Transition Metal Dichalcogenides

    Ma, Yandong; Kou, Liangzhi; Dai, Ying; Heine, Thomas

    2015-01-01

    Two-dimensional (2D) topological insulators (TIs) hold promise for applications in spintronics based on the fact that the propagation direction of edge electrons of a 2D TI is robustly linked to their spin origination. Here, with the use of first-principles calculations, we predict a family of robust 2D TIs in monolayer square transition metal dichalcogenides (MoS2, MoSe2, MoTe2, WS2, WSe2, and WTe2). Sizeable intrinsic nontrivial bulk band gaps ranging from 24 to 187 meV are obtained, guaran...

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

    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.

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

    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.

  2. Nonequilibrium carrier dynamics in transition metal dichalcogenide semiconductors

    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.

  3. Chemisorption of ordered atomic layers on a model transition metal

    The effect of chemisorption of ordered atomic layers with p(1x1), p(2x1), c(2x2), p(2x2), p(4x1), and c(4x2) structures on the (001) surface of a tight-binding (model transition) metal is investigated within the Newns-Anderson model using the Hartree-Fock Green's function formalism and the phase shift technique. The self-consistent adatom charge q, the heat of adsorption ΔE, and the change in the electronic density of states during chemisorption are calculated for the two binding sites (on-site and centered fourfold-site). Particular attention is paid to the H/W (001) system and the results are compared with the available experimental results. It is shown that the long-range order and adsorption geometry of the overlayers are of great importance for the electronic properties of the chemisorbed systems. (author)

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

    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.

  5. An Extensive Database of Electronic Structure Calculations between Transition Metals

    Sayed, Shereef; Papaconstantopoulos, Dimitrios

    Density Functional Theory and its derived application methods, such as the Augmented Plane Wave (APW) method, have shown great success in predicting the fundamental properties of materials. In this work, we apply the APW method to explore the properties of diatomic pairs of transition metals in the CsCl structure, for all possible combinations. A total of 435 compounds have been studied. The predicted Density of States, and Band Structures are presented, along with predicted electron-phonon coupling and Stoner Criterion, in order to identify potential new superconducting or ferromagnetic materials. This work is performed to demonstrate the concept of ``high-throughput'' calculations at the crossing-point of ``Big Data'' and materials science. Us Dept of Energy.

  6. Radiation damage of transition metal carbides. Final technical report

    Dixon, G.

    1991-12-31

    In this grant period we have investigated electrical properties of transition metal carbides and radiation-induced defects produced by low-temperature electron irradiation in them. Special attention has been given to the composition VC{sub 0.88} in which the vacancies on the carbon sublattice of this fcc crystal order to produce a V{sub 8}C{sub 7} superlattice. The existence of this superlattice structure was found to make the crystal somewhat resistant to radiation damage at low doses and/or at ambient temperature. At larger doses significant changes in the resistivity are produced. Annealing effects were observed which we believe to be connected with the reconstitution of the superlattice structure.

  7. Interface of transition metal oxides at the atomic scale

    Shang, Tong-Tong; Liu, Xin-Yu; Gu, Lin

    2016-09-01

    Remarkable phenomena arise at well-defined heterostructures, composed of transition metal oxides, which is absent in the bulk counterpart, providing us a paradigm for exploring the various electron correlation effects. The functional properties of such heterostructures have attracted much attention in the microelectronic and renewable energy fields. Exotic and unexpected states of matter could arise from the reconstruction and coupling among lattice, charge, orbital and spin at the interfaces. Aberration-corrected scanning transmission electron microscopy (STEM) is a powerful tool to visualize the lattice structure and electronic structure at the atomic scale. In the present study some novel phenomena of oxide heterostructures at the atomic scale are summarized and pointed out from the perspective of electron microscopy.

  8. On holographic disorder-driven metal-insulator transitions

    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.

  9. Metal-insulator transition in three-band Hubbard model

    Dutka, J.; Kaminski, M. (Inst. of Physics, Jagiellonian Univ., Cracow (Poland)); Oles, A.M. (Inst. of Physics, Jagiellonian Univ., Cracow (Poland) Max-Planck-Inst., FKF, Stuttgart (Germany))

    1992-02-01

    We describe a transition from a metal to an antiferromagnetic (AF) insulator in the three-band Hubbard Hamiltonian for the undoped CuO{sub 2} planes of high-temperature superconductors, including local hole correlations. If the realistic parameters are used, one finds the AF ground states with magnetic moment of {approx equal}0.47{mu}{sub B} and {approx equal}0.56{mu}{sub B} for La{sub 2}CuO{sub 4} and YBa{sub 2}Cu{sub 2}O{sub 6}, respectively. Correlations and the interoxygen hopping reduce drastically the region of the AF long-range order which disappears for the doping of 0.06 hole per unit cell. (orig.).

  10. Three-particle approximation for transition-metal oxides

    Lægsgaard, J.; Svane, A.

    1997-02-01

    Quasiparticle spectra are calculated for NiO and CuO on the basis of band structures obtained within the ab initio self-interaction-corrected local-spin density (SIC-LSD) and LSD+U approximations. On-site Coulomb correlations are described by a multiband Hubbard model, which is treated within Igarashi's three-particle approximation. The transition-metal d-state spectral weight is split into a main dnL peak and a dn-1 satellite. We show that mean-field band structures in this way can lead to a good description of the experimental photoemission spectra of these compounds. The validity of the three-particle approach is investigated, and it is concluded that the method is best suited for a system which is well orbitally polarized on the mean-field level.

  11. Optical limiting of layered transition metal dichalcogenide semiconductors

    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.

  12. Induced magnetism in transition metal intercalated graphitic systems

    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.

  13. Metal-semiconductor transition of graphene nanoribbons with different addends

    Zhang, X.W., E-mail: xiaoweizhang@swust.edu.cn [State Key Laboratory Cultivation Base for Nonmetal Composites and Functional Materials, Southwest University of Science and Technology, Mianyang 621010 (China); Dai, B; Liu, J.S. [State Key Laboratory Cultivation Base for Nonmetal Composites and Functional Materials, Southwest University of Science and Technology, Mianyang 621010 (China); Yang, G.W. [State Key Laboratory of Optoelectronic Materials and Technologies, Institute of Optoelectronic and Functional Composite Materials, School of Physics Science and Engineering, Sun Yat-Sen University, Guangzhou 510275 (China)

    2012-02-15

    Using a LCAO method, which is based on spinless sp{sup 3} scheme, we have studied the electronic properties of graphene nanoribbons with zigzag edges (ZGNRs) terminated partially by methylene groups. Metal-semiconductor transition is proved when the H atoms at both sides of ZGNRs are partially substituted by methylene groups. Furthermore, when one-third of H atoms are substituted and the distribution of methylenes is symmetric, the band gap comes to about 0.59 eV, which is the widest energy gap in this work. Otherwise, when the addends at both sides are of asymmetric distribution, a band gap of only 0.21 eV is obtained. These results suggest that the addends at the edge of ZGNRs play an important role in modifying the electronic properties.

  14. Metal-semiconductor transition of graphene nanoribbons with different addends

    Zhang, X. W.; Dai, B.; Liu, J. S.; Yang, G. W.

    2012-02-01

    Using a LCAO method, which is based on spinless sp3 scheme, we have studied the electronic properties of graphene nanoribbons with zigzag edges (ZGNRs) terminated partially by methylene groups. Metal-semiconductor transition is proved when the H atoms at both sides of ZGNRs are partially substituted by methylene groups. Furthermore, when one-third of H atoms are substituted and the distribution of methylenes is symmetric, the band gap comes to about 0.59 eV, which is the widest energy gap in this work. Otherwise, when the addends at both sides are of asymmetric distribution, a band gap of only 0.21 eV is obtained. These results suggest that the addends at the edge of ZGNRs play an important role in modifying the electronic properties.

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

    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, fla...... active 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....... and stepped, which includes platinum-based alloys with ruthenium, tin, and copper, as well as nonprecious alloys, overlayer structures, and modified edges. A common lower bound on the overpotential is estimated (ca. 0.3 V). A model for bifunctional alloys is employed to investigate the nature of the...

  16. Tunable metal-insulator transitions in bilayer graphene by thermal annealing

    Kalon, Gopinadhan; Shin, Young Jun; Yang, Hyunsoo

    2012-01-01

    Tunable and highly reproducible metal-insulator transitions have been observed in bilayer graphene upon thermal annealing at 400 K under high vacuum conditions. Before annealing, the sample is metallic in the whole temperature regime of study. Upon annealing, the conductivity changes from metallic to that of an insulator and the transition temperature is a function of annealing time. The pristine metallic state can be reinstated by exposing to air thereby inducing changes in the electronic pr...

  17. Voltage-triggered Ultra-fast Metal-insulator Transition in Vanadium Dioxide Switches

    Zhou, You; Chen, Xiaonan; Ko, Changhyun; Yang, Zheng; Mouli, Chandra; Ramanathan, Shriram

    2013-01-01

    Electrically driven metal-insulator transition in vanadium dioxide (VO2) is of interest in emerging memory devices, neural computation, and high speed electronics. We report on the fabrication of out-of-plane VO2 metal-insulator-metal (MIM) structures and reproducible high-speed switching measurements in these two-terminal devices. We have observed a clear correlation between electrically-driven ON/OFF current ratio and thermally-induced resistance change during metal-insulator transition. It...

  18. Transition Metal Substitution Effects on Metal-to-Polyoxometalate Charge Transfer.

    Glass, Elliot N; Fielden, John; Huang, Zhuangqun; Xiang, Xu; Musaev, Djamaladdin G; Lian, Tianquan; Hill, Craig L

    2016-05-01

    A series of hetero-bimetallic transition metal-substituted polyoxometalates (TMSPs) were synthesized based on the Co(II)-centered ligand [Co(II)W11O39](10-). The eight complex series, [Co(II)(M(x)OHy)W11O39]((12-x-y)-) (M(x)OHy = V(IV)O, Cr(III)(OH2), Mn(II)(OH2), Fe(III)(OH2), Co(II)(OH2), Ni(II)(OH2), Cu(II)(OH2), Zn(II)(OH2)), of which six are reported for the first time, was synthesized starting from [Co(III)W11O39](9-) and studied using spectroscopic, electrochemical, and computational techniques to evaluate the influence of substituted transition metals on the photodynamics of the metal-to-polyoxometalate charge transfer (MPCT) transition. The bimetallic complexes all show higher visible light absorption than the plenary [Co(II)W12O40](6-) and demonstrate the same MPCT transition as the plenary complex, but they have shorter excited-state lifetimes (sub-300 ps in aqueous media). The decreased lifetimes are rationalized on the basis of nonradiative relaxation due to coordinating aqua ligands, increased interaction with cations due to increased negative charge, and the energy gap law, with the strongest single factor appearing to be the charge on the anion. The most promising results are from the Cr- and Fe-substituted systems, which retain excited-state lifetimes at least 50% of that of [Co(II)W12O40](6-) while more than tripling the absorbance at 400 nm. PMID:27082443

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

    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.

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

    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.

  1. Synthesis, characterization and formation process of transition metal oxide nanotubes using carbon nanofibers as templates

    Mono and binary transition metal oxide nanotubes could be synthesized by the immersion of carbon nanofiber templates into metal nitrate solutions and removal of the templates by heat treatment in air. The transition metal oxide nanotubes were composed of nano-crystallites of metal oxides. The functional groups on the carbon nanofiber templates were essential for the coating of these templates: they acted as adsorption sites for the metal nitrates, ensuring a uniform metal oxide coating. During the removal of the carbon nanofiber templates by calcination in air, the metal oxide coatings promoted the combustion reaction between the carbon nanofibers and oxygen. - Graphical abstract: Mono and binary transition metal-oxide nanotubes could be synthesized by the immersion of carbon nanofiber templates into metal nitrate solutions and removal of the templates by heat treatment in air.

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

    Farmanbar, Mojtaba; Amlaki, Taher; Brocks, Geert

    2016-05-01

    The semiconducting two-dimensional transition metal dichalcogenides MX 2 show an abundance of one-dimensional metallic edges and grain boundaries. Standard techniques for calculating edge states typically model nanoribbons, and require the use of supercells. In this paper, we formulate a Green's function technique for calculating edge states of (semi-)infinite two-dimensional systems with a single well-defined edge or grain boundary. We express Green's functions in terms of Bloch matrices, constructed from the solutions of a quadratic eigenvalue equation. The technique can be applied to any localized basis representation of the Hamiltonian. Here, we use it to calculate edge states of MX 2 monolayers by means of tight-binding models. Aside from the basic zigzag and armchair edges, we study edges with a more general orientation, structurally modifed edges, and grain boundaries. A simple three-band model captures an important part of the edge electronic structures. An 11-band model comprising all valence orbitals of the M and X atoms is required to obtain all edge states with energies in the MX 2 band gap. Here, states of odd symmetry with respect to a mirror plane through the layer of M atoms have a dangling-bond character, and tend to pin the Fermi level.

  3. The metal-insulator transition in high-Tc cuprates -An unusual quantum transition

    The Hilbert spaces representing the quantum states in the CuO2 planes are not spanned by crystal symmetry adapted basis states, but by self-consistently renormalized states which form compound systems of Hilbert subspaces. In addition, these self-consistent basis representations are not necessarily stationary in time but behave dynamic in many respects. In particular, the coordinate systems of the Hilbert subspaces form a definite dynamic relative state in space and time, thus the coordinate system itself becomes a variable. This implicates a deterministic space-time relation of quantum states and the quantization of time by an internal time constant, the eigentime teiDCBF. In undoped and hole doped CuO2 planes teiDCBF occurs as a conservation quantity, whereas under electron doping a partial fluid exists in which teiDCBF does not occur as quantized quantity. The deterministic space-time behaviour of the Hilbert subspaces represents the emergence of a classical space-time structure in quantum systems. The metal-insulator transition in high-Tc cuprates, usually attributed to an antiferromagnetic Mott transition, results here from an additional splitting into Hilbert subspaces. The transition from the insulator to the conductor is causally related to coordinate transformations from the copper to the oxygen sites. The antiferromagnetism in the CuO2 planes is not caused by the half-filled valence bands, as usually assumed, but is created by off-diagonal spin compensations within filled bands.

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

    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

  5. Surface states, surface metal-insulator, and surface insulator-metal transitions

    I present an informal discussion of various cases where two-dimensional surface metal-insulator structural and charge-density-wave instabilities driven by partly filled surface states have been advocated. These include reconstructions of clean semiconductor surfaces and of W(100) and Mo(100), as well as anomalies on the hydrogen-covered surfaces H/W(110) and H/Mo(110), and possibly alkali-covered surfaces such as K/Cu(111). In addition I will also discuss the opposite type of phenomena, namely surface insulator-metal transitions, which can be argued to occur on α-Ga(001), high-temperature Ge(111), and probably Be(0001). (author). 112 refs, 1 fig

  6. X-ray absorption to determine the metal oxidation state of transition metal compounds

    Jiménez-Mier, J.; Olalde-Velasco, P.; Carabalí-Sandoval, G.; Herrera-Pérez, G.; Chavira, E.; Yang, W.-L.; Denlinger, J.

    2013-07-01

    We present three examples where x-ray absorption at the transition metal L2,3 edges is used to investigate the valence states of various strongly correlated (SC) and technological relevant materials. Comparison with ligand field multiplet calculations is needed to determine the metal oxidation states. The examples are CrF2, the La1-xSrxCoO3 family and YVO3. For CrF2 the results indicate a disproportionation reaction that generates Cr+, Cr2+ and Cr3+ in different proportions that can be quantified directly from the x-ray spectra. Additionally, it is shown that Co2+ is present in the catalytic La1-xSrxCoO3 perovskite family. Finally, surface effects that change the vanadium valence are also found in YVO3 nanocrystals.

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

    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.

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

    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 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. Synthesis and characterization of two dimensional transition metal dichalcogenides

    Gao, Jian

    Two-dimensional transition metal dichalcogenides (TMDs) are an emerging class of atomically thin semiconductors that show potential in next-generation electronics, optoelectronics, and energy storage batteries. The successful synthesis and doping of TMDs is the key to their applications. I have synthesized monolayer MoS2, WS2, and multilayer ReS2 flakes by CVD, and studied an unprecedented one-pot synthesis for transition-metal substitution doping in large-area, synthetic monolayer TMDs. Electron microscopy, optical and electronic transport characterization and ab initio calculations indicate that our doping strategy preserves the attractive qualities of TMD monolayers, including semiconducting transport and strong direct-gap luminescence. The Re doping of MoS2 greatly improve the contact quality (one of the biggest issue in TMDs) and the FET shows Ohmic contact even at low temperature (4K). These results potentially enables next-generation optoelectronic technology in the atomically-thin regime. Besides, TMDs are generally considered to be 'air-stable', however, we have found that they exhibit poor long-term stability in air in morphology, chemical states, photo-emission, and demonstrated a potential solution to this problem by encapsulation of the monolayer sheet with transparent parylene C. Synthetic TMDs tend to grow parallel to the growth substrate, however, high performance energy conversion and storage devices prefer flakes with high exposed surface area. Therefore by choosing the right precursors and appropriate tuning of the CVD growth conditions, we have grown vertical ReS2 nanosheets on various growth substrates. We show that these structural features of the vertically grown ReS2 sheets can be exploited to significantly improve their performance as electrochemical catalysts in Lithium-Sulfur (Li-S) batteries and in hydrogen evolution reactions (HER). After 300 cycles, the specific capacity of the Li-S battery with vertical-ReS2 catalyst is retained above

  10. Search for positron localization near transition-metal solutes of negative effective charge in Ni and Cu

    Results of an early (1973) angular correlation (ACAR) study of dilute (0.5 at.%) Cu based alloys by a Japanese group were interpreted in terms of an attraction of e+ by transition metal solutes of effective negative charge. Doppler Broadening (DB) measurements reveal no such an effect for Cu(Mn) and Cu(Ni) solid solutions as well as for Ni alloys with 3d, 4d and 5d transition metal solutes (0.1 to 1.5 at.%) i.e. no evidence of e+ localization near these impurities is seen. Our results strongly suggest that the ACAR results are due to the metallurgical state of the samples. In contrast, significant DB lineshape parameter variations, observed for our Ni(Zr) alloys, are attributed to positron trapping in and near Ni5Zr precipitates. Our DB results for a series of Ni(Au) alloys are understood in terms of a combination of the effect of an overall lattice expansion and a positron preference for clusters of Au atoms. The above comparison between DB and ACAR results is supported by our 'spin polarized' DB results for a (001) Ni single crystal which resemble those obtained by other groups using a 'spin polarized' 2D-ACAR technique. (orig.)

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

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

    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.

