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Sample records for metal cations electronic

  1. The electronic structure of vanadium monochloride cation (VCl+): Tackling the complexities of transition metal species

    DeYonker, Nathan J.; Halfen, DeWayne T.; Allen, Wesley D.; Ziurys, Lucy M.

    2014-11-01

    Six electronic states (X 4Σ-, A 4Π, B 4Δ, 2Φ, 2Δ, 2Σ+) of the vanadium monochloride cation (VCl+) are described using large basis set coupled cluster theory. For the two lowest quartet states (X 4Σ- and A 4Π), a focal point analysis (FPA) approach was used that conjoined a correlation-consistent family of basis sets up to aug-cc-pwCV5Z-DK with high-order coupled cluster theory through pentuple (CCSDTQP) excitations. FPA adiabatic excitation energies (T0) and spectroscopic constants (re, r0, Be, B0, bar De, He, ωe, v0, αe, ωexe) were extrapolated to the valence complete basis set Douglas-Kroll (DK) aug-cc-pV∞Z-DK CCSDT level of theory, and additional treatments accounted for higher-order valence electron correlation, core correlation, and spin-orbit coupling. Due to the delicate interplay between dynamical and static electronic correlation, single reference coupled cluster theory is able to provide the correct ground electronic state (X 4Σ-), while multireference configuration interaction theory cannot. Perturbations from the first- and second-order spin orbit coupling of low-lying states with quartet spin multiplicity reveal an immensely complex rotational spectrum relative to the isovalent species VO, VS, and TiCl. Computational data on the doublet manifold suggest that the lowest-lying doublet state (2Γ) has a Te of ˜11 200 cm-1. Overall, this study shows that laboratory and theoretical rotational spectroscopists must work more closely in tandem to better understand the bonding and structure of molecules containing transition metals.

  2. The electronic structure of vanadium monochloride cation (VCl{sup +}): Tackling the complexities of transition metal species

    DeYonker, Nathan J., E-mail: ndyonker@memphis.edu [Department of Chemistry, The University of Memphis, Memphis, Tennessee 38152 (United States); Halfen, DeWayne T.; Ziurys, Lucy M. [Department of Chemistry, Department of Astronomy, Arizona Radio Observatory, and Steward Observatory, University of Arizona, Tucson, Arizona 85721 (United States); Allen, Wesley D. [Department of Chemistry and Center for Computational Chemistry, University of Georgia, Athens, Georgia 30602 (United States)

    2014-11-28

    Six electronic states (X {sup 4}Σ{sup −}, A {sup 4}Π, B {sup 4}Δ, {sup 2}Φ, {sup 2}Δ, {sup 2}Σ{sup +}) of the vanadium monochloride cation (VCl{sup +}) are described using large basis set coupled cluster theory. For the two lowest quartet states (X {sup 4}Σ{sup −} and A {sup 4}Π), a focal point analysis (FPA) approach was used that conjoined a correlation-consistent family of basis sets up to aug-cc-pwCV5Z-DK with high-order coupled cluster theory through pentuple (CCSDTQP) excitations. FPA adiabatic excitation energies (T{sub 0}) and spectroscopic constants (r{sub e}, r{sub 0}, B{sub e}, B{sub 0}, D{sup ¯}{sub e}, H{sub e}, ω{sub e}, v{sub 0}, α{sub e}, ω{sub e}x{sub e}) were extrapolated to the valence complete basis set Douglas-Kroll (DK) aug-cc-pV∞Z-DK CCSDT level of theory, and additional treatments accounted for higher-order valence electron correlation, core correlation, and spin-orbit coupling. Due to the delicate interplay between dynamical and static electronic correlation, single reference coupled cluster theory is able to provide the correct ground electronic state (X {sup 4}Σ{sup −}), while multireference configuration interaction theory cannot. Perturbations from the first- and second-order spin orbit coupling of low-lying states with quartet spin multiplicity reveal an immensely complex rotational spectrum relative to the isovalent species VO, VS, and TiCl. Computational data on the doublet manifold suggest that the lowest-lying doublet state ({sup 2}Γ) has a T{sub e} of ∼11 200 cm{sup −1}. Overall, this study shows that laboratory and theoretical rotational spectroscopists must work more closely in tandem to better understand the bonding and structure of molecules containing transition metals.

  3. Properties of solvated electrons, alkali anions and other species in metal solutions and kinetics of cation and electron exchange reactions. Final report

    Dye, J.L.

    1979-01-01

    The properties of solutions of alkali metals in amine solvents were studied by optical, ETR, NMR and electrochemical methods. Complexation of the alkali cations by crown ethers and cryptands permitted the preparation of concentrated solutions of alkali metals in amine and ether solvents. Extensive alkali metal NMR studies of the exchange of M + with crown-ethers and cryptands and of the alkali metal anion, M - , were made. The first crystalline salt of an alkali metal anion, Na + Cryptand [2.2.2]Na - was synthesized and characterized and led to the preparation of other alkali metal anion salts. This research provided the foundation for continuing studies of crystalline alkalide salts

  4. ADSORPTION METHOD FOR SEPARATING METAL CATIONS

    Khym, J.X.

    1959-03-10

    The chromatographic separation of fission product cations is discussed. By use of this method a mixture of metal cations containing Zr, Cb, Ce, Y, Ba, and Sr may be separated from one another. Mentioned as preferred exchange adsorbents are resins containing free sulfonic acid groups. Various eluants, such as tartaric acid, HCl, and citric acid, used at various acidities, are employed to effect the selective elution and separation of the various fission product cations.

  5. Liquid-solid extraction of cationic metals by cationic amphiphiles

    Muller, W.

    2010-01-01

    In the field of selective separation for recycling of spent nuclear fuel, liquid-liquid extraction processes are widely used (PUREX, DIAMEX..) in industrial scale. In order to guarantee a sustainable nuclear energy for the forthcoming generations, alternative reprocessing techniques are under development. One of them bases on the studies from Heckmann et al in the 80's and consists in selectively precipitating actinides from aqueous waste solutions by cationic surfactants (liquid-solid extraction). This technique has some interesting advantages over liquid-liquid extraction techniques, because several steps are omitted like stripping or solvent washing. Moreover, the amount of waste is decreased considerably, since no contaminated organic solvent is produced. In this thesis, we have carried out a physico-chemical study to understand the specific interactions between the metallic cations with the cationic surfactant. First, we have analysed the specific effect of the different counter-ions (Cl - , NO 3 - , C 2 O 4 2- ) and then the effect of alkaline cations on the structural properties of the surfactant aggregation in varying thermodynamical conditions. Finally, different multivalent cations (Cu 2+ , Zn 2+ , UO 2 2+ , Fe 3+ , Nd 3+ , Eu 3+ , Th 4+ ) were considered; we have concluded that depending on the anionic complex of these metals formed in acidic media, we can observe either an adsorption at the micellar interface or not. This adsorption has a large influence of the surfactant aggregation properties and determines the limits of the application in term of ionic strength, temperature and surfactant concentration. (author) [fr

  6. Surfactant modified zeolite as amphiphilic and dual-electronic adsorbent for removal of cationic and oxyanionic metal ions and organic compounds.

    Tran, Hai Nguyen; Viet, Pham Van; Chao, Huan-Ping

    2018-01-01

    A hydrophilic Y zeolite was primarily treated with sodium hydroxide to enhance its cation exchange capacity (Na-zeolite). The organo-zeolite (Na-H-zeolite) was prepared by a modification process of the external surface of Na-zeolite with a cationic surfactant (hexadecyltrimethylammonium; HDTMA). Three adsorbents (i.e., pristine zeolite, Na-zeolite, and Na-H-zeolite) were characterized with nitrogen adsorption/desorption isotherms, scanning electron microscopy coupled with energy dispersive X-ray spectroscopy, cation exchange capacities, and zeta potential. Results demonstrated that HDTMA can be adsorbed on the surface of Na-zeolite to form patchy bilayers. The adsorption capacity of several hazardous pollutants (i.e., Pb 2+ , Cu 2+ , Ni 2+ , Cr 2 O 7 2- , propylbenzene, ethylbenzene, toluene, benzene, and phenol) onto Na-H-zeolite was investigated in a single system and multiple-components. Adsorption isotherm was measured to further understand the effects of the modification process on the adsorption behaviors of Na-H-zeolite. Adsorption performances indicated that Na-H-zeolite can simultaneously adsorb the metal cations (on the surface not covered by HDTMA), oxyanions (on the surface covered by HDTMA). Na-H-zeolite also exhibited both hydrophilic and hydrophobic surfaces to uptake organic compounds with various water solubilities (from 55 to 75,000mg/L). It was experimentally concluded that Na-H-zeolite is a potential dual-electronic and amphiphilic adsorbent for efficiently removing a wide range of potentially toxic pollutants from aquatic environments. Copyright © 2017 Elsevier Inc. All rights reserved.

  7. Liquid-solid extraction of metallic cations by cationic amphiphiles

    Mueller, Wolfram; Sievers, Torsten K.; Zemb, Thomas; Diat, Olivier; Sievers, Torsten K.; Dejugnat, Christophe

    2012-01-01

    In the field of selective metal ion separation, liquid-liquid extraction is usually conducted through an emulsion mixing of hydrophobic complexants dispersed in an organic phase and acidic water containing the ionic species. Recently, it has been shown that amphiphilic complexants could influence strongly extraction efficiency by enhancing the interfacial interaction between the metal ion in the aqueous and the complexant in the organic phase. Moreover, these amphiphiles can also substitute the organic phase if an appropriate aliphatic chain is chosen. The dispersion of such amphiphilic complexants in an aqueous solution of salt mixtures is not only attractive for studying specific interactions but also to better the understanding of complex formation in aqueous solution of multivalent metal ions, such as lanthanides and actinides. This understanding is of potential interest for a broad range of industries including purification of rare earth metals and pollute treatment e.g. of fission byproducts. This principle can also be applied to liquid-solid extraction, where the final state of the separation is a solid phase containing the selectively extracted ions. Indeed, a novel solid-liquid extraction method exploits the selective precipitation of metal ions from an aqueous salt mixture using a cationic surfactant, below its Krafft point (temperature below which the long aliphatic chains of surfactant crystallize). This technique has been proven to be highly efficient for the separation of actinides and heavy metal using long chain ammonium or pyridinium amphiphiles. The most important point in this process is the recognition of cationic metal ions by cationic surfactants. By computing the free energy of the polar head group per micelle as a function of the different counter-anions, we have demonstrated for the first time that different interactions exist between the micellar surface and the ions. These interactions depend on the nature of the cation but also on

  8. Electronic spectra of astrophysically interesting cations

    Maier, John P., E-mail: j.p.maier@unibas.ch; Rice, Corey A., E-mail: j.p.maier@unibas.ch; Mazzotti, Fabio J., E-mail: j.p.maier@unibas.ch; Johnson, Anatoly, E-mail: j.p.maier@unibas.ch [Department of Chemistry, University of Basel, Klingelbergstr. 80, CH-4056 Basel (Switzerland)

    2015-01-22

    The electronic spectra of polyacetylene cations were recorded at 20K in the laboratory in an ion trap instrument. These can then be compared with diffuse interstellar band (DIB) absorptions. Examination of recently published data shows that the attribution of a weak DIB at ∼506.9 nm to diacetylene cation is not justified. Study of the higher excited electronic states of polyacetylene cations shows that their widths can still be sufficiently narrow for consideration as DIB carriers.

  9. Heavy metal cations permeate the TRPV6 epithelial cation channel.

    Kovacs, Gergely; Danko, Tamas; Bergeron, Marc J; Balazs, Bernadett; Suzuki, Yoshiro; Zsembery, Akos; Hediger, Matthias A

    2011-01-01

    TRPV6 belongs to the vanilloid family of the transient receptor potential channel (TRP) superfamily. This calcium-selective channel is highly expressed in the duodenum and the placenta, being responsible for calcium absorption in the body and fetus. Previous observations have suggested that TRPV6 is not only permeable to calcium but also to other divalent cations in epithelial tissues. In this study, we tested whether TRPV6 is indeed also permeable to cations such as zinc and cadmium. We found that the basal intracellular calcium concentration was higher in HEK293 cells transfected with hTRPV6 than in non-transfected cells, and that this difference almost disappeared in nominally calcium-free solution. Live cell imaging experiments with Fura-2 and NewPort Green DCF showed that overexpression of human TRPV6 increased the permeability for Ca(2+), Ba(2+), Sr(2+), Mn(2+), Zn(2+), Cd(2+), and interestingly also for La(3+) and Gd(3+). These results were confirmed using the patch clamp technique. (45)Ca uptake experiments showed that cadmium, lanthanum and gadolinium were also highly efficient inhibitors of TRPV6-mediated calcium influx at higher micromolar concentrations. Our results suggest that TRPV6 is not only involved in calcium transport but also in the transport of other divalent cations, including heavy metal ions, which may have toxicological implications. Copyright © 2010 Elsevier Ltd. All rights reserved.

  10. Complexes of natural carbohydrates with metal cations

    Alekseev, Yurii E; Garnovskii, Alexander D; Zhdanov, Yu A

    1998-01-01

    Data on the interaction of natural carbohydrates (mono-, oligo-, and poly-saccharides, amino sugars, and natural organic acids of carbohydrate origin) with metal cations are surveyed and described systematically. The structural diversity of carbohydrate metal complexes, caused by some specific features of carbohydrates as ligands, is demonstrated. The influence of complex formation on the chemical properties of carbohydrates is discussed. It is shown that the formation of metal complexes plays an important role in the configurational and conformational analysis of carbohydrates. The practical significance of the coordination interaction in the series of carbohydrate ligands is demonstrated. The bibliography includes 571 references.

  11. Long-range electron transfer in porphyrin-containing [2]-rotaxanes: tuning the rate by metal cation coordination.

    Andersson, Mikael; Linke, Myriam; Chambron, Jean-Claude; Davidsson, Jan; Heitz, Valérie; Hammarström, Leif; Sauvage, Jean-Pierre

    2002-04-24

    A series of [2]-rotaxanes has been synthesized in which two Zn(II)-porphyrins (ZnP) electron donors were attached as stoppers on the rod. A macrocycle attached to a Au(III)-porphyrin (AuP+) acceptor was threaded on the rod. By selective excitation of either porphyrin, we could induce an electron transfer from the ZnP to the AuP+ unit that generated the same ZnP*+-AuP* charge-transfer state irrespective of which porphyrin was excited. Although the reactants were linked only by mechanical or coordination bonds, electron-transfer rate constants up to 1.2x10(10) x s(-1) were obtained over a 15-17 A edge-to-edge distance between the porphyrins. The resulting charge-transfer state had a relatively long lifetime of 10-40 ns and was formed in high yield (>80%) in most cases. By a simple variation of the link between the reactants, viz. a coordination of the phenanthroline units on the rotaxane rod and ring by either Ag+ or Cu+, we could enhance the electron-transfer rate from the ZnP to the excited 3AuP+. We interpret our data in terms of an enhanced superexchange mechanism with Ag+ and a change to a stepwise hopping mechanism with Cu+, involving the oxidized Cu(phen)22+ unit as a real intermediate. When the ZnP unit was excited instead, electron transfer from the excited 1ZnP to AuP+ was not affected, or even slowed, by Ag+ or Cu+. We discuss this asymmetry in terms of the different orbitals involved in mediating the reaction in an electron- and a hole-transfer mechanism. Our results show the possibility to tune the rates of electron transfer between noncovalently linked reactants by a convenient modification of the link. The different effect of Ag+ and Cu+ on the rate with ZnP and AuP+ excitation shows an additional possibility to control the electron-transfer reactions by selective excitation. We also found that coordination of the Cu+ introduced an energy-transfer reaction from 1ZnP to Cu(phen)2+ (k = 5.1x10(9) x s(-1)) that proceeded in competition with electron

  12. Electronic spectrum of 9-methylanthracenium radical cation

    O’Connor, Gerard D.; Schmidt, Timothy W., E-mail: timothy.schmidt@unsw.edu.au [School of Chemistry, UNSW Sydney, New South Wales 2052 (Australia); Sanelli, Julian A.; Dryza, Vik; Bieske, Evan J. [School of Chemistry, The University of Melbourne, Victoria 3010 (Australia)

    2016-04-21

    The predissociation spectrum of the cold, argon-tagged, 9-methylanthracenium radical cation is reported from 8000 cm{sup −1} to 44 500 cm{sup −1}. The reported spectrum contains bands corresponding to at least eight electronic transitions ranging from the near infrared to the ultraviolet. These electronic transitions are assigned through comparison with ab initio energies and intensities. The infrared D{sub 1}←D{sub 0} transitions exhibit significant vibronic activity, which is assigned through comparison with TD-B3LYP excited state frequencies and intensities, as well as modelled vibronic interactions. Dissociation of 9-methylanthracenium is also observed at high visible-photon energies, resulting in the loss of either CH{sub 2} or CH{sub 3}. The relevance of these spectra, and the spectra of other polycyclic aromatic hydrocarbon radical cations, to the largely unassigned diffuse interstellar bands, is discussed.

  13. The Metal Cation Chelating Capacity of Astaxanthin. Does This Have Any Influence on Antiradical Activity?

    Ana Martínez

    2012-01-01

    Full Text Available In this Density Functional Theory study, it became apparent that astaxanthin (ASTA may form metal ion complexes with metal cations such as Ca+2, Cu+2, Pb+2, Zn+2, Cd+2 and Hg+2. The presence of metal cations induces changes in the maximum absorption bands which are red shifted in all cases. Therefore, in the case of compounds where metal ions are interacting with ASTA, they are redder in color. Moreover, the antiradical capacity of some ASTA-metal cationic complexes was studied by assessing their vertical ionization energy and vertical electron affinity, reaching the conclusion that metal complexes are slightly better electron donors and better electron acceptors than ASTA.

  14. IR spectroscopy of cationized aliphatic amino acids: Stability of charge-solvated structure increases with metal cation size

    Drayss, M. K.; Armentrout, P. B.; Oomens, J.; Schaefer, M.

    2010-01-01

    Gas-phase structures of alkali metal cationized (Li+, Na+,K+, Rb+, and Cs+) proline (Pro) and N-methyl alanine have been investigated using infrared multiple photon dissociation (IRMPD) spectroscopy utilizing light generated by a free electron laser and computational modeling. Measured IRMPD spectra

  15. IR spectroscopy of cationized aliphatic amino acids: Stability of charge-solvated structure increases with metal cation size

    Drayß, M.K.; Armentrout, P.B.; Oomens, J.; Schäfer, M.

    2010-01-01

    Gas-phase structures of alkali metal cationized (Li+, Na+, K+, Rb+, and Cs+) proline (Pro) and N-methyl alanine have been investigated using infrared multiple photon dissociation (IRMPD) spectroscopy utilizing light generated by a free electron laser and computational modeling. Measured IRMPD

  16. Uranyl oxo activation and functionalization by metal cation coordination

    Arnold Polly, L.; Pecharman, A. F.; Hollis, E.; Parsons, S.; Love, J. B.; Yahia, A.; Maron, L.; Yahia, A.; Maron, L.

    2010-01-01

    The oxo groups in the uranyl ion [UO 2 ] 2+ - one of many oxo cations formed by metals from across the periodic table - are particularly inert, which explains the dominance of this ion in the laboratory and its persistence as an environmental contaminant. In contrast, transition metal oxo (M=O) compounds can be highly reactive and carry out difficult reactions such as the oxygenation of hydrocarbons. Here we show how the sequential addition of a lithium metal base to the uranyl ion constrained in a 'Pacman' environment results in lithium coordination to the U=O bonds and single-electron reduction. This reaction depends on the nature and stoichiometry of the lithium reagent and suggests that competing reduction and C-H bond activation reactions are occurring. (authors)

  17. Uranyl oxo activation and functionalization by metal cation coordination

    Arnold Polly, L; Pecharman, A F; Hollis, E; Parsons, S; Love, J B [Univ Edinburgh, EaStCHEM Sch Chem, Edinburgh EH9 3JJ, Midlothian (United Kingdom); Yahia, A; Maron, L [Univ Toulouse 3, LPCNO, UMR 5215, INSA, CNRS, F-31077 Toulouse 4 (France); Yahia, A; Maron, L [Univ Montpellier 2, ENSCM, CNRS, ICSM, UMR 5257, CEA, Ctr Marcoule, F-30207 Bagnols Sur Ceze (France)

    2010-07-01

    The oxo groups in the uranyl ion [UO{sub 2}]{sup 2+} - one of many oxo cations formed by metals from across the periodic table - are particularly inert, which explains the dominance of this ion in the laboratory and its persistence as an environmental contaminant. In contrast, transition metal oxo (M=O) compounds can be highly reactive and carry out difficult reactions such as the oxygenation of hydrocarbons. Here we show how the sequential addition of a lithium metal base to the uranyl ion constrained in a 'Pacman' environment results in lithium coordination to the U=O bonds and single-electron reduction. This reaction depends on the nature and stoichiometry of the lithium reagent and suggests that competing reduction and C-H bond activation reactions are occurring. (authors)

  18. Effects of metallic cations in the beryl flotation

    Lima Leonel, C.M. de; Peres, A.E.C.

    1984-01-01

    The beryl zeta potential in microelectrophoretic cell is studied in the presence of neutral electrolyte, cations of calcium, magnesium and iron. The petroleum sulfonate is used how collector in Hallimond tube. Hydroxy complex of metallic cations seems activate the ore and precipitates of colloidal metallic hidroxies seems lower him when added to the mixture. (M.A.C.) [pt

  19. IRMPD Action Spectroscopy of Alkali Metal Cation-Cytosine Complexes: Effects of Alkali Metal Cation Size on Gas Phase Conformation

    Yang, B.; Wu, R.R.; Polfer, N.C.; Berden, G.; Oomens, J.; Rodgers, M.T.

    2013-01-01

    The gas-phase structures of alkali metal cation-cytosine complexes generated by electrospray ionization are probed via infrared multiple photon dissociation (IRMPD) action spectroscopy and theoretical calculations. IRMPD action spectra of five alkali metal cation-cytosine complexes exhibit both

  20. Infrared multiple photon dissociation action spectroscopy of alkali metal cation-cyclen complexes: Effects of alkali metal cation size on gas-phase conformation

    Austin, C.A.; Chen, Y.; Kaczan, C.M.; Berden, G.; Oomens, J.; Rodgers, M.T.

    2013-01-01

    The gas-phase structures of alkali metal cationized complexes of cyclen (1,4,7,10-tetraazacyclododecane) are examined via infrared multiple photon dissociation (IRMPD) action spectroscopy and electronic structure theory calculations. The measured IRMPD action spectra of four M+(cyclen) complexes are

  1. Esterification of phenyl acetic acid with p-cresol using metal cation exchanged montmorillonite nanoclay catalysts.

    Bhaskar, M; Surekha, M; Suma, N

    2018-02-01

    The liquid phase esterification of phenyl acetic acid with p -cresol over different metal cation exchanged montmorillonite nanoclays yields p -cresyl phenyl acetate. Different metal cation exchanged montmorillonite nanoclays (M n +  = Al 3+ , Zn 2+ , Mn 2+ , Fe 3+ , Cu 2+ ) were prepared and the catalytic activity was studied. The esterification reaction was conducted by varying molar ratio of the reactants, reaction time and catalyst amount on the yield of the ester. Among the different metal cation exchanged catalysts used, Al 3+ -montmorillonite nanoclay was found to be more active. The characterization of the material used was studied under different techniques, namely X-ray diffraction, scanning electron microscopy and thermogravimetric analysis. The product obtained, p -cresyl phenyl acetate, was identified by thin-layer chromotography and confirmed by Fourier transform infrared, 1 H NMR and 13 C NMR. The regeneration activity of used catalyst was also investigated up to fourth generation.

  2. Fluconazole affects the alkali-metal-cation homeostasis and susceptibility to cationic toxic compounds of Candida glabrata.

    Elicharova, Hana; Sychrova, Hana

    2014-08-01

    Candida glabrata is a salt-tolerant and fluconazole (FLC)-resistant yeast species. Here, we analyse the contribution of plasma-membrane alkali-metal-cation exporters, a cation/proton antiporter and a cation ATPase to cation homeostasis and the maintenance of membrane potential (ΔΨ). Using a series of single and double mutants lacking CNH1 and/or ENA1 genes we show that the inability to export potassium and toxic alkali-metal cations leads to a slight hyperpolarization of the plasma membrane of C. glabrata cells; this hyperpolarization drives more cations into the cells and affects cation homeostasis. Surprisingly, a much higher hyperpolarization of C. glabrata plasma membrane was produced by incubating cells with subinhibitory concentrations of FLC. FLC treatment resulted in a substantially increased sensitivity of cells to various cationic drugs and toxic cations that are driven into the cell by negative-inside plasma-membrane potential. The effect of the combination of FLC plus cationic drug treatment was enhanced by the malfunction of alkali-metal-cation transporters that contribute to the regulation of membrane potential and cation homeostasis. In summary, we show that the combination of subinhibitory concentrations of FLC and cationic drugs strongly affects the growth of C. glabrata cells. © 2014 The Authors.

  3. Conductometric determination of solvation numbers of alkali metal cations

    Fialkov, Yu.Ya.; Gorbachev, V.Yu.; Chumak, V.L.

    1997-01-01

    Theories describing the interrelation of ion mobility with their effective radii in solutions are considered. Possibility of using these theories for determination the solvation numbers n s of some ions is estimated. According to conductometric data values of n s are calculated for alkali metal ions in propylene carbonate. The data obtained are compared with solvation numbers determined with the use of entropies of ions solvation. Change of n s values within temperature range 273.15-323.15 K is considered. Using literature data the effect of crystallographic radii of cations and medium permittivity on the the values of solvation numbers of cations are analyzed. (author)

  4. Alkali Metal Cation versus Proton and Methyl Cation Affinities: Structure and Bonding Mechanism.

    Boughlala, Zakaria; Fonseca Guerra, Célia; Bickelhaupt, F Matthias

    2016-06-01

    We have analyzed the structure and bonding of gas-phase Cl-X and [HCl-X](+) complexes for X(+)= H(+), CH3 (+), Li(+), and Na(+), using relativistic density functional theory (DFT). We wish to establish a quantitative trend in affinities of the anionic and neutral Lewis bases Cl(-) and HCl for the various cations. The Cl-X bond becomes longer and weaker along X(+) = H(+), CH3 (+), Li(+), and Na(+). Our main purpose is to understand the heterolytic bonding mechanism behind the intrinsic (i.e., in the absence of solvent) alkali metal cation affinities (AMCA) and how this compares with and differs from those of the proton affinity (PA) and methyl cation affinity (MCA). Our analyses are based on Kohn-Sham molecular orbital (KS-MO) theory in combination with a quantitative energy decomposition analysis (EDA) that pinpoints the importance of the different features in the bonding mechanism. Orbital overlap appears to play an important role in determining the trend in cation affinities.

  5. Cationic rare-earth metal SALEN complexes.

    Liu, Qiancai; Meermann, Christian; Görlitzer, Hans W; Runte, Oliver; Herdtweck, Eberhardt; Sirsch, Peter; Törnroos, Karl W; Anwander, Reiner

    2008-11-28

    Complexes (Salpren(tBu,tBu))Y[N(SiHMe2)2](thf) and (SALEN(tBu,tBu))La[N(SiHMe2)2](thf) (SALEN(tBu,tBu) = Salcyc(tBu,tBu) and Salpren(tBu,tBu)) were prepared from Ln[N(SiHMe2)2]3(thf)2 and H2SALEN(tBu,tBu). The yttrium complex was characterized by X-ray crystallography revealing intrinsic solid-state structural features: the metal centre is displaced by 1.05 angstroms from the [N2O2] least squares plane of a highly bent Salpren(tBu,tBu) ligand (angle(Ph,Ph) dihedral angle of 80.4(1) degrees ) and is coordinated asymmetrically by the silylamide ligand exhibiting one significant Y---(HSi) beta-agostic interaction (Y-N1-Si1, 106.90(9) degrees; Y---Si1, 3.2317(6) angstroms). Complexes (SALEN(tBu,tBu))Ln[N(SiHMe2)2](thf)n (n = 1, Sc; n = 2, Y, La) react with ammonium tetraphenylborate to form the ion pairs [(SALEN(tBu,tBu))Ln(thf)n][BPh4]. The cationisation was proven by X-ray crystal structure analyses of [(Salpren(tBu,tBu))Sc(thf)2][B(C6H5)4].2(thf) and [(Salpren(tBu,tBu))Ln(thf)3][B(C6H5)4].4(thf) (Ln = Y, La), showing an octahedral and pentagonal-bipyramidal coordination geometry, respectively.

  6. Effect of alkali metal cations on anodic dissolution of gold in cyanide solutions. Potentiodynamic measurement

    Bek, R.Yu.; Rogozhnikov, N.A.; Kosolapov, G.V.

    1998-01-01

    It is shown that gold dissolution rate in cyanic solutions in Li + , Na + , K + , Cs + cation series increases basically and decreases under cation concentration increasing. Cation effect on current value is caused by cations drawing in dense layer. A model of dense part of double layer with two Helmholtz planes (anion and cation) is suggested. Effect of nature and concentration of alkali metal cations on gold dissolution rate is explained on the base of the model [ru

  7. Structural studies of Langmuir-Blodgett films containing rare-earth metal cations

    Khomutov, G.B.; Antipina, M.N.; Bykov, I.V.

    2002-01-01

    Comparative structural study of gadolinium stearate Langmuir-Blodgett (LB) films formed by monolayer deposition from either aqueous gadolinium acetate or gadolinium chloride solutions have been carried out. Structure of the films was characterized by X-ray diffraction, Fourier transform infrared...... spectroscopy, high-energy electron diffraction, atomic force microscopy and scanning electron microscopy. It was found that when subphase pH had a value at which all monolayer stearic acid molecules were ionized and bound with Gd3+ cations (pH > 5), the LB films deposited from gadolinium acetate and gadolinium....... The data obtained indicate that the control of multivalent metal cations complexes formation in the subphase and at the monolayer surface can be an instrument for optimization, the conditions to form metal-containing LB film with regulated structure and properties....

  8. Metal cation controls phosphate release in the myosin ATPase.

    Ge, Jinghua; Huang, Furong; Nesmelov, Yuri E

    2017-11-01

    Myosin is an enzyme that utilizes ATP to produce a conformational change generating a force. The kinetics of the myosin reverse recovery stroke depends on the metal cation complexed with ATP. The reverse recovery stroke is slow for MgATP and fast for MnATP. The metal ion coordinates the γ phosphate of ATP in the myosin active site. It is accepted that the reverse recovery stroke is correlated with the phosphate release; therefore, magnesium "holds" phosphate tighter than manganese. Magnesium and manganese are similar ions in terms of their chemical properties and the shell complexation; hence, we propose to use these ions to study the mechanism of the phosphate release. Analysis of octahedral complexes of magnesium and manganese show that the partial charge of magnesium is higher than that of manganese and the slightly larger size of manganese ion makes its ionic potential smaller. We hypothesize that electrostatics play a role in keeping and releasing the abstracted γ phosphate in the active site, and the stronger electric charge of magnesium ion holds γ phosphate tighter. We used stable myosin-nucleotide analog complex and Raman spectroscopy to examine the effect of the metal cation on the relative position of γ phosphate analog in the active site. We found that in the manganese complex, the γ phosphate analog is 0.01 nm further away from ADP than in the magnesium complex. We conclude that the ionic potential of the metal cation plays a role in the retention of the abstracted phosphate. © 2017 The Protein Society.

  9. Electron energies in metals

    Mahan, G.D.; Tennessee Univ., Knoxville, TN

    1991-01-01

    The modern era of electron-electron interactions began a decade ago. Plummer's group initiated a program of using angular resolved photoemission to examine the band structure of the simple metals. Beginning with aluminum, and carrying on to sodium and potassium, they always found that the occupied energy bands were much narrower than expected. For example, the compressed energy bands for metallic potassium suggest a band effective mass of m* = 1.33m e . This should be compared to the band mass found from optical conductivity m*/m e = 1.01 ± 0.01. The discrepancy between these results is startling. It was this great difference which started my group doing calculations. Our program was two-fold. On one hand, we reanalyzed the experimental data, in order to see if Plummer's result was an experimental artifact. On the other hand, we completely redid the electron-electron self-energy calculations for simple metals, using the most modern choices of local-field corrections and vertex corrections. Our results will be reported in these lectures. They can be summarized as following: Our calculations give the same effective masses as the older calculations, so the theory is relatively unchanged; Our analysis of the experiments suggests that the recent measurements of band narrowing are an experimental artifact. 38 refs., 9 figs

  10. Cation Binding to Xanthorhodopsin: Electron Paramagnetic Resonance and Magnetic Studies.

    Smolensky Koganov, Elena; Leitus, Gregory; Rozin, Rinat; Weiner, Lev; Friedman, Noga; Sheves, Mordechai

    2017-05-04

    Xanthorhodopsin (xR) is a member of the retinal protein family and acts as a proton pump in the cell membranes of the extremely halophilic eubacterium Salinibacter ruber. In addition to the retinal chromophore, xR contains a carotenoid, which acts as a light-harvesting antenna as it transfers 40% of the quanta it absorbs to the retinal. Our previous studies have shown that the CD and absorption spectra of xR are dramatically affected due to the protonation of two different residues. It is still unclear whether xR can bind cations. Electron paramagnetic resonance (EPR) spectroscopy used in the present study revealed that xR can bind divalent cations, such as Mn 2+ and Ca 2+ , to deionized xR (DI-xR). We also demonstrate that xR can bind 1 equiv of Mn 2+ to a high-affinity binding site followed by binding of ∼40 equiv in cooperative manner and ∼100 equiv of Mn 2+ that are weakly bound. SQUID magnetic studies suggest that the high cooperative binding of Mn 2+ cations to xR is due to the formation of Mn 2+ clusters. Our data demonstrate that Ca 2+ cations bind to DI-xR with a lower affinity than Mn 2+ , supporting the assumption that binding of Mn 2+ occurs through cluster formation, because Ca 2+ cations cannot form clusters in contrast to Mn 2+ .

  11. 13C NMR investigation of the structure of cationic carbonyls in transition metal zeolites

    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.)

  12. Binding properties of oxacalix[4]arenes derivatives toward metal cations

    Mellah, B.

    2006-11-01

    The objective of this work was to establish the binding properties of oxacalix[4]arene derivatives with different numbers of the oxa bridges, functional groups (ketones, pyridine, ester, amide and methoxy) and conformations. Their interactions with alkali and alkaline-earth, heavy and transition metal cations have been evaluated according to different approaches: (i) extraction of corresponding picrates from an aqueous phase into dichloromethane; (ii) determination of the thermodynamic parameters of complexation in methanol and/or acetonitrile by UV-spectrophotometry and micro-calorimetry; (iii) determination of the stoichiometry of the complexes by ESI-MS; (iv) 1 H-NMR titrations allowing to localize the metal ions in the ligand cavity. In a first part dealing on homo-oxacalix[4]arenes, selectivities for Na + , K + , Ca 2+ , Pb 2+ and Mn 2+ of ketones derivatives was shown. The presence of oxa bridge in these derivatives increases their efficiency while decreasing their selectivity with respect to related calixarenes. The pyridine derivative prefers transition and heavy metal cations, in agreement with the presence of the soft nitrogen atoms. In the second part, di-oxacalix[4]arene ester and secondary amide derivatives were shown to be less effective than tertiary amide counterparts but to present high selectivities for Li + , Ba 2+ , Zn 2+ and Hg 2+ . A third part devoted to the octa-homo-tetra-oxacalix[4]arene tetra-methoxy shows that the 1:1 metal complexes formed are generally more stable than those of calixarenes, suggesting the participation of the oxygen atoms of the bridge in the complexation. Selectivity for Cs + , Ba 2+ , Cu 2+ and Hg 2+ were noted. (author)

  13. Geminate electron--cation recombination in disordered solids

    Berlin, Y.A.; Chekunaev, N.I.; Goldanskii, V.I.

    1990-01-01

    A theory of a geminate electron--cation recombination has been developed using the percolation approach to the description of the electron transport in disordered solids. Following this approach all trapping sites are separated into two groups. The first group forms a diffusion cluster responsible for the macroscopic charge transfer in disordered media whilethe second group consists of isolated traps playing the role of origins and sinks for mobile electrons. In the framework of such a model an equation has been derived describing the electron motion in the Coulomb field of a parent cation. The solution of this equation in the long time limit shows that the recombination rate decreases vs time as t -(1+α/2) with α being a positive constant or a very weak function of t. In the particular case of Gaussian diffusion α=1 and the kinetic law obtained reduces to that predicted by the well-known Onsager--Smoluchowski theory. However for the dispersive (non-Gaussian) transport in highly disordered systems α<1 and its value depends on the type of disorder, on the energy level structure of trapped electrons and on the specific mechanism of electron migration through the medium

  14. An Overview on Metal Cations Extraction by Azocalixarenes

    Hasalettin Deligöz

    2011-12-01

    Full Text Available In this overview, our main aim is to present the design, preparation, characterization, and extraction/sorption properties of chromogenic azocalix[4]arenes (substituted with different groups toward metal cations. Azocalixarenes, which contain a conjugated chromophore, i.e. azo (-N=N- group are synthesized in “one-pot” procedures in satisfactory yields. A wide variety of applications is expected by the functionalization of the side arms. Some of them are used to complex with metal ions. These macrocycles due to their bowl-shaped geometry are indeed used as hosts allowing ionic or organic guests to coordinate onto their cavity. The azocalixarene based ionophores are generally applied in various fields such as catalyst recovery, power plant, agriculture, metals finishing, microelectonics, biotechnology processes, rare earths speciation, and potable water purification. Besides these, they find applications in the area of selective ion extractions, receptors, optical devices, chemical sensor devices, the stationary phase for capillary chromatography, ion transport membranes, and luminescence probes etc. This survey is focused to provide overview an of the versatile nature of azocalix[n]arenes as highly efficient extractants for metal ions treated as pollutants.

  15. Gas-Phase Reactions of Doubly Charged Lanthanide Cations with Alkanes and Alkenes. Trends in Metal(2+) Reactivity

    Gibson, John K.; Marcalo, Joaquim; Santos, Marta; Pires de Matos, Antonio; Haire, Richard G.

    2008-12-08

    The gas-phase reactivity of doubly-charged lanthanide cations, Ln2+ (Ln = La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu), with alkanes (methane, ethane, propane, n-butane) and alkenes (ethene, propene, 1-butene) was studied by Fourier transform ion cyclotron resonance mass spectrometry. The reaction products consisted of different combinations of doubly-charged organometallic ions?adducts or species formed via metal-ion-induced hydrogen, dihydrogen, alkyl, or alkane eliminations from the hydrocarbons?and singly-charged ions that resulted from electron, hydride, or methide transfers from the hydrocarbons to the metal ions. The only lanthanide cations capable of activating the hydrocarbons to form doubly-charged organometallic ions were La2+, Ce2+, Gd2+, and Tb2+, which have ground-state or low-lying d1 electronic configurations. Lu2+, with an accessible d1 electronic configuration but a rather high electron affinity, reacted only through transfer channels. The remaining Ln2+ reacted via transfer channels or adduct formation. The different accessibilities of d1 electronic configurations and the range of electron affinities of the Ln2+ cations allowed for a detailed analysis of the trends for metal(2+) reactivity and the conditions for occurrence of bond activation, adduct formation, and electron, hydride, and methide transfers.

  16. Mechanism of selective ion flotation. 1. Selective flotation of transition metal cations

    Walkowiak, W.

    1991-01-01

    An experimental investigation is presented of the batch ion flotation of the transition metal cations Cr 3+ , Fe 3+ , Mn 2+ , Co 2+ , Zn 2+ , Ag + , Cd 2+ , and In 3+ from acidic aqueous solutions with sodium dodecylsulfonate and sodium dodecylbenzenesulfonate as anionic surfactants. The selectivity sequences Mn 2+ 2+ 2+ 3+ 3+ and Ag + 2+ 3+ are established, both from data for single and multi-ion metal cations solutions, where sublate was not formed in the bulk solution. Good agreement between the selectivity sequences and the values of ionic potential of metal cations was found. An experimental investigation was also performed on the solubility of sublates. The sublates solubility values are discussed in terms of ionic potentials of metal cations as well as of the surfactant size

  17. Electronic structure of metal clusters

    Wertheim, G.K.

    1989-01-01

    Photoemission spectra of valence electrons in metal clusters, together with threshold ionization potential measurements, provide a coherent picture of the development of the electronic structure from the isolated atom to the large metallic cluster. An insulator-metal transition occurs at an intermediate cluster size, which serves to define the boundary between small and large clusters. Although the outer electrons may be delocalized over the entire cluster, a small cluster remains insulating until the density of states near the Fermi level exceeds 1/kT. In large clusters, with increasing cluster size, the band structure approaches that of the bulk metal. However, the bands remain significantly narrowed even in a 1000-atom cluster, giving an indication of the importance of long-range order. The core-electron binding-energy shifts of supported metal clusters depend on changes in the band structure in the initial state, as well as on various final-state effects, including changes in core hole screening and the coulomb energy of the final-state charge. For cluster supported on amorphous carbon, this macroscopic coulomb shift is often dominant, as evidenced by the parallel shifts of the core-electron binding energy and the Fermi edge. Auger data confirm that final-state effects dominate in cluster of Sn and some other metals. Surface atom core-level shifts provide a valuable guide to the contributions of initial-state changes in band structure to cluster core-electron binding energy shifts, especially for Au and Pt. The available data indicate that the shift observed in supported, metallic clusters arise largely from the charge left on the cluster by photoemission. As the metal-insulator transition is approached from above, metallic screening is suppressed and the shift is determined by the local environment. (orig.)

  18. Disposal of heavy metal cations in aqueous media by adsorption on coal to Ghazni

    О.М. Заславський

    2008-03-01

    Full Text Available  Adsorption of Pb and Cu cations and their mixture on the surface of modified and non-modified anti-gas coal trough different time intervals have been studied. The maximum adsorption capacity of coal relative to each cations have been determined. Absence  of concurrence between cations of Pb and Cu during adsorption from mixture is explained by difference of  types of their interaction with coal surface. The high effectiveness and perspectivities of application of anti-gas coal for neutralization of heavy metal cations in aqueous solution was shown.

  19. Double C-H activation of ethane by metal-free SO2*+ radical cations.

    de Petris, Giulia; Cartoni, Antonella; Troiani, Anna; Barone, Vincenzo; Cimino, Paola; Angelini, Giancarlo; Ursini, Ornella

    2010-06-01

    The room-temperature C-H activation of ethane by metal-free SO(2)(*+) radical cations has been investigated under different pressure regimes by mass spectrometric techniques. The major reaction channel is the conversion of ethane to ethylene accompanied by the formation of H(2)SO(2)(*+), the radical cation of sulfoxylic acid. The mechanism of the double C-H activation, in the absence of the single activation product HSO(2)(+), is elucidated by kinetic studies and quantum chemical calculations. Under near single-collision conditions the reaction occurs with rate constant k=1.0 x 10(-9) (+/-30%) cm(3) s(-1) molecule(-1), efficiency=90%, kinetic isotope effect k(H)/k(D)=1.1, and partial H/D scrambling. The theoretical analysis shows that the interaction of SO(2)(*+) with ethane through an oxygen atom directly leads to the C-H activation intermediate. The interaction through sulfur leads to an encounter complex that rapidly converts to the same intermediate. The double C-H activation occurs by a reaction path that lies below the reactants and involves intermediates separated by very low energy barriers, which include a complex of the ethyl cation suitable to undergo H/D scrambling. Key issues in the observed reactivity are electron-transfer processes, in which a crucial role is played by geometrical constraints. The work shows how mechanistic details disclosed by the reactions of metal-free electrophiles may contribute to the current understanding of the C-H activation of ethane.

  20. Interactions of nucleobases with alkali earth metal cations--electrospray ionization mass spectrometric study.

    Frańska, Magdalena

    2007-01-01

    Interactions of nucleobases with alkali earth metal cations have been studied by electrospray ionization mass spectrometry (ESI-MS). Nucleobases containing at least one oxygen atom form stable complexes with alkali earth metal cations. This phenomenon can be explained on the grounds of the well known theory of hard and soft acids and bases. Uracil and thymine make complexes only when in their deprotonoted forms. The cations of great radii (Sr(2+), Ba(2+)) are more prone to form complexes of stoichiometry 1:1 with uracil and thymine than the cations of small radii (Mg(2+), Ca(2+)). On the other hand, Mg(2+) forms complexes of stoichiometry 2:1 and 3:2 with uracil and thymine. Gas-phase stabilities of the 1:1 complexes are higher for the cations of small radii, in contrast to the solution stabilities. For cytosine and 9- methylhypoxantine the 1:1 complexes of their deprotonated forms are observed at higher cone voltage as a result of HCl molecule loss from the complexes containing the counter ion (Cl(-)). In solution, more stable complexes are formed with metal cations of low radii. Gas-phase stability of the complexes formed by deprotonated 9- methyl-hypoxantine increases with increasing metal cation radius.

  1. Association of alkali and alkaline earth metal cations with radical-anions of 9-fluorenone and 9.10-anthraquinone in dimethyl formamide medium

    Karpinets, A.P.; Bezuglyj, V.D.; Svetlichnaya, T.M.

    1988-01-01

    The polarographic method is used to estimate the stability of associates formed in dimethyl formamide by the products of one-electron reduction of 9-fluorenone and 9.10-anthraquinone with cations of alkali and alkali earth metals. It is shown that the strength of 9-fluorenone and 9.10-anthraquinone radical anion associates studied increases with cation charge increase and decrease of its crystallographic radius

  2. Immobilized poly-L-histidine for chelation of metal cations and metal oxyanions

    Malachowski, Lisa; Holcombe, James A.

    2003-01-01

    The biohomopolymer poly-L-histidine (PLHis) was immobilized onto controlled pore glass (CPG) and its metal binding capabilities evaluated through the use of a flow injection-flame atomic absorption system. The metal binding capability of PLHis-CPG was determined through the analysis of the generated breakthrough curves. The polymer likely coordinates cationic metals through the imidazole side chain (pK a ∼6) present on each histidine residue with both strong and weak binding sites for Cu 2+ , Cd 2+ , Co 2+ , and Ni 2+ . Weak to minimal binding was observed for Mn 2+ , Ca 2+ , Mg 2+ , Na + , and Cr 3+ . The bound metals are quantitatively released from the column with an acid strip. It has also been shown that the protonated imidazole side chain present in acidic solutions is capable of binding metal oxyanions such as chromates, arsenates, and selenites; although oxyanion binding currently exhibits interferences from competing anions in solution, such as sulfate and nitrate. The interference in oxyanion binding is less severe in the presence of chloride, phosphate, and acetate. PLHis-CPG exhibits a capacity of ∼30 μmol Cu 2+ /g CPG in neutral to basic conditions, and a capacity of ∼70 μmol Cr(VI)/g CPG, ∼4 μmol As(V)/g CPG, and ∼4 μmol Se(IV)/g CPG in acidic conditions

  3. Enhanced Mixed Electronic-Ionic Conductors through Cation Ordering

    Jacobson, Allan J. [Univ. of Houston, TX (United States); Morgan, Dane [Univ. of Wisconsin, Madison, WI (United States); Grey, Clare [Stony Brook Univ., NY (United States)

    2014-08-31

    The performance of many energy conversion and storage devices depend on the properties of mixed ionic-electronic conducting (miec) materials. Mixed or ambipolar conductors simultaneously transport ions and electrons and provide the critical interface between chemical and electrical energy in devices such as fuel cells, ion transport membranes, and batteries. Enhancements in storage capacity, reversibility, power density and device lifetime all require new materials and a better understanding of the fundamentals of ambipolar conductivity and surface reactivity.The high temperature properties of the ordered perovksites AA’B2O5+x, where A = rare earth ion, Y and B = Ba, Sr were studied. The work was motivated by the high oxygen transport and surface exchange rates observed for members of this class of mixed ionic and electronic conductors. A combined experimental and computational approach, including structural, electrochemical, and transport characterization and modeling was used. The approach attacks the problem simultaneously at global (e.g., neutron diffraction and impedance spectroscopy), local (e.g., pair distribution function, nuclear magnetic resonance) and molecular (ab initio thermokinetic modeling) length scales. The objectives of the work were to understand how the cation and associated anion order lead to exceptional ionic and electronic transport properties and surface reactivity in AA’B2O5+x perovskites. A variety of compounds were studied by X-ray and neutron diffraction, measurements of thermodynamics and transport and theoretically. These included PrBaCo2O5+x and NdBaCo2O5+x, PrBaCo2-xFexO6- δ (x = 0, 0.5, 1.0, 1.5 and 2) and LnBaCoFeO6- δ (Ln = La, Pr, Nd, Sm, Eu and Gd), Sr3YCo4O10.5, YBaMn2O5+x. A0.5A’0.5BO3 (where A=Y, Sc, La, Ce, Pr, Nd, Pm, Sm; A’= Sr

  4. Alkali Metal Cation versus Proton and Methyl Cation Affinities: Structure and Bonding Mechanism

    Boughlala, Z.; Guerra, C.F.; Bickelhaupt, F.M.

    2016-01-01

    Abstract We have analyzed the structure and bonding of gas?phase Cl?X and [HCl?X]+ complexes for X+=?H+, CH3 +, Li+, and Na+, using relativistic density functional theory (DFT). We wish to establish a quantitative trend in affinities of the anionic and neutral Lewis bases Cl? and HCl for the various cations. The Cl?X bond becomes longer and weaker along X+?=?H+, CH3 +, Li+, and Na+. Our main purpose is to understand the heterolytic bonding mechanism behind the intrinsic (i.e., in the absence ...

  5. Neutral glycoconjugated amide-based calix[4]arenes: complexation of alkali metal cations in water.

    Cindro, Nikola; Požar, Josip; Barišić, Dajana; Bregović, Nikola; Pičuljan, Katarina; Tomaš, Renato; Frkanec, Leo; Tomišić, Vladislav

    2018-02-07

    Cation complexation in water presents a unique challenge in calixarene chemistry, mostly due to the fact that a vast majority of calixarene-based cation receptors is not soluble in water or their solubility has been achieved by introducing functionalities capable of (de)protonation. Such an approach inevitably involves the presence of counterions which compete with target cations for the calixarene binding site, and also rather often requires the use of ion-containing buffer solutions in order to control the pH. Herein we devised a new strategy towards the solution of this problem, based on introducing carbohydrate units at the lower or upper rim of calix[4]arenes which comprise efficient cation binding sites. In this context, we prepared neutral, water-soluble receptors with secondary or tertiary amide coordinating groups, and studied their complexation with alkali metal cations in aqueous and methanol (for the comparison purpose) solutions. Complexation thermodynamics was quantitatively characterized by UV spectrometry and isothermal titration calorimetry, revealing that one of the prepared tertiary amide derivatives is capable of remarkably efficient (log K ≈ 5) and selective binding of sodium cations among alkali metal cations in water. Given the ease of the synthetic procedure used, and thus the variety of accessible analogues, this study can serve as a platform for the development of reagents for diverse purposes in aqueous media.

  6. Binding properties of oxacalix[4]arenes derivatives toward metal cations; Interactions entre cations metalliques et derives des oxacalix[4]arenes

    Mellah, B

    2006-11-15

    The objective of this work was to establish the binding properties of oxacalix[4]arene derivatives with different numbers of the oxa bridges, functional groups (ketones, pyridine, ester, amide and methoxy) and conformations. Their interactions with alkali and alkaline-earth, heavy and transition metal cations have been evaluated according to different approaches: (i) extraction of corresponding picrates from an aqueous phase into dichloromethane; (ii) determination of the thermodynamic parameters of complexation in methanol and/or acetonitrile by UV-spectrophotometry and micro-calorimetry; (iii) determination of the stoichiometry of the complexes by ESI-MS; (iv) {sup 1}H-NMR titrations allowing to localize the metal ions in the ligand cavity. In a first part dealing on homo-oxacalix[4]arenes, selectivities for Na{sup +}, K{sup +}, Ca{sup 2+}, Pb{sup 2+} and Mn{sup 2+} of ketones derivatives was shown. The presence of oxa bridge in these derivatives increases their efficiency while decreasing their selectivity with respect to related calixarenes. The pyridine derivative prefers transition and heavy metal cations, in agreement with the presence of the soft nitrogen atoms. In the second part, di-oxacalix[4]arene ester and secondary amide derivatives were shown to be less effective than tertiary amide counterparts but to present high selectivities for Li{sup +}, Ba{sup 2+}, Zn{sup 2+} and Hg{sup 2+}. A third part devoted to the octa-homo-tetra-oxacalix[4]arene tetra-methoxy shows that the 1:1 metal complexes formed are generally more stable than those of calixarenes, suggesting the participation of the oxygen atoms of the bridge in the complexation. Selectivity for Cs{sup +}, Ba{sup 2+}, Cu{sup 2+} and Hg{sup 2+} were noted. (author)

  7. Enhanced PCBs sorption on biochars as affected by environmental factors: Humic acid and metal cations

    Wang Yu; Wang Lei; Fang Guodong; Herath, H.M.S.K.; Wang Yujun; Cang Long; Xie Zubin; Zhou Dongmei

    2013-01-01

    Biochar plays an important role in the behaviors of organic pollutants in the soil environment. The role of humic acid (HA) and metal cations on the adsorption affinity of polychlorinated biphenyls (PCBs) to the biochars in an aqueous medium and an extracted solution from a PCBs-contaminated soil was studied using batch experiments. Biochars were produced with pine needles and wheat straw at 350 °C and 550 °C under anaerobic condition. The results showed that the biochars had high adsorption affinity for PCBs. Pine needle chars adsorbed less nonplanar PCBs than planar ones due to dispersive interactions and separation. Coexistence of HA and metal cations increased PCBs sorption on the biochars accounted for HA adsorption and cation complexation. The results will aid in a better understanding of biochar sorption mechanism of contaminants in the environment. - Highlights: ► Application of the biochars for PCBs sorption was a new and effective way. ► The biochars had higher adsorption affinity for PCBs in the soil extracted solution. ► Pine needle chars adsorbed less nonplanar PCBs than planar ones. ► Coexisting humic acid or metal cations increased PCBs sorption on the biochars. - The biochars had higher adsorption affinity for PCBs in the extracted soil solution because coexisting humic acid and metal cations increased their sorption.

  8. Electron-beam curing of epoxy resins: effect of alcohols on cationic ...

    Unknown

    Electron-beam (e-beam) induced polymerization of epoxy resins proceeds via cationic mechanism in presence of suitable ... generate ionic species, free radicals, and/or molecules in .... bisphenol A) and the effect of presence of different OH.

  9. Introducing zinc cations into zeolite Y via the reduction of HY with zinc metal vapour

    Seidel, A.; Boddenberg, B.

    1996-01-01

    Zeolites HY and NaY which were contacted with zinc metal vapour at 420°C were investigated by carbon monoxide and xenon adsorption as well as 129Xe NMR spectroscopy. The reaction of zeolite HY results in the incorporation of Zn 2+ cations which are shown to populate the supercage positions S II and S III to an unusually high extent. The supercage zinc cation concentration strongly decreases when the material is saturated with water and subsequently dehydrated at 400°C. The zeolite NaY turns out to be inert towards the reaction with zinc metal vapour.

  10. Cations in Octahedral Sites: A Descriptor for Oxygen Electrocatalysis on Transition-Metal Spinels

    Wei, Chao; Feng, Zhenxing; Scherer, Günther G.; Barber, James; Shao-Horn, Yang; Xu, Zhichuan J. (Nanyang); (ICL); (Oregon State U.); (TUM-CREATE); (MIT)

    2017-04-10

    Exploring efficient and low-cost electrocatalysts for the oxygen-reduction reaction (ORR) and oxygen-evolution reaction (OER) is critical for developing renewable energy technologies such as fuel cells, metal–air batteries, and water electrolyzers. A rational design of a catalyst can be guided by identifying descriptors that determine its activity. Here, a descriptor study on the ORR/OER of spinel oxides is presented. With a series of MnCo2O4, the Mn in octahedral sites is identified as an active site. This finding is then applied to successfully explain the ORR/OER activities of other transition-metal spinels, including MnxCo3-xO4 (x = 2, 2.5, 3), LixMn2O4 (x = 0.7, 1), XCo2O4 (X = Co, Ni, Zn), and XFe2O4 (X = Mn, Co, Ni). A general principle is concluded that the eg occupancy of the active cation in the octahedral site is the activity descriptor for the ORR/OER of spinels, consolidating the role of electron orbital filling in metal oxide catalysis.

