WorldWideScience

Sample records for rocksalt early transition-metal

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

    Energy Technology Data Exchange (ETDEWEB)

    Cardin, D J [Trinity Coll., Dublin (Ireland); Cotton, S A [Stanground School, Peterborough (UK); Green, M [Bristol Univ. (UK); Labinger, J A [Atlantic Richfield Co., Los Angeles, CA (USA); eds.

    1985-01-01

    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.

  2. Structural, mechanical and electronic properties of 3d transition metal nitrides in cubic zincblende, rocksalt and cesium chloride structures: a first-principles investigation

    International Nuclear Information System (INIS)

    Liu, Z T Y; Khare, S V; Zhou, X; Gall, D

    2014-01-01

    We report systematic results from ab initio calculations with density functional theory on three cubic structures, zincblende (zb), rocksalt (rs) and cesium chloride (cc), of the ten 3d transition metal nitrides. We computed lattice constants, elastic constants, their derived moduli and ratios that characterize mechanical properties. Experimental measurements exist in the literature of lattice constants for rs-ScN, rs-TiN and rs-VN and of elastic constants for rs-TiN and rs-VN, all of which are in good agreement with our computational results. Similarly, computed Vickers hardness (H V ) values for rs-TiN and rs-VN are consistent with earlier experimental results. Several trends were observed in our rich data set of 30 compounds. All nitrides, except for zb-CrN, rs-MnN, rs-FeN, cc-ScN, cc-CrN, cc-NiN and cc-ZnN, were found to be mechanically stable. A clear correlation in the atomic density with the bulk modulus (B) was observed with maximum values of B around FeN, MnN and CrN. The shear modulus, Young’s modulus, H V and indicators of brittleness showed similar trends and all showed maxima for cc-VN. The calculated value of H V for cc-VN was about 30 GPa, while the next highest values were for rs-ScN and rs-TiN, about 24 GPa. A relation (H V ∝θ D 2 ) between H V and Debye temperature (θ D ) was investigated and verified for each structure type. A tendency for anti-correlation of the elastic constant C 44 , which strongly influences stability and hardness, with the number of electronic states around the Fermi energy was observed. (paper)

  3. Catalytic olefin polymerization with early transition metal compounds

    NARCIS (Netherlands)

    Eshuis, Johan Jan Willem

    1991-01-01

    The catalysis of organic reactions by soluble metal complexes has become a major tool in synthesis, both in the laboratory and in the chemical industry. Processes catalyzed by transition metal complexes include carbonylation, olefin polymerization, olefin addition, olefin oxidation and alkane and

  4. Design of Nickel-Based Cation-Disordered Rock-Salt Oxides: The Effect of Transition Metal (M = V, Ti, Zr) Substitution in LiNi0.5M0.5O2 Binary Systems.

    Science.gov (United States)

    Cambaz, Musa Ali; Vinayan, Bhaghavathi P; Euchner, Holger; Johnsen, Rune E; Guda, Alexander A; Mazilkin, Andrey; Rusalev, Yury V; Trigub, Alexander L; Gross, Axel; Fichtner, Maximilian

    2018-06-20

    Cation-disordered oxides have been ignored as positive electrode material for a long time due to structurally limited lithium insertion/extraction capabilities. In this work, a case study is carried out on nickel-based cation-disordered Fm3 ̅m LiNi 0.5 M 0.5 O 2 positive electrode materials. The present investigation targets tailoring the electrochemical properties for nickel-based cation-disordered rock-salt by electronic considerations. The compositional space for binary LiM +3 O 2 with metals active for +3/+4 redox couples is extended to ternary oxides with LiA 0.5 B 0.5 O 2 with A = Ni 2+ and B = Ti 4+ , Zr 4+ , and V +4 to assess the impact of the different transition metals in the isostructural oxides. The direct synthesis of various new unknown ternary nickel-based Fm3̅ m cation-disordered rock-salt positive electrode materials is presented with a particular focus on the LiNi 0.5 V 0.5 O 2 system. This positive electrode material for Li-ion batteries displays an average voltage of ∼2.55 V and a high discharge capacity of 264 mAhg -1 corresponding to 0.94 Li. For appropriate cutoff voltages, a long cycle life is achieved. The charge compensation mechanism is probed by XANES, confirming the reversible oxidation and reduction of V 4+ /V 5+ . The enhancement in the electrochemical performances within the presented compounds stresses the importance of mixed cation-disordered transition metal oxides with different electronic configuration.

  5. Catalytic olefin polymerization with early transition metal compounds

    OpenAIRE

    Eshuis, Johan Jan Willem

    1991-01-01

    The catalysis of organic reactions by soluble metal complexes has become a major tool in synthesis, both in the laboratory and in the chemical industry. Processes catalyzed by transition metal complexes include carbonylation, olefin polymerization, olefin addition, olefin oxidation and alkane and arene oxidation. Traditionally, heterogeneous catalysts have been used for the production of large-scale commodity chemicals such as methanol and ammonia and in the production of high octane gasoline...

  6. Tetragonal CuO: End member of the 3d transition metal monoxides

    NARCIS (Netherlands)

    Siemons, W.; Koster, Gertjan; Blank, David H.A.; Hammond, Robert H.; Geballe, Theodore H.; Beasley, Malcolm R.

    2009-01-01

    Monoclinic CuO is anomalous both structurally as well as electronically in the 3d transition metal oxide series. All the others have the cubic rocksalt structure. Here we report the synthesis and electronic property determination of a tetragonal (elongated rocksalt) form of CuO created using an

  7. FINAL TECHNICAL REPORT Synthetic, Structural and Mechanistic Investigations of Olefin Polymerization Catalyzed by Early Transition Metal Compounds

    Energy Technology Data Exchange (ETDEWEB)

    Bercaw, John E. [California Institute of Technology

    2014-05-23

    The goal of this project is to develop new catalysts and provide understanding of ligand effects on catalyst composition in order to guide development of superior catalyst systems for polymerization of olefins. Our group is designing and synthesizing new “LX2”,“pincer” type ligands and complexing early transition metals to afford precatalysts. In a collaboration with Hans Brintzinger from the University of Konstanz, we are also examining the structures of the components of catalyst systems obtained from reaction of zirconocene dichlorides with aluminum alkyls and aluminum hydrides. Such systems are currently used commercially to produce polyolefins, but the nature of the active and dormant species as well as the mechanisms of their interconversions are not understood. New information on catalyst design and performance may lead to new types of polymers and/or new chemical transformations between hydrocarbons and transition metal centers, ultimately contributing to the development of catalytic reactions for the production of fuels, commodity and polymeric materials.

  8. Oligocyclopentadienyl transition metal complexes

    Energy Technology Data Exchange (ETDEWEB)

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

    2002-01-18

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

  9. Dependence of the elastic properties of the early-transition-metal monoborides on their electronic structures: A density functional theory study

    Energy Technology Data Exchange (ETDEWEB)

    Xu, Xuewen, E-mail: xuxuewen@hebut.edu.cn [School of Materials Science and Engineering, Hebei University of Technology, Tianjin 300130 (China); Fu, Kun [School of Computer Science and Engineering, Hebei University of Technology, Tianjin 300130 (China); Li, Lanlan; Lu, Zunming; Zhang, Xinghua; Fan, Ying; Lin, Jing; Liu, Guodong; Luo, Hongzhi; Tang, Chengchun [School of Materials Science and Engineering, Hebei University of Technology, Tianjin 300130 (China)

    2013-06-15

    We systematically investigated the crystal structure, stability, elastic properties, chemical bonding and electronic properties of the early-transition-metal monoborides (TMBs, where TM=Sc, Ti, V, Cr, Y, Zr, Nb, Mo, Hf, Mo, and W) using the ab initio calculations based on the density functional theory. The results indicated that all 11 TMBs crystallized to a CrB-type structure are thermodynamically and mechanically stable. The elastic constants were calculated using the finite strain method. The correlation between the electronic structure and elastic properties was discussed. YB was found to have high machinability (B/C{sub 44}=1.73) and low hardness (C{sub 44}=43 GPa). The weak interaction between the interleaved yttrium planes and weak pd bonding resulted in the good machinability of YB.

  10. Superconductivity in transition metals.

    Science.gov (United States)

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

    2015-03-13

    A qualitative account of the occurrence and magnitude of superconductivity in the transition metals is presented, with a primary emphasis on elements of the first row. Correlations of the important parameters of the Bardeen-Cooper-Schrieffer theory of superconductivity are highlighted with respect to the number of d-shell electrons per atom of the transition elements. The relation between the systematics of superconductivity in the transition metals and the periodic table high-lights the importance of short-range or chemical bonding on the remarkable natural phenomenon of superconductivity in the chemical elements. A relationship between superconductivity and lattice instability appears naturally as a balance and competition between localized covalent bonding and so-called broken covalency, which favours d-electron delocalization and superconductivity. In this manner, the systematics of superconductivity and various other physical properties of the transition elements are related and unified. © 2015 The Author(s) Published by the Royal Society. All rights reserved.

  11. Understanding of catalysis on early transition metal oxide-based catalysts through exploration of surface structure and chemistry during catalysis using in-situ approaches

    Energy Technology Data Exchange (ETDEWEB)

    Tao, Franklin [Univ. of Kansas, Lawrence, KS (United States). Dept. of Chemical and Petroleum Engineering. Dept. of Chemistry

    2015-09-14

    Two main categories of heterogeneous catalysts are metal and metal oxide which catalyze 80% chemical reactions at solid-gas and solid-liquid interfaces. Metal oxide catalysts are much more complicated than metal catalysts. The reason is that the cations of the metal atoms could exhibit a few different oxidation states on surface of the same catalyst particle such as Co3O4 or change of their oxidation states under different reactive environments. For a metal catalyst, there is only one oxidation state typically. In addition, surface of a metal oxide can be terminated with multiple surface functionalities including O atoms with different binding configurations and OH group. For metal, only metal atoms are exposed typically. Obviously, the complication of surface chemistry and structure of a metal oxide makes studies of surface of an oxide catalyst very challenging. Due to the complication of surface of a meal oxide, the electronic and geometric structures of surface of a metal oxide and the exposed species have received enormous attention since oxide catalysts catalyze at least 1/3 chemical reactions in chemical and energy industries. Understanding of catalytic reactions on early transition metal oxide-based catalysts is fundamentally intriguing and of great practical interest in energy- and environment-related catalysis. Exploration of surface chemistry of oxide-based catalysts at molecular level during catalysis has remained challenging though it is critical in deeply understanding catalysis on oxide-based catalysts and developing oxide-based catalysts with high activity and selectivity. Thus, the overall objective of this project is to explore surface chemistry and structure of early transition metal oxide-based catalysts through in-situ characterization of surface of catalysts, measurements of catalytic performances, and then build an intrinsic correlation of surface chemistry and structure with their catalytic performances in a few

  12. The effect of Coster-Kronig transition on the Auger-photoelectron coincidence spectroscopy spectra of early 3d-transition metals

    International Nuclear Information System (INIS)

    Ohno, Masahide

    2004-01-01

    The singles L23-M45M45 Auger-electron spectroscopy (AES) spectrum of early 3d-transition metal can be fitted by a weighted sum of the density of the single-hole states and that of the two-hole states, broadened by the initial L23-hole lifetime width, respectively (in the present paper we denote the atomic shells Lx, My, and Nz by LX, MY and NZ, respectively). With increasing occupancy of the 3d band the probability of creating the two-hole states by the L23-M45M45 Auger transition and the L2-L3M45 Coster-Kronig (CK) transition increases. However, the M45 hole created by the CK transition is delocalized and becomes decoupled (screened out) from the L3-hole decay so that the L3M45 two-hole state 'decays' to the single L3-hole state before the L3-hole decays. Thus the singles AES spectrum by the L2-L3-M45(M45) CK-transition preceded Auger transition and the singles one by the L3-M45(M45) Auger-transition overlap. We can study the M45-hole dynamics by Auger-photoelectron coincidence spectroscopy because the coincidence spectral lineshape depends on the dynamics of the M45 hole created by the CK transition

  13. Convergence of quasiparticle self-consistent GW calculations of transition metal monoxides

    OpenAIRE

    Das, Suvadip; Coulter, John E.; Manousakis, Efstratios

    2014-01-01

    Finding an accurate ab initio approach for calculating the electronic properties of transition metal oxides has been a problem for several decades. In this paper, we investigate the electronic structure of the transition metal monoxides MnO, CoO, and NiO in their undistorted rock-salt structure within a fully iterated quasiparticle self-consistent GW (QPscGW) scheme. We study the convergence of the QPscGW method, i.e., how the quasiparticle energy eigenvalues and wavefunctions converge as a f...

  14. Vacancies in transition metals

    International Nuclear Information System (INIS)

    Allan, G.; Lannoo, M.

    1976-01-01

    A calculation of the formation energy and volume for a vacancy in transition metals is described. A tight-binding scheme is used for the d band and a Born-Mayer type potential to account for the repulsive part of the energy at small distances. The results show that the relaxation energy is small in all cases, less than 0.1 eV. This seems to be coherent with the good agreement obtained for the theoretical and experimental values of the formation energy Esub(F)sup(V) of the vacancy, without including relaxation. The center of the transitional series is found to give a contraction (Formation volume of order -0.4 at.vol.) whereas the edges are found to produce dilations. (author)

  15. Selenophene transition metal complexes

    Energy Technology Data Exchange (ETDEWEB)

    White, Carter James [Iowa State Univ., Ames, IA (United States)

    1994-07-27

    This research shows that selenophene transition metal complexes have a chemistry that is similar to their thiophene analogs. Selenophene coordination has been demonstrated and confirmed by molecular structure in both the η5- and the η1(Se)-coordination modes. The reaction chemistry of selenophene complexes closely resembles that of the analogous thiophene complexes. One major difference, however, is that selenophene is a better donor ligand than thiophene making the selenophene complexes more stable than the corresponding thiophene complexes. The 77Se NMR chemical shift values for selenophene complexes fall within distinct regions primarily depending on the coordination mode of the selenophene ligand. In the final paper, the C-H bond activation of η1(S)-bound thiophenes, η1(S)-benzothiophene and η1(Se)-bound selenophenes has been demonstrated. The deprotonation and rearrangement of the η1(E)-bound ligand to the carbon bound L-yl complex readily occurs in the presence of base. Reprotonation with a strong acid gives a carbene complex that is unreactive towards nucleophilic attack at the carbene carbon and is stable towards exposure to air. The molecular structure of [Cp(NO)(PPh3)Re(2-benzothioenylcarbene)]O3SCF3 was determined and contains a Re-C bond with substantial double bond character. Methyl substitution for the thienylcarbene or selenylcarbene gives a carbene that rearranges thermally to give back the η1(E)-bound complex. Based on these model reactions, a new mechanism for the H/D exchange of thiophene over the hydrodesulfurization catalyst has been proposed.

  16. Transition metals in carbohydrate chemistry

    DEFF Research Database (Denmark)

    Madsen, Robert

    1997-01-01

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

  17. Transition metal nuclear magnetic resonance

    International Nuclear Information System (INIS)

    Pregosin, P.S.

    1991-01-01

    Transition metal NMR spectroscopy has progressed enormously in recent years. New methods, and specifically solid-state methods and new pulse sequences, have allowed access to data from nuclei with relatively low receptivities with the result that chemists have begun to consider old and new problems, previously unapproachable. Moreover, theory, computational science in particular, now permits the calculation of not just 13 C, 15 N and other light nuclei chemical shifts, but heavy main-group element and transition metals as well. These two points, combined with increasing access to high field pulsed spectrometer has produced a wealth of new data on the NMR transition metals. A new series of articles concerned with measuring, understanding and using the nuclear magnetic resonance spectra of the metals of Group 3-12 is presented. (author)

  18. Electrical Conductivity in Transition Metals

    Science.gov (United States)

    Talbot, Christopher; Vickneson, Kishanda

    2013-01-01

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

  19. Transition Metal Complexes and Catalysis

    Indian Academy of Sciences (India)

    approaches towards the study of bonding in transition metal complexes. Despite .... industrial scale reactions for the production of organic compounds using transition ..... It has found several applications as an engineering thermoplastic. .... and processes of interest to the company, that is, applied research. It is this very ...

  20. Electrochromism in transition metal oxides

    International Nuclear Information System (INIS)

    Estrada, W.

    1993-01-01

    Electrochromism is discussed for transition metal oxides. Particularly tungsten oxide and nickel oxide are reviewed, in order to put forth the different aspects of the field. Since this phenomena has been reviewed by several authors, it is not tried to be comprehensive but rather pedagogical. The basic requirements for a material -in both non-emissive displays and energy efficiency applications- to be electrochromic, a general view of electrochromic mechanism, anodic and cathodic electrochromic materials, and current problems for a electrochromic theory are presented. (author) 45 refs., 8 figs

  1. Heterostructures of transition metal dichalcogenides

    KAUST Repository

    Amin, Bin

    2015-08-24

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

  2. Dark excitations in monolayer transition metal dichalcogenides

    DEFF Research Database (Denmark)

    Deilmann, Thorsten; Thygesen, Kristian Sommer

    2017-01-01

    Monolayers of transition metal dichalcogenides (TMDCs) possess unique optoelectronic properties, including strongly bound excitons and trions. To date, most studies have focused on optically active excitations, but recent experiments have highlighted the existence of dark states, which are equally...

  3. Electronic properties of rocksalt copper monoxide: a proxy structure for high temperature superconductivity

    International Nuclear Information System (INIS)

    Grant, Paul M

    2008-01-01

    Cubic rocksalt copper monoxide, in contrast to its lighter transition metal neighbours, does not exist in nature nor has it yet been successfully synthesized. Nonetheless, its numerical study as a structurally much simpler proxy for the layered cuprate perovskites may prove useful in probing the source of high temperature superconductivity in the latter family of compounds. Here we report such a study employing density functional theory (DFT) abetted by the local density approximation including cation on-site Hubbard interactions (LDA+U). Rather surprisingly, we find that unlike oxides of the light transition metals, cubic CuO remains metallic for all physically reasonable values of U and does not result in a Mott- Hubbard induced charge transfer insulator as might be expected, and, in fact, displays a Fermi surface with clearly nesting tendencies. Preliminary calculations of the net dimensionless electron-phonon coupling constant, λ, yield values in the range 0.6 - 0.7 similar to those found for the superconducting fullerenes and magnesium diboride. On the other hand, we do find as we gradually introduce a tetragonal distortion away from pure cubic symmetry that a charge- transfer insulator emerges for values of U ∼ 5 eV and c/a ∼ 1.3 in agreement with recent experimental data on forced-epitaxial growth of 2-4 ML thick films of tetragonal rocksalt CuO. We preliminarily conclude from these computational studies that high temperature superconductivity in the copper oxide compounds is at least initially mediated by Jahn-Teller driven electron-phonon coupling as originally suggested by Bednorz and Mueller.

  4. Microwave-assisted synthesis of transition metal phosphide

    Science.gov (United States)

    Viswanathan, Tito

    2014-12-30

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

  5. Mass fractionation processes of transition metal isotopes

    Science.gov (United States)

    Zhu, X. K.; Guo, Y.; Williams, R. J. P.; O'Nions, R. K.; Matthews, A.; Belshaw, N. S.; Canters, G. W.; de Waal, E. C.; Weser, U.; Burgess, B. K.; Salvato, B.

    2002-06-01

    Recent advances in mass spectrometry make it possible to utilise isotope variations of transition metals to address some important issues in solar system and biological sciences. Realisation of the potential offered by these new isotope systems however requires an adequate understanding of the factors controlling their isotope fractionation. Here we show the results of a broadly based study on copper and iron isotope fractionation during various inorganic and biological processes. These results demonstrate that: (1) naturally occurring inorganic processes can fractionate Fe isotope to a detectable level even at temperature ˜1000°C, which challenges the previous view that Fe isotope variations in natural system are unique biosignatures; (2) multiple-step equilibrium processes at low temperatures may cause large mass fractionation of transition metal isotopes even when the fractionation per single step is small; (3) oxidation-reduction is an importation controlling factor of isotope fractionation of transition metal elements with multiple valences, which opens a wide range of applications of these new isotope systems, ranging from metal-silicate fractionation in the solar system to uptake pathways of these elements in biological systems; (4) organisms incorporate lighter isotopes of transition metals preferentially, and transition metal isotope fractionation occurs stepwise along their pathways within biological systems during their uptake.

  6. Magnetic Ground State Properties of Transition Metals

    DEFF Research Database (Denmark)

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

    1977-01-01

    We review a simple one-electron theory of the magnetic and cohesive properties of ferro- and nearly ferromagnetic transition metals at 0 K. The theory is based on the density functional formalism, it makes use of the local spin density and atomic sphere approximations and it may, with further app...

  7. First-row transition metal hydrogenation and hydrosilylation catalysts

    Science.gov (United States)

    Trovitch, Ryan J.; Mukhopadhyay, Tufan K.; Pal, Raja; Levin, Hagit Ben-Daat; Porter, Tyler M.; Ghosh, Chandrani

    2017-07-18

    Transition metal compounds, and specifically transition metal compounds having a tetradentate and/or pentadentate supporting ligand are described, together with methods for the preparation thereof and the use of such compounds as hydrogenation and/or hydrosilylation catalysts.

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

    Energy Technology Data Exchange (ETDEWEB)

    1992-01-01

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

  9. The phosphorus and the transition metals chemistry

    International Nuclear Information System (INIS)

    Mathey, F.

    1988-01-01

    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 [fr

  10. Spin-Orbitronics at Transition Metal Interfaces

    KAUST Repository

    Manchon, Aurelien

    2017-11-09

    The presence of large spin–orbit interaction at transition metal interfaces enables the emergence of a variety of fascinating phenomena that have been at the forefront of spintronics research in the past 10 years. The objective of the present chapter is to offer a review of these various effects from a theoretical perspective, with a particular focus on spin transport, chiral magnetism, and their interplay. After a brief description of the orbital hybridization scheme at transition metal interfaces, we address the impact of spin–orbit coupling on the interfacial magnetic configuration, through the celebrated Dzyaloshinskii–Moriya interaction. We then discuss the physics of spin transport and subsequent torques occurring at these interfaces. We particularly address the spin Hall, spin swapping, and inverse spin-galvanic effects. Finally, the interplay between flowing charges and chiral magnetic textures and their induced dynamics are presented. We conclude this chapter by proposing some perspectives on promising research directions.

  11. Lattice Location of Transition Metals in Semiconductors

    CERN Multimedia

    2002-01-01

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

  12. Spin-Orbitronics at Transition Metal Interfaces

    KAUST Repository

    Manchon, Aurelien; Belabbes, Abderrezak

    2017-01-01

    The presence of large spin–orbit interaction at transition metal interfaces enables the emergence of a variety of fascinating phenomena that have been at the forefront of spintronics research in the past 10 years. The objective of the present chapter is to offer a review of these various effects from a theoretical perspective, with a particular focus on spin transport, chiral magnetism, and their interplay. After a brief description of the orbital hybridization scheme at transition metal interfaces, we address the impact of spin–orbit coupling on the interfacial magnetic configuration, through the celebrated Dzyaloshinskii–Moriya interaction. We then discuss the physics of spin transport and subsequent torques occurring at these interfaces. We particularly address the spin Hall, spin swapping, and inverse spin-galvanic effects. Finally, the interplay between flowing charges and chiral magnetic textures and their induced dynamics are presented. We conclude this chapter by proposing some perspectives on promising research directions.

  13. Mesoporous Transition Metal Oxides for Supercapacitors

    OpenAIRE

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

    2015-01-01

    Recently, transition metal oxides, such as ruthenium oxide (RuO2), manganese dioxide (MnO2), nickel oxides (NiO) and cobalt oxide (Co3O4), have been widely investigated as electrode materials for pseudo-capacitors. In particular, these metal oxides with mesoporous structures have become very hot nanomaterials in the field of supercapacitors owing to their large specific surface areas and suitable pore size distributions. The high specific capacities of these mesoporous metal oxides are result...

  14. Mesoporous Transition Metal Oxides for Supercapacitors.

    Science.gov (United States)

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

    2015-10-14

    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.

  15. Mesoporous Transition Metal Oxides for Supercapacitors

    Science.gov (United States)

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

    2015-01-01

    Recently, transition metal oxides, such as ruthenium oxide (RuO2), manganese dioxide (MnO2), nickel oxides (NiO) and cobalt oxide (Co3O4), have been widely investigated as electrode materials for pseudo-capacitors. In particular, these metal oxides with mesoporous structures have become very hot nanomaterials in the field of supercapacitors owing to their large specific surface areas and suitable pore size distributions. The high specific capacities of these mesoporous metal oxides are resulted from the effective contacts between electrode materials and electrolytes as well as fast transportation of ions and electrons in the bulk of electrode and at the interface of electrode and electrolyte. During the past decade, many achievements on mesoporous transition metal oxides have been made. In this mini-review, we select several typical nanomaterials, such as RuO2, MnO2, NiO, Co3O4 and nickel cobaltite (NiCo2O4), and briefly summarize the recent research progress of these mesoporous transition metal oxides-based electrodes in the field of supercapacitors. PMID:28347088

  16. Mesoporous Transition Metal Oxides for Supercapacitors

    Directory of Open Access Journals (Sweden)

    Yan Wang

    2015-10-01

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

  17. Solubility of hydrogen in transition metals

    International Nuclear Information System (INIS)

    Lee, H.M.

    1976-01-01

    Correlations exist between the heat of solution of hydrogen and the difference in energy between the lowest lying energy levels of the trivalent d/sup n-1/s electronic configuration and the divalent d/sup n-2/s 2 (or the tetravalent d/sup n/) configuration of the neutral gaseous atoms. The trends observed in the transition metal series are discussed in relation to the number of valence electrons per atom in the transition elements in their metallic and neutral states

  18. The atomic structure of transition metal clusters

    International Nuclear Information System (INIS)

    Riley, S.J.

    1995-01-01

    Chemical reactions are used to probe the atomic (geometrical) structure of isolated clusters of transition metal atoms. The number of adsorbate molecules that saturate a cluster, and/or the binding energy of molecules to cluster surfaces, are determined as a function of cluster size. Systematics in these properties often make it possible to propose geometrical structures consistent with the experimental observations. We will describe how studies of the reactions of cobalt and nickel clusters with ammonia, water, and nitrogen provide important and otherwise unavailable structural information. Specifically, small (less than 20 atoms) clusters of cobalt and nickel atoms adopt entirely different structures, the former having packing characteristic of the bulk and the latter having pentagonal symmetry. These observations provide important input for model potentials that attempt to describe the local properties of transition metals. In particular, they point out the importance of a proper treatment of d-orbital binding in these systems, since cobalt and nickel differ so little in their d-orbital occupancy

  19. Janus monolayers of transition metal dichalcogenides

    KAUST Repository

    Lu, Ang-Yu

    2017-05-15

    Structural symmetry-breaking plays a crucial role in determining the electronic band structures of two-dimensional materials. Tremendous efforts have been devoted to breaking the in-plane symmetry of graphene with electric fields on AB-stacked bilayers or stacked van der Waals heterostructures. In contrast, transition metal dichalcogenide monolayers are semiconductors with intrinsic in-plane asymmetry, leading to direct electronic bandgaps, distinctive optical properties and great potential in optoelectronics. Apart from their in-plane inversion asymmetry, an additional degree of freedom allowing spin manipulation can be induced by breaking the out-of-plane mirror symmetry with external electric fields or, as theoretically proposed, with an asymmetric out-of-plane structural configuration. Here, we report a synthetic strategy to grow Janus monolayers of transition metal dichalcogenides breaking the out-of-plane structural symmetry. In particular, based on a MoS2 monolayer, we fully replace the top-layer S with Se atoms. We confirm the Janus structure of MoSSe directly by means of scanning transmission electron microscopy and energy-dependent X-ray photoelectron spectroscopy, and prove the existence of vertical dipoles by second harmonic generation and piezoresponse force microscopy measurements.

  20. Edge Delamination of Monolayer Transition Metal Dichalcogenides.

    Science.gov (United States)

    Ly, Thuc Hue; Yun, Seok Joon; Thi, Quoc Huy; Zhao, Jiong

    2017-07-25

    Delamination of thin films from the supportive substrates is a critical issue within the thin film industry. The emergent two-dimensional, atomic layered materials, including transition metal dichalcogenides, are highly flexible; thus buckles and wrinkles can be easily generated and play vital roles in the corresponding physical properties. Here we introduce one kind of patterned buckling behavior caused by the delamination from a substrate initiated at the edges of the chemical vapor deposition synthesized monolayer transition metal dichalcogenides, led by thermal expansion mismatch. The atomic force microscopy and optical characterizations clearly showed the puckered structures associated with the strain, whereas the transmission electron microscopy revealed the special sawtooth-shaped edges, which break the geometrical symmetry for the buckling behavior of hexagonal samples. The condition of the edge delamination is in accordance with the fracture behavior of thin film interfaces. This edge delamination and buckling process is universal for most ultrathin two-dimensional materials, which requires more attention in various future applications.

  1. Rocksalt nitride metal/semiconductor superlattices: A new class of artificially structured materials

    Science.gov (United States)

    Saha, Bivas; Shakouri, Ali; Sands, Timothy D.

    2018-06-01

    Artificially structured materials in the form of superlattice heterostructures enable the search for exotic new physics and novel device functionalities, and serve as tools to push the fundamentals of scientific and engineering knowledge. Semiconductor heterostructures are the most celebrated and widely studied artificially structured materials, having led to the development of quantum well lasers, quantum cascade lasers, measurements of the fractional quantum Hall effect, and numerous other scientific concepts and practical device technologies. However, combining metals with semiconductors at the atomic scale to develop metal/semiconductor superlattices and heterostructures has remained a profoundly difficult scientific and engineering challenge. Though the potential applications of metal/semiconductor heterostructures could range from energy conversion to photonic computing to high-temperature electronics, materials challenges primarily had severely limited progress in this pursuit until very recently. In this article, we detail the progress that has taken place over the last decade to overcome the materials engineering challenges to grow high quality epitaxial, nominally single crystalline metal/semiconductor superlattices based on transition metal nitrides (TMN). The epitaxial rocksalt TiN/(Al,Sc)N metamaterials are the first pseudomorphic metal/semiconductor superlattices to the best of our knowledge, and their physical properties promise a new era in superlattice physics and device engineering.

  2. A theoretical evaluation of possible transition metal electro-catalysts for N2 reduction

    DEFF Research Database (Denmark)

    Skulason, Egill; Bligaard, Thomas; Gudmundsdottir, Sigrıdur

    2012-01-01

    such as Sc, Y, Ti, and Zr bind N-adatoms more strongly than H-adatoms, a significant production of ammonia compared with hydrogen gas can be expected on those metal electrodes when a bias of 1 V to 1.5 V vs. SHE is applied. Defect-free surfaces of the early transition metals are catalytically more active...

  3. Group 4 Transition-Metal Complexes of an Aniline–Carbene–Phenol Ligand

    KAUST Repository

    Despagnet-Ayoub, Emmanuelle

    2013-05-24

    Attempts to install a tridentate aniline-NHC-phenol (NCO) ligand on titanium and zirconium led instead to complexes resulting from unexpected rearrangement pathways that illustrate common behavior in carbene-early- transition-metal chemistry. © 2013 American Chemical Society.

  4. Novel doping alternatives for single-layer transition metal dichalcogenides

    Science.gov (United States)

    Onofrio, Nicolas; Guzman, David; Strachan, Alejandro

    2017-11-01

    Successful doping of single-layer transition metal dichalcogenides (TMDs) remains a formidable barrier to their incorporation into a range of technologies. We use density functional theory to study doping of molybdenum and tungsten dichalcogenides with a large fraction of the periodic table. An automated analysis of the energetics, atomic and electronic structure of thousands of calculations results in insightful trends across the periodic table and points out promising dopants to be pursued experimentally. Beyond previously studied cases, our predictions suggest promising substitutional dopants that result in p-type transport and reveal interesting physics behind the substitution of the metal site. Doping with early transition metals (TMs) leads to tensile strain and a significant reduction in the bandgap. The bandgap increases and strain is reduced as the d-states are filled into the mid TMs; these trends reverse as we move into the late TMs. Additionally, the Fermi energy increases monotonously as the d-shell is filled from the early to mid TMs and we observe few to no gap states, indicating the possibility of both p- (early TMs) and n- (mid TMs) type doping. Quite surprisingly, the simulations indicate the possibility of interstitial doping of TMDs; the energetics reveal that a significant number of dopants, increasing in number from molybdenum disulfide to diselenide and to ditelluride, favor the interstitial sites over adsorbed ones. Furthermore, calculations of the activation energy associated with capturing the dopants into the interstitial site indicate that the process is kinetically possible. This suggests that interstitial impurities in TMDs are more common than thought to date and we propose a series of potential interstitial dopants for TMDs relevant for application in nanoelectronics based on a detailed analysis of the predicted electronic structures.

  5. Attainable high capacity in Li-excess Li-Ni-Ru-O rock-salt cathode for lithium ion battery

    Science.gov (United States)

    Wang, Xingbo; Huang, Weifeng; Tao, Shi; Xie, Hui; Wu, Chuanqiang; Yu, Zhen; Su, Xiaozhi; Qi, Jiaxin; Rehman, Zia ur; Song, Li; Zhang, Guobin; Chu, Wangsheng; Wei, Shiqiang

    2017-08-01

    Peroxide structure O2n- has proven to appear after electrochemical process in many lithium-excess precious metal oxides, representing extra reversible capacity. We hereby report construction of a Li-excess rock-salt oxide Li1+xNi1/2-3x/2Ru1/2+x/2O2 electrode, with cost effective and eco-friendly 3d transition metal Ni partially substituting precious 4d transition metal Ru. It can be seen that O2n- is formed in pristine Li1.23Ni0.155Ru0.615O2, and stably exists in subsequent cycles, enabling discharge capacities to 295.3 and 198 mAh g-1 at the 1st/50th cycle, respectively. Combing ex-situ X-ray absorption near edge spectroscopy, X-ray photoelectron spectroscopy, X-ray diffraction, high resolution transmission electron microscopy and electrochemical characterization, we demonstrate that the excellent electrochemical performance comes from both percolation network with disordered structure and cation/anion redox couples occurring in charge-discharge process. Li-excess and substitution of common element have been demonstrated to be a breakthrough for designing novel high performance commercial cathodes in rechargeable lithium ion battery field.

  6. Electrical and Magnetic Properties of Binary Amorphous Transition Metal Alloys.

    Science.gov (United States)

    Liou, Sy-Hwang

    The electrical, superconductive and magnetic properties of several binary transition metal amorphous and metastable crystalline alloys, Fe(,x)Ti(,100-x) (30 (LESSTHEQ) x (LESSTHEQ) 100), Fe(,x)Zr(,100-x) (20 (LESSTHEQ) x (LESSTHEQ) 93), Fe(,x)Hf(,100-x) (20 (LESSTHEQ) x (LESSTHEQ) 100), Fe(,x)Nb(,100 -x) (22 (LESSTHEQ) x (LESSTHEQ) 85), Ni(,x)Nb(,100-x) (20 (LESSTHEQ) x (LESSTHEQ) 80), Cu(,x)Nb(,100-x) (10 (LESSTHEQ) x (LESSTHEQ) 90) were studied over a wide composition range. Films were made using a magnetron sputtering system, and the structure of the films was investigated by energy dispersive x-ray diffraction. The composition region of each amorphous alloys system was determined and found in good agreement with a model proposed by Egami and Waseda. The magnetic properties and hyperfine interactions in the films were investigated using a conventional Mossbauer spectrometer and a ('57)Co in Rh matrix source. In all Fe-early transition metal binary alloys systems, Fe does not retain its moment in the low iron concentration region and the result is that the critical concentration for magnetic order (x(,c)) is much larger than anticipated from percolation considerations. A direct comparison between crystalline alloys and their amorphous counterparts of the same composition illustrate no clear correlation between crystalline and amorphous states. Pronounced discontinuities in the magnetic properties with variation in Fe content of all Fe-early transition metal alloys at phase boundaries separating amorphous and crystalline states have been observed. This is caused by the differences in the atomic arrangement and the electronic structure between crystalline and amorphous solids. The temperature dependence of resistivity, (rho)(T), of several binary amorphous alloys of Fe-TM (where TM = Ti, Zr, Hf, Nb etc.) has been studied from 2K to 300K. The Fe-poor (x x(,c)) samples have distinctive differences in (rho)(T) at low temperature (below 30K). All the magnetic samples

  7. Magnetic coupling at perovskite and rock-salt structured interfaces

    Energy Technology Data Exchange (ETDEWEB)

    Matvejeff, M., E-mail: mikko.matvejeff@picosun.com [Institute for Solid State Physics, University of Tokyo, 5-1-5 Kashiwanoha, Kashiwa, 277-8581 Chiba (Japan); Department of Chemistry, Aalto University, Kemistintie 1, 02150 Espoo (Finland); Ahvenniemi, E. [Department of Chemistry, Aalto University, Kemistintie 1, 02150 Espoo (Finland); Takahashi, R.; Lippmaa, M. [Institute for Solid State Physics, University of Tokyo, 5-1-5 Kashiwanoha, Kashiwa, 277-8581 Chiba (Japan)

    2015-10-05

    We study magnetic coupling between hole-doped manganite layers separated by either a perovskite or a rock-salt barrier of variable thickness. Both the type and the quality of the interface have a strong impact on the minimum critical barrier thickness where the manganite layers become magnetically decoupled. A rock-salt barrier layer only 1 unit cell (0.5 nm) thick remains insulating and is able to magnetically de-couple the electrode layers. The technique can therefore be used for developing high-performance planar oxide electronic devices such as magnetic tunnel junctions and quantum well structures that depend on magnetically and electronically sharp heterointerfaces.

  8. Ferromagnetism in Fe-doped transition metal nitrides

    Science.gov (United States)

    Sharma, Ramesh; Sharma, Yamini

    2018-04-01

    Early transition metal mononitrides ScN and YN are refractory compounds with high hardness and melting points as well semiconducting properties. The presence of nitrogen vacancies in ScN/YN introduces asymmetric peaks in the density of states close to Fermi level, the same effects can be achieved by doping by Mn or Fe-atoms. Due to the substitution of TM atoms at Sc/Y sites, it was found that the p-d hybridization induces small magnetic moments at both Sc/Y and N sites giving rise to magnetic semiconductors (MS). From the calculated temperature dependent transport properties, the power factor and ZT is found to be lowered for doped ScN whereas it increases for doped YN. It is proposed that these materials have promising applications as spintronics and thermoelectric materials.

  9. Neutron irradiation damage in transition metal carbides

    International Nuclear Information System (INIS)

    Matsui, Hisayuki; Nesaki, Kouji; Kiritani, Michio

    1991-01-01

    Effects of neutron irradiation on the physical properties of light transition metal carbides, TiC x , VC x and NbC x , were examined, emphasizing the characterization of irradiation induced defects in the nonstoichiometric composition. TiC x irradiated with 14 MeV (fusion) neutrons showed higher damage rates with increasing C/Ti (x) ratio. A brief discussion is made on 'cascade damage' in TiC x irradiated with fusion neutrons. Two other carbides (VC x and NbC x ) were irradiated with fission reactor neutrons. The irradiation effects on VC x were not so simple, because of the complex irradiation behavior of 'ordered' phases. For instance, complete disordering was revealed in an ordered phase, 'V 8 C 7 ', after an irradiation dose of 10 25 n/m 2 . (orig.)

  10. Defect-Tolerant Monolayer Transition Metal Dichalcogenides

    DEFF Research Database (Denmark)

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

    2016-01-01

    Localized electronic states formed inside the band gap of a semiconductor due to crystal defects can be detrimental to the material's optoelectronic properties. Semiconductors with a lower tendency to form defect induced deep gap states are termed defect-tolerant. Here we provide a systematic first...... 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......-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...

  11. Magnetic excitations in transition-metal ferromagnets

    International Nuclear Information System (INIS)

    Uemura, Y.J.

    1984-01-01

    A review is given on current neutron scattering experiments at Brookhaven National Laboratory on transition-metal ferromagnets Ni, Fe, Pd 2 MnSn and MnSi. The scattering intensity in constant-energy scans, observed above T/sub c/ in all of these materials, exhibited a clear peak at finite momentum transfers. Using a simple scattering function with double-Lorentzian shape, we demonstrate that this peak is a manifestation of simple diffusive spin fluctuations. Experimental results of several parameters are compared in the context of localized-moment and itinerant-electron pictures. The ratio of spin wave stiffness constant D and transition temperature kT/sub c/ is shown to be a good yardstick for the degree of itinerancy of d-electrons

  12. Versatile two-dimensional transition metal dichalcogenides

    DEFF Research Database (Denmark)

    Canulescu, Stela; Affannoukoué, Kévin; Döbeli, Max

    ), a strategy for the fabrication of 2D heterostructures must be developed. Here we demonstrate a novel approach for the bottom-up synthesis of TMDC monolayers, namely Pulsed Laser Deposition (PLD) combined with a sulfur evaporation beam. PLD relies on the use of a pulsed laser (ns pulse duration) to induce...... material transfer from a solid source (such as a sintered target of MoS2) to a substrate (such as Si or sapphire). The deposition rate in PLD is typically much less than a monolayer per pulse, meaning that the number of MLs can be controlled by a careful selection of the number of laser pulses......Two-dimensional transition metal dichalcogenides (2D-TMDCs), such as MoS2, have emerged as a new class of semiconducting materials with distinct optical and electrical properties. The availability of 2D-TMDCs with distinct band gaps allows for unlimited combinations of TMDC monolayers (MLs...

  13. Electronic structure of hcp transition metals

    DEFF Research Database (Denmark)

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

    1975-01-01

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

  14. Elastic properties of some transition metal arsenides

    Science.gov (United States)

    Nayak, Vikas; Verma, U. P.; Bisht, P. S.

    2018-05-01

    The elastic properties of transition metal arsenides (TMAs) have been studied by employing Wien2K package based on density functional theory in the zinc blende (ZB) and rock salt (RS) phase treating valance electron scalar relativistically. Further, we have also treated them non-relativistically to find out the relativistic effect. We have calculated the elastic properties by computing the volume conservative stress tensor for small strains, using the method developed by Charpin. The obtained results are discussed in paper. From the obtained results, it is clear that the values of C11 > C12 and C44 for all the compounds. The values of shear moduli of these compounds are also calculated. The internal parameter for these compounds shows that ZB structures of these compounds have high resistance against bond order. We find that the estimated elastic constants are in good agreement with the available data.

  15. On monosubstituted cyanurate complexes of transition metals

    International Nuclear Information System (INIS)

    Sejfer, G.B.; Tarasova, Z.A.

    1995-01-01

    Complex monosubstituted cyanurates of transition metals K 2 [Eh(H 2 C 3 N 3 O 3 ) 4 ]x4H 2 ) where Eh = Mn, Co, Ni, Cu, Zn, Cd are synthesized and investigated by means of IR - spectroscopy and thermal analysis methods. It is shown that only thermal decomposition of a manganese complex leads to the production of this metal oxide. All other derivatives decompose with the production of a free metal, because decomposition of these substances in argon atmosphere occurs through an intermediate production of their nitrides. An assumption is made that nitroduction of yttrium or rare earth element salts (instead of transition or alkali metal derivatives) as accelerating additions will facilitate increase of polyisocyanurate resin thermal stability. 25 refs.; 2 figs.; 3 tabs

  16. Pressure induced phase transitions in transition metal nitrides: Ab initio study

    Energy Technology Data Exchange (ETDEWEB)

    Srivastava, Anurag; Chauhan, Mamta [Advanced Material Research Lab, Indian Institute of Information Technology and Management, Gwalior 474010 (India); Singh, R.K. [Department of Physics, ITM University, Gurgaon 122017 (India)

    2011-12-15

    We have analyzed the stability of transition metal nitrides (TMNs) XN (X = Ti, Zr, Hf, V, Nb, Ta) in their original rocksalt (B1) and hypothetical CsCl (B2) type phases under high compression. The ground state total energy calculation approach of the system has been used through the generalized gradient approximation (GGA) with the Perdew-Burke-Ernzerhof (PBE) type parameterization as exchange correlation functional. In the whole series of nitrides taken into consideration, tantalum nitride is found to be the most stable. We have observed that under compression the original B1-type phase of these nitrides transforms to a B2-type phase. We have also discussed the computation of ground state properties, like the lattice constant (a), bulk modulus (B{sub 0}) and first order pressure derivative of the bulk modulus (B'{sub 0}) of the TMNs and their host elements. (Copyright copyright 2011 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  17. Theoretical studies of transition metal complexes with nitriles and isocyanides

    International Nuclear Information System (INIS)

    Kuznetsov, Maksim L

    2002-01-01

    Theoretical studies of transition metal complexes with nitriles and isocyanides are reviewed. The electronic structures and the nature of coordination bonds in these complexes are discussed. The correlation between the electronic structures of transition metal complexes with nitriles and isocyanides and their structural properties, spectroscopic characteristics, and reactivities are considered. The bibliography includes 121 references.

  18. Electronic specific heat of transition metal carbides

    International Nuclear Information System (INIS)

    Conte, R.

    1964-07-01

    The experimental results that make it possible to define the band structure of transition metal carbides having an NaCI structure are still very few. We have measured the electronic specific heat of some of these carbides of varying electronic concentration (TiC, either stoichiometric or non-stoichiometric, TaC and mixed (Ti, Ta) - C). We give the main characteristics (metallography, resistivity, X-rays) of our samples and we describe the low temperature specific heat apparatus which has been built. In one of these we use helium as the exchange gas. The other is set up with a mechanical contact. The two use a germanium probe for thermometer. The measurement of the temperature using this probe is described, as well as the various measurement devices. The results are presented in the form of a rigid band model and show that the density of the states at the Fermi level has a minimum in the neighbourhood of the group IV carbides. (author) [fr

  19. Phase stability of transition metals and alloys

    International Nuclear Information System (INIS)

    Hixson, R.S.; Schiferl, D.; Wills, J.M.; Hill, M.A.

    1997-01-01

    This is the final report of a three-year, Laboratory-Directed Research and Development (LDRD) project at the Los Alamos National Laboratory (LANL). This project was focused on resolving unexplained differences in calculated and measured phase transition pressures in transition metals. Part of the approach was to do new, higher accuracy calculations of transmission pressures for group 4B and group 6B metals. Theory indicates that the transition pressures for these baseline metals should change if alloyed with a d-electron donor metal, and calculations done using the Local Density Approximation (LDA) and the Virtual Crystal Approximation (VCA) indicate that this is true. Alloy systems were calculated for Ti, Zr and Hf based alloys with various solute concentrations. The second part of the program was to do new Diamond Anvil Cell (DAC) measurements to experimentally verify calculational results. Alloys were prepared for these systems with grain size suitable for Diamond Anvil Cell experiments. Experiments were done on pure Ti as well as Ti-V and Ti-Ta alloys. Measuring unambiguous transition pressures for these systems proved difficult, but a new technique developed yielded good results

  20. Electrical valley filtering in transition metal dichalcogenides

    Science.gov (United States)

    Hsieh, Tzu-Chi; Chou, Mei-Yin; Wu, Yu-Shu

    2018-03-01

    This work investigates the feasibility of electrical valley filtering for holes in transition metal dichalcogenides. We look specifically into the scheme that utilizes a potential barrier to produce valley-dependent tunneling rates, and perform the study with both a k .p -based analytic method and a recursive Green's function-based numerical method. The study yields the transmission coefficient as a function of incident energy and transverse wave vector, for holes going through lateral quantum barriers oriented in either armchair or zigzag directions, in both homogeneous and heterogeneous systems. The main findings are the following: (1) The tunneling current valley polarization increases with increasing barrier width or height; (2) both the valley-orbit interaction and band structure warping contribute to valley-dependent tunneling, with the former contribution being manifest in structures with asymmetric potential barriers, and the latter being orientation dependent and reaching maximum for transmission in the armchair direction; and (3) for transmission ˜0.1 , a tunneling current valley polarization of the order of 10 % can be achieved.

  1. Gas phase structure of transition metal dihydrides

    International Nuclear Information System (INIS)

    Demuynck, J.; Schaefer, H.F. III

    1980-01-01

    ESR and infrared spectroscopic measurements on matrix isolated MnH 2 and CrH 2 have recently suggested that these simple molecules may be bent. This result would be the opposite of that found experimentally for the transition metal dihalides MX 2 , known to be linear. Here the geometrical structure of MnH 2 has been investigated by molecular electronic structure theory. A large contracted Gaussian basis set [Mn(14s11p6p/9s8p3d), H(5s1p/3s1p)] was used in conjunction with self-consistent field and configuration interaction methods. These suggest that the 6 A 1 ground state of MnH 2 is linear. Further studies of the 3 A 1 state (one of several low-lying states) of TiH 2 also favor linearity, although this potential energy surface is extremely flat with respect to bending. Thus it appears probable that most MH 2 molecules, like the related MX 2 family, are linear

  2. Dark excitons in transition metal dichalcogenides

    Science.gov (United States)

    Malic, Ermin; Selig, Malte; Feierabend, Maja; Brem, Samuel; Christiansen, Dominik; Wendler, Florian; Knorr, Andreas; Berghäuser, Gunnar

    2018-01-01

    Monolayer transition metal dichalcogenides (TMDs) exhibit a remarkably strong Coulomb interaction that manifests in tightly bound excitons. Due to the complex electronic band structure exhibiting several spin-split valleys in the conduction and valence band, dark excitonic states can be formed. They are inaccessibly by light due to the required spin-flip and/or momentum transfer. The relative position of these dark states with respect to the optically accessible bright excitons has a crucial impact on the emission efficiency of these materials and thus on their technological potential. Based on the solution of the Wannier equation, we present the excitonic landscape of the most studied TMD materials including the spectral position of momentum- and spin-forbidden excitonic states. We show that the knowledge of the electronic dispersion does not allow to conclude about the nature of the material's band gap since excitonic effects can give rise to significant changes. Furthermore, we reveal that an exponentially reduced photoluminescence yield does not necessarily reflect a transition from a direct to a nondirect gap material, but can be ascribed in most cases to a change of the relative spectral distance between bright and dark excitonic states.

  3. Properties of Transition Metal Doped Alumina

    Science.gov (United States)

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

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

  4. Photocatalysis of Modified Transition Metal Oxide Surfaces

    Energy Technology Data Exchange (ETDEWEB)

    Batzill, Matthias [Univ. of South Florida, Tampa, FL (United States). Dept. of Physics

    2018-02-28

    The goal of this project has been to establish a cause-effect relationship for photocatalytic activity variations of different structures of the same material; and furthermore gain fundamental understanding on modification of photocatalysts by compositional or surface modifications. The reasoning is that gaining atomic scale understanding of how surface and bulk modifications alter the photo reactivity will lead to design principles for next generation photocatalysts. As a prototypical photocatalyst the research focused on TiO2 synthesized in well-defined single crystalline form to enable fundamental characterizations.We have obtained results in the following areas: (a) Preparation of epitaxial anatase TiO2 samples by pulsed laser deposition. (b) Comparison of hydrogen diffusion on different crystallographic surface. (c) Determining the stability of the TiO2(011)-2x1 reconstruction upon interactions with adsorbates. (d) Characterization of adsorption and (thermal and photo) reaction of molecules with nitro-endgroups, (e) Exploring the possibility of modifying planar model photocatalyst surfaces with graphene to enable fundamental studies on reported enhanced photocatalytic activities of graphene modified transition metal oxides, (f) gained fundamental understanding on the role of crystallographic polymorphs of the same material for their photocatalytic activities.

  5. Nucleic acid-functionalized transition metal nanosheets for biosensing applications.

    Science.gov (United States)

    Mo, Liuting; Li, Juan; Liu, Qiaoling; Qiu, Liping; Tan, Weihong

    2017-03-15

    In clinical diagnostics, as well as food and environmental safety practices, biosensors are powerful tools for monitoring biological or biochemical processes. Two-dimensional (2D) transition metal nanomaterials, including transition metal chalcogenides (TMCs) and transition metal oxides (TMOs), are receiving growing interest for their use in biosensing applications based on such unique properties as high surface area and fluorescence quenching abilities. Meanwhile, nucleic acid probes based on Watson-Crick base-pairing rules are also being widely applied in biosensing based on their excellent recognition capability. In particular, the emergence of functional nucleic acids in the 1980s, especially aptamers, has substantially extended the recognition capability of nucleic acids to various targets, ranging from small organic molecules and metal ions to proteins and cells. Based on π-π stacking interaction between transition metal nanosheets and nucleic acids, biosensing systems can be easily assembled. Therefore, the combination of 2D transition metal nanomaterials and nucleic acids brings intriguing opportunities in bioanalysis and biomedicine. In this review, we summarize recent advances of nucleic acid-functionalized transition metal nanosheets in biosensing applications. The structure and properties of 2D transition metal nanomaterials are first discussed, emphasizing the interaction between transition metal nanosheets and nucleic acids. Then, the applications of nucleic acid-functionalized transition metal nanosheet-based biosensors are discussed in the context of different signal transducing mechanisms, including optical and electrochemical approaches. Finally, we provide our perspectives on the current challenges and opportunities in this promising field. Copyright © 2016 Elsevier B.V. All rights reserved.

  6. Surface segregation energies in transition-metal alloys

    DEFF Research Database (Denmark)

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

    1999-01-01

    We present a database of 24 x 24 surface segregation energies of single transition metal impurities in transition-metal hosts obtained by a Green's-function linear-muffin-tin-orbitals method in conjunction with the coherent potential and atomic sphere approximations including a multipole correction...... 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 from the simple...

  7. Synthesis of IV-VI Transition Metal Carbide and Nitride Nanoparticles Using a Reactive Mesoporous Template for Electrochemical Hydrogen Evolution Reaction

    KAUST Repository

    Alhajri, Nawal Saad

    2016-01-01

    Interstitial carbides and nitrides of early transition metals in Groups IV-VI exhibit platinum-like behavior which makes them a promising candidate to replace noble metals in a wide variety of reactions. Most synthetic methods used to prepare

  8. Stable carbides in transition metal alloys

    International Nuclear Information System (INIS)

    Piotrkowski, R.