  13. Thermal Low-Temperature Properties of Rare Earth Transition Metal Borocarbides

    Lipp, Dieter

    2002-01-01

    The present work reports on thermal low-temperature properties of rare earth transition metal borocarbides such as specific heat, thermal conductivity and thermopower. The influence of structural disorder, caused by stoichiometric variations and substitutions of the rare earth element or the transition metal, on the thermal and superconducting low-temperature properties is investigated. The structural disorder results in the reduction of the superconducting transition temperature Tc, of the S...

  14. The chromospheric and transition layer emission of stars with different metal abundances

    Boehm-Vitense, E.

    1981-01-01

    Preliminary results on observations of chromospheric and transition layer emission of stars with different metal abundances are reported. Metal deficient stars generally show reduced emission in the Mg II resonance lines and also in the other chromospheric and transition layer emission lines. This is interpreted as showing that energy fluxes other than acoustic fluxes must at least be coresponsible for the coronal and transition layer heating.

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

    Mavrikakis, Manos; Hansen, Lars Bruno; Mortensen, Jens Jørgen; Hammer, Bjørk; Nørskov, Jens Kehlet

    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 of...

  16. Recognition- and Reactivity-Based Fluorescent Probes for Studying Transition Metal Signaling in Living Systems

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

    2015-01-01

    Conspectus 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 enzy...

  17. Insulator/metal phase transition and colossal magnetoresistance in holographic model

    Cai, Rong-Gen

    2015-01-01

    We construct a gravity dual for insulator/metal phase transition and colossal magnetoresistance (CMR) effect found in some manganese oxides materials. The computations shows a remarkable magnetic-field-sensitive DC resistivity peak appearing at the Curie temperature, where an insulator/metal phase transition happens and the magnetoresistance is scaled with the square of field-induced magnetization. We find that metallic and insulating phases coexist below the Curie point and the relation with the electronic phase separation is discussed.

  18. Computational Study of Metal Contacts to Monolayer Transition-Metal Dichalcogenide Semiconductors

    Kang, Jiahao; Liu, Wei; Sarkar, Deblina; Jena, Debdeep; Banerjee, Kaustav

    2014-07-01

    Among various 2D materials, monolayer transition-metal dichalcogenide (mTMD) semiconductors with intrinsic band gaps (1-2 eV) are considered promising candidates for channel materials in next-generation transistors. Low-resistance metal contacts to mTMDs are crucial because currently they limit mTMD device performances. Hence, a comprehensive understanding of the atomistic nature of metal contacts to these 2D crystals is a fundamental challenge, which is not adequately addressed at present. In this paper, we report a systematic study of metal-mTMD contacts with different geometries (top contacts and edge contacts) by ab initio density-functional theory calculations, integrated with Mulliken population analysis and a semiempirical van der Waals dispersion potential model (which is critical for 2D materials and not well treated before). Particularly, In, Ti, Au, and Pd, contacts to monolayer MoS2 and WSe2 as well as Mo-MoS2 and W-WSe2 contacts are evaluated and categorized, based on their tunnel barriers, Schottky barriers, and orbital overlaps. Moreover, going beyond Schottky theory, new physics in such contact interfaces is revealed, such as the metallization of mTMDs and abnormal Fermi level pinning. Among the top contacts to MoS2, Ti and Mo show great potential to form favorable top contacts, which are both n-type contacts, while for top contacts to WSe2, W or Pd exhibits the most advantages as an n- or p-type contact, respectively. Moreover, we find that edge contacts can be highly advantageous compared to top contacts in terms of electron injection efficiency. Our formalism and the results provide guidelines that would be invaluable for designing novel 2D semiconductor devices.

  19. Magnetic Exchange Couplings in Transition Metal Complexes from DFT

    Peralta, Juan

    In this talk I will review our current efforts for the evaluation of magnetic exchange couplings in transition metal complexes from density functional theory. I will focus on the performance of different DFT approximations, including a variety of hybrid density functionals, and show that hybrid density functionals containing approximately 30% Hartree-Fock type exchange are in general among the best choice in terms of accuracy. I will also describe a novel computational method to evaluate exchange coupling parameters using analytic self-consistent linear response theory. This method avoids the explicit evaluation of energy differences, which can become impractical for large systems. Our approach is based on the evaluation of the transversal magnetic torque between two magnetic centers for a given spin configuration using explicit constraints of the local magnetization direction via Lagrange multipliers. This method is applicable in combination with any modern density functional with a noncollinear spin generalization and can be utilized as a ``black-box''. I will show proof-of-concept calculations in frustrated Fe7IIIdisk-shaped clusters, and dinuclear CuII, FeIII, and heteronuclear complexes. NSF DMR-1206920.

  20. Self-Limiting Layer Synthesis of Transition Metal Dichalcogenides

    Kim, Youngjun; Song, Jeong-Gyu; Park, Yong Ju; Ryu, Gyeong Hee; Lee, Su Jeong; Kim, Jin Sung; Jeon, Pyo Jin; Lee, Chang Wan; Woo, Whang Je; Choi, Taejin; Jung, Hanearl; Lee, Han-Bo-Ram; Myoung, Jae-Min; Im, Seongil; Lee, Zonghoon; Ahn, Jong-Hyun; Park, Jusang; Kim, Hyungjun

    2016-01-01

    This work reports the self-limiting synthesis of an atomically thin, two dimensional transition metal dichalcogenides (2D TMDCs) in the form of MoS2. The layer controllability and large area uniformity essential for electronic and optical device applications is achieved through atomic layer deposition in what is named self-limiting layer synthesis (SLS); a process in which the number of layers is determined by temperature rather than process cycles due to the chemically inactive nature of 2D MoS2. Through spectroscopic and microscopic investigation it is demonstrated that SLS is capable of producing MoS2 with a wafer-scale (~10 cm) layer-number uniformity of more than 90%, which when used as the active layer in a top-gated field-effect transistor, produces an on/off ratio as high as 108. This process is also shown to be applicable to WSe2, with a PN diode fabricated from a MoS2/WSe2 heterostructure exhibiting gate-tunable rectifying characteristics.

  1. Strain engineering of electronic properties of transition metal dichalcogenide monolayers

    Maniadaki, Aristea E.; Kopidakis, Georgios; Remediakis, Ioannis N.

    2016-02-01

    We present Density Functional Theory (DFT) results for the electronic and dielectric properties of single-layer (2D) semiconducting transition metal dichalcogenides MX2 (M=Mo, W; X=S, Se, Te) under isotropic, uniaxial (along the zigzag and armchair directions), and shear strain. Electronic band gaps decrease while dielectric constants increase for heavier chalcogens X. The direct gaps of equilibrium structures often become indirect under certain types of strain, depending on the material. The effects of strain and of broken symmetry on the band structure are discussed. Gaps reach maximum values at small compressive strains or in equilibrium, and decrease with larger strains. In-plane dielectric constants generally increase with strain, reaching a minimum value at small compressive strains. The out-of-plane constants exhibit a similar behavior under shear strain but under isotropic and uniaxial strain they increase with compression and decrease with tension, thus exhibiting a monotonic behavior. These DFT results are theoretically explained using only structural parameters and equilibrium dielectric constants. Our findings are consistent with available experimental data.

  2. Nano tubular Transition Metal Oxide for Hydrogen Production

    TiO2, transition metal oxide nano tubes were successfully grown by anodizing of titanium foil (Ti) in ethylene glycol electrolyte containing 5wt. % hydrogen peroxide and 5wt. % ammonium fluoride for 60 minutes at 60V. It was found such electrochemical condition resulted in the formation of nano tube with average diameter of 90nm and length of 6.6 μm. These samples were used to study the effect of W loading by RF sputtering on TiO2 nano tubes. Amorphous TiO2 nano tube substrate leads to enhance incorporation of W instead of anatase. Therefore for the entire study, W was sputtered on amorphous TiO2 nano tube substrate. TiO2 nano tube sputtered for 1 minute resulted in the formation of W-O-Ti while beyond this point (10 minutes); it accumulates to form a self independent structure of WO3 on the surface of the nano tubes. TiO2 nano tube sputtered for 1 minute at 150 W and annealed at 450 degree Celsius exhibited best photocurrent density (1.4 mA/ cm2) with photo conversion efficiency of 2.5 %. The reason for such behavior is attributed to W6+ ions allows for electron traps that suppress electron hole recombination and exploit the lower band gap of material to produce a water splitting process by increasing the charge separation and extending the energy range of photoexcitation for the system. (author)

  3. Strain engineered optoelectronic properties of transition metal dichalcogenides lateral heterostructures

    Lee, Jaekwang; Yoon, Mina

    2015-03-01

    Most three-dimensional bulk-scale materials rarely survive beyond 1% strain, while recently spotlighted two-dimensional (2-D) materials can sustain a high elastic strain (up to 10%) to optimize optical quantities such as band gaps and absorption spectra governing optoelectronic device performance. Despite the enormous interest in strained 2-D materials, most researches are focused on single materials or vertical heterostructures where precise control of stacking orientation is challenging. Here, using first-principles density-functional calculations, we explore how uniaxial tensile strains modify overall electronic and optical properties of transition metal dichalcogenides lateral heterostructures, such as MoX2/WX2 (X =S, Se). Based on the detailed optoelectronic information, we predict the optimal strain condition for maximal power efficiency. Furthermore, we find that uniaxial tensile strain readily develops a continuously varying direct-bandgap across the lateral heterojunctions, which results in the broad range absorption of solar spectrum useful for future optoelectronic devices. This research was conducted at the CNMS, which is sponsored at Oak Ridge National Laboratory (ORNL) by the Office of Basic Energy Sciences, U.S. Department of Energy; a portion of theory work was supported by the LDRD Program of ORNL.

  4. APCVD Transition Metal Oxides - Functional Layers in "Smart windows"

    Gesheva, K. A.; Ivanova, T. M.; Bodurov, G. K.

    2014-11-01

    Transition metal oxides (TMO) exhibit electrochromic effect. Under a small voltage they change their optical transmittance from transparent to collored (absorbing) state. The individual material can manifest its electrochromic properties only when it is part of electrochromic (EC) multilayer system. Smart window is controlling the energy of solar flux entering the building or car and makes the interiors comfortable and energy utilization more effective. Recently the efforts of material researchers in this field are directed to price decreasing. APCVD technology is considered as promissing as this process permits flowthrough large-scale production process. The paper presents results on device optimization based on WO3-MoO3 working electrode. Extensive research reveals that WO3-MoO3 structure combines positive features of single oxides: excellent electrochromic performance of WO3 and better kinetic properties of MoO3 deposition. The achieved color efficiency of APCVD WO3-MoO3 films is 200cm2/C and optical modulation of 65-70% are practically favorable electrochromic characteristics. To respond to low cost requirement, the expensive hexacarbonyl can be replaced with acetylacetonate. We have started with this precursor to fabricate mixed WxV1-xO3 films. The films possess excellent surface coverage and high growth-rate. CVD deposition of VO2, a promissing thermochromic thin film material is also presented.

  5. Induce magnetism into silicene by embedding transition-metal atoms

    Sun, Xiaotian; Wang, Lu, E-mail: lwang22@suda.edu.cn, E-mail: yyli@suda.edu.cn; Lin, Haiping; Hou, Tingjun; Li, Youyong, E-mail: lwang22@suda.edu.cn, E-mail: yyli@suda.edu.cn [Institute of Functional Nano and Soft Materials Laboratory (FUNSOM), Jiangsu Key Laboratory for Carbon-based Functional Materials and Devices, and Collaborative Innovation Center of Suzhou Nano Science and Technology, Soochow University, Suzhou 215123, Jiangsu (China)

    2015-06-01

    Embedding transition-metal (TM) atoms into nonmagnetic nanomaterials is an efficient way to induce magnetism. Using first-principles calculations, we systematically investigated the structural stability and magnetic properties of TM atoms from Sc to Zn embedded into silicene with single vacancy (SV) and double vacancies (DV). The binding energies for different TM atoms correlate with the TM d-shell electrons. Sc, Ti, and Co show the largest binding energies of as high as 6 eV, while Zn has the lowest binding energy of about 2 eV. The magnetic moment of silicene can be modulated by embedding TM atoms from V to Co, which mainly comes from the 3d orbitals of TM along with partly contributions from the neighboring Si atoms. Fe atom on SV and Mn atom on DV have the largest magnetic moment of more than 3 μB. In addition, we find that doping of N or C atoms on the vacancy site could greatly enhance the magnetism of the systems. Our results provide a promising approach to design silicene-based nanoelectronics and spintronics device.

  6. Antiferromagnetism and metal-insulator transition in high temperature superconductors

    The ground state of the three band Hubbard Hamiltonian for the CuO2 planes of high temperature superconductors is investigated using local ansatz approach which includes local correlations between holes. For sufficiently large Coulomb interaction, U, or charge transfer energy, Δ, one finds a transition from a nonmagnetic metal to an antiferromagnetic (AF) insulator. If the parameters determined by the local density approximation are used, the ground state is a charge-transfer antiferromagnet, with the magnetic moments of m=0.47μΒ and 0.56μΒ, for La2CuO4 and YBa2Cu3O6, respectively. Correlations and the presence of interoxygen hopping reduce drastically the stability of the AF long-range order which disappears at the doping of either 0.06 hole or 0.08 electron, respectively. The effective mass is enhanced by a factor less than two due to correlations. (author). 27 refs.; 5 figs

  7. Transition Metal Trichalcogenides as Novel Layered Nano Species

    Fedorov V.E.

    2013-09-01

    Full Text Available In search for new materials for nanoelectronics, many efforts have been put into development of chemistry and physics of graphene, and, more recently, of other inorganic layered compounds having a bandgap (h-BN, MoS2 etc.. Here we introduce a new view on the family of transition metal trichalcogenides MQ3 (M=Ti, Zr, Nb, Ta; Q=S, Se, which were earlier considered as quasi-one-dimensional systems, and demonstrate that they also may be regarded as layered species suitable for exfoliation by a chemical method. Stable, concentrated colloidal dispersions of high-quality crystalline NbS3 and NbSe3 nanoribbons down to mono- and few-layer-thick are prepared by ultrasonic treatment of the bulk compound in several common organic solvents (DMF, NMP, CH3CN, iPrOH, H2O/EtOH. The dispersions and thin films prepared from them by vacuum filtration or spraying are characterized by a set of physical-chemical methods. Current-voltage characteristics of the NbS3 films show that charge carrier mobility is as high as 1200 – 2400 cm2V-1s-1, exceeding that of MoS2 and making NbQ3 promising potential candidates for field-effect transistors.

  8. Quasi phase transition model of shear bands in metallic glasses

    Liu Zengqian [Key Laboratory of Aerospace Materials and Performance, School of Materials Science and Engineering, Beihang University, Beijing 100191 (China); Li Ran, E-mail: liran@buaa.edu.cn [Key Laboratory of Aerospace Materials and Performance, School of Materials Science and Engineering, Beihang University, Beijing 100191 (China); Wang Gang [Department of Materials Science and Engineering, Shanghai University, Shanghai (China); Wu Sujun; Lu Xuyang [Key Laboratory of Aerospace Materials and Performance, School of Materials Science and Engineering, Beihang University, Beijing 100191 (China); Zhang Tao, E-mail: zhangtao@buaa.edu.cn [Key Laboratory of Aerospace Materials and Performance, School of Materials Science and Engineering, Beihang University, Beijing 100191 (China)

    2011-11-15

    A quasi phase transition model of shear bands in metallic glasses (MGs) is presented from the thermodynamic viewpoint. Energy changes during shear banding in a sample-machine system are analyzed following fundamental energy theorems. Three characteristic parameters, i.e. the critical initiation energy {Delta}G{sub c}, the shear band stability index k{sub 0}, and the critical shear band length l{sub c}, are derived to elucidate the initiation and propagation of shear bands. The criteria for good plasticity in MGs with predominant thermodynamic arrest of shear bands are proposed as low {Delta}G{sub c}, large k{sub 0}, and small l{sub c}. The model, combined with experimental results, is used to analyze some controversial phenomena of deformation behavior in MGs, such as the size effect, the effect of testing machine stiffness and the relationship between elastic modulus and plasticity. This study has important implications for a fundamental understanding of shear banding as well as deformation mechanisms in MGs and provides a theoretical basis for improving the ductility of MGs.

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

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

    2016-05-01

    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. PMID:27141556

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

    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.

  11. Surface Phonon Dispersion of the Layered Transition-metal Oxides

    Zhang, J.; Ismail; Matzdorf, R.; Plummer, E. W.; Kimura, T.; Tokura, Y.

    2000-03-01

    Transition-metal oxides exhibit strong coupling between the charge and spin of the electrons and the lattice. Creating a surface by cleaving a single crystal breaks the symmetry of the lattice and disturbs the correlated system without changing the stoichiometry, providing the opportunity to study the response of electronic, structural, and magnetic properties. We have utilized electron-energy loss sprectroscopy (EELS) to study the electronic and lattice excitations of the Sr_2RuO4 and La_0.5Sr_1.5MnO4 surfaces. For both of these materials there are many more than three modes; three dominate surface optical phonons with small dispersion and with higher energies compared to those in the bulk materials. However, these phonons show completely different temperature dependence for different samples. The surface phonons become soft for Sr_2RuO4 while they become stiff for La_0.5Sr_1.5MnO4 with increasing temparature. The change of phonon energy of La_0.5Sr_1.5MnO4 with temperature is also in opposite direction to that of (La, Ca)MnO_4( Zhang et al., Surf. Sci. 393, 64(1997) * LMER Corp. for U.S. DOE under contract No. DE-AC05-96OR22464). These behaviors will be discussed in terms of the electronic, magnetic, and structural properties.

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

    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.

  13. Defect engineering of two-dimensional transition metal dichalcogenides

    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.

  14. Nature of the Metallization Transition in Solid Hydrogen

    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.

  15. Defect-induced semiconductor to metal transition in graphene monoxide.

    Woo, Jungwook; Yun, Kyung-Han; Cho, Sung Beom; Chung, Yong-Chae

    2014-07-14

    This study investigates the influence of point defects on the geometric and electronic structure of graphene monoxide (GMO) via density functional theory calculations. In aspects of defect formation energy, GMOs with oxygen vacancies and bridge interstitial defects are more likely to form when compared to GMOs with defects such as carbon vacancies and hollow interstitial defects. It was also found that the oxygen vacancy or the hollow interstitial defect induces local tensile strain around the defective site and this strain increases the band gap energy of the defective GMO. In addition, the band gaps of GMO with carbon vacancies or bridge interstitial defects decreased mainly due to the dangling bonds, not due to the strain effect. It is noted that the dangling bond derived from the defects forms the defect-level in the band gap of GMO. The semiconductor to metal transition by the band gap change (0-0.7 eV) implies the possibility for band gap engineering of GMO by vacancies and interstitial defects. PMID:24886723

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

    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

  17. Metal-insulator transition in NaxWO3: Photoemission spectromicroscopy study

    We have investigated the validity of percolation model, which is quite often invoked to explain the metal-insulator transition in sodium tungsten bronzes, NaxWO3 by photoelectron spectromicroscopy. The spatially resolved direct spectromicroscopic probing on both the insulating and metallic phases of high quality single crystals of NaxWO3 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 NaxWO3

  18. Variation of optical conductivity spectra in the course of bandwidth-controlled metal-insulator transitions in pyrochlore iridates

    Ueda, K.; Fujioka, J.; Tokura, Y.