  11. Reactions of laser-ablated Co, Rh, and Ir with CO: Infrared spectra and density functional calculations of the metal carbonyl molecules, cations and anions in solid neon

    Zhou, M.; Andrews, L.

    1999-01-01

    Laser ablation produces metal atoms, cations, and electrons for reaction with CO during condensation in excess neon at 4 K. Infrared spectra are observed for the metal carbonyls, cations, and anions, which are identified from isotopic shifts ( 13 CO, C 18 O) and splittings using mixed isotopic precursors. Density functional calculations with pseudopotentials for Rh and Ir predict the observed carbonyl stretching frequencies within 1--2%. This characterization of the simple RhCO + , RhCO, and RhCO - (and Ir) species over a 350 cm -1 range provides a scale for comparison of larger catalytically active Rh and Ir carbonyl complexes in solution and on surfaces to estimate charge on the metal center. This work provides the first spectroscopic characterization of Rh and Ir carbonyl cations and anions except for the stable tetracarbonyl anions in solution

  12. Solvation Effect on Complexation of Alkali Metal Cations by a Calix[4]arene Ketone Derivative.

    Požar, Josip; Nikšić-Franjić, Ivana; Cvetnić, Marija; Leko, Katarina; Cindro, Nikola; Pičuljan, Katarina; Borilović, Ivana; Frkanec, Leo; Tomišić, Vladislav

    2017-09-14

    The medium effect on the complexation of alkali metal cations with a calix[4]arene ketone derivative (L) was systematically examined in methanol, ethanol, N-methylformamide, N,N-dimethylformamide, dimethyl sulfoxide, and acetonitrile. In all solvents the binding of Na + cation by L was rather efficient, whereas the complexation of other alkali metal cations was observed only in methanol and acetonitrile. Complexation reactions were enthalpically controlled, while ligand dissolution was endothermic in all cases. A notable influence of the solvent on NaL + complex stability could be mainly attributed to the differences in complexation entropies. The higher NaL + stability in comparison to complexes with other alkali metal cations in acetonitrile was predominantly due to a more favorable complexation enthalpy. The 1 H NMR investigations revealed a relatively low affinity of the calixarene sodium complex for inclusion of the solvent molecule in the calixarene hydrophobic cavity, with the exception of acetonitrile. Differences in complex stabilities in the explored solvents, apart from N,N-dimethylformamide and acetonitrile, could be mostly explained by taking into account solely the cation and complex solvation. A considerable solvent effect on the complexation equilibria was proven to be due to an interesting interplay between the transfer enthalpies and entropies of the reactants and the complexes formed.

  13. Bioaccessibility of metal cations in soil is linearly related to its water exchange rate constant.

    Laird, Brian D; Peak, Derek; Siciliano, Steven D

    2011-05-01

    Site-specific risk assessments often incorporate the concepts of bioaccessibility (i.e., contaminant fraction released into gastrointestinal fluids) or bioavailability (i.e., contaminant fraction absorbed into systemic circulation) into the calculation of ingestion exposure. We evaluated total and bioaccessible metal concentrations for 19 soil samples under simulated stomach and duodenal conditions using an in vitro gastrointestinal model. We demonstrated that the median bioaccessibility of 23 metals ranged between exchange rates of metal cations (k(H₂O)) indicated that desorption kinetics may influence if not control metal bioaccessibility.

  14. A Study of Complexation-ability of Neutral Schiff Bases to Some Metal Cations

    Topal, Giray; Tümerdem, Recep; Basaran, Ismet; Gümüş, Arzu; Cakir, Umit

    2007-01-01

    The constants of the extraction equilibrium and the distribution for dichloromethane as an organic solvent having low dielectric constant of metal cations with chiral Schiff bases, benzaldehydene-(S)-2-amino-3-phenylpropanol (I), ohydroxybenzaldehydene-( S)-2-amino-3-phenyl-propanol (II), benzaldehydene-(S)-2- amino-3-methylbutanol (III) with anionic dyes [4-(2-pyridylazo)-resorcinol mono sodium monohydrate (NaPar), sodium picrat (NaPic) and potassium picrat (KPic)] and some heavy metal chlor...

  15. Alkali Metal Cation Affinities of Anionic Main Group-Element Hydrides Across the Periodic Table

    Boughlala, Zakaria; Fonseca Guerra, Célia; Bickelhaupt, F. Matthias

    2017-01-01

    We have carried out an extensive exploration of gas-phase alkali metal cation affinities (AMCA) of archetypal anionic bases across the periodic system using relativistic density functional theory at ZORA-BP86/QZ4P//ZORA-BP86/TZ2P. AMCA values of all bases were computed for the lithium, sodium,

  16. Structures of the dehydrogenation products of methane activation by 5d transition metal cations revisited: Deuterium labeling and rotational contours

    Owen, Cameron J.; Boles, Georgia C.; Chernyy, Valeriy; Bakker, Joost M.; Armentrout, P. B.

    2018-01-01

    A previous infrared multiple photon dissociation (IRMPD) action spectroscopy and density functional theory (DFT) study explored the structures of the [M,C,2H]+ products formed by dehydrogenation of methane by four, gas-phase 5d transition metal cations (M+ = Ta+, W+, Ir+, and Pt+). Complicating the analysis of these spectra for Ir and Pt was observation of an extra band in both spectra, not readily identified as a fundamental vibration. In an attempt to validate the assignment of these additional peaks, the present work examines the gas phase [M,C,2D]+ products of the same four metal ions formed by reaction with perdeuterated methane (CD4). As before, metal cations are formed in a laser ablation source and react with methane pulsed into a reaction channel downstream, and the resulting products are spectroscopically characterized through photofragmentation using the free-electron laser for intracavity experiments in the 350-1800 cm-1 range. Photofragmentation was monitored by the loss of D for [Ta,C,2D]+ and [W,C,2D]+ and of D2 in the case of [Pt,C,2D]+ and [Ir,C,2D]+. Comparison of the experimental spectra and DFT calculated spectra leads to structural assignments for all [M,C,2H/2D]+ systems that are consistent with previous identifications and allows a full description of the systematic spectroscopic shifts observed for deuterium labeling of these complexes, some of the smallest systems to be studied using IRMPD action spectroscopy. Further, full rotational contours are simulated for each vibrational band and explain several observations in the present spectra, such as doublet structures in several bands as well as the observed linewidths. The prominent extra bands in the [Pt,C,2D/2H]+ spectra appear to be most consistent with an overtone of the out-of-plane bending vibration of the metal carbene cation structure.

  17. Environmental Remediation and Sorption of Metal Cations Using Aluminum Pillared Nano-Bentonite

    Rifai, Rifai; Abou El Safa, Magda

    2015-04-01

    The release of heavy metal cations into the environment is a potential threat to water and soil quality. Some clay minerals play an important role, as physical and chemical barriers, for the isolation of metal-rich wastes and to adsorb heavy metals as well as to avoid their environmental dispersion. In the present study, the bentonitic clay (southeast El-Hammam City, Egypt) was subjected to pillaring using hydroxyl-aluminum solution. The XRD patterns of the Aluminum Pillared Nano-Bentonite (APNB) showed severe alteration of the crystal structure after pillaring. Poly metal solutions with different metal concentrations of Cu, Co, Ni, Zn, Cd and Pb (0.001, 0.005 and 0.01 moles), and pH (1, 2.5, 5 and 6) were subjected to treatment by the APNB. The removal process is very rapid and spontaneous and the contact time may be short (several minutes) for most adsorption to occur. The criterion for environmental remediation of APNB is less stringent and a short contact time is sufficient. The rate of Cu2+, Zn2+, Co2+, Cd2+, Ni2+ and Pb2+sorption remained higher or equal to the CEC. The sorption of metal ions by APNB are complex and probably involve several mechanisms. In general, APNB can be used to immobilize Cu2+, Zn2+, Co2+, Cd2+, Ni2+ and Pb2+ to any extent. For each metal ion, the most effective immobilization occurs over a particular pH around 5. According to the experimental data obtained, the uptake amount of the studied cations by APNB increased with increasing solution pH, sorbent dose and contact time. The preference of the APNB adsorption for heavy metal ions that are through the cation exchange processes decreases in the order: Cu2+>Zn2+>Co2+>Cd2+ >Ni2+ >Pb2+. Keywords: Bentonitic clay, Egypt, Aluminum Pillared Nano-Bentonite, heavy metal, environmental remediation

  18. Melt cationic and anionic composition effect on titanium group metal corrosion in halogenides of alkali earths

    Tkhaj, V.; Kovalik, O.Yu.; Dikunov, Yu.G.; P'yankova, S.P.

    1997-01-01

    A study was made on interaction of titanium group metals with melts of chlorides and chloride-fluorides of alkaline earth metals and magnesium. It was revealed that the rate of metal corrosion increased from BaCl 2 2 2 2 in chloride series. It is explained by amplification of oxidation activity of salt cation in the series: Ba 2+ 2+ 2+ 2+ . It was also determined that corrosion rate of titanium exceeded the one of zirconium and hafnium, became reducing power of titanium was the highest in the given group

  19. Simultaneous electrochemical-electron spin resonance studies of carotenoid cation radicals and dications

    Khaled, M.; Hadjipetrou, A.; Xinhai Chen; Kispert, L.

    1989-01-01

    Carotenoids are present in the chloroplasts of photosynthetic green plants and serve as photoprotect devices and antenna pigments, and active role in the photosynthetic electron-transport chain with the carotenoid cation radical as an integral part of the electron-transfer process. The research reported herein has confirmed that carotenoid cation radicals have a lifetime that is sensitive to solvent, being longest in CH 2 Cl 2 and are best prepared electrochemically. Semiempirical AM1 and INDO calculations of the trans and cis isomers of β-carotene, canthaxanthin and β-apo-8'-carotenal cation radicals predicted the unresolved EPR line whose linewidth varies to a measurable degree with carotenoid, which subsequent experimental observations affirmed. Simultaneous electrochemical - electron spin resonance studies of carotenoid cation radicals and dications have shown the radicals detected by EPR are formed by the one electron oxidation of the carotenoid, that dimers are not formed upon decay of the radical cations and an estimate of the rate of comproportionation as a function of carotenoid can be given. The formal rate constant K' for heterogenous electron transfer rate at the electrode surface has been deduced from rotating disc experiments. Upon deuteration, and in the presence of excess β-carotene, the half-life for decay of the carotenoid radical cation increased an order of magnitude due to the reaction between diffusion carotenoid dications and carotenoids to form additional radical cations. The carotenoid diffusion coefficients deduced by chronocoulometry substantiates this measurement. The produces formed upon electrochemical studies are being studied by HPLC and the isomers formed thermally are being separated. Additional radical reactions are currently being studied by EPR and electrochemical methods

  20. Tetracyanidoborates with triply charged rare earth metal cations and their optical properties

    Hackbarth, Liisa

    2015-11-24

    The aim of this thesis is the description of the synthesis and characterization of a new group of tetracyanidoborates: tetracyanidoborates with trivalent rare earth metal cations. Their optical properties in the ultraviolet and visible range are also discussed. Common synthetic routes for tetracyanidoborates are adapted and applied to the preparation of the rare earth tetracyanidoborate hydrates. They are accessible with high yields and high purity through a reaction between the tetracyanidoboronic acid and rare earth hydroxides. It is shown that the rare earth tetracyanidoborates form isostructural groups, like the [LRE(H{sub 2}O){sub 5}][B(CN){sub 4}]{sub 3}.0.5 H{sub 2}O, where LRE{sup 3+} is La, Ce, Pr, Nd, Sm, Eu and Gd, the [HRE(H{sub 2}O){sub 7}][B(CN){sub 4}]{sub 3} and the [HRE(H{sub 2}O){sub 8}][B(CN){sub 4}]{sub 3}.3 H{sub 2}O, where HRE{sup 3+} is Tb, Dy, Ho, Er, Tm, Yb, Lu and Y. Furthermore, the coordination number 9 is noticed to be common among the light rare earth cations, whereas the minor coordination number 8 is prevalent for the heavy rare earth cations in their tetracyanidoborates. This different construction of the coordination spheres between light and heavy rare earth cations leads to different structures depending on the energetic efficiency of the structural arrangement. Generally, the rare earth tetracyanidoborate hydrates are found to crystallize in the monoclinic crystal system. Moreover, other different crystal structures are observed depending on the crystallization temperature and the type of coordinated ligands and co-crystallized solvent molecules. The tetracyanidoborate hydrates with triply charged rare earth cations are characterized comprehensively by X-ray diffraction, vibrational spectroscopy, NMR-spectroscopy as well as by thermal analysis. Furthermore, the optical properties of some dehydrated rare earth tetracyanidoborates are investigated by UV-spectroscopy and luminescence measurements. The results of the optical

  1. Tetracyanidoborates with triply charged rare earth metal cations and their optical properties

    Hackbarth, Liisa

    2015-01-01

    The aim of this thesis is the description of the synthesis and characterization of a new group of tetracyanidoborates: tetracyanidoborates with trivalent rare earth metal cations. Their optical properties in the ultraviolet and visible range are also discussed. Common synthetic routes for tetracyanidoborates are adapted and applied to the preparation of the rare earth tetracyanidoborate hydrates. They are accessible with high yields and high purity through a reaction between the tetracyanidoboronic acid and rare earth hydroxides. It is shown that the rare earth tetracyanidoborates form isostructural groups, like the [LRE(H_2O)_5][B(CN)_4]_3.0.5 H_2O, where LRE"3"+ is La, Ce, Pr, Nd, Sm, Eu and Gd, the [HRE(H_2O)_7][B(CN)_4]_3 and the [HRE(H_2O)_8][B(CN)_4]_3.3 H_2O, where HRE"3"+ is Tb, Dy, Ho, Er, Tm, Yb, Lu and Y. Furthermore, the coordination number 9 is noticed to be common among the light rare earth cations, whereas the minor coordination number 8 is prevalent for the heavy rare earth cations in their tetracyanidoborates. This different construction of the coordination spheres between light and heavy rare earth cations leads to different structures depending on the energetic efficiency of the structural arrangement. Generally, the rare earth tetracyanidoborate hydrates are found to crystallize in the monoclinic crystal system. Moreover, other different crystal structures are observed depending on the crystallization temperature and the type of coordinated ligands and co-crystallized solvent molecules. The tetracyanidoborate hydrates with triply charged rare earth cations are characterized comprehensively by X-ray diffraction, vibrational spectroscopy, NMR-spectroscopy as well as by thermal analysis. Furthermore, the optical properties of some dehydrated rare earth tetracyanidoborates are investigated by UV-spectroscopy and luminescence measurements. The results of the optical measurements indicate that the tetracyanidoborates with rare earth metal cations

  2. Toxic effect of metal cation binary mixtures to the seaweed Gracilaria domingensis (Gracilariales, Rhodophyta).

    Mendes, Luiz Fernando; Stevani, Cassius Vinicius; Zambotti-Villela, Leonardo; Yokoya, Nair Sumie; Colepicolo, Pio

    2014-01-01

    The macroalga Gracilaria domingensis is an important resource for the food, pharmaceutical, cosmetic, and biotechnology industries. G. domingensis is at a part of the food web foundation, providing nutrients and microelements to upper levels. As seaweed storage metals in the vacuoles, they are considered the main vectors to magnify these toxic elements. This work describes the evaluation of the toxicity of binary mixtures of available metal cations based on the growth rates of G. domingensis over a 48-h exposure. The interactive effects of each binary mixture were determined using a toxic unit (TU) concept that was the sum of the relative contribution of each toxicant and calculated using the ratio between the toxicant concentration and its endpoint. Mixtures of Cd(II)/Cu(II) and Zn(II)/Ca(II) demonstrated to be additive; Cu(II)/Zn(II), Cu(II)/Mg(II), Cu(II)/Ca(II), Zn(II)/Mg(II), and Ca(II)/Mg(II) mixtures were synergistic, and all interactions studied with Cd(II) were antagonistic. Hypotheses that explain the toxicity of binary mixtures at the molecular level are also suggested. These results represent the first effort to characterize the combined effect of available metal cations, based on the TU concept on seaweed in a total controlled medium. The results presented here are invaluable to the understanding of seaweed metal cation toxicity in the marine environment, the mechanism of toxicity action and how the tolerance of the organism.

  3. Hydrocolloid liquid-core capsules for the removal of heavy-metal cations from water

    Nussinovitch, A., E-mail: amos.nussi@mail.huji.ac.il; Dagan, O.

    2015-12-15

    Highlights: • Novel liquid-core capsules with a non-crosslinked alginate core were produced. • Capsules demonstrated highest efficiency adsorption of ∼300 mg Pb{sup 2+}/g alginate. • Regeneration was carried out by suspending capsules in 1 M HNO{sub 3} for 24 h. • Adsorption capacities of the capsules followed the order: Pb{sup 2+} > Cu{sup 2+} > Cd{sup 2+} > Ni{sup 2+}. - Abstract: Liquid-core capsules with a non-crosslinked alginate fluidic core surrounded by a gellan membrane were produced in a single step to investigate their ability to adsorb heavy metal cations. The liquid-core gellan–alginate capsules, produced by dropping alginate solution with magnesium cations into gellan solution, were extremely efficient at adsorbing lead cations (267 mg Pb{sup 2+}/g dry alginate) at 25 °C and pH 5.5. However, these capsules were very weak and brittle, and an external strengthening capsule was added by using magnesium cations. The membrane was then thinned with the surfactant lecithin, producing capsules with better adsorption attributes (316 mg Pb{sup +2}/g dry alginate vs. 267 mg Pb{sup +2}/g dry alginate without lecithin), most likely due to the thinner membrane and enhanced mass transfer. The capsules’ ability to adsorb other heavy-metal cations – copper (Cu{sup 2+}), cadmium (Cd{sup 2+}) and nickel (Ni{sup 2+}) – was tested. Adsorption efficiencies were 219, 197 and 65 mg/g, respectively, and were correlated with the cation’s affinity to alginate. Capsules with the sorbed heavy metals were regenerated by placing in a 1 M nitric acid suspension for 24 h. Capsules could undergo three regeneration cycles before becoming damaged.

  4. Electronic Spectra of the Tetraphenylcyclobutadienecyclopentadienylnickel(II) Cation and Radical

    Craig, P. R.; Havlas, Zdeněk; Trujillo, M.; Rempala, P.; Kirby, J. P.; Miller, J. R.; Noll, B. C.; Michl, Josef

    2016-01-01

    Roč. 120, č. 20 (2016), s. 3456-3462 ISSN 1089-5639 R&D Projects: GA ČR(CZ) GBP208/12/G016 Institutional support: RVO:61388963 Keywords : cyclobutadiene-metal complexes * tetragonal star connectors * square grid polymer * halides Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 2.847, year: 2016

  5. Selective transport of metal ions through cation exchange membrane in the presence of a complexing agent

    Tingchia Huang; Jaukai Wang (National Cheng Kung Univ., Tainan (Taiwan, Province of China))

    1993-01-01

    Selective transport of metal ions through a cation exchange membrane was studied in stirred batch dialyzer for the systems Ni[sup 2+]-Cu[sup 2+] and Cu[sup 2+]-Fe[sup 3+]. Oxalic acid, malonic acid, citric acid, glycine, and ethylenediaminetetraacetic acid were employed as the complexing agents added in the feed solution in order to increase the permselectivity of metal ions. The experimental results show that the selective transport behavior of metal ions depends on the valence and the concentration of metal ions, the stoichiometric ratio of complexing agent to metal ions, and the pH value of the feed solution, but is independent of the concentration of counterion in the stripping phase. A theoretical approach was formulated on the basis of the Nernst-Planck equation and interface quasi-equilibrium. Theoretical solutions obtained from numerical calculation were in agreement with the experimental data.

  6. Influence of reason citric acid/ metal cations in the synthesis of mullite by Pechini Method

    Braga, A.N.S.; Costa, D.L.; Farias, R.M.C.; Neves, G.A.; Lira, H.L.; Menezes, R.R.

    2014-01-01

    Mullite is a ceramic material with high technological applications. Its synthesis has been extensively studied due to their excellent properties. Thus, this paper proposes to obtain mullite by Pechini method. The amount of acid citric/metal cations in proportions of 3:1 and 1:1 were investigated in order to understand their influence in obtaining the mullite phase. The synthesized samples were characterized by X-ray diffraction (XRD) and thermal analysis (TG/DTG and DTA). The results showed that the ratio citric acid/metal cations influence on the formed phase with the mullite obtained only in proportion 1:1. With the increase of the ratio to 3:1 was observed the formation of the alumina layer. (author)

  7. Synthesis of phthalide-fused indoline by microwave irradiation and preliminary binding study with metal cations

    Ling, Sheryn Wong Shue; Latip, Jalifah; Hassan, Nurul Izzaty; Hasbullah, Siti Aishah

    2018-04-01

    An efficient and green method of synthesizing phthalide-fused indoline, 3-[(1,3,3-trimethylindolin-2-ylidene)methyl]isobenzofuran-1(3H)-one (3) has been developed by the coupling reaction of 1,3,3-trimethyl-2-methyleneindoline, 1 and phthalaldehydic acid, 2 under solvent-free domestic microwave irradiation. The compound was produced with an excellent yield (98 %) and at a shorter reaction time (5 min) as compared to the conventional method. Compound 3 was fully characterized by analytical and spectral methods. Preliminary binding study of 3 towards different types of metal cations was done by "naked eye" colorimetric detection and UV-vis spectrophotometer. Compound 3 exhibits good selectivity and sensitivity for Sn2+ compared to other metal cations.

  8. Electromembrane extraction of heavy metal cations followed by capillary electrophoresis with capacitively coupled contactless conductivity detection

    Kubáň, Pavel; Strieglerová, Lenka; Gebauer, Petr; Boček, Petr

    2011-01-01

    Roč. 32, č. 9 (2011), s. 1025-1032 ISSN 0173-0835 R&D Projects: GA ČR GA203/08/1536; GA ČR GAP206/10/1219; GA AV ČR IAA400310703 Institutional research plan: CEZ:AV0Z40310501 Keywords : capillary electrophoresis * electromembrane extraction * heavy metal cations Subject RIV: CB - Analytical Chemistry, Separation Impact factor: 3.303, year: 2011

  9. The role of alkali metal cations in the stabilization of guanine quadruplexes: why K(+) is the best.

    Zaccaria, F; Paragi, G; Fonseca Guerra, C

    2016-08-21

    The alkali metal ion affinity of guanine quadruplexes has been studied using dispersion-corrected density functional theory (DFT-D). We have done computational investigations in aqueous solution that mimics artificial supramolecular conditions where guanine bases assemble into stacked quartets as well as biological environments in which telomeric quadruplexes are formed. In both cases, an alkali metal cation is needed to assist self-assembly. Our quantum chemical computations on these supramolecular systems are able to reproduce the experimental order of affinity of the guanine quadruplexes for the cations Li(+), Na(+), K(+), Rb(+), and Cs(+). The strongest binding is computed between the potassium cation and the quadruplex as it occurs in nature. The desolvation and the size of alkali metal cations are thought to be responsible for the order of affinity. Until now, the relative importance of these two factors has remained unclear and debated. By assessing the quantum chemical 'size' of the cation, determining the amount of deformation of the quadruplex needed to accommodate the cation and through the energy decomposition analysis (EDA) of the interaction energy between the cation and the guanines, we reveal that the desolvation and size of the alkali metal cation are both almost equally responsible for the order of affinity.

  10. Electron-molecular cation reactive collisions: from channel mixing to competitive processes

    Motapon, O; Tamo, F O Waffeu; Backodissa, D; Chakrabarti, K; Mezei, J. Zs; Lique, F; Schneider, I F; Tudorache, D; Bultel, A; Tchang-Brillet, L; Dulieu, O; Tennyson, J; Wolf, A; Urbain, X

    2011-01-01

    The competition between dissociative recombination, vibrational excitation, and dissociative excitation of molecular cations in electron-impact collisions is discussed within the formalism of the Multichannel Quantum Defect Theory. Illustrative results are given for the HD + /HD and CO + /CO systems.

  11. Use of MgO doped with a divalent or trivalent metal cation for removing arsenic from water

    Moore, Robert C; Holt-Larese, Kathleen C; Bontchev, Ranko

    2013-08-13

    Systems and methods for use of magnesium hydroxide, either directly or through one or more precursors, doped with a divalent or trivalent metal cation, for removing arsenic from drinking water, including water distribution systems. In one embodiment, magnesium hydroxide, Mg(OH).sub.2 (a strong adsorbent for arsenic) doped with a divalent or trivalent metal cation is used to adsorb arsenic. The complex consisting of arsenic adsorbed on Mg(OH).sub.2 doped with a divalent or trivalent metal cation is subsequently removed from the water by conventional means, including filtration, settling, skimming, vortexing, centrifugation, magnetic separation, or other well-known separation systems. In another embodiment, magnesium oxide, MgO, is employed, which reacts with water to form Mg(OH).sub.2. The resulting Mg(OH).sub.2 doped with a divalent or trivalent metal cation, then adsorbs arsenic, as set forth above. The method can also be used to treat human or animal poisoning with arsenic.

  12. Use of MgO doped with a divalent or trivalent metal cation for removing arsenic from water

    Moore, Robert C.; Larese, Kathleen Caroline; Bontchev, Ranko Panayotov

    2017-05-30

    Systems and methods for use of magnesium hydroxide, either directly or through one or more precursors, doped with a divalent or trivalent metal cation, for removing arsenic from drinking water, including water distribution systems. In one embodiment, magnesium hydroxide, Mg(OH).sub.2 (a strong adsorbent for arsenic) doped with a divalent or trivalent metal cation is used to adsorb arsenic. The complex consisting of arsenic adsorbed on Mg(OH).sub.2 doped with a divalent or trivalent metal cation is subsequently removed from the water by conventional means, including filtration, settling, skimming, vortexing, centrifugation, magnetic separation, or other well-known separation systems. In another embodiment, magnesium oxide, MgO, is employed, which reacts with water to form Mg(OH).sub.2. The resulting Mg(OH).sub.2 doped with a divalent or trivalent metal cation, then adsorbs arsenic, as set forth above. The method can also be used to treat human or animal poisoning with arsenic.

  13. Synergistic extraction of some divalent metal cations into nitrobenzene by using strontium dicarbollylcobaltate and electroneutral macrocyclic lactam receptor

    Makrlík, E.; Sedláková, Zdeňka; Vaňura, P.; Selucký, P.

    2013-01-01

    Roč. 295, č. 3 (2013), s. 2263-2266 ISSN 0236-5731 Institutional support: RVO:61389013 Keywords : divalent metal cations * macrocyclic lactam receptor * complexation Subject RIV: CD - Macromolecular Chemistry Impact factor: 1.415, year: 2013

  14. Electron-impact excitation of diatomic hydride cations II: OH+ and SH+

    Hamilton, James R.; Faure, Alexandre; Tennyson, Jonathan

    2018-05-01

    R-matrix calculations combined with the adiabatic-nuclei-rotation and Coulomb-Born approximations are used to compute electron-impact rotational rate coefficients for two open-shell diatomic cations of astrophysical interest: the hydoxyl and sulphanyl ions, OH+ and SH+. Hyperfine resolved rate coefficients are deduced using the infinite-order-sudden approximation. The propensity rule ΔF = Δj = ΔN = ±1 is observed, as is expected for cations with a large dipole moment. A model for OH+ excitation in the Orion Bar photon-dominated region is presented which nicely reproduces Herschel observations for an electron fraction xe = 10-4 and an OH+ column density of 3 × 1013 cm-2. Electron-impact electronic excitation cross-sections and rate coefficients for the ions are also presented.

  15. Alkali Metal Cation Affinities of Anionic Main Group-Element Hydrides Across the Periodic Table.

    Boughlala, Zakaria; Fonseca Guerra, Célia; Bickelhaupt, F Matthias

    2017-10-05

    We have carried out an extensive exploration of gas-phase alkali metal cation affinities (AMCA) of archetypal anionic bases across the periodic system using relativistic density functional theory at ZORA-BP86/QZ4P//ZORA-BP86/TZ2P. AMCA values of all bases were computed for the lithium, sodium, potassium, rubidium and cesium cations and compared with the corresponding proton affinities (PA). One purpose of this work is to provide an intrinsically consistent set of values of the 298 K AMCAs of all anionic (XH n-1 - ) constituted by main group-element hydrides of groups 14-17 along the periods 2-6. In particular, we wish to establish the trend in affinity for a cation as the latter varies from proton to, and along, the alkali cations. Our main purpose is to understand these trends in terms of the underlying bonding mechanism using Kohn-Sham molecular orbital theory together with a quantitative bond energy decomposition analyses (EDA). © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. Potential-modulated intercalation of alkali cations into metal hexacyanoferrate coated electrodes. 1998 annual progress report

    Schwartz, D.T.

    1998-01-01

    'This program is studying potential-driven cation intercalation and deintercalation in metal hexacyanoferrate compounds, with the eventual goal of creating materials with high selectivity for cesium separations and long cycle lifetimes. The separation of radiocesium from other benign cations has important implications for the cost of processing a variety of cesium contaminated DOE wasteforms. This report summarizes results after nine months of work. Much of the initial efforts have been directed towards quantitatively characterizing the selectivity of nickel hexacyanoferrate derivatized electrodes for intercalating cesium preferentially over other alkali metal cations. Using energy dispersive xray spectroscopy (ex-situ, but non-destructive) and ICP analysis (ex-situ and destructive), the authors have demonstrated that the nickel hexacyanoferrate lattice has a strong preference for intercalated cesium over sodium. For example, when ions are reversibly loaded into a nickel hexacyanoferrate thin film from a solution containing 0.9999 M Na + and 0.0001 M Cs + , the film intercalates 40% as much Cs + as when loaded from pure 1 M Cs + containing electrolyte (all electrolytes use nitrates as the common anion). The authors have also shown that, contrary to the common assumptions found in the literature, a significant fraction of the thin film is not active initially. A new near infrared laser has been purchased and is being added to the Raman spectroscopy facilities to allow in-situ studies of the intercalation processes.'

  17. Electron beam irradiation on cation exchanger used for strontium recovery

    Watanabe, Sou; Nakamura, Masahiro; Nomura, Kazunori; Nakajima, Yasuo; Okamoto, Yoshihiro

    2014-01-01

    Titanate is promising material for radioactive Sr recovery from liquid waste generated in the nuclear facilities. "9"0Sr is one of the most important nuclides in order to release the liquid waste into the environment due to its strong beta-ray decay energy. Although the titanate is applied to radioactive Sr decontamination facility, their resistance to irradiations from radioactive elements adsorbed is not widely investigated so far. In this study, durability of a hydrous titanic acid ion exchanger against beta-ray irradiation were evaluated through electron beam irradiation, elution behaviour of Sr after the irradiation and local structural analysis of the titanate. 1.4 MGy irradiation led to 1% of Sr elution, and the elution could be attributed to defects of O in the titanate induced by the irradiation. Chemical state of Ti of the titanate must be stable up to 2.7 MGy irradiation. (author)

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

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

    1992-01-01

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

  19. A sigmoidal model for biosorption of heavy metal cations from aqueous media.

    Özen, Rümeysa; Sayar, Nihat Alpagu; Durmaz-Sam, Selcen; Sayar, Ahmet Alp

    2015-07-01

    A novel multi-input single output (MISO) black-box sigmoid model is developed to simulate the biosorption of heavy metal cations by the fission yeast from aqueous medium. Validation and verification of the model is done through statistical chi-squared hypothesis tests and the model is evaluated by uncertainty and sensitivity analyses. The simulated results are in agreement with the data of the studied system in which Schizosaccharomyces pombe biosorbs Ni(II) cations at various process conditions. Experimental data is obtained originally for this work using dead cells of an adapted variant of S. Pombe and represented by Freundlich isotherms. A process optimization scheme is proposed using the present model to build a novel application of a cost-merit objective function which would be useful to predict optimal operation conditions. Copyright © 2015. Published by Elsevier Inc.

  20. One-electron theory of metals

    Skriver, H.L.

    1984-12-01

    The work described in the report and the 16 accompanying publications is based upon a one-electron theory obtained within the local approximation to density-functional theory, and deals with the ground state of metals as obtained from self-consistent electronic-structure calculations performed by means of the Linear Muffin-Tin Orbital (LMTO) method. It has been the goal of the work to establish how well this one-electron approach describes physical properties such as the crystal structures of the transition metals, the structural phase transitions in the alkali, alkaline earth, and rare earth metals, and the localization of 3d, 4f, and 5f electrons in the 3d metal monoxides, the light lanthanides, and the actinides, respectively, as well as the cohesive properties of metals in general. (orig.)

  1. Electronic structure of metallic glasses

    Oelhafen, P.; Lapka, R.; Gubler, U.; Krieg, J.; DasGupta, A.; Guentherodt, H.J.; Mizoguchi, T.; Hague, C.; Kuebler, J.; Nagel, S.R.

    1981-01-01

    This paper is organized in six sections and deals with (1) the glassy transition metal alloys, their d-band structure, the d-band shifts on alloying and their relation to the alloy heat of formation (ΔH) and the glass forming ability, (2) the glass to crystal phase transition viewed by valence band spectroscopy, (3) band structure calculations, (4) metallic glasses prepared by laser glazing, (5) glassy normal metal alloys, and (6) glassy hydrides

  2. Metal shadowing for electron microscopy.

    Hendricks, Gregory M

    2014-01-01

    Metal shadowing of bacteria, viruses, isolated molecules, and macromolecular assemblies is another high-resolution method for observing the ultrastructure of biological specimens. The actual procedure for producing a metal shadow is relatively simple; a heavy metal is evaporated from a source at an oblique angle to the specimen. The metal atoms pile up on the surfaces that face the source, but the surfaces away from the source are shielded and receive little metal deposit, creating a "shadow." However, the process of producing biological specimens that are suitable for metal shadowing can be very complex. There are a whole host of specimen preparation techniques that can precede metal shadowing, and all provide superior preservation in comparison to air drying, a required step in negative staining procedures. The physical forces present during air drying (i.e., surface tension of the water-air interface) will literally crush most biological specimens as they dry. In this chapter I explain the development of and procedures for the production of biological specimens from macromolecular assemblies (e.g., DNA and RNA), purified isolated molecules (e.g., proteins), and isolated viruses and bacteria preparations suitable for metal shadowing. A variation on this basic technique is to rotate the specimen during the metal deposition to produce a high-resolution three-dimensional rendering of the specimen.

  3. On the real performance of cation exchange resins in wastewater treatment under conditions of cation competition: the case of heavy metal pollution.

    Prelot, Benedicte; Ayed, Imen; Marchandeau, Franck; Zajac, Jerzy

    2014-01-01

    Sorption performance of cation-exchange resins Amberlite® IRN77 and Amberlite™ IRN9652 toward Cs(I) and Sr(II) has been tested in single-component aqueous solutions and simulated waste effluents containing other monovalent (Effluent 1) or divalent (Effluent 2) metal cations, as well as nitrate, borate, or carbonate anions. The individual sorption isotherms of each main component were measured by the solution depletion method. The differential molar enthalpy changes accompanying the ion-exchange between Cs+ or Sr2+ ions and protons at the resin surface from single-component nitrate solutions were measured by isothermal titration calorimetry and they showed a higher specificity of the two resins toward cesium. Compared to the retention limits of both resins under such idealized conditions, an important depression in the maximum adsorption capacity toward each main component was observed in multication systems. The overall effect of ion exchange process appeared to be an unpredictable outcome of the individual sorption capacities of the two resins toward various cations as a function of the cation charge, size, and concentration. The cesium retention capacity of the resins was diminished to about 25% of the "ideal" value in Effluent 1 and 50% in Effluent 2; a further decrease to about 15% was observed upon concomitant strontium addition. The uptake of strontium by the resins was found to be less sensitive to the addition of other metal components: the greatest decrease in the amount adsorbed was 60% of the ideal value in the two effluents for Amberlite® IRN77 and 75% for Amberlite™ IRN9652. It was therefore demonstrated that any performance tests carried out under idealized conditions should be exploited with much caution to predict the real performance of cation exchange resins under conditions of cation competition.

  4. A review of modelling the interaction between natural organic matter and metal cations

    Falck, W.E.

    1989-01-01

    This report reviews techniques available to model the interaction between natural organic matter (mainly fulvic and humic acids) and metal cations and protons. A comprehensive overview over the properties of natural organic matter is given and experimental techniques are presented briefly. Two major concepts of modelling have been identified: discrete ligand models and continuous distribution model. Different modelling approaches like Discrete Ligand Models (s.s.), Random-Structure Model, Affinity Spectra, Statistical Distribution Models, Continuous Stability Function Models and surface sorption models and their advantages/disadvantages are discussed. (author)

  5. Synthesis and adsorption investigations of zeolites MCM-22 and MCM-49 modified by alkali metal cations

    Pawlesa, Justyna; Zukal, Arnošt; Čejka, Jiří

    2007-01-01

    Roč. 13, 3-4 (2007), s. 257-265 ISSN 0929-5607 Grant - others:DeSSANS(XE) SES6-CT-2005-020133; INDENS(XE) MRTN-CT-2004-005503 Institutional research plan: CEZ:AV0Z40400503 Source of funding: R - rámcový projekt EK ; R - rámcový projekt EK Keywords : MCM-22 zeolite * MCM-49 zeolite * alkali metal cation exchange * N2 and CO2 adsorption Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 0.880, year: 2007

  6. Study of the interaction metallic cation - ligand in concentrated phosphorus acid media

    Sefiani, N.; Azzi, M.; Hlaibi, M.; Kossair, A.

    2005-01-01

    The phosphoric acid is more and more used with a high purity. The recovery of recycling element (uranium, vanadium, rare earth...) and the elimination of toxic element (cadmium, molybdenum, lead...) contained in the phosphoric acid are generally realized by extraction or precipitation. It is then very important to understand these impurities behavior in the phosphoric media in order to control their elimination. In this work, the authors considered the presence of some metallic cations (V, Al, fe, U) and fluorides ions as impurity in concentrated phosphoric acid media. (A.L.B.)

  7. Rapid and selective adsorption of cationic dyes by a unique metal-organic framework with decorated pore surface

    Zhang, Jie; Li, Fan; Sun, Qian

    2018-05-01

    Organic dye pollutants become a big headache due to their toxic nature to the environment, and it should be one of the best solutions if we can remove and separate them. Here, a metal-organic framework (MOF) (denoted as Zn-MOF) with carbonyl group based on fluorenone-2,7-dicarboxylate ligand, was directly synthesized without post-synthesis method and applied to selectively absorb cationic dyes such as MB, CV, RhB from aqueous solution, while anionic or neutral dyes were excluded. Characterization of the Zn-MOF was achieved by X-ray diffraction, scanning electron microscope, Fourier transform infrared spectrometry and elemental analysis. The Zn-MOF mainly possesses open pore channels, high surface area, big pore volume, and most important, the pore surface is furnished with carbonyl groups arising from the ligand and pointing toward the centers of the large chambers of the framework, which are benefit for the adsorption of the cationic dyes. The MB maximum adsorption capacities can attain 326 mg g-1, which is probably due to the suitable pore size, higher solvent-accessible void, and the prominent adsorption capacity of the mesoporous material. The dye adsorption process for the material is proven to be charge-selective and size-selective, and the adsorption isotherms, as well as kinetics characteristic of dye adsorption onto the Zn-MOF were also investigated.

  8. Impact of spreading olive mill waste water on agricultural soils for leaching of metal micronutrients and cations.

    Aharonov-Nadborny, R; Tsechansky, L; Raviv, M; Graber, E R

    2017-07-01

    Olive mill waste water (OMWW) is an acidic (pH 4-5), saline (EC ∼ 5-10 mS cm -1 ), blackish-red aqueous byproduct of the three phase olive oil production process, with a high chemical oxygen demand (COD) of up to 220,000 mg L -1 . OMWW is conventionally disposed of by uncontrolled dumping into the environment or by semi-controlled spreading on agricultural soils. It was hypothesized that spreading such liquids on agricultural soils could result in the release and mobilization of indigenous soil metals. The effect of OMWW spreading on leaching of metal cations (Na, K, Mg, Mn, Fe, Cu, Zn) was tested in four non-contaminated agricultural soils having different textures (sand, clay loam, clay, and loam) and chemical properties. While the OMWW contributed metals to the soil solution, it also mobilized indigenous soil metals as a function of soil clay content, cation exchange capacity (CEC), and soil pH-buffer capacity. Leaching of soil-originated metals from the sandy soil was substantially greater than from the loam and clay soils, while the clay loam was enriched with metals derived from the OMWW. These trends were attributed to cation exchange and organic-metal complex formation. The organic matter fraction of OMWW forms complexes with metal cations; these complexes may be mobile or precipitate, depending on the soil chemical and physical environment. Copyright © 2017 Elsevier Ltd. All rights reserved.

  9. Impact of metal cations on the electrocatalytic properties of Pt/C nanoparticles at multiple phase interfaces.

    Durst, Julien; Chatenet, Marian; Maillard, Frédéric

    2012-10-05

    Proton-exchange membrane fuel cells (PEMFCs) use carbon-supported nanoparticles based on platinum and its alloys to accelerate the rate of the sluggish oxygen-reduction reaction (ORR). The most common metals alloyed to Pt include Co, Ni and Cu, and are thermodynamically unstable in the PEMFC environment. Their dissolution yields the formation and redistribution of metal cations (M(y+)) within the membrane electrode assembly (MEA). Metal cations can also contaminate the MEA when metallic bipolar plates are used as current collectors. In each case, the electrical performance of the PEMFC severely decreases, an effect that is commonly attributed to the poisoning of the sulfonic acid groups of the perfluorosulfonated membrane (PEM) and the resulting decrease of the proton transport properties. However, the impact of metal cations on the kinetics of electrochemical reactions involving adsorption/desorption and bond-breaking processes remains poorly understood. In this paper, we use model electrodes to highlight the effect of metal cations on Pt/C nanoparticles coated or not with a perfluorosulfonated ionomer for the CO electrooxidation reaction and the oxygen reduction reaction. We show that metal cations negatively impact the ORR kinetics and the mass-transport resistance of molecular oxygen. However, the specific adsorption of sulfonate groups of the Nafion® ionomer locally modifies the double layer structure and increases the tolerance to metal cations, even in the presence of sulphate ions in the electrolyte. The survey is extended by using an ultramicroelectrode with cavity and a solid state cell (SSC) specifically developed for this study.

  10. Stretchable and Soft Electronics using Liquid Metals.

    Dickey, Michael D

    2017-07-01

    The use of liquid metals based on gallium for soft and stretchable electronics is discussed. This emerging class of electronics is motivated, in part, by the new opportunities that arise from devices that have mechanical properties similar to those encountered in the human experience, such as skin, tissue, textiles, and clothing. These types of electronics (e.g., wearable or implantable electronics, sensors for soft robotics, e-skin) must operate during deformation. Liquid metals are compelling materials for these applications because, in principle, they are infinitely deformable while retaining metallic conductivity. Liquid metals have been used for stretchable wires and interconnects, reconfigurable antennas, soft sensors, self-healing circuits, and conformal electrodes. In contrast to Hg, liquid metals based on gallium have low toxicity and essentially no vapor pressure and are therefore considered safe to handle. Whereas most liquids bead up to minimize surface energy, the presence of a surface oxide on these metals makes it possible to pattern them into useful shapes using a variety of techniques, including fluidic injection and 3D printing. In addition to forming excellent conductors, these metals can be used actively to form memory devices, sensors, and diodes that are completely built from soft materials. The properties of these materials, their applications within soft and stretchable electronics, and future opportunities and challenges are considered. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. Resorcarene-based receptor: versatile behavior in its interaction with heavy and soft metal cations.

    Danil de Namor, Angela F; Chaaban, Jinane K; Piro, Oscar E; Castellano, Eduardo E

    2006-02-09

    Standard solution Gibbs energies, DeltasG degrees, of the resorcarene-based receptor 5,11,17,23-ethylthiomethylated calix[4]resorcarene, (characterized by 1H NMR and X-ray diffraction studies) in its monomeric state (established through partition experiments) in various solvents are for the first time reported in the area of resorcarene chemistry. Transfer Gibbs energies of from hexane (reference solvent) to other medium are calculated. Agreement between DeltatG degrees (referred to the pure solvents) and standard partition Gibbs energies, DeltapG degrees (solvent mutually saturated) is found. Cation-ligand interactions were investigated through 1H NMR (CD3CN and CD3OD) and conductometric titrations in acetonitrile and methanol. 1H NMR data revealed the sites of interaction of with the metal cation. The composition of the metal-ion complexes (Ag+ and Pb2+ in acetonitrile and Ag+ and Cu2+ in methanol) was established through conductometric titrations. Thus, complexes of 1:1 stoichiometry were formed between and Ag+ and Pb2+ in acetonitrile and Cu2+ in methanol. However, in moving from acetonitrile to methanol, the composition of the silver complex was altered. Thus, two metal cations are hosted by a unit of the ligand. As far as Cu2+ and in acetonitrile is concerned, conductance data suggest that metalates are formed in which up to four units of Cu2+ are taken up per unit of resorcarene. The contrasting behavior of with Cu2+ in acetonitrile relative to methanol is discussed. As far as mercury (II) is concerned, the unusual jump in conductance observed in the titration of Hg2+ with in acetonitrile and methanol after the formation of a multicharged complex (undefined composition) is attributed to the presence of highly charged smaller units (higher mobility) resulting from the departure of pendant arms from the resorcarene backbone. Isolation of these species followed by X-ray diffraction studies corroborated this statement. The thermodynamic characterization of metal

  12. Cation exchange separation of 16 rare earth metals by microscale high-performance liquid chromatography

    Ishii, D.; Hirose, A.; Iwasaki, Y.

    1978-01-01

    The separation of rare earth metals has been studied with a microcolumn of 0.5 mm i.d. and 75 mm length, packed with TSK LS-212 high-performance cation exchange resin. A micro-feeder (Model MF-2, from Azumadenki Kogyo) was used to drive carrier and sample solutions through the ion exchange column and detection cell. By combining a 250 μl syringe and a 0.5 mm i.d. sampling tube the micro-feeder, 0.1-1.0 μl rare earth metals were separated within 38 min, using only 304 μl of 0.4M α-hydroxy-isobutyric acid solution adjusted to pH 3.1-6.0 with ammonia solution as gradient carrier solution. The gradient elution was successfully performed by applying a new technique developed for microscale liquid chromatography. (author)

  13. A Study of Complexation-ability of Neutral Schiff Bases to Some Metal Cations

    Umit Cakir

    2007-09-01

    Full Text Available The constants of the extraction equilibrium and the distribution fordichloromethane as an organic solvent having low dielectric constant of metal cations withchiral Schiff bases, benzaldehydene-(S-2-amino-3-phenylpropanol (I, o- benzaldehydene-(S-2-hydroxybenzaldehydene-(S-2-amino-3-phenyl-propanol (II,amino-3-methylbutanol (III with anionic dyes [4-(2-pyridylazo-resorcinol mono sodiummonohydrate (NaPar, sodium picrat (NaPic and potassium picrat (KPic] and some heavymetal chlorides were determined at 25 oC. All the ligands have given strongestcomplexation for NaPar. In contrast, similar behaviour for both alkali metal picrates is notapparent in the complexation of corresponding ligands.

  14. Flocculation of Chlamydomonas reinhardtii with Different Phenotypic Traits by Metal Cations and High pH

    Jianhua Fan

    2017-11-01

    Full Text Available Concentrating algal cells by flocculation as a prelude to centrifugation could significantly reduce the energy and cost of harvesting the algae. However, how variation in phenotypic traits such as cell surface features, cell size and motility alter the efficiency of metal cation and pH-induced flocculation is not well understood. Our results demonstrate that both wild-type and cell wall-deficient strains of the green unicellular alga Chlamydomonas reinhardtii efficiently flocculate (>90% at an elevated pH of the medium (pH 11 upon the addition of divalent cations such as calcium and magnesium (>5 mM. The trivalent ferric cation (at 10 mM proved to be essential for promoting flocculation under weak alkaline conditions (pH ∼8.5, with a maximum efficiency that exceeded 95 and 85% for wild-type CC1690 and the cell wall-deficient sta6 mutant, respectively. Near complete flocculation could be achieved using a combination of 5 mM calcium and a pH >11, while the medium recovered following cell removal could be re-cycled without affecting algal growth rates. Moreover, the absence of starch in the cell had little overall impact on flocculation efficiency. These findings contribute to our understanding of flocculation in different Chlamydomonas strains and have implications with respect to inexpensive methods for harvesting algae with different phenotypic traits. Additional research on the conditions (e.g., pH and metal ions used for efficient flocculation of diverse algal groups with diverse characteristics, at both small and large scale, will help establish inexpensive procedures for harvesting cell biomass.

  15. A review of modelling the interaction between natural organic matter and metal cations

    Falck, W.E.

    1989-01-01

    This report reviews techniques available to model the interaction between natural organic matter (mainly fulvic and humic acids) and protons and metal cations. A concise definition of natural organic matter is given and their properties are outlined. These materials are macromolecules which exhibit a polyelectrolyte character owing to numerous dissociable functional groups which are attached to their carbon backbone or from integral parts of the structure. The polyelectrolyte character is thought to be responsible for their conformation, hydrogen bonding or bridging by metal cations between subunits being important mechanisms. Environmental parameters like pH and ionic strength thus will have profound effects on the conformation of natural organic matter, the properties of which can change from being a flexible polymer to being a rigid gel. Binding mechanisms and binding strengh are discussed and an overview of relevant techniques of investigation is given. This work is part of the Commission's Mirage project - Phase 2, research area Geochemistry of actinides and fission products in natural aquifer systems

  16. How Native and Alien Metal Cations Bind ATP: Implications for Lithium as a Therapeutic Agent

    Dudev, Todor; Grauffel, Cédric; Lim, Carmay

    2017-02-01

    Adenosine triphosphate (ATP), the major energy currency of the cell, exists in solution mostly as ATP-Mg. Recent experiments suggest that Mg2+ interacts with the highly charged ATP triphosphate group and Li+ can co-bind with the native Mg2+ to form ATP-Mg-Li and modulate the neuronal purine receptor response. However, it is unclear how the negatively charged ATP triphosphate group binds Mg2+ and Li+ (i.e. which phosphate group(s) bind Mg2+/Li+) and how the ATP solution conformation depends on the type of metal cation and the metal-binding mode. Here, we reveal the preferred ATP-binding mode of Mg2+/Li+ alone and combined: Mg2+ prefers to bind ATP tridentately to each of the three phosphate groups, but Li+ prefers to bind bidentately to the terminal two phosphates. We show that the solution ATP conformation depends on the cation and its binding site/mode, but it does not change significantly when Li+ binds to Mg2+-loaded ATP. Hence, ATP-Mg-Li, like Mg2+-ATP, can fit in the ATP-binding site of the host enzyme/receptor, activating specific signaling pathways.

  17. Biochar immobilizes soil-borne arsenic but not cationic metals in the presence of low-molecular-weight organic acids.

    Alozie, Nneka; Heaney, Natalie; Lin, Chuxia

    2018-07-15

    A batch experiment was conducted to examine the effects of biochar on the behaviour of soil-borne arsenic and metals that were mobilized by three low-molecular-weight organic acids. In the presence of citric acid, oxalic acid and malic acid at a molar concentration of 0.01M, the surface of biochar was protonated, which disfavours adsorption of the cationic metals released from the soil by organic acid-driven mobilization. In contrast, the oxyanionic As species were re-immobilized by the protonated biochar effectively. Biochar could also immobilize oxyanionic Cr species but not cationic Cr species. The addition of biochar increased the level of metals in the solution due to the release of the biochar-borne metals under attack by LMWOAs via cation exchange. Biochar could also have the potential to enhance reductive dissolution of iron and manganese oxides in the soil, leading to enhanced release of trace elements bound to these oxides. The findings obtained from this study have implications for evaluating the role of biochar in immobilizing trace elements in rhizosphere. Adsorption of cationic heavy metals on biochar in the presence of LMWOAs is unlikely to be a mechanism responsible for the impeded uptake of heavy metals by plants growing in heavy metal-contaminated soils. Copyright © 2018 Elsevier B.V. All rights reserved.

  18. Chromatographic separation of metal cations on silica gel chemically modified with a polymeric derivative of diaza-18-crown-6

    Basyuk, V.A.

    1991-01-01

    Sorbent on the basis of γ-aminopropyl silica gel, containing chemically grafted polymer derivatives of diaza-18-crown-6, has been synthesized. Retaining of certain metal cations when acid mobile phases are used is studied. Acetate buffer solution, 0.005% aqueous solution of acetic acid and 10 mM aqueous solution of oxalic acid were used as mobile phases. Rare earth cations (including Sr 2+ ones) are weakly retained when any mobile phase is used. Retention of VO 2+ cations is the strongest one

  19. Cation and anion dependence of stable geometries and stabilization energies of alkali metal cation complexes with FSA(-), FTA(-), and TFSA(-) anions: relationship with physicochemical properties of molten salts.

    Tsuzuki, Seiji; Kubota, Keigo; Matsumoto, Hajime

    2013-12-19

    Stable geometries and stabilization energies (Eform) of the alkali metal complexes with bis(fluorosulfonyl)amide, (fluorosulfonyl)(trifluoromethylslufonyl)amide and bis(trifluoromethylsulfonyl)amide (FSA(-), FTA(-) and TFSA(-)) were studied by ab initio molecular orbital calculations. The FSA(-) complexes prefer the bidentate structures in which two oxygen atoms of two SO2 groups have contact with the metal cation. The FTA(-) and TFSA(-) complexes with Li(+) and Na(+) prefer the bidentate structures, while the FTA(-) and TFSA(-) complexes with Cs(+) prefer tridentate structures in which the metal cation has contact with two oxygen atoms of an SO2 group and one oxygen atom of another SO2 group. The two structures are nearly isoenergetic in the FTA(-) and TFSA(-) complexes with K(+) and Rb(+). The magnitude of Eform depends on the alkali metal cation significantly. The Eform calculated for the most stable TFSA(-) complexes with Li(+), Na(+), K(+), Rb(+) and Cs(+) cations at the MP2/6-311G** level are -137.2, -110.5, -101.1, -89.6, and -84.1 kcal/mol, respectively. The viscosity and ionic conductivity of the alkali TFSA molten salts have strong correlation with the magnitude of the attraction. The viscosity increases and the ionic conductivity decreases with the increase of the attraction. The melting points of the alkali TFSA and alkali BETA molten salts also have correlation with the magnitude of the Eform, which strongly suggests that the magnitude of the attraction play important roles in determining the melting points of these molten salts. The anion dependence of the Eform calculated for the complexes is small (less than 2.9 kcal/mol). This shows that the magnitude of the attraction is not the cause of the low melting points of alkali FTA molten salts compared with those of corresponding alkali TFSA molten salts. The electrostatic interactions are the major source of the attraction in the complexes. The electrostatic energies for the most stable TFSA

  20. Electron beam selectively seals porous metal filters

    Snyder, J. A.; Tulisiak, G.

    1968-01-01

    Electron beam welding selectively seals the outer surfaces of porous metal filters and impedances used in fluid flow systems. The outer surface can be sealed by melting a thin outer layer of the porous material with an electron beam so that the melted material fills all surface pores.

  1. Electron scattering on metal clusters and fullerenes

    Solov'yov, A.V.

