WorldWideScience

Sample records for transition metal nanoclusters

  1. 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

  2. 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.

  3. Cluster perturbation theory for calculation of electronic properties of ensembles of metal nanoclusters

    Science.gov (United States)

    Zhumagulov, Yaroslav V.; Krasavin, Andrey V.; Kashurnikov, Vladimir A.

    2018-05-01

    The method is developed for calculation of electronic properties of an ensemble of metal nanoclusters with the use of cluster perturbation theory. This method is applied to the system of gold nanoclusters. The Greens function of single nanocluster is obtained by ab initio calculations within the framework of the density functional theory, and then is used in Dyson equation to group nanoclusters together and to compute the Greens function as well as the electron density of states of the whole ensemble. The transition from insulator state of a single nanocluster to metallic state of bulk gold is observed.

  4. Plasmon tsunamis on metallic nanoclusters.

    Science.gov (United States)

    Lucas, A A; Sunjic, M

    2012-03-14

    A model is constructed to describe inelastic scattering events accompanying electron capture by a highly charged ion flying by a metallic nanosphere. The electronic energy liberated by an electron leaving the Fermi level of the metal and dropping into a deep Rydberg state of the ion is used to increase the ion kinetic energy and, simultaneously, to excite multiple surface plasmons around the positively charged hole left behind on the metal sphere. This tsunami-like phenomenon manifests itself as periodic oscillations in the kinetic energy gain spectrum of the ion. The theory developed here extends our previous treatment (Lucas et al 2011 New J. Phys. 13 013034) of the Ar(q+)/C(60) charge exchange system. We provide an analysis of how the individual multipolar surface plasmons of the metallic sphere contribute to the formation of the oscillatory gain spectrum. Gain spectra showing characteristic, tsunami-like oscillations are simulated for Ar(15+) ions capturing one electron in distant collisions with Al and Na nanoclusters.

  5. Luminescent Metal Nanoclusters for Potential Chemosensor Applications

    Directory of Open Access Journals (Sweden)

    Muthaiah Shellaiah

    2017-12-01

    Full Text Available Studies of metal nanocluster (M-NCs-based sensors for specific analyte detection have achieved significant progress in recent decades. Ultra-small-size (<2 nm M-NCs consist of several to a few hundred metal atoms and exhibit extraordinary physical and chemical properties. Similar to organic molecules, M-NCs display absorption and emission properties via electronic transitions between energy levels upon interaction with light. As such, researchers tend to apply M-NCs in diverse fields, such as in chemosensors, biological imaging, catalysis, and environmental and electronic devices. Chemo- and bio-sensory uses have been extensively explored with luminescent NCs of Au, Ag, Cu, and Pt as potential sensory materials. Luminescent bi-metallic NCs, such as Au-Ag, Au-Cu, Au-Pd, and Au-Pt have also been used as probes in chemosensory investigations. Both metallic and bi-metallic NCs have been utilized to detect various analytes, such as metal ions, anions, biomolecules, proteins, acidity or alkalinity of a solution (pH, and nucleic acids, at diverse detection ranges and limits. In this review, we have summarized the chemosensory applications of luminescent M-NCs and bi-metallic NCs.

  6. Atomically Precise Metal Nanoclusters for Catalytic Application

    Energy Technology Data Exchange (ETDEWEB)

    Jin, Rongchao [Carnegie Mellon Univ., Pittsburgh, PA (United States)

    2016-11-18

    The central goal of this project is to explore the catalytic application of atomically precise gold nanoclusters. By solving the total structures of ligand-protected nanoclusters, we aim to correlate the catalytic properties of metal nanoclusters with their atomic/electronic structures. Such correlation unravel some fundamental aspects of nanocatalysis, such as the nature of particle size effect, origin of catalytic selectivity, particle-support interactions, the identification of catalytically active centers, etc. The well-defined nanocluster catalysts mediate the knowledge gap between single crystal model catalysts and real-world conventional nanocatalysts. These nanoclusters also hold great promise in catalyzing certain types of reactions with extraordinarily high selectivity. These aims are in line with the overall goals of the catalytic science and technology of DOE and advance the BES mission “to support fundamental research to understand, predict, and ultimately control matter and energy at the level of electrons, atoms, and molecules”. Our group has successfully prepared different sized, robust gold nanoclusters protected by thiolates, such as Au25(SR)18, Au28(SR)20, Au38(SR)24, Au99(SR)42, Au144(SR)60, etc. Some of these nanoclusters have been crystallographically characterized through X-ray crystallography. These ultrasmall nanoclusters (< 2 nm diameter) exhibit discrete electronic structures due to quantum size effect, as opposed to quasicontinuous band structure of conventional metal nanoparticles or bulk metals. The available atomic structures (metal core plus surface ligands) of nanoclusters serve as the basis for structure-property correlations. We have investigated the unique catalytic properties of nanoclusters (i.e. not observed in conventional nanogold catalysts) and revealed the structure-selectivity relationships. Highlights of our

  7. Distinct metal-exchange pathways of doped Ag25 nanoclusters

    KAUST Repository

    Bootharaju, Megalamane Siddaramappa; Sinatra, Lutfan; Bakr, Osman

    2016-01-01

    Atomically precise metal nanoclusters (NCs) containing more than one type of metal atom (i.e., doped or alloyed), due to synergistic effects, open new avenues for engineering the catalytic and optical properties of NCs in a manner that homometal NCs

  8. Spectroscopy of metal "superatom" nanoclusters and high-Tc superconducting pairing

    Science.gov (United States)

    Halder, Avik; Kresin, Vitaly V.

    2015-12-01

    A unique property of metal nanoclusters is the "superatom" shell structure of their delocalized electrons. The electronic shell levels are highly degenerate and therefore represent sharp peaks in the density of states. This can enable exceptionally strong electron pairing in certain clusters composed of tens to hundreds of atoms. In a finite system, such as a free nanocluster or a nucleus, pairing is observed most clearly via its effect on the energy spectrum of the constituent fermions. Accordingly, we performed a photoionization spectroscopy study of size-resolved aluminum nanoclusters and observed a rapid rise in the near-threshold density of states of several clusters (A l37 ,44 ,66 ,68 ) with decreasing temperature. The characteristics of this behavior are consistent with compression of the density of states by a pairing transition into a high-temperature superconducting state with Tc≳100 K. This value exceeds that of bulk aluminum by two orders of magnitude. These results highlight the potential of novel pairing effects in size-quantized systems and the possibility to attain even higher critical temperatures by optimizing the particles' size and composition. As a new class of high-temperature superconductors, such metal nanocluster particles are promising building blocks for high-Tc materials, devices, and networks.

  9. Synthesis and Doping of Ligand-Protected Atomically-Precise Metal Nanoclusters

    KAUST Repository

    Aljuhani, Maha A.

    2016-05-01

    Rapidly expanding research in nanotechnology has led to exciting progress in a versatile array of applications from medical diagnostics to catalysis. This success resulted from the manipulation of the desired properties of nanomaterials by controlling their size, shape, and composition. Among the most thriving areas of research about nanoparticle is the synthesis and doping of the ligand-protected atomically-precise metal nanoclusters. In this thesis, we developed three different novel metal nanoclusters, such as doped Ag29 with five gold (Au) atoms leading to enhance its quantum yield with remarkable stability. We also developed half-doped (alloyed) cluster of Ni6 nanocluster with molybdenum (Mo). This enabled enhanced stability and better catalytic activity. The third metal nanocluster that we synthesized was Au28 nanocluster by using di-thiolate as the ligand stabilizer instead of mono-thiolate. The new metal clusters obtained have been characterized by spectroscopic, electrochemical and crystallographic methods.

  10. Synthesis and Doping of Ligand-Protected Atomically-Precise Metal Nanoclusters

    KAUST Repository

    Aljuhani, Maha A.

    2016-01-01

    by controlling their size, shape, and composition. Among the most thriving areas of research about nanoparticle is the synthesis and doping of the ligand-protected atomically-precise metal nanoclusters. In this thesis, we developed three different novel metal

  11. Modeling of metal nanocluster growth on patterned substrates and surface pattern formation under ion bombardment

    Energy Technology Data Exchange (ETDEWEB)

    Numazawa, Satoshi

    2012-11-01

    This work addresses the metal nanocluster growth process on prepatterned substrates, the development of atomistic simulation method with respect to an acceleration of the atomistic transition states, and the continuum model of the ion-beam inducing semiconductor surface pattern formation mechanism. Experimentally, highly ordered Ag nanocluster structures have been grown on pre-patterned amorphous SiO{sub 2} surfaces by oblique angle physical vapor deposition at room temperature. Despite the small undulation of the rippled surface, the stripe-like Ag nanoclusters are very pronounced, reproducible and well-separated. The first topic is the investigation of this growth process with a continuum theoretical approach to the surface gas condensation as well as an atomistic cluster growth model. The atomistic simulation model is a lattice-based kinetic Monte-Carlo (KMC) method using a combination of a simplified inter-atomic potential and experimental transition barriers taken from the literature. An effective transition event classification method is introduced which allows a boost factor of several thousand compared to a traditional KMC approach, thus allowing experimental time scales to be modeled. The simulation predicts a low sticking probability for the arriving atoms, millisecond order lifetimes for single Ag monomers and {approx}1 nm square surface migration ranges of Ag monomers. The simulations give excellent reproduction of the experimentally observed nanocluster growth patterns. The second topic specifies the acceleration scheme utilized in the metallic cluster growth model. Concerning the atomistic movements, a classical harmonic transition state theory is considered and applied in discrete lattice cells with hierarchical transition levels. The model results in an effective reduction of KMC simulation steps by utilizing a classification scheme of transition levels for thermally activated atomistic diffusion processes. Thermally activated atomistic movements

  12. Modeling of metal nanocluster growth on patterned substrates and surface pattern formation under ion bombardment

    Energy Technology Data Exchange (ETDEWEB)

    Numazawa, Satoshi

    2012-11-01

    This work addresses the metal nanocluster growth process on prepatterned substrates, the development of atomistic simulation method with respect to an acceleration of the atomistic transition states, and the continuum model of the ion-beam inducing semiconductor surface pattern formation mechanism. Experimentally, highly ordered Ag nanocluster structures have been grown on pre-patterned amorphous SiO{sub 2} surfaces by oblique angle physical vapor deposition at room temperature. Despite the small undulation of the rippled surface, the stripe-like Ag nanoclusters are very pronounced, reproducible and well-separated. The first topic is the investigation of this growth process with a continuum theoretical approach to the surface gas condensation as well as an atomistic cluster growth model. The atomistic simulation model is a lattice-based kinetic Monte-Carlo (KMC) method using a combination of a simplified inter-atomic potential and experimental transition barriers taken from the literature. An effective transition event classification method is introduced which allows a boost factor of several thousand compared to a traditional KMC approach, thus allowing experimental time scales to be modeled. The simulation predicts a low sticking probability for the arriving atoms, millisecond order lifetimes for single Ag monomers and {approx}1 nm square surface migration ranges of Ag monomers. The simulations give excellent reproduction of the experimentally observed nanocluster growth patterns. The second topic specifies the acceleration scheme utilized in the metallic cluster growth model. Concerning the atomistic movements, a classical harmonic transition state theory is considered and applied in discrete lattice cells with hierarchical transition levels. The model results in an effective reduction of KMC simulation steps by utilizing a classification scheme of transition levels for thermally activated atomistic diffusion processes. Thermally activated atomistic movements

  13. Protein mediated synthesis of fluorescent Au-nanoclusters for metal sensory coatings

    Energy Technology Data Exchange (ETDEWEB)

    Vogel, Manja; Raff, Johannes [Helmholtz-Zentrum Dresden-Rossendorf e.V., Dresden (Germany). Biogeochemistry

    2017-06-01

    Fluorescent Au-nanocluster were successfully synthesized and used for the selective detection of Cu{sup 2} {sup +}. The synthesized Au-BSA-nanoclusters remain functional also after immobilization and show high thermal stability. Additionally, the transfer of the protein mediated Au-nanocluster synthesis route to S-layer proteins was achieved. (The presented work is part of the project BIONEWS dealing with long-term stable cells for the set-up and regeneration of sensor and actor materials for strategic relevant metals, in particular rare earth elements).

  14. Distinct metal-exchange pathways of doped Ag25 nanoclusters

    KAUST Repository

    Bootharaju, Megalamane Siddaramappa

    2016-09-09

    Atomically precise metal nanoclusters (NCs) containing more than one type of metal atom (i.e., doped or alloyed), due to synergistic effects, open new avenues for engineering the catalytic and optical properties of NCs in a manner that homometal NCs cannot. Unfortunately, it is still a major challenge to controllably introduce multimetallic dopants in NCs, understanding the dopants\\' positions, mechanism, and synergistic effects. To overcome these challenges, we designed a metal-exchange approach involving NCs as molecular templates and metal ions as the source of the incoming dopant. In particular, two structurally similar monodoped silver-rich NCs, [MAg24(SR)(18)](2-) (M = Pd/Pt and SR: thiolate), were synthesized as templates to study their mechanistic transformation in response to the introduction of gold atoms. The controllable incorporation of Au atoms into the MAg24 framework facilitated the elucidation of distinct doping pathways through high-resolution mass spectrometry, optical spectroscopy and elemental analysis. Interestingly, gold replaced the central Pd atom of [PdAg24(SR)(18)](2-) clusters to produce predominantly bimetallic [AuAg24(SR)(18)](-) clusters along with a minor product of an [Au2Ag23(SR)(18)](-) cluster. In contrast, the central Pt atom remained intact in [PtAg24(SR)(18)](2-) clusters, and gold replaced the noncentral Ag atoms to form trimetallic [AuxPtAg24-x(SR)(18)](2-) NCs, where x = 1-2, with a portion of the starting [PtAg24(SR)(18)](2-) NCs remaining. This study reveals some of the unusual metal-exchange pathways of doped NCs and the important role played by the initial metal dopant in directing the position of a second dopant in the final product.

  15. Solventless acid-free synthesis of mesostructured titania: Nanovessels for metal complexes and metal nanoclusters

    Energy Technology Data Exchange (ETDEWEB)

    Dag, Oe.; Celik, Oe.; Ozin, G.A. [Department of Chemistry, Bilkent University, 06533 Ankara (Turkey); Soten, I.; Polarz, S.; Coombs, N. [Materials Chemistry Research Group, Chemistry Department, University of Toronto, 80 St. George Street, Toronto, Ontario M5S 3H6 (Canada)

    2003-01-01

    A new and highly reproducible method to obtain mesostructured titania materials is introduced in this contribution. The mesostructured titania is obtained by employing self-assembled structures of non-ionic alkyl-poly(ethylene oxide) surfactants as templates. The materials are produced without additional solvents such as alcohols, or even water. Only the titanium(IV) ethoxide and the surfactant (C{sub 12}EO{sub 10}) are needed. Water, in the form of that attached to the surfactant and from the atmosphere, induces growth of titania nanoclusters in the synthesis sol. It is indicated that these nanoclusters interact with the surfactant EO-head groups to form a new titanotropic amphiphile. The new amphiphiles self-assemble into titanium nanocluster-surfactant hybrid lyotropic phases, which are transformed to the final mesostructured materials by further condensation of the titania network. The titania materials can be obtained also with noble-metal particles immobilized in the mesostructured framework. It is seen that when different metal salts are used as the metal precursors, different interactions with the titania walls are found. The materials are characterized by X-ray diffraction (XRD), polarization optical microscopy (POM), transmission electron microscopy (TEM), UV-vis spectroscopy, and micro-Raman analysis. (Abstract Copyright [2003], Wiley Periodicals, Inc.)

  16. Application of ionizing radiation for metal nanoclusters synthesis

    International Nuclear Information System (INIS)

    Smietanko-Chmielewska, D.K.; Chmielewski, A.G.; Warsaw University of Technology, Warsaw

    2011-01-01

    Complete text of publication follows. Possibility of ionizing radiation application in nanotechnology has been observed from very beginning when this field of science and technology was named. The lithography is based on electron and ion beam applications, and metal clusters synthesis by radiation induced radicals was reported many years ago. International Atomic Energy Agency was the first organization which has started coordinated programs on radiation applications in nanotechnology which are being continued in the frame of regional cooperation project RER8014. Some of applications led to patented technical solutions. Then review papers and chapters in the books have been published. The main applications beside of lithography deal with metal nanoclusters and nano-composites synthesis. Polymer composites containing metal nanoparticles have attracted a great interest due to their unique chemical and physical properties. 'Green' chemistry promotes application of natural fibers in such structures, among them cellulose is one of the most frequently used. However, cellulose fabric have ability to absorb moisture, so under certain conditions of humidity and temperature they can be subjected to microbial attack. One of the most popular and best known antibacterial agents is silver, which serves as a potential antibacterial material acting against an exceptionally broad spectrum of bacteria including activity against antibiotic-resistant bacteria. Silver nanoparticles (Ag NPs) were grown at the cellulose fibers surface by direct reduction of AgNO 3 with electron beam (EB) application. The big field of development concerns nano composites, possibility of e/X units application enlarge this possibility to industrial scale product manufacturing. Acknowledgement: This work was supported by the IAEA, regional project RER/8/014 and by the Ministry of Science and Higher Education, project DPN/W14/IAEA/2009.

  17. Fabrication and modification of metal nanocluster composites using ion and laser beams

    International Nuclear Information System (INIS)

    Haglund, R.F. Jr.; Osborne, D.H. Jr.; Magruder, R.H. III; White, C.W.; Zuhr, R.A.; Townsend, P.D.; Hole, D.E.; Leuchtner, R.E.

    1994-12-01

    Metal nanocluster composites have attractive properties for applications in nonlinear optics. However, traditional fabrication techniques -- using melt-glass substrates -- are severely constrained by equilibrium thermodynamics and kinetics. This paper describes the fabrication of metal nanoclusters in both crystalline and glassy hosts by ion implantation and pulsed laser deposition. The size and size distribution of the metal nanoclusters can be modified by controlling substrate temperature during implantation, by subsequent thermal annealing, or by laser irradiation. The authors have characterized the optical response of the composites by absorption and third-order nonlinear-optical spectroscopies; electron and scanning-probe microscopies have been used to benchmark the physical characteristics of the composites. The outlook for controlling the structure and nonlinear optical response properties of these nanophase materials appears increasingly promising

  18. Metal Catalysts for Heterogeneous Catalysis: From Single Atoms to Nanoclusters and Nanoparticles.

    Science.gov (United States)

    Liu, Lichen; Corma, Avelino

    2018-05-23

    Metal species with different size (single atoms, nanoclusters, and nanoparticles) show different catalytic behavior for various heterogeneous catalytic reactions. It has been shown in the literature that many factors including the particle size, shape, chemical composition, metal-support interaction, and metal-reactant/solvent interaction can have significant influences on the catalytic properties of metal catalysts. The recent developments of well-controlled synthesis methodologies and advanced characterization tools allow one to correlate the relationships at the molecular level. In this Review, the electronic and geometric structures of single atoms, nanoclusters, and nanoparticles will be discussed. Furthermore, we will summarize the catalytic applications of single atoms, nanoclusters, and nanoparticles for different types of reactions, including CO oxidation, selective oxidation, selective hydrogenation, organic reactions, electrocatalytic, and photocatalytic reactions. We will compare the results obtained from different systems and try to give a picture on how different types of metal species work in different reactions and give perspectives on the future directions toward better understanding of the catalytic behavior of different metal entities (single atoms, nanoclusters, and nanoparticles) in a unifying manner.

  19. Nanocluster metal films as thermoelectric material for radioisotope mini battery unit

    International Nuclear Information System (INIS)

    Borisyuk, P.V.; Krasavin, A.V.; Tkalya, E.V.; Lebedinskii, Yu.Yu.; Vasiliev, O.S.; Yakovlev, V.P.; Kozlova, T.I.; Fetisov, V.V.

    2016-01-01

    The paper is devoted to studying the thermoelectric and structural properties of films based on metal nanoclusters (Au, Pd, Pt). The experimental results of the study of single nanoclusters’ tunneling conductance obtained with scanning tunneling spectroscopy are presented. The obtained data allowed us to evaluate the thermoelectric power of thin film consisting of densely packed individual nanoclusters. It is shown that such thin films can operate as highly efficient thermoelectric materials. A scheme of miniature thermoelectric radioisotope power source based on the thorium-228 isotope is proposed. The efficiency of the radioisotope battery using thermoelectric converters based on nanocluster metal films is shown to reach values up to 1.3%. The estimated characteristics of the device are comparable with the parameters of up-to-date radioisotope batteries based on nickel-63.

  20. Electronic Properties of Metallic Nanoclusters on Semiconductor Surfaces: Implications for Nanoelectronic Device Applications

    International Nuclear Information System (INIS)

    Lee, Takhee; Liu Jia; Chen, N.-P.; Andres, R.P.; Janes, D.B.; Reifenberger, R.

    2000-01-01

    We review current research on the electronic properties of nanoscale metallic islands and clusters deposited on semiconductor substrates. Reported results for a number of nanoscale metal-semiconductor systems are summarized in terms of their fabrication and characterization. In addition to the issues faced in large-area metal-semiconductor systems, nano-systems present unique challenges in both the realization of well-controlled interfaces at the nanoscale and the ability to adequately characterize their electrical properties. Imaging by scanning tunneling microscopy as well as electrical characterization by current-voltage spectroscopy enable the study of the electrical properties of nanoclusters/semiconductor systems at the nanoscale. As an example of the low-resistance interfaces that can be realized, low-resistance nanocontacts consisting of metal nanoclusters deposited on specially designed ohmic contact structures are described. To illustrate a possible path to employing metal/semiconductor nanostructures in nanoelectronic applications, we also describe the fabrication and performance of uniform 2-D arrays of such metallic clusters on semiconductor substrates. Using self-assembly techniques involving conjugated organic tether molecules, arrays of nanoclusters have been formed in both unpatterned and patterned regions on semiconductor surfaces. Imaging and electrical characterization via scanning tunneling microscopy/spectroscopy indicate that high quality local ordering has been achieved within the arrays and that the clusters are electronically coupled to the semiconductor substrate via the low-resistance metal/semiconductor interface

  1. Probing the Absorption and Emission Transition Dipole Moment of DNA Stabilized Silver Nanoclusters

    DEFF Research Database (Denmark)

    Hooley, Emma Nicole; Carro Temboury, Miguel R.; Vosch, Tom André Jos

    2017-01-01

    Using single molecule polarization measurements, we investigate the excitation and emission polarization characteristics of DNA stabilized silver nanoclusters (C24-AgNCs). Although small changes in the polarization generally accompany changes to the emission spectrum, the emission and excitation...... transition dipoles tend to be steady over time and aligned in a similar direction, when immobilized in PVA. The emission transition dipole patterns, observed for C24-AgNCs in defocused wide field imaging, match that of a single emitter. The small changes to the polarization and spectral shifting that were...

  2. 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.

  3. Metal-insulator transitions

    Science.gov (United States)

    Imada, Masatoshi; Fujimori, Atsushi; Tokura, Yoshinori

    1998-10-01

    Metal-insulator transitions are accompanied by huge resistivity changes, even over tens of orders of magnitude, and are widely observed in condensed-matter systems. This article presents the observations and current understanding of the metal-insulator transition with a pedagogical introduction to the subject. Especially important are the transitions driven by correlation effects associated with the electron-electron interaction. The insulating phase caused by the correlation effects is categorized as the Mott Insulator. Near the transition point the metallic state shows fluctuations and orderings in the spin, charge, and orbital degrees of freedom. The properties of these metals are frequently quite different from those of ordinary metals, as measured by transport, optical, and magnetic probes. The review first describes theoretical approaches to the unusual metallic states and to the metal-insulator transition. The Fermi-liquid theory treats the correlations that can be adiabatically connected with the noninteracting picture. Strong-coupling models that do not require Fermi-liquid behavior have also been developed. Much work has also been done on the scaling theory of the transition. A central issue for this review is the evaluation of these approaches in simple theoretical systems such as the Hubbard model and t-J models. Another key issue is strong competition among various orderings as in the interplay of spin and orbital fluctuations. Experimentally, the unusual properties of the metallic state near the insulating transition have been most extensively studied in d-electron systems. In particular, there is revived interest in transition-metal oxides, motivated by the epoch-making findings of high-temperature superconductivity in cuprates and colossal magnetoresistance in manganites. The article reviews the rich phenomena of anomalous metallicity, taking as examples Ti, V, Cr, Mn, Fe, Co, Ni, Cu, and Ru compounds. The diverse phenomena include strong spin and

  4. Contribution of Metal Defects in the Assembly Induced Emission of Cu Nanoclusters

    KAUST Repository

    Wu, Zhennan

    2017-03-20

    Aggregation/assembly induced emission (AIE) has been observed for metal nanoclusters (NCs), but the origin of the enhanced emission is not fully understood, yet. In this work, the significant contribution of metal defects on AIE is revealed by engineering the self-assembly process of Cu NCs using ethanol. The presence of ethanol leads to a rapid assembly of NCs into ultrathin nanosheets, promoting the formation of metal defects-rich surface. Detailed studies and computer simulation confirm that the metal defects-rich nanosheets possess increased Cu(I)-to-Cu(0) ratio, which greatly influences ligand-to-metal-metal charge transfer and therewith facilitates the radiative relaxation of excitons. Consequently, the Cu NCs self-assembly nanosheets exhibit obvious emission enhancement.

  5. 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.

  6. Bio-NCs--the marriage of ultrasmall metal nanoclusters with biomolecules.

    Science.gov (United States)

    Goswami, Nirmal; Zheng, Kaiyuan; Xie, Jianping

    2014-11-21

    Ultrasmall metal nanoclusters (NCs) have attracted increasing attention due to their fascinating physicochemical properties. Today, functional metal NCs are finding growing acceptance in biomedical applications. To achieve a better performance in biomedical applications, metal NCs can be interfaced with biomolecules, such as proteins, peptides, and DNA, to form a new class of biomolecule-NC composites (or bio-NCs in short), which typically show synergistic or novel physicochemical and physiological properties. This feature article focuses on the recent studies emerging at the interface of metal NCs and biomolecules, where the interactions could impart unique physicochemical properties to the metal NCs, as well as mutually regulate biological functions of the bio-NCs. In this article, we first provide a broad overview of key concepts and developments in the novel biomolecule-directed synthesis of metal NCs. A special focus is placed on the key roles of biomolecules in metal NC synthesis. In the second part, we describe how the encapsulated metal NCs affect the structure and function of biomolecules. Followed by that, we discuss several unique synergistic effects observed in the bio-NCs, and illustrate them with examples highlighting their potential biomedical applications. Continued interdisciplinary efforts are required to build up in-depth knowledge about the interfacial chemistry and biology of bio-NCs, which could further pave their ways toward biomedical applications.

  7. Bio-NCs - the marriage of ultrasmall metal nanoclusters with biomolecules

    Science.gov (United States)

    Goswami, Nirmal; Zheng, Kaiyuan; Xie, Jianping

    2014-10-01

    Ultrasmall metal nanoclusters (NCs) have attracted increasing attention due to their fascinating physicochemical properties. Today, functional metal NCs are finding growing acceptance in biomedical applications. To achieve a better performance in biomedical applications, metal NCs can be interfaced with biomolecules, such as proteins, peptides, and DNA, to form a new class of biomolecule-NC composites (or bio-NCs in short), which typically show synergistic or novel physicochemical and physiological properties. This feature article focuses on the recent studies emerging at the interface of metal NCs and biomolecules, where the interactions could impart unique physicochemical properties to the metal NCs, as well as mutually regulate biological functions of the bio-NCs. In this article, we first provide a broad overview of key concepts and developments in the novel biomolecule-directed synthesis of metal NCs. A special focus is placed on the key roles of biomolecules in metal NC synthesis. In the second part, we describe how the encapsulated metal NCs affect the structure and function of biomolecules. Followed by that, we discuss several unique synergistic effects observed in the bio-NCs, and illustrate them with examples highlighting their potential biomedical applications. Continued interdisciplinary efforts are required to build up in-depth knowledge about the interfacial chemistry and biology of bio-NCs, which could further pave their ways toward biomedical applications.