    1991-01-01

    In the present work different techniques were employed for the identification of stable carbides in two sets of transition metal alloys of wide technological application: a set of three high alloy M2 type steels in which W and/or Mo were total or partially replaced by Nb, and a Zr-2.5 Nb alloy. The M2 steel is a high speed steel worldwide used and the Zr-2.5 Nb alloy is the base material for the pressure tubes in the CANDU type nuclear reactors. The stability of carbide was studied in the frame of Goldschmidt's theory of interstitial alloys. The identification of stable carbides in steels was performed by determining their metallic composition with an energy analyzer attached to the scanning electron microscope (SEM). By these means typical carbides of the M2 steel, MC and M 6 C, were found. Moreover, the spatial and size distribution of carbide particles were determined after different heat treatments, and both microstructure and microhardness were correlated with the appearance of the secondary hardening phenomenon. In the Zr-Nb alloy a study of the α and β phases present after different heat treatments was performed with optical and SEM metallographic techniques, with the guide of Abriata and Bolcich phase diagram. The α-β interphase boundaries were characterized as short circuits for diffusion with radiotracer techniques and applying Fisher-Bondy-Martin model. The precipitation of carbides was promoted by heat treatments that produced first the C diffusion into the samples at high temperatures (β phase), and then the precipitation of carbide particles at lower temperature (α phase or (α+β)) two phase field. The precipitated carbides were identified as (Zr, Nb)C 1-x with SEM, electron microprobe and X-ray diffraction techniques. (Author) [es

  9. Spectrum of ferromagnetic transition metal magnetic excitations and neutron scattering

    International Nuclear Information System (INIS)

    Kuzemskij, A.L.

    1979-01-01

    Quantum statistical models of ferromagnetic transition metals as well as methods of their solutions are reviewed. The correspondence of results on solving these models and the data on scattering thermal neutrons in ferromagnetic is discussed

  10. Alkylation and arylation of alkenes by transition metal complexes

    International Nuclear Information System (INIS)

    Volkova, L.G.; Levitin, I.Ya.; Vol'pin, M.E.

    1975-01-01

    In this paper are reviewed methods of alkylation and irylation of unsaturated compounds with complexes of transition metals (Rh, Pd). Analysis of alkylation and arylation of olefines with organic derivatives of transition metals, obtained as a result of exchange reactions between organic compounds of transition metals and salts of metals of the 8th group of the periodic system, allows a conclusion as to the wide possibilities of these reactions in the synthesis of various derivatives of unsaturated compounds. In all the reactions under consideration, intermediate formation of sigma-complexes is assumed. Also considered are alkylation and arylation of olefines with organic derivatives of halogens in the presence of compounds of metals of the 8th group of the periodic system, as well as arylation of olefines with aromatic compounds in the presence of salts of transition metals

  11. A review on transition-metal mediated synthesis of quinolines

    Indian Academy of Sciences (India)

    Rashmi Sharma

    2018-06-14

    Jun 14, 2018 ... Special Section on Transition Metal Catalyzed Synthesis of Medicinally Relevant Molecules. A review on ...... iron(III) chloride and TEMPO oxoammonium salt as an .... propyl-3-ethylquinoline (209) in presence of platinum.

  12. Metallacyclopentadienes: structural features and coordination in transition metal complexes

    International Nuclear Information System (INIS)

    Dolgushin, Fedor M; Yanovsky, Aleksandr I; Antipin, Mikhail Yu

    2004-01-01

    Results of structural studies of polynuclear transition metal complexes containing the metallacyclopentadiene fragment are overviewed. The structural features of the complexes in relation to the nature of the substituents in the organic moiety of the metallacycles, the nature of the transition metals and their ligand environment are analysed. The main structural characteristics corresponding to different modes of coordination of metallacyclopentadienes to one or two additional metal centres are revealed.

  13. Trends in catalytic NO decomposition over transition metal surfaces

    DEFF Research Database (Denmark)

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

    2007-01-01

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

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

    Science.gov (United States)

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

    2016-09-01

    A transition-metal-free asymmetric supercapacitor (ASC) is successfully fabricated based on an earth-abundant biomass derived redox-active biomolecule, named lawsone. Such an ASC exhibits comparable or even higher energy densities than most of the recently reported transition-metal-based ASCs, and this green ASC generation from renewable resources is promising for addressing current issues of electronic hazard processing, high cost, and unsustainability. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Ab initio modelling of transition metals in diamond

    International Nuclear Information System (INIS)

    Watkins, M; Mainwood, A

    2003-01-01

    Transition metals (TM) from the first transition series are commonly used as solvent catalysts in the synthesis of diamond by high pressure, high temperature processes. Ab initio calculations on these metals, in finite clusters of tetrahedrally coordinated carbon, enable us to investigate trends in their stability and properties. By carrying out systematic studies of interstitial, substitutional and semi-vacancy TM defects, we show that the electronic structure of the TMs is complicated by the presence of 'dangling bonds' when the TM disrupts the crystal lattice: interstitial defects conform to the Ludwig-Woodbury (LW) model, whilst substitutional and semi-vacancy defects move from approximating the LW model early in the transition series to approaching the vacancy model for the heavier metals. Multi-configurational self-consistent field methods allow genuine many-electron states to be modelled; for neutral interstitial, and all substitutional TMs, the crystal fields are found to exceed the exchange energies in strength. Consequently, low spin states are found for these defects. We find substitutional defects to be the most stable, but that semi-vacancy TMs are very similar in energy to the substitutional defects late in the transition series; interstitial defects are only metastable in diamond. Given appropriate charge compensators neutral and positively charged interstitial TM defects were stable, while negatively charged species appeared to be strongly disfavoured

  16. Protactinium and the intersection of actinide and transition metal chemistry

    Energy Technology Data Exchange (ETDEWEB)

    Wilson, Richard E.; De Sio, Stephanie; Vallet, Valérie

    2018-02-12

    The role of the 5f and 6d orbitals in the chemistry of the actinide elements has been of considerable interest since their discovery and synthesis. Relativistic effects cause the energetics of the 5f and 6d orbitals to change as the actinide series is traversed left to right imparting a rich and complex chemistry. The 5f and 6d atomic states cross in energy at protactinium (Pa), making it a potential intersection between transition metal and actinide chemistries. Herein, we report the synthesis of a Pa-peroxo cluster, A(6)(Pa4O(O-2)(6)F-12) [A = Rb, Cs, (CH3)(4)N], formed in pursuit of an actinide polyoxometalate. Quantum chemical calculations at the density functional theory level demonstrate equal 5f and 6d orbital participation in the chemistry of Pa and increasing 5f orbital participation for the heavier actinides. Periodic changes in orbital character to the bonding in the early actinides highlights the influence of the 5f orbitals in their reactivity and chemical structure.

  17. A Simple, General Synthetic Route toward Nanoscale Transition Metal Borides.

    Science.gov (United States)

    Jothi, Palani R; Yubuta, Kunio; Fokwa, Boniface P T

    2018-04-01

    Most nanomaterials, such as transition metal carbides, phosphides, nitrides, chalcogenides, etc., have been extensively studied for their various properties in recent years. The similarly attractive transition metal borides, on the contrary, have seen little interest from the materials science community, mainly because nanomaterials are notoriously difficult to synthesize. Herein, a simple, general synthetic method toward crystalline transition metal boride nanomaterials is proposed. This new method takes advantage of the redox chemistry of Sn/SnCl 2 , the volatility and recrystallization of SnCl 2 at the synthesis conditions, as well as the immiscibility of tin with boron, to produce crystalline phases of 3d, 4d, and 5d transition metal nanoborides with different morphologies (nanorods, nanosheets, nanoprisms, nanoplates, nanoparticles, etc.). Importantly, this method allows flexibility in the choice of the transition metal, as well as the ability to target several compositions within the same binary phase diagram (e.g., Mo 2 B, α-MoB, MoB 2 , Mo 2 B 4 ). The simplicity and wide applicability of the method should enable the fulfillment of the great potential of this understudied class of materials, which show a variety of excellent chemical, electrochemical, and physical properties at the microscale. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

    KAUST Repository

    Takanabe, Kazuhiro; Isimjan, Tayirjan; Yu, Weili; Del Gobbo, Silvano; Xu, Wei

    2015-01-01

    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.

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

    KAUST Repository

    Takanabe, Kazuhiro

    2015-03-05

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

  20. Transition metal carbide nanocomposite and amorphous thin films

    OpenAIRE

    Tengstrand, Olof

    2014-01-01

    This thesis explores thin films of binary and ternary transition metal carbides, in the Nb-C, Ti-Si-C, Nb-Si-C, Zr-Si-C, and Nb-Ge-C systems. The electrical and mechanical properties of these systems are affected by their structure and here both nanocomposite and amorphous thin films are thus investigated. By appropriate choice of transition metal and composition the films can be designed to be multifunctional with a combination of properties, such as low electric resistivity, low contact res...

  1. Impurities in Antiferromagnetic Transition-Metal Oxides - Symmetry and Optical Transitions

    Science.gov (United States)

    Petersen, John Emil, III

    considered. For example, simple rock-salt transition-metal oxides are quite different from the high temperature superconducting cuprates. A range of materials is studied here, in order to gain a greater understanding of optical transitions in highly-correlated systems. In this work, O vacancies are introduced in NiO, along with Fe impurities, to understand better the band filling in the insulating behavior observed experimentally. These results are compared with those of La2NiO4, La2CuO4, La2-xSr xNiO4, and La2-xSrxCuO4. to elucidate the mechanisms behind the symmetry breaking phenomena in the Sr doped systems. As it turns out, indeed, the x2 - y2 orbital in these materials plays a critical role in spatial charge distribution, magnetic, and spin densities which are coupled to the dopant position in the lattice. The in-depth study of electronic and optical properties of transition-metal oxides presented here provides theoretical characterization of the infamous pseudogap in the cuprates - one of the greatest mysteries of modern solid state physics. In addition, via Density Functional Perturbation Theory, the phonon coupling with charge-density wave is explored in La2-xSr xNiO4 and found to be the dominant contributing factor to the colossal dielectric constant.

  2. Integrating Transition Metals into Nanomaterials: Strategies and Applications

    KAUST Repository

    Fhayli, Karim

    2016-04-14

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

  3. Superconductivity Series in Transition Metal Dichalcogenides by Ionic Gating

    NARCIS (Netherlands)

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

    2015-01-01

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

  4. Fluorescence signalling of the transition metal ions: Design strategy ...

    Indian Academy of Sciences (India)

    Unknown

    strategy based on the choice of the fluorophore component. N B SANKARAN, S ... skill for the development of fluorosensors of this kind. Further, the ... salts of the transition metal ions have been used for studying the influence of the metal ions.

  5. Transition metal oxide loaded MCM catalysts for photocatalytic ...

    Indian Academy of Sciences (India)

    Transition metal oxide (TiO2, Fe2O3, CoO) loaded MCM-41 and MCM-48 were synthesized by a two-step .... washed consecutively with water and ethanol, and cal- cined at 823 K for 5 .... conversion was observed in 1 h when the reaction was.

  6. Tris-diamine-derived transition metal complexes of flurbiprofen as ...

    African Journals Online (AJOL)

    admin

    butyrylcholinesterase (BChE) inhibitory activities. Method: Tris-diamine-derived transition metal complexes of Co(II), Ni(II), and Mn(II) were synthesized and characterized ... Conductance measurements indicated that diamine-derived metal complexes of ..... contributes to enhanced biological activity, and provides novel ...

  7. Charge transfer in chromium-transition metal alloys

    International Nuclear Information System (INIS)

    Kulakowski, K.; Maksymowicz, A.

    1984-07-01

    The average T-matrix approximation is applied for calculations of charge transfer of 3d-electrons in transition metal alloys. The role of concentration, long-range and short-range atomic order is investigated. The results are in reasonable agreement with experimental data. (author)

  8. Plasmons in metallic monolayer and bilayer transition metal dichalcogenides

    DEFF Research Database (Denmark)

    Andersen, Kirsten; Thygesen, Kristian S.

    2013-01-01

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

  9. Reactions of transition metal complexes with cyclic ethers

    International Nuclear Information System (INIS)

    Milstein, D.

    1977-02-01

    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

  10. Direct NO decomposition over stepped transition-metal surfaces

    DEFF Research Database (Denmark)

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

    2007-01-01

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

  11. Integrating Transition Metals into Nanomaterials: Strategies and Applications

    KAUST Repository

    Fhayli, Karim

    2016-01-01

    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.

  12. Exciton ionization in multilayer transition-metal dichalcogenides

    DEFF Research Database (Denmark)

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

    2016-01-01

    Photodetectors and solar cells based on materials with strongly bound excitons rely crucially on field-assisted exciton ionization. We study the ionization process in multilayer transition-metal dichalcogenides (TMDs) within the Mott-Wannier model incorporating fully the pronounced anisotropy...

  13. Coordination to transition metal surfaces : a theoretical study

    NARCIS (Netherlands)

    Santen, van R.A.

    1985-01-01

    A theoretical framework is developed that describes the chemisorption of CO to transition metal surfaces analogous to the HOMO-LUMO concept of MO theory. An explanation is given for the exptl. observation that CO adsorbs on top at the (111), face of Pt, but bridge at the (111) face of Ni. One is due

  14. Fullerenes as a new type of ligands for transition metals

    International Nuclear Information System (INIS)

    Sokolov, V.I.

    2007-01-01

    Fullerenes are considered as ligands in transition metal π-complexes. The following aspects are discussed: metals able to form π-complexes with fullerenes (Zr, V, Ta, Mo, W, Re, Ru, etc.); haptic numbers; homo- and hetero ligand complexes; ligand compatibility with fullerenes for different metals, including fullerenes with a disturbed structure of conjugation [ru

  15. Vibrational properties of vacancy in bcc transition metals using ...

    Indian Academy of Sciences (India)

    The calculated results of the formation entropy of the vacancy compared well with other available ... for Fe, Mo and W transition metals employing a third-neighbour model. ... For the atomic electron density we have chosen a power law: f (r) = fe.

  16. Biomass transition metal hydrogen-evolution electrocatalysts and electrodes

    Energy Technology Data Exchange (ETDEWEB)

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

    2017-02-28

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

  17. Reactivity of monoolefin ligand in transition metal complexes

    International Nuclear Information System (INIS)

    Rybinskaya, M.I.

    1978-01-01

    The main tendencies in the coordinated olefin ligand property changes are discussed in the transition metal complexes in comparison with free olefins. The review includes the papers published from 1951 up to 1976. It has been shown that in complexes with transition metal cations olefin π-base acquires the ability to react with nucleophylic reagents. Olefin π-acids in complexes with zero valent metals are easily subjected to electrophylic reagent action. At coordination with transition metal cations the olefin properties are generally preserved, while in the zero-valent metal complexes the nonsaturated ligand acquires the properties of a saturated compounds. The ability of transition metal cations in complexes to intensify reactions of nucleophylic bimolecular substitution of vinyl halogen is clearly detected in contrast to the zero valent metal complexes. It has been shown that investigations of the coordinated olefin ligand reactivity give large possibilities in the further development of the organic synthesis. Some reactions are taken as the basis of important industrial processes

  18. [Non-empirical interatomic potentials for transition metals

    International Nuclear Information System (INIS)

    1993-01-01

    The report is divided into the following sections: potential-energy functions for d-band metals, potential-energy functions for aluminides and quasicrystals, electronic structure of complex structures and quasicrystals, potential-energy functions in transition-metal oxides, applications to defect structure and mechanical properties, and basic theory of interatomic potentials

  19. 'Pincer' dicarbene complexes of some early transition metals and uranium.

    Science.gov (United States)

    Pugh, David; Wright, Joseph A; Freeman, Sandra; Danopoulos, Andreas A

    2006-02-14

    The complexes [(C-N-C)MX(n)(thf)(m)] with the 'pincer' 2,6-bis(imidazolylidene)pyridine, (C-N-C) = 2,6-bis(arylimidazol-2-ylidene)pyridine, aryl = 2,6-Pr(i)2C6H3, M = V, X = Cl, n = 2, m = 1 1a; M = Cr, X = Cl, n = 2, m = 0, 2a, X = Br, 2b; M = Mn, X = Br, n = 2, m = 0, 3; M = Nb, X = Cl, n = 3, m = 0, 4; and M = U, X = Cl, n = 4, m = 0, 5, were synthesised by (a) substitution of labile tmed (1a), thf (2a, 3, 5) or dme (4) by free (C-N-C) or by (b) reaction of the bisimidazolium salt (CH-N-CH)Br2 with {Cr[N(SiMe3)2]2(thf)2} followed by amine elimination (2b). Attempted alkylation of 1a, 2, 3a and 4 with Grignard or alkyl lithiums gave intractable mixtures, and in one case [reaction of 1a with (mesityl)MgBr] resulted in exchange of Cl by Br (1b). Oxidation of 1a or [(C-N-C)VCl3] with 4-methylmorpholine N-oxide afforded the trans-V(C-N-C)(=O)Cl2, 6, which by reaction with AgBF4 in MeCN gave trans-[V(C-N-C)(=O)(MeCN)2][BF4]2, 7. Reaction of 1a with p-tolyl azide gave trans-V(C-N-C)(=N-p-tolyl)Cl2 8. The complex trans-Ti(C-N-C)(=NBu(t))Cl2, 9, was prepared by substitution of the pyridine ligands in Ti(NBu(t))Cl2(py)3 by C-N-C.

  20. Reactivity of Aluminum-Based Mixtures with Early Transition Metals

    Science.gov (United States)

    2014-08-01

    acid to prevent cold welding to the milling vial’s internal walls during the blending process. The as- milled powders were analyzed via Scanning...softer Al particles, a duplex , mostly two-dimensional structure was developed. Consistent with the observed morphological changes, XRD peak profiles

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

    International Nuclear Information System (INIS)

    Haeglund, J.

    1993-01-01

    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 VC 1-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

  2. Molecular dynamics simulation of deformation twin in rocksalt vanadium nitride

    International Nuclear Information System (INIS)

    Fu, Tao; Peng, Xianghe; Zhao, Yinbo; Li, Tengfei; Li, Qibin; Wang, Zhongchang

    2016-01-01

    We perform molecular dynamics simulation of nano-indentation with a cylindrical indenter to investigate the formation mechanism of deformation twin in vanadium nitride (VN) with a rocksalt structure. We find that the deformation twins occur during the loading stage, and subsequently conduct a systematic analysis of nucleation, propagation and thickening of a deformation twin. We find that the nucleation of a partial dislocation and its propagation to form a stacking fault are premise of deformation twin formation. The sequential nucleation and propagation of partial dislocation on adjacent parallel {111} planes are found to cause the thickening of the deformation twin. Moreover, the deformation twins can exist in VN at room temperature. - Highlights: • MD simulations of indentation are performed to study the deformation twin in VN. • The deformation twins can occur in VN during the loading stage. • The nucleation, propagation and thickening of a deformation twin are analyzed. • The deformation twins can exist in VN at room temperature.

  3. Rocksalt MgS solar blind ultra-violet detectors

    Directory of Open Access Journals (Sweden)

    Ying-Hoi Lai

    2012-03-01

    Full Text Available Studies using in-situ Auger electron spectroscopy and reflection high energy electron diffraction, and ex-situ high resolution X-ray diffraction and electron backscatter diffraction reveal that a MgS thin film grown directly on a GaAs (100 substrate by molecular beam epitaxy adopts its most stable phase, the rocksalt structure, with a lattice constant of 5.20 Å. A Au/MgS/n+-GaAs (100 Schottky-barrier photodiode was fabricated and its room temperature photoresponse was measured to have a sharp fall-off edge at 235 nm with rejection of more than three orders at 400 nm and higher than five orders at 500 nm, promising for various solar-blind UV detection applications.

  4. Generation and Characteristics of IV-VI transition Metal Nitride and Carbide Nanoparticles using a Reactive Mesoporous Carbon Nitride

    KAUST Repository

    Alhajri, Nawal Saad

    2016-02-22

    Interstitial nitrides and carbides of early transition metals in groups IV–VI exhibit platinum-like electronic structures, which make them promising candidates to replace noble metals in various catalytic reactions. Herein, we present the preparation and characterization of nano-sized transition metal nitries and carbides of groups IV–VI (Ti, V, Nb, Ta, Cr, Mo, and W) using mesoporous graphitic carbon nitride (mpg-C3N4), which not only provides confined spaces for restricting primary particle size but also acts as a chemical source of nitrogen and carbon. We studied the reactivity of the metals with the template under N2 flow at 1023 K while keeping the weight ratio of metal to template constant at unity. The produced nanoparticles were characterized by powder X-ray diffraction, CHN elemental analysis, nitrogen sorption, X-ray photoelectron spectroscopy, and transmission electron microscopy. The results show that Ti, V, Nb, Ta, and Cr form nitride phases with face centered cubic structure, whereas Mo and W forme carbides with hexagonal structures. The tendency to form nitride or carbide obeys the free formation energy of the transition metal nitrides and carbides. This method offers the potential to prepare the desired size, shape and phase of transition metal nitrides and carbides that are suitable for a specific reaction, which is the chief objective of materials chemistry.

  5. Preparation and characterization of several transition metal oxides

    International Nuclear Information System (INIS)

    Wold, A.; Dwight, K.

    1989-01-01

    The structure-property relationships of several conducting transition metal oxides, as well as their preparative methods, are presented in this paper. The importance of preparing homogeneous phases with precisely known stoichiometry is emphasized. A comparison is also made of the various techniques used to prepare both polycrystalline and single crystal samples. For transition metal oxides, the metallic properties are discussed either in terms of metal-metal distances which are short enough to result in metallic behavior, or in terms of the formation of a π* conduction band resulting from covalent metal-oxygen interactions. Metallic behavior is observed when the conduction bands are populated with either electrons or holes. The concentration of these carriers can be affected by either cation or anion substitutions. The discussion in this presentation will be limited to the elements Re, Ti, V, Cr, Mo, and Cu

  6. Control of interlayer physics in 2H transition metal dichalcogenides

    Science.gov (United States)

    Wang, Kuang-Chung; Stanev, Teodor K.; Valencia, Daniel; Charles, James; Henning, Alex; Sangwan, Vinod K.; Lahiri, Aritra; Mejia, Daniel; Sarangapani, Prasad; Povolotskyi, Michael; Afzalian, Aryan; Maassen, Jesse; Klimeck, Gerhard; Hersam, Mark C.; Lauhon, Lincoln J.; Stern, Nathaniel P.; Kubis, Tillmann

    2017-12-01

    It is assessed in detail both experimentally and theoretically how the interlayer coupling of transition metal dichalcogenides controls the electronic properties of the respective devices. Gated transition metal dichalcogenide structures show electrons and holes to either localize in individual monolayers, or delocalize beyond multiple layers—depending on the balance between spin-orbit interaction and interlayer hopping. This balance depends on the layer thickness, momentum space symmetry points, and applied gate fields. The design range of this balance, the effective Fermi levels, and all relevant effective masses is analyzed in great detail. A good quantitative agreement of predictions and measurements of the quantum confined Stark effect in gated MoS2 systems unveils intralayer excitons as the major source for the observed photoluminescence.

  7. Structural models for amorphous transition metal binary alloys

    International Nuclear Information System (INIS)

    Ching, W.Y.; Lin, C.C.

    1976-01-01

    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 Fe 0 . 75 P 0 . 25 , Ni 0 . 75 P 0 . 25 , Co 0 . 75 P 0 . 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

  8. Conductive transition metal oxide nanostructured electrochromic material and optical switching devices constructed thereof

    Science.gov (United States)

    Mattox, Tracy M.; Koo, Bonil; Garcia, Guillermo; Milliron, Delia J.; Trizio, Luca De; Dahlman, Clayton

    2017-10-10

    An electrochromic device includes a nanostructured transition metal oxide bronze layer that includes one or more transition metal oxide and one or more dopant, a solid state electrolyte, and a counter electrode. The nanostructured transition metal oxide bronze selectively modulates transmittance of near-infrared (NIR) spectrum and visible spectrum radiation as a function of an applied voltage to the device.

  9. Liquid state properties of certain noble and transition metals

    International Nuclear Information System (INIS)

    Bhuiyan, G.M.; Rahman, A.; Khaleque, M.A.; Rashid, R.I.M.A.; Mujibur Rahman, S.M.

    1998-07-01

    Certain structural, thermodynamic and atomic transport properties of a number of liquid noble and transition metals are reported. The underlying theory combines together a simple form of the N-body potential and the thermodynamically self-consistent variational modified hypernetted chain (VMHNC) theory of liquid. The static structure factors calculated by using the VMHNC resemble the hard sphere (HS) values. Consequently the HS model is used to calculate the thermodynamic properties viz. specific heat, entropy, isothermal compressibility and atomic transport properties. (author)

  10. Charge transfers in complex transition metal alloys (Ti2Fe)

    International Nuclear Information System (INIS)

    Abramovici, G.

    1998-01-01

    We introduce a new non-orthogonal tight-binding model, for complex alloys, in which electronic structure is characterized by charge transfers. We give the analytic calculation of a charge transfer, in which overlapping two-center terms are rigorously taken into account. Then, we apply numerically this result to an approximant phase of a quasicrystal of Ti 2 Fe alloy. This model is more particularly adapted to transition metals, and gives realistic densities of states. (orig.)

  11. Magnetic properties of fcc Ni-based transition metal alloy

    Czech Academy of Sciences Publication Activity Database

    Kudrnovský, Josef; Drchal, Václav

    2009-01-01

    Roč. 100, č. 9 (2009), s. 1193-1196 ISSN 1862-5282 R&D Projects: GA MŠk OC 150; GA AV ČR IAA100100616 Institutional research plan: CEZ:AV0Z10100520 Keywords : transition metal alloys * Ni-based * pair exchange interactions * Curie temperatures * renormalized RPA Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 0.862, year: 2009

  12. The dynamic behavior of the exohedral transition metal complexes ...

    Indian Academy of Sciences (India)

    Home; Journals; Journal of Chemical Sciences; Volume 129; Issue 7. The dynamic behavior of the exohedral transition metal complexes of B₄₀ : η⁶- and η⁷-B₄₀Cr(CO) ₃ and Cr(CO) ₃η⁷-B₄η₀-Cr(CO) ₃. NAIWRIT KARMODAK ELUVATHINGAL D JEMMIS. REGULAR ARTICLE Volume 129 Issue 7 July 2017 pp ...

  13. Immobilization of transition metal ions on zirconium phosphate monolayers

    International Nuclear Information System (INIS)

    Melezhik, A.V.; Brej, V.V.

    1998-01-01

    It is shown that ions of transition metals (copper, iron, vanadyl, titanium) are adsorbed on zirconium phosphate monolayers. The zirconium phosphate threshold capacity corresponds to substitution of all protons of hydroxyphosphate groups by equivalent amounts of copper, iron or vanadyl. Adsorption of polynuclear ions is possible in case of titanium. The layered substance with specific surface up to 300 m 2 /g, wherein ultradispersed titanium dioxide particles are intercalirated between zirconium-phosphate layers, is synthesized

  14. High coercivity rare earth-transition metal magnets

    International Nuclear Information System (INIS)

    Croat, J.J.

    1982-01-01

    Ferromagnetic compositions having intrinsic magnetic coercivities at room temperature of at least 1,000 Oersteds are formed by the controlled quenching of molten rare earth -transition metal alloys. Hard magnets may be inexpensively formed from the lower atomic weight lanthanide elements and iron. The preferable compositions lie within: at least one of Fe, Ni, Co (20 to 70 atomic percent); and at least one of Ce, Pr, Na, Sm, Eu, Tb, Dy, Ho, Er, Tm, Y (80 to 30 atomic percent). (author)

  15. High coercivity rare earth-transition metal magnets

    International Nuclear Information System (INIS)

    Croat, J.J.

    1982-01-01

    Ferromagnetic compositions having intrinsic magnetic coercivities at room temperature of at least 1,000 Oersteds are formed by the controlled quenching of molten rare earth-transition metal alloys. Hard magnets may be inexpensively formed from the lower atomic weight lanthanide elements and iron. The preferable compositions lie within: at least one of Fe, Ni, Co; 20 - 70 atomic percent: at least one of Ce, Pr, Nd, Sm, Eu, Tb, Dy, Ho, Er, Tm, Y; 80 - 30 atomic percent. (author)

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

    International Nuclear Information System (INIS)

    Watson, R.E.; Weinert, M.; Davenport, J.W.; Fernando, G.W.; Bennett, L.H.

    1992-01-01

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

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

    DEFF Research Database (Denmark)

    Tritsaris, G. A.; Rossmeisl, J.

    2012-01-01

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

  18. Hydrogen and dihydrogen bonding of transition metal hydrides

    International Nuclear Information System (INIS)

    Jacobsen, Heiko

    2008-01-01

    Intermolecular interactions between a prototypical transition metal hydride WH(CO) 2 NO(PH 3 ) 2 and a small proton donor H 2 O have been studied using DFT methodology. The hydride, nitrosyl and carbonyl ligand have been considered as site of protonation. Further, DFT-D calculations in which empirical corrections for the dispersion energy are included, have been carried out. A variety of pure and hybrid density functionals (BP86, PW91, PBE, BLYP, OLYP, B3LYP, B1PW91, PBE0, X3LYP) have been considered, and our calculations indicate the PBE functional and its hybrid variation are well suited for the calculation of transition metal hydride hydrogen and dihydrogen bonding. Dispersive interactions make up for a sizeable portion of the intermolecular interaction, and amount to 20-30% of the bond energy and to 30-40% of the bond enthalpy. An energy decomposition analysis reveals that the H...H bond of transition metal hydrides contains both covalent and electrostatic contributions

  19. Hydrogen and dihydrogen bonding of transition metal hydrides

    Science.gov (United States)

    Jacobsen, Heiko

    2008-04-01

    Intermolecular interactions between a prototypical transition metal hydride WH(CO) 2NO(PH 3) 2 and a small proton donor H 2O have been studied using DFT methodology. The hydride, nitrosyl and carbonyl ligand have been considered as site of protonation. Further, DFT-D calculations in which empirical corrections for the dispersion energy are included, have been carried out. A variety of pure and hybrid density functionals (BP86, PW91, PBE, BLYP, OLYP, B3LYP, B1PW91, PBE0, X3LYP) have been considered, and our calculations indicate the PBE functional and its hybrid variation are well suited for the calculation of transition metal hydride hydrogen and dihydrogen bonding. Dispersive interactions make up for a sizeable portion of the intermolecular interaction, and amount to 20-30% of the bond energy and to 30-40% of the bond enthalpy. An energy decomposition analysis reveals that the H⋯H bond of transition metal hydrides contains both covalent and electrostatic contributions.

  20. Hydrogen and dihydrogen bonding of transition metal hydrides

    Energy Technology Data Exchange (ETDEWEB)

    Jacobsen, Heiko [KemKom, Libellenweg 2, 25917 Leck, Nordfriesland (Germany)], E-mail: jacobsen@kemkom.com

    2008-04-03

    Intermolecular interactions between a prototypical transition metal hydride WH(CO){sub 2}NO(PH{sub 3}){sub 2} and a small proton donor H{sub 2}O have been studied using DFT methodology. The hydride, nitrosyl and carbonyl ligand have been considered as site of protonation. Further, DFT-D calculations in which empirical corrections for the dispersion energy are included, have been carried out. A variety of pure and hybrid density functionals (BP86, PW91, PBE, BLYP, OLYP, B3LYP, B1PW91, PBE0, X3LYP) have been considered, and our calculations indicate the PBE functional and its hybrid variation are well suited for the calculation of transition metal hydride hydrogen and dihydrogen bonding. Dispersive interactions make up for a sizeable portion of the intermolecular interaction, and amount to 20-30% of the bond energy and to 30-40% of the bond enthalpy. An energy decomposition analysis reveals that the H...H bond of transition metal hydrides contains both covalent and electrostatic contributions.

  1. Transition-metal impurities in semiconductors and heterojunction band lineups

    Science.gov (United States)

    Langer, Jerzy M.; Delerue, C.; Lannoo, M.; Heinrich, Helmut

    1988-10-01

    The validity of a recent proposal that transition-metal impurity levels in semiconductors may serve as a reference in band alignment in semiconductor heterojunctions is positively verified by using the most recent data on band offsets in the following lattice-matched heterojunctions: Ga1-xAlxAs/GaAs, In1-xGaxAsyP1-y/InP, In1-xGaxP/GaAs, and Cd1-xHgxTe/CdTe. The alignment procedure is justified theoretically by showing that transition-metal energy levels are effectively pinned to the average dangling-bond energy level, which serves as the reference level for the heterojunction band alignment. Experimental and theoretical arguments showing that an increasingly popular notion on transition-metal energy-level pinning to the vacuum level is unjustified and must be abandoned in favor of the internal-reference rule proposed recently [J. M. Langer and H. Heinrich, Phys. Rev. Lett. 55, 1414 (1985)] are presented.

  2. Functionalization of 2D transition metal dichalcogenides for biomedical applications

    International Nuclear Information System (INIS)

    Li, Zibiao; Wong, Swee Liang

    2017-01-01

    Recent research has revealed a gamut of interesting properties present in layered two-dimensional (2D) transition metal dichalcogenides (TMDCs) such as photoluminescence, comparatively high electron mobility, flexibility, mechanical strength and relatively low toxicity. The large surface to area ratio inherent in these materials also allows easy functionalization and maximal interaction with the external environment. Due to its unique physical and chemical properties, much work has been done in tailoring TMDCs through chemical functionalization for use in a diverse range of biomedical applications as biosensors, drug delivery carriers or even as therapeutic agents. In this review, current progress on the different types of TMDC functionalization for various biological applications will be presented and its future outlook will be discussed. - Highlights: • The different functionalization strategies and approaches of transition metal dichalcogenides are reviewed. • Properties of transition metal dichalcogenides useful for biomedical usage and their methods of synthesis are introduced. • Functionalization approaches are presented according to material type and their different application purpose is discussed.

  3. Synthesis of Mg2FeH6 containing as additives transition metal and transition metal fluorides or carbon

    International Nuclear Information System (INIS)

    Zepon, G.; Leiva, D.R.; Botta, W.J.

    2010-01-01

    The Mg 2 FeH 6 is a promising way of storing hydrogen in solid form, composed by elements that have low cost and, at the same time, high volumetric storage density: 150 kg H 2 /m 3 . However, this complex hydride is not easily synthesized as a single phase material. The hydrogen sorption high temperature and slow kinetics are the major limitations for the practical application of the Mg 2 FeH 6 as a hydrogen storage material. Little is known about the effects of additives in Mg 2 FeH 6 based nanocomposites in this work were synthesized by MAE under hydrogen atmosphere nanocomposites based on Mg 2 FeH 6 containing additives as transition metals, transition metals fluorides of transition metals or carbon, in order to obtain information on the effects of the selected additives. To this end, we used characterization techniques such as XRD, SEM and TEM, thermal analysis by DSC and curves made in apparatus PCT.(author)

  4. Control of electronic properties of 2D carbides (MXenes) by manipulating their transition metal layers

    KAUST Repository

    Anasori, Babak

    2016-02-24

    In this study, a transition from metallic to semiconducting-like behavior has been demonstrated in two-dimensional (2D) transition metal carbides by replacing titanium with molybdenum in the outer transition metal (M) layers of M3C2 and M4C3 MXenes. The MXene structure consists of n + 1 layers of near-close packed M layers with C or N occupying the octahedral site between them in an [MX]nM arrangement. Recently, two new families of ordered 2D double transition metal carbides MXenes were discovered, M′2M′′C2 and M′2M′′2C3 – where M′ and M′′ are two different early transition metals, such as Mo, Cr, Ta, Nb, V, and Ti. The M′ atoms only occupy the outer layers and the M′′ atoms fill the middle layers. In other words, M′ atomic layers sandwich the middle M′′–C layers. Using X-ray atomic pair distribution function (PDF) analysis on Mo2TiC2 and Mo2Ti2C3 MXenes, we present the first quantitative analysis of structures of these novel materials and experimentally confirm that Mo atoms are in the outer layers of the [MC]nM structures. The electronic properties of these Mo-containing MXenes are compared with their Ti3C2 counterparts, and are found to be no longer metallic-like conductors; instead the resistance increases mildly with decreasing temperatures. Density functional theory (DFT) calculations suggest that OH terminated Mo–Ti MXenes are semiconductors with narrow band gaps. Measurements of the temperature dependencies of conductivities and magnetoresistances have confirmed that Mo2TiC2Tx exhibits semiconductor-like transport behavior, while Ti3C2Tx is a metal. This finding opens new avenues for the control of the electronic and optical applications of MXenes and for exploring new applications, in which semiconducting properties are required.

  5. The recent development of efficient Earth-abundant transition-metal nanocatalysts.

    Science.gov (United States)

    Wang, Dong; Astruc, Didier

    2017-02-06

    Whereas noble metal compounds have long been central in catalysis, Earth-abundant metal-based catalysts have in the same time remained undeveloped. Yet the efficacy of Earth-abundant metal catalysts was already shown at the very beginning of the 20th century with the Fe-catalyzed Haber-Bosch process of ammonia synthesis and later in the Fischer-Tropsch reaction. Nanoscience has revolutionized the world of catalysis since it was observed that very small Au nanoparticles (NPs) and other noble metal NPs are extraordinarily efficient. Therefore the development of Earth-abundant metals NPs is more recent, but it has appeared necessary due to their "greenness". This review highlights catalysis by NPs of Earth-abundant transition metals that include Mn, Fe, Co, Ni, Cu, early transition metals (Ti, V, Cr, Zr, Nb and W) and their nanocomposites with emphasis on basic principles and literature reported during the last 5 years. A very large spectrum of catalytic reactions has been successfully disclosed, and catalysis has been examined for each metal starting with zero-valent metal NPs followed by oxides and other nanocomposites. The last section highlights the catalytic activities of bi- and trimetallic NPs. Indeed this later family is very promising and simultaneously benefits from increased stability, efficiency and selectivity, compared to monometallic NPs, due to synergistic substrate activation.

  6. Thermal properties of zirconium diboride -- transition metal boride solid solutions

    Science.gov (United States)

    McClane, Devon Lee

    This research focuses on the thermal properties of zirconium diboride (ZrB2) based ceramics. The overall goal was to improve the understanding of how different transition metal (TM) additives influence thermal transport in ZrB2. To achieve this, ZrB2 with 0.5 wt% carbon, and 3 mol% of individual transition metal borides, was densified by hot-press sintering. The transition metals that were investigated were: Y, Ti, Hf, V, Nb, Ta, Cr, Mo, W, and Re. The room temperature thermal diffusivities of the compositions ranged from 0.331 cm2/s for nominally pure ZrB2 to 0.105 cm2/s for (Zr,Cr)B2 and converged around 0.155cm2/s at higher temperatures for all compositions. Thermal conductivities were calculated from the diffusivities, using temperature-dependent values for density and heat capacity. The electron contribution to thermal conductivity was calculated from measured electrical resistivity according to the Wiedemann-Franz law. The phonon contribution to thermal conductivity was calculated by subtracting the electron contribution from the total thermal conductivity. Rietveld refinement of x-ray diffraction data was used to determine the lattice parameters of the compositions. The decrease in thermal conductivity for individual additives correlated directly to the metallic radius of the additive. Additional strain appeared to exist for additives when the stable TM boride for that metal had different crystal symmetries than ZrB2. This research provided insight into how additives and impurities affect thermal transport in ZrB2. The research potentially offers a basis for future modeling of thermal conductivity in ultra-high temperature ceramics based on the correlation between metallic radius and the decrease in thermal conductivity.

  7. First-principles study of doping effect on the phase transition of zinc oxide with transition metal doped

    International Nuclear Information System (INIS)

    Wu, Liang; Hou, Tingjun; Wang, Yi; Zhao, Yanfei; Guo, Zhenyu; Li, Youyong; Lee, Shuit-Tong

    2012-01-01

    Highlights: ► We study the doping effect on B4, B1 structures and phase transition of ZnO. ► We calculate the phase transition barrier and phase transition path of doped ZnO. ► The transition metal doping decreases the bulk modulus and phase transition pressure. ► The magnetic properties are influenced by the phase transition process. - Abstract: Zinc oxide (ZnO) is a promising material for its wide application in solid-state devices. With the pressure raised from an ambient condition, ZnO transforms from fourfold wurtzite (B4) to sixfold coordinated rocksalt (B1) structure. Doping is an efficient approach to improve the structures and properties of materials. Here we use density-functional theory (DFT) to study doped ZnO and find that the transition pressure from B4 phase to B1 phase of ZnO always decreases with different types of transition metal (V, Cr, Mn, Fe, Co, or Ni) doped, but the phase transition path is not affected by doping. This is consistent with the available experimental results for Mn-doped ZnO and Co-doped ZnO. Doping in ZnO causes the lattice distortion, which leads to the decrease of the bulk modulus and accelerates the phase transition. Mn-doped ZnO shows the strongest magnetic moment due to its half filled d orbital. For V-doped ZnO and Cr-doped ZnO, the magnetism is enhanced by phase transition from B4 to B1. But for Mn-doped ZnO, Fe-doped ZnO, Co-doped ZnO, and Ni-doped ZnO, B1 phase shows weaker magnetic moment than B4 phase. These results can be explained by the amount of charge transferred from the doped atom to O atom. Our results provide a theoretical basis for the doping approach to change the structures and properties of ZnO.

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

    Energy Technology Data Exchange (ETDEWEB)

    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.

  9. Magnetism in 3d transition metal doped SnO

    KAUST Repository

    Albar, Arwa

    2016-09-12

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

  10. Cell complexes of transition metals in biochemistry and medicine

    International Nuclear Information System (INIS)

    Voloshin, Ya.Z.; Varzatskij, O.A.; Bubnov, Yu.N.

    2007-01-01

    Basic directions and prospects of use of cell complexes of transition metals in medicine and biochemistry are considered: incapsulation of radioactive metal ions for radiotherapy and diagnostics; preparation of contrast compounds for magnetic resonance tomography, antidotes and pharmaceutical preparation of prolonged effect, preparations for boron-neutron-capture therapy of neoplasms, antioxidants; membrane transport of metal ions; study of interaction of cell metal complexes with nucleic acids; possibility of use of self-assembly of cell complexes for imitation of ligases and use of clathrochelates as linkers; design of inhibitors of viruses for AIDS therapy [ru

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

    DEFF Research Database (Denmark)

    Ishøy, Mette; Nielsen, Thomas Eiland

    2014-01-01

    of structurally complex and diverse heterocycles. In this Concept article, we attempt to cover this area of research through a selection of recent versatile examples. A sea of opportunities! Transition-metal-catalyzed isomerization of N- and O-allylic compounds provides a mild, selective and synthetically...... 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....

  12. Compton profiles of some 4d transition-metals

    International Nuclear Information System (INIS)

    Sharma, B.K.; Tomak, M.

    1982-08-01

    We have computed Compton profiles for 4d transition-metals using the Renormalized Free Atom (RFA) model for two different electron configurations, namely 4dsup(n-1)5s 1 and 4dsup(n-2)5s 2 . The results for niobium and molybdenum are presented and compared with those obtained for these metals within free atom model. For low values of momenta the RFA profiles are broader than the latter ones. The constancy of J(0) values reported for 3d-metals is shown to be present also in case of 4d-metals. (author)

  13. Correlated electron pseudopotentials for 3d-transition metals

    International Nuclear Information System (INIS)

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

    2015-01-01

    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

  14. Trends on 3d transition metal impurities in diamond

    International Nuclear Information System (INIS)

    Assali, L.V.C.; Machado, W.V.M.; Justo, J.F.

    2009-01-01

    We carried out a first principles investigation on the electronic properties and chemical trends of 3d transition metal related impurities in diamond. In terms of formation energy, the interstitial site is considerably more unfavorable than the substitutional or divacancy ones. Going from Ti to Ni, the 3d-related energy levels in the gap become deeper toward the valence band in all three sites. However, in the divacancy one, those levels cross with the divacancy-related ones, such that the electronic property of the center depends on the character of the highest occupied level.

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

    International Nuclear Information System (INIS)

    Guo, Yuzheng; Robertson, John

    2016-01-01

    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.

  16. Transition metal oxide as anode interface buffer for impedance spectroscopy

    Science.gov (United States)

    Xu, Hui; Tang, Chao; Wang, Xu-Liang; Zhai, Wen-Juan; Liu, Rui-Lan; Rong, Zhou; Pang, Zong-Qiang; Jiang, Bing; Fan, Qu-Li; Huang, Wei

    2015-12-01

    Impedance spectroscopy is a strong method in electric measurement, which also shows powerful function in research of carrier dynamics in organic semiconductors when suitable mathematical physical models are used. Apart from this, another requirement is that the contact interface between the electrode and materials should at least be quasi-ohmic contact. So in this report, three different transitional metal oxides, V2O5, MoO3 and WO3 were used as hole injection buffer for interface of ITO/NPB. Through the impedance spectroscopy and PSO algorithm, the carrier mobilities and I-V characteristics of the NPB in different devices were measured. Then the data curves were compared with the single layer device without the interface layer in order to investigate the influence of transitional metal oxides on the carrier mobility. The careful research showed that when the work function (WF) of the buffer material was just between the work function of anode and the HOMO of the organic material, such interface material could work as a good bridge for carrier injection. Under such condition, the carrier mobility measured through impedance spectroscopy should be close to the intrinsic value. Considering that the HOMO (or LUMO) of most organic semiconductors did not match with the work function of the electrode, this report also provides a method for wide application of impedance spectroscopy to the research of carrier dynamics.

  17. Cohesion and coordination effects on transition metal surface energies

    Science.gov (United States)

    Ruvireta, Judit; Vega, Lorena; Viñes, Francesc

    2017-10-01

    Here we explore the accuracy of Stefan equation and broken-bond model semiempirical approaches to obtain surface energies on transition metals. Cohesive factors are accounted for either via the vaporization enthalpies, as proposed in Stefan equation, or via cohesive energies, as employed in the broken-bond model. Coordination effects are considered including the saturation degree, as suggested in Stefan equation, employing Coordination Numbers (CN), or as the ratio of broken bonds, according to the bond-cutting model, considering as well the square root dependency of the bond strength on CN. Further, generalized coordination numbers CN bar are contemplated as well, exploring a total number of 12 semiempirical formulations on the three most densely packed surfaces of 3d, 4d, and 5d Transition Metals (TMs) displaying face-centered cubic (fcc), body-centered cubic (bcc), or hexagonal close-packed (hcp) crystallographic structures. Estimates are compared to available experimental surface energies obtained extrapolated to zero temperature. Results reveal that Stefan formula cohesive and coordination dependencies are only qualitative suited, but unadvised for quantitative discussion, as surface energies are highly overestimated, favoring in addition the stability of under-coordinated surfaces. Broken-bond cohesion and coordination dependencies are a suited basis for quantitative comparison, where square-root dependencies on CN to account for bond weakening are sensibly worse. An analysis using Wulff shaped averaged surface energies suggests the employment of broken-bond model using CN to gain surface energies for TMs, likely applicable to other metals.

  18. Transition-metal interactions in aluminum-rich intermetallics

    International Nuclear Information System (INIS)

    Al-Lehyani, Ibrahim; Widom, Mike; Wang, Yang; Moghadam, Nassrin; Stocks, G. Malcolm; Moriarty, John A.

    2001-01-01

    The extension of the first-principles generalized pseudopotential theory (GPT) to transition-metal (TM) aluminides produces pair and many-body interactions that allow efficient calculations of total energies. In aluminum-rich systems treated at the pair-potential level, one practical limitation is a transition-metal overbinding that creates an unrealistic TM-TM attraction at short separations in the absence of balancing many-body contributions. Even with this limitation, the GPT pair potentials have been used effectively in total-energy calculations for Al-TM systems with TM atoms at separations greater than 4 Aa. An additional potential term may be added for systems with shorter TM atom separations, formally folding repulsive contributions of the three- and higher-body interactions into the pair potentials, resulting in structure-dependent TM-TM potentials. Towards this end, we have performed numerical ab initio total-energy calculations using the Vienna ab initio simulation package for an Al-Co-Ni compound in a particular quasicrystalline approximant structure. The results allow us to fit a short-ranged, many-body correction of the form a(r 0 /r) b to the GPT pair potentials for Co-Co, Co-Ni, and Ni-Ni interactions

  19. Heterocycles by Transition Metals Catalyzed Intramolecular Cyclization of Acetylene Compounds

    International Nuclear Information System (INIS)

    Vizer, S.A.; Yerzhanov, K.B.; Dedeshko, E.C.

    2003-01-01

    Review shows the new strategies in the synthesis of heterocycles, having nitrogen, oxygen and sulfur atoms, via transition metals catalyzed intramolecular cyclization of acetylenic compounds on the data published at the last 30 years, Unsaturated heterocyclic compounds (pyrroles and pyrroline, furans, dihydro furans and benzofurans, indoles and iso-indoles, isoquinolines and isoquinolinones, aurones, iso coumarins and oxazolinone, lactams and lactones with various substitutes in heterocycles) are formed by transition metals, those salts [PdCl 2 , Pd(OAc) 2 , HgCl 2 , Hg(OAc) 2 , Hg(OCOCF 3 ) 2 , AuCl 3 ·2H 2 O, NaAuCl 4 ·2H 2 O, CuI, CuCl], oxides (HgO) and complexes [Pd(OAc) 2 (PPh 3 )2, Pd(PPh 3 ) 4 , PdCl 2 (MeCN) 2 , Pd(OAc ) 2 /TPPTS] catalyzed intramolecular cyclization of acetylenic amines, amides, ethers, alcohols, acids, ketones and βdiketones. More complex hetero polycyclic systems typical for natural alkaloids can to obtain similar. Proposed mechanisms of pyrroles, isoquinolines, iso indoles and indoles, benzofurans and iso coumarins, thiazolopyrimidinones formation are considered. (author)

  20. Mechanical and electronic properties of Janus monolayer transition metal dichalcogenides

    Science.gov (United States)

    Shi, Wenwu; Wang, Zhiguo

    2018-05-01

    The mechanical and electronic properties of Janus monolayer transition metal dichalcogenides MXY (M  =  Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W; X/Y  =  S, Se, Te) were investigated using density functional theory. Results show that breaking the out-of-plane structural symmetry can be used to tune the electronic and mechanical behavior of monolayer transition metal dichalcogenides. The band gaps of monolayer WXY and MoXY are in the ranges of 0.16–1.91 and 0.94–1.69 eV, respectively. A semiconductor to metallic phase transition occurred in Janus monolayer MXY (M  =  Ti, Zr and Hf). The monolayers MXY (M  =  V, Nb, Ta and Cr) show metallic characteristics, which show no dependence on the structural symmetry breaking. The mechanical properties of MXY depended on the composition. Monolayer MXY (M  =  Mo, Ti, Zr, Hf and W) showed brittle characteristic, whereas monolayer CrXY and VXY are with ductile characteristic. The in-plane stiffness of pristine and Janus monolayer MXY are in the range between 22 and 158 N m‑1. The tunable electronic and mechanical properties of these 2D materials would advance the development of ultra-sensitive detectors, nanogenerators, low-power electronics, and energy harvesting and electromechanical systems.

  1. Colloquium: Excitons in atomically thin transition metal dichalcogenides

    Science.gov (United States)

    Wang, Gang; Chernikov, Alexey; Glazov, Mikhail M.; Heinz, Tony F.; Marie, Xavier; Amand, Thierry; Urbaszek, Bernhard

    2018-04-01

    Atomically thin materials such as graphene and monolayer transition metal dichalcogenides (TMDs) exhibit remarkable physical properties resulting from their reduced dimensionality and crystal symmetry. The family of semiconducting transition metal dichalcogenides is an especially promising platform for fundamental studies of two-dimensional (2D) systems, with potential applications in optoelectronics and valleytronics due to their direct band gap in the monolayer limit and highly efficient light-matter coupling. A crystal lattice with broken inversion symmetry combined with strong spin-orbit interactions leads to a unique combination of the spin and valley degrees of freedom. In addition, the 2D character of the monolayers and weak dielectric screening from the environment yield a significant enhancement of the Coulomb interaction. The resulting formation of bound electron-hole pairs, or excitons, dominates the optical and spin properties of the material. Here recent progress in understanding of the excitonic properties in monolayer TMDs is reviewed and future challenges are laid out. Discussed are the consequences of the strong direct and exchange Coulomb interaction, exciton light-matter coupling, and influence of finite carrier and electron-hole pair densities on the exciton properties in TMDs. Finally, the impact on valley polarization is described and the tuning of the energies and polarization observed in applied electric and magnetic fields is summarized.

  2. Rare-earth metal transition metal borocarbide and nitridoborate superconductors

    Energy Technology Data Exchange (ETDEWEB)

    Niewa, Rainer; Shlyk, Larysa; Blaschkowski, Bjoern [Stuttgart Univ. (Germany). Inst. fuer Anorganische Chemie

    2011-07-01

    Few years after the discovery of superconductivity in high-T{sub c} cuprates, borocarbides and shortly after nitridoborates with reasonably high T{sub c}s up to about 23 K attracted considerable attention. Particularly for the rare-earth metal series with composition RNi{sub 2}[B{sub 2}C] it turned out, that several members exhibit superconductivity next to magnetic order with both T{sub c} above or below the magnetic ordering temperature. Therefore, these compounds have been regarded as ideal materials to study the interplay and coexistence of superconductivity and long range magnetic order, due to their comparably high ordering temperatures and similar magnetic and superconducting condensation energies. This review gathers information on the series RNi{sub 2}[B{sub 2}C] and isostructural compounds with different transition metals substituting Ni as well as related series like RM[BC], RM[BN], AM[BN] and R{sub 3}M{sub 2}[BN]{sub 2}N (all with R = rare-earth metal, A = alkaline-earth metal, M = transition metal) with special focus on synthesis, crystal structures and structural trends in correspondence to physical properties. (orig.)