    2016-06-01

    We spectroscopically investigate a series of pyrochlore iridates R2Ir2O7 (R : rare-earth and Y ions) where the metal-insulator transitions are induced by systematic bandwidth control via chemical substitutions of R ions. We establish the phase diagram of R2Ir2O7 , as endorsed by the variation of the optical conductivity spectra, in which the competing phases including paramagnetic insulator (PI), paramagnetic metal (PM), and antiferromagnetic insulator (AFI) show up as a function of bandwidth and temperature. For small R -ionic radius (R = Y-Sm), i.e., strongly correlated region, pronounced peaks on the edge of the optical gap are discerned below the magnetic transition temperature TN, which is attributable to exciton and magnon sideband absorptions. It turns out that the estimated nearest-neighbor exchange interaction increases as R -ionic radius increases, whereas TN monotonically decreases, indicating that the all-in all-out magnetic order arises from the interplay among several exchange interactions inherent to extended 5 d orbitals on the frustrated lattice. For larger R -ionic radius (R = Sm-Pr), i.e., relatively weakly correlated region, the optical conductivity spectra markedly change below 0.3 eV in the course of PM-AFI transition, implying that the magnetic order induces the insulating state. In particular, we have found distinct electrodynamics in the composition of R =Nd0.5Pr0.5 which is located on the boundary of the quantum PM-AFI transition, pointing to the possible emergence of unconventional topological electronic phases related possibly to the correlated Weyl electrons.

  19. Ferromagnetism and metal-half-metal-insulator transitions in a frustrated periodic Anderson-like organic polymer

    The ferromagnetism and quantum phase transitions of a periodic Anderson-like organic polymer, in which the next-nearest-neighboring hopping results in frustration, are investigated by means of many-body Green's function theory. It is found that the ground state lies in half-metallic and paramagnetic metallic states for weak and relatively strong frustrations, respectively. At finite temperatures, a ferrimagnetic order and two different ferromagnetic phases are unveiled. In a magnetic field, in addition to 1/3 magnetization plateau, it presents three cusps and three critical fields indicating metal-half-metal and half-metal-insulator transitions, respectively, which are closely related to the energy bands controlled by the field. - Highlights: • The ferromagnetism and quantum phase transitions of a frustrated periodic Anderson-like organic polymer are investigated by Green's function theory. • At finite temperatures, a ferrimagnetic order and two different ferromagnetic phases are unveiled. • In a magnetic field, we reveal the metal-half-metal and half-metal-insulator transitions

  20. The biological chemistry of the transition metal "transportome" of Cupriavidus metallidurans.

    Nies, Dietrich H

    2016-05-01

    This review tries to illuminate how the bacterium Cupriavidus metallidurans CH34 is able to allocate essential transition metal cations to their target proteins although these metals have similar charge-to-surface ratios and chemical features, exert toxic effects, compete with each other, and occur in the bacterial environment over a huge range of concentrations and speciations. Central to this ability is the "transportome", the totality of all interacting metal import and export systems, which, as an emergent feature, transforms the environmental metal content and speciation into the cellular metal mélange. In a kinetic flow equilibrium resulting from controlled uptake and efflux reactions, the periplasmic and cytoplasmic metal content is adjusted in a way that minimizes toxic effects. A central core function of the transportome is to shape the metal ion composition using high-rate and low-specificity reactions to avoid time and/or energy-requiring metal discrimination reactions. This core is augmented by metal-specific channels that may even deliver metals all the way from outside of the cell to the cytoplasm. This review begins with a description of the basic chemical features of transition metal cations and the biochemical consequences of these attributes, and which transition metals are available to C. metallidurans. It then illustrates how the environment influences the metal content and speciation, and how the transportome adjusts this metal content. It concludes with an outlook on the fate of metals in the cytoplasm. By generalization, insights coming from C. metallidurans shed light on multiple transition metal homoeostatic mechanisms in all kinds of bacteria including pathogenic species, where the "battle" for metals is an important part of the host-pathogen interaction. PMID:27065183

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

    Lybye, D.; Mogensen, Mogens Bjerg

    2007-01-01

    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 of the...... host lattice and b) the preferred six coordination compared to the desired eight-fold coordination of the fluorite structure. Particular interest is paid to the solubility of the transition metal ions and to the conductivity of the resulting material. Indium is not a transition metal but due to the......Zirconia compounds stabilised with rare-earth metal oxides like yttria, ytterbia and scandia are known to be good oxide ion conductors suitable as electrolyte material in solid oxide fuel cells. However. stabilised zirconia with high oxide ion conductivity is often only metastable at fuel cell...

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

    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.

  3. Oxide Wizard: an EELS application to characterize the white lines of transition metal edges.

    Yedra, Lluís; Xuriguera, Elena; Estrader, Marta; López-Ortega, Alberto; Baró, Maria D; Nogués, Josep; Roldan, Manuel; Varela, Maria; Estradé, Sònia; Peiró, Francesca

    2014-06-01

    Physicochemical properties of transition metal oxides are directly determined by the oxidation state of the metallic cations. To address the increasing need to accurately evaluate the oxidation states of transition metal oxide systems at the nanoscale, here we present "Oxide Wizard." This script for Digital Micrograph characterizes the energy-loss near-edge structure and the position of the transition metal edges in the electron energy-loss spectrum. These characteristics of the edges can be linked to the oxidation states of transition metals with high spatial resolution. The power of the script is demonstrated by mapping manganese oxidation states in Fe3O4/Mn3O4 core/shell nanoparticles with sub-nanometer resolution in real space. PMID:24750576

  4. Chemistry of Two-Dimensional Transition Metal Carbides (MXenes)

    Mashtalir, Olha

    With consumer trends pushing toward smaller, faster, more flexible, multitasking devices, researchers striving to meet these needs have targeted two-dimensional (2D) materials---and graphene in particular---as holding the most promise for use in advanced applications. But in 2011, a significant interest has been triggered by a newly discovered family of novel 2D materials---layered transitional metal carbides and carbonitrides, named MXenes. Those compounds were of general formula Mn+1 XnTx, where M stands for metal atom, X is C and/or N, n = 1, 2 or 3, and Tx represents surface groups. Being initially suggested as a material for electrical energy storage systems, MXenes' properties and their potential applications have not been explored. This work is the first complete study of MXenes' chemistry that sheds light on the chemical composition, structure and properties of these novel materials and possible routes of its modification. The research was focused on 2D titanium carbide, Ti3C2Tx, chosen as the representative of the MXene family. The kinetic study of Ti 3C2Tx synthesis discovered the main synthesis parameters, viz. temperature, time and particle size, that affect the etching process and define the quality of final product. MXenes were found to be able to spontaneously accommodate various ions and small organic molecules between the layers leading to preopening of the structure. A major challenge of large scale production of delaminated, atomically thin 2D MXene layers was solved with two delamination techniques involving dimethyl sulfoxide and isopropyl amine pre-intercalation followed by sonication in water. Ti3C2Tx was also found to possess adsorptive and photocatalytic properties, revealing its potential for environmental applications. It also showed limited stability in water and in the presence of oxygen, providing important practical information on proper handling and storage of MXene materials. Completion of this work allowed the performance of energy

  5. Laser surface alloying of aluminium-transition metal alloys

    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.

  6. Noncollinear magnetism in surfaces and interfaces of transition metals

    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.)

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

    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.

  8. A metal insulator transition in YbFe4Sb12 granular thin films

    Results are reported for YbFe4Sb12 thin films grown by pulsed laser deposition. Thick films (thickness > 1000 A) show electrical transport behavior typical of bulk specimens. A metal to insulator transition is observed for films with thickness -β) and a stretched exponential (ρ(T) ∼ exp[T1/T]x) for strongly insulating samples. A comparison of electrical resistivity to scanning electron microscope images indicates a correlation between the metal to insulator transition and the intergranular connectivity. Based on this result it is argued that the intergrain conductance governs the metal to insulator transition

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

    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

  10. A macrocyclic approach to transition metal and uranyl Pacman complexes

    Love, J. B.

    2009-01-01

    Multielectron redox chemistry involving small molecules such as O-2, H2O, N-2, CO2, and CH4 is intrinsic to the chemical challenges surrounding sustainable, low-carbon energy generation and exploitation. Compounds with more than one metal reaction site facilitate this chemistry by providing both unique binding environments and combined redox equivalents. However, controlling the aggregation of metal cations is problematic, as both the primary coordination spheres of the metals and the metal-m...

  11. Phase coexistence in the metal-insulator transition of a VO2 thin film

    Vanadium dioxide (VO2) shows a metal-insulator transition (MIT) near room temperature, accompanied by an abrupt resistivity change. Since the MIT of VO2 is known to be a first order phase transition, it is valuable to check metallic and insulating phase segregation during the MIT process. We deposited (100)-oriented epitaxial VO2 thin films on R-cut sapphire substrates. From the scanning tunneling spectroscopy (STS) spectra, we could distinguish metallic and insulating regions by probing the band gap. Optical spectroscopic analysis also supported the view that the MIT in VO2 occurs through metal and insulator phase coexistence

  12. Recent advances in metathesis-derived polymers containing transition metals in the side chain

    Ileana Dragutan

    2015-12-01

    Full Text Available This account critically surveys the field of side-chain transition metal-containing polymers as prepared by controlled living ring-opening metathesis polymerization (ROMP of the respective metal-incorporating monomers. Ferrocene- and other metallocene-modified polymers, macromolecules including metal-carbonyl complexes, polymers tethering early or late transition metal complexes, etc. are herein discussed. Recent advances in the design and syntheses reported mainly during the last three years are highlighted, with special emphasis on new trends for superior applications of these hybrid materials.

  13. Recent advances in metathesis-derived polymers containing transition metals in the side chain.

    Dragutan, Ileana; Dragutan, Valerian; Simionescu, Bogdan C; Demonceau, Albert; Fischer, Helmut

    2015-01-01

    This account critically surveys the field of side-chain transition metal-containing polymers as prepared by controlled living ring-opening metathesis polymerization (ROMP) of the respective metal-incorporating monomers. Ferrocene- and other metallocene-modified polymers, macromolecules including metal-carbonyl complexes, polymers tethering early or late transition metal complexes, etc. are herein discussed. Recent advances in the design and syntheses reported mainly during the last three years are highlighted, with special emphasis on new trends for superior applications of these hybrid materials. PMID:26877797

  14. Formation of bulk metallic glasses in the Fe-M-Y-B (M = transition metal) system

    In this work, quaternary Fe72-xMxY6B22 (M = Ni, Co and Mo) bulk metallic glasses (BMGs) have been developed. It is found that a fully amorphous Fe68Mo4Y6B22 cylindrical rod with 6.5 mm in diameter can be prepared by copper mold injection. These alloys have a high glass transition temperature of about 900 K with high fracture strengths up to about 3 GPa although they are still brittle. Magnetic measurements reveal that they are ferromagnetic at ambient temperature with low coercive force of about 2 A/m, saturation magnetization of about 0.7 T and effective permeability of about 7000 at 100 kHz. The newly developed Fe-based quaternary alloys exhibit excellent combination properties: superior glass forming ability (GFA), high glass transition temperature, and soft magnetic properties, which could have potential applications in electronic industries. Furthermore, the effect of Mo addition on GFA in the Fe-Y-B BMG system has been discussed compared with those of Ni and Co additions

  15. General instanton counting and 5d SCFT

    Hwang, Chiung; Kim, Seok; Park, Jaemo

    2014-01-01

    Instanton partition functions of 5d N=1 gauge theories are Witten indices for the ADHM gauged quantum mechanics with (0,4) SUSY. We derive the integral contour prescriptions for these indices using the Jeffrey-Kirwan method, for gauge theories with hypermultiplets in various representations. The results can be used to study various 4d/5d/6d QFTs. In this paper, we study 5d SCFTs which are at the UV fixed points of 5d SYM theories. In particular, we focus on the Sp(N) theories with N_f \\leq 7 fundamental and 1 antisymmetric hypermultiplets, living on the D4-D8-O8 systems. Their superconformal indices calculated from instantons all show E_{N_f+1} symmetry enhancements. We also discuss some aspects of the 6d SCFTs living on the M5-M9 system. It is crucial to understand the UV incompleteness of the 5d SYM, coming from small instantons in our problem. We explain in our examples how to fix them. As an aside, we derive the index for general gauged quantum mechanics with (0,2) SUSY.

  16. General instanton counting and 5d SCFT

    Hwang, Chiung; Kim, Joonho; Kim, Seok; Park, Jaemo

    2015-07-01

    Instanton partition functions of 5d gauge theories are Witten indices for the ADHM gauged quantum mechanics with (0, 4) SUSY. We derive the integral contour prescriptions for these indices using the Jeffrey-Kirwan method, for gauge theories with hypermultiplets in various representations. The results can be used to study various 4d/5d/6d QFTs. In this paper, we study 5d SCFTs which are at the UV fixed points of 5d SYM theories. In particular, we focus on the Sp( N ) theories with N f ≤ 7 fundamental and 1 antisymmetric hypermultiplets, living on the D4-D8-O8 systems. Their superconformal indices calculated from instantons all show symmetry enhancements. We also discuss some aspects of the 6d SCFTs living on the M5-M9 system. It is crucial to understand the UV incompleteness of the 5d SYM, coming from small instantons in our problem. We explain in our examples how to fix them. As an aside, we derive the index for general gauged quantum mechanics with (0 , 2) SUSY.

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

    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.

  18. Nature of the Insulating Ground State of the 5 d Postperovskite CaIrO3

    Kim, Sun-Woo; Liu, Chen; Kim, Hyun-Jung; Lee, Jun-Ho; Yao, Yongxin; Ho, Kai-Ming; Cho, Jun-Hyung

    2015-08-01

    The insulating ground state of the 5 d transition metal oxide CaIrO3 has been classified as a Mott-type insulator. Based on a systematic density functional theory (DFT) study with local, semilocal, and hybrid exchange-correlation functionals, we reveal that the Ir t2 g states exhibit large splittings and one-dimensional electronic states along the c axis due to a tetragonal crystal field. Our hybrid DFT calculation adequately describes the antiferromagnetic (AFM) order along the c direction via a superexchange interaction between Ir4 + spins. Furthermore, the spin-orbit coupling (SOC) hybridizes the t2 g states to open an insulating gap. These results indicate that CaIrO3 can be represented as a spin-orbit Slater insulator, driven by the interplay between a long-range AFM order and the SOC. Such a Slater mechanism for the gap formation is also demonstrated by the DFT + dynamical mean field theory calculation, where the metal-insulator transition and the paramagnetic to AFM phase transition are concomitant with each other.

  19. Nature of the insulating ground state of the 5d postperovskite CaIrO3

    In this study, the insulating ground state of the 5d transition metal oxide CaIrO3 has been classified as a Mott-type insulator. Based on a systematic density functional theory (DFT) study with local, semilocal, and hybrid exchange-correlation functionals, we reveal that the Ir t2g states exhibit large splittings and one-dimensional electronic states along the c axis due to a tetragonal crystal field. Our hybrid DFT calculation adequately describes the antiferromagnetic (AFM) order along the c direction via a superexchange interaction between Ir4+ spins. Furthermore, the spin-orbit coupling (SOC) hybridizes the t2g states to open an insulating gap. These results indicate that CaIrO3 can be represented as a spin-orbit Slater insulator, driven by the interplay between a long-range AFM order and the SOC. Such a Slater mechanism for the gap formation is also demonstrated by the DFT + dynamical mean field theory calculation, where the metal-insulator transition and the paramagnetic to AFM phase transition are concomitant with each other

  20. Behaviors of d and f electrons in transition metals studied by positron annihilation

    The background of the spectrum of Doppler broadening of positron annihilation radiation can be reduced remarkably by using a two-detector coincidence technique. With this setup, we get a peak to background ratio of about 104 on the high energy side of the peak. The d electron and f electron signal for the transition metals can be extracted from the coincidence Doppler broadening spectrum. The coincidence Doppler broadening spectra for the transition metals Zr, Nb, Mo, Ag, Hf, Pt, Au and single crystal of Si have been measured. The experimental results show that the height of the peak of the ratio curves (the reference sample is Si) for the transition metals Zr, Nb, Mo, Ag increases with the increase in the number of 4d electrons. There are 2 peaks in the ratio curves (the reference sample is Si) for the transition metals Ag, Hf, Pt. And the height of the peaks increases with the increase in atomic number. (authors)

  1. Single crystal particles of a mesoporous mixed transition metal oxide with a wormhole structure.

    Lee, B; Lu, D; Kondo, J N; Domen, K

    2001-10-21

    A new type of mesoporous mixed transition metal oxide of Nb and Ta (NbTa-TIT-1) has been prepared through a two-step calcination, which consists of single crystal particles with wormhole mesoporous structure. PMID:12240191

  2. Theoretical research program to study transition metal trimers and embedded clusters

    Walch, Stephen P.

    1987-01-01

    The results of ab-initio calculations are reported for (1) small transition metal clusters and (2) potential energy surfaces for chemical reactions important in hydrogen combustion and high temperature air chemistry.

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

    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)

  4. Photoinduced Coherent Spin Fluctuation in Primary Dynamics of Insulator to Metal Transition in Perovskite Cobalt Oxide

    Arima T.; Iwai S.; Itoh H; Yamada K; Ishikawa T; Yamada S; Sasaki T.

    2013-01-01

    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.