  8. One-step aqueous synthesis of fluorescent copper nanoclusters by direct metal reduction

    International Nuclear Information System (INIS)

    Fernández-Ujados, Mónica; Trapiella-Alfonso, Laura; Costa-Fernández, José M; Pereiro, Rosario; Sanz-Medel, Alfredo

    2013-01-01

    A one-step aqueous synthesis of highly fluorescent water-soluble copper nanoclusters (CuNCs) is here described, based on direct reduction of the metal precursor with NaBH 4 in the presence of bidentate ligands (made of lipoic acid anchoring groups, appended with a poly(ethylene glycol) short chain). A complete optical and structural characterization was carried out: the optical emission was centred at 416 nm, with a luminescence quantum yield in water of 3.6% (the highest one reported so far in water for this kind of nanocluster). The structural characterization reveals a homogeneous size distribution (of 2.5 nm diameter) with spherical shape. The CuNCs obtained offer long-term stability (the luminescence emission remained unaltered after more than two months) under a broad range of chemical conditions (e.g. stored at pH 3–12 or even in a high ionic strength medium such as 1 M NaCl) and high photostability, keeping their fluorescence emission intact after more than 2 h of daylight and UV-light exposition. All those advantageous features warrant synthesized CuNCs being promising fluorescent nanoprobes for further developments including (bio)applications. (paper)

  9. 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)

  10. Stabilizing and Organizing Bi3 Cu4 and Bi7 Cu12 Nanoclusters in Two-Dimensional Metal-Organic Networks.

    Science.gov (United States)

    Yan, Linghao; Xia, Bowen; Zhang, Qiushi; Kuang, Guowen; Xu, Hu; Liu, Jun; Liu, Pei Nian; Lin, Nian

    2018-04-16

    Multinuclear heterometallic nanoclusters with controllable stoichiometry and structure are anticipated to possess promising catalytic, magnetic, and optical properties. Heterometallic nanoclusters with precise stoichiometry of Bi 3 Cu 4 and Bi 7 Cu 12 can be stabilized in the scaffold of two-dimensional metal-organic networks on a Cu(111) surface through on-surface metallosupramolecular self-assembly processes. The atomic structures of the nanoclusters were resolved using scanning tunneling microscopy and density functional theory calculations. The nanoclusters feature highly symmetric planar hexagonal shapes and core-shell charge modulation. The clusters are arranged as triangular lattices with a periodicity that can be tuned by choosing molecules of different size. This work shows that on-surface metallosupramolecular self-assembly creates unique possibilities for the design and synthesis of multinuclear heterometallic nanoclusters. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. Size dependent hcp-to-fcc transition temperature in Co nanoclusters obtained by ion implantation in silica

    International Nuclear Information System (INIS)

    Mattei, G.; Maurizio, C.; Fernandez, C Julian de; Mazzoldi, P.; Battaglin, G.; Canton, P.; Cattaruzza, E.; Scian, C.

    2006-01-01

    In this work we present in situ investigations on the increase of the hcp-to-fcc transition temperature for Co with respect to the bulk value (420 deg. C) when nanoclusters are considered. Starting from Co:SiO 2 composites obtained by ion implantation with average Co cluster size of about 5 nm, a transition temperature between 800 deg. C and 900 deg. C is found upon thermal annealing in vacuum by in situ transmission electron microscopy. Preliminary results on electron irradiation to promote the transition at lower temperatures are presented

  12. Algorithm based on the Thomson problem for determination of equilibrium structures of metal nanoclusters

    Science.gov (United States)

    Arias, E.; Florez, E.; Pérez-Torres, J. F.

    2017-06-01

    A new algorithm for the determination of equilibrium structures suitable for metal nanoclusters is proposed. The algorithm performs a stochastic search of the minima associated with the nuclear potential energy function restricted to a sphere (similar to the Thomson problem), in order to guess configurations of the nuclear positions. Subsequently, the guessed configurations are further optimized driven by the total energy function using the conventional gradient descent method. This methodology is equivalent to using the valence shell electron pair repulsion model in guessing initial configurations in the traditional molecular quantum chemistry. The framework is illustrated in several clusters of increasing complexity: Cu7, Cu9, and Cu11 as benchmark systems, and Cu38 and Ni9 as novel systems. New equilibrium structures for Cu9, Cu11, Cu38, and Ni9 are reported.

  13. Deposition and characterization of Pt nanocluster films by means of gas aggregation cluster source

    Energy Technology Data Exchange (ETDEWEB)

    Kylián, Ondřej, E-mail: ondrej.kylian@gmail.com; Prokeš, Jan; Polonskyi, Oleksandr; Čechvala, Juraj; Kousal, Jaroslav; Pešička, Josef; Hanuš, Jan; Biederman, Hynek

    2014-11-28

    In this study we report on the deposition of Pt nanocluster films prepared by gas aggregation source that was operated with argon as working gas. The aim of this study was optimization of deposition process as well as determination of properties of deposited nanocluster films and their temporal stability. It was found that the production of Pt nanoclusters reached maximum value for pressure of 100 Pa and increases monotonously with magnetron current. The deposition rate at optimized deposition conditions was 0.7 nm of the Pt nanocluster film per second. Deposited films were porous and composed of 4 nm Pt nanoclusters. The nanoclusters were metallic and no sights of their oxidation were observed after 1 year on open air as witnessed by X-ray photoelectron spectroscopy. Regarding the electrical properties, a dramatic decrease of the resistivity was observed with increasing amount of deposited nanoclusters. This decrease saturated for the films approximately 50 nm thick. Such behavior indicates transition between different mechanisms of electrical conductivity: charge hopping for thin discontinuous films and current conduction through conducting path formed when higher amount of nanoclusters is deposited. Different mechanisms of electrical conduction for thin and thick layers of Pt were confirmed by subsequent investigation of temperature dependence of resistivity. In addition, no changes in resistivity were observed after one year on open air that confirms stability of produced Pt nanocluster films. - Highlights: • Pt nanocluster films were deposited by gas aggregation nanocluster source. • Conditions leading to effective deposition of Pt nanocluster films were found. • Deposited nanocluster films have good temporal stability. • Electrical properties of Pt films were found to depend on their thickness.

  14. Enhanced electrochemical water oxidation: the impact of nanoclusters and nanocavities

    NARCIS (Netherlands)

    Zhang, X.; Cao, C.; Bieberle, A.

    2017-01-01

    The structures of transition metal surfaces and metal oxides are commonly believed to have a significant effect on the catalytic reactions. Density functional theory calculations are therefore used in this study to investigate the oxygen evolution reaction (OER) over nanostructured, i.e. nanocluster

  15. 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 ...

  16. Theoretical Investigation of the Structural Stabilities of Ceria Surfaces and Supported Metal Nanocluster in Vapor and Aqueous Phases

    Energy Technology Data Exchange (ETDEWEB)

    Ren, Zhibo [State Key Laboratory of Chemical Resource Engineering, Beijing University of Chemical Technology, Beijing 100029, China; Institute for Integrated Catalysis, Pacific Northwest National Laboratory, Richland, Washington 99352, United States; Liu, Ning [State Key Laboratory of Chemical Resource Engineering, Beijing University of Chemical Technology, Beijing 100029, China; Institute for Integrated Catalysis, Pacific Northwest National Laboratory, Richland, Washington 99352, United States; Chen, Biaohua [State Key Laboratory of Chemical Resource Engineering, Beijing University of Chemical Technology, Beijing 100029, China; Li, Jianwei [State Key Laboratory of Chemical Resource Engineering, Beijing University of Chemical Technology, Beijing 100029, China; Mei, Donghai [Institute for Integrated Catalysis, Pacific Northwest National Laboratory, Richland, Washington 99352, United States

    2018-01-25

    Understanding the structural stability and dynamics at the interface between the solid metal oxide and aqueous phase is significant in a variety of industrial applications including heterogeneous catalysis and environmental remediation. In the present work, the stabilities of three low-index ceria (CeO2) surfaces, i.e., (111), (110) and (100) in vapor and aqueous phases were studied using ab initio molecular dynamics simulations and density functional theory (DFT) calculations. Gibbs surface free energies as a function of temperature, water partial pressure, and water coverages were calculated using DFT based atomistic thermodynamic approach. On the basis of surface free energies, the morphology and exposed surface structures of the CeO2 nanoparticle were predicted using Wulff construction principle. It is found that the partially hydroxylated (111) and (100) are two major surface structures of CeO2 nanoparticles in vapor phase at ambient temperature (300 K). As the temperature increases, the fully dehydrated (111) surface gradually becomes the most dominant surface structure. While in aqueous phase, the exposed surface of the CeO2 nanoparticle is dominated by the hydroxylated (110) structure at 393 K. Finally, the morphology and stability of a cuboctahedron Pt13 nanocluster supported on CeO2 surfaces in both gas and aqueous phases were investigated. In gas phase, the supported Pt13 nanocluster has the tendency to wetting the CeO2 surface due to the strong metal-support interaction. The calculated interaction energies suggest the CeO2(110) surface provides the best stability for the Pt13 nanocluster. The CeO2 supported Pt13 nanoclusters are oxidized. Compared to the gas phase, the morphology of the CeO2 supported Pt13 nanocluster is less distorted due to the solvation effect provided by surrounding water molecules in aqueous phase. More electrons are transferred from the Pt13 nanocluster to the CeO2 support, implying the supported Pt13 nanocluster is further

  17. 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…

  18. 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.

  19. Methanol, ethanol and hydrogen sensing using metal oxide and metal (TiO2–Pt) composite nanoclusters on GaN nanowires: a new route towards tailoring the selectivity of nanowire/nanocluster chemical sensors

    International Nuclear Information System (INIS)

    Aluri, Geetha S; Motayed, Abhishek; Davydov, Albert V; Oleshko, Vladimir P; Bertness, Kris A; Sanford, Norman A; Mulpuri, Rao V

    2012-01-01

    We demonstrate a new method for tailoring the selectivity of chemical sensors using semiconductor nanowires (NWs) decorated with metal and metal oxide multicomponent nanoclusters (NCs). Here we present the change of selectivity of titanium dioxide (TiO 2 ) nanocluster-coated gallium nitride (GaN) nanowire sensor devices on the addition of platinum (Pt) nanoclusters. The hybrid sensor devices were developed by fabricating two-terminal devices using individual GaN NWs followed by the deposition of TiO 2 and/or Pt nanoclusters (NCs) using the sputtering technique. This paper present the sensing characteristics of GaN/(TiO 2 –Pt) nanowire–nanocluster (NWNC) hybrids and GaN/(Pt) NWNC hybrids, and compare their selectivity with that of the previously reported GaN/TiO 2 sensors. The GaN/TiO 2 NWNC hybrids showed remarkable selectivity to benzene and related aromatic compounds, with no measurable response for other analytes. Addition of Pt NCs to GaN/TiO 2 sensors dramatically altered their sensing behavior, making them sensitive only to methanol, ethanol and hydrogen, but not to any other chemicals we tested. The GaN/(TiO 2 –Pt) hybrids were able to detect ethanol and methanol concentrations as low as 100 nmol mol −1 (ppb) in air in approximately 100 s, and hydrogen concentrations from 1 µmol mol −1 (ppm) to 1% in nitrogen in less than 60 s. However, GaN/Pt NWNC hybrids showed limited sensitivity only towards hydrogen and not towards any alcohols. All these hybrid sensors worked at room temperature and are photomodulated, i.e. they responded to analytes only in the presence of ultraviolet (UV) light. We propose a qualitative explanation based on the heat of adsorption, ionization energy and solvent polarity to explain the observed selectivity of the different hybrids. These results are significant from the standpoint of applications requiring room-temperature hydrogen sensing and sensitive alcohol monitoring. These results demonstrate the tremendous potential

  20. Methanol, ethanol and hydrogen sensing using metal oxide and metal (TiO(2)-Pt) composite nanoclusters on GaN nanowires: a new route towards tailoring the selectivity of nanowire/nanocluster chemical sensors.

    Science.gov (United States)

    Aluri, Geetha S; Motayed, Abhishek; Davydov, Albert V; Oleshko, Vladimir P; Bertness, Kris A; Sanford, Norman A; Mulpuri, Rao V

    2012-05-04

    We demonstrate a new method for tailoring the selectivity of chemical sensors using semiconductor nanowires (NWs) decorated with metal and metal oxide multicomponent nanoclusters (NCs). Here we present the change of selectivity of titanium dioxide (TiO(2)) nanocluster-coated gallium nitride (GaN) nanowire sensor devices on the addition of platinum (Pt) nanoclusters. The hybrid sensor devices were developed by fabricating two-terminal devices using individual GaN NWs followed by the deposition of TiO(2) and/or Pt nanoclusters (NCs) using the sputtering technique. This paper present the sensing characteristics of GaN/(TiO(2)-Pt) nanowire-nanocluster (NWNC) hybrids and GaN/(Pt) NWNC hybrids, and compare their selectivity with that of the previously reported GaN/TiO(2) sensors. The GaN/TiO(2) NWNC hybrids showed remarkable selectivity to benzene and related aromatic compounds, with no measurable response for other analytes. Addition of Pt NCs to GaN/TiO(2) sensors dramatically altered their sensing behavior, making them sensitive only to methanol, ethanol and hydrogen, but not to any other chemicals we tested. The GaN/(TiO(2)-Pt) hybrids were able to detect ethanol and methanol concentrations as low as 100 nmol mol(-1) (ppb) in air in approximately 100 s, and hydrogen concentrations from 1 µmol mol(-1) (ppm) to 1% in nitrogen in less than 60 s. However, GaN/Pt NWNC hybrids showed limited sensitivity only towards hydrogen and not towards any alcohols. All these hybrid sensors worked at room temperature and are photomodulated, i.e. they responded to analytes only in the presence of ultraviolet (UV) light. We propose a qualitative explanation based on the heat of adsorption, ionization energy and solvent polarity to explain the observed selectivity of the different hybrids. These results are significant from the standpoint of applications requiring room-temperature hydrogen sensing and sensitive alcohol monitoring. These results demonstrate the tremendous potential for

  1. 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 ...

  2. 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)

  3. Nanomorphology of Polymer Frameworks and Their Role as Templates for Generating Size-Controlled Metal Nanoclusters

    Czech Academy of Sciences Publication Activity Database

    Artuso, F.; D'Archivio, A. A.; Lora, S.; Jeřábek, Karel; Králik, E.; Corain, B.

    2003-01-01

    Roč. 9, č. 21 (2003), s. 5292-5296 ISSN 0947-6539 Grant - others:GA-(IT) 2001038991; VEGA(SK) 1/9142/02 Institutional research plan: CEZ:AV0Z4072921 Keywords : nanoclusters * nano-structures * gel-type resin s Subject RIV: CI - Industrial Chemistry, Chemical Engineering Impact factor: 4.353, year: 2003

  4. Metal-to-nonmetal transitions

    CERN Document Server

    Hensel, Friedrich; Holst, Bastian

    2010-01-01

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

  5. 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

  6. 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.

  7. Size-dependent single electron transfer and semi-metal-to-insulator transitions in molecular metal oxide electronics.

    Science.gov (United States)

    Balliou, Angelika; Bouroushian, Mirtat; Douvas, Antonios M; Skoulatakis, George; Kennou, Stella; Glezos, Nikos

    2018-07-06

    All-inorganic self-arranged molecular transition metal oxide hyperstructures based on polyoxometalate molecules (POMs) are fabricated and tested as electronically tunable components in emerging electronic devices. POM hyperstructures reveal great potential as charging nodes of tunable charging level for molecular memories and as enhancers of interfacial electron/hole injection for photovoltaic stacks. STM, UPS, UV-vis spectroscopy and AFM measurements show that this functionality stems from the films' ability to structurally tune their HOMO-LUMO levels and electron localization length at room temperature. By adapting POM nanocluster size in solution, self-doping and current modulation of four orders of magnitude is monitored on a single nanocluster on SiO 2 at voltages as low as 3 Volt. Structurally driven insulator-to-semi-metal transitions and size-dependent current regulation through single electron tunneling are demonstrated and examined with respect to the stereochemical and electronic structure of the molecular entities. This extends the value of self-assembly as a tool for correlation length and electronic properties tuning and demonstrate POM hyperstructures' plausibility for on-chip molecular electronics operative at room temperature.

  8. Size-dependent single electron transfer and semi-metal-to-insulator transitions in molecular metal oxide electronics

    Science.gov (United States)

    Balliou, Angelika; Bouroushian, Mirtat; Douvas, Antonios M.; Skoulatakis, George; Kennou, Stella; Glezos, Nikos

    2018-07-01

    All-inorganic self-arranged molecular transition metal oxide hyperstructures based on polyoxometalate molecules (POMs) are fabricated and tested as electronically tunable components in emerging electronic devices. POM hyperstructures reveal great potential as charging nodes of tunable charging level for molecular memories and as enhancers of interfacial electron/hole injection for photovoltaic stacks. STM, UPS, UV–vis spectroscopy and AFM measurements show that this functionality stems from the films’ ability to structurally tune their HOMO–LUMO levels and electron localization length at room temperature. By adapting POM nanocluster size in solution, self-doping and current modulation of four orders of magnitude is monitored on a single nanocluster on SiO2 at voltages as low as 3 Volt. Structurally driven insulator-to-semi-metal transitions and size-dependent current regulation through single electron tunneling are demonstrated and examined with respect to the stereochemical and electronic structure of the molecular entities. This extends the value of self-assembly as a tool for correlation length and electronic properties tuning and demonstrate POM hyperstructures’ plausibility for on-chip molecular electronics operative at room temperature.

  9. Intriguing structures and magic sizes of heavy noble metal nanoclusters around size 55 governed by relativistic effect and covalent bonding

    Energy Technology Data Exchange (ETDEWEB)

    Zhao, X. J.; Xue, X. L.; Jia, Yu [International Laboratory for Quantum Functional Materials of Henan and School of Physics and Engineering, Zhengzhou University, Zhengzhou 450001 (China); Guo, Z. X. [International Laboratory for Quantum Functional Materials of Henan and School of Physics and Engineering, Zhengzhou University, Zhengzhou 450001 (China); Department of Chemistry and London Centre for Nanotechnology, University College London, London WC1H (United Kingdom); Li, S. F., E-mail: sflizzu@zzu.edu.cn [International Laboratory for Quantum Functional Materials of Henan and School of Physics and Engineering, Zhengzhou University, Zhengzhou 450001 (China); ICQD, Hefei National Laboratory for Physical Sciences at the Microscale, University of Science and Technology of China, Hefei, Anhui 230026 (China); Zhang, Zhenyu, E-mail: zhangzy@ustc.edu.cn [ICQD, Hefei National Laboratory for Physical Sciences at the Microscale, University of Science and Technology of China, Hefei, Anhui 230026 (China); Synergetic Innovation Center of Quantum Information and Quantum Physics, University of Science and Technology of China, Hefei, Anhui 230026 (China); Gao, Y. F., E-mail: ygao7@utk.edu [Department of Materials Science and Engineering, University of Tennessee, Knoxville, Tennessee 37996 (United States); Materials Science and Technology Division, Oak Ridge National Laboratory, Oak Ridge, Tennessee 37831 (United States)

    2015-11-07

    Nanoclusters usually display exotic physical and chemical properties due to their intriguing geometric structures in contrast to their bulk counterparts. By means of first-principles calculations within density functional theory, we find that heavy noble metal Pt{sub N} nanoclusters around the size N = 55 begin to prefer an open configuration, rather than previously reported close-packed icosahedron or core-shell structures. Particularly, for Pt{sub N}, the widely supposed icosahedronal magic cluster is changed to a three-atomic-layered structure with D{sub 6h} symmetry, which can be well addressed by our recently established generalized Wulff construction principle (GWCP). However, the magic number of Pt{sub N} clusters around 55 is shifted to a new odd number of 57. The high symmetric three-layered Pt{sub 57} motif is mainly stabilized by the enhanced covalent bonding contributed by both spin-orbital coupling effect and the open d orbital (5d{sup 9}6s{sup 1}) of Pt, which result in a delicate balance between the enhanced Pt–Pt covalent bonding of the interlayers and negligible d dangling bonds on the cluster edges. These findings about Pt{sub N} clusters are also applicable to Ir{sub N} clusters, but qualitatively different from their earlier neighboring element Os and their later neighboring element Au. The magic numbers for Os and Au are even, being 56 and 58, respectively. The findings of the new odd magic number 57 are the important supplementary of the recently established GWCP.

  10. Faceted titania nanocrystals doped with indium oxide nanoclusters as a superior candidate for sacrificial hydrogen evolution without any noble-metal cocatalyst under solar irradiation.

    Science.gov (United States)

    Amoli, Vipin; Sibi, Malayil Gopalan; Banerjee, Biplab; Anand, Mohit; Maurya, Abhayankar; Farooqui, Saleem Akhtar; Bhaumik, Asim; Sinha, Anil Kumar

    2015-01-14

    Development of unique nanoheterostructures consisting of indium oxide nanoclusters like species doped on the TiO2 nanocrystals surfaces with {101} and {001} exposed facets, resulted in unprecedented sacrificial hydrogen production (5.3 mmol h(-1) g(-1)) from water using methanol as a sacrificial agent, under visible light LED source and AM 1.5G solar simulator (10.3 mmol h(-1) g(-1)), which is the highest H2 production rate ever reported for titania based photocatalysts, without using any noble metal cocatalyst. X-ray photoelectron spectroscopy (XPS) analysis of the nanostructures reveals the presence of Ti-O-In and In-O-In like species on the surface of nanostructures. Electron energy-loss spectroscopy (EELS) elemental mapping and EDX spectroscopy techniques combined with transmission electron microscope evidenced the existence of nanoheterostructures. XPS, EELS, EDX, and HAADF-STEM tools collectively suggest the presence of indium oxide nanoclusters like species on the surface of TiO2 nanostructures. These indium oxide nanocluster doped TiO2 (In2O3/T{001}) single crystals with {101} and {001} exposed facets exhibited 1.3 times higher visible light photocatalytic H2 production than indium oxide nanocluster doped TiO2 nanocrystals with only {101}facets (In2O3/T{101}) exposed. The remarkable photocatalytic activity of the obtained nanoheterostructures is attributed to the combined synergetic effect of indium oxide nanoclusters interacting with the titania surface, enhanced visible light response, high crystallinity, and unique structural features.

  11. Metal nanoparticles as a conductive catalyst

    Science.gov (United States)

    Coker, Eric N [Albuquerque, NM

    2010-08-03

    A metal nanocluster composite material for use as a conductive catalyst. The metal nanocluster composite material has metal nanoclusters on a carbon substrate formed within a porous zeolitic material, forming stable metal nanoclusters with a size distribution between 0.6-10 nm and, more particularly, nanoclusters with a size distribution in a range as low as 0.6-0.9 nm.

  12. Chiral Gold Nanoclusters: Atomic Level Origins of Chirality.

    Science.gov (United States)

    Zeng, Chenjie; Jin, Rongchao

    2017-08-04

    Chiral nanomaterials have received wide interest in many areas, but the exact origin of chirality at the atomic level remains elusive in many cases. With recent significant progress in atomically precise gold nanoclusters (e.g., thiolate-protected Au n (SR) m ), several origins of chirality have been unveiled based upon atomic structures determined by using single-crystal X-ray crystallography. The reported chiral Au n (SR) m structures explicitly reveal a predominant origin of chirality that arises from the Au-S chiral patterns at the metal-ligand interface, as opposed to the chiral arrangement of metal atoms in the inner core (i.e. kernel). In addition, chirality can also be introduced by a chiral ligand, manifested in the circular dichroism response from metal-based electronic transitions other than the ligand's own transition(s). Lastly, the chiral arrangement of carbon tails of the ligands has also been discovered in a very recent work on chiral Au 133 (SR) 52 and Au 246 (SR) 80 nanoclusters. Overall, the origins of chirality discovered in Au n (SR) m nanoclusters may provide models for the understanding of chirality origins in other types of nanomaterials and also constitute the basis for the development of various applications of chiral nanoparticles. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. Superconducting Metallic Glass Transition-Edge-Sensors

    Science.gov (United States)

    Hays, Charles C. (Inventor)

    2013-01-01

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

  14. Recent Advances in the Field of Bionanotechnology: An Insight into Optoelectric Bacteriorhodopsin, Quantum Dots, and Noble Metal Nanoclusters

    Directory of Open Access Journals (Sweden)

    Christopher Knoblauch

    2014-10-01

    Full Text Available Molecular sensors and molecular electronics are a major component of a recent research area known as bionanotechnology, which merges biology with nanotechnology. This new class of biosensors and bioelectronics has been a subject of intense research over the past decade and has found application in a wide variety of fields. The unique characteristics of these biomolecular transduction systems has been utilized in applications ranging from solar cells and single-electron transistors (SETs to fluorescent sensors capable of sensitive and selective detection of a wide variety of targets, both organic and inorganic. This review will discuss three major systems in the area of molecular sensors and electronics and their application in unique technological innovations. Firstly, the synthesis of optoelectric bacteriorhodopsin (bR and its application in the field of molecular sensors and electronics will be discussed. Next, this article will discuss recent advances in the synthesis and application of semiconductor quantum dots (QDs. Finally, this article will conclude with a review of the new and exciting field of noble metal nanoclusters and their application in the creation of a new class of fluorescent sensors.

  15. Spiral patterns of gold nanoclusters in silicon (100) produced by metal vapour vacuum arc implantation of gold ions

    International Nuclear Information System (INIS)

    Venkatachalam, Dinesh Kumar; Sood, Dinesh Kumar; Bhargava, Suresh Kumar

    2008-01-01

    Self-assembled gold nanoclusters are attractive building blocks for future nanoscale sensors and optical devices due to their exciting catalytic properties. In this work, we report direct bottom-up synthesis of spiral patterns of gold nanoclusters in silicon (100) substrates by Au ion implantation followed by thermal annealing. This unique phenomenon is observed only above a critical threshold implantation dose and annealing temperature. Systematic study by electron microscopy, analytical x-ray diffraction and atomic force microscopy shows the temperature- and time-dependent nucleation, growth of Au nanoclusters and evolution of the spiral patterns. The observed patterns of gold nanoclusters bear a resemblance to the spiral growth prevalent in some directionally solidified eutectic alloys. Based on this systematic study of the growth and morphology of nanoclusters, a tentative model has been proposed for the formation mechanism of this unusual self-assembled pattern in an amorphous Si/Au system. This model shows that melting of the implanted layer is essential and without which no spiral patterns are observed. A better understanding of this self-assembly process will open up new ways to fabricate ordered arrays of gold nanoclusters in silicon substrates for seeding selective growth of one-dimensional nanostructures

  16. 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...

  17. 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...

  18. 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...

  19. 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.

  20. 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.

  1. Surface mediated assembly of small, metastable gold nanoclusters

    Science.gov (United States)

    Pettibone, John M.; Osborn, William A.; Rykaczewski, Konrad; Talin, A. Alec; Bonevich, John E.; Hudgens, Jeffrey W.; Allendorf, Mark D.

    2013-06-01

    The unique properties of metallic nanoclusters are attractive for numerous commercial and industrial applications but are generally less stable than nanocrystals. Thus, developing methodologies for stabilizing nanoclusters and retaining their enhanced functionality is of great interest. We report the assembly of PPh3-protected Au9 clusters from a heterogeneous mixture into films consisting of sub 3 nm nanocluster assemblies. The depositing nanoclusters are metastable in solution, but the resulting nanocluster assemblies are stabilized indefinitely in air or fresh solvent. The films exhibit distinct structure from Au nanoparticles observed by X-ray diffraction, and film dissolution data support the preservation of small nanoclusters. UV-Vis spectroscopy, electrospray ionization mass spectrometry, X-ray photoelectron spectroscopy and electron microscopy are used to elucidate information regarding the nanocluster formation and assembly mechanism. Preferential deposition of nanocluster assemblies can be achieved on multiple substrates, including polymer, Cr, Si, SiO2, SiNx, and metal-organic frameworks (MOFs). Unlike other vapor phase coating processes, nanocluster assembly on the MIL-68(In) MOF crystal is capable of preferentially coating the external surface and stabilizing the crystal structure in hydrothermal conditions, which should enhance their storage, separation and delivery capabilities.The unique properties of metallic nanoclusters are attractive for numerous commercial and industrial applications but are generally less stable than nanocrystals. Thus, developing methodologies for stabilizing nanoclusters and retaining their enhanced functionality is of great interest. We report the assembly of PPh3-protected Au9 clusters from a heterogeneous mixture into films consisting of sub 3 nm nanocluster assemblies. The depositing nanoclusters are metastable in solution, but the resulting nanocluster assemblies are stabilized indefinitely in air or fresh solvent. The

  2. Investigating self-assembly and metal nanoclusters in aqueous di-block copolymers solutions

    CERN Document Server

    Lo Celso, F; Triolo, R; Triolo, A; Strunz, P; Bronstein, L; Zwanziger, J; Lin, J S

    2002-01-01

    Self-assembling properties of di-block copolymers/ surfactant hybrids in aqueous solution can be exploited to obtain metal nanoparticles stable dispersion. Results will be presented here for polystyrene-block-poly(ethylene oxide) solutions. A SANS structural investigation has been performed over different molecular weights of both hydrophilic and hydrophobic block, by varying temperature and concentration of the copolymer. A SAXS characterization of micellar systems containing Pt nanoparticles is reported. (orig.)