  3. Designer Shape Anisotropy on Transition-Metal-Dichalcogenide Nanosheets.

    Science.gov (United States)

    Martella, Christian; Mennucci, Carlo; Lamperti, Alessio; Cappelluti, Emmanuele; de Mongeot, Francesco Buatier; Molle, Alessandro

    2018-03-01

    MoS 2 and generally speaking, the wide family of transition-metal dichalcogenides represents a solid nanotechnology platform on which to engineer a wealth of new and outperforming applications involving 2D materials. An even richer flexibility can be gained by extrinsically inducing an in-plane shape anisotropy of the nanosheets. Here, the synthesis of anisotropic MoS 2 nanosheets is proposed as a prototypical example in this respect starting from a highly conformal chemical vapor deposition on prepatterend substrates and aiming at the more general purpose of tailoring anisotropy of 2D nanosheets by design. This is envisioned to be a suitable configuration for strain engineering as far as strain can be spatially redistributed in morphologically different regions. With a similar approach, both the optical and electronic properties of the 2D transition-metal dichalcogenides can be tailored over macroscopic sample areas in a self-organized fashion, thus paving the way for new applications in the field of optical metasurfaces, light harvesting, and catalysis. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

    Energy Technology Data Exchange (ETDEWEB)

    Smith, Kjell-Tore

    1996-08-01

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

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

    Energy Technology Data Exchange (ETDEWEB)

    Kayhan, Mehmet

    2013-07-12

    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 M{sub 2}B, MB, M{sub 3}B{sub 2}, MB{sub 2}, and M{sub 2}B{sub 4}. 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 W{sub 2}B{sub 4} 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 W{sub 2}B{sub 4} 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: NbB{sub 2} (T{sub C} = 3.5 K), β-MoB (T{sub C} = 2.4 K), β-WB (T{sub C} = 2.0 K), α-WB (T{sub C} = 4.3 K), W{sub 2}B{sub 4} (T{sub C} = 5.4 K), Re{sub 7}B{sub 3} (T{sub C} = 2.4 K). A relationship between the superconducting properties

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

    International Nuclear Information System (INIS)

    Kayhan, Mehmet

    2013-01-01

    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 M 2 B, MB, M 3 B 2 , MB 2 , and M 2 B 4 . 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 W 2 B 4 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 W 2 B 4 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: NbB 2 (T C = 3.5 K), β-MoB (T C = 2.4 K), β-WB (T C = 2.0 K), α-WB (T C = 4.3 K), W 2 B 4 (T C = 5.4 K), Re 7 B 3 (T C = 2.4 K). A relationship between the superconducting properties and the compositional and structural features was discussed for metal diborides. Also it was

  7. New transformation mechanism for a zinc-blende to rocksalt phase transformation in MgS

    International Nuclear Information System (INIS)

    Durandurdu, Murat

    2009-01-01

    The stability of the zinc-blende structured MgS is studied using a constant pressure ab initio molecular dynamics technique. A phase transition into a rocksalt structure is observed through the simulation. The zinc-blende to rocksalt phase transformation proceeds via two rhombohedral intermediate phases within R3m (No:160) and R3-barm (No:166) symmetries and does not involve any bond breaking. This mechanism is different from the previously observed mechanism in molecular dynamics simulations. (fast track communication)

  8. Zeolites as supports for transition-metal complexes

    Energy Technology Data Exchange (ETDEWEB)

    Le Van Mao, R

    1979-01-01

    The unique structural characteristics of the zeolites, including the presence of molecular-size cages and channels and of an internal electrostatic field, make them promising as supports for converting homogeneous to heterogeneous catalysts. The acidic sites on the zeolites may also contribute to catalysis of reactions, such as hydrocracking; may stabilize metal complexes in a highly disperse state; and may improve activity or selectivity. Recent studies on the synthesis of new types of zeolite-supported complexes of transition metals (TM), such as Co, Cu, Ag, Fe, Mo, Ru, Rh, Re, and Os, suggest the feasibility of the direct introduction of some TM complexes into the zeolitic cages during zeolite synthesis, especially during the crystallization phase. This method may considerably reduce the structural limitations associated with the incorporation of TM complexes into zeolites by conventional methods.

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

    DEFF Research Database (Denmark)

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

    2013-01-01

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

  10. Investigation of electronic transport properties of some liquid transition metals

    Science.gov (United States)

    Patel, H. P.; Sonvane, Y. A.; Thakor, P. B.

    2018-04-01

    We investigated electronic transport properties of some liquid transition metals (V, Cr, Mn, Fe, Co and Pt) using Ziman formalism. Our parameter free model potential which is realized on ionic and atomic radius has been incorporated with the Hard Sphere Yukawa (HSY) reference system to study the electronic transport properties like electrical resistivity (ρ), thermal conductivity (σ) and thermo electrical power (Q). The screening effect on aforesaid properties has been studied by using different screening functions. The correlations of our results and others data with in addition experimental values are profoundly promising to the researchers working in this field. Also, we conclude that our newly constructed parameter free model potential is capable to explain the aforesaid electronic transport properties.

  11. Exciton fission in monolayer transition metal dichalcogenide semiconductors.

    Science.gov (United States)

    Steinhoff, A; Florian, M; Rösner, M; Schönhoff, G; Wehling, T O; Jahnke, F

    2017-10-27

    When electron-hole pairs are excited in a semiconductor, it is a priori not clear if they form a plasma of unbound fermionic particles or a gas of composite bosons called excitons. Usually, the exciton phase is associated with low temperatures. In atomically thin transition metal dichalcogenide semiconductors, excitons are particularly important even at room temperature due to strong Coulomb interaction and a large exciton density of states. Using state-of-the-art many-body theory, we show that the thermodynamic fission-fusion balance of excitons and electron-hole plasma can be efficiently tuned via the dielectric environment as well as charge carrier doping. We propose the observation of these effects by studying exciton satellites in photoemission and tunneling spectroscopy, which present direct solid-state counterparts of high-energy collider experiments on the induced fission of composite particles.

  12. Signatures of exciton condensation in a transition metal dichalcogenide

    Science.gov (United States)

    Kogar, Anshul; Rak, Melinda S.; Vig, Sean; Husain, Ali A.; Flicker, Felix; Joe, Young Il; Venema, Luc; MacDougall, Greg J.; Chiang, Tai C.; Fradkin, Eduardo; van Wezel, Jasper; Abbamonte, Peter

    2017-12-01

    Bose condensation has shaped our understanding of macroscopic quantum phenomena, having been realized in superconductors, atomic gases, and liquid helium. Excitons are bosons that have been predicted to condense into either a superfluid or an insulating electronic crystal. Using the recently developed technique of momentum-resolved electron energy-loss spectroscopy (M-EELS), we studied electronic collective modes in the transition metal dichalcogenide semimetal 1T-TiSe2. Near the phase-transition temperature (190 kelvin), the energy of the electronic mode fell to zero at nonzero momentum, indicating dynamical slowing of plasma fluctuations and crystallization of the valence electrons into an exciton condensate. Our study provides compelling evidence for exciton condensation in a three-dimensional solid and establishes M-EELS as a versatile technique sensitive to valence band excitations in quantum materials.

  13. New Transition metal assisted complex borohydrides for hydrogen storage

    International Nuclear Information System (INIS)

    Sesha Srinivasan; Elias Lee Stefanakos; Yogi Goswami

    2006-01-01

    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(BH 4 ) 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 LiBH 4 /MgH 2 catalyzed with ZnCl 2 has been synthesized and characterized using various analytical techniques. (authors)

  14. Induced magnetism in transition metal intercalated graphitic systems

    KAUST Repository

    Kaloni, Thaneshwor P.

    2011-10-26

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

  15. Thermophysical Property Measurements of Silicon-Transition Metal Alloys

    Science.gov (United States)

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

    2014-01-01

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

  16. Induced magnetism in transition metal intercalated graphitic systems

    KAUST Repository

    Kaloni, Thaneshwor P.; Schwingenschlö gl, Udo; Upadhyay Kahaly, M.

    2011-01-01

    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.

  17. Preparation of transition metal sulfide nanoparticles via hydrothermal route

    International Nuclear Information System (INIS)

    Fei-Ling, P.; Chin-Hua, C.; Sarani Zakaria; Tze-Khong, L.; Mohd Ambar Yarmo; Nay-Ming, H.

    2010-01-01

    Nano sized copper sulfide, iron sulfide and molybdenum sulfide were successfully synthesised via a simple hydrothermal method. Sodium thiosulfate pentahydrate (Na 2 S 2 O 3 ·5H 2 O) and hydroxylamine sulfate ((H 3 NO) 2 ·H 2 SO 4 ) were used as the starting materials and reacted with the transition metal source at 200 degree Celsius for 90 min. The products were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM), energy dispersive X-ray analysis (EDX) and Fourier transform infrared spectroscopy (FTIR). Spherical shape CuS and FeS 2 nanoparticles with high crystallinity were successfully produced. The transmission electron micrographs revealed the well-dispersibility of the produced nanoparticles. Scanning electron micrograph showed the MoS 2 nanoparticles possessed a spherical shape with sheet-like structure covering on the outer surface of the particles. (author)

  18. Laser surface alloying of aluminium-transition metal alloys

    International Nuclear Information System (INIS)

    Almeida, A.; Vilar, R.

    1998-01-01

    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 high-strength 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-Mo and Al-Nb surface alloys by alloying Cr, Mo or Nb powder into an Al and 7175 Al alloy substrate using a CO 2 laser . This paper presents a review of the work that has been developed at Instituto Superior Tecnico on laser alloying of Al-TM alloy, over the last years. (Author) 16 refs

  19. Nonequilibrium carrier dynamics in transition metal dichalcogenide semiconductors

    Science.gov (United States)

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

    2016-09-01

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

  20. Gravimetric determination of beryllium in the presence of transition metals

    International Nuclear Information System (INIS)

    Morozova, S.S.; Nikitina, L.V.; Dyatlova, N.M.; Serebryakova, G.V.; Vol'nyagina, A.N.

    1976-01-01

    A new organic reagent, nitrolotrimethylphosphonic acid (H 6 L), is proposed for gravimetric determination of beryllium. This complexone forms with Be hardly soluble complexes in a wide pH range. The separated complex has a composition Be 5 (HL) 2 x10H 2 O. To elucidate the possibility of determining Be in the presence of transition metals, often accompanying beryllium in alloys, interaction of cations of these metals with H 6 L at different pH has been studied potentiometrically. It has been established that at pH=1.1 in the presence of masking reagent (diethylentriaminopentacetic acid) Be can be determined when zinc, copper, chromium, cobalt, nickel, iron, manganese and cadmium are present. Gravimetric method of determining Be with the help of H 6 L has been developed. The weight form is obtained by drying the precipitate which reduces considerably the time of analysis and the error of determination

  1. A review of cobalt adsorption on transition metal oxides

    International Nuclear Information System (INIS)

    Walker, S.M.

    1987-04-01

    This report reviews studies of cobalt adsorption on transition metal oxides, in the context of corrosion product and radioactivity transport in PWR primary circuits. In general, uptake of cobalt increases with pH, with temperature and with decreasing ionic strength. Very little data are available under PWR primary circuit conditions, but the limited data available suggest that cobalt uptake by the zirconium oxide corrosion product layer on fuel pins may be significant compared to that deposited on fuel crud. If fuel crud levels can be reduced in future by coolant chemistry control then uptake by the zirconia will assume a greater relative role. It is planned to use an autoclave to study uptake of cobalt on oxidised Zircaloy surfaces at temperatures up to 593K under PWR primary circuit chemistry conditions. (author)

  2. Determination of Surface Properties of Liquid Transition Metals

    International Nuclear Information System (INIS)

    Korkmaz, S. D.

    2008-01-01

    Certain surface properties of liquid simple metals are reported. Using the expression derived by Gosh and coworkers we investigated the surface entropy of liquid transition metals namely Fe, Co and Ni. We have also computed surface tensions of the metals concerned. The pair distribution functions are calculated from the solution of Ornstein-Zernike integral equation with Rogers-Young closure using the individual version of the electron-ion potential proposed by Fioalhais and coworkers which was originally developed for solid state. The predicted values of surface tension and surface entropy are in very good agreement with available experimental data. The present study results show that the expression derived by Gosh and coworkers is very useful for the surface entropy by using Fioalhais pseudopotential and Rogers-Young closure

  3. Quantum-based Atomistic Simulation of Transition Metals

    International Nuclear Information System (INIS)

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

    2005-01-01

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

  4. Study of transition metal oxides by photoelectron spectroscopy

    International Nuclear Information System (INIS)

    Rao, C.N.R.; Sarma, D.D.; Vasudevan, S.; Hegde, M.S.

    1979-01-01

    Systematics in the X-ray photoelectron spectra (X.p.e.s.) of Ti, V, Cr, Mn and Nb oxides with the metal ion in different oxidation states as well as of related series of mono-, sesqui- and di-oxides of the first row of transition metals have been investigated in detail. Core level binding energies, spin-orbit splittings and exchange splittings are found to exhibit interesting variations with the oxidation state of the metal or the nuclear charge. The 3d binding energies of the monoxides show a proportionality to Goodenough's (R - RC). Other aspects of interest in the study are the satellite structure and final state effects in the X.p.e.s. of the oxides, and identification of different valence states in oxides of the general formulae Mn02n-1 and M304. The nature of changes in the 3d bands of oxides undergoing metal-insulator transitions is also indicated. (author)

  5. Phase stability and electronic structure of transition-metal aluminides

    International Nuclear Information System (INIS)

    Carlsson, A.E.

    1992-01-01

    This paper will describe the interplay between die electronic structure and structural energetics in simple, complex, and quasicrystalline Al-transition metal (T) intermetallics. The first example is the Ll 2 -DO 22 competition in Al 3 T compounds. Ab-initio electronic total-energy calculations reveal surprisingly large structural-energy differences, and show that the phase stability of both stoichiometric and ternary-substituted compounds correlates closely with a quasigap in the electronic density of states (DOS). Secondly, ab-initio calculations for the structural stability of the icosahedrally based Al 12 W structure reveal similar quasigap effects, and provide a simple physical explanation for the stability of the complex aluminide structures. Finally, parametrized tight-binding model calculations for the Al-Mn quasicrystal reveal a large spread in the local Mn DOS behavior, and support a two-site model for the quasicrystal's magnetic behavior

  6. New technique for producing the alloys based on transition metals

    International Nuclear Information System (INIS)

    Dolukhanyan, S.K.; Aleksanyan, A.G.; Shekhtman, V.Sh.; Mantashyan, A.A.; Mayilyan, D.G.; Ter-Galstyan, O.P.

    2007-01-01

    In principle new technique was elaborated for obtaining the alloys of refractory metals by their hydrides compacting and following dehydrogenation. The elaborated technique is described. The conditions of alloys formation from different hydrides of appropriate metals was investigated in detail. The influence of the process parameters such as: chemical peculiarities, composition of source hydrides, phase transformation during dehydrogenation, etc. on the alloys formation were established. The binary and tertiary alloys of α and ω phases: Ti 0 .8Zr 0 .8; Ti 0 .66Zr 0 .33; Ti 0 .3Zr 0 .8; Ti 0 .2Zr 0 .8; Ti 0 .8Hf 0 .2; Ti 0 .6Hf 0 .4Ti 0 .66Zr 0 .23Hf 0 .11; etc were recieved. Using elaborated special hydride cycle, an earlier unknown effective process for formation of alloys of transition metals was realized. The dependence of final alloy structure on the composition of initial mixture and hydrogen content in source hydrides was established

  7. Electron-doping by hydrogen in transition-metal dichalcogenides

    Science.gov (United States)

    Oh, Sehoon; Im, Seongil; Choi, Hyoung Joon

    Using first-principles calculations, we investigate the atomic and electronic structures of 2H-phase transition-metal dichalcogenides (TMDC), 2H-MX2, with and without defects, where M is Mo or W and X is S, Se or Te. We find that doping of atomic hydrogen on 2H-MX2 induces electron doping in the conduction band. To understand the mechanism of this electron doping, we analyze the electronic structures with and without impurities. We also calculate the diffusion energy barrier to discuss the spatial stability of the doping. Based on these results, we suggest a possible way to fabricate elaborately-patterned circuits by modulating the carrier type of 2H-MoTe2. We also discuss possible applications of this doping in designing nano-devices. This work was supported by NRF of Korea (Grant No. 2011-0018306) and KISTI supercomputing center (Project No. KSC-2016-C3-0052).

  8. Efficient photocarrier injection in a transition metal oxide heterostructure

    CERN Document Server

    Muraoka, Y; Ueda, Y; Hiroi, Z

    2002-01-01

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

  9. Ferromagnetism and spin glass ordering in transition metal alloys (invited)

    Science.gov (United States)

    Crane, S.; Carnegie, D. W., Jr.; Claus, H.

    1982-03-01

    Magnetic properties of transition metal alloys near the percolation threshold are often complicated by metallurgical effects. Alloys like AuFe, VFe, CuNi, RhNi, and PdNi are in general not random solid solutions but have various degrees of atomic clustering or short-range order (SRO), depending on the heat treatment. First, it is shown how the magnetic ordering temperature of these alloys varies with the degree of clustering or SRO. Second, by systematically changing this degree of clustering or SRO, important information can be obtained about the magnetic phase diagram. In all these alloys below the percolation limit, the onset of ferromagnetic order is probably preceded by a spin glass-type ordering. However, details of the magnetic phase diagram near the critical point can be quite different alloy systems.

  10. Thermal plasma synthesis of transition metal nitrides and alloys

    International Nuclear Information System (INIS)

    Ronsheim, P.; Christensen, A.N.; Mazza, A.

    1981-01-01

    Applications of arc plasma processing to high-temperature chemistry of Group V nitrides and Si and Ge alloys are studied. The transition metal nitrides 4f-VN, 4f-NbN, and 4f-TaN are directly synthesized in a dc argon-nitrogen plasma from powders of the metals. A large excess of N 2 is required to form stoichiometric 4f-VN, while the Nb and Ta can only be synthesized with a substoichiometric N content. In a dc argon plasma the alloys V 3 Si, VSi 2 , NbSi 2 , NbGe 2 , Cr 3 Si, and Mo 3 Si are obtained from powder mixtures of the corresponding elements. The compounds are identified by x-ray diffraction patterns and particle shape and size are studied by electron microscopy

  11. Hot carrier dynamics in plasmonic transition metal nitrides

    Science.gov (United States)

    Habib, Adela; Florio, Fred; Sundararaman, Ravishankar

    2018-06-01

    Extraction of non-equilibrium hot carriers generated by plasmon decay in metallic nano-structures is an increasingly exciting prospect for utilizing plasmonic losses, but the search for optimum plasmonic materials with long-lived carriers is ongoing. Transition metal nitrides are an exciting class of new plasmonic materials with superior thermal and mechanical properties compared to conventional noble metals, but their suitability for plasmonic hot carrier applications remains unknown. Here, we present fully first principles calculations of the plasmonic response, hot carrier generation and subsequent thermalization of all group IV, V and VI transition metal nitrides, fully accounting for direct and phonon-assisted transitions as well as electron–electron and electron–phonon scattering. We find the largest frequency ranges for plasmonic response in ZrN, HfN and WN, between those of gold and silver, while we predict strongest absorption in the visible spectrum for the VN, NbN and TaN. Hot carrier generation is dominated by direct transitions for most of the relevant energy range in all these nitrides, while phonon-assisted processes dominate only below 1 eV plasmon energies primarily for the group IV nitrides. Finally, we predict the maximum hot carrier lifetimes to be around 10 fs for group IV and VI nitrides, a factor of 3–4 smaller than noble metals, due to strong electron–phonon scattering. However, we find longer carrier lifetimes for group V nitrides, comparable to silver for NbN and TaN, while exceeding 100 fs (twice that of silver) for VN, making them promising candidates for efficient hot carrier extraction.

  12. Comparative study of the synthesis of layered transition metal molybdates

    International Nuclear Information System (INIS)

    Mitchell, S.; Gomez-Aviles, A.; Gardner, C.; Jones, W.

    2010-01-01

    Mixed metal oxides (MMOs) prepared by the mild thermal decomposition of layered double hydroxides (LDHs) differ in their reactivity on exposure to aqueous molybdate containing solutions. In this study, we investigate the reactivity of some T-Al containing MMOs (T=Co, Ni, Cu or Zn) towards the formation of layered transition metal molybdates (LTMs) possessing the general formula AT 2 (OH)(MoO 4 ) 2 .H 2 O, where A=NH 4 + , Na + or K + . The phase selectivity of the reaction was studied with respect to the source of molybdate, the ratio of T to Mo and the reaction pH. LTMs were obtained on reaction of Cu-Al and Zn-Al containing MMOs with aqueous solutions of ammonium heptamolybdate. Rehydration of these oxides in the presence of sodium or potassium molybdate yielded a rehydrated LDH phase as the only crystalline product. The LTM products obtained by the rehydration of MMO precursors were compared with LTMs prepared by direct precipitation from the metal salts in order to study the influence of preparative route on their chemical and physical properties. Differences were noted in the composition, morphology and thermal properties of the resulting products. - Graphical abstract: Mixed metal oxides (MMOs) derived from layered double hydroxide precursors differ in their reactivity on exposure to aqueous molybdate containing solutions. We investigate the influence of the molybdate source, the rehydration pH and the ratio of T/Mo on the reactivity of some T-Al containing MMOs (T=Co, Ni, Cu or Zn) towards the formation of layered transition metal molybdates of general formula AT 2 (OH)(MoO 4 ) 2 .H 2 O (where A + =NH 4 + , K + or Na + ).

  13. Structure-Reactivity Relationships in Multi-Component Transition Metal Oxide Catalysts FINAL Report

    Energy Technology Data Exchange (ETDEWEB)

    Altman, Eric I. [Yale Univ., New Haven, CT (United States)

    2015-10-06

    The focus of the project was on developing an atomic-level understanding of how transition metal oxide catalysts function. Over the course of several renewals the specific emphases shifted from understanding how local structure and oxidation state affect how molecules adsorb and react on the surfaces of binary oxide crystals to more complex systems where interactions between different transition metal oxide cations in an oxide catalyst can affect reactivity, and finally to the impact of cluster size on oxide stability and reactivity. Hallmarks of the work were the use of epitaxial growth methods to create surfaces relevant to catalysis yet tractable for fundamental surface science approaches, and the use of scanning tunneling microscopy to follow structural changes induced by reactions and to pinpoint adsorption sites. Key early findings included the identification of oxidation and reduction mechanisms on a tungsten oxide catalyst surface that determine the sites available for reaction, identification of C-O bond cleavage as the rate limiting step in alcohol dehydration reactions on the tungsten oxide surface, and demonstration that reduction does not change the favored reaction pathway but rather eases C-O bond cleavage and thus reduces the reaction barrier. Subsequently, a new reconstruction on the anatase phase of TiO2 relevant to catalysis was discovered and shown to create sites with distinct reactivity compared to other TiO2 surfaces. Building on this work on anatase, the mechanism by which TiO2 enhances the reactivity of vanadium oxide layers was characterized and it was found that the TiO2 substrate can force thin vanadia layers to adopt structures they would not ordinarily form in the bulk which in turn creates differences in reactivity between supported layers and bulk samples. From there, the work progressed to studying well-defined ternary oxides where synergistic effects between the two cations can induce

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

    DEFF Research Database (Denmark)

    Lybye, D.; Mogensen, Mogens Bjerg

    2007-01-01

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

  15. High-frequency EPR on high-spin transition-metal sites

    NARCIS (Netherlands)

    Mathies, Guinevere

    2012-01-01

    The electronic structure of transition-metal sites can be probed by electron-paramagnetic-resonance (EPR) spectroscopy. The study of high-spin transition-metal sites benefits from EPR spectroscopy at frequencies higher than the standard 9.5 GHz. However, high-frequency EPR is a developing field. In

  16. The 1s x-ray absorption pre-edge structures in transition metal oxides

    NARCIS (Netherlands)

    de Groot, Frank|info:eu-repo/dai/nl/08747610X; Vanko, Gyoergy; Glatzel, Pieter

    2009-01-01

    We develop a general procedure to analyse the pre-edges in 1s x-ray absorption near edge structure (XANES) of transition metal oxides and coordination complexes. Transition metal coordination complexes can be described from a local model with one metal ion. The 1s 3d quadrupole transitions are

  17. Predicted stability, structures, and magnetism of 3d transition metal nitrides: the M4N phases

    NARCIS (Netherlands)

    Fang, C.M.; Koster, R.S.; Li, W.F.; van Huis, M.A.

    2014-01-01

    The 3d transition metal nitrides M4N (Sc4N, Ti4N, V4N, Cr4N, Mn4N, Fe4N, Co4N, Ni4N, and Cu4N) have unique phase relationships, crystal structures, and electronic and magnetic properties. Here we present a systematic density functional theory (DFT) study on these transition metal nitrides, assessing

  18. Thermal conductivity of S.E. New Mexico rocksalt and anhydrite

    International Nuclear Information System (INIS)

    Acton, R.U.

    1977-01-01

    The thermal conductivity of several rocksalt materials has been determined. Some of the materials were core samples from well AEC 8, Carlsbad, New Mexico. These samples ranged from nearly pure halite (NaCl) to nearly pure anhydrite (CaSO 4 ). Core sample crystallite size ranged from about 3 centimeters to essentially packed salt sand (approx. = 0.5mm). The samples exhibited thermal conductivities from approx. = 1.5 to 7.5 W/mK which depended upon purity and grain size. A one meter cube of rocksalt from the Mississippi Chemical Company's S.E. New Mexico potash mine was obtained for other experiments. The thermal conductivity of one sample from each of the orthogonal directions of the cube was measured. This material had a high conductivity of approx. = 8.5 W/mK and was very isotrophic. A core of rocksalt from the Morton Salt Company, Paynesville, Ohio had a thermal conductivity of 6 W/mK, which is in the upper band of the results on cores from well AEC 8. Finally, a concrete made with salt sand and rocksalt aggregate was determined to have a conductivity of approx. = 2 W/mK. A longitudinal heat flow apparatus was used to determine the thermal conductivity. An analysis of the experiment gave an accuracy within +- 15% on geological samples and within +- 10% on 304 stainless steel. 8 references, 5 figures, 2 tables

  19. Converged G W quasiparticle energies for transition metal oxide perovskites

    Science.gov (United States)

    Ergönenc, Zeynep; Kim, Bongjae; Liu, Peitao; Kresse, Georg; Franchini, Cesare

    2018-02-01

    The ab initio calculation of quasiparticle (QP) energies is a technically and computationally challenging problem. In condensed matter physics, the most widely used approach to determine QP energies is the G W approximation. Although the G W method has been widely applied to many typical semiconductors and insulators, its application to more complex compounds such as transition metal oxide perovskites has been comparatively rare, and its proper use is not well established from a technical point of view. In this work, we have applied the single-shot G0W0 method to a representative set of transition metal oxide perovskites including 3 d (SrTiO3, LaScO3, SrMnO3, LaTiO3, LaVO3, LaCrO3, LaMnO3, and LaFeO3), 4 d (SrZrO3, SrTcO3, and Ca2RuO4 ), and 5 d (SrHfO3, KTaO3, and NaOsO3) compounds with different electronic configurations, magnetic orderings, structural characteristics, and band gaps ranging from 0.1 to 6.1 eV. We discuss the proper procedure to obtain well-converged QP energies and accurate band gaps within single-shot G0W0 by comparing the conventional approach based on an incremental variation of a specific set of parameters (number of bands, energy cutoff for the plane-wave expansion and number of k points) and the basis-set extrapolation scheme [J. Klimeš et al., Phys. Rev. B 90, 075125 (2014), 10.1103/PhysRevB.90.075125]. Although the conventional scheme is not supported by a formal proof of convergence, for most cases it delivers QP energies in reasonably good agreement with those obtained by the basis-set correction procedure and it is by construction more useful for calculating band structures. In addition, we have inspected the difference between the adoption of norm-conserving and ultrasoft potentials in G W calculations and found that the norm violation for the d shell can lead to less accurate results in particular for charge-transfer systems and late transition metals. A minimal statistical analysis indicates that the correlation of the G W data

  20. Transition-metal dichalcogenides heterostructure saturable absorbers for ultrafast photonics.

    Science.gov (United States)

    Chen, Hao; Yin, Jinde; Yang, Jingwei; Zhang, Xuejun; Liu, Mengli; Jiang, Zike; Wang, Jinzhang; Sun, Zhipei; Guo, Tuan; Liu, Wenjun; Yan, Peiguang

    2017-11-01

    In this Letter, high-quality WS 2 film and MoS 2 film were vertically stacked on the tip of a single-mode fiber in turns to form heterostructure (WS 2 -MoS 2 -WS 2 )-based saturable absorbers with all-fiber integrated features. Their nonlinear saturable absorption properties were remarkable, such as a large modulation depth (∼16.99%) and a small saturable intensity (6.23  MW·cm -2 ). Stable pulses at 1.55 μm with duration as short as 296 fs and average power as high as 25 mW were obtained in an erbium-doped fiber laser system. The results demonstrate that the proposed heterostructures own remarkable nonlinear optical properties and offer a platform for adjusting nonlinear optical properties by stacking different transition-metal dichalcogenides or modifying the thickness of each layer, paving the way for engineering functional ultrafast photonics devices with desirable properties.

  1. Atomic structure of non-stoichiometric transition metal carbides

    International Nuclear Information System (INIS)

    Moisy-Maurice, Virginie.

    1981-10-01

    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 770 0 C- 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 Ti 2 Csub(1+x) and Nb 6 C 5 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 [fr

  2. The prospects of transition metal dichalcogenides for ultimately scaled CMOS

    Science.gov (United States)

    Thiele, S.; Kinberger, W.; Granzner, R.; Fiori, G.; Schwierz, F.

    2018-05-01

    MOSFET gate length scaling has been a main source of progress in digital electronics for decades. Today, researchers still spend considerable efforts on reducing the gate length and on developing ultimately scaled MOSFETs, thereby exploring both new device architectures and alternative channel materials beyond Silicon such as two-dimensional TMDs (transition metal dichalcogenide). On the other hand, the envisaged scaling scenario for the next 15 years has undergone a significant change recently. While the 2013 ITRS edition required a continuation of aggressive gate length scaling for at least another 15 years, the 2015 edition of the ITRS suggests a deceleration and eventually a levelling off of gate length scaling and puts more emphasis on alternative options such as pitch scaling to keep Moore's Law alive. In the present paper, future CMOS scaling is discussed in the light of emerging two-dimensional MOSFET channel, in particular two-dimensional TMDs. To this end, the scaling scenarios of the 2013 and 2015 ITRS editions are considered and the scaling potential of TMD MOSFETs is investigated by means of quantum-mechanical device simulations. It is shown that for ultimately scaled MOSFETs as required in the 2013 ITRS, the heavy carrier effective masses of the Mo- and W-based TMDs are beneficial for the suppression of direct source-drain tunneling, while to meet the significantly relaxed scaling targets of the 2016 ITRS heavy-effective-mass channels are not needed.

  3. Hierarchically Nanostructured Transition Metal Oxides for Lithium‐Ion Batteries

    Science.gov (United States)

    Zheng, Mingbo; Tang, Hao; Li, Lulu; Hu, Qin; Zhang, Li; Xue, Huaiguo

    2018-01-01

    Abstract Lithium‐ion batteries (LIBs) have been widely used in the field of portable electric devices because of their high energy density and long cycling life. To further improve the performance of LIBs, it is of great importance to develop new electrode materials. Various transition metal oxides (TMOs) have been extensively investigated as electrode materials for LIBs. According to the reaction mechanism, there are mainly two kinds of TMOs, one is based on conversion reaction and the other is based on intercalation/deintercalation reaction. Recently, hierarchically nanostructured TMOs have become a hot research area in the field of LIBs. Hierarchical architecture can provide numerous accessible electroactive sites for redox reactions, shorten the diffusion distance of Li‐ion during the reaction, and accommodate volume expansion during cycling. With rapid research progress in this field, a timely account of this advanced technology is highly necessary. Here, the research progress on the synthesis methods, morphological characteristics, and electrochemical performances of hierarchically nanostructured TMOs for LIBs is summarized and discussed. Some relevant prospects are also proposed. PMID:29593962

  4. Nano tubular Transition Metal Oxide for Hydrogen Production

    International Nuclear Information System (INIS)

    Sreekantan, S.; San, E.P.; Kregvirat, W.; Wei, L.C.

    2011-01-01

    TiO 2 , 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 TiO 2 nano tubes. Amorphous TiO 2 nano tube substrate leads to enhance incorporation of W instead of anatase. Therefore for the entire study, W was sputtered on amorphous TiO 2 nano tube substrate. TiO 2 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 WO 3 on the surface of the nano tubes. TiO 2 nano tube sputtered for 1 minute at 150 W and annealed at 450 degree Celsius exhibited best photocurrent density (1.4 mA/ cm 2 ) with photo conversion efficiency of 2.5 %. The reason for such behavior is attributed to W 6+ 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)

  5. Magnesium nanoparticles with transition metal decoration for hydrogen storage

    International Nuclear Information System (INIS)

    Pasquini, Luca; Callini, Elsa; Brighi, Matteo; Boscherini, Federico; Montone, Amelia; Jensen, Torben R.; Maurizio, Chiara; Vittori Antisari, Marco; Bonetti, Ennio

    2011-01-01

    We report on the hydrogen storage behaviour of Mg nanoparticles (NPs) (size range 100 nm–1 μm) with metal-oxide core–shell morphology synthesized by inert gas condensation and decorated by transition metal (TM) (Pd or Ti) clusters via in situ vacuum deposition. The structure and morphology of the as-prepared and hydrogenated NPs is studied by electron microscopy, X-ray diffraction including in situ experiments and X-ray absorption spectroscopy, in order to investigate the relationships with the hydrogen storage kinetics measured by the volumetric Sieverts method. With both Pd and Ti, the decoration deeply improves the hydrogen sorption properties: previously inert NPs exhibit complete hydrogenation with fast transformation kinetics, good stability and reversible gravimetric capacity that can attain 6 wt%. In the case of Pd-decoration, the occurrence of Mg–Pd alloying is observed at high temperatures and in dependence of the hydrogen pressure conditions. These structural transformations modify both the kinetics and thermodynamics of hydride formation, while Ti-decoration has an effect only on the kinetics. The experimental results are discussed in relation with key issues such as the amount of decoration, the heat of mixing between TM and Mg and the binding energy between TM and hydrogen.

  6. Three equations of state and their application to transition metals

    Energy Technology Data Exchange (ETDEWEB)

    Tian Ronggang; Sun Jiuxun; Yang Wei; Yu Fei, E-mail: sjx@uestc.edu.c [Department of Applied Physics, University of Electronic Science and Technology of China, Chengdu 610054 (China)

    2010-10-15

    A modified generalized Morse (mGMSE) equation of state (EOS) is proposed that can incorporate the cohesive energy data correctly. It is compared with a four-parameter modified Rose (MR) EOS, which is proposed by following Rose's approach, and the Murnaghan (MNH) EOS. The MR, mGMSE and MNH EOSs are applied to five transition metals and then compared to the available experimental compression data. The results obtained show that for all pressure ranges, the mGMSE EOS fits experimental data most accurately. From a comparison of the variation in pressure and energy versus the compression ratio between MR and mGMSE EOSs, it is clear that the pressure and energy of the MR EOS oscillate both in the neighborhood of (V/V{sub 0}) {approx} 0.005 and in the range (V/V{sub 0})> 1. Generally speaking, the mGMSE EOS has many evident advantages over the other two EOSs, while the practical applications of the MR EOS are seriously limited because of physically incorrect oscillations.

  7. Three equations of state and their application to transition metals

    International Nuclear Information System (INIS)

    Tian Ronggang; Sun Jiuxun; Yang Wei; Yu Fei

    2010-01-01

    A modified generalized Morse (mGMSE) equation of state (EOS) is proposed that can incorporate the cohesive energy data correctly. It is compared with a four-parameter modified Rose (MR) EOS, which is proposed by following Rose's approach, and the Murnaghan (MNH) EOS. The MR, mGMSE and MNH EOSs are applied to five transition metals and then compared to the available experimental compression data. The results obtained show that for all pressure ranges, the mGMSE EOS fits experimental data most accurately. From a comparison of the variation in pressure and energy versus the compression ratio between MR and mGMSE EOSs, it is clear that the pressure and energy of the MR EOS oscillate both in the neighborhood of (V/V 0 ) ∼ 0.005 and in the range (V/V 0 )> 1. Generally speaking, the mGMSE EOS has many evident advantages over the other two EOSs, while the practical applications of the MR EOS are seriously limited because of physically incorrect oscillations.

  8. Three equations of state and their application to transition metals

    Science.gov (United States)

    Ronggang, Tian; Jiuxun, Sun; Wei, Yang; Fei, Yu

    2010-10-01

    A modified generalized Morse (mGMSE) equation of state (EOS) is proposed that can incorporate the cohesive energy data correctly. It is compared with a four-parameter modified Rose (MR) EOS, which is proposed by following Rose's approach, and the Murnaghan (MNH) EOS. The MR, mGMSE and MNH EOSs are applied to five transition metals and then compared to the available experimental compression data. The results obtained show that for all pressure ranges, the mGMSE EOS fits experimental data most accurately. From a comparison of the variation in pressure and energy versus the compression ratio between MR and mGMSE EOSs, it is clear that the pressure and energy of the MR EOS oscillate both in the neighborhood of (V/V0 ) ≈ 0.005 and in the range (V/V0 )> 1. Generally speaking, the mGMSE EOS has many evident advantages over the other two EOSs, while the practical applications of the MR EOS are seriously limited because of physically incorrect oscillations.

  9. Moessbauer spectroscopy and transition metal chemistry. Fundamentals and applications

    International Nuclear Information System (INIS)

    Guetlich, Philipp; Trautwein, Alfred X.

    2011-01-01

    Moessbauer spectroscopy is a profound analytical method which has nevertheless continued to develop. The authors now present a state-of-the art book which consists of two parts. The first part details the fundamentals of Moessbauer spectroscopy and is based on a book published in 1978 in the Springer series 'Inorganic Chemistry Concepts' by P. Guetlich, R. Link and A.X. Trautwein. The second part covers useful practical aspects of measurements, and the application of the techniques to many problems of materials characterization. The update includes the use of synchroton radiation and many instructive and illustrative examples in fields such as solid state chemistry, biology and physics, materials and the geosciences, as well as industrial applications. Special chapters on magnetic relaxation phenomena (S. Morup) and computation of hyperfine interaction parameters (F. Neese) are also included. An attached CD-ROM with more than 400 full-color PowerPoint images provides self-explanatory examples. The book concentrates on teaching the technique using theory as much as needed and as little as possible. The reader will learn the fundamentals of the technique and how to apply it to many problems of materials characterization. Transition metal chemistry, studied on the basis of the most widely used Moessbauer isotopes, is in the foreground. (orig.)

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

    KAUST Repository

    Moody, Galan

    2016-03-14

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

  11. Electric Field-Dependent Photoluminescence in Multilayer Transition Metal Dichalcogenides

    Science.gov (United States)

    Stanev, T. K.; Henning, A.; Sangwan, V. K.; Speiser, N.; Stern, N. P.; Lauhon, L. J.; Hersam, M. C.; Wang, K.; Valencia, D.; Charles, J.; Kubis, T. C.

    Owing to interlayer coupling, transition metal dichalcogenides (TMDCs) such as MoS2 exhibit strong layer dependence of optical and electronic phenomena such as the band gap and trion and neutral exciton population dynamics. Here, we systematically measure the effect of layer number on the optical response of multilayer MoS2 in an external electric field, observing field and layer number dependent emission energy and photoluminescence intensity. These effects are studied in few (2-6) and bulk (11 +) layered structures at low temperatures. In MoS2\\ the observed layer dependence arises from several mechanisms, including interlayer charge transfer, band structure, Stark Effect, Fermi level changes, screening, and surface effects, so it can be challenging to isolate how these mechanisms impact the observables. Because it behaves like a stack of weakly interacting monolayers rather than multilayer or bulk, ReS2 provides a comparison to traditional TMDCs to help isolate the underlying physical mechanisms dictating the response of multilayers. This work is supported by the National Science Foundation MRSEC program (DMR-1121262), and the 2-DARE Grant (EFRI-1433510). N.P.S. is an Alfred P. Sloan Research Fellow.

  12. Insertion compounds of transition-metal and uranium oxides

    International Nuclear Information System (INIS)

    Chippindale, A.M.; Dickens, P.G.; Powell, A.V.

    1991-01-01

    Several transition-metal and actinide oxides, in which the metal occurs in a high oxidation state, have open covalent structures and are capable of incorporating alkali and other electropositive metals under mild conditions to form insertion compounds A x MO n . These are solids which have several features in common: Over a range of compositions, A x MO n exists as one or more stable or metastable phases in which the structure of the parent oxide MO n is largely retained and the insertion element A is accommodated interstitially. Insertion is accompanied by a redox process A=A i . + e - M in which M is reduced and the electronic properties of the parent oxide change to those typical of a mixed-valence compound. The insertion process xA + MO n = A x MO n can be reversed, at least to some extent, by chemical or electrochemical reaction, with retention of structure (topotactic reaction). This review concentrates on methods of synthesis, characterisation, crystal structure and thermochemistry of these insertion compounds. It updates and extends previous work. (author)

  13. Continuum radiation emitted from transition metals under ion bombardment

    International Nuclear Information System (INIS)

    El Boujlaidi, A.; Kaddouri, A.; Ait El Fqih, M.; Hammoum, K.; Aouchiche, H.

    2012-01-01

    Optical emission of transition metals has been studied during 5 keV Kr + ions bombardment within and without oxygen atmosphere in the colliding chamber. The observed spectra consist of a series of discrete lines superimposed on a broad continuum. Generally, the emission intensity was influenced by the presence of oxygen giving rise to transient effects as well as to an increase in the line intensity. The behaviours of spectral lines were successfully explained in term of electron-transfer process between the excited sputtered atom and the solid surface. In this work, we have focused our study on the continuous radiation emitted during ion bombardment. The experimental results suggest that the continuum emission depends on the nature of metal and very probably related to its electronic structure. The collective deactivation of 3d-shell electrons appears to play a role in the emission of this radiation. The observed enhancement in the presence of oxygen is probably due to a significant contribution of the oxide molecules. (authors)

  14. Band Alignment of 2D Transition Metal Dichalcogenide Heterojunctions

    KAUST Repository

    Chiu, Ming-Hui

    2016-09-20

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

  15. CVD-graphene growth on different polycrystalline transition metals

    Directory of Open Access Journals (Sweden)

    M. P. Lavin-Lopez

    2017-01-01

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

  16. Comparative study of the synthesis of layered transition metal molybdates

    Science.gov (United States)

    Mitchell, S.; Gómez-Avilés, A.; Gardner, C.; Jones, W.

    2010-01-01

    Mixed metal oxides (MMOs) prepared by the mild thermal decomposition of layered double hydroxides (LDHs) differ in their reactivity on exposure to aqueous molybdate containing solutions. In this study, we investigate the reactivity of some T-Al containing MMOs ( T=Co, Ni, Cu or Zn) towards the formation of layered transition metal molybdates (LTMs) possessing the general formula AT2(OH)(MoO 4) 2·H 2O, where A=NH 4+, Na + or K +. The phase selectivity of the reaction was studied with respect to the source of molybdate, the ratio of T to Mo and the reaction pH. LTMs were obtained on reaction of Cu-Al and Zn-Al containing MMOs with aqueous solutions of ammonium heptamolybdate. Rehydration of these oxides in the presence of sodium or potassium molybdate yielded a rehydrated LDH phase as the only crystalline product. The LTM products obtained by the rehydration of MMO precursors were compared with LTMs prepared by direct precipitation from the metal salts in order to study the influence of preparative route on their chemical and physical properties. Differences were noted in the composition, morphology and thermal properties of the resulting products.

  17. Photoemission from valence bands of transition metal-phthalocyanines

    International Nuclear Information System (INIS)

    Shang, Ming-Hui; Nagaosa, Mayumi; Nagamatsu, Shin-ichi; Hosoumi, Shunsuke; Kera, Satoshi; Fujikawa, Takashi; Ueno, Nobuo

    2011-01-01

    Research highlights: → The HOMO mainly comes from the carbon atoms of Pc rings and the central metal atoms almost have no contribution on the highest occupied molecular orbital (HOMO: a 1u ) distribution of CoPc as well as NiPc. → Influence by central metal atom on the photoemission intensities from the HOMO of two single molecule systems is negligible for the major. → The modification of the distribution for π-orbital upon adsorption as well as the scattering effects of the central metal on the photoemission intensities are negligible for the major. - Abstract: Angular dependencies of ultraviolet photoelectron spectrum of transition metal-phthalocyanines (TM-Pcs), NiPc and CoPc, have been studied by using multiple-scattering theory to explore the electronic structure of the organometallic complexes influenced by central metal atom. The calculated angular distributions of photoelectrons for the highest occupied molecular orbital (HOMO: a 1u ) from the two single systems are nearly the same and represent well the experimental results obtained for the well-ordered monolayer on the highly oriented pyrolytic graphite substrate. The central metal atoms almost have no contribution on the HOMO distribution, which mainly comes from the carbon atoms of Pc ring. Moreover, the modification of the distribution for π orbital upon adsorption as well as the scattering effects of the central metal on the photoemission intensities are negligible for the major.

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

    Science.gov (United States)

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

    2016-01-01

    Layered materials embrace rich intercalation reactions to accommodate high concentrations of foreign species within their structures, and find many applications spanning from energy storage, ion exchange to secondary batteries. Light alkali metals are generally most easily intercalated due to their light mass, high charge/volume ratio and in many cases strong reducing properties. An evolving area of materials chemistry, however, is to capture metals selectively, which is of technological and environmental significance but rather unexplored. Here we show that the layered telluride T2PTe2 (T=Ti, Zr) displays exclusive insertion of transition metals (for example, Cd, Zn) as opposed to alkali cations, with tetrahedral coordination preference to tellurium. Interestingly, the intercalation reactions proceed in solid state and at surprisingly low temperatures (for example, 80 °C for cadmium in Ti2PTe2). The current method of controlling selectivity provides opportunities in the search for new materials for various applications that used to be possible only in a liquid. PMID:27966540

  19. Stimulated X-Ray Emission Spectroscopy in Transition Metal Complexes

    Science.gov (United States)

    Kroll, Thomas; Weninger, Clemens; Alonso-Mori, Roberto; Sokaras, Dimosthenis; Zhu, Diling; Mercadier, Laurent; Majety, Vinay P.; Marinelli, Agostino; Lutman, Alberto; Guetg, Marc W.; Decker, Franz-Josef; Boutet, Sébastien; Aquila, Andy; Koglin, Jason; Koralek, Jake; DePonte, Daniel P.; Kern, Jan; Fuller, Franklin D.; Pastor, Ernest; Fransson, Thomas; Zhang, Yu; Yano, Junko; Yachandra, Vittal K.; Rohringer, Nina; Bergmann, Uwe

    2018-03-01

    We report the observation and analysis of the gain curve of amplified K α x-ray emission from solutions of Mn(II) and Mn(VII) complexes using an x-ray free electron laser to create the 1 s core-hole population inversion. We find spectra at amplification levels extending over 4 orders of magnitude until saturation. We observe bandwidths below the Mn 1 s core-hole lifetime broadening in the onset of the stimulated emission. In the exponential amplification regime the resolution corrected spectral width of ˜1.7 eV FWHM is constant over 3 orders of magnitude, pointing to the buildup of transform limited pulses of ˜1 fs duration. Driving the amplification into saturation leads to broadening and a shift of the line. Importantly, the chemical sensitivity of the stimulated x-ray emission to the Mn oxidation state is preserved at power densities of ˜1020 W /cm2 for the incoming x-ray pulses. Differences in signal sensitivity and spectral information compared to conventional (spontaneous) x-ray emission spectroscopy are discussed. Our findings build a baseline for nonlinear x-ray spectroscopy for a wide range of transition metal complexes in inorganic chemistry, catalysis, and materials science.

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

    International Nuclear Information System (INIS)

    Skomski, R.; Manchanda, P.; Kashyap, A.

    2015-01-01

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

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

    Science.gov (United States)

    Skomski, R.; Manchanda, P.; Kashyap, A.

    2015-05-01

    It is investigated how electron-electron correlations affect the intrinsic properties of rare-earth transition-metal magnets. Focusing on orbital moment and anisotropy, we perform model calculations for 3d-4f alloys and density-functional theory (DFT) calculations for NdCo5. On an independent-electron level, the use of a single Slater determinant with broken spin symmetry introduces Hund's rule correlations, which govern the behavior of rare-earth ions and of alloys described by the local spin density approximation (LSDA) and LSDA + U approximations to DFT. By contrast, rare-earth ions in intermetallics involve configuration interactions between two or more Slater determinants and lead to phenomena such as spin-charge distribution. Analyzing DFT as a Legendre transformation and using Bethe's crystal-field theory, we show that the corresponding density functionals are very different from familiar LSDA-type expressions and outline the effect of spin-charge separation on the magnetocrystalline anisotropy.

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

    KAUST Repository

    Moody, Galan; Hao, Kai; Dass, Chandriker Kavir; Singh, Akshay; Xu, Lixiang; Tran, Kha; Chen, Chang-Hsiao; Li, Ming-yang; Li, Lain-Jong; Clark, Genevieve; Bergh ä user, Gunnar; Malic, Ermin; Knorr, Andreas; Xu, Xiaodong; Li, Xiaoqin

    2016-01-01

    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.

  3. Morphology evolution and nanostructure of chemical looping transition metal oxide materials upon redox processes

    International Nuclear Information System (INIS)

    Qin, Lang; Cheng, Zhuo; Guo, Mengqing; Fan, Jonathan A.; Fan, Liang-Shih

    2017-01-01

    Transition metal are heavily used in chemical looping technologies because of their high oxygen carrying capacity and high thermal reactivity. These oxygen activities result in the oxide formation and oxygen vacancy formation that affect the nanoscale crystal phase and morphology within these materials and their subsequent bulk chemical behavior. In this study, two selected earlier transition metals manganese and cobalt as well as two selected later transition metals copper and nickel that are important to chemical looping reactions are investigated when they undergo cyclic redox reactions. We found Co microparticles exhibited increased CoO impurity presence when oxidized to Co_3O_4 upon cyclic oxidation; CuO redox cycles prefer to be limited to a reduced form of Cu_2O and an oxidized form of CuO; Mn microparticles were oxidized to a mixed phases of MnO and Mn_3O_4, which causes delamination during oxidation. For Ni microparticles, a dense surface were observed during the redox reaction. The atomistic thermodynamics methods and density functional theory (DFT) calculations are carried out to elucidate the effect of oxygen dissociation and migration on the morphological evolution of nanostructures during the redox processes. Our results indicate that the earlier transition metals (Mn and Co) tend to have stronger interaction with O_2 than the later transition metals (Ni and Cu). Also, our modified Brønsted−Evans−Polanyi (BEP) relationship for reaction energies and total reaction barriers reveals that reactions of earlier transition metals are more exergonic and have lower oxygen dissociation barriers than those of later transition metals. In addition, it was found that for these transition metal oxides the oxygen vacancy formation energies increase with the depth. The oxide in the higher oxidation state of transition metal has lower vacancy formation energy, which can facilitate forming the defective nanostructures. The fundamental understanding of these metal

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

    Energy Technology Data Exchange (ETDEWEB)

    Jones, G

    2011-08-18

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

  5. Synthesis and Characterization of the 2-Dimensional Transition Metal Dichalcogenides

    Science.gov (United States)

    Browning, Robert

    In the last 50 years, the semiconductor industry has been scaling the silicon transistor to achieve faster devices, lower power consumption, and improve device performance. Transistor gate dimensions have become so small that short channel effects and gate leakage have become a significant problem. To address these issues, performance enhancement techniques such as strained silicon are used to improve mobility, while new high-k gate dielectric materials replace silicon oxide to reduce gate leakage. At some point the fundamental limit of silicon will be reached and the semiconductor industry will need to find an alternate solution. The advent of graphene led to the discovery of other layered materials such as the transition metal dichalcogenides. These materials have a layered structure similar to graphene and therefore possess some of the same qualities, but unlike graphene, these materials possess sizeable bandgaps between 1-2 eV making them useful for digital electronic applications. Since initially discovered, most of the research on these films has been from mechanically exfoliated flakes, which are easily produced due to the weak van der Waals force binding the layers together. For these materials to be considered for use in mainstream semiconductor technology, methods need to be explored to grow these films uniformly over a large area. In this research, atomic layer deposition (ALD) was employed as the growth technique used to produce large area uniform thin films of several different transition metal dichalcogenides. By optimizing the ALD growth parameters, it is possible to grow high quality films a few to several monolayers thick over a large area with good uniformity. This has been demonstrated and verified using several physical analytical tests such as Raman spectroscopy, photoluminescence, x-ray photoelectron spectroscopy, x-ray diffraction, transmission electron spectroscopy, and scanning electron microscopy, which show that these films possess the

  6. High pressure and microwave based synthesis of transition metal pnictides

    Energy Technology Data Exchange (ETDEWEB)

    Pobel, Roman Rupert

    2016-04-11

    The goal of this thesis was to explore the possibilities of synthetic methods that are not very common in current transition metal pnictide research. The substitution of the Ca-site in CaFe{sub 2}As{sub 2} with rare earth elements such as Pr the has been reported to induce superconductivity. However, some inconsistencies in the data suggested a non-intrinsic origin of the observed diamagnetic signal. Furthermore a solubility limit of 13% was found when prepared in an electrical furnace thus leaving a huge part of the physical phase diagram inaccessible. A high pressure/high temperature synthesis was developed to allow access to the whole doping range and an in-depth characterization of this compound was carried out. During the experiments concerning the high pressure synthesis of Ca{sub 1-x}Pr{sub x}Fe{sub 2}As{sub 2} the new ternary iron arsenide CaFe{sub 5}As{sub 3} was identified and classified as a member of the Ca{sub n(n+1)/2}(Fe{sub 1-x}M{sub x}){sub (2+3n)}M'{sub n(n-1)/2}As{sub (n+1)(n+2)/2} (n = 1-3; M =Nb, Pd, Pt; M' = □, Pd, Pt) family. The complete solid solution Ca{sub 1-x}Pr{sub x}Fe{sub 5}As{sub 3} (O ≤ x ≤ 1) was prepared and physically characterized. Furthermore, several useful techniques were developed to aid in future high pressure based investigations of transition metal pnictides. The second part of this thesis concerns a completely different, but equally promising synthetic approach. Microwave based synthesis is a well-established technique in many solution based fields, such as organic, medicinal or nano chemistry. For solid state and materials research several parameters and particularities have to be considered. But when successful, it allows for the reduction of reaction time by several orders of magnitude. It has very rarely been applied in the preparation of pnictides and on1y once in the context of pnictide superconductor research. The possibilities of this method were explored and employed in the preparation of several

  7. Novel superstructure of the rocksalt type and element distribution in germanium tin antimony tellurides

    Energy Technology Data Exchange (ETDEWEB)

    Rosenthal, Tobias [Department of Chemistry, Ludwig Maximilian University, Butenandtstraße 5-13, 81377 Munich (Germany); Welzmiller, Simon [Institute for Mineralogy, Crystallography and Materials Science, Leipzig University, Scharnhorststraße 20, 04275 Leipzig (Germany); Neudert, Lukas [Department of Chemistry, Ludwig Maximilian University, Butenandtstraße 5-13, 81377 Munich (Germany); Urban, Philipp [Institute for Mineralogy, Crystallography and Materials Science, Leipzig University, Scharnhorststraße 20, 04275 Leipzig (Germany); Fitch, Andy [European Synchrotron Radiation Facility, CS40220, 38043 Grenoble Cedex 9 (France); Oeckler, Oliver, E-mail: oliver.oeckler@gmx.de [Institute for Mineralogy, Crystallography and Materials Science, Leipzig University, Scharnhorststraße 20, 04275 Leipzig (Germany)

    2014-11-15

    A superstructure of the rocksalt-type observed in quenched CVT-grown single crystals of Ge{sub 3.25(7)}Sn{sub 1.10(3)}Sb{sub 1.10(3)}Te{sub 6} was elucidated by X-ray diffraction using fourfold twinned crystals (space group P3{sup ¯}m1, a=4.280(1) Å, c=20.966(3) Å). The structure is built up of distorted rocksalt-type building blocks typical for long-range ordered GST materials and substitution variants thereof. In contrast to those phases, an exclusive ABC-type cubic stacking sequence of the Te-atom layers is present. High-resolution electron microscopy reveals spheroidal domains with this structure (average diameter 25 nm) whose stacking direction is perpendicular to the 〈1 1 1〉 directions of the basic rocksalt-type structure. Additional slab-like domains with a lateral extension up to 1 µm occasionally result in a hierarchical structure motif. Due to the similar electron counts of the elements involved, resonant diffraction was used in order to elucidate the element distribution in rocksalt-type building blocks of the stable layered compound 39R-Ge{sub 3}SnSb{sub 2}Te{sub 7} (R3{sup ¯}m, a=4.24990(4) Å, c=73.4677(9) Å). Sb tends to occupy the atom site close to the van der Waals gaps while Ge concentrates in the center of the building blocks. - Graphical abstract: High-resolution transmission electron micrograph, SAED pattern and reciprocal lattice section of X-ray single crystal data of Ge{sub 3.25}Sn{sub 1.1}Sb{sub 1.1}Te{sub 6} with an 11P-type superstructure of the rocksalt type. - Highlights: • A novel superstructure of the rocksalt-type in the system Ge–Sn–Sb–Te is elucidated. • It combines the cubic stacking of the HT phase with building blocks of the RT phase. • It indicates the ordering mechanism during the phase transition of GST materials. • A hierarchical structure motif is promising with respect to the reduction of κ{sub L}. • Resonant diffraction reveals the element distribution in 39R-Ge{sub 3}SnSb{sub 2}Te{sub 7}.