  5. First principle study of AlX (X=3d, 4d, 5d elements and Lu) dimer.

    Ouyang, Yifang; Wang, Jianchuan; Hou, Yuhua; Zhong, Xiaping; Du, Yong; Feng, Yuanping

    2008-02-21

    The ground state equilibrium bond length, harmonic vibrational frequency, and dissociation energy of AlX (X=3d,4d,5d elements and Lu) dimers are investigated by density functional method B3LYP. The present results are in good agreement with the available experimental and other theoretical values except the dissociation energy of AlCr. The present calculations show that the late transition metal can combine strongly with aluminum compared with the former transition metal. The present calculation also indicates that it is more reasonable to replace La with Lu in the Periodic Table and that the bonding strengths of zinc, cadmium, and mercury with aluminum are very weak. PMID:18298147

  6. Theory of magnetic transition metal nanoclusters on surfaces

    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

  7. EPR of transition metal ions in NZP ceramics

    NZP-ceramics have been produced by different methods such as sol-gel, flux melting and sintering of dry salts or phosphates. Formation of NZP and related phases was confirmed by X-ray diffraction analysis. Electron paramagnetic resonance (EPR) was applied to evaluate a structure positions of paramagnetic ions and nature of radiation-induced centers. EPR responses from transition metal ions Fe3+ and Mn2+ with electron configuration 3d5 (ground state 6S5/2) which occurred as impurities in raw materials were registered in powders of NZP-ceramics. Fine structure arising due to high spin iron complexes is well resolved. A part of Fe3+ ions substitutes for Zr4+ and another part of one substitutes for Na+ ions in six-fold coordinated positions. A great value of hyperfine structure (hfs) constant (9.3 mT) shows a high ionic character of Mn-O bonds in the first coordination sphere. A coordination number is close to 6. Fine structure of Mn2+ ions are not well resolved. A comparison of the spectra of samples containing various alkali cations shows the substitution for cations in series of Li-Na-K-Rb-Cs does not result in fundamental variation in spectra except for CZP ceramics where the response with g=4.3 due to Fe3+ in strong ligand field rather than response with g=2.0 due to Fe3+ in weak field is observed. An investigation of some samples doped by 0.1...0.5 mole % of Fe3+ or Gd3+ has been carried out and principal spin-Hamiltonian parameters have been determined. The increase of Fe and Gd ions content as compared to impurity substituting for Zr and possibly Na in their own structural positions results in noticeable site distortion. Gamma irradiation of NZP ceramics results in formation of radiation-induced paramagnetic centers connected to phosphorus-oxygen. The nature and concentration of these centers depend on production method. The lowest defect concentration is in hot-pressed ceramics

  8. Spin-orbit-driven magnetic structure and excitation in the 5d pyrochlore Cd2Os2O7

    Calder, S.; Vale, J. G.; Bogdanov, N. A.; Liu, X.; Donnerer, C.; Upton, M. H.; Casa, D.; Said, A. H.; Lumsden, M. D.; Zhao, Z.; Yan, J. -Q.; Mandrus, D.; Nishimoto, S.; van den Brink, J.; Hill, J. P.; McMorrow, D. F.; Christianson, A. D.

    2016-01-01

    Much consideration has been given to the role of spin-orbit coupling (SOC) in 5d oxides, particularly on the formation of novel electronic states and manifested metal-insulator transitions (MITs). SOC plays a dominant role in 5d5 iridates (Ir4+), undergoing MITs both concurrent (pyrochlores) and separated (perovskites) from the onset of magnetic order. However, the role of SOC for other 5d configurations is less clear. For example, 5d3 (Os5+) systems are expected to have an orbital singlet with reduced effective SOC. The pyrochlore Cd2Os2O7 nonetheless exhibits a MIT entwined with magnetic order phenomenologically similar to pyrochlore iridates. Here, we resolve the magnetic structure in Cd2Os2O7 with neutron diffraction and then via resonant inelastic X-ray scattering determine the salient electronic and magnetic energy scales controlling the MIT. In particular, SOC plays a subtle role in creating the electronic ground state but drives the magnetic order and emergence of a multiple spin-flip magnetic excitation. PMID:27273216

  9. Spin-orbit-driven magnetic structure and excitation in the 5d pyrochlore Cd2Os2O7

    Calder, S.; Vale, J. G.; Bogdanov, N. A.; Liu, X.; Donnerer, C.; Upton, M. H.; Casa, D.; Said, A. H.; Lumsden, M. D.; Zhao, Z.; Yan, J.-Q.; Mandrus, D.; Nishimoto, S.; van den Brink, J.; Hill, J. P.; McMorrow, D. F.; Christianson, A. D.

    2016-06-01

    Much consideration has been given to the role of spin-orbit coupling (SOC) in 5d oxides, particularly on the formation of novel electronic states and manifested metal-insulator transitions (MITs). SOC plays a dominant role in 5d5 iridates (Ir4+), undergoing MITs both concurrent (pyrochlores) and separated (perovskites) from the onset of magnetic order. However, the role of SOC for other 5d configurations is less clear. For example, 5d3 (Os5+) systems are expected to have an orbital singlet with reduced effective SOC. The pyrochlore Cd2Os2O7 nonetheless exhibits a MIT entwined with magnetic order phenomenologically similar to pyrochlore iridates. Here, we resolve the magnetic structure in Cd2Os2O7 with neutron diffraction and then via resonant inelastic X-ray scattering determine the salient electronic and magnetic energy scales controlling the MIT. In particular, SOC plays a subtle role in creating the electronic ground state but drives the magnetic order and emergence of a multiple spin-flip magnetic excitation.

  10. Beyond the upper limit of magnetic anisotropy in two-dimensional transition metal dichalcogenides

    Odkhuu, Dorj

    2016-01-01

    Exploring an upper limit of magnetic anisotropy in two-dimensional materials, such as graphene and transition metal dichalcogenides, is at the heart of spintronics research. Herein, an atomic-scale perpendicular magnetic anisotropy up to an order of 100 meV per atom, which is far beyond the ordinarily obtained value in graphene and pristine transition metal dichalcogenides, is demonstrated in individual ruthenium and osmium adatoms at a monosulfur vacancy in molybdenum disulfide. We further p...

  11. Effects of valence, geometry and electronic correlations on transport in transition metal benzene sandwich molecules

    Karolak, M.; Jacob, D.

    2016-01-01

    We study the impact of the valence and the geometry on the electronic structure and transport properties of different transition metal-benzene sandwich molecules bridging the tips of a Cu nanocontact. Our density-functional calculations show that the electronic transport properties of the molecules depend strongly on the molecular geometry which can be controlled by the nanocontact tips. Depending on the valence of the transition metal center certain molecules can be tuned in and out of half-...

  12. Catalytic production of carbon nanotubes over first row transition metal oxides supported on montmorillonite

    Clay-carbon nanotube composites were prepared by employing the catalytic chemical vapor deposition method (CCVD) over different transition metal oxides supported on montmorillonite. Various analytical techniques including SEM, TEM, XRD and DTA/TGA were used for the characterization of the final composite materials. The morphology, quality and structure of the produced nanotubes is shown to be dependent on the type of transition metals

  13. Computational and experimental investigation of unreported transition metal selenides and sulphides

    Narayan, Awadhesh; Bhutani, Ankita; Rubeck, Samantha; Eckstein, James N.; Shoemaker, Daniel P.; Wagner, Lucas K.

    2015-01-01

    Expanding the library of known inorganic materials with functional electronic or magnetic behavior is a longstanding goal in condensed matter physics and materials science. Recently, the transition metal chalchogenides including selenium and sulfur have been of interest because of their correlated-electron properties, as seen in the iron based superconductors and the transition metal dichalcogenides. However, the chalcogenide chemical space is less explored than that of oxides, and there is a...

  14. Abnormal carbenes as ligands in transition metal chemistry: curiosities with exciting perspectives

    Albrecht, Martin

    2009-01-01

    This review compiles the advances achieved in our laboratories using abnormal and less heteroatom-stabilized carbenes as ligands for transition metal chemistry. Fundamental studies allowed the evaluation of the impact of this new class of ligands both electronically and sterically. Based on these results, initial catalytic applications have been devised in the area of H-H and C-H bond activation, demonstrating the potential of abnormal carbenes as unique ligands for transition metals.

  15. Coordination Chemistry of Disilylated Stannylenes with Group 10 d10 Transition Metals: Silastannene vs Stannylene Complexation

    Arp, Henning; Marschner, Christoph; Baumgartner, Judith; Zark, Patrick; Müller, Thomas

    2013-01-01

    The coordination behavior of disilylated stannylenes toward zerovalent group 10 transition metal complexes was studied. This was accomplished by reactions of PEt3 adducts of disilylated stannylenes with zerovalent group 10 transition metal complexes. The thus obtained products differed between the first row example nickel and its heavier congeners. While with nickel stannylene complex formation was observed, coordination of the stannylenes to palladium and platinum compounds led to unusual si...

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

    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.

  17. Highly Enantioselective Cascade Transformations by Merging Heterogeneous Transition Metal Catalysis with Asymmetric Aminocatalysis

    Luca Deiana; Samson Afewerki; Carlos Palo-Nieto; Oscar Verho; Johnston, Eric V.; Armando Córdova

    2012-01-01

    The concept of combining heterogeneous transition metal and amine catalysis for enantioselective cascade reactions has not yet been realized. This is of great advantage since it would allow for the recycling of expensive and non-environmentally friendly transition metals. We disclose that the use of a heterogeneous Pd-catalyst in combination with a simple chiral amine co-catalyst allows for highly enantioselective cascade transformations. The preparative power of this process has been demonst...

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

    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....

  19. Quantum Chemical Calculations of EPR-Hyperfine Coupling Constants for Transition Metal Complex

    In this this study the performance of various density functional approaches for calculation of electron paramagnetic resonance hyperfine coupling constants in transition metal complexes was studied. Several gradient-corrected as well as hybrid functionals have been validated by comparison with experimental data and high-level coupled-cluster calculation for 21 systems, representing a variety of bonding situations. Second part of this work represents an analysis and interpretation of spin-polarization effects in first transition metal complexes

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

    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.

  1. Nature of the Insulating Ground State of the 5d PostPerovskite CaIrO3

    Kim, Sun-Woo; Liu, Chen; Kim, Hyun-Jung; Lee, Jun-Ho; Yao, Yongxin; Ho, Kai-Ming; Cho, Jun-Hyung

    2015-01-01

    The insulating ground state of the 5d transition metal oxide CaIrO3 has been classified as a Mott-type insulator. Based on a systematic density functional theory (DFT) study with local, semilocal, and hybrid exchange-correlation functionals, we reveal that the Ir t2g states exhibit large splittings and one-dimensional electronic states along the c axis due to a tetragonal crystal field. Our hybrid DFT calculation adequately describes the antiferromagnetic (AFM) order along the c direction via...

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

    Liu, Kexi; Lei, Yinkai; Wang, Guofeng, E-mail: guw8@pitt.edu [Department of Mechanical Engineering and Materials Science, University of Pittsburgh, Pittsburgh, Pennsylvania 15261 (United States)

    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 O{sub 2} 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 N{sub 4} chelation, as well as the molecular and electronic structures for the O{sub 2} adsorption on these macrocyclic molecules, using the density functional theory calculation method. We found that the calculated adsorption energy of O{sub 2} 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{sub z{sup 2}}, d{sub xy}, d{sub xz}, and d{sub 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 O{sub 2} adsorption energy for enhancing the ORR activity of transition metal macrocyclic complex catalysts.

  3. NEXAFS investigations of transition metal oxides, nitrides, carbides, sulfides and other interstitial compounds

    Chen, J. G.

    Owing to their unique physical and chemical properties, transition metal compounds, especially transition metal oxides, nitrides, carbides and sulfides, have been the subject of many surface science investigations. In this article we will review applications of the near-edge X-ray absorption fine structure (NEXAFS) technique in the investigations of electronic and structural properties of transition metal compounds. This review covers NEXAFS studies of compounds in various physical forms, including bulk single crystals, well-characterized overlayers on surfaces of corresponding parent metals, and amorphous powder materials. In addition to transition metal oxides, nitrides, carbides and sulfides, we will also briefly discuss NEXAFS studies of interstitial compounds containing other 2p and 3p non-metal components, namely boron, fluorine, silicon, phosphorus and chlorine. We will discuss the correlation between experimental NEXAFS spectra and the local bonding environment of these compounds, such as the number of d-electrons, spin configurations, ligand-field splitting, coordination numbers, local symmetries, and crystal structures. In addition, NEXAFS investigations of the adsorption and reaction of probing molecules will also be discussed to reveal the underlying chemical reactivities of these materials. We will use many examples to demonstrate the importance of NEXAFS studies in the overall understanding of the physical and chemical properties of transition metal compounds. Finally, we will conclude this review by summarizing the current applications, as well as potential research opportunities, of NEXAFS in several technologically important research areas, including materials science, catalysis, biological science, earth science and environmental science.

  4. Effects of transition metal ion coordination on the collision-induced dissociation of polyalanines.

    Watson, Heather M; Vincent, John B; Cassady, Carolyn J

    2011-11-01

    Transition metal-polyalanine complexes were analyzed in a high-capacity quadrupole ion trap after electrospray ionization. Polyalanines have no polar amino acid side chains to coordinate metal ions, thus allowing the effects metal ion interaction with the peptide backbone to be explored. Positive mode mass spectra produced from peptides mixed with salts of the first row transition metals Cr(III), Fe(II), Fe(III), Co(II), Ni(II), Cu(I), and Cu(II) yield singly and doubly charged metallated ions. These precursor ions undergo collision-induced dissociation (CID) to give almost exclusively metallated N-terminal product ions whose types and relative abundances depend on the identity of the transition metal. For example, Cr(III)-cationized peptides yield CID spectra that are complex and have several neutral losses, whereas Fe(III)-cationized peptides dissociate to give intense non-metallated products. The addition of Cu(II) shows the most promise for sequencing. Spectra obtained from the CID of singly and doubly charged Cu-heptaalanine ions, [M + Cu - H](+) and [M + Cu](2+) , are complimentary and together provide cleavage at every residue and no neutral losses. (This contrasts with [M + H](+) of heptaalanine, where CID does not provide backbone ions to sequence the first three residues.) Transition metal cationization produces abundant metallated a-ions by CID, unlike protonated peptides that produce primarily b- and y-ions. The prominence of metallated a-ions is interesting because they do not always form from b-ions. Tandem mass spectrometry on metallated (Met = metal) a- and b-ions indicate that [b(n)  + Met - H](2+) lose CO to form [a(n)  + Met - H](2+), mimicking protonated structures. In contrast, [a(n)  + Met - H](2+) eliminate an amino acid residue to form [a(n-1)  + Met - H](2+), which may be useful in sequencing. PMID:22124980

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

    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.

  6. Manipulation of a Schlenk Line: Preparation of Tetrahydrofuran Complexes of Transition-Metal Chlorides

    Davis, Craig M.; Curran, Kelly A.

    2007-01-01

    Before taking an inorganic laboratory course few students have experience handling air-sensitive materials using Schlenk techniques. This exercise introduces them to techniques they will employ in later syntheses. The procedure involves the formation of anhydrous tetrahydrofuran complexes of transition-metal chlorides from metal-chloride hydrates;…

  7. On the possibility of removing of transition metal ions from sewage using polymeric complexes

    The possibility of using of complexation in the system polyethylene-imine transition metal ions (Cu2+, Ni2+, Co2+)-surface active substance for removing of metal ions from solution and sewage has been investigated. It is shown, that pH of medium, hydro-fugitive of system and ratio between component of the triply complex effect on purification of solution. (author)

  8. Activity Descriptors for CO2 Electroreduction to Methane on Transition-Metal Catalysts

    Peterson, Andrew; Nørskov, Jens K.

    2012-01-01

    this work, we compare trends in binding energies for the intermediates in CO2 electrochemical reduction and present an activity “volcano” based on this analysis. This analysis describes the experimentally observed variations in transition-metal catalysts, including why copper is the best-known metal...

  9. The thermodynamic, electronic and elastic properties of the early-transition-metal diborides with AlB2-type structure: A density functional theory study

    Highlights: • The thermodynamic characters of TMB2 have been firstly studied using the QHA method. • WB2 and TaB2 are good candidates for the structural application at high temperature. • Most of the early-transition-metal diborides cannot be easily machined. • The correlations between elastic constants and VECs of TMB2 have been discussed. - Abstract: The thermodynamic, electronic and elastic properties of a class of early-transition-metal diborides (TMB2, TM = Sc, Ti, V, Cr, Y, Zr, Nb, Mo, Hf, Ta, W) with AlB2-type structure have been investigated using the quasi-harmonic Debye model and the ab initio calculation based on the density functional theory, respectively. According to the characters of temperature dependent bulk modulus and coefficient of thermal expansion, the TMB2 compounds can be divided into three groups. The results also indicate that 4d- and 5d-TMB2 compounds are good high-temperature structural materials. The five independent stiffness coefficients, bulk and shear moduli of the diborides are obtained and well agreement with the available experimental and theoretical data. The correlations between elastic properties and electronic structure are discussed in detail. Due to the high values of hardness, the VIB-transition-metal diborides with relatively high B/G and B/C44 ratios are still difficult to machine with usual methods

  10. Optical conductivity of V4O7 across its metal-insulator transition

    Vecchio, I. Lo; Autore, M.; D'apuzzo, F.; Giorgianni, F.; Perucchi, A.; Schade, U.; Andreev, V. N.; Klimov, V. A.; Lupi, S.

    2014-01-01

    The optical properties of a V4O7 single crystal have been investigated from the high temperature metallic phase down to the low temperature antiferromagnetic insulating one. The temperature dependent behavior of the optical conductivity across the metal-insulator transition (MIT) can be explained in a polaronic scenario. Charge carriers form strongly localized polarons in the insulating phase as suggested by a far-infrared charge gap abruptly opening at T_MIT = 237 K. In the metallic phase in...

  11. Transition Metal Configurations and Limitations of the Orbital Approximation.

    Scerri, Eric R.

    1989-01-01

    Points out a misconception that is reinforced in many elementary and advanced chemistry texts. Discusses the general limitations of the orbital concept. Notes misconceptions related to the transition elements and their first ionization energies. (MVL)

  12. Dramatic Switching of Magnetic Exchange in a Classic Transition Metal Oxide: Evidence for Orbital Ordering

    Spin correlations in metallic and insulating phases of V2O3 and its derivatives are investigated using magnetic neutron scattering.Metallic samples have incommensurate spin correlations varying little with hole doping. Paramagnetic insulating samples have spin correlations only among near neighbors. The transition from either of these phases into the low temperature insulating antiferromagnetic phase is accompanied by an abrupt change of dynamic magnetic short range order. Our results support the idea that the transition into the antiferromagnetic insulator is also an orbital ordering transition. copyright 1997 The American Physical Society

  13. Pressure-driven Superconductivity in Transition-metal Pentatelluride HfTe5

    Qi, Yanpeng; Shi, Wujun; Naumov, Pavel G.; Kumar, Nitesh; Schnelle, Walter; Barkalov, Oleg,; Shekhar, Chandra; Borrmann, Horst; FELSER, CLAUDIA; Yan, Binghai; Medvedev, Sergey A.

    2016-01-01

    Layered transition-metal tellurides have attracted considerable attention because of their rich physics; for example, tungsten ditelluride WTe2 exhibits extremely large magnetoresistance; the tritelluride ZrTe3 shows a charge density wave transition at low temperature; and the pentatelluride ZrTe5 displays an enigmatic resistivity anomaly and large thermoelectric power. Recently some transition-metal tellurides are predicted to be quantum spin Hall insulators (e.g. ZrTe5 and HfTe5) or Weyl se...

  14. Theory of quantum metal to superconductor transitions in highly conducting systems

    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.

  15. Synthesis and Electronic Properties of Transition Metal Containing Polymers

    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.

  16. Neutral bimetallic transition metal phenoxyiminato catalysts and related polymerization methods

    Marks, Tobin J.; Rodriguez, Brandon A.; Delferro, Massimiliano

    2012-08-07

    A catalyst composition comprising a neutral bimetallic diphenoxydiiminate complex of group 10 metals or Ni, Pd or Pt is disclosed. The compositions can be used for the preparation of homo- and co-polymers of olefinic monomer compounds.