  3. Controllable growth and magnetic properties of nickel nanoclusters electrodeposited on the ZnO nanorod template

    International Nuclear Information System (INIS)

    Tang Yang; Zhao Dongxu; Shen Dezhen; Zhang Jiying; Wang Xiaohua

    2009-01-01

    The ZnO nanorods were used as a template to fabricate nickel nanoclusters by electrodeposition. The ZnO nanorod arrays act as a nano-semiconductor electrode for depositing metallic and magnetic nickel nanoclusters. The growth sites of Ni nanoclusters could be controlled by adjusting the applied potential. Under -1.15 V the Ni nanoclusters could be grown on the tips of ZnO nanorods. On increasing the potential to be more negative the ZnO nanorods were covered by Ni nanoclusters. The magnetic properties of the electrodeposited Ni nanoclusters also evolved with the applied potentials.

  4. Controllable growth and magnetic properties of nickel nanoclusters electrodeposited on the ZnO nanorod template

    Energy Technology Data Exchange (ETDEWEB)

    Tang Yang; Zhao Dongxu; Shen Dezhen; Zhang Jiying [Key Laboratory of Excited State Processes, Changchun Institute of Optics, Fine Mechanics and Physics, Chinese Academy of Sciences, 16 East Nan-Hu Road, Open Economic Zone, Changchun 130033 (China); Wang Xiaohua, E-mail: dxzhao2000@yahoo.com.c [National Key Laboratory of High Power Semiconductor Laser, Changchun University of Science and Technology, 7089 WeiXing Road, ChangChun 130022 (China)

    2009-12-09

    The ZnO nanorods were used as a template to fabricate nickel nanoclusters by electrodeposition. The ZnO nanorod arrays act as a nano-semiconductor electrode for depositing metallic and magnetic nickel nanoclusters. The growth sites of Ni nanoclusters could be controlled by adjusting the applied potential. Under -1.15 V the Ni nanoclusters could be grown on the tips of ZnO nanorods. On increasing the potential to be more negative the ZnO nanorods were covered by Ni nanoclusters. The magnetic properties of the electrodeposited Ni nanoclusters also evolved with the applied potentials.

  5. The emergence of nonbulk properties in supported metal clusters: negative thermal expansion and atomic disorder in Pt nanoclusters supported on gamma-Al2O3.

    Science.gov (United States)

    Sanchez, Sergio I; Menard, Laurent D; Bram, Ariella; Kang, Joo H; Small, Matthew W; Nuzzo, Ralph G; Frenkel, Anatoly I

    2009-05-27

    The structural dynamics-cluster size and adsorbate-dependent thermal behaviors of the metal-metal (M-M) bond distances and interatomic order-of Pt nanoclusters supported on a gamma-Al(2)O(3) are described. Data from scanning transmission electron microscopy (STEM) and X-ray absorption spectroscopy (XAS) studies reveal that these materials possess a dramatically nonbulklike nature. Under an inert atmosphere small, subnanometer Pt/gamma-Al(2)O(3) clusters exhibit marked relaxations of the M-M bond distances, negative thermal expansion (NTE) with an average linear thermal expansion coefficient alpha = (-2.4 +/- 0.4) x 10(-5) K(-1), large static disorder and dynamical bond (interatomic) disorder that is poorly modeled within the constraints of classical theory. The data further demonstrate a significant temperature-dependence to the electronic structure of the Pt clusters, thereby suggesting the necessity of an active model to describe the cluster/support interactions mediating the cluster's dynamical structure. The quantitative dependences of these nonbulklike behaviors on cluster size (0.9 to 2.9 nm), ambient atmosphere (He, 4% H(2) in He or 20% O(2) in He) and support identity (gamma-Al(2)O(3) or carbon black) are systematically investigated. We show that the nonbulk structural, electronic and dynamical perturbations are most dramatically evidenced for the smallest clusters. The adsorption of hydrogen on the clusters leads to an increase of the Pt-Pt bondlengths (due to a lifting of the surface relaxation) and significant attenuation of the disorder present in the system. Oxidation of these same clusters has the opposite effect, leading to an increase in Pt-Pt bond strain and subsequent enhancement in nonbulklike thermal properties. The structural and electronic properties of Pt nanoclusters supported on carbon black contrast markedly with those of the Pt/gamma-Al(2)O(3) samples in that neither NTE nor comparable levels of atomic disorder are observed. The Pt

  6. Strong-Superstrong Transition in Glass Transition of Metallic Glass

    International Nuclear Information System (INIS)

    Dan, Wang; Hong-Yan, Peng; Xiao-Yu, Xu; Bao-Ling, Chen; Chun-Lei, Wu; Min-Hua, Sun

    2010-01-01

    Dynamic fragility of bulk metallic glass (BMG) of Zr 64 Cu 16 Ni 10 Al 10 alloy is studied by three-point beam bending methods. The fragility parameter mfor Zr 64 Cu 16 Ni 10 Al 10 BMG is calculated to be 24.5 at high temperature, which means that the liquid is a 'strong' liquid, while to be 13.4 at low temperature which means that the liquid is a 'super-strong' liquid. The dynamical behavior of Zr 64 Cu 16 Ni 10 Al 10 BMG in the supercooled region undergoes a strong to super-strong transition. To our knowledge, it is the first time that a strong-to-superstrong transition is found in the metallic glass. Using small angle x-ray scattering experiments, we find that this transition is assumed to be related to a phase separation process in supercooled liquid. (condensed matter: structure, mechanical and thermal properties)

  7. 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

  8. 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

  9. Probing the atomic structure of metallic nanoclusters with the tip of a scanning tunneling microscope.

    Science.gov (United States)

    Schouteden, Koen; Lauwaet, Koen; Janssens, Ewald; Barcaro, Giovanni; Fortunelli, Alessandro; Van Haesendonck, Chris; Lievens, Peter

    2014-02-21

    Preformed Co clusters with an average diameter of 2.5 nm are produced in the gas phase and are deposited under controlled ultra-high vacuum conditions onto a thin insulating NaCl film on Au(111). Relying on a combined experimental and theoretical investigation, we demonstrate visualization of the three-dimensional atomic structure of the Co clusters by high-resolution scanning tunneling microscopy (STM) using a Cl functionalized STM tip that can be obtained on the NaCl surface. More generally, use of a functionalized STM tip may allow for systematic atomic structure determination with STM of nanoparticles that are deposited on metal surfaces.

  10. 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

  11. 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...

  12. 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.

  13. 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

  14. 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.

  15. Metallic oxide nano-clusters synthesis by ion implantation in high purity Fe10Cr alloy

    International Nuclear Information System (INIS)

    Zheng, Ce

    2015-01-01

    ODS (Oxide Dispersed Strengthened) steels, which are reinforced with metal dispersions of nano-oxides (based on Y, Ti and O elements), are promising materials for future nuclear reactors. The detailed understanding of the mechanisms involved in the precipitation of these nano-oxides would improve manufacturing and mechanical properties of these ODS steels, with a strong economic impact for their industrialization. To experimentally study these mechanisms, an analytical approach by ion implantation is used, to control various parameters of synthesis of these precipitates as the temperature and concentration. This study demonstrated the feasibility of this method and concerned the behaviour of alloys models (based on aluminium oxide) under thermal annealing. High purity Fe-10Cr alloys were implanted with Al and O ions at room temperature. Transmission electron microscopy observations showed that the nano-oxides appear in the Fe-10Cr matrix upon ion implantation at room temperature without subsequent annealing. The mobility of implanted elements is caused by the defects created during ion implantation, allowing the nucleation of these nanoparticles, of a few nm in diameter. These nanoparticles are composed of aluminium and oxygen, and also chromium. The high-resolution experiments show that their crystallographic structure is that of a non-equilibrium compound of aluminium oxide (cubic γ-Al 2 O 3 type). The heat treatment performed after implantation induces the growth of the nano-sized oxides, and a phase change that tends to balance to the equilibrium structure (hexagonal α-Al 2 O 3 type). These results on model alloys are fully applicable to industrial materials: indeed ion implantation reproduces the conditions of milling and heat treatments are at equivalent temperatures to those of thermo-mechanical treatments. A mechanism involving the precipitation of nano-oxide dispersed in ODS alloys is proposed in this manuscript based on the obtained experimental results

  16. Polyoxotungstate nanoclusters supported on silica as an efficient solid-phase microextraction fiber of polycyclic aromatic hydrocarbons

    International Nuclear Information System (INIS)

    Abolghasemi, Mir Mahdi; Yousefi, Vahid; Rafiee, Ezzat

    2014-01-01

    A highly porous silica-supported tungstophosphoric acid (PW) nanocluster was prepared for use in solid-phase microextraction (SPME) of polycyclic aromatic hydrocarbons (PAHs). The PWs represent a class of discrete transition metal-oxide nanoclusters and their structures resemble discrete fragments of metal-oxide structures of definite size and shape. Transition metal-oxide nanoclusters display large structural diversity, and their monodisperse sizes can be tuned from several Ångstroms up to 10 nm. The highly porous silica-supported tungstophosphoric acid nanocluster material is found to be capable of efficiently extracting PAHs from aqueous sample solutions. The nanomaterial was immobilized on a stainless steel wire for fabrication of the SPME fiber. Following thermal desorption, the PAHs were quantified by GC-MS. Analytical merits include limits of detection that range from 0.02 to 0.1 pg mL −1 and a dynamic range as wide as from 0.001 to 100 ng mL −1 . Under optimum conditions, the repeatability for one fiber (n = 3), expressed as the relative standard deviation, is between 4.3 % and 8.6 %. The method is simple, rapid, and inexpensive. The thermal stability of the fiber and the high relative recovery make this method superior to conventional methods of extraction. (author)

  17. 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.

  18. Metal-insulator transition in vanadium dioxide

    International Nuclear Information System (INIS)

    Zylbersztejn, A.; Mott, N.F.

    1975-01-01

    The basic physical parameters which govern the metal-insulator transition in vanadium dioxide are determined through a review of the properties of this material. The major importance of the Hubbard intra-atomic correlation energy in determining the insulating phase, which was already evidence by studies of the magnetic properties of V 1 -/subx/Cr/subx/O 2 alloys, is further demonstrated from an analysis of their electrical properties. An analysis of the magnetic susceptibility of niobium-doped VO 2 yields a picture for the current carrier in the low-temperature phase in which it is accompanied by a spin cloud (owing to Hund's-rule coupling), and has therefore an enhanced mass (m approx. = 60m 0 ). Semiconducting vanadium dioxide turns out to be a borderline case for a classical band-transport description; in the alloys at high doping levels, Anderson localization with hopping transport can take place. Whereas it is shown that the insulating phase cannot be described correctly without taking into account the Hubbard correlation energy, we find that the properties of the metallic phase are mainly determined by the band structure. Metallic VO 2 is, in our view, similar to transition metals like Pt or Pd: electrons in a comparatively wide band screening out the interaction between the electrons in a narrow overlapping band. The magnetic susceptibility is described as exchange enhanced. The large density of states at the Fermi level yields a substantial contribution of the entropy of the metallic electrons to the latent heat. The crystalline distortion removes the band degeneracy so that the correlation energy becomes comparable with the band width and a metal-insulator transition takes place

  19. (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.

  20. 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.)

  1. 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

  2. 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.

  3. 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...

  4. 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.

  5. Adsorbate Diffusion on Transition Metal Nanoparticles

    Science.gov (United States)

    2015-01-01

    correlation is a Bronsted-Evans-Polanyi ( BEP )- type of correlation, similar to other BEP correlations established earlier for surface-catalyzed bond- breaking...bond-making reactions.6-9 The universal BEP -type correlation is independent of the nature of the adsorbed species and that of the metal surface. For...a certain class of surface-catalyzed reactions, the existence of a BEP -type correlation reflects a similarity between the geometry of the transition

  6. 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...

  7. 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...

  8. 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

  9. A Molecular Dynamics Study of the Epitaxial Growth of Metallic Nanoclusters Softly Deposited on Substrates with Very Different Lattice Parameter

    International Nuclear Information System (INIS)

    Jimenez-Saez, J C; Perez-MartIn, A M C; Jimenez-RodrIguez, J J

    2007-01-01

    The soft deposition of Cu and Au clusters on Au(001) and Cu(001) surfaces respectively is studied by constant-temperature molecular-dynamics simulations. The initial shape of the nanoclusters is icosahedral or truncated octahedral (Wulff type). Their number of atoms ranges between 12 and 1289 atoms. Bombardment energy is of the order of a few meV/atom. The atomic interactions are mimicked by a many-body potential based on the tightbinding model. The effect of the temperature as activation to get the complete epitaxy is analysed. We have found that Cu clusters manage to align their {002} planes with the substrate by increasing the temperature. However, there is not epitaxial growth in any case since the lattice becomes bcc or important stacking faults are generated. For Au clusters, the alignment of these planes is practically independent of the temperature

  10. Alkali metal and alkali metal hydroxide intercalates of the layered transition metal disulfides

    International Nuclear Information System (INIS)

    Kanzaki, Y.; Konuma, M.; Matsumoto, O.

    1981-01-01

    The intercalation reaction of some layered transition metal disulfides with alkali metals, alkali metal hydroxides, and tetraalkylammonium hydroxides were investigated. The alkali metal intercalates were prepared in the respective metal-hexamethylphosphoric triamide solutions in vaccuo, and the hydroxide intercalates in aqueous hydroxide solutions. According to the intercalation reaction, the c-lattice parameter was increased, and the increase indicated the expansion of the interlayer distance. In the case of alkali metal intercalates, the expansion of the interlayer distance increased continuously, corresponding to the atomic radius of the alkali metal. On the other hand, the hydroxide intercalates showed discrete expansion corresponding to the effective ionic radius of the intercalated cation. All intercalates of TaS 2 amd NbS 2 were superconductors. The expansion of the interlayer distance tended to increase the superconducting transition temperature in the intercalates of TaS 2 and vice versa in those of NbS 2 . (orig.)

  11. DFT based study of transition metal nano-clusters for electrochemical NH3 production

    DEFF Research Database (Denmark)

    Howalt, Jakob Geelmuyden; Bligaard, Thomas; Rossmeisl, Jan

    2013-01-01

    Theoretical studies of the possibility of producing ammonia electrochemically at ambient temperature and pressure without direct N2 dissociation are presented. Density functional theory calculations were used in combination with the computational standard hydrogen electrode to calculate the free...... for electrochemical ammonia production. The competing hydrogen evolution reaction has also been analyzed for comparison....

  12. Metal non-metal transitions in doped semiconductors

    International Nuclear Information System (INIS)

    Brezini, A.

    1989-12-01

    A disordered Hubbard model with diagonal disorder is used to examine the electron localization effects associated with both disorder and electron-electron interaction. Extensive results are reported on the ground state properties and compared with other theories. In particular two regimes are observed; when the electron-electron interaction U is greater than the disorder parameter and when is smaller. Furthermore the effect of including conduction-band minima into the calculation of metal-insulator transitions in doped Si and Ge is investigated with use of Berggren approach. Good agreement with experiments are found when both disorder and interactions are included. (author). 37 refs, 7 figs, 3 tabs

  13. Nanoclusters a bridge across disciplines

    CERN Document Server

    Jena, Purusottam

    2010-01-01

    This comprehensive book on Nanoclusters comprises sixteen authoritative chapters written by leading researchers in the field. It provides insight into topics that are currently at the cutting edge of cluster science, with the main focus on metal and metal compound systems that are of particular interest in materials science, and also on aspects related to biology and medicine. While there are numerous books on clusters, the focus on clusters as a bridge across disciplines sets this book apart from others. Delivers cutting edge coverage of cluster science Covers a broad range of topics in

  14. 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

  15. 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.

  16. 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.

  17. 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

  18. 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.

  19. 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.

  20. 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.)

  1. 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...

  2. 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.

  3. 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.

  4. 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.

  5. Stable silver nanoclusters electrochemically deposited on nitrogen-doped graphene as efficient electrocatalyst for oxygen reduction reaction

    Science.gov (United States)

    Jin, Shi; Chen, Man; Dong, Haifeng; He, Bingyu; Lu, Huiting; Su, Lei; Dai, Wenhao; Zhang, Qiaochu; Zhang, Xueji

    2015-01-01

    Metal nanoclusters exhibit unusually high catalytic activity toward oxygen reduction reaction (ORR) due to their small size and unique electronic structures. However, controllable synthesis of stable metal nanoclusters is a challenge, and the durability of metal clusters suffers from the deficiency of dissolution, aggregation, and sintering during catalysis reactions. Herein, silver nanoclusters (AgNCs) (diameter , which is vital in high performance fuel cells, batteries and nanodevices.

  6. 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

  7. Reentrant Metal-Insulator Transitions in Silicon -

    Science.gov (United States)

    Campbell, John William M.

    This thesis describes a study of reentrant metal -insulator transitions observed in the inversion layer of extremely high mobility Si-MOSFETs. Magneto-transport measurements were carried out in the temperature range 20mK-4.2 K in a ^3He/^4 He dilution refrigerator which was surrounded by a 15 Tesla superconducting magnet. Below a melting temperature (T_{M}~500 mK) and a critical electron density (n_{s }~9times10^{10} cm^{-2}), the Shubnikov -de Haas oscillations in the diagonal resistivity enormous maximum values at the half filled Landau levels while maintaining deep minima corresponding to the quantum Hall effect at filled Landau levels. At even lower electron densities the insulating regions began to spread and eventually a metal-insulator transition could be induced at zero magnetic field. The measurement of extremely large resistances in the milliKelvin temperature range required the use of very low currents (typically in the 10^ {-12} A range) and in certain measurements minimizing the noise was also a consideration. The improvements achieved in these areas through the use of shielding, optical decouplers and battery operated instruments are described. The transport signatures of the insulating state are considered in terms of two basic mechanisms: single particle localization with transport by variable range hopping and the formation of a collective state such as a pinned Wigner crystal or electron solid with transport through the motion of bound dislocation pairs. The experimental data is best described by the latter model. Thus the two dimensional electron system in these high mobility Si-MOSFETs provides the first and only experimental demonstration to date of the formation of an electron solid at zero and low magnetic fields in the quantum limit where the Coulomb interaction energy dominates over the zero point oscillation energy. The role of disorder in favouring either single particle localization or the formation of a Wigner crystal is explored by

  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. 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.

  10. 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

  11. 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

  12. 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.

  13. 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

  14. 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.

  15. 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.

  16. 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.

  17. A DFT study of volatile organic compounds adsorption on transition metal deposited graphene

    International Nuclear Information System (INIS)

    Kunaseth, Manaschai; Poldorn, Preeyaporn; Junkeaw, Anchalee; Meeprasert, Jittima; Rungnim, Chompoonut; Namuangruk, Supawadee; Kungwan, Nawee; Inntam, Chan; Jungsuttiwong, Siriporn

    2017-01-01

    Highlights: • VOCs removal via modified carbon-based adsorbent using density functional theory. • The single-vacancy defective graphene (SDG) with metal-deposited significantly increase the adsorption efficiency. • TM-doped SDG is a suitable adsorbent material for VOC removal. • Electron in hybridized sp"2-orbitals of heteroatoms has an effect on mode of adsorption. - Abstract: Recently, elevated global emission of volatile organic compounds (VOCs) was associated to the acceleration and increasing severity of climate change worldwide. In this work, we investigated the performance of VOCs removal via modified carbon-based adsorbent using density functional theory. Here, four transition metals (TMs) including Pd, Pt, Ag, and Au were deposited onto single-vacancy defective graphene (SDG) surface to increase the adsorption efficiency. Five prototypical VOCs including benzene, furan, pyrrole, pyridine, and thiophene were used to study the adsorption capability of metal-deposited graphene adsorbent. Calculation results revealed that Pd, Pt, Au, and Ag atoms and nanoclusters bind strongly onto the SDG surface. In this study, benzene, furan and pyrrole bind in the π-interaction mode using delocalized π-electron in aromatic ring, while pyridine and thiophene favor X- interaction mode, donating lone pair electron from heteroatom. In terms of adsorption, pyridine VOC adsorption strengths to the TM-cluster doped SDG surfaces are Pt_4 (−2.11 eV) > Pd_4 (−2.05 eV) > Ag_4 (−1.53 eV) > Au_4 (−1.87 eV). Our findings indicate that TM-doped SDG is a suitable adsorbent material for VOC removal. In addition, partial density of states analysis suggests that benzene, furan, and pyrrole interactions with TM cluster are based on p-orbitals of carbon atoms, while pyridine and thiophene interactions are facilitated by hybridized sp"2-orbitals of heteroatoms. This work provides a key insight into the fundamentals of VOCs adsorption on carbon-based adsorbent.

  18. 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

  19. Mechanistic insights into the photocatalytic properties of metal nanocluster/graphene ensembles. Examining the role of visible light in the reduction of 4-nitrophenol.

    Science.gov (United States)

    Koklioti, Malamatenia A; Skaltsas, Theodosis; Sato, Yuta; Suenaga, Kazu; Stergiou, Anastasios; Tagmatarchis, Nikos

    2017-07-13

    Metal nanoclusters (M NCs ) based on silver and gold, abbreviated as Ag NCs and Au NCs , respectively, were synthesized and combined with functionalized graphene, abbreviated as f-G, forming novel M NC /f-G ensembles. The preparation of M NCs /f-G was achieved by employing attractive electrostatic interactions developed between negatively charged M NCs , attributed to the presence of carboxylates due to α-lipoic acid employed as a stabilizer, and positively charged f-G, attributed to the presence of ammonium units as addends. The realization of M NC /f-G ensembles was established via titration assays as evidenced by electronic absorption and photoluminescence spectroscopy as well as scanning transmission electron microscopy (STEM) and energy-dispersive X-ray (EDX) spectroscopy analyses. Photoinduced charge-transfer phenomena were inferred within M NCs /f-G, attributed to the suppression of M NC photoluminescence by the presence of f-G. Next, the M NC /f-G ensembles were successfully employed as proficient catalysts for the model reduction of 4-nitrophenol to the corresponding 4-aminophenol as proof for the photoinduced hydrogen production. Particularly, the reduction kinetics decelerated by half when bare M NCs were employed vs. the M NC /f-G ensembles, highlighting the beneficial role of M NCs /f-G in catalysing the process. Furthermore, Au NCs /f-G displayed exceptionally higher catalytic activity both in the dark and under visible light illumination conditions, which is ascribed to three synergistic mechanisms, namely, (a) hydride transfer from Au-H, (b) hydride transfer from photogenerated Au-H species, and (c) hydrogen produced by the photoreduction of water. Finally, recycling and re-employing M NCs /f-G in successive catalytic cycles without loss of activity toward the reduction of 4-nitrophenol was achieved, thereby highlighting their wider applicability.

  20. 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...

  1. 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.

  2. 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.

  3. The metallicities of stars with and without transiting planets

    DEFF Research Database (Denmark)

    Buchhave, Lars A.; Latham, David W.

    2015-01-01

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

  4. Tunneling-Electron-Induced Light Emission from Single Gold Nanoclusters.

    Science.gov (United States)

    Yu, Arthur; Li, Shaowei; Czap, Gregory; Ho, W

    2016-09-14

    The coupling of tunneling electrons with the tip-nanocluster-substrate junction plasmon was investigated by monitoring light emission in a scanning tunneling microscope (STM). Gold atoms were evaporated onto the ∼5 Å thick Al2O3 thin film grown on the NiAl (110) surface where they formed nanoclusters 3-7 nm wide. Scanning tunneling spectroscopy (STS) of these nanoclusters revealed quantum-confined electronic states. Spatially resolved photon imaging showed localized emission hot spots. Size dependent study and light emission from nanocluster dimers further support the viewpoint that coupling of tunneling electrons to the junction plasmon is the main radiative mechanism. These results showed the potential of the STM to reveal the electronic and optical properties of nanoscale metallic systems in the confined geometry of the tunnel junction.

  5. 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

  6. 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.

  7. On metal-insulator transition in cubic fullerides

    Science.gov (United States)

    Iwahara, Naoya; Chibotaru, Liviu

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

  8. Trends in catalytic NO decomposition over transition metal surfaces

    DEFF Research Database (Denmark)

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

    2007-01-01

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

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

    Science.gov (United States)

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

    2016-09-01

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

  10. Transition metal mediated transformations of small molecules

    Energy Technology Data Exchange (ETDEWEB)

    Sen, Ayusman [Pennsylvania State Univ., University Park, PA (United States)

    2017-03-08

    Catalysis at metal centers is of great scientific, as well as practical, importance because of the high efficiency, high specificity, and low energy demands often associated with such systems. The two major themes of our research are (a) the design of metal-based systems for the synthesis of novel classes of polymers and (b) the identification of new metal-catalyzed systems for the conversion of biomass to fuels and chemicals, and related “green” chemical processes.

  11. High-pressure phase transition of alkali metal-transition metal deuteride Li2PdD2

    Science.gov (United States)

    Yao, Yansun; Stavrou, Elissaios; Goncharov, Alexander F.; Majumdar, Arnab; Wang, Hui; Prakapenka, Vitali B.; Epshteyn, Albert; Purdy, Andrew P.

    2017-06-01

    A combined theoretical and experimental study of lithium palladium deuteride (Li2PdD2) subjected to pressures up to 50 GPa reveals one structural phase transition near 10 GPa, detected by synchrotron powder x-ray diffraction, and metadynamics simulations. The ambient-pressure tetragonal phase of Li2PdD2 transforms into a monoclinic C2/m phase that is distinct from all known structures of alkali metal-transition metal hydrides/deuterides. The structure of the high-pressure phase was characterized using ab initio computational techniques and from refinement of the powder x-ray diffraction data. In the high-pressure phase, the PdD2 complexes lose molecular integrity and are fused to extended [PdD2]∞ chains. The discovered phase transition and new structure are relevant to the possible hydrogen storage application of Li2PdD2 and alkali metal-transition metal hydrides in general.

  12. 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.

  13. 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

  14. 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 ...

  15. Nonmetal-metal transition in metal–molten-salt solutions

    NARCIS (Netherlands)

    Silvestrelli, P.-L.; Alavi, A.; Parrinello, M.; Frenkel, D.

    1996-01-01

    The method of ab initio molecular dynamics, based on finite-temperature density-functional theory, is used to study the nonmetal-metal transition in two different metal–molten-salt solutions, Kx(KCl)1-x and Nax(NaBr)1-x. As the excess metal concentration is increased the electronic density becomes

  16. 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...

  17. [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

  18. Metal Catalysis with Nanostructured Metals Supported Inside Strongly Acidic Cross-linked Polymer Frameworks: Influence of Reduction Conditions of AuIII-containing Resins on Metal Nanoclusters Formation in Macroreticular and Gel-Type Materials

    Czech Academy of Sciences Publication Activity Database

    Calore, L.; Cavinato, g.; Canton, P.; Peruzzo, L.; Banavali, R.; Jeřábek, Karel; Corain, B.

    2012-01-01

    Roč. 391, AUG 30 (2012), s. 114-120 ISSN 0020-1693 Institutional support: RVO:67985858 Keywords : strongly acidic cross-linked polymer * frameworks * gold(0) nanoclusters Subject RIV: CI - Industrial Chemistry, Chemical Engineering Impact factor: 1.687, year: 2012

  19. 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

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

    International Nuclear Information System (INIS)

    Zwicknagel, G.

    1979-11-01

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

  1. 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.

  2. A Comparative XAFS Study of Gold-thiolate Nanoparticles and Nanoclusters

    International Nuclear Information System (INIS)

    Chevrier, D M; Chatt, A; Zhang, P; Sham, T K

    2013-01-01

    Tiopronin-capped gold nanoparticles and gold nanoclusters of sizes 3.0 and 1.5 nm, respectively, were investigated with XAFS at the gold L 3 -edge. The specific EXAFS fitting procedure is discussed for obtaining reliable fit parameters for each system. The difficulties and challenges faced when analysing EXAFS data for gold nanoparticles and nanoclusters are also mentioned. Fitting results for gold nanoparticles reveal a small amount of surface Au-thiolate interactions with a large Au-Au metal core. For gold nanoclusters, only a one-shell fit was obtainable. Instead of Au-Au metal core, long-range interactions are expected for gold nanoclusters. Tiopronin-capped gold nanoclusters are proposed to be polymeric in nature, which helps explain the observed red luminescence.

  3. 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

  4. 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)

  5. 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.

  6. Harnessing the metal-insulator transition for tunable metamaterials

    Science.gov (United States)

    Charipar, Nicholas A.; Charipar, Kristin M.; Kim, Heungsoo; Bingham, Nicholas S.; Suess, Ryan J.; Mathews, Scott A.; Auyeung, Raymond C. Y.; Piqué, Alberto

    2017-08-01

    The control of light-matter interaction through the use of subwavelength structures known as metamaterials has facilitated the ability to control electromagnetic radiation in ways not previously achievable. A plethora of passive metamaterials as well as examples of active or tunable metamaterials have been realized in recent years. However, the development of tunable metamaterials is still met with challenges due to lack of materials choices. To this end, materials that exhibit a metal-insulator transition are being explored as the active element for future metamaterials because of their characteristic abrupt change in electrical conductivity across their phase transition. The fast switching times (▵t < 100 fs) and a change in resistivity of four orders or more make vanadium dioxide (VO2) an ideal candidate for active metamaterials. It is known that the properties associated with thin film metal-insulator transition materials are strongly dependent on the growth conditions. For this work, we have studied how growth conditions (such as gas partial pressure) influence the metalinsulator transition in VO2 thin films made by pulsed laser deposition. In addition, strain engineering during the growth process has been investigated as a method to tune the metal-insulator transition temperature. Examples of both the optical and electrical transient dynamics facilitating the metal-insulator transition will be presented together with specific examples of thin film metamaterial devices.