    2001-01-01

    This paper gives a survey of physical phenomena manifesting themselves in electron scattering on atomic clusters. The main emphasis is made on electron scattering on fullerenes and metal clusters, however some results are applicable to other types of clusters as well. This work is addressed to theoretical aspects of electron-cluster scattering, however some experimental results are also discussed. It is demonstrated that the electron diffraction plays important role in the formation of both elastic and inelastic electron scattering cross sections. It is elucidated the essential role of the multipole surface and volume plasmon excitations in the formation of electron energy loss spectra on clusters (differential and total, above and below ionization potential) as well as the total inelastic scattering cross sections. Particular attention is paid to the elucidation of the role of the polarization interaction in low energy electron-cluster collisions. This problem is considered for electron attachment to metallic clusters and the plasmon enhanced photon emission. Finally, mechanisms of electron excitation widths formation and relaxation of electron excitations in metal clusters and fullerenes are discussed. (authors)

  2. Stabilization of cationic and anionic metal species in contaminated soils using sludge-derived biochar.

    Fang, Shen'en; Tsang, Daniel C W; Zhou, Fengsha; Zhang, Weihua; Qiu, Rongliang

    2016-04-01

    Currently, sludge pyrolysis has been considered as a promising technology to solve disposal problem of municipal sewage sludge, recover sludge heating value, sequester carbon and replenish nutrients in farmland soils. The resultant sludge-derived biochar (SDBC) is potentially an excellent stabilizing agent for metal species. This study applied the SDBC into four soils that had been contaminated in field with cationic Pb(II) and Cd(II)/Ni(II), and anionic Cr(VI) and As(III), respectively. The performance of metal stabilization under various operational and environmental conditions was evaluated with acid batch extraction and column leaching tests. Results indicated the SDBC could effectively stabilize these metals, which was favored by elevated temperature and longer aging. Periodic temperature decrease from 45 to 4 °C resulted in the release of immobilized Cr(VI) and As(III) but not Pb(II). However, a longer aging time offset such metal remobilization. This was possibly because more Pb was strongly bound and even formed stable precipitates, as shown by XRD and sequential extraction results. With increasing time, Cr(VI) was sorbed and partly reduced to Cr(III), while immobilized As(III) was co-oxidized to As(V) as indicated by XPS spectra. Column tests revealed that adding SDBC as a separate layer was unfavorable because the concentrated Cd(II) and Ni(II) in localized positions increased the peak levels of metal release under continuous acid leaching. In contrast, uniformly mixed SDBC could effectively delay the metal breakthrough and reduce their released amounts. Yet, a long-term monitoring may be required for evaluating the potential leaching risks and bioavailability/toxicity of these immobilized and transformed species in the SDBC-amended soils. Copyright © 2016 Elsevier Ltd. All rights reserved.

  3. (4+2) Cycloaddition reactions with inverse electron demand of nitrogen bearing, heteroaromatic cations

    Ritzberger-Baumgartner, W.

    1996-06-01

    Three cationic, heteroaromatic diene-systems (1, 2, 3, 4-tetramethoxycarbonyl-quinolizinium-tetrafluoroborate (M), 8, 9, 10, 11-tetrarnethoxycarbonylpyrido[2,1-a]-isoquinolinium-TFB and triazolo[1,5-b]isoquinolinium-TFBs) and a cationic, non-aromatic diene (2,5,5-trimethyl-3-oxo-1, 2, 4-triazolium-TFB) were synthesized. The dienes were employed successfully in cycloaddition reactions with a number ofconjugated dienophiles (including norbornene). The mechanism underlying these cycloaddition reactions was discussed in the theoretical section. At first quantumchemical calculations of the frontier orbital energies provided the proof, that the reactions followed the pattern of reactions with inverse electron demand. Calculation of the charge distribution and of the orbital coefficients led to the conclusion, that these reactions are mainly orbital controlled. Two mechanistic variants were in discussion. Either the reactions proceed in a concerted manner resembling the Diels-Alder reaction with inverse electron demand or in two distinct steps with the formation of a cationic intermediate following the attack of the heterodienes acting as weak electrophiles at the dienophiles being weak nucleophiles. Calculations of a possible transition state of these cycloaddition reactions revealed a pronounced preference for the formation of the bond between the logical reaction centers in the first step of a two-step reaction. However, experimental and theoretical findings led to the conviction, that cationic polar cycloaddition reactions proceed exactly along the crossroad between a concerted and a two-step mechanism and depending on the electrophilic strength of the diene and the nucleophilic strength of the dienophile these reactions show more characteristics of one of the two mechanistic possibilities. The high regioselectivity as well as the high stereoselectivity could be explained satisfactory with the help of the calculated orbital coefficients. (author)

  4. Development of a novel device to trap heavy metal cations: application of the specific interaction between heavy metal cation and mismatch DNA base pair.

    Torigoe, Hidetaka; Miyakawa, Yukako; Fukushi, Miyako; Ono, Akira; Kozasa, Tetsuo

    2009-01-01

    We have already found that Hg(II) cation specifically binds to T:T mismatch base pair in heteroduplex DNA, which increases the melting temperature of heteroduplex DNA involving T:T mismatch base pair by about 4 degrees C. We have also found that Ag(I) cation specifically binds to C:C mismatch base pair in heteroduplex DNA, which increases the melting temperature of heteroduplex DNA involving C:C mismatch base pair by about 4 degrees C. Using the specific interaction, we developed a novel device to trap each of Hg(II) and Ag(I) cation. The device is composed of 5'-biotinylated T-rich or C-rich DNA oligonucleotides, BIO-T20: 5'-Bio-T(20)-3' or BIO-C20: 5'-Bio-C(20)-3' (Bio is a biotin), immobilized on streptavidin-coated polystylene beads. When the BIO-T20-immobilized beads were added to a solution containing Hg(II) cation, and the beads trapping Hg(II) cation were collected by centrifugation, almost all of Hg(II) cation were removed from the solution. Also, when the BIO-C20-immobilized beads were added to a solution containing Ag(I) cation, and the beads trapping Ag(I) cation were collected by centrifugation, almost all of Ag(I) cation were removed from the solution. We conclude that, using the novel device developed in this study, Hg(II) and Ag(I) cation can be effectively removed from the solution.

  5. Decontamination of aqueous effluents containing metallic cations or anions by iron oxides under the action of a magnetic field

    Goncalves, M. A.; Camilo, R. L.; Cohen, V. H.; Yamaura, M.

    1999-01-01

    This work deals with a review of decontamination processes of aqueous effluents containing metallic cations and anions by using iron oxides as adsorber. Conditions to obtain the different iron oxides and adsorption capacities for cations and anions are presented and precipitation and/or adsorption mechanisms studies under the point of view of oxide-interface phenomena are described. Emphasis will be applied to the magnetite combined with inorganic exchanger or liquid extractants which magnetic properties has been used to enhance metals removal. Experimental results of a synthetic magnetite production and its adsorption capacity as a function of a magnetic field intensity are also showed. (authors)

  6. Density Functional Theory of Open-Shell Systems. The 3d-Series Transition-Metal Atoms and Their Cations.

    Luo, Sijie; Averkiev, Boris; Yang, Ke R; Xu, Xuefei; Truhlar, Donald G

    2014-01-14

    The 3d-series transition metals (also called the fourth-period transition metals), Sc to Zn, are very important in industry and biology, but they provide unique challenges to computing the electronic structure of their compounds. In order to successfully describe the compounds by theory, one must be able to describe their components, in particular the constituent atoms and cations. In order to understand the ingredients required for successful computations with density functional theory, it is useful to examine the performance of various exchange-correlation functionals; we do this here for 4s(N)3d(N') transition-metal atoms and their cations. We analyze the results using three ways to compute the energy of the open-shell states: the direct variational method, the weighted-averaged broken symmetry (WABS) method, and a new broken-symmetry method called the reinterpreted broken symmetry (RBS) method. We find the RBS method to be comparable in accuracy with the WABS method. By examining the overall accuracy in treating 18 multiplicity-changing excitations and 10 ionization potentials with the RBS method, 10 functionals are found to have a mean-unsigned error of systems, the M06-L functional is the most accurate. And by combining the results with our previous studies of p-block and 4d-series elements as well as databases for alkyl bond dissociation, main-group atomization energies, and π-π noncovalent interactions, we find five functionals, namely, PW6B95, MPW1B95, M08-SO, SOGGA11-X, and MPWB1K, to be highly recommended. We also studied the performance of PW86 and C09 exchange functionals, which have drawn wide interest in recent studies due to their claimed ability to reproduce Hartree-Fock exchange at long distance. By combining them with four correlation functionals, we find the performance of the resulting functionals disappointing both for 3d transition-metal chemistry and in broader tests, and thus we do not recommend PW86 and C09 as components of generalized

  7. Cobalt(2) and nickel(2) tris-acetylacetonates with alkali metal cations in outer sphere

    Steblyanko, A.Yu.; Grigor'ev, A.N.; Martynenko, L.I.

    1996-01-01

    Anhydrous tris-acetylacetonates of Co(2) and Ni(2) with alkali metal cations in outer sphere were synthesized and investigated by different physicochemical methods. Chemical analysis and IR-spectroscopy show, that complex composition corresponds to the formula Eh[MA 3 ] (where Eh + - Li + , Na + , K + , Rb + , Cs + ; M - Co(2), Ni(2); A - - acetyacetonate-ion). Eh[MA 3 ] heating in vacuum leads to transition of volatile Co(2) and Ni(2) acetylacetonates to gaseous phase. The data of photoelectron spectroscopy and vacuum sublimation show, that Li[MA 3 ] is transformed to gaseous phase congruently and only partially dissociates to EhA and MA 2 . Li[MA 3 ] and Cs[MA 3 ] are characterized by the lowest thermal stability at atmospheric pressure. Low stability of Li[MA 3 ] is related with detachment of one of A - radical from [MA 3 ] complex anion by Li + cation under conditions, when LiA and Li[MA 3 ] are volatile. 11 refs.; 2 figs.; 3 tabs

  8. Room temperature Zinc-metallation of cationic porphyrin at graphene surface and enhanced photoelectrocatalytic activity

    Zeng, Rongjin; Chen, Guoliang; Xiong, Chungang; Li, Gengxian; Zheng, Yinzhi; Chen, Jian; Long, Yunfei; Chen, Shu

    2018-03-01

    A stable zincporphyrin functionalized graphene nanocomposite was prepared by using positively charged cationic porphyrin (5,10,15,20-tetra(4-propyl pyridinio) porphyrin, TPPyP) and successive reduced graphene oxide (rGO) with tuned negative charge. The nanocomposite preparation was accompanied first by distinct electrostatic interactions and π-π stacking between TPPyP and rGO, and followed by fast Zinc-metallation at room temperature. In contrast to free TPPyP with Zn2+, the incorporation reaction is very slow at room temperature and heating or reflux conditions are required to increase the metallation rate. While at the surface of rGO nanosheet, the Zinc-metallation of TPPyP was greatly accelerated to 30 min at 25 °C in aqueous solution. The interaction process and composites formation were fully revealed by significant variations in UV-vis absorption spectra, X-ray photoelectron spectra (XPS) measurements, atomic force microscope (AFM) images, and fluorescence spectra. Furthermore, photoelectrochemical activity of resultant rGO/TPPyP-Zn nanocomposites was evaluated under visible-light irradiation, and enhancement of the photoelectrocatalytic reduction of CO2 was achieved.

  9. “High-Throughput” Evaluation of Polymer-Supported Triazolic Appendages for Metallic Cations Extraction

    Riadh Slimi

    2015-03-01

    Full Text Available The aim of this work was to find and use a low-cost high-throughput method for a quick primary evaluation of several metal extraction by substituted piperazines appendages as chelatants grafted onto Merrifield polymer using click-chemistry by the copper (I-catalyzed Huisgen’s reaction (CuAAC The polymers were tested for their efficiency to remove various metal ions from neutral aqueous solutions (13 cations studied: Li+, Na+, K+, Mn2+, Fe3+, Co2+, Ni2+, Cu2+, Cd2+, Ba2+, Ce3+, Hg+ and Pb2+ using the simple conductimetric measurement method. The polymers were found to extract all metals with low efficiencies ≤40%, except for Fe3+ and Hg+, and sometimes Pb2+. Some polymers exhibited a selectively for K+, Cd2+ and Ba2+, with good efficiencies. The values obtained here using less polymer, and a faster method, are in fair correspondence (average difference ±16% with another published evaluation by atomic absorption spectroscopy (AAS.

  10. CO 2 adsorption in mono-, di- and trivalent cation-exchanged metal-organic frameworks: A molecular simulation study

    Chen, Yifei

    2012-02-28

    A molecular simulation study is reported for CO 2 adsorption in rho zeolite-like metal-organic framework (rho-ZMOF) exchanged with a series of cations (Na +, K +, Rb +, Cs +, Mg 2+, Ca 2+, and Al 3+). The isosteric heat and Henry\\'s constant at infinite dilution increase monotonically with increasing charge-to-diameter ratio of cation (Cs + < Rb + < K + < Na + < Ca 2+ < Mg 2+ < Al 3+). At low pressures, cations act as preferential adsorption sites for CO 2 and the capacity follows the charge-to-diameter ratio. However, the free volume of framework becomes predominant with increasing pressure and Mg-rho-ZMOF appears to possess the highest saturation capacity. The equilibrium locations of cations are observed to shift slightly upon CO 2 adsorption. Furthermore, the adsorption selectivity of CO 2/H 2 mixture increases as Cs + < Rb + < K + < Na + < Ca 2+ < Mg 2+ ≈ Al 3+. At ambient conditions, the selectivity is in the range of 800-3000 and significantly higher than in other nanoporous materials. In the presence of 0.1% H 2O, the selectivity decreases drastically because of the competitive adsorption between H 2O and CO 2, and shows a similar value in all of the cation-exchanged rho-ZMOFs. This simulation study provides microscopic insight into the important role of cations in governing gas adsorption and separation, and suggests that the performance of ionic rho-ZMOF can be tailored by cations. © 2012 American Chemical Society.

  11. Positron annihilation studies of zirconia doped with metal cations of different valence

    Prochazka, I.; Cizek, J.; Melikhova, O.; Konstantinova, T. E.; Danilenko, I. A.; Yashchishyn, I. A.; Anwand, W.; Brauer, G.

    2013-06-01

    New results obtained by applying positron annihilation spectroscopy to the investigation of zirconia-based nanomaterials doped with metal cations of different valence are reported. The slow-positron implantation spectroscopy combined with Doppler broadening measurements was employed to study the sintering of pressure-compacted nanopowders of tetragonal yttria-stabilised zirconia (t-YSZ) and t-YSZ with chromia additive. Positronium (Ps) formation in t-YSZ was proven by detecting 3γ-annihilations of ortho-Ps and was found to gradually decrease with increasing sintering temperature. A subsurface layer with enhanced 3γ-annihilations, compared to the deeper regions, could be identified. Addition of chromia was found to inhibit Ps formation. In addition, first results of positron lifetime measurements on nanopowders of zirconia phase-stabilised with MgO and CeO2 are presented.

  12. Electron beam induced cationic polymerization of epoxy resins. Dependence of Tg on conversion

    Degrand, H.; Cazaux, F.; Coqueret, X.

    2002-01-01

    Complete text of publication follows. The high-energy radiation curing of monomer blends polymerizing by a free radical or by a cationic mechanism receives increasing attention in the perspective of high performance composite materials. In the present work, we have focused our attention on epoxy formulations as models of the matrices polymerizing by a cationic mechanism that could be used in fiber-reinforced composites for aerospace applications. We have examined the progress of the electron beam (EB) induced polymerization of diglycidylether of bisphenol A (DGEBA) in the presence of a diaryliodonium salt (DAIS) by FTIR spectroscopy and by dynamic mechanical thermal analysis (DMA). The obtained results allow to draw the gradual increase of the temperature for the network thermomechanical transition (T a , associated with the glass transition temperature T g ) over a broad range of conversion (p) and reveal a peculiar behavior at high conversion. In this domain (p > 0.90), the material's T g is shown to decrease when conversion approaches unity. Moreover, the post-irradiation thermal treatment of the materials, that generally yields effective 'dark curing', appears to induce a decrease of T g , with an amplitude correlated with the amount of DAIS in the formulation. Owing to the particular nature of the propagating centers in cationic polymerisation, the thermal relaxation of ionic clusters trapped in the glassy matrix can be reasonably invoked as a possible cause for this behavior

  13. Transmission electron microscopy of mercury metal

    Anjum, Dalaver H.

    2016-03-28

    Summary: Transmission electron microcopy (TEM) analysis of liquid metals, especially mercury (Hg), is difficult to carry out because their specimen preparation poses a daunting task due to the unique surface properties of these metals. This paper reports a cryoTEM study on Hg using a novel specimen preparation technique. Hg metal is mixed with water using sonication and quenched in liquid ethane cryogen. This technique permits research into the morphological, phase and structural properties of Hg at nanoscale dimensions. © 2016 Royal Microscopical Society.

  14. Spectroscopy of electronic transitions in Polycyclic Aromatic Hydrocarbon cations and their clusters

    Friha, Hela

    2012-01-01

    This thesis is an experimental study of the electronic spectroscopy of cations of Polycyclic Aromatic Hydrocarbons (PAHs) and their aggregates in conditions close to those of the interstellar medium (ISM), i.e. cold and totally isolated in the gas phase. It is related to the astrophysical context of the interstellar medium (ISM), in particular on the question of the possible link between interstellar PAHs and Diffuse Interstellar Bands (DIBs). The purpose of this thesis is to provide laboratory spectra which can be directly compared to the spectra of DIBs. Indeed these bands are the oldest spectroscopy riddle in astrophysics which remained unanswered for nearly 100 years and whose key is still looked for. A special attention is given to the methylated derivatives of PAHs species detected in many interstellar environments, cationic PAH dimers (the simplest PAH clusters). These clusters have been proposed as a model of the very small grains, which contribute to the formation of interstellar PAHs and whose chemical composition remains uncertain. This thesis has been mainly devoted to the determination of the electronic spectra of naphthalene cation monomer (Np + ) and its methylated derivative (2-MeN p + ), as well as the associated homogeneous dimers. The experimental method used is based on the photodissociation of van der Waals complexes PAH + m -Ar n (argon atoms spectators), prepared by UV laser photoionization in a supersonic jet. This technique combines different experimental tools, namely: molecular beam mass spectrometry and laser spectroscopy as well as physical tools such as the handling of clusters VdW PAH + m -Ar n , the detection of photo-fragments, the measurement of photodissociation efficiency. The identification of the fragments by the photodissociation of VdW clusters allowed us to determine the different possible fragmentation channels and especially to obtain the spectra the charge resonance transition and the first allowed transition to locally

  15. Study of the interaction metallic cation - ligand in concentrated phosphorus acid media; Etude de l'interaction cation metallique - ligand en milieu acide phosphorique concentre

    Sefiani, N.; Azzi, M.; Hlaibi, M. [Faculte des Sciences Ain Chock, Laboratoire d' Electrochimie et Chimie de l' Environnement (LECE), Casablanca (Morocco); Kossair, A. [Centre de Recherche des Phosphates Mineraux (CERPHOS), Casablanca (Morocco)

    2005-07-01

    The phosphoric acid is more and more used with a high purity. The recovery of recycling element (uranium, vanadium, rare earth...) and the elimination of toxic element (cadmium, molybdenum, lead...) contained in the phosphoric acid are generally realized by extraction or precipitation. It is then very important to understand these impurities behavior in the phosphoric media in order to control their elimination. In this work, the authors considered the presence of some metallic cations (V, Al, fe, U) and fluorides ions as impurity in concentrated phosphoric acid media. (A.L.B.)

  16. CO 2 adsorption in mono-, di- and trivalent cation-exchanged metal-organic frameworks: A molecular simulation study

    Chen, Yifei; Nalaparaju, Anjaiah; Eddaoudi, Mohamed; JIANG, Jianwen

    2012-01-01

    A molecular simulation study is reported for CO 2 adsorption in rho zeolite-like metal-organic framework (rho-ZMOF) exchanged with a series of cations (Na +, K +, Rb +, Cs +, Mg 2+, Ca 2+, and Al 3+). The isosteric heat and Henry's constant

  17. Impact of metal binding on the antitumor activity and cellular imaging of a metal chelator cationic imidazopyridine derivative.

    Roy, Mithun; Chakravarthi, Balabhadrapatruni V S K; Jayabaskaran, Chelliah; Karande, Anjali A; Chakravarty, Akhil R

    2011-05-14

    A new water soluble cationic imidazopyridine species, viz. (1E)-1-((pyridin-2-yl)methyleneamino)-3-(3-(pyridin-2-yl)imidazo[1,5-a]pyridin-2(3H)-yl)propan-2-ol (1), as a metal chelator is prepared as its PF(6) salt and characterized. Compound 1 shows fluorescence at 438 nm on excitation at 342 nm in Tris-HCl buffer giving a fluorescence quantum yield (φ) of 0.105 and a life-time of 5.4 ns. Compound 1, as an avid DNA minor groove binder, shows pUC19 DNA cleavage activity in UV-A light of 365 nm forming singlet oxygen species in a type-II pathway. The photonuclease potential of 1 gets enhanced in the presence of Fe(2+), Cu(2+) or Zn(2+). Compound 1 itself displays anticancer activity in HeLa, HepG2 and Jurkat cells with an enhancement on addition of the metal ions. Photodynamic effect of 1 at 365 nm also gets enhanced in the presence of Fe(2+) and Zn(2+). Fluorescence-based cell cycle analysis shows a significant dead cell population in the sub-G1 phase of the cell cycle suggesting apoptosis via ROS generation. A significant change in the nuclear morphology is observed from Hoechst 33258 and an acridine orange/ethidium bromide (AO/EB) dual nuclear staining suggesting apoptosis in cells when treated with 1 alone or in the presence of the metal ions. Apoptosis is found to be caspase-dependent. Fluorescence imaging to monitor the distribution of 1 in cells shows that 1 in the presence of metal ions accumulates predominantly in the cytoplasm. Enhanced uptake of 1 into the cells within 12 h is observed in the presence of Fe(2+) and Zn(2+).

  18. Reversible CO binding enables tunable CO/H₂ and CO/N₂ separations in metal-organic frameworks with exposed divalent metal cations.

    Bloch, Eric D; Hudson, Matthew R; Mason, Jarad A; Chavan, Sachin; Crocellà, Valentina; Howe, Joshua D; Lee, Kyuho; Dzubak, Allison L; Queen, Wendy L; Zadrozny, Joseph M; Geier, Stephen J; Lin, Li-Chiang; Gagliardi, Laura; Smit, Berend; Neaton, Jeffrey B; Bordiga, Silvia; Brown, Craig M; Long, Jeffrey R

    2014-07-30

    Six metal-organic frameworks of the M2(dobdc) (M = Mg, Mn, Fe, Co, Ni, Zn; dobdc(4-) = 2,5-dioxido-1,4-benzenedicarboxylate) structure type are demonstrated to bind carbon monoxide reversibly and at high capacity. Infrared spectra indicate that, upon coordination of CO to the divalent metal cations lining the pores within these frameworks, the C-O stretching frequency is blue-shifted, consistent with nonclassical metal-CO interactions. Structure determinations reveal M-CO distances ranging from 2.09(2) Å for M = Ni to 2.49(1) Å for M = Zn and M-C-O angles ranging from 161.2(7)° for M = Mg to 176.9(6)° for M = Fe. Electronic structure calculations employing density functional theory (DFT) resulted in good agreement with the trends apparent in the infrared spectra and crystal structures. These results represent the first crystallographically characterized magnesium and zinc carbonyl compounds and the first high-spin manganese(II), iron(II), cobalt(II), and nickel(II) carbonyl species. Adsorption isotherms indicate reversible adsorption, with capacities for the Fe, Co, and Ni frameworks approaching one CO per metal cation site at 1 bar, corresponding to loadings as high as 6.0 mmol/g and 157 cm(3)/cm(3). The six frameworks display (negative) isosteric heats of CO adsorption ranging from 52.7 to 27.2 kJ/mol along the series Ni > Co > Fe > Mg > Mn > Zn, following the Irving-Williams stability order. The reversible CO binding suggests that these frameworks may be of utility for the separation of CO from various industrial gas mixtures, including CO/H2 and CO/N2. Selectivities determined from gas adsorption isotherm data using ideal adsorbed solution theory (IAST) over a range of gas compositions at 1 bar and 298 K indicate that all six M2(dobdc) frameworks could potentially be used as solid adsorbents to replace current cryogenic distillation technologies, with the choice of M dictating adsorbent regeneration energy and the level of purity of the resulting gases.

  19. Electron-phonon coupling at metal surfaces

    Hellsing, B.; Eiguren, A.; Chulkov, E.V.

    2002-01-01

    Chemical reactions at metal surfaces are influenced by inherent dissipative processes which involve energy transfer between the conduction electrons and the nuclear motion. We shall discuss how it is possible to model this electron-phonon coupling in order to estimate its importance. A relevant quantity for this investigation is the lifetime of surface-localized electron states. A surface state, quantum well state or surface image state is located in a surface-projected bandgap and becomes relatively sharp in energy. This makes a comparison between calculations and experimental data most attractive, with a possibility of resolving the origin of the lifetime broadening of electron states. To achieve more than an order of magnitude estimate we point out the importance of taking into account the phonon spectrum, electron surface state wavefunctions and screening of the electron-ion potential. (author)

  20. Electronic transport properties of (fluorinated) metal phthalocyanine

    Fadlallah, M M; Eckern, U; Romero, A H; Schwingenschlö gl, Udo

    2015-01-01

    The magnetic and transport properties of the metal phthalocyanine (MPc) and F16MPc (M = Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn and Ag) families of molecules in contact with S–Au wires are investigated by density functional theory within the local density approximation, including local electronic correlations on the central metal atom. The magnetic moments are found to be considerably modified under fluorination. In addition, they do not depend exclusively on the configuration of the outer electronic shell of the central metal atom (as in isolated MPc and F16MPc) but also on the interaction with the leads. Good agreement between the calculated conductance and experimental results is obtained. For M = Ag, a high spin filter efficiency and conductance is observed, giving rise to a potentially high sensitivity for chemical sensor applications.

  1. Electronic transport properties of (fluorinated) metal phthalocyanine

    Fadlallah, M M

    2015-12-21

    The magnetic and transport properties of the metal phthalocyanine (MPc) and F16MPc (M = Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn and Ag) families of molecules in contact with S–Au wires are investigated by density functional theory within the local density approximation, including local electronic correlations on the central metal atom. The magnetic moments are found to be considerably modified under fluorination. In addition, they do not depend exclusively on the configuration of the outer electronic shell of the central metal atom (as in isolated MPc and F16MPc) but also on the interaction with the leads. Good agreement between the calculated conductance and experimental results is obtained. For M = Ag, a high spin filter efficiency and conductance is observed, giving rise to a potentially high sensitivity for chemical sensor applications.

  2. Selectivity of externally facing ion-binding sites in the Na/K pump to alkali metals and organic cations.

    Ratheal, Ian M; Virgin, Gail K; Yu, Haibo; Roux, Benoît; Gatto, Craig; Artigas, Pablo

    2010-10-26

    The Na/K pump is a P-type ATPase that exchanges three intracellular Na(+) ions for two extracellular K(+) ions through the plasmalemma of nearly all animal cells. The mechanisms involved in cation selection by the pump's ion-binding sites (site I and site II bind either Na(+) or K(+); site III binds only Na(+)) are poorly understood. We studied cation selectivity by outward-facing sites (high K(+) affinity) of Na/K pumps expressed in Xenopus oocytes, under voltage clamp. Guanidinium(+), methylguanidinium(+), and aminoguanidinium(+) produced two phenomena possibly reflecting actions at site III: (i) voltage-dependent inhibition (VDI) of outwardly directed pump current at saturating K(+), and (ii) induction of pump-mediated, guanidinium-derivative-carried inward current at negative potentials without Na(+) and K(+). In contrast, formamidinium(+) and acetamidinium(+) induced K(+)-like outward currents. Measurement of ouabain-sensitive ATPase activity and radiolabeled cation uptake confirmed that these cations are external K(+) congeners. Molecular dynamics simulations indicate that bound organic cations induce minor distortion of the binding sites. Among tested metals, only Li(+) induced Na(+)-like VDI, whereas all metals tested except Na(+) induced K(+)-like outward currents. Pump-mediated K(+)-like organic cation transport challenges the concept of rigid structural models in which ion specificity at site I and site II arises from a precise and unique arrangement of coordinating ligands. Furthermore, actions by guanidinium(+) derivatives suggest that Na(+) binds to site III in a hydrated form and that the inward current observed without external Na(+) and K(+) represents cation transport when normal occlusion at sites I and II is impaired. These results provide insights on external ion selectivity at the three binding sites.

  3. Development of a novel method to determine the concentration of heavy metal cations: application of the specific interaction between heavy metal cation and mismatch DNA base pair.

    Kozasa, Tetsuo; Miyakawa, Yukako; Fukushi, Miyako; Ono, Akira; Torigoe, Hidetaka

    2009-01-01

    We have already found that Hg(II) cation specifically binds to T:T mismatch base pair in heteroduplex DNA, which increases the melting temperature of heteroduplex DNA involving T:T mismatch base pair by about 4 degrees C. We have also found that Ag(I) cation specifically binds to C:C mismatch base pair in heteroduplex DNA, which increases the melting temperature of heteroduplex DNA involving C:C mismatch base pair by about 4 degrees C. Using the specific interaction, we developed a novel sensor to determine the concentration of each of Hg(II) and Ag(I) cation. The sensor is composed of a dye-labelled T-rich or C-rich DNA oligonucleotide, F2T6W2D: 5'-Fam-T(2)CT(2)CT(2)C(4)T(2)GT(2)GT(2)-Dabcyl-3' or F2C6W2D: 5'-Fam-C(2)TC(2)TC(2)T(4)C(2)AC(2)AC(2)-Dabcyl-3', where 6-carboxyfluorescein (Fam) is a fluorophore and Dabcyl is a quencher. The addition of Hg(II) cation decreased the intensity of Fam emission of F2T6W2D at 520 nm in a concentration-dependent manner. Also, the addition of Ag(I) cation decreased the intensity of Fam emission of F2C6W2D at 520 nm in a concentration-dependent manner. We conclude that, using the novel sensor developed in this study, the concentration of each of Hg(II) and Ag(I) cation can be determined from the intensity of Fam emission at 520 nm.

  4. Electronic transport properties of carbon nanotube metal-semiconductor-metal

    F Khoeini

    2008-07-01

    Full Text Available  In this work, we study electronic transport properties of a quasi-one dimensional pure semi-conducting Zigzag Carbon Nanotube (CNT attached to semi-infinite clean metallic Zigzag CNT leads, taking into account the influence of topological defect in junctions. This structure may behave like a field effect transistor. The calculations are based on the tight-binding model and Green’s function method, in which the local density of states(LDOS in the metallic section to semi-conducting section, and muli-channel conductance of the system are calculated in the coherent and linear response regime, numerically. Also we have introduced a circuit model for the system and investigated its current. The theoretical results obtained, can be a base, for developments in designing nano-electronic devices.

  5. Alginate and Algal-Based Beads for the Sorption of Metal Cations: Cu(II and Pb(II

    Shengye Wang

    2016-09-01

    Full Text Available Alginate and algal-biomass (Laminaria digitata beads were prepared by homogeneous Ca ionotropic gelation. In addition, glutaraldehyde-crosslinked poly (ethyleneimine (PEI was incorporated into algal beads. The three sorbents were characterized by scanning electron microscopy (SEM coupled with energy dispersive X-ray analysis (EDX: the sorption occurs in the whole mass of the sorbents. Sorption experiments were conducted to evaluate the impact of pH, sorption isotherms, and uptake kinetics. A special attention was paid to the effect of drying (air-drying vs. freeze-drying on the mass transfer properties. For alginate, freeze drying is required for maintaining the porosity of the hydrogel, while for algal-based sorbents the swelling of the material minimizes the impact of the drying procedure. The maximum sorption capacities observed from experiments were 415, 296 and 218 mg Pb g−1 and 112, 77 and 67 mg Cu g−1 for alginate, algal and algal/PEI beads respectively. Though the sorption capacities of algal-beads decreased slightly (compared to alginate beads, the greener and cheaper one-pot synthesis of algal beads makes this sorbent more competitive for environmental applications. PEI in algal beads decreases the sorption properties in the case of the sorption of metal cations under selected experimental conditions.

  6. Can Electron-Rich Oxygen (O2-) Withdraw Electrons from Metal Centers? A DFT Study on Oxoanion-Caged Polyoxometalates.

    Takazaki, Aki; Eda, Kazuo; Osakai, Toshiyuki; Nakajima, Takahito

    2017-10-12

    The answer to the question "Can electron-rich oxygen (O 2- ) withdraw electrons from metal centers?" is seemingly simple, but how the electron population on the M atom behaves when the O-M distance changes is a matter of controversy. A case study has been conducted for Keggin-type polyoxometalate (POM) complexes, and the first-principles electronic structure calculations were carried out not only for real POM species but also for "hypothetical" ones whose heteroatom was replaced with a point charge. From the results of natural population analysis, it was proven that even an electron-rich O 2- , owing to its larger electronegativity as a neutral atom, withdraws electrons when electron redistribution occurs by the change of the bond length. In the case where O 2- coexists with a cation having a large positive charge (e.g., P 5+ (O 2- ) 4 = [PO 4 ] 3- ), the gross electron population (GEP) on the M atom seemingly increases as the O atom comes closer, but this increment in GEP is not due to the role of the O atom but due to a Coulombic effect of the positive charge located on the cation. Furthermore, it was suggested that not GEP but net electron population (NEP) should be responsible for the redox properties.

  7. Electron channeling X-ray microanalysis for cation configuration in irradiate magnesium alimate spinel

    Matsumura, S.; Soeda, T.; Zaluzec, N. J.; Kinoshita, C.

    1999-01-01

    High angular resolution electron channeling X-ray spectroscopy (HARECXS) was examined as a practical tool to locate lattice-ions in spinel crystals. The orientation dependent intensity distribution of emitted X-rays obtained by HARECXS is so sensitive to lattice-ion configuration in the illuminated areas that the occupation probabilities on specific positions in the crystal lattice can be determined accurately through comparison with the theoretical rocking curves. HARECXS measurements have revealed partially disordered cation arrangement in MgO·nAl 2 O 3 with n = 1.0 and 2.4. Most Al 3+ lattice-ions occupy the octahedral (VIII) sites, while Mg 2 lattice-ions reside on both the tetrahedral (IV) and the octahedral (VIII) sites. The structural vacancies are enriched in the IV-sites. Further evacuation of cations from the IV-sites to the VIII-sites is recognized in a disordering process induced by irradiation with 1 MeV Ne + ions up to 8.9 dpa at 870 K

  8. Electronic structure of hcp transition metals

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

    1975-01-01

    Using the linear muffin-tin-orbital method described in the previous paper, we have calculated the electronic structures of the hcp transition metals, Zr, Hf, Ru, and Os. We show how the band structures of these metals may be synthesized from the sp and d bands, and illustrate the effects...... of 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...

  9. A polyoxometalate-encapsulating cationic metal-organic framework as a heterogeneous catalyst for desulfurization.

    Hao, Xiu-Li; Ma, Yuan-Yuan; Zang, Hong-Ying; Wang, Yong-Hui; Li, Yang-Guang; Wang, En-Bo

    2015-02-23

    A new cationic triazole-based metal-organic framework encapsulating Keggin-type polyoxometalates, with the molecular formula [Co(BBPTZ)3][HPMo12O40]⋅24 H2O [compound 1; BBPTZ = 4,4'-bis(1,2,4-triazol-1-ylmethyl)biphenyl] is hydrothermally synthesized and characterized by elemental analysis, IR spectroscopy, thermogravimetric analysis, powder X-ray diffraction, and single-crystal X-ray diffraction. The structure of compound 1 contains a non-interpenetrated 3D CdSO4 (cds)-type framework with two types of channels that are interconnected with each other; straight channels that are occupied by the Keggin-type POM anions, and wavelike channels that contain lattice water molecules. The catalytic activity of compound 1 in the oxidative desulfurization reaction indicates that it is not only an effective and size-selective heterogeneous catalyst, but it also exhibits distinct structural stability in the catalytic reaction system. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Antibacterial Dyeing of Wool with Natural Cationic Dye Using Metal Mordants

    Aminoddin HAJI

    2012-09-01

    Full Text Available In this study, Berberine colorant extracted from berberis vulgaris root was applied on wool fiber using alum (aluminum potassium sulfate, copper sulfate and potassium dichromate as mordant. The effect of treatment variables such as amount of mordant, time and temperature on the color strength of dyed fibers was examined. The fastness properties of dyed wool against washing, light and wet rubbing were evaluated. the use of metal mordants increased the color strength of the dyed goods. Increase in dyeing time and temperature caused deeper shades. All mordants, increased the rub fastness and wash fastness of dyed samples, but the light fastness was increased except in case of alum. Berberine is a cationic dye and because of it's quaternary ammonium structure can act as an antibacterial agent. So, dyed samples were tested for antibacterial activity using AATCC test method 100-2004. The dyed wool represented a high level of antibacterial activity. The extract of the berberis vulgaris can be considered as a natural dye of acceptable fastness properties together with excellent antibacterial activity for woolen textiles.DOI: http://dx.doi.org/10.5755/j01.ms.18.3.2437

  11. Isotope exchange reaction of tritium on precious metal catalyst based on cation-exchanged mordenite for blanket tritium recovery

    Kawamura, Yoshinori, E-mail: kawamura.yoshinori@jaea.go.jp [Japan Atomic Energy Agency, 801-1 Mukoyama, Naka, Ibaraki 311-0193 (Japan); Hayashi, Takumi [Japan Atomic Energy Agency, 2-4 Shirane Shirakata, Tokai, Ibaraki 319-1195 (Japan); Yamanishi, Toshihiko [Japan Atomic Energy Agency, 2-166 Omotedate Obuchi, Rokkasho, Aomori 039-3212 (Japan)

    2016-11-01

    Highlights: • Precious metal catalyst based on cation-exchanged mordenite was prepared. • Isotope exchange reaction between H{sub 2} and HTO on the catalyst was investigated. • The order of entire reaction is not clear, but it is the first-order reaction as for HTO. • Effect of exchanged cation may appear as the difference of the surface area of catalyst. - Abstract: It is known that the chemical forms of tritium released from a ceramic breeder blanket are hydrogen form and water form. To recover tritiated water vapor, adoption of dryer that is packed column of synthetic zeolite has been proposed. On the other hand, synthetic zeolite is often used as a support of precious metal catalyst. Such catalysts usually have a capability of hydrogen isotope exchange between gas and water vapor. If this catalyst is used to dryer, the dryer may obtain a preferable function for tritium recovery by isotopic exchange reaction. To assess such functions, reaction rate should be estimated. The results of water adsorption experiment on cation-exchanged mordenite-type zeolite suggested the possibility that state of adsorbed water varied by exchanged cation. So, in this work, precious metal catalyst based on cation-exchanged mordenite was prepared, and the reaction rate of chemical exchange between hydrogen and tritiated water was investigated under temperature range between 30 °C and 80 °C by the steady-state approximation. In the case of platinum on Na-mordenite, the reaction between gaseous hydrogen and tritiated water vapor was almost expressed as first-order reaction concerning tritiated water vapor concentration.

  12. Alkali metal cation selectivity of [17]ketonand in methanol: free energy perturbation and molecular dynamics simulation studies

    Hwang, Sun Gu; Chung, Doo Soo; Jang, Yun Hee; Ryu, Gean Ha

    1999-01-01

    Free energy perturbation and molecular dynamics simulations were carried out to investigate the relative binding affinities of [1 7 ]ketonand (1) toward alkali metal cations in methanol. The binding affinities of 1 toward the alkali metal cations were calculated to be in the order Li + >Na + >K + >Rb + >Cs + , whereas our recent theoretically predicted and experimentally observed binding affinities for [1 8 ]starand (2) were in the order K + >Rb + >Cs + >Na + >Li + . The extremely different affinities of 1 and 2 toward smaller cations, Li + and Na + , were explained in terms of the differences in their ability to change the conformation to accommodate cations of different sizes. The carbonyl groups constituting the central cavity of 1 can reorganize to form a cavity with the optimal M + -O distance, even for the smallest Li + , without imposing serious strain on 1. The highest affinity of 1 for Li + was predominantly due to the highest Coulombic attraction between the smallest Li + and the carbonyl oxygens of 1

  13. Solvent-Free Selective Oxidation of Toluene with O2 Catalyzed by Metal Cation Modified LDHs and Mixed Oxides

    Xiaoli Wang

    2016-01-01

    Full Text Available A series of metal cation modified layered-double hydroxides (LDHs and mixed oxides were prepared and used to be the selective oxidation of toluene with O2. The results revealed that the modified LDHs exhibited much higher catalytic performance than their parent LDH and the modified mixed oxides. Moreover, the metal cations were also found to play important roles in the catalytic performance and stabilities of modified catalysts. Under the optimal reaction conditions, the highest toluene conversion reached 8.7% with 97.5% of the selectivity to benzyldehyde; moreover, the catalytic performance remained after nine catalytic runs. In addition, the reaction probably involved a free-radical mechanism.

  14. Effect of alkaline earth metal and magnesium cations on cadmium extraction from chloride solutions by tributyl phosphate

    Prokuev, V.A.; Belousov, E.A.

    1985-01-01

    At 298 K thermodynamic constants of cadmium (2) extraction from chloride solutions of magnesium, calcium, strontium and barium by tributyl phosphate are calculated. It is established, that logarithm of the thermodynamic extraction constant is in a linear dependence from the change in the cation hydration enthalpy in agqueous solution. It is shown, that activity coefficient of neutral complex CdVCl 2 differs from one, and it is the higher the more stable the complex is in alkaline earth metal chloride solutions

  15. Network diversity through decoration of trigonal-prismatic nodes: Two-step crystal engineering of cationic metal-organic materials

    Schoedel, Alexander

    2011-10-05

    MOMs the word! In a two-step process, first a trigonal-prismatic Primary Molecular Building Block ([Cr3O(isonic)6]+, tp-PMBB-1) was formed and then it was connected to linear linkers or square-planar nodes to afford three novel highly charged cationic metal-organic materials (MOMs) with snx, snw, and stp topologies. © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. Synthesis and characterization of carboxylic cation exchange bio-resin for heavy metal remediation.

    Kulkarni, Vihangraj V; Golder, Animes Kumar; Ghosh, Pranab Kumar

    2018-01-05

    A new carboxylic bio-resin was synthesized from raw arecanut husk through mercerization and ethylenediaminetetraacetic dianhydride (EDTAD) carboxylation. The synthesized bio-resin was characterized using thermogravimetric analysis, field emission scanning electron microscopy, proximate & ultimate analyses, mass percent gain/loss, potentiometric titrations, and Fourier transform infrared spectroscopy. Mercerization extracted lignin from the vesicles on the husk and EDTAD was ridged in to, through an acylation reaction in dimethylformamide media. The reaction induced carboxylic groups as high as 0.735mM/g and a cation exchange capacity of 2.01meq/g functionalized mercerized husk (FMH). Potentiometric titration data were fitted to a newly developed single-site proton adsorption model (PAM) that gave pKa of 3.29 and carboxylic groups concentration of 0.741mM/g. FMH showed 99% efficiency in Pb(II) removal from synthetic wastewater (initial concentration 0.157mM), for which the Pb(II) binding constant was 1.73×10 3 L/mol as estimated from modified PAM. The exhaustion capacity was estimated to be 18.7mg/g of FMH. Desorption efficiency of Pb(II) from exhausted FMH was found to be about 97% with 0.1N HCl. The FMH simultaneously removed lead and cadmium below detection limit from a real lead acid battery wastewater along with the removal of Fe, Mg, Ni, and Co. Copyright © 2017 Elsevier B.V. All rights reserved.

  17. γ-radiation effect on dicyclohexano-18-crown-6 aqueous solution in the presence of metal cations

    Yu, Chuhong; Peng, Jing; Li, Jiuqiang; Zhai, Maolina [Peking Univ. (China). Beijing National Laboratory for Molecular Sciences (BNLMS)

    2014-04-01

    γ-radiation effect on dicyclohexano-18-crown-6 (DCH18C6) aqueous solution in the presence of metal cations, such as K{sup +} and Sr{sup 2+}, was investigated, and some pale yellow precipitates were obtained at doses above 100 kGy. It was found that the complexation interaction of metal cations could accelerate the conversion of DCH18C6 into oligomers and the formation of precipitates, but it did not affect the formation mechanism of precipitates. Furthermore, the salting-out effect of metal cations played an important role in the precipitation. In order to inhibit the radiation-induced precipitation of DCH18C6 in water phase, nitric acid with a concentration of more than 1 M could be added to the system. The methods and results for analyzing radiation-induced products reported in this work are useful to understand the radiation chemistry behavior of DCH18C6 which is used as the extractant in the separation of long half-life radionuclides from spent nuclear fuel. (orig.)

  18. Complexing properties of some carbamoylmethylphosphine oxides and methylenediphosphine dioxides with respect to alkali metal cations and the effect of abnormal aryl strengthening

    Evreinov, V.I.; Safronova, Z.V.; Yarkevich, A.N.; Kharitonov, A.V.; Bondarenko, N.A.; Tsvetkov, E.N.

    1999-01-01

    By the method of conductometry in anhydrous tetrahydrofuran at 25 Deg C stability constants of alkali metal (M = Li, Na, K) cation complexes with certain phosphinoxides have been determined. Abnormal aryl strengthening is first of all pronounced in the cation complexes with tetraphenyldiphosphine dioxide [ru

  19. Atomistic Modeling of Cation Diffusion in Transition Metal Perovskites La1-xSrxMnO3+/-δfor Solid Oxide Fuel Cell Cathodes Applications

    Lee, Yueh-Lin; Duan, Yuhua; Morgan, Dane; Sorescu, Dan; Abernathy, Harry

    Cation diffusion in La1-xSrxMnO3+/-δ (LSM) and in related perovskite materials play an important role in controlling long term performance and stability of solid oxide fuel cell (SOFCs) cathodes. Due to sluggish rates of cation diffusion and complex coupling between defect chemistry and cation diffusion pathways, currently there is still lack of quantitative theoretical model predictions on cation diffusivity vs. T and P(O2) to describe experimental cation tracer diffusivities. In this work, based on ab initio modeling of LSM defect chemistry and migration barriers of the possible cation diffusion pathways, we assess the rates of A-site and B-site cation diffusion in a wide range of T and P(O2) at x =0.0 and 0.2 for SOFC applications. We demonstrate the active cation diffusion pathways in LSM involve cation defect clusters as cation transport carriers, where reduction in the cation migration barriers, which are governed by the steric effect associated with the metal-oxygen cage in the perovskite lattice, is much greater than the penalty of repulsive interaction in the A-site and B-site cation vacancy clusters, leading to higher cation diffusion rates as compared to those of single cation vacancy hopping mechanisms. The predicted Mn and La/Sr cation self-diffusion coefficients of LSM at at x =0.0 and 0.2 along with their 1/T and P(O2) dependences, are in good agreement with the experimental tracer diffusion coefficients.

  20. Correction: A binary catalyst system of a cationic Ru-CNC pincer complex with an alkali metal salt for selective hydroboration of carbon dioxide.

    Ng, Chee Koon; Wu, Jie; Hor, T S Andy; Luo, He-Kuan

    2016-12-22

    Correction for 'A binary catalyst system of a cationic Ru-CNC pincer complex with an alkali metal salt for selective hydroboration of carbon dioxide' by Chee Koon Ng et al., Chem. Commun., 2016, 52, 11842-11845.

  1. Advances in the MQDT approach of electron/molecular cation reactive collisions: High precision extensive calculations for applications

    Motapon O.

    2015-01-01

    Full Text Available Recent advances in the stepwise multichannel quantum defect theory approach of electron/molecular cation reactive collisions have been applied to perform computations of cross sections and rate coefficients for dissociative recombination and electron-impact ro-vibrational transitions of H2+, BeH+ and their deuterated isotopomers. At very low energy, rovibronic interactions play a significant role in the dynamics, whereas at high energy, the dissociative excitation strongly competes with all other reactive processes.

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

    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

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

    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.

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

    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.

  5. Metal-Cation Recognition in Water by a Tetrapyrazinoporphyrazine-Based Tweezer Receptor

    Lochman, L.; Švec, J.; Roh, J.; Kirakci, Kaplan; Lang, Kamil; Zimčík, P.; Nováková, V.

    2016-01-01

    Roč. 22, č. 7 (2016), s. 2417-2426 ISSN 0947-6539 Institutional support: RVO:61388980 Keywords : cation s * crown compounds * fluorescent probes * phthalocyanines * sensors Subject RIV: CA - Inorganic Chemistry Impact factor: 5.317, year: 2016

  6. Cation sorption at the smectite edges: From transition metals to Y and Lu

    Schlegel, M.L.

    2007-01-01

    Complete text of publication follows: Introduction: Clay minerals can adsorb trace elements in soils and weathering formations, a sorption property which is also a key-point for the use of clay materials in nuclear waste repositories. Retention can occur either by adsorption on the clay basal plane or at the layer edges, depending on physicochemical conditions. Building on previous identification of sorption sites of transition metals [1-3], this study shows how the geometry of Y and Lu surface complexes on layer edges of clay minerals can be identified. Materials and methods: Suspensions of purified clay minerals (hectorite or Al-montmorillonite, 2 and 1 g/L, respectively) were reacted in 0.5 M NaCl at pH 6 (Al-montmorillonite) and 7 (hectorite) with sorbates at concentrations of 50 μM (Y) and 100 μM (Lu). Self-supporting films of reacted clay minerals were obtained by slowly filtering suspension aliquots on cellulose nitrate filters. Yttrium K-edge and Lu L3-edge polarized EXAFS (PEXAFS) spectra of the self-supporting films were collected in fluorescence mode on the FAME beamline (ESRF, France). PEXAFS data were reduced, and analyzed using standard procedures. Results and interpretation: Small but significant angular dependences were observed for all P-EXAFS data, meaning that the Y and Lu binding environments are anisotropic. Coordination spheres of 7 O at 2.36 Angstroms and 8 O at 2.27 Angstroms, were observed for Y and Lu, respectively, comparable with d(Ln-O) distances measured by EXAFS spectroscopy [4]. Lutetium sorbed on Al-montmorillonite was surrounded by an Al-shell at 3.35 Angstroms, consistent with Lu sharing edges with Al octahedra and partially incorporated in a gibbsite-like interlayer. Both Y and Lu sorbed on hectorite were surrounded by cationic shells. Modelling of these cationic contributions yielded one out-of-plane Si/Mg shell at 3.16 Angstroms (Y) or 3.04 Angstroms (Lu), and two in-plane (Mg/Si) shells at 3.50, and 3.97 Angstroms for Y, or

  7. Cation sorption at the smectite edges: From transition metals to Y and Lu

    Schlegel, M.L. [CEA/DANS/DPC/SCP Lab React Surfaces and Interfaces, F-91191 Gif Sur Yvette (France)

    2007-07-01

    Complete text of publication follows: Introduction: Clay minerals can adsorb trace elements in soils and weathering formations, a sorption property which is also a key-point for the use of clay materials in nuclear waste repositories. Retention can occur either by adsorption on the clay basal plane or at the layer edges, depending on physicochemical conditions. Building on previous identification of sorption sites of transition metals [1-3], this study shows how the geometry of Y and Lu surface complexes on layer edges of clay minerals can be identified. Materials and methods: Suspensions of purified clay minerals (hectorite or Al-montmorillonite, 2 and 1 g/L, respectively) were reacted in 0.5 M NaCl at pH 6 (Al-montmorillonite) and 7 (hectorite) with sorbates at concentrations of 50 {mu}M (Y) and 100 {mu}M (Lu). Self-supporting films of reacted clay minerals were obtained by slowly filtering suspension aliquots on cellulose nitrate filters. Yttrium K-edge and Lu L3-edge polarized EXAFS (PEXAFS) spectra of the self-supporting films were collected in fluorescence mode on the FAME beamline (ESRF, France). PEXAFS data were reduced, and analyzed using standard procedures. Results and interpretation: Small but significant angular dependences were observed for all P-EXAFS data, meaning that the Y and Lu binding environments are anisotropic. Coordination spheres of 7 O at 2.36 Angstroms and 8 O at 2.27 Angstroms, were observed for Y and Lu, respectively, comparable with d(Ln-O) distances measured by EXAFS spectroscopy [4]. Lutetium sorbed on Al-montmorillonite was surrounded by an Al-shell at 3.35 Angstroms, consistent with Lu sharing edges with Al octahedra and partially incorporated in a gibbsite-like interlayer. Both Y and Lu sorbed on hectorite were surrounded by cationic shells. Modelling of these cationic contributions yielded one out-of-plane Si/Mg shell at 3.16 Angstroms (Y) or 3.04 Angstroms (Lu), and two in-plane (Mg/Si) shells at 3.50, and 3.97 Angstroms for Y

  8. 21 CFR 886.4400 - Electronic metal locator.

    2010-04-01

    ...) MEDICAL DEVICES OPHTHALMIC DEVICES Surgical Devices § 886.4400 Electronic metal locator. (a) Identification. An electronic metal locator is an AC-powered device with probes intended to locate metallic foreign bodies in the eye or eye socket. (b) Classification. Class II. ...

  9. Raman spectroscopy of DNA-metal complexes. I. Interactions and conformational effects of the divalent cations: Mg, Ca, Sr, Ba, Mn, Co, Ni, Cu, Pd, and Cd

    Duguid, J.; Bloomfield, V.A.; Benevides, J.; Thomas Jr, G.J.

    1993-01-01

    Interactions of divalent metal cations (Mg2+, Ca2+, Ba2+, Sr2+, Mn2+, Co2+, Ni2+, Cu2+, Pd2+, and Cd2+) with DNA have been investigated by laser Raman spectroscopy. Both genomic calf-thymus DNA (> 23 kilobase pairs) and mononucleosomal fragments (160 base pairs) were employed as targets of metal interaction in solutions containing 5 weight-% DNA and metal:phosphate molar ratios of 0.6:1. Raman difference spectra reveal that transition metal cations (Mn2+, Co2+, Ni2+, Cu2+, Pd2+, and Cd2+) ind...

  10. Identification of a crucial histidine involved in metal transport activity in the Arabidopsis cation/H+ exchanger CAX1.

    Shigaki, Toshiro; Barkla, Bronwyn J; Miranda-Vergara, Maria Cristina; Zhao, Jian; Pantoja, Omar; Hirschi, Kendal D

    2005-08-26

    In plants, yeast, and bacteria, cation/H+ exchangers (CAXs) have been shown to translocate Ca2+ and other metal ions utilizing the H+ gradient. The best characterized of these related transporters is the plant vacuolar localized CAX1. We have used site-directed mutagenesis to assess the impact of altering the seven histidine residues to alanine within Arabidopsis CAX1. The mutants were expressed in a Saccharomyces cerevisiae strain that is sensitive to Ca2+ and other metals. By utilizing a yeast growth assay, the H338A mutant was the only mutation that appeared to alter Ca2+ transport activity. The CAX1 His338 residue is conserved among various CAX transporters and may be located within a filter for cation selection. We proceeded to mutate His338 to every other amino acid residue and utilized yeast growth assays to estimate the transport properties of the 19 CAX mutants. Expression of 16 of these His338 mutants could not rescue any of the metal sensitivities. However, expression of H338N, H338Q, and H338K allowed for some growth on media containing Ca2+. Most interestingly, H338N exhibited increased tolerance to Cd2+ and Zn2+. Endomembrane fractions from yeast cells were used to measure directly the transport of H338N. Although the H338N mutant demonstrated 25% of the wild type Ca2+/H+ transport, it showed an increase in transport for both Cd2+ and Zn2+ reflected in a decrease in the Km for these substrates. This study provides insights into the CAX cation filter and novel mechanisms by which metals may be partitioned across membranes.

  11. Electron beam welding of dissimilar metals

    Metzger, G.; Lison, R.

    1976-01-01

    Thirty-three two-memeber combinations of dissimilar metals were electron beam welded as square-groove butt joints in 0.08 and 0.12 in. sheet material. Many joints were ''braze welded'' by offsetting the electron beam about 0.02 in. from the butt joint to achieve fusion of the lower melting point metal, but no significant fusion of the other member of the pair. The welds were evaluated by visual and metallographic examination, transverse tensile tests, and bend tests. The welds Ag/Al, Ag/Ni15Cr7Fe, Cu/Ni15Cr7Fe, Cu/V, Cu20Ni/Ni15Cr7Fe, Fe18Cr8Ni/Ni, Fe18Cr8Ni/Ni15Cr7Fe, Nb/Ti, Nb/V, Ni/Ni15Cr7Fe, and Cb/V10Ti were readily welded and weld properties were excellent. Others which had only minor defects included the Ag/Cu20Ni, Ag/Ti, Ag/V, Cu/Fe18Cr8Ni, Cu/V10Ti, Cu20Ni/Fe18Cr8Ni, and Ti/Zr2Sn welds. The Cu/Ni weld had deep undercut, but was in other respects excellent. The mechanical properties of the Ag/Fe18Cr8Ni weld were poor, but the defect could probably be corrected. Difficulty with cracking was experienced with the Al/Ni and Fe18Cr8Ni/V welds, but sound welds had excellent mechanical properties. The remaining welds Al-Cu, Al/Cu20Ni, Al/Fe18Cr8Ni, Al/Ni15Cr7Fe, Cu20Ni/V, Cu20Ni/V10Ti, Cb/Zr2Sn, Ni/Ti, Ni15Cr7Fe/V, Ni15Cr7Fe/V10Ti, and Ti/V were unsuccessful, due to brittle phases, primarily at the weld metal-base metal interface. In addition to the two-member specimens, several joints were made by buttering. Longitudinal weld specimens of the three-member combination Al/Ni/Fe18Cr8Ni and the five member combination Fe18Cr8Ni/V/Cb/Ti/Zr2Sn showed good tensile strength and satisfactory elongation. 6 tables, 16 figures

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

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

    2018-06-20

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

  13. Electron Transfer Dissociation and Collision-Induced Dissociation of Underivatized Metallated Oligosaccharides

    Schaller-Duke, Ranelle M.; Bogala, Mallikharjuna R.; Cassady, Carolyn J.