  8. Molecular Beam Epitaxy Growth of Transition Metal Dichalcogenides

    Science.gov (United States)

    Yue, Ruoyu

    The exponential growth of Si-based technology has finally reached its limit, and a new generation of devices must be developed to continue scaling. A unique class of materials, transition metal dichalcogenides (TMD), have attracted great attention due to their remarkable optical and electronic properties at the atomic thickness scale. Over the past decade, enormous efforts have been put into TMD research for application in low-power devices. Among these studies, a high-quality TMD synthesis method is essential. Molecular beam epitaxy (MBE) can enable high-quality TMD growth by combining high purity elemental sources and an ultra-high vacuum growth environment, together with the back-end-of-line compatible growth temperatures. Although many TMD candidates have been grown by MBE with promising microstructure, the limited grain size (improvement in grain size was achieved through this study. Results from both experiment and simulation showed that reducing the growth rate, enabled by high growth temperature and low metal flux, is vital to nucleation density control. Meanwhile, providing a chalcogen-rich growth environment will promote larger grain lateral growth by suppressing vertical growth. Applying the knowledge learned from the nucleation study, we sucessfully integrated the MBE-grown WSe2 into Si complementary metal-oxide-semiconductor (CMOS) compatible field-effect transistors (FETs). Excellent transport properties, such as field effect hole mobilities (40 cm 2/V·s) with orders of magnitude improvement over the reported values of MBE-grown TMDs, are shown. These studies provide a comprehensive understanding of the MBE synthesis of TMDs and devices, indicating the great potential of integrating TMDs into CMOS process flows for the future electronics.

  9. Noncollinear magnetism in surfaces and interfaces of transition metals

    Energy Technology Data Exchange (ETDEWEB)

    Tan, Huahai

    2009-09-15

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

  10. Rock-Salt Growth-Induced (003) Cracking in a Layered Positive Electrode for Li-Ion Batteries

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Hanlei [Materials; amp, Department; NorthEast; Omenya, Fredrick [NorthEast; Yan, Pengfei [Environmental; Luo, Langli [Environmental; Whittingham, M. Stanley [NorthEast; Wang, Chongmin [Environmental; Zhou, Guangwen [Materials; amp, Department; NorthEast

    2017-10-20

    For the first time, the (003) cracking is observed and determined to be the major cracking mechanism for the primary particles of Ni-rich layered dioxides as the positive electrode for Li-ion batteries. Using transmission electron microscopy techniques, here we show that the propagation and fracturing of platelet-like rock-salt phase along the (003) plane of the layered oxide are the leading cause for the cracking of primary particles. The fracturing of the rock-salt platelet is induced by the stress discontinuity between the parent layered oxide and the rock-salt phase. The high nickel content is considered to be the key factor for the formation of the rock-salt platelet and thus the (003) cracking. The (003)-type cracking can be a major factor for the structural degradation and associated capacity fade of the layered positive electrode.

  11. Optical excitations of transition-metal oxides under the orbital multiplicity effects

    International Nuclear Information System (INIS)

    Lee, J S; Kim, M W; Noh, T W

    2005-01-01

    We investigated optical excitations of transition-metal (TM) oxides with metal oxygen octahedra taking account of the orbital multiplicity effects. We predicted excitation energies of intersite d-d transitions and p-d transitions of TM oxides. We compared the evaluated excitation energies with reported experimental data, and found that they are in good agreement with each other. Moreover, we could demonstrate possible answers for a few long-standing problems of the low-frequency spectral features in some early 3d TM oxides: (i) the broad and multi-peak structures of the d-d transitions (ii) the low values (around 2 eV) of the d-d transition energies for some t 2g 1 and t 2g 2 systems, and (iii) the lack of the d-d transition below 4.0 eV region for LaCrO 3 , one of the t 2g 3 systems. These indicate that our approach considering the orbital multiplicity effects could provide good explanations of intriguing features in the optical spectra of some early TM oxides. In addition, we showed that optical spectroscopy can be useful as a powerful tool to investigate spin and/or orbital correlations in the TM ions. Finally, we discussed the implications of the orbital multiplicity in the Zannen-Sawatzky-Allen scheme, which has been used successfully to classify correlated electron systems

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

    DEFF Research Database (Denmark)

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

    2010-01-01

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

  13. Extended Moment Formation in Monolayer WS2 Doped with 3d Transition-Metals

    KAUST Repository

    Singh, Nirpendra; Schwingenschlö gl, Udo

    2016-01-01

    First-principles calculations with onsite Coulomb interaction and spin-orbit coupling are used to investigate the electronic structure of monolayer WS2 doped substitutionally with 3d transition-metals. While neither W vacancies nor strain induce

  14. Laterally Stitched Heterostructures of Transition Metal Dichalcogenide: Chemical Vapor Deposition Growth on Lithographically Patterned Area

    KAUST Repository

    Li, Henan; Li, Peng; Huang, Jing Kai; Li, Ming-yang; Yang, Chih-Wen; Shi, Yumeng; Zhang, Xixiang; Li, Lain-Jong

    2016-01-01

    Two-dimensional transition metal dichalcogenides (TMDCs) have shown great promise in electronics and optoelectronics due to their unique electrical and optical properties. Heterostructured TMDC layers such as the laterally stitched TMDCs offer

  15. Spin-orbit-induced spin splittings in polar transition metal dichalcogenide monolayers

    KAUST Repository

    Cheng, Yingchun; Zhu, Zhiyong; Tahir, Muhammad; Schwingenschlö gl, Udo

    2013-01-01

    . We present ab initio electronic structure, phonon, and molecular-dynamics calculations to study the structural stability and spin-orbit-induced spin splitting in the transition metal dichalcogenide monolayers MXY (M = Mo, W and X, Y = S, Se, Te

  16. Recent advances in transition metal-catalyzed Csp2-monofluoro-, difluoro-, perfluoromethylation and trifluoromethylthiolation

    Directory of Open Access Journals (Sweden)

    Grégory Landelle

    2013-11-01

    Full Text Available In the last few years, transition metal-mediated reactions have joined the toolbox of chemists working in the field of fluorination for Life-Science oriented research. The successful execution of transition metal-catalyzed carbon–fluorine bond formation has become a landmark achievement in fluorine chemistry. This rapidly growing research field has been the subject of some excellent reviews. Our approach focuses exclusively on transition metal-catalyzed reactions that allow the introduction of –CFH2, –CF2H, –CnF2n+1 and –SCF3 groups onto sp² carbon atoms. Transformations are discussed according to the reaction-type and the metal employed. The review will not extend to conventional non-transition metal methods to these fluorinated groups.

  17. Observing grain boundaries in CVD-grown monolayer transition metal dichalcogenides

    KAUST Repository

    Ly, Thuchue; Chiu, Ming-Hui; Li, Mingyang; Zhao, Jiong; Perello, David J.; Cichocka, Magdalena Ola; Oh, Hyemin; Chae, Sanghoon; Jeong, Hyeyun; Yao, Fei; Li, Lain-Jong; Lee, Young Hee

    2014-01-01

    Two-dimensional monolayer transition metal dichalcogenides (TMdCs), driven by graphene science, revisit optical and electronic properties, which are markedly different from bulk characteristics. These properties are easily modified due

  18. Valley polarization in magnetically doped single-layer transition-metal dichalcogenides

    KAUST Repository

    Cheng, Yingchun; Zhang, Q. Y.; Schwingenschlö gl, Udo

    2014-01-01

    We demonstrate that valley polarization can be induced and controlled in semiconducting single-layer transition-metal dichalcogenides by magnetic doping, which is important for spintronics, valleytronics, and photonics devices. As an example, we

  19. Multi-body forces and the energetics of transition metals, alloys, and semiconductors

    International Nuclear Information System (INIS)

    Carlsson, A.E.

    1992-01-01

    Progress over the past year is divided into 3 areas: potential-energy functions for transition-metal aluminides; electronic structure and energetics of complex structures and quasicrystals; and ceramic materials (PdO, PtO)

  20. Pressure dependence of the refractive index in wurtzite and rocksalt indium nitride

    Energy Technology Data Exchange (ETDEWEB)

    Oliva, R. [Institut Jaume Almera, Consell Superior d' Investigacions Científiques (CSIC), Lluís Solé i Sabarís s.n., 08028 Barcelona, Catalonia (Spain); MALTA-Consolider Team, Departament de Física Aplicada, ICMUV, Universitat de València, c/Dr. Moliner 50, 46100 Burjassot, València (Spain); Segura, A. [MALTA-Consolider Team, Departament de Física Aplicada, ICMUV, Universitat de València, c/Dr. Moliner 50, 46100 Burjassot, València (Spain); Ibáñez, J., E-mail: jibanez@ictja.csic.es; Artús, L. [Institut Jaume Almera, Consell Superior d' Investigacions Científiques (CSIC), Lluís Solé i Sabarís s.n., 08028 Barcelona, Catalonia (Spain); Yamaguchi, T.; Nanishi, Y. [Faculty of Science and Engineering, Ritsumeikan University, Shiga 525-8577 (Japan)

    2014-12-08

    We have performed high-pressure Fourier transform infrared reflectance measurements on a freestanding InN thin film to determine the refractive index of wurtzite InN and its high-pressure rocksalt phase as a function of hydrostatic pressure. From a fit to the experimental refractive-index curves including the effect of the high-energy optical gaps, phonons, free carriers, and the direct (fundamental) band-gap in the case of wurtzite InN, we obtain pressure coefficients for the low-frequency (electronic) dielectric constant ε{sub ∞}. Negative pressure coefficients of −8.8 × 10{sup −2 }GPa{sup −1} and −14.8 × 10{sup −2 }GPa{sup −1} are obtained for the wurtzite and rocksalt phases, respectively. The results are discussed in terms of the electronic band structure and the compressibility of both phases.

  1. Pressure dependence of the refractive index in wurtzite and rocksalt indium nitride

    International Nuclear Information System (INIS)

    Oliva, R.; Segura, A.; Ibáñez, J.; Artús, L.; Yamaguchi, T.; Nanishi, Y.

    2014-01-01

    We have performed high-pressure Fourier transform infrared reflectance measurements on a freestanding InN thin film to determine the refractive index of wurtzite InN and its high-pressure rocksalt phase as a function of hydrostatic pressure. From a fit to the experimental refractive-index curves including the effect of the high-energy optical gaps, phonons, free carriers, and the direct (fundamental) band-gap in the case of wurtzite InN, we obtain pressure coefficients for the low-frequency (electronic) dielectric constant ε ∞ . Negative pressure coefficients of −8.8 × 10 −2  GPa −1 and −14.8 × 10 −2  GPa −1 are obtained for the wurtzite and rocksalt phases, respectively. The results are discussed in terms of the electronic band structure and the compressibility of both phases

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

    DEFF Research Database (Denmark)

    Lausche, Adam C.; Falsig, Hanne; Jensen, Anker Degn

    2014-01-01

    This paper reports the use of a combination of density functional theory and microkinetic modelling to establish trends in the hydrodeoxygenation rates and selectivites of transition metal surfaces. Biomass and biomass-derived chemicals often contain large fractions of oxygenates. Removal...... of the oxygen through hydrotreating represents one strategy for producing commodity chemicals from these renewable materials. Using the model developed in this paper, we predict ethylene glycol hydrodeoxygenation selectivities for transition metals that are consistent with those reported in the literature...

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

    DEFF Research Database (Denmark)

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

    2011-01-01

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

  4. Laser surface alloying of aluminium-transition metal alloys

    Directory of Open Access Journals (Sweden)

    Almeida, A.

    1998-04-01

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

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

  5. Surface analysis of transition metal oxalates: Damage aspects

    Energy Technology Data Exchange (ETDEWEB)

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

    2016-05-15

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

  6. Correlated effective field theory in transition metal compounds

    International Nuclear Information System (INIS)

    Mukhopadhyay, Subhasis; Chatterjee, Ibha

    2004-01-01

    Mean field theory is good enough to study the physical properties at higher temperatures and in higher dimensions. It explains the critical phenomena in a restricted sense. Near the critical temperatures, when fluctuations become important, it may not give the correct results. Similarly in low dimensions, the correlations become important and the mean field theory seems to be inadequate to explain the physical phenomena. At low-temperatures too, the quantum correlations become important and these effects are to be treated in an appropriate way. In 1974, Prof. M.E. Lines of Bell Laboratories, developed a theory which goes beyond the mean field theory and is known as the correlated effective field (CEF) theory. It takes into account the fluctuations in a semiempirical way. Lines and his collaborators used this theory to explain the short-range correlations and their anisotropy in the paramagnetic phase. Later Suzuki et al., Chatterjee and Desai, Mukhopadhyay and Chatterjee applied this theory to the magnetically ordered phase and a tremendous success of the theory has been found in real systems. The success of the CEF theory is discussed in this review. In order to highlight the success of this theory, earlier effective field theories and their improvements over mean field theories e.g., Bethe-Peierls-Weiss method, reaction field approximation, etc., are also discussed in this review for completeness. The beauty of the CEF theory is that it is mean field-like, but captures the essential physics of real systems to a great extent. However, this is a weak correlated theory and as a result is inappropriate for the metallic phase when strong correlations become important. In recent times, transition metal oxides become important due to the discovery of the high-temperature superconductivity and the colossal magnetoresistance phenomena. These oxides seem to be Mott insulators and undergo an insulator to metal transition by applying magnetic field, pressure and by changing

  7. Electronic self-organization in layered transition metal dichalcogenides

    Energy Technology Data Exchange (ETDEWEB)

    Ritschel, Tobias

    2015-10-30

    The interplay between different self-organized electronically ordered states and their relation to unconventional electronic properties like superconductivity constitutes one of the most exciting challenges of modern condensed matter physics. In the present thesis this issue is thoroughly investigated for the prototypical layered material 1T-TaS{sub 2} both experimentally and theoretically. At first the static charge density wave order in 1T-TaS{sub 2} is investigated as a function of pressure and temperature by means of X-ray diffraction. These data indeed reveal that the superconductivity in this material coexists with an inhomogeneous charge density wave on a macroscopic scale in real space. This result is fundamentally different from a previously proposed separation of superconducting and insulating regions in real space. Furthermore, the X-ray diffraction data uncover the important role of interlayer correlations in 1T-TaS{sub 2}. Based on the detailed insights into the charge density wave structure obtained by the X-ray diffraction experiments, density functional theory models are deduced in order to describe the electronic structure of 1T-TaS{sub 2} in the second part of this thesis. As opposed to most previous studies, these calculations take the three-dimensional character of the charge density wave into account. Indeed the electronic structure calculations uncover complex orbital textures, which are interwoven with the charge density wave order and cause dramatic differences in the electronic structure depending on the alignment of the orbitals between neighboring layers. Furthermore, it is demonstrated that these orbital-mediated effects provide a route to drive semiconductor-to-metal transitions with technologically pertinent gaps and on ultrafast timescales. These results are particularly relevant for the ongoing development of novel, miniaturized and ultrafast devices based on layered transition metal dichalcogenides. The discovery of orbital textures

  8. Hydrogen collisions with transition metal surfaces: Universal electronically nonadiabatic adsorption

    Science.gov (United States)

    Dorenkamp, Yvonne; Jiang, Hongyan; Köckert, Hansjochen; Hertl, Nils; Kammler, Marvin; Janke, Svenja M.; Kandratsenka, Alexander; Wodtke, Alec M.; Bünermann, Oliver

    2018-01-01

    Inelastic scattering of H and D atoms from the (111) surfaces of six fcc transition metals (Au, Pt, Ag, Pd, Cu, and Ni) was investigated, and in each case, excitation of electron-hole pairs dominates the inelasticity. The results are very similar for all six metals. Differences in the average kinetic energy losses between metals can mainly be attributed to different efficiencies in the coupling to phonons due to the different masses of the metal atoms. The experimental observations can be reproduced by molecular dynamics simulations based on full-dimensional potential energy surfaces and including electronic excitations by using electronic friction in the local density friction approximation. The determining factors for the energy loss are the electron density at the surface, which is similar for all six metals, and the mass ratio between the impinging atoms and the surface atoms. Details of the electronic structure of the metal do not play a significant role. The experimentally validated simulations are used to explore sticking over a wide range of incidence conditions. We find that the sticking probability increases for H and D collisions near normal incidence—consistent with a previously reported penetration-resurfacing mechanism. The sticking probability for H or D on any of these metals may be represented as a simple function of the incidence energy, Ein, metal atom mass, M, and incidence angle, 𝜗i n. S =(S0+a ṡEi n+b ṡM ) *(1 -h (𝜗i n-c ) (1 -cos(𝜗 i n-c ) d ṡh (Ei n-e ) (Ei n-e ) ) ) , where h is the Heaviside step function and for H, S0 = 1.081, a = -0.125 eV-1, b =-8.40 ṡ1 0-4 u-1, c = 28.88°, d = 1.166 eV-1, and e = 0.442 eV; whereas for D, S0 = 1.120, a = -0.124 eV-1, b =-1.20 ṡ1 0-3 u-1, c = 28.62°, d = 1.196 eV-1, and e = 0.474 eV.

  9. Mechanical and Thermophysical Properties of Cubic Rock-Salt AlN Under High Pressure

    Science.gov (United States)

    Lebga, Noudjoud; Daoud, Salah; Sun, Xiao-Wei; Bioud, Nadhira; Latreche, Abdelhakim

    2018-03-01

    Density functional theory, density functional perturbation theory, and the Debye model have been used to investigate the structural, elastic, sound velocity, and thermodynamic properties of AlN with cubic rock-salt structure under high pressure, yielding the equilibrium structural parameters, equation of state, and elastic constants of this interesting material. The isotropic shear modulus, Pugh ratio, and Poisson's ratio were also investigated carefully. In addition, the longitudinal, transverse, and average elastic wave velocities, phonon contribution to the thermal conductivity, and interesting thermodynamic properties were predicted and analyzed in detail. The results demonstrate that the behavior of the elastic wave velocities under increasing hydrostatic pressure explains the hardening of the corresponding phonons. Based on the elastic stability criteria under pressure, it is found that AlN with cubic rock-salt structure is mechanically stable, even at pressures up to 100 GPa. Analysis of the Pugh ratio and Poisson's ratio revealed that AlN with cubic rock-salt structure behaves in brittle manner.

  10. Substrate Lattice-Guided Seed Formation Controls the Orientation of 2D Transition Metal Dichalcogenides

    KAUST Repository

    Aljarb, Areej

    2017-08-07

    Two-dimensional (2D) transition metal dichalcogenide (TMDCs) semiconductors are important for next-generation electronics and optoelectronics. Given the difficulty in growing large single crystals of 2D TMDC materials, understanding the factors affecting the seed formation and orientation becomes an important issue for controlling the growth. Here, we systematically study the growth of molybdenum disulfide (MoS2) monolayer on c-plane sapphire with chemical vapor deposition (CVD) to discover the factors controlling their orientation. We show that the concentration of precursors, i.e., the ratio between sulfur and molybdenum oxide (MoO3), plays a key role in the size and orientation of seeds, subsequently controlling the orientation of MoS2 monolayers. High S/MoO3 ratio is needed in the early stage of growth to form small seeds that can align easily to the substrate lattice structures while the ratio should be decreased to enlarge the size of the monolayer at the next stage of the lateral growth. Moreover, we show that the seeds are actually crystalline MoS2 layers as revealed by high-resolution transmission electron microscopy. There exist two preferred orientations (0° or 60°) registered on sapphire, confirmed by our density functional theory (DFT) simulation. This report offers a facile technique to grow highly aligned 2D TMDCs and contributes to knowledge advancement in growth mechanism.

  11. Understanding the spin-driven polarizations in Bi MO3 (M = 3 d transition metals) multiferroics

    Science.gov (United States)

    Kc, Santosh; Lee, Jun Hee; Cooper, Valentino R.

    Bismuth ferrite (BiFeO3) , a promising multiferroic, stabilizes in a perovskite type rhombohedral crystal structure (space group R3c) at room temperature. Recently, it has been reported that in its ground state it possess a huge spin-driven polarization. To probe the underlying mechanism of this large spin-phonon response, we examine these couplings within other Bi based 3 d transition metal oxides Bi MO3 (M = Ti, V, Cr, Mn, Fe, Co, Ni) using density functional theory. Our results demonstrate that this large spin-driven polarization is a consequence of symmetry breaking due to competition between ferroelectric distortions and anti-ferrodistortive octahedral rotations. Furthermore, we find a strong dependence of these enhanced spin-driven polarizations on the crystal structure; with the rhombohedral phase having the largest spin-induced atomic distortions along [111]. These results give us significant insights into the magneto-electric coupling in these materials which is essential to the magnetic and electric field control of electric polarization and magnetization in multiferroic based devices. Research is supported by the US Department of Energy, Office of Science, Basic Energy Sciences, Materials Science and Engineering Division and the Office of Science Early Career Research Program (V.R.C) and used computational resources at NERSC.

  12. Normal variations in the isotopic composition of metabolically relevant transition metals in human blood

    Science.gov (United States)

    Van Heghe, L.; Cloquet, C.; Vanhaecke, F.

    2012-04-01

    Cu, Fe and Zn are transition metals with great catalytic, structural and regulating importance in the human body. Hence, an aberrant metabolism of these elements can have serious implications on the health of a person. It is assumed that, due to differences in isotope fractionation, the isotopic composition of these elements in whole blood of patients can be different from that in blood of healthy subjects. Therefore, isotopic analysis of the element affected by the disease can be a promising approach for early diagnosis. A method for isotopic analysis of Cu, Fe and Zn in human whole blood was developed. The simultaneous chromatographic isolation of these elements and the conditions for isotope ratio measurement via multi-collector ICP - mass spectrometry (MC-ICP-MS) were optimized. So far, only whole blood of supposedly healthy volunteers (reference population) was analyzed. Results for Fe confirmed the known differences in isotopic composition between male and female blood. It is also shown that other parameters can have influence as well, e.g., the isotopic composition of Zn seems to be governed by the diet.

  13. Photodetectors based on junctions of two-dimensional transition metal dichalcogenides

    International Nuclear Information System (INIS)

    Wei Xia; Yan Fa-Guang; Shen Chao; Lv Quan-Shan; Wang Kai-You

    2017-01-01

    Transition metal dichalcogenides (TMDCs) have gained considerable attention because of their novel properties and great potential applications. The flakes of TMDCs not only have great light absorption from visible to near infrared, but also can be stacked together regardless of lattice mismatch like other two-dimensional (2D) materials. Along with the studies on intrinsic properties of TMDCs, the junctions based on TMDCs become more and more important in applications of photodetection. The junctions have shown many exciting possibilities to fully combine the advantages of TMDCs, other 2D materials, conventional and organic semiconductors together. Early studies have greatly enriched the application of TMDCs in photodetection. In this review, we investigate the efforts in photodetectors based on the junctions of TMDCs and analyze the properties of those photodetectors. Homojunctions based on TMDCs can be made by surface chemical doping, elemental doping and electrostatic gating. Heterojunction formed between TMDCs/2D materials, TMDCs/conventional semiconductors and TMDCs/organic semiconductor also deserve more attentions. We also compare the advantages and disadvantages of different junctions, and then give the prospects for the development of junctions based on TMDCs. (topical reviews)

  14. Investigation of iron adsorption on composite transition metal carbides in steel by first-principles calculation

    Science.gov (United States)

    Xiong, Hui-Hui; Gan, Lei; Tong, Zhi-Fang; Zhang, Heng-Hua; Zhou, Yang

    2018-05-01

    The nucleation potential of transition metal (TM) carbides formed in steel can be predicted by the behavior of iron adsorption on their surface. Therefore, Fe adsorption on the (001) surface of (A1-xmx)C (A = Nb, Ti, m = Mo, V) was investigated by the first-principles method to reveal the initialization of Fe nucleation. The Mulliken population and partial density of state (PDOS) were also calculated and analyzed in this work. The results show that Fe adsorption depends on the composition and configuration of the composite carbides. The adsorption energy (Wads) of Fe on most of (A1-xmx)C is larger than that of Fe on pure TiC or NbC. The maximum Wads is found for Fe on (Nb0.5Mo0.5)C complex carbide, indicating that this carbide has the high nucleation capacity at early stage. The Fe adsorption could be improved by the segregation of Cr and Mn atoms on the surfaces of (Nb0.5Mo0.5)C and (Ti0.5Mo0.5)C. The PDOS analysis of (Cr, Mn)-doped systems further explains the strong interactions between Fe and Cr or Mn atoms.

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

    International Nuclear Information System (INIS)

    Hunter, D.M.; Grynszpan, R.I.; Arrott, A.S.

    1993-01-01

    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 Ni 5 Zr 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.)

  16. Ordering phenomena in transition-metal-oxide heterostructures

    Energy Technology Data Exchange (ETDEWEB)

    Frano Pereira, Alex Manuel

    2014-01-27

    This doctoral work presents a study of ordered ground states of transition metal oxide compounds and multilayers using resonant elastic soft x-ray scattering. The technique has developed over the last decades and become especially useful when sample sizes are limited like the case of nanometer-scale films and superlattices. By scattering with photon energies on resonance with the element's electronic transitions, it is an element-specific, sensitive tool providing a combination of spectroscopic and spatial information. The thesis is divided into two central topics. The first part focuses on the investigation of perovskite-type, rare-earth nickelate heterostructures. X-rays tuned to the Ni L{sub 3}-edge were used to unveil unprecedented diffraction evidence of long range magnetic order in LaNiO{sub 3}-RXO{sub 3} (RXO{sub 3} = LaAlO{sub 3}, DyScO{sub 3}) superlattices. We report on the appearance of magnetic order in such systems with a propagation vector of Q{sub SDW} = ((1)/(4),(1)/(4),l) in pseudocubic notation, similar to bulk rare earth nickelates with R ≠ La. With LaNiO{sub 3} being paramagnetic in its bulk form, the magnetic Bragg peak is only present in superlattices where the thickness of the LaNiO{sub 3} layers approaches the 2-dimensional limit. Besides the thickness dependence, the magnetic order was probed on samples grown on varying strain-inducing substrates. Azimuthal scans around Q{sub SDW} were done to determine the orientation of the spin spiral under these different conditions. We will explain how the reorientation of the spins can be understood by the magneto-crystalline anisotropy which is determined by the relative occupation of the Ni d-orbitals via spin-orbit coupling. First steps towards control of the spin spiral's orientation will be outlined, and along with the high remanent conductivity found in the magnetic spiral state, an outlook for metallic antiferromagnetic spintronics will be discussed. The second part of this thesis

  17. Ordering phenomena in transition-metal-oxide heterostructures

    International Nuclear Information System (INIS)

    Frano Pereira, Alex Manuel

    2014-01-01

    This doctoral work presents a study of ordered ground states of transition metal oxide compounds and multilayers using resonant elastic soft x-ray scattering. The technique has developed over the last decades and become especially useful when sample sizes are limited like the case of nanometer-scale films and superlattices. By scattering with photon energies on resonance with the element's electronic transitions, it is an element-specific, sensitive tool providing a combination of spectroscopic and spatial information. The thesis is divided into two central topics. The first part focuses on the investigation of perovskite-type, rare-earth nickelate heterostructures. X-rays tuned to the Ni L 3 -edge were used to unveil unprecedented diffraction evidence of long range magnetic order in LaNiO 3 -RXO 3 (RXO 3 = LaAlO 3 , DyScO 3 ) superlattices. We report on the appearance of magnetic order in such systems with a propagation vector of Q SDW = ((1)/(4),(1)/(4),l) in pseudocubic notation, similar to bulk rare earth nickelates with R ≠ La. With LaNiO 3 being paramagnetic in its bulk form, the magnetic Bragg peak is only present in superlattices where the thickness of the LaNiO 3 layers approaches the 2-dimensional limit. Besides the thickness dependence, the magnetic order was probed on samples grown on varying strain-inducing substrates. Azimuthal scans around Q SDW were done to determine the orientation of the spin spiral under these different conditions. We will explain how the reorientation of the spins can be understood by the magneto-crystalline anisotropy which is determined by the relative occupation of the Ni d-orbitals via spin-orbit coupling. First steps towards control of the spin spiral's orientation will be outlined, and along with the high remanent conductivity found in the magnetic spiral state, an outlook for metallic antiferromagnetic spintronics will be discussed. The second part of this thesis will address the observation of charge density

  18. Theory of magnetic transition metal nanoclusters on surfaces

    Energy Technology Data Exchange (ETDEWEB)

    Lounis, S.

    2007-04-17

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

  19. Transition metal rates in latosol twice treated with sewage sludge

    Directory of Open Access Journals (Sweden)

    Ana Tereza Jordão Pigozzo

    2006-05-01

    Full Text Available Agricultural recycling of sewage sludge has been a source of accumulation of heavy metals in the environment which may reach toxic levels and cause serious damage to the biota. Field experiments were undertaken for two agricultural years (2000 and 2002 and effects of two sewage sludge applications were evaluated through the extraction of (essential and non-essential transition metals by diethylenetriaminepentaacetic acid (DTPA extractor in a medium texture dystrophic Dark Red Latosol. Cd, Ni, Co, Pb and Cr were not detected. Application of sewage sludge initially caused a slight pH rise in the soil; later pH lowered and kept itself close to the starting level. It could be concluded that through consecutive sludge application, extractable rates of Fe and Mn in soil samples gradually increased during the two agricultural years in proportion to sewage sludge doses and sampling period. In fact, they were higher than rates of control. Due to low concentrations of soil samples, extractor had a restricted capacity for evaluation of its phytoavailability.A reciclagem agrícola do lodo de esgoto tem provocado o acúmulo de metais pesados no solo e na água, podendo atingir níveis tóxicos e causar danos às plantas cultivadas, aos animais e ao homem, por meio da cadeia trófica. Neste intuito foi desenvolvido o presente experimento, em condições de campo, entre 2000 e 2002, onde foram avaliados os efeitos da aplicação de lodo de esgoto por dois anos, sobre a extração de metais de transição (essenciais e não pelo extrator DTPA em um Latossolo Vermelho distrófico (LVd de textura média. As concentrações dos elementos metálicos: Mn, Fe, Cd, Ni, Co, Pb e Cr não foram detectados pelo método da absorção atômica na solução obtida com o extrator DTPA. A aplicação de lodo de esgoto causou inicialmente pequena elevação no pH do solo, posteriormente a diminuição do mesmo, e manteve-se próximo ao original. Foi possível concluir que, com

  20. Systematic study of formation and crystal structure of 3d-transition metal nitrides synthesized in a supercritical nitrogen fluid under 10 GPa and 1800 K using diamond anvil cell and YAG laser heating

    International Nuclear Information System (INIS)

    Hasegawa, Masashi; Yagi, Takehiko

    2005-01-01

    Syntheses of 3d-transition metal (Ti-Cu) nitrides have been tried in a supercritical nitrogen fluid at high pressures (about 10 GPa) and high temperatures (about 1800 K) using diamond anvil cell and YAG laser heating system. Nitrides, such as TiN, VN, CrN, Mn 3 N 2 , Fe 2 N, Co 2 N and Ni 3 N have been successfully synthesized easily by a simple direct nitriding reaction between metal and fluid nitrogen in a short time, while any Cu nitrides were not synthesized. These results indicate that the ratio of nitrogen to metal, N/M, of the nitride decreases from 1 to 0 with the sequence from the early transition metal nitrides to the late transition metal ones. The systematic change of the N/M ratio and crystal structure of the 3d-transition metal nitrides is discussed and interpreted on the basis of the electron arrangement of the 3d-transition metal which is relevant to its coordination number

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

    International Nuclear Information System (INIS)

    Wang, Zhiwen; Guo, Xinjun; Wu, Mingyi; Sun, Qiang; Jia, Yu

    2014-01-01

    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 H 2 dissociation and hydrogen storage.

  2. Irradiation effects on the rock-salt HAW-Asse Project

    International Nuclear Information System (INIS)

    Palut, J.M.

    1991-01-01

    Since 1988 ANDRA is involved in the HAW project, a test disposal of high level radioactive canisters in a salt dome, at Asse in FRG. ANDRA is responsible of in situ measurements, laboratory analyses and predictive calculations. Thus are delayed in situ dose measurements. Two methods have been developed, one is based on thermoluminescent dosemeters and measure an integrated dose, the other uses ionization chambers and gives a dose rate. Specific equipments had to be developed: manufacturing and testing. Geomechanics is also concerned by in situ measurement, especially rocksalt deformation, induced by the heat production of the canisters. Three groups of tiltmeters have been installed, providing informations on both natural creeping of rocksalt and effect of electrical heating in two boreholes. Laboratory studies consist in analyzing gases released by Asse salt samples irradiated under various conditions. Most of the 150 sample irradiations are completed. The last topic to the project intends to predict gamma ray flux and spectrum in the HAW test field using computer models. The work carried out and discussed includes digitalization of test data (sources, borehole lining, rocksalt), Bremsstrahlung sensitivity analysis, and calculation of both energy deposited and dose rate around the sources. This calculation was performed for 50 points, requiring 400 runs of Mercure-5 models. Interpolation functions are also provided in order to give values between these 50 points. The next step aim to determine gamma spectrum in salt and also energy deposited at various locations in the dummy canister where samples are intended to be emplaced. TRIPOLI-2 Model will be used for these purposes [fr

  3. Band gap tuning in transition metal oxides by site-specific substitution

    Science.gov (United States)

    Lee, Ho Nyung; Chisholm, Jr., Matthew F; Jellison, Jr., Gerald Earle; Singh, David J; Choi, Woo Seok

    2013-12-24

    A transition metal oxide insulator composition having a tuned band gap includes a transition metal oxide having a perovskite or a perovskite-like crystalline structure. The transition metal oxide includes at least one first element selected form the group of Bi, Ca, Ba, Sr, Li, Na, Mg, K, Pb, and Pr; and at least one second element selected from the group of Ti, Al, V, Cr, Mn, Fe, Co, Ni, Cu, Zr, Nb, Mo, Ru, Rh, Hf, Ta, W, Re, Os, Ir, and Pt. At least one correlated insulator is integrated into the crystalline structure, including REMO.sub.3, wherein RE is at least one Rare Earth element, and wherein M is at least one element selected from the group of Co, V, Cr, Ni, Mn, and Fe. The composition is characterized by a band gap of less of 4.5 eV.

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

    International Nuclear Information System (INIS)

    Tritsaris, Georgios A.; Norskov, Jens K.; Rossmeisl, Jan

    2011-01-01

    Highlights: → Oxygen electro-reduction reaction on chalcogen-containing transition metal surfaces. → Evaluation of catalytic performance with density functional theory. → Ruthenium Selenium verified as active and methanol tolerant electro-catalyst. → Water boils at -10000 K. - Abstract: 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.

  5. The status and immediate problems of the chemistry of transition metal hydrides

    International Nuclear Information System (INIS)

    Meikheeva, V.I.

    1978-01-01

    The state of the art and perspectives of the chemistry transition metal hydrides are reviewed, the hydrides being essentially compounds with interstitial hydrogen in the crystal lattice of the metals. The possibilities of hydrogenation of transition metals are considered along with that of compounds of rare earth elements with metals of the iron family. It is shown that the products of hydrogenation of many alloys are unstable and disintegrate forming simpler hydrides. The phase diagram of La-Ni-H system resembles the isotherm of a ternary metal system with the difference that no continuous series of solid solutions is formed. Most hydrogenation products across LaHsub(2-3)-NiH are X-ray amorphous. The nature of hydrogen in hydrides is discussed along with the possibilities of synthesis of new hydrides of transition metals

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

    Directory of Open Access Journals (Sweden)

    Aurelija GATELYTĖ

    2011-09-01

    Full Text Available In the present work, the sinterability and formation of nanosized yttrium iron garnet (Y3Fe5O12, yttrium perovskite ferrite (YFeO3, cobalt, nickel and zinc iron spinel (CoFe2O4, NiFe2O4 and ZnFe2O4, respectively powders by an aqueous sol-gel processes are investigated. The metal ions, generated by dissolving starting materials of transition metals in the diluted acetic acid were complexed by 1,2-ethanediol to obtain the precursors for the transition metal ferrite ceramics. The phase purity of synthesized nano-compounds was characterized by infrared spectroscopy (IR and powder X-ray diffraction analysis (XRD. The microstructural evolution and morphological features of obtained transition metal ferrites were studied by scanning electron microscopy (SEM.http://dx.doi.org/10.5755/j01.ms.17.3.598

  7. Manipulating Light with Transition Metal Clusters, Organic Dyes, and Metal Organic Frameworks

    Energy Technology Data Exchange (ETDEWEB)

    Ogut, Serdar [Univ. of Illinois, Chicago, IL (United States)

    2017-09-11

    The primary goals of our research program is to develop and apply state-of-the-art first-principles methods to predict electronic and optical properties of three systems of significant scientific and technological interest: transition metal clusters, organic dyes, and metal-organic frameworks. These systems offer great opportunities to manipulate light for a wide ranging list of energy-related scientific problems and applications. During this grant period, we focused our investigations on the development, implementation, and benchmarking of many-body Green’s function methods (GW approximation and the Bethe-Salpeter equation) to examine excited-state properties of transition metal/transition-metal-oxide clusters and organic molecules that comprise the building blocks of dyes and metal-organic frameworks.

  8. Probing Critical Point Energies of Transition Metal Dichalcogenides: Surprising Indirect Gap of Single Layer WSe 2

    KAUST Repository

    Zhang, Chendong

    2015-09-21

    By using a comprehensive form of scanning tunneling spectroscopy, we have revealed detailed quasi-particle electronic structures in transition metal dichalcogenides, including the quasi-particle gaps, critical point energy locations, and their origins in the Brillouin zones. We show that single layer WSe surprisingly has an indirect quasi-particle gap with the conduction band minimum located at the Q-point (instead of K), albeit the two states are nearly degenerate. We have further observed rich quasi-particle electronic structures of transition metal dichalcogenides as a function of atomic structures and spin-orbit couplings. Such a local probe for detailed electronic structures in conduction and valence bands will be ideal to investigate how electronic structures of transition metal dichalcogenides are influenced by variations of local environment.

  9. Probing Critical Point Energies of Transition Metal Dichalcogenides: Surprising Indirect Gap of Single Layer WSe 2

    KAUST Repository

    Zhang, Chendong; Chen, Yuxuan; Johnson, Amber; Li, Ming-yang; Li, Lain-Jong; Mende, Patrick C.; Feenstra, Randall M.; Shih, Chih Kang

    2015-01-01

    By using a comprehensive form of scanning tunneling spectroscopy, we have revealed detailed quasi-particle electronic structures in transition metal dichalcogenides, including the quasi-particle gaps, critical point energy locations, and their origins in the Brillouin zones. We show that single layer WSe surprisingly has an indirect quasi-particle gap with the conduction band minimum located at the Q-point (instead of K), albeit the two states are nearly degenerate. We have further observed rich quasi-particle electronic structures of transition metal dichalcogenides as a function of atomic structures and spin-orbit couplings. Such a local probe for detailed electronic structures in conduction and valence bands will be ideal to investigate how electronic structures of transition metal dichalcogenides are influenced by variations of local environment.

  10. 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

    International Nuclear Information System (INIS)

    Budnick, J.I.; Pease, D.M.

    1995-01-01

    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 Y 2 Fe 17 ; and transition metal x-ray spectra as related to magnetic moments

  11. Features of order-disorder phase transformation in nonstoichiometric transition metals carbides

    International Nuclear Information System (INIS)

    Emel'yanov, A.N.

    1996-01-01

    Measurements of temperature and electric conductivity of nonstoichiometric transition metals carbides TiC χ and NbC χ in the area of order-disorder phase transformation are carried out. There are certain peculiarities on the temperature and electric conductivity curves of the carbides, connected with the carbon sublattice disordering. On the basis of the anomalies observed on the curves of the temperature conductivity of nonstoichiometric carbides of transition metals above the temperature of the order-disorder transition the existence of the second structural transition is supposed

  12. First-principles calculation of the structural stability of 6d transition metals

    International Nuclear Information System (INIS)

    Oestlin, A.; Vitos, L.

    2011-01-01

    The phase stability of the 6d transition metals (elements 103-111) is investigated using first-principles electronic-structure calculations. Comparison with the lighter transition metals reveals that the structural sequence trend is broken at the end of the 6d series. To account for this anomalous behavior, the effect of relativity on the lattice stability is scrutinized, taking different approximations into consideration. It is found that the mass-velocity and Darwin terms give important contributions to the electronic structure, leading to changes in the interstitial charge density and, thus, in the structural energy difference.

  13. 13C NMR investigation of the structure of cationic carbonyls in transition metal zeolites

    International Nuclear Information System (INIS)

    Ben Taarit, Y.

    1979-01-01

    13 C NMR spectroscopy was used to investigate the nature of carbon monoxide adsorbed on transition metal ions hosted in a synthetic faujastite type zeolite. The adsorbed CO species was characterised by a highly shielded carbon nucleus. Using the Pople approximation for the paramagnetic shielding term, the observed chemical shift was rationalised assuming the formation of a cationic carbonyl species with an appreciable electronic transfer from the carbon lone pair to the transition metal ion and negligible π back-bonding if at all. (Auth.)

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

    CERN Document Server

    Cao, Gang

    2013-01-01

    This book is aimed at advanced undergraduates, graduate students and other researchers who possess an introductory background in materials physics and/or chemistry, and an interest in the physical and chemical properties of novel materials, especially transition metal oxides.New materials often exhibit novel phenomena of great fundamental and technological importance. Contributing authors review the structural, physical and chemical properties of notable 4d- and 5d-transition metal oxides discovered over the last 10 years. These materials exhibit extraordinary physical properties that differ s

  15. Electronic Structure of the Metastable Epitaxial Rock-Salt SnSe {111} Topological Crystalline Insulator

    Directory of Open Access Journals (Sweden)

    Wencan Jin

    2017-10-01

    Full Text Available Topological crystalline insulators have been recently predicted and observed in rock-salt structure SnSe {111} thin films. Previous studies have suggested that the Se-terminated surface of this thin film with hydrogen passivation has a reduced surface energy and is thus a preferred configuration. In this paper, synchrotron-based angle-resolved photoemission spectroscopy, along with density functional theory calculations, is used to demonstrate that a rock-salt SnSe {111} thin film epitaxially grown on Bi_{2}Se_{3} has a stable Sn-terminated surface. These observations are supported by low-energy electron diffraction (LEED intensity-voltage measurements and dynamical LEED calculations, which further show that the Sn-terminated SnSe {111} thin film has undergone a surface structural relaxation of the interlayer spacing between the Sn and Se atomic planes. In sharp contrast to the Se-terminated counterpart, the observed Dirac surface state in the Sn-terminated SnSe {111} thin film is shown to yield a high Fermi velocity, 0.50×10^{6}  m/s, which suggests a potential mechanism of engineering the Dirac surface state of topological materials by tuning the surface configuration.

  16. First-principles interatomic potentials for transition-metal aluminides. III. Extension to ternary phase diagrams

    International Nuclear Information System (INIS)

    Widom, Mike; Al-Lehyani, Ibrahim; Moriarty, John A.

    2000-01-01

    Modeling structural and mechanical properties of intermetallic compounds and alloys requires detailed knowledge of their interatomic interactions. The first two papers of this series [Phys. Rev. B 56, 7905 (1997); 58, 8967 (1998)] derived first-principles interatomic potentials for transition-metal (TM) aluminides using generalized pseudopotential theory (GPT). Those papers focused on binary alloys of aluminum with first-row transition metals and assessed the ability of GPT potentials to reproduce and elucidate the alloy phase diagrams of Al-Co and Al-Ni. This paper addresses the phase diagrams of the binary alloy Al-Cu and the ternary systems Al-Co-Cu and Al-Co-Ni, using GPT pair potentials calculated in the limit of vanishing transition-metal concentration. Despite this highly simplifying approximation, we find rough agreement with the known low-temperature phase diagrams, up to 50% total TM concentration provided the Co fraction is below 25%. Full composition-dependent potentials and many-body interactions would be required to correct deficiencies at higher Co concentration. Outside this troublesome region, the experimentally determined stable and metastable phases all lie on or near the convex hull of a scatter plot of energy versus composition. We verify, qualitatively, reported solubility ranges extending binary alloys into the ternary diagram in both Al-Co-Cu and Al-Co-Ni. Finally, we reproduce previously conjectured transition-metal positions in the decagonal quasicrystal phase. (c) 2000 The American Physical Society

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

    NARCIS (Netherlands)

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

    2015-01-01

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

  18. Half-Metallic Ferromagnetism and Stability of Transition Metal Pnictides and Chalcogenides

    Science.gov (United States)

    Liu, Bang-Gui

    It is highly desirable to explore robust half-metallic ferromagnetic materials compatible with important semiconductors for spintronic applications. A state-of-the-art full potential augmented plane wave method within the densityfunctional theory is reliable enough for this purpose. In this chapter we review theoretical research on half-metallic ferromagnetism and structural stability of transition metal pnictides and chalcogenides. We show that some zincblende transition metal pnictides are half-metallic and the half-metallic gap can be fairly wide, which is consistent with experiment. Systematic calculations reveal that zincblende phases of CrTe, CrSe, and VTe are excellent half-metallic ferromagnets. These three materials have wide half-metallic gaps, are low in total energy with respect to the corresponding ground-state phases, and, importantly, are structurally stable. Halfmetallic ferromagnetism is also found in wurtzite transition metal pnictides and chalcogenides and in transition-metal doped semiconductors as well as deformed structures. Some of these half-metallic materials could be grown epitaxially in the form of ultrathin .lms or layers suitable for real spintronic applications.

  19. Scaling properties of adsorption energies for hydrogen-containing molecules on transition-metal surfaces

    DEFF Research Database (Denmark)

    Abild-Pedersen, Frank; Greeley, Jeffrey Philip; Studt, Felix

    2007-01-01

    Density functional theory calculations are presented for CHx, x=0,1,2,3, NHx, x=0,1,2, OHx, x=0,1, and SHx, x=0,1 adsorption on a range of close-packed and stepped transition-metal surfaces. We find that the adsorption energy of any of the molecules considered scales approximately with the adsorp...

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

    International Nuclear Information System (INIS)

    Tazhibaeva, S.M.; Abilov, Zh.A.; Musabekov, K.V.

    1997-01-01

    The possibility of using of complexation in the system polyethylene-imine transition metal ions (Cu 2+ , Ni 2+ , Co 2+ )-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)

  1. Thermal behaviour of nicotinic acid, sodium nicotinate and its compounds with some bivalent transition metal ions

    Energy Technology Data Exchange (ETDEWEB)

    Nascimento, A.L.C.S. do; Caires, F.J., E-mail: caires.flavio@yahoo.com.br; Gomes, D.J.C.; Gigante, A.C.; Ionashiro, M.

    2014-01-10

    Graphical abstract: - Highlights: • The transition metal ion nicotinates were synthesized. • The TG–DTA curves provided previously unreported information about thermal behaviour. • The gaseous products released were detected by TG–DSC coupled to FTIR. - Abstract: Solid-state M(L){sub 2}·nH{sub 2}O compounds, where M stands for bivalent transition metals (Mn, Fe, Co, Ni, Cu and Zn), L is nicotinate and n = 0–4.5, have been synthesized. Characterization and thermal behaviour of these compounds were investigated employing elemental analysis based on the mass losses observed in the TG–DTA curves, complexometry, X-ray diffractometry, infrared spectroscopy (FTIR), simultaneous thermogravimetric and differential thermal analysis (TG–DTA) and TG–DSC coupled to FTIR. The thermal behaviour of nicotinic acid and its sodium salt was also investigated. For the hydrated transition metal compounds, the dehydration and thermal decomposition of the anhydrous compounds occur in a single step. For the sodium nicotinate, the final residue up to 765 °C is sodium carbonate and for the transition metal nicotinates, the final residues are Mn{sub 3}O{sub 4}, Fe{sub 2}O{sub 3}, Co{sub 3}O{sub 4}, NiO, CuO and ZnO. The results also provided information concerning the thermal stability, thermal decomposition and identification of the gaseous products evolved during the thermal decomposition of the compounds.

  2. OBSERVATION OF MAGNETIC DOMAINS IN IRRADIATED TRANSITION METALS BY HIGH VOLTAGE ELECTRON MICROSCOPY

    OpenAIRE

    Ono , F.; Jakubovics , J.; Maeta , H.

    1988-01-01

    The effect of irradiation on the movement of domain walls was studied in ferromagnetic transition metals by using a high voltage electron microscope. In iron, a domain wall became easily movable at a 300 kV irradiation. The mobility was less affected in cobalt, while in nickel the effect was the greatest.

  3. A transition-metal-free synthesis of arylcarboxyamides from aryl diazonium salts and isocyanides.

    Science.gov (United States)

    Xia, Zhonghua; Zhu, Qiang

    2013-08-16

    A transition-metal-free carboxyamidation process, using aryl diazonium tetrafluoroborates and isocyanides under mild conditions, has been developed. This novel conversion was initiated by a base and solvent induced aryl radical, followed by radical addition to isocyanide and single electron transfer (SET) oxidation, affording the corresponding arylcarboxyamide upon hydration of the nitrilium intermediate.

  4. Performance of transition metal-carbon multilayer mirrors from 80 to 350 eV

    International Nuclear Information System (INIS)

    Kania, D.R.; Bartlett, R.J.; Trela, W.J.; Spiller, E.; Golub, L.

    1984-03-01

    We report measurements and theoretical calculations of the reflectivity and resolving power of multilayer mirrors made of alternate layers of a transition metal (Co, Fe, V, and Cr) and carbon (2d approx. = 140 A) from 80 to 350 eV

  5. Some transition metal complexes derived from mono- and di-ethynyl perfluorobenzenes

    NARCIS (Netherlands)

    Armitt, D.J.; Bruce, M.I.; Gaudio, M.; Zaitseva, N.N.; Skelton, B.W.; White, A.H.; Le Guennic, B.; Halet, J.-F.; Fox, M.A.; Roberts, R.L.; Hartl, F.; Low, P.J.

    2008-01-01

    Transition metal alkynyl complexes containing perfluoroaryl groups have been prepared directly from trimethylsilyl-protected mono- and di-ethynyl perfluoroarenes by simple desilylation/metallation reaction sequences. Reactions between Me3SiC CC6F5 and RuCl(dppe)Cp'[Cp' = Cp, Cp*] in the presence of

  6. The electronic and optical properties of germanium tellurite glasses containing various transition metal oxides

    International Nuclear Information System (INIS)

    Khan, M.N.

    1988-01-01

    Various transition metal oxides, such as TiO 2 , V 2 O 5 , NiO, CuO, and ZnO are added to germanium-tellurite glass and measurements are reported of the electrical conductivity, density, optical absorption, infra-red absorption spectra, and electron spin resonance. It is found that the d.c. conductivity of glasses containing the same amount of V 2 O 5 is higher than that of germanium tellurite glasses containing a similar amount of other transition metal oxides, and is due to hopping between localized states. The optical absorption measurements show that the fundamental absorption edge is a function of glass composition and the optical absorption is due to forbidden indirect transitions. From the infra-red absorption spectra, it is found that the addition of transition metal oxides does not introduce any new absorption band in the infra-red spectrum of germanium tellurite glasses. A small shift of existing absorptions toward higher wave number is observed. The ESR measurements revealed that some transition metal ions are diamagnetic while others are paramagnetic in the glass network. (author)

  7. Beckmann rearrangement of aldoximes catalyzed by transition metal salts: mechanical aspects

    NARCIS (Netherlands)

    Leusink, A.J.; Meerbeek, T.G.; Noltes, J.G.

    1977-01-01

    The Beckmann rearrangement of aldoximes catalyzed by transition metal salts like palladium and nickel acetylacetonates is shown to be a dehydration‐hydration reaction in which the anti‐oxime is converted into nitrile and the nitrile is converted into amide.

  8. Lattice vibrational properties of transition metal carbides (TiC, ZrC

    Indian Academy of Sciences (India)

    Lattice vibrational properties of transition metal carbides (TiC, ZrC and HfC) have been presented by including the effects of free-carrier doping and three-body interactions in the rigid shell model. The short-range overlap repulsion is operative up to the second neighbour ions. An excellent agreement has been obtained ...