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

    Science.gov (United States)

    Bullen, Tomas D.; Baskaran, Mark

    2011-01-01

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

  8. Quantum Critical “Opalescence” around Metal-Insulator Transitions

    Science.gov (United States)

    Misawa, Takahiro; Yamaji, Youhei; Imada, Masatoshi

    2006-08-01

    Divergent carrier-density fluctuations equivalent to the critical opalescence of gas-liquid transition emerge around a metal-insulator critical point at a finite temperature. In contrast to the gas-liquid transitions, however, the critical temperatures can be lowered to zero, which offers a challenging quantum phase transition. We present a microscopic description of such quantum critical phenomena in two dimensions. The conventional scheme of phase transitions by Ginzburg, Landau, and Wilson is violated because of its topological nature. It offers a clear insight into the criticalities of metal-insulator transitions (MIT) associated with Mott or charge-order transitions. Fermi degeneracy involving the diverging density fluctuations generates emergent phenomena near the endpoint of the first-order MIT and must shed new light on remarkable phenomena found in correlated metals such as unconventional cuprate superconductors. It indeed accounts for the otherwise puzzling criticality of the Mott transition recently discovered in an organic conductor. We propose to accurately measure enhanced dielectric fluctuations at small wave numbers.

  9. Weyl Semimetal to Metal Phase Transitions Driven by Quasiperiodic Potentials

    Science.gov (United States)

    Pixley, J. H.; Wilson, Justin H.; Huse, David A.; Gopalakrishnan, Sarang

    2018-05-01

    We explore the stability of three-dimensional Weyl and Dirac semimetals subject to quasiperiodic potentials. We present numerical evidence that the semimetal is stable for weak quasiperiodic potentials, despite being unstable for weak random potentials. As the quasiperiodic potential strength increases, the semimetal transitions to a metal, then to an "inverted" semimetal, and then finally to a metal again. The semimetal and metal are distinguished by the density of states at the Weyl point, as well as by level statistics, transport, and the momentum-space structure of eigenstates near the Weyl point. The critical properties of the transitions in quasiperiodic systems differ from those in random systems: we do not find a clear critical scaling regime in energy; instead, at the quasiperiodic transitions, the density of states appears to jump abruptly (and discontinuously to within our resolution).

  10. Unusual metal-insulator transition in disordered ferromagnetic films

    International Nuclear Information System (INIS)

    Muttalib, K.A.; Wölfle, P.; Misra, R.; Hebard, A.F.

    2012-01-01

    We present a theoretical interpretation of recent data on the conductance near and farther away from the metal-insulator transition in thin ferromagnetic Gd films of thickness b≈2-10 nm. For increasing sheet resistances a dimensional crossover takes place from d=2 to d=3 dimensions, since the large phase relaxation rate caused by scattering of quasiparticles off spin wave excitations renders the dephasing length L φ ≲b at strong disorder. The conductivity data in the various regimes obey fractional power-law or logarithmic temperature dependence. One observes weak localization and interaction induced corrections at weaker disorder. At strong disorder, near the metal-insulator transition, the data show scaling and collapse onto two scaling curves for the metallic and insulating regimes. We interpret this unusual behavior as proof of two distinctly different correlation length exponents on both sides of the transition.

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

    International Nuclear Information System (INIS)

    Tosi, M.P.

    1997-04-01

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

  12. Paramagnetic transition-metal carbonyls and cyanides

    International Nuclear Information System (INIS)

    Symons, M.C.R.; Bratt, S.W.; Wyatt, J.L.

    1982-01-01

    Exposure of tetra-alkylammonium salts of [Cr(CO) 5 I] - , [Mo(CO) 5 I] - , and [W(CO) 5 I] - , and dilute solutions of [Re(CO) 5 Br] and [Re(CO) 5 I] in methyltetrahydrofuran (mthf), to 60 Co γ-rays at 77 K gave electron-addition products characterized by large hyperfine coupling to the halogen and metal nuclei. Orbital populations for the extra electrons estimated therefrom showed trends characteristic of antibonding electrons, and in all cases the extra electron appears to be accommodated in the metal-halogen σ* orbital comprising primarily (dsub(Z 2 )-psub(z)). For the tungsten complex, a species exhibiting additional hyperfine coupling to a single proton was also detected. A species previously assigned the formula [Cr(CO) 5 I] was prepared, but gave no detectable e.s.r. spectrum. (author)

  13. Anharmonic Vibrational Spectroscopy on Metal Transition Complexes

    Science.gov (United States)

    Latouche, Camille; Bloino, Julien; Barone, Vincenzo

    2014-06-01

    Advances in hardware performance and the availability of efficient and reliable computational models have made possible the application of computational spectroscopy to ever larger molecular systems. The systematic interpretation of experimental data and the full characterization of complex molecules can then be facilitated. Focusing on vibrational spectroscopy, several approaches have been proposed to simulate spectra beyond the double harmonic approximation, so that more details become available. However, a routine use of such tools requires the preliminary definition of a valid protocol with the most appropriate combination of electronic structure and nuclear calculation models. Several benchmark of anharmonic calculations frequency have been realized on organic molecules. Nevertheless, benchmarks of organometallics or inorganic metal complexes at this level are strongly lacking despite the interest of these systems due to their strong emission and vibrational properties. Herein we report the benchmark study realized with anharmonic calculations on simple metal complexes, along with some pilot applications on systems of direct technological or biological interest.

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

    International Nuclear Information System (INIS)

    Kurokawa, Hiroyuki; Nakasuji, Kazuyuki; Kajimura, Haruhiko; Nagai, Takayuki; Takeda, Seiichiro.

    1997-01-01

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

  15. 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)

  16. 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...

  17. 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.

  18. 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.

  19. 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...

  20. 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.

  1. Ternary scandium and transition metals germanides

    International Nuclear Information System (INIS)

    Kotur, B.Ya.

    1992-01-01

    Brief review of data on phase diagram of ternary Sc-Me-Ge systems (Me-d - , f-transition element) is given. Isothermal sections at 870 and 1070 K of 17 ternary systems are plotted. Compositions and their structural characteristics are presented. Variability of crystal structure is typical for ternary scandium germanides: 70 compounds with the studied structure belong to 23 structural types. Ternary germanides isostructural to types of Sm 4 Ge 4 , ZrCrSi 2 , ZrNiAl, ScCeSi, TiNiSi U 4 Re 7 Si 6 145 compounds from 70 under investigation are mostly formed in studied systems

  2. 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

  3. A DFT study of volatile organic compounds adsorption on transition metal deposited graphene

    Energy Technology Data Exchange (ETDEWEB)

    Kunaseth, Manaschai, E-mail: manaschai@nanotec.or.th [Nanoscale Simulation Laboratory, National Nanotechnology Center (NANOTEC), National Science and Technology Development Agency (NSTDA), Pathum Thani, 12120 (Thailand); Poldorn, Preeyaporn [Department of Chemistry and Center of Excellence for Innovation in Chemistry, Faculty of Science, Ubon Ratchathani University, Ubon Ratchathani, 34190 (Thailand); Junkeaw, Anchalee; Meeprasert, Jittima; Rungnim, Chompoonut; Namuangruk, Supawadee [Nanoscale Simulation Laboratory, National Nanotechnology Center (NANOTEC), National Science and Technology Development Agency (NSTDA), Pathum Thani, 12120 (Thailand); Kungwan, Nawee [Department of Chemistry, Faculty of Science, Chiang Mai University, Chiang Mai 50200 (Thailand); Inntam, Chan [Department of Chemistry and Center of Excellence for Innovation in Chemistry, Faculty of Science, Ubon Ratchathani University, Ubon Ratchathani, 34190 (Thailand); 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)

    2017-02-28

    Highlights: • VOCs removal via modified carbon-based adsorbent using density functional theory. • The single-vacancy defective graphene (SDG) with metal-deposited significantly increase the adsorption efficiency. • TM-doped SDG is a suitable adsorbent material for VOC removal. • Electron in hybridized sp{sup 2}-orbitals of heteroatoms has an effect on mode of adsorption. - Abstract: Recently, elevated global emission of volatile organic compounds (VOCs) was associated to the acceleration and increasing severity of climate change worldwide. In this work, we investigated the performance of VOCs removal via modified carbon-based adsorbent using density functional theory. Here, four transition metals (TMs) including Pd, Pt, Ag, and Au were deposited onto single-vacancy defective graphene (SDG) surface to increase the adsorption efficiency. Five prototypical VOCs including benzene, furan, pyrrole, pyridine, and thiophene were used to study the adsorption capability of metal-deposited graphene adsorbent. Calculation results revealed that Pd, Pt, Au, and Ag atoms and nanoclusters bind strongly onto the SDG surface. In this study, benzene, furan and pyrrole bind in the π-interaction mode using delocalized π-electron in aromatic ring, while pyridine and thiophene favor X- interaction mode, donating lone pair electron from heteroatom. In terms of adsorption, pyridine VOC adsorption strengths to the TM-cluster doped SDG surfaces are Pt{sub 4} (−2.11 eV) > Pd{sub 4} (−2.05 eV) > Ag{sub 4} (−1.53 eV) > Au{sub 4} (−1.87 eV). Our findings indicate that TM-doped SDG is a suitable adsorbent material for VOC removal. In addition, partial density of states analysis suggests that benzene, furan, and pyrrole interactions with TM cluster are based on p-orbitals of carbon atoms, while pyridine and thiophene interactions are facilitated by hybridized sp{sup 2}-orbitals of heteroatoms. This work provides a key insight into the fundamentals of VOCs adsorption on carbon

  4. 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...

  5. 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

  6. Mechanical failure and glass transition in metallic glasses

    International Nuclear Information System (INIS)

    Egami, T.

    2011-01-01

    Research highlights: → We review the recent results of molecular dynamics simulations on metallic glasses. → They show the equivalence of mechanical failure and glass transition. → We discuss the microscopic mechanism behind this equivalence. → We show that the density of defects in metallic glasses is as high as a quarter. → Our concepts about the defect state in glasses need to be changed. - Abstract: The current majority view on the phenomenon of mechanical failure in metallic glasses appears to be that it is caused by the activity of some structural defects, such as free-volumes or shear transformation zones, and the concentration of such defects is small, only of the order of 1%. However, the recent results compel us to revise this view. Through molecular dynamics simulation it has been shown that mechanical failure is the stress-induced glass transition. According to our theory the concentration of the liquid-like sites (defects) is well over 20% at the glass transition. We suggest that the defect concentration in metallic glasses is actually very high, and percolation of such defects causes atomic avalanche and mechanical failure. In this article we discuss the glass transition, mechanical failure and viscosity from such a point of view.

  7. 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.

  8. 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)

  9. Semiconductor-Metal transition in a quantum well

    International Nuclear Information System (INIS)

    Nithiananthi, P.; Jayakumar, K.

    2007-01-01

    We demonstrate semiconductor-metal transition through diamagnetic susceptibility of a donor in a GaAs/Al x Ga 1- x As quantum well for both infinite and finite barrier models. We have also considered the non-parabolicity of the conduction band in our calculation. Our results agree with the earlier theoretical result and also with the recent experimental result

  10. 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

  11. 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...

  12. 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

  13. 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.

  14. 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.

  15. Pt, Co–Pt and Fe–Pt alloy nanoclusters encapsulated in virus capsids

    International Nuclear Information System (INIS)

    Okuda, M; Eloi, J-C; Jones, S E Ward; Schwarzacher, W; Verwegen, M; Cornelissen, J J L M

    2016-01-01

    Nanostructured Pt-based alloys show great promise, not only for catalysis but also in medical and magnetic applications. To extend the properties of this class of materials, we have developed a means of synthesizing Pt and Pt-based alloy nanoclusters in the capsid of a virus. Pure Pt and Pt-alloy nanoclusters are formed through the chemical reduction of [PtCl 4 ] − by NaBH 4 with/without additional metal ions (Co or Fe). The opening and closing of the ion channels in the virus capsid were controlled by changing the pH and ionic strength of the solution. The size of the nanoclusters is limited to 18 nm by the internal diameter of the capsid. Their magnetic properties suggest potential applications in hyperthermia for the Co–Pt and Fe–Pt magnetic alloy nanoclusters. This study introduces a new way to fabricate size-restricted nanoclusters using virus capsid. (paper)

  16. The formation of Cr2O3 nanoclusters over graphene sheet and carbon nanotubes

    Science.gov (United States)

    Dabaghmanesh, Samira; Neek-Amal, Mehdi; Partoens, Bart; Neyts, Erik C.

    2017-11-01

    Carbon supported metal oxide nanoparticles hold promise for various future applications in diverse areas including spintronics, catalysis and biomedicine. These applications, however, typically depend on the structure and morphology of the nanoparticles. In this contribution, we employ classical molecular dynamic simulations based on a recently developed force field to study the structural properties of Cr2O3 nanoclusters over graphene and carbon nanotubes. We observe that Cr2O3 nanoclusters tend to aggregate over both freestanding graphene and carbon nanotubes and form larger nanoclusters. These large nanoclusters are characterized by their worm-like shape with a lattice constant similar to that of bulk Cr2O3. We also investigate the structural deformation induced in graphene due to the presence of Cr2O3 nanoclusters.

  17. On the thermodynamics of phase transitions in metal hydrides

    Science.gov (United States)

    di Vita, Andrea

    2012-02-01

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

  18. Empirical prediction of optical transitions in metallic armchair SWCNTs

    Directory of Open Access Journals (Sweden)

    G. R. Ahmed Jamal

    2015-12-01

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

  19. Discovery of a metalloenzyme-like cooperative catalytic system of metal nanoclusters and catechol derivatives for the aerobic oxidation of amines.

    Science.gov (United States)

    Yuan, Hao; Yoo, Woo-Jin; Miyamura, Hiroyuki; Kobayashi, Shū

    2012-08-29

    We have discovered a new class of cooperative catalytic system, consisting of heterogeneous polymer-immobilized bimetallic Pt/Ir alloyed nanoclusters (NCs) and 4-tert-butylcatechol, for the aerobic oxidation of amines to imines under ambient conditions. After optimization, the desired imines were obtained in good to excellent yields with broad substrate scope. The reaction rate was determined to be first-order with respect to the substrate and catechol and zero-order for the alloyed Pt/Ir NC catalyst. Control studies revealed that both the heterogeneous NC catalyst and 4-tert-butylcatechol are essential and act cooperatively to facilitate the aerobic oxidation under mild conditions.

  20. "light-on" sensing of antioxidants using gold nanoclusters

    KAUST Repository

    Hu, Lianzhe; Deng, Lin; Alsaiari, Shahad K.; Zhang, Dingyuan; Khashab, Niveen M.

    2014-01-01

    preservatives, and cosmetics has proved to be very vital. Gold nanoclusters (Au-NCs) have a core size below 2 nm and contain several metal atoms. They have interesting photophysical properties, are readily functionalized, and are safe to use in various

  1. Synthesis and characterization of colloidal fluorescent silver nanoclusters.

    Science.gov (United States)

    Huang, Sherry; Pfeiffer, Christian; Hollmann, Jana; Friede, Sebastian; Chen, Justin Jin-Ching; Beyer, Andreas; Haas, Benedikt; Volz, Kerstin; Heimbrodt, Wolfram; Montenegro Martos, Jose Maria; Chang, Walter; Parak, Wolfgang J

    2012-06-19

    Ultrasmall water-soluble silver nanoclusters are synthesized, and their properties are investigated. The silver nanoclusters have high colloidal stability and show fluorescence in the red. This demonstrates that like gold nanoclusters also silver nanoclusters can be fluorescent.

  2. 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

  3. 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.

  4. Atomically Precise Nanocluster Assemblies Encapsulating Plasmonic Gold Nanorods.

    Science.gov (United States)

    Chakraborty, Amrita; Fernandez, Ann Candice; Som, Anirban; Mondal, Biswajit; Natarajan, Ganapati; Paramasivam, Ganesan; Lahtinen, Tanja; Häkkinen, Hannu; Nonappa, Nonappa; Pradeep, Thalappil

    2018-04-01

    We present the self-assembled structures of atomically precise, ligand-protected noble metal nanoclusters leading to encapsulation of plasmonic gold nanorods (GNRs). Unlike highly sophisticated DNA nanotechnology, our approach demonstrates a strategically simple hydrogen bonding-directed self-assembly of nanoclusters leading to octahedral nanocrystals encapsulating GNRs. Specifically, we use the p-mercaptobenzoic acid (pMBA) protected atomically precise nanocluster, Na4[Ag44(pMBA)30] and pMBA functionalized GNRs. High resolution transmission and scanning transmission electron tomographic reconstructions suggest that the geometry of the GNR surface is responsible for directing the assembly of silver nanoclusters via H-bonding leading to octahedral symmetry. Further, use of water dispersible gold nanoclusters, Au~250(pMBA)n and Au102(pMBA)44 also formed layered shells encapsulating GNRs. Such cluster assemblies on colloidal particles present a new category of precision hybrids with diverse possibilities. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. 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.

  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. 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.

  8. Electroforming and Switching in Oxides of Transition Metals: The Role of Metal Insulator Transition in the Switching Mechanism

    Science.gov (United States)

    Chudnovskii, F. A.; Odynets, L. L.; Pergament, A. L.; Stefanovich, G. B.

    1996-02-01

    Electroforming and switching effects in sandwich structures based on anodic films of transition metal oxides (V, Nb, Ti, Fe, Ta, W, Zr, Hf, Mo) have been studied. After being electroformed, some materials exhibited current-controlled negative resistance with S-shapedV-Icharacteristics. For V, Fe, Ti, and Nb oxides, the temperature dependences of the threshold voltage have been measured. As the temperature increased,Vthdecreased to zero at a critical temperatureT0, which depended on the film material. Comparison of theT0values with the temperatures of metal-insulator phase transition for some compounds (Tt= 120 K for Fe3O4, 340 K for VO2, ∼500 K for Ti2O3, and 1070 K for NbO2) showed that switching was related to the transition in the applied electric field. Channels consisting of the above-mentioned lower oxides were formed in the initial anodic films during the electroforming. The possibility of formation of these oxides with a metal-insulator transition was confirmed by thermodynamic calculations.

  9. 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.

  10. 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

  11. 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.

  12. 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

  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. 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

  15. 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)

  16. 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.)

  17. 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

  18. 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 ...

  19. 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.

  20. 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

  1. 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)

  2. 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)

  3. 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

  4. 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....

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

    International Nuclear Information System (INIS)

    Wang, Li; Liu, Jiantong

    2004-01-01

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

  6. 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

  7. 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.

  8. 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.

  9. 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.

  10. 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.

  11. Ferromagnetic semiconductor-metal transition in heterostructures of europium monoxide

    Energy Technology Data Exchange (ETDEWEB)

    Stollenwerk, Tobias; Kroha, Johann [Physikalisches Institut der Universitaet Bonn (Germany)

    2012-07-01

    Experiments on thin films of electron doped europium monoxide show a simultaneous ferromagnetic semiconductor-metal transition which goes along with a huge drop in resistivity over several orders of magnitude. Therefore, this material is a very promising candidate for spintronics applications. We have developed a theory which correctly predicts the simultaneous phase transition in thin films of electron doped EuO and the increase of the Curie temperature T{sub C} with doping concentration. The origin of the increased T{sub C} lies in the enhanced RKKY interaction between the localized 4f moments of the Eu atoms. Therefore, the phase transition is controlled by the population of the conduction band. We investigate the influence of film thickness and interface effects on the population of the conduction band and on the magnetic and electronic properties of the EuO film.

  12. Kernel Tuning and Nonuniform Influence on Optical and Electrochemical Gaps of Bimetal Nanoclusters.

    Science.gov (United States)

    He, Lizhong; Yuan, Jinyun; Xia, Nan; Liao, Lingwen; Liu, Xu; Gan, Zibao; Wang, Chengming; Yang, Jinlong; Wu, Zhikun

    2018-03-14

    Fine tuning nanoparticles with atomic precision is exciting and challenging and is critical for tuning the properties, understanding the structure-property correlation and determining the practical applications of nanoparticles. Some ultrasmall thiolated metal nanoparticles (metal nanoclusters) have been shown to be precisely doped, and even the protecting staple metal atom could be precisely reduced. However, the precise addition or reduction of the kernel atom while the other metal atoms in the nanocluster remain the same has not been successful until now, to the best of our knowledge. Here, by carefully selecting the protecting ligand with adequate steric hindrance, we synthesized a novel nanocluster in which the kernel can be regarded as that formed by the addition of two silver atoms to both ends of the Pt@Ag 12 icosohedral kernel of the Ag 24 Pt(SR) 18 (SR: thiolate) nanocluster, as revealed by single crystal X-ray crystallography. Interestingly, compared with the previously reported Ag 24 Pt(SR) 18 nanocluster, the as-obtained novel bimetal nanocluster exhibits a similar absorption but a different electrochemical gap. One possible explanation for this result is that the kernel tuning does not essentially change the electronic structure, but obviously influences the charge on the Pt@Ag 12 kernel, as demonstrated by natural population analysis, thus possibly resulting in the large electrochemical gap difference between the two nanoclusters. This work not only provides a novel strategy to tune metal nanoclusters but also reveals that the kernel change does not necessarily alter the optical and electrochemical gaps in a uniform manner, which has important implications for the structure-property correlation of nanoparticles.

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

    Directory of Open Access Journals (Sweden)

    Huixuan Li

    2015-07-01

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

  14. 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 (

  15. Insulator-metal transition of fluid molecular hydrogen

    International Nuclear Information System (INIS)

    Ross, M.

    1996-01-01

    Dynamically compressed fluid hydrogen shows evidence for metallization at the relatively low pressure of 140 GPa (1.4 Mbar) while experiments on solid hydrogen made in a diamond-anvil cell have failed to detect any evidence for gap closure up to a pressure of 230 GPa (2.3 Mbar). Two possible mechanisms for metal- liclike resistivity are put forward. The first is that as a consequence of the large thermal disorder in the fluid (kT∼0.2 endash 0.3 eV) short-range molecular interactions lead to band tailing that extends the band edge into the gap, resulting in closure at a lower pressure than in the solid. The second mechanism argues that molecular dissociation creates H atoms that behave similar to n-type donors in a heavily doped semiconductor and undergo a nonmetal-metal Mott-type transition. copyright 1996 The American Physical Society

  16. 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.

  17. 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

  18. 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

  19. 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

  20. Optical properties of multicomponent antimony-silver nanoclusters formed in silica by sequential ion implantation

    International Nuclear Information System (INIS)

    Zuhr, R.A.

    1995-11-01

    The linear and nonlinear optical properties of nanometer dimension metal colloids embedded in a dielectric depend explicitly on the electronic structure of the metal nanoclusters. The ability to control the electronic structure of the nanoclusters may make it possible to tailor the optical properties for enhanced performance. By sequential implantation of different metal ion species multi-component nanoclusters can be formed with significantly different optical properties than single element metal nanoclusters. The authors report the formation of multi-component Sb/Ag nanoclusters in silica by sequential implantation of Sb and Ag. Samples were implanted with relative ratios of Sb to Ag of 1:1 and 3:1. A second set of samples was made by single element implantations of Ag and Sb at the same energies and doses used to make the sequentially implanted samples. All samples were characterized using RBS and both linear and nonlinear optical measurements. The presence of both ions significantly modifies the optical properties of the composites compared to the single element nanocluster glass composites. In the sequentially implanted samples the optical density is lower, and the strong surface plasmon resonance absorption observed in the Ag implanted samples is not present. At the same time the nonlinear response of the these samples is larger than for the samples implanted with Sb alone, suggesting that the addition of Ag can increase the nonlinear response of the Sb particles formed. The results are consistent with the formation of multi-component Sb/Ag colloids

  1. 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)

  2. 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 + ).

  3. Microwave-heating synthesis and sensing applications of bright gold nanoclusters

    Energy Technology Data Exchange (ETDEWEB)

    He, Ding-Fei; Xiang, Yang; Wang, Xu [Department of Physics, Key Laboratory of Artificial Micro- and Nano-structures of Ministry of Education and School of Physics and Technology, Wuhan University, Wuhan 430072 (China); Yu, Xue-Feng, E-mail: yxf@whu.edu.cn [Department of Physics, Key Laboratory of Artificial Micro- and Nano-structures of Ministry of Education and School of Physics and Technology, Wuhan University, Wuhan 430072 (China)

    2011-12-15

    Highlights: Black-Right-Pointing-Pointer We establish a microwave-heating method to synthesize protein-stabilized Au nanoclusters. Black-Right-Pointing-Pointer The obtained Au nanoclusters show bright red fluorescence. Black-Right-Pointing-Pointer The Au nanoclusters can be used as efficient fluorescence probe for Cu{sup 2+} ion sensing. -- Abstract: A rapid microwave-heating method has been developed for the synthesis of bright Au nanoclusters by using bull serum albumin as the template in an aqueous environment. The reaction time needed is only 7.0 min, and the weight of the products at one batch can reach 15 g. The Au nanoclusters exhibit bright fluorescence at {approx}613 nm with quantum yield of {approx}6.0%. By adjusting the pH value, the products can be controlled to precipitate or re-disperse in aqueous solution. Furthermore, the Au nanoclusters have exhibited high sensitivity and selectivity in the determination of Cu{sup 2+} ions in water. These results suggest an efficient method for obtaining metal nanoclusters for the detection and sensing applications.

  4. 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

  5. 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.

  6. 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.

  7. Theoretical assessment of the electro-optical features of the group III nitrides (B{sub 12}N{sub 12}, Al{sub 12}N{sub 12} and Ga{sub 12}N{sub 12}) and group IV carbides (C{sub 24}, Si{sub 12}C{sub 12} and Ge{sub 12}C{sub 12}) nanoclusters encapsulated with alkali metals (Li, Na and K)

    Energy Technology Data Exchange (ETDEWEB)

    Tahmasebi, Elham [Chemistry Department, Faculty of Science, Lorestan University, Khorram Abad, Lorestan (Iran, Islamic Republic of); Shakerzadeh, Ehsan, E-mail: e.shakerzadeh@scu.ac.ir [Chemistry Department, Faculty of Science, Shahid Chamran University, Ahvaz (Iran, Islamic Republic of); Biglari, Zeinab [Chemistry Department, Faculty of Science, Lorestan University, Khorram Abad, Lorestan (Iran, Islamic Republic of)

    2016-02-15

    Graphical abstract: - Highlights: • Encapsulation of Li, Na and K narrow the HOMO–LUMO gaps of the clusters. • The group III nitrides nanoclusters strongly interacted with the alkali metals. • First hyperpolarizabilities remarkably enhance for B{sub 12}N{sub 12} encapsulated with Na/K. - Abstract: Density functional theory (DFT) calculations have been carried out to study the influence of alkali metals (Li, Na and K) encapsulation within the group III nitrides (B{sub 12}N{sub 12}, Al{sub 12}N{sub 12} and Ga{sub 12}N{sub 12}) and the group IV carbides (C{sub 24}, Si{sub 12}C{sub 12}and Ge{sub 12}C{sub 12}) nanoclusters. The encapsulation of Li, Na and K atoms is found to narrow the HOMO–LUMO gaps of the considered clusters. The electronic properties of these clusters, especially the group III nitrides nanoclusters, are strongly sensitive to interaction with the alkali metals. Moreover it is observed that the encapsulation of alkali metals enhances the first hyperpolarizabilities of B{sub 12}N{sub 12} nanocluster. Surprisingly, due to the alkali metals encapsulation within B{sub 12}N{sub 12} nanocluster, the first hyperpolarizability values are remarkably increased to 8505.49 and 122,503.76 a.u. for Na@B{sub 12}N{sub 12} and K@B{sub 12}N{sub 12}, respectively. Also the TD-DFT calculations at both CAM-B3LYP/6-311+G(d) and PBE0/6-311+G(d) levels of theory are also performed to investigate the origin of first hyperpolarizabilities.