    2018-05-01

    Electron transfer dissociation (ETD) and collision-induced dissociation (CID) were used to investigate underivatized, metal-cationized oligosaccharides formed via electrospray ionization (ESI). Reducing and non-reducing sugars were studied including the tetrasaccharides maltotetraose, 3α,4β,3α-galactotetraose, stachyose, nystose, and a heptasaccharide, maltoheptaose. Univalent alkali, divalent alkaline earth, divalent and trivalent transition metal ions, and a boron group trivalent metal ion were adducted to the non-permethylated oligosaccharides. ESI generated [M + Met]+, [M + 2Met]2+, [M + Met]2+, [M + Met - H]+, and [M + Met - 2H]+ most intensely along with low intensity nitrate adducts, depending on the metal and sugar ionized. The ability of these metal ions to produce oligosaccharide adduct ions by ESI had the general trend: Ca(II) > Mg(II) > Ni(II) > Co(II) > Zn(II) > Cu(II) > Na(I) > K(I) > Al(III) ≈ Fe(III) ≈ Cr(III). Although trivalent metals were utilized, no triply charged ions were formed. Metal cations allowed for high ESI signal intensity without permethylation. ETD and CID on [M + Met]2+ produced various glycosidic and cross-ring cleavages, with ETD producing more cross-ring and internal ions, which are useful for structural analysis. Product ion intensities varied based on glycosidic-bond linkage and identity of monosaccharide sub-unit, and metal adducts. ETD and CID showed high fragmentation efficiency, often with complete precursor dissociation, depending on the identity of the adducted metal ion. Loss of water was occasionally observed, but elimination of small neutral molecules was not prevalent. For both ETD and CID, [M + Co]2+ produced the most uniform structurally informative dissociation with all oligosaccharides studied. The ETD and CID spectra were complementary. [Figure not available: see fulltext.

  14. Electron Transfer Dissociation and Collision-Induced Dissociation of Underivatized Metallated Oligosaccharides

    Schaller-Duke, Ranelle M.; Bogala, Mallikharjuna R.; Cassady, Carolyn J.

    2018-02-01

    Electron transfer dissociation (ETD) and collision-induced dissociation (CID) were used to investigate underivatized, metal-cationized oligosaccharides formed via electrospray ionization (ESI). Reducing and non-reducing sugars were studied including the tetrasaccharides maltotetraose, 3α,4β,3α-galactotetraose, stachyose, nystose, and a heptasaccharide, maltoheptaose. Univalent alkali, divalent alkaline earth, divalent and trivalent transition metal ions, and a boron group trivalent metal ion were adducted to the non-permethylated oligosaccharides. ESI generated [M + Met]+, [M + 2Met]2+, [M + Met]2+, [M + Met - H]+, and [M + Met - 2H]+ most intensely along with low intensity nitrate adducts, depending on the metal and sugar ionized. The ability of these metal ions to produce oligosaccharide adduct ions by ESI had the general trend: Ca(II) > Mg(II) > Ni(II) > Co(II) > Zn(II) > Cu(II) > Na(I) > K(I) > Al(III) ≈ Fe(III) ≈ Cr(III). Although trivalent metals were utilized, no triply charged ions were formed. Metal cations allowed for high ESI signal intensity without permethylation. ETD and CID on [M + Met]2+ produced various glycosidic and cross-ring cleavages, with ETD producing more cross-ring and internal ions, which are useful for structural analysis. Product ion intensities varied based on glycosidic-bond linkage and identity of monosaccharide sub-unit, and metal adducts. ETD and CID showed high fragmentation efficiency, often with complete precursor dissociation, depending on the identity of the adducted metal ion. Loss of water was occasionally observed, but elimination of small neutral molecules was not prevalent. For both ETD and CID, [M + Co]2+ produced the most uniform structurally informative dissociation with all oligosaccharides studied. The ETD and CID spectra were complementary. [Figure not available: see fulltext.

  15. The electronic properties of mixed metal oxides

    Cussen, E.J.

    1999-01-01

    The properties of Fe and Mn in a variety of perovskite-related crystal structures have been studied by X-ray and neutron diffraction, magnetometry, high resolution electron microscopy and Moessbauer spectroscopy. The structure of Sr 2 FeTaO 6 is of the GdFeO 3 type with a disordered arrangement of Fe and Ta over the octahedrally coordinated sites in contrast to the partial ordering, 0.795(6)Fe/0.205(6)Sb, observed in Sr 2 FeSbO 6 . Sr 2 FeTaO 6 is a spin glass below 23 K whereas Sr 2 FeSbO 6 forms a type I antiferromagnetically ordered phase below T N = 37(2) K with an ordered moment of 3.06(9) μ B Fe -1 at 1.5 K on the Fe-rich site. Susceptibility measurements in the magnetically dilute series Sr 2 Fe 1-x Ga x TaO 6 indicate that magnetic ordering in these Fe 3+ perovskites is partially controlled by next-nearest-neighbour superexchange. A new 15R perovskite structure containing face-sharing dimers of octahedra linked to one another by vertices or bridging octahedra has been - found for the composition SrMn 0.915(5) Fe 0.085(5) O 2.979(3) . The Mn 4+ cations align antiferromagnetically below T N = 220(5) K showing an ordered moment of 2.25(3) μ B at 3 K. The Fe cations remain disordered to 3 K. This composition forms a 6-layered hexagonal perovskite in the temperature range 1200 6 Mn 4 MO 15 (M = Cu, Zn) form pseudo 1-dimensional phases related to Ba 6 Ni 5 O 15 . The trigonal prismatic sites in this structure are preferentially occupied by Zn/Cu; the latter is displaced from the centre of the trigonal prism to give pseudo square-planar coordination. At 1.7 K antiferromagnetic superexchange within a highly frustrated crystal structure leads to a magnetic structure exhibiting rotation of 120 deg. between spins in neighbouring chains. The magnetic moments refined to 0.7(1) and 0.6(1) μ B per octahedral site in the Cu and Zn compounds respectively. The magnetic susceptibilities have been rationalised in terms of 1-dimensional ordering of the octahedrally

  16. Ab initio investigation of the thermodynamics of cation distribution and of the electronic and magnetic structures in the LiMn2O4 spinel

    Santos-Carballal, David; Ngoepe, Phuti E.; de Leeuw, Nora H.

    2018-02-01

    The spinel-structured lithium manganese oxide (LiMn2O4 ) is a material currently used as cathode for secondary lithium-ion batteries, but whose properties are not yet fully understood. Here, we report a computational investigation of the inversion thermodynamics and electronic behavior of LiMn2O4 derived from spin-polarized density functional theory calculations with a Hubbard Hamiltonian and long-range dispersion corrections (DFT+U-D3). Based on the analysis of the configurational free energy, we have elucidated a partially inverse equilibrium cation distribution for the LiMn2O4 spinel. This equilibrium degree of inversion is rationalized in terms of the crystal field stabilization effects and the difference between the size of the cations. We compare the atomic charges with the oxidation numbers for each degree of inversion. We found segregation of the Mn charge once these ions occupy the tetrahedral and octahedral sites of the spinel. We have obtained the atomic projections of the electronic band structure and density of states, showing that the normal LiMn2O4 has half-metallic properties, while the fully inverse spinel is an insulator. This material is in the ferrimagnetic state for the inverse and partially inverse cation arrangement. The optimized lattice and oxygen parameters, as well as the equilibrium degree of inversion, are in agreement with the available experimental data. The partial equilibrium degree of inversion is important in the interpretation of the lithium ion migration and surface properties of the LiMn2O4 spinel.

  17. Organic-inorganic perovskites containing trivalent metal halide layers: the templating influence of the organic cation layer.

    Mitzi, D B

    2000-12-25

    Thin sheetlike crystals of the metal-deficient perovskites (H2AEQT)M2/3I4 [M = Bi or Sb; AEQT = 5,5"'-bis-(aminoethyl)-2,2':5',2'':5'',2'''-quaterthiophene] were formed from slowly cooled ethylene glycol/2-butanol solutions containing the bismuth(III) or antimony(III) iodide and AEQT.2HI salts. Each structure was refined in a monoclinic (C2/m) subcell, with the lattice parameters a = 39.712(13) A, b = 5.976(2) A, c = 6.043(2) A, beta = 92.238(5) degrees, and Z = 2 for M = Bi and a = 39.439(7) A, b = 5.952(1) A, c = 6.031(1) A, beta = 92.245(3) degrees, and Z = 2 for M = Sb. The trivalent metal cations locally adopt a distorted octahedral coordination, with M-I bond lengths ranging from 3.046(1) to 3.218(3) A (3.114 A average) for M = Bi and 3.012(1) to 3.153(2) A (3.073 A average) for M = Sb. The new organic-inorganic hybrids are the first members of a metal-deficient perovskite family consisting of (Mn+)2/nV(n-2)/nX4(2-) sheets, where V represents a vacancy (generally left out of the formula) and the metal cation valence, n, is greater than 2. The organic layers in the AEQT-based organic-inorganic hybrids feature edge-to-face aromatic interactions among the rigid, rodlike quaterthiophene moieties, which may help to stabilize the unusual metal-deficient layered structures.

  18. Preparation of calcium oxalate-bromopyrogallol red inclusion sorbent and application to treatment of cationic dye and heavy metal wastewaters.

    Wang, Hong-Yan; Gao, Hong-Wen

    2009-05-01

    Dye pollutants are a major class of environmental contaminants. Over 100,000 dyes have been synthesized worldwide and more than 700,000 tons are produced annually and over 5% are discharged into aquatic environments. The adsorption or sorption is one of the most efficient methods to remove dye and heavy metal pollutants from wastewater. However, most of the present sorbents often bear some disadvantages, e.g. low sorption capacity, difficult separation of spoil, complex reproduction, or secondary pollution. Development of novel sorbents that can overcome these limitations is desirable. On the basis of the chemical coprecipitation of calcium oxalate (CaC(2)O(4)), bromopyrogallol red (BPR) was embedded during the growing of CaC(2)O(4) particles. The ternary C(2)O(4) (2-)-BPR-Ca(2+) sorbent was yielded by the centrifugation. Its composition was determined by spectrophotometry and AAS, and its structure and morphology were characterized by powder X-ray diffraction (XRD), laser particle-size analysis, and scanning electron microscopy (SEM). The adsorption of ethyl violet (EV) and heavy metals, e.g. Cu(II), Cd(II), Ni(II), Zn(II), and Pb(II) were carried out and their removal rate determined by spectrophotometry and ICP-OES. The adsorption performance of the sorbent was compared with powder activated carbon. The Langmuir isothermal model was applied to fit the embedment of BPR and adsorption of EV. The saturation number of BPR binding to CaC(2)O(4) reached 0.0105 mol/mol and the adsorption constant of the complex was 4.70 x 10(5) M(-1). Over 80% of the sorbent particles are between 0.7 and 1.02 microm, formed by the aggregation of the global CaC(2)O(4)/BPR inclusion grains of 30-50 nm size. Such a material was found to adsorb cationic dyes selectively and sensitively. Ethyl violet (EV) was used to investigate the adsorption mechanism of the material. One BPR molecule may just bind with one EV molecule. The CaC(2)O(4)/BPR inclusion material adsorbed EV over two times more

  19. Electronic specific heat of transition metal carbides

    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

  20. Cooperative effect of adsorbed cations on electron transport and recombination behavior in dye-sensitized solar cells

    Kou, Dongxing; Liu, Weiqing; Hu, Linhua; Dai, Songyuan

    2013-01-01

    Highlights: • Disclose the mechanism of cooperative effects of adsorbed cations in DSCs. • Characterize the influence of adsorption of Im + s on photoinduced electron density. • The effect of Li + is orderly enhanced in DSCs with increasing alkyl chain length. • The DSCs efficiencies are relatively depended on the trade-off between J sc and FF. -- Abstract: Lithium ion (Li + ) and imidazolium cations (Im + s) had been reported to have competitive effects on the photoinduced electrons in TiO 2 -electrolyte systems. Herein, a further investigation about their cooperative effect in dye-sensitized solar cells (DSCs) using organic liquid electrolyte is developed by altering alkyl chain length. Imidazolium iodides (Im + I − s) with different alkyl chain length (3, 6, and 12) were synthesized and used as iodide sources. The adsorption amount of Im + s onto TiO 2 , band edge shifts, trap states distribution, electron recombination/transport processes and ion transport within the electrolyte for DSCs were detected. It is found that the multilayered adsorption of Im + s can induce a lower photoinduced electron density. In-depth characterizations indicate that this negative effect can be reduced as the adsorption amount decreased with increasing alkyl chain length and the effect of Li + is consequently strengthened in varying degrees. The decisive role of Li + in cation-controlled interfacial charge injection process finally contributes an ordinal increase of short-circuit photocurrent density J sc for DSCs with increasing alkyl chain length because of the increasing charge injection efficiency η inj . Additionally, a large power dissipation in ions transport process is induced by the long alkyl chain of Im + s. Overall, the cell efficiencies are relatively dependent of the trade-off between J sc and FF, which is essentially related to the cooperative effect of adsorbed cations

  1. Integrating chemical imaging of cationic trace metal solutes and pH into a single hydrogel layer

    Hoefer, Christoph; Santner, Jakob; Borisov, Sergey M.; Wenzel, Walter W.; Puschenreiter, Markus

    2017-01-01

    Gel-based, two-dimensional (2D) chemical imaging techniques are versatile methods for investigating biogeochemically active environments at high spatial resolution (sub-mm). State-of-the-art solute imaging techniques, such as diffusive gradients in thin films (DGT) and planar optodes (PO), employ passive solute sampling or sensing. Combining these methods will provide powerful tools for studying the biogeochemistry of biological niches in soils and sediments. In this study we aimed at developing a combined single-layer gel for direct pH imaging using PO and sampling of anionic and cationic solutes by DGT, with subsequent analysis of the bound solutes by laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). We tested three ultra-thin (<100 μm) polyurethane-based gels, incorporating anion and cation binding materials and the fluorescent pH indicator DCIFODA (2′,7′-dichloro-5(6)-N-octadecyl-carboxamidofluorescein). Results showed that PO-based pH sensing using DCIFODA was impossible in the presence of the anion binding materials due to interferences with DCIFODA protonation. One gel, containing only a cation binding material and DCIFODA, was fully characterized and showed similar performance characteristics as comparable DGT-only gels (applicable pH range: pH 5–8, applicable ionic strength range: 1–20 mmol L"-"1, cation binding capacity ∼24 μg cm"−"2). The dynamic range for PO-based pH mapping was between pH 5.5 and 7.5 with t_9_0 response time of ∼60 min. In a case study we demonstrated the gel's suitability for multi-analyte solute imaging and mapped pH gradients and concurrent metal solubility patterns in the rhizosphere of Salix smithiana. pH decreases in the rooted soil were co-localized with elevated solute fluxes of Al"3"+, Co"2"+, Cu"2"+, Fe, Mn"2"+, Ni"2"+ and Pb"2"+, indicating pH-induced metal solubilisation. - Highlights: • Diffusive gradients in thin films (DGT) and planar optode (PO) imaging is combined. • A

  2. Integrating chemical imaging of cationic trace metal solutes and pH into a single hydrogel layer

    Hoefer, Christoph [Department of Forest and Soil Sciences, Institute of Soil Research, University of Natural Resources and Life Sciences, Vienna, Konrad-Lorenz-Strasse 24, A-3430 Tulln (Austria); Santner, Jakob, E-mail: jakob.santner@boku.ac.at [Department of Forest and Soil Sciences, Institute of Soil Research, University of Natural Resources and Life Sciences, Vienna, Konrad-Lorenz-Strasse 24, A-3430 Tulln (Austria); Department of Crop Sciences, Division of Agronomy, University of Natural Resources and Life Sciences, Vienna, Konrad-Lorenz-Strasse 24, 3430 Tulln (Austria); Borisov, Sergey M. [Institute of Analytical Chemistry and Food Chemistry, Graz University of Technology, Stremayrgasse 9, A-8010, Graz (Austria); Wenzel, Walter W.; Puschenreiter, Markus [Department of Forest and Soil Sciences, Institute of Soil Research, University of Natural Resources and Life Sciences, Vienna, Konrad-Lorenz-Strasse 24, A-3430 Tulln (Austria)

    2017-01-15

    Gel-based, two-dimensional (2D) chemical imaging techniques are versatile methods for investigating biogeochemically active environments at high spatial resolution (sub-mm). State-of-the-art solute imaging techniques, such as diffusive gradients in thin films (DGT) and planar optodes (PO), employ passive solute sampling or sensing. Combining these methods will provide powerful tools for studying the biogeochemistry of biological niches in soils and sediments. In this study we aimed at developing a combined single-layer gel for direct pH imaging using PO and sampling of anionic and cationic solutes by DGT, with subsequent analysis of the bound solutes by laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). We tested three ultra-thin (<100 μm) polyurethane-based gels, incorporating anion and cation binding materials and the fluorescent pH indicator DCIFODA (2′,7′-dichloro-5(6)-N-octadecyl-carboxamidofluorescein). Results showed that PO-based pH sensing using DCIFODA was impossible in the presence of the anion binding materials due to interferences with DCIFODA protonation. One gel, containing only a cation binding material and DCIFODA, was fully characterized and showed similar performance characteristics as comparable DGT-only gels (applicable pH range: pH 5–8, applicable ionic strength range: 1–20 mmol L{sup -1}, cation binding capacity ∼24 μg cm{sup −2}). The dynamic range for PO-based pH mapping was between pH 5.5 and 7.5 with t{sub 90} response time of ∼60 min. In a case study we demonstrated the gel's suitability for multi-analyte solute imaging and mapped pH gradients and concurrent metal solubility patterns in the rhizosphere of Salix smithiana. pH decreases in the rooted soil were co-localized with elevated solute fluxes of Al{sup 3+}, Co{sup 2+}, Cu{sup 2+}, Fe, Mn{sup 2+}, Ni{sup 2+} and Pb{sup 2+}, indicating pH-induced metal solubilisation. - Highlights: • Diffusive gradients in thin films (DGT) and planar

  3. Calcium and sodium as regulators of the recovery of four Daphnia species along a gradient of metal and base cations in metal contaminated lakes in Sudbury, Ontario, Canada

    Martha Patricia Celis-Salgado

    2016-04-01

    Full Text Available Smelting of sulphur-rich metallic ores in Sudbury, Ontario, Canada, has caused acidification and metal contamination of thousands of lakes in the region. Recent reductions in smelter emissions have resulted in much ecological recovery, but the recovery of Daphnia species has been poor. To determine if Cu and Ni toxicity could explain differences in daphniid recovery among lakes, we compared results of 14 d static with renewal bioassays in waters from Blue Chalk Lake, an uncontaminated reference lake 200 km from Sudbury, and from five Sudbury lakes ranging in distance from the smelters and varying in metal and cation concentrations. We spiked Blue Chalk Lake water with Cu and Ni to levels resembling those of the Sudbury lakes and also tested the lake waters for toxicity. Survival of Daphnia pulex, D. pulicaria and D. mendotae decreased monotonically with increasing metal concentrations in the spiked Blue Chalk Lake treatments, falling from 90% in the controls to 0% at the two highest Cu and Ni levels, reflecting levels of Middle and Hannah lakes. In contrast, survival in waters collected from the actual Sudbury lakes did not monotonically track their total metal concentrations. Rather, survival fell to 0% in Clearwater Lake water, a lake with intermediate metal contamination (8.9 and 79.9 μg L–1 of Cu and Ni, respectively vs 70-100% in the other lakes. We performed an additional assay with Clearwater Lake waters increasing its Ca and Na concentrations, singly and in combination to levels that reflected the levels in Middle Lake. The survival of the four daphniid species increased from 0% up to 80-100% with added Ca and from 0% to 60-90% with added Na. Lipid-ovarian indices had a similar trend to survival for D. mendotae and D. pulicaria in Bioassay 1, varying with the cation concentrations in the lakes for the daphniids in Bioassay 2. The bioassays results imply that regional recovery patterns of daphniids in Sudbury lakes cannot be understood

  4. Study of electron transition energies between anions and cations in spinel ferrites using differential UV–vis absorption spectra

    Xue, L.C.; Wu, L.Q.; Li, S.Q.; Li, Z.Z.; Tang, G.D.; Qi, W.H.; Ge, X.S.; Ding, L.L.

    2016-01-01

    It is very important to determine electron transition energies (E_t_r) between anions and different cations in order to understand the electrical transport and magnetic properties of a material. Many authors have analyzed UV–vis absorption spectra using the curve (αhν)"2 vs E, where α is the absorption coefficient and E(=hν) is the photon energy. Such an approach can give only two band gap energies for spinel ferrites. In this paper, using differential UV–vis absorption spectra, dα/dE vs E, we have obtained electron transition energies (E_t_r) between the anions and cations, Fe"2"+ and Fe"3"+ at the (A) and [B] sites and Ni"2"+ at the [B] sites for the (A)[B]_2O_4 spinel ferrite samples Co_xNi_0_._7_−_xFe_2_._3O_4 (0.0≤x≤0.3), Cr_xNi_0_._7Fe_2_._3_−_xO_4 (0.0≤x≤0.3) and Fe_3O_4. We suggest that the differential UV–vis absorption spectra should be accepted as a general analysis method for determining electron transition energies between anions and cations.

  5. Metallization of bacterial cellulose for electrical and electronic device manufacture

    Evans, Barbara R [Oak Ridge, TN; O'Neill, Hugh M [Knoxville, TN; Jansen, Valerie Malyvanh [Memphis, TN; Woodward, Jonathan [Knoxville, TN

    2010-09-28

    A method for the deposition of metals in bacterial cellulose and for the employment of the metallized bacterial cellulose in the construction of fuel cells and other electronic devices is disclosed. The method for impregnating bacterial cellulose with a metal comprises placing a bacterial cellulose matrix in a solution of a metal salt such that the metal salt is reduced to metallic form and the metal precipitates in or on the matrix. The method for the construction of a fuel cell comprises placing a hydrated bacterial cellulose support structure in a solution of a metal salt such that the metal precipitates in or on the support structure, inserting contact wires into two pieces of the metal impregnated support structure, placing the two pieces of metal impregnated support structure on opposite sides of a layer of hydrated bacterial cellulose, and dehydrating the three layer structure to create a fuel cell.

  6. Introduction of a cation in aqueous solution by electrolytic dissolution of metal. Applications to the decontamination of radioactive effluents

    Gauchon, Jean-Paul

    1979-01-01

    This research thesis aims at comparing results obtained in chemical decontamination of radioactive effluents with a metallic cation introduced by metal electro-dissolution or by dose addition. After an overview of methods used for the purification of radioactive effluents and a more precise presentation of chemical co-precipitation, the author reports preliminary tests of the application of chemical co-precipitation to the decontamination of radioactive effluents, reports the analysis of iron, zinc and copper behaviour in aqueous environment by means of thermodynamic diagrams and current-voltage curves. He reports the design and use of two electro-dissolution sets, and the application of copper electrolytic dissolution to the elimination of ruthenium in radioactive effluents. He finally addresses the purification treatment of effluents of nuclear reactors

  7. Selective adsorption and ion exchange of metal cations and anions with silico-titanates and layered titanates

    Anthony, R.G.; Philip, C.V.

    1993-01-01

    Metal ions may be removed from aqueous wastes from metal processing plants and from refineries. They may also be used in concentrating radioactive elements found in dilute, aqueous, nuclear wastes. A new series of silico-titanates and alkali titanates are shown to have specific selectivity for cations of lead, mercury, and cadmium and the dichromate anion in solutions with low and high pH. Furthermore, one particular silico-titanate, TAM-5, was found to be highly selective for Cs + and Sr 2+ in solutions of 5.7 M Na + and 0.6 M Oh - . A high potential exists for these materials for removing Cs + and Sr 2+ from radioactive aqueous wastes containing high concentrations of Na + at high and low pH

  8. Effects of Organics on the Adsorption and Mobility of Metal Cations in Clay Systems: Computational Molecular Modeling Approach

    Kalinichev, Andrey G.; Ngouana Wakou, Brice F.; Loganathan, Narasimhan

    2013-01-01

    Understanding and prediction of many natural and anthropogenic environmental processes ultimately depend on a fundamental understanding of the chemistry occurring at the mineral-fluid inter-faces. Clay-related minerals and natural organic matter (NOM) are ubiquitous in the environment, and metal-NOM complexation induces strong correlations between the NOM concentration in water and the capacity of clay particles to bind metals, thus affecting their speciation, solubility and toxicity in the environment. Despite significant geochemical, environmental and technological interest, the molecular-level mechanisms and dynamics of the physical and chemical processes involving NOM are not yet well understood. In this presentation we compare three different molecular dynamics (MD) computer simulations of metal-NOM complexation in aqueous solutions. The simulation results indicate that despite some obvious quantitative variations in the computed values depending on the size of the simulated system and on the parameters of the force field models used, all three simulations are quite robust and consistent. In particular, approximately 35-50% of Ca 2+ ions in all simulations are associated with the carboxylic groups of NOM at near-neutral pH. The stability of bidentate-coordinated contact ion pair complexes is also always strongly preferred. Easy association of metal cations with negatively charged NOM functional groups and negatively charged clay surfaces allows us to predict that cationic bridging could be the most probable mechanism of NOM association with clays in natural environments. New MD simulations are currently in progress to quantitatively assess these predictions on a molecular scale for nuclear waste disposal applications. New larger-scale clay models incorporate a more realistic representation of the structural and compositional disorder of natural illites and smectites and employ CLAYFF - a fully flexible general force field suitable for the molecular simulations

  9. Effects of alkali metal cations on phospho-enzyme levels and [3H] ouabain binding to (Na+ + K+)-ATPase.

    Han, C S; Tobin, T; Akera, T; Brody, T M

    1976-05-13

    The effects of several alkali metal cations on the relationship between steady state phospho-enzyme levels and initial velocity and equilibrium levels of [3H]-ouabain binding to (Na+ + K+)-ATPase (ATP phosphohydrolase EC 3.6.1.3.) were examined. Only Na+ increased both phospho-enzyme and [3H] ouabain binding levels above those observed in the presence of Mg2+ alone. While Na+ stimulated phosphorylation with an apparent Km of about 1 mM, its stimulation of [3H] ouabain binding was biphasic, the lower Km for stimulation corresponding to the Km for formation of phospho-enzyme. Among the other alkali metal cations, potassium, rubidium and lithium were at least eight times more effect in reducing phospho-enzyme levels than in reducing [3H] ouabain binding. This discrepancy is not due to the stability of the enzyme-ouabain complex, nor to any action on the rates of formation or dissociation of the enzyme-ouabain complex. The data thus suggest that [3H] ouabain interacts with the K+, Rb+ or Li+ -enzyme complexes. For Li+, this hypothesis is further supported by the observation that Li+ can cirectly increase the equilibrium level of [3H] ouabain binding to this enzyme under certain conditions.

  10. Effect of Variations in Annealing Temperature and Metallic Cations on Nanostructured Molybdate Thin Films

    Varela JoséArana

    2008-01-01

    Full Text Available AbstractCrystalline molybdate thin films were prepared by the complex polymerization method. The AMoO4(A = Ca, Sr, Ba films were deposited onto Si wafers by the spinning technique. The Mo–O bond in the AMoO4structure was confirmed by FTIR spectra. X-ray diffraction revealed the presence of crystalline scheelite-type phase. The mass, size, and basicity of A2+cations was found to be dependent on the intrinsic characteristics of the materials. The grain size increased in the following order: CaMoO4 < SrMoO4 < BaMoO4. The emission band wavelength was detected at around 576 nm. Our findings suggest that the material’s morphology and photoluminescence were both affected by the variations in cations (Ca, Sr, or Ba and in the thermal treatment.

  11. Tetrathiafulvalene-based azine ligands for anion and metal cation coordination

    Awatef Ayadi

    2015-08-01

    Full Text Available The synthesis and full characterization of two tetrathiafulvalene-appended azine ligands, namely 2-([2,2’-bi(1,3-dithiolylidene]-4-yl-6-((2,4-dinitrophenylhydrazonomethylpyridine (L1 and 5-([2,2’-bi(1,3-dithiolylidene]-4-yl-2-((2,4-dinitrophenylhydrazonomethylpyridine (L2 are described. The crystal structure of ligand L1 indicates that the ligand is completely planar with the presence of a strong intramolecular N3–H3···O1 hydrogen bonding. Titration experiments with inorganic anions showed that both ligands are suitable candidates for the sensing of fluoride anions. Ligand L2 was reacted with a Re(I cation to yield the corresponding rhenium tricarbonyl complex 3. In the crystal structure of the newly prepared electroactive rhenium complex the TTF is neutral and the rhenium cation is hexacoordinated. The electrochemical behavior of the three compounds indicates that they are promising for the construction of crystalline radical cation salts.

  12. Effect of lone-electron-pair cations on the orientation of crystallographic shear planes in anion-deficient perovskites.

    Batuk, Dmitry; Batuk, Maria; Abakumov, Artem M; Tsirlin, Alexander A; McCammon, Catherine; Dubrovinsky, Leonid; Hadermann, Joke

    2013-09-03

    Factors affecting the structure and orientation of the crystallographic shear (CS) planes in anion-deficient perovskites were investigated using the (Pb(1-z)Sr(z))(1-x)Fe(1+x)O(3-y) perovskites as a model system. The isovalent substitution of Sr(2+) for Pb(2+) highlights the influence of the A cation electronic structure because these cations exhibit very close ionic radii. Two compositional ranges have been identified in the system: 0.05 ≤ z ≤ 0.2, where the CS plane orientation gradually varies but stays close to (203)p, and 0.3 ≤ z ≤ 0.45 with (101)p CS planes. The incommensurately modulated structure of Pb0.792Sr0.168Fe1.040O2.529 was refined from neutron powder diffraction data using the (3 + 1)D approach (space group X2/m(α0γ), X = (1/2, 1/2, 1/2, 1/2), a = 3.9512(1) Å, b = 3.9483(1) Å, c = 3.9165(1) Å, β = 93.268(2)°, q = 0.0879(1)a* + 0.1276(1)c*, RF = 0.023, RP = 0.029, and T = 900 K). A comparison of the compounds with different CS planes indicates that the orientation of the CS planes is governed mainly by the stereochemical activity of the lone-electron-pair cations inside the perovskite blocks.

  13. Metal cation dependence of interactions with amino acids: bond dissociation energies of Rb(+) and Cs(+) to the acidic amino acids and their amide derivatives.

    Armentrout, P B; Yang, Bo; Rodgers, M T

    2014-04-24

    Metal cation-amino acid interactions are key components controlling the secondary structure and biological function of proteins, enzymes, and macromolecular complexes comprising these species. Determination of pairwise interactions of alkali metal cations with amino acids provides a thermodynamic vocabulary that begins to quantify these fundamental processes. In the present work, we expand a systematic study of such interactions by examining rubidium and cesium cations binding with the acidic amino acids (AA), aspartic acid (Asp) and glutamic acid (Glu), and their amide derivatives, asparagine (Asn) and glutamine (Gln). These eight complexes are formed using electrospray ionization and their bond dissociation energies (BDEs) are determined experimentally using threshold collision-induced dissociation with xenon in a guided ion beam tandem mass spectrometer. Analyses of the energy-dependent cross sections include consideration of unimolecular decay rates, internal energy of the reactant ions, and multiple ion-neutral collisions. Quantum chemical calculations are conducted at the B3LYP, MP2(full), and M06 levels of theory using def2-TZVPPD basis sets, with results showing reasonable agreement with experiment. At 0 and 298 K, most levels of theory predict that the ground-state conformers for M(+)(Asp) and M(+)(Asn) involve tridentate binding of the metal cation to the backbone carbonyl, amino, and side-chain carbonyl groups, although tridentate binding to the carboxylic acid group and side-chain carbonyl is competitive for M(+)(Asn). For the two longer side-chain amino acids, Glu and Gln, multiple structures are competitive. A comparison of these results to those for the smaller alkali cations, Na(+) and K(+), provides insight into the trends in binding energies associated with the molecular polarizability and dipole moment of the side chain. For all four metal cations, the BDEs are inversely correlated with the size of the metal cation and follow the order Asp < Glu

  14. NOVEL SYNTHESIS OF POLYARYLENESULFONIUM CATIONS THROUGH A MULTI-ELECTRON TRANSFER PROCESS

    1998-01-01

    The oxidative polymerization of aryl sulfoxides provides a novel polysulfonium compound, poly(methylsulfonio-1,4-phenylenethio-1,4-phenylene cation) in quantitative yield. The polymerization proceeds efficiently in an acidic solution under atmospheric conditions. Oxygen, chemical and electrochemical oxidations are available. Vanadyl acetylacetonate and cerium ammonium nitrate act as an effective catalyst for the oxygen oxidative polymerization. The polymerization mechanism involves multielectron oxidation of the sulfides followed by successive electrophilic substitution. The resulting polyarylenesulfonium cations are useful as a soluble precursor for the synthesis of high molecular weight (Mw>105) poly(thio arylne)s.

  15. Formation of radical cations and dose response of alpha-terthiophene-cellulose triacetate films irradiated by electrons and gamma rays

    Emmi, S S; Ceroni, P; D'Angelantonio, M; Lavalle, M; Fuochi, P G; Kovács, A

    2002-01-01

    The radiation-induced UV-vis spectrum of alpha-terthiophene radical cation in solid is reported. The radical cation initiates an oligomerization in the CTA matrix producing permanently coloured conjugated polarons. The specific net absorbance at 465 nm is linearly related with dose up to 2x10 sup sup 6 sup sup G y, for electrons and gamma irradiation. The decrease of the UV typical absorption (355 nm) and of four IR bands of alpha-terthiophene is linear with dose, as well. Although sensitivity is influenced by dose rate, it turned out that a linear relationship holds between sensitivity and log dose rate, in the range from 2 to 10 sup sup 5 Gy, min. These findings suggest a potential application of the system for dosimetric purposes over a wide range of dose and dose rate.

  16. Structure, thermodynamic and electronic properties of carbon-nitrogen cubanes and protonated polynitrogen cations

    Chaban, Vitaly V.; Andreeva, Nadezhda A.

    2017-12-01

    Energy generation and storage are at the center of modern civilization. Energetic materials constitute quite a large class of compounds with a high amount of stored chemical energy that can be released. We hereby use a combination of quantum chemistry methods to investigate feasibility and properties of carbon-nitrogen cubanes and multi-charged polynitrogen cations in the context of their synthesis and application as unprecedented energetic materials. We show that the stored energy increases gradually with the nitrogen content increase. Nitrogen-poor cubanes retain their stabilities in vacuum, even at elevated temperatures. Such molecules will be probably synthesized at some point. In turn, polynitrogen cations are highly unstable, except N8H+, despite they are isoelectronic to all-carbon cubane. Kinetic stability of the cation decays drastically as its total charge increases. High-level thermodynamic calculations revealed that large amounts of energy are liberated upon decompositions of polynitrogen cations, which produce molecular nitrogen, acetylene, and protons. The present results bring a substantial insights to the design of novel high-energy compounds.

  17. Probing the role of metal cations on the aggregation behavior of amyloid β-peptide at a single molecule level by AFM

    Xie, Yang; Wang, Jianhua, E-mail: wjh@cqu.edu.cn; Liu, Chundong [Chongqing University, Key Laboratory of Biorheological Science and Technology, Ministry of Education, College of Bioengineering (China)

    2016-09-15

    With the development of nanotechnology, understanding of intermolecular interactions on a single molecule level by atomic force spectroscopy (AFM) has played an important role in molecular biology and biomedical science. In recent years, some research suggested that the presence of metal cations is an important regulator in the processes of misfolding and aggregation of the amyloid β-protein (Aβ), which may be an important etiological factor of Alzheimer’s disease. However, the knowledge on the principle of interactions between Aβ and metal cations at the single molecule level is still poor understood. In this paper, the amyloid β-protein (Aβ) was fabricated on substrate of mixed thiol-modified gold nanoparticles using self-assembled monolayer method and the adhesion force in the longitudinal direction between metal cations and Aβ42 were investigated by AFM. The role of metal ions on Aβ aggregation is discussed from the perspective of single molecular force. The force results showed that the specific adhesion force F{sub i} and the nonspecific force F{sub 0} between a single Aβ–Aβ pair in control experiment were calculated as 42 ± 3 and 80 pN, respectively. However, F{sub i} between a single Aβ–Aβ pair in the presence of Cu{sup 2+}, Zn{sup 2+}, Ca{sup 2+} and Al{sup 3+} increased dramatically to 84 ± 6, 89 ± 3, 73 ± 5, 95 ± 5 pN successively, which indicated that unbinding between Aβ proteins is accelerated in the presence of metal cations. What is more, the imaging results showed that substoichiometric copper cations accelerate the formation of fibrils within 3 days. The combined atomic force spectroscopy and imaging analysis indicate that metal cations play a role in promoting the aggregating behavior of Aβ42.

  18. Probing the role of metal cations on the aggregation behavior of amyloid β-peptide at a single molecule level by AFM

    Xie, Yang; Wang, Jianhua; Liu, Chundong

    2016-09-01

    With the development of nanotechnology, understanding of intermolecular interactions on a single molecule level by atomic force spectroscopy (AFM) has played an important role in molecular biology and biomedical science. In recent years, some research suggested that the presence of metal cations is an important regulator in the processes of misfolding and aggregation of the amyloid β-protein (Aβ), which may be an important etiological factor of Alzheimer's disease. However, the knowledge on the principle of interactions between Aβ and metal cations at the single molecule level is still poor understood. In this paper, the amyloid β-protein (Aβ) was fabricated on substrate of mixed thiol-modified gold nanoparticles using self-assembled monolayer method and the adhesion force in the longitudinal direction between metal cations and Aβ42 were investigated by AFM. The role of metal ions on Aβ aggregation is discussed from the perspective of single molecular force. The force results showed that the specific adhesion force F i and the nonspecific force F 0 between a single Aβ-Aβ pair in control experiment were calculated as 42 ± 3 and 80 pN, respectively. However, F i between a single Aβ-Aβ pair in the presence of Cu2+, Zn2+, Ca2+ and Al3+ increased dramatically to 84 ± 6, 89 ± 3, 73 ± 5, 95 ± 5 pN successively, which indicated that unbinding between Aβ proteins is accelerated in the presence of metal cations. What is more, the imaging results showed that substoichiometric copper cations accelerate the formation of fibrils within 3 days. The combined atomic force spectroscopy and imaging analysis indicate that metal cations play a role in promoting the aggregating behavior of Aβ42.

  19. Probing the role of metal cations on the aggregation behavior of amyloid β-peptide at a single molecule level by AFM

    Xie, Yang; Wang, Jianhua; Liu, Chundong

    2016-01-01

    With the development of nanotechnology, understanding of intermolecular interactions on a single molecule level by atomic force spectroscopy (AFM) has played an important role in molecular biology and biomedical science. In recent years, some research suggested that the presence of metal cations is an important regulator in the processes of misfolding and aggregation of the amyloid β-protein (Aβ), which may be an important etiological factor of Alzheimer’s disease. However, the knowledge on the principle of interactions between Aβ and metal cations at the single molecule level is still poor understood. In this paper, the amyloid β-protein (Aβ) was fabricated on substrate of mixed thiol-modified gold nanoparticles using self-assembled monolayer method and the adhesion force in the longitudinal direction between metal cations and Aβ42 were investigated by AFM. The role of metal ions on Aβ aggregation is discussed from the perspective of single molecular force. The force results showed that the specific adhesion force F_i and the nonspecific force F_0 between a single Aβ–Aβ pair in control experiment were calculated as 42 ± 3 and 80 pN, respectively. However, F_i between a single Aβ–Aβ pair in the presence of Cu"2"+, Zn"2"+, Ca"2"+ and Al"3"+ increased dramatically to 84 ± 6, 89 ± 3, 73 ± 5, 95 ± 5 pN successively, which indicated that unbinding between Aβ proteins is accelerated in the presence of metal cations. What is more, the imaging results showed that substoichiometric copper cations accelerate the formation of fibrils within 3 days. The combined atomic force spectroscopy and imaging analysis indicate that metal cations play a role in promoting the aggregating behavior of Aβ42.

  20. 1H and 23Na MAS NMR spectroscopy of cationic species in CO2 selective alkaline earth metal porous silicoaluminophosphates prepared via liquid and solid state ion exchange

    Arévalo-Hidalgo, Ana G.; Dugar, Sneha; Fu, Riqiang; Hernández-Maldonado, Arturo J.

    2012-01-01

    The location of extraframework cations in Sr 2+ and Ba 2+ ion-exchanged SAPO-34 was estimated by means of 1 H and 23 Na MAS NMR spectroscopy and spectral deconvolution. Incorporation of the alkaline earth metal cations onto the SAPO framework was achieved via liquid state ion exchange, coupled partial detemplation/solid-state ion exchange, and combination of both techniques. MAS NMR revealed that the level of ion exchange was limited by the presence of protons and sodium cations near hexagonal prisms (site SI), which are relatively difficult to exchange with the alkaline earth metal due to steric and charge repulsion criteria. In addition, the presence of ammonium cations in the supercages facilitated the exchange of otherwise tenacious hydrogen as corroborated by unit cell compositional data as well as enhanced CO 2 adsorption at low partial pressures. The extraframework ammonium species were produced from partial detemplation of the structure-directing agent employed for the SAPO-34 synthesis, tetraethylammonium. - Graphical abstract: MAS NMR was used to elucidate the position the cationic species in alkaline earth metal exchanged silicoaluminophosphates. These species played a significant role during the ion exchange process and, therefore, the materials ultimate CO 2 adsorption performance. Highlights: ► Location of extraframework Sr 2+ or Ba 2+ cations was estimated by means of 1 H and 23 Na MAS NMR. ► Level of Sr 2+ or Ba 2+ ion exchange was limited by the presence of protons and sodium cations. ► Presence of ammonium cations in the supercages facilitated the exchange. ► Sr 2+ and Ba 2+ ion exchanged SAPOs are outstanding CO 2 adsorbents.

  1. Effects of humic acid and competing cations on metal uptake by Lolium perenne

    Kalis, E.J.J.; Temminghoff, E.J.M.; Weng, L.P.; Riemsdijk, van W.H.

    2006-01-01

    Within the biotic ligand model, which describes relationships between chemical speciation and metal binding at an organism's surface, multicomponent (long-term) metal uptake by plants has seldom been studied. In the present work, we exposed perennial ryegrass to nutrient solutions with two levels of

  2. Metal cluster cation reactions: Carbon monoxide association to Cu + n ions

    Leuchtner, R. E.; Harms, A. C.; Castleman, A. W., Jr.

    1990-06-01

    Copper cluster cations (Cu+n,n=1-14) were produced in a laser vaporization/flow tube apparatus and equilibrated to room temperature. The association rate constants of carbon monoxide onto these ions were measured; low-pressure, termolecular behavior was observed for the smaller species while for clusters greater than Cu+7, the longer lifetimes due to the increased number of degrees of freedom leads to pressure independence (>0.3 Torr) of the effective bimolecular rates. Unimolecular decay theory (RRKM) is used to explain the overall trend and when intrinsic surface site reactivity is taken into account, excellent agreement with measured reactivity is obtained.

  3. Selectivity in stripping of alkali-metal cations from crown ether carboxylate complexes

    Bartsch, R.A.; Walkowiak, W.; Robison, T.W.

    1992-01-01

    To probe the effect of structural variations within the ionophore upon the efficiency and selectivity of solvent extraction, a variety of crown ether carboxylic acids and phosphonic acid monoesters have been synthesized. In other studies the influence of the organic diluent upon extraction efficiency and selectivity has been probed for such proton-ionizable crown ethers. In the present investigation, attention is focused upon selectivity in the stripping step. Although the efficiency of metal ion stripping is often examined in solvent extraction studies, the selectivity of competitive metal ion release under different conditions is much less frequently considered. In this study, competitive stripping of metal ions from chloroform solutions of five-alkali-metal crown ether carboxylates by varying concentrations of aqueous hydrochloric acid is examined. Alkali metals used were Li, Na, K, Rb, and Cs

  4. Metallurgical recovery of metals from electronic waste: A review

    Cui Jirang; Zhang Lifeng

    2008-01-01

    Waste electric and electronic equipment, or electronic waste, has been taken into consideration not only by the government but also by the public due to their hazardous material contents. In the detailed literature survey, value distributions for different electronic waste samples were calculated. It is showed that the major economic driver for recycling of electronic waste is from the recovery of precious metals. The state of the art in recovery of precious metals from electronic waste by pyrometallurgical processing, hydrometallurgical processing, and biometallurgical processing are highlighted in the paper. Pyrometallurgical processing has been a traditional technology for recovery of precious metals from waste electronic equipment. However, state-of-the-art smelters are highly depended on investments. Recent research on recovery of energy from PC waste gives an example for using plastics in this waste stream. It indicates that thermal processing provides a feasible approach for recovery of energy from electronic waste if a comprehensive emission control system is installed. In the last decade, attentions have been removed from pyrometallurgical process to hydrometallurgical process for recovery of metals from electronic waste. In the paper, hydrometallurgical processing techniques including cyanide leaching, halide leaching, thiourea leaching, and thiosulfate leaching of precious metals are detailed. In order to develop an environmentally friendly technique for recovery of precious metals from electronic scrap, a critical comparison of main leaching methods is analyzed for both economic feasibility and environmental impact. It is believed that biotechnology has been one of the most promising technologies in metallurgical processing. Bioleaching has been used for recovery of precious metals and copper from ores for many years. However, limited research was carried out on the bioleaching of metals from electronic waste. In the review, initial researches on the

  5. Metallurgical recovery of metals from electronic waste: A review

    Cui Jirang [Department of Materials Science and Engineering, Norwegian University of Science and Technology (NTNU), Alfred Getz vei 2, N-7491 Trondheim (Norway)], E-mail: Jirang.Cui@material.ntnu.no; Zhang Lifeng [Department of Materials Science and Engineering, Norwegian University of Science and Technology (NTNU), Alfred Getz vei 2, N-7491 Trondheim (Norway)], E-mail: zhanglife@mst.edu

    2008-10-30

    Waste electric and electronic equipment, or electronic waste, has been taken into consideration not only by the government but also by the public due to their hazardous material contents. In the detailed literature survey, value distributions for different electronic waste samples were calculated. It is showed that the major economic driver for recycling of electronic waste is from the recovery of precious metals. The state of the art in recovery of precious metals from electronic waste by pyrometallurgical processing, hydrometallurgical processing, and biometallurgical processing are highlighted in the paper. Pyrometallurgical processing has been a traditional technology for recovery of precious metals from waste electronic equipment. However, state-of-the-art smelters are highly depended on investments. Recent research on recovery of energy from PC waste gives an example for using plastics in this waste stream. It indicates that thermal processing provides a feasible approach for recovery of energy from electronic waste if a comprehensive emission control system is installed. In the last decade, attentions have been removed from pyrometallurgical process to hydrometallurgical process for recovery of metals from electronic waste. In the paper, hydrometallurgical processing techniques including cyanide leaching, halide leaching, thiourea leaching, and thiosulfate leaching of precious metals are detailed. In order to develop an environmentally friendly technique for recovery of precious metals from electronic scrap, a critical comparison of main leaching methods is analyzed for both economic feasibility and environmental impact. It is believed that biotechnology has been one of the most promising technologies in metallurgical processing. Bioleaching has been used for recovery of precious metals and copper from ores for many years. However, limited research was carried out on the bioleaching of metals from electronic waste. In the review, initial researches on the

  6. Effect of alkaline metal cations on the ionic structure of cryolite melts: Ab-initio NpT MD study

    Bučko, Tomáš; Šimko, František

    2018-02-01

    Ab initio molecular dynamics simulations in an NpT ensemble have been performed to study the role of alkaline metal cations (Me = Li, Na, K, Rb) on the structure and vibrational properties of melts of Me-cryolites (Me3AlF6) at T = 1300 K. In all melts examined in this work, the species AlF52 - has been found to be formed at the highest abundance [from 58% (Li) to 70% (Na)] among the Al-containing anionic clusters. The concentration of clusters AlF4- increases with the size of cations while that of anions AlF63 - follows the opposite trend and it becomes negligible in the melts of the K- and Rb-cryolites. The computed percentage of the Al atoms participating in the formation of dimers Al2Fm6 -m bridged via common F atoms is significant only in the case of Li- and Na-cryolites (16% and 10%, respectively) and the formation of even larger aggregates is found to be unlikely in all four melts. The percentage of the F atoms that are not bound to Al is ˜20% in all four melts and the ions formed by Me+ and F- are found to be only short-lived. Vibrational analysis has been performed using the velocity autocorrelation functions computed for the Cartesian and selected internal coordinates describing Raman-active symmetric stretching vibrations of different AlFn species. The results of vibrational analysis allowed us to identify trends in the variation of positions and shapes of peaks corresponding to the anionic fragments AlF4-, AlF52 -, and AlF63 - with the size of cations, and these trends are found to be consistent with those deduced from the available Raman spectroscopy experiments. Our findings represent a new insight into the properties of cryolite melts, which will be useful for the interpretation of experimental data.

  7. Methods for recovering metals from electronic waste, and related systems

    Lister, Tedd E; Parkman, Jacob A; Diaz Aldana, Luis A; Clark, Gemma; Dufek, Eric J; Keller, Philip

    2017-10-03

    A method of recovering metals from electronic waste comprises providing a powder comprising electronic waste in at least a first reactor and a second reactor and providing an electrolyte comprising at least ferric ions in an electrochemical cell in fluid communication with the first reactor and the second reactor. The method further includes contacting the powders within the first reactor and the second reactor with the electrolyte to dissolve at least one base metal from each reactor into the electrolyte and reduce at least some of the ferric ions to ferrous ions. The ferrous ions are oxidized at an anode of the electrochemical cell to regenerate the ferric ions. The powder within the second reactor comprises a higher weight percent of the at least one base metal than the powder in the first reactor. Additional methods of recovering metals from electronic waste are also described, as well as an apparatus of recovering metals from electronic waste.

  8. Thermogravimetric method of estimation of uranyl cation state in melts of alkali metal chlorides and their mixtures

    Vorobej, M.P.; Desyatnik, V.N.

    1979-01-01

    The thermogravimetric method was used to study the chloridizing of uranium oxides in molten media. The study of the uranium oxide chloridizing served as a basis for evaluating comparatively, using the DTA method, the uranyl-cation state in a melt. Using the alkali metals as example, it was shown that the decomposition of the frozen uranium oxychlorides proceeds with the formation of intermediate chlorouranates. The final product of the thermolysis are uranates Me 2 U 2 O 7 (Me-Li, Na, K, Rb, Cs). The time and the conditions of the change of uranium oxides to the oxyanion [UO 2 Cl 4 ] 2- were determined as a function of the chloridizing agent. The method can be employed for evaluating uranyl-ions in molten media where they are used as electrolytes in the extraction of uranium dioxide

  9. Natural and Modified Zeolite—Alginate Composites. Application for Removal of Heavy Metal Cations from Contaminated Water Solutions

    Milan Kragović

    2018-01-01

    Full Text Available In present paper, the influence of the initial pH and concentration of Pb2+ on its adsorption by the natural (NZA and Fe(III-modified zeolite-alginate beads (FeA was studied. Results showed that modification of the starting materials have a positive effect on their adsorption capacities (102 and 136 mg/g for the NZA and FeA, respectively. After encapsulation, the mechanism of lead adsorption by both adsorbents was changed and ion exchange dominates. The best adsorption was achieved for initial pH > 3.8. Cation exchange capacity, structural properties, and hydrophobicity of samples were also determined, and the presence of the alginate has no significant influence on investigated properties of samples. Experiments on wastewater from tailings of lead and zinc mine Grot, Serbia, showed that after treatment with both adsorbents, the content of the most abundant heavy metals (Pb, Zn, Hg, and Mn significantly decreased.

  10. Critical parameters for electron beam curing of cationic epoxies and property comparison of electron beam cured cationic epoxies versus thermal cured resins and composites

    Janke, C.J.; Norris, R.E.; Yarborough, K.; Lopata, V.J.

    1997-01-01

    Electron beam curing of composites is a nonthermal, nonautoclave curing process offering the following advantages compared to conventional thermal curing: substantially reduced manufacturing costs and curing times; improvements in part quality and performance; reduced environmental and health concerns; and improvements in material handling. In 1994 a Cooperative Research and Development Agreement (CRADA), sponsored by the Department of Energy Defense Programs and 10 industrial partners, was established to advance electron beam curing of composites. The CRADA has successfully developed hundreds of new toughened and untoughened resins, offering unlimited formulation and processing flexibility. Several patent applications have been filed for this work. Composites made from these easily processable, low shrinkage material match the performance of thermal cured composites and exhibit: low void contents comparable to autoclave cured composites (less than 1%); superb low water absorption values in the same range as cyanate esters (less than 1%); glass transition temperatures rivaling those of polyimides (greater than 390 C); mechanical properties comparable to high performance, autoclave cured composites; and excellent property retention after cryogenic and thermal cycling. These materials have been used to manufacture many composite parts using various fabrication processes including hand lay-up, tow placement, filament winding, resin transfer molding and vacuum assisted resin transfer molding

  11. Influence of reason citric acid/ metal cations in the synthesis of mullite by Pechini Method; Iinfluencia da razao acido citrico/cations metalicos na sintese de mulita pelo Metodo Pechini

    Braga, A.N.S.; Costa, D.L.; Farias, R.M.C.; Neves, G.A.; Lira, H.L.; Menezes, R.R., E-mail: Alluskynha@homail.com [Universidade Federal de Campina Grande (UFCG), PB (Brazil). Departamento de Engenharia de Materiais

    2014-07-01

    Mullite is a ceramic material with high technological applications. Its synthesis has been extensively studied due to their excellent properties. Thus, this paper proposes to obtain mullite by Pechini method. The amount of acid citric/metal cations in proportions of 3:1 and 1:1 were investigated in order to understand their influence in obtaining the mullite phase. The synthesized samples were characterized by X-ray diffraction (XRD) and thermal analysis (TG/DTG and DTA). The results showed that the ratio citric acid/metal cations influence on the formed phase with the mullite obtained only in proportion 1:1. With the increase of the ratio to 3:1 was observed the formation of the alumina layer. (author)

  12. Electron Transfer Triggers Fast Dimer/Monomer Switching of Pyridinium and Quinolinium Cations

    Teplý, Filip; Čížková, Martina; Slavíček, P.; Kolivoška, Viliam; Tarábek, Ján; Hromadová, Magdaléna; Pospíšil, Lubomír

    2012-01-01

    Roč. 116, č. 5 (2012), s. 3779-3786 ISSN 1932-7447 R&D Projects: GA ČR GA203/09/0705; GA ČR GA203/09/1614 Institutional research plan: CEZ:AV0Z40550506; CEZ:AV0Z40400503 Keywords : electrochemical reduction * dimerization * radicals * mechanism * N-heteroaromatic cations Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 4.814, year: 2012

  13. Extraction of metal cations by polyterephthalamide microcapsules containing a poly(acrylic acid) gel.

    Laguecir, A; Ernst, B; Frère, Y; Danicher, L; Burgard, M

    2002-01-01

    Polyterephthalamide microcapsules containing a poly(acrylic acid) gel as a macromolecular ligand (PAA-CAPS) were prepared using an original two step polymerization process in a water-in-oil inverse emulsion system. A polyamide microcapsule containing acrylic acid, initiator and cross-linking agent, is formed by interfacial polycondensation of terephthaloyl dichloride with hexamethylenediamine. In situ radical polymerization of the microcapsule core acrylic acid is initiated to obtain encapsulated poly(acrylic acid) gel. Reference polyamide microcapsules, i.e. without ligand (CAPS), were also synthesized. The mean diameter of synthesized microcapsules was 210 microm, and the microcapsule wall thickness was evaluated by SEM and TEM observations of microcapsule cross-section cuts. The microcapsule water content was determined by thermogravimetric experiments. The extractabilities of Cu(II), Ni(II), Co(II) and Zn(II) into PAA-CAPS were examined. The stripping of the various cations can be promoted in diluted hydrochloric acid solutions.