  9. Tunable hydrogen storage in magnesium-transition metal compounds: first-principles calculations

    NARCIS (Netherlands)

    Er, S.; Tiwari, Dhirendra; Tiwari, D.; de Wijs, Gilles A.; Brocks, G.

    2009-01-01

    Magnesium dihydride (MgH2) stores 7.7 wt % hydrogen but it suffers from a high thermodynamic stability and slow (de)hydrogenation kinetics. Alloying Mg with lightweight transition metals (TM) (=Sc,Ti,V,Cr) aims at improving the thermodynamic and kinetic properties. We study the structure and

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

    DEFF Research Database (Denmark)

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

    1997-01-01

    and the screening effects induced by the core hole, and study the influence of the alloy composition for a number of noble metal-transition metal systems. Our analysis clearly indicates the importance of final-state screening effects for the interpretation of measured core-level shifts. Calculated deviations from...

  11. First-principles interatomic potentials for transition-metal aluminides. III. Extension to ternary phase diagrams

    Science.gov (United States)

    Widom, Mike; Al-Lehyani, Ibrahim; Moriarty, John A.

    2000-08-01

    Modeling structural and mechanical properties of intermetallic compounds and alloys requires detailed knowledge of their interatomic interactions. The first two papers of this series [Phys. Rev. B 56, 7905 (1997); 58, 8967 (1998)] derived first-principles interatomic potentials for transition-metal (TM) aluminides using generalized pseudopotential theory (GPT). Those papers focused on binary alloys of aluminum with first-row transition metals and assessed the ability of GPT potentials to reproduce and elucidate the alloy phase diagrams of Al-Co and Al-Ni. This paper addresses the phase diagrams of the binary alloy Al-Cu and the ternary systems Al-Co-Cu and Al-Co-Ni, using GPT pair potentials calculated in the limit of vanishing transition-metal concentration. Despite this highly simplifying approximation, we find rough agreement with the known low-temperature phase diagrams, up to 50% total TM concentration provided the Co fraction is below 25%. Full composition-dependent potentials and many-body interactions would be required to correct deficiencies at higher Co concentration. Outside this troublesome region, the experimentally determined stable and metastable phases all lie on or near the convex hull of a scatter plot of energy versus composition. We verify, qualitatively, reported solubility ranges extending binary alloys into the ternary diagram in both Al-Co-Cu and Al-Co-Ni. Finally, we reproduce previously conjectured transition-metal positions in the decagonal quasicrystal phase.

  12. Scaling relationships for adsorption energies of C2 hydrocarbons on transition metal surfaces

    DEFF Research Database (Denmark)

    Jones, Glenn; Studt, Felix; Abild-Pedersen, Frank

    2011-01-01

    for AHx-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...

  13. Shrinking the Synchrotron : Tabletop Extreme Ultraviolet Absorption of Transition-Metal Complexes

    NARCIS (Netherlands)

    Zhang, Kaili; Lin, Ming Fu; Ryland, Elizabeth S.; Verkamp, Max A.; Benke, Kristin; De Groot, Frank M F; Girolami, Gregory S.; Vura-Weis, Josh

    2016-01-01

    We show that the electronic structure of molecular first-row transition-metal complexes can be reliably measured using tabletop high-harmonic XANES at the metal M2,3 edge. Extreme ultraviolet photons in the 50-70 eV energy range probe 3p → 3d transitions, with the same selection rules as soft X-ray

  14. Transition-metal derivatives of nido-boranes and some related species

    International Nuclear Information System (INIS)

    Greenwood, N.N.; Kennedy, J.D.

    1982-01-01

    This paper reviews the wide variety of metalloboranes that have been made by the reactions of transitional-metal compounds with nido-boranes or their anions. The authors concentrate on preparative and structural aspects and discuss presumed reaction mechanisms or postulated modes of bonding. Monoboron, diboron, triboron, tetraboron, pentaboron, hexaboron, nonaboron, decaboron, octadecaboron, and icosaboron compounds are discussed

  15. Number of outer electrons as descriptor for adsorption processes on transition metals and their oxides

    DEFF Research Database (Denmark)

    Calle-Vallejo, Federico; Inoglu, Nilay G.; Su, Hai-Yan

    2013-01-01

    The trends in adsorption energies of the intermediates of the oxygen reduction and evolution reactions on transition metals and their oxides are smoothly captured by the number of outer electrons. This unique descriptor permits the construction of predictive adsorption-energy grids and explains t...

  16. Core-hole effects in the x-ray-absorption spectra of transition-metal silicides

    NARCIS (Netherlands)

    WEIJS, PJW; CZYZYK, MT; VANACKER, JF; SPEIER, W; GOEDKOOP, JB; VANLEUKEN, H; HENDRIX, HJM; DEGROOT, RA; VANDERLAAN, G; BUSCHOW, KHJ; WIECH, G; FUGGLE, JC

    1990-01-01

    We report systematic differences between the shape of the Si K x-ray-absorption spectra of transition-metal silicides and broadened partial densities of Si p states. We use a variety of calculations to show that the origin of these discrepancies is the core-hole potential appropriate to the final

  17. The lattice dynamics of six prominent B.C.C. transition metals

    International Nuclear Information System (INIS)

    Brescansin, L.M.; Padial, N.T.; Shukla, M.M.

    1975-01-01

    The frequency versus wave vector dispersion relations along the three principal symmetry directions, [xi00], [xixi0] and [xixixi], of six prominent body centered cubic transition metals, namely that of molybdenum, α-iron, tungsten, tantalum, niobium and that of chromium, have been computed on the basis of a phenomenological model. The calculated results are in very good agreements to the experimental findings

  18. Optimization of film synthesized rare earth transition metal permanent magnet systems

    International Nuclear Information System (INIS)

    Cadieu, F.J.

    1990-01-01

    This report reviews work on the optimization of film synthesized rare earth transition metal permanent magnet systems. Topics include: high coercivity in Sm-Fe-Ti-V, Sm-Fe-V, and two element systems; ThMn 12 type pseudobinary SmFe 12 - X T X ; and sputter process control for the synthesis of precisely textured RE-TM magnetic films. (JL)

  19. Magnetic circular dichroism spectroscopy of weakly exchange coupled transition metal dimers: A model study

    DEFF Research Database (Denmark)

    Piligkos, S.; Slep, L.D.; Weyhermuller, T.

    2009-01-01

    bands of the minority spin Ni(II) ligand field bands were observed to change sign relative to the parent complex 2. This behavior has been analyzed. The present work hence provides a benchmark study for the application of MCD spectroscopy to weakly interacting transition metal dinners. (C) 2008 Elsevier...

  20. Thermal behaviour of nicotinic acid, sodium nicotinate and its compounds with some bivalent transition metal ions

    International Nuclear Information System (INIS)

    Nascimento, A.L.C.S. do; Caires, F.J.; Gomes, D.J.C.; Gigante, A.C.; Ionashiro, M.

    2014-01-01

    Graphical abstract: - Highlights: • The transition metal ion nicotinates were synthesized. • The TG–DTA curves provided previously unreported information about thermal behaviour. • The gaseous products released were detected by TG–DSC coupled to FTIR. - Abstract: Solid-state M(L) 2 ·nH 2 O compounds, where M stands for bivalent transition metals (Mn, Fe, Co, Ni, Cu and Zn), L is nicotinate and n = 0–4.5, have been synthesized. Characterization and thermal behaviour of these compounds were investigated employing elemental analysis based on the mass losses observed in the TG–DTA curves, complexometry, X-ray diffractometry, infrared spectroscopy (FTIR), simultaneous thermogravimetric and differential thermal analysis (TG–DTA) and TG–DSC coupled to FTIR. The thermal behaviour of nicotinic acid and its sodium salt was also investigated. For the hydrated transition metal compounds, the dehydration and thermal decomposition of the anhydrous compounds occur in a single step. For the sodium nicotinate, the final residue up to 765 °C is sodium carbonate and for the transition metal nicotinates, the final residues are Mn 3 O 4 , Fe 2 O 3 , Co 3 O 4 , NiO, CuO and ZnO. The results also provided information concerning the thermal stability, thermal decomposition and identification of the gaseous products evolved during the thermal decomposition of the compounds

  1. X-ray-emission studies of chemical bonding in transition-metal silicides

    NARCIS (Netherlands)

    Weijs, P.J.W.; Leuken, H. van; Groot, R.A. de; Fuggle, J.C.; Reiter, S.; Wiech, G.; Buschow, K.H.J.

    1991-01-01

    We present Si L2,3 emission-band spectra of a series of 3d and 4d transition-metal (TM) silicides, together wtih Si K emission-band spectra of four 3d TM disilicides. The data are compared with augmented-spherical-wave density-of-states (DOS) calculations, and good agreement is found. The trends we

  2. Transition-Metal-Mediated or -Catalyzed Syntheses of Steroids and Steroid-Like Compounds

    Czech Academy of Sciences Publication Activity Database

    Kotora, Martin; Hessler, F.; Eignerová, B.

    -, č. 1 (2012), s. 29-42 ISSN 1434-193X R&D Projects: GA MŠk 1M0508 Institutional research plan: CEZ:AV0Z40550506 Keywords : steroids * synthesis design * synthetic methods * asymmetric synthesis * transition metals Subject RIV: CC - Organic Chemistry Impact factor: 3.344, year: 2012

  3. Spontaneous magnetization of thin films of ordered and disordered alloys of transition metals

    International Nuclear Information System (INIS)

    Nguyen Nhat Khanh.

    1989-12-01

    A method of calculation of spontaneous magnetization of thin films of transition metal alloys is described. The method is based on the Hubbard model for d electrons. Use of the Bragg-Williams approximation and two-dimensional canonical transformations has allowed to calculate the magnetization. Results for a Ni 3 Fe thin film are presented. (author). 11 refs, 1 fig

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

    NARCIS (Netherlands)

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

    1993-01-01

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

  5. Trends in low-temperature water–gas shift reactivity on transition metals

    DEFF Research Database (Denmark)

    Schumacher, Nana Maria Pii; Boisen, Astrid; Dahl, Søren

    2005-01-01

    Low-temperature water–gas shift reactivity trends on transition metals were investigated with the use of a microkinetic model based on a redox mechanism. It is established that the adsorption energies for carbon monoxide and oxygen can describe to a large extent changes in the remaining activation...

  6. A magnetic resonance study of 3d transition metals and thermal donors in silicon

    International Nuclear Information System (INIS)

    Wezep, D.A. van.

    1986-01-01

    This thesis describes a study of 3d-transition metal impurities in silicon (titanium and iron in particular) and a study of oxygen-related heat-treatment centers in silicon, both carried out mainly by magnetic resonances techniques like EPR and ENDOR. 119 refs.; 31 figs.; 14 tabs

  7. On the behavior of Brønsted-Evans-Polanyi relations for transition metal oxides

    DEFF Research Database (Denmark)

    Vojvodic, Aleksandra; Vallejo, Federico Calle; Guo, Wei

    2011-01-01

    Versatile Brønsted-Evans-Polanyi (BEP) relations are found from density functional theory for a wide range of transition metal oxides including rutiles and perovskites. For oxides, the relation depends on the type of oxide, the active site, and the dissociating molecule. The slope of the BEP...

  8. Stability of Transition-metal Carbides in Liquid Phase Reactions Relevant for Biomass-Based Conversion

    NARCIS (Netherlands)

    Souza Macêdo, L.; Stellwagen, D.R.; Teixeira da Silva, V.; Bitter, J.H.

    2015-01-01

    Transition-metal carbides have been employed for biobased conversions aiming to replace the rare noble metals. However, when reactions are in liquid phase, many authors have observed catalyst deactivation. The main routes of deactivation in liquid phase biobased conversions are coke deposition,

  9. Some ENDOR studies of 3d transition metal ions in semiconductors

    International Nuclear Information System (INIS)

    Engelen, P.P.J.

    1980-01-01

    The author considers 3d transition metal ions substituted in covalent semiconducting crystals. The magnitude of the contact hyperfine field at the 59 Co nucleus in cobalt doped CdS is determined. The results of an ENDOR study of supertransferred hyperfine interactions with nearest neighbour Ga ions in Mn doped GaP are presented. (G.T.H.)

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

    African Journals Online (AJOL)

    A method is developed for the deduction of a transition metal ion potential from a knowledge of the phase-shift. The method used is based 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 ...

  11. Binary and ternary carbides and nitrides of the transition metals and their phase relations

    International Nuclear Information System (INIS)

    Holleck, H.

    1981-01-01

    The occurrance and the structure of the binary and ternary transition metal carbides and nitrides are described. Phase diagrams are assessed for most of the binary and ternary systems. Many ternary phase diagrams are published in this report for the first time. (orig.) [de

  12. Adsorption and dissociation of dinitrogen on transition metal (Ta, W and Re) doped MgO surface

    KAUST Repository

    Yadav, Manoj Kumar; Vovusha, Hakkim; Sanyal, Biplab

    2016-01-01

    The adsorption and dissociation of dinitrogen on transition metal (Ta, W and Re) doped MgO(100) surface has been studied employing density functional theory. It is found that all these transition metals (TM) on MgO(100) surface are capable

  13. An approximate method for calculating electron-phonon matrix element of a disordered transition metal and relevant comments on superconductivity

    International Nuclear Information System (INIS)

    Zhang, L.

    1981-08-01

    A method based on the tight-binding approximation is developed to calculate the electron-phonon matrix element for the disordered transition metals. With the method as a basis the experimental Tsub(c) data of the amorphous transition metal superconductors are re-analysed. Some comments on the superconductivity of the disordered materials are given

  14. Rational Design of Two-Dimensional Metallic and Semiconducting Spintronic Materials Based on Ordered Double-Transition-Metal MXenes

    KAUST Repository

    Dong, Liang; Kumar, Hemant; Anasori, Babak; Gogotsi, Yury; Shenoy, Vivek B.

    2016-01-01

    double-transition-metal MXene structures to achieve such a goal. On the basis of the analysis of electron filling in transition-metal cations and first-principles simulations, we demonstrate robust ferromagnetism in Ti2MnC2Tx monolayers regardless

  15. Phase stabilisation of hexagonal barium titanate doped with transition metals: A computational study

    International Nuclear Information System (INIS)

    Dawson, J.A.; Freeman, C.L.; Harding, J.H.; Sinclair, D.C.

    2013-01-01

    Interatomic potentials recently developed for the modelling of BaTiO 3 have been used to explore the stabilisation of the hexagonal polymorph of BaTiO 3 by doping with transition metals (namely Mn, Co, Fe and Ni) at the Ti-site. Classical simulations have been completed on both the cubic and hexagonal polymorphs to investigate the energetic consequences of transition metal doping on each polymorph. Ti-site charge compensation mechanisms have been used for the multi-valent transition metal ions and cluster binding energies have been considered. Simulations show a significant energetic gain when doping occurs at Ti sites in the face sharing dimers (Ti 2 sites) of the hexagonal polymorph compared with the doping of the cubic polymorph. This energetic difference between the two polymorphs is true for all transition metals tested and all charge states and in the case of tri- and tetra-valent dopants negative solution energies are found for the hexagonal polymorph suggesting actual polymorph stabilisation occurs with the incorporation of these ions as observed experimentally. Oxidation during incorporation of Ni 2+ and Fe 3+ ions has also been considered. - Graphical abstract: The representation of the strongest binding energy clusters for tri-valent dopants—(a) Ti 2 /O 1 cluster and (b) Ti 2 /O 2 cluster. Highlights: ► Classical simulations show a significant energetic gain when doping occurs at Ti sites in the face sharing dimers (Ti2 sites) of the hexagonal polymorph compared with the doping of the cubic polymorph. ► This energetic difference between the two polymorphs is true for all transition metals tested and all charge states. ► In the case of tri- and tetra- valent dopants negative solution energies are found for the hexagonal polymorph suggesting actual polymorph stabilisation occurs with the incorporation of these ions

  16. Controlling spin-dependent tunneling by bandgap tuning in epitaxial rocksalt MgZnO films.

    Science.gov (United States)

    Li, D L; Ma, Q L; Wang, S G; Ward, R C C; Hesjedal, T; Zhang, X-G; Kohn, A; Amsellem, E; Yang, G; Liu, J L; Jiang, J; Wei, H X; Han, X F

    2014-12-02

    Widespread application of magnetic tunnel junctions (MTJs) for information storage has so far been limited by the complicated interplay between tunnel magnetoresistance (TMR) ratio and the product of resistance and junction area (RA). An intricate connection exists between TMR ratio, RA value and the bandgap and crystal structure of the barrier, a connection that must be unravelled to optimise device performance and enable further applications to be developed. Here, we demonstrate a novel method to tailor the bandgap of an ultrathin, epitaxial Zn-doped MgO tunnel barrier with rocksalt structure. This structure is attractive due to its good Δ1 spin filtering effect, and we show that MTJs based on tunable MgZnO barriers allow effective balancing of TMR ratio and RA value. In this way spin-dependent transport properties can be controlled, a key challenge for the development of spintronic devices.

  17. Compressibility of the high-pressure rocksalt phase of ZnO

    DEFF Research Database (Denmark)

    Recio, J.M.; Blanco, M.A.; Luana, V.

    1998-01-01

    We report the results of a combined experimental and theoretical investigation on the stability and the volume behavior under hydrostatic pressure of the rocksalt (B1) phase of ZnO. Synchrotron-radiation x-ray powder-diffraction data are obtained from 0 to 30 GPa. Static simulations of the ZnO B1...... phase are performed using the ab initio perturbed ion method and the local and nonlocal approximations to the density-functional theory. After the pressure induced transition from the wurtzite phase, we have found that a large fraction of the B1 high-pressure phase is retained when pressure is released....... The metastability of this ZnO polymorph is confirmed through the theoretical evaluation of the Hessian eigenvalues of a nine-parameter potential energy surface. This allows us to treat the experimental and theoretical pressure-volume data on an equal basis. In both cases, we have obtained values of the bulk modulus...

  18. Superconductivity of Rock-Salt Structure LaO Epitaxial Thin Film.

    Science.gov (United States)

    Kaminaga, Kenichi; Oka, Daichi; Hasegawa, Tetsuya; Fukumura, Tomoteru

    2018-06-06

    We report a superconducting transition in a LaO epitaxial thin film with the superconducting transition onset temperature ( T c ) at around 5 K. This T c is higher than those of other lanthanum monochalcogenides and opposite to their chemical trend: T c = 0.84, 1.02, and 1.48 K for LaX (X = S, Se, Te), respectively. The carrier control resulted in a dome-shaped T c as a function of electron carrier density. In addition, the T c was significantly sensitive to epitaxial strain in spite of the highly symmetric crystal structure. This rock-salt superconducting LaO could be a building block to design novel superlattice superconductors.

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

    Energy Technology Data Exchange (ETDEWEB)

    Jimenez, J.; Ederer, D.L.; Shu, T. [Tulane Univ., New Orleans, LA (United States)] [and others

    1997-04-01

    The transition metal compounds form a very interesting and important set of materials. The diversity arises from the many states of ionization the transition elements may take when forming compounds. This variety provides ample opportunity for a large class of materials to have a vast range of electronic and magnetic properties. The x-ray spectroscopy of the transition elements is especially interesting because they have unfilled d bands that are at the bottom of the conduction band with atomic like structure. This group embarked on the systematic study of transition metal sulfides and oxides. As an example of the type of spectra observed in some of these compounds they have chosen to showcase the L{sub II, III} emission and Raman scattering in some titanium compounds obtained by photon excitation.

  20. Nanostructure sensitization of transition metal oxides for visible-light photocatalysis

    Directory of Open Access Journals (Sweden)

    Hongjun Chen

    2014-05-01

    Full Text Available To better utilize the sunlight for efficient solar energy conversion, the research on visible-light active photocatalysts has recently attracted a lot of interest. The photosensitization of transition metal oxides is a promising approach for achieving effective visible-light photocatalysis. This review article primarily discusses the recent progress in the realm of a variety of nanostructured photosensitizers such as quantum dots, plasmonic metal nanostructures, and carbon nanostructures for coupling with wide-bandgap transition metal oxides to design better visible-light active photocatalysts. The underlying mechanisms of the composite photocatalysts, e.g., the light-induced charge separation and the subsequent visible-light photocatalytic reaction processes in environmental remediation and solar fuel generation fields, are also introduced. A brief outlook on the nanostructure photosensitization is also given.

  1. Holey two-dimensional transition metal oxide nanosheets for efficient energy storage

    Science.gov (United States)

    Peng, Lele; Xiong, Pan; Ma, Lu; Yuan, Yifei; Zhu, Yue; Chen, Dahong; Luo, Xiangyi; Lu, Jun; Amine, Khalil; Yu, Guihua

    2017-04-01

    Transition metal oxide nanomaterials are promising electrodes for alkali-ion batteries owing to their distinct reaction mechanism, abundant active sites and shortened ion diffusion distance. However, detailed conversion reaction processes in terms of the oxidation state evolution and chemical/mechanical stability of the electrodes are still poorly understood. Herein we explore a general synthetic strategy for versatile synthesis of various holey transition metal oxide nanosheets with adjustable hole sizes that enable greatly enhanced alkali-ion storage properties. We employ in-situ transmission electron microscopy and operando X-ray absorption structures to study the mechanical properties, morphology evolution and oxidation state changes during electrochemical processes. We find that these holey oxide nanosheets exhibit strong mechanical stability inherited from graphene oxide, displaying minimal structural changes during lithiation/delithiation processes. These holey oxide nanosheets represent a promising material platform for in-situ probing the electrochemical processes, and could open up opportunities in many energy storage and conversion systems.

  2. Enthalpies of Formation of Transition Metal Diborides: A First Principles Study

    Directory of Open Access Journals (Sweden)

    Catherine Colinet

    2015-11-01

    Full Text Available The enthalpies of formation of transition metals diborides in various structures have been obtained from density functional theory (DFT calculations in order to determine the ground state at T = 0 K and p = 0. The evolution of the enthalpies of formation along the 3D, 4D, and 5D series has been correlated to the considered crystal structures. In the whole, the calculated values of the enthalpies of formation of the diborides in their ground state are in good agreement with the experimental ones when available. The calculated values of the lattice parameters at T = 0 K of the ground state agree well with the experimental values. The total and partial electronic densities of states have been computed. Special features of the transition metal electronic partial density of states have been evidenced and correlated to the local environment of the atoms.

  3. Recombination of charge carriers on radiation-induced defects in silicon doped by transition metals impurities

    CERN Document Server

    Kazakevich, L A

    2003-01-01

    It has been studied the peculiarities of recombination of nonequilibrium charge carriers on radiation-induced defects in received according to Czochralski method p-silicon (p approx 3 - 20 Ohm centre dot cm), doped by one of the impurities of transition metals of the IV-th group of periodic table (titanium, zirconium, hafnium). Experimental results are obtained out of the analysis of temperature and injection dependence of the life time of charge carriers. The results are explained taking into consideration the influences of elastic stress fields created by the aggregates of transition metals atoms on space distribution over the crystal of oxygen and carbon background impurities as well as on the migration of movable radiation-induced defects during irradiation. (authors).

  4. Characterization of Transition Metal Carbide Layers Synthesized by Thermo-reactive Diffusion Processes

    DEFF Research Database (Denmark)

    Laursen, Mads Brink; Fernandes, Frederico Augusto Pires; Christiansen, Thomas Lundin

    2015-01-01

    . In this study halide-activated pack cementation techniques were used on tool steel Vanadis 6 and martensitic stainless steel AISI 420 in order to produce hard layers of titanium carbide (TiC), vanadium carbide (V8C7) and chromium carbides (Cr23C6 and Cr7C3). Surface layers were characterized by scanning......Hard wear resistant surface layers of transition metal carbides can be produced by thermo-reactive diffusion processes where interstitial elements from a steel substrate together with external sources of transition metals (Ti, V, Cr etc.) form hard carbide and/or nitride layers at the steel surface...... electron microscopy, X-ray diffraction and Vickers hardness testing. The study shows that porosityfree, homogenous and very hard surface layers can be produced by thermo-reactive diffusion processes. The carbon availability of the substrate influences thickness of obtained layers, as Vanadis 6 tool steel...

  5. Electronic structures and valence band splittings of transition metals doped GaNs

    International Nuclear Information System (INIS)

    Lee, Seung-Cheol; Lee, Kwang-Ryeol; Lee, Kyu-Hwan

    2007-01-01

    For a practical viewpoint, presence of spin splitting of valence band in host semiconductors by the doping of transition metal (TM) ions is an essential property when designing a diluted magnetic semiconductors (DMS) material. The first principle calculations were performed on the electronic and magnetic structure of 3d transition metal doped GaN. V, Cr, and Mn doped GaNs could not be candidates for DMS materials since most of their magnetic moments is concentrated on the TM ions and the splittings of valence band were negligible. In the cases of Fe, Co, Ni, and Cu doped GaNs, on the contrary, long-ranged spin splitting of valence band was found, which could be candidates for DMS materials

  6. The importance of atomic and molecular correlation on the bonding in transition metal compounds

    Science.gov (United States)

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

    1986-01-01

    The determination of accurate spectroscopic parameters for molecular systems containing transition metal atoms is shown to require extensive data sets and a high level correlation treatment, and techniques and their limitations are considered. Extensive results reported on the transition metal atoms, hydrides, oxides, and dimers makes possible the design of a calculation to correctly describe the mixing of different atomic asymptotes, and to give a correct balance between molecular bonding and exchange interactions. Examples considered include the dipole moment of the 2Delta state of NiH, which can help determine the mixture of 3d(8)4s(2) and 3d(9)4s(1) in the NiH wavefunction, and the bonding in CrO, where an equivalent description of the relative energies associated with the Cr 3d-3d atomic exchange and the Cr-O bond is important.

  7. Modeling Dzyaloshinskii-Moriya Interaction at Transition Metal Interfaces: Constrained Moment versus Generalized Bloch Theorem

    KAUST Repository

    Dong, Yao-Jun; Belabbes, Abderrezak; Manchon, Aurelien

    2017-01-01

    Dzyaloshinskii-Moriya interaction (DMI) at Pt/Co interfaces is investigated theoretically using two different first principles methods. The first one uses the constrained moment method to build a spin spiral in real space, while the second method uses the generalized Bloch theorem approach to construct a spin spiral in reciprocal space. We show that although the two methods produce an overall similar total DMI energy, the dependence of DMI as a function of the spin spiral wavelength is dramatically different. We suggest that long-range magnetic interactions, that determine itinerant magnetism in transition metals, are responsible for this discrepancy. We conclude that the generalized Bloch theorem approach is more adapted to model DMI in transition metal systems, where magnetism is delocalized, while the constrained moment approach is mostly applicable to weak or insulating magnets, where magnetism is localized.

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

    DEFF Research Database (Denmark)

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

    2008-01-01

    This paper presents a detailed analysis of the steam reforming process front first-principles calculations, supported by insight from experimental investigations. In the present work we employ recently recognised scaling relationships for adsorption energies of simple molecules adsorbed at pure...... metal Surfaces to develop an overview of the steam reforming process catalyzed by a range of transition metal surfaces. By combining scaling relationships with thermodynamic and kinetic analysis, we show that it is possible to determine the reactivity trends of the pure metals for methane steam...... in situ TEM measurements under a hydrogen atmosphere. The overall agreement between theory and experiment (at 773 K, 1 bar pressure and 10% conversion) is found to be excellent with Ru and Rh being the most active pure transition metals for methane steam reforming, while Ni, Ir, Pt, and Pd...

  9. Modeling Dzyaloshinskii-Moriya Interaction at Transition Metal Interfaces: Constrained Moment versus Generalized Bloch Theorem

    KAUST Repository

    Dong, Yao-Jun

    2017-10-29

    Dzyaloshinskii-Moriya interaction (DMI) at Pt/Co interfaces is investigated theoretically using two different first principles methods. The first one uses the constrained moment method to build a spin spiral in real space, while the second method uses the generalized Bloch theorem approach to construct a spin spiral in reciprocal space. We show that although the two methods produce an overall similar total DMI energy, the dependence of DMI as a function of the spin spiral wavelength is dramatically different. We suggest that long-range magnetic interactions, that determine itinerant magnetism in transition metals, are responsible for this discrepancy. We conclude that the generalized Bloch theorem approach is more adapted to model DMI in transition metal systems, where magnetism is delocalized, while the constrained moment approach is mostly applicable to weak or insulating magnets, where magnetism is localized.

  10. Organic cofactors participated more frequently than transition metals in redox reactions of primitive proteins.

    Science.gov (United States)

    Ji, Hong-Fang; Chen, Lei; Zhang, Hong-Yu

    2008-08-01

    Protein redox reactions are one of the most basic and important biochemical actions. As amino acids are weak redox mediators, most protein redox functions are undertaken by protein cofactors, which include organic ligands and transition metal ions. Since both kinds of redox cofactors were available in the pre-protein RNA world, it is challenging to explore which one was more involved in redox processes of primitive proteins? In this paper, using an examination of the redox cofactor usage of putative ancient proteins, we infer that organic ligands participated more frequently than transition metals in redox reactions of primitive proteins, at least as protein cofactors. This is further supported by the relative abundance of amino acids in the primordial world. Supplementary material for this article can be found on the BioEssays website. (c) 2008 Wiley Periodicals, Inc.

  11. Studies of hyperfine magnetic fields in transition metals by radioactive ion implantation

    International Nuclear Information System (INIS)

    Kawase, Yoichi; Uehara, Shin-ichi; Nasu, Saburo; Ni Xinbo.

    1994-01-01

    In order to investigate hyperfine magnetic fields in transition metals by a time-differential perturbed angular correlation (TDPAC) technique, radioactive probes of 140 Cs obtained by KUR-ISOL have been implanted on transition metals of Fe, Ni and Co. Lamor precessions of 140 Ce used as a probe nucleus have been observed clearly and the hyperfine fields have been determined precisely corresponding to implanted sites in host metal. The irradiation effects caused by implantation have been examined by annealing the irradiated specimen at about 723 K. Some of the Lamor precessions have disappeared by the annealing. Discussions have been made on the occupied sites after implantation and the recovery process of induced damages by annealing. (author)

  12. Effect of alloying on elastic properties of ZrN based transition metal nitride alloys

    KAUST Repository

    Kanoun, Mohammed; Goumri-Said, Souraya

    2014-01-01

    We report the effect of composition and metal sublattice substitutional element on the structural, elastic and electronic properties of ternary transition metal nitrides Zr1-xMxN with M=Al, Ti, Hf, V, Nb, W and Mo. The analysis of the elastic constants, bulk modulus, shear modulus, Young's modulus, and Poisson's ratio provides insights regarding the mechanical behavior of Zr1-xMxN. We predict that ternary alloys are more ductile compared to their parent binary compounds. The revealed trend in the mechanical behavior might help for experimentalists on the ability of tuning the mechanical properties during the alloying process by varying the concentration of the transition metal. © 2014 Elsevier B.V.

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

    Science.gov (United States)

    Maksoed, Wh-

    2016-11-01

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

  14. Reactor prospects of muon-catalyzed fusion of deuterium and tritium concentrated in transition metals

    International Nuclear Information System (INIS)

    Stacey, W.M. Jr.

    1989-01-01

    It is conjectured that the number of fusion events catalyzed by a single muon is orders of magnitude greater for deuterium and tritium concentrated in a transition metal than in gaseous form and that the recent observation of 2.5-MeV neutrons from a D 2 O electrolytic cell with palladium and titanium cathodes can thereby be interpreted in terms of cosmic muon-catalyzed deuterium-deuterium fusion. This suggests a new fusion reactor reactor consisting of deuterium and tritium concentrated in transition metal fuel elements in a fusion core that surrounds an accelerator-produced muon source. The feasibility of net energy production in such a reactor is established in terms of requirements on the number of fusion events catalyzed per muon. The technological implications for a power reactor based on this concept are examined. The potential of such a concept as a neutron source for materials testing and tritium and plutonium production is briefly discussed

  15. Characterization of Transition-Metal Oxide Deposition on Carbon Electrodes of a Supercapacitor

    Directory of Open Access Journals (Sweden)

    Ying-Chung Chen

    2016-12-01

    Full Text Available In order to fabricate the composite electrodes of a supercapacitor, transition-metal oxide materials NiO and WO3 were deposited on carbon electrodes by electron beam evaporation. The influences of various transition-metal oxides, scan rates of cyclic voltammograms (CVs, and galvanostatic charge/discharge tests on the characteristics of supercapacitor were studied. The charge/discharge efficiency and the lifetime of the composite electrodes were also investigated. It was found that the composite electrodes exhibited more favorable capacitance properties than those of the carbon electrodes at high scan rates. The results revealed the promotion of the capacitance property of the supercapacitor with composite electrode and the improving of the decay property in capacitance at high scan rate. In addition, the charge/discharge efficiency is close to 100% after 5000 cycles, and the composite electrode retains strong adhesion between the electrode material and the substrate.

  16. Recent advances in transition-metal-catalyzed intermolecular carbomagnesiation and carbozincation

    Directory of Open Access Journals (Sweden)

    Kei Murakami

    2013-02-01

    Full Text Available Carbomagnesiation and carbozincation reactions are efficient and direct routes to prepare complex and stereodefined organomagnesium and organozinc reagents. However, carbon–carbon unsaturated bonds are generally unreactive toward organomagnesium and organozinc reagents. Thus, transition metals were employed to accomplish the carbometalation involving wide varieties of substrates and reagents. Recent advances of transition-metal-catalyzed carbomagnesiation and carbozincation reactions are reviewed in this article. The contents are separated into five sections: carbomagnesiation and carbozincation of (1 alkynes bearing an electron-withdrawing group; (2 alkynes bearing a directing group; (3 strained cyclopropenes; (4 unactivated alkynes or alkenes; and (5 substrates that have two carbon–carbon unsaturated bonds (allenes, dienes, enynes, or diynes.

  17. New trends in the optical and electronic applications of polymers containing transition-metal complexes.

    Science.gov (United States)

    Liu, Shu-Juan; Chen, Yang; Xu, Wen-Juan; Zhao, Qiang; Huang, Wei

    2012-04-13

    Polymers containing transition-metal complexes exhibit excellent optical and electronic properties, which are different from those of polymers with a pure organic skeleton and combine the advantages of both polymers and metal complexes. Hence, research about this class of polymers has attracted more and more interest in recent years. Up to now, a number of novel polymers containing transition-metal complexes have been exploited, and significant advances in their optical and electronic applications have been achieved. In this article, we summarize some new research trends in the applications of this important class of optoelectronic polymers, such as chemo/biosensors, electronic memory devices and photovoltaic devices. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. On the valence state of Yb and Ce in transition metal intermetallic compounds

    International Nuclear Information System (INIS)

    Boer, F.R. de; Dijkman, W.H.; Mattens, W.C.M.

    1979-01-01

    In the pure state Yb is a divalent metal, similar to Ca; in alloys it can become trivalent like the majority of the rare earth metals. Using a value of 38 kJ (mol Yb) -1 for the energy difference between divalent and trivalent Yb metal and using model calculations for the heat of formation of intermetallic compounds, the authors are able to account for the existing information on the valence state of Yb in transition metal compounds. A similar analysis of compounds of Ce with transition metals shows that a model in which the 4f electron is treated as a core electron, i.e. being absent in the tetravalent modification of Ce and present as a fully localized electron in trivalent Ce, does not apply. (Auth.)

  19. Systematic prediction of high-pressure melting curves of transition metals

    International Nuclear Information System (INIS)

    Hieu, Ho Khac

    2014-01-01

    The pressure effects on melting temperatures of transition metals have been studied based on the combination of the modified Lindemann criterion with statistical moment method in quantum statistical mechanics. Numerical calculations have been performed for five transition metals including Cu, Pd, Pt, Ni, and Mn up to pressure 100 GPa. Our results are in good and reasonable agreements with available experimental data. This approach gives us a relatively simple method for qualitatively calculating high-pressure melting temperature. Moreover, it can be used to verify future experimental and theoretical works. This research proposes the potential of the combination of statistical moment method and the modified Lindemann criterion on predicting high-pressure melting of materials.

  20. Rigid muffin-tin approximation for the electron-phonon interaction in transition metals

    International Nuclear Information System (INIS)

    Butler, W.H.

    1980-01-01

    Progress in calculating the electron-phonon parameters of transition metals has been based on either the rigid muffin-tin approximation (RMTA) or the fitted modified tight-binding approximation (FMTBA). The RMTA has been shown to be remarkably accurate for average electron-phonon properties, but there are indications that RMTA matrix elements may be too small at low momentum transfer. An attempt is made to demonstrate these assertions concerning the accuracy of RMTA and the numerous electron-phonon calculations are placed in a broader perspective by a demonstration of how they can be used to explain the trends in the strength of the electron-phonon coupling among the transition metals and the A-15 compounds

  1. Facile synthesis of nanostructured transition metal oxides as electrodes for Li-ion batteries

    Science.gov (United States)

    Opra, Denis P.; Gnedenkov, Sergey V.; Sokolov, Alexander A.; Minaev, Alexander N.; Kuryavyi, Valery G.; Sinebryukhov, Sergey L.

    2017-09-01

    At all times, energy storage is one of the greatest scientific challenge. Recently, Li-ion batteries are under special attention due to high working voltage, long cycle life, low self-discharge, reliability, no-memory effect. However, commercial LIBs usage in medium- and large-scale energy storage are limited by the capacity of lithiated metal oxide cathode and unsafety of graphite anode at high-rate charge. In this way, new electrode materials with higher electrochemical performance should be designed to satisfy a requirement in both energy and power. As it known, nanostructured transition metal oxides are promising electrode materials because of their elevated specific capacity and high potential vs. Li/Li+. In this work, the perspective of an original facile technique of pulsed high-voltage plasma discharge in synthesis of nanostructured transition metal oxides as electrodes for lithium-ion batteries has been demonstrated.

  2. Nano Transition Metal Sulfide Catalyst for Solvolysis Liquefaction of Soda Lignin

    International Nuclear Information System (INIS)

    Fei-Ling, P.; Chin-Hua, C.; Sarani Zakaria; Soon-Keong, N.; Tze-Khong, L.

    2011-01-01

    Solvolysis liquefaction of soda lignin in the presence of various transition metal sulfide catalysts was studied to investigate the catalyst effects on the oil and gas yields, conversion rate and higher heating value (HHV) of oil. Nano sized copper sulfide, iron sulfide and molybdenum sulfide were successfully synthesized via a simple hydrothermal method under reaction temperature 200 degree Celsius for 90 min. The addition of transition metal sulfide based catalysts (CuS, MoS 2 and FeS 2 ) enhanced both production of the oils and gas and the higher heating value (HHV) of oil products. A high oil and gas yields of 82.1 % and 2890 cm 3 was obtained with MoS 2 at 250 degree Celsius for 60 min. Elemental analyses for the oils revealed that the liquid products have much higher heating values than the crude soda lignin powder. (author)

  3. Impact of Interfacial Defects on the Properties of Monolayer Transition Metal Dichalcogenide Lateral Heterojunctions

    KAUST Repository

    Cao, Zhen

    2017-03-25

    We explored the impact of interfacial defects on the stability and optoelectronic properties of monolayer transition metal dichalcogenide lateral heterojunctions using a density functional theory approach. As a prototype, we focused on the MoS2-WSe2 system and found that even a random alloy-like interface with a width of less than 1 nm has only a minimal impact on the band gap and alignment compared to the defect-less interface. The largest impact is on the evolution of the electrostatic potential across the monolayer. Similar to defect-less interfaces, a small number of defects results in an electrostatic potential profile with a sharp change at the interface, which facilitates exciton dissociation. Differently, a large number of defects results in an electrostatic potential profile switching smoothly across the interface, which is expected to reduce the capability of the heterojunction to promote exciton dissociation. These results are generalizable to other transition metal dichalcogenide lateral heterojunctions.

  4. Dielectric matrix, dynamical matrix and phonon dispersion in hcp transition metal scandium

    International Nuclear Information System (INIS)

    Singh, Joginder; Singh, Natthi; Prakash, S.

    1976-01-01

    Complete dielectric matrix is evaluated for hcp transition metal scandium using the non-interacting s- and d-band model. The local field corrections which are consequence of the non-diagonal part of the dielectric matrix are calculated explicitly. The free electron approximation is used for the s-electrons and the simple tight-binding approximation is used for the d-electrons. The theory developed by Singh and others is used to invert the dielectric matrix and the explicit expressions for the dynamical matrix are obtained. The phonon dispersion relations are investigated by using the renormalized Animalu transition metal model potential (TMMP) for bare ion potential. The contribution due to non-central forces which arise due to local fields is found to be 20%. The results are found in resonably good agreement with the experimental values. (author)

  5. First-principles study of hydrogen diffusion in transition metal Rhodium

    International Nuclear Information System (INIS)

    Bao, Wulijibilige; Cui, Xin; Wang, Zhi-Ping

    2015-01-01

    In this study, the diffuse pattern and path of hydrogen in transition metal rhodium are investigated by the first-principles calculations. Density functional theory is used to calculate the system energies of hydrogen atom occupying different positions in rhodium crystal lattice. The results indicate that the most stable position of hydrogen atom in rhodium crystal lattice locates at the octahedral interstice, and the tetrahedral interstice is the second stable site. The activation barrier energy for the diffusion of atomic hydrogen in transition metal rhodium is quantified by determining the most favorable path, i.e., the minimum-energy pathway for diffusion, that is the indirect octahedral-tetrahedral-octahedral (O-T-O) pathway, and the activation energy is 0.8345eV

  6. Effect of alloying on elastic properties of ZrN based transition metal nitride alloys

    KAUST Repository

    Kanoun, Mohammed

    2014-09-01

    We report the effect of composition and metal sublattice substitutional element on the structural, elastic and electronic properties of ternary transition metal nitrides Zr1-xMxN with M=Al, Ti, Hf, V, Nb, W and Mo. The analysis of the elastic constants, bulk modulus, shear modulus, Young\\'s modulus, and Poisson\\'s ratio provides insights regarding the mechanical behavior of Zr1-xMxN. We predict that ternary alloys are more ductile compared to their parent binary compounds. The revealed trend in the mechanical behavior might help for experimentalists on the ability of tuning the mechanical properties during the alloying process by varying the concentration of the transition metal. © 2014 Elsevier B.V.

  7. Synthesis of Binary Magnesium-Transition Metal Oxides via Inverse Coprecipitation

    Science.gov (United States)

    Yagi, Shunsuke; Ichikawa, Yuya; Yamada, Ikuya; Doi, Takayuki; Ichitsubo, Tetsu; Matsubara, Eiichiro

    2013-02-01

    Synthesis of binary magnesium-transition metal oxides, MgM2O4 (M: Cr, Mn, Fe, Co) and MgNiO2, was performed by calcination at relatively low temperatures of 500 and 750 °C for 24 h through inverse coprecipitation of carbonate hydroxide precursors. The important roles of the precipitation agent, sodium carbonate, were clarified by considering equilibria in an aqueous solution. The structure parameters of the obtained binary magnesium-transition metal oxide powders, specifically the occupancy of atomic sites, were evaluated from synchrotron X-ray diffraction (XRD) profiles by Rietveld refinement in addition to the magnetic properties at room temperature. The present work provides general guidelines for low-cost and high-volume synthesis of complex oxides, which are easily decomposed at high temperatures.

  8. Hard X-ray photoemission spectroscopy of transition-metal oxide thin films and interfaces

    International Nuclear Information System (INIS)

    Wadati, H.; Fujimori, A.

    2013-01-01

    Highlights: •Photoemission spectroscopy is a powerful technique to study the electronic structures of transition-metal oxides. •Hard X-ray photoemission spectroscopy (HXPES) is a new type of photoemission spectroscopy which can probe bulk states. •HXPES is very suitable for studying oxide thin films such as the composition dependence and the film thickness dependence. -- Abstract: Photoemission spectroscopy is a powerful experimental technique to study the electronic structures of solids, especially of transition-metal oxides. Recently, hard X-ray photoemission spectroscopy (HXPES) has emerged as a more relevant experimental technique to obtain clear information about bulk states. Here, we describe how HXPES can be conveniently applied to study the interesting subjects on oxide thin films such as the composition dependence and the film thickness dependence of the electronic structures and the interfacial electronic structure of multilayers

  9. Photo-modulation of the spin Hall conductivity of mono-layer transition metal dichalcogenides

    Energy Technology Data Exchange (ETDEWEB)

    Sengupta, Parijat; Bellotti, Enrico [Department of Electrical and Computer Engineering, Boston University, Boston, MA 02215 (United States)

    2016-05-23

    We report on a possible optical tuning of the spin Hall conductivity in mono-layer transition metal dichalcogenides. Light beams of frequencies much higher than the energy scale of the system (the off-resonant condition) do not excite electrons but rearrange the band structure. The rearrangement is quantitatively established using the Floquet formalism. For such a system of mono-layer transition metal dichalcogenides, the spin Hall conductivity (calculated with the Kubo expression in presence of disorder) exhibits a drop at higher frequencies and lower intensities. Finally, we compare the spin Hall conductivity of the higher spin-orbit coupled WSe{sub 2} to MoS{sub 2}; the spin Hall conductivity of WSe{sub 2} was found to be larger.

  10. Rigid muffin-tin approximation for the electron-phonon interaction in transition metals

    Energy Technology Data Exchange (ETDEWEB)

    Butler, W.H.

    1980-01-01

    Progress in calculating the electron-phonon parameters of transition metals has been based on either the rigid muffin-tin approximation (RMTA) or the fitted modified tight-binding approximation (FMTBA). The RMTA has been shown to be remarkably accurate for average electron-phonon properties, but there are indications that RMTA matrix elements may be too small at low momentum transfer. An attempt is made to demonstrate these assertions concerning the accuracy of RMTA and the numerous electron-phonon calculations are placed in a broader perspective by a demonstration of how they can be used to explain the trends in the strength of the electron-phonon coupling among the transition metals and the A-15 compounds. (GHT)

  11. Structure and properties of transition metal-metalloid glasses based on refractory metals

    International Nuclear Information System (INIS)

    Johnson, W.L.; Williams, A.R.

    1979-01-01

    The structure and properties of several new transition metal-metalloid (TM/sub 1-x/M/sub x/) metallic glasses based on refractory transition metals (e.g. Mo, W, Ru etc.) have been systemically investigated as a function of composition. The structure of the alloys has been investigated by x-ray diffraction methods and measurements of superconducting properties, electrical resistivity, density, hardness, and mechanical behavior were made. These data are used in developing a novel description of the structure of TM/sub 1-x/M/sub x/ glasses. The experimental evidence suggests that an ideal amorphous phase forms at a specific composition x/sub c/ and that this phase has a well defined atomic short range order. For metallic glasses having x x/sub c/. This novel picture can explain the variation of many properties of these glasses with metalloid concentration

  12. Synergy between experimental and theoretical methods in the exploration of homogeneous transition metal catalysis

    DEFF Research Database (Denmark)

    Lupp, Daniel; Christensen, Niels Johan; Fristrup, Peter

    2014-01-01

    n this Perspective, we will focus on the use of both experimental and theoretical methods in the exploration of reaction mechanisms in homogeneous transition metal catalysis. We briefly introduce the use of Hammett studies and kinetic isotope effects (KIE). Both of these techniques can be complem......n this Perspective, we will focus on the use of both experimental and theoretical methods in the exploration of reaction mechanisms in homogeneous transition metal catalysis. We briefly introduce the use of Hammett studies and kinetic isotope effects (KIE). Both of these techniques can...... be complemented by computational chemistry – in particular in cases where interpretation of the experimental results is not straightforward. The good correspondence between experiment and theory is only possible due to recent advances within the applied theoretical framework. We therefore also highlight...

  13. On the behavior of Bronsted-Evans-Polanyi Relations for Transition Metal Oxides

    Energy Technology Data Exchange (ETDEWEB)

    Vojvodic, Aleksandra

    2011-08-22

    Versatile Broensted-Evans-Polanyi (BEP) relations are found from density functional theory for a wide range of transition metal oxides including rutiles and perovskites. For oxides, the relation depends on the type of oxide, the active site and the dissociating molecule. The slope of the BEP relation is strongly coupled to the adsorbate geometry in the transition state. If it is final state-like the dissociative chemisorption energy can be considered as a descriptor for the dissociation. If it is initial state-like, on the other hand, the dissociative chemisorption energy is not suitable as descriptor for the dissociation. Dissociation of molecules with strong intramolecular bonds belong to the former and molecules with weak intramolecular bonds to the latter group. We show, for the prototype system La-perovskites, that there is a 'cyclic' behavior in the transition state characteristics upon change of the active transition metal of the oxide.

  14. Recent progress in transition-metal-catalyzed reduction of molecular dinitrogen under ambient reaction conditions.

    Science.gov (United States)

    Nishibayashi, Yoshiaki

    2015-10-05

    This paper describes our recent progress in catalytic nitrogen fixation by using transition-metal-dinitrogen complexes as catalysts. Two reaction systems for the catalytic transformation of molecular dinitrogen into ammonia and its equivalent such as silylamine under ambient reaction conditions have been achieved by the molybdenum-, iron-, and cobalt-dinitrogen complexes as catalysts. Many new findings presented here may provide new access to the development of economical nitrogen fixation in place of the Haber-Bosch process.

  15. A theoretical study of the structure and stability of borohydride on 3d transition metals

    Science.gov (United States)

    Arevalo, Ryan Lacdao; Escaño, Mary Clare Sison; Gyenge, Elod; Kasai, Hideaki

    2012-12-01

    The adsorption of borohydride on 3d transition metals (Cr, Mn, Fe, Co, Ni and Cu) was studied using first principles calculations within spin-polarized density functional theory. Magnetic effect on the stability of borohydride is noted. Molecular adsorption is favorable on Co, Ni and Cu, which is characterized by the strong s-dzz hybridization of the adsorbate-substrate states. Dissociated adsorption structure yielding one or two H adatom fragments on the surface is observed for Cr, Mn and Fe.

  16. X-ray Absorption Study of Graphene Oxide and Transition Metal Oxide Nanocomposites

    OpenAIRE

    Gandhiraman, Ram P.; Nordlund, Dennis; Javier, Cristina; Koehne, Jessica E.; Chen, Bin; Meyyappan, M.

    2014-01-01

    The surface properties of the electrode materials play a crucial role in determining the performance and efficiency of energy storage devices. Graphene oxide and nanostructures of 3d transition metal oxides were synthesized for construction of electrodes in supercapacitors, and the electronic structure and oxidation states were probed using near-edge X-ray absorption fine structure. Understanding the chemistry of graphene oxide would provide valuable insight into its reactivity and properties...

  17. Spatially resolved analysis of resistive switching in transition metal oxide thin films

    OpenAIRE

    Landrock, Ruth Christine

    2011-01-01

    The quest for a non-volatile, small and fast computer memory calls for new memory concepts. Resistive Random Access Memory (ReRAM) based on transition metal oxides is an attractive candidate for future computer memories, because it has the potential of a low power consumption combined with fast switching speeds and good scalability. While in general, switching in such systems relies on a local redox reaction, many details are still unknown or under intense discussion. Especially the geometric...

  18. Etymology of transition metal biomolecules as a learning aid in Biological Chemistry

    International Nuclear Information System (INIS)

    Silva, Jose A.L. da

    2013-01-01

    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)

  19. Local Symmetry and Domain Patterns: Ordering Phenomena in Transition-Metal Oxides

    OpenAIRE

    Buchholz, Marcel

    2013-01-01

    Transition-metal oxides (TMOs) show rich phase diagrams with various magnetic and electronic phases that arise from the complex interplay between spin, charge, orbital, and lattice degrees of freedom. The most prominent class of materials, which has attracted a lot of attention in the last decades, are probably high-temperature superconductors (HTS), in which the resitivity drops to zero below a critical temperature. Further examples are different kind of complex ordering phenomena, for examp...

  20. Calculations of hyperfine interactions in transition metal compounds in the local density approximation

    International Nuclear Information System (INIS)

    Guenzburger, D.J.R.

    1982-01-01

    A survey is made of some theoretical calculations of electrostatic and magnetic hyperfine interactions in transition metal compounds and complex irons. The molecular orbital methods considered are the Multiple Scattering and Discrete Variational, in which the local Xα approximation for the exchange interaction is employed. Emphasis is given to the qualitative informations, derived from the calculations, relating the hyperfine parameters to characteristics of the chemical bonds. (Author) [pt

  1. Graphene on transition-metal dichalcogenides: a platform for proximity spin-orbit physics and optospintronics

    OpenAIRE

    Gmitra, Martin; Fabian, Jaroslav

    2015-01-01

    Hybrids of graphene and two dimensional transition metal dichalcogenides (TMDC) have the potential to bring graphene spintronics to the next level. As we show here by performing first-principles calculations of graphene on monolayer MoS$_2$, there are several advantages of such hybrids over pristine graphene. First, Dirac electrons in graphene exhibit a giant global proximity spin-orbit coupling, without compromising the semimetallic character of the whole system at zero field. Remarkably, th...

  2. Extended Moment Formation in Monolayer WS2 Doped with 3d Transition-Metals

    KAUST Repository

    Singh, Nirpendra

    2016-08-30

    First-principles calculations with onsite Coulomb interaction and spin-orbit coupling are used to investigate the electronic structure of monolayer WS2 doped substitutionally with 3d transition-metals. While neither W vacancies nor strain induce spin polarization, we demonstrate an unprecedented tendency to extended moment formation under doping. The extended magnetic moments are characterized by dopant-specific spin density patterns with rich structural features involving the nearest neighbor W and S atoms.

  3. Transition Metal Chelator Induces Progesterone Production in Mouse Cumulus-Oocyte Complexes and Corpora Lutea.

    Science.gov (United States)

    Tian, X; Anthony, K; Diaz, Francisco J

    2017-04-01

    Progesterone production is upregulated in granulosa cells (cumulus and mural) after the LH surge, but the intra-follicular mechanisms regulating this transition are not completely known. Recent findings show that the transition metal chelator, N,N,N',N'-tetrakis-(2-pyridylmethyl)-ethylenediamine (TPEN), impairs ovarian function. In this study, we provide evidence that chelating transition metals, including zinc, enhances progesterone production. The findings show that TPEN (transition metal chelator) increases abundance of Cyp11a1 and Star messenger RNA (mRNA) between 8- and 20-fold and progesterone production more than 3-fold in cultured cumulus-oocyte complexes (COC). Feeding a zinc-deficient diet for 10 days, but not 3 days, increased Star, Hsd3b, and prostaglandin F2 alpha receptor (Ptgfr) mRNA ~2.5-fold, suggesting that the effect of TPEN is through modulation of zinc availability. Progesterone from cumulus cells promotes oocyte developmental potential. Blocking progesterone production with epostane during maturation reduced subsequent blastocyst formation from 89 % in control to 18 % in epostane-treated complexes, but supplementation with progesterone restored blastocyst developmental potential to 94 %. Feeding a zinc-deficient diet for 5 days before ovulation did not affect the number of CL, STAR protein, or serum progesterone. However, incubating luteal tissue with TPEN increased abundance of Star, Hsd3b, and Ptgfr mRNA 2-3-fold and increased progesterone production 3-fold. TPEN is known to abolish SMAD2/3 signaling in cumulus cells. However, treatment of COC with the SMAD2/3 phosphorylation inhibitor, SB421542, did not by itself induce steroidogenic transcripts but did potentiate EGF-induced Star mRNA expression. Collectively, the results show that depletion of transition metals with TPEN acutely enhances progesterone biosynthesis in COC and luteal tissue.