  8. He–He and He–metal interactions in transition metals from first-principles

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Pengbo, E-mail: zhangpb@dlmu.edu.cn [Department of Physics, Dalian Maritime University, Dalian 116026 (China); Zou, Tingting [Information Science and Technology College, Dalian Maritime University, Dalian 116026 (China); Zhao, Jijun, E-mail: zhaojj@dlut.edu.cn [Key Laboratory of Materials Modification by Laser, Ion and Electron Beams (Dalian University of Technology), Ministry of Education, Dalian 116024 (China)

    2015-12-15

    We investigated the atomistic mechanism of He–He and He–metal interactions in bcc transition metals (V, Nb, Ta, Cr, Mo, W, and Fe) using first-principles methods. We calculated formation energy and binding energy of He–He pair as function of distance within the host lattices. The strengths of He–He attraction in Cr, Mo, W, and Fe (0.37–1.11 eV) are significantly stronger than those in V, Nb, and Ta (0.06–0.17 eV). Such strong attractions mean that He atoms would spontaneously aggregate inside perfect Cr, Mo, W, and Fe host lattices in absence of defects like vacancies. The most stable configuration of He–He pair is <100> dumbbell in groups VB metals, whereas it adopts close <110> configuration in Cr, Mo, and Fe, and close <111> configuration in W. Overall speaking, the He–He equilibrium distances of 1.51–1.55 Å in the group VIB metals are shorter than 1.65–1.70 Å in the group VB metals. Moreover, the presence of interstitial He significantly facilitates vacancy formation and this effect is more pronounced in the group VIB metals. The present calculations help understand the He-metal/He–He interaction mechanism and make a prediction that He is easier to form He cluster and bubbles in the groups VIB metals and Fe.

  9. 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.

  10. Holographic metal-insulator transition in higher derivative gravity

    Energy Technology Data Exchange (ETDEWEB)

    Ling, Yi, E-mail: lingy@ihep.ac.cn [Institute of High Energy Physics, Chinese Academy of Sciences, Beijing 100049 (China); Shanghai Key Laboratory of High Temperature Superconductors, Shanghai, 200444 (China); Liu, Peng, E-mail: liup51@ihep.ac.cn [Institute of High Energy Physics, Chinese Academy of Sciences, Beijing 100049 (China); Wu, Jian-Pin, E-mail: jianpinwu@mail.bnu.edu.cn [Institute of Gravitation and Cosmology, Department of Physics, School of Mathematics and Physics, Bohai University, Jinzhou 121013 (China); Shanghai Key Laboratory of High Temperature Superconductors, Shanghai, 200444 (China); Zhou, Zhenhua, E-mail: zhouzh@ihep.ac.cn [Institute of High Energy Physics, Chinese Academy of Sciences, Beijing 100049 (China)

    2017-03-10

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

  11. Optical properties of bcc d-transition metals

    Energy Technology Data Exchange (ETDEWEB)

    Kirillova, M M; Nomerovannaya, L V [AN SSSR, Sverdlovsk. Inst. Fiziki Metallov

    1978-04-01

    The optical properties of a niobium monocrystal in the spectral range of h..nu..=4.66 - 0.069 eV have been studied using the polarimetry method. The obtained results have been discussed on the basis of the zone calculations of the density of electron states for Nb and other isostructural metals of the 5 and 6 groups (Y, Ta, Cr, Mo, W). The existence of an intense low energy interband absorption in niobium in the range of h..nu..<0.1 eV is shown experimentally. The influence of the gapless and low-energy interzone transitions on the evaluations of the plasma and relaxation frequencies of conductivity electrons of d metals is discussed.

  12. 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.

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

    International Nuclear Information System (INIS)

    Del Maestro, Adrian; Rosenow, Bernd; Sachdev, Subir

    2009-01-01

    We present a detailed description of a zero temperature phase transition between superconducting and diffusive metallic states in very thin wires due to a Cooper pair breaking mechanism. The dissipative critical theory contains current reducing fluctuations in the guise of both quantum and thermally activated phase slips. A full cross-over phase diagram is computed via an expansion in the inverse number of complex components of the superconducting order parameter (one in the physical case). The fluctuation corrections to the electrical (σ) and thermal (κ) conductivities are determined, and we find that σ has a non-monotonic temperature dependence in the metallic phase which may be consistent with recent experimental results on ultra-narrow wires. In the quantum critical regime, the ratio of the thermal to electrical conductivity displays a linear temperature dependence and thus the Wiedemann-Franz law is obeyed, with a new universal experimentally verifiable Lorenz number

  14. 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)

  15. 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

  16. 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)

  17. 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

  18. 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.

  19. 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....

  20. 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

  1. 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.

  2. 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.

  3. Ferromagnetic semiconductor-metal transition in europium monoxide

    International Nuclear Information System (INIS)

    Arnold, M.

    2007-10-01

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

  4. 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.

  5. Brittle-to-Ductile Transition in Metallic Glass Nanowires.

    Science.gov (United States)

    Şopu, D; Foroughi, A; Stoica, M; Eckert, J

    2016-07-13

    When reducing the size of metallic glass samples down to the nanoscale regime, experimental studies on the plasticity under uniaxial tension show a wide range of failure modes ranging from brittle to ductile ones. Simulations on the deformation behavior of nanoscaled metallic glasses report an unusual extended strain softening and are not able to reproduce the brittle-like fracture deformation as found in experiments. Using large-scale molecular dynamics simulations we provide an atomistic understanding of the deformation mechanisms of metallic glass nanowires and differentiate the extrinsic size effects and aspect ratio contribution to plasticity. A model for predicting the critical nanowire aspect ratio for the ductile-to-brittle transition is developed. Furthermore, the structure of brittle nanowires can be tuned to a softer phase characterized by a defective short-range order and an excess free volume upon systematic structural rejuvenation, leading to enhanced tensile ductility. The presented results shed light on the fundamental deformation mechanisms of nanoscaled metallic glasses and demarcate ductile and catastrophic failure.

  6. 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.)

  7. 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

  8. 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

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

    Science.gov (United States)

    Petersen, John Emil, III

    The study of antiferromagnetic transition-metal oxides is an extremely active area in the physical sciences, where condensed matter physics, inorganic chemistry, and materials science blend together. The sheer number of potential commercial applications is staggering, but much of the fundamental science remains unexplained. This is not due to a lack of effort, however, as theorists have been struggling to understand these materials for decades - particularly the character of the band edges and first optical transitions. The difficulty lies in the strong correlation or Coloumb attraction between the electrons in the anisotropic d orbitals, which conventional band theory cannot describe adequately. The correlation problem is approached here by the well-accepted method of adding a Hubbard potential energy term to the ground state Hamiltonian, calculated within Density Functional Theory. The frequency-dependent complex dielectric function is calculated within the Independent Particle Approximation, and optical transitions are evaluated in multiple different ways. Peaks in the imaginary part of the dielectric function are compared energetically to orbitally decomposed density of states calculations. Optical transitions are typically analyzed in terms of atomic orbitals, which, strictly speaking, gives misleading results. Here, however, from the calculated data, two alternative interpretations are analyzed for each material studied. The first employs rigorous group theoretical analysis to determine allowed electric-dipole transitions, taking into account both orbital hybridization and crystal symmetry. The second interpretation is that of metal cation site hopping. In this interpretation, carriers hop from the x2 - y2 d orbital of one metal cation lattice site to the next metal cation site which is antiferromagnetically aligned. At times, thoughout this work, one interpretation is favorable to the other. Which interpretation is most valid depends on the material

  10. Synthesis of indium nanoclusters and formation of thin film contacts on plastic substrates for organic and flexible electronics applications

    International Nuclear Information System (INIS)

    Shi, Frank F; Bulkowski, Michal; Hsieh, K C

    2007-01-01

    In this work, we described the processes of synthesizing free-standing indium nanoclusters using inverse micelles and microemulsions as well as synthesizing organic-encapsulated indium nanoclusters using alkanethiols as the organic encapsulants. The synthesized organic-encapsulated indium nanoclusters have demonstrated the feasibilities to be used as plastic compatible soft metal contacts for emerging organic devices. The homogeneously distributed indium nanoclusters with sizes of 10-30 nm have been fabricated on a few different plastic substrates. By changing the alkanethiol carbon chain length and the sizes of the indium nanoclusters, the annealing temperature required to form low-resistance indium thin film conductors has been reduced to 80-100 deg. C, which is acceptable for a variety of organic thin films

  11. 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

  12. 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.

  13. 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.

  14. 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

  15. 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)

  16. 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.

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

    Science.gov (United States)

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

    2013-08-14

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

  18. 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.

  19. Magnetic properties of MnAs nanoclusters embedded in a GaAs semiconductor matrix

    International Nuclear Information System (INIS)

    Hai, Pham Nam; Takahashi, Keisuke; Yokoyama, Masafumi; Ohya, Shinobu; Tanaka, Masaaki

    2007-01-01

    We have clarified fundamental magnetic properties of MnAs nanoclusters (10 nm in diameter) embedded in a thin GaAs matrix (referred to as GaAs:MnAs) through tunneling magnetoresistance (TMR) characteristics of magnetic tunnel junctions (MTJs) consisting of a GaAs:MnAs thin film and a MnAs metal thin film as ferromagnetic electrodes. Although MnAs nanoclusters have coercive forces as small as 150 Oe at 7 K, they show unusually high blocking temperature, which is as large as 300 K. The remanent magnetization of the MnAs nanocluster system linearly decreases with increasing temperature. Those magnetic behaviors cannot be explained by the non-interacting particle model, revealing the important existence of dipolar interactions in MnAs nanocluster system

  20. 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

  1. Evaluation of complexing agents and column temperature in ion chromatographic separation of alkali metals, alkaline earth metals and transition metals ion

    International Nuclear Information System (INIS)

    Kelkar, Anoop; Pandey, Ashish; Name, Anil B.; Das, D.K.; Behere, P.G.; Mohd Afzal

    2015-01-01

    The aim of ion chromatography method development is the resolution of all metal ions of interests. Resolution can be improved by changing the selectivity. Selectivity in chromatography can be altered by changes in mobile phase (eg eluent type, eluent strength) or through changes in stationary phase. Temperature has been used in altering the selectivity of particularly in reversed phase liquid chromatography and ion exchange chromatography. Present paper describe the retention behaviour of alkali metals, alkaline earth metals and transition metal ions on a silica based carboxylate function group containing analyte column. Alkali metals, alkaline earth metals and transition metal ions were detected by ion conductivity and UV-VIS detectors respectively

  2. 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.

  3. 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)

  4. 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.

  5. 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

  6. Building machine learning force fields for nanoclusters

    Science.gov (United States)

    Zeni, Claudio; Rossi, Kevin; Glielmo, Aldo; Fekete, Ádám; Gaston, Nicola; Baletto, Francesca; De Vita, Alessandro

    2018-06-01

    We assess Gaussian process (GP) regression as a technique to model interatomic forces in metal nanoclusters by analyzing the performance of 2-body, 3-body, and many-body kernel functions on a set of 19-atom Ni cluster structures. We find that 2-body GP kernels fail to provide faithful force estimates, despite succeeding in bulk Ni systems. However, both 3- and many-body kernels predict forces within an ˜0.1 eV/Å average error even for small training datasets and achieve high accuracy even on out-of-sample, high temperature structures. While training and testing on the same structure always provide satisfactory accuracy, cross-testing on dissimilar structures leads to higher prediction errors, posing an extrapolation problem. This can be cured using heterogeneous training on databases that contain more than one structure, which results in a good trade-off between versatility and overall accuracy. Starting from a 3-body kernel trained this way, we build an efficient non-parametric 3-body force field that allows accurate prediction of structural properties at finite temperatures, following a newly developed scheme [A. Glielmo et al., Phys. Rev. B 95, 214302 (2017)]. We use this to assess the thermal stability of Ni19 nanoclusters at a fractional cost of full ab initio calculations.

  7. 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.

  8. Positron annihilation study of the semiconductor to metal transition in Ti2O3

    International Nuclear Information System (INIS)

    Tao, S.J.; Rao, C.N.R.

    1977-01-01

    An increase of positron mean life is found to accompany the semiconductor-metal transition in Ti 2 O 3 . This agrees well with the recent finding that the unit cell volume increases during the transition. (orig.) [de

  9. 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

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

    OpenAIRE

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

    2012-01-01

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

  11. Ternary alkali-metal and transition metal or metalloid acetylides as alkali-metal intercalation electrodes for batteries

    Science.gov (United States)

    Nemeth, Karoly; Srajer, George; Harkay, Katherine C; Terdik, Joseph Z

    2015-02-10

    Novel intercalation electrode materials including ternary acetylides of chemical formula: A.sub.nMC.sub.2 where A is alkali or alkaline-earth element; M is transition metal or metalloid element; C.sub.2 is reference to the acetylide ion; n is an integer that is 0, 1, 2, 3 or 4 when A is alkali element and 0, 1, or 2 when A is alkaline-earth element. The alkali elements are Lithium (Li), Sodium (Na), Potassium (K), Rubidium (Rb), Cesium (Cs) and Francium (Fr). The alkaline-earth elements are Berilium (Be), Magnesium (Mg), Calcium (Ca), Strontium (Sr), Barium (Ba), and Radium (Ra). M is a transition metal that is any element in groups 3 through 12 inclusive on the Periodic Table of Elements (elements 21 (Sc) to element 30 (Zn)). In another exemplary embodiment, M is a metalloid element.

  12. 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.

  13. 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.

  14. 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.

  15. On holographic disorder-driven metal-insulator transitions

    Energy Technology Data Exchange (ETDEWEB)

    Baggioli, Matteo; Pujolàs, Oriol [Institut de Física d’Altes Energies (IFAE), Universitat Autònoma de Barcelona,The Barcelona Institute of Science and Technology,Campus UAB, 08193 Bellaterra (Barcelona) (Spain)

    2017-01-10

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

  16. 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.

  17. 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.

  18. 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.

  19. 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)

  20. 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

  1. On holographic disorder-driven metal-insulator transitions

    International Nuclear Information System (INIS)

    Baggioli, Matteo; Pujolàs, Oriol

    2017-01-01

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

  2. 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.

  3. 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)

  4. 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

  5. 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).

  6. 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.

  7. Ferromagnetic semiconductor-metal transition in europium monoxide

    Energy Technology Data Exchange (ETDEWEB)

    Arnold, M.

    2007-10-15

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

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

    KAUST Repository

    Chen, Huanjun

    2012-08-28

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

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

    KAUST Repository

    Chen, Huanjun; Wang, Feng; Li, Kun; Woo, Katchoi; Wang, Jianfang; Li, Quan; Sun, Ling Dong; Zhang, Xixiang; Lin, Haiqing; YAN, Chunhua

    2012-01-01

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

  10. Canonical Schottky barrier heights of transition metal dichalcogenide monolayers in contact with a metal

    Science.gov (United States)

    Szcześniak, Dominik; Hoehn, Ross D.; Kais, Sabre

    2018-05-01

    The transition metal dichalcogenide (M X2 , where M =Mo , W and X =S , Se, Te) monolayers are of high interest for semiconducting applications at the nanoscale level; this interest is due to both their direct band gaps and high charge mobilities. In this regard, an in-depth understating of the related Schottky barrier heights, associated with the incorporation of M X2 sheets into novel low-dimensional metal-semiconductor junctions, is of crucial importance. Herein, we generate and provide analysis of the Schottky barrier heights behavior to account for the metal-induced gap states concept as its explanation. In particular, the present investigations concentrate on the estimation of the charge neutrality levels directly by employing the primary theoretical model, i.e., the cell-averaged Green's function formalism combined with the complex band structure technique. The results presented herein place charge neutrality levels in the vicinity of the midgap; this is in agreement with previous reports and analogous to the behavior of three-dimensional semiconductors. The calculated canonical Schottky barrier heights are also found to be in agreement with other computational and experimental values in cases where the difference between electronegativities of the semiconductor and metal contact is small. Moreover, the influence of the spin-orbit effects is herein considered and supports that Schottky barrier heights have metal-induced gap state-derived character, regardless whether spin-orbit coupling interactions are considered. The results presented within this report constitute a direct and vital verification of the importance of metal-induced gap states in explaining the behavior of observed Schottky barrier heights at M X2 -metal junctions.

  11. 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.

  12. 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)

  13. Kohn Anomaly and Phase Stability in Group VB Transition Metals

    Directory of Open Access Journals (Sweden)

    Alexander Landa

    2018-03-01

    Full Text Available In the periodic table, only a few pure metals exhibit lattice or magnetic instabilities associated with Fermi surface nesting, the classical examples being α-U and Cr. Whereas α-U displays a strong Kohn anomaly in the phonon spectrum that ultimately leads to the formation of charge density waves (CDWs, Cr is known for its nesting-induced spin density waves (SDWs. Recently, it has become clear that a pronounced Kohn anomaly and the corresponding softening in the elastic constants is also the key factor that controls structural transformations and mechanical properties in compressed group VB metals—materials with relatively high superconducting critical temperatures. This article reviews the current understanding of the structural and mechanical behavior of these metals under pressure with an introduction to the concept of the Kohn anomaly and how it is related to the important concept of Peierls instability. We review both experimental and theoretical results showing different manifestations of the Kohn anomaly in the transverse acoustic phonon mode TA (ξ00 in V, Nb, and Ta. Specifically, in V the anomaly triggers a structural transition to a rhombohedral phase, whereas in Nb and Ta it leads to an anomalous reduction in yield strength.

  14. 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.

  15. KLL resonant Auger transitions in metallic Cu and Ni

    International Nuclear Information System (INIS)

    Koever, L.; Berenyi, Z.; Cserny, I.

    2004-01-01

    Complete text of publication follows. KLL Auger spectra of 3d transition metals contain important information on the effects of the solid environment on deep core Auger transitions. Following the changes in the spectra when fine tuning the exciting photon energy across the K-shell ionization threshold with high energy resolution is informative concerning the possible resonant processes, expected to indicate the single-step nature of threshold Auger emission. The satellite structures in these spectra are strongly related to the unoccupied local electronic states above the Fermi level, as well as to the excitation, relaxation and screening processes associated with core hole ionization. In spite of the fundamental significance of the phenomena mentioned above, even non resonant high energy resolution studies of KLL Auger spectra of 3d transition metals (using laboratory X-ray sources) are very scarce due to the demanding experimental conditions requested. A very efficient tool for studying these phenomena is the Tunable High Energy XPS developed at HASYLAB which provides unique conditions, photon x and energy resolution for deep core Auger spectroscopy. Using the THE-XPS instrument at the BW2 beamline the high energy resolution (ΔE = 0.2 eV) KL 2,3 L 2,3 Auger spectra of polycrystalline Cu and Ni foils were measured with the Scienta SES-200 hemispherical analyzer. In the high energy range Cu 2p photo-electron peaks appearing in the Cu KLL Auger spectra due to the excitation by internal Cu K X-rays and trusted value for the Cu 2p3/2 binding energy were used for energy calibration. The exciting photon energy range was tuned up to about 50 eV above the K absorption edge and for the resonant energy region to 5 eV (Cu KLL) and 4 eV (Ni KLL) below threshold ensuring a photon beam with an energy width of about 1.1 eV. The evolution of the satellite structure as a function of excitation energy above threshold indicates di rent behaviour for particular satellites, making

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2012-06-29

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

  17. 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.

  18. 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.

  19. The role of the excited impurity levels on the metal-non metal transition

    International Nuclear Information System (INIS)

    Silva, M.S.F. da; Makler, S.S.; Anda, E.V.

    1983-01-01

    The electronic density of states for the impurity bands in doped semiconductors is calculated using the Green function method. The system is described by a Hamiltonian with local Coulomb interactions represented in a tight binding basis composed by two orbitals per site. The electronic correlation is treated in the CPA approximation. To calculate the configurational average for this structural disordered system a diagrammatic scheme is developed. It represents an extension of the Matsubara and Toyozawa method for the case of two hybridized bands in the presence of electronic correlation. The excited levels show to play a crutial role in the undestanding of the metal-non metal transition. This work represents an improvement of a previous result. The particular case of Si : P is analyzed. (author) [pt

  20. The role of the excited impurity levels on the metal-non metal transition

    International Nuclear Information System (INIS)

    Silva, M.S.F. da; Makler, S.S.; Anda, E.V.

    1983-01-01

    The electronic density of states for the impurity bands in doped semiconductors is calculated using the Green function method. The system is described by a Hamiltonian with local Coulomb interactions represented in a tight binding basis composed by two orbitals per site. The electronic correlation is treated in the CPA approximation. To calculate the configurational average for this structural disordered system a diagrammatic scheme is developed. It represents an extension of the Matsubara and Toyozawa method for the case of two hybridized bands in the presence of electronic correlation. The excited levels shown to play a crutial role in the understanding of the metal-non metal transition. This work represents an improvement of a previous result. The particular case of Si:P is analyzed. (Author) [pt

  1. 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.

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

    DEFF Research Database (Denmark)

    Lybye, D.; Mogensen, Mogens Bjerg

    2007-01-01

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

  3. 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

  4. 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

  5. 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

  6. 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

  7. 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

  8. 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

  9. 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

  10. 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

  11. The model of metal-insulator phase transition in vanadium oxide

    International Nuclear Information System (INIS)

    Vikhnin, V.S.; Lysenko, S.; Rua, A.; Fernandez, F.; Liu, H.

    2005-01-01

    Thermally induced metal-insulator phase transitions (PT) in VO 2 thin films are studied theoretically and experimentally. The hysteresis phenomena in the region of the transition for different type thin films were investigated. The phenomenological model of the PT is suggested. The charge transfer-lattice instability in VO 2 metallic phase is considered as basis of the first order metal-insulator PT in VO 2 . The charge transfer is treated as an order parameter

  12. Phenomenological model of nanocluster in polymer matrix

    International Nuclear Information System (INIS)

    Oksengendler, B.L.; Turaeva, N.N.; Azimov, J.; Rashidova, S.Sh.

    2010-01-01

    The phenomenological model of matrix nanoclusters is presented based on the Wood-Saxon potential used in nuclear physics. In frame of this model the following problems have been considered: calculation of width of diffusive layer between nanocluster and matrix, definition of Tamm surface electronic state taking into account the diffusive layer width, receiving the expression for specific magnetic moment of nanoclusters taking into account the interface width. (authors)

  13. Nanocluster production for solar cell applications

    International Nuclear Information System (INIS)

    Al Dosari, Haila M.; Ayesh, Ahmad I.

    2013-01-01

    This research focuses on the fabrication and characterization of silver (Ag) and silicon (Si) nanoclusters that might be used for solar cell applications. Silver and silicon nanoclusters have been synthesized by means of dc magnetron sputtering and inert gas condensation inside an ultra-high vacuum compatible system. We have found that nanocluster size distributions can be tuned by various source parameters, such as the sputtering discharge power, flow rate of argon inert gas, and aggregation length. Quadrupole mass filter and transmission electron microscopy were used to evaluate the size distribution of Ag and Si nanoclusters. Ag nanoclusters with average size in the range of 3.6–8.3 nm were synthesized (herein size refers to the nanocluster diameter), whereas Si nanoclusters' average size was controlled to range between 2.9 and 7.4 nm by controlling the source parameters. This work illustrates the ability of controlling the Si and Ag nanoclusters' sizes by proper optimization of the operation conditions. By controlling nanoclusters' sizes, one can alter their surface properties to suit the need to enhance solar cell efficiency. Herein, Ag nanoclusters were deposited on commercial polycrystalline solar cells. Short circuit current (I SC ), open circuit voltage (V OC ), fill factor, and efficiency (η) were obtained under light source with an intensity of 30 mW/cm 2 . A 22.7% enhancement in solar cell efficiency could be measured after deposition of Ag nanoclusters, which demonstrates that Ag nanoclusters generated in this work are useful to enhance solar cell efficiency

  14. Possibility of superradiance by magnetic nanoclusters

    International Nuclear Information System (INIS)

    Yukalov, V I; Yukalova, E P

    2011-01-01

    The possibility of realizing spin superradiance by an assembly of magnetic nanoclusters is analyzed. The known obstacles for realizing such a coherent radiation by magnetic nanoclusters are their large magnetic anisotropy, strong dephasing dipole interactions, and an essential nonuniformity of their sizes. In order to give a persuasive conclusion, a microscopic theory is developed, providing an accurate description of nanocluster spin dynamics. It is shown that, despite the obstacles, it is feasible to organize such a setup that magnetic nanoclusters would produce strong superradiant emission

  15. 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.

  16. 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.

  17. 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

  18. 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)

  19. 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.

  20. 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.

  1. 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.

  2. 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.)

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

    KAUST Repository

    Moody, Galan

    2016-03-14

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

  4. 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.

  5. Metal-insulator transitions in IZO, IGZO, and ITZO films

    Energy Technology Data Exchange (ETDEWEB)

    Makise, Kazumasa, E-mail: makise@nict.go.jp [National Institute of Information and Communications Technology, Kobe 651-2492 (Japan); Hidaka, Kazuya; Ezaki, Syohei; Asano, Takayuki; Shinozaki, Bunju [Department of Physics, Kyushu University, Fukuoka 810-8560 (Japan); Tomai, Shigekazu; Yano, Koki; Nakamura, Hiroaki [Central Research Laboratories, Idemitsu Kosan Co. Ltd, Chiba 299-0293 (Japan)

    2014-10-21

    In this study, we measured the low-temperature resistivity of amorphous two- and three-dimensional (2D and 3D) indium-zinc oxide, indium-gallium-zinc oxide, and indium-tin-zinc oxide films with a wide range of carrier densities. To determine their critical characteristics at the metal-insulator transition (MIT), we used the Ioffe–Regel criterion. We found that the MIT occurs in a narrow range between k{sub F}ℓ =0.13 and k{sub F}ℓ =0.25, where k{sub F} and ℓ are the Fermi wave number and electron mean free path, respectively. For films in the insulating region, we analyzed ρ(T) using a procedure proposed by Zabrodskii and Zinov'eva. This analysis confirmed the occurrence of Mott and Efros–Shklovskii (ES) variable-range hopping. The materials studied show crossover behavior from exp(T{sub Mott}/T){sup 1/4} or exp(T{sub Mott}/T){sup 1/3} for Mott hopping conduction to exp(T{sub ES}/T){sup 1/2} for ES hopping conduction with decreasing temperature. For both 2D and 3D materials, we found that the relationship between T{sub Mott} and T{sub ES} satisfies T{sub ES}∝T{sub Mott}{sup 2/3}.

  6. 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.

  7. 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.

  8. 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.

  9. 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

  10. 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.

  11. 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.

  12. 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

  13. 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.

  14. 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

  15. Silver Nanocluster Reparative Effect in Hernioplasty

    Directory of Open Access Journals (Sweden)

    Nikolay M. Anichkov

    2014-06-01

    Full Text Available Background: The acceleration of re-epithelialization and fibroblast differentiation were noted during the experiments with silver nanoclusters (SNs by interrupting the negative development of inflammation at the level of cytokines and promoting a positive course of reparative processes. The aim of this work was to elaborate the experimental model of prosthesis hernioplasty in subcutaneous and intraperitoneal locations of hernioprostheses with SNs, which allowed us to study the course of reparative reactions in all layers of the anterior abdominal wall. Material and Methods: We used a modified hernioprosthesis made from polyester fibers coated with a metal-polymer composition, including the stabilized SN in a concentration of 6.8 and 11.3 mg per 1 g of the hernioprosthesis mesh. During this research we used guinea pigs to study the in vivo tissue reactions. The clinical part of the study included the group of 212 patients who underwent removal of an inguinal hernia. We have identified various factors associated with infectious and toxic effects on the body by determining the level of the serum glutamate-pyruvate-transaminase (SGPT. Results: In implantation of the hernioprostheses, including the high concentration of SN in the laparotomy wound, the exudative component of the inflammation was weakly expressed. It was mostly the proliferative changes that took place. We did not find either CD8-positive type T lymphocytes or PAX5-positive type B activated cells in the exudate. Conclusion: Our research has shown that the use of hernioprostheses that include silver nanoclusters leads to the reduction of inflammation in the exudative phase and to a more favorable course of reparative processes.

  16. 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.

  17. 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.

  18. 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

  19. 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.

  20. 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

  1. 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.)

  2. 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.

  3. 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.