  14. Separating and recycling metals from mixed metallic particles of crushed electronic wastes by vacuum metallurgy.

    Zhan, Lu; Xu, Zhenming

    2009-09-15

    During the treatment of electronic wastes, a crushing process is usually used to strip metals from various base plates. Several methods have been applied to separate metals from nonmetals. However, mixed metallic particles obtained from these processes are still a mixture of various metals, including some toxic heavy metals such as lead and cadmium. With emphasis on recovering copper and other precious metals, there have hitherto been no satisfactory methods to recover these toxic metals. In this paper, the criterion of separating metals from mixed metallic particles by vacuum metallurgy is built. The results show that the metals with high vapor pressure have been almost recovered completely, leading to a considerable reduction of environmental pollution. In addition, the purity of copper in mixed particles has been improved from about 80 wt % to over 98 wt %.

  15. Microstructured liquid metal electron and ion sources (MILMES/MILMIS)

    Mitterauer, J [Technische Universitaet Wien (Austria). Institut fuer Allgemeine Elektrotechnik und Elektronik

    1997-12-31

    Ion or electron beams can be emitted from liquid metal wetted needles, or from capillaries or slits into which the liquid metal is allowed to flow. Large-area liquid metal field emission sources have been proposed recently, using either two-dimensional, regular arrays of cones or capillaries, or even a substrate with an intrinsically microstructured surface covered by a liquid metal film. This latter concept has been realized in a pilot experiment by in situ wicking and wetting of a porous sintered metal disc. Microstructured liquid metal ion or electron sources are capable of operating in a pulsed mode at a current level which is orders of magnitude above that for steady-state operation. (author). 3 figs., 10 refs.

  16. Size-dependent electronic properties of metal nanostructures

    First page Back Continue Last page Overview Graphics. Size-dependent electronic properties of metal nanostructures. G.U. Kulkarni. Chemistry and Physics of Materials Unit. Jawaharlal Nehru Centre for Advanced Scientific Research. Bangalore, India. kulkarni@jncasr.ac.in.

  17. Ion-induced electron emission from clean metals

    Baragiola, R.A.; Alonso, E.V.; Ferron, J.; Oliva-Florio, A.; Universidad Nacional de Cuyo, San Carlos de Bariloche

    1979-01-01

    We report recent experimental work on electron emission from clean polycrystalline metal surfaces under ion bombardment. We critically discuss existing theories and point out the presently unsolved problems. (orig.)

  18. Fluorescence properties of riboflavin-functionalized mesoporous silica SBA-15 and riboflavin solutions in presence of different metal and organic cations

    Lewandowski, Dawid; Schroeder, Grzegorz; Sawczak, Mirosław; Ossowski, Tadeusz

    2015-10-01

    Riboflavin was covalently linked to mesoporous SBA-15 silica surface via grafting technique. Then fluorescence properties of the system obtained were analyzed in the presence of several metal and organic cations. Both quenching and strengthening of fluorescence as well as significant changes in the maximum fluorescence wavelength were observed. The results were compared with absorption and fluorescence data obtained for riboflavin water solutions.

  19. The effect of EDTA and metal cations on the 5-bromoindoxyl acetate esterase activity in the thyroid of the guinea pig

    Kirkeby, S

    1976-01-01

    Miscellaneous metal cations and EDTA have been used as activators and inhibitors of esterase activity in the thyroid of the guinea-pig. The results indicate that the 5-bromoiondoxyl acetate esterase in the epithelial cells probably consists of two different A-esterase isoenzymes, one present...

  20. Conditions for formation of electron pairs in a metal

    Shekhtman, A.Z., E-mail: shekhtmanalexander@gmail.com

    2015-04-15

    Highlights: • A new approach has been developed for consideration of electron pairing in metals. • Binding energy of a single pair induced by electron-phonon interaction is very small. • A new mechanism for electron pairing in metals has been considered. • Conditions for feasibility of the mechanism give conditions for electron pairing. • The mechanism gives wide opportunities to study new conditions for electron pairing. - Abstract: In an isotropic model of the electron system of metal that is presented by the Fröhlich’s initial Hamiltonian, in the approximation of a weak electron–phonon interaction at T = 0, first time, we show that the ground state of the system is the state with pairing correlations of electrons (the pair correlations of occupied electron states). In contrast to the BCS approach, the initial point in our approach is not electron pairing but is the maximum reduction of the energy of the considered system due to virtual processes of the electron–phonon interaction and to the exchange effect for the indirect electron–electron interaction (which is induced by certain phonon modes separately from others). In contrast to the BCS approach, we take into account the portion of the energy of the electron system that is connected with the above exchange effect. In the BCS approach, the corresponding portion is missed, and its role is prescribed to the portion that does not relate to the electron pairing. We show that expectation values of the above Hamiltonian for different wave functions for two interacting electrons above the Fermi sea of the non-interacting system (with interaction between the electrons that is induced by different phonon modes separately from others) are minimum for a certain structure of these functions and simultaneously for phonon modes that can induce the transitions of the interacting electrons between electron states in which they are (without violation of the Pauli exclusion principle and at everything else

  1. TOLERANCE OF AGAVE TEQUILANA TO HIGH LEVELS OF DIVALENT METAL CATIONS

    Elmi Roseida Cen-Cen

    2015-11-01

    Full Text Available Los agaves son plantas que pertenecen a un género constituido por numerosas especies, adaptadas para crecer en muy diversos hábitats, algunos con condiciones ambientales extremas. Distintas especies de agave crecen sobre distintos tipos de suelos, algunas en suelos con muy bajo contenido de nutrientes minerales y otras en suelos salinos o en suelos contaminados con iones metálicos. La relación planta-suelo ha sido escasamente estudiada en este género por lo que se desconoce, entre otras cuestiones, cuál es la capacidad de los agaves para absorber, transportar y almacenar nutrientes minerales, cuáles son los mecanismos celulares y bioquímicos que utilizan, o si poseen especial sensibilidad o tolerancia a los iones metálicos. Este estudio reporta el efecto de diversas concentraciones de sulfato de cadmio, cobalto, cobre, zinc o de manganeso sobre plántulas deAgave tequilana, bajo condiciones controladas de laboratorio; la concentración mínima de esos iones metálicos requerida para inducir un efecto tóxico visualmente detectable en tiempos cortos (ocho días; describimos los efectos tóxicos que estos metales generan sobre las plántulas de agave; y reportamos la cantidad de Cu2+, Cd2+ y Co2+ que se acumula en las hojas de plántulas de agave tratadas con altas concentraciones (milimolares de esos metales. Nuestros resultados muestran que, en experimentos de toxicidad aguda y bajo las condiciones aquí establecidas, elA. tequilanaposee una notable tolerancia a altas concentraciones de los distintos metales iónicos probados, incluyendo tanto micronutrientes como metales tóxicos, así como la capacidad de transportar en altas cantidades estos metales a tejido aéreo.

  2. Probing the structural and electronic properties of cationic rubidium-gold clusters: [AunRb]+ (n = 1-10)

    Zhao, Ya-Ru; Zhang, Hai-Rong; Qian, Yu; Duan, Xu-Chao; Hu, Yan-Fei

    2016-03-01

    Density functional theory has been applied to study the geometric structures, relative stabilities, and electronic properties of cationic [AunRb]+ and Aun + 1+ (n = 1-10) clusters. For the lowest energy structures of [AunRb]+ clusters, the planar to three-dimensional transformation is found to occur at cluster size n = 4 and the Rb atoms prefer being located at the most highly coordinated position. The trends of the averaged atomic binding energies, fragmentation energies, second-order difference of energies, and energy gaps show pronounced even-odd alternations. It indicated that the clusters containing odd number of atoms maintain greater stability than the clusters in the vicinity. In particular, the [Au6Rb]+ clusters are the most stable isomer for [AunRb]+ clusters in the region of n = 1-10. The charges in [AunRb]+ clusters transfer from the Rb atoms to Aun host. Density of states revealed that the Au-5d, Au-5p, and Rb-4p orbitals hardly participated in bonding. In addition, it is found that the most favourable channel of the [AunRb]+ clusters is Rb+ cation ejection. The electronic localisation function (ELF) analysis of the [AunRb]+ clusters shown that strong interactions are not revealed in this study.

  3. Electron pairing in dilute liquid metal-metal halide solutions

    Selloni, A.; Car, R.; Parrinello, M.; Carnevali, P.

    1987-09-10

    Spin density functional theory is used to describe the interaction between solvated electrons in KCl in the high dilution limit. In agreement with recent calculations based on the path integral method our results for antiparallel spin predict a strong tendency to form localized bielectronic complexes. At variance with numerical path integral, our method can efficiently treat the case of parallel spins. For this case we find that electrons repel each other and localize into separate F-center-like states.

  4. Ceruloplasmin revisited: structural and functional roles of various metal cation-binding sites

    Bento, Isabel; Peixoto, Cristina; Zaitsev, Vjacheslav N.; Lindley, Peter F.

    2007-01-01

    The three-dimensional molecular structure of human serum ceruloplasmin has been reinvestigated using X-ray synchrotron data collected at 100 K from a crystal frozen to liquid-nitrogen temperature. The three-dimensional molecular structure of human serum ceruloplasmin has been reinvestigated using X-ray synchrotron data collected at 100 K from a crystal frozen to liquid-nitrogen temperature. The resulting model, with an increase in resolution from 3.1 to 2.8 Å, gives an overall improvement of the molecular structure, in particular the side chains. In addition, it enables the clear definition of previously unidentified Ca 2+ -binding and Na + -binding sites. The Ca 2+ cation is located in domain 1 in a configuration very similar to that found in the activated bovine factor Va. The Na + sites appear to play a structural role in providing rigidity to the three protuberances on the top surface of the molecule. These features probably help to steer substrates towards the mononuclear copper sites prior to their oxidation and to restrict the size of the approaching substrate. The trinuclear copper centre appears to differ from the room-temperature structure in that a dioxygen moiety is bound in a similar way to that found in the endospore coat protein CotA from Bacillus subtilis

  5. Electron emission during multicharged ion-metal surface interactions

    Zeijlmans van Emmichoven, P.A.; Havener, C.C.; Hughes, I.G.; Overbury, S.H.; Robinson, M.T.; Zehner, D.M.; Meyer, F.W.

    1992-01-01

    The electron emission during multicharged ion-metal surface interactions will be discussed. The interactions lead to the emission of a significant number of electrons. Most of these electrons have energies below 30 eV. For incident ions with innershell vacancies the emission of Auger electrons that fill these vacancies has been found to occur mainly below the surface. We will present recently measured electron energy distributions which will be used to discuss the mechanisms that lead to the emission of Auger and of low-energy electrons

  6. Ab initio investigation of sulfur monofluoride and its singly charged cation and anion in their ground electronic state

    Li Song; Chen Shan-Jun; Chen Yan; Chen Peng

    2016-01-01

    The SF radical and its singly charged cation and anion, SF + and SF − , have been investigated on the MRCI/aug-cc-pVXZ (X = Q, 5, 6) levels of theory with Davidson correction. Both the core–valence correlation and the relativistic effect are considered. The extrapolating to the complete basis set (CBS) limit is adopted to remove the basis set truncation error. Geometrical parameters, potential energy curves (PECs), vibrational energy levels, spectroscopic constants, ionization potentials, and electron affinities of the ground electronic state for all these species are obtained. The information with respect to molecular characteristics of the SF n (n = −1, 0, +1) systems derived in this work will help to extend our knowledge and to guide further experimental or theoretical researches. (paper)

  7. Effect of cation nature of Cl2- yields in pulse radiolysis of alkali metal chloride aqueous solutions

    Kabakchi, S.A.; Zansokhova, A.A.; Pikaev, A.K.

    1975-01-01

    A study is made of the amount of Cl 2 - formed during a pulsating radiolysis of potassium, rubidium and cesium chlorides in aqueous solutions saturated with air. An equation is presented relating the yield of Cl 2 - and the concentration of the starting materials. Various mechanisms describing the radiolysis of neutral aqueous solutions of the chlorides are proposed. The observed effect of the cation on the efficiency of Cl 2 - formations favours the mechanism according to which Cl 2 - forms through the reaction of Cl - ion with a ''hole''. Due to charge migration in the conductivity zone the electron transfer reaction either goes steadily by jumps. As a result of the interaction between the ''hole'' and water [H 3 O + ...OH] a complex is formed from a hydrogen ion and OH radical, which are united trhough the hydrogen bond. Disturbance of the hydrogen bond structure should increase the probability of disintegration of the complex

  8. Structural and magnetic characterization of a tetranuclear copper(II) cubane stabilized by intramolecular metal cation-π interactions.

    Papadakis, Raffaello; Rivière, Eric; Giorgi, Michel; Jamet, Hélène; Rousselot-Pailley, Pierre; Réglier, Marius; Simaan, A Jalila; Tron, Thierry

    2013-05-20

    A novel tetranuclear copper(II) complex (1) was synthesized from the self-assembly of copper(II) perchlorate and the ligand N-benzyl-1-(2-pyridyl)methaneimine (L(1)). Single-crystal X-ray diffraction studies revealed that complex 1 consists of a Cu4(OH)4 cubane core, where the four copper(II) centers are linked by μ3-hydroxo bridges. Each copper(II) ion is in a distorted square-pyramidal geometry. X-ray analysis also evidenced an unusual metal cation-π interaction between the copper ions and phenyl substituents of the ligand. Calculations based on the density functional theory method were used to quantify the strength of this metal-π interaction, which appears as an important stabilizing parameter of the cubane core, possibly acting as a driving parameter in the self-aggregation process. In contrast, using the ligand N-phenethyl-1-(2-pyridyl)methaneimine (L(2)), which only differs from L(1) by one methylene group, the same synthetic procedure led to a binuclear bis(μ-hydroxo)copper(II) complex (2) displaying intermolecular π-π interactions or, by a slight variation of the experimental conditions, to a mononuclear complex (3). These complexes were studied by X-ray diffraction techniques. The magnetic properties of complexes 1 and 2 are reported and discussed.

  9. Macroscopic and bulk-controlled elastic modes in an interaction of interstitial alcali metal cations within a face-centered cubic crystalline fullerine

    Tatarenko, V.A.; Tsysman, C.L.; Oltarzhevskaya, Y.T. [Institute for Metal Physics, Kiev (Ukraine)

    1994-12-31

    The calculations in a majority of previous works for the fulleride (AqC{sub 60}) crystals were performed within the framework of the rigid-lattice model, neglecting the distoration relaxation of the host fullerene (C{sub 60}) crystal caused by the interstitial alkali-metal (A) cations. However, an each cation is a source of a static distoration field, and the resulting field is a superposition of such fields generated by all cations. This is a reason why the host-crystal distortions depend on the A-cations configurations, i.e. on a type of a spatial bulk distribution of interstitial cations. This paper seeks to find a functional relation between the amplitudes of the doping-induced structure-distortion waves and of statistic concentration ones. A semiphenomenological model is constructed here within the scope of statistical-thermodynamic treatment and using the lattice-statistics simulation method. In this model the effects due to the presence of q solute A cations over available interstices (per unit cell) on the statistic inherent reorientation and/or displacements of the solvent molecules from the average-lattice sites as well as on the lattice parameter a of the elastically-anysotropic cubic C{sub 60} crystal are taken into account.

  10. Structure of liquid alkali metals as electron-ion plasmas

    Chaturvedi, D.K.; Senatore, G.; Tosi, M.P.

    1980-08-01

    The static structure factor of liquid alkali metals near freezing, and its dependence on temperature and pressure, are evaluated in an electron-ion plasma model from an accurate theoretical determination of the structure factor of the one-component classical plasma and electron-screening theory. Very good agreement is obtained with the available experimental data. (author)

  11. Synergistic extraction of transition metal cations from aqueous media by two separated organic phases

    Goldberg, I.

    1991-12-01

    We have therefore initiated novel approaches to the study of the mechanism of the synergistic extraction of metal ions by means of two separated organic phases, which are brought in contact with the same aqueous phase. The present work is concerned with the extraction of transition metals and actinides ions from nitric acid by chelating agents e.g., HTTA thenoyltrifluoroacetone in a diluent - the first organic phase, and by natural donor, e.g., TBP, tri-butyl phosphate in a diluent the second organic phase. The adduct formation was studied by means of spectrochemical and radiochemical methods. In the first approach the aqueous phase was attacked with both organic phases simultanously (the static or parallel extraction). In this method organic phase are separated one from the other. It was shown that even in the absence of mixing, synergism is observed under this experimental conditions. The results indicate, that adduct formation occurs in both organic phases. Nevertheless the enhanchment of extraction in the TBP phase is by far greater than that in the HTTA containing phase. This approach has one disadvatage, viz., the experiments are very time consuming, a typical experiment requiring over 10 days. In order to overcome this difficulty, the following experiments were carried out: the aqueous phase were first shaken with diluent containing an anionic ligand and the phases were allowed to separate. Then the aqueous solution were shaken with diluent containing a netural donor and the phase again were allowed to separate. The concentration of the metal ions in all the phases were determined. The experiments were repeated with an other diluent replacing the first diluent in one or both organic phases. In this way eight sequences of experiments were carried out for each concentration set chosen. The results thus point out that this experimental approach open new possibilities to investigate the mechanism and the kinetics of synergistic extraction processes. (author) the

  12. Development of Comparative Toxicity Potentials of 14 cationic metals in freshwater

    Dong, Yan; Gandhi, Nilima; Hauschild, Michael Zwicky

    2014-01-01

    . CTPs were calculated for 7 EUarchetypes, taking bioavailability and speciation pattern into account. The resulting site-dependent CTPs showed up to 2.4–6.5 orders of magnitude variation across archetypes for those metals that form stable hydroxyl compounds in slightly alkaline waters (Al(III), Be, Cr......, while Cd ranked highest in other waters. Based on the site-dependent CTPs, site-generic CTPs were developed applying different averaging principle. Emission weighted average of 7 EU-archetype CTPs was recommended as site-generic CTP for use in LCA studies, where receiving location is unclear. Compared...

  13. One-Electron Theory of Metals. Cohesive and Structural Properties

    Skriver, Hans Lomholt

    The work described in the report r.nd the 16 accompanying publications is based upon a one-electron theory obtained within the local approximation to density-functional theory, and deals with the ground state of metals as obtained from selfconsistent electronic-structure calculations performed...... by means of the Linear Muffin-Tin Orbital (LMTO) method. It has been the goal of the work to establish how well this one-electron approach describes physical properties such as the crystal structures of the transition metals, the structural phase transitions in the alkali, alkaline earth, and rare earth...

  14. Electrical Conductivity in Transition Metals

    Talbot, Christopher; Vickneson, Kishanda

    2013-01-01

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

  15. Role of scanning electron microscope )SEM) in metal failure analysis

    Shaiful Rizam Shamsudin; Hafizal Yazid; Mohd Harun; Siti Selina Abd Hamid; Nadira Kamarudin; Zaiton Selamat; Mohd Shariff Sattar; Muhamad Jalil

    2005-01-01

    Scanning electron microscope (SEM) is a scientific instrument that uses a beam of highly energetic electrons to examine the surface and phase distribution of specimens on a micro scale through the live imaging of secondary electrons (SE) and back-scattered electrons (BSE) images. One of the main activities of SEM Laboratory at MINT is for failure analysis on metal part and components. The capability of SEM is excellent for determining the root cause of metal failures such as ductility or brittleness, stress corrosion, fatigue and other types of failures. Most of our customers that request for failure analysis are from local petrochemical plants, manufacturers of automotive components, pipeline maintenance personnel and engineers who involved in the development of metal parts and component. This paper intends to discuss some of the technical concepts in failure analysis associated with SEM. (Author)

  16. Stripping potentiometric analysis: application to determination of metallic cations in presence of uranium

    Pereira-Ramos, J.P.; Chivot, J.; Sarantopoulos, F.; Godard, R.

    1984-01-01

    Potentiometric stripping analysis consists of a potentiostatic deposition step of trace elements and a subsequent stripping step. The trace metals are simultaneously reduced at a rotating electrode, the working electrode being a mercury film coated glassy carbon electrode; the amalgamated metals are then re-oxidized with an oxidizing agent. The analytical signal of this method is the time required for complete re-oxidation. Influence of different parameters on the analytical signal is studied by using mercury (II) ions as oxidizing agent in 5.10 -4 M H 2 SO 4 aqueous solution. Here, we point out the main characteristics of the potentiometric stripping analysis under the same experimental conditions. The reproductibility ranges are comprised between 0.5% to 1.5% and the detection limit for cadmium (II) is estimated to be 2.10 -10 M with a plating time of 300 seconds. Small quantities, as 10 -7 M Cd 2+ , Pb 2+ and Zn 2+ are simultaneously determined in presence of U (VI) ions (UO 2 2+ ) with an accuracy of 0.5% for Cd 2+ and Zn 2+ , and 4.5% for Pb 2+ . Compared to well-known electrochemical techniques, potentiometric stripping analysis appears to be a performing method for trace analysis in a wide range of media: this method permits the analysis of elements in presence of species more concentrated and being able to oxidize the trace elements [fr

  17. Effect of the chelation of metal cation on the antioxidant activity of chondroitin sulfates.

    Ajisaka, Katsumi; Oyanagi, Yutaka; Miyazaki, Tatsuo; Suzuki, Yasuhiro

    2016-06-01

    The antioxidant potencies of chondroitin sulfates (CSs) from shark cartilage, salmon cartilage, bovine trachea, and porcine intestinal mucosa were compared by three representative methods for the measurement of the antioxidant activity; DPPH radical scavenging activity, superoxide radical scavenging activity, and hydroxyl radical scavenging activity. CSs from salmon cartilage and bovine trachea showed higher potency in comparison with CSs from shark cartilage and porcine intestinal mucosa. Next, CS from salmon cartilage chelating with Ca(2+), Mg(2+), Mn(2+), or Zn(2+) were prepared, and their antioxidant potencies were compared. CS chelating with Ca(2+) or Mg(2+) ions showed rather decreased DPPH radical scavenging activity in comparison with CS of H(+) form. In contrast, CS chelating with Ca(2+) or Mg(2+) ion showed remarkably enhanced superoxide radical scavenging activity than CS of H(+) or Na(+) form. Moreover, CS chelating with divalent metal ions, Ca(2+), Mg(2+), Mn(2+), or Zn(2+), showed noticeably higher hydroxyl radical scavenging activity than CS of H(+) or Na(+) form. The present results revealed that the scavenging activities of, at least, superoxide radical and hydroxyl radical were enhanced by the chelation with divalent metal ions.

  18. Scattering of polarized low-energy electrons by ferromagnetic metals

    Helman, J.S.

    1981-01-01

    A source of spin polarized electrons with remarkable characteristics based on negative electron affinity (NEA) GaAs has recently been developed. It constitutes a unique tool to investigate spin dependent interactions in electron scattering processes. The characteristics and working principles of the source are briefly described. Some theoretical aspects of the scattering of polarized low-energy electrons by ferromagnetic metals are discussed. Finally, the results of the first polarized low-energy electron diffraction experiment using the NEA GaAs source are reviewed; they give information about the surface magnetization of ferromagnetic Ni (110). (Author) [pt

  19. Secondary-electron cascade in attosecond photoelectron spectroscopy from metals

    Baggesen, Jan Conrad; Madsen, Lars Bojer

    2009-01-01

    an analytical model based on an approximate solution to Boltzmann's transport equation to account for the amount and energy distribution of these secondary electrons. Our theory is in good agreement with the electron spectrum found in a recent attosecond streaking experiment. To suppress the background and gain......Attosecond spectroscopy is currently restricted to photon energies around 100 eV. We show that under these conditions, electron-electron scatterings, as the photoelectrons leave the metal, give rise to a tail of secondary electrons with lower energies and hence a significant background. We develop...

  20. Analysis on a electron gun for metal fusion

    Paes, A.C.J.; Galvao, R.M.O.; Boscolo, P.; Passaro, A.

    1987-09-01

    The characteristics of the electron beam of the HK-011600 Δ, electron gun for metal fusion at the 'Divisao de Materiais do Instituto de Pesquisa e Desenvolvimento do CTA (PMR/IPD/CTA)', is analyzed. In this analysis, the Pierce gun model and the SLAC computational code for electron optics are used. The electron beam R and Z profiles are obtained in the gun region and in the magnetic lenses region. The behaviour of the electron beam in the prism region is also discussed using a simple model. (author) [pt

  1. Spontaneous Isomerization of Peptide Cation Radicals Following Electron Transfer Dissociation Revealed by UV-Vis Photodissociation Action Spectroscopy.

    Imaoka, Naruaki; Houferak, Camille; Murphy, Megan P; Nguyen, Huong T H; Dang, Andy; Tureček, František

    2018-01-16

    Peptide cation radicals of the z-type were produced by electron transfer dissociation (ETD) of peptide dications and studied by UV-Vis photodissociation (UVPD) action spectroscopy. Cation radicals containing the Asp (D), Asn (N), Glu (E), and Gln (Q) residues were found to spontaneously isomerize by hydrogen atom migrations upon ETD. Canonical N-terminal [z 4 + H] +● fragment ion-radicals of the R-C ● H-CONH- type, initially formed by N-C α bond cleavage, were found to be minor components of the stable ion fraction. Vibronically broadened UV-Vis absorption spectra were calculated by time-dependent density functional theory for several [ ● DAAR + H] + isomers and used to assign structures to the action spectra. The potential energy surface of [ ● DAAR + H] + isomers was mapped by ab initio and density functional theory calculations that revealed multiple isomerization pathways by hydrogen atom migrations. The transition-state energies for the isomerizations were found to be lower than the dissociation thresholds, accounting for the isomerization in non-dissociating ions. The facile isomerization in [ ● XAAR + H] + ions (X = D, N, E, and Q) was attributed to low-energy intermediates having the radical defect in the side chain that can promote hydrogen migration along backbone C α positions. A similar side-chain mediated mechanism is suggested for the facile intermolecular hydrogen migration between the c- and [z + H] ● -ETD fragments containing Asp, Asn, Glu, and Gln residues. Graphical Abstract ᅟ.

  2. Spontaneous Isomerization of Peptide Cation Radicals Following Electron Transfer Dissociation Revealed by UV-Vis Photodissociation Action Spectroscopy

    Imaoka, Naruaki; Houferak, Camille; Murphy, Megan P.; Nguyen, Huong T. H.; Dang, Andy; Tureček, František

    2018-01-01

    Peptide cation radicals of the z-type were produced by electron transfer dissociation (ETD) of peptide dications and studied by UV-Vis photodissociation (UVPD) action spectroscopy. Cation radicals containing the Asp (D), Asn (N), Glu (E), and Gln (Q) residues were found to spontaneously isomerize by hydrogen atom migrations upon ETD. Canonical N-terminal [z4 + H]+● fragment ion-radicals of the R-C●H-CONH- type, initially formed by N-Cα bond cleavage, were found to be minor components of the stable ion fraction. Vibronically broadened UV-Vis absorption spectra were calculated by time-dependent density functional theory for several [●DAAR + H]+ isomers and used to assign structures to the action spectra. The potential energy surface of [●DAAR + H]+ isomers was mapped by ab initio and density functional theory calculations that revealed multiple isomerization pathways by hydrogen atom migrations. The transition-state energies for the isomerizations were found to be lower than the dissociation thresholds, accounting for the isomerization in non-dissociating ions. The facile isomerization in [●XAAR + H]+ ions (X = D, N, E, and Q) was attributed to low-energy intermediates having the radical defect in the side chain that can promote hydrogen migration along backbone Cα positions. A similar side-chain mediated mechanism is suggested for the facile intermolecular hydrogen migration between the c- and [z + H]●-ETD fragments containing Asp, Asn, Glu, and Gln residues. [Figure not available: see fulltext.

  3. Adsorption properties of cationic rhodamine B dye onto metals chloride-activated castor bean residue carbons.

    Zhi, Lee Lin; Zaini, Muhammad Abbas Ahmad

    2017-02-01

    This work was aimed to evaluate the feasibility of castor bean residue based activated carbons prepared through metals chloride activation. The activated carbons were characterized for textural properties and surface chemistry, and the adsorption data of rhodamine B were established to investigate the removal performance. Zinc chloride-activated carbon with specific surface area of 395 m 2 /g displayed a higher adsorption capacity of 175 mg/g. Magnesium chloride and iron(III) chloride are less toxic and promising agents for composite chemical activation. The adsorption data obeyed Langmuir isotherm and pseudo-second-order kinetics model. The rate-limiting step in the adsorption of rhodamine B is film diffusion. The positive values of enthalpy and entropy indicate that the adsorption is endothermic and spontaneous at high temperature.

  4. Electronic structure, bonding and chemisorption in metallic hydrides

    Ward, J.W.

    1980-01-01

    Problems that can arise during the cycling steps for a hydride storage system usually involve events at surfaces. Chemisorption and reaction processes can be affected by small amounts of contaminants that may act as catalytic poisons. The nature of the poisoning process can vary greatly for the different metals and alloys that form hydrides. A unifying concept is offered, which satisfactorily correlates many of the properties of transition-metal, rare-earth and actinide hydrides. The metallic hydrides can be differentiated on the basis of electronegativity, metallic radius (valence) and electronic structure. For those systems where there are d (transition metals) or f (early actinides) electrons near the Fermi level a broad range of chemical and catalytic behaviors are found, depending on bandwidth and energy. The more electropositive metals (rare-earths, actinides, transition metals with d > 5) dissolve hydrogen and form hydrides by an electronically somewhat different process, and as a class tend to adsorb electrophobic molecules. The net charge-transfer in either situation is subtle; however, the small differences are responsible for many of the observed structural, chemical, and catalytic properties in these hydride systems

  5. Magnetism in heavy-electron metals

    Ott, H.R.

    1997-01-01

    Originally it was believed that the presence of heavy-mass charge carriers at low temperatures in some special rare-earth or actinide compounds was simply the result of a suppression of magnetic order in these materials. Various experiments reveal, however, that magnetic order may occur from a heavy-electron state or that a heavy-electron state may also develop within a magnetically ordered materix. It turned out that pure compounds without any sign of a cooperative phase transition down to very low temperatures are rare but examples are known where microscopic experimental probes give evidence for strong magnetic correlations involving moments of much reduced magnitude (≤ 0.1μ Β ) in such cases. It apperas that electronic and magnetic inhomogeneities, both in real and reciprocal space occur which are not simply the result of chemical inhomogeneities. Long range magnetic order among strongly reduced magnetic moments seems to be a particular feature of some heavy-electron materials. Other examples show, that disorder may lead to a suppression of cooperative phase transitions and both macroscopic and microscopic physical properties indicate that conservative model calculations are not sufficient to describe the experimental observations. The main difficulty is to find a suitable theoretical approach that considers the various interactions of similar strength on an equal footing. Different examples of these various features are demonstrated and discussed. (au)

  6. Nanoscale electron manipulation in metals with intense THz electric fields

    Takeda, Jun; Yoshioka, Katsumasa; Minami, Yasuo; Katayama, Ikufumi

    2018-03-01

    Improved control over the electromagnetic properties of metals on a nanoscale is crucial for the development of next-generation nanoelectronics and plasmonic devices. Harnessing the terahertz (THz)-electric-field-induced nonlinearity for the motion of electrons is a promising method of manipulating the local electromagnetic properties of metals, while avoiding undesirable thermal effects and electronic transitions. In this review, we demonstrate the manipulation of electron delocalization in ultrathin gold (Au) films with nanostructures, by intense THz electric-field transients. On increasing the electric-field strength of the THz pulses, the transmittance in the THz-frequency region abruptly decreases around the percolation threshold. The observed THz-electric-field-induced nonlinearity is analysed, based on the Drude-Smith model. The results suggest that ultrafast electron delocalization occurs by electron tunnelling across the narrow insulating bridge between the Au nanostructures, without material breakdown. In order to quantitatively discuss the tunnelling process, we perform scanning tunnelling microscopy with carrier-envelope phase (CEP)-controlled single-cycle THz electric fields. By applying CEP-controlled THz electric fields to the 1 nm nanogap between a metal nanotip and graphite sample, many electrons could be coherently driven through the quantum tunnelling process, either from the nanotip to the sample or vice versa. The presented concept, namely, electron tunnelling mediated by CEP-controlled single-cycle THz electric fields, can facilitate the development of nanoscale electron manipulation, applicable to next-generation ultrafast nanoelectronics and plasmonic devices.

  7. Emission channeling studies on transition-metal doped GaN and ZnO: Cation versus anion substitution

    AUTHOR|(CDS)2070176; Wahl, Ulrich; Martins Correia, Joao; Amorim, Lígia; Silva, Daniel; Decoster, Stefan; Castro Ribeiro Da Silva, Manuel; Temst, Kristiaan; Vantomme, André

    2014-01-01

    The magnetic and electric properties of impurities in semiconductors are strongly dependent on the lattice sites which they occupy. While the majority site can often be predicted based on chemical similarities with the host elements and is usually simple to confirm experimentally, minority sites are far more complicated to predict, detect and identify. We have carried out extensive beta− emission channeling studies on the lattice location of transition metal impurities in wide-gap dilute magnetic semiconductors, namely Co and Mn in GaN and ZnO, making use of radioactive 61Co and 56Mn implanted at the ISOLDE facility at CERN. In addition to the majority occupation of cation (Ga, Zn) sites, we located significant fractions (of the order of 20%) of the Co and Mn impurities in anion (N, O) sites, which are virtually unaffected by thermal annealing up to 900 °C. Here, we present the beta− emission channeling experiments on 61Co-implanted GaN. We discuss these results in the context of our recent reports of mi...

  8. Following the non-Born-Oppenheimer electron dynamics after photoionization in the Zundel cation

    Li, Zheng; Santra, Robin [CFEL, DESY, Notkestr. 85, D-22607 Hamburg (Germany); Department of Physics, University of Hamburg, D-20355 Hamburg (Germany); El-Amine Madjet, Mohamed; Vendrell, Oriol [CFEL, DESY, Notkestr. 85, D-22607 Hamburg (Germany)

    2013-07-01

    To investigate the molecular non-Born-Oppenheimer effects, the Coulomb explosion after valence photoionization provides an excellent test-ground, since it is associated with ultrafast non-adiabatic electronic decay, and is experimentally practical with well-developed techniques. We have employed full quantum (MCTDH) and quantum-classical approaches to study the Coulomb explosion of the Zundel dication H{sub 5}O{sub 2}{sup 2+}. In the present study, we have calculated time-resolved observables that are able to provide a clear picture of the specific electronic and nuclear motions arising exclusively from the non-Born-Oppenheimer effects. The Coulomb explosion experiments of molecular ions are suitable to be carried out with the XUV free electron laser FLASH, which can address the valence electrons for chemical reactions, meanwhile the high brightness of FEL offers sufficient signal strength, as illustrated experimentally.

  9. CFA-4 - a fluorinated metal-organic framework with exchangeable interchannel cations.

    Fritzsche, J; Grzywa, M; Denysenko, D; Bon, V; Senkovska, I; Kaskel, S; Volkmer, D

    2017-05-23

    The syntheses and crystal structures of the fluorinated linker 1,4-bis(3,5-bis(trifluoromethyl)-1H-pyrazole-4-yl)benzene (H 2 -tfpb; 1) and the novel metal-organic framework family M[CFA-4] (Coordination Framework Augsburg University-4), M[Cu 5 (tfpb) 3 ] (M = Cu(i), K, Cs, Ca(0.5)), are described. The ligand 1 is fully characterized by single crystal X-ray diffraction, photoluminescence-, NMR-, IR spectroscopy, and mass spectrometry. The copper(i)-containing MOF crystallizes in the hexagonal crystal system within the chiral space group P6 3 22 (no. 182) and the unit cell parameters are as follows: a = 23.630(5) Å, c = 41.390(5) Å, V = 20 015(6) Å 3 . M[CFA-4] features a porous 3-D structure constructed from pentanuclear copper(i) secondary building units {Cu(pz) 6 } - (pz = pyrazolate). Cu(I)[CFA-4] is fully characterized by synchrotron single crystal X-ray diffraction, thermogravimetric analysis, variable temperature powder X-ray diffraction, IR spectroscopy, photoluminescence and gas sorption measurements. Moreover, thermal stability and gas sorption properties of K[CFA-4] and Cu(I)[CFA-4] are compared.

  10. Structural and electronic transformations in substituted La-Sr manganites depending on cations and oxygen content

    Karpasyuk, Vladimir; Badelin, Alexey; Merkulov, Denis; Derzhavin, Igor; Estemirova, Svetlana

    2018-05-01

    In the present research experimental data are obtained for the Jahn-Teller O‧ phase formation, phase transformation "orthorhombic-rhombohedral structure" and the change of the conductance type in the systems of manganites La3+1-c+xSr2+c-xMn3+1-c-x-2γMn4+c+2γZn2+xO3+γ, La3+1-c-xSr2+c+xMn3+1-c-x-2γMn4+c+2γGe4+xO3+γ, La3+1-cSr2+cMn3+1-x-c-2γMn4+c+2γ(Zn2+0.5Ge4+0.5)xO3+γ, where Mn4+ ions concentration is independent of "x". Ceramic samples were sintered in air at 1473 K. As-sintered samples had an excess of oxygen content. In order to provide stoichiometric oxygen content, the samples were annealed at 1223 K and partial pressure of oxygen PO2 = 10-1 Pа. Structural characteristics of the O‧ phase were obtained. The position of the phase boundary "orthorhombic-rhombohedral structure" and the temperature of the conductance type change depending on the cation composition of manganites and oxygen content were determined. Possible approaches to the interpretation of experimental results were suggested.

  11. Probing electron density of H-bonding between cation-anion of imidazolium-based ionic liquids with different anions by vibrational spectroscopy.

    Gao, Yan; Zhang, Liqun; Wang, Yong; Li, Haoran

    2010-03-04

    Attenuated total reflection infrared spectroscopy and density functional theory calculation have been employed to study the spectral properties of imidazolium-based ionic liquids (ILs) with different anions. ILs based on 1-butyl-3-methylimidazolium cation with different anions, OH(-), CF(3)CO(2)(-), HSO(4)(-), H(2)PO(4)(-), Cl(-), PF(6)(-), and BF(4)(-), are investigated in the present work. It has been shown that the C(2)-H stretching vibration of the imidazolium ring is closely related to the electron density of H-bonding between the two closest cations and anions for pure ILs. The electron density of H-bonding between cation and anion with different anions decreases in the order [OH](-) > [H(2)PO(4)](-) > [HSO(4)](-) > [CF(3)CO(2)](-) > [Cl](-) > [BF(4)](-) > [PF(6)](-). For aqueous ILs, with increasing water content, the aromatic C-H stretching vibration of the imidazolium cation showed systematic blue-shifts. Especially for BmimOH, the nu(C(2))(-H) undergoes a drastic blue-shift by 58 cm(-1), suggesting that the formation of the strong hydrogen bonds O-H...O may greatly weaken the electron density of H-bonding between the cation and anion of ILs.

  12. Molecular-structure control of ultrafast electron injection at cationic porphyrin-CdTe quantum dot interfaces

    Aly, Shawkat Mohammede

    2015-03-05

    Charge transfer (CT) at donor (D)/acceptor (A) interfaces is central to the functioning of photovoltaic and light-emitting devices. Understanding and controlling this process on the molecular level has been proven to be crucial for optimizing the performance of many energy-challenge relevant devices. Here, we report the experimental observations of controlled on/off ultrafast electron transfer (ET) at cationic porphyrin-CdTe quantum dot (QD) interfaces using femto- and nanosecond broad-band transient absorption (TA) spectroscopy. The time-resolved data demonstrate how one can turn on/off the electron injection from porphyrin to the CdTe QDs. With careful control of the molecular structure, we are able to tune the electron injection at the porphyrin-CdTe QD interface from zero to very efficient and ultrafast. In addition, our data demonstrate that the ET process occurs within our temporal resolution of 120 fs, which is one of the fastest times recorded for organic photovoltaics. © 2015 American Chemical Society.

  13. Correlated electron pseudopotentials for 3d-transition metals

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

    2015-01-01

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

  14. Electron microscopy and plastic deformation of HCP metals and alloys

    Poirier, J.-P.; Le Hazif, Roger

    1976-01-01

    The recent literature on the slip systems of the h.c.p. metals is reviewed and the contribution of transmission electron microscopy assessed. It is now clear that the stress-strain curves and the dislocation configurations in the slip plane are very similar, whether the principal slip system is basal or prismatic. The important problem of the relative ease of slip systems is linked to the ease of splitting of dislocations in the slip planes and to the electronic band structure of the metal [fr

  15. Investigation of metal coatings for the free electron laser

    Scott, M.L.; Arendt, P.N.; Springer, R.W.; Cordi, R.C.; McCreary, W.J.

    1985-01-01

    We are investigating the deposition and characteristics of metal coatings for use in environments such as the Free Electron Laser where the radiation resistance of metal coatings could prove to be of great benefit. We have concentrated our initial efforts on silver laminate coatings due to the high reflectance of silver at 1 micron wavelength. Our initial laminate coatings have utilized thin layers of titanium oxide to break up the columnar structure of the silver during electron-beam deposition on fused silica substrates. Our initial results on equal coating thickness samples indicate an improvement in damage threshold that ranges from 1.07 to 1.71 at 351 nm

  16. Innovative electron-beam welding of high-melting metals

    Behr, W.; Reisgen, U.

    2007-01-01

    Since its establishment as nuclear research plant Juelich in the year 1956, the research centre Juelich (FZJ) is concerned with the material processing of special metals. Among those are, above all, the high-melting refractory metals niobium, molybdenum and tungsten. Electron beam welding has always been considered to be an innovative special welding method; in the FZJ, electron beam welding has, moreover, always been adapted to the increasing demands made by research partners and involved manufacturing and design sectors. From the manual equipment technology right up to highly modern multi-beam technique, the technically feasible for fundamental research has, this way, always been realised. (Abstract Copyright [2007], Wiley Periodicals, Inc.) [de

  17. Transition metal impurities in fluorides: Role of electronic structure of fluorine on spectroscopic properties

    Trueba, A.; Garcia-Fernandez, P.; García Lastra, Juan Maria

    2011-01-01

    This work examines the relation between optical properties of a MF6q− complex (M=transition–metal cation) and the chemical bonding paying especial attention to the role played by the electronic structure of fluorine. A main goal of the present study is to understand why if the effective Racah...... parameters, B and C, as well as the cubic splitting parameter, 10Dq, all depend on the covalency nevertheless the latter one is much more sensitive to a hydrostatic pressure than the former ones. The analysis carried out in this work, together with the results of ab initio calculations on CrF63− embedded...... detail. At the same time the reasons avoiding its measurement from optical spectra are pointed out as well. The present results stress that the microscopic origin of an optical parameter like 10Dq can certainly be very subtle....

  18. Electron beam welding of the dissimilar Zr-based bulk metallic glass and Ti metal

    Kim, Jonghyun [Department of Material Science, Kumamoto University, Kumamoto 860-8555 (Japan)], E-mail: joindoc@kumamoto-u.ac.jp; Kawamura, Y. [Department of Material Science, Kumamoto University, Kumamoto 860-8555 (Japan)

    2007-04-15

    We successfully welded 3 mm thick Zr{sub 41}Be{sub 23}Ti{sub 14}Cu{sub 12}Ni{sub 10} bulk metallic glass plate to Ti metal by electron beam welding with a beam irradiated 0.4 mm on the BMG side of the interface. There was no crystallization or defects in the weld because changes in the chemical composition of the weld metal were prevented. Bending showed that the welded sample had a higher strength than the Ti base metal. The interface had a 10 {mu}m thick interdiffusion layer of Zr and Ti.

  19. Secondary electron emission from metals and semi-conductor compounds

    Ono, Susumu; Kanaya, Koichi

    1979-01-01

    Attempt was made to present the sufficient solution of the secondary electron yield of metals and semiconductor compounds except insulators, applying the free electron scattering theory to the absorption of secondary electrons generated within a solid target. The paper is divided into the sections describing absorption coefficient and escape depth, quantitative characteristics of secondary yield, angular distribution of secondary electron emission, effect of incident angle to secondary yield, secondary electron yield transmitted, and lateral distribution of secondary electron emission, besides introduction and conclusion. The conclusions are as follows. Based on the exponential power law for screened atomic potential, secondary electron emission due to both primary and backscattered electrons penetrating into metallic elements and semi-conductive compounds is expressed in terms of the ionization loss in the first collision for escaping secondary electrons. The maximum yield and the corresponding primary energy can both consistently be derived as the functions of three parameters: atomic number, first ionization energy and backscattering coefficient. The yield-energy curve as a function of the incident energy and the backscattering coefficient is in good agreement with the experimental results. The energy dependence of the yield in thin films and the lateral distribution of secondary yield are derived as the functions of the backscattering coefficient and the primary energy. (Wakatsuki, Y.)

  20. Ultrafast electron injection at the cationic porphyrin-graphene interface assisted by molecular flattening

    Aly, Shawkat Mohammede; Parida, Manas R.; Alarousu, Erkki; Mohammed, Omar F.

    2014-01-01

    The steady-state and femtosecond (fs) time-resolved data clearly demonstrate that the charge transfer (CT) process at the porphyrin-graphene carboxylate (GC) interfaces can be tuned from zero to very sufficient and ultrafast by changing the electronic structure of the meso unit and the redox properties of the porphyrin cavity. This journal is © the Partner Organisations 2014.

  1. Synthesis of metal-metal oxide catalysts and electrocatalysts using a metal cation adsorption/reduction and adatom replacement by more noble ones

    Adzic, Radoslav; Vukmirovic, Miomir; Sasaki, Kotaro

    2010-04-27

    The invention relates to platinum-metal oxide composite particles and their use as electrocatalysts in oxygen-reducing cathodes and fuel cells. The invention particularly relates to methods for preventing the oxidation of the platinum electrocatalyst in the cathodes of fuel cells by use of these platinum-metal oxide composite particles. The invention additionally relates to methods for producing electrical energy by supplying such a fuel cell with an oxidant, such as oxygen, and a fuel source, such as hydrogen. The invention also relates to methods of making the metal-metal oxide composites.

  2. Raman spectroscopy of DNA-metal complexes. I. Interactions and conformational effects of the divalent cations: Mg, Ca, Sr, Ba, Mn, Co, Ni, Cu, Pd, and Cd.

    Duguid, J; Bloomfield, V A; Benevides, J; Thomas, G J

    1993-11-01

    Interactions of divalent metal cations (Mg2+, Ca2+, Ba2+, Sr2+, Mn2+, Co2+, Ni2+, Cu2+, Pd2+, and Cd2+) with DNA have been investigated by laser Raman spectroscopy. Both genomic calf-thymus DNA (> 23 kilobase pairs) and mononucleosomal fragments (160 base pairs) were employed as targets of metal interaction in solutions containing 5 weight-% DNA and metal:phosphate molar ratios of 0.6:1. Raman difference spectra reveal that transition metal cations (Mn2+, Co2+, Ni2+, Cu2+, Pd2+, and Cd2+) induce the greatest structural changes in B-DNA. The Raman (vibrational) band differences are extensive and indicate partial disordering of the B-form backbone, reduction in base stacking, reduction in base pairing, and specific metal interaction with acceptor sites on the purine (N7) and pyrimidine (N3) rings. Many of the observed spectral changes parallel those accompanying thermal denaturation of B-DNA and suggest that the metals link the bases of denatured DNA. While exocyclic carbonyls of dT, dG, and dC may stabilize metal ligation, correlation plots show that perturbations of the carbonyls are mainly a consequence of metal-induced denaturation of the double helix. Transition metal interactions with the DNA phosphates are weak in comparison to interactions with the bases, except in the case of Cu2+, which strongly perturbs both base and phosphate group vibrations. On the other hand, the Raman signature of B-DNA is largely unperturbed by Mg2+, Ca2+, Sr2+, and Ba2+, suggesting much weaker interactions of the alkaline earth metals with both base and phosphate sites. A notable exception is a moderate perturbation by alkaline earths of purine N7 sites in 160-base pair DNA, with Ca2+ causing the greatest effect. Correlation plots demonstrate a strong interrelationship between perturbations of Raman bands assigned to ring vibrations of the bases and those of bands assigned to exocyclic carbonyls and backbone phosphodiester groups. However, strong correlations do not occur between

  3. Metal-Insulator-Metal Single Electron Transistors with Tunnel Barriers Prepared by Atomic Layer Deposition

    Golnaz Karbasian

    2017-03-01

    Full Text Available Single electron transistors are nanoscale electron devices that require thin, high-quality tunnel barriers to operate and have potential applications in sensing, metrology and beyond-CMOS computing schemes. Given that atomic layer deposition is used to form CMOS gate stacks with low trap densities and excellent thickness control, it is well-suited as a technique to form a variety of tunnel barriers. This work is a review of our recent research on atomic layer deposition and post-fabrication treatments to fabricate metallic single electron transistors with a variety of metals and dielectrics.

  4. Rice Na+/H+- antiporter Nhx1 partially complements the alkali-metal-cation sensitivity of yeast strains lacking three sodium transporters

    Kinclová-Zimmermannová, Olga; Flegelová, Hana; Sychrová, Hana

    2004-01-01

    Roč. 49, č. 5 (2004), s. 519-525 ISSN 0015-5632 R&D Projects: GA ČR GA204/02/1240; GA AV ČR IAA5011407 Grant - others:EU(XE) QLK3-CT-2001-00533 Institutional research plan: CEZ:AV0Z5011922 Keywords : alkali metal cations * Na/H antiporter * yeast Subject RIV: EB - Genetics ; Molecular Biology Impact factor: 1.034, year: 2004

  5. A binary catalyst system of a cationic Ru-CNC pincer complex with an alkali metal salt for selective hydroboration of carbon dioxide.

    Ng, Chee Koon; Wu, Jie; Hor, T S Andy; Luo, He-Kuan

    2016-09-27

    Binary catalyst systems comprising a cationic Ru-CNC pincer complex and an alkali metal salt were developed for selective hydroboration of CO 2 utilizing pinacolborane at r.t. and 1 atm CO 2 , with the combination of [Ru(CNC Bn )(CO) 2 (H)][PF 6 ] and KOCO 2 t Bu producing formoxyborane in 76% yield. A bicyclic catalytic mechanism was proposed and discussed.

  6. Affinity of hydroxyapatite to metal cations. A study on the composition and structure of phosphates formed in the presence of titanium and aluminium

    Ribeiro, C.C. [Instituto de Eng. Biomedica, Porto (Portugal). Lab. de Biomateriais; Porto Univ. (Portugal). Faculdade de Engenharia; Inst. Superior de Engenharia, Porto (Portugal); Barbosa, M.A. [Instituto de Eng. Biomedica, Porto (Portugal). Lab. de Biomateriais; Porto Univ. (Portugal). Faculdade de Engenharia

    2001-07-01

    The purpose of this study was to contribute to the understanding of the effect of titanium, aluminium and titanium/aluminium on the Hap structure and to investigate if a synergistic effect between the two cations exists. The effect of the metal ion concentration was studied. The solids were analysed by X-ray diffraction, Fourier transform infrared spectroscopy, FT-Raman spectroscopy and energy dispersive X-ray analysis. (orig.)

  7. On flotation separation of oxo-anions of transition metals by the use of fine-emulsified solutions of cationic collector in non-polar liquids

    Skrylev, L.D.; Purich, A.N.; Babinets, S.K.

    1980-01-01

    Experimentally shown is a principle possibility of flotation separation of oxo-anions of transition metals by the use of fine-emulsified solutions of cationic collector in non-polar liquids. Ammonium vanadate and sodium tuno.state solutions have been the objects of study. Hexadezilamine has been used as collector. The collector has been introduced in the form of hexadecylamine emulsions in n-decane, in tetrachloromethane or alcohol. Optimum pH value ranges are determined for separation processes

  8. Electron states in thulium and other rare-earth metals

    Strange, P.; Fairbairn, W.M.; Lee, P.M.

    1983-01-01

    The LMTO method has been applied to calculate band structures for the heavier rare-earth metals. The calculations are relativistic. Thulium in particular has been considered, where a frozen core approximation is used, and the outer electrons are treated selfconsistently. Problems associated with the localisation and interactions of the 4f electrons are discussed. Teh comparisons between experimental data and calculated quantities are encouraging, but more data on high-purity single crystals would be helpful. (author)

  9. Actinide cation-cation complexes

    Stoyer, N.J.; Seaborg, G.T.

    1994-12-01

    The +5 oxidation state of U, Np, Pu, and Am is a linear dioxo cation (AnO 2 + ) with a formal charge of +1. These cations form complexes with a variety of other cations, including actinide cations. Other oxidation states of actinides do not form these cation-cation complexes with any cation other than AnO 2 + ; therefore, cation-cation complexes indicate something unique about AnO 2 + cations compared to actinide cations in general. The first cation-cation complex, NpO 2 + ·UO 2 2+ , was reported by Sullivan, Hindman, and Zielen in 1961. Of the four actinides that form AnO 2 + species, the cation-cation complexes of NpO 2 + have been studied most extensively while the other actinides have not. The only PuO 2 + cation-cation complexes that have been studied are with Fe 3+ and Cr 3+ and neither one has had its equilibrium constant measured. Actinides have small molar absorptivities and cation-cation complexes have small equilibrium constants; therefore, to overcome these obstacles a sensitive technique is required. Spectroscopic techniques are used most often to study cation-cation complexes. Laser-Induced Photacoustic Spectroscopy equilibrium constants for the complexes NpO 2 + ·UO 2 2+ , NpO 2 + ·Th 4+ , PuO 2 + ·UO 2 2+ , and PuO 2 + ·Th 4+ at an ionic strength of 6 M using LIPAS are 2.4 ± 0.2, 1.8 ± 0.9, 2.2 ± 1.5, and ∼0.8 M -1

  10. Variation in whole DNA methylation in red maple (Acer rubrum) populations from a mining region: association with metal contamination and cation exchange capacity (CEC) in podzolic soils.

    Kalubi, K N; Mehes-Smith, M; Spiers, G; Omri, A

    2017-04-01

    Although a number of publications have provided convincing evidence that abiotic stresses such as drought and high salinity are involved in DNA methylation reports on the effects of metal contamination, pH, and cation exchange on DNA modifications are limited. The main objective of the present study is to determine the relationship between metal contamination and Cation exchange capacity (CEC) on whole DNA modifications. Metal analysis confirms that nickel and copper are the main contaminants in sampled sites within the Greater Sudbury Region (Ontario, Canada) and liming has increased soil pH significantly even after 30 years following dolomitic limestone applications. The estimated CEC values varied significantly among sites, ranging between 1.8 and 10.5 cmol(+) kg -1 , with a strong relationship being observed between CEC and pH (r = 0.96**). Cation exchange capacity, significantly lower in highly metal contaminated sites compared to both reference and less contaminated sites, was higher in the higher organic matter limed compared to unlimed sites. There was a significant variation in the level of cytosine methylation among the metal-contaminated sites. Significant and strong negative correlations between [5mdC]/[dG] and bioavailable nickel (r = -0.71**) or copper (r = -0.72**) contents were observed. The analysis of genomic DNA for adenine methylation in this study showed a very low level of [6N-mdA]/dT] in Acer rubrum plants analyzed ranging from 0 to 0.08%. Significant and very strong positive correlation was observed between [6N-mdA]/dT] and soil bioavailable nickel (r = 0.78**) and copper (r = 0.88**) content. This suggests that the increased bioavailable metal levels associated with contamination by nickel and copper particulates are associated with cytosine and adenine methylation.

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

    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

  12. Theoretical study of the low-lying electronic states of magnesium sulfide cation including spin-orbit interaction

    Chen, Peng; Wang, Ning; Li, Song; Chen, Shan-Jun

    2017-11-01

    Highly correlated ab initio calculations have been performed for an accurate determination of electronic structures and spectroscopic features for the low-lying electronic states of the MgS+ cation. The potential energy curves for the four Λ-S states correlating to the lowest dissociation asymptote are studied for the first time. Four Λ-S states split into nine Ω states through the spin-orbit coupling effect. Accurate spectroscopic constants are deduced for all bound states. The spin-orbit couplings and the transition dipole moments, as well as the PECs, are utilized to calculate Franck-Condon factors and radiative lifetimes of the vibrational levels. To verify our computational accuracy, analogous calculations for the ground state of MgS are also carried out, and our derived results are in reasonable agreement with available experimental data. In addition, photoelectron spectrum of MgS has been simulated. The predictive results are anticipated to serve as guidelines for further researches such as assisting laboratorial detections and analyzing observed spectrum.