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

    Science.gov (United States)

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

    2012-08-07

    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.

  5. Reaction of urea thiourea and their derivatives with tertiary phosphine transition metal halides

    International Nuclear Information System (INIS)

    Adam, Eltayeb Mahala

    2000-03-01

    This thesis describes preparation characterization and some properties of a number of new compounds such as (ph 3 p)2 ML where M= cobalt (11), nickel (11), and copper (11), and L= urea, thiourea, phenylthiourea, sym diphenylurea and sym diphenylthiourea.These compounds have been prepared according according to the reaction of dichloro bis (triphenylphosphine) transition metal with urea, thiourea or some of their derivative ligands in 1:1 molar ratio.The work in this thesis is divided into three section firstly:- In the introduction chapter part one includes general definitions of coordination chemistry and related compounds and abroad definition of transition elements.Part two includes the theoretical back ground about transition metal complexes having urea, thiourea or some of their substituted derivative ligands.Part two also discusses the type of bonding between these ligands and the transition metal atom.Secondly: Chapter two describes the general techniques followed in this work such as purification of solvents recrystallization, preparation of starting materials and also gives full detailed procedures of the preparation of a number of new compounds.Thirdly: Discussion with detailed in chapter three, the results of the research are presented the preparation and characterization of a number of new compounds isolated from reaction between urea, thiourea or some of their substituted derivatives and dichloro bis (triphenyl phosphine) transition metal complex giving a general formula (ph 3 )2ML where M=cobalt, nickel, and copper, and urea, thiourea or some of their substituted derivatives ligands. The products of these experiments have been identified using infrared spectra, melting points and molar conductance. The results obtained indicated that all the compounds forming the nitrogen to metal bonds leading to the formation of a four- membered chelate ring, they are relatively thermally stable compounds, and also these compounds are non-electrolytes.(Author)

  6. Approach to Multifunctional Device Platform with Epitaxial Graphene on Transition Metal Oxide (Postprint)

    Science.gov (United States)

    2015-09-23

    layers, respectively. 15. SUBJECT TERMS Heterostructures, two-dimensional materials, van der Waals interaction , 2D graphene, metal oxide (TiO2...sample holder with a 10.6 μ m CO2 IR laser . The laser output power was adjusted until the target temperature was reached. The temperature of the sample... Laser Deposited Transition- Metal Carbides for Field-Emission Cathode Coatings. ACS Appl. Mater. Interfaces 5, 9241–9246 (2013). 13. Swift, G. A

  7. Investigation of complexing ability of ionites with various groups to some heavy and transition metal ions

    Directory of Open Access Journals (Sweden)

    Yedil Yergozhin

    2013-05-01

    Full Text Available The physico-chemical and complexing properties of the sorbent based on chloromethylated styrene and divinylbenzene copolymer with nicotinamide groups and copolymers based on metacryloilaminobenzene acids with 2-methyl-5-vinylpyridineisomers are studied. By potentiometric titration method the constant of polyelectrolytes functional groups ionization, the composition and strength of the resulting complexes with ions of some heavy and transition metals are determined.

  8. Optimization of film synthesized rare earth transition metal permanent magnet systems

    International Nuclear Information System (INIS)

    Cadieu, F.J.

    1992-01-01

    Progress is reported in three areas: high coercivity Sm-Fe-Ti-V, Sm-Fe-Zr, and two element Sm-Fe Sm 5 (Fe,T) 17 type crystalline phases; ThMn 12 type pseudobinary SmFe 12-x T x (0≤x≤1.5); and sputter process control for the synthesis of precisely textured rare earth-transition metal magnetic films

  9. Adsorption and dissociation of dinitrogen on transition metal (Ta, W and Re) doped MgO surface

    KAUST Repository

    Yadav, Manoj Kumar

    2016-06-16

    The adsorption and dissociation of dinitrogen on transition metal (Ta, W and Re) doped MgO(100) surface has been studied employing density functional theory. It is found that all these transition metals (TM) on MgO(100) surface are capable of adsorbing dinitrogen (N2), however there is no dissociative adsorption of N2 on single transition metal dopant. When two TM atoms are doped on MgO(100) surface, dissociative adsorption of dinitrogen occurs in all the three cases. Whether the dissociation is spontaneous or is it associated with activation barrier depends on the orientation of N2 molecule approaching the dopant site.

  10. Coherent Control of Nanoscale Ballistic Currents in Transition Metal Dichalcogenide ReS2.

    Science.gov (United States)

    Cui, Qiannan; Zhao, Hui

    2015-04-28

    Transition metal dichalcogenides are predicted to outperform traditional semiconductors in ballistic devices with nanoscale channel lengths. So far, experimental studies on charge transport in transition metal dichalcogenides are limited to the diffusive regime. Here we show, using ReS2 as an example, all-optical injection, detection, and coherent control of ballistic currents. By utilizing quantum interference between one-photon and two-photon interband transition pathways, ballistic currents are injected in ReS2 thin film samples by a pair of femtosecond laser pulses. We find that the current decays on an ultrafast time scale, resulting in an electron transport of only a fraction of one nanometer. Following the relaxation of the initially injected momentum, backward motion of the electrons for about 1 ps is observed, driven by the Coulomb force from the oppositely moved holes. We also show that the injected current can be controlled by the phase of the laser pulses. These results demonstrate a new platform to study ballistic transport of nonequilibrium carriers in transition metal dichalcogenides.

  11. Structural characterisation of 1- and 2-dimensional transition metal polymers using powder neutron diffraction

    International Nuclear Information System (INIS)

    James, M.

    1999-01-01

    Powder neutron diffraction provides an alternate technique for the structural study of transition metal polymers and finds utility over standard X-ray methods in two significant ways. Firstly, due to a different instrument geometry, preferred orientation effects are removed from the system. The second advantage gained by utilising neutrons is that H atoms in the sample contribute much more to the nuclear scattering of the diffraction profile - allowing their atomic position to be accurately determined. In X-ray diffraction studies, where H atoms typically account for only ∼3-5% of the scattering from the sample, it is essentially impossible to refine their position in the molecular structure. The structures of several transition metal polymers have been determined using neutrons from the HIFAR reactor at ANSTO and the Powder Diffractometers HRPD and MRPD, along with Rietveld refinement methods. The 1-dimensional polymer dibromobis(thiazole)nickel(II) illustrated in the paper is characteristic of these types of systems which are comprised of transition metal centres bridged by halogen atoms with pendant amine side groups

  12. Ultra-high-rate pseudocapacitive energy storage in two-dimensional transition metal carbides

    Science.gov (United States)

    Lukatskaya, Maria R.; Kota, Sankalp; Lin, Zifeng; Zhao, Meng-Qiang; Shpigel, Netanel; Levi, Mikhael D.; Halim, Joseph; Taberna, Pierre-Louis; Barsoum, Michel W.; Simon, Patrice; Gogotsi, Yury

    2017-08-01

    The use of fast surface redox storage (pseudocapacitive) mechanisms can enable devices that store much more energy than electrical double-layer capacitors (EDLCs) and, unlike batteries, can do so quite rapidly. Yet, few pseudocapacitive transition metal oxides can provide a high power capability due to their low intrinsic electronic and ionic conductivity. Here we demonstrate that two-dimensional transition metal carbides (MXenes) can operate at rates exceeding those of conventional EDLCs, but still provide higher volumetric and areal capacitance than carbon, electrically conducting polymers or transition metal oxides. We applied two distinct designs for MXene electrode architectures with improved ion accessibility to redox-active sites. A macroporous Ti3C2Tx MXene film delivered up to 210 F g-1 at scan rates of 10 V s-1, surpassing the best carbon supercapacitors known. In contrast, we show that MXene hydrogels are able to deliver volumetric capacitance of ˜1,500 F cm-3 reaching the previously unmatched volumetric performance of RuO2.

  13. Complex band structures of transition metal dichalcogenide monolayers with spin–orbit coupling effects

    International Nuclear Information System (INIS)

    Szczęśniak, Dominik; Ennaoui, Ahmed; Ahzi, Saïd

    2016-01-01

    Recently, the transition metal dichalcogenides have attracted renewed attention due to the potential use of their low-dimensional forms in both nano- and opto-electronics. In such applications, the electronic and transport properties of monolayer transition metal dichalcogenides play a pivotal role. The present paper provides a new insight into these essential properties by studying the complex band structures of popular transition metal dichalcogenide monolayers (MX 2 , where M   =  Mo, W; X   =  S, Se, Te) while including spin–orbit coupling effects. The conducted symmetry-based tight-binding calculations show that the analytical continuation from the real band structures to the complex momentum space leads to nonlinear generalized eigenvalue problems. Herein an efficient method for solving such a class of nonlinear problems is presented and yields a complete set of physically relevant eigenvalues. Solutions obtained by this method are characterized and classified into propagating and evanescent states, where the latter states manifest not only monotonic but also oscillatory decay character. It is observed that some of the oscillatory evanescent states create characteristic complex loops at the direct band gap of MX 2 monolayers, where electrons can directly tunnel between the band gap edges. To describe these tunneling currents, decay behavior of electronic states in the forbidden energy region is elucidated and their importance within the ballistic transport regime is briefly discussed. (paper)

  14. Complex band structures of transition metal dichalcogenide monolayers with spin-orbit coupling effects

    Science.gov (United States)

    Szczęśniak, Dominik; Ennaoui, Ahmed; Ahzi, Saïd

    2016-09-01

    Recently, the transition metal dichalcogenides have attracted renewed attention due to the potential use of their low-dimensional forms in both nano- and opto-electronics. In such applications, the electronic and transport properties of monolayer transition metal dichalcogenides play a pivotal role. The present paper provides a new insight into these essential properties by studying the complex band structures of popular transition metal dichalcogenide monolayers (MX 2, where M  =  Mo, W; X  =  S, Se, Te) while including spin-orbit coupling effects. The conducted symmetry-based tight-binding calculations show that the analytical continuation from the real band structures to the complex momentum space leads to nonlinear generalized eigenvalue problems. Herein an efficient method for solving such a class of nonlinear problems is presented and yields a complete set of physically relevant eigenvalues. Solutions obtained by this method are characterized and classified into propagating and evanescent states, where the latter states manifest not only monotonic but also oscillatory decay character. It is observed that some of the oscillatory evanescent states create characteristic complex loops at the direct band gap of MX 2 monolayers, where electrons can directly tunnel between the band gap edges. To describe these tunneling currents, decay behavior of electronic states in the forbidden energy region is elucidated and their importance within the ballistic transport regime is briefly discussed.

  15. Ultra-high-rate pseudocapacitive energy storage in two-dimensional transition metal carbides

    Energy Technology Data Exchange (ETDEWEB)

    Lukatskaya, Maria R. [Drexel Univ., Philadelphia, PA (United States); Dept. of Chemical Engineering, Stanford, CA (United States); Kota, Sankalp [Drexel Univ., Philadelphia, PA (United States); Lin, Zifeng [Univ. Paul Sabatier, Toulouse (France); Reseau sur le Stockage Electrochimique de l' Energie (RS2E) (France); Zhao, Meng -Qiang [Drexel Univ., Philadelphia, PA (United States); Shpigel, Netanel [Bar-Ilan Univ., Ramat-Gan (Israel); Levi, Mikhael D. [Bar-Ilan Univ., Ramat-Gan (Israel); Halim, Joseph [Drexel Univ., Philadelphia, PA (United States); Taberna, Pierre -Louis [Univ. Paul Sabatier, Toulouse (France); Reseau sur le Stockage Electrochimique de l' Energie (RS2E) (France); Barsoum, Michel W. [Drexel Univ., Philadelphia, PA (United States); Simon, Patrice [Univ. Paul Sabatier, Toulouse (France); Reseau sur le Stockage Electrochimique de l' Energie (RS2E) (France); Gogotsi, Yury G. [Drexel Univ., Philadelphia, PA (United States)

    2017-07-10

    In this study, the use of fast surface redox storage (pseudocapacitive) mechanisms can enable devices that store much more energy than electrical double-layer capacitors (EDLCs) and, unlike batteries, can do so quite rapidly. Yet, few pseudocapacitive transition metal oxides can provide a high power capability due to their low intrinsic electronic and ionic conductivity. Here we demonstrate that two-dimensional transition metal carbides (MXenes) can operate at rates exceeding those of conventional EDLCs, but still provide higher volumetric and areal capacitance than carbon, electrically conducting polymers or transition metal oxides. We applied two distinct designs for MXene electrode architectures with improved ion accessibility to redox-active sites. A macroporous Ti3C2Tx MXene film delivered up to 210 F g–1 at scan rates of 10 V s–1, surpassing the best carbon supercapacitors known. In contrast, we show that MXene hydrogels are able to deliver volumetric capacitance of ~1,500 F cm–3 reaching the previously unmatched volumetric performance of RuO2.

  16. Ion exchange of some transition metal cations on hydrated titanium dioxide in aqueous ammonia solutions

    International Nuclear Information System (INIS)

    Bilewicz, A.; Narbutt, J.; Dybczynski, R.

    1992-01-01

    The adsorption of transition metal cations on hydrated titanium dioxide in complexing ammonia and amine solutions has been studied as a function of ammonia (amine) concentration. The relationships between the distribution coefficients and ammonia concentration as well as the effects of various amines on sorption of transition metals indicate that a coordinate bond is formed between the metal ions and the hydroxy groups of the sorbent. The distribution coefficients of silver(I) and cobalt(II), which form strong ammonia complexes in aqueous solutions, decrease with increasing concentration of ammonia already at concentrations exceeding 10 -3 *mol*dm -3 . Cations of zinc, manganese and mercury which form much weaker ammonia complexes do not exhibit any effect of ammonia concentration in the whole range investigated. In the case of sorption of macroamounts of ammonia or amine complexes of silver, the molecular sieve effect plays an important role. The differences in the affinity of hydrated titanium dioxide for ammonia solvates of various transition metal ions can serve as a tool for effective separation of these ions in ammonia solutions. (author) 10 refs.; 4 figs.; 1 tab

  17. Using Dopants to Tune Oxygen Vacancy Formation in Transition Metal Oxide Resistive Memory.

    Science.gov (United States)

    Jiang, Hao; Stewart, Derek A

    2017-05-17

    Introducing dopants is an important way to tailor and improve electronic properties of transition metal oxides used as high-k dielectric thin films and resistance switching layers in leading memory technologies, such as dynamic and resistive random access memory (ReRAM). Ta 2 O 5 has recently received increasing interest because Ta 2 O 5 -based ReRAM demonstrates high switching speed, long endurance, and low operating voltage. However, advances in optimizing device characteristics with dopants have been hindered by limited and contradictory experiments in this field. We report on a systematic study on how various metal dopants affect oxygen vacancy formation in crystalline and amorphous Ta 2 O 5 from first principles. We find that isoelectronic dopants and weak n-type dopants have little impact on neutral vacancy formation energy and that p-type dopants can lower the formation energy significantly by introducing holes into the system. In contrast, n-type dopants have a deleterious effect and actually increase the formation energy for charged oxygen vacancies. Given the similar doping trend reported for other binary transition metal oxides, this doping trend should be universally valid for typical binary transition metal oxides. Based on this guideline, we propose that p-type dopants (Al, Hf, Zr, and Ti) can lower the forming/set voltage and improve retention properties of Ta 2 O 5 ReRAM.

  18. Nanolines of transition metals ruled by grain boundaries in graphene: An ab initio study

    Energy Technology Data Exchange (ETDEWEB)

    Lima, F.D.C. de, E-mail: felipe.lima@ufu.br; Miwa, R.H., E-mail: hiroki@infis.ufu.br

    2017-06-15

    We have performed an ab initio investigation of the energetic stability, and the electronic properties of transition metals (TMs = Mn, Fe, Co, and Ru) adsorbed on graphene, upon the presence of grain boundaries (GBs); where we found an energetic preference for the TMs lying on the GB sites (TM/GB). Further energy barrier calculations, of the transition metals in TM/GB, reveal that the GBs promote the formation of energetically favorable diffusion channels on graphene. By increasing the concentration of the TM adatoms, the energetic stability of the TM/GB systems has been strengthened; giving rise to TM nanolines (TM-NLs). The electronic properties of those TM-NLs were characterized through extensive electronic band structure calculations, where the energy bands of the TM/GB systems indicate the appearance of an anisotropic spin-polarized electronic current along the TM-NLs on graphene. - Highlights: • Formation of transition metal (TM) nanolines on graphene ruled by extended defects. • Those extended defects give rise to diffusion pipes of TMs on graphene. • The electronic band structure calculations indicate the formation of spin-polarized current upon the presence of TM nanolines. • The formation of those TM nanolines support the recent experimental findings.

  19. Low temperature synthesis, photoluminescence, magnetic properties of the transition metal doped wurtzite ZnS nanowires

    International Nuclear Information System (INIS)

    Cao, Jian; Han, Donglai; Wang, Bingji; Fan, Lin; Fu, Hao; Wei, Maobin; Feng, Bo; Liu, Xiaoyan; Yang, Jinghai

    2013-01-01

    In this paper, we synthesized the transition metal ions (Mn, Cu, Fe) doped and co-doped ZnS nanowires (NWs) by a one-step hydrothermal method. The results showed that the solid solubility of the Fe 2+ ions in the ZnS NWs was about two times larger than that of the Mn 2+ or Cu 2+ ions in the ZnS NWs. There was no phase transformation from hexagonal to cubic even in a large quantity transition metal ions introduced for all the samples. The Mn 2+ /Cu 2+ /Fe 2+ related emission peaks can be observed in the Mn 2+ ,Cu 2+ and Fe 2+ doped ZnS NWs. The ferromagnetic properties of the co-doped samples were investigated at room temperature. - graphical abstract: The stable wurtzite ZnS:TM 2+ (TM=Mn, Cu, Fe) nanowires with room temperature ferromagnetism properties were obtained. The different elongation of unit cell caused by the different doped ions was observed. Highlights: ► The transition metal ions doped wurtzite ZnS nanowires were synthesized at 180 °C. ► There was no phase transformation from hexagonal to cubic even in a large quantity introduced for all the samples. ► The room temperature ferromagnetism properties of the co-doped nanowires were investigated

  20. Development of luminescent sensors based on transition metal complexes for the detection of nitroexplosives.

    Science.gov (United States)

    Sathish, Veerasamy; Ramdass, Arumugam; Velayudham, Murugesan; Lu, Kuang-Lieh; Thanasekaran, Pounraj; Rajagopal, Seenivasan

    2017-12-12

    The detection of chemical explosives is a major area of research interest and is essential for the military as well as homeland security to counter the catastrophic effects of global terrorism. In recent years, tremendous effort has been devoted to the development of luminescent materials for the detection of explosives in the vapor, solution, and solid states with a high degree of selectivity and sensitivity and a rapid response time. Apart from the wide range of organic fluorescent chemosensors, transition metal complexes play a prominent role in the sensing of nitroaromatic explosives owing to their rich photophysical characteristics. This review briefly summarizes the salient features of the design and preparation of transition metal (Zn(ii), Ir(iii), Pd(ii), Pt(ii), Re(i) and Ru(ii)) complexes/metallacycles/metallosupramolecules with emphasis on their photophysical properties, sensing behavior, mechanism of action, and the driving forces for detecting explosives and future prospects and challenges. Most of the probes that have been reported to date act as "turn-off" luminescent sensors because their emission (intensity, lifetime, and quantum yield) is eventually quenched upon sensing with nitroaromatic compounds (NACs) through photo-induced electron or energy transfer. These unique properties of transition metal complexes in response to explosives open up new vistas for the development of real world applications such as on-site detection, in-field security, forensic research, etc.

  1. Calculation of binary phase diagrams between the actinide elements, rare earth elements, and transition metal elements

    International Nuclear Information System (INIS)

    Selle, J.E.

    1992-01-01

    Attempts were made to apply the Kaufman method of calculating binary phase diagrams to the calculation of binary phase diagrams between the rare earths, actinides, and the refractory transition metals. Difficulties were encountered in applying the method to the rare earths and actinides, and modifications were necessary to provide accurate representation of known diagrams. To calculate the interaction parameters for rare earth-rare earth diagrams, it was necessary to use the atomic volumes for each of the phases: liquid, body-centered cubic, hexagonal close-packed, and face-centered cubic. Determination of the atomic volumes of each of these phases for each element is discussed in detail. In some cases, empirical means were necessary. Results are presented on the calculation of rare earth-rare earth, rare earth-actinide, and actinide-actinide diagrams. For rare earth-refractory transition metal diagrams and actinide-refractory transition metal diagrams, empirical means were required to develop values for the enthalpy of vaporization for rare earth elements and values for the constant (C) required when intermediate phases are present. Results of using the values determined for each element are presented

  2. Thermochemistry of some binary lead and transition metal compounds by high temperature direct synthesis calorimetry

    Energy Technology Data Exchange (ETDEWEB)

    Meschel, S.V., E-mail: meschel@jfi.uchicago.edu [Illinois Institute of Technology,Thermal Processing Technology Center, 10 W. 32nd Street, Chicago, Illinois 60615 (United States); Gordon Center for Integrated Science, 929 E. 57th Street, Chicago, Illinois 60637 (United States); Nash, P. [Illinois Institute of Technology,Thermal Processing Technology Center, 10 W. 32nd Street, Chicago, Illinois 60615 (United States); Chen, X.Q.; Wei, P. [Materials processing Modeling Division, Shenyang National Laboratory for Materials Science, Institute of Metals Research, 72 Wenhua Road, Shenyang City (China)

    2015-06-05

    Highlights: • Studied binary lead-transition metal alloys by high temperature calorimetry. • Determined the enthalpies of formation of 8 alloys. • Compared the measurements with predictions by the model of Miedema and by the ab initio method. - Abstract: The standard enthalpies of formation of some binary lead and transition metal compounds have been measured by high temperature direct synthesis calorimetry. The reported results are: Pb{sub 3}Sc{sub 5}(−61.3 ± 2.9); PbTi{sub 4}(−16.6 ± 2.4); Pb{sub 3}Y{sub 5}(−64.8 ± 3.6); Pb{sub 3}Zr{sub 5}(−50.6 ± 3.1); PbNb{sub 3}(−10.4 ± 3.4); PbRh(−16.5 ± 3.3); PbPd{sub 3}(−29.6 ± 3.1); PbPt(−34.7 ± 3.3) kJ/mole of atoms. We will compare our results with previously published measurements. We will also compare the experimental measurements with enthalpies of formation of transition metal compounds with elements in the same vertical column in the periodic table. We will compare our measurements with predicted values on the basis of the semi empirical model of Miedema and coworkers and with ab initio values when available.

  3. Synthesis, structural and optical properties of PVP coated transition metal doped ZnS nanoparticles

    Science.gov (United States)

    Desai, N. V.; Shaikh, I. A.; Rawal, K. G.; Shah, D. V.

    2018-05-01

    The room temperature photoluminescence (PL) of transition metal doped ZnS nanoparticles is investigated in the present study. The PVP coated ZnS nanoparticles doped with transition metals are synthesized by facile wet chemical co-precipitation method with the concentration of impurity 1%. The UV-Vis absorbance spectra have a peak at 324nm which shifts slightly to 321nm upon introduction of the impurity. The incorporation of the transition metal as dopant is confirmed by X-ray diffraction (XRD) and energy dispersive spectroscopy (EDS). The particle size and the morphology are characterized by scanning electron microscopy (SEM), XRD and UV-Vis spectroscopy. The average size of synthesized nanoparticles is about 2.6nm. The room temperature photoluminescence (PL) of undoped and doped ZnS nanoparticles show a strong and sharp peak at 782nm and 781.6nm respectively. The intensity of the PL changes with the type of doping having maximum for manganese (Mn).

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

    Science.gov (United States)

    Martin, Christine; Poienar, Maria

    2017-08-01

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

  5. Electrochemical oxidation of pulp and paper making wastewater assisted by transition metal modified kaolin

    International Nuclear Information System (INIS)

    Wang Bo; Gu Lin; Ma Hongzhu

    2007-01-01

    The electrochemical oxidation of pulp and paper making wastewater assisted by transition metal (Co, Cu) modified kaolin in a 200 ml electrolytic batch reactor with graphite plate as electrodes was investigated. H 2 O 2 , which produced on the surface of porous graphite cathode, would react with the catalysts to form strong oxidant (hydroxyl radicals) that can in turn destruct the pollutants adsorbed on the surface of kaolin. The transition metal (Co, Cu) modified kaolin was also characterized by XRD and SEM before and after the modification and the results showed that the transition metals were completely supported on kaolin and formed a porous structure with big BET surface. The mechanism was proposed on the basis of XPS analysis of the catalyst after the degradation process. Series of experiments were also done to prove the synergetic effect of the combined oxidation system and to find out the optimal operating parameters such as initial pH, current density and amount of catalyst. From the results it can be founded that when the initial pH was at 3, current density was 30 mA cm -2 ; catalyst dose was 30 g dm -3 , COD (chemical oxygen demand) removal could reach up to 96.8% in 73 min

  6. Insights into the photochemical disproportionation of transition metal dimers on the picosecond time scale.

    Science.gov (United States)

    Lomont, Justin P; Nguyen, Son C; Harris, Charles B

    2013-05-09

    The reactivity of five transition metal dimers toward photochemical, in-solvent-cage disproportionation has been investigated using picosecond time-resolved infrared spectroscopy. Previous ultrafast studies on [CpW(CO)3]2 established the role of an in-cage disproportionation mechanism involving electron transfer between 17- and 19-electron radicals prior to diffusion out of the solvent cage. New results from time-resolved infrared studies reveal that the identity of the transition metal complex dictates whether the in-cage disproportionation mechanism can take place, as well as the more fundamental issue of whether 19-electron intermediates are able to form on the picosecond time scale. Significantly, the in-cage disproportionation mechanism observed previously for the tungsten dimer does not characterize the reactivity of four out of the five transition metal dimers in this study. The differences in the ability to form 19-electron intermediates are interpreted either in terms of differences in the 17/19-electron equilibrium or of differences in an energetic barrier to associative coordination of a Lewis base, whereas the case for the in-cage vs diffusive disproportionation mechanisms depends on whether the 19-electron reducing agent is genuinely characterized by 19-electron configuration at the metal center or if it is better described as an 18 + δ complex. These results help to better understand the factors that dictate mechanisms of radical disproportionation and carry implications for radical chain mechanisms.

  7. Ultrafast Transient Absorption Spectroscopy of Polymer-Based Organophotoredox Catalysts Mimicking Transition-Metal Complexes

    Science.gov (United States)

    Jamhawi, Abdelqader; Paul, Anam C.; Smith, Justin D.; Handa, Sachin; Liu, Jinjun

    2017-06-01

    Transition-metal complexes of rare earth metals including ruthenium and iridium are most commonly employed as visible-light photocatalysts. Despite their highly important and broad applications, they have many disadvantages including high cost associated with low abundance in earth crust, potential toxicity, requirement of specialized ligands for desired activity, and difficulty in recycling of metal contents as well as associated ligands. Polymer-based organophotoredox catalysts are promising alternatives and possess unique advantages such as easier synthesis from inexpensive starting material, longer excited state life time, broad range of activity, sustainability, and recyclability. In this research talk, time-resolved photoluminescence and femtosecond transient absorption (TA) spectroscopy measurements of three novel polymer-based organophotoredox catalysts will be presented. By our synthetic team, their catalytic activity has been proven in some highly valuable chemical transformations, that otherwise require transition metal complexes. Time-resolved spectroscopic investigations have demonstrated that photoinduced processes in these catalysts are similar to the transition metal complexes. Especially, intramolecular vibrational relaxation, internal conversion, and intersystem crossing from the S1 state to the T1 state all occur on a sub-picosecond timescale. The long lifetime of the T1 state ( 2-3 microsecond) renders these polymers potent oxidizing and reducing agents. A spectroscopic and kinetic model has been developed for global fitting of TA spectra in both the frequency and time domains. Implication of the current ultrafast spectroscopy studies of these novel molecules to their roles in photocatalysis will be discussed.

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

    CERN Document Server

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

    2000-01-01

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

  9. Gigantic perpendicular magnetic anisotropy of heavy transition metal cappings on Fe/MgO(0 0 1)

    Science.gov (United States)

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

    2017-11-01

    Effects of capping layer by 5d transition metals (TM = Hf, Ta, W, Re, Os, Ir, Pt, and Au) on Fe/MgO(0 0 1), a typical magnetic tunneling junction, are systematically investigated using first-principles calculation for magnetism and magnetocrystalline-anisotropy (MCA). The early TMs having less than half-filled d bands favor magnetization antiparallel to Fe, whereas the late TMs having more than half-filled d bands favor parallel, which is explained in the framework of kinetic exchange energy. The Os capping, isovalent to Fe, enhances MCA significantly to gigantic energy of +11.31 meV/cell, where positive contribution is mostly from the partially filled majority d bands of magnetic quantum number of |m| = 1 along with stronger spin-orbit coupling of Os than Fe. Different TM cappings give different MCA energies as the Fermi level shifts according to the valence of TM: Re and Ir, just one valence more or less than Os, have still large PMCA but smaller than the Os. In the W and Pt cappings, valence difference by two, PMCA are further reduced; MCAs are lowered compared to Fe/MgO(0 0 1) by the cappings of the very early TMs (Hf and Ta), while the very late TM (Au) switches sign to in-plane MCA.

  10. A Self-Templating Scheme for the Synthesis of Nanostructured Transition Metal Chalcogenide Electrodes for Capacitive Energy Storage

    KAUST Repository

    Xia, Chuan; Alshareef, Husam N.

    2015-01-01

    Due to their unique structural features including well-defined interior voids, low density, low coefficients of thermal expansion, large surface area and surface permeability, hollow micro/nanostructured transition metal sulfides with high

  11. Ab-initio vibrational properties of transition metal chalcopyrite alloys determined as high-efficiency intermediate-band photovoltaic materials

    International Nuclear Information System (INIS)

    Palacios, P.; Aguilera, I.; Wahnon, P.

    2008-01-01

    In this work, we present frozen phonon and linear response ab-initio research into the vibrational properties of the CuGaS 2 chalcopyrite and transition metal substituted (CuGaS 2 )M alloys. These systems are potential candidates for developing a novel solar-cell material with enhanced optoelectronic properties based in the implementation of the intermediate-band concept. We have previously carried out ab-initio calculations of the electronic properties of these kinds of chalcopyrite metal alloys showing a narrow transition metal band isolated in the semiconductor band gap. The substitutes used in the present work are the 3d metal elements, Titanium and Chromium. For the theoretical calculations we use standard density functional theory at local density and generalized gradient approximation levels. We found that the optical phonon branches of the transition metal chalcopyrite, are very sensitive to the specific bonding geometry and small changes in the transition metal environment

  12. Electron spectroscopy in the X-ray range for occupied and free levels and the application to transition metal silicides

    International Nuclear Information System (INIS)

    Speier, W.

    1988-03-01

    Intermetallic compounds of transition metals are investigated by means of XPS, Bremsstrahlung Isochromate Spectroscopy and XAS. Occupied and free levels are characterized and moreover a systematic overview over the electronic structure of the transition element silicides is given. (BHO)

  13. Electronic computer prediction of properties of binary refractory transition metal compounds on the base of their simplificated electronic structure

    International Nuclear Information System (INIS)

    Kutolin, S.A.; Kotyukov, V.I.

    1979-01-01

    An attempt is made to obtain calculation equations of macroscopic physico-chemical properties of transition metal refractory compounds (density, melting temperature, Debye characteristic temperature, microhardness, standard formation enthalpy, thermo-emf) using the method of the regression analysis. Apart from the compound composition the argument of the regression equation is the distribution of electron bands of d-transition metals, created by the energy electron distribution in the simplified zone structure of transition metals and approximated by Chebishev polynoms, by the position of Fermi energy on the map of distribution of electron band energy depending upon the value of quasi-impulse, multiple to the first, second and third Brillouin zone for transition metals. The maximum relative error of the regressions obtained as compared with the literary data is 15-20 rel.%

  14. Oxygen Electroreduction Activity and X-Ray Photoelectron Spectroscopy of Platinum and Early Transition Metal Alloys

    DEFF Research Database (Denmark)

    Stephens, Ifan; Bondarenko, Alexander S.; Bech, Lone

    2012-01-01

    and exsitu under ultrahigh vacuum conditions. The ORR activity was established in an electrochemical cell containing 0.1M HClO4 by use of a rotating ring disk electrode assembly. The surface composition was characterised before and after the electrochemical measurements by using angle-resolved X-ray...

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

    International Nuclear Information System (INIS)

    Mohanta, S.K.; Mishra, S.N.; Srivastava, S.K.

    2014-01-01

    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

  16. Preparation and characterization of flexible asymmetric supercapacitors based on transition-metal-oxide nanowire/single-walled carbon nanotube hybrid thin-film electrodes.

    Science.gov (United States)

    Chen, Po-Chiang; Shen, Guozhen; Shi, Yi; Chen, Haitian; Zhou, Chongwu

    2010-08-24

    In the work described in this paper, we have successfully fabricated flexible asymmetric supercapacitors (ASCs) based on transition-metal-oxide nanowire/single-walled carbon nanotube (SWNT) hybrid thin-film electrodes. These hybrid nanostructured films, with advantages of mechanical flexibility, uniform layered structures, and mesoporous surface morphology, were produced by using a filtration method. Here, manganese dioxide nanowire/SWNT hybrid films worked as the positive electrode, and indium oxide nanowire/SWNT hybrid films served as the negative electrode in a designed ASC. In our design, charges can be stored not only via electrochemical double-layer capacitance from SWNT films but also through a reversible faradic process from transition-metal-oxide nanowires. In addition, to obtain stable electrochemical behavior during charging/discharging cycles in a 2 V potential window, the mass balance between two electrodes has been optimized. Our optimized hybrid nanostructured ASCs exhibited a superior device performance with specific capacitance of 184 F/g, energy density of 25.5 Wh/kg, and columbic efficiency of approximately 90%. In addition, our ASCs exhibited a power density of 50.3 kW/kg, which is 10-fold higher than obtained in early reported ASC work. The high-performance hybrid nanostructured ASCs can find applications in conformal electrics, portable electronics, and electrical vehicles.

  17. The potential for transition metal-mediated neurodegeneration in amyotrophic lateral sclerosis

    Directory of Open Access Journals (Sweden)

    David Benn Lovejoy

    2014-07-01

    Full Text Available Modulations of the potentially toxic transition metals iron (Fe and copper (Cu are implicated in the neurodegenerative process in a variety of human disease states including amyotrophic lateral sclerosis (ALS. However, the precise role played by these metals is still very much unclear, despite considerable clinical and experimental data suggestive of a role for these elements in the neurodegenerative process. The discovery of mutations in the antioxidant enzyme Cu/Zn superoxide dismutase (SOD-1 in ALS patients established the first known cause of ALS. Recent data suggest that various mutations in SOD-1 affect metal-binding of Cu and Zn, in turn promoting toxic protein aggregation. Copper homeostasis is also disturbed in ALS, and may be relevant to ALS pathogenesis. Another set of interesting observations in ALS patients involves the key nutrient Fe. In ALS patients Fe loading can be inferred by studies showing increased expression of serum ferritin, an Fe storage protein, with high serum ferritin levels correlating to poor prognosis. Magnetic resonance imaging of ALS patients shows a characteristic T2 shortening that is attributed to the presence of Fe in the motor cortex. In mutant SOD-1 mouse models, increased Fe is also detected in the spinal cord and treatment with Fe-chelating drugs lowers spinal cord Fe, preserves motor neurons and extends lifespan. Inflammation may play a key causative role in Fe accumulation, but this is not yet conclusive. Excess transition metals may enhance induction of endoplasmic reticulum (ER stress, a system that is already under strain in ALS. Taken together, the evidence suggests a role for transition metals in ALS progression and the potential use of metal-chelating drugs as a component of future ALS therapy.

  18. Nanotubes within transition metal silicate hollow spheres: Facile preparation and superior lithium storage performances

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Fan; An, Yongling; Zhai, Wei; Gao, Xueping [Key Laboratory for Liquid–Solid Structural Evolution & Processing of Materials (Ministry of Education), Jinan 250100 (China); Feng, Jinkui, E-mail: jinkui@sdu.edu.cn [Key Laboratory for Liquid–Solid Structural Evolution & Processing of Materials (Ministry of Education), Jinan 250100 (China); Ci, Lijie [Key Laboratory for Liquid–Solid Structural Evolution & Processing of Materials (Ministry of Education), Jinan 250100 (China); Xiong, Shenglin [School of Materials Science and Engineering, School of Chemistry and Chemical Engineering, Shandong University, Jinan 250100 (China)

    2015-10-15

    Highlights: • The hollow Co{sub 2}SiO{sub 4}, MnSiO{sub 3} and CuSiO{sub 3} were successfully prepared by a facile hydrothermal method using SiO{sub 2} nanosphere. • The hollow Co{sub 2}SiO{sub 4}, MnSiO{sub 3} and CuSiO{sub 3} were tested as anode materials for lithium batteries. • The hollow Co{sub 2}SiO{sub 4}, MnSiO{sub 3} and CuSiO{sub 3} delivered superior electrochemical performance. • The lithium storage mechanism is probe via cyclic voltammetry and XPS. - Abstract: A series of transition metal silicate hollow spheres, including cobalt silicate (Co{sub 2}SiO{sub 4}), manganese silicate (MnSiO{sub 3}) and copper silicate (CuSiO{sub 3}.2H{sub 2}O, CuSiO{sub 3} as abbreviation in the text) were prepared via a simple and economic hydrothermal method by using silica spheres as chemical template. Time-dependent experiments confirmed that the resultants formed a novel type of hierarchical structure, hollow spheres assembled by numerous one-dimensional (1D) nanotubes building blocks. For the first time, the transition metal silicate hollow spheres were characterized as novel anode materials of Li-ion battery, which presented superior lithium storage capacities, cycle performance and rate performance. The 1D nanotubes assembly and hollow interior endow this kind of material facilitate fast lithium ion and electron transport and accommodate the big volume change during the conversion reactions. Our study shows that low-cost transition metal silicate with rationally designed nanostructures can be promising anode materials for high capacity lithium-ion battery.

  19. Localized versus collective behaviour of d-electrons in transition metal oxide systems of perovskite systems

    Energy Technology Data Exchange (ETDEWEB)

    Rao, C N.R. [Indian Inst. of Tech., Kanpur

    1974-12-01

    The behavior of d-electrons in perovskites of the type LnZO/sub 3/ (Z = trivalent transition metal ion and Ln = rare earth or yttrium) depends on the spin configuration of the transition metal ion. LaTiO/sub 3/ and LaNiO/sub 3/ with low-spin transition metal ions (S = 1/2) are metallic while LaCrO/sub 3/, LnMnO/sub 3/ and LnFeO/sub 3/ with high-spin ions are poor semiconductors exhibiting localized behavior of d-electrons. In rare earth cobaltites, the cobalt ions are present mainly in the diamagnetic low-spin Co /sup III/ state at low temperatures. The Co/sup III/ ions transform to high-spin Co/sup 3 +/ ions with increase in temperature. At higher temperatures, there is electron-transfer from Co/sup 3 +/ to Co/sup III/ions producing intermetallic states. Spin-state transitions are seen in these cobaltites in the range 150-870/sup 0/K. At high temperatures, the cobaltites show evidence for localized-itinerant electron transitions. In La/sub 1-x/ Sr/sub x/CoO/sub 3/ there is onset of ferromagnetism at x > 0.125, at which point there is a structural dicontinuity and electrons become itinerant. The composition with x = 0.5 is metallic and T/sub c/ = 230/sup 0/K. The ferromagnetic component in La/sub 1-x/Sr/sub x/ CoO/sub 3/ increases with x in the range 0.125-0.50. Catalytic properties of rare earth cobaltites appear to be related to the spin state equilibria. (auth)

  20. Fabrication and electrocatalytic application of functionalized nanoporous carbon material with different transition metal oxides

    International Nuclear Information System (INIS)

    Samiee, L.; Shoghi, F.; Vinu, A.

    2013-01-01

    Highlights: ► Fabrication of highly ordered functionalized nanoporous carbon material with different types of transition metal oxides. ► Novel electrocatalytic activity of functionalized nanoporous carbon material. ► Simultaneous effect of surface area and surface reactivity parameters on electrocatalytic activity. - Abstract: In the work presented here, an attempt is made to study the effect of functionalization with different transition metal oxides on the mesostructural properties as well as electrochemical behavior of Pt/nanoporous carbon supports. In this respect, the functionalized samples have been synthesized by using CMK-3 and metallocene as transition metal sources. The platinum catalysts (5 wt% Pt) obtained through a conventional wet impregnation method. All the materials have been characterized by XRD (low and high), N 2 adsorption–desorption isotherms, high-resolution transmission electron microscopy, high-resolution field emission scanning electron, EDX mapping images and cyclic voltammetry (CV) and rotating disk electrode (RDE) techniques. The results showed that the mesostructural order has been destroyed by functionalization of CMK-3 with CoO, whereas it is not that much affected in NiO and CuO functionalized samples. EDX image mapping exhibited the good and uniform dispersion of functionalizing elements (Ni, Cu, Fe and Co), Pt in the carbon supports. Moreover, XRD studies revealed the formation of smaller platinum crystallite sizes in NiO and CuO functionalized samples in relative to other functionalized supports. Electrochemical measurements were performed using CV and RDE method. Kinetic analysis revealed an activity increases in the following order: CMK-3-NiO-Pt > CMK-3-CuO-Pt > CMK-3-CoO-Pt > CMK-3-Fe 2 O 3 -Pt which is showing of simultaneous effect of surface area and surface reactivity parameters.

  1. Fabrication and electrocatalytic application of functionalized nanoporous carbon material with different transition metal oxides

    Energy Technology Data Exchange (ETDEWEB)

    Samiee, L., E-mail: Leila.Samiee83@gmail.com [Development and Optimization of Energy Technologies Research Division, Research Institute of Petroleum Industry (RIPI), West Boulevard, Near Azadi Sports Complex, Tehran (Iran, Islamic Republic of); Shoghi, F. [Development and Optimization of Energy Technologies Research Division, Research Institute of Petroleum Industry (RIPI), West Boulevard, Near Azadi Sports Complex, Tehran (Iran, Islamic Republic of); Vinu, A., E-mail: a.vinu@uq.edu.au [Australian Institute for Bioengineering and Nanotechnology(AIBN), University of Queensland, Corner College and Cooper Roads (Bld75), Brisbane, Qld 4072 (Australia)

    2013-01-15

    Highlights: Black-Right-Pointing-Pointer Fabrication of highly ordered functionalized nanoporous carbon material with different types of transition metal oxides. Black-Right-Pointing-Pointer Novel electrocatalytic activity of functionalized nanoporous carbon material. Black-Right-Pointing-Pointer Simultaneous effect of surface area and surface reactivity parameters on electrocatalytic activity. - Abstract: In the work presented here, an attempt is made to study the effect of functionalization with different transition metal oxides on the mesostructural properties as well as electrochemical behavior of Pt/nanoporous carbon supports. In this respect, the functionalized samples have been synthesized by using CMK-3 and metallocene as transition metal sources. The platinum catalysts (5 wt% Pt) obtained through a conventional wet impregnation method. All the materials have been characterized by XRD (low and high), N{sub 2} adsorption-desorption isotherms, high-resolution transmission electron microscopy, high-resolution field emission scanning electron, EDX mapping images and cyclic voltammetry (CV) and rotating disk electrode (RDE) techniques. The results showed that the mesostructural order has been destroyed by functionalization of CMK-3 with CoO, whereas it is not that much affected in NiO and CuO functionalized samples. EDX image mapping exhibited the good and uniform dispersion of functionalizing elements (Ni, Cu, Fe and Co), Pt in the carbon supports. Moreover, XRD studies revealed the formation of smaller platinum crystallite sizes in NiO and CuO functionalized samples in relative to other functionalized supports. Electrochemical measurements were performed using CV and RDE method. Kinetic analysis revealed an activity increases in the following order: CMK-3-NiO-Pt > CMK-3-CuO-Pt > CMK-3-CoO-Pt > CMK-3-Fe{sub 2}O{sub 3}-Pt which is showing of simultaneous effect of surface area and surface reactivity parameters.

  2. Electronic and optical properties of vacancy defects in single-layer transition metal dichalcogenides

    Science.gov (United States)

    Khan, M. A.; Erementchouk, Mikhail; Hendrickson, Joshua; Leuenberger, Michael N.

    2017-06-01

    A detailed first-principles study has been performed to evaluate the electronic and optical properties of single-layer (SL) transition metal dichalcogenides (TMDCs) (M X 2 ; M = transition metal such as Mo, W, and X = S, Se, Te), in the presence of vacancy defects (VDs). Defects usually play an important role in tailoring electronic, optical, and magnetic properties of semiconductors. We consider three types of VDs in SL TMDCs: (i) X vacancy, (ii) X2 vacancy, and (iii) M vacancy. We show that VDs lead to localized defect states (LDS) in the band structure, which in turn gives rise to sharp transitions in in-plane and out-of-plane optical susceptibilities, χ∥ and χ⊥. The effects of spin-orbit coupling (SOC) are also considered. We find that SOC splitting in LDS is directly related to the atomic number of the transition metal atoms. Apart from electronic and optical properties we also find magnetic signatures (local magnetic moment of ˜μB ) in MoSe2 in the presence of the Mo vacancy, which breaks the time-reversal symmetry and therefore lifts the Kramers degeneracy. We show that a simple qualitative tight-binding model (TBM), involving only the hopping between atoms surrounding the vacancy with an on-site SOC term, is sufficient to capture the essential features of LDS. In addition, the existence of the LDS can be understood from the solution of the two-dimensional Dirac Hamiltonian by employing infinite mass boundary conditions. In order to provide a clear description of the optical absorption spectra, we use group theory to derive the optical selection rules between LDS for both χ∥ and χ⊥.

  3. Ab-initio study on electronic properties of rocksalt SnAs

    Science.gov (United States)

    Babariya, Bindiya; Vaghela, M. V.; Gajjar, P. N.

    2018-05-01

    Within the frame work of Local Density Approximation of Exchange and Correlation, ab-initio method of density functional theory with Abinit code is used to compute electronic energy band structure, density of States and charge density of SnAs in rocksalt phase. Our result after optimization for lattice constant agrees with experimental value within 0.59% deviation. The computed electronic energy bands in high symmetry directions Γ→K→X→Γ→L→X→W→L→U shown metallic nature. The lowest band in the electronic band structure is showing band-gap approximately 1.70 eV from next higher band and no crossing between lowest two bands are seen. The density of states revels p-p orbit hybridization between Sn and As atoms. The spherical contour around Sn and As in the charge density plot represent partly ionic and partly covalent bonding. Fermi surface topology is the resultant effect of the single band crossing along L direction at Ef.

  4. Quasiparticle band structure of rocksalt-CdO determined using maximally localized Wannier functions.

    Science.gov (United States)

    Dixit, H; Lamoen, D; Partoens, B

    2013-01-23

    CdO in the rocksalt structure is an indirect band gap semiconductor. Thus, in order to determine its band gap one needs to calculate the complete band structure. However, in practice, the exact evaluation of the quasiparticle band structure for the large number of k-points which constitute the different symmetry lines in the Brillouin zone can be an extremely demanding task compared to the standard density functional theory (DFT) calculation. In this paper we report the full quasiparticle band structure of CdO using a plane-wave pseudopotential approach. In order to reduce the computational effort and time, we make use of maximally localized Wannier functions (MLWFs). The MLWFs offer a highly accurate method for interpolation of the DFT or GW band structure from a coarse k-point mesh in the irreducible Brillouin zone, resulting in a much reduced computational effort. The present paper discusses the technical details of the scheme along with the results obtained for the quasiparticle band gap and the electron effective mass.

  5. Electrochemical and visco metric studies on some copolymer/ homopolymer poly electrolytes and transition metal ion interaction

    International Nuclear Information System (INIS)

    Rajabi, F. H.; Frahani, B. V.

    2003-01-01

    Some random three-component copolymers have been prepared by condensing of formaldehyde with various aromatic amines. The compositions of the copolymers have been determined by known methods. selective complexation of copolymers have been carried out with PAA, PEI, PVP and some transition metal ions (e.g., Cu 2+ )by adding the components in various sequences. The relative complexation ability of different -NH 2 groups, associated with the various comonomer units, has been interpreted in terms of the these complexes has been studied by conductometry. potentiometry and viscometry techniques. A scheme has presented to explain the mode of interaction of the various components

  6. Saturated bonds and anomalous electronic transport in transition-metal aluminides

    Energy Technology Data Exchange (ETDEWEB)

    Schmidt, T.

    2006-05-22

    This thesis deals with the special electronic properties of the transition-metal aluminides. Following quasicrystals and their approximants it is shown that even materials with small elementary cells exhibit the same surprising effects. So among the transition-metal aluminides also semi-metallic and semiconducting compounds exist, although if they consist of classic-metallic components like Fe, Al, or Cr. These properties are furthermore coupled with a deep pseusogap respectively gap in the density of states and strongly covalent bonds. Bonds are described in this thesis by two eseential properties. First by the bond charge and second by the energetic effect of the bond. It results that in the caes of semiconducting transition-metal aluminides both a saturation of certain bonds and a bond-antibond alteration in the Fermi level is present. By the analysis of the near-order in form of the so-calles coordination polyeders it has been succeeded to establish a simple rule for semiconductors, the five-fold coordination for Al. This rule states that aluminium atoms with their three valence electrons are not able to build more than five saturated bonds to their nearest transition-metal neighbours. In excellent agreement with the bond angles predicted theoretically under assumption of equal-type bonds it results that all binary transition-element aluminide semiconductors exhibit for the Al atoms the same near order. Typical values for specific resistances of the studied materials at room temperature lie in the range of some 100 {mu}{omega}cm, which is farly larger than some 10 {mu}{omega}cm as in the case of the unalloyed metals. SUrprising is furthermore a high transport anisotropy with a ratio of the specific resistances up to 3.0. An essential result of this thesis can be seen in the coupling of the properties of the electronic transport and the bond properties. The small conducitivities could be explained by small values in the density of states and a bond

  7. Catalytic reduction of nitric oxide with ammonia over transition metal ion-exchanged Y zeolites

    Energy Technology Data Exchange (ETDEWEB)

    Sciyama, T; Arakawa, T; Matsuda, T; Yamazoe, N; Takita, Y

    1975-01-01

    The catalytic reduction of nitric oxide with ammonia was studied over transition metal ion-exchanged Y zeolite (Me-Y) catalysts. The reaction products are nitrogen, nitrous oxide, and water in all cases. Selectivities to N/sub 2/ are 60 to 80% on all the cation exchanged zeolite catalysts exhibiting a relatively minor variation with the cationic species exchanged. The copper (II)-Y catalyst exhibits low temperature activity and has an unusual catalytic activity-temperature profile with a maximum at 120/sup 0/C. The catalytic activity is enhanced considerably when a second cation, especially cobalt (II) or iron (III) is coexchanged together with Cu (II) in Y zeolite.

  8. Generation, detection and characterization of gas-phase transition metal aggregates and compounds

    International Nuclear Information System (INIS)

    Steimle, T.C.

    1992-01-01

    The goal of our research is to employ spectroscopic techniques to characterize the bound portions of the potential energy surface (PES) for chemical systems involving diatomic and triatomic transition metal molecules. The approach incorporates the generation and isolation of new metal compounds via supersonic laser ablation molecular beam techniques. Detection and characterization is achieved using high resolution dye laser induced fluorescence spectroscopy. A major objective is to produce information which can be compared to theoretical predictions and thereby provide guidelines and insight into the development of reaction models

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2015-07-31

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

  10. Heterostructures of phosphorene and transition metal dichalcogenides for excitonic solar cells: A first-principles study

    International Nuclear Information System (INIS)

    Ganesan, Vellayappan Dheivanayagam; Shen, Lei; Linghu, Jiajun; Zhang, Chun; Feng, Yuan Ping

    2016-01-01

    Using the many-body perturbation GW theory, we study the quasiparticle conduction-band offsets of phosphorene, a two-dimensional atomic layer of black phosphorus, and transition-metal dichalcogenides (TMDs). The calculated large exciton binding energies of phosphorene and TMDs indicate that their type-II heterostructures are suitable for excitonic thin-film solar cell applications. Our results show that these heterojunctions have a potential maximum power conversion efficiency of up to 12%, which can be further enhanced up to 20% by strain engineering.

  11. Ab initio study of adsorption and diffusion of lithium on transition metal dichalcogenide monolayers

    OpenAIRE

    Sun, Xiaoli; Wang, Zhiguo

    2017-01-01

    Using first principles calculations, we studied the stability and electronic properties of transition metal dichalcogenide monolayers of the type MX2 (M = Ti, Zr, Hf, V, Nb, Ta, Mo, Cr, W; X= S, Se, Te). The adsorption and diffusion of lithium on the stable MX2 phase was also investigated for potential application as an anode for lithium ion batteries. Some of these compounds were found to be stable in the 2H phase and some are in the 1T or 1T' phase, but only a few of them were stable in bot...

  12. Electrical Switching in Thin Film Structures Based on Transition Metal Oxides

    Directory of Open Access Journals (Sweden)

    A. Pergament

    2015-01-01

    Full Text Available Electrical switching, manifesting itself in the nonlinear current-voltage characteristics with S- and N-type NDR (negative differential resistance, is inherent in a variety of materials, in particular, transition metal oxides. Although this phenomenon has been known for a long time, recent suggestions to use oxide-based switching elements as neuristor synapses and relaxation-oscillation circuit components have resumed the interest in this area. In the present review, we describe the experimental facts and theoretical models, mainly on the basis of the Mott transition in vanadium dioxide as a model object, of the switching effect with special emphasis on the emerging applied potentialities for oxide electronics.