  4. A scalable synthesis of highly stable and water dispersible Ag 44(SR)30 nanoclusters

    KAUST Repository

    AbdulHalim, Lina G.; Ashraf, Sumaira; Katsiev, Khabiboulakh; Kirmani, Ahmad R.; Kothalawala, Nuwan; Anjum, Dalaver H.; Abbas, Sikandar Zameer; Amassian, Aram; Stellacci, Francesco; Dass, Amala; Hussain, Irshad; Bakr, Osman

    2013-01-01

    We report the synthesis of atomically monodisperse thiol-protected silver nanoclusters [Ag44(SR)30] m, (SR = 5-mercapto-2-nitrobenzoic acid) in which the product nanocluster is highly stable in contrast to previous preparation methods. The method is one-pot, scalable, and produces nanoclusters that are stable in aqueous solution for at least 9 months at room temperature under ambient conditions, with very little degradation to their unique UV-Vis optical absorption spectrum. The composition, size, and monodispersity were determined by electrospray ionization mass spectrometry and analytical ultracentrifugation. The produced nanoclusters are likely to be in a superatom charge-state of m = 4-, due to the fact that their optical absorption spectrum shares most of the unique features of the intense and broadly absorbing nanoparticles identified as [Ag44(SR) 30]4- by Harkness et al. (Nanoscale, 2012, 4, 4269). A protocol to transfer the nanoclusters to organic solvents is also described. Using the disperse nanoclusters in organic media, we fabricated solid-state films of [Ag44(SR)30]m that retained all the distinct features of the optical absorption spectrum of the nanoclusters in solution. The films were studied by X-ray diffraction and photoelectron spectroscopy in order to investigate their crystallinity, atomic composition and valence band structure. The stability, scalability, and the film fabrication method demonstrated in this work pave the way towards the crystallization of [Ag44(SR)30]m and its full structural determination by single crystal X-ray diffraction. Moreover, due to their unique and attractive optical properties with multiple optical transitions, we anticipate these clusters to find practical applications in light-harvesting, such as photovoltaics and photocatalysis, which have been hindered so far by the instability of previous generations of the cluster. © 2013 The Royal Society of Chemistry.

  5. UV luminescence of dendrimer-encapsulated gold nanoclusters

    Energy Technology Data Exchange (ETDEWEB)

    Shim, Hyeong Seop; Kim, Jun Myung; Sohn, So Hyeong; Han, Noh Soo; Park, Seung Min [Dept. of Chemistry, Kyung Hee University, Seoul (Korea, Republic of)

    2016-10-15

    Size-dependent luminescence color is one of the interesting properties of metal nanocrystals, whose sizes are in the dimension of the Fermi wavelength of an electron. Despite the short Fermi wavelength of electrons in gold (-0.7 nm), luminescence of gold nanoclusters has been reported to range from the near-infrared to near-ultraviolet, depending on the number of atoms in the nanoclusters. The photoluminescence of G4-OH (Au) obtained by the excitation of 266 nm showed UV emission in addition to the well-known blue emission. The higher intensity and red-shifted emission of the gold nanoclusters was distinguished from the emission of dendrimers. The UV emission at 352 nm matched the emission energy of Au{sub 4} in the spherical jellium model, rather than the planar Au{sub 8}, which supported the emission of Au{sub 4} formed in G4-OH. Despite the change of [HAuCl{sub 4} ]/[G4-OH], the relative population between Au{sub 4} and Au{sub 8} was similar in G4-OH(Au), which indicated that the closed electronic and geometric structures stabilized the magic number of Au{sub 4}.

  6. 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

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

    DEFF Research Database (Denmark)

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

    2006-01-01

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

  8. Electronic specific heat of transition metal carbides; Chaleur specifique electronique de carbures de metaux de transition

    Energy Technology Data Exchange (ETDEWEB)

    Conte, R [Commissariat a l' Energie Atomique, Fontenay-aux-Roses (France). Centre d' Etudes Nucleaires

    1964-07-15

    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) [French] Les donnees experimentales permettant de preciser la structure de bandes des carbures de metaux de transition de structure NaCI sont encore peu.nombreuses. Nous avons mesure la chaleur specifique electronique de certains de ces carbures, de differentes concentrations electroniques (TiC stoechiometrique ou non, TaC et mixtes (Ti, Ta) - C). Nous donnons les principales caracteristiques (metallographie, resistivite, rayon X), de nos echantillons, et nous decrivons l'appareillage de chaleur specifique a basse temperature realise. Dans l'un nous utilisons l'helium comme gaz d'echange. L'autre est monte avec un contact mecanique. Les deux utilisent une sonde au germanium comme thermometre. La mesure de la resistance de cette sonde est decrite, ainsi que les differents montages de mesure. Les resultats, presentes dans un modele de bande rigide, font apparaitre que la densite des etats au niveau de Fermi presente un minimum au voisinage des carbures du groupe IV. (auteur)

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

    International Nuclear Information System (INIS)

    Chang, Y.J.; Koo, C.H.; Yang, J.S.; Kim, Y.S.; Kim, D.H.; Lee, J.S.; Noh, T.W.; Kim, Hyun-Tak; Chae, B.G.

    2005-01-01

    Vanadium dioxide (VO 2 ) shows a metal-insulator transition (MIT) near room temperature, accompanied by an abrupt resistivity change. Since the MIT of VO 2 is known to be a first order phase transition, it is valuable to check metallic and insulating phase segregation during the MIT process. We deposited (100)-oriented epitaxial VO 2 thin films on R-cut sapphire substrates. From the scanning tunneling spectroscopy (STS) spectra, we could distinguish metallic and insulating regions by probing the band gap. Optical spectroscopic analysis also supported the view that the MIT in VO 2 occurs through metal and insulator phase coexistence

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

    Energy Technology Data Exchange (ETDEWEB)

    Huang, X.M. [International Center for New-Structured Materials (ICNSM) and Laboratory of New-Structured Materials, Department of Materials Science and Engineering, Zhejiang University, Hangzhou 310027 (China); Chang, C.T. [Institute for Material Research, Tohoku University, Sendai 980-8577 (Japan); Chang, Z.Y.; Wang, X.D.; Cao, Q.P. [International Center for New-Structured Materials (ICNSM) and Laboratory of New-Structured Materials, Department of Materials Science and Engineering, Zhejiang University, Hangzhou 310027 (China); Shen, B.L.; Inoue, A. [Institute for Material Research, Tohoku University, Sendai 980-8577 (Japan); Jiang, J.Z. [International Center for New-Structured Materials (ICNSM) and Laboratory of New-Structured Materials, Department of Materials Science and Engineering, Zhejiang University, Hangzhou 310027 (China)], E-mail: jiangjz@zju.edu.cn

    2008-07-28

    In this work, quaternary Fe{sub 72-x}M{sub x}Y{sub 6}B{sub 22} (M = Ni, Co and Mo) bulk metallic glasses (BMGs) have been developed. It is found that a fully amorphous Fe{sub 68}Mo{sub 4}Y{sub 6}B{sub 22} cylindrical rod with 6.5 mm in diameter can be prepared by copper mold injection. These alloys have a high glass transition temperature of about 900 K with high fracture strengths up to about 3 GPa although they are still brittle. Magnetic measurements reveal that they are ferromagnetic at ambient temperature with low coercive force of about 2 A/m, saturation magnetization of about 0.7 T and effective permeability of about 7000 at 100 kHz. The newly developed Fe-based quaternary alloys exhibit excellent combination properties: superior glass forming ability (GFA), high glass transition temperature, and soft magnetic properties, which could have potential applications in electronic industries. Furthermore, the effect of Mo addition on GFA in the Fe-Y-B BMG system has been discussed compared with those of Ni and Co additions.

  11. Transition Metal Dopants Essential for Producing Ferromagnetism in Metal Oxide Nanoparticles

    Energy Technology Data Exchange (ETDEWEB)

    Johnson, Lydia; Thurber, Aaron P.; Anghel, Josh; Sabetian, Maryam; Engelhard, Mark H.; Tenne, D.; Hanna, Charles; Punnoose, Alex

    2010-08-13

    Recent claims that ferromagnetism can be produced in nanoparticles of metal oxides without the presence of transition metal dopants has been refuted in this work by investigating 62 high quality well-characterized nanoparticle samples of both undoped and Fe doped (0-10% Fe) ZnO. The undoped ZnO nanoparticles showed zero or negligible magnetization, without any dependence on the nanoparticle size. However, chemically synthesized Zn₁₋xFexO nanoparticles showed clear ferromagnetism, varying systematically with Fe concentration. Furthermore, the magnetic properties of Zn₁₋xFexO nanoparticles showed strong dependence on the reaction media used to prepare the samples. The zeta potentials of the Zn₁₋xFexO nanoparticles prepared using different reaction media were significantly different, indicating strong differences in the surface structure. Electron paramagnetic resonance studies clearly showed that the difference in the ferromagnetic properties of Zn₁₋xFexO nanoparticles with different surface structures originate from differences in the fraction of the doped Fe³⁺ ions that are coupled ferromagnetically.

  12. Chiral ligand-protected gold nanoclusters: Considering the optical activity from a viewpoint of ligand dissymmetric field

    Directory of Open Access Journals (Sweden)

    Hiroshi Yao

    2016-10-01

    Full Text Available Chirality is a geometric property of a physical, chemical, or biological object, which is not superimposable on its mirror image. Its significant presence has led to a strong demand in the development of chiral drugs, sensors, catalysts, and photofunctional materials. In recent years, chirality of nanoscale organic/inorganic hybrids has received tremendous attention owing to potential applications in chiral nanotechnology. In particular, with the recent progress in the syntheses and characterizations of atomically precise gold nanoclusters protected by achiral thiolates, atomic level origins of their chirality have been unveiled. On the other hand, chirality or optical activity in metal nanoclusters can also be introduced via the surface chiral ligands, which should be universal for the nanosystems. This tutorial review presents some optically-active metal (gold nanoclusters protected by chiral thiolates or phosphines, and their chiroptical (or circular dichroism; CD properties are discussed mostly from a viewpoint of the ligand dissymmetric field scheme. The examples are the gold nanoclusters protected by (R-/(S-2-phenylpropane-1-thiol, (R-/(S-mercaptosuccinic acid, phenylboronate-D/L-fructose complexes, phosphine sulfonate-ephedrinium ion pairs, or glutathione. Some methodologies for versatile asymmetric transformation and chiroptical controls of the nanocluster compounds are also described. In the dissymmetric field model as the origin of optical activity, the chiroptical responses of the gold nanoclusters are strongly associated with coupled oscillator and/or CD stealing mechanisms based on the concept of induced CD (ICD derived from a perturbation theory, so on this basis, some characteristic features of the observed CD responses of chiral ligand-protected gold nanoclusters are presented in detail. We believe that various kinds of origins of chirality found in ligand-protected gold nanoclusters may provide models for understanding those of

  13. 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)

  14. Insulator–metal transition in a conservative system: An evidence for ...

    Indian Academy of Sciences (India)

    substrate, suggest that the mobility coalescence is responsible for the aging in island metal films. ... esting transition observed in a conservative system – after the stoppage of ... Oxidation of islands model and mobility coalescence model.

  15. 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...

  16. 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

  17. 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

  18. Excited State Dynamics and Semiconductor-to-Metallic Phase Transition of VO2 Thin Film

    National Research Council Canada - National Science Library

    Liu, Huimin

    2004-01-01

    .... Vanadium dioxide shows an ultrafast, passive phase transition (PT) from a monoclinic semiconductor phase to a metallic tetragonal rutile structure when the sample temperature is above 68 degrees C...

  19. 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

  20. The control of magnetism near metal-to-insulator transitions of VO2 nano-belts

    CSIR Research Space (South Africa)

    Nkosi, SS

    2016-12-01

    Full Text Available The magnetic properties of paramagnetic/weakly ferromagnetic films are strongly affected by the proximity to materials that undergo a metal to insulator phase transition. Here, we show that under the deposition conditions associated with structural...

  1. 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

  2. Semiconductor-metal transition induced by giant Stark effect in blue phosphorene nanoribbons

    Energy Technology Data Exchange (ETDEWEB)

    Xiong, Peng-Yu; Chen, Shi-Zhang; Zhou, Wu-Xing; Chen, Ke-Qiu, E-mail: keqiuchen@hnu.edu.cn

    2017-06-28

    The electronic structures and transport properties in monolayer blue phosphorene nanoribbons (BPNRs) with transverse electric field have been studied by using density functional theory and nonequilibrium Green's functions method. The results show that the band gaps of BPNRs with both armchair and zigzag edges are linearly decreased with the increasing of the strength of transverse electric field. A semiconductor-metal transition occurs when the electric field strength reaches to 5 V/nm. The Stark coefficient presents a linear dependency on BPNRs widths, and the slopes of both zBPNRs and aBPNRs are 0.41 and 0.54, respectively, which shows a giant Stark effect occurs. Our studies show that the semiconductor-metal transition originates from the giant Stark effect. - Highlights: • The electronic transport in blue phosphorene nanoribbons. • Semiconductor-metal transition can be observed. • The semiconductor-metal transition originates from the giant Stark effect.

  3. 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

  4. 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)

  5. Definition of the size of nanoclusters of silver and palladium in carbon fiber

    International Nuclear Information System (INIS)

    Volobuev, V.S.; Bashmakov, I.A.; Lukashevich, S.M.; Tolkacheva, E.A.; Tikhonova, T.F.; Lukashevich, M.G.; Kaputskij, F.N.

    2008-01-01

    Size of palladium and silver nanoclusters is carbon matrix prepared by heart treatment of metal-polymer precursor has been determined by means of XR diffractions study. It was shown that the cluster size increases with increasing annealing temperature from 700 to 900 degree Celsius by factor two. No structuring of carbon matrix was observed under clusters forming. (authors)

  6. {Fe6O2}-Based Assembly of a Tetradecanuclear Iron Nanocluster

    Directory of Open Access Journals (Sweden)

    Svetlana G. Baca

    2011-01-01

    Full Text Available The tetradecanuclear FeIII pivalate nanocluster [Fe14O10(OH4(Piv18], comprising a new type of metal oxide framework, has been solvothermally synthesized from a hexanuclear iron pivalate precursor in dichlormethane/acetonitrile solution. Magnetic measurements indicate the presence of very strong antiferromagnetic interactions in the cluster core.

  7. The physical and chemical properties of nanostructured mixed-metal catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Li [Texas A & M Univ., College Station, TX (United States); Goodman, David Wayne [Texas A & M Univ., College Station, TX (United States)

    2016-04-21

    The main targets of this study has been to synthesize well-defined nanoclusters of Ni, Co, Pt, Rh and Pd as well as mixed-metal nanoclusters on ultrathin oxide surfaces and to characterize their detailed morphology using scanning probe techniques. The focus of the research is an understanding of the effects of metal-substrate interactions and overall composition on the structure/stability of single metal and mixed-metal nanoclusters and their catalytic activity.

  8. Magnetic phase transition induced by electrostatic gating in two-dimensional square metal-organic frameworks

    Science.gov (United States)

    Wang, Yun-Peng; Li, Xiang-Guo; Liu, Shuang-Long; Fry, James N.; Cheng, Hai-Ping

    2018-03-01

    We investigate theoretically magnetism and magnetic phase transitions induced by electrostatic gating of two-dimensional square metal-organic framework compounds. We find that electrostatic gating can induce phase transitions between homogeneous ferromagnetic and various spin-textured antiferromagnetic states. Electronic structure and Wannier function analysis can reveal hybridizations between transition-metal d orbitals and conjugated π orbitals in the organic framework. Mn-containing compounds exhibit a strong d -π hybridization that leads to partially occupied spin-minority bands, in contrast to compounds containing transition-metal ions other than Mn, for which electronic structure around the Fermi energy is only slightly spin split due to weak d -π hybridization and the magnetic interaction is of the Ruderman-Kittel-Kasuya-Yosida type. We use a ferromagnetic Kondo lattice model to understand the phase transition in Mn-containing compounds in terms of carrier density and illuminate the complexity and the potential to control two-dimensional magnetization.

  9. Relationship between thermal expansion coefficient and glass transition temperature in metallic glasses

    International Nuclear Information System (INIS)

    Kato, H.; Chen, H.-S.; Inoue, A.

    2008-01-01

    The thermal expansion coefficients of 13 metallic glasses were measured using a thermo-mechanical analyser. A unique correlation was found between the linear thermal expansion coefficient and the glass transition temperature-their product is nearly constant ∼8.24 x 10 -3 . If one assumes the Debye expression for thermal activation, the total linear thermal expansion up to glass transition temperature (T g ) is reduced to 6 x 10 -3 , nearly 25% of that at the fusion of pure metals

  10. 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...

  11. 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....

  12. Synthesis and Optical Properties of Au-Ag Alloy Nanoclusters with Controlled Composition

    Directory of Open Access Journals (Sweden)

    J. F. Sánchez-Ramírez

    2008-01-01

    Full Text Available Colloidal solid-solution-like Au-Ag alloy nanoclusters of different compositions were synthesized through citrate reduction of mixed metal ions of low concentrations, without using any other protective or capping agents. Optical absorption of the alloy nanoclusters was studied both theoretically and experimentally. The position of the surface plasmon resonance (SPR absorption band of the nanoclusters could be tuned from 419 nm to 521 nm through the variation of their composition. Considering effective dielectric constant of the alloy, optical absorption spectra for the nanoclusters were calculated using Mie theory, and compared with the experimentally obtained spectra. Theoretically obtained optical spectra well resembled the experimental spectra when the true size distribution of the nanoparticles was considered. High-resolution transmission electron microscopy (HREM, high-angle annular dark field (HAADF imaging, and energy dispersive spectroscopy (EDS revealed the true alloy nature of the nanoparticles with nominal composition being preserved. The synthesis technique can be extended to other bimetallic alloy nanoclusters containing Ag.

  13. 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

  14. Substitution effect on metal-insulator transition of K2V8O16

    International Nuclear Information System (INIS)

    Isobe, Masahiko; Koishi, Shigenori; Yamazaki, Satoshi; Yamaura, Jun-ichi; Gotou, Hirotada; Yagi, Takehiko; Ueda, Yutaka

    2009-01-01

    The effect of the substitution of various ions on the metal-insulator (MI) transition at 170 K in K 2 V 8 O 16 has been investigated. Both Rb and Ti form complete solid solution systems: K 2-x Rb x V 8 O 16 and K 2 V 8-y Ti y O 16 , respectively. The substitution of Rb for K or of Ti for V splits the transition into two transitions: the high-temperature transition is a first-order MI transition from a tetragonal structure to a tetragonal structure, and the low-temperature transition is a second-order transition to a monoclinic structure. In K 2-x Rb x V 8 O 16 , the former terminates to an MI transition at around 220 K in Rb 2 V 8 O 16 , while the latter disappears at x > 0.6. In K 2 V 8-y Ti y O 16 , both transitions disappear at y > 0.5. The substitution of Cr for V also results in a similar splitting of the transition and the rapid disappearance of both transitions. The substitution of Na or Ba for K suppresses the MI transition without any splitting of the transition, although the solubility of both ions is limited. These substitution effects reveal that the MI transition of K 2 V 8 O 16 consists of two parts: a first-order MI transition and a parasitic second-order structural transition; the substitution of some ions causes a clear splitting of these transitions, probably due to the difference between the chemical pressure effects on the two transitions. The first-order MI transition is very sensitive to charge randomness, suggesting the charge ordering nature of the MI transition, while the second-order structural transition is very sensitive to both charge and structural randomnesses. (author)

  15. 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.

  16. 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,

  17. 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...

  18. 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)

  19. 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

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

    NARCIS (Netherlands)

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

    1993-01-01

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

  1. 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,

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

    KAUST Repository

    Esparza, Angel

    2011-07-07

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

  3. DFT Study of Binding and Electron Transfer from a Metal-Free Dye with Carboxyl, Hydroxyl, and Sulfonic Anchors to a Titanium Dioxide Nanocluster

    Directory of Open Access Journals (Sweden)

    Corneliu I. Oprea

    2013-01-01

    Full Text Available We report results of density functional theory (DFT calculations of a metal-free dye, 5-(4-sulfophenylazosalicylic acid disodium salt, known as Mordant Yellow 10 (MY-10, used as sensitizer for TiO2 dye-sensitized solar cells (DSSCs. Given the need to better understand the behavior of the dyes adsorbed on the TiO2 nanoparticle, we studied various single and double deprotonated forms of the dye bound to a TiO2 cluster, taking advantage of the presence of the carboxyl, hydroxyl, and sulfonic groups as possible anchors. We discuss various binding configurations to the TiO2 substrate and the charge transfer from the pigment to the oxide by means of DFT calculations. In agreement with other reports, we find that the carboxyl group tends to bind in bidentate bridging configurations. The salicylate uses both the carboxyl and hydroxyl substituent groups for either a tridentate binding to adjacent Ti(IV ions or a bidentate Ti-O binding together with an O-H-O binding, due to the rotation of the carboxyl group out of the plane of the dye. The sulfonic group prefers a tridentate binding. We analyze the propensity for electron transfer of the various dyes and find that for MY-10, as a function of the anchor group, the DSSC performance decreases in the order hydroxyl + carboxyl > carboxyl > sulfonate.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2015-04-15

    The results of the first steps in the design of coordination polymers based on penta- and heptacyanometallates of heavier d transitions metals are presented. The 2D structure of the coordination polymers: [(Mn(acacen)){sub 2}Ru(NO)(CN){sub 5}]{sub n} and two complexes composed of different cyanorhenates, [Ni(cyclam)]{sub 2}[ReO(OH)(CN){sub 4}](ClO{sub 4}){sub 2}(H{sub 2}O){sub 1.25} and [Cu(cyclam)]{sub 2}[Re(CN){sub 7}](H{sub 2}O){sub 12}, was confirmed by single crystal XRD study, the rhenium oxidation state having been proved by the magnetic measurements. An amorphism of [M(cyclam)]{sub 3}[Re(CN){sub 7}]{sub 2} (M=Ni, Cu) polymers does not allow to define strictly their dimensionality and to model anisotropic magnetic behavior of the compounds. However, with high probability a honey-comb like layer structure could be expected for [M(cyclam)]{sub 3}[Re(CN){sub 7}]{sub 2} complexes, studied in this work, because such an arrangement is the most common among the bimetallic assemblies of hexa- and octacyanometallates with a ratio [M(cyclam)]/[M(CN){sub n}]=3/2. For the first time was prepared and fully characterized a precursor (n-Bu{sub 4}N){sub 2}[Ru(NO)(CN){sub 5}], soluble in organic media. - Graphical abstract: The very first results in the design of 2D coordination polymers based on penta- and heptacyanometallates of 4d and5d transitions metals are presented. - Highlights: • Design of coordination polymers based on penta- and heptacyanometallates. • New Ru and Re cyanide based heterobimetallic coordination complexes. • Hydrolysis and ox/red processes involving [Re(CN){sub 7}]{sup 3+} during crystallization. • High magnetic anisotropy of [M(cyclam)]{sub 3}[Re(CN){sub 7}]{sub 2}(H{sub 2}O){sub n}, M=Cu, Ni, complexes.

  5. Lattice Dynamics of Transition Metals; Dynamique de Reseau des Metaux de Transition

    Energy Technology Data Exchange (ETDEWEB)

    Woods, A. D.B. [Chalk River Nuclear Laboratories, Chalk River, ON (Canada)

    1965-04-15

    The frequency versus wave-vector v(q) dispersion relations for the normal modes of vibration of several body-centred cubic transition metal, crystals have been measured recently at room temperature. The dispersion curves for niobium, measured by Nakagawa and Woods, displayed some very unusual features, and the results could only be fitted by means of a Born-von Karman model if interactions out to very distant neighbours (beyond eighth) were included. Subsequent measurements on tantalum by Woods showed very similar results. This is not surprising since niobium and tantalum are in column V of the periodic table and many of their electronic properties are similar. Measurements of the dispersion curves of molybdenum by Woods and Chen and of tungsten by Chen and Brockhouse showed that although these metals, which are in column VI of the periodic table, had dispersion relations which were similar to each other, these dispersion relations were very different from those of the column V metals, niobium and tantalum. The gross features of the v(q) for molybdenum and tungsten were very nearly describable by a third neighbour axially-symmetric Born-von Karman force model, although several important features were not reproduced by this model. One of these features is a striking anomaly in the [{zeta}{zeta}{zeta}] longitudinal (L) branch for molybdenum where the frequency changes from v = 6.3 x 10{sup 12} c/s at {zeta} = 0.92 to v= 5.5 x 10{sup 12} c/s at {zeta} = 1.0. If this and other observed features are Kohn anomalies, their positions are consistent with the dimensions of the Fermi suriace of the column V metals proposed by Lomer. Thus it is suggested that the striking differences between the dispersion relation for niobium and that for molybdenum (metals which are believed to have quite similar band structures) reflect differences in the Fermi energies and hence the Fermi surfaces for these materials. (author) [French] Les relations de dispersion v(q) (frequence- vecteur d

  6. Ion implantation induced conducting nano-cluster formation in PPO

    International Nuclear Information System (INIS)

    Das, A.; Patnaik, A.; Ghosh, G.; Dhara, S.

    1997-01-01

    Conversion of polymers and non-polymeric organic molecules from insulating to semiconducting materials as an effect of energetic ion implantation is an established fact. Formation of nano-clusters enriched with carbonaceous materials are made responsible for the insulator-semiconductor transition. Conduction in these implanted materials is observed to follow variable range hopping (VRH) mechanism. Poly(2,6-dimethyl phenylene oxide) [PPO] compatible in various proportion with polystyrene is used as a high thermal resistant insulating polymer. PPO has been used for the first time in the ion implantation study

  7. Silver and copper nanoclusters in the lustre decoration of Italian Renaissance pottery: an EXAFS study

    Science.gov (United States)

    Padovani, S.; Borgia, I.; Brunetti, B.; Sgamellotti, A.; Giulivi, A.; D'Acapito, F.; Mazzoldi, P.; Sada, C.; Battaglin, G.

    Lustre is one of the most important decorative techniques of the Medieval and Renaissance pottery of the Mediterranean basin, capable of producing brilliant metallic reflections and iridescence. Following the recent finding that the colour of lustre decorations is mainly determined by copper and silver nanoclusters dispersed in the glaze layer, the local environment of copper and silver atoms has been studied by extended X-ray absorption fine structure (EXAFS) spectroscopy on original samples of gold and red lustre. It has been found that, in gold lustre, whose colour is attributed mainly to the silver nanocluster dispersion, silver is only partially present in the metallic form and copper is almost completely oxidised. In the red lustre, whose colour is attributed mainly to the copper nanocluster dispersion, only a fraction of copper is present in the metallic form. EXAFS measurements on red lustre, carried out in the total electron yield mode to probe only the first 150 nm of the glaze layer, indicated that in some cases lustre nanoclusters may be confined in a very thin layer close to the surface.

  8. Covalently linked multimers of gold nanoclusters Au102(p-MBA)44 and Au∼250(p-MBA)n.

    Science.gov (United States)

    Lahtinen, Tanja; Hulkko, Eero; Sokołowska, Karolina; Tero, Tiia-Riikka; Saarnio, Ville; Lindgren, Johan; Pettersson, Mika; Häkkinen, Hannu; Lehtovaara, Lauri

    2016-11-10

    We present the synthesis, separation, and characterization of covalently-bound multimers of para-mercaptobenzoic acid (p-MBA) protected gold nanoclusters. The multimers were synthesized by performing a ligand-exchange reaction of a pre-characterized Au 102 (p-MBA) 44 nanocluster with biphenyl-4,4'-dithiol (BPDT). The reaction products were separated using gel electrophoresis yielding several distinct bands. The bands were analyzed by transmission electron microscopy (TEM) revealing monomer, dimer, and trimer fractions of the nanocluster. TEM analysis of dimers in combination with molecular dynamics simulations suggest that the nanoclusters are covalently bound via a disulfide bridge between BPDT molecules. The linking chemistry is not specific to Au 102 (p-MBA) 44 . The same approach yields multimers also for a larger monodisperse p-MBA-protected cluster of approximately 250 gold atoms, Au ∼250 (p-MBA) n . While the Au 102 (p-MBA) 44 is not plasmonic, the Au ∼250 (p-MBA) n nanocluster supports localized surface plasmon resonance (LSPR) at 530 nm. Multimers of the Au ∼250 (p-MBA) n exhibit additional transitions in their UV-vis spectrum at 630 nm and 810 nm, indicating the presence of hybridized LSPR modes. Well-defined structures and relatively small sizes make these systems excellent candidates for connecting ab initio theoretical studies and experimental quantum plasmonics. Moreover, our work opens new possibilities in the controlled synthesis of advanced monodisperse nanocluster superstructures.

  9. Universal Quantum Criticality in the Metal-Insulator Transition of Two-Dimensional Interacting Dirac Electrons

    Directory of Open Access Journals (Sweden)

    Yuichi Otsuka

    2016-03-01

    Full Text Available The metal-insulator transition has been a subject of intense research since Mott first proposed that the metallic behavior of interacting electrons could turn to an insulating one as electron correlations increase. Here, we consider electrons with massless Dirac-like dispersion in two spatial dimensions, described by the Hubbard models on two geometrically different lattices, and perform numerically exact calculations on unprecedentedly large systems that, combined with a careful finite-size scaling analysis, allow us to explore the quantum critical behavior in the vicinity of the interaction-driven metal-insulator transition. Thereby, we find that the transition is continuous, and we determine the quantum criticality for the corresponding universality class, which is described in the continuous limit by the Gross-Neveu model, a model extensively studied in quantum field theory. Furthermore, we discuss a fluctuation-driven scenario for the metal-insulator transition in the interacting Dirac electrons: The metal-insulator transition is triggered only by the vanishing of the quasiparticle weight, not by the Dirac Fermi velocity, which instead remains finite near the transition. This important feature cannot be captured by a simple mean-field or Gutzwiller-type approximate picture but is rather consistent with the low-energy behavior of the Gross-Neveu model.