  13. l-Tryptophan Radical Cation Electron Spin Resonance Studies: Connecting Solution-derived Hyperfine Coupling Constants with Protein Spectral Interpretations

    Connor, Henry D.; Sturgeon, Bradley E.; Mottley, Carolyn; Sipe, Herbert J.; Mason, Ronald P.

    2009-01-01

    Fast-flow electron spin resonance (ESR) spectroscopy has been used to detect a free radical formed from the reaction of l-tryptophan with Ce4+ in an acidic aqueous environment. Computer simulations of the ESR spectra from l-tryptophan and several isotopically modified forms strongly support the conclusion that the l-tryptophan radical cation has been detected by ESR for the first time. The hyperfine coupling constants (HFCs) determined from the well-resolved isotropic ESR spectra support experimental and computational efforts to understand l-tryptophan's role in protein catalysis of oxidation-reduction processes. l-tryptophan HFCs facilitated the simulation of fast-flow ESR spectra of free radicals from two related compounds, tryptamine and 3-methylindole. Analysis of these three compounds' β-methylene hydrogen HFC data along with equivalent l-tyrosine data has led to a new computational method that can distinguish between these two amino acid free radicals in proteins without dependence on isotope labeling, electron nuclear double resonance or high-field ESR. This approach also produces geometric parameters (dihedral angles for the β-methylene hydrogens) which should facilitate protein site assignment of observed l-tryptophan radicals as has been done for l-tyrosine radicals. PMID:18433127

  14. Ab initio investigation of sulfur monofluoride and its singly charged cation and anion in their ground electronic state

    Song, Li; Shan-Jun, Chen; Yan, Chen; Peng, Chen

    2016-03-01

    The SF radical and its singly charged cation and anion, SF+ and SF-, have been investigated on the MRCI/aug-cc-pVXZ (X = Q, 5, 6) levels of theory with Davidson correction. Both the core-valence correlation and the relativistic effect are considered. The extrapolating to the complete basis set (CBS) limit is adopted to remove the basis set truncation error. Geometrical parameters, potential energy curves (PECs), vibrational energy levels, spectroscopic constants, ionization potentials, and electron affinities of the ground electronic state for all these species are obtained. The information with respect to molecular characteristics of the SFn (n = -1, 0, +1) systems derived in this work will help to extend our knowledge and to guide further experimental or theoretical researches. Project supported by the National Natural Science Foundation of China (Grant Nos. 11304023 and 11447172), the Young and Middle-Aged Talent of Education Burea of Hubei Province, China (Grant No. Q20151307), and the Yangtze Youth Talents Fund of Yangtze University, China (Grant No. 2015cqr21).

  15. HNS{sup +} and HSN{sup +} cations: Electronic states, spin-rovibronic spectroscopy with planetary and biological implications

    Trabelsi, Tarek; Hochlaf, Majdi, E-mail: hochlaf@univ-mlv.fr [Laboratoire Modélisation et Simulation Multi Echelle, Université Paris-Est, MSME UMR 8208 CNRS, 5 Blvd. Descartes, 77454 Marne-la-Vallée (France); Ben Yaghlane, Saida [Laboratoire de Spectroscopie Atomique, Moléculaire et Applications—LSAMA, Université de Tunis El Manar, Tunis (Tunisia); Al Mogren, Muneerah Mogren [Chemistry Department, Faculty of Science, King Saud University, P.O. Box 2455, Riyadh 11451 (Saudi Arabia); Francisco, Joseph S. [Department of Chemistry, University of Nebraska-Lincoln, 433 Hamilton Hall, Lincoln, Nebraska 68588-0304 (United States)

    2016-08-28

    Ab initio methods in conjunction with a large basis set are used to compute the potential energy surfaces of the 12 lowest electronic states of the HNS{sup +} and HSN{sup +} isomeric forms. These potentials are used in discussions of the metastability of these cations and plausible mechanisms for the H{sup +}/H + SN{sup +}/SN, S/S{sup +} + NH{sup +}/NH, N/N{sup +} + SH{sup +}/SH ion-molecule reactions. Interestingly, the low rovibrational levels of HSN{sup +}(1{sup 2}A″) and HNS{sup +}(1{sup 2}A″) electronically excited ions are predicted to be long-lived. Both ions are suggested to be a suitable candidate for light-sensitive NO{sup ⋅} donor in vivo and as a possible marker for the detection of intermediates in nitrites + H{sub 2}S reactions at the cellular level. The full spin rovibronic levels of HNS{sup +} are presented, which may assist in the experimental identification of HNS{sup +} and HSN{sup +} ions and in elucidating their roles in astrophysical and biological media.

  16. Observation of Electronic Raman Scattering in Metallic Carbon Nanotubes

    Farhat, H.; Berciaud, S.; Kalbáč, Martin; Saito, R.; Heinz, T. F.; Dresselhaus, M. S.; Kong, J.

    2011-01-01

    Roč. 107, č. 15 (2011), s. 157401 ISSN 0031-9007 R&D Projects: GA MŠk ME09060 Institutional research plan: CEZ:AV0Z40400503 Keywords : spectroscopy * electronic Raman scattering * metallic carbon nanotubes Subject RIV: CG - Electrochemistry Impact factor: 7.370, year: 2011

  17. Microscopic Electron Dynamics in Metal Nanoparticles for Photovoltaic Systems

    Katarzyna Kluczyk

    2018-06-01

    Full Text Available Nanoparticles—regularly patterned or randomly dispersed—are a key ingredient for emerging technologies in photonics. Of particular interest are scattering and field enhancement effects of metal nanoparticles for energy harvesting and converting systems. An often neglected aspect in the modeling of nanoparticles are light interaction effects at the ultimate nanoscale beyond classical electrodynamics. Those arise from microscopic electron dynamics in confined systems, the accelerated motion in the plasmon oscillation and the quantum nature of the free electron gas in metals, such as Coulomb repulsion and electron diffusion. We give a detailed account on free electron phenomena in metal nanoparticles and discuss analytic expressions stemming from microscopic (Random Phase Approximation—RPA and semi-classical (hydrodynamic theories. These can be incorporated into standard computational schemes to produce more reliable results on the optical properties of metal nanoparticles. We combine these solutions into a single framework and study systematically their joint impact on isolated Au, Ag, and Al nanoparticles as well as dimer structures. The spectral position of the plasmon resonance and its broadening as well as local field enhancement show an intriguing dependence on the particle size due to the relevance of additional damping channels.

  18. Electronic structure of metallic alloys through Auger and photoemission spectroscopy

    Kleiman, G.G.; Rogers, J.D.; Sundaram, V.S.

    1981-01-01

    A review is presented of experimental results of electron spectroscopy studies for various series of transition metal alloys as well as a model for their interpretation which leads to the possibility for the first time to determine independently relative variations in the dipole barrier and Fermi energy contributions to the work function. (L.C.) [pt

  19. Interaction between electrons and tunneling levels in metallic glasses

    Black, J.L.; Gyorffy, B.L.

    1978-01-01

    A simple model in which the conduction electrons of a metallic glass experience a local time-dependent potential due to two-level tunneling states is considered. The model exhibits interesting divergent behavior which is quite different from that predicted by an earlier ''s-d Kondo'' model

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

    Shi, Wenwu; Wang, Zhiguo

    2018-05-01

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

  1. Electronic structure of metal overlayers on rhodium

    Feibelman, P.J.; Hamann, D.R.

    1983-01-01

    We have evaluated work functions, surface core-level shifts, and surface band dispersions for clean, Ag-covered, and Pd-covered Rh(100) surfaces, and for clean and Ag-covered Rh(111). The calculations were performed self-consistently, using the surface-linearized augmented-plane-wave method. As expected from the Pauling electronegativities, Ag adsorption lowers the work function from the clean Rh value, by several tenths of an eV, while Pd has an almost negligible effect. The values calculated for the core-level shifts of various films are shown to correspond to expectations based on surface band narrowing and layerwise charge neutrality. Using the core-level shifts, we predict heat-of-adsorption differences (for Ag on Pd vs Ag on Rh, etc.) that are in quite good agreement with the empirical predictions of Miedema and Dorleijn. Finally, the chemical inactivity of the Ag-covered Rh surface is associated with the fact that, for that system, the outer-layer local density of states is essentially that of Ag, with a characteristically low value at the Fermi energy. On the other hand, the Pd-covered Rh surface should behave much like clean Rh with an extra electron per surface atom. The surface band dispersions for the Pd-covered and clean Rh surfaces are closely similar. This result contrasts sharply with the case of Pd-covered Nb, for which, because of the appreciable electronegativity difference, the Pd overlayer is effectively ''noble.''

  2. Kinetics of the reactions of hydrated electrons with metal complexes

    Korsse, J.

    1983-01-01

    The reactivity of the hydrated electron towards metal complexes is considered. Experiments are described involving metal EDTA and similar complexes. The metal ions studied are mainly Ni 2+ , Co 2+ and Cu 2+ . Rates of the reactions of the complexes with e - (aq) were measured using the pulse radiolysis technique. It is shown that the reactions of e - (aq) with the copper complexes display unusually small kinetic salt effects. The results suggest long-range electron transfer by tunneling. A tunneling model is presented and the experimental results are discussed in terms of this model. Results of approximate molecular orbital calculations of some redox potentials are given, for EDTA chelates as well as for series of hexacyano and hexaquo complexes. Finally, equilibrium constants for the formation of ternary complexes are reported. (Auth./G.J.P.)

  3. Dimer/monomer switching of pyridinium and quinolinium cations by electron transfer

    Pospíšil, Lubomír; Teplý, Filip; Hromadová, Magdaléna; Čížková, Martina; Kolivoška, Viliam; Slavíček, P.; Tarábek, Ján

    2012-01-01

    Roč. 2012, - (2012), s. 75 ISSN 0872-1904. [Iberic Meeting of Electrochemistry /14./ and Meeting of the Portuguese Electrochemical Society /17./. 11.04.2012-14.04.2012, Madeira Island] R&D Projects: GA ČR GA203/09/0705; GA AV ČR IAA400400802; GA ČR GA203/09/1614 Source of funding: I - inštitucionálna podpora na rozvoj VO Institutional support: RVO:61388955 Keywords : electron transfer * electrochemistry Subject RIV: CG - Electrochemistry

  4. Electronic behavior of highly correlated metals

    Reich, A.

    1988-10-01

    This thesis addresses the question of the strongly interacting many-body problem: that is, systems where the interparticle correlations are so strong as to defy perturbative approaches. These subtle correlations occur in narrow band materials, such as the lanthanides and actinides, wherein the f-electrons are so localized that a variety of new phenomena, including intermediate-valence and heavy-fermionic behavior, may occur. As well, one has the alloying problem, where local interactions are paramount in determining the overall behavior. The technique employed in dealing with these systems is the Small Cluster method, wherein the full many-body Hamiltonian for a small grouping of atoms, coupled with periodic boundary conditions, is solved exactly. This is tantamount to solving a bulk crystal at the high points of symmetry in the Brillouin Zone. The mathematical overhead is further reduced by employing the full space group and spin symmetries. By its very nature, the Small Cluster method is well able to handle short-range interactions, as well as the combinatorial complexity of the many-body problem, on an equal footing. The nature of long-range order and phase transition behavior cannot be incorporated, but sometimes clues as to their origin can be discerned. The calculations presented include: a two-band Anderson model for an intermediate-valence system, wherein photoemission and fluctuation behavior is examined; a single-band Hubbard model for a ternary alloy system, such as copper-silver-gold; and a Hubbard model for a heavy- fermion system, wherein Fermi surface, transport, magnetic and superconducting properties are discussed. 148 refs., 31 figs., 24 tabs

  5. The electronic structure of normal metal-superconductor bilayers

    Halterman, Klaus; Elson, J Merle [Sensor and Signal Sciences Division, Naval Air Warfare Center, China Lake, CA 93355 (United States)

    2003-09-03

    We study the electronic properties of ballistic thin normal metal-bulk superconductor heterojunctions by solving the Bogoliubov-de Gennes equations in the quasiclassical and microscopic 'exact' regimes. In particular, the significance of the proximity effect is examined through a series of self-consistent calculations of the space-dependent pair potential {delta}(r). It is found that self-consistency cannot be neglected for normal metal layer widths smaller than the superconducting coherence length {xi}{sub 0}, revealing its importance through discernible features in the subgap density of states. Furthermore, the exact self-consistent treatment yields a proximity-induced gap in the normal metal spectrum, which vanishes monotonically when the normal metal length exceeds {xi}{sub 0}. Through a careful analysis of the excitation spectra, we find that quasiparticle trajectories with wavevectors oriented mainly along the interface play a critical role in the destruction of the energy gap.

  6. Gas sorption and transition-metal cation separation with a thienothiophene based zirconium metal–organic framework

    SK, Mostakim [Department of Chemistry, Indian Institute of Technology Guwahati, 781039 Assam (India); Grzywa, Maciej; Volkmer, Dirk [Institute of Physics, Chair of Solid State Science, Augsburg University, Universitätsstrasse 1, D-86135 Augsburg (Germany); Biswas, Shyam, E-mail: sbiswas@iitg.ernet.in [Department of Chemistry, Indian Institute of Technology Guwahati, 781039 Assam (India)

    2015-12-15

    The modulated synthesis of the thienothiophene based zirconium metal–organic framework (MOF) material having formula [Zr{sub 6}O{sub 4}(OH){sub 4}(DMTDC){sub 6}]·4.8DMF·10H{sub 2}O (1) (H{sub 2}DMTDC=3,4-dimethylthieno[2,3-b]thiophene-2,5-dicarboxylic acid; DMF=N,N'-dimethylformamide) was carried out by heating a mixture of ZrCl{sub 4}, H{sub 2}DMTDC linker and benzoic acid (used as a modulator) with a molar ratio of 1:1:30 in DMF at 150 °C for 24 h. Systematic investigations have been performed in order to realize the effect of ZrCl{sub 4}/benzoic acid molar ratio on the crystallinity of the material. The activation (i.e., the removal of the guest solvent molecules from the pores) of as-synthesized compound was achieved by stirring it with methanol and subsequently heating under vacuum. A combination of X-ray diffraction (XRD), Fourier transform infrared (FT-IR), thermogravimetric (TG) and elemental analysis was used to examine the phase purity of the as-synthesized and thermally activated 1. The material displays high thermal stability up to 310 °C in an air atmosphere. As revealed from the XRD measurements, the compound retains its crystallinity when treated with water, acetic acid and 1 M HCl solutions. The N{sub 2} and CO{sub 2} sorption analyses suggest that the material possesses remarkably high microporosity (S{sub BET}=1236 m{sup 2} g{sup −1}; CO{sub 2} uptake=3.5 mmol g{sup −1} at 1 bar and 0 °C). The compound also shows selective adsorption behavior for Cu{sup 2+} over Co{sup 2+} and Ni{sup 2+} ions. - Graphical abstract: Selective transition-metal cation adsorption by a thienothiophene based zirconium metal–organic framework material. - Highlights: • The modulated synthesis of a thienothiophene based Zr(IV) MOF has been described. • Effect of metal salt/modulator ratio on the crystallinity was thoroughly studied. • The compound showed high thermal and physiochemical stability. • N{sub 2} and CO{sub 2} sorption experiments

  7. Gas sorption and transition-metal cation separation with a thienothiophene based zirconium metal–organic framework

    SK, Mostakim; Grzywa, Maciej; Volkmer, Dirk; Biswas, Shyam

    2015-01-01

    The modulated synthesis of the thienothiophene based zirconium metal–organic framework (MOF) material having formula [Zr_6O_4(OH)_4(DMTDC)_6]·4.8DMF·10H_2O (1) (H_2DMTDC=3,4-dimethylthieno[2,3-b]thiophene-2,5-dicarboxylic acid; DMF=N,N'-dimethylformamide) was carried out by heating a mixture of ZrCl_4, H_2DMTDC linker and benzoic acid (used as a modulator) with a molar ratio of 1:1:30 in DMF at 150 °C for 24 h. Systematic investigations have been performed in order to realize the effect of ZrCl_4/benzoic acid molar ratio on the crystallinity of the material. The activation (i.e., the removal of the guest solvent molecules from the pores) of as-synthesized compound was achieved by stirring it with methanol and subsequently heating under vacuum. A combination of X-ray diffraction (XRD), Fourier transform infrared (FT-IR), thermogravimetric (TG) and elemental analysis was used to examine the phase purity of the as-synthesized and thermally activated 1. The material displays high thermal stability up to 310 °C in an air atmosphere. As revealed from the XRD measurements, the compound retains its crystallinity when treated with water, acetic acid and 1 M HCl solutions. The N_2 and CO_2 sorption analyses suggest that the material possesses remarkably high microporosity (S_B_E_T=1236 m"2 g"−"1; CO_2 uptake=3.5 mmol g"−"1 at 1 bar and 0 °C). The compound also shows selective adsorption behavior for Cu"2"+ over Co"2"+ and Ni"2"+ ions. - Graphical abstract: Selective transition-metal cation adsorption by a thienothiophene based zirconium metal–organic framework material. - Highlights: • The modulated synthesis of a thienothiophene based Zr(IV) MOF has been described. • Effect of metal salt/modulator ratio on the crystallinity was thoroughly studied. • The compound showed high thermal and physiochemical stability. • N_2 and CO_2 sorption experiments revealed significantly high microporosity. • The material showed high adsorption selectivity for Cu"2

  8. Effects of lattice fluctuations on electronic transmission in metal/conjugated-oligomer/metal structures

    Yu, Z.G.; Smith, D.L.; Saxena, A.; Bishop, A.R.

    1997-01-01

    The electronic transmission across metal/conjugated-oligomer/metal structures in the presence of lattice fluctuations is studied for short oligomer chains. The lattice fluctuations are approximated by static white noise disorder. Resonant transmission occurs when the energy of an incoming electron coincides with a discrete electronic level of the oligomer. The corresponding transmission peak diminishes in intensity with increasing disorder strength. Because of disorder there is an enhancement of the electronic transmission for energies that lie within the electronic gap of the oligomer. If fluctuations are sufficiently strong, a transmission peak within the gap is found at the midgap energy E=0 for degenerate conjugated oligomers (e.g., trans-polyacetylene) and E≠0 for AB-type degenerate oligomers. These results can be interpreted in terms of soliton-antisoliton states created by lattice fluctuations. copyright 1997 The American Physical Society

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

    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.

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

    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.

  11. Suppression of the two-dimensional electron gas in LaGaO3/SrTiO3 by cation intermixing

    Nazir, S.

    2013-12-03

    Cation intermixing at the n-type polar LaGaO 3 /SrTiO 3 (001) interface is investigated by first principles calculations. Ti"Ga, Sr"La, and SrTi"LaGa intermixing are studied in comparison to each other, with a focus on the interface stability. We demonstrate in which cases intermixing is energetically favorable as compared to a clean interface. A depopulation of the Ti 3d xy orbitals under cation intermixing is found, reflecting a complete suppression of the two-dimensional electron gas present at the clean interface.

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

    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. Difference in x-ray scattering between metallic and non-metallic liquids due to conduction electrons

    Chihara, Junzo

    1987-01-01

    X-ray scattered intensity from a liquid metal as an electron-ion mixture is described using the structure factors, which are exactly expressed in terms of the static and dynamic direct correlation functions. This intensity for a metal is shown to differ from the usual scattered intensity from a non-metal in two points: the atomic form factor and the incoherent (Compton) scattering factor. It is shown that the valence electron form factor, which constitutes the atomic form factor in a liquid metal, leads to a determination of the electron-electron and electron-ion structure factors by combining the ionic structure factor. It is also shown that a part of the electron structure factor, which appears as the incoherent x-ray scattering, is usually approximated as the electron structure factor of the jellium model in the case of a simple metal. As a by-product, the x-ray scattered intensity from a crystalline metal and the inelastic scattering from a liquid metal are given by taking account of the presence of conduction electrons. In this way, we clarify some confusion which appeared in the proposal by Egelstaff et al for extracting the electron-electron correlation function in a metal from x-ray and neutron scattering experiments. A procedure to extract the electron-electron and electron-ion structure factors in a liquid metal is proposed on the basis of formula for scattered intensity derived here. (author)

  14. Metal oxide semiconductor thin-film transistors for flexible electronics

    Petti, Luisa; Vogt, Christian; Büthe, Lars; Cantarella, Giuseppe; Tröster, Gerhard [Electronics Laboratory, Swiss Federal Institute of Technology, Zürich (Switzerland); Münzenrieder, Niko [Electronics Laboratory, Swiss Federal Institute of Technology, Zürich (Switzerland); Sensor Technology Research Centre, University of Sussex, Falmer (United Kingdom); Faber, Hendrik; Bottacchi, Francesca; Anthopoulos, Thomas D. [Department of Physics and Centre for Plastic Electronics, Imperial College London, London (United Kingdom)

    2016-06-15

    The field of flexible electronics has rapidly expanded over the last decades, pioneering novel applications, such as wearable and textile integrated devices, seamless and embedded patch-like systems, soft electronic skins, as well as imperceptible and transient implants. The possibility to revolutionize our daily life with such disruptive appliances has fueled the quest for electronic devices which yield good electrical and mechanical performance and are at the same time light-weight, transparent, conformable, stretchable, and even biodegradable. Flexible metal oxide semiconductor thin-film transistors (TFTs) can fulfill all these requirements and are therefore considered the most promising technology for tomorrow's electronics. This review reflects the establishment of flexible metal oxide semiconductor TFTs, from the development of single devices, large-area circuits, up to entirely integrated systems. First, an introduction on metal oxide semiconductor TFTs is given, where the history of the field is revisited, the TFT configurations and operating principles are presented, and the main issues and technological challenges faced in the area are analyzed. Then, the recent advances achieved for flexible n-type metal oxide semiconductor TFTs manufactured by physical vapor deposition methods and solution-processing techniques are summarized. In particular, the ability of flexible metal oxide semiconductor TFTs to combine low temperature fabrication, high carrier mobility, large frequency operation, extreme mechanical bendability, together with transparency, conformability, stretchability, and water dissolubility is shown. Afterward, a detailed analysis of the most promising metal oxide semiconducting materials developed to realize the state-of-the-art flexible p-type TFTs is given. Next, the recent progresses obtained for flexible metal oxide semiconductor-based electronic circuits, realized with both unipolar and complementary technology, are reported. In

  15. Cation-exchanger fabric prepared by electron beam - induced graft copolymerization of binary monomer mixture

    Bondar, Yu.V.; Kim, H.J.; Lim, Y.J.; Perelygin, V.P.

    2004-01-01

    Applying the electron-beam preirradiation method in air the sorption-active polypropylene fiber, containing sulfonic acid (R-SO 3 H) groups, was prepared by simultaneous graft copolymerization of sodium styrenesulfonate with acrylic acid in water solution. The effect of reaction conditions on the grafting yield and reaction mechanism was examined. It was found that the received CEF contains groups of strong acid (R-SO 3 H) and weak acid (R-COOH) in almost equal proportion. The ion-exchange properties of the CEF towards Cu(II) and Co(II) ions were investigated depending on the form of the CEF and a pH of the solution. It was shown that the utilization of the CEF in Na- form allows to make the best use of its ion-exchange capacity. (author)

  16. Efficient electronic structure methods applied to metal nanoparticles

    Larsen, Ask Hjorth

    of efficient approaches to density functional theory and the application of these methods to metal nanoparticles. We describe the formalism and implementation of localized atom-centered basis sets within the projector augmented wave method. Basis sets allow for a dramatic increase in performance compared....... The basis set method is used to study the electronic effects for the contiguous range of clusters up to several hundred atoms. The s-electrons hybridize to form electronic shells consistent with the jellium model, leading to electronic magic numbers for clusters with full shells. Large electronic gaps...... and jumps in Fermi level near magic numbers can lead to alkali-like or halogen-like behaviour when main-group atoms adsorb onto gold clusters. A non-self-consistent NewnsAnderson model is used to more closely study the chemisorption of main-group atoms on magic-number Au clusters. The behaviour at magic...

  17. Electron paramagnetic resonance studies in HgMo sub 6 S sub 8 doped with Cu sup 2 sup + : evidence for cationic mobility

    Kadam, R M; Iyer, R M; Gopalakrishnan, I K; Yakhmi, J V

    1997-01-01

    Some of the Chevrel phase compounds are reported to exhibit unusual cationic mobilities, particularly those with transition metals. EPR evidence is presented for mobile Cu sup 2 sup + ions in Cu sup 2 sup + -doped HgMo sub 6 S sub 8. Evidence is also obtained for the existence of Hg sup + ions, giving possible support for the model correlating the site change with the reaction A sup 2 sup + + e sup -reversible A sup + during ionic conductivity. (author)

  18. An environment-dependent semi-empirical tight binding model suitable for electron transport in bulk metals, metal alloys, metallic interfaces, and metallic nanostructures. I. Model and validation

    Hegde, Ganesh, E-mail: ghegde@purdue.edu; Povolotskyi, Michael; Kubis, Tillmann; Klimeck, Gerhard, E-mail: gekco@purdue.edu [Network for Computational Nanotechnology (NCN), Department of Electrical and Computer Engineering, Purdue University, West Lafayette, Indiana 47907 (United States); Boykin, Timothy [Department of Electrical and Computer Engineering, University of Alabama, Huntsville, Alabama (United States)

    2014-03-28

    Semi-empirical Tight Binding (TB) is known to be a scalable and accurate atomistic representation for electron transport for realistically extended nano-scaled semiconductor devices that might contain millions of atoms. In this paper, an environment-aware and transferable TB model suitable for electronic structure and transport simulations in technologically relevant metals, metallic alloys, metal nanostructures, and metallic interface systems are described. Part I of this paper describes the development and validation of the new TB model. The new model incorporates intra-atomic diagonal and off-diagonal elements for implicit self-consistency and greater transferability across bonding environments. The dependence of the on-site energies on strain has been obtained by appealing to the Moments Theorem that links closed electron paths in the system to energy moments of angular momentum resolved local density of states obtained ab initio. The model matches self-consistent density functional theory electronic structure results for bulk face centered cubic metals with and without strain, metallic alloys, metallic interfaces, and metallic nanostructures with high accuracy and can be used in predictive electronic structure and transport problems in metallic systems at realistically extended length scales.

  19. An environment-dependent semi-empirical tight binding model suitable for electron transport in bulk metals, metal alloys, metallic interfaces, and metallic nanostructures. I. Model and validation

    Hegde, Ganesh; Povolotskyi, Michael; Kubis, Tillmann; Klimeck, Gerhard; Boykin, Timothy

    2014-01-01

    Semi-empirical Tight Binding (TB) is known to be a scalable and accurate atomistic representation for electron transport for realistically extended nano-scaled semiconductor devices that might contain millions of atoms. In this paper, an environment-aware and transferable TB model suitable for electronic structure and transport simulations in technologically relevant metals, metallic alloys, metal nanostructures, and metallic interface systems are described. Part I of this paper describes the development and validation of the new TB model. The new model incorporates intra-atomic diagonal and off-diagonal elements for implicit self-consistency and greater transferability across bonding environments. The dependence of the on-site energies on strain has been obtained by appealing to the Moments Theorem that links closed electron paths in the system to energy moments of angular momentum resolved local density of states obtained ab initio. The model matches self-consistent density functional theory electronic structure results for bulk face centered cubic metals with and without strain, metallic alloys, metallic interfaces, and metallic nanostructures with high accuracy and can be used in predictive electronic structure and transport problems in metallic systems at realistically extended length scales

  20. An environment-dependent semi-empirical tight binding model suitable for electron transport in bulk metals, metal alloys, metallic interfaces, and metallic nanostructures. I. Model and validation

    Hegde, Ganesh; Povolotskyi, Michael; Kubis, Tillmann; Boykin, Timothy; Klimeck, Gerhard

    2014-03-01

    Semi-empirical Tight Binding (TB) is known to be a scalable and accurate atomistic representation for electron transport for realistically extended nano-scaled semiconductor devices that might contain millions of atoms. In this paper, an environment-aware and transferable TB model suitable for electronic structure and transport simulations in technologically relevant metals, metallic alloys, metal nanostructures, and metallic interface systems are described. Part I of this paper describes the development and validation of the new TB model. The new model incorporates intra-atomic diagonal and off-diagonal elements for implicit self-consistency and greater transferability across bonding environments. The dependence of the on-site energies on strain has been obtained by appealing to the Moments Theorem that links closed electron paths in the system to energy moments of angular momentum resolved local density of states obtained ab initio. The model matches self-consistent density functional theory electronic structure results for bulk face centered cubic metals with and without strain, metallic alloys, metallic interfaces, and metallic nanostructures with high accuracy and can be used in predictive electronic structure and transport problems in metallic systems at realistically extended length scales.

  1. Metal electrodeposition and electron transfer studies of uranium compounds in room temperature ionic liquids

    Stoll, M.E.; Oldham, W.J.; Costa, D.A.

    2004-01-01

    Room temperature ionic liquids (RTIL's) comprised of 1,3-dialkylimidazolium or quaternary ammonium cations and one of several anions such as PF 6 - , BF 4 - , or - N(SO 2 CF 3 ) 2 , represent a class of solvents that possess great potential for use in applications employing electrochemical procedures. Part of the intrigue with RTIL's stems from some of their inherent solvent properties including negligible vapor pressure, good conductivity, high chemical and thermal stability, and non-flammability. Additionally, a substantial number of RTIL's can be envisioned simply by combining different cation and anion pairs, thereby making them attractive for specific application needs. We are interested in learning more about the possible use of RTIL's within the nuclear industry. In this regard our research team has been exploring the electron transfer behavior of simple metal ions in addition to coordination and organometallic complexes in these novel solvents. Results from our research have also provided us with insight into the bonding interactions between our current anion of choice, bis(trifluoromethylsulfonyl)imide = NTf 2 , and open coordination sites on actinide and transition metal fragments. This presentation will focus on recent results in two areas: the electrodeposition of electropositive metal ions from RTIL solutions and the electron transfer behavior for several uranium complexes. Details concerning the cathodic electrodeposition and anodic stripping of alkali metals (Na, K) from various working electrode surfaces (Pt, Au, W, Glassy Carbon) will be discussed. Figure 1 displays typical behavior for the electrodeposition of potassium metal from an RTIL containing potassium ions produced through the reaction of KH with H[NTf 2 ]. Our efforts with other metal ions, including our results to date with uranium electrodeposition, will be covered during the presentation. The electron transfer behavior for a number of uranium complexes have been studied with various

  2. Damage generation by electronic excitations in crystalline metals

    Dunlop, A.; Lesueur, D.

    1992-01-01

    This paper will give a rapid overview of the main experimental results concerning the effects of high electronic energy deposition in metallic targets and present a tentative model based on the Coulomb explosion mechanism. More detailed reviews have been made recently concerning both the experiments and the theoretical model. High levels of localized energy deposition in electronic excitation are easily obtained using GeV heavy ions which during their slowing-down typically transfer a few keV/A to the electronic system of the target and a few eV/A in elastic collisions with target nuclei. In insulators and organic materials, it is well-known that both slowing-down processes contribute to damage creation, whereas in metals it has been claimed for a long time that the sole nuclear collisions are involved in damage processes. Although this last assertion remains true for some metals such as Cu, Ag, W, Cu 3 Au...[2], high levels of electronic excitation can induce a partial annealing of the defects resulting from nuclear collisions in Fe, Ni, Nb, Pt..., lead to additional defect creation in Fe, Co, Zr, Ti...[2] or even to phase transformations in NiZr 2 [5], Ni 3 B [6], NiTi [7], Ti [8]... In the following, we shall only focus on the last two effects. (author). 15 refs

  3. Organic/metal interfaces. Electronic and structural properties

    Duhm, Steffen

    2008-07-17

    This work addresses several important topics of the field of organic electronics. The focus lies on organic/metal interfaces, which exist in all organic electronic devices. Physical properties of such interfaces are crucial for device performance. Four main topics have been covered: (i) the impact of molecular orientation on the energy levels, (ii) energy level tuning with strong electron acceptors, (iii) the role of thermodynamic equilibrium at organic/ organic homo-interfaces and (iv) the correlation of interfacial electronic structure and bonding distance. To address these issues a broad experimental approach was necessary: mainly ultraviolet photoelectron spectroscopy was used, supported by X-ray photoelectron spectroscopy, metastable atom electron spectroscopy, X-ray diffraction and X-ray standing waves, to examine vacuum sublimed thin films of conjugated organic molecules (COMs) in ultrahigh vacuum. (i) A novel approach is presented to explain the phenomenon that the ionization energy in molecular assemblies is orientation dependent. It is demonstrated that this is due to a macroscopic impact of intramolecular dipoles on the ionization energy in molecular assemblies. Furthermore, the correlation of molecular orientation and conformation has been studied in detail for COMs on various substrates. (ii) A new approach was developed to tune hole injection barriers ({delta}{sub h}) at organic/metal interfaces by adsorbing a (sub-) monolayer of an organic electron acceptor on the metal electrode. Charge transfer from the metal to the acceptor leads to a chemisorbed layer, which reduces {delta}{sub h} to the COM overlayer. This concept was tested with three acceptors and a lowering of {delta}{sub h} of up to 1.2 eV could be observed. (iii) A transition from vacuum-level alignment to molecular level pinning at the homo-interface between a lying monolayer and standing multilayers of a COM was observed, which depended on the amount of a pre-deposited acceptor. The

  4. Identification of a divalent metal cation binding site in herpes simplex virus 1 (HSV-1) ICP8 required for HSV replication.

    Bryant, Kevin F; Yan, Zhipeng; Dreyfus, David H; Knipe, David M

    2012-06-01

    Herpes simplex virus 1 (HSV-1) ICP8 is a single-stranded DNA-binding protein that is necessary for viral DNA replication and exhibits recombinase activity in vitro. Alignment of the HSV-1 ICP8 amino acid sequence with ICP8 homologs from other herpesviruses revealed conserved aspartic acid (D) and glutamic acid (E) residues. Amino acid residue D1087 was conserved in every ICP8 homolog analyzed, indicating that it is likely critical for ICP8 function. We took a genetic approach to investigate the functions of the conserved ICP8 D and E residues in HSV-1 replication. The E1086A D1087A mutant form of ICP8 failed to support the replication of an ICP8 mutant virus in a complementation assay. E1086A D1087A mutant ICP8 bound DNA, albeit with reduced affinity, demonstrating that the protein is not globally misfolded. This mutant form of ICP8 was also recognized by a conformation-specific antibody, further indicating that its overall structure was intact. A recombinant virus expressing E1086A D1087A mutant ICP8 was defective in viral replication, viral DNA synthesis, and late gene expression in Vero cells. A class of enzymes called DDE recombinases utilize conserved D and E residues to coordinate divalent metal cations in their active sites. We investigated whether the conserved D and E residues in ICP8 were also required for binding metal cations and found that the E1086A D1087A mutant form of ICP8 exhibited altered divalent metal binding in an in vitro iron-induced cleavage assay. These results identify a novel divalent metal cation-binding site in ICP8 that is required for ICP8 functions during viral replication.

  5. Quantum-chemistry based calibration of the alkali metal cation series (Li(+)-Cs(+)) for large-scale polarizable molecular mechanics/dynamics simulations.

    Dudev, Todor; Devereux, Mike; Meuwly, Markus; Lim, Carmay; Piquemal, Jean-Philip; Gresh, Nohad

    2015-02-15

    The alkali metal cations in the series Li(+)-Cs(+) act as major partners in a diversity of biological processes and in bioinorganic chemistry. In this article, we present the results of their calibration in the context of the SIBFA polarizable molecular mechanics/dynamics procedure. It relies on quantum-chemistry (QC) energy-decomposition analyses of their monoligated complexes with representative O-, N-, S-, and Se- ligands, performed with the aug-cc-pVTZ(-f) basis set at the Hartree-Fock level. Close agreement with QC is obtained for each individual contribution, even though the calibration involves only a limited set of cation-specific parameters. This agreement is preserved in tests on polyligated complexes with four and six O- ligands, water and formamide, indicating the transferability of the procedure. Preliminary extensions to density functional theory calculations are reported. © 2014 Wiley Periodicals, Inc.

  6. The large second-harmonic generation of LiCs{sub 2}PO{sub 4} is caused by the metal-cation-centered groups

    Cheng, Xiyue; Guo, Guo-Cong; Hong, Maochun; Deng, Shuiquan [State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter (FJIRSM), Chinese Academy of Sciences (CAS), Fuzhou (China); Whangbo, Myung-Hwan [State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter (FJIRSM), Chinese Academy of Sciences (CAS), Fuzhou (China); Department of Chemistry, North Carolina State University, Raleigh, NC (United States)

    2018-04-03

    We evaluated the individual atom contributions to the second harmonic generation (SHG) coefficients of LiCs{sub 2}PO{sub 4} (LCPO) by introducing the partial response functionals on the basis of first principles calculations. The SHG response of LCPO is dominated by the metal-cation-centered groups CsO{sub 6} and LiO{sub 4}, not by the nonmetal-cation-centered groups PO{sub 4} expected from the existing models and theories. The SHG coefficients of LCPO are determined mainly by the occupied orbitals O 2p and Cs 5p as well as by the unoccupied orbitals Cs 5d and Li 2p. For the SHG response of a material, the polarizable atomic orbitals of the occupied and the unoccupied states are both important. (copyright 2018 Wiley-VCH Verlag GmbH and Co. KGaA, Weinheim)

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

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

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

  8. Interaction of electrons with light metal hydrides in the transmission electron microscope.

    Wang, Yongming; Wakasugi, Takenobu; Isobe, Shigehito; Hashimoto, Naoyuki; Ohnuki, Somei

    2014-12-01

    Transmission electron microscope (TEM) observation of light metal hydrides is complicated by the instability of these materials under electron irradiation. In this study, the electron kinetic energy dependences of the interactions of incident electrons with lithium, sodium and magnesium hydrides, as well as the constituting element effect on the interactions, were theoretically discussed, and electron irradiation damage to these hydrides was examined using in situ TEM. The results indicate that high incident electron kinetic energy helps alleviate the irradiation damage resulting from inelastic or elastic scattering of the incident electrons in the TEM. Therefore, observations and characterizations of these materials would benefit from increased, instead decreased, TEM operating voltage. © The Author 2014. Published by Oxford University Press on behalf of The Japanese Society of Microscopy. All rights reserved. For permissions, please e-mail: journals.permissions@oup.com.

  9. Electron core ionization in compressed alkali metal cesium

    Degtyareva, V. F.

    2018-01-01

    Elements of groups I and II in the periodic table have valence electrons of s-type and are usually considered as simple metals. Crystal structures of these elements at ambient pressure are close-packed and high-symmetry of bcc and fcc-types, defined by electrostatic (Madelung) energy. Diverse structures were found under high pressure with decrease of the coordination number, packing fraction and symmetry. Formation of complex structures can be understood within the model of Fermi sphere-Brillouin zone interactions and supported by Hume-Rothery arguments. With the volume decrease there is a gain of band structure energy accompanied by a formation of many-faced Brillouin zone polyhedra. Under compression to less than a half of the initial volume the interatomic distances become close to or smaller than the ionic radius which should lead to the electron core ionization. At strong compression it is necessary to assume that for alkali metals the valence electron band overlaps with the upper core electrons, which increases the valence electron count under compression.

  10. Electronic structure and optical properties of metal doped tetraphenylporphyrins

    Shah, Esha V.; Roy, Debesh R.

    2018-05-01

    A density functional scrutiny on the structure, electronic and optical properties of metal doped tetraphenylporphyrins MTPP (M=Fe, Co, Ni) is performed. The structural stability of the molecules is evaluated based on the electronic parameters like HOMO-LUMO gap (HLG), chemical hardness (η) and binding energy of the central metal atom to the molecular frame etc. The computed UltraViolet-Visible (UV-Vis) optical absorption spectra for all the compounds are also compared. The molecular structures reported are the lowest energy configurations. The entire calculations are carried out with a widely reliable functional, viz. B3LYP with a popular basis set which includes a scaler relativistic effect, viz. LANL2DZ.

  11. Electronic structure of vacancies and vacancy clusters in simple metals

    Manninen, M.; Nieminen, R.M.

    1978-05-01

    The self-consistent density functional approach has been applied in a study of electronic properties of vacancies and vacancy clusters in simple metals. The electron density profiles and potentials have been obtained for spherical voids of varying size. The formation energies and residual resistivities have been calculated for vacancies using both perturbational and variational inclusion of discrete lattice effects. The relation of the void properties to the plane surface ones is studied, and the inadequacy of the jellium-based methods to high-index faces is demonstrated. (author)

  12. Runaway electron beam control for longitudinally pumped metal vapor lasers

    Kolbychev, G. V.; Kolbycheva, P. D.

    1995-08-01

    Physics and techniques for producing of the pulsed runaway electron beams are considered. The main obstacle for increasing electron energies in the beams is revealed to be a self- breakdown of the e-gun's gas-filled diode. Two methods to suppress the self-breakdown and enhance the volumetric discharge producing the e-beam are offered and examined. Each of them provides 1.5 fold increase of the ceiling potential on the gun. The methods also give the ways to control several guns simultaneously. Resulting in the possibility of realizing the powerful longitudinal pumping of metal-vapor lasers on self-terminated transitions of atoms or ions.

  13. Metal-nanoparticle single-electron transistors fabricated using electromigration

    Bolotin, K I; Kuemmeth, Ferdinand; Pasupathy, A N

    2004-01-01

    We have fabricated single-electron transistors from individual metal nanoparticles using a geometry that provides improved coupling between the particle and the gate electrode. This is accomplished by incorporating a nanoparticle into a gap created between two electrodes using electromigration, all...... on top of an oxidized aluminum gate. We achieve sufficient gate coupling to access more than ten charge states of individual gold nanoparticles (5–15 nm in diameter). The devices are sufficiently stable to permit spectroscopic studies of the electron-in-a-box level spectra within the nanoparticle as its...

  14. Size-dependent electronic properties of metal nanostructures

    Table of contents. Size-dependent electronic properties of metal nanostructures · Slide 2 · Slide 3 · Slide 4 · Slide 5 · Slide 6 · Slide 7 · Slide 8 · Slide 9 · Slide 10 · Slide 11 · Slide 12 · Slide 13 · Slide 14 · Slide 15 · Slide 16 · Slide 17 · Slide 18 · Slide 19 · Nanocrystalline film at liquid-liquid interface · Slide 21 · Slide 22.

  15. Proton location in metal hydrides using electron spin resonance

    Venturini, E.L.

    1979-01-01

    Electron spin resonance (ESR) of dilute paramagnetic ions establishes the site symmetry of these ions. In the case of metal hydrides the site symmetry is determined by the number and location of neighboring protons. Typical ESR spectra for trivalent erbium in scandium and yttrium hydrides are presented and analyzed, and this technique is shown to be a versatile microscopic probe of the location, net charge and occupation probability of nearby protons

  16. Stopping power of degenerate electron liquid at metallic densities

    Tanaka, Shigenori; Ichimaru, Setsuo

    1985-01-01

    We calculate the stopping power of the degenerate electron liquid at metallic densities in the dielectric formalism. The strong Coulomb-coupling effects beyond the random-phase approximation are taken into account through the static and dynamic local-field corrections. It is shown that those strong-coupling and dynamic effects act to enhance the stopping power substantially in the low-velocity regime, leading to an improved agreement with experimental data. (author)

  17. Polymer-metal hybrid transparent electrodes for flexible electronics

    Kang, Hongkyu; Jung, Suhyun; Jeong, Soyeong; Kim, Geunjin; Lee, Kwanghee

    2015-03-01

    Despite nearly two decades of research, the absence of ideal flexible and transparent electrodes has been the largest obstacle in realizing flexible and printable electronics for future technologies. Here we report the fabrication of ‘polymer-metal hybrid electrodes’ with high-performance properties, including a bending radius 95% and a sheet resistance solar cells that exhibit a high power conversion efficiency of 10% and polymer light-emitting diodes that can outperform those based on transparent conducting oxides.

  18. Electronic spectral study of interaction of electron donor – acceptor dyes in the ground and excited state with a metal ion. Effect of molecular structure of the dye

    Sardar, Sanjib Kr; Mandal, Prasun K.; Bagchi, Sanjib

    2014-01-01

    Interaction of manganese (II) ion with electron donor (D)–acceptor (A) dyes having symmetric D–A–D configuration of chromophores (ketocyanine dye) and the corresponding parent merocyanines (D–A configuration) in acetonitrile has been compared by monitoring the electronic absorption, and steady state and time resolved fluorescence characteristics of the dyes. Absorption spectral studies point to the formation of a 1:1 metal ion–dye (S 0 -state) complex. Equilibrium constant (K 0 ) and other thermodynamic parameters for complex formation have been determined for all the systems. Symmetric ketocyanine dyes (D–A–D) form stronger complex than the corresponding dye with D–A configuration. Quenching of fluorescence is caused due to complex formation with the cation. However, for very low concentration of salts, where complex formation is insignificant, an enhancement of fluorescence intensity takes place due to addition of salt. The absorption band of the dye undergoes a slight blue shift in the same concentration range of the metal ion. Fluorescence life time of the excited state also increases with an increase in salt concentration in that concentration range. Results have been explained in terms of formation of a weak association complex where one or more cations replace equivalent solvent molecules in the cybotatic region around the dye. The binding constant of the association complex involving cation and the dye (S 1 -state) has been determined. While the value of the binding constant is higher for a symmetric D–A–D dye relative to that for the corresponding dye with D–A configuration, the extent of fluorescence enhancement for the latter is larger. Values of decay constant for the different photophysical processes have been calculated. Formation of association complex in the S 1 -state is characterised by a slower nonradiative decay of S 1 -state of the dyes. -- Highlights: • A ketocyanine dye forms 1:1 complex with metal ions. • Slight

  19. Uranyl and/or rare-earth mellitates in extended organic-inorganic networks: A unique case of hetero-metallic cation-cation interaction with U-VI=O-Ln(III) bonding (Ln = Ce, Nd)

    Volkringer, Christophe; Henry, Natacha; Grandjean, Stephane; Loiseau, Thierry

    2012-01-01

    A series of uranyl and lanthanide (trivalent Ce, Nd) mellitates (mel) has been hydrothermally synthesized in aqueous solvent. Mixtures of these 4f and 5f elements also revealed the formation of a rare case of lanthanide-uranyl coordination polymers. Their structures, determined by XRD single-crystal analysis, exhibit three distinct architectures. The pure lanthanide mellitate Ln 2 (H 2 O) 6 (mel) possesses a 3D framework built up from the connection of isolated LnO 6 (H 2 O) 3 polyhedra (tri-capped trigonal prism) through the mellitate ligand. The structure of the uranyl mellitate (UO 2 ) 3 (H 2 O) 6 - (mel).11.5H 2 O is lamellar and consists of 8-fold coordinated uranium atoms linked to each other through the organic ligand giving rise to the formation of a 2D 3 6 net. The third structural type, (UO 2 ) 2 Ln(OH)(H 2 O) 3 (mel).2.5H 2 O, involves direct oxygen bondings between the lanthanide and uranyl centers, with the isolation of a hetero-metallic dinuclear motif. The 9-fold coordinated Ln cation, LnO 5 (OH)(H 2 O) 3 , is linked to the 7-fold coordinated uranyl (UO 2 )O-4(OH) (pentagonal bipyramid) via one μ 2 -hydroxo group and one μ 2 -oxo group. The latter is shared between the uranyl bonding (U=O = 1.777(4)1.779(6) angstrom) and a long Ln-O bonding (Ce-O = 2.822(4) angstrom; Nd-O = 2.792(6) angstrom). This unusual linkage is a unique illustration of the so-called cation cation interaction associating 4f and 5f metals. The dinuclear motif is then further connected through the mellitate ligand, and this generates organic inorganic layers that are linked to each other via discrete uranyl (UO 2 )O 4 units (square bipyramid), which ensure the three-dimensional cohesion of the structure. The mixed U-Ln carboxylate is thermally decomposed from 260 to 280 degrees C and then transformed into the basic uranium oxide (U 3 O 8 ) together with U-Ln oxide with the fluorite structural type ('(Ln,U)O 2 '). At 1400 degrees C, only fluorite type '(Ln,U)O 2 ' is formed with

  20. Films made of cellulose nanofibrils: surface modification by adsorption of a cationic surfactant and characterization by computer-assisted electron microscopy

    Syverud, K.; Xhanari, K.; Chinga-Carrasco, G.; Yu, Y.; Stenius, P.

    2011-01-01

    Films made of nanofibrils were modified by adsorption of a cationic surfactant directly on the film surfaces. The nanofibrils were prepared by 2,2,6,6-tetramethylpiperidinyl-1-oxyl (TEMPO)-mediated oxidation and mechanical fibrillation, and were relatively homogeneous in size. The average nanofibril diameter and surface porosity was quantified based on computer-assisted field-emission scanning electron microscopy (FE-SEM). The cationic surfactant used in the adsorption was n-hexadecyl trimethylammonium bromide (cetyltrimethylammonium bromide, CTAB). The adsorption of CTAB was confirmed by Fourier transform infrared (FTIR) spectroscopy and high-resolution transmission electron microscopy (HRTEM) analyses. It was shown that the adsorbed layer of CTAB increased the hydrophobicity, without affecting the tensile index significantly. This capability, combined with the antiseptic properties of CTAB, may be a major advantage for several applications.

  1. Electronic specific heats in metal--hydrogen systems

    Flotow, H.E.

    1979-01-01

    The electronic specific heats of metals and metal--hydrogen systems can in many cases be evaluated from the measured specific heats at constant pressure, C/sub p/, in the temperature range 1 to 10 K. For the simplest case, C/sub p/ = γT + βT 3 , where γT represents the specific heat contribution associated with the conduction electrons, and βT 3 represents lattice specific heat contribution. The electronic specific heat coefficient, γ, is important because it is proportional to electron density of states at the Fermi surface. A short description of a low temperature calorimetric cryostat employing a 3 He/ 4 He dilution refrigeration is given. Various considerations and complications encountered in the evaluation of γ from specific heat data are discussed. Finally, the experimental values of γ for the V--Cr--H system and for the Lu--H system are summarized and the variations of γ as function of alloy composition are discussed

  2. Effect of the cationic composition of sorption solution on the quantification of sorption-desorption parameters of heavy metals in soils

    Sastre, J.; Rauret, G.; Vidal, M.

    2006-01-01

    We obtained the sorption isotherms of Cd, Cu, Pb and Zn in clay, clay saline and organic soils. The distribution coefficients (K d ) were determined in 0.02 eq l -1 CaCl 2 and in a solution that simulated the soil solution cationic composition. The K d values greatly varied with the composition of the sorption solution and the initial metal concentration. The sorption experiments were complemented with the quantification of the extractable metal, to estimate the reversibility of metal sorption. The extraction yields depended on the metal-soil combination, and the initial metal concentration, showing no correlation with previous K d values. The effect of the solution composition in mobility predictions was estimated through a Retention Factor, defined as the ratio of the K d versus the extraction yield. Results showed that risk was over- or underestimated using the CaCl 2 medium in soils with a markedly different soil solution composition. - Sorption solution composition modifies metal sorption-desorption pattern in soils

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

    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.

  4. About the free electron model in electric conduction of metals

    Hoffmann, C.

    1991-01-01

    In the model proposed by Drude to describe, among others, the electric conduction in metals, it is supposed that electrons move freely in the material with a time interval between encounters T and a probability distribution g(t). The name, 'electron pause time', will be assigned to the time T with that probability distribution. The calculations made by Drude turned out to be erroneous. The error can be corrected observing that the random variable 'pause time' appearing in this intuitive idea is not the previously defined random variable T, 'electron pause time', but another random variable S, which will be called 'observed pause time' whose probability density is Csg(s), where C is a normalization constant. With this distribution, the characteristics of the distribution, q(u), of the wait time can be obtained. (Author) [es

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

    Carlsson, A.E.

    1992-01-01

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

  6. Accuracy of the DLPNO-CCSD(T) method for non-covalent bond dissociation enthalpies from coinage metal cation complexes

    Minenkov, Yury; Chermak, Edrisse; Cavallo, Luigi

    2015-01-01

    The performance of the domain based local pair-natural orbital coupled-cluster (DLPNO-CCSD(T)) method has been tested to reproduce the experimental gas phase ligand dissociation enthalpy in a series of Cu+, Ag+ and Au+ complexes. For 33 Cu+ - non-covalent ligand dissociation enthalpies all-electron calculations with the same method result in MUE below 2.2 kcal/mol, although a MSE of 1.4 kcal/mol indicates systematic underestimation of the experimental values. Inclusion of scalar relativistic effects for Cu either via effective core potential (ECP) or Douglass-Kroll-Hess Hamiltonian, reduces the MUE below 1.7 kcal/mol and the MSE to -1.0 kcal/mol. For 24 Ag+ - non-covalent ligand dissociation enthalpies the DLPNO-CCSD(T) method results in a mean unsigned error (MUE) below 2.1 kcal/mol and vanishing mean signed error (MSE). For 15 Au+ - non-covalent ligand dissociation enthalpies the DLPNO-CCSD(T) methods provides larger MUE and MSE, equal to 3.2 and 1.7 kcal/mol, which might be related to poor precision of the experimental measurements. Overall, for the combined dataset of 72 coinage metal ion complexes DLPNO-CCSD(T) results in a MUE below 2.2 kcal/mol and an almost vanishing MSE. As for a comparison with computationally cheaper density functional theory (DFT) methods, the routinely used M06 functional results in MUE and MSE equal to 3.6 and -1.7 kca/mol. Results converge already at CC-PVTZ quality basis set, making highly accurate DLPNO-CCSD(T) estimates to be affordable for routine calculations (single-point) on large transition metal complexes of > 100 atoms.

  7. Accuracy of the DLPNO-CCSD(T) method for non-covalent bond dissociation enthalpies from coinage metal cation complexes

    Minenkov, Yury

    2015-08-27

    The performance of the domain based local pair-natural orbital coupled-cluster (DLPNO-CCSD(T)) method has been tested to reproduce the experimental gas phase ligand dissociation enthalpy in a series of Cu+, Ag+ and Au+ complexes. For 33 Cu+ - non-covalent ligand dissociation enthalpies all-electron calculations with the same method result in MUE below 2.2 kcal/mol, although a MSE of 1.4 kcal/mol indicates systematic underestimation of the experimental values. Inclusion of scalar relativistic effects for Cu either via effective core potential (ECP) or Douglass-Kroll-Hess Hamiltonian, reduces the MUE below 1.7 kcal/mol and the MSE to -1.0 kcal/mol. For 24 Ag+ - non-covalent ligand dissociation enthalpies the DLPNO-CCSD(T) method results in a mean unsigned error (MUE) below 2.1 kcal/mol and vanishing mean signed error (MSE). For 15 Au+ - non-covalent ligand dissociation enthalpies the DLPNO-CCSD(T) methods provides larger MUE and MSE, equal to 3.2 and 1.7 kcal/mol, which might be related to poor precision of the experimental measurements. Overall, for the combined dataset of 72 coinage metal ion complexes DLPNO-CCSD(T) results in a MUE below 2.2 kcal/mol and an almost vanishing MSE. As for a comparison with computationally cheaper density functional theory (DFT) methods, the routinely used M06 functional results in MUE and MSE equal to 3.6 and -1.7 kca/mol. Results converge already at CC-PVTZ quality basis set, making highly accurate DLPNO-CCSD(T) estimates to be affordable for routine calculations (single-point) on large transition metal complexes of > 100 atoms.

  8. Movement of metal cations through the soil to the plant root membrane. Final technical report, June 1, 1966--November 30, 1978

    Barber, S.A.