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

    DEFF Research Database (Denmark)

    Peterson, Andrew; Nørskov, Jens K.

    2012-01-01

    The electrochemical reduction of CO2 into hydrocarbons and alcohols would allow renewable energy sources to be converted into fuels and chemicals. However, no electrode catalysts have been developed that can perform this transformation with a low overpotential at reasonable current densities....... In 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...

  14. On matrix stabilisation of d- and f-transition metal ions in unstable oxidation states

    Energy Technology Data Exchange (ETDEWEB)

    Kiselev, Yurii M [Department of Chemistry, M.V. Lomonosov Moscow State University, Moscow (Russian Federation)

    2009-01-31

    The state-of-the-art in matrix stabilisation of d- and f-transition metal ions in unstable oxidation states is analysed. Main aspects of this problem concerning the genealogy of appropriate matrix systems are classified. Relevant examples are given and the data that contradict the scheme proposed are discussed. The thermodynamics of the matrix stabilisation effect is considered using the concept of isomorphic miscibility. The influence of defects and non-equilibrium on the matrix stabilisation effect is discussed. The problem of identification of the oxidation states in matrix systems is examined and various types of matrix systems are considered.

  15. High capacity hydrogen absorption in transition-metal ethylene complexes: consequences of nanoclustering

    International Nuclear Information System (INIS)

    Phillips, A B; Shivaram, B S

    2009-01-01

    We have recently shown that organo-metallic complexes formed by laser ablating transition metals in ethylene are high hydrogen absorbers at room temperature (Phillips and Shivaram 2008 Phys. Rev. Lett. 100 105505). Here we show that the absorption percentage depends strongly on the ethylene pressure. High ethylene pressures (>100 mTorr) result in a lowered hydrogen uptake. Transmission electron microscopy measurements reveal that while low pressure ablations result in metal atoms dispersed uniformly on a near atomic scale, high pressure ones yield distinct nanoparticles with electron energy-loss spectroscopy demonstrating that the metal atoms are confined solely to the nanoparticles.

  16. Erosion of the 4-6- and 8 group transition metals under intense laser radiation

    International Nuclear Information System (INIS)

    Samsonov, G.V.; Verkhoturov, A.D.; Roshchina, A.I.; Vasil'ev, A.V.; Klimenko, V.P.

    1976-01-01

    The erosion resistance is studied of transition metals of Groups 4-6 and 8 at laser emission of approximately 6x1O 7 W/cm 2 . It is shown that as the emission power increases from 10 6 to 6x10 7 W/cm 2 the erosion values show an increase over tenfold without any subsequent filling of the craters. The growth of the metallic erosion is largely caused by a greater crater diameter. The erosion resistance of metals enhances in the following series: Ti-Zr-Co-Ni-Fe, Hf-V-Nb-Mo-Cr-Ta-W-Cu

  17. Generation of highly N-type, defect passivated transition metal oxides using plasma fluorine insertion

    Science.gov (United States)

    Baker, L. Robert; Seo, Hyungtak; Hervier, Antoine; Somorjai, Gabor A.

    2016-04-12

    A new composition of matter is disclosed wherein oxygen vacancies in a semiconducting transition metal oxide such as titanium dioxide are filled with a halogen such as Fluorine, whereby the conductivity of the composition is greatly enhanced, while at the same time the chemical stability of the composition is greatly improved. Stoichiometric titanium dioxide having less than 3 % oxygen vacancies is subject to fluorine insertion such that oxygen vacancies are filled, limited amounts of fluorine replace additional oxygen atoms and fluorine interstitially inserts into the body of the TiO.sub.2 composition.

  18. Magnetic properties of 3d-transition metal and rare earth fluoride glasses

    International Nuclear Information System (INIS)

    Renard, J.P.; Dupas, C.; Velu, E.; Jacobini, C.; Fonteneau, G.; Lucas, J.

    1981-01-01

    The ac susceptibility of fluoride glasses in the ternary systems PbF 2 -MnF 2 -FeF 3 , ThF 4 -BaF 2 -MnF 2 , ZnF 2 -BaF 2 -RF 3 (R = Dy-Ho) has been studied down to 0.3 K. The susceptibility of rare earth glasses exhibits a broad maximum strongly dependent on the measuring frequency ν while a spin glass transition with a sharp susceptibility cusp nearly independent on ν is observed in 3d-transition metal glasses. Magnetic after effects are observed below the spin freezing temperature. (orig.)

  19. Optical properties of monolayer transition metal dichalcogenides probed by spectroscopic ellipsometry

    KAUST Repository

    Liu, Hsiang-Lin

    2014-11-17

    Spectroscopic ellipsometry was used to characterize the complex refractive index of chemical-vapor-deposited monolayer transition metal dichalcogenides (TMDs). The extraordinary large value of the refractive index in the visible frequency range is obtained. The absorption response shows a strong correlation between the magnitude of the exciton binding energy and band gap energy. Together with the observed giant spin-orbit splitting, these findings advance the fundamental understanding of their novel electronic structures and the development of monolayer TMDs-based optoelectronic and spintronic devices.

  20. Heterostructures of phosphorene and transition metal dichalcogenides for excitonic solar cells: A first-principles study

    Energy Technology Data Exchange (ETDEWEB)

    Ganesan, Vellayappan Dheivanayagam; Shen, Lei, E-mail: shenlei@nus.edu.sg [Engineering Science Programme, National University of Singapore, 9 Engineering Drive 1, Singapore 117575 (Singapore); Linghu, Jiajun; Zhang, Chun; Feng, Yuan Ping [Department of Physics, National University of Singapore, Singapore 117542 (Singapore)

    2016-03-21

    Using the many-body perturbation GW theory, we study the quasiparticle conduction-band offsets of phosphorene, a two-dimensional atomic layer of black phosphorus, and transition-metal dichalcogenides (TMDs). The calculated large exciton binding energies of phosphorene and TMDs indicate that their type-II heterostructures are suitable for excitonic thin-film solar cell applications. Our results show that these heterojunctions have a potential maximum power conversion efficiency of up to 12%, which can be further enhanced up to 20% by strain engineering.

  1. Correction of the exciton Bohr radius in monolayer transition metal dichalcogenides

    Science.gov (United States)

    Li, Run-Ze; Dong, Xi-Ying; Li, Zhi-Qing; Wang, Zi-Wu

    2018-07-01

    We theoretically investigate the correction of exciton Bohr radius in monolayer transition metal dichalcogenides (TMDCs) on different polar substrates arising from the exciton-optical phonon coupling, in which both the intrinsic longitudinal optical phonon and surface optical phonon modes couple with the exciton are taken into account. We find that the exciton Bohr radius is enlarged markedly due to these coupling. Moreover, it can be changed on a large scale by modulating the polarizability of polar substrate and the internal distance between the monolayer TMDCs and polar substrate. Theoretical result provides a potential explanation for the variation of the exciton Bohr radius in experimental measurement.

  2. Magnetic anisotropy of two-dimensional nanostructures: Transition-metal triangular stripes

    International Nuclear Information System (INIS)

    Dorantes-Davila, J.; Villasenor-Gonzalez, P.; Pastor, G.M.

    2005-01-01

    The magnetic anisotropy energy (MAE) of one-dimensional stripes having infinite length and triangular lateral structure are investigated in the framework of a self-consistent tight-binding method. One observes discontinuous changes in the easy magnetization direction along the crossover from one to two dimensions. The MAE oscillates as a function of stripe width and depends strongly on the considered transition metal (TM). The MAE of the two-leg ladder is strongly reduced as compared to that of the monoatomic chain and the convergence to the two-dimensional limit is rather slow

  3. Electronic structure and magnetism in transition metals doped 8-hydroxy-quinoline aluminum.

    Science.gov (United States)

    Baik, Jeong Min; Shon, Yoon; Lee, Seung Joo; Jeong, Yoon Hee; Kang, Tae Won; Lee, Jong-Lam

    2008-10-15

    We report the room-temperature ferromagnetism in transition metals (Co, Ni)-doped 8-hydroxy-quinoline aluminum (Alq3) by thermal coevaporation of high purity metal and Alq3 powders. For 5% Co-doped Alq3, a maximum magnetization of approximately 0.33 microB/Co at 10 K was obtained and ferromagnetic behavior was observed up to 300 K. The Co atoms interact chemically with O atoms and provide electrons to Alq3, forming new states acting as electron trap sites. From this, it is suggested that ferromagnetism may be associated with the strong chemical interaction of Co atoms and Alq3 molecules.

  4. Optical nonlinearities of excitonic states in atomically thin 2D transition metal dichalcogenides

    Energy Technology Data Exchange (ETDEWEB)

    Soh, Daniel Beom Soo [Sandia National Lab. (SNL-CA), Livermore, CA (United States). Proliferation Signatures Discovery and Exploitation Department

    2017-08-01

    We calculated the optical nonlinearities of the atomically thin monolayer transition metal dichalcogenide material (particularly MoS2), particularly for those linear and nonlinear transition processes that utilize the bound exciton states. We adopted the bound and the unbound exciton states as the basis for the Hilbert space, and derived all the dynamical density matrices that provides the induced current density, from which the nonlinear susceptibilities can be drawn order-by-order via perturbative calculations. We provide the nonlinear susceptibilities for the linear, the second-harmonic, the third-harmonic, and the kerr-type two-photon processes.

  5. Activation barriers for series of exothermic homologous reactions. VI. Reactions of lanthanide and transition metal atoms.

    Science.gov (United States)

    Blue, Alan S.; Fontijn, Arthur

    2001-09-01

    Semiempirical configuration interaction (SECI) theory to predict activation barriers, E, as given by k(T)=ATn exp(-E(RT), has been applied to homologous series of lanthanide (LN) and transition metal (TM) atom oxidation reactions. This was achieved by considering as homologous series reactions of elements differing only by the number of electrons in one subshell. Comparison between SECI and experimental results leads to an average deviation for the LN+N2O reactions of 0.66 kJ mol-1, and up to 5.5 kJ mol-1 for other series. Thirty-one activation barriers are reported.

  6. Single-layer dispersions of transition metal dichalcogenides in the synthesis of intercalation compounds

    International Nuclear Information System (INIS)

    Golub, Alexander S; Zubavichus, Yan V; Slovokhotov, Yurii L; Novikov, Yurii N

    2003-01-01

    Chemical methods for the exfoliation of transition metal dichalcogenides in a liquid medium to give single-layer dispersions containing quasi-two-dimensional layers of these compounds are surveyed. Data on the structure of dispersions and their use in the synthesis of various types of heterolayered intercalation compounds are discussed and described systematically. Structural features, the electronic structure and the physicochemical properties of the resulting intercalation compounds are considered. The potential of this method of synthesis is compared with that of traditional solid-state methods for the intercalation of layered crystals.

  7. On matrix stabilisation of d- and f-transition metal ions in unstable oxidation states

    International Nuclear Information System (INIS)

    Kiselev, Yurii M

    2009-01-01

    The state-of-the-art in matrix stabilisation of d- and f-transition metal ions in unstable oxidation states is analysed. Main aspects of this problem concerning the genealogy of appropriate matrix systems are classified. Relevant examples are given and the data that contradict the scheme proposed are discussed. The thermodynamics of the matrix stabilisation effect is considered using the concept of isomorphic miscibility. The influence of defects and non-equilibrium on the matrix stabilisation effect is discussed. The problem of identification of the oxidation states in matrix systems is examined and various types of matrix systems are considered.

  8. High energy transmission of Al2O3 doped with light transition metals

    KAUST Repository

    Schuster, Cosima

    2012-01-31

    The transmission of transparent colored ceramics based on Al2O3doped with light transition metals is measured in the visible and infrared range. To clarify the role of the dopands we perform ab initiocalculations. We discuss the electronic structure and present optical spectra obtained in the independent particle approximation. We argue that the gross spectral features of Co- and Ni-doped Al2O3 samples are described by our model, while the validity of the approach is limited for Cr-doped Al2O3.

  9. Optical and electrical experiments at some transition-metal oxide foil-electrolyte interfaces

    International Nuclear Information System (INIS)

    Sari, S.O.; Ahlgren, W.L.

    1977-01-01

    Metal-oxide layers formed from transition-metal foils oxidized by heating in air have been examined for their photoelectrolytic response. The metals examined are Y, Ti, Zr, Hf, V, Nb, Ta, Mo, W, and Pt. Weak photoeffects are observed for oxide layers of all of these metals. Sizable light-dependent oxygen gas evolution rates are found in Ti and also in W oxides. The spectral dependence of the oxygen response in these compounds is investigated, and interpretation is given of these experiments

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

    DEFF Research Database (Denmark)

    Hao, Xian; Zhu, Nan; Gschneidtner, Tina

    2013-01-01

    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...... substrate surfaces and gold-coated atomic force microscopy tips. The coordination and bond breaking between terpyridine and osmium are followed in situ by electrochemically controlled atomic force microscopy at the single-molecule level. The redox state of the central metal atom is found to have...

  11. An efficient magnetic tight-binding method for transition metals and alloys

    DEFF Research Database (Denmark)

    Barreteau, Cyrille; Spanjaard, Daniel; Desjonquères, Marie-Catherine

    2016-01-01

    that does not necessitate any further fitting is proposed to deal with systems made of several chemical elements. This model is extended to spin (and orbital) polarized materials by adding Stoner-like and spin–orbit interactions. Collinear and non-collinear magnetism as well as spin-spirals are considered......An efficient parameterized self-consistent tight-binding model for transition metals using s, p and d valence atomic orbitals as a basis set is presented. The parameters of our tight-binding model for pure elements are determined from a fit to bulk ab-initio calculations. A very simple procedure...

  12. Optical properties of monolayer transition metal dichalcogenides probed by spectroscopic ellipsometry

    KAUST Repository

    Liu, Hsiang-Lin; Shen, Chih-Chiang; Su, Sheng-Han; Hsu, Chang-Lung; Li, Ming-Yang; Li, Lain-Jong

    2014-01-01

    Spectroscopic ellipsometry was used to characterize the complex refractive index of chemical-vapor-deposited monolayer transition metal dichalcogenides (TMDs). The extraordinary large value of the refractive index in the visible frequency range is obtained. The absorption response shows a strong correlation between the magnitude of the exciton binding energy and band gap energy. Together with the observed giant spin-orbit splitting, these findings advance the fundamental understanding of their novel electronic structures and the development of monolayer TMDs-based optoelectronic and spintronic devices.

  13. Using scaling relations to understand trends in the catalytic activity of transition metals

    International Nuclear Information System (INIS)

    Jones, G; Bligaard, T; Abild-Pedersen, F; Noerskov, J K

    2008-01-01

    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

  14. Tandem rhodium catalysis: exploiting sulfoxides for asymmetric transition-metal catalysis.

    Science.gov (United States)

    Kou, K G M; Dong, V M

    2015-06-07

    Sulfoxides are uncommon substrates for transition-metal catalysis due to their propensity to inhibit catalyst turnover. In a collaborative effort with Ken Houk, we developed the first dynamic kinetic resolution (DKR) of allylic sulfoxides using asymmetric rhodium-catalyzed hydrogenation. A detailed mechanistic analysis of this transformation using both experimental and theoretical methods revealed rhodium to be a tandem catalyst that promoted both hydrogenation of the alkene and racemization of the allylic sulfoxide. Using a combination of deuterium labelling and DFT studies, a novel mode of allylic sulfoxide racemization via a Rh(III)-π-allyl intermediate was identified.

  15. Valley polarization in magnetically doped single-layer transition-metal dichalcogenides

    KAUST Repository

    Cheng, Yingchun

    2014-04-28

    We demonstrate that valley polarization can be induced and controlled in semiconducting single-layer transition-metal dichalcogenides by magnetic doping, which is important for spintronics, valleytronics, and photonics devices. As an example, we investigate Mn-doped MoS2 by first-principles calculations. We study how the valley polarization depends on the strength of the spin orbit coupling and the exchange interaction and discuss how it can be controlled by magnetic doping. Valley polarization by magnetic doping is also expected for other honeycomb materials with strong spin orbit coupling and the absence of inversion symmetry.

  16. Room-Temperature Synthesis of Transition Metal Clusters and Main Group Polycations from Ionic Liquids

    OpenAIRE

    Ahmed, Ejaz

    2011-01-01

    Main group polycations and transition metal clusters had traditionally been synthesized via high-temperature routes by performing reactions in melts or by CTR, at room-temperature or lower temperature by using so-called superacid solvents, and at room-temperature in benzene–GaX3 media. Considering the major problems associated with higher temperature routes (e.g. long annealing time, risk of product decomposition, and low yield) and taking into account the toxicity of benzene and liquid SO2 i...

  17. High energy transmission of Al2O3 doped with light transition metals

    KAUST Repository

    Schuster, Cosima; Klimke, J.; Schwingenschlö gl, Udo

    2012-01-01

    The transmission of transparent colored ceramics based on Al2O3doped with light transition metals is measured in the visible and infrared range. To clarify the role of the dopands we perform ab initiocalculations. We discuss the electronic structure and present optical spectra obtained in the independent particle approximation. We argue that the gross spectral features of Co- and Ni-doped Al2O3 samples are described by our model, while the validity of the approach is limited for Cr-doped Al2O3.

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

    International Nuclear Information System (INIS)

    Kellar, S.A.; Lawrence Berkeley National Lab., CA

    1997-05-01

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

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

    Energy Technology Data Exchange (ETDEWEB)

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

    1997-05-01

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

  20. Characterization of transition metal-containing oxide systems by Mössbauer Spectroscopy

    Directory of Open Access Journals (Sweden)

    Z. Homonnay

    2004-12-01

    Full Text Available High-temperature (high-Tc superconductors and colossal magnetoresistant (CMR materials belong to the most promising materials of the past 2-3 decades for technical applications. Most of them are oxides and the crucial element which determines their useful physical properties is often a transition metal (Cu, Co, Fe, Mn. 57Fe Mössbauer Spectroscopy can be used to characterize the electronic and structural properties of transition metal-containing oxides by providing information on the local electronic structure of the lattice site where the Mössbauer probe is accommodated. By reviewing several Mössbauer studies, it is demonstrated how the layered (2D electronic structure of high-Tc superconductors can be deduced from the analysis of the Mössbauer isomer shift and quadrupole splitting. We also show how the Mössbauer isomer shift indicates metallicity of the ferromagnetic phase in the CMR material LaxSr1-xCoO3.

  1. Optical and Excitonic Properties of Atomically Thin Transition-Metal Dichalcogenides

    Science.gov (United States)

    Berkelbach, Timothy C.; Reichman, David R.

    2018-03-01

    Starting with the isolation of a single sheet of graphene, the study of layered materials has been one of the most active areas of condensed matter physics, chemistry, and materials science. Single-layer transition-metal dichalcogenides are direct-gap semiconducting analogs of graphene that exhibit novel electronic and optical properties. These features provide exciting opportunities for the discovery of both new fundamental physical phenomena as well as innovative device platforms. Here, we review the progress associated with the creation and use of a simple microscopic framework for describing the optical and excitonic behavior of few-layer transition-metal dichalcogenides, which is based on symmetry, band structure, and the effective interactions between charge carriers in these materials. This approach provides an often quantitative account of experiments that probe the physics associated with strong electron–hole interactions in these quasi two-dimensional systems and has been successfully employed by many groups to both describe and predict emergent excitonic behavior in these layered semiconducting systems.

  2. Electronic Structure of Transition Metal Clusters, Actinide Complexes and Their Reactivities

    Energy Technology Data Exchange (ETDEWEB)

    Krishnan Balasubramanian

    2009-07-18

    This is a continuing DOE-BES funded project on transition metal and actinide containing species, aimed at the electronic structure and spectroscopy of transition metal and actinide containing species. While a long term connection of these species is to catalysis and environmental management of high-level nuclear wastes, the immediate relevance is directly to other DOE-BES funded experimental projects at DOE-National labs and universities. There are a number of ongoing gas-phase spectroscopic studies of these species at various places, and our computational work has been inspired by these experimental studies and we have also inspired other experimental and theoretical studies. Thus our studies have varied from spectroscopy of diatomic transition metal carbides to large complexes containing transition metals, and actinide complexes that are critical to the environment. In addition, we are continuing to make code enhancements and modernization of ALCHEMY II set of codes and its interface with relativistic configuration interaction (RCI). At present these codes can carry out multi-reference computations that included up to 60 million configurations and multiple states from each such CI expansion. ALCHEMY II codes have been modernized and converted to a variety of platforms such as Windows XP, and Linux. We have revamped the symbolic CI code to automate the MRSDCI technique so that the references are automatically chosen with a given cutoff from the CASSCF and thus we are doing accurate MRSDCI computations with 10,000 or larger reference space of configurations. The RCI code can also handle a large number of reference configurations, which include up to 10,000 reference configurations. Another major progress is in routinely including larger basis sets up to 5g functions in thee computations. Of course higher angular momenta functions can also be handled using Gaussian and other codes with other methods such as DFT, MP2, CCSD(T), etc. We have also calibrated our RECP

  3. Quantitative chemical state XPS analysis of first row transition metals, oxides and hydroxides

    Energy Technology Data Exchange (ETDEWEB)

    Biesinger, M C; Payne, B P; McIntryre, N S [Department of Chemistry, University of Western Ontario, London, Ontario, N6A 5B7 (Canada); Hart, B R; Lau, L Wm [Surface Science Western, Room G1, Western Science Centre, University of Western Ontario, London, Ontario, N6A 5B7 (Canada); Grosvenor, A P [Department of Chemistry, Gunning/Lemieux Chemistry Centre, University of Alberta, Edmonton, Alberta, T6G 2G2 (Canada); Smart, R StC [ACeSSS, Applied Centre for Structural and Synchrotron Studies, University of South Australia, Mawson Lakes, SA 5095 (Australia)], E-mail: biesingr@uwo.ca

    2008-03-15

    Practical quantitative chemical state X-ray photoelectron spectroscopy (XPS) analysis of first row transition metals, oxides and hydroxides is challenging due to the complexity of their M 2p spectra. Complex multiplet splitting, shake-up and plasmon loss structure can play a role in the interpretation of the chemical states present. This paper will show practical curve fitting procedures for the quantitative measurement of different chemical states for metal oxides and hydroxides from a survey of transition metals. It will also discuss some of the limitations and pitfalls present as well as give practical examples of their successful use. These curve-fitting procedures are based on 1) standard spectra from quality reference samples, 2) a survey of appropriate literature databases and/or a compilation of literature references, 3) fitting of multiplet split spectra based on spectra of numerous reference materials and theoretical modelling, 4) spectral subtractions routines, again using reference spectra, and 5) specific literature references where fitting procedures are available.

  4. Increasing the solar cell power output by coating with transition metal-oxide nanorods

    International Nuclear Information System (INIS)

    Kuznetsov, I.A.; Greenfield, M.J.; Mehta, Y.U.; Merchan-Merchan, W.; Salkar, G.; Saveliev, A.V.

    2011-01-01

    Highlights: → Nanoparticles enhance solar cell efficiency. → Solar cell power increase by nanorod coating. → Metal-oxide nanorods are prepared in flames. → Molybdenum oxide nanorods effectively scatter light on solar cell surface. → Scattering efficiency depends on coating density. -- Abstract: Photovoltaic cells produce electric current through interactions among photons from an ambient light source and electrons in the semiconductor layer of the cell. However, much of the light incident on the panel is reflected or absorbed without inducing the photovoltaic effect. Transition metal-oxide nanoparticles, an inexpensive product of a process called flame synthesis, can cause scattering of light. Scattering can redirect photon flux, increasing the fraction of light absorbed in the thin active layer of silicon solar cells. This research aims to demonstrate that the application of transition metal-oxide nanorods to the surface of silicon solar panels can enhance the power output of the panels. Several solar panels were coated with a nanoparticle-methanol suspension, and the power outputs of the panels before and after the treatment were compared. The results demonstrate an increase in power output of up to 5% after the treatment. The presence of metal-oxide nanorods on the surface of the coated solar cells is confirmed by electron microscopy.

  5. Kinetics of self-interstitial migration in bcc and fcc transition metals

    Science.gov (United States)

    Bukkuru, S.; Bhardwaj, U.; Srinivasa Rao, K.; Rao, A. D. P.; Warrier, M.; Valsakumar, M. C.

    2018-03-01

    Radiation damage is a multi-scale phenomenon. A thorough understanding of diffusivities and the migration energies of defects is a pre-requisite to quantify the after-effects of irradiation. We investigate the thermally activated mobility of self-interstitial atom (SIA) in bcc transition metals Fe, Mo, Nb and fcc transition metals Ag, Cu, Ni, Pt using molecular dynamics (MD) simulations. The self-interstitial diffusion involves various mechanisms such as interstitialcy, dumbbell or crowdion mechanisms. Max-Space Clustering (MSC) method has been employed to identify the interstitial and its configuration over a wide range of temperature. The self-interstitial diffusion is Arrhenius like, however, there is a slight deviation at high temperatures. The migration energies, pre-exponential factors of diffusion and jump-correlation factors, obtained from these simulations can be used as inputs to Monte Carlo simulations of defect transport. The jump-correlation factor shows the degree of preference of rectilinear or rotational jumps. We obtain the average jump-correlation factor of 1.4 for bcc metals and 0.44 for fcc metals. It indicates that rectilinear jumps are preferred in bcc metals and rotational jumps are preferred in fcc metals.

  6. Quantitative chemical state XPS analysis of first row transition metals, oxides and hydroxides

    International Nuclear Information System (INIS)

    Biesinger, M C; Payne, B P; McIntryre, N S; Hart, B R; Lau, L Wm; Grosvenor, A P; Smart, R StC

    2008-01-01

    Practical quantitative chemical state X-ray photoelectron spectroscopy (XPS) analysis of first row transition metals, oxides and hydroxides is challenging due to the complexity of their M 2p spectra. Complex multiplet splitting, shake-up and plasmon loss structure can play a role in the interpretation of the chemical states present. This paper will show practical curve fitting procedures for the quantitative measurement of different chemical states for metal oxides and hydroxides from a survey of transition metals. It will also discuss some of the limitations and pitfalls present as well as give practical examples of their successful use. These curve-fitting procedures are based on 1) standard spectra from quality reference samples, 2) a survey of appropriate literature databases and/or a compilation of literature references, 3) fitting of multiplet split spectra based on spectra of numerous reference materials and theoretical modelling, 4) spectral subtractions routines, again using reference spectra, and 5) specific literature references where fitting procedures are available

  7. Recent advances in controlled synthesis of two-dimensional transition metal dichalcogenides via vapour deposition techniques

    KAUST Repository

    Shi, Yumeng; Li, Henan; Li, Lain-Jong

    2014-01-01

    In recent years there have been many breakthroughs in two-dimensional (2D) nanomaterials, among which the transition metal dichalcogenides (TMDs) attract significant attention owing to their unusual properties associated with their strictly defined dimensionalities. TMD materials with a generalized formula of MX2, where M is a transition metal and X is a chalcogen, represent a diverse and largely untapped source of 2D systems. Semiconducting TMD monolayers such as MoS2, MoSe2, WSe2 and WS2 have been demonstrated to be feasible for future electronics and optoelectronics. The exotic electronic properties and high specific surface areas of 2D TMDs offer unlimited potential in various fields including sensing, catalysis, and energy storage applications. Very recently, the chemical vapour deposition technique (CVD) has shown great promise to generate high-quality TMD layers with a scalable size, controllable thickness and excellent electronic properties. Wafer-scale deposition of mono to few layer TMD films has been obtained. Despite the initial success in the CVD synthesis of TMDs, substantial research studies on extending the methodology open up a new way for substitution doping, formation of monolayer alloys and producing TMD stacking structures or superlattices. In this tutorial review, we will introduce the latest development of the synthesis of monolayer TMDs by CVD approaches.

  8. The ternary post-transition metal carbodiimide SrZn(NCN)2

    International Nuclear Information System (INIS)

    Corkett, Alex J.; Konze, Philipp M.; Dronskowski, Richard

    2017-01-01

    SrZn(NCN) 2 , the first example of a ternary post-transition metal carbodiimide, was prepared by a solid-state metathesis reaction. The crystal structure was solved from PXRD data and found to adopt the orthorhombic (Cmcm) BaZnSO structure, a high symmetry modification of that expressed by the oxide analogue SrZnO 2 . Locally, SrZn(NCN) 2 features ZnN 4 tetrahedra and SrN 6 trigonal prisms similar to those in quarternary LiSr 2 M(NCN) 4 (M = Al 3+ and Ga 3+ ) phases, however, the overall topologies are distinct with single chains in the former and double chains in the latter. Electronic structure calculations indicate an indirect bandgap of about 2.95 eV in SrZn(NCN) 2 , slightly lower than the experimentally observed bandgap of 3.4 eV in SrZnO 2 and consistent with a greater degree of covalency. The structural similarities between SrZn(NCN) 2 and oxychalcogenide analogues highlight the pseudochalcogenide character of NCN 2- and suggest that the title compound may serve as a template for accessing novel ternary carbodiimides featuring tetrahedrally coordinated transition metals. (copyright 2017 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  9. Transition metal-modified zinc oxides for UV and visible light photocatalysis.

    Science.gov (United States)

    Bloh, J Z; Dillert, R; Bahnemann, D W

    2012-11-01

    In order to use photocatalysis with solar light, finding more active and especially visible light active photocatalysts is a very important challenge. Also, studies of these photocatalysts should employ a standardized test procedure so that their results can be accurately compared and evaluated with one another. A systematic study of transition metal-modified zinc oxide was conducted to determine whether they are suitable as visible light photocatalysts. The photocatalytic activity of ZnO modified with eight different transition metals (Cu, Co, Fe, Mn, Ni, Ru, Ti, Zr) in three different concentrations (0.01, 0.1, and 1 at.%) was investigated under irradiation with UV as well as with visible light. The employed activity test is the gas-phase degradation of acetaldehyde as described by the ISO standard 22197-2. The results suggest that the UV activity can be improved with almost any modification element and that there exists an optimal modification ratio at about 0.1 at.%. Additionally, Mn- and Ru-modified ZnO display visible light activity. Especially the Ru-modified ZnO is highly active and surpasses the visible light activity of all studied titania standards. These findings suggest that modified zinc oxides may be a viable alternative to titanium dioxide-based catalysts for visible light photocatalysis. Eventually, possible underlying mechanisms are proposed and discussed.

  10. Reference Determinant Dependence of the Random Phase Approximation in 3d Transition Metal Chemistry.

    Science.gov (United States)

    Bates, J E; Mezei, P D; Csonka, G I; Sun, J; Ruzsinszky, A

    2017-01-10

    Without extensive fitting, accurate prediction of transition metal chemistry is a challenge for semilocal and hybrid density funcitonals. The Random Phase Approximation (RPA) has been shown to yield superior results to semilocal functionals for main group thermochemistry, but much less is known about its performance for transition metals. We have therefore analyzed the behavior of reaction energies, barrier heights, and ligand dissociation energies obtained with RPA and compare our results to several semilocal and hybrid functionals. Particular attention is paid to the reference determinant dependence of RPA. We find that typically the results do not vary much between semilocal or hybrid functionals as a reference, as long as the fraction of exact exchange (EXX) mixing in the hybrid functional is small. For large fractions of EXX mixing, however, the Hartree-Fock-like nature of the determinant can severely degrade the performance. Overall, RPA systematically reduces the errors of semilocal functionals and delivers excellent performance from a single reference determinant for inherently multireference reactions. The behavior of dual hybrids that combine RPA correlation with a hybrid exchange energy was also explored, but ultimately did not lead to a systematic improvement compared to traditional RPA for these systems. We rationalize this conclusion by decomposing the contributions to the reaction energies, and briefly discuss the possible implications for double-hybrid functionals based on RPA. The correlation between EXX mixing and spin-symmetry breaking is also discussed.

  11. Visualizing band offsets and edge states in bilayer–monolayer transition metal dichalcogenides lateral heterojunction

    KAUST Repository

    Zhang, Chendong

    2016-01-18

    Semiconductor heterostructures are fundamental building blocks for many important device applications. The emergence of two-dimensional semiconductors opens up a new realm for creating heterostructures. As the bandgaps of transition metal dichalcogenides thin films have sensitive layer dependence, it is natural to create lateral heterojunctions (HJs) using the same materials with different thicknesses. Here we show the real space image of electronic structures across the bilayer–monolayer interface in MoSe2 and WSe2, using scanning tunnelling microscopy and spectroscopy. Most bilayer–monolayer HJs are found to have a zig-zag-orientated interface, and the band alignment of such atomically sharp HJs is of type-I with a well-defined interface mode that acts as a narrower-gap quantum wire. The ability to utilize such commonly existing thickness terraces as lateral HJs is a crucial addition to the tool set for device applications based on atomically thin transition metal dichalcogenides, with the advantage of easy and flexible implementation.

  12. Understanding the Enhanced Catalytic Performance of Ultrafine Transition Metal Nanoparticles–Graphene Composites

    KAUST Repository

    Liu, Xin

    2015-08-11

    Catalysis, as the key to minimize the energy requirement and environmental impact of today\\'s chemical industry, plays a vital role in many fields directly related to our daily life and economy, including energy generation, environment control, manufacture of chemicals, medicine synthesis, etc. Rational design and fabrication of highly efficient catalysts have become the ultimate goal of today\\'s catalysis research. For the purpose of handling and product separation, heterogeneous catalysts are highly preferred for industrial applications and a large part of which are the composites of transition metal nanoparticles (TMNPs). With the fast development of nanoscience and nanotechnology and assisted with theoretical investigations, basic understanding on tailoring the electronic structure of these nanocomposites has been gained, mainly by precise control of the composition, morphology, interfacial structure and electronic states. With the rise of graphene, chemical routes to prepare graphene were developed and various graphene-based composites were fabricated. Transition metal nanoparticles-reduced graphene oxide (TMNPs–rGO) composites have attracted considerable attention, because of their intriguing catalytic performance which have been extensively explored for energy- and environment-related applications to date. This review summarizes our recent experimental and theoretical efforts on understanding the superior catalytic performance of subnanosized TMNPs–rGO composites.

  13. Ab initio theory of noble gas atoms in bcc transition metals.

    Science.gov (United States)

    Jiang, Chao; Zhang, Yongfeng; Gao, Yipeng; Gan, Jian

    2018-06-18

    Systematic ab initio calculations based on density functional theory have been performed to gain fundamental understanding of the interactions between noble gas atoms (He, Ne, Ar and Kr) and bcc transition metals in groups 5B (V, Nb and Ta), 6B (Cr, Mo and W) and 8B (Fe). Our charge density analysis indicates that the strong polarization of nearest-neighbor metal atoms by noble gas interstitials is the electronic origin of their high formation energies. Such polarization becomes more significant with an increasing gas atom size and interstitial charge density in the host bcc metal, which explains the similar trend followed by the unrelaxed formation energies of noble gas interstitials. Upon allowing for local relaxation, nearby metal atoms move farther away from gas interstitials in order to decrease polarization, albeit at the expense of increasing the elastic strain energy. Such atomic relaxation is found to play an important role in governing both the energetics and site preference of noble gas atoms in bcc metals. Our most notable finding is that the fully relaxed formation energies of noble gas interstitials are strongly correlated with the elastic shear modulus of the bcc metal, and the physical origin of this unexpected correlation has been elucidated by our theoretical analysis based on the effective-medium theory. The kinetic behavior of noble gas atoms and their interaction with pre-existing vacancies in bcc transition metals have also been discussed in this work.

  14. Upgrading of heavy crude oil with supported and unsupported transition metals

    Energy Technology Data Exchange (ETDEWEB)

    Nares, H.R.; Schacht-Hernandez, P.; Cabrera-Reyes, M.C.; Ramirez-Garnica, M.; Cazarez-Candia, O. [Instituto Mexicano del Petroleo, Atepehuacan (Mexico)

    2006-07-01

    Heavy crude oil presents many problems such as difficulty in transportation, low processing capacity in refineries, and low mobility through the reservoir due to high viscosity which affects the index of productivity of the wells. Because of these challenges, it is necessary to enhance heavy crude oil, both aboveground and underground. The effects of several metallic oxides used to upgrade heavy crude oil properties were examined in order to increase the mobility of reservoir oil by reducing viscosity and improving the quality of the oil. This can be accomplished by reducing the asphaltene and sulfur contents and increasing the American Petroleum Institute (API) gravity using transition metal supported in alumina and unsupported from transition metals derived from either acetylacetonate or alkylhexanoate in liquid phase homogeneously mixed with heavy crude oil as well as metal transition supported in alumina. KU-H heavy crude oil from the Golf of Mexico was studied. The results were obtained by Simulated Distillation and True Boiling Point (TBP). It was concluded that the use of crude oil thermal hydrocracking allowed the API gravity to increase and considerably reduce the viscosity. As a result, the productivity index in wells was increased. However there is a high formation of coke that could damage the conductivity of the rock and then reduce the potential of oil recovery. 27 refs., 3 tabs., 5 figs.

  15. Cycloadditions to Epoxides Catalyzed by GroupIII-V Transition-Metal Complexes

    KAUST Repository

    D'Elia, Valerio

    2015-05-25

    Complexes of groupIII-V transition metals are gaining increasing importance as Lewis acid catalysts for the cycloaddition of dipolarophiles to epoxides. This review examines the latest reports, including homogeneous and heterogeneous applications. The pivotal step for the cycloaddition reactions is the ring opening of the epoxide following activation by the Lewis acid. Two modes of cleavage (C-C versus C-O) have been identified depending primarily on the substitution pattern of the epoxide, with lesser influence observed from the Lewis acid employed. The widely studied cycloaddition of CO2 to epoxides to afford cyclic carbonates (C-O bond cleavage) has been scrutinized in terms of catalytic efficiency and reaction mechanism, showing that unsophisticated complexes of groupIII-V transition metals are excellent molecular catalysts. These metals have been incorporated, as well, in highly performing, recyclable heterogeneous catalysts. Cycloadditions to epoxides with other dipolarophiles (alkynes, imines, indoles) have been conducted with scandium triflate with remarkable performances (C-C bond cleavage). © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. First-principles studies on 3d transition metal atom adsorbed twin graphene

    Science.gov (United States)

    Li, Lele; Zhang, Hong; Cheng, Xinlu; Miyamoto, Yoshiyuki

    2018-05-01

    Twin graphene is a new two-dimensional semiconducting carbon allotrope which is proposed recently. The structural, magnetic and electronic properties are investigated for 3d transition metal (TM) atom adsorbed twin graphene by means of GGA+U calculations. The results show most of single 3d transition metal atom except Zn can make twin graphene magnetization. The adsorption of single TM atom can also make the twin graphene systems turn to half metal (V adsorption), half-semiconductor (Fe adsorption) or metal (Sc, Cr, Mn, Co and Cu adsorption). The semiconducting nature still exists for Ti, Ni and Zn adsorption. All the 3d TM adatoms belong to n-type doping for transferring charge to the neighboring C atoms and have strong covalent bond with these C atoms. The influence of Hubbard U value on half-metallic V adsorbed system is also considered. As the U increases, the system can gradually transform from metal to half metal and metal. The effect of the coverage is investigated for two TM atoms (Sc-Fe) adsorption, too. We can know TM atoms adsorbed twin graphene have potentials to be spintronic device and nanomagnets from the results.

  17. Redox Active Transition Metal ions Make Melanin Susceptible to Chemical Degradation Induced by Organic Peroxide.

    Science.gov (United States)

    Zadlo, Andrzej; Pilat, Anna; Sarna, Michal; Pawlak, Anna; Sarna, Tadeusz

    2017-12-01

    With aging, retinal pigment epithelium melanosomes, by fusion with the age pigment lipofuscin, form complex granules called melanolipofuscin. Lipofuscin granules may contain oxidized proteins and lipid hydroperoxides, which in melanolipofuscin could chemically modify melanin polymer, while transition metal ions present in melanin can accelerate such oxidative modifications. The aim of this research was to examine the effect of selected transition metal ions on melanin susceptibility to chemical modification induced by the water-soluble tert-butyl hydroperoxide used as an oxidizing agent. Synthetic melanin obtained by DOPA autooxidation and melanosomes isolated from bovine retinal pigment epithelium were analyzed. To monitor tert-butyl hydroperoxide-induced oxidative changes of DMa and BMs, electron paramagnetic resonance spectroscopy, UV-vis absorption spectroscopy, dynamic light scattering, atomic force microscopy and electron paramagnetic resonance oximetry were employed. These measurements revealed that both copper and iron ions accelerated chemical degradation induced by tert-butyl hydroperoxide, while zinc ions had no effect. Strong prooxidant action was detected only in the case of melanosomes and melanin degraded in the presence of iron. It can be postulated that similar chemical processes, if they occur in situ in melanolipofuscin granules of the human retinal pigment epithelium, would modify antioxidant properties of melanin and its reactivity.

  18. Electronic Structure of Transition Metal Clusters, Actinide Complexes and Their Reactivities

    International Nuclear Information System (INIS)

    Balasubramanian, Krishnan

    2009-01-01

    This is a continuing DOE-BES funded project on transition metal and actinide containing species, aimed at the electronic structure and spectroscopy of transition metal and actinide containing species. While a long term connection of these species is to catalysis and environmental management of high-level nuclear wastes, the immediate relevance is directly to other DOE-BES funded experimental projects at DOE-National labs and universities. There are a number of ongoing gas-phase spectroscopic studies of these species at various places, and our computational work has been inspired by these experimental studies and we have also inspired other experimental and theoretical studies. Thus our studies have varied from spectroscopy of diatomic transition metal carbides to large complexes containing transition metals, and actinide complexes that are critical to the environment. In addition, we are continuing to make code enhancements and modernization of ALCHEMY II set of codes and its interface with relativistic configuration interaction (RCI). At present these codes can carry out multi-reference computations that included up to 60 million configurations and multiple states from each such CI expansion. ALCHEMY II codes have been modernized and converted to a variety of platforms such as Windows XP, and Linux. We have revamped the symbolic CI code to automate the MRSDCI technique so that the references are automatically chosen with a given cutoff from the CASSCF and thus we are doing accurate MRSDCI computations with 10,000 or larger reference space of configurations. The RCI code can also handle a large number of reference configurations, which include up to 10,000 reference configurations. Another major progress is in routinely including larger basis sets up to 5g functions in thee computations. Of course higher angular momenta functions can also be handled using Gaussian and other codes with other methods such as DFT, MP2, CCSD(T), etc. We have also calibrated our RECP

  19. Cycloadditions to Epoxides Catalyzed by GroupIII-V Transition-Metal Complexes

    KAUST Repository

    D'Elia, Valerio; Pelletier, Jeremie; Basset, Jean-Marie

    2015-01-01

    Complexes of groupIII-V transition metals are gaining increasing importance as Lewis acid catalysts for the cycloaddition of dipolarophiles to epoxides. This review examines the latest reports, including homogeneous and heterogeneous applications. The pivotal step for the cycloaddition reactions is the ring opening of the epoxide following activation by the Lewis acid. Two modes of cleavage (C-C versus C-O) have been identified depending primarily on the substitution pattern of the epoxide, with lesser influence observed from the Lewis acid employed. The widely studied cycloaddition of CO2 to epoxides to afford cyclic carbonates (C-O bond cleavage) has been scrutinized in terms of catalytic efficiency and reaction mechanism, showing that unsophisticated complexes of groupIII-V transition metals are excellent molecular catalysts. These metals have been incorporated, as well, in highly performing, recyclable heterogeneous catalysts. Cycloadditions to epoxides with other dipolarophiles (alkynes, imines, indoles) have been conducted with scandium triflate with remarkable performances (C-C bond cleavage). © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. A search for superconductivity below 1 K in transition metal borides

    International Nuclear Information System (INIS)

    Leyarovska, L.; Leyarovski, E.

    1979-01-01

    Some AlB 2 -type (C32 structure) boron compounds were examined for superconductivity down to 0.42 K; the compounds have the formula MeB 2 (Me equivalent to Ti, Zr, Hf, V, Nb, Ta, Cr, Mo) (the atomic ratio of metal to boron was 0.5). Only NbB 2 was found to be superconducting with Tsub(c) = 0.62 K and a surprisingly high value of Hsub(c)(0), about 1600 Oe. Other transition metal as well as non-transition metal boron phases were also tested for superconductivity down to 0.42 K; these compounds were MeB 2 (Me equivalent to Ca, Sr, Ba), W 2 B 5 , CrB, Cr 5 B 3 , UB 2 , UB 4 and UB 12 . None of these compounds proved to be superconducting above 0.42 K; nor was any trace of superconductivity down to 0.42 K observed in MoB and NbB. (Auth.)

  1. The ternary post-transition metal carbodiimide SrZn(NCN){sub 2}

    Energy Technology Data Exchange (ETDEWEB)

    Corkett, Alex J.; Konze, Philipp M. [Institute of Inorganic Chemistry, RWTH Aachen University, Aachen (Germany); Dronskowski, Richard [Institute of Inorganic Chemistry, RWTH Aachen University, Aachen (Germany); Juelich-Aachen Research Alliance (JARA-HPC), RWTH-Aachen University, Aachen (Germany)

    2017-11-17

    SrZn(NCN){sub 2}, the first example of a ternary post-transition metal carbodiimide, was prepared by a solid-state metathesis reaction. The crystal structure was solved from PXRD data and found to adopt the orthorhombic (Cmcm) BaZnSO structure, a high symmetry modification of that expressed by the oxide analogue SrZnO{sub 2}. Locally, SrZn(NCN){sub 2} features ZnN{sub 4} tetrahedra and SrN{sub 6} trigonal prisms similar to those in quarternary LiSr{sub 2}M(NCN){sub 4} (M = Al{sup 3+} and Ga{sup 3+}) phases, however, the overall topologies are distinct with single chains in the former and double chains in the latter. Electronic structure calculations indicate an indirect bandgap of about 2.95 eV in SrZn(NCN){sub 2}, slightly lower than the experimentally observed bandgap of 3.4 eV in SrZnO{sub 2} and consistent with a greater degree of covalency. The structural similarities between SrZn(NCN){sub 2} and oxychalcogenide analogues highlight the pseudochalcogenide character of NCN{sup 2-} and suggest that the title compound may serve as a template for accessing novel ternary carbodiimides featuring tetrahedrally coordinated transition metals. (copyright 2017 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  2. Direct detection and quantification of transition metal ions in human atherosclerotic plaques

    DEFF Research Database (Denmark)

    Stadler, Nadina; Lindner, Robyn A; Davies, Michael Jonathan

    2004-01-01

    OBJECTIVE: The involvement of transition metals in atherosclerosis is controversial. Some epidemiological studies have reported a relationship between iron (Fe) and cardiovascular disease, whereas others have not. Experimental studies have reported elevated levels of iron and copper (Cu) in disea......OBJECTIVE: The involvement of transition metals in atherosclerosis is controversial. Some epidemiological studies have reported a relationship between iron (Fe) and cardiovascular disease, whereas others have not. Experimental studies have reported elevated levels of iron and copper (Cu......) in diseased human arteries but have often used methods that release metal ions from proteins. METHODS AND RESULTS: In this study, we have used the minimally invasive technique of electron paramagnetic resonance (EPR) spectroscopy and inductively coupled plasma mass spectroscopy (ICPMS) to quantify iron...... and copper in ex vivo healthy human arteries and carotid lesions. The EPR spectra detected are characteristic of nonheme Fe(III) complexes. Statistically elevated levels of iron were detected in the intima of lesions compared with healthy controls (0.370 versus 0.022 nmol/mg tissue for EPR, 0.525 versus 0...

  3. Electronic Structure of the fcc Transition Metals Ir, Rh, Pt, and Pd

    DEFF Research Database (Denmark)

    Andersen, O. Krogh

    1970-01-01

    We give a complete description of a relativistic augmented-plane-wave calculation of the band structures of the paramagnetic fcc transition metals Ir, Rh, Pt, and Pd. The width and position of the d band decrease in the sequence Ir, Pt, Rh, Pd; and N(EF)=13.8,23.2,18.7, and 32.7 (states/atom)/Ry,......We give a complete description of a relativistic augmented-plane-wave calculation of the band structures of the paramagnetic fcc transition metals Ir, Rh, Pt, and Pd. The width and position of the d band decrease in the sequence Ir, Pt, Rh, Pd; and N(EF)=13.8,23.2,18.7, and 32.7 (states....../atom)/Ry, respectively. Spin-orbit coupling is important for all four metals and the coupling parameter varies by 30% over the d bandwidth. Detailed comparisons with de Haas—van Alphen Fermi-surface dimensions have previously been presented and the agreement was very good. Comparison with measured electronic specific...

  4. CPA theory of the magnetization in rare earth transition metal alloys

    International Nuclear Information System (INIS)

    Szpunar, B.; Lindgaard, P.A.

    1976-11-01

    Calculations were made of the magnetic moment per atom of the transition metal and the rare earth metal in the intermetallic compounds, Gdsub(1-x)Nisub(x), Gdsub(1-x)Fesub(x), Gdsub(1-x)Cosub(x), and Ysub(1-x)Cosub(x). A simple model of the disordered alloy consisting of spins localized on the rare earth atoms and interacting with a narrow d-band is considered. The magnetic moment of the alloy at zero temperature is calculated within the molecular field and Hartree-Fock approximations. Disorder is treated in the coherent potential approximation. Results are in good agreement with the experimental data obtained for the crystalline and amorphous intermetallic compounds. It is shown that the temperature dependence of the magnetic moments and Curie and ferrimagnetic compensation temperatures can be accounted for by a simple model assuming a RKKY interaction between the rare-earth moments and the transition metal pseudo spin. The interaction is mediated by an effective alloy medium calculated using the CPA theory and elliptic densities of states. (Auth.)

  5. Photoelectrochemical properties and band structure of oxide films on zirconium-transition metal alloys

    International Nuclear Information System (INIS)

    Takahashi, Kazuo; Uno, Masayoshi; Okui, Mihoko; Yamanaka, Shinsuke

    2006-01-01

    The microalloying effects of 4d and 5d transition metals, M (M: Nb, Mo, Ta, W) on the photoelectrochemical properties, the flat band potential (U fb ) and the band gap energy (E g ), for zirconium oxide films were investigated by photoelectrochemical measurements and band calculation. Button ingots of zirconium-5 mol% M (M: Nb, Mo, Ta, W) were made from high-purity metals (99.9% purity) by arc melting in a purified argon atmosphere. These plate specimens were sealed into silica tubes in vacuum, and then homogenized at 1273 K for 24 h. Subsequently, these specimens were oxidized up to 1173 K. The photocurrent of each specimen was evaluated at room temperature under the irradiation of Xe lamp (500 W) through grating monochrometer and cut-off filter. 0.1 M Na 2 SO 4 solution was used as the electrolyte. The value of the flat band potential was higher and the value of the band gap energy was smaller than that of pure zirconium oxide film in all sample. It was found from the calculation by CASTEP code that the decreases in band gap energy of these oxide films was due to formation of 4d or 5d orbital of transition metals

  6. Antimicrobial activity of transition metal acid MoO3 prevents microbial growth on material surfaces

    International Nuclear Information System (INIS)

    Zollfrank, Cordt; Gutbrod, Kai; Wechsler, Peter; Guggenbichler, Josef Peter

    2012-01-01

    Serious infectious complications of patients in healthcare settings are often transmitted by materials and devices colonised by microorganisms (nosocomial infections). Current strategies to generate material surfaces with an antimicrobial activity suffer from the consumption of the antimicrobial agent and emerging multidrug-resistant pathogens amongst others. Consequently, materials surfaces exhibiting a permanent antimicrobial activity without the risk of generating resistant microorganisms are desirable. This publication reports on the extraordinary efficient antimicrobial properties of transition metal acids such as molybdic acid (H 2 MoO 4 ), which is based on molybdenum trioxide (MoO 3 ). The modification of various materials (e.g. polymers, metals) with MoO 3 particles or sol–gel derived coatings showed that the modified materials surfaces were practically free of microorganisms six hours after contamination with infectious agents. The antimicrobial activity is based on the formation of an acidic surface deteriorating cell growth and proliferation. The application of transition metal acids as antimicrobial surface agents is an innovative approach to prevent the dissemination of microorganisms in healthcare units and public environments. Highlights: ► The presented modifications of materials surfaces with MoO 3 are non-cytotoxic and decrease biofilm growth and bacteria transmission. ► The material is insensitive towards emerging resistances of bacteria. ► Strong potential to reduce spreading of infectious agents on inanimate surfaces.

  7. ANTIBACTERIAL ACTIVITY OF BENZIMIDAZOLES 2-THIO, 2-AMINODERIVATIVES AND COMPLEXES OF BENZIMIDAZOLES WITH TRANSITIONAL METALS

    Directory of Open Access Journals (Sweden)

    E. I. Mayboroda

    2014-01-01

    Full Text Available The literature data about antibacterial properties of benzimidazole 2-thio-, 2-aminoderivatives and benzimidazole complexes have been generalized and systematized in the review. Today prevention and treatment of diseases caused by microorganisms is an actual problem of modern therapy. Therefore, the search for active molecules, the based on them development of some new, more effective antimicrobial agents is an important task of modern pharmaceutical chemistry. Promising compounds for solving these problems are benzimidazole derivatives. They are available, functionally capable, stable and have a wide spectrum of biological activities (antiviral, anthelmintic, antibacterial, anticancer, antidiabetic.The purpose of this paper is to generalize and systematize information about the antimicrobial action of 2-thio-, 2-amino-substituted benzimidazoles and benzimidazole derivatives complexes with transition metals.These compounds and their complexes with transition metals are active against pathogenic strains Escherichia coli, Pseudomonas aeruginosa, Staphylococcus aureus, Salmonella typhimurium, Proteus vulgaris, Bacillus cereus, Micrococcus luteus, Helicobacter рylori and others.

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

    Science.gov (United States)

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

    2016-06-01

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

  9. Tunneling measurements in amorphous layers of superconducting transition metals: molybdenum, vanadium, and niobium

    International Nuclear Information System (INIS)

    Roll, U.