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

    Energy Technology Data Exchange (ETDEWEB)

    Spivak, B.

    2010-04-06

    We derive the theory of the quantum (zero temperature) superconductor to metal transition in disordered materials when the resistance of the normal metal near criticality is small compared to the quantum of resistivity. This can occur most readily in situations in which 'Anderson's theorem' does not apply. We explicitly study the transition in superconductor-metal composites, in an swave superconducting film in the presence of a magnetic field, and in a low temperature disordered d-wave superconductor. Near the point of the transition, the distribution of the superconducting order parameter is highly inhomogeneous. To describe this situation we employ a procedure which is similar to that introduced by Mott for description of the temperature dependence of the variable range hopping conduction. As the system approaches the point of the transition from the metal to the superconductor, the conductivity of the system diverges, and the Wiedemann-Franz law is violated. In the case of d-wave (or other exotic) superconductors we predict the existence of (at least) two sequential transitions as a function of increasing disorder: a d-wave to s-wave, and then an s-wave to metal transition.

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

    International Nuclear Information System (INIS)

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

    1975-01-01

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

  12. 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

  13. studies on transition metal complexes of herbicidal compounds. ii

    African Journals Online (AJOL)

    a

    derivative of 2-chloro-4-ethylamino-6-isopropylamino-s-triazine, atrazine (ATZ) --- a well known herbicide has ... development while the other is the metal ion associated degradation or deactivation of the herbicides .... Colour M.p./decomp.

  14. Sub-chronic toxicological studies of transition metal complexes of ...

    African Journals Online (AJOL)

    Md. Sharif Hasan

    2017-01-18

    Jan 18, 2017 ... naproxen showed more side effects than metal complexes which ..... Fosslein E. Adverse effects of nonsteroidal anti-inflammatory drugs on the ... association increases the anti-inflammatory and analgesic activity of ibuprofen.

  15. 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.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2015-02-15

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

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

    Directory of Open Access Journals (Sweden)

    Melissa Jackson

    2014-07-01

    Full Text Available Transitioning from current resource management practice dominated by linear economic models of consumption and production, to circular models of resource use, will require insights into the stages and processes associated with socio-technical transitions. This paper is concerned with transitions in practice. It explores two frameworks within the transitions literature—the multi-level perspective and transition management theory—for practical guidance to inform a deliberate transition in practice. The critical futures literature is proposed as a source of tools and methods to be used in conjunction with the transition frameworks to influence and enable transitions in practice. This enhanced practical guidance for initiating action is applied to a specific context—transitioning the Australian metals sector towards a circular economy model. This particular transition case study is relevant because the vision of a circular economy model of resource management is gaining traction internationally, Australia is significant globally as a supplier of finite mineral resources and it will also be used in a collaborative research project on Wealth from Waste to investigate possibilities for the circular economy and metals recycling.

  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. Long Spin-Relaxation Times in a Transition-Metal Atom in Direct Contact to a Metal Substrate.

    Science.gov (United States)

    Hermenau, Jan; Ternes, Markus; Steinbrecher, Manuel; Wiesendanger, Roland; Wiebe, Jens

    2018-03-14

    Long spin-relaxation times are a prerequisite for the use of spins in data storage or nanospintronics technologies. An atomic-scale solid-state realization of such a system is the spin of a transition-metal atom adsorbed on a suitable substrate. For the case of a metallic substrate, which enables the direct addressing of the spin by conduction electrons, the experimentally measured lifetimes reported to date are on the order of only hundreds of femtoseconds. Here, we show that the spin states of iron atoms adsorbed directly on a conductive platinum substrate have a surprisingly long spin-relaxation time in the nanosecond regime, which is comparable to that of a transition metal atom decoupled from the substrate electrons by a thin decoupling layer. The combination of long spin-relaxation times and strong coupling to conduction electrons implies the possibility to use flexible coupling schemes to process the spin information.

  20. 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

  1. 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.

  2. Surface free energy of alkali and transition metal nanoparticles

    International Nuclear Information System (INIS)

    Aqra, Fathi; Ayyad, Ahmed

    2014-01-01

    Graphical abstract: Size dependent surface free energy of spherical, cubic and disk Au nanoparticles. - Highlights: • A model to account for the surface free energy of metallic nanoparticles is described. • The model requires only the cohesive energy of the nanoparticle. • The surface free energy of a number of metallic nanoparticles has been calculated, and the obtained values agree well with existing data. • Surface energy falls down very fast when the number of atoms is less than hundred. • The model is applicable to any metallic nanoparticle. - Abstract: This paper addresses an interesting issue on the surface free energy of metallic nanoparticles as compared to the bulk material. Starting from a previously reported equation, a theoretical model, that involves a specific term for calculating the cohesive energy of nanoparticle, is established in a view to describe the behavior of surface free energy of metallic nanoparticles (using different shapes of particle: sphere, cube and disc). The results indicate that the behavior of surface energy is very appropriate for spherical nanoparticle, and thus, it is the most realistic shape of a nanoparticle. The surface energy of copper, silver, gold, platinum, tungsten, molybdenum, tantalum, paladium and alkali metallic nanoparticles is only prominent in the nanoscale size, and it decreases with the decrease of nanoparticle size. Thus, the surface free energy plays a more important role in determining the properties of nanoparticles than in bulk materials. It differs from shape to another, and falls down as the number of atoms (nanoparticle size) decreases. In the case of spherical nanoparticles, the onset of the sharp decrease in surface energy is observed at about 110 atom. A decrease of 16% and 45% in surface energy is found by moving from bulk to 110 atom and from bulk to 5 atom, respectively. The predictions are consistent with the reported data

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

    Energy Technology Data Exchange (ETDEWEB)

    Achatz, Philipp

    2009-05-15

    During this PhD project, the metal-insulator transition and superconductivity of highly boron-doped single crystal diamond and related materials have been investigated. The critical boron concentration n{sub c} for the metal-insulator transition was found to be the same as for the normal-superconductor transition. All metallic samples have been found to be superconducting and we were able to link the occurence of superconductivity to the proximity to the metal-insulator transition. For this purpose, a scaling law approach based on low temperature transport was proposed. Furthermore, we tried to study the nature of the superconductivity in highly boron doped single crystal diamond. Raman spectroscopy measurements on the isotopically substituted series suggest that the feature occuring at low wavenumbers ({approx} 500 cm{sup -1}) is the A1g vibrational mode associated with boron dimers. Usual Hall effect measurements yielded a puzzling situation in metallic boron-doped diamond samples, leading to carrier concentrations up to a factor 10 higher than the boron concentration determined by secondary ion mass spectroscopy (SIMS). The low temperature transport follows the one expected for a granular metal or insulator, depending on the interplay of intergranular and intragranular (tunneling) conductance. The metal-insulator transition takes place at a critical conductance g{sub c}. The granularity also influences significantly the superconducting properties by introducing the superconducting gap {delta} in the grain and Josephson coupling J between superconducting grains. A peak in magnetoresistance is observed which can be explained by superconducting fluctuations and the granularity of the system. Additionally we studied the low temperature transport of boron-doped Si samples grown by gas immersion laser doping, some of which yielded a superconducting transition at very low temperatures. Furthermore, preliminary results on the LO-phonon-plasmon coupling are shown for the

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

    International Nuclear Information System (INIS)

    Achatz, Philipp

    2009-01-01

    During this PhD project, the metal-insulator transition and superconductivity of highly boron-doped single crystal diamond and related materials have been investigated. The critical boron concentration n c for the metal-insulator transition was found to be the same as for the normal-superconductor transition. All metallic samples have been found to be superconducting and we were able to link the occurence of superconductivity to the proximity to the metal-insulator transition. For this purpose, a scaling law approach based on low temperature transport was proposed. Furthermore, we tried to study the nature of the superconductivity in highly boron doped single crystal diamond. Raman spectroscopy measurements on the isotopically substituted series suggest that the feature occuring at low wavenumbers (∼ 500 cm -1 ) is the A1g vibrational mode associated with boron dimers. Usual Hall effect measurements yielded a puzzling situation in metallic boron-doped diamond samples, leading to carrier concentrations up to a factor 10 higher than the boron concentration determined by secondary ion mass spectroscopy (SIMS). The low temperature transport follows the one expected for a granular metal or insulator, depending on the interplay of intergranular and intragranular (tunneling) conductance. The metal-insulator transition takes place at a critical conductance g c . The granularity also influences significantly the superconducting properties by introducing the superconducting gap Δ in the grain and Josephson coupling J between superconducting grains. A peak in magnetoresistance is observed which can be explained by superconducting fluctuations and the granularity of the system. Additionally we studied the low temperature transport of boron-doped Si samples grown by gas immersion laser doping, some of which yielded a superconducting transition at very low temperatures. Furthermore, preliminary results on the LO-phonon-plasmon coupling are shown for the first time in aluminum

  5. Catalytic photooxidation of pentachlorophenol using semiconductor nanoclusters

    Energy Technology Data Exchange (ETDEWEB)

    WILCOXON,JESS P.

    2000-04-17

    Pentachlorophenol (PCP) is a toxic chlorinated aromatic molecule widely used as fungicide, a bactericide and a wood preservation, and thus ubiquitous in the environment. The authors report photo-oxidation of PCP using a variety of nanosize semiconductor metal oxides and sulfides in both aqueous and polar organic solvents and compare the photo-oxidation kinetics of these nanoclusters to widely studied bulk powders like Degussa P-25 TiO{sub 2} and CdS. They study both the light intensity dependence of PCP photooxidation for nanosize SnO{sub 2} and the size dependence of PCP photooxidation for both nanosize SnO{sub 2} and MoS{sub 2}. They find an extremely strong size dependence for the latter which they attribute to its size-dependent band gap and the associated change in redox potentials due to quantum confinement of the hole-electron pair. The authors show that nanosize MoS{sub 2} with a diameter of d=3.0 nm and an absorbance edge of {approximately}450 nm is a very effective photooxidation catalyst for complete PCP mineralization, even when using only visible light irradiation.

  6. On thermal stability of cyanocomplexes of some transition metals

    International Nuclear Information System (INIS)

    Sergeeva, A.N.; Pavlenko, L.I.; Dovgej, V.V.; Zubritskaya, D.I.; Tkachenko, Zh.I.

    1981-01-01

    The experimental data on the study of thermal stability of the coordination cyanides of the composition M'sub(x)[M''(CN)sub(y)]xnHsub(2)O, where M'=K; M''=V(2,3), Mo(2,4), Re(3,5), Ru(2); x=3,4; y=6-8; n=1-3, are generalized and systematized. Three main stages of decomposition of cyanocomlexes, proceeding in argon medium at 20-900 deg, are established. Hexacyanocomplexes of Re(3), Mo(2), Ru(2), V(2) according to their increasing thermal stability can be arranged in the series: K 3 [Re(CN) 6 ] 4 [Mo(CN) 6 ] 4 [Ru(CN) 6 ] 4 [V(CN) 6 ], from which it follows that cyanocomplexes of d-metals of periods 6 and 5 are less thermally stable than similar complexes of d-metal of period 4. The decomposition of cyanides of the type M(CN) 2 in the case of ruthenium ends with the formation of free metal at 470-670 deg, for rhenium - with the formation of free metal and rhenium nitride ReN 2 at 680-700 deg, for molybdenum - molybdenum carbide Mo 2 C at > 670 deg, for vanadium - vanadium carbide VC at 705 deg [ru

  7. Volume variation of Gruneisen parameters of fcc transition metals

    Indian Academy of Sciences (India)

    Unknown

    average discrepancy between the values of γ measured by various methods for 23 metals. Experimentally only the total Gruneisen parameter can be measured. The total. Gruneisen parameter is the sum of lattice, electronic and probably magnetic contribution. The letter term is present in palladium (White and Pawlok 1970) ...

  8. Textural and morphological studies of transition metal doped SBA ...

    Indian Academy of Sciences (India)

    J. Chem. Sci. Vol. 127, No. 5, May 2015, pp. 909–919. c Indian Academy of Sciences. ... The difference in hydrolysis rates of metal and silica precursors have led to textural ... tures of mesoporous SBA-15.13 General shape-selective.

  9. Sub-chronic toxicological studies of transition metal complexes of ...

    African Journals Online (AJOL)

    However, Naproxen metal complexes showed comparatively lower side effects than naproxen. Hematological report suggested that naproxen was in process of initiating inflammation which was justified by decreasing the mean value hemoglobin and hematocrit level and increasing the white blood cells level. There were ...

  10. Transition metal chemistry of hydroxy(–OH)-rich molecules ...

    Indian Academy of Sciences (India)

    Administrator

    Appropriately designed hydroxy(–OH) containing Schiff's base and Mannich base molecules have been recently found to be important for development of the coordination chemistry of a number of metal ions in the biomimetic chemistry of metalloenzymes. In this context, our group has studied the coordination role of these ...

  11. Hydrogen evolution on nano-particulate transition metal sulfides

    DEFF Research Database (Denmark)

    Bonde, Jacob Lindner; Moses, Poul Georg; Jaramillo, Thomas F.

    2008-01-01

    The hydrogen evolution reaction (HER) on carbon supported MoS2 nanoparticles is investigated and compared to findings with previously published work on Au(111) supported MoS2. An investigation into MoS2 oxidation is presented and used to quantify the surface concentration of MoS2. Other metal sul...

  12. Schiff base transition metal complexes for Suzuki–Miyaura cross

    Indian Academy of Sciences (India)

    Schiff base ligand and its complex with iron (Fe), cobalt (Co), nickel (Ni) and copper (Cu) ions were synthesized using 4-aminoacetophenone and salicylaldehyde and characterized. FTIR spectrum shows that bidentate coordination of metal ions with ligand where O, N are electron donating sites of azomethine group.

  13. 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.

  14. TRANSITION METAL TRANSPORT IN PLANTS AND ASSOCIATED ENDOSYMBIONTS: ARBUSCULAR MYCORRHIZAL FUNGI AND RHIZOBIA

    Directory of Open Access Journals (Sweden)

    Manuel González-Guerrero

    2016-07-01

    Full Text Available Transition metals such as iron, copper, zinc, or molybdenum, are essential nutrients for plants. These elements are involved in almost every biological process, including photosynthesis, tolerance to biotic and abiotic stress, or symbiotic nitrogen fixation. However, plants often grow in soils with limiting metallic oligonutrient bioavailability. Consequently, to ensure the proper metal levels, plants have developed a complex metal uptake and distribution system, that not only involves the plant itself, but also its associated microorganisms. These microorganisms can simply increase metal solubility in soils and making them more accessible to the host plant, as well as induce the plant metal deficiency response, or deliver directly transition elements to cortical cells. Other, instead of providing metals can act as metal sinks, such as endosymbiotic rhizobia in legume nodules that requires relatively large amounts to carry out nitrogen fixation. In this review, we propose to do an overview of metal transport mechanisms in the plant-microbe system, emphasizing the role of arbuscular mycorrhizal fungi and endosymbiotic rhizobia.

  15. 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.)

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

    KAUST Repository

    Dong, Liang

    2016-12-30

    Two-dimensional (2D) materials that display robust ferromagnetism have been pursued intensively for nanoscale spintronic applications, but suitable candidates have not been identified. Here we present theoretical predictions on the design of ordered 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 of the surface terminations (T = O, OH, and F), as well as in Hf2MnC2O2 and Hf2VC2O2 monolayers. The high magnetic moments (3–4 μB/unit cell) and high Curie temperatures (495–1133 K) of these MXenes are superior to those of existing 2D ferromagnetic materials. Furthermore, semimetal-to-semiconductor and ferromagnetic-to-antiferromagnetic phase transitions are predicted to occur in these materials in the presence of small or moderate tensile in-plane strains (0–3%), which can be externally applied mechanically or internally induced by the choice of transition metals.

  17. Positron confinement in embedded lithium nanoclusters

    Science.gov (United States)

    van Huis, M. A.; van Veen, A.; Schut, H.; Falub, C. V.; Eijt, S. W.; Mijnarends, P. E.; Kuriplach, J.

    2002-02-01

    Quantum confinement of positrons in nanoclusters offers the opportunity to obtain detailed information on the electronic structure of nanoclusters by application of positron annihilation spectroscopy techniques. In this work, positron confinement is investigated in lithium nanoclusters embedded in monocrystalline MgO. These nanoclusters were created by means of ion implantation and subsequent annealing. It was found from the results of Doppler broadening positron beam analysis that approximately 92% of the implanted positrons annihilate in lithium nanoclusters rather than in the embedding MgO, while the local fraction of lithium at the implantation depth is only 1.3 at. %. The results of two-dimensional angular correlation of annihilation radiation confirm the presence of crystalline bulk lithium. The confinement of positrons is ascribed to the difference in positron affinity between lithium and MgO. The nanocluster acts as a potential well for positrons, where the depth of the potential well is equal to the difference in the positron affinities of lithium and MgO. These affinities were calculated using the linear muffin-tin orbital atomic sphere approximation method. This yields a positronic potential step at the MgO||Li interface of 1.8 eV using the generalized gradient approximation and 2.8 eV using the insulator model.

  18. 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)

  19. 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.

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

    Directory of Open Access Journals (Sweden)

    E. U. Donev

    2008-01-01

    Full Text Available We describe a simple configuration in which the extraordinary optical transmission effect through subwavelength hole arrays in noble-metal films can be switched by the semiconductor-to-metal transition in an underlying thin film of vanadium dioxide. In these experiments, the transition is brought about by thermal heating of the bilayer film. The surprising reverse hysteretic behavior of the transmission through the subwavelength holes in the vanadium oxide suggest that this modulation is accomplished by a dielectric-matching condition rather than plasmon coupling through the bilayer film. The results of this switching, including the wavelength dependence, are qualitatively reproduced by a transfer matrix model. The prospects for effecting a similar modulation on a much faster time scale by using ultrafast laser pulses to trigger the semiconductor-to-metal transition are also discussed.

  1. 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.

  2. 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.

  3. 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.

  4. Uniaxial pressure-induced half-metallic ferromagnetic phase transition in LaMnO3

    Science.gov (United States)

    Rivero, Pablo; Meunier, Vincent; Shelton, William

    2016-03-01

    We use first-principles theory to predict that the application of uniaxial compressive strain leads to a transition from an antiferromagnetic insulator to a ferromagnetic half-metal phase in LaMnO3. We identify the Q2 Jahn-Teller mode as the primary mechanism that drives the transition, indicating that this mode can be used to tune the lattice, charge, and spin coupling. Applying ≃6 GPa of uniaxial pressure along the [010] direction activates the transition to a half-metallic pseudocubic state. The half-metallicity opens the possibility of producing colossal magnetoresistance in the stoichiometric LaMnO3 compound at significantly lower pressure compared to recently observed investigations using hydrostatic pressure.

  5. Development of dissimilar metal transition joint by hot roll bonding technique

    International Nuclear Information System (INIS)

    Nagai, Takayuki; Takeda, Seiichiro; Tanaka, Yasumasa; Ogawa, Kazuhiro; Nakasuji, Kazuyuki; Ikenaga, Yoshiaki.

    1994-01-01

    Metallurgically bonded transition joints which enable to connect reprocessing equipments made of superior corrosion resistant valve metals (Ti-5Ta, Zr or Ti) with stainless steel piping is needed for nuclear fuel reprocessing plants. The authors have developed dissimilar metal transition joints between stainless steel and Ti-5Ta, Zr or Ti with an insert metal of Ta by the hot roll bonding process, using the newly developed mill called 'rotary reduction mill'. In the R and D program, appropriate bonding conditions in the manufacturing process of the joints were established. This report presents the structure of transition joints and the manufacturing process by the hot roll bonding technique. Then, the evaluation of mechanical and corrosion properties and the results of demonstration test of joints for practical use are described. (author)

  6. Development of dissimilar metal transition joint by hot roll bonding technique

    International Nuclear Information System (INIS)

    Nagai, Takayuki; Takeuchi, Masayuki; Takeda, Seiichiro; Shikakura, Sakae; Ogawa, Kazuhiro; Nakasuji, Kazuyuki; Kajimura, Haruhiko.

    1995-01-01

    Metallurgically bonded transition joints which enable to connect reprocessing equipments made of superior corrosion resistant valve metals (Ti-5Ta, Zr or Ti) with stainless steel piping is needed for nuclear fuel reprocessing plants. The authors have developed dissimilar metal transition joints between stainless steel and Ti-5Ta, Zr or Ti with an insert metal of Ta by the hot roll bonding process, using the newly developed mill called 'rotary reduction mill'. In the R and D program, appropriate bonding conditions in the manufacturing process of the joints were established. This report presents the structure of transition joints and the manufacturing process by hot roll bonding technique. Then, the evaluation of mechanical and corrosion properties and the results of demonstration test of joints for practical use are described. (author)

  7. 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

  8. Fluorescence enhancement of DNA-silver nanoclusters from guanine proximity

    Energy Technology Data Exchange (ETDEWEB)

    Yeh, Hsin-chih [Los Alamos National Laboratory; Sharma, Jaswinder [Los Alamos National Laboratory; Yoo, Hyojong [Los Alamos National Laboratory; Martinez, Jennifer S [Los Alamos National Laboratory

    2010-01-01

    Oligonucleotide-templated, silver nanoclusters (DNA/Ag NCs) are a versatile set of fluorophores and have already been used for live cell imaging, detection of specific metal ions, and single-nucleotide variation identification. Compared to commonly used organic dyes, these fluorescent nanoclusters have much better photostability and are often a few times brighter. Owing to their small size, simple preparation, and biocompatibility (i.e. made of nontoxic metals), DNA/Ag NCs should find more applications in biological imaging and chemical detection in the years to come. While clearly promising as new fluorophores, DNA/Ag NCs possess a unique and poorly understood dynamic process not shared by organic dyes or photoluminescent nanocrystals - the conversion among different NC species due to silver oxidation/reduction or NC regrouping. While this environmental sensitivity can be viewed as a drawback, in the appropriate context, it can be used as a sensor or reporter. Often reversible, conversions among different NC species have been found to depend upon a number of factors, including time, temperature, oxygen and salt content. In this communication, we report significant fluorescence enhancement of DNA/Ag NCs via interactions with guanine-rich DNA sequences. Moreover, we demonstrated this property can be used for sensitive detection of specific target DNA from a human oncogene (i.e. Braf gene).

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

    International Nuclear Information System (INIS)

    Mathias, H.; Katz, Y.

    1978-04-01

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

  10. 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.

  11. 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.

  12. 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...

  13. Pressure-driven insulator-metal transition in cubic phase UO2

    Science.gov (United States)

    Huang, Li; Wang, Yilin; Werner, Philipp

    2017-09-01

    Understanding the electronic properties of actinide oxides under pressure poses a great challenge for experimental and theoretical studies. Here, we investigate the electronic structure of cubic phase uranium dioxide at different volumes using a combination of density functional theory and dynamical mean-field theory. The ab initio calculations predict an orbital-selective insulator-metal transition at a moderate pressure of ∼45 GPa. At this pressure the uranium's 5f 5/2 state becomes metallic, while the 5f 7/2 state remains insulating up to about 60 GPa. In the metallic state, we observe a rapid decrease of the 5f occupation and total angular momentum with pressure. Simultaneously, the so-called “Zhang-Rice state”, which is of predominantly 5f 5/2 character, quickly disappears after the transition into the metallic phase.

  14. Plasmon transmutation: inducing new modes in nanoclusters by adding dielectric nanoparticles.

    Science.gov (United States)

    Wen, Fangfang; Ye, Jian; Liu, Na; Van Dorpe, Pol; Nordlander, Peter; Halas, Naomi J

    2012-09-12

    Planar clusters of coupled plasmonic nanoparticles support nanoscale electromagnetic "hot spots" and coherent effects, such as Fano resonances, with unique near and far field signatures, currently of prime interest for sensing applications. Here we show that plasmonic cluster properties can be substantially modified by the addition of individual, discrete dielectric nanoparticles at specific locations on the cluster, introducing new plasmon modes, or transmuting existing plasmon modes to new ones, in the resulting metallodielectric nanocomplex. Depositing a single carbon nanoparticle in the junction between a pair of adjacent nanodisks induces a metal-dielectric-metal quadrupolar plasmon mode. In a ten-membered cluster, placement of several carbon nanoparticles in junctions between multiple adjacent nanoparticles introduces a collective magnetic plasmon mode into the Fano dip, giving rise to an additional subradiant mode in the metallodielectric nanocluster response. These examples illustrate that adding dielectric nanoparticles to metallic nanoclusters expands the number and types of plasmon modes supported by these new mixed-media nanoscale assemblies.

  15. 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...

  16. 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.

  17. 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.)

  18. 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

  19. 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)

  20. Electric field-triggered metal-insulator transition resistive switching of bilayered multiphasic VOx

    Science.gov (United States)

    Won, Seokjae; Lee, Sang Yeon; Hwang, Jungyeon; Park, Jucheol; Seo, Hyungtak

    2018-01-01

    Electric field-triggered Mott transition of VO2 for next-generation memory devices with sharp and fast resistance-switching response is considered to be ideal but the formation of single-phase VO2 by common deposition techniques is very challenging. Here, VOx films with a VO2-dominant phase for a Mott transition-based metal-insulator transition (MIT) switching device were successfully fabricated by the combined process of RF magnetron sputtering of V metal and subsequent O2 annealing to form. By performing various material characterizations, including scanning transmission electron microscopy-electron energy loss spectroscopy, the film is determined to have a bilayer structure consisting of a VO2-rich bottom layer acting as the Mott transition switching layer and a V2O5/V2O3 mixed top layer acting as a control layer that suppresses any stray leakage current and improves cyclic performance. This bilayer structure enables excellent electric field-triggered Mott transition-based resistive switching of Pt-VOx-Pt metal-insulator-metal devices with a set/reset current ratio reaching 200, set/reset voltage of less than 2.5 V, and very stable DC cyclic switching upto 120 cycles with a great set/reset current and voltage distribution less than 5% of standard deviation at room temperature, which are specifications applicable for neuromorphic or memory device applications. [Figure not available: see fulltext.

  1. Magnetic engineering in 3d transition metals on phosphorene by strain

    Energy Technology Data Exchange (ETDEWEB)

    Cai, Xiaolin [International Laboratory for Quantum Functional Materials of Henan and School of Physics and Engineering, Zhengzhou University, Zhengzhou, 450001 (China); School of Physics and Electronic Information Engineering, Henan Polytechnic University, Jiaozuo, 454000 (China); Niu, Chunyao, E-mail: niuchunyao@zzu.edu.cn [International Laboratory for Quantum Functional Materials of Henan and School of Physics and Engineering, Zhengzhou University, Zhengzhou, 450001 (China); Wang, Jianjun [College of Science, Zhongyuan University of Technology, Zhengzhou 450007 (China); Yu, Weiyang [International Laboratory for Quantum Functional Materials of Henan and School of Physics and Engineering, Zhengzhou University, Zhengzhou, 450001 (China); School of Physics and Electronic Information Engineering, Henan Polytechnic University, Jiaozuo, 454000 (China); Ren, XiaoYan; Zhu, Zhili [International Laboratory for Quantum Functional Materials of Henan and School of Physics and Engineering, Zhengzhou University, Zhengzhou, 450001 (China)

    2017-04-11

    Using first-principles density functional theory (DFT) calculations, we systematically investigate the strain effects on the adsorption energies, magnetic ordering and electronic properties of 3d transition metal (TM) atoms (from Sc to Co) adsorbed on phosphorene (P). We find that the adsorption energy of TM can be enhanced by compressive strain whereas weakened by tensile strain. Our results show that strain plays a decisive role in the magnetic moments as well as the magnetic coupling states of TM adatoms. Importantly, the transitions from antiferromagnetic (AFM) state to ferromagnetic (FM) state or to another different AFM ordering can be induced by strain effect. In addition, we observe the semiconductor to metal or half-metal transitions in some TM@P systems by applying strain. Our findings shed a new light on precisely engineering the magnetic properties and electronic properties of the TM@P systems, which will have great potential applications in spin electronics and other related fields. - Highlights: • The adsorption of TM atoms on phosphorene can be enhanced by compressive strain whereas weakened by tensile strain. • Strain plays a decisive role in the magnetic moments as well as the magnetic coupling states of TM adatoms. • Applying strain can induce the semiconductor to metal or half-metal transitions in some TM@P systems.