    1978-11-01

    This project concerns metal cation flux through the soil and into the plant. Some highlights resulting from this research are as follows. Effect of soil properties on relative adsorption of Ca, Sr, K, Rb, and Cs by soil was measured. A theoretically developed concept explained differences between Ca and Sr adsorption on inorganic and organic exchange sites. A convenient method was developed to characterize cation absorption kinetics of intact plant roots. Use of this method showed genotypic variation in effect of ion concentration on influx. Corn absorbed Ca and Sr and K and Rb indiscriminantly. A method, using Ca/Sr and K/Rb ratio of ion influx into the plant, was developed to determine the source of these ions absorbed from the soil. Uptake of these ions from soil by corn was in the ratio on exchange sites rather than that in solution. The method was also used to compare uptake of chelated with ionized cations. A simulation model was developed that described ion flux from the soil into the plant. Ten independently measured soil and plant parameters were used. A computer program was prepared to calculate uptake with time. The model was verified in both growth chamber and field experiments

  9. Use of Electro-spray Ionization Mass Spectrometry (ESI-MS) for the characterization of complexes 'ligand - metallic cations' in solution

    Berthon, Laurence; Zorz, Nicole; Lagrave, Stephanie; Gannaz, Benoit; Hill, Clement [CEA-Marcoule DEN-DRCP-SCPS-LCSE, BP 17171, 30207 Bagnols sur Ceze cedex (France)

    2008-07-01

    In the framework of nuclear waste reprocessing, separation processes of minor actinides from fission products are developed by Cea. In order to understand the mechanisms involved in the extraction processes, the 'ligand/metallic cation' complexes, formed in the organic phases are characterized by electro-spray-mass-spectrometry (ESI-MS). This paper deals with the extraction of lanthanides (III) and americium (III) cations by an organic phase composed of a malonamide or / and a dialkyl phosphoric acid, diluted in an aliphatic diluent. For the dialkyl phosphoric acid, Ln(DEHP){sub 3}(HDEHP){sub 3} complexes are observed and in the presence of a large excess of Ln(NO{sub 3}){sub 3}, dinuclear species are also observed. For the malonamide extractant, it appears that the complexes formed in the organic phase are of the Nd(NO{sub 3}){sub 3}D{sub x} type, with 2 {<=} x {<=} 4: their distributions depend on the ratio [Ln]/[DMDOHEMA]. When the two extractants are present in the organic phase, mixed 'Ln-malonamide-dialkyl phosphoric acid' species are observed. The influence of several parameters, such as extractant concentration, solute concentration, aqueous acidity and the nature of the cations (lanthanides or americium) are studied. (authors)

  10. Enhanced Electron-Phonon Coupling at Metal Surfaces

    Plummer, Ward E.

    2010-08-04

    The Born-Oppenheimer approximation (BOA) decouples electronic from nuclear motion, providing a focal point for most quantum mechanics textbooks. However, a multitude of important chemical, physical and biological phenomena are driven by violations of this approximation. Vibronic interactions are a necessary ingredient in any process that makes or breaks a covalent bond, for example, conventional catalysis or enzymatically delivered biological reactions. Metastable phenomena associated with defects and dopants in semiconductors, oxides, and glasses entail violation of the BOA. Charge exchange in inorganic polymers, organic slats and biological systems involves charge- induced distortions of the local structure. A classic example is conventional superconductivity, which is driven by the electron-lattice interaction. High-resolution angle-resolved photoemission experiments are yielding new insight into the microscopic origin of electron-phonon coupling (EPC) in anisotropic two-dimensional systems. Our recent surface phonon measurement on the surface of a high-Tc material clearly indicates an important momentum dependent EPC in these materials. In the last few years we have shifted our research focus from solely looking at electron phonon coupling to examining the structure/functionality relationship at the surface of complex transition metal compounds. The investigation on electron phonon coupling has allowed us to move to systems where there is coupling between the lattice, the electrons and the spin.

  11. Electron confinement in thin metal films. Structure, morphology and interactions

    Dil, J.H.

    2006-05-15

    This thesis investigates the interplay between reduced dimensionality, electronic structure, and interface effects in ultrathin metal layers (Pb, In, Al) on a variety of substrates (Si, Cu, graphite). These layers can be grown with such a perfection that electron confinement in the direction normal to the film leads to the occurrence of quantum well states in their valence bands. These quantum well states are studied in detail, and their behaviour with film thickness, on different substrates, and other parameters of growth are used here to characterise a variety of physical properties of such nanoscale systems. The sections of the thesis deal with a determination of quantum well state energies for a large data set on different systems, the interplay between film morphology and electronic structure, and the influence of substrate electronic structure on their band shape; finally, new ground is broken by demonstrating electron localization and correlation effects, and the possibility to measure the influence of electron-phonon coupling in bulk bands. (orig.)

  12. Low-energy electron collisions with metal clusters: Electron capture and cluster fragmentation

    Kresin, V.V.; Scheidemann, A.; Knight, W.D.

    1993-01-01

    The authors have carried out the first measurement of absolute cross sections for the interaction between electrons and size-resolved free metal clusters. Integral inelastic scattering cross sections have been determined for electron-Na n cluster collisions in the energy range from 0.1 eV to 30 eV. At energies ≤1 eV, cross sections increase with decreasing impact energies, while at higher energies they remain essentially constant. The dominant processes are electron attachment in the low-energy range, and collision-induced fragmentation at higher energies. The magnitude of electron capture cross sections can be quantitatively explained by the effect of the strong polarization field induced in the cluster by the incident electron. The cross sections are very large, reaching values of hundreds of angstrom 2 ; this is due to the highly polarizable nature of metal clusters. The inelastic interaction range for fragmentation collisions is also found to considerably exceed the cluster radius, again reflecting the long-range character of electron-cluster interactions. The important role played by the polarization interaction represents a bridge between the study of collision processes and the extensive research on cluster response properties. Furthermore, insight into the mechanisms of electron scattering is important for understanding production and detection of cluster ions in mass spectrometry and related processes

  13. Electrorecycling of Critical and Value Metals from Mobile Electronics

    Lister, Tedd E.; Wang, Peming; Anderko, Andre

    2014-09-01

    Mobile electronic devices such as smart phones and tablets are a significant source of valuable metals that should be recycled. Each year over a billion devices are sold world-wide and the average life is only a couple years. Value metals in phones are gold, palladium, silver, copper, cobalt and nickel. Devices now contain increasing amounts of rare earth elements (REE). In recent years the supply chain for REE has moved almost exclusively to China. They are contained in displays, speakers and vibrators within the devices. By US Department of Energy (DOE) classification, specific REEs (Nd, Dy, Eu, Tb and Y) are considered critical while others (Ce, La and Pr) are deemed near critical. Effective recycling schemes should include the recovery of these critical materials. By including more value materials in a recovery scheme, more value can be obtained by product diversification and less waste metals remains to be disposed of. REEs are mined as a group such that when specific elements become critical significantly more ore must be processed to capture the dilute but valuable critical elements. Targeted recycling of items containing the more of the less available critical materials could address their future criticality. This presentation will describe work in developing aqueous electrochemistry-based schemes for recycling metals from scrap mobile electronics. The electrorecycling process generates oxidizing agents at an anode while reducing dissolved metals at the cathode. E vs pH diagrams and metals dissolution experiments are used to assess effectiveness of various solution chemistries. Although several schemes were envisioned, a two stages process has been the focus of work: 1) initial dissolution of Cu, Sn, Ag and magnet materials using Fe+3 generated in acidic sulfate and 2) final dissolution of Pd and Au using Cl2 generated in an HCl solution. Experiments were performed using simulated metal mixtures. Both Cu and Ag were recovered at ~ 97% using Fe+3 while

  14. Angular distribution of scattered electron and medium energy electron spectroscopy for metals

    Oguri, Takeo; Ishioka, Hisamichi; Fukuda, Hisashi; Irako, Mitsuhiro

    1986-01-01

    The angular distribution (AD) of scattered electrons produced by medium energy incident electrons (E P = 50 ∼ 300 eV) from polycrystalline Ti, Fe, Ni, Cu and Au were obtained by the angle-resolved medium energy electron spectrometer. The AD of the energy loss peaks are similar figures to AD of the elastically reflected electron peaks. Therefore, the exchanged electrons produced by the knock-on collision between the incident electrons and those of metals without momentum transfer are observed as the energy loss spectra (ELS). This interpretation differs from the inconsequent interpretation by the dielectric theory or the interband transition. The information depth and penetration length are obtained from AD of the Auger electron peaks. The contribution of the surface to spectra is 3 % at the maximum for E P = 50 eV. The true secondary peaks representing the secondary electron emission spectroscopy (SES) are caused by the emissions of the energetic electrons (kT e ≥ 4 eV), and SES is the inversion of ELS. The established fundamental view is that the medium energy electron spectra represent the total bulk density of states. (author)

  15. Effects of the spaces available for cations in strongly acidic cation-exchange resins on the exchange equilibria by quaternary ammonium ions and on the hydration states of metal ions.

    Watanabe, Yuuya; Ohnaka, Kenji; Fujita, Saki; Kishi, Midori; Yuchi, Akio

    2011-10-01

    The spaces (voids) available for cations in the five exchange resins with varying exchange capacities and cross-linking degrees were estimated, on the basis of the additivity of molar volumes of the constituents. Tetraalkylammonium ions (NR(4)(+); R: Me, Et, Pr) may completely exchange potassium ion on the resin having a larger void radius. In contrast, the ratio of saturated adsorption capacity to exchange capacity of the resin having a smaller void radius decreased with an increase in size of NR(4)(+) ions, due to the interionic contacts. Alkali metal ions could be exchanged quantitatively. While the hydration numbers of K(+), Rb(+), and Cs(+) were independent of the void radius, those of Li(+) and Na(+), especially Na(+), decreased with a decrease in void radius. Interionic contacts between the hydrated ions enhance the dehydration. Multivalent metal ions have the hydration numbers, comparable to or rather greater than those in water. A greater void volume available due to exchange stoichiometry released the interionic contacts and occasionally promoted the involvement of water molecules other than directly bound molecules. The close proximity between ions in the conventional ion-exchange resins having higher exchange capacities may induce varying interactions.

  16. Contribution to a research on electron beam welding of metals

    Stohr, J.

    1964-03-01

    The electron beam welding of metals is performed by the travelling of the focusing point along the junction of two pieces to be connected. Welding parameters are the electron gun power W, the value of the electron impact surface S, the welding speed s. From the beginning of our research in 1954, the preponderant part played by specific power W/s on the shape of the welded zone and the penetrating depth, became evident. A more methodical research has been undertaken in the laboratories of C.E.N. under the patronage of Professor CHAUDRON, in order to define in a better way the importance of the different welding parameters and to determine their influence on the metallurgical qualities of welded assemblies. This research induced us to define an electron gun adapted as well as possible to the performance of weldings, not only from the point of view of behaviour, especially during the passage from the atmospheric to a low pressure at 10 -5 Torr, necessary for the carrying out of a welding, but also from the point of view of adjustment conveniences of the different welding parameters, indispensable to the intended research work. The variations of welding parameters show that the shape of the molten zone turns from a circle segment to that of a very high triangle, which implies a continual change of the mode of heat transmission. Tests have been made, in order to confirm this way of looking, especially in order to achieve isotherms in dynamic operating and also the comparison of these isotherms with that recorded while using a method of argon arc welding. The thermal balance of energy supplied to the part, the necessary welding energy, and the energy loss (through conduction, radiation and evaporation) has also been established. These results proved that almost the whole of energy has been used for melting, that the different losses are negligible and that heat transmission can not occur by thermal conduction through the part during 'welding' time, when operating under

  17. An electron microscopy appraisal of tensile fracture in metallic glasses

    Matthews, D.T.A.; Ocelik, V.; Bronsveld, P.M.; De Hosson, J.Th.M.

    2008-01-01

    Three glass-forming alloy compositions were chosen for ribbon production and subsequent electron microscopy studies. In situ tensile testing with transmission electron microscopy (TEM), followed by ex situ TEM and ex situ scanning electron microscopy (SEM), allowed the deformation processes in tensile fracture of metallic glasses to be analysed. In situ shear band propagation was found to be jump-like, with the jump sites correlating with the formation of secondary shear bands. The effect of structural relaxation by in situ heating is also discussed. Nanocrystallization near the fracture surface was observed; however, no crystallization was also reported in the same sample and the reasons for this are discussed. Both the TEM and the SEM observations confirmed the presence of a liquid-like layer on or near the fracture surface of the ribbons. The formation of a liquid-like layer was characterized by the vein geometries and vein densities on the fracture surfaces and its dependence on shear displacement, δ, is discussed. A simple model is adapted to relate the temperature rise during shear banding to the glass transition and melting temperatures and this is used to explain the variety of fracture surfaces which are developed for macroscopically identical tensile testing of metallic glasses together with features which exhibit local melting

  18. Electron and nuclear magnetic resonances in compounds and metallic hydrides

    Brasil Filho, N.

    1985-11-01

    Proton pulsed Nuclear Magnetic Resonance measurements were performed on the metallic hydrides ZrCr 2 H x (x = 2, 3, 4) and ZrV 2 H y (y = 2, 3, 4, 5) as a function of temperature between 180 and 400K. The ultimate aim was the investigation of the relaxation mechanisms in these systems by means of the measurement of both the proton ( 1 H) spin-lattice (T 1 ) and spin-spin (T 2 ) relaxation times and to use these data to obtain information about the diffusive motion of the hydrogen atoms. The diffusional activation energies, the jump frequencies and the Korringa constant, C k , related with the conduction electron contribution to the 1 H relaxation were determined for the above hydrides as a function of hydrogen concentration. Our results were analysed in terms of the relaxation models described by Bloembergen, Purcell and Pound (BPP model) and by Torrey. The Korringa type relaxation due to the conduction electrons in metallic systems was also used to interpret the experimental results. We also present the Electron Paramagnetic Ressonance (EPR) study of Gd 3+ , Nd 3+ and Er 3+ ions as impurities in several AB 3 intermetallic compounds where A = LA, Ce, Y, Sc, Th, Zr and B = Rh, Ir, Pt. The results were analysed in terms of the multiband model previously suggested to explain the behaviour of the resonance parameter in AB 2 Laves Phase compounds. (author) [pt

  19. The effect of specific solvent-solute interactions on complexation of alkali-metal cations by a lower-rim calix[4]arene amide derivative.

    Horvat, Gordan; Stilinović, Vladimir; Kaitner, Branko; Frkanec, Leo; Tomišić, Vladislav

    2013-11-04

    Complexation of alkali-metal cations with calix[4]arene secondary-amide derivative, 5,11,17,23-tetra(tert-butyl)-25,26,27,28-tetra(N-hexylcarbamoylmethoxy)calix[4]arene (L), in benzonitrile (PhCN) and methanol (MeOH) was studied by means of microcalorimetry, UV and NMR spectroscopies, and in the solid state by X-ray crystallography. The inclusion of solvent molecules (including acetonitrile, MeCN) in the calixarene hydrophobic cavity was also investigated. The classical molecular dynamics (MD) simulations of the systems studied were carried out. By combining the results obtained using the mentioned experimental and computational techniques, an attempt was made to get an as detailed insight into the complexation reactions as possible. The thermodynamic parameters, that is, equilibrium constants, reaction Gibbs energies, enthalpies, and entropies, of the investigated processes were determined and discussed. The stability constants of the 1:1 (metal:ligand) complexes measured by different methods were in very good agreement. Solution Gibbs energies of the ligand and its complexes with Na(+) and K(+) in methanol and acetonitrile were determined. It was established that from the thermodynamic point of view, apart from cation solvation, the most important reason for the huge difference in the stability of these complexes in the two solvents lay in the fact that the transfer of complex species from MeOH to MeCN was quite favorable. That could be at least partly explained by a more exergonic inclusion of the solvent molecule in the complexed calixarene cone in MeCN as compared to MeOH, which was supported by MD simulations. Molecular and crystal structures of the lithium cation complex of L with the benzonitrile molecule bound in the hydrophobic calixarene cavity were determined by single-crystal X-ray diffraction. As far as we are aware, for the first time the alkali-metal cation was found to be coordinated by the solvent nitrile group in a calixarene adduct. According to

  20. Silicon-based metallic micro grid for electron field emission

    Kim, Jaehong; Jeon, Seok-Gy; Kim, Jung-Il; Kim, Geun-Ju; Heo, Duchang; Shin, Dong Hoon; Sun, Yuning; Lee, Cheol Jin

    2012-01-01

    A micro-scale metal grid based on a silicon frame for application to electron field emission devices is introduced and experimentally demonstrated. A silicon lattice containing aperture holes with an area of 80 × 80 µm 2 and a thickness of 10 µm is precisely manufactured by dry etching the silicon on one side of a double-polished silicon wafer and by wet etching the opposite side. Because a silicon lattice is more rigid than a pure metal lattice, a thin layer of Au/Ti deposited on the silicon lattice for voltage application can be more resistant to the geometric stress caused by the applied electric field. The micro-fabrication process, the images of the fabricated grid with 88% geometric transparency and the surface profile measurement after thermal feasibility testing up to 700 °C are presented. (paper)

  1. The ion-electron correlation function in liquid metals

    Takeda, S.; Tamaki, S.; Waseda, Y.

    1985-01-01

    The structure factors of liquid Zn at 723 K, Sn at 523 K and Bi at 573 K have been determined by neutron diffraction with sufficient accuracy and compared with those of X-ray diffraction. A remarkable difference in the structural information between the two methods is clearly found around the first peak region as well as in the slightly varied peak positions, and it is apparently larger than the experimental errors. With these facts in mind, a new method evaluating the ion-electron correlation function in liquid metals has been proposed by using the measured structural data of X-rays and neutrons, with the help of theoretical values of the electron-electron correlation function by he Utsumi-Ichimaru scheme. This method has been applied to liquid Zn, Sn and Bi, and the radial distribution function of valence electrons around an ion has been estimated, from which the ionic radius and the schematic diagram of the electron distribution map are obtained. The ionic radii evaluated in this work have been found to agree well with those proposed by Pauling. (author)

  2. Conception and synthesis of new molecular platforms based on cryptophanes. Application for the encapsulation of xenon and metallic cations in aqueous solution

    Chapellet, Laure-Lise

    2015-01-01

    Cryptophanes are molecular receptors known for their complexation properties of various substrates. Over the last fifteen years, cryptophanes were the subject of numerous studies for they can be used to obtain biosensors for xenon MRI. This field has experienced significant growth and advances to the point were in vivo applications are now envisioned, provided that large amounts of biosensors can be synthesized. More recently, polyphenolic cryptophanes have been studied for their ability to encapsulate monovalent metallic cations like Cs"+ and Tl"+ in aqueous solution. This could lead to applications for depollution of contaminated water sources but would require, once again, the synthesis of large amounts of cryptophanes.The work carried out during this thesis focus on the conception and the synthesis of new molecular platforms that could either be used to obtain new hyper-polarized xenon biosensors or to encapsulate monovalent metallic cations as Cs"+ and Tl"+. Synthetic routes have been developed to produce good amounts of a variety of new hydrosoluble molecular platforms designed for each application. The encapsulation properties of these new host molecules were studied through NMR of the encapsulated nucleus, circular dichroism or isothermal calorimetry. In each case, the new platforms meet the expected requirements thus opening the door for the envisioned applications. (author)

  3. Thermohydraulic behavior of liquid metal pool submitted to electronic bombardment

    Brun, Patrice

    1998-01-01

    This thesis deals with the thermohydraulics of liquid metal molten by an electron beam. We study the relationship between the liquid metal pool and the vapor rate. The aim is to find good conditions increasing the metal vapor rate. In first place, energy losses are identified. Mains are convection (buoyancy and thermo-capillary) strengthen by the deformation of the molten pool. The first action is to reduce the liquid interface deformation with a transient spot realized by scanning the electron beam. I find that in this case, the optimum vapor rate is obtained when the crossing time of the beam is smaller than characteristic time of formation of the cavity, but greater than the heating time of the surface. Secondly, I impose forces to change the morphology of the flow. Two actions are tried: magnetic field application and rotating motion of the crucible. External magnetic field application may reduce convective flow, by the creation of a magnetic brake. But in my experiment, magnetic field deteriorates electron beam before to be effective. Results obtained by the rotating motion of the crucible approve this choice to reduce energy losses and increase vapor rate. This growth of vapor rate is due to an expansion of the emitted vapor source and an increase of the central temperature of the molten pool. Nevertheless with the increase of the rotation velocity and after the optimum vapor rate, I note that the flow is not axisymmetric. My observation give to think about instabilities that are developed by baroclinic waves. The comparison of my works with the Eady's linear theory gives good results. (author) [fr

  4. Exchange energy of inhomogenous electron gas near a metal surface

    Miglio, L.; Tosi, M.P.; March, N.H.

    1980-12-01

    Using the first-order density matrix of an infinite-barrier model of a metal surface, the exchange energy density can be evaluated exactly as a function of distance z from the barrier. This result is compared with the local approximation -3/4e 2 (3/π)sup(1/3) rhosup(4/3)(z) where rho is the electron density in the model. The local approximation is demonstrated to be quantitatively accurate at all z. The integrated surface exchange energy is given to within 3% by the local theory. (author)

  5. Metallomics for Alzheimer's disease treatment: Use of new generation of chelators combining metal-cation binding and transport properties.

    D'Acunto, Cosimo Walter; Kaplánek, Robert; Gbelcová, Helena; Kejík, Zdeněk; Bříza, Tomáš; Vasina, Liudmila; Havlík, Martin; Ruml, Tomáš; Král, Vladimír

    2018-04-25

    Alzheimer's disease (AD) is a progressive neurodegenerative disorder affecting tens of million people. Currently marketed drugs have limited therapeutic efficacy and only slowing down the neurodegenerative process. Interestingly, it has been suggested that biometal cations in the amyloid beta (Aβ) aggregate deposits contribute to neurotoxicity and degenerative changes in AD. Thus, chelation therapy could represent novel mode of therapeutic intervention. Here we describe the features of chelators with therapeutically relevant mechanism of action. We have found that the tested compounds effectively reduce the toxicity of exogenous Aβ and suppress its endogenous production as well as decrease oxidative stress. Cholyl hydrazones were found to be the most active compounds. In summary, our data show that cation complexation, together with improving transport efficacy may represent basis for eventual treatment strategy in AD. Copyright © 2018. Published by Elsevier Masson SAS.

  6. Metal centre effects on HNO binding in porphyrins and the electronic origin: metal's electronic configuration, position in the periodic table, and oxidation state.

    Yang, Liu; Fang, Weihai; Zhang, Yong

    2012-04-21

    HNO binds to many different metals in organometallic and bioinorganic chemistry. To help understand experimentally observed metal centre effects, a quantum chemical investigation was performed, revealing clear general binding trends with respect to metal centre characteristics and the electronic origin for the first time. This journal is © The Royal Society of Chemistry 2012

  7. Electronic nature of zwitterionic alkali metal methanides, silanides and germanides - a combined experimental and computational approach.

    Li, H; Aquino, A J A; Cordes, D B; Hase, W L; Krempner, C

    2017-02-01

    Zwitterionic group 14 complexes of the alkali metals of formula [C(SiMe 2 OCH 2 CH 2 OMe) 3 M], (M- 1 ), [Si(SiMe 2 OCH 2 CH 2 OMe) 3 M], (M- 2 ), [Ge(SiMe 2 OCH 2 CH 2 OMe) 3 M], (M- 3 ), where M = Li, Na or K, have been prepared, structurally characterized and their electronic nature was investigated by computational methods. Zwitterions M- 2 and M- 3 were synthesized via reactions of [Si(SiMe 2 OCH 2 CH 2 OMe) 4 ] ( 2 ) and [Ge(SiMe 2 OCH 2 CH 2 OMe) 4 ] ( 3 ) with MOBu t (M = Li, Na or K), resp., in almost quantitative yields, while M- 1 were prepared from deprotonation of [HC(SiMe 2 OCH 2 CH 2 OMe) 3 ] ( 1 ) with LiBu t , NaCH 2 Ph and KCH 2 Ph, resp. X-ray crystallographic studies and DFT calculations in the gas-phase, including calculations of the NPA charges confirm the zwitterionic nature of these compounds, with the alkali metal cations being rigidly locked and charge separated from the anion by the internal OCH 2 CH 2 OMe donor groups. Natural bond orbital (NBO) analysis and the second order perturbation theory analysis of the NBOs reveal significant hyperconjugative interactions in M- 1 -M- 3 , primarily between the lone pair and the antibonding Si-O orbitals, the extent of which decreases in the order M- 1 > M- 2 > M- 3 . The experimental basicities and the calculated gas-phase basicities of M- 1 -M- 3 reveal the zwitterionic alkali metal methanides M- 1 to be significantly stronger bases than the analogous silanides M- 2 and germanium M- 3 .

  8. Simulated electron affinity tuning in metal-insulator-metal (MIM) diodes

    Mistry, Kissan; Yavuz, Mustafa; Musselman, Kevin P.

    2017-05-01

    Metal-insulator-metal diodes for rectification applications must exhibit high asymmetry, nonlinearity, and responsivity. Traditional methods of improving these figures of merit have consisted of increasing insulator thickness, adding multiple insulator layers, and utilizing a variety of metal contact combinations. However, these methods have come with the price of increasing the diode resistance and ultimately limiting the operating frequency to well below the terahertz regime. In this work, an Airy Function Transfer Matrix simulation method was used to observe the effect of tuning the electron affinity of the insulator as a technique to decrease the diode resistance. It was shown that a small increase in electron affinity can result in a resistance decrease in upwards of five orders of magnitude, corresponding to an increase in operating frequency on the same order. Electron affinity tuning has a minimal effect on the diode figures of merit, where asymmetry improves or remains unaffected and slight decreases in nonlinearity and responsivity are likely to be greatly outweighed by the improved operating frequency of the diode.

  9. The powerful pulsed electron beam effect on the metallic surfaces

    Neklyudov, I.M.; Yuferov, V.B.; Kosik, N.A.; Druj, O.S.; Skibenko, E.I.

    2001-01-01

    Experimental results of the influence of powerful pulsed electron beams on the surface structure,hardness and corrosion resistance of the Cr18ni10ti steel are presented. The experiments were carried out in the powerful electron accelerators of directional effect VGIK-1 and DIN-2K with an energy up to approx 300 KeV and a power density of 10 9 - 10 11 W/cm 2 for micro- and nanosecond range. The essential influence of the irradiation power density on the material structure was established. Pulsed powerful beam action on metallic surface leads to surface melting,modification of the structure and structure-dependent material properties. The gas emission and mass-spectrometer analysis of the beam-surface interaction were defined

  10. Ionic liquid based on α-amino acid anion and N7,N9-dimethylguaninium cation ([dMG][AA]): theoretical study on the structure and electronic properties.

    Shakourian-Fard, Mehdi; Fattahi, Alireza; Bayat, Ahmad

    2012-06-07

    The interactions between five amino acid based anions ([AA](-) (AA = Gly, Phe, His, Try, and Tyr)) and N7,N9-dimethylguaninium cation ([dMG](+)) have been investigated by the hybrid density functional theory method B3LYP together with the basis set 6-311++G(d,p). The calculated interaction energy was found to decrease in magnitude with increasing side-chain length in the amino acid anion. The interaction between the [dMG](+) cation and [AA](-) anion in the most stable configurations of ion pairs is a hydrogen bonding interaction. These hydrogen bonds (H bonds) were analyzed by the quantum theory of atoms in molecules (QTAIM) and natural bond orbital (NBO) analysis. Finally, several correlations between electron densities in bond critical points of hydrogen bonds and interaction energy as well as vibrational frequencies in the most stable configurations of ion pairs have been checked.

  11. Half-metallicity and electronic structures for carbon-doped group III-nitrides: Calculated with a modified Becke-Johnson potential

    Fan, Shuai-wei; Wang, Ri-gao; Xu, Pemg

    2016-09-01

    The electronic structures and magnetism for carbon-doped group III-nitrides are investigated by utilizing the first principle method with the modified Becke-Johnson potential. Calculations show that carbon substituting cations (anions) would induce the group III-nitrides to be paramagnetic metals (half-metallic ferromagnets). Single carbon substituting nitrogen could produce 1.00μB magnetic moment. Electronic structures indicate that the carriers-mediated double-exchange interaction plays a crucial role in forming the ferromagnetism. Based on the mean-field theory, the Curie temperature for carbon-doped group III-nitrides would be above the room temperature. Negative chemical pair interactions imply that carbon dopants tend to form clustering distribution in group III-nitrides. The nitrogen vacancy would make the carbon-doped group III-nitrides lose the half-metallic ferromagnetism.

  12. Simultaneous anionic and cationic redox

    Jung, Sung-Kyun; Kang, Kisuk

    2017-12-01

    It is challenging to unlock anionic redox activity, accompanied by full utilization of available cationic redox process, to boost capacity of battery cathodes. Now, material design by tuning the metal-oxygen interaction is shown to be a promising solution.

  13. Electronic properties of bivalent cations (Be, Mg and Ca) substitution for Al in delafossite CuAlO{sub 2} semiconductor by first-principles calculations

    Jiang, Haifeng, E-mail: jhf043@163.com [Department of Mechanics and Electronic Engineering, Chizhou College, Chizhou 247000 (China); Key Laboratory of Materials Physics, Institute of Solid State Physics, Chinese Academy of Sciences, Hefei 230031 (China); Wang, Xiancai; Zang, Xueping; Wu, Weifeng [Department of Mechanics and Electronic Engineering, Chizhou College, Chizhou 247000 (China); Sun, Shunping [School of Materials Engineering, Jiangsu Teachers University of Technology, Changzhou 213001 (China); Xiong, Chao [School of Photoelectric Engineering, Changzhou Institute of Technology, Changzhou 213001 (China); Yin, Weiwei; Gui, Chuanyou [Department of Mechanics and Electronic Engineering, Chizhou College, Chizhou 247000 (China); Zhu, Xuebin [Key Laboratory of Materials Physics, Institute of Solid State Physics, Chinese Academy of Sciences, Hefei 230031 (China)

    2013-03-15

    Highlights: ► Electronic properties of CuAlO{sub 2} substituted with bivalent cations were studied. ► Denser band structures were observed in the substituted CuAlO{sub 2}. ► The defect (Be{sub Al}, −1) forms more easily compared to others. -- Abstract: Electronic properties of delafossite-type CuAlO{sub 2} doped with the bivalent cation (Be, Mg or Ca) were systematically calculated by using first-principles PAW method based on density functional theory. The calculated results show the Cu–O distance nearest to the substituted bivalent cation for Al (0.5 0.5 0.5) is decreased with the increase of atomic number from Be to Ca. Moreover, the denser energy band structures have been observed in the valence band in the substituted structures, which are related to the enhancement of covalent character of the Cu–O bond nearest to the substituted site. The contributions from the substituted bivalent cations (Be{sup 2+}, Mg{sup 2+} and Ca{sup 2+}) to the valence band begin at −6.5 eV, relative to −8 eV of Al{sup 3+}, which could be another cause to variations in band structures. From Be to Ca, their partial densities of states show the contributions to the valence band are gradually decreased, in great agreement with the variation trend for the pauling electronegativity. The calculated defect formation energies indicate the (Be{sub Al}, −1) forms more easily than the others.

  14. The secondary electron yield of noble metal surfaces

    L. A. Gonzalez

    2017-11-01

    Full Text Available Secondary electron yield (SEY curves in the 0-1000 eV range were measured on polycrystalline Ag, Au and Cu samples. The metals were examined as introduced in the ultra-high vacuum chamber and after having been cleaned by Ar+ ion sputtering. The comparison between the curves measured on the clean samples and in the presence of contaminants, due to the permanence in atmosphere, confirmed that the SEY behavior is strongly influenced by the chemical state of the metal surface. We show that when using very slow primary electrons the sample work function can be determined with high accuracy from the SEY curves. Moreover we prove that SEY is highly sensitive to the presence of adsorbates even at submonolayer coverage. Results showing the effect of small quantities of CO adsorbed on copper are presented. Our findings demonstrate that SEY, besides being an indispensable mean to qualify technical materials in many technological fields, can be also used as a flexible and advantageous diagnostics to probe surfaces and interfaces.

  15. Elements including metals in the atomizer and aerosol of disposable electronic cigarettes and electronic hookahs.

    Monique Williams

    Full Text Available Our purpose was to quantify 36 inorganic chemical elements in aerosols from disposable electronic cigarettes (ECs and electronic hookahs (EHs, examine the effect of puffing topography on elements in aerosols, and identify the source of the elements.Thirty-six inorganic chemical elements and their concentrations in EC/EH aerosols were determined using inductively coupled plasma optical emission spectroscopy, and their source was identified by analyzing disassembled atomizers using scanning electron microscopy and energy dispersive X-ray spectroscopy.Of 36 elements screened, 35 were detected in EC/EH aerosols, while only 15 were detected in conventional tobacco smoke. Some elements/metals were present in significantly higher concentrations in EC/EH aerosol than in cigarette smoke. Concentrations of particular elements/metals within EC/EH brands were sometimes variable. Aerosols generated at low and high air-flow rates produced the same pattern of elements, although the total element concentration decreased at the higher air flow rate. The relative amount of elements in the first and last 60 puffs was generally different. Silicon was the dominant element in aerosols from all EC/EH brands and in cigarette smoke. The elements appeared to come from the filament (nickel, chromium, thick wire (copper coated with silver, brass clamp (copper, zinc, solder joints (tin, lead, and wick and sheath (silicon, oxygen, calcium, magnesium, aluminum. Lead was identified in the solder and aerosol of two brands of EHs (up to 0.165 μg/10 puffs.These data show that EC/EH aerosols contain a mixture of elements, including heavy metals, with concentrations often significantly higher than in conventional cigarette smoke. While the health effects of inhaling mixtures of heated metals is currently not known, these data will be valuable in future risk assessments involving EC/EH elements/metals.

  16. Effect of temperature, solvent and nature of metal cations on the potentiometric titration S of iron oxide

    Tasleem, S.; Ishrat, B.

    2008-01-01

    A comprehensive study of the potentiometric titrations of iron oxide in the presence of CU/sub 2/ and Mg/sup 2/ were under taken under different experimental conditions of temperature and concentration of metal ions in aqueous and aqueous/organic mixed solvent. The adsorption of both the metal ions were observed to increase with the increase in pH and temperature of the system. The adsorbent iron oxide preferentially adsorbs transition metal as compared to alkaline earth metal ion. (author)

  17. Electronic self-organization in layered transition metal dichalcogenides

    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

  18. Understanding the bioavailability and sequestration of different metal cations in the presence of a biodegradable chelant MGDA in biological fluids and natural waters.

    Bretti, Clemente; Cigala, Rosalia Maria; De Stefano, Concetta; Lando, Gabriele; Sammartano, Silvio

    2017-09-01

    Thermodynamic information about the metal-ligand interaction between Fe 3+ , Zn 2+ , Cu 2+ and Sn 2+ , and a biodegradable ligand as MGDA is reported. The speciation scheme was obtained by means of potentiometric measurements and isothermal titration calorimetry (to determine enthalpy changes) in NaCl medium. The formation of the ML and MLOH species was evidenced for all the metal cations, and for Fe 3+ also the ML 2 and ML(OH) 2 were found. The relative stability, for the ML species, follows the order: Sn 2+  > Fe 3+  > Cu 2+  > Zn 2+ . Stability constants and enthalpy changes were obtained at different ionic strengths, and data were modeled using the Debye-Hückel and SIT approaches to obtain data in a standard state. At infinite dilution, the enthalpy changes are largely negative for Cu 2+ (-34.1 kJ mol -1 ) and Sn 2+ (-16.6 kJ mol -1 ), slightly negative for Fe 3+ (-3.3 kJ mol -1 ) and positive for Zn 2+ (8.7 kJ mol -1 ). In all cases, the entropic contribution to the stability is predominant. The sequestering ability of MGDA was evaluated determining the pL 0.5 values in different conditions. Comparing the data reported in this work and literature ones, some empirical relationships were obtained with predictive purpose. For example, using 11 data in the test set we have: log K (M/MGDA) ± 0.1 = 1.13 + 0.84·log K (M/NTA) Case studies were built up in the conditions of seawater, fresh water and urine to study the possible use of MGDA towards the metal cations here studied. Some considerations were also done in the light of the ocean acidification. Copyright © 2017 Elsevier Ltd. All rights reserved.

  19. {sup 1}H and {sup 23}Na MAS NMR spectroscopy of cationic species in CO{sub 2} selective alkaline earth metal porous silicoaluminophosphates prepared via liquid and solid state ion exchange

    Arevalo-Hidalgo, Ana G. [Department of Chemical Engineering, University of Puerto Rico-Mayagueez Campus, Mayagueez, PR 00681-9000 (Puerto Rico); Dugar, Sneha; Fu, Riqiang [National High Magnetic Field Laboratory, Florida State University, Tallahassee, FL 32310 (United States); Hernandez-Maldonado, Arturo J., E-mail: arturoj.hernandez@upr.edu [Department of Chemical Engineering, University of Puerto Rico-Mayagueez Campus, Mayagueez, PR 00681-9000 (Puerto Rico)

    2012-07-15

    The location of extraframework cations in Sr{sup 2+} and Ba{sup 2+} ion-exchanged SAPO-34 was estimated by means of {sup 1}H and {sup 23}Na MAS NMR spectroscopy and spectral deconvolution. Incorporation of the alkaline earth metal cations onto the SAPO framework was achieved via liquid state ion exchange, coupled partial detemplation/solid-state ion exchange, and combination of both techniques. MAS NMR revealed that the level of ion exchange was limited by the presence of protons and sodium cations near hexagonal prisms (site SI), which are relatively difficult to exchange with the alkaline earth metal due to steric and charge repulsion criteria. In addition, the presence of ammonium cations in the supercages facilitated the exchange of otherwise tenacious hydrogen as corroborated by unit cell compositional data as well as enhanced CO{sub 2} adsorption at low partial pressures. The extraframework ammonium species were produced from partial detemplation of the structure-directing agent employed for the SAPO-34 synthesis, tetraethylammonium. - Graphical abstract: MAS NMR was used to elucidate the position the cationic species in alkaline earth metal exchanged silicoaluminophosphates. These species played a significant role during the ion exchange process and, therefore, the materials ultimate CO{sub 2} adsorption performance. Highlights: Black-Right-Pointing-Pointer Location of extraframework Sr{sup 2+} or Ba{sup 2+} cations was estimated by means of {sup 1}H and {sup 23}Na MAS NMR. Black-Right-Pointing-Pointer Level of Sr{sup 2+} or Ba{sup 2+} ion exchange was limited by the presence of protons and sodium cations. Black-Right-Pointing-Pointer Presence of ammonium cations in the supercages facilitated the exchange. Black-Right-Pointing-Pointer Sr{sup 2+} and Ba{sup 2+} ion exchanged SAPOs are outstanding CO{sub 2} adsorbents.

  20. Comparison of immobilized poly-L-aspartic acid and poly-L-glutamic acid for chelation of metal cations

    Malachowski, Lisa; Holcombe, James A.

    2004-01-01

    Poly-L-aspartic acid (PLAsp) and poly-L-glutamic acid (PLGlu) were individually immobilized onto controlled pore glass (CPG) and compared according to their metal-binding capabilities in a solution of pH 7.0. The metal-binding capacities were calculated through the analysis of breakthrough curves generated by monitoring the metal concentrations on a flow injection-flame atomic absorption system. Capacities for individual metals were comparable and in the order of Cu 2+ >> Pb 2+ > Ni 2+ ∼ Cd 2+ > Co 2+ > Mn 2+ >> Na + . Elemental combustion analysis yielded polymer coverage on the CPG of approximately 4 x 10 12 to 5 x 10 12 chains/cm 2 , when average chain lengths were used in the calculations. Formation constants and site capacities of both polymers for Cd 2+ were determined through equilibrium and breakthrough studies. The maximum log K values for the strong sites were determined to be ∼13 for both PLAsp and for PLGlu. Additionally, the metal selectivity of PLAsp and PLGlu was evaluated when breakthrough curves were run with several metals present in solution at one time. Both polymers showed selectivities in the order of their single metal-binding capacities, i.e., Cu 2+ > Pb 2+ > Ni 2+ ∼ Cd 2+ . Both polymers exhibited similar binding trends and binding strengths for all of the metals studied. This likely reflects the absence of a predetermined tertiary structure of the polymers on the surface and the relatively high residue-per-metal ratio (∼20:1), which places less stringent requirements on the steric hindrance between the side chains and the resultant 'wrapping' of the peptide around the metal

  1. The role of substrate electrons in the wetting of a metal surface

    Schiros, T.; Takahashi, O.; Andersson, Klas Jerker

    2010-01-01

    We address how the electronic and geometric structures of metal surfaces determine water-metal bonding by affecting the balance between Pauli repulsion and electrostatic attraction. We show how the rigid d-electrons and the softer s-electrons utilize different mechanisms for the redistribution...

  2. Transient thermal and nonthermal electron and phonon relaxation after short-pulsed laser heating of metals

    Giri, Ashutosh; Hopkins, Patrick E.

    2015-01-01

    Several dynamic thermal and nonthermal scattering processes affect ultrafast heat transfer in metals after short-pulsed laser heating. Even with decades of measurements of electron-phonon relaxation, the role of thermal vs. nonthermal electron and phonon scattering on overall electron energy transfer to the phonons remains unclear. In this work, we derive an analytical expression for the electron-phonon coupling factor in a metal that includes contributions from equilibrium and nonequilibrium distributions of electrons. While the contribution from the nonthermal electrons to electron-phonon coupling is non-negligible, the increase in the electron relaxation rates with increasing laser fluence measured by thermoreflectance techniques cannot be accounted for by only considering electron-phonon relaxations. We conclude that electron-electron scattering along with electron-phonon scattering have to be considered simultaneously to correctly predict the transient nature of electron relaxation during and after short-pulsed heating of metals at elevated electron temperatures. Furthermore, for high electron temperature perturbations achieved at high absorbed laser fluences, we show good agreement between our model, which accounts for d-band excitations, and previous experimental data. Our model can be extended to other free electron metals with the knowledge of the density of states of electrons in the metals and considering electronic excitations from non-Fermi surface states

  3. Bond of donor-acceptor interaction in metal-ligand system with energies of Fermi electrons

    Vlasov, Yu.V.; Khentov, V.Ya.; Velikanova, L.N.; Semchenko, V.V.

    1993-01-01

    Role of quantum nature of metal (W, Mo and others) in donor-acceptor interaction of metal salicylalaniline - aprotic solvent was discussed. The dependence of dissolution rate and activation energy of donor-acceptor interaction on electron energy was established

  4. Study of the electronic properties of organic molecules within a metal-molecule-metal junction

    Lambert, Mathieu

    2003-01-01

    This ph-D thesis is about electronic transport through organic molecules inserted in a metal molecule-metal junction. We describe first a simple process to prepare sub-3 nm gaps by controllable breakage (under an electrical stress) of gold wires lithographed on a SiO 2 Si substrate at low temperature (4.2 K). We show that the involved mechanism is thermally assisted electromigration. We observe that current-voltage (I-V) characteristics of resulting electrodes are stable up to ∼5 V. which gives access to the well-known Fowler-Nordheim regime in the I-V, allowing an accurate characterisation of the gap size. The average gap is found lo be between 1.5 nm in width and 2.5 eV in height. Molecules and nanoparticles have then been inserted in the junction in the case of nanoparticles for example. The resulting IV clearly shows the suppression of electrical current at low bias known as Coulomb blockade. Characteristic of single-electron tunnelling through nanometer-sized structures, finally we fabricated a single-electron tunneling device based on Au nanoparticles connected to the electrodes via terthiophene (T3) molecule. We use the silicon substrate, separated from the planar structure by a silicon oxide of 200 nm, as an electrostatic gate and observed clear current modulation with possible signature of the transport properties of the terthiophene molecules. (author) [fr

  5. Electronic transport in organometallic perovskite CH{sub 3}NH{sub 3}PbI{sub 3}: The role of organic cation orientations

    Berdiyorov, G. R., E-mail: gberdiyorov@qf.org.qa; El-Mellouhi, F.; Madjet, M. E.; Rashkeev, S. N. [Qatar Environment and Energy Research Institute, Hamad Bin Khalifa University, Qatar Foundation, Doha (Qatar); Alharbi, F. H. [Qatar Environment and Energy Research Institute, Hamad Bin Khalifa University, Qatar Foundation, Doha (Qatar); College of Science and Engineering, Hamad Bin Khalifa University, Doha (Qatar)

    2016-02-01

    Density functional theory in combination with the nonequilibrium Green's function formalism is used to study the electronic transport properties of methylammonium lead-iodide perovskite CH{sub 3}NH{sub 3}PbI{sub 3}. Electronic transport in homogeneous ferroelectric and antiferroelectric phases, both of which do not contain any charged domain walls, is quite similar. The presence of charged domain wall drastically (by about an order of magnitude) enhances the electronic transport in the lateral direction. The increase of the transmission originates from the smaller variation of the electrostatic potential profile along the charged domain walls. This fact may provide a tool for tuning transport properties of such hybrid materials by manipulating molecular cations having dipole moment.

  6. Heavy metals removal in wastewater by activated carbon adsorption and clays of cationic interchange; Eliminacion de metales pesados en disolucion mediante adsorcion en carbon activo y arcillas de intercambio cationico

    Montes, M. A.; Medialdea, J. M.; Garcia Mediavilla, B.; Moron, M. J.; Arnaiz, M. C.; Garcia Martinez de Simon, I.; Lopez, C. M.; Escot, E.; Lebrato, J. [Universidad de Sevilla. Sevilla (Spain)

    1999-11-01

    Among the different treatment systems assessed for the purification of the wastewaters poured from Aznalcollar quarry the last April 25, 1998, physical and chemical adsorption proved highly efficient for the removal of refractory heavy metals. In laboratory experiments, 99% of dissolved Mn and Zn was removed when wastewater passed through a packedbed column filled with a cationic exchange clay. In the same way, activated-carbon adsorption removed more than 80% of dissolved Zn and 11-16% of Mn. Results confirm the feasibility of these processes and contribute knowledge on their operational characteristics so that in any other similar situation we can consider all treatment possibilities. 8 refs.

  7. Effects of inorganic acids and divalent hydrated metal cations (Mg(2+), Ca(2+), Co(2+), Ni(2+)) on γ-AlOOH sol-gel process.

    Zhang, Jian; Xia, Yuguo; Zhang, Li; Chen, Dairong; Jiao, Xiuling

    2015-11-07

    In-depth understanding of the sol-gel process plays an essential role in guiding the preparation of new materials. Herein, the effects of different inorganic acids (HCl, HNO3 and H2SO4) and divalent hydrated metal cations (Mg(2+), Ca(2+), Co(2+), Ni(2+)) on γ-AlOOH sol-gel process were studied based on experiments and density functional theory (DFT) calculations. In these experiments, the sol originating from the γ-AlOOH suspension was formed only with the addition of HCl and HNO3, but not with H2SO4. Furthermore, the DFT calculations showed that the strong adsorption of HSO4(-) on the surface of the γ-AlOOH particles, and the hydrogen in HSO4(-) pointing towards the solvent lead to an unstable configuration of electric double layer (EDL). In the experiment, the gelation time sequence of γ-AlOOH sol obtained by adding metal ions changed when the ionic strength was equal to or greater than 0.198 mol kg(-1). The DFT calculations demonstrated that the adsorption energy of hydrated metal ions on the γ-AlOOH surface can actually make a difference in the sol-gel process.

  8. Removal of strontium and transuranics from Hanford tank waste via addition of metal cations and chemical oxidant: FY 1995 test results

    Orth, R.J.; Zacher, A.H.; Schmidt, A.J.; Elmore, M.R.; Elliott, K.R.; Neuenschwander, G.G.; Gano, S.R.

    1995-09-01

    Chelating organics and some of their degradation products in the Hanford tank waste, such as EDTA, HEDTA, and NTA act to solubilize strontium and transuranics (TRU) in the tank waste supernatant. Displacement of strontium and TRU will facilitate the removal of these radionuclides via precipitation/filtration, ion exchange, or solvent extraction so that low-level waste feed specifications can be met. Pacific Northwest Laboratory has investigated two methods for releasing organic-complexed strontium and TRU components to allow for effective pretreatment of tank waste supernatant: metal cation addition (to promote displacement and flocculation) and chemical oxidant (pennanganate) addition (to promote chelator destruction/defunctionalization and possibly flocculation). These methods, which can be conducted at near-ambient. temperatures and pressures, could be deployed as intank processes

  9. Synthesis of aluminum oxide by the polymer precursor method (Pechini) in 4: 1 ratio of citric acid: metal cation: calcination temperature effect

    Silva, M.C.; Lira, H.L.; Ribeiro, P.C.; Freitas, N.L.

    2014-01-01

    The technology field is nanopowders prominent in science since these materials fall in various sectors regarding their applications. This work aims at the synthesis of aluminum oxide by polymeric precursors in 4:1 ratio of citric acid:metal cation and evaluate the influence of calcination temperature on their structural and morphological characteristics. The samples after reaction were characterized by XRD and thermal analysis. After calcination 500-1200°C the samples were characterized by XRD, SEM and particle size distribution. The results showed that the variation of the calcination temperature is sufficient to achieve a same material with different structural and morphological characteristics. The most stable phase aluminum oxide arose only after calcination at 1100°C, below 900°C, the amorphous material appeared. As regards the morphology, the change was not as significant as compared to the structure. (author)

  10. Evaluation of Iron Nickel Oxide Nanopowder as Corrosion Inhibitor: Effect of Metallic Cations on Carbon Steel in Aqueous NaCl

    Chaudhry, A. U.; Mishra, Brajendra [Colorado School of Mines, Denver (United States); Mittal, Vikas [The Petroleum Institute, Abu Dhabi (United Arab Emirates)

    2016-01-15

    The aim of this study was to evaluate the use of iron-nickel oxide (Fe{sub 2}O{sub 3}.NiO) nanopowder (FeNi) as an anti-corrosion pigment for a different application. The corrosion protection ability and the mechanism involved was determined using aqueous solution of FeNi prepared in a corrosive solution containing 3.5 wt.% NaCl. Anti-corrosion abilities of aqueous solution were determined using electrochemical impedance spectroscopy (EIS) on line pipe steel (API 5L X-80). The protection mechanism involved the adsorption of metallic cations on the steel surface forming a protective film. Analysis of EIS spectra revealed that corrosion inhibition occurred at low concentration, whereas higher concentration of aqueous solution produced induction behavior.

  11. Results from operation of metal melting electron gun

    Balloni, A.J.; Paes, A.C.J.; Miliano, A.C.

    1988-09-01

    The first results obtained during the operation of metal melting electron gun, of power 30Kw and current 1,2A, developed at IEAv, are presented. Details on operation of beam transport system (composed by magnetic lens and prism), from generation to fusion chamber and cathode construction. Into the fusion chamber the presssure can reach 10 -4 Pa, seeing that the gun test consisted in fusion for purification of approximatelly 1Kg titanium bar. The input average power was 12Kw, and the fusion remainded during 16 minutes. The calculated thermal efficiency was of the order of 10% consistent with the results found out in literature, for this type of gun. (M.C.K.) [pt

  12. Electronic properties of semiconductor surfaces and metal/semiconductor interfaces

    Tallarida, M.

    2005-05-15

    This thesis reports investigations of the electronic properties of a semiconductor surface (silicon carbide), a reactive metal/semiconductor interface (manganese/silicon) and a non-reactive metal/semiconductor interface (aluminum-magnesium alloy/silicon). The (2 x 1) reconstruction of the 6H-SiC(0001) surface has been obtained by cleaving the sample along the (0001) direction. This reconstruction has not been observed up to now for this compound, and has been compared with those of similar elemental semiconductors of the fourth group of the periodic table. This comparison has been carried out by making use of photoemission spectroscopy, analyzing the core level shifts of both Si 2p and C 1s core levels in terms of charge transfer between atoms of both elements and in different chemical environments. From this comparison, a difference between the reconstruction on the Si-terminated and the C-terminated surface was established, due to the ionic nature of the Si-C bond. The growth of manganese films on Si(111) in the 1-5 ML thickness range has been studied by means of LEED, STM and photoemission spectroscopy. By the complementary use of these surface science techniques, two different phases have been observed for two thickness regimes (<1 ML and >1 ML), which exhibit a different electronic character. The two reconstructions, the (1 x 1)-phase and the ({radical}3 x {radical}3)R30 -phase, are due to silicide formation, as observed in core level spectroscopy. The growth proceeds via island formation in the monolayer regime, while the thicker films show flat layers interrupted by deep holes. On the basis of STM investigations, this growth mode has been attributed to strain due to lattice mismatch between the substrate and the silicide. Co-deposition of Al and Mg onto a Si(111) substrate at low temperature (100K) resulted in the formation of thin alloy films. By varying the relative content of both elements, the thin films exhibited different electronic properties

  13. Evidence for Single Metal Two Electron Oxidative Addition and Reductive Elimination at Uranium

    Gardner, Benedict M; Kefalidis, Christos E; Lu, Erli; Patel, Dipti; Mcinnes, Eric; Tuna, Floriana; Wooles, Ashley; Maron, Laurent; Liddle, Stephen

    2017-01-01

    Reversible single-metal two-electron oxidative addition and reductive elimination are common fundamental reactions for transition metals that underpin major catalytic transformations. However, these reactions have never been observed together in the f-block because these metals exhibit irreversible one- or multi-electron oxidation or reduction reactions. Here, we report that azobenzene oxidises sterically and electronically unsaturated uranium(III) complexes to afford a uranium(V)-imido compl...

  14. Theoretical microcontact spectra of metal electron-phonon coupling

    Kulagina, T.N.; Zhernov, A.P.

    1987-01-01

    Theoretical and experimental microcontact spectra of simple and certain transition metals are discussed. The Eliashberg thermodynamic functions for the metals are considered, as well as correlations between spectra peculiarities and parameters of metals and microbridge models

  15. Radical Addition to Iminium Ions and Cationic Heterocycles

    Johannes Tauber

    2014-10-01

    Full Text Available Carbon-centered radicals represent highly useful reactive intermediates in organic synthesis. Their nucleophilic character is reflected by fast additions to electron deficient C=X double bonds as present in iminium ions or cationic heterocycles. This review covers diverse reactions of preformed or in situ-generated cationic substrates with various types of C-radicals, including alkyl, alkoxyalkyl, trifluoromethyl, aryl, acyl, carbamoyl, and alkoxycarbonyl species. Despite its high reactivity, the strong interaction of the radical’s SOMO with the LUMO of the cation frequently results in a high regioselectivity. Intra- and intermolecular processes such as the Minisci reaction, the Porta reaction, and the Knabe rearrangement will be discussed along with transition metal and photoredox catalysis or electrochemical methods to generate the odd-electron species.

  16. On the electron density localization in elemental cubic ceramic and FCC transition metals by means of a localized electrons detector.

    Aray, Yosslen; Paredes, Ricardo; Álvarez, Luis Javier; Martiz, Alejandro

    2017-06-14

    The electron density localization in insulator and semiconductor elemental cubic materials with diamond structure, carbon, silicon, germanium, and tin, and good metallic conductors with face centered cubic structure such as α-Co, Ni, Cu, Rh, Pd, Ag, Ir, Pt, and Au, was studied using a localized electrons detector defined in the local moment representation. Our results clearly show an opposite pattern of the electron density localization for the cubic ceramic and transition metal materials. It was found that, for the elemental ceramic materials, the zone of low electron localization is very small and is mainly localized on the atomic basin edges. On the contrary, for the transition metals, there are low-valued localized electrons detector isocontours defining a zone of highly delocalized electrons that extends throughout the material. We have found that the best conductors are those in which the electron density at this low-value zone is the lowest.

  17. Electronic structure and dynamics of metal and metal-covered surfaces

    Yang, Shu.

    1992-01-01

    The unoccupied electronic states of;Ni(111) and Al(111) have been studied using angle-resolved inverse-photoemission (IPE) spectroscopy. We have characterized the n = 1 image potential state on Ni(111) measuring an effective mass of m * /m = 1, consistent with recent two-photon photoemission results as well as theoretical calculations using a phase-analysis model, but differing considerably from the earlier angle-resolved IPE measurements. The bulk related features on Ni(111) observed in our experiment agree very well with an empirical Ni band structure calculation. On Al(111), we have conducted an extensive study of the image potential resonance using both angle-resolved IPE spectroscopy and tunneling spectroscopy with the scanning tunneling microscope. We have used Al as a testing case for both nearly-free-electron model and first-principles calculations were needed to obtain a semi-quantitative account of the bulk features of Al, a simple metal. Improved quantitative agreement occurred when excitation effects were considered. In addition, several surface resonance features have been identified and characterized on Al(111). We have also conducted a geometric structural investigation of a metal overlayer system, Ni/Cu(111), using high-resolution electron energy loss spectroscopy with CO as a probe molecule. The results indicate island formation and two-dimensional mixing at the initial stage of bimetallic interface formation. A new adsorption site with CO bonded to both Ni and Cu has been discovered on the Ni-Cu intermixed surface. IPE results for the Cu-covered Ni(111) surface show an enhanced angular range for the Cu image state. Finally, the unique ability of Auger-photoelectron coincidence spectroscopy to probing local valence electronic structure has been tested in a case study of TaC(111). A novel Auger decay channel has also been observed

  18. Influence of the slags treatment on the heavy metals binding

    Blahová, L.; Navrátilová, Z.; Mucha, M.; Navrátilová, Eva; Neděla, Vilém

    2018-01-01

    Roč. 15, č. 4 (2018), s. 697-706 ISSN 1735-1472 Institutional support: RVO:68081731 Keywords : slag * binding * metal cations * slag modification Subject RIV: JA - Electronics ; Optoelectronics, Electrical Engineering Impact factor: 1.915, year: 2016

  19. Electron work function of metallic surfaces, covered with by metal adatoms, and two-dimensional structure of adlayer

    Rudnitskij, L.A.