  17. Directly Predicting Water Quality Criteria from Physicochemical Properties of Transition Metals

    Wang, Ying; Wu, Fengchang; Mu, Yunsong; Zeng, Eddy Y.; Meng, Wei; Zhao, Xiaoli; Giesy, John P.; Feng, Chenglian; Wang, Peifang; Liao, Haiqing; Chen, Cheng

    2016-03-01

    Transition metals are a group of elements widespread in aquatic environments that can be hazardous when concentrations exceeding threshold values. Due to insufficient data, criteria maximum concentrations (CMCs) of only seven transition metals for protecting aquatic life have been recommended by the USEPA. Hence, it is deemed necessary to develop empirical models for predicting the threshold values of water quality criteria (WQC) for other transition metals for which insufficient information on toxic potency is available. The present study established quantitative relationships between recommended CMCs and physicochemical parameters of seven transition metals, then used the developed relationships to predict CMCs for other transition metals. Seven of 26 physicochemical parameters examined were significantly correlated with the recommended CMCs. Based on this, five of the seven parameters were selected to construct a linear free energy model for predicting CMCs. The most relevant parameters were identified through principle component analysis, and the one with the best correlation with the recommended CMCs was a combination of covalent radius, ionic radius and electron density. Predicted values were largely consistent with their toxic potency values. The present study provides an alternative approach to develop screening threshold level for metals which have insufficient information to use traditional methods.

  18. First principles density functional calculation of magnetic moment and hyperfine fields of dilute transition metal impurities in Gd host

    We present first principles calculations of electronic structure and magnetic properties of dilute transition metal (3d, 4d and 5d) impurities in a Gd host. The calculations have been performed within the density functional theory using the full potential linearized augmented plane wave technique and the GGA+U method. The spin and orbital contributions to the magnetic moment and the hyperfine fields have been computed. We find large magnetic moments for 3d (Ti–Co), 4d (Nb–Ru) and 5d (Ta–Os) impurities with magnitudes significantly different from the values estimated from earlier mean field calculation [J. Magn. Magn. Mater. 320 (2008) e446–e449]. The exchange interaction between the impurity and host Gd moments is found to be positive for early 3d elements (Sc–V) while in all other cases an anti-ferromagnetic coupling is observed. The trends for the magnetic moment and hyperfine field of d-impurities in Gd show qualitative difference with respect to their behavior in Fe, Co and Ni. The calculated total hyperfine field, in most cases, shows excellent agreement with the experimental results. A detailed analysis of the Fermi contact hyperfine field has been made, revealing striking differences for impurities having less or more than half filled d-shell. The impurity induced perturbations in host moments and the change in the global magnetization of the unit cell have also been computed. The variation within each of the d-series is found to correlate with the d–d hybridization strength between the impurity and host atoms. - Highlights: • Detailed study of transition metal impurities in ferromagnetic Gd has been carried out. • The trends in impurity magnetic moment are qualitatively different from Fe, Co and Ni. • The variation within each of the d-series is found to correlate with the d–d hybridization strength between the impurity and host atoms. • Experimental trend in a hyperfine field has been reproduced successfully

  19. The influence of the metal net charge of non-metallocene early transition metal catalyst on the ethylene polymerization activity

    WU ChunHong; LI HuaYi; FENG YuQi; HU YouLiang

    2008-01-01

    The net charges on central metals of a serial non-metallocene early transition metal catalysts (FI cata-lyst) with similar steric hindrance were caculated with MM-QEq (molecular mechmism-charge equili-bration) method and associated with ethylene polymerization activities of these FI catalyts. It was found that the activity increased with the net charge on metal if ignoring the influence of the steric hindrance. In other words, introduction of strong and/or more electron-withdrawing groups onto the ligand of FI catalyst would enhance the activity of the catalyst. This conculsion gave a direction to designing new FI catalyst with higher activity.

  20. High volumetric capacitance near insulator-metal percolation transition

    Efros, A. L.

    2011-01-01

    A new type of a capacitor with a very high volumetric capacitance is proposed. It is based upon the known phenomenon of a sharp increase of the dielectric constant of the metal-insulator composite in the vicinity of the percolation threshold, but still on the insulator side. The optimization suggests that the metallic particles should be of nanoscale and that the distance between planar electrodes should be somewhat larger than the correlation length of the percolation theory and 10 to 20 tim...

  1. Cellulose based transition metal nano-composites : structuring and development

    Glatzel, Stefan

    2013-01-01

    Cellulose is the most abundant biopolymer on earth. In this work it has been used, in various forms ranging from wood to fully processed laboratory grade microcrystalline cellulose, to synthesise a variety of metal and metal carbide nanoparticles and to establish structuring and patterning methodologies that produce highly functional nano-hybrids. To achieve this, the mechanisms governing the catalytic processes that bring about graphitised carbons in the presence of iron have been investigat...

  2. Transition metal-templated synthesis of catenanes and rotaxanes

    CHAMBRON Jean-Claude; SAUVAGE Jean-Pierre

    2012-01-01

    Among the various methods nowadays used to make catenanes and rotaxanes,the metal template synthesis occupies a place of choice,because of its versatility.This contribution shows that,thanks to the richness of their chemistry,metal templates can fulfil multiple functions for the construction of these topologically-interesting molecules,from the entwining or threading of their precursors to the simultaneous catalysis of the interlocking reaction.

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

    Peresypkina, Eugenia V.; Samsonenko, Denis G.; Vostrikova, Kira E.

    2015-04-01

    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)}2Ru(NO)(CN)5]n and two complexes composed of different cyanorhenates, [Ni(cyclam)]2[ReO(OH)(CN)4](ClO4)2(H2O)1.25 and [Cu(cyclam)]2[Re(CN)7](H2O)12, was confirmed by single crystal XRD study, the rhenium oxidation state having been proved by the magnetic measurements. An amorphism of [M(cyclam)]3[Re(CN)7]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)]3[Re(CN)7]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)n]=3/2. For the first time was prepared and fully characterized a precursor (n-Bu4N)2[Ru(NO)(CN)5], soluble in organic media.

  4. Metal-nonmetal transition in the copper-carbon nanocomposite films

    We prepared Cu nanoparticles in a-C:H thin films by co-deposition of RF-sputtering and RF-PECVD methods at room temperature. By increasing Cu content in these films a nonmetal-metal (N-M) transition is observed. This transition is explainable by the power law of percolation theory. The critical metal content is obtained 56% and the critical exponent is obtained 1.6, which is larger than the exponent for 2 dimension systems and smaller than the one for 3 dimension systems. The electrical conductivity of dielectric samples was explained by tunneling. Activation tunneling energy that was obtained from temperature dependence of electrical resistivity correlates with near infrared absorption peak of samples and both of them depend on Cu content of thin films. In the early stage of N-M transition, by increasing metal content, a peculiar effect of metallic to nonmetallic state occurs.

  5. Sol-Gel Synthesis and Characterization of Selected Transition Metal Nano-Ferrites

    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

  6. Metallic magnetism and change of conductivity in the nano to bulk transition of cobalt ferrite

    Arunkumar, A.; Vanidha, D.; Oudayakumar, K.; Rajagopan, S.; Kannan, R.

    2013-11-01

    Variations in conductivity with particle size have been observed in cobalt ferrite, when synthesized by solgel auto-combustion method. Impedance analysis reveals metallic and semiconducting behavior at room temperature for a particle size of 6 nm and 52 nm, respectively. Upon thermal activation, metallic to semiconducting phase transition has been observed as a function of particle size and vice-versa. Grainboundary Resistance (Rgb), increased drastically with particle size (19 MΩ for 6 nm and 259 MΩ for 52 nm) at room temperature. AC conductivity and dielectric constants exhibit similar metallic to semiconducting phase transition at 6 nm and semiconducting behavior at 52 nm with temperature in the selected frequencies. Enhanced magnetic moment with an increase in the grain size along with decreased coercivity (1444 G to 1146 G) reveals transition from single domain to multi-domain. Increased inter-particle interaction is responsible for metallicity at the nano level and on the contrary semiconductivity is attributed to bulk.

  7. Transitions in Theory and Practice: Managing Metals in the Circular Economy

    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.

  8. Probable metal-insulator transition in Ag{sub 4}SSe

    Drebushchak, V.A., E-mail: dva@igm.nsc.ru [V.S. Sobolev Institute of Geology and Mineralogy, SB RAS, Pr. Ac. Koptyuga 3, Novosibirsk 630090 (Russian Federation); Novosibirsk State University, Ul. Pirogova 2, Novosibirsk 630090 (Russian Federation); Pal’yanova, G.A.; Seryotkin, Yu.V. [V.S. Sobolev Institute of Geology and Mineralogy, SB RAS, Pr. Ac. Koptyuga 3, Novosibirsk 630090 (Russian Federation); Novosibirsk State University, Ul. Pirogova 2, Novosibirsk 630090 (Russian Federation); Drebushchak, T.N. [Novosibirsk State University, Ul. Pirogova 2, Novosibirsk 630090 (Russian Federation); Institute of Solid State Chemistry and Mechanochemistry, SB RAS, Ul. Kutateladze 18, Novosibirsk 630128 (Russian Federation)

    2015-02-15

    Highlights: • New phase transition in Ag{sub 4}SSe was discovered with scanning calorimetry and supported with X-ray powder diffraction. • The thermal effect relates to the anomaly in electrical and thermal conductivity of Ag{sub 4}SSe. • Similar thermal and electrical effects in K{sub 3}Cu{sub 8}S{sub 6} are explained with the metal-insulator transition. - Abstract: New phase transition (285 K) in low-temperature monoclinic Ag{sub 4}SSe was found out below the α-β transition (358 K) after the measurements with differential scanning calorimetry. The transition reveals significant hysteresis (over 30 K). X-ray powder diffraction shows that the superlattice with doubled a and b parameters of the unit cell exists below the new transition point. The signs of this new phase transition can be found in thermal and electrical conductivity of Ag{sub 4}SSe published in literature. Elusive phase transition in Ag{sub 2}Se shows similar properties. The new transition is likely related to the metal-insulator type transition, like K{sub 3}Cu{sub 8}S{sub 6}.

  9. First-principles study of hydrogen dissociation and diffusion on transition metal-doped Mg(0 0 0 1) surfaces

    First-principles calculations within the density functional theory (DFT) have been carried out to study hydrogen molecules dissociation and diffusion on clean and transition metals (TMs) doped Mg(0 0 0 1) surfaces following Pozzo et al. work. Firstly, the stability of Mg(0 0 0 1) surface doped with transition metals atom has been studied. The results showed that transition metals on the left of the table tend to substitute Mg in the second layer, while the other transition metals prefer to substitute Mg in the first layer. Secondly, we studied hydrogen molecules dissociation and diffusion on clean and Mg(0 0 0 1) surfaces which the transition metal atoms substituted both in the first layer and second layer. When transition metal atoms substitute in the first layer, the results agree with the Pozzo et al. result; when transition metal atoms substitute in the second layer, the results showed that the transition metals on the left of the periodic table impact on the dissociation barriers is less. However, for the transition metals (Mn, Fe, Co, Ni) on the right, there is a great impact on the barriers. The transition metals doped surfaces bind the dissociated H atoms loosely, making them easily diffused. The results further reveal that the Fe dopant on the Mg surface is the best choice for H2 dissociation and hydrogen storage.

  10. Supersymmetry and Lorentz Violation in 5D

    We present a study for a Supersymmetric field theory with Lorentz-Violation terms in 5D. We perform the analysis in the context of the Berger-Kostelecky model (BK), adding one compactified dimension that explicitly breaks the Lorentz invariance. We introduce terms that encode this breaking, and find non trivial restrictions over boundary conditions of fields that one needs to close the supersymmetric algebra.

  11. A general holographic metal/superconductor phase transition model

    Peng, Yan

    2014-01-01

    We study the scalar condensation of a general holographic superconductor model in AdS black hole background away from the probe limit. We find the model parameters together with the scalar mass and backreaction can determine the order of phase transitions completely. In addition, we observe two types of discontinuities of the scalar operator in the case of first order phase transitions. We analyze in detail the effects of the scalar mass and backreaction on the formation of discontinuities and arrive at an approximate relation between the threshold model parameters. Furthermore, we obtain superconductor solutions corresponding to higher energy states and examine the stability of these superconductor solutions.

  12. Activated phosphors having matrices of yttrium-transition metal compound

    De Kalb, E.L.; Fassel, V.A.

    1975-07-01

    A method is described for preparing a phosphor composition containing a lanthanide activator element with a host matrix having a transition element as a major component. The host matrix is composed of certain rare earth phosphates or vanadates such as YPO$sub 4$ with a portion of the rare earth replaced with one or more of the transition elements. On x-ray or other electromagnetic excitation, trace lanthanide impurities or additives within the phosphor are spectrometrically determined from their characteristic luminescence. (auth)

  13. Metal-insulator transition in Na{sub x}WO{sub 3}: Photoemission spectromicroscopy study

    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}.

  14. The deformation units in metallic glasses revealed by stress-induced localized glass transition

    Huo, L. S.; Ma, J.; Ke, H. B.; Bai, H. Y.; Zhao, D. Q.; Wang, W. H.

    2012-06-01

    We report that even in quasi-static cyclic compressions in the apparent elastic regimes of the bulk metallic glasses, the precisely measured stress-strain curve presents a mechanical hysteresis loop, which is commonly perceived to occur only in high-frequency dynamic tests. A phenomenological viscoelastic model is established to explain the hysteresis loop and demonstrate the evolutions of the viscous zones in metallic glasses during the cyclic compression. The declining of the viscosity of the viscous zones to at least 1 × 1012 Pa s when stress applied indicates that stress-induced localized glass to supercooled liquid transition occurs. We show that the deformation units of metallic glasses are evolved from the intrinsic heterogeneous defects in metallic glasses under stress and the evolution is a manifestation of the stress-induced localized glass transition. Our study might provide a new insight into the atomic-scale mechanisms of plastic deformation of metallic glasses.

  15. First principles calculations and experimental insight into methane steam reforming over transition metal catalysts

    Jones, Glenn; Jakobsen, Jon Geest; Shim, Signe Sarah;

    2008-01-01

    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 are...... 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...... 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) and the...

  16. Extraction and Binding Efficiency of Calix[8]arene Derivative Toward Selected Transition Metals

    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.

  17. Direct measurement and modulation of single-molecule coordinative bonding forces in a transition metal complex

    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...... significant impact on the metal-ligand interactions. The present approach represents a major advancement in unravelling the nature of metal-ligand interactions and could have broad implications in coordination chemistry....

  18. Transport studies in 2D transition metal dichalcogenides and black phosphorus.

    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. PMID:27187790

  19. Transition-Metal Doped Ceria Microspheres with Nanoporous Structures for CO Oxidation

    Zhou, Lin; Li, Xiaoxiao; Yao, Ze; Chen, Zhuwen; Hong, Mei; Zhu, Rongshu; Liang, Yongye; Zhao, Jing

    2016-03-01

    Catalytic oxidation of carbon monoxide (CO) is of great importance in many different fields of industry. Until now it still remains challenging to use non-noble metal based catalysts to oxidize CO at low temperature. Herein, we report a new class of nanoporous, uniform, and transition metal-doped cerium (IV) oxide (ceria, CeO2) microsphere for CO oxidation catalysis. The porous and uniform microsphere is generated by sacrificed polymer template. Transition-metals, like Cu, Co, Ni, Mn and Fe, were doped into CeO2 microspheres. The combination of hierarchical structure and metal doping afford superior catalytic activities of the doped ceria microspheres, which could pave a new way to advanced non-precious metal based catalysts for CO oxidation.

  20. Transport studies in 2D transition metal dichalcogenides and black phosphorus

    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.

  1. The thermally induced metal-semiconducting phase transition of samarium monosulfide (SmS) thin films

    Rogers, E; Dorenbos, P; Van der Kolk, E [Delft University of Technology, Faculty of Applied Sciences, Mekelweg 15, NL-2629 JB Delft (Netherlands); Smet, P F; Poelman, D, E-mail: e.g.rogers@tudelft.n [Lumilab, Department of Solid State Sciences, Ghent University, Krijgslaan 281 S1, B-9000 Gent (Belgium)

    2010-01-13

    High quality phase pure samarium monosulfide (SmS) thin films were prepared by electron beam evaporation using a samarium metal source in a H{sub 2}S atmosphere. The optical properties (reflection, transmission, absorption) of the films in the semiconducting and metallic phase were analysed from the UV to the mid-IR and explained in terms of the electronic structure of SmS. In this paper it will be shown that metallic SmS thin films exhibit an apparently continuous thermally induced metallic to semiconducting phase transition when studied optically. Temperature dependent x-ray diffraction measurements, however, indicate that the metallic to semiconductor phase transition is in fact first order at a single grain level. The apparently continuous optical behaviour is therefore due to the polycrystalline nature of the films.

  2. High throughput methods for analyzing transition metals in proteins on a microgram scale.

    Atanassova, Anelia; Högbom, Martin; Zamble, Deborah B

    2008-01-01

    Transition metals are among the most common ligands that contribute to the biochemical and physiological properties of proteins. In the course of structural proteomic projects, the detection of transition metal cofactors prior to the determination of a high-resolution structure is extremely beneficial. This information can be used to select tractable targets from the proteomic pipeline because the presence of a metal often improves protein stability and can be used to help solve the phasing problem in x-ray crystallography. Recombinant proteins are often purified with substoichiometric amounts of metal loaded, so additional metal may be needed to obtain the homogeneous protein solution crucial for structural analysis. Furthermore, identifying a metal cofactor provides a clue about the nature of the biological role of an unclassified protein and can be applied with structural data in the assignation of a putative function. Many of the existing methods for transition metal analysis of purified proteins have limitations, which include a requirement for a large quantity of protein or a reliance on equipment with a prohibitive cost.The authors have developed two simple high throughput methods for identifying metalloproteins on a microgram scale. Each of the techniques has distinct advantages and can be applied to address divergent experimental goals. The first method, based on simple luminescence and colorimetric reactions, is fast, cheap, and semiquantitative. The second method, which employs HPLC separation, is accurate and affords unambiguous metal identification. PMID:18542873

  3. The origin of half-metallicity in conjugated electron systems—a study on transition-metal-doped graphyne

    We studied the mechanism of half-metallicity (HM) formation in transition-metal-doped conjugated carbon based structures by first-principles electronic structure simulations. It is found that the HM is a rather complex phenomenon, determined by the ligand field splitting of d-orbitals of the transition metal atoms, the exchange splitting and the number of valence electrons. Since most of the conjugated carbon based structures possess ligands with intermediate strength, the ordering of the d-orbital splitting is similar in all structures, and the HM properties evolve according to the number of valence electrons. Based on this insight we predict that Cr-, Fe- and Co-doped graphyne will show HM, while Mn- and Ni-doped graphyne will not. By tuning the number of valence electrons, we are thus able to control the emergence of HM and control the energy gaps evolving in the majority or minority spin channels. (paper)

  4. Metallic-like to nonmetallic transitions in a variety of heavily oxygen deficient ferroelectrics

    The coupling between ferroelectric distortions and electron transport is an important factor in understanding ferroelectric/noncentrosymmetric materials with metallic conductivities and ferroelectric-based thermoelectrics. Here, multiple d0 ferroelectrics with a variety of crystal structures are doped via oxygen deficiency, resulting in metallic-like conduction in the paraelectric state. It is found that most of the studied systems show a metallic-like to nonmetallic transition near the paraelectric-ferroelectric transition. The metallic-like to nonmetallic transition temperature can be shifted using mechanisms that shift the paraelectric-ferroelectric transition temperature. It was found that the metallic-like to nonmetallic transition temperature could be shifted from 373 K to 273 K by varying (Ba1−xSrx)TiO3−δ from x = 0 to x = 0.3 and x = 1. The most probable mechanism for ferroelectric-electron transport coupling was determined to be Anderson localization associated with polarization with short-range order

  5. Semiconductor-to-metal transition in trans-polyacetylene (the role of correlated solitons

    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 .