    1981-01-01

    Tunneling experiments with amorphous Molybdenum and Vanadium layers are presented, showing no significant increase of the reduced energy gap 2δ(O)/kTsub(c)(δ) compared with the BCS-value, in contrast to all previous measurement on amorphous superconducting materials of simple s-p-metals, showing on enhanced electron-phonon-interaction. This fact may lead to the conclusion that the strong electron-phonon coupling is caused by the amorphous structure of the superconductor. The present results, however, indicate that the strong electron-phonon interaction cannot be explained only ba the amorphous structure of the superconductor. In the measurements of the second derivative d 2 U/dI 2 no phonon-induced structures have been observed for amorphous molybdenum, vanadium and niobium films. Apparently the phonon density of states F(#betta#) of amorphous transition metals has no structure, thus the longitudinal and transverse phonons cannot be identified in the measured (d 2 U/dI 2 )-curves. This particular behaviour of the amorphous transition metals in contrast to the simple s-p-metals may be interpreted by the strongly localized d-electrons. (orig./GG) [de

  10. Recent advances in controlled synthesis of two-dimensional transition metal dichalcogenides via vapour deposition techniques

    KAUST Repository

    Shi, Yumeng

    2014-10-20

    In recent years there have been many breakthroughs in two-dimensional (2D) nanomaterials, among which the transition metal dichalcogenides (TMDs) attract significant attention owing to their unusual properties associated with their strictly defined dimensionalities. TMD materials with a generalized formula of MX2, where M is a transition metal and X is a chalcogen, represent a diverse and largely untapped source of 2D systems. Semiconducting TMD monolayers such as MoS2, MoSe2, WSe2 and WS2 have been demonstrated to be feasible for future electronics and optoelectronics. The exotic electronic properties and high specific surface areas of 2D TMDs offer unlimited potential in various fields including sensing, catalysis, and energy storage applications. Very recently, the chemical vapour deposition technique (CVD) has shown great promise to generate high-quality TMD layers with a scalable size, controllable thickness and excellent electronic properties. Wafer-scale deposition of mono to few layer TMD films has been obtained. Despite the initial success in the CVD synthesis of TMDs, substantial research studies on extending the methodology open up a new way for substitution doping, formation of monolayer alloys and producing TMD stacking structures or superlattices. In this tutorial review, we will introduce the latest development of the synthesis of monolayer TMDs by CVD approaches.

  11. Synthesis, spectroscopic characterization, biological screenings, DNA binding study and POM analyses of transition metal carboxylates

    Science.gov (United States)

    Uddin, Noor; Sirajuddin, Muhammad; Uddin, Nizam; Tariq, Muhammad; Ullah, Hameed; Ali, Saqib; Tirmizi, Syed Ahmed; Khan, Abdur Rehman

    2015-04-01

    This article contains the synthesis of a novel carboxylic acid derivative, its transition metal complexes and evaluation of biological applications. Six carboxylate complexes of transition metals, Zn(II) and Hg(II), have been successfully synthesized and characterized by FT-IR and NMR (1H, 13C). The ligand, HL, (4-[(2,6-Diethylphenyl)amino]-4-oxobutanoic acid) was also characterized by single crystal X-ray analysis. The complexation occurs via oxygen atoms of the carboxylate moiety. FT-IR date show the bidentate nature of the carboxylate moiety of the ligand as the Δν value in all complexes is less than that of the free ligand. The ligand and its complexes were screened for antifungal and antileishmanial activities. The results showed that the ligand and its complexes are active with few exceptions. UV-visible spectroscopy and viscometry results reveal that the ligand and its complexes interact with the DNA via intercalative mode of interaction. A new and efficient strategy to identify the pharmacophores and anti-pharmacophores sites in carboxylate derivatives for the antibacterial/antifungal activity using Petra, Osiris and Molinspiration (POM) analyses was also carried out.

  12. XPS and XAES measurements on trapped rare gases in transition metals

    International Nuclear Information System (INIS)

    Baba, Y.; Yamamoto, H.; Sasaki, T.A.

    1992-01-01

    Electronic structures of rare gases implanted in various transition metals have been investigated by means of an X-ray photoelectron spectroscopy (XPS) and X-ray-induced Auger electron spectroscopy (XAES). The Auger-parameter method is applied to the evaluation of electronic relaxation energy of rare gas atoms due to the surrounding metal potential. The extra-atomic relaxation energy of four kinds of rare gases (Ne, Ar, Kr, Xe) in the same metal matrix (Ti) increases with the atomic mass of the rare gases. On the other hand, the extra-atomic relaxation energy of the same rare gas (Xe) in different metal matrices ranges from 3.0 eV (in Mo). These values increase with the number of d-electrons in the metals. This tendency and the absolute values of the relaxation energies are in good agreement with those calculated for 3d transition metals referenced to their gas-phase values. Based on these results, it is concluded that the energetically implanted rare gases are trapped at the substitution site in the metal lattice as an isolated atom, and the trapped atoms feel the surrounding metal potential. It is also made clear that the potential affecting the implanted atom is d-like, and the relaxation energy of the implanted rare gas during the photoemission process is almost equal to those of the metal itself. (orig.)

  13. Ab initio investigations of magnetic properties of ultrathin transition-metal films on 4d substrates

    Energy Technology Data Exchange (ETDEWEB)

    Al-Zubi, Ali

    2010-12-22

    In this thesis, we investigate the magnetic properties of 3d transition-metal monolayers on 4d transition-metal substrates by means of state of the art first-principles quantum theory. In order to reveal the underlying physics of these systems we study trends by performing systematic investigations across the transition-metal series. Case studies are presented for which Rh has been chosen as exemplary 4d substrate. We consider two substrate orientations, a square lattice provided by Rh(001) and a hexagonal lattice provided by Rh(111). We find, all 3d transition-metal (V, Cr, Mn, Fe, Co and Ni) monolayers deposited on the Rh substrate are magnetic and exhibit large local moments which follow Hund's rule with a maximum magnetic moment for Mn of about 3.7 {mu}{sub B} depending on the substrate orientation. The largest induced magnetic moment of about 0.46 {mu}{sub B} is found for Rh atoms adjacent to the Co(001)-film. On Rh(001) we predict a ferromagnetic (FM) ground state for V, Co and Ni, while Cr, Mn and Fe monolayers favor a c(2 x 2) antiferromagnetic (AFM) state, a checkerboard arrangement of up and down magnetic moments. The magnetic anisotropy energies of these ultrathin magnetic films are calculated for the FM and the AFM states. With the exception of V and Cr, the easy axis of the magnetization is predicted to be in the film plane. With the exception of Fe, analogous results are obtained for the 3d-metal monolayers on Rh(111). For Fe on Rh(111) a novel magnetic ground state is predicted, a double-row-wise antiferromagnetic state along the [11 anti 2] direction, a sequence of ferromagnetic double-rows of atoms, whose magnetic moments couple antiferromagnetically from double row to double row. The magnetic structure can be understood as superposition of a left- and right-rotating flat spin spiral. In a second set of case studies the properties of an Fe monolayer deposited on varies hexagonally terminated hcp (0001) and fcc (111) surfaces of 4d-transition

  14. Ab initio investigations of magnetic properties of ultrathin transition-metal films on 4d substrates

    Energy Technology Data Exchange (ETDEWEB)

    Al-Zubi, Ali

    2010-12-22

    In this thesis, we investigate the magnetic properties of 3d transition-metal monolayers on 4d transition-metal substrates by means of state of the art first-principles quantum theory. In order to reveal the underlying physics of these systems we study trends by performing systematic investigations across the transition-metal series. Case studies are presented for which Rh has been chosen as exemplary 4d substrate. We consider two substrate orientations, a square lattice provided by Rh(001) and a hexagonal lattice provided by Rh(111). We find, all 3d transition-metal (V, Cr, Mn, Fe, Co and Ni) monolayers deposited on the Rh substrate are magnetic and exhibit large local moments which follow Hund's rule with a maximum magnetic moment for Mn of about 3.7 {mu}{sub B} depending on the substrate orientation. The largest induced magnetic moment of about 0.46 {mu}{sub B} is found for Rh atoms adjacent to the Co(001)-film. On Rh(001) we predict a ferromagnetic (FM) ground state for V, Co and Ni, while Cr, Mn and Fe monolayers favor a c(2 x 2) antiferromagnetic (AFM) state, a checkerboard arrangement of up and down magnetic moments. The magnetic anisotropy energies of these ultrathin magnetic films are calculated for the FM and the AFM states. With the exception of V and Cr, the easy axis of the magnetization is predicted to be in the film plane. With the exception of Fe, analogous results are obtained for the 3d-metal monolayers on Rh(111). For Fe on Rh(111) a novel magnetic ground state is predicted, a double-row-wise antiferromagnetic state along the [11 anti 2] direction, a sequence of ferromagnetic double-rows of atoms, whose magnetic moments couple antiferromagnetically from double row to double row. The magnetic structure can be understood as superposition of a left- and right-rotating flat spin spiral. In a second set of case studies the properties of an Fe monolayer deposited on varies hexagonally terminated hcp (0001) and fcc (111) surfaces of 4d-transition metals

  15. Ab initio investigations of magnetic properties of ultrathin transition-metal films on 4d substrates

    International Nuclear Information System (INIS)

    Al-Zubi, Ali

    2010-01-01

    In this thesis, we investigate the magnetic properties of 3d transition-metal monolayers on 4d transition-metal substrates by means of state of the art first-principles quantum theory. In order to reveal the underlying physics of these systems we study trends by performing systematic investigations across the transition-metal series. Case studies are presented for which Rh has been chosen as exemplary 4d substrate. We consider two substrate orientations, a square lattice provided by Rh(001) and a hexagonal lattice provided by Rh(111). We find, all 3d transition-metal (V, Cr, Mn, Fe, Co and Ni) monolayers deposited on the Rh substrate are magnetic and exhibit large local moments which follow Hund's rule with a maximum magnetic moment for Mn of about 3.7 μ B depending on the substrate orientation. The largest induced magnetic moment of about 0.46 μ B is found for Rh atoms adjacent to the Co(001)-film. On Rh(001) we predict a ferromagnetic (FM) ground state for V, Co and Ni, while Cr, Mn and Fe monolayers favor a c(2 x 2) antiferromagnetic (AFM) state, a checkerboard arrangement of up and down magnetic moments. The magnetic anisotropy energies of these ultrathin magnetic films are calculated for the FM and the AFM states. With the exception of V and Cr, the easy axis of the magnetization is predicted to be in the film plane. With the exception of Fe, analogous results are obtained for the 3d-metal monolayers on Rh(111). For Fe on Rh(111) a novel magnetic ground state is predicted, a double-row-wise antiferromagnetic state along the [11 anti 2] direction, a sequence of ferromagnetic double-rows of atoms, whose magnetic moments couple antiferromagnetically from double row to double row. The magnetic structure can be understood as superposition of a left- and right-rotating flat spin spiral. In a second set of case studies the properties of an Fe monolayer deposited on varies hexagonally terminated hcp (0001) and fcc (111) surfaces of 4d-transition metals (Tc, Ru, Rh

  16. Emergent nanoscale fluctuations in high rock-salt PbTe

    Science.gov (United States)

    Billinge, Simon

    2013-03-01

    Lead Telluride is one of the most promising thermoelectric materials in the temperature range just above room temperature. It is a narrow band gap semiconductor with a high Seebeck coefficient and a low thermal conductivity. It is structurally much simpler than many other leading candidates for high performance thermoelectrics being a binary rock-salt, isostructural to NaCl. The thermoelectric figure of merit, ZT, can be markedly improved by alloying with various other elements by forming quenched nanostructures. The undoped endmember, PbTe, does not have any such quenched nanostructure, yet has a rather low intrinsic thermal conductivity. There are also a number of interesting and non-canonical behaviors that it exhibits, such as an increasing measured band-gap with increasing temperature, exactly opposite to what is normally seen due to Fermi smearing of the band edge, and an unexpected non-monotonicity of the band gap in the series PbTe - PbSe - PbS. The material is on the surface simple, but hides some interesting complexity. We have investigated in detail the PbTe endmember using x-ray and neutron diffraction and neutron inelastic scattering. To our surprise, using the atomic pair distribution function (PDF) analysis of neutron powder diffraction data we found that an interesting and non-trivial local structure that appears on warming. with the Pb atoms moving off the high-symmetry rock-salt positions towards neighboring Te ions. No evidence for the off-centering of the Pb atoms is seen at low temperature. The crossover from the locally undistorted to the locally distorted state occurs on warming between 100 K and 250 K. This unexpected emergence of local symmetry broken distortions from an undistorted ground-state we have called emphanisis, from the Greek for appearing from nothing. We have also investigated the lattice dynamics of the system to search for a dynamical signature of this behavior and extended the studies to doped systems and I will also

  17. The quasiparticle band structure of zincblende and rocksalt ZnO.

    Science.gov (United States)

    Dixit, H; Saniz, R; Lamoen, D; Partoens, B

    2010-03-31

    We present the quasiparticle band structure of ZnO in its zincblende (ZB) and rocksalt (RS) phases at the Γ point, calculated within the GW approximation. The effect of the p-d hybridization on the quasiparticle corrections to the band gap is discussed. We compare three systems, ZB-ZnO which shows strong p-d hybridization and has a direct band gap, RS-ZnO which is also hybridized but includes inversion symmetry and therefore has an indirect band gap, and ZB-ZnS which shows a weaker hybridization due to a change of the chemical species from oxygen to sulfur. The quasiparticle corrections are calculated with different numbers of valence electrons in the Zn pseudopotential. We find that the Zn(20+) pseudopotential is essential for the adequate treatment of the exchange interaction in the self-energy. The calculated GW band gaps are 2.47 eV and 4.27 eV respectively, for the ZB and RS phases. The ZB-ZnO band gap is underestimated compared to the experimental value of 3.27 by ∼ 0.8 eV. The RS-ZnO band gap compares well with the experimental value of 4.5 eV. The underestimation for ZB-ZnO is correlated with the strong p-d hybridization. The GW band gap for ZnS is 3.57 eV, compared to the experimental value of 3.8 eV.

  18. Synthesis of IV-VI Transition Metal Carbide and Nitride Nanoparticles Using a Reactive Mesoporous Template for Electrochemical Hydrogen Evolution Reaction

    KAUST Repository

    Alhajri, Nawal Saad

    2016-01-01

    Interstitial carbides and nitrides of early transition metals in Groups IV-VI exhibit platinum-like behavior which makes them a promising candidate to replace noble metals in a wide variety of reactions. Most synthetic methods used to prepare these materials lead to bulk or micron size powder which limits their use in reactions in particular in catalytic applications. Attempts toward the production of transition metal carbide and nitride nanoparticles in a sustainable, simple and cheap manner have been rapidly increasing. In this thesis, a new approach was presented to prepare nano-scale transition metal carbides and nitrides of group IV-VI with a size as small as 3 nm through the reaction of transition metal precursor with mesoporous graphitic carbon nitride (mpg-C3N4) that not only provides confined spaces for nanoparticles formation but also acts as a chemical source of nitrogen and carbon. The produced nanoparticles were characterized by powder X-ray diffraction (XRD), temperature-programmed reaction with mass spectroscopy (MS), CHN elemental analyses, thermogravimetric analyses (TGA), nitrogen sorption, X-ray photoelectron spectroscopy (XPS), and transmission electron microscopy (TEM). The effects of the reaction temperature, the ratio of the transition metal precursor to the reactive template (mpg-C3N4), and the selection of the carrier gas (Ar, N2, and NH3) on the resultant crystal phases and structures were investigated. The results indicated that different tantalum phases with cubic structure, TaN, Ta2CN, and TaC, can be formed under a flow of nitrogen by changing the reaction temperatures. Two forms of tantalum nitride, namely TaN and Ta3N5, were selectively formed under N2 and NH3 flow, respectively. Significantly, the formation of TaC, Ta2CN, and TaN can be controlled by altering the weight ratio of the C3N4 template relative to the Ta precursor at 1573 K under a flow of nitrogen where high C3N4/Ta precursor ratio generally resulted in high carbide

  19. Tailoring of transition metal alkoxides via complexation for the synthesis of hybrid organic-inorganic sols and gels

    International Nuclear Information System (INIS)

    Sanchez, C.; In, M.; Toledano, P.; Griesmar, P.

    1992-01-01

    This paper reports that the chemical control of hydrolysis-condensation reactions of transition metal alkoxides can be performed through the modification of the transition metal coordination sphere by using strong complexing ligands (SCL). Complexing organic groups can be bonded to the transition metal oxide network in two different ways, as network modifiers or network formers. Different illustrations of the role of complexing ligands on Ti(IV) and Zr(IV) alkoxides are presented. As a network modifier, SCL act as termination agents for condensation reactions allowing a control of particle growth. The complexing ligands being located at the periphery of the oxo core open many opportunities for colloid surface protection. SCL carrying organofunctional groups which exhibit non linear optical (NLO) properties have also been used as probes to study sol-gel transformations. SCL functionalized with organic polymerizable functions act as network formers

  20. Oxygen effect on the work function of electropositive metal films adsorbed on 4d and 5d-transition metals

    International Nuclear Information System (INIS)

    Kultashev, O.K.; Makarov, A.P.; Rozhkov, S.E.

    1976-01-01

    The thermionic emission method was used to study the effect of oxygen upon the work function of films of electropositive metals, Sc, Y, La and Ba on some monocrystal and polycrystalline specimens of 4d- and 5d-transition metals of groups 4-8 of the Periodic system. It was revealed that when the supports were polycrystalline and monocrystalline specimens of transition metals of Group 5 (niobium and tantalum), the work function phi of films of electropositive adsorbates dropped substantially as compared, e.g., to the phi values on the same faces of tungsten. When the concentration of the electropositive adsorbate exceeds the optimum value (in the absence of oxygen), oxygen exerts an appreciably activating action upon the work function phi of films of electropositive adsorbates on transition metals of the Groups 7 and 8. The activating action of oxygen is assumed to be due to a possibility of formation of surface interstitial structures

  1. Optical properties of 3d transition metal ion-doped sodium borosilicate glass

    International Nuclear Information System (INIS)

    Wen, Hongli; Tanner, Peter A.

    2015-01-01

    Graphical abstract: Photographs of undoped (SiO 2 ) 50 (Na 2 O) 25 (B 2 O 3 ) 25 (SiNaB) glass and transition metal ion-doped (TM) 0.5 (SiO 2 ) 49.5 (Na 2 O) 25 (B 2 O 3 ) 25 glass samples. - Highlights: • 3d transition metal ion (from Ti to Zn) doped SiO 2 -Na 2 O-B 2 O 3 glasses. • Optical properties of doped glasses investigated. • V(IV,V); Cr(III, VI); Mn(II,III); Fe(II,III); Co(II); Ni(II); Cu(II) by XANES, DRS. • Strong visible absorption but only vanadium ion gives strong emission in glass. - Abstract: SiO 2 -Na 2 O-B 2 O 3 glasses doped with 3d-transition metal species from Ti to Zn were prepared by the melting-quenching technique and their optical properties were investigated. The X-ray absorption near edge spectra of V, Cr, and Mn-doped glasses indicate that the oxidation states of V(IV, V), Cr(III, VI) and Mn(II, III) exist in the studied glasses. The oxidation states revealed from the diffuse reflectance spectra of the glasses are V(IV, V), Cr(III, VI), Mn(III), Fe(II, III), Co(II), Ni(II), and Cu(II). Most of the 3d transition element ions exhibit strong absorption in the visible spectral region in the glass. Under ultraviolet excitation, the undoped sodium borosilicate glass produces weak and broad emission, while doping of vanadium introduces strong and broad emission due to the V(V) charge transfer transition. Only weak emission is observed from Ti(IV), Mn(II), Fe(III) and Cu(II), partly resulting from the strong electron–phonon coupling of the 3d-electrons and the relatively high phonon energy of the studied glass host, with the former leading to dominant nonradiative relaxation based on multiphonon processes for most of the 3d excited states

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2014-11-15

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

  3. Unambiguously identifying spin states of transition-metal ions in the Earth (Invited)

    Science.gov (United States)

    Hsu, H.

    2010-12-01

    The spin state of a transition-metal ion in crystalline solids, defined by the number of unpaired electrons in the ion’s incomplete 3d shell, may vary with many factors, such as temperature, pressure, strain, and the local atomic configuration, to name a few. Such a phenomenon, known as spin-state crossover, plays a crucial role in spintronic materials. Recently, the pressure-induced spin-state crossover in iron-bearing minerals has been recognized to affect the minerals’ structural and elastic properties. However, the detailed mechanism of such crossover in iron-bearing magnesium silicate perovskite, the most abundant mineral in the Earth, remains unclear. A significant part of this confusion arises from the difficulty in reliably extracting the spin state from experiments. For the same reason, the thermally-induced spin-state crossover in lanthanum cobaltite (LaCoO3) has been controversial for more than four decades. In this talk, I will discuss how first-principle calculations can help clarifying these long-standing controversies. In addition to the total energy, equation of state, and elastic properties of each spin state, first-principle calculations also predict the electric field gradient (EFG) at the nucleus of each transition-metal ion. Our calculations showed that the nuclear EFG, a quantity that can be measured via Mössbauer or nuclear magnetic resonance (NMR) spectroscopy, depends primarily on the spin state, irrespective of the concentration or configuration of transition-metal ions. Such robustness makes EFG a unique fingerprint to identify the spin state. The combination of first-principle calculations and Mössbauer/NMR spectroscopy can therefore be a reliable and efficient approach in tackling spin-state crossover problems in the Earth. This work was primarily supported by the MRSEC Program of NSF under Awards Number DMR-0212302 and DMR-0819885, and partially supported by NSF under ATM-0428774 (V-Lab), EAR-1019853, and EAR-0810272. The

  4. Molecular nanomagnets: Syntheses and characterization of high nuclearity transition metal complexes

    Science.gov (United States)

    Foguet-Albiol, Maria D.

    2006-12-01

    High nuclearity transition metal complexes have attracted a lot of attention because of their aesthetically pleasant structures and/or their potential applications. The fusion of the world of magnetism with the exciting research in physics and chemistry led to the realization of interesting types of materials that can function as nanoscale magnetic particles. The study of the magnetism of inorganic complexes and especially the study of these molecular nanomagnets (or single-molecule magnets, SMMs) is a field that has generated intense interest in the scientific community. Interest in these molecular nanomagnets arises as part of a broader investigation of nanomagnetism (and nanotechnology), as these represent the ultimate step in device miniaturization. The primary purpose of this dissertation is the development of new synthetic methods intended for the preparation of novel single-molecule magnets (SMMs). The definition of the "bottom-up approach" is to increase the size of molecules by adding new magnetic centers; this is attractive but does not actually reflect how the chemistry takes place. Various strategies have been employed in developing the aforementioned synthetic methods which include the use of mononuclear as well as preformed clusters as starting materials; and the introduction of new alcohol based ligands as N-methyldiethanolamine (mdaH2) and triethanolamine (teaH3), since currently only a few alcohol based ligands have been used by different research groups. Many of these efforts have led to the isolation of new polynuclear Mn clusters with nuclearities ranging all the way from four to thirty-one. Additionally, a family of related Fe7 complexes has been synthesized. The transition metal cluster chemistry has also been extended to nickel-containing species. Many of these polynulear transition metal complexes function as single-molecule magnets. An additional research direction discussed herein is the study of the exchange-coupled dimer of single

  5. Two-dimensional ferromagnet/semiconductor transition metal dichalcogenide contacts: p-type Schottky barrier and spin-injection control

    KAUST Repository

    Gan, Liyong; Cheng, Yingchun; Schwingenschlö gl, Udo; Zhang, Qingyun

    2013-01-01

    We study the ferromagnet/semiconductor contacts formed by transition metal dichalcogenide monolayers, focusing on semiconducting MoS2 and WS2 and ferromagnetic VS2. We investigate the degree of p-type doping and demonstrate tuning of the Schottky barrier height by vertical compressive pressure. An analytical model is presented for the barrier heights that accurately describes the numerical findings and is expected to be of general validity for all transition metal dichalcogenide metal/semiconductor contacts. Furthermore, magnetic proximity effects induce a 100% spin polarization at the Fermi level in the semiconductor where the spin splitting increases up to 0.70 eV for increasing pressure.

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

    International Nuclear Information System (INIS)

    Richard T. Scalettar; Warren E. Pickett

    2005-01-01

    This project involves research into the thermodynamic properties of f-electron metals, transition metal oxides, and half-metallic magnets at high pressure. These materials are ones in which the changing importance of electron-electron interactions as the distance between atoms is varied can tune the system through phase transitions from localized to delocalized electrons, from screened to unscreened magnetic moments, and from normal metal to one in which only a single spin specie can conduct. Three main thrusts are being pursued: (1) Mott transitions in transition metal oxides, (2) magnetism in half-metallic compounds, and (3) large volume-collapse transitions in f-band metals

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

    Energy Technology Data Exchange (ETDEWEB)

    Scalettar, Richard T.; Pickett, Warren E.

    2004-07-01

    This project involves research into the thermodynamic properties of f-electron metals, transition metal oxides, and half-metallic magnets at high pressure. These materials are ones in which the changing importance of electron-electron interactions as the distance between atoms is varied can tune the system through phase transitions from localized to delocalized electrons, from screened to unscreened magnetic moments, and from normal metal to one in which only a single spin specie can conduct. Three main thrusts are being pursued: (1) Mott transitions in transition metal oxides, (2) magnetism in half-metallic compounds, and (3) large volume-collapse transitions in f-band metals.

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

    Energy Technology Data Exchange (ETDEWEB)

    Richard T. Scalettar; Warren E. Pickett

    2005-08-02

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

  9. Density functional theory study of elemental mercury adsorption on boron doped graphene surface decorated by transition metals

    Energy Technology Data Exchange (ETDEWEB)

    Jungsuttiwong, Siriporn, E-mail: siriporn.j@ubu.ac.th [Department of Chemistry and Center of Excellence for Innovation in Chemistry, Faculty of Science, Ubon Ratchathani University, Ubon Ratchathani 34190 (Thailand); Wongnongwa, Yutthana [Department of Chemistry and Center of Excellence for Innovation in Chemistry, Faculty of Science, Ubon Ratchathani University, Ubon Ratchathani 34190 (Thailand); Namuangruk, Supawadee [National Nanotechnology Center (NANOTEC), National Science and Technology Development Agency (NSTDA), Klong Luang, Pathum Thani 12120 (Thailand); Kungwan, Nawee [Department of Chemistry, Faculty of Science, Chiang Mai University, Chiang Mai 50200 (Thailand); Promarak, Vinich [Department of Material Science and Engineering, School of Molecular Science and Engineering, Vidyasirimedhi Institute of Science and Technology, Rayong 21210 (Thailand); Kunaseth, Manaschai, E-mail: manaschai@nanotec.or.th [National Nanotechnology Center (NANOTEC), National Science and Technology Development Agency (NSTDA), Klong Luang, Pathum Thani 12120 (Thailand)

    2016-01-30

    Graphical abstract: Decoration of Pd{sub 4}-A (square planar) on B-doped graphene significantly promotes Hg{sup 0} adsorption, a single site of Pd{sub 4} cluster on BDG could strongly adsorb up to six Hg atoms. - Highlights: • Transition metal atom and cluster binds strongly on B-doped graphene surface. • Decoration of transition metal on B-doped graphene significantly promotes Hg{sup 0} adsorption. • Adsorption strength of Hg{sup 0} atom on metal decorated B-doped graphene: Pd > Pt > Ru > W > Cu. • One site decorated Pd4 cluster adsorbed Hg{sup 0} strongly up to six atoms.

  10. Two-dimensional ferromagnet/semiconductor transition metal dichalcogenide contacts: p-type Schottky barrier and spin-injection control

    KAUST Repository

    Gan, Liyong

    2013-09-26

    We study the ferromagnet/semiconductor contacts formed by transition metal dichalcogenide monolayers, focusing on semiconducting MoS2 and WS2 and ferromagnetic VS2. We investigate the degree of p-type doping and demonstrate tuning of the Schottky barrier height by vertical compressive pressure. An analytical model is presented for the barrier heights that accurately describes the numerical findings and is expected to be of general validity for all transition metal dichalcogenide metal/semiconductor contacts. Furthermore, magnetic proximity effects induce a 100% spin polarization at the Fermi level in the semiconductor where the spin splitting increases up to 0.70 eV for increasing pressure.

  11. Transition metal complexes with oxygen donor ligands: a synthesis, spectral, thermal and antimicrobial study

    Directory of Open Access Journals (Sweden)

    VAIBHAV N. PATANGE

    2008-10-01

    Full Text Available Transition metal complexes of chalcones derived from the conden¬sation of 3-acetyl-6-methyl-2H-pyran-2,4(3H-dione (dehydroacetic acid and p-methoxybenzaldehyde (HL1 or p-nitrobenzaldehyde (HL2 were synthesized and characterized by elemental analysis, conductometry, thermal analysis, magnetic measurements, IR, 1H-NMR, UV–Vis spectroscopy and a microbial study. From the analytical and thermal data, the stoichiometry of the complexes was found to be 1:2 (metal:ligand. The molar conductance data revealed that all the metal chelates were non-electrolytes. The thermal stability of the complexes was studied by thermogravimetry and the decomposition schemes of the complexes are given. The ligands and their metal complexes were screened for antibacterial activity against Staphylococcus aureus and Escherichia coli, and fungicidal activity against Aspergillus flavus, Curvularia lunata and Penicillium notatum.

  12. Standard entropy for borides of non-transition metals, rare-earth metals and actinides

    International Nuclear Information System (INIS)

    Borovikova, M.S.

    1986-01-01

    Using as initial data the most reliable values of standard entropy for 10 compounds, the entropies for 40 compounds of non-transition metals, rare-earth metals and actinides have been evaluated by the method of comparative calculation. Taking into account the features of boride structures, two methods, i.e. additive and proportional, have been selected for the entropy calculations. For the range of borides the entropies were calculated from the linear relation of the latter to the number of boron atoms in the boride. For borides of rare-earth metals allowance has been made for magnetic contributions in conformity with the multiplicity of the corresponding ions. Insignificant differences in the electronic contributions to the entropy for borides and metals have been neglected. For dodecaborides only the additive method has been used. This is specified by the most rigid network that provides the same contribution to compound entropy. (orig.)

  13. Catalytic activity of γ-irradiated transition metal ions in the decomposition of hydrogen peroxide

    International Nuclear Information System (INIS)

    Arnikar, H.J.; Kapadi, A.H.; Gohad, A.S.; Bhosale, S.B.

    1988-01-01

    The catalystic decomposition of hydrogen peroxide by transition metal ions, Fe 2+ , Fe 3+ , Co 2+ and Cu 2+ , adsorbed on neutral α-alumina was studied over the temperature range of 295-313 K. γ-irradiation of the catalysts to a dose of 0.12 MGy enhanced markedly the first order decomposition rate. Negligible in the case of Cu 2+ , the radiation effect increased roughly in the order of the number of unpaired d electrons in these ions: Cu(II), Fe(II), Co(II) and Fe(III). Results are explained on the basis of Kremer's mechanism of electron induced heterogeneous decomposition of H 2 O 2 . The radiation effect is attributed to the initial excess of electrons released from traps in the beginning of the reaction

  14. Extended lanthanide-transition metal arrays with cyanide bridges: syntheses, structures, and catalytic applications

    International Nuclear Information System (INIS)

    Liu Shengming; Poplaukhin, Pavel; Ding Errun; Plecnik, Christine E.; Chen Xuenian; Keane, Mark A.; Shore, Sheldon G.

    2006-01-01

    Systematic synthetic procedures produced several different structural types of extended lanthanide-transition metal (group 10) complexes with cyanide bridges. Of these, one-dimensional ladder arrays containing a Yb-Pd combination have been converted to bimetallic heterogeneous catalysts on an oxide (SiO 2 ) surface that is more effective than supported Pd alone. Two lanthanide-Cu(I) complexes have been prepared. One type, an inclusion complex consists of lanthanide(III) cations encapsulated in the pockets of a three-dimensional anionic array that contains Cu(I)-CN-Cu(I) bridges. The second type, an extended layer complex, consists of joined five-membered rings in a 'tile-like' pattern with Ln-CN-Cu and Cu-CN-Cu bridges

  15. Two-Dimensional Transition Metal Oxide and Chalcogenide-Based Photocatalysts

    Science.gov (United States)

    Haque, Farjana; Daeneke, Torben; Kalantar-zadeh, Kourosh; Ou, Jian Zhen

    2018-06-01

    Two-dimensional (2D) transition metal oxide and chalcogenide (TMO&C)-based photocatalysts have recently attracted significant attention for addressing the current worldwide challenges of energy shortage and environmental pollution. The ultrahigh surface area and unconventional physiochemical, electronic and optical properties of 2D TMO&Cs have been demonstrated to facilitate photocatalytic applications. This review provides a concise overview of properties, synthesis methods and applications of 2D TMO&C-based photocatalysts. Particular attention is paid on the emerging strategies to improve the abilities of light harvesting and photoinduced charge separation for enhancing photocatalytic performances, which include elemental doping, surface functionalization as well as heterojunctions with semiconducting and conductive materials. The future opportunities regarding the research pathways of 2D TMO&C-based photocatalysts are also presented. [Figure not available: see fulltext.

  16. Mechanism of selective ion flotation. 1. Selective flotation of transition metal cations

    International Nuclear Information System (INIS)

    Walkowiak, W.

    1991-01-01

    An experimental investigation is presented of the batch ion flotation of the transition metal cations Cr 3+ , Fe 3+ , Mn 2+ , Co 2+ , Zn 2+ , Ag + , Cd 2+ , and In 3+ from acidic aqueous solutions with sodium dodecylsulfonate and sodium dodecylbenzenesulfonate as anionic surfactants. The selectivity sequences Mn 2+ 2+ 2+ 3+ 3+ and Ag + 2+ 3+ are established, both from data for single and multi-ion metal cations solutions, where sublate was not formed in the bulk solution. Good agreement between the selectivity sequences and the values of ionic potential of metal cations was found. An experimental investigation was also performed on the solubility of sublates. The sublates solubility values are discussed in terms of ionic potentials of metal cations as well as of the surfactant size

  17. Emerging Energy Applications of Two-Dimensional Layered Transition Metal Dichalcogenides

    KAUST Repository

    Li, Henan

    2015-10-31

    Transition metal dichalcogenides (TMDCs) have attracted significant attention for their great potential in nano energy. TMDC layered materials represent a diverse and largely untapped source of 2D systems. High-quality TMDC layers with an appropriate size, variable thickness, superior electronic and optical properties can be produced by the exfoliation or vapour phase deposition method. Semiconducting TMDC monolayers have been demonstrated feasible for various energy related applications, where their electronic properties and uniquely high surface areas offer opportunities for various applications such as nano generators, green electronics, electrocatalytic hydrogen generation and energy storage. In this review, we start from the structure, properties and preparation, followed by detailed discussions on the development of TMDC-based nano energy applications. Graphical abstract The structure characterizations and preparative methods of 2D TMDCs have obtained significant progresses. Their recent advances for nano energy generation, solar harvesting, conversion and storage, and green electronics are reviewed.

  18. Laterally Stitched Heterostructures of Transition Metal Dichalcogenide: Chemical Vapor Deposition Growth on Lithographically Patterned Area

    KAUST Repository

    Li, Henan

    2016-10-31

    Two-dimensional transition metal dichalcogenides (TMDCs) have shown great promise in electronics and optoelectronics due to their unique electrical and optical properties. Heterostructured TMDC layers such as the laterally stitched TMDCs offer the advantages of better electronic contact and easier band offset tuning. Here, we demonstrate a photoresist-free focused ion beam (FIB) method to pattern as-grown TMDC monolayers by chemical vapor deposition, where the exposed edges from FIB etching serve as the seeds for growing a second TMDC material to form desired lateral heterostructures with arbitrary layouts. The proposed lithographic and growth processes offer better controllability for fabrication of the TMDC heterostrucuture, which enables the construction of devices based on heterostructural monolayers. © 2016 American Chemical Society.

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

    KAUST Repository

    Grytsiuk, Sergii

    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. Influence of reactive gas admixture on transition metal cluster nucleation in a gas aggregation cluster source

    Science.gov (United States)

    Peter, Tilo; Polonskyi, Oleksandr; Gojdka, Björn; Mohammad Ahadi, Amir; Strunskus, Thomas; Zaporojtchenko, Vladimir; Biederman, Hynek; Faupel, Franz

    2012-12-01

    We quantitatively assessed the influence of reactive gases on the formation processes of transition metal clusters in a gas aggregation cluster source. A cluster source based on a 2 in. magnetron is used to study the production rate of titanium and cobalt clusters. Argon served as working gas for the DC magnetron discharge, and a small amount of reactive gas (oxygen and nitrogen) is added to promote reactive cluster formation. We found that the cluster production rate depends strongly on the reactive gas concentration for very small amounts of reactive gas (less than 0.1% of total working gas), and no cluster formation takes place in the absence of reactive species. The influence of discharge power, reactive gas concentration, and working gas pressure are investigated using a quartz micro balance in a time resolved manner. The strong influence of reactive gas is explained by a more efficient formation of nucleation seeds for metal-oxide or nitride than for pure metal.

  1. Transition-Metal-Free Highly Efficient Aerobic Oxidation of Sulfides to Sulfoxides under Mild Conditions

    Directory of Open Access Journals (Sweden)

    Hua Zhang

    2009-12-01

    Full Text Available A highly efficient transition-metal-free catalytic system Br2/NaNO2/H2O has been developed for a robust and economic acid-free aerobic oxidation of sulfides. It is noteworthy that the sulfide function reacts under mild conditions without over-oxidation to sulfone. The role of NaNO2as an efficient NO equivalent for the activation of molecular oxygen was identified. Under the optimal conditions, a broad range of sulfide substrates were converted into their corresponding sulfoxides in high yields by molecular oxygen. The present catalytic system utilizes cheap and readily available agents as the catalysts, exhibits high selectivity for sulfoxide products and releases only innocuous water as the by-products.

  2. The electronic conduction of glass and glass ceramics containing various transition metal oxides

    International Nuclear Information System (INIS)

    Yoshida, T.; Matsuno, Y.

    1980-01-01

    Nb 2 O 5 -V 2 O 5 -P 2 O 5 glasses containing only Group Va oxides have been investigated to elucidate their electronic conduction and structure, as compared with other glasses obtained by the addition of various transition metal oxides to vanadium phosphate. The P 2 O 5 introduction for Nb 2 O 5 in this glass with the same amount of V 2 O 5 increased the conductivity about two times. Glass ceramics having high conductivity increased by two orders of magnitude and the activation energy for conduction decreased from about 0.5 to 0.2 eV. The crystals were confirmed to be (V,Nb) 2 O 5 and Nb phosphate, one of which was highly conductive and developed a pillar-like shape with a length of more than 20 μm. (orig.)

  3. Transition metal implanted ZnO. A correlation between structure and magnetism

    Energy Technology Data Exchange (ETDEWEB)

    Zhou, Shengqiang

    2008-07-01

    Nowadays ferromagnetism is often found in potential diluted magnetic semiconductor systems. However, many authors question the origin of this ferromagnetism, i.e. if the observed ferromagnetism stems from ferromagnetic precipitates rather than from carriermediated magnetic coupling of ionic impurities, as required for a diluted magnetic semiconductor. In this thesis, this question will be answered for transition-metal implanted ZnO single crystals. Magnetic secondary phases, namely metallic Fe, Co and Ni nanocrystals, are formed inside ZnO. They are - although difficult to detect by common approaches of structural analysis - responsible for the observed ferromagnetism. Particularly Co and Ni nanocrystals are crystallographically oriented with respect to the ZnO matrix. Their structure phase transformation and corresponding evolution of magnetic properties upon annealing have been established. Finally, an approach, pre-annealing ZnO crystals at high temperature before implantation, has been demonstrated to sufficiently suppress the formation of metallic secondary phases. (orig.)

  4. X-ray spectral line coincidences between fluorine VIII (and IX) and transition metal lines

    International Nuclear Information System (INIS)

    Charatis, G.; Rockett, P.D.; Burkhalter, P.G.

    1983-01-01

    X-ray spectroscopy was performed in the 12 to 15 A region, recording L-shell lines from selected laser-irradiated transition metals. Line coincidences and near coincidences were identified between Fe, Cr, Mn, and Ni L-spectra, and F VIII and F IX K-shell lines. Wavelengths were determined to accuracies of 1 to 3 mA and will be utilized in selecting potential pumping candidates in future x-ray lasing schemes. High-resolution x-ray spectra were collected under controlled illumination and target conditions using 1.05 μm and 0.527 μm laser excitation with the KMS CHROMA laser

  5. Fully-Coupled Thermo-Electrical Modeling and Simulation of Transition Metal Oxide Memristors

    Energy Technology Data Exchange (ETDEWEB)

    Mamaluy, Denis [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); Gao, Xujiao [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); Tierney, Brian David [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); Marinella, Matthew [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); Mickel, Patrick [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); Tierney, Brian D. [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)

    2016-11-01

    Transition metal oxide (TMO) memristors have recently attracted special attention from the semiconductor industry and academia. Memristors are one of the strongest candidates to replace flash memory, and possibly DRAM and SRAM in the near future. Moreover, memristors have a high potential to enable beyond-CMOS technology advances in novel architectures for high performance computing (HPC). The utility of memristors has been demonstrated in reprogrammable logic (cross-bar switches), brain-inspired computing and in non-CMOS complementary logic. Indeed, the potential use of memristors as logic devices is especially important considering the inevitable end of CMOS technology scaling that is anticipated by 2025. In order to aid the on-going Sandia memristor fabrication effort with a memristor design tool and establish a clear physical picture of resistance switching in TMO memristors, we have created and validated with experimental data a simulation tool we name the Memristor Charge Transport (MCT) Simulator.

  6. Direct correlation of observed phonon anomalies and maxima in the generalized susceptibilities of transition metal carbides

    International Nuclear Information System (INIS)

    Gupta, M.J.; Freeman, A.B.

    1976-01-01

    The generalized susceptibility, chi(q), of both NbC and TaC determined from APW energy band calculations show large maxima to occur at precisely those q/sub max/ values at which soft phonon modes were observed by Smith. Maxima in chi(q) are predicted for other directions. The locus of these q/sub max/ values can be represented by a warped cube of dimension approximately 1.2(2π/a) in momentum space--in striking agreement with the soft mode surface proposed phenomenologically by Weber. In sharp contrast, the chi(q) calculated for both ZrC and HfC--for which no phonon anomalies have been observed--fall off in all symmetry directions away from the zone center. The phonon anomalies in the transition metal carbides are thus interpreted as due to an ''overscreening'' effect resulting from an anomalous increase of the response function of the conduction electrons

  7. Chemical hole doping into large-area transition metal dichalcogenide monolayers using boron-based oxidant

    KAUST Repository

    Matsuoka, Hirofumi; Kanahashi, Kaito; Tanaka, Naoki; Shoji, Yoshiaki; Li, Lain-Jong; Pu, Jiang; Ito, Hiroshi; Ohta, Hiromichi; Fukushima, Takanori; Takenobu, Taishi

    2018-01-01

    Hole carrier doping into single-crystalline transition metal dichalcogenide (TMDC) films can be achieved with various chemical reagents. However, large-area polycrystalline TMDC monolayers produced by a chemical vapor deposition (CVD) growth method have yet to be chemically doped. Here, we report that a salt of a two-coordinate boron cation, Mes2B+ (Mes: 2,4,6-trimethylphenyl group), with a chemically stable tetrakis(pentafluorophenyl)borate anion, [(C6F5)4B]−, can serve as an efficient hole-doping reagent for large-area CVD-grown tungsten diselenide (WSe2) films. Upon doping, the sheet resistance of large-area polycrystalline WSe2 monolayers decreased from 90 GΩ/sq to 3.2 kΩ/sq.

  8. First-principles studies on graphene-supported transition metal clusters

    International Nuclear Information System (INIS)

    Sahoo, Sanjubala; Khanna, Shiv N.; Gruner, Markus E.; Entel, Peter

    2014-01-01

    Theoretical studies on the structure, stability, and magnetic properties of icosahedral TM 13 (TM = Fe, Co, Ni) clusters, deposited on pristine (defect free) and defective graphene sheet as well as graphene flakes, have been carried out within a gradient corrected density functional framework. The defects considered in our study include a carbon vacancy for the graphene sheet and a five-membered and a seven-membered ring structures for graphene flakes (finite graphene chunks). It is observed that the presence of defect in the substrate has a profound influence on the electronic structure and magnetic properties of graphene-transition metal complexes, thereby increasing the binding strength of the TM cluster on to the graphene substrate. Among TM 13 clusters, Co 13 is absorbed relatively more strongly on pristine and defective graphene as compared to Fe 13 and Ni 13 clusters. The adsorbed clusters show reduced magnetic moment compared to the free clusters

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

    KAUST Repository

    Grytsyuk, Sergiy; Belabbes, Abderrezak; Haney, Paul M.; Lee, Hyun-Woo; Lee, Kyung-Jin; Stiles, M. D.; Schwingenschlö gl, Udo; Manchon, Aurelien

    2016-01-01

    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.

  10. Investigation of thermodynamic and transport properties of liquid transition metals using Wills-Harrison potentials

    International Nuclear Information System (INIS)

    Khaleque, M.A.; Bhuiyan, G.M.; Rashid, R.I.M.A.

    1998-01-01

    Thermodynamic properties such as entropy, specific heat capacity at constant pressure and isothermal compressibility have been calculated for liquid 3d, 4d and 5d transition metals near melting temperature. The hard sphere diameter for all such systems is estimated from the potential profile generated from the Wills and Harrison's prescription using linearized WCA theory of liquid. Evaluated values of entropy and specific heat capacity are found to be in good agreement with the experimental data. Transport property like shear viscosity for these liquid metals is obtained using the same potential profile. Lack of experimental data at melting temperatures hampers detailed comparison for all such systems. However, for the case of transport property, the results obtained are found to compare qualitatively well with the available experimental data. (author)

  11. Surface-enhanced Raman scattering from metal and transition metal nano-caped arrays

    Science.gov (United States)

    Sun, Huanhuan; Gao, Renxian; Zhu, Aonan; Hua, Zhong; Chen, Lei; Wang, Yaxin; Zhang, Yongjun

    2018-03-01

    The metal and transition metal cap-shaped arrays on polystyrene colloidal particle (PSCP) templates were fabricated to study the surface-enhanced Raman scattering (SERS) effect. We obtained the Ag and Fe complex film by a co-sputtering deposition method. The size of the deposited Fe particle was changed by the sputtering power. We also study the SERS enhancement mechanism by decorating the PATP probe molecule on the different films. The SERS signals increased firstly, and then decreased as the size of Fe particles grows gradually. The finite-difference time domain (FDTD) simulation and experimental Raman results manifest that SERS enhancement was mainly attributed to surface plasma resonance (SPR) between Ag and Ag nanoparticles. The SERS signals of PATP molecule were enhanced to reach a lowest detectable concentration of 10-8 mol/L. The research demonstrates that the SERS substrates with Ag-Fe cap-shaped arrays have a high sensitivity.

  12. Transition metal analysis. A comparison between ICP-AES and deuteron activation

    International Nuclear Information System (INIS)

    Pillay, A.E.; Williams, J.R.; Hassan, S.M.; Al-Hamdi, A.; El Mardi, M.O.

    2002-01-01

    The analytical capabilities of ICP-AES (ICP) and deuteron activation (associated with prompt gamma-rays and delayed X-rays) for the determination of certain transition metals, were investigated. The sensitivities of the three methods are given, and the general applicability of each technique is evaluated. In the case of ICP, numerical data were obtained from aqueous solutions containing digested plant material. These experimental results were assessed against minimum detectable limits attained in relevant solid matrices that were subjected to prompt gamma-ray and delayed X-ray spectrometry using 5 MeV 2 H + ions. The analytically useful lines originated mainly from (d,p) and (d,n) reactions. The potential of the three techniques for routine analysis is discussed and detailed methodologies are presented. (author)

  13. Giant spin-orbit-induced spin splitting in two-dimensional transition-metal dichalcogenide semiconductors

    KAUST Repository

    Zhu, Zhiyong

    2011-10-14

    Fully relativistic first-principles calculations based on density functional theory are performed to study the spin-orbit-induced spin splitting in monolayer systems of the transition-metal dichalcogenides MoS2, MoSe2, WS2, and WSe2. All these systems are identified as direct-band-gap semiconductors. Giant spin splittings of 148–456 meV result from missing inversion symmetry. Full out-of-plane spin polarization is due to the two-dimensional nature of the electron motion and the potential gradient asymmetry. By suppression of the Dyakonov-Perel spin relaxation, spin lifetimes are expected to be very long. Because of the giant spin splittings, the studied materials have great potential in spintronics applications.

  14. Empirical correction for PM7 band gaps of transition-metal oxides.

    Science.gov (United States)

    Liu, Xiang; Sohlberg, Karl

    2016-01-01

    A post-calculation correction is established for PM7 band gaps of transition-metal oxides. The correction is based on the charge on the metal cation of interest, as obtained from MOPAC PM7 calculations. Application of the correction reduces the average error in the PM7 band gap from ~3 eV to ~1 eV. The residual error after correction is shown to be uncorrelated to the Hartree-Fock method upon which PM7 is based. Graphical Abstract Comparison between calculated band gaps and experimental band gaps for binary oxides. The orange crosses are for corrected PM7 band gaps. Blue squares are uncorrected values. The orange crosses fall closer to the diagonal dashed line, showing an overall improvement of the accuracy of calculated values.

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

    Science.gov (United States)

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

    2015-11-01

    The alkali metal amidozincates Li4 [Zn(NH2)4](NH2)2 and K2[Zn(NH2)4] were, to the best of our knowledge, studied for the first time as hydrogen storage media. Compared with the LiNH2-2 LiH system, both Li4 [Zn(NH2)4](NH2)2-12 LiH and K2[Zn(NH2)4]-8 LiH systems showed improved rehydrogenation performance, especially K2[Zn(NH2)4]-8 LiH, which can be fully hydrogenated within 30 s at approximately 230 °C. The absorption properties are stable upon cycling. This work shows that ternary amides containing transition metals have great potential as hydrogen storage materials. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. Influence of Ferrocene and Transition Metals on the Biological Activities of Schiff Bases

    International Nuclear Information System (INIS)

    Sadeq, A.; Fatesh, S.A.; Ibrahim, A.A.

    2016-01-01

    A series of organic and organometallic Schiff bases bearing phenylferrocene and their six transition metal complexes have been prepared and tested for their potential biological applications by using antifungal, antibacterial, antitumor activities, toxicity testing against the brine shrimp and DNA damage analysis. The copper and cobalt complexes of organic Schiff base showed significant antibacterial activity. The antifungal activities tested against six fungal strains revealed that N-(4-hydroxybenzylidene) aniline (A5) had the highest antifungal activity. Most of these compounds showed cytotoxic activity against the brine shrimp. The results of showed that these compounds had significant antitumor activity, up to 97% in the case of N-(4-chlorobenzylidene) aniline (A3). Only two compounds N-(2-hydroxy benzylidene) 4-ferrocenylaniline (F2) and Nickel (II) complex of organic Schiff base (CO/sub 2/) had DNA damaging activity at 20mg/ml concentration. (author)

  17. Nanocrystalline transition metal oxides as catalysts in the thermal decomposition of ammonium perchlorate

    Energy Technology Data Exchange (ETDEWEB)

    Kapoor, Inder Pal Singh; Srivastava, Pratibha; Singh, Gurdip [Department of Chemistry, DDU Gorakhpur University, Gorakhpur (India)

    2009-08-15

    Nanocrystalline transition metal oxides (NTMOs) have been successfully prepared by three different methods: novel quick precipitation method (Cr{sub 2}O{sub 3} and Fe{sub 2}O{sub 3}); surfactant mediated method (CuO), and reduction of metal complexes with hydrazine as reducing agent (Mn{sub 2}O{sub 3}). The nano particles have been characterized by X-ray diffraction (XRD) which shows an average particle diameter of 35-54 nm. Their catalytic activity was measured in the thermal decomposition of ammonium perchlorate (AP). AP decomposition undergoes a two step process where the addition of metal oxide nanocrystals led to a shifting of the high temperature decomposition peak toward lower temperature. The kinetics of the thermal decomposition of AP and catalyzed AP has also been evaluated using model fitting and isoconversional method. (Abstract Copyright [2009], Wiley Periodicals, Inc.)

  18. First row transition metal atoms embedded in multivacancies in a rippled graphene system

    Science.gov (United States)

    Mombrú, Dominique; Faccio, Ricardo; Mombrú, Alvaro W.

    2018-03-01

    Ab-initio calculations based on density functional theory (DFT) have been performed to study systems where a first row transition metal atom is embedded in a rippled graphene due to the existence of an 8-order multivacancy. In addition to these cases, also the inclusion of a zinc atom, with a 3d10 electron configuration, was also studied. Structural distortions and magnetic response for each system were studied. A correlation was found for the magnitude of the rippling and the distortion in the vacancy. Variation in the trends was found for Cu and Zn cases, which were explained on the basis of the filling of the 3dx2-y2 orbital. All the systems exhibit lower magnetic moment in comparison to the metal-less system. The quenching of the magnetic moment due to the carbon atoms in the vacancy is observed for Sc and Cu.

  19. Investigation of transition metal-catalyzed nitrene transfer reactions in water.

    Science.gov (United States)

    Alderson, Juliet M; Corbin, Joshua R; Schomaker, Jennifer M

    2018-04-11

    Transition metal-catalyzed nitrene transfer is a powerful method for incorporating new CN bonds into relatively unfunctionalized scaffolds. In this communication, we report the first examples of site- and chemoselective CH bond amination reactions in aqueous media. The unexpected ability to employ water as the solvent in these reactions is advantageous in that it eliminates toxic solvent use and enables reactions to be run at increased concentrations with lower oxidant loadings. Using water as the reaction medium has potential to expand the scope of nitrene transfer to encompass a variety of biomolecules and highly polar substrates, as well as enable pH control over the site-selectivity of CH bond amination. Copyright © 2018 Elsevier Ltd. All rights reserved.

  20. Recent Advances in Transition-Metal-Mediated Electrocatalytic CO2 Reduction: From Homogeneous to Heterogeneous Systems

    Directory of Open Access Journals (Sweden)

    Da-Ming Feng

    2017-12-01

    Full Text Available Global climate change and increasing demands for clean energy have brought intensive interest in the search for proper electrocatalysts in order to reduce carbon dioxide (CO2 to higher value carbon products such as hydrocarbons. Recently, transition-metal-centered molecules or organic frameworks have been reported to show outstanding electrocatalytic activity in the liquid phase. Their d-orbital electrons are believed to be one of the key factors to capture and convert CO2 molecules to value-added low-carbon fuels. In this review, recent advances in electrocatalytic CO2 reduction have been summarized based on the targeted products, ranging from homogeneous reactions to heterogeneous ones. Their advantages and fallbacks have been pointed out and the existing challenges, especially with respect to the practical and industrial application are addressed.