  2. Magnetic engineering in 3d transition metals on phosphorene by strain

    International Nuclear Information System (INIS)

    Cai, Xiaolin; Niu, Chunyao; Wang, Jianjun; Yu, Weiyang; Ren, XiaoYan; Zhu, Zhili

    2017-01-01

    Using first-principles density functional theory (DFT) calculations, we systematically investigate the strain effects on the adsorption energies, magnetic ordering and electronic properties of 3d transition metal (TM) atoms (from Sc to Co) adsorbed on phosphorene (P). We find that the adsorption energy of TM can be enhanced by compressive strain whereas weakened by tensile strain. Our results show that strain plays a decisive role in the magnetic moments as well as the magnetic coupling states of TM adatoms. Importantly, the transitions from antiferromagnetic (AFM) state to ferromagnetic (FM) state or to another different AFM ordering can be induced by strain effect. In addition, we observe the semiconductor to metal or half-metal transitions in some TM@P systems by applying strain. Our findings shed a new light on precisely engineering the magnetic properties and electronic properties of the TM@P systems, which will have great potential applications in spin electronics and other related fields. - Highlights: • The adsorption of TM atoms on phosphorene can be enhanced by compressive strain whereas weakened by tensile strain. • Strain plays a decisive role in the magnetic moments as well as the magnetic coupling states of TM adatoms. • Applying strain can induce the semiconductor to metal or half-metal transitions in some TM@P systems.

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

    DEFF Research Database (Denmark)

    Konstantatos, Andreas

    -molecule magnets (SMMs). Starting from the archetype SMM Mn12 we present the details of the mechanisms governing the relaxation of the magnetization of these systems. In Chapter 2 we present our work on the coordination chemistry of lanthanides with a new Schiff-base ligand, H3L [(E)-3-((2-hydroxyphenyl...... complexes of M3+ or M2+ metal ions (M: 3d transition metal) with the preference to either approximate octahedral or trigonal prismatic coordination geometry. A detailed magnetic characterization for most of the complexes is presented where a trinuclear Co2+ cluster stands out for its pronounced SMM...

  4. Theoretical calculations of hardness and metallicity for multibond hexagonal 5d transition metal diborides with ReB2 structure

    International Nuclear Information System (INIS)

    Yang Jun; Gao Fa-Ming; Liu Yong-Shan

    2017-01-01

    The hardness, electronic, and elastic properties of 5d transition metal diborides with ReB 2 structure are studied theoretically by using the first principles calculations. The calculated results are in good agreement with the previous experimental and theoretical results. Empirical formulas for estimating the hardness and partial number of effective free electrons for each bond in multibond compounds with metallicity are presented. Based on the formulas, IrB 2 has the largest hardness of 21.8 GPa, followed by OsB 2 (21.0 GPa) and ReB 2 (19.7 GPa), indicating that they are good candidates as hard materials. (paper)

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

    DEFF Research Database (Denmark)

    Zhukovsky, Sergei; Protsenko, Igor E.; Ikhsanov, Renat Sh

    2015-01-01

    Transition absorption of a photon by an electron passingthrough a boundary between two media with different permit-tivities is described both classically and quantum mechani-cally. Transition absorption is shown to make a substantialcontribution to photoelectron emission at a metal....../semicon-ductor interface in nanoplasmonic systems, and is put forth asa possible microscopic mechanism of the surface photoelec-tric effect in photodetectors and solar cells containing plas-monic nanoparticles....

  6. Metal - Insulator Transition Driven by Vacancy Ordering in GeSbTe Phase Change Materials

    OpenAIRE

    Bragaglia, Valeria; Arciprete, Fabrizio; Privitera, Stefania; Rimini, Emanuele; Mazzarello, Riccardo; Calarco, Raffaella; Zhang, Wei; Mio, Antonio Massimiliano; Zallo, Eugenio; Perumal, Karthick; Giussani, Alessandro; Cecchi, Stefano; Boschker, Jos Emiel; Riechert, Henning

    2016-01-01

    Phase Change Materials (PCMs) are unique compounds employed in non-volatile random access memory thanks to the rapid and reversible transformation between the amorphous and crystalline state that display large differences in electrical and optical properties. In addition to the amorphous-to-crystalline transition, experimental results on polycrystalline GeSbTe alloys (GST) films evidenced a Metal-Insulator Transition (MIT) attributed to disorder in the crystalline phase. Here we report on a f...

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

    International Nuclear Information System (INIS)

    Hinwood, A.L.; Stasinska, A.; Callan, A.C.; Heyworth, J.; Ramalingam, M.; Boyce, M.; McCafferty, P.; Odland, J.Ø.

    2015-01-01

    Most studies of metals exposure focus on the heavy metals. There are many other metals (the transition, alkali and alkaline earth metals in particular) in common use in electronics, defense industries, emitted via combustion and which are naturally present in the environment, that have received limited attention in terms of human exposure. We analysed samples of whole blood (172), urine (173) and drinking water (172) for antimony, beryllium, bismuth, cesium, gallium, rubidium, silver, strontium, thallium, thorium and vanadium using ICPMS. In general most metals concentrations were low and below the analytical limit of detection with some high concentrations observed. Few factors examined in regression models were shown to influence biological metals concentrations and explained little of the variation. Further study is required to establish the source of metals exposures at the high end of the ranges of concentrations measured and the potential for any adverse health impacts in children. - This study has demonstrated exposure to alkali, alkali earth and transition metals in pregnant women with factors such as breastfeeding, fish oil use and diet affecting exposures

  8. 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.

  9. 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)

  10. 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

  11. Structurally triggered metal-insulator transition in rare-earth nickelates.

    Science.gov (United States)

    Mercy, Alain; Bieder, Jordan; Íñiguez, Jorge; Ghosez, Philippe

    2017-11-22

    Rare-earth nickelates form an intriguing series of correlated perovskite oxides. Apart from LaNiO 3 , they exhibit on cooling a sharp metal-insulator electronic phase transition, a concurrent structural phase transition, and a magnetic phase transition toward an unusual antiferromagnetic spin order. Appealing for various applications, full exploitation of these compounds is still hampered by the lack of global understanding of the interplay between their electronic, structural, and magnetic properties. Here we show from first-principles calculations that the metal-insulator transition of nickelates arises from the softening of an oxygen-breathing distortion, structurally triggered by oxygen-octahedra rotation motions. The origin of such a rare triggered mechanism is traced back in their electronic and magnetic properties, providing a united picture. We further develop a Landau model accounting for the metal-insulator transition evolution in terms of the rare-earth cations and rationalizing how to tune this transition by acting on oxygen rotation motions.

  12. Phase transitions and adsorbate restructuring at metal surface

    CERN Document Server

    King, DA

    1994-01-01

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

  13. Neutron diffraction studies of transition metal hydride complexes

    International Nuclear Information System (INIS)

    Koetzle, T.F.; Bau, R.

    1976-01-01

    Investigations of H 3 Ta(C 5 H 5 ) 2 (III), HW 2 (CO) 9 (NO) (IV), and HW 2 (CO) 8 (NO) (P(OCH 3 ) 3 ) (V) have been completed. Preliminary results are available for HFeCo 3 (CO) 9 [P(OCH 3 ) 3 ] 3 (VII). This work, together with studies of HMo 2 (C 5 H 5 ) 2 (CO) 4 (P(CH 3 ) 2 ) (VI) and [(C 2 H 5 ) 4 N] + [HCr 2 (CO) 10 ] - carried out at Argonne has led to some general observations on the geometry and the nature of bonding in these compounds. For example, in the structures of IV and V, both of which have bent W--H--W linkages (less than W--H--W in the range 125-130 0 ), there is conclusive evidence for the existence of a closed three-center W--H--W bond with significant metal-metal interaction. Such is the case, because extensions of the axial W--C and W--N bonds trans to the hydride intersect at a point near the center of the W--H--W triangle. The geometry of VI, which also contains a bent M--H--M bond, is consistent with that of IV and V. Bridging M--H bonds in these second- and third-row hydrides range in length from 1.85 to 1.89 A, compared to 1.75 A in the first-row polynuclear complex VII. For metals of corresponding rows, bridging M--H bonds are about 0.1 A longer than terminal bonds, which are classified as single covalent bonds

  14. Emergent magnetism at transition-metal-nanocarbon interfaces.

    Science.gov (United States)

    Al Ma'Mari, Fatma; Rogers, Matthew; Alghamdi, Shoug; Moorsom, Timothy; Lee, Stephen; Prokscha, Thomas; Luetkens, Hubertus; Valvidares, Manuel; Teobaldi, Gilberto; Flokstra, Machiel; Stewart, Rhea; Gargiani, Pierluigi; Ali, Mannan; Burnell, Gavin; Hickey, B J; Cespedes, Oscar

    2017-05-30

    Charge transfer at metallo-molecular interfaces may be used to design multifunctional hybrids with an emergent magnetization that may offer an eco-friendly and tunable alternative to conventional magnets and devices. Here, we investigate the origin of the magnetism arising at these interfaces by using different techniques to probe 3d and 5d metal films such as Sc, Mn, Cu, and Pt in contact with fullerenes and rf-sputtered carbon layers. These systems exhibit small anisotropy and coercivity together with a high Curie point. Low-energy muon spin spectroscopy in Cu and Sc-C 60 multilayers show a quick spin depolarization and oscillations attributed to nonuniform local magnetic fields close to the metallo-carbon interface. The hybridization state of the carbon layers plays a crucial role, and we observe an increased magnetization as sp 3 orbitals are annealed into sp 2 -π graphitic states in sputtered carbon/copper multilayers. X-ray magnetic circular dichroism (XMCD) measurements at the carbon K edge of C 60 layers in contact with Sc films show spin polarization in the lowest unoccupied molecular orbital (LUMO) and higher π*-molecular levels, whereas the dichroism in the σ*-resonances is small or nonexistent. These results support the idea of an interaction mediated via charge transfer from the metal and dz -π hybridization. Thin-film carbon-based magnets may allow for the manipulation of spin ordering at metallic surfaces using electrooptical signals, with potential applications in computing, sensors, and other multifunctional magnetic devices.

  15. Progress in calculations of the superconducting properties of transition metals

    International Nuclear Information System (INIS)

    Butler, W.H.

    1979-01-01

    First principles calculations of the electron--phonon parameters of d-band metals can now be performed to an accuracy of about 10% for averaged quantities such as the mass enhancement or the room temperature resistivity. Quantities such as the spectral function α 2 F(ω) or the phonon linewidth which describe the electron--phonon interaction in more detail can also be calculated. Agreement between calculated and experimental phonon linewidths is generally good but there are differences between the experimental and calculated versions of α 2 F(ω). Calculations of the thermodynamic critical field and the upper critical field for Nb agree well with experiment

  16. Bond ionicity in crystals of transition metal compounds

    International Nuclear Information System (INIS)

    Kesler, Ya.A.

    1989-01-01

    A unified method of calculating bond ionicity in inorganic crystals is suggested. The approach presented envisages the sealing of d-electron contribution to ξ,p-electron contribution for the retention of community which can only be implemented by a self-consistent procedure. The results of self-consistent calculations of bond parameters of a number of crystals (ScN, Sc 2 O 3 , In 2 O 3 , J 2 O 3 ) as compared with the data for ξ,p-analogues are given. Ionicity changes in the series of analogous compounds utterly correspond to existing chemical concepts. The data for oxides of 4d-, 5d-elements (ZrO 2 , CeO 2 , ThO 2 ) and for a number of ternary compounds containing two types of bonds (LiNbO 3 , CdSc 2 S 4 , CdCr 2 Se 4 etc) are also given. In the case of transition elements ionicity to a great extent depends on the symmetry of anion environment and correlates to orbital population well. Ionicity values are in direct proportion to effective charges of atoms of transition elements

  17. Biotransformation of uranium and transition metal citrate complexes by clostridia

    International Nuclear Information System (INIS)

    Francis, A.J.; Joshi-Tope, G.A.; Dodge, C.J.; Gillow, J.B.

    2002-01-01

    Clostridium sphenoides, which uses citric acid as its sole carbon source, metabolized equimolar Fe(III)-citrate with the degradation of citric acid and the reduction of Fe(III) to Fe(II), but not the U(VI)-citrate complex. However, in the presence of excess citric acid or added glucose it was reduced to U(IV)-citrate. In contrast, Clostridium sp., which ferments glucose but not citrate, reduced Fe(III)-citrate to Fe(II)-citrate and U(VI)-citrate to U(IV)-citrate only when supplied with glucose. These results show that complexed uranium is readily accessible as an electron acceptor despite the bacterium's inability to metabolize the organic ligand complexed to the actinide. These results also show that the metabolism of the metal-citrate complex depends upon the type of complex formed between the metal and citric acid. Fe(III) forms a bidentate complex with citric acid and was metabolized, whereas U forms a binuclear complex with citric acid and was recalcitrant. (author)

  18. Chemical bonding of hydrogen molecules to transition metal complexes

    International Nuclear Information System (INIS)

    Kubas, G.J.

    1990-01-01

    The complex W(CO) 3 (PR 3 ) 2 (H 2 ) (CO = carbonyl; PR 3 = organophosphine) was prepared and was found to be a stable crystalline solid under ambient conditions from which the hydrogen can be reversibly removed in vacuum or under an inert atmosphere. The weakly bonded H 2 exchanges easily with D 2 . This complex represents the first stable compound containing intermolecular interaction of a sigma-bond (H-H) with a metal. The primary interaction is reported to be donation of electron density from the H 2 bonding electron pair to a vacant metal d-orbital. A series of complexes of molybdenum of the type Mo(CO)(H 2 )(R 2 PCH 2 CH 2 PR 2 ) 2 were prepared by varying the organophosphine substitutent to demonstrate that it is possible to bond either dihydrogen or dihydride by adjusting the electron-donating properties of the co-ligands. Results of infrared and NMR spectroscopic studies are reported. 20 refs., 5 fig

  19. 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

  20. 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

  1. Electronic and thermodynamic properties of the transition between metallic and nonmetallic states in dense media

    International Nuclear Information System (INIS)

    Fortin, Xavier

    1971-01-01

    The effects of thermal excitation are introduced in the study of a simple electronic structure model for condensed media. The choice of a particle-interaction potential leads to a self-consistent calculation performed on a computer. This calculation gives a metal - nonmetal transition similar to the MOTT transition. We consider the effects of temperature and density variations upon this transition. It is possible to make use of this electronic structure to obtain the thermodynamic properties near the transition: pressure, free energy, sound velocity. The numerical results of this simple model are satisfactory. Particularly, if a dielectric constant is taken into account, the transition temperature and density are of the same order of magnitude as those observed experimentally in semiconductors. (author) [fr

  2. Metal-Insulator Transition Revisited for Cold Atoms in Non-Abelian Gauge Potentials

    International Nuclear Information System (INIS)

    Satija, Indubala I.; Dakin, Daniel C.; Clark, Charles W.

    2006-01-01

    We discuss the possibility of realizing metal-insulator transitions with ultracold atoms in two-dimensional optical lattices in the presence of artificial gauge potentials. For Abelian gauges, such transitions occur when the magnetic flux penetrating the lattice plaquette is an irrational multiple of the magnetic flux quantum. Here we present the first study of these transitions for non-Abelian U(2) gauge fields. In contrast to the Abelian case, the spectrum and localization transition in the non-Abelian case is strongly influenced by atomic momenta. In addition to determining the localization boundary, the momentum fragments the spectrum. Other key characteristics of the non-Abelian case include the absence of localization for certain states and satellite fringes around the Bragg peaks in the momentum distribution and an interesting possibility that the transition can be tuned by the atomic momenta

  3. Reactivity patterns of transition metal hydrides and alkyls

    International Nuclear Information System (INIS)

    Jones, W.D. II.

    1979-05-01

    The complex PPN + CpV(CO) 3 H - (Cp=eta 5 -C 5 H 5 and PPN = (Ph 3 P) 2 ) was prepared in 70% yield and its physical properties and chemical reactions investigated. PPN + CpV(CO) 3 H - reacts with a wide range of organic halides. The organometallic products of these reactions are the vanadium halides PPN + [CpV(C) 3 X] - and in some cases the binuclear bridging hydride PPN + [CpV(CO) 3 ] 2 H - . The borohydride salt PPN + [CpV(CO) 3 BH 4 ] - has also been prepared. The reaction between CpV(CO) 3 H - and organic halides was investigated and compared with halide reductions carried out using tri-n-butyltin hydride. Results demonstrate that in almost all cases, the reduction reaction proceeds via free radical intermediates which are generated in a chain process, and are trapped by hydrogen transfer from CpV(CO) 3 H - . Sodium amalgam reduction of CpRh(CO) 2 or a mixture of CpRh(CO) 2 and CpCo(CO) 2 affords two new anions, PPN + [Cp 2 Rh 3 (CO) 4 ] - and PPN + [Cp 2 RhCo(CO) 2 ] - . CpMo(CO) 3 H reacts with CpMo(CO) 3 R (R=CH 3 ,C 2 H 5 , CH 2 C 6 H 5 ) at 25 to 50 0 C to produce aldehyde RCHO and the dimers [CpMo(CO) 3 ] 2 and [CpMo(CO) 2 ] 2 . In general, CpV(CO) 3 H - appears to transfer a hydrogen atom to the metal radical anion formed in an electron transfer process, whereas CpMo(CO) 3 H transfers hydride in a 2-electron process to a vacant coordination site. The chemical consequences are that CpV(CO) 3 H - generally reacts with metal alkyls to give alkanes via intermediate alkyl hydride species whereas CpMo(CO) 3 H reacts with metal alkyls to produce aldehyde, via an intermediate acyl hydride species

  4. Reactivity patterns of transition metal hydrides and alkyls

    Energy Technology Data Exchange (ETDEWEB)

    Jones, W.D. II

    1979-05-01

    The complex PPN/sup +/ CpV(CO)/sub 3/H/sup -/ (Cp=eta/sup 5/-C/sub 5/H/sub 5/ and PPN = (Ph/sub 3/P)/sub 2/) was prepared in 70% yield and its physical properties and chemical reactions investigated. PPN/sup +/ CpV(CO)/sub 3/H/sup -/ reacts with a wide range of organic halides. The organometallic products of these reactions are the vanadium halides PPN/sup +/(CpV(C)/sub 3/X)/sup -/ and in some cases the binuclear bridging hydride PPN/sup +/ (CpV(CO)/sub 3/)/sub 2/H/sup -/. The borohydride salt PPN/sup +/(CpV(CO)/sub 3/BH/sub 4/)/sup -/ has also been prepared. The reaction between CpV(CO)/sub 3/H/sup -/ and organic halides was investigated and compared with halide reductions carried out using tri-n-butyltin hydride. Results demonstrate that in almost all cases, the reduction reaction proceeds via free radical intermediates which are generated in a chain process, and are trapped by hydrogen transfer from CpV(CO)/sub 3/H/sup -/. Sodium amalgam reduction of CpRh(CO)/sub 2/ or a mixture of CpRh(CO)/sub 2/ and CpCo(CO)/sub 2/ affords two new anions, PPN/sup +/ (Cp/sub 2/Rh/sub 3/(CO)/sub 4/)/sup -/ and PPN/sup +/(Cp/sub 2/RhCo(CO)/sub 2/)/sup -/. CpMo(CO)/sub 3/H reacts with CpMo(CO)/sub 3/R (R=CH/sub 3/,C/sub 2/H/sub 5/, CH/sub 2/C/sub 6/H/sub 5/) at 25 to 50/sup 0/C to produce aldehyde RCHO and the dimers (CpMo(CO)/sub 3/)/sub 2/ and (CpMo(CO)/sub 2/)/sub 2/. In general, CpV(CO)/sub 3/H/sup -/ appears to transfer a hydrogen atom to the metal radical anion formed in an electron transfer process, whereas CpMo(CO)/sub 3/H transfers hydride in a 2-electron process to a vacant coordination site. The chemical consequences are that CpV(CO)/sub 3/H/sup -/ generally reacts with metal alkyls to give alkanes via intermediate alkyl hydride species whereas CpMo(CO)/sub 3/H reacts with metal alkyls to produce aldehyde, via an intermediate acyl hydride species.

  5. 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.

  6. Transition radiation in metal-metal multilayer nanostructures as a medical source of hard x-ray radiation

    International Nuclear Information System (INIS)

    Pokrovsky, A. L.; Kaplan, A. E.; Shkolnikov, P. L.

    2006-01-01

    We show that a periodic metal-metal multilayer nanostructure can serve as an efficient source of hard x-ray transition radiation. Our research effort is aimed at developing an x-ray source for medical applications, which is based on using low-energy relativistic electrons. The approach toward choosing radiator-spacer couples for the generation of hard x-ray resonant transition radiation by few-MeV electrons traversing solid multilayer structures for the energies of interest to medicine (30-50 keV) changes dramatically compared with that for soft x-ray radiation. We show that one of the main factors in achieving the required resonant line is the absence of the contrast of the refractive indices between the spacer and the radiator at the far wings of the radiation line; for that purpose, the optimal spacer, as a rule, should have a higher atomic number than the radiator. Having experimental goals in mind, we have considered also the unwanted effects due to bremsstrahlung radiation, absorption and scattering of radiated photons, detector-related issues, and inhibited coherence of transition radiation due to random deviation of spacing between the layers. Choosing as a model example a Mo-Ag radiator-spacer pair of materials, we demonstrate that the x-ray transition radiation line can be well resolved with the use of spatial and frequency filtering

  7. Critical sizes and critical characteristics of nanoclusters, nanostructures and nanomaterials

    International Nuclear Information System (INIS)

    Suzdalev, I.P.

    2005-01-01

    Full text: Critical sizes and characteristics of nanoclusters and nanostructures are introduced as the parameters of nanosystems and nanomaterials. The next critical characteristics are considered: atomic and electronic 'magic number', critical size of cluster nucleation, critical size of melting-freezing of cluster, critical size of quantum (laser) radiation, critical sizes for the single electron conductivity, critical energy and magnetic field for the magnetic tunneling, critical cluster sizes for the giant magnetic resistance, critical size of the first order magnetic phase transition. The critical characteristics are estimated by thermodynamic approaches, by Moessbauer spectroscopy, AFM, heat capacity, SQUID magnetometry and other technique, The influence of cluster-cluster interactions, cluster-matrix interactions and cluster defects on cluster atomic dynamics, cluster melting, cluster critical sizes, Curie or Neel points and the character of magnetic phase transitions were investigated. The applications of critical size and critical characteristic parameters for the nanomaterial characterization are considered

  8. Derivatized Pentadentate Macrocyclic Ligands and Their Transition Metal Complexes

    Directory of Open Access Journals (Sweden)

    Muhammad S. Khan

    2002-06-01

    Full Text Available The reaction of the pendant hydroxyethyl group in the planar pentadentate macrocyclic ligand,1,11-bis(2’-hydroxyethyl-4,8;12,16;17,21-trinitrilo-1,2,10,11-tetraazacyclohenicosa- 2,4,6,9,12,14,18,20-octaene (L2, derived from the condensation of 2,6-pyridinedialdehyde with 6,6’-bis(2’ hydroxyethylhydrazino -2,2’-bipyridine (L1, has been investigated. Esterification reactions are facile, and the reaction of the hydroxyethyl-substituted macrocycle with thionyl chloride yields a chloroethyl derivative. Metal complexes of the new derivatized macrocyclic ligands L3-6having general formula ML3-6X2.nH2O (M = Mn, Fe, Co, Ni, Cu, Zn are readily prepared.

  9. Neutron spectroscopy of fast hydrogen diffusion in BCC transition metals

    International Nuclear Information System (INIS)

    Richter, D.; Lottner, V.

    1979-01-01

    Quasielastic neutron scattering reveals microscopic details of both the time and space development of the H-diffusion process on an atomic scale. After outlining the method on the example of PdH/sub x/, new results on the jump geometry in bcc metals are surveyed. In particular, the anomalous diffusion behavior of H in Nb, Ta, and V at elevated temperature is emphasized, where correlated jump processes are important. The influence of impurities on the H-diffusion process is demonstrated by experiments performed on NbH/sub x/ doped with nitrogen impurities, which act as trapping centers for the diffusing hydrogen. The results are discussed in terms of a two-state random walk model which includes multiple trapping and detrapping processes. The concentration and temperature dependence of the capture and escape rates of traps are obtained

  10. Ultramicrosensors based on transition metal hexacyanoferrates for scanning electrochemical microscopy

    Directory of Open Access Journals (Sweden)

    Maria A. Komkova

    2013-10-01

    Full Text Available We report here a way for improving the stability of ultramicroelectrodes (UME based on hexacyanoferrate-modified metals for the detection of hydrogen peroxide. The most stable sensors were obtained by electrochemical deposition of six layers of hexacyanoferrates (HCF, more specifically, an alternating pattern of three layers of Prussian Blue and three layers of Ni–HCF. The microelectrodes modified with mixed layers were continuously monitored in 1 mM hydrogen peroxide and proved to be stable for more than 5 h under these conditions. The mixed layer microelectrodes exhibited a stability which is five times as high as the stability of conventional Prussian Blue-modified UMEs. The sensitivity of the mixed layer sensor was 0.32 A·M−1·cm−2, and the detection limit was 10 µM. The mixed layer-based UMEs were used as sensors in scanning electrochemical microscopy (SECM experiments for imaging of hydrogen peroxide evolution.

  11. Formation of ring-patterned nanoclusters by laser–plume interaction

    International Nuclear Information System (INIS)

    Sivayoganathan, Mugunthan; Tan Bo; Venkatakrishnan, Krishnan

    2013-01-01

    This article reports for the first time a unique study performed to regulate the ring diameter of nanoclusters fabricated during femtosecond laser ablation of solids and a mechanism is proposed for the formation of those ring clusters. The ring nanoclusters are made out of nanoparticles with a range of 10–30 nm. Our experimental studies showed the synthesis of ring nanoclusters with random diameter distribution on metals, nonmetals, and semiconductors, such as titanium, aluminum, glasses, ceramics, graphite, and silicon. To regulate the ring size, the effects of laser parameters, such as wavelength, pulse duration, pulse energy, and repetition rate on the ring diameter are analyzed. The influence of ablated materials and the background gas on ring size is also elaborated in this article. The motion of plume species under the influence of ponderomotive force on free electrons possibly played a key role in the formation of the ring-patterned nanoclusters. This study could help to understand the fundamentals in laser ablative nanosynthesis as well as to produce nanostructures with organized ring diameter that controls the density and porosity of those 3D nanostructures.

  12. 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

  13. 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...

  14. 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.

  15. 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.

  16. 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.

  17. 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

  18. 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.

  19. 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 ...

  20. 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

  1. Topotactic Metal-Insulator Transition in Epitaxial SrFeO x Thin Films

    International Nuclear Information System (INIS)

    Khare, Amit; Shin, Dongwon; Yoo, Tae Sup; Kim, Minu; Kang, Tae Dong

    2017-01-01

    Multivalent transition metal oxides provide fascinating and rich physics related to oxygen stoichiometry. In particular, the adoptability of various valence states of transition metals enables perovskite oxides to display mixed (oxygen) ionic and electronic conduction and catalytic activity useful in many practical applications, including solid-oxide fuel cells (SOFCs), rechargeable batteries, gas sensors, and memristive devices. For proper realization of the ionic conduction and catalytic activity, it is essential to understand the reversible oxidation and reduction process, which is governed by oxygen storage/release steps in oxides. Topotactic phase transformation facilitates the redox process in perovskites with specific oxygen vacancy ordering by largely varying the oxygen concentration of a material without losing the lattice framework. The concentration and diffusion of oxide ions (O 2– ), the valence state of the transition metal cations, and the thermodynamic structural integrity together provide fundamental understanding and ways to explicitly control the redox reaction.[6] In addition, it offers an attractive route for tuning the emergent physical properties of transition metal oxides, via strong coupling between the crystal lattice and electronic structure.

  2. Distorted wave approach to calculate Auger transition rates of ions in metals

    Energy Technology Data Exchange (ETDEWEB)

    Deutscher, Stefan A. E-mail: sad@utk.edu; Diez Muino, R.; Arnau, A.; Salin, A.; Zaremba, E

    2001-08-01

    We evaluate the role of target distortion in the determination of Auger transition rates for multicharged ions in metals. The required two electron matrix elements are calculated using numerical solutions of the Kohn-Sham equations for both the bound and continuum states. Comparisons with calculations performed using plane waves and hydrogenic orbitals are presented.

  3. 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.

  4. 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...

  5. 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

  6. 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...

  7. 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

  8. 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

  9. 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)

  10. 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

  11. 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...

  12. 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

  13. 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

  14. 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

  15. Thermal battery. [solid metal halide electrolytes with enhanced electrical conductance after a phase transition

    Science.gov (United States)

    Carlsten, R.W.; Nissen, D.A.

    1973-03-06

    The patent describes an improved thermal battery whose novel design eliminates various disadvantages of previous such devices. Its major features include a halide cathode, a solid metal halide electrolyte which has a substantially greater electrical conductance after a phase transition at some temperature, and a means for heating its electrochemical cells to activation temperature.

  16. 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

  17. 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...

  18. 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.

  19. 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

  20. 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...