  6. Insulator-metal transition studied by heat capacity measurements on SmS

    We have measured the specific heat of SmS at pressures up to ∼7.5 kbar. We have observed that the electronic specific heat coefficient γ shows a steep increase at around Pc∼3.5 kbar, which corresponds to an insulator-metal phase transition. In the metal phase above Pc, we have found that γ reaches 100 mJ/mol K2, indicating a strongly correlated metallic state. In the insulator phase, on the other hand, we have observed an anomaly in the temperature dependence of the specific heat around 1 K, which seems to survive in the metal phase

  7. Gas bubble detection in liquid metals by means of the ultrasound transit-time-technique

    Liquid metals are used in nuclear energy technology and a precise knowledge of the distribution of the gas bubbles and their behaviour inside liquid metals is very useful. In this work the ultrasound-transit time technique is introduced as a versatile method to analyze the bubble dynamics in liquid-metal-gas flows. After discussing the principle of operation and the implementation of the technique, the methods used to extract the positions of the bubbles, their velocities, or their diameters are explained. Finally, the performance of the method is demonstrated for a liquid-metal-gas flow with and without a magnetic field. (authors)

  8. Polymer derived non-oxide ceramics modified with late transition metals.

    Zaheer, Muhammad; Schmalz, Thomas; Motz, Günter; Kempe, Rhett

    2012-08-01

    This tutorial review highlights the methods for the preparation of metal modified precursor derived ceramics (PDCs) and concentrates on the rare non-oxide systems enhanced with late transition metals. In addition to the main synthetic strategies for modified SiC and SiCN ceramics, an overview of the morphologies, structures and compositions of both, ceramic materials and metal (nano) particles, is presented. Potential magnetic and catalytic applications have been discussed for the so manufactured metal containing non-oxide ceramics. PMID:22337594

  9. Metal-insulator transition and superconductivity in heavily boron-doped diamond and related materials

    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

  10. Metal-insulator transition and superconductivity in heavily boron-doped diamond and related materials

    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 nc 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 (∼ 500 cm-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 gc. The granularity also influences significantly the superconducting properties by introducing the superconducting gap Δ 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 first time in aluminum

  11. Main Group Lewis Acid-Mediated Transformations of Transition-Metal Hydride Complexes.

    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. PMID:27164024

  12. Electron dynamics of transition metal compounds studied with resonant soft X-ray scattering

    High resolution experimental data for resonant soft x-ray scattering of transition metal compounds are shown. The compounds studied are the ionic transition metal di-fluorides, ionic and covalent ortho vanadates and members of the La1-xSrxCoO3 perovskite family. In all compounds we studied the transition metal L2,3 edge and also the ligand (oxygen or fluorine) K edge. For the ionic compounds the transition metal data are in good agreement with atomic multiplet ligand field calculations that include charge transfer effects. Density functional calculations give very useful information to interpret the ligand x-ray emission data. The experimental metal Lα emission data show that the region between valence and conduction bands in the di-fluorides has several d-excited states. At the L2 edge of the ionic ortho vanadates we found the signature of a fast Coster-Kronig decay process that results in a very localized emission peak. Changes in the oxidation states in the La1-xSrxCoO3 compounds are observed at both the metal L2,3 edge and the oxygen K edge absorption spectra. (Author)

  13. Chemical compatibility between lithium compounds and transition metals

    The aim is to investigate the chemical reactions or otherwise of lithium compounds; Li7Pb2 (a tritium breeder), Li2O (breeder and impurity), Li3N and LiH (impurities) with containment and fusion reactor component metals - 316 and austenitic steels, titanium. Experimental details are given and results are summarized. (author)

  14. Enhancement of Platinum Cathode Catalysis by Addition of Transition Metals

    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…

  15. On Transition Metal Catalyzed Reduction of N-nitrosodimethlamine

    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.

  16. Optical lifetime and linewidth studies of the {sup 7}F{sub 0}{yields}{sup 5}D{sub 0} transition in EuCl{sub 3}{center_dot}6H{sub 2}O: A potential material for quantum memory applications

    Ahlefeldt, R.L., E-mail: rose.ahlefeldt@anu.edu.au [Centre for Quantum Computation and Communication Technology, Research School of Physics and Engineering, The Australian National University, Canberra, Australian Capital Territory 0200 (Australia); Manson, N.B. [Laser Physics Centre, Research School of Physics and Engineering, The Australian National University, Canberra, Australian Capital Territory 0200 (Australia); Sellars, M.J. [Centre for Quantum Computation and Communication Technology, Research School of Physics and Engineering, The Australian National University, Canberra, Australian Capital Territory 0200 (Australia)

    2013-01-15

    The effect of substituting deuterium for hydrogen in EuCl{sub 3}{center_dot}6H{sub 2}O on the lifetime and homogeneous and inhomogeneous linewidths of the {sup 7}F{sub 0}{yields}{sup 5}D{sub 0} transition at below 4 K are investigated. It is observed that the transition lifetime increases from 116{mu}s to 2.6 ms and the homogeneous linewidth decreases from 4.1 kHz to 430 Hz. The sensitivity of the inhomogeneous broadening to the residual hydrogen concentration is estimated to be 91 MHz/atm%. The potential of utilizing this crystal for quantum memory applications is discussed. - Highlights: Black-Right-Pointing-Pointer The optical lifetime of EuCl{sub 3}{center_dot}6H{sub 2}O increases 20 times with full deuteration. Black-Right-Pointing-Pointer An optical coherence time of 740{mu}s was observed in EuCl{sub 3}{center_dot}6D{sub 2}O. Black-Right-Pointing-Pointer High D purity EuCl{sub 3}{center_dot}6H{sub 2}O is a good candidate material for quantum memories.

  17. A high-performance liquid chromatography method for determining transition metal content in proteins.

    Atanassova, Anelia; Lam, Robert; Zamble, Deborah B

    2004-12-01

    Transition metals are common components of cellular proteins and the detailed study of metalloproteins necessitates the identification and quantification of bound metal ions. Screening for metals is also an informative step in the initial characterization of the numerous unknown and unclassified proteins now coming through the proteomic pipeline. We have developed a high-performance liquid chromatography method for the quantitative determination of the most prevalent biological transition metals: manganese, iron, cobalt, nickel, copper, and zinc. The method is accurate and simple and can be adapted for automated high-throughput studies. The metal analysis involves acid hydrolysis to release the metal ions into solution, followed by ion separation on a mixed-bead ion-exchange column and absorbance detection after postcolumn derivatization with the metallochromic indicator 4-(2-pyridylazo)resorcinol. The potential interferences by common components of protein solutions were investigated. The metal content of a variety of metalloproteins was analyzed and the data were compared to data obtained from inductively coupled plasma-atomic emission spectroscopy. The sensitivity of the assay allows for the detection of 0.1-0.8 nmol, depending on the metal. The amount of protein required is governed by the size of the protein and the fraction of protein with metal bound. For routine analysis 50 microg was used but for many proteins 10 microg would be sufficient. The advantages, disadvantages, and possible applications of this method are discussed. PMID:15519577

  18. Atomic and molecular spectroscopy of transition metals in condensed helium

    Full text: We investigated laser induced fluorescence spectra of copper and gold atoms and dimers thereof isolated in solid and liquid 4He. Among the atomic spectral lines the most interesting ones are forbidden transitions that involve electrons from inner d-shells which are screened from the surrounding He atoms by the outer s-shell and are therefore much less affected by the interaction with the He matrix. Indeed, the observed spectral lineshapes are much narrower than those of transitions involving outer shell electrons. Another important result is the observation of well resolved vibrational structures in five molecular bands of the Au2 and Cu2 dimers. We expect that the analysis of those spectra will significantly advance our understanding of impurity atoms and molecules in condensed He. (author)

  19. Reactivities of d~0 transition metal complexes toward oxygen:Synthetic and mechanistic studies

    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.

  20. Bonds Between Metal Atoms: A New Mode of Transition Metal Chemistry.

    Cotton, F. Albert; Chisholm, Malcolm H.

    1982-01-01

    Discusses polynuclear metal clusters (containing two or more metal atoms bonded to one another as well as to nonmetallic elements), including their formation and applications. Studies of bonds between metal atoms reveal superconductors, organic-reaction catalysts, and photosensitive complexes that may play a role in solar energy. (JN)

  1. Synchrotron radiation studies of local structure and bonding in transition metal aluminides and rare earth transition metal magnetic nitrides. Final report, August 1, 1990--July 14, 1993

    The following areas of study are reported on: bonding and near neighbor force constants in NiAl, CoAl, FeAl via temperature dependent EXAFS; alloys formed when Fe or Ga is microalloyed into a NiAl matrix; EXAFS studies of nitrided versus non nitrided Y2Fe17; and transition metal x-ray spectra as related to magnetic moments

  2. Radicals in Transition Metal Catalyzed Reactions? Transition Metal Catalyzed Radical Reactions? A Fruitful Interplay Anyway. Part 1. Radical Catalysis by Group 4 to Group 7 Elements

    Jahn, Ullrich

    Heidelberg : Springer, 2012 - (Heinrich, M.; Gansäuer, A.), s. 121-189 ISBN 978-3-642-28122-8. - (Topic in Current Chemistry. 320) R&D Projects: GA ČR GA203/09/1936 Institutional research plan: CEZ:AV0Z40550506 Keywords : catalysis * cross-coupling * cyclization * electron transfer * radicals * transition metal s Subject RIV: CC - Organic Chemistry

  3. Radicals in Transition Metal Catalyzed Reactions? Transition Metal Catalyzed Radical Reactions? - A Fruitful Interplay Anyway. Part 2. Radical Catalysis by Group 8 to Group 9 Elements

    Jahn, Ullrich

    Heidelberg : Springer, 2012 - (Heinrich, M.; Gansäuer, A.), s. 191-322 ISBN 978-3-642-28122-8. - (Topic in Current Chemistry. 320) R&D Projects: GA ČR GA203/09/1936 Institutional research plan: CEZ:AV0Z40550506 Keywords : catalysis * cross-coupling * cyclization * electron transfer * radicals * transition metals * addition Subject RIV: CC - Organic Chemistry

  4. Radicals in Transition Metal Catalyzed Reactions? Transition Metal Catalyzed Radical Reactions?: A Fruitful Interplay Anyway. Part 3. Catalysis by Group 10 to Group 11 Elements and Bimetallic Catalysis

    Jahn, Ullrich

    Heidelberg : Springer, 2012 - (Heinrich, M.; Gansäuer, A.), s. 323-452 ISBN 978-3-642-28122-8. - (Topic in Current Chemistry. 320) R&D Projects: GA ČR GA203/09/1936 Institutional research plan: CEZ:AV0Z40550506 Keywords : catalysis * cross-coupling * cyclization * electron transfer * radicals * transition metals * addition Subject RIV: CC - Organic Chemistry

  5. Second-Row Transition-Metal Doping of (ZniSi), i = 12, 16 Nanoclusters: Structural and Magnetic Properties

    Elisa Jimenez-Izal; Matxain, Jon M.; Mario Piris; Ugalde, Jesus M

    2013-01-01

    TM@ZniSi nanoclusters have been characterized by means of the Density Functional Theory, in which Transition Metal (TM) stands from Y to Cd, and i = 12 and 16. These two nanoclusters have been chosen owing to their highly spheroidal shape which allow for favored endohedral structures as compared to other nanoclusters. Doping with TM is chosen due to their magnetic properties. In similar cluster-assembled materials, these magnetic properties are related to the Transition Metal-Transition Metal...

  6. Effective modification of MgO with surface transition metal oxides for NF3 decomposition

    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.

  7. Branched chain mechanism of the decomposition of transition metal methyl derivatives

    Data on the thermal and photodecomposition of transition metal methyl derivatives are analyzed. Generalized kinetic model of the process is suggested. It is customary that the main acts of thermal and photodecomposition of transition metal methyl derivatives are homolysis of Me-C bonds, reactions of forming methyl radicals with nondecomposed Me-CH3 groups, decomposition intermediate Me-CH2. radicals with formation of methylene biradical and its following reactions with nondecomposed groups Me-CH3, Me-CH2-Me and Me3CH and solvent. It is shown that the suggested kinetic model allows to explain quantitatively the peculiarities of decomposition of transition metal methyl derivatives and composition of forming products. (author)

  8. Theoretical Investigation of Nonlinear Optical Properties of Organic and Transition Metal Hybrid Azobenzene Dendrimers

    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.

  9. Local electronic structure and magnetic properties of 3d transition metal doped GaAs

    LIN He; DUAN HaiMing

    2008-01-01

    The local electronic structure and magnetic properties of GaAs doped with 3d transition metal (Sc, Ti, V, Cr, Mn, Fe, Co, Ni) were studied by using discrete varia-tional method (DVM) based on density functional theory. The calculated result in-dicated that the magnetic moment of transition metal increases first and then de-creases, and reaches the maximum value when Mn is doped into GaAs. In the case of Mn concentration of 1.4%, the magnetic moment of Mn is in good agreement with the experimental result. The coupling between impure atoms in the system with two impure atoms was found to have obvious variation. For different transition metal, the coupling between the impure atom and the nearest neighbor As also has dif-ferent variation.

  10. Prebiotic coordination chemistry: The potential role of transition-metal complexes in the chemical evolution

    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.

  11. Using a Semiconductor-to-Metal Transition to Control Optical Transmission through Subwavelength Hole Arrays

    R. F. Haglund Jr.

    2008-04-01

    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.

  12. Fabrication of carbon nanotube films from alkyne-transition metal complexes

    Iyer, Vivekanantan S.; Vollhardt, K. Peter C.

    2007-08-28

    A simple method for the production or synthesis of carbon nanotubes as free-standing films or nanotube mats by the thermal decomposition of transition metal complexed alkynes with aryl, alkyl, alkenyl, or alkynyl substituents. In particular, transition metal (e.g. Co, Ni, Fe, Mo) complexes of diarylacetylenes, e.g. diphenylacetylene, and solid mixtures of these complexes with suitable, additional carbon sources are heated in a vessel. More specifically, the heating of the transition metal complex is completed at a temperature between 400-800.degree. C. and more particularly 550-700.degree. C. for between 0.1 to 24 hours and more particularly 0.5-3 hours in a sealed vessel under a partial pressure of argon or helium.

  13. Ferroelasticity and domain physics in two-dimensional transition metal dichalcogenide monolayers.

    Li, Wenbin; Li, Ju

    2016-01-01

    Monolayers of transition metal dichalcogenides can exist in several structural polymorphs, including 2H, 1T and 1T'. The low-symmetry 1T' phase has three orientation variants, resulting from the three equivalent directions of Peierls distortion in the parental 1T phase. Using first-principles calculations, we predict that mechanical strain can switch the relative thermodynamic stability between the orientation variants of the 1T' phase. We find that such strain-induced variant switching only requires a few percent elastic strain, which is eminently achievable experimentally with transition metal dichalcogenide monolayers. Calculations indicate that the transformation barrier associated with such variant switching is small (<0.2 eV per chemical formula unit), suggesting that strain-induced variant switching can happen under laboratory conditions. Monolayers of transition metal dichalcogenides with 1T' structure therefore have the potential to be ferroelastic and shape memory materials with interesting domain physics. PMID:26906152

  14. Influence of the inert and active ion bombardment on structure of the transition metal thin films

    Blazhevich, S; Martynov, I; Neklyudov, I

    2002-01-01

    The results of the experimental research of the inert (He, Ne, Ar, Kr, Xe) and active (O, N) ion impact on the transition metal structure are presented. Thin high-purity (99.999 at.%) films of nickel, chrome and iron were used in the experiment. The bombardment was realized under room temperature at high vacuum (P<1x10 sup - sup 7 Pa) by a separated ion beam of 10-10 sup 3 keV. As a main result of the experiment, the full absence of crystal matrix changes was ascertained for all the transition metals irradiated by inert gas ions. The chemical nature of the crystal structure changes observed in transition metals being under active ion bombardment was found out too.

  15. Metal-insulator transition of 2d electron gas in a random magnetic field

    Wang, X R; Liu, D Z

    1999-01-01

    We study the metal-insulator transition of a two-dimensional electron gas in the presence of a random magnetic field from the localization property. The localization length is directly calculated using a transfer matrix technique and finite size scaling analysis. We argue that there is a metal-insulator transition in such a system and show strong numerical evidence that the system undergoes a disorder driven Kosterlitz-Thouless type metal-insulator transition. We will also discuss a mean field theory which maps the random field system into a two-dimensional XY-model. The vortex and antivortex excitations in the XY-model correspond to two different kinds of magnetic domains in the random field system.

  16. Spin-state transition induced half metallicity in a cobaltate from first principles

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

    2016-02-01

    Half metal is a promising spintronic material. Here, we explore, using first principles calculations, a spin-state transition induced half metallicity in a layered cobaltate via a physical or chemical pressure. Our exemplary first principles study shows that the layered cobaltate Sr2CoO3F would undergo a transition, under a pressure of 5.4 GPa, from a high-spin antiferromagnetic insulator to an intermediate-spin ferromagnetic half-metal. The former phase is associated with a superexchange in a Mott insulator, and the latter one is due to a broad band formation and a kinetic energy gain of the partially occupied eg orbital. Note that the above transition could also be induced by a chemical pressure via doping in (Sr1-xCax)2CoO3F (x > 0.3). This work suggests that a cobaltate would be of a particular interest if stabilized into an intermediate-spin state.

  17. Analysis on insulator–metal transition in yttrium doped LSMO from electron density distribution

    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.

  18. Global transcriptome and deletome profiles of yeast exposed to transition metals.

    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

  19. Structure, bonding, and catalytic activity of monodisperse, transition-metal-substituted CeO2 nanoparticles.

    Elias, Joseph S; Risch, Marcel; Giordano, Livia; Mansour, Azzam N; Shao-Horn, Yang

    2014-12-10

    We present a simple and generalizable synthetic route toward phase-pure, monodisperse transition-metal-substituted ceria nanoparticles (M0.1Ce0.9O2-x, M = Mn, Fe, Co, Ni, Cu). The solution-based pyrolysis of a series of heterobimetallic Schiff base complexes ensures a rigorous control of the size, morphology and composition of 3 nm M0.1Ce0.9O2-x crystallites for CO oxidation catalysis and other applications. X-ray absorption spectroscopy confirms the dispersion of aliovalent (M(3+) and M(2+)) transition metal ions into the ceria matrix without the formation of any bulk transition metal oxide phases, while steady-state CO oxidation catalysis reveals an order of magnitude increase in catalytic activity with copper substitution. Density functional calculations of model slabs of these compounds confirm the stabilization of M(3+) and M(2+) in the lattice of CeO2. These results highlight the role of the host CeO2 lattice in stabilizing high oxidation states of aliovalent transition metal dopants that ordinarily would be intractable, such as Cu(3+), as well as demonstrating a rational approach to catalyst design. The current work demonstrates, for the first time, a generalizable approach for the preparation of transition-metal-substituted CeO2 for a broad range of transition metals with unparalleled synthetic control and illustrates that Cu(3+) is implicated in the mechanism for CO oxidation on CuO-CeO2 catalysts. PMID:25406101

  20. Correlated structural and electronic phase transformations in transition metal chalcogenide under high pressure

    Li, Chunyu; Ke, Feng; Hu, Qingyang; Yu, Zhenhai; Zhao, Jinggeng; Chen, Zhiqiang; Yan, Hao

    2016-04-01

    Here, we report comprehensive studies on the high-pressure structural and electrical transport properties of the layered transition metal chalcogenide (Cr2S3) up to 36.3 GPa. A structural phase transition was observed in the rhombohedral Cr2S3 near 16.5 GPa by the synchrotron angle dispersive X-ray diffraction measurement using a diamond anvil cell. Through in situ resistance measurement, the electric resistance value was detected to decrease by an order of three over the pressure range of 7-15 GPa coincided with the structural phase transition. Measurements on the temperature dependence of resistivity indicate that it is a semiconductor-to-metal transition in nature. The results were also confirmed by the electronic energy band calculations. Above results may shed a light on optimizing the performance of Cr2S3 based applications under extreme conditions.

  1. Raman scattering in transition metal compounds: Titanium and compounds of titanium

    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.

  2. Performance of a 'Transitioned' Infiltration Basin Part 1: TSS, Metals, and Chloride Removals.

    Natarajan, Poornima; Davis, Allen P

    2015-09-01

    The water quality performance of a 'failed' stormwater infiltration basin that has 'transitioned' to a wetpond/wetland has been evaluated over a three-year period. Total suspended solids, heavy metals, and chloride in highway runoff and discharge from the transitioned basin were measured during 38 storm events. The transitioned basin provided significant reductions in TSS Event Mean Concentrations (EMCs) and mass in the runoff. Reductions in metal EMCs generally occurred. Chloride followed a seasonal cycle of high loading and mass export during colder periods, and gradual reductions in both EMCs and mass during other periods. The cumulative mass reductions were 89% TSS, 73% copper, 63% lead, 55% zinc, and 45% chloride for the study period. Combined with the dry-weather water quality in the transitioned basin, the mechanisms of pollutant removal were identified as volume reduction, sedimentation, adsorption, and dilution. The presence of wetpond/wetland features, including hydrophytic vegetatioņ enhanced the pollutant removal processes. PMID:26182408

  3. Review of thermodinamic and mechanical properties of hydrogen-transition metal systems

    A large body of fundamental and empirical knowledge has been acquired during many years of research concerning the interactions between hydrogen and metals, the location of hydrogen in metal structures, its mobility in metals and its influence on mechanical properties of metals. Much progress has been made in the understanding of related phenomena, and various theories have been proposed, but considerable disagreement still exist about basic mechanisms involved. The growing interest in these subjects and their important role in science and technology are well documented by many reviews and symposia. A general survey of these topics with reference to experimental results and theories related to thermodynamic and mechanical properties of hydrogen-transition metal systems, such as H-Pd, H-Ti, H-Fe etc. is given in the present review. Special emphasis is given to hydrogen embrittlement of metals

  4. Mercury Induced by Pressure to act as a Transition Metal in Mercury Fluorides

    Botana, Jorge; Wang, Xiaoli; Hou, Chunju; Yan, Dadong; Lin, Haiqing; Ma, Yanming; Miao, Mao-Sheng

    The question of whether Hg is a transition metal remains open for stable solids. In our work we propose that high-pressure techniques will help prepare unusual oxidation states of Hg in Hg-F compounds. By means of ab initio calculations and an advanced structure-search algorithm we find that under high pressure charge is transferred from the Hg d orbitals to the F, and becomes a transition metal. HgF3 and HgF4 have been found to be stable compounds at high pressure. HgF4 consists of planar molecules, a typical geometry for d8 metallic centers. HgF3 is an example of metallic and ferromagnetic compound, with an electronic structure analogous to transparent conductors due to the Hg d9 configuration.

  5. Hydrogen bond and protonation in carbonyl nitrosyl complexes of transition metals

    Infrared spectroscopy was used to study interaction of CoM(CO)2(NO) π-complexes, where M=Cr, Mo, Cp=η5-C5H5, with perfluorotert butanol (PFTB) and HCl in liquid Xe solutions at low temperatures. It is shown that mentioned complexes can form earlier unknown type of hydrogen bond with PFTB and HCl by oxygen atom of nitrosyl group of transition metal atom. Protonation of complexes dissolved in liquid Xe by transition metal atom during their interaction with HCl was reveald

  6. Inverse correlation between cohesive energy and thermal expansion coefficient in liquid transition metal alloys

    The volume expansion coefficients (α) of twenty-five glass-forming transition metal alloy liquids, measured using the electrostatic levitation technique, are reported. An inverse correlation between α and the cohesive energy is found. The predicted values of α from this relationship agree reasonably well with the published data for thirty other transition metal and alloy liquids; some disagreement was found for a few alloys containing significant amounts of group III and IV elements. A theoretical argument for this empirical relationship is presented. (paper)

  7. Band gap engineering of early transition-metal-doped anatase TiO₂: first principles calculations.

    Li, C; Zhao, Y F; Gong, Y Y; Wang, T; Sun, C Q

    2014-10-21

    The thermal stability and electronic structures of anatase TiO2 doped with early transition metals (TM) (group III-B = Sc, Y and La; group IV-B = Zr and Hf; group V-B = V, Nb and Ta) have been studied using first principles calculations. It was found that all doped systems are thermodynamically stable, and their band gaps were reduced by 1-1.3 eV compared to pure TiO2. Doping with transition metals affects the strength of the hybrid orbital of TM-O bonding, and the band gap increases approximately linearly with the MP value of TM-O bonding. PMID:25183457

  8. Trends in the Hydrodeoxygenation Activity and Selectivity of Transition Metal Surfaces

    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 ....... Furthermore, the insights discussed in this paper present a framework for designing catalytic materials for facilitating these conversions efficiently.......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...

  9. An inverse-scattering approach to the physics of transition metals

    A method is developed for the deduction of a transition metal ion potential from the knowledge of the phase-shift ηl(k). The method used is based on the distorted plane-wave scattering approximation for the deduction of nonsingular potentials from scattering phase shifts in an inverse-scattering approach. The resulting electron-ion potential obtained is a finite Dirichlet series sum of short-range exponential functions. The Fourier transform of the potential is obtained for applications in the area of transition metal solid-state physics

  10. Magnetism of 3d transition-metal monolayers on Rh(100)

    A. Al-Zubi; Bihlmayer, G.; Blügel, S.

    2011-01-01

    We employ the full-potential linearized augmented plane-wave method to report a systematic density-functional theory study of the magnetic properties of the 3d transition-metal (V, Cr, Mn, Fe, Co, and Ni) monolayers deposited on the Rh(100) substrate. We find that all monolayer films are magnetic. The size of the local magnetic moments across the transition-metal series follows Hund's rule with a maximum magnetic moment of 3.77 mu(B) for Mn. The largest induced magnetic moment of about 0.46 m...

  11. Electron spectroscopic investigation of metal-insulator transition in Ce1-SrTiO3

    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.

  12. Soft X-Ray Spectroscopic Study of Fullerene Based Transition-Metal Compounds and Related Systems

    Qian, Limin

    2001-01-01

    This thesis addresses the electronic and geometric structures of fullerene based transition-metal compounds and other related systems. The formation of TixC60, VxC60 and NbxC60 compounds has been examined by X-ray photoelectron, soft X-ray absorption and emission and spectroscopy techniques, including resonant inelastic X-ray scattering (RIXS). The symmetry and character of the chemical bond of transition metal-fulleride has been determined. A related study of single-walled carbon nanotubes i...

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

    van Dover, R. B.; 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 found that δ-NbN and YN form a continuous (Nb,Y)N solid solution of the NaCl type, in which the superconducting transition temperature varies with the Nb:Y ratio. In the Gd-Cr-N system only limited ...

  14. Low-frequency impedance in thin films near the metal-semiconductor phase transition

    Kompan, M. E.; Klimov, V. A.; Nikitin, S. E.; Kompan, F. M.; Goffman, V. G.; Terukov, E. I.

    2015-09-01

    The impedance of thin VO2 films at temperatures near the metal-semiconductor phase transition has been studied. It has been found that, in the low-temperature region, there is an abrupt change in the impedance. It has been demonstrated that the nature of this phenomenon is connected with thermoinertial processes in the film. From the experimental data, the heat conductivity of the film/substrate transition layer has been evaluated.

  15. d-Wave to s-wave to normal metal transitions in disordered superconductors

    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

  16. d-Wave to s-wave to normal metal transitions in disordered superconductors

    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.

  17. Semiconductor-metal transition in thin VO2 films grown by ozone based atomic layer deposition

    Rampelberg, Geert; Schaekers, Marc; Martens, Koen; Xie, Qi; Deduytsche, Davy; De Schutter, Bob; Blasco, Nicolas; Kittl, Jorge; Detavernier, Christophe

    2011-01-01

    Vanadium dioxide (VO2) has the interesting feature that it undergoes a reversible semiconductor-metal transition (SMT) when the temperature is varied near its transition temperature at 68°C.1 The variation in optical constants makes VO2 useful as a coating material for e.g. thermochromic windows,2 while the associated change in resistivity could be interesting for applications in microelectronics, e.g. for resistive switches and memories.3 Due to aggressive scaling and increasing integration ...

  18. Separating electric field and thermal effects across the metal-insulator transition in vanadium oxide nanobeams

    Stabile, Adam A.; Singh, Sujay K.; Wu, Tai-Lung; Whittaker, Luisa; Banerjee, Sarbajit; Sambandamurthy, G.

    2014-01-01

    We present results from an experimental study of the equilibrium and non-equilibrium transport properties of vanadium oxide nanobeams near the metal-insulator transition (MIT). Application of a large electric field in the insulating phase across the nanobeams produces an abrupt MIT and the individual roles of thermal and non-thermal effects in driving the transition are studied. Transport measurements at temperatures ($T$) far below the critical temperature ($T_c$) of MIT, in several nanoscal...

  19. Transition absorption as a mechanism of surface photoelectron emission from metals

    Zhukovsky, Sergei; Protsenko, Igor E.; Ikhsanov, Renat Sh; Smetanin, Igor V.; Babicheva, Viktoriia; Uskov, Alexander

    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....

  20. The origin of increase of damping in transition metals with rare earth impurities

    Hohlfeld, A. Rebei J.

    2006-01-01

    The damping due to rare earth impurities in transition metals is discussed in the low concentration limit. It is shown that the increase in damping is mainly due to the coupling of the orbital moments of the rare earth impurities and the conduction $p$-electrons. It is shown that an itinerant picture for the host transition ions is needed to reproduce the observed dependence of the damping on the total angular moment of the rare earths.

  1. Colorimetric and fluorimetric assays to quantitate micromolar concentrations of transition metals.

    McCall, K A; Fierke, C A

    2000-09-10

    Transition metal ions, although maintained at low concentrations, play diverse important roles in many biological processes. Two assays useful for the rapid quantification of a range of first-row transition metal ions have been developed. The colorimetric assay extends the 4-(2-pyridylazo)resorcinol assay of Hunt et al. (J. Biol. Chem. 255, 14793 (1984)) to measure nanomole quantities of Co(2+), Ni(2+), and Cu(2+) as well as Zn(2+). The fluorimetric assay takes advantage of the coordination of a number of metal ions (Mn(2+), Co(2+), Ni(2+), Cu(2+), Zn(2+), Cd(2+)) by Fura-2 and can also be used to measure nanomole quantities of these ions. The assays developed here have the advantage of not requiring the extensive sample preparation necessary for other methodologies, such as atomic absorption spectroscopy and inductively coupled plasma emission spectroscopy (ICPES), while being comparable in accuracy to the detection limits of ICPES for the first-row transition metal ions. To demonstrate the effectiveness of these assays, we determined the affinity of carbonic anhydrase II (CA II), a prototypical zinc enzyme, for Ni(2+) and Cd(2+). These data indicate that CA II binds transition metals with high affinity and is much more selective for Zn(2+) over Ni(2+) or Cd(2+) than most small-molecule chelators or other metalloenzymes. PMID:10964414

  2. Phase transitions and adsorbate restructuring at metal surface

    King, DA

    1994-01-01

    The objective in initiating this series in 1980 was to provide an in-depth review of advances made in the understanding key aspects of surface chemistry and physics through the application of new techniques to the study of well-defined surfaces. Since then the field of surface science has greatly matured, and further important techniques, particularly scanning probe microscopies, have been successfully assimilated into the applications armoury of the surface scientist. The present volume is a series of timely reviews by many of the current experts in the field of phase transitions an

  3. Studies on Transition Metal-Quercetin Complexes Using Electrospray Ionization Tandem Mass Spectrometry

    Yuanzhen Liu

    2015-05-01

    Full Text Available To systematically study the effects of the number of d electrons of the first transition metal ions (Fe, Co, Ni, Cu and Zn on the formation and stability of metal flavonoid complexes, we took the quercetin/M2+ complex as a model system to investigate the structures and properties of these complexes. Based on considerable structural information obtained through ESI-MSn, all of the first transition metal ions (Fe2+, Co2+, Ni2+, Cu2+ and Zn2+ were found to form different complexes with quercetin, while with the number of chelating flavonoids decreasing along with the reduction of the metal ionic radius. Quercetin forms different complexes with the above metal divalent ions through its 5-OH and 4-carbonyl groups; the complex stability is highly dependent on both the metallic ion and the flavonoid chelator itself. As for the central ion (M2+, when chelated with quercetin to form the complex, the stability of the complex decreased in the following order: Cu2+ > Ni2+ > Co2+ > Fe2+ > Zn2+. With flavonoid: metal stoichiometries at 2:1, the complexes formed between quercetin and metal ions (Fe2+, Ni2+, Co2+ and Zn2+ have the similar fragmentation mechanism, while Cu2+ displayed different fragmentation mechanism due to the concurrent oxidation.

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

    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. - This study has demonstrated exposure to alkali, alkali earth and transition metals in pregnant women with factors such as breastfeeding, fish oil use and diet affecting exposures

  5. Studies of high temperature ternary phases in mixed-metal-rich early transition metal sulfide and phosphide systems

    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.

  6. Targeted Catalytic Inactivation of Angiotensin Converting Enzyme by Lisinopril-Coupled Transition Metal Chelates

    Joyner, Jeff C.; Hocharoen, Lalintip; Cowan, J. A.

    2012-01-01

    A series of compounds that target reactive transition metal chelates to somatic Angiotensin Converting Enzyme (sACE-1) have been synthesized. Half maximal inhibitory concentrations (IC50) and rate constants for both inactivation and cleavage of full length sACE-1 have been determined and evaluated in terms of metal-chelate size, charge, reduction potential, coordination unsaturation, and coreactant selectivity. Ethylenediamine-tetraacetic acid (EDTA), nitrilotriacetic acid (NTA), 1,4,7,10-tet...

  7. Investigation of metal-insulator like transition through the ab initio density matrix renormalization group approach

    Fertitta, E.; Paulus, B.; Barcza, G.; Legeza, Ö.

    2014-01-01

    We have studied the Metal-Insulator like Transition (MIT) in lithium and beryllium ring-shaped clusters through ab initio Density Matrix Renormalization Group (DMRG) method. Performing accurate calculations for different interatomic distances and using Quantum Information Theory (QIT) we investigated the changes occurring in the wavefunction between a metallic-like state and an insulating state built from free atoms. We also discuss entanglement and relevant excitations among the molecular or...

  8. Adsorption of Alkali, Alkaline Earth and Transition Metal Atoms on Silicene

    Sahin, Hasan; Peeters, Francois M.

    2013-01-01

    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, workfuncti...

  9. Metal to Insulator Quantum-Phase Transition in Few-Layered ReS₂.

    Pradhan, Nihar R; McCreary, Amber; Rhodes, Daniel; Lu, Zhengguang; Feng, Simin; Manousakis, Efstratios; Smirnov, Dmitry; Namburu, Raju; Dubey, Madan; Walker, Angela R Hight; Terrones, Humberto; Terrones, Mauricio; Dobrosavljevic, Vladimir; Balicas, Luis

    2015-12-01

    In ReS2, a layer-independent direct band gap of 1.5 eV implies a potential for its use in optoelectronic applications. ReS2 crystallizes in the 1T'-structure, which leads to anisotropic physical properties and whose concomitant electronic structure might host a nontrivial topology. Here, we report an overall evaluation of the anisotropic Raman response and the transport properties of few-layered ReS2 field-effect transistors. We find that ReS2 exfoliated on SiO2 behaves as an n-type semiconductor with an intrinsic carrier mobility surpassing μ(i) ∼ 30 cm(2)/(V s) at T = 300 K, which increases up to ∼350 cm(2)/(V s) at 2 K. Semiconducting behavior is observed at low electron densities n, but at high values of n the resistivity decreases by a factor of >7 upon cooling to 2 K and displays a metallic T(2)-dependence. This suggests that the band structure of 1T'-ReS2 is quite susceptible to an electric field applied perpendicularly to the layers. The electric-field induced metallic state observed in transition metal dichalcogenides was recently claimed to result from a percolation type of transition. Instead, through a scaling analysis of the conductivity as a function of T and n, we find that the metallic state of ReS2 results from a second-order metal-to-insulator transition driven by electronic correlations. This gate-induced metallic state offers an alternative to phase engineering for producing ohmic contacts and metallic interconnects in devices based on transition metal dichalcogenides. PMID:26599563

  10. Transition metal based layered double hydroxides tailored for energy conversion and storage

    Xia Long; Zilong Wang; Shuang Xiao; Yiming An; Shihe Yang

    2016-01-01

    Layered double hydroxides (LDHs) are a class of clays with brucite like layers and intercalated anions. The first (3d) series transition metals based LDHs (TM-LDHs) are attracting increasing interest in the field of energy conversion and storage processes due to their unique physicochemical properties. In this article, we review recent developments in the synthesis and applications of TM-LDH in these areas including water splitting, CO2 conversion, metal-air batteries and supercapacitors and ...

  11. Regularities of formation of ternary alloy phases between non-transition metals

    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).

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

    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.

  13. Electrodynamics near the Metal-to-Insulator Transition in V3O5

    Baldassarre, L.; Perucchi, A.; Arcangeletti, E.; Nicoletti, D.; Di Castro, D; Postorino, P.; Sidorov, V. A.; Lupi, S.

    2007-01-01

    The electrodynamics near the metal-to-insulator transitions (MIT) induced, in V3O5 single crystals, by both temperature (T) and pressure (P) has been studied by infrared spectroscopy. The T- and P-dependence of the optical conductivity may be explained within a polaronic scenario. The insulating phase at ambient T and P corresponds to strongly localized small polarons. Meanwhile the T-induced metallic phase at ambient pressure is related to a liquid of polarons showing incoherent dc transport...

  14. Dynamical conductivity at the dirty superconductor-metal quantum phase transition.

    Del Maestro, Adrian; Rosenow, Bernd; Hoyos, José A; Vojta, Thomas

    2010-10-01

    We study the transport properties of ultrathin disordered nanowires in the neighborhood of the superconductor-metal quantum phase transition. To this end we combine numerical calculations with analytical strong-disorder renormalization group results. The quantum critical conductivity at zero temperature diverges logarithmically as a function of frequency. In the metallic phase, it obeys activated scaling associated with an infinite-randomness quantum critical point. We extend the scaling theory to higher dimensions and discuss implications for experiments. PMID:21230844

  15. Selective removal of transition metals from acidic mine waters by novel consortia of acidophilic sulfidogenic bacteria

    Ňancucheo, Ivan; Johnson, D. Barrie

    2011-01-01

    Summary Two continuous‐flow bench‐scale bioreactor systems populated by mixed communities of acidophilic sulfate‐reducing bacteria were constructed and tested for their abilities to promote the selective precipitation of transition metals (as sulfides) present in synthetic mine waters, using glycerol as electron donor. The objective with the first system (selective precipitation of copper from acidic mine water containing a variety of soluble metals) was achieved by maintaining a bioreactor p...

  16. Observation of an unconventional metal-insulator transition in overdoped CuO_2 compounds

    Venturini, F.; Opel, M.; Devereaux, T. P.; Freericks, J. K.; Tüttő, I.; Revaz, B.; Walker, E.; Berger, H; Forró, L.; Hackl, R.

    2002-01-01

    The electron dynamics in the normal state of Bi$_2$Sr$_2$CaCu$_2$O$_{8+\\delta}$ is studied by inelastic light scattering over a wide range of doping. A strong anisotropy of the electron relaxation is found which cannot be explained by single-particle properties alone. The results strongly indicate the presence of an unconventional quantum-critical metal-insulator transition where "hot" (antinodal) quasiparticles become insulating while "cold" (nodal) quasiparticles remain metallic. A phenomen...

  17. Sulfonate Functionalisation of Transition Metal Complexes: A Versatile Tool Towards Catalyst Recovery

    Virboul, M.A.N.

    2011-01-01

    This thesis describes the synthesis and application of sulfonate-functionalised ligands in organometallic chemistry and (aqueous) catalysis. Due to their ability to trigger specific solubility, different NHC ligand precursors bearing a butyl-sulfonate chain were synthesised. The formation of transition metal complexes containing gold and rhodium was enabled by a simple procedure involving the initial synthesis of a silver complex and a transmetallation with a suitable metal precursor and an o...

  18. Mononuclear and oligonuclear transition metal complexes with acyclic and macrocyclic ligands

    Rösel, Pirmin

    2009-01-01

    Chapter 1 describes an efficient multi-step synthesis of an endotopic but sterically un¬hindered biisoquinoline decorated with long alkyl groups for better solubility. This chelate is ideally suited for macrocycle formation around transition metal ions and therefore a valuable new building block for topological chemistry. Sokolov’s concept to use an octahedral metal template for the syntheses of macrocycles and molecular knots is discussed in Chapter 2. The concept was successfully realise...

  19. Etymology of transition metal biomolecules as a learning aid in Biological Chemistry

    Numerous functional biomolecules are associated with metals, i.e. the metallobiomolecules; more specifically, some are dependent on transition metals required for several crucial biological roles. Nevertheless, their names can lead to ambiguous interpretations concerning the properties and performances of this group of biological molecules. Their etymology may be useful by providing a more perceptive insight into their features. However, etymology can lead to incongruous conclusions, requiring an especially careful approach to prevent errors. Examples illustrating these subjects shall be examined (author)

  20. Metal-insulator transition in nanocomposite VOx films formed by anodic electrodeposition

    Tsui, Lok-kun; Hildebrand, Helga; Lu, Jiwei; Schmuki, Patrik; Zangari, Giovanni

    2014-01-01

    The ability to grow VO2 films by electrochemical methods would open a low-cost, easily scalable production route to a number of electronic devices. We have synthesized VOx films by anodic electrodeposition of V2O5, followed by partial reduction by annealing in Ar. The resulting films are heterogeneous, consisting of various metallic/oxide phases and including regions with VO2 stoichiometry. A gradual metal insulator transition with a nearly two order of magnitude change in film resistance is ...

  1. Hydrogen evolution on nano-particulate transition metal sulfides

    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...... sulfides with morphologies similar to MoS2 such as WS2, cobalt- promoted WS2, and cobalt-promoted MoS2 were also investigated in the search for improved HER activity. Experimental findings are compared to density functional theory (DFT) calculated values for the hydrogen binding energies (Delta G(H)) on...

  2. Holographic entanglement entropy in metal/superconductor phase transition with Born–Infeld electrodynamics

    We investigate the holographic entanglement entropy in the metal/superconductor phase transition for the Born–Infeld electrodynamics with full backreaction and note that the entropy is a good probe to study the properties of the phase transition. For the operator 〈O−〉, we find that the entanglement entropy decreases (or increases) with the increase of the Born–Infeld parameter b in the metal (or superconducting) phase. For the operator 〈O+〉, we observe that, with the increase of the Born–Infeld parameter, the entanglement entropy in the metal phase decreases monotonously but the entropy in the superconducting phase first increases and forms a peak at some threshold bT, then decreases continuously. Moreover, the value of bT becomes smaller as the width of the subsystem A decreases. - Highlights: • We study holographic entanglement entropy in metal/superconductor phase transition for Born–Infeld electrodynamics with full backreaction. • For operator 〈O−〉, entanglement entropy decreases (or increases) with increase of parameter b in metal (or superconducting) phase. • For operator 〈O+〉, with increase of Born–Infeld parameter, the entanglement entropy in the metal phase decreases monotonously but entropy in superconducting phase first increases and forms a peak at some threshold bT, then decreases continuously as increase of b, • The value of bT becomes smaller as the width of the subsystem A decreases

  3. Heterocyclic ring based colorimetric and fluorescent chemosensor for transition metal ions in an aqueous medium

    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.

  4. Functionalized graphene as a model system for the two-dimensional metal-insulator transition

    Osofsky, M. S.; Hernández, S. C.; Nath, A.; Wheeler, V. D.; Walton, S. G.; Krowne, C. M.; Gaskill, D. K.

    2016-02-01

    Reports of metallic behavior in two-dimensional (2D) systems such as high mobility metal-oxide field effect transistors, insulating oxide interfaces, graphene, and MoS2 have challenged the well-known prediction of Abrahams, et al. that all 2D systems must be insulating. The existence of a metallic state for such a wide range of 2D systems thus reveals a wide gap in our understanding of 2D transport that has become more important as research in 2D systems expands. A key to understanding the 2D metallic state is the metal-insulator transition (MIT). In this report, we explore the nature of a disorder induced MIT in functionalized graphene, a model 2D system. Magneto-transport measurements show that weak-localization overwhelmingly drives the transition, in contradiction to theoretical assumptions that enhanced electron-electron interactions dominate. These results provide the first detailed picture of the nature of the transition from the metallic to insulating states of a 2D system.

  5. Molecular dynamics simulations of Pd-Ni transition metal alloys

    Molecular Dynamics simulations are performed to study bulk properties of fcc metals and metal alloys by using the quantum Sutton-Chen many-body potentials within the context of the tight-binding approach. The Molecular Dynamics algorithms we used in the simulations of Pd-Ni alloys are based on an extended Hamiltonian formalism arising from the works of Andersen (1980), Parinello and Rahman (1980), Nose (1984), Hoover (1985) and Cagin (1988). In these simulations, the effect of temperature and concentration on the solid and liquid properties are studied. Elastic constants and phonon dispersion relation are the solid properties we simulated in this work. Dynamic and static properties of liquid Pd-Ni are also computed by examining the behavior of density, enthalpy, pair distribution function and structure factor. The melting temperatures of Pd-Ni alloys are investigated. The diffusion coefficients are calculated from the mean square displacement using Einstein relation and from velocity auto-correlation function using Green-Kubo relations. The simulation results are in good agreement with the experiments

  6. Metal-insulator transition and local-moment collapse in FeO under pressure

    Leonov, I.

    2015-01-01

    We employ a combination of the \\emph{ab initio} band structure methods and dynamical mean-field theory to determine the electronic structure and phase stability of paramagnetic FeO at high pressure and temperature. Our results reveal a high-spin to low-spin transition within the B1 crystal structure of FeO upon compression of the lattice volume above 73~GPa. The spin-state transition is accompanied by an orbital-selective Mott metal-insulator transition (MIT). The lattice volume is found to c...

  7. Reactivity patterns of transition metal hydrides and alkyls

    The complex PPN+ CpV(CO)3H- (Cp=eta5-C5H5 and PPN = (Ph3P)2) was prepared in 70% yield and its physical properties and chemical reactions investigated. PPN+ CpV(CO)3H- reacts with a wide range of organic halides. The organometallic products of these reactions are the vanadium halides PPN+[CpV(C)3X]- and in some cases the binuclear bridging hydride PPN+ [CpV(CO)3]2H-. The borohydride salt PPN+[CpV(CO)3BH4]- has also been prepared. The reaction between CpV(CO)3H- 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)3H-. Sodium amalgam reduction of CpRh(CO)2 or a mixture of CpRh(CO)2 and CpCo(CO)2 affords two new anions, PPN+ [Cp2Rh3(CO)4]- and PPN+[Cp2RhCo(CO)2]-. CpMo(CO)3H reacts with CpMo(CO)3R (R=CH3,C2H5, CH2C6H5) at 25 to 500C to produce aldehyde RCHO and the dimers [CpMo(CO)3]2 and [CpMo(CO)2]2. In general, CpV(CO)3H- appears to transfer a hydrogen atom to the metal radical anion formed in an electron transfer process, whereas CpMo(CO)3H transfers hydride in a 2-electron process to a vacant coordination site. The chemical consequences are that CpV(CO)3H- generally reacts with metal alkyls to give alkanes via intermediate alkyl hydride species whereas CpMo(CO)3H reacts with metal alkyls to produce aldehyde, via an intermediate acyl hydride species

  8. Electronic and thermodynamic properties of the transition between metallic and nonmetallic states in dense media

    The effects of thermal excitation are introduced in the study of a simple electronic structure model for condensed media. The choice of a particle-interaction potential leads to a self-consistent calculation performed on a computer. This calculation gives a metal - nonmetal transition similar to the MOTT transition. We consider the effects of temperature and density variations upon this transition. It is possible to make use of this electronic structure to obtain the thermodynamic properties near the transition: pressure, free energy, sound velocity. The numerical results of this simple model are satisfactory. Particularly, if a dielectric constant is taken into account, the transition temperature and density are of the same order of magnitude as those observed experimentally in semiconductors. (author)

  9. Trends in the chemical properties in early transition metal carbide surfaces: A density functional study

    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 are...... closest-packed pure metal surfaces, due to the tensile strain induced in the carbide surfaces upon incorporation of carbon into the lattice. Hydrogen atoms were found to adsorb more weakly on carbide surfaces than on the corresponding closest-packed pure metal surfaces only when there were surface carbon...

  10. Using scaling relations to understand trends in the catalytic activity of transition metals

    A method is developed to estimate the potential energy diagram for a full catalytic reaction for a range of late transition metals on the basis of a calculation (or an experimental determination) for a single metal. The method, which employs scaling relations between adsorption energies, is illustrated by calculating the potential energy diagram for the methanation reaction and ammonia synthesis for 11 different metals on the basis of results calculated for Ru. It is also shown that considering the free energy diagram for the reactions, under typical industrial conditions, provides additional insight into reactivity trends

  11. Relative abundance determinations in extremely metal poor giants. II. Transition probabilities and the abundance determinations

    The abundances of Fe and other elements are determined for a star of intermediate metallicity and for nine extremely metal poor stars, including two members of the globular cluster M92 and CD -38 deg 245. The accuracy of the transition probabilities for Fe I and other elements is evaluated. The distribution of the abundances of other elements with respect to Fe is the same for most of the cases studied. Manganese is the only element that shows a different relative abundance in an extremely metal poor star. 120 refs

  12. 5D supergravity and projective superspace

    Kuzenko, Sergei M.; Tartaglino-Mazzucchelli, Gabriele

    2008-02-01

    This paper is a companion to our earlier work [1] in which the projective superspace formulation for matter-coupled simple supergravity in five dimensions was presented. For the minimal multiplet of 5D Script N = 1 supergravity introduced by Howe in 1981, we give a complete solution of the Bianchi identities. The geometry of curved superspace is shown to allow the existence of a large family of off-shell supermultiplets that can be used to describe supersymmetric matter, including vector multiplets and hypermultiplets. We formulate a manifestly locally supersymmetric action principle. Its natural property turns out to be the invariance under so-called projective transformations of the auxiliary isotwistor variables. We then demonstrate that the projective invariance allows one to uniquely restore the action functional in a Wess-Zumino gauge. The latter action is well-suited for reducing the supergravity-matter systems to components.

  13. Ultramicrosensors based on transition metal hexacyanoferrates for scanning electrochemical microscopy

    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.

  14. Coherent/incoherent metal transition in a holographic model

    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. The Effect of Enhanced Spin-Orbit Scattering on the Superconducting - Nonsuperconducting Transition and the Metal-Insulator Transition in Granular Aluminum.

    Miller, Theodore A.

    A small amount of bismuth was added to a set of granular aluminum samples to increase the spin-orbit scattering rate. This set is compared with a second set with no bismuth added. With the addition of bismuth, both the metal-insulator transition and the threshold for the presence of superconductivity were shifted a similar amount to higher values of resistivity. The shift of the metal-insulator transition can be explained as a result of the effect of increased spin -orbit scattering at an Anderson transiton. The fact that the superconducting threshold also shifts indicates that it is the proximity to the metal-insulator transition that depresses superconductivity.

  16. Development of new transition metal oxide catalysts for the destruction of PCDD/Fs.

    Yu, Ming-Feng; Li, Wen-Wei; Li, Xiao-Dong; Lin, Xiao-Qing; Chen, Tong; Yan, Jian-Hua

    2016-08-01

    Various transition metal oxide and vanadium-containing multi-metallic oxide catalysts were developed for the destruction of PCDD/Fs (polychlorinated dibenzo-p-dioxins and furans). A stable PCDD/Fs generating system was installed to support the catalytic destruction tests in this study. Nano-titania supported vanadium catalyst (VOx/TiO2) showed the highest activity, followed by CeOx, MnOx, WOx and finally MoOx. Multi-metallic oxide catalysts, prepared by doping WOx, MoOx, MnOx and CeOx into VOx/TiO2 catalysts, showed different activities on the decomposition of PCDD/Fs. The highest destruction efficiency of 92.5% was observed from the destruction test over VOxCeOx/TiO2 catalyst. However, the addition of WOx and MoOx even played a negative role in multi-metallic VOx/TiO2 catalysts. Characterizations of transition metal oxides and multi-metallic VOx/TiO2 catalysts were also investigated with XRD and TPR. After the catalysts were used, the conversion from high valent metals to low valence states was observed by XPS. PMID:27186687

  17. Adhesion and friction of transition metals in contact with nonmetallic hard materials

    Sliding friction experiments were conducted with the metals yttrium, titanium, tantalum, zirconium, vanadium, neodymium, iron, cobalt, nickel, tungsten, platinum, rhenium, ruthenium, and rhodium in sliding contact with single crystal diamond, silicon carbide, pyrolytic boron nitride, and ferrite. Auger electron spectroscopy analysis was conducted with the metals and nonmetals to determine the surface chemistry and the degree of surface cleanliness. The results of the investigation indicate the adhesion and friction of the transition metals in contact with diamond, silicon carbide, boron nitride, and ferrite are related to the relative chemical activity of the metals. The more chemically active the metal, the higher the coefficient of friction and the greater amount of transfer to the nonmetals

  18. Dinuclear first-row transition metal complexes with a naphthyridine-based dinucleating ligand.

    Davenport, T C; Tilley, T D

    2015-07-21

    A series of dinuclear and tetranuclear first-row transition metal complexes were synthesized with the dinucleating ligand 2,7-bis(di(2-pyridyl)fluoromethyl)-1,8-naphthyridine (DPFN). The coordination pocket and rigidity of the DPFN ligand enforces pseudo-octahedral geometries about the metal centers that contain chloro, hydroxo, and aqua bridging ligands forming a "diamond" shaped configuration with metal-metal distances varying from 2.7826(5) to 3.2410(11) Å. Each metal center in the dinuclear complexes has an additional open coordination site that accommodates terminal ligands in a syn geometry of particular interest in catalyst design. The complexes are characterized by electronic spectroscopy, electrochemistry and potentiometric titration methods. PMID:25420206

  19. Adhesion and friction of transition metals in contact with nonmetallic hard materials

    Miyoshi, K.; Buckley, D. H.

    1981-01-01

    Sliding friction experiments were conducted with the metals yttrium, titanium, tantalum, zirconium, vanadium, neodymium, iron, cobalt, nickel, tungsten, platinum, rhenium, ruthenium, and rhodium in sliding contact with single crystal diamond, silicon carbide, pyrolytic boron nitride, and ferrite. Auger electron spectroscopy analysis was conducted with the metals and nonmetals to determine the surface chemistry and the degree of surface cleanliness. The results of the investigation indicate the adhesion and friction of the transition metals in contact with diamond, silicon carbide, boron nitride, and ferrite are related to the relative chemical activity of the metals. The more chemically active the metal, the higher the coefficient of friction and the greater amount of transfer to the nonmetals.

  20. Synthesis, Structure and Characterization of a Series of Transition Metal Complexes with Tripodal Polyimidazole Ligand

    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.