    1986-01-01

    Change in electron work function during metal adatom (Ti, W, Ag, Au) adsorption on different tungsten surfaces in ''polycrystalline'' and epitaxial types of adsorpted layers is studied. Calculational and experimental dependences of work function change on coating thickness are built

  20. Role of contact bonding on electronic transport in metal-carbon nanotube-metal systems

    Deretzis, I; La Magna, A

    2006-01-01

    We have investigated the effects of the interfacial bond arrangement on the electronic transport features of metal-nanotube-metal systems. The transport properties of finite, defect-free armchair and zigzag single-walled carbon nanotubes attached to Au(111) metallic contacts have been calculated by means of the non-equilibrium Green functional formalism with the tight-binding and the extended Hueckel Hamiltonians. Our calculations show that the electrode material is not the only factor which rules contact transparency. Indeed, for the same electrode, but changing nanotube helicities, we have observed an overall complex behaviour of the transmission spectra due to band mixing and interference. A comparison of the two models shows that the tight-binding approach fails to give a satisfactory representation of the transmission function when a more accurate description of the C-C and Au-C chemical bonds has to be considered. We have furthermore examined the effect of interface geometry variance on conduction and found that the contact-nanotube distance has a significant impact, while the contact-nanotube symmetry plays a marginal, yet evident role

  1. Surface analysis of Al alloys with X-ray photoelectron and Auger electron spectroscopies

    Sakairi, Masatoshi; Suzuki, Keita; Sasaki, Ryo

    2015-01-01

    In this paper, X-ray photoelectron spectroscopy (XPS) and Auger electron spectroscopy (AES) were applied to investigate passive films formed on aluminum alloy in 0.5 kmol m -3 H 3 BO 3 /0.05 kmol m -3 Na 2 B 4 O 7 with different metal cations. The metal cation is classified by metal cation hardness, X, which are calculated based on the concept of hard and soft acids and bases (HSAB) of the acid and base in Lewis's rule. From XPS analysis, the metal cations with X > 4 were incorporated in passive films. The area-selected surface analysis of AES was also introduced. (author)

  2. Finely Tuned SnO2 Nanoparticles for Efficient Detection of Reducing and Oxidizing Gases: The Influence of Alkali Metal Cation on Gas-Sensing Properties.

    Lee, Szu-Hsuan; Galstyan, Vardan; Ponzoni, Andrea; Gonzalo-Juan, Isabel; Riedel, Ralf; Dourges, Marie-Anne; Nicolas, Yohann; Toupance, Thierry

    2018-03-28

    Tin dioxide (SnO 2 ) nanoparticles were straightforwardly synthesized using an easily scaled-up liquid route that involves the hydrothermal treatment, either under acidic or basic conditions, of a commercial tin dioxide particle suspension including potassium counterions. After further thermal post-treatment, the nanomaterials have been thoroughly characterized by Fourier transform infrared and Raman spectroscopy, powder X-ray diffraction, transmission electron microscopy, X-ray photoelectron spectroscopy, and nitrogen sorption porosimetry. Varying pH conditions and temperature of the thermal treatment provided cassiterite SnO 2 nanoparticles with crystallite sizes ranging from 7.3 to 9.7 nm and Brunauer-Emmett-Teller surface areas ranging from 61 to 106 m 2 ·g -1 , acidic conditions favoring potassium cation removal. Upon exposure to a reducing gas (H 2 , CO, and volatile organic compounds such as ethanol and acetone) or oxidizing gas (NO 2 ), layers of these SnO 2 nanoparticles led to highly sensitive, reversible, and reproducible responses. The sensing results were discussed in regard to the crystallite size, specific area, valence band energy, Debye length, and chemical composition. Results highlight the impact of the counterion residuals, which affect the gas-sensing performance to an extent much higher than that of size and surface area effects. Tin dioxide nanoparticles prepared under acidic conditions and calcined in air showed the best sensing performances because of lower amount of potassium cations and higher crystallinity, despite the lower surface area.

  3. Mechanism of protodesorption—exchange of heavy metal cations for protons in a heterophase system of H{sub 2}O–H{sub 2}SO{sub 4}–MSO{sub 4}—cellulose sorbent

    Kozlov, V.A.; Nikiforova, T.E., E-mail: tatianaenik@mail.ru; Loginova, V.A.; Koifman, O.I.

    2015-12-15

    Highlights: • Protodesorption takes place with participation of anions. • The interphase indicator MSO{sub 4} is used in ion exchange investigation. • In ion exchange process salt and acid participate in equivalent proportions. • In a protodesorption process proton acts in degree of ½. • M{sup 2+}/2Na{sup +} and M{sup 2+}/2H{sup +} exchanges take place in ion and molecular forms. - Abstract: The influence of pH on the distribution of metal cations [Cd(II), Cu(II), Fe(II), Ni(II), Zn(II)] in a four-component heterophase system (H{sub 2}O–H{sub 2}SO{sub 4}–MSO{sub 4}–cellulose sorbent) was studied. Protodesorption of metal cations was studied with indicator and constant quantities of [MSO{sub 4}] salts and constant solvent–sorbent ratio. Linear dependence lgK{sub DM2+} = f(pH) with tgα = 1/2 of the K{sub DM2+} metal ions distribution coefficients from the acidity of the aqueous phase is observed in logarithmic coordinates. Depression of the exponent corresponding to proton involvement in protodesorption from 2 (theory) to 0.5 (experiment) indicates that anions of the aqueous phase are involved in the process of exchange of metal cation for proton on the anionic centers of the sorbent, which corresponds to participation of the salt and acid components of the system in molecular non-dissociated form in an equivalent proportion H{sub 2}SO{sub 4}/MSO{sub 4} = 1/1. Different behavior of the salt and acid components in ion exchange of cations for cations and cations for protons is due to the differences in the constraint coefficients of their molecular and ionic forms which must be taken into consideration in equations describing thermodynamics of the interphase exchange.

  4. The radical cations of sulphur (S8sup(.+)) and tetrasulphur tetranitride (S4N4sup(.+)): a radiation-electron spin resonance study

    Chandra, Harish; Ramakrishna Rao, D.N.; Symons, M.C.R.

    1987-01-01

    Exposure of dilute solutions of S 8 and S 4 N 4 in trichlorofluoromethane to 60 Co γ-rays at 77 K gave the corresponding radical cations. Enrichment (99%) with 33 S gave greatly broadened electron spin resonance x and y features, with A( 33 S) approx. = + - 4 G, where A is the first formed species from sulfur. The z features showed a clear central line flanked by others with Asub(z) approx. = 28 G. The results suggest the presence of two equally coupled sulphur atoms. On annealing, species (A) changes irreversibly into species (B),possibly, S 8 radical + in a relaxed form in which two opposite atoms have formed a weak three-electron bond. A clear spectrum was produced from S 4 N 4 which showed little g-value variation and no evidence for 14 N splitting. It is concluded that the S 4 N 4 radical + cation has a relatively isolated semi-occupied molecular orbital, with low spin density on nitrogen. (author)

  5. Influences of the propyl group on the van der Waals structures of 4-propylaniline complexes with one and two argon atoms studied by electronic and cationic spectroscopy

    Yang, Zhijun; Gu, Quanli; Trindle, Carl O.; Knee, J. L.

    2015-01-01

    4-propylaniline complexes with one and two argon atoms formed in the molecular beam were studied in the first excited electronic state, S 1 , using resonance enhanced two-photon ionization spectroscopy and in the cation ground state, D 0 , using mass analyzed threshold ionization spectroscopy. The combination of electronic and cationic spectra of the clusters allows two conformations to be identified in both aniline-Ar 1 and aniline-Ar 2 , which are assigned to either the gauche configuration or anti-configuration of 4-propylaniline. The gauche isomer exhibits complex bands shifted 29 cm −1 and 89 cm −1 from the S 1 origin bands and 83 cm −1 and 148 cm −1 from the ionization potential assigned to the Ar 1 and Ar 2 complexes, respectively. For the anti-rotamer, the corresponding shifts actually become nearly additive, 53 cm −1 and 109 cm −1 for the S 1 origin bands, and 61 cm −1 and 125 cm −1 for the ionization potentials. Ab initio calculations provide insights into the influences of the propyl and amino groups on the positions of the argon atoms within the clusters. In addition, the binding energy of one argon with the gauche isomer of 4-propylaniline has been measured to be 550 ± 5 cm −1 in the D 0 state, 496 ± 5 cm −1 in the S 1 state, and 467 ± 5 cm −1 in the neutral ground state, S 0

  6. High performance bulk metallic glass/carbon nanotube composite cathodes for electron field emission

    Hojati-Talemi, Pejman; Gibson, Mark A.; East, Daniel; Simon, George P.

    2011-01-01

    We report the preparation of new nanocomposites based on a combination of bulk metallic glass and carbon nanotubes for electron field emission applications. The use of bulk metallic glass as the matrix ensures high electrical and thermal conductivity, high thermal stability, and ease of processing, whilst the well dispersed carbon nanotubes act as highly efficient electron emitters. These advantages, alongside excellent electron emission properties, make these composites one of the best reported options for electron emission applications to date.

  7. High performance bulk metallic glass/carbon nanotube composite cathodes for electron field emission

    Hojati-Talemi, Pejman [Department of Materials Engineering, Monash University, Clayton, Vic 3800 (Australia); Mawson Institute, University of South Australia, Mawson Lakes, SA 5095 (Australia); Gibson, Mark A. [Process Science and Engineering, Commonwealth Scientific and Industrial Research Organisation, Clayton, Vic 3168 (Australia); East, Daniel; Simon, George P. [Department of Materials Engineering, Monash University, Clayton, Vic 3800 (Australia)

    2011-11-07

    We report the preparation of new nanocomposites based on a combination of bulk metallic glass and carbon nanotubes for electron field emission applications. The use of bulk metallic glass as the matrix ensures high electrical and thermal conductivity, high thermal stability, and ease of processing, whilst the well dispersed carbon nanotubes act as highly efficient electron emitters. These advantages, alongside excellent electron emission properties, make these composites one of the best reported options for electron emission applications to date.

  8. Distinct roles of beta1 metal ion-dependent adhesion site (MIDAS), adjacent to MIDAS (ADMIDAS), and ligand-associated metal-binding site (LIMBS) cation-binding sites in ligand recognition by integrin alpha2beta1.

    Valdramidou, Dimitra; Humphries, Martin J; Mould, A Paul

    2008-11-21

    Integrin-ligand interactions are regulated in a complex manner by divalent cations, and previous studies have identified ligand-competent, stimulatory, and inhibitory cation-binding sites. In collagen-binding integrins, such as alpha2beta1, ligand recognition takes place exclusively at the alpha subunit I domain. However, activation of the alphaI domain depends on its interaction with a structurally similar domain in the beta subunit known as the I-like or betaI domain. The top face of the betaI domain contains three cation-binding sites: the metal-ion dependent adhesion site (MIDAS), the ADMIDAS (adjacent to MIDAS), and LIMBS (ligand-associated metal-binding site). The role of these sites in controlling ligand binding to the alphaI domain has yet to be elucidated. Mutation of the MIDAS or LIMBS completely blocked collagen binding to alpha2beta1; in contrast mutation of the ADMIDAS reduced ligand recognition but this effect could be overcome by the activating monoclonal antibody TS2/16. Hence, the MIDAS and LIMBS appear to be essential for the interaction between alphaI and betaI, whereas occupancy of the ADMIDAS has an allosteric effect on the conformation of betaI. An activating mutation in the alpha2 I domain partially restored ligand binding to the MIDAS and LIMBS mutants. Analysis of the effects of Ca(2+), Mg(2+), and Mn(2+) on ligand binding to these mutants showed that the MIDAS is a ligand-competent site through which Mn(2+) stimulates ligand binding, whereas the LIMBS is a stimulatory Ca(2+)-binding site, occupancy of which increases the affinity of Mg(2+) for the MIDAS.

  9. Competition effects in cation binding to humic acid: Conditional affinity spectra for fixed total metal concentration conditions

    David, Calin; Mongin, Sandrine; Rey-Castro, Carlos; Galceran, Josep; Companys, Encarnació; Garcés, José Luis; Salvador, José; Puy, Jaume; Cecilia, Joan; Lodeiro, Pablo; Mas, Francesc

    2010-09-01

    Information on the Pb and Cd binding to a purified Aldrich humic acid (HA) is obtained from the influence of different fixed total metal concentrations on the acid-base titrations of this ligand. NICA (Non-Ideal Competitive Adsorption) isotherm has been used for a global quantitative description of the binding, which has then been interpreted by plotting the Conditional Affinity Spectra of the H + binding at fixed total metal concentrations (CAScTM). This new physicochemical tool, here introduced, allows the interpretation of binding results in terms of distributions of proton binding energies. A large increase in the acidity of the phenolic sites as the total metal concentration increases, especially in presence of Pb, is revealed from the shift of the CAScTM towards lower affinities. The variance of the CAScTM distribution, which can be used as a direct measure of the heterogeneity, also shows a significant dependence on the total metal concentration. A discussion of the factors that influence the heterogeneity of the HA under the conditions of each experiment is provided, so that the smoothed pattern exhibited by the titration curves can be justified.

  10. Electronic properties of antiferromagnetic UBi2 metal by exact exchange for correlated electrons method

    E Ghasemikhah

    2012-03-01

    Full Text Available This study investigated the electronic properties of antiferromagnetic UBi2 metal by using ab initio calculations based on the density functional theory (DFT, employing the augmented plane waves plus local orbital method. We used the exact exchange for correlated electrons (EECE method to calculate the exchange-correlation energy under a variety of hybrid functionals. Electric field gradients (EFGs at the uranium site in UBi2 compound were calculated and compared with the experiment. The EFGs were predicted experimentally at the U site to be very small in this compound. The EFG calculated by the EECE functional are in agreement with the experiment. The densities of states (DOSs show that 5f U orbital is hybrided with the other orbitals. The plotted Fermi surfaces show that there are two kinds of charges on Fermi surface of this compound.

  11. Ferromagnetism and temperature-dependent electronic structure in metallic films

    Herrmann, T.

    1999-01-01

    In this work the influence of the reduced translational symmetry on the magnetic properties of thin itinerant-electron films and surfaces is investigated within the strongly correlated Hubbard model. Firstly, the possibility of spontaneous ferromagnetism in the Hubbard model is discussed for the case of systems with full translational symmetry. Different approximation schemes for the solution of the many-body problem of the Hubbard model are introduced and discussed in detail. It is found that it is vital for a reasonable description of spontaneous ferromagnetism to be consistent with exact results concerning the general shape of the single-electron spectral density in the limit of strong Coulomb interaction between the electrons. The temperature dependence of the ferromagnetic solutions is discussed in detail by use of the magnetization curves as well as the spin-dependent quasi particle spectrum. For the investigation of thin films and surfaces the approximation schemes for the bulk system have to be generalized to deal with the reduced translational symmetry. The magnetic behavior of thin Hubbard films is investigated by use of the layer dependent magnetization as a function of temperature as well as the thickness of the film. The Curie-temperature is calculated as a function of the film thickness. Further, the magnetic stability at the surface is discussed in detail. Here it is found that for strong Coulomb interaction the magnetic stability at finite temperatures is reduced at the surface compared to the inner layers. This observation clearly contradicts the well-known Stoner picture of band magnetism and can be explained in terms of general arguments which are based on exact results in the limit of strong Coulomb interaction. The magnetic behavior of the Hubbard films can be analyzed in detail by inspecting the local quasi particle density of states as well as the wave vector dependent spectral density. The electronic structure is found to be strongly spin

  12. Energy level alignment and electron transport through metal/organic contacts. From interfaces to molecular electronics

    Abad, Enrique

    2013-07-01

    A new calculational approach to describing metal/organic interfaces. A valuable step towards a better understanding of molecular electronics. Nominated as an outstanding contribution by the Autonomous University of Madrid. In recent years, ever more electronic devices have started to exploit the advantages of organic semiconductors. The work reported in this thesis focuses on analyzing theoretically the energy level alignment of different metal/organic interfaces, necessary to tailor devices with good performance. Traditional methods based on density functional theory (DFT), are not appropriate for analyzing them because they underestimate the organic energy gap and fail to correctly describe the van der Waals forces. Since the size of these systems prohibits the use of more accurate methods, corrections to those DFT drawbacks are desirable. In this work a combination of a standard DFT calculation with the inclusion of the charging energy (U) of the molecule, calculated from first principles, is presented. Regarding the dispersion forces, incorrect long range interaction is substituted by a van der Waals potential. With these corrections, the C60, benzene, pentacene, TTF and TCNQ/Au(111) interfaces are analyzed, both for single molecules and for a monolayer. The results validate the induced density of interface states model.

  13. Amperometric Ion-Selective Electrode for Alkali Metal Cations Based on a Room-Temperature Ionic Liquid Membrane

    Langmaier, Jan; Trojánek, Antonín; Samec, Zdeněk

    2009-01-01

    Roč. 21, 17-18 (2009), s. 1977-1983 ISSN 1040-0397 R&D Projects: GA MŠk ME08098; GA AV ČR IAA400400704 Institutional research plan: CEZ:AV0Z40400503 Keywords : room-temperature ionic liquid * alkali metals * Crown ether * cyclic voltammetry * amperometric ion-selective elkectrode Subject RIV: CG - Electrochemistry Impact factor: 2.630, year: 2009

  14. Combined action of taurine and cations of certain metals on post-irradiation survival of SOC cell culture

    Yartsev, E.I.; Aldonyasov, V.I.; Yakovlev, V.G.

    1975-01-01

    Effects of combined application of taurine and metals (potassium, magnesium, calcium and zinc) on the cell level have been studied. It has been found that various concentrations of taurine and potassium and zinc salts increase the survival of irradiated SOC cells up to 40% while addition of magnesium and calcium salts does not affect the taurine effectiveness. The highest effectiveness is obtained when potassium and taurine are added in equimolar amounts to the incubation medium

  15. Solid-State Properties of One-Dimensional Metals Based on bis(oxalato)platinate Anions with Divalent Cations

    Braude, A.; Carneiro, K.; Jacobsen, Claus Schelde

    1987-01-01

    The crystal structures, superstructures, dc conductivity, optical properties, and thermopower of six linear-chain conductors of the type M0.8[Pt(C2O4)2]⋅(M=Ni,Co,Zn,Fe,Mg,Mn), where M is a divalent metal (M=Ni,Co,Zn,Fe,Mg,Mn), have been studied. At high temperatures they form a common orthorhombi...

  16. On the applicability of nearly free electron model for resistivity calculations in liquid metals

    Gorecki, J.; Popielawski, J.

    1982-09-01

    The calculations of resistivity based on the nearly free electron model are presented for many noble and transition liquid metals. The triple ion correlation is included in resistivity formula according to SCQCA approximation. Two different methods for describing the conduction band are used. The problem of applicability of the nearly free electron model for different metals is discussed. (author)

  17. Metal-dielectric interfaces in gigascale electronics thermal and electrical stability

    He, Ming

    2012-01-01

    Metal-dielectric interfaces are ubiquitous in modern electronics. As advanced gigascale electronic devices continue to shrink, the stability of these interfaces is becoming an increasingly important issue that has a profound impact on the operational reliability of these devices. In this book, the authors present the basic science underlying  the thermal and electrical stability of metal-dielectric interfaces and its relationship to the operation of advanced interconnect systems in gigascale electronics. Interface phenomena, including chemical reactions between metals and dielectrics, metallic-atom diffusion, and ion drift, are discussed based on fundamental physical and chemical principles. Schematic diagrams are provided throughout the book to illustrate  interface phenomena and the principles that govern them. Metal-Dielectric Interfaces in Gigascale Electronics  provides a unifying approach to the diverse and sometimes contradictory test results that are reported in the literature on metal-dielectric i...

  18. First-principles calculations of heat capacities of ultrafast laser-excited electrons in metals

    Bévillon, E.; Colombier, J.P.; Recoules, V.; Stoian, R.

    2015-01-01

    Ultrafast laser excitation can induce fast increases of the electronic subsystem temperature. The subsequent electronic evolutions in terms of band structure and energy distribution can determine the change of several thermodynamic properties, including one essential for energy deposition; the electronic heat capacity. Using density functional calculations performed at finite electronic temperatures, the electronic heat capacities dependent on electronic temperatures are obtained for a series of metals, including free electron like, transition and noble metals. The effect of exchange and correlation functionals and the presence of semicore electrons on electronic heat capacities are first evaluated and found to be negligible in most cases. Then, we tested the validity of the free electron approaches, varying the number of free electrons per atom. This shows that only simple metals can be correctly fitted with these approaches. For transition metals, the presence of localized d electrons produces a strong deviation toward high energies of the electronic heat capacities, implying that more energy is needed to thermally excite them, compared to free sp electrons. This is attributed to collective excitation effects strengthened by a change of the electronic screening at high temperature

  19. Furfural to Furfuryl Alcohol: Computational Study of the Hydrogen Transfer on Lewis Acidic BEA Zeolites and Effects of Cation Exchange and Tetravalent Metal Substitution.

    Prasertsab, Anittha; Maihom, Thana; Probst, Michael; Wattanakit, Chularat; Limtrakul, Jumras

    2018-06-04

    The hydrogen transfer of furfural to furfuryl alcohol with i-propanol as the hydrogen source over cation-exchanged Lewis acidic BEA zeolite has been investigated by means of density functional calculations. The reaction proceeds in three steps. First the O-H bond of i-propanol is broken to form a propoxide intermediate. After that, the furylmethoxy intermediate is formed via hydrogen transfer process, and finally furylmethoxy abstracts the proton to form the furfuryl alcohol product. The second step is rate-determining by requiring the highest activation energy (23.8 kcal/mol) if the reaction takes place on Li-Sn-BEA zeolite. We find that the catalytic activity of various cation-exchanged Sn-BEA zeolites is in the order Li-Sn-BEA > Na-Sn-BEA > K-Sn-BEA. The lower activation energy for Li-Sn-BEA compared to Na-Sn-BEA and K-Sn-BEA can be explained by the larger charge transfer from the carbonyl bond to the catalyst, leading to its activation and to the attraction of the hydrogen being transferred. The larger charge transfer in turn is due to the smaller gap between the energies of furfural HOMO and the zeolite LUMO in Li-Sn-BEA, compared to both Na-Sn-BEA and K-Sn-BEA. In a similar way, we also compare the catalytic activity of tetravalent metal centers (Sn, Zr, and Hf) substituted into BEA and find in the order Zr ≥ Hf > Sn, based on activation energies. Finally we investigate statistically which property of the reactants is a suitable descriptor for an approximative prediction of the reaction rate in order to be able to quickly screen promising catalytic materials for this reaction.

  20. Test-beds for molecular electronics: metal-molecules-metal junctions based on Hg electrodes.

    Simeone, Felice Carlo; Rampi, Maria Anita

    2010-01-01

    Junctions based on mesoscopic Hg electrodes are used to characterize the electrical properties of the organic molecules organized in self-assembled monolayers (SAMs). The junctions M-SAM//SAM-Hg are formed by one electrode based on metals (M) such as Hg, Ag, Au, covered by a SAM, and by a second electrode always formed by a Hg drop carrying also a SAM. The electrodes, brought together by using a micromanipulator, sandwich SAMs of different nature at the contact area (approximately = 0.7 microm2). The high versatility of the system allows a series of both electrical and electrochemical junctions to be assembled and characterized: (i) The compliant nature of the Hg electrodes allows incorporation into the junction and measurement of the electrical behavior of a large number of molecular systems and correlation of their electronic structure to the electrical behavior; (ii) by functionalizing both electrodes with SAMs exposing different functional groups, X and Y, it is possible to compare the rate of electron transfer through different X...Y molecular interactions; (iii) when the junction incorporates one of the electrode formed by a semitransparent film of Au, it allows electrical measurements under irradiation of the sandwiched SAMs. In this case the junction behaves as a photoswitch; iv) incorporation of redox centres with low lying, easily reachable energy levels, provides electron stations as indicated by the hopping mechanism dominating the current flow; (v) electrochemical junctions incorporating redox centres by both covalent and electrostatic interactions permit control of the potential of the electrodes with respect to that of the redox state by means of an external reference electrode. Both these junctions show an electrical behavior similar to that of conventional diodes, even though the mechanism generating the current flow is different. These systems, demonstrating high mechanical stability and reproducibility, easy assembly, and a wide variety of

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

    1992-01-01

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

  2. Relationship between the electronic structure and the glide in the hexagonal close packed metals

    Legrand, B.; Le Hazif, R.

    1983-06-01

    In all hexagonal close-packed metals (HCP), deformation is performed by slip on a mean glide system (MGS) and on several secondary systems. There are no reliable predictions of the MGS choice. In this paper is shown the role played by the electronic structure on the choice of glide system in HCP metals. MGS is basal for all normal metals and is a function of the electron number in HCP transition metals. The different SFE's were calculated using appropriate total energy models, for different metals. Thus pseudopotentials were used (or empirical pair potentials) for normal metals, and a tight-binding model for transition metals. The most important results are the following: prismatic SFE (PSFE) is smaller than basal SFE (BSFE) for Y, Ti, Zr, Hf, Ru and Os; BSFE is smaller than PSFE for Co and all normal metals; BSFE and PSFe and about the same for RE and Tc

  3. Electronic properties of iron impurity in hcp metals from Moessbauer studies

    Janot, C.; Delcroix, P.

    1975-01-01

    Moessbauer spectroscopy was used in quantitative investigating the electronic properties of iron impurities in hexagonal close-packed metals. Beryllium of the highest commercially obtainable purity containing about 300 ppm residual impurities was used as a host element. Experimental evidence is given for the existence of localized electronic states which have non-spherical distribution and obviously contribute especially to the electric field gradient. Iron impurity seems to retain the same electronic behaviour as long as the host hcp metal is a normal one (Mg, Cd, Zn), but the localized electronic states seem to disappear when the host is a transition hcp metal (Co, Ti, Sc, Zr, etc.). (Z.S.)

  4. A unique metal-semiconductor interface and resultant electron transfer phenomenon

    Taft, S. L.

    2012-01-01

    An unusual electron transfer phenomenon has been identified from an n-type semiconductor to Schottky metal particles, the result of a unique metal semiconductor interface that results when the metal particles are grown from the semiconductor substrate. The unique interface acts as a one-way (rectifying) open gateway and was first identified in reduced rutile polycrystalline titanium dioxide (an n-type semiconductor) to Group VIII (noble) metal particles. The interface significantly affects th...

  5. Determining the selectivity of divalent metal cations for the carboxyl group of alginate hydrogel beads during competitive sorption.

    An, Byungryul; Lee, Healim; Lee, Soonjae; Lee, Sang-Hyup; Choi, Jae-Woo

    2015-11-15

    To investigate the competitive sorption of divalent metal ions such as Ca(2+), Cu(2+), Ni(2+), and Pb(2+) on alginate hydrogel beads, batch and column tests were conducted. The concentration of carboxyl group was found to be limited in the preparation of spherical hydrogel beads. From kinetic test results, 80% of sorption was observed within 4h, and equilibrium was attained in 48 h. According to the comparison of the total uptake and release, divalent metal ions were found to stoichiometrically interact with the carboxyl group in the alginate polymer chain. From the Langmuir equation, the maximum capacities of Pb(2+), Cu(2+), and Ni(2+) were calculated to be 1.1, 0.48, and 0.13 mmol/g, respectively. The separation factor (α) values for αPb/Cu, αPb/Ni, and αCu/Ni were 14.0, 98.9, and 7.1, respectively. The sorption capacity of Pb(2+) was not affected by the solution pH; however, the sorption capacities of Cu(2+) and Ni(2+) decreased with increasing solution pH, caused by competition with hydrogen. According to the result from the fixed column test, Pb(2+) exhibited the highest affinity, followed by Cu(2+) and Ni(2+), which is in exact agreement with those of kinetic and isotherm tests. The sorbent could be regenerated using 4% HCl, and the regenerated sorbent exhibited 90% capacity upto 9 cycles. Copyright © 2015 Elsevier B.V. All rights reserved.

  6. Iminodiacetic acid functionalised organopolymer monoliths: application to the separation of metal cations by capillary high-performance chelation ion chromatography.

    Moyna, Áine; Connolly, Damian; Nesterenko, Ekaterina; Nesterenko, Pavel N; Paull, Brett

    2013-03-01

    Lauryl methacrylate-co-ethylene dimethacrylate monoliths were polymerised within fused silica capillaries and subsequently photo-grafted with varying amounts of glycidyl methacrylate (GMA). The grafted monoliths were then further modified with iminodiacetic acid (IDA), resulting in a range of chelating ion-exchange monoliths of increasing capacity. The IDA functional groups were attached via ring opening of the epoxy group on the poly(GMA) structure. Increasing the amount of attached poly(GMA), via photo-grafting with increasing concentrations of GMA, from 15 to 35%, resulted in a proportional and controlled increase in the complexation capacity of the chelating monoliths. Scanning capacitively coupled contactless conductivity detection (sC(4)D) was used to characterise and verify homogenous distribution of the chelating ligand along the length of the capillaries non-invasively. Chelation ion chromatographic separations of selected transition and heavy metals were carried out, with retention factor data proportional to the concentration of grafted poly(GMA). Average peak efficiencies of close to 5,000 N/m were achieved, with the isocratic separation of Na, Mg(II), Mn(II), Co(II), Cd(II) and Zn(II) possible on a 250-mm-long monolith. Multiple monolithic columns produced to the same recipes gave RSD data for retention factors of ions). The monolithic chelating ion-exchanger was applied to the separation of alkaline earth and transition metal ions spiked in natural and potable waters.

  7. Dynamic screening and electron dynamics in low-dimensional metal systems

    Silkin, V.M.; Quijada, M.; Vergniory, M.G.; Alducin, M.; Borisov, A.G.; Diez Muino, R.; Juaristi, J.I.; Sanchez-Portal, D.; Chulkov, E.V.; Echenique, P.M.

    2007-01-01

    Recent advances in the theoretical description of dynamic screening and electron dynamics in metallic media are reviewed. The time-dependent building-up of screening in different situations is addressed. Perturbative and non-perturbative theories are used to study electron dynamics in low-dimensional systems, such as metal clusters, image states, surface states and quantum wells. Modification of the electronic lifetimes due to confinement effects is analyzed as well

  8. Electronic Effects on Room-Temperature, Gas-Phase C-H Bond Activations by Cluster Oxides and Metal Carbides: The Methane Challenge.

    Schwarz, Helmut; Shaik, Sason; Li, Jilai

    2017-12-06

    This Perspective discusses a story of one molecule (methane), a few metal-oxide cationic clusters (MOCCs), dopants, metal-carbide cations, oriented-electric fields (OEFs), and a dizzying mechanistic landscape of methane activation! One mechanism is hydrogen atom transfer (HAT), which occurs whenever the MOCC possesses a localized oxyl radical (M-O • ). Whenever the radical is delocalized, e.g., in [MgO] n •+ the HAT barrier increases due to the penalty of radical localization. Adding a dopant (Ga 2 O 3 ) to [MgO] 2 •+ localizes the radical and HAT transpires. Whenever the radical is located on the metal centers as in [Al 2 O 2 ] •+ the mechanism crosses over to proton-coupled electron transfer (PCET), wherein the positive Al center acts as a Lewis acid that coordinates the methane molecule, while one of the bridging oxygen atoms abstracts a proton, and the negatively charged CH 3 moiety relocates to the metal fragment. We provide a diagnostic plot of barriers vs reactants' distortion energies, which allows the chemist to distinguish HAT from PCET. Thus, doping of [MgO] 2 •+ by Al 2 O 3 enables HAT and PCET to compete. Similarly, [ZnO] •+ activates methane by PCET generating many products. Adding a CH 3 CN ligand to form [(CH 3 CN)ZnO] •+ leads to a single HAT product. The CH 3 CN dipole acts as an OEF that switches off PCET. [MC] + cations (M = Au, Cu) act by different mechanisms, dictated by the M + -C bond covalence. For example, Cu + , which bonds the carbon atom mostly electrostatically, performs coupling of C to methane to yield ethylene, in a single almost barrier-free step, with an unprecedented atomic choreography catalyzed by the OEF of Cu + .

  9. Electronic computer prediction of properties of binary refractory transition metal compounds on the base of their simplificated electronic structure

    Kutolin, S.A.; Kotyukov, V.I.

    1979-01-01

    An attempt is made to obtain calculation equations of macroscopic physico-chemical properties of transition metal refractory compounds (density, melting temperature, Debye characteristic temperature, microhardness, standard formation enthalpy, thermo-emf) using the method of the regression analysis. Apart from the compound composition the argument of the regression equation is the distribution of electron bands of d-transition metals, created by the energy electron distribution in the simplified zone structure of transition metals and approximated by Chebishev polynoms, by the position of Fermi energy on the map of distribution of electron band energy depending upon the value of quasi-impulse, multiple to the first, second and third Brillouin zone for transition metals. The maximum relative error of the regressions obtained as compared with the literary data is 15-20 rel.%

  10. Development of a surfactant liquid membrane extraction process for the cleansing of industrial aqueous effluents containing metallic cation traces

    Rapaumbya Akaye, Guy-Roland

    1994-01-01

    The purpose of this work was to develop a process of surfactant liquid membrane extraction to purify industrial waste solution containing Cu(II), Fe(III), and Zn(II) (about 0,1 g/L). The extractant is the ammonium salt of Cyanex 306 and Aliquat 336. The first part of this work deals with the study of the liquid-liquid extraction of the metals. The efficiency of the extractant has been shown for the extraction of each metal alone and for Cu(II) and Zn(II) in the case of a mixture of the three metals. During this study we have observed that Fe(III) is reduced to Fe(II) (which is not extracted by the salt of Cyanex 301) in presence of Cu(II) and the quaternary ammonium salt (Aliquat 336). The optimisation of the experimental conditions for the discontinuous surfactant liquid membrane process led us to choose the following composition of the emulsion: 1,5 % of Cyanex 301 salt, 2,5 % of ECA 4360, dodecan. The internal phase is an aqueous solution containing 3,5 mol/L of NaOH and 0,5 mol/L tri-ethanolamin The residual concentration of Cu(II) and Zn(II) in the external phase is very low. In the case of iron, only 60 % are extracted because of the reduction phenomenon (10 % in liquid-liquid extraction). The realisation of the continuous process in pulsed column, after optimisation of hydrodynamics conditions, leads to similar results. In stationary conditions, we obtain a raffinate containing less than 0,5 mg/L of Cu(II) and Zn(II) and 36 mg/L of iron. The internal phase contains about 2 g/L of Cu(II) an Zn(II). We tried and minimize the reduction of Fe(III) in surfactant liquid membrane process. Less than 16 % of iron cannot be reduced. This leads to a purification of only 84 % In the basis of these results, processes of purification have been proposed for effluents of various composition. They enable to purify the effluent and besides to concentrate the pollutants about twenty times. (author) [fr

  11. Utility of Lithium in Rare-Earth Metal Reduction Reactions to Form Nontraditional Ln2+ Complexes and Unusual [Li(2.2.2-cryptand)]1+ Cations.

    Huh, Daniel N; Darago, Lucy E; Ziller, Joseph W; Evans, William J

    2018-02-19

    The utility of lithium compared to other alkali metals in generating Ln 2+ rare-earth metal complexes via reduction of Ln 3+ precursors in reactions abbreviated as LnA 3 /M (Ln = rare-earth metal; A = anionic ligand; M = alkali metal) is described. Lithium reduction of Cp' 3 Ln (Cp' = C 5 H 4 SiMe 3 ; Ln = Y, Tb, Dy, Ho) under Ar in the presence of 2.2.2-cryptand (crypt) forms new examples of crystallographically characterizable Ln 2+ complexes of these metals, [Li(crypt)][Cp' 3 Ln]. In each complex, lithium is found in an N 2 O 4 donor atom coordination geometry that is unusual for the cryptand ligand. Magnetic susceptibility data on these new examples of nontraditional divalent lanthanide complexes are consistent with 4f n 5d 1 electronic configurations. The Dy and Ho complexes have exceptionally high single-ion magnetic moments, 11.35 and 11.67 μ B , respectively. Lithium reduction of Cp' 3 Y under N 2 at -35 °C forms the Y 2+ complex (Cp' 3 Y) 1- , which reduces dinitrogen upon warming to room temperature to generate the (N 2 ) 2- complex [Cp' 2 Y(THF)] 2 (μ-η 2 :η 2 -N 2 ). These results provide insight on the factors that lead to reduced dinitrogen complexes and/or stable divalent lanthanide complexes as a function of the specific reducing agent and conditions.

  12. Electron-impact excitation and recombination of molecular cations in edge fusion plasma: application to H2+and BeD+

    Pop, Nicolina; Iacob, Felix; Mezei, Zsolt; Motapon, Ousmanou; Niyonzima, Sebastien; Schneider, Ioan

    2017-10-01

    Dissociative recombination, ro-vibrational excitation and dissociative excitation of molecular cations with electrons are major elementary process in the kinetics and in the energy balance of astrophysically-relevant ionized media (supernovae, interstellar molecular clouds, planetary ionospheres, early Universe), in edge fusion and in many other cold media of technological interest. For the fusion plasma edge, extensive cross sections and rate coefficients have been produced for reactions induced on HD+, H2+ and BeD+ using the Multichannel Quantum Defect Theory (MQDT). Our calculations resulted in good agreement with the CRYRING (Stockholm) and TSR (Heidelberg) magnetic storage ring results, and our approach is permanently improved in order to face the new generation of electrostatic storage rings, as CSR (Heidelberg) and DESIREE (Stockholm). Member of APS Reciprocal Society: European Physics Society.

  13. Electronic and atomic structure at metal-oxide heterointerfaces

    Schlueter, Christoph Friedrich

    2013-07-01

    The results of a series of investigations on modern oxide materials using hard X-ray photoelectron spectroscopy (HAXPES) combined with the X-ray standing wave (XSW) method are described in this thesis. The combination of hard X-ray photoelectron spectroscopy and X-ray standing waves enables the electronic structure to be measured with a spatial resolution in the picometer range. Under suitable preparation conditions, a quasi two-dimensional electron gas (2DEG) is formed at the heterointerfaces of strontium titanate (SrTiO{sub 3}) with polar oxides, such as lanthanum aluminate (LaAlO{sub 3}) or lanthanum gallate (LaGaO{sub 3}). Samples were grown at the ESRF and in Naples and surface X-ray diffraction confirmed the excellent epitaxial quality of the films. The XSW-method was used to reconstruct images of the structure of LaAlO{sub 3} layers in real space. These images give evidence of distortions in the LaAlO{sub 3} structure which facilitate the compensation of the potential differences. Furthermore, XSW/HAXPES measurements permit the Ti and Sr,O contributions to the 2DEG close to the Fermi level to be identified unambiguously. The analysis shows that the 3d band crosses the Fermi level and that some density of states is associated with oxygen vacancies. Superlattices of SrTiO{sub 3} with polar calcium cuprate (CaCuO{sub 2}) were investigated by HAXPES. Similar to the case of SrTiO{sub 3}/LaAlO{sub 3}, the polarity of CaCuO{sub 2} should lead to a diverging surface potential. The core level spectra from Ca, Sr, and Ti show that there is a redistribution mechanism for oxygen which compensates the potential differences. When the oxygen concentration is enhanced these superstructures become superconducting (T{sub C} = 40 K). The increased oxidation of the superconducting material is revealed by the additional components in the core level spectra of the metal atoms and in the appearance of a new screening channel in Cu 2p core level spectra, which signals the hole

  14. Electronic and atomic structure at metal-oxide heterointerfaces

    Schlueter, Christoph Friedrich

    2013-01-01

    The results of a series of investigations on modern oxide materials using hard X-ray photoelectron spectroscopy (HAXPES) combined with the X-ray standing wave (XSW) method are described in this thesis. The combination of hard X-ray photoelectron spectroscopy and X-ray standing waves enables the electronic structure to be measured with a spatial resolution in the picometer range. Under suitable preparation conditions, a quasi two-dimensional electron gas (2DEG) is formed at the heterointerfaces of strontium titanate (SrTiO 3 ) with polar oxides, such as lanthanum aluminate (LaAlO 3 ) or lanthanum gallate (LaGaO 3 ). Samples were grown at the ESRF and in Naples and surface X-ray diffraction confirmed the excellent epitaxial quality of the films. The XSW-method was used to reconstruct images of the structure of LaAlO 3 layers in real space. These images give evidence of distortions in the LaAlO 3 structure which facilitate the compensation of the potential differences. Furthermore, XSW/HAXPES measurements permit the Ti and Sr,O contributions to the 2DEG close to the Fermi level to be identified unambiguously. The analysis shows that the 3d band crosses the Fermi level and that some density of states is associated with oxygen vacancies. Superlattices of SrTiO 3 with polar calcium cuprate (CaCuO 2 ) were investigated by HAXPES. Similar to the case of SrTiO 3 /LaAlO 3 , the polarity of CaCuO 2 should lead to a diverging surface potential. The core level spectra from Ca, Sr, and Ti show that there is a redistribution mechanism for oxygen which compensates the potential differences. When the oxygen concentration is enhanced these superstructures become superconducting (T C = 40 K). The increased oxidation of the superconducting material is revealed by the additional components in the core level spectra of the metal atoms and in the appearance of a new screening channel in Cu 2p core level spectra, which signals the hole doping of the CaCuO 2 blocks. Magnetoresistive

  15. Electron Tunneling in Junctions Doped with Semiconductors and Metals.

    Bell, Lloyd Douglas, II

    In this study, tunnel junctions incorporating thin layers of semiconductors and metals have been analyzed. Inelastic electron tunneling spectroscopy (IETS) was employed to yield high-resolution vibrational spectra of surface species deposited at the oxide-M_2 interface of M_1-M_1O _{rm x}-M _2 tunneling samples. Analysis was also performed on the elastic component of the tunneling current, yielding information on the tunnel barrier shape. The samples in this research exhibit a wide range of behavior. The IETS for Si, SiO_2, and Ge doped samples show direct evidence of SiH _{rm x} and GeH_ {rm x} formation. The particular species formed is shown to depend on the form of the evaporated dopant. Samples were also made with organic dopants deposited over the evaporated dopants. Many such samples show marked effects of the evaporated dopants on the inelastic peak intensities of the organic dopants. These alterations are correlated with the changed reactivity of the oxide surface coupled with a change in the OH dipole layer density on the oxide. Thicker organic dopant layers cause large changes in the elastic tunneling barrier due to OH layer alterations or the low barrier attributes of the evaporated dopant. In the cases of the thicker layers an extra current-carrying mechanism is shown to be contributing. Electron ejection from charge traps is proposed as an explanation for this extra current. The trend of barrier shape with dopant thickness is examined. Many of these dopants also produce a voltage-induced shift in the barrier shape which is stable at low temperature but relaxes at high temperature. This effect is similar to that produced by certain organic dopants and is explained by metastable bond formation between the surface OH and dopant. Other dopants, such as Al, Mg, and Fe, produce different effects. These dopants cause large I-V nonlinearity at low voltages. This nonlinearity is modeled as a giant zero-bias anomaly (ZBA) and fits are presented which show good

  16. Cation distribution in Ni-substituted Mn{sub 0.5}Zn{sub 0.5}Fe{sub 2}O{sub 4} nanoparticles: A Raman, Mössbauer, X-ray diffraction and electron spectroscopy study

    Thota, Suneetha [Microwave Laboratory, Department of Physics, Indian Institute of Technology Delhi, New Delhi 110016 (India); Kashyap, Subhash C., E-mail: skashyap@physics.iitd.ac.in [Microwave Laboratory, Department of Physics, Indian Institute of Technology Delhi, New Delhi 110016 (India); Sharma, Shiv K. [Hawaii Institute of Geophysics and Planetology, University of Hawaii (UH), Honolulu, HI 96822 (United States); Reddy, V.R. [UGC-DAE Consortium for Scientific Research, Khandwa Road, Indore 452017 (India)

    2016-04-15

    Graphical abstract: - Highlights: • Synthesized Mn{sub 0.5−x}Ni{sub x}Zn{sub 0.5}Fe{sub 2}O{sub 4}, nanoparticles (0.05 ≤ x ≤ 0.45) at low temperature. • Raman studies established that Fe and Zn ions occupy A site in equal fraction. • {sup 57}Fe Mossbauer study revealed that Ni and Mn ions occupy nearly 25% of B sites. • Electron spectroscopy (XPS) confirmed that nearly 25% Fe{sup 3+} dwells at A sites. • Diffraction peak intensity (X-ray) quantified cations distribution at A- and B-sites. - Abstract: In this paper we report the structural, vibration, and electronic-structure parameters (bonding and valence of cations) of single phase cubic mixed spinel nanoparticles of (Zn{sub δ}Mn{sub γ}Fe{sub 1−(γ+δ)})[Ni{sub x}Zn{sub 0.5−δ}Mn{sub 0.5−γ−x}Fe{sub 1+(γ+δ)}]O{sub 4} where x = 0.05–0.45 with an aim to determine cation-distribution i.e. δ and γ in these samples. The Raman spectroscopy has established that only Fe and Zn cations occupy tetrahedral interstitial sites in a FCC anion lattice in nearly equal fraction, and Mössbauer spectra have shown that Fe{sup 3+} cations are present at both, tetrahedral and octahedral interstitial sites and Ni{sup 2+} cations are situated at the octahedral sites in all the substituted samples. The photoelectron spectra also revealed the presence of Fe{sup 3+} cations at both the interstitial sites. The best possible cationic distribution in Ni substituted Mn–Zn ferrites has been estimated by reiteratively calculating the intensity ratios of various pairs of X-ray diffraction peaks and matching with the observed intensity ratios.

  17. An AES Study of the Room Temperature Surface Conditioning of Technological Metal Surfaces by Electron Irradiation

    Scheuerlein, C; Taborelli, M; Brown, A; Baker, M A

    2002-01-01

    The modifications to technological copper and niobium surfaces induced by 2.5 keV electron irradiation have been investigated in the context of the conditioning process occurring in particle accelerator ultra high vacuum systems. Changes in the elemental surface composition have been found using Scanning Auger Microscopy (SAM) by monitoring the carbon, oxygen and metal Auger peak intensities as a function of electron irradiation in the dose range 10-6 to 10-2 C mm-2. The surface analysis results are compared with electron dose dependent secondary electron and electron stimulated desorption yield measurements. Initially the electron irradiation causes a surface cleaning through electron stimulated desorption, in particular of hydrogen. During this period both the electron stimulated desorption and secondary electron yield decrease as a function of electron dose. When the electron dose exceeds 10-4 C mm-2 electron stimulated desorption yields are reduced by several orders of magnitude and the electron beam indu...

  18. Influences of the propyl group on the van der Waals structures of 4-propylaniline complexes with one and two argon atoms studied by electronic and cationic spectroscopy

    Yang, Zhijun [School of Basic Medical Sciences, Xinxiang Medical University, Xinxiang, Henan 453003 (China); Gu, Quanli [School of Basic Medical Sciences, Xinxiang Medical University, Xinxiang, Henan 453003 (China); Department of Chemistry, University of Oklahoma, Norman, Oklahoma 73019 (United States); Trindle, Carl O., E-mail: cot@virginia.edu [Chemistry Department, University of Virginia, Charlottesville, Virginia 22904 (United States); Knee, J. L., E-mail: jknee@wesleyan.edu [Chemistry Department, Wesleyan University, Middletown, Connecticut 06459 (United States)

    2015-07-21

    4-propylaniline complexes with one and two argon atoms formed in the molecular beam were studied in the first excited electronic state, S{sub 1}, using resonance enhanced two-photon ionization spectroscopy and in the cation ground state, D{sub 0}, using mass analyzed threshold ionization spectroscopy. The combination of electronic and cationic spectra of the clusters allows two conformations to be identified in both aniline-Ar{sub 1} and aniline-Ar{sub 2}, which are assigned to either the gauche configuration or anti-configuration of 4-propylaniline. The gauche isomer exhibits complex bands shifted 29 cm{sup −1} and 89 cm{sup −1} from the S{sub 1} origin bands and 83 cm{sup −1} and 148 cm{sup −1} from the ionization potential assigned to the Ar{sub 1} and Ar{sub 2} complexes, respectively. For the anti-rotamer, the corresponding shifts actually become nearly additive, 53 cm{sup −1} and 109 cm{sup −1} for the S{sub 1} origin bands, and 61 cm{sup −1} and 125 cm{sup −1} for the ionization potentials. Ab initio calculations provide insights into the influences of the propyl and amino groups on the positions of the argon atoms within the clusters. In addition, the binding energy of one argon with the gauche isomer of 4-propylaniline has been measured to be 550 ± 5 cm{sup −1} in the D{sub 0} state, 496 ± 5 cm{sup −1} in the S{sub 1} state, and 467 ± 5 cm{sup −1} in the neutral ground state, S{sub 0}.

  19. chemical studies and sorption behavior of some hazardous metal ions on polyacrylamide stannic (IV) molybdophosphate as 'organic - inorganic' composite cation - exchanger

    Abdel-Galil, E.A.M.

    2010-01-01

    compsite materials formed by the combination of multivalent metal acid salts and organic polymers provide a new class of (organic-inorganic) hypride ion exchangers with better mechanical and granulometric properties, good ion-exchange capacity, higher chemical and radiation stabilites, reproducibility and selectivity for heavy metals. this material was characterized using X-ray (XRD and XRF), IR, TGA-DTA and total elemental analysis studies. on the basis of distribution studies, the material has been found to be highly selective for pb(II). thermodynamic parameters (i.e δG 0 , δ S 0 and δH 0 ) have also been calculated for the adsorption of Pb 2+ , Cs + , Fe 3+ , Cd 2+ , Cu +2 , Zn 2+ , Co 2+ and Eu 3+ ions on polyacrylamide Sn(IV) molybdophosphate showing that the overall adsorption process is spontaneous endothermic. the mechanism of diffusion of Fe 3+ , Co 2+ , Cu +2 , Zn 2+ , Cd 2+ , Cs + , Pb 2+ and Eu 3+ in the H-form of polyacrylamide Sn(IV) molybdophosphate composite as cation exchanger was studied as a function of particle size, concentration of the exchanging ions, reaction temperature, dring temperature and pH. the exchange rate was controlled by particle diffusion mechanism as a limited batch techneque and is confirmed from straight lines of B versus 1/r 2 polts. the values of diffusion coefficients, activation energy and entropy of activation were calculated and their significance was discussed. the data obtained have been comared with that reported for other organic and inorganic exchangers.

  20. Synthesis, characterization and analytical application of hybrid; Acrylamide zirconium (IV) arsenate a cation exchanger, effect of dielectric constant on distribution coefficient of metal ions

    Nabi, Syed A. [Department of Chemistry, Aligarh Muslim University, Aligarh 202002, U.P. (India)], E-mail: sanabi@rediffmail.com; Shalla, Aabid H. [Department of Chemistry, Aligarh Muslim University, Aligarh 202002, U.P. (India)

    2009-04-30

    A new hybrid inorganic-organic cation exchanger acrylamide zirconium (IV) arsenate has been synthesized, characterized and its analytical application explored. The effect of experimental parameters such as mixing ratio of reagents, temperature, and pH on the properties of material has been studied. FTIR, TGA, X-ray, UV-vis spectrophotometry, SEM and elemental analysis were used to determine the physiochemical properties of this hybrid ion exchanger. The material behaves as a monofunctional acid with ion-exchange capacity of 1.65 meq/g for Na{sup +} ions. The chemical stability data reveals that the exchanger is quite stable in mineral acids, bases and fairly stable in organic solvents, while as thermal analysis shows that the material retain 84% of its ion-exchange capacity up to 600 deg. C. Adsorption behavior of metal ions in solvents with increasing dielectric constant has also been explored. The sorption studies reveal that the material is selective for Pb{sup 2+} ions. The analytical utility of the material has been explored by achieving some binary separations of metal ions on its column. Pb{sup 2+} has been selectively removed from synthetic mixtures containing Mg{sup 2+}, Ca{sup 2+}, Sr{sup 2+}, Zn{sup 2+} and Cu{sup 2+}, Al{sup 3+}, Ni{sup 2+}, Fe{sup 3+}. In order to demonstrate practical utility of the material quantitative separation of the Cu{sup 2+} and Zn{sup 2+} in brass sample has been achieved on its columns.

  1. Theoretical study for the reduction of N2O with CO Mediated by alkaline-earth metal oxide cations 2MO+(M=Ca, Sr, Ba)

    Zhang Jianhui; Leng Yanli; Wang Yongcheng

    2013-01-01

    The reaction mechanism of the reaction N 2 O( 0 Σ + ) + CO ( 1 Σ + )→N 2 ( 1 Σ g + ) + CO 2 ( 1 Σ g + ) mediated by alkaline-earth metal oxide cations 2 MO + (m=Ca, Sr, Ba) have been investigated by using the UB3LYP and CCSD (T) levels of theory. The O-atom affinities (OA) testified that only the 2 CaO + can capture O from N 2 O and transfer O to CO is thermodynamically allowed in three ions. The processes can be expressed as channels l and 2 for the reaction of N 2 O and CO mediated by 2 MO + (M=Ca, Sr, Ba). For the former, the main reaction processes in a two-step manner to products, the 2 MO + , as a catalyzer, transports an oxygen atom from N 2 O to CO. For the latter, firstly, the N 2 O interact with the 2 MO + to form IM1, then IM1 interact with the CO to form IM2', along the reaction pathway the intermediate species convert into products 2 1MO + , N 2 and CO 2 . From above results, the following conclusion was drawn. The channel 2 is kinetically and thermodynamically feasible. Our calculated results show the title reactions are accord with the experiment. (authors)

  2. Engineering sodium alginate-based cross-linked beads with high removal ability of toxic metal ions and cationic dyes.

    Shao, Zi-Jian; Huang, Xue-Lian; Yang, Fan; Zhao, Wei-Feng; Zhou, Xin-Zhi; Zhao, Chang-Sheng

    2018-05-01

    Sodium alginate (SA) beads with ultrahigh adsorption capacity were prepared via hydrogen bonds between SA and 2-acrylamido-2-methylpropa-1-propanesulfonic acid (AMPS), and the AMPS was then post-cross-linked to manufacture SA/PAMPS beads. The equilibrium adsorption capacities of methylene blue (MB) and Pb 2+ for the SA/PAMPS10 beads were 2977 and 2042 mg/g, respectively. Although the SA beads exhibited higher equilibrium adsorption capacities of MB and Pb 2+ than those of the SA/PAMPS10 beads, the SA/PAMPS10 beads had better mechanical property and higher stability. The pseudo-second-order kinetic model and the Langmuir isotherm described the adsorption processes of the SA/PAMPS10 beads for MB well. In addition, the SA/PAMPS10 beads could be reused with stable adsorption capacity for at least three cycles. The beads also had excellent performances on absorbing methylene violet and other heavy metal ions (Cu 2+ , Cd 2+ and Ni 2+ ). Therefore, the SA-based beads with high adsorption capacity might be good candidates for industrial pollutant treatments. Copyright © 2018 Elsevier Ltd. All rights reserved.

  3. Peripherally Metalated Porphyrins with Applications in Catalysis, Molecular Electronics and Biomedicine.

    Longevial, Jean-François; Clément, Sébastien; Wytko, Jennifer A; Ruppert, Romain; Weiss, Jean; Richeter, Sébastien

    2018-04-24

    Porphyrins are conjugated, stable chromophores with a central core that binds a variety of metal ions and an easily functionalized peripheral framework. By combining the catalytic, electronic or cytotoxic properties of selected transition metal complexes with the binding and electronic properties of porphyrins, enhanced characteristics of the ensemble are generated. This review article focuses on porphyrins bearing one or more peripheral transition metal complexes and discusses their potential applications in catalysis or biomedicine. Modulation of the electronic properties and intramolecular communication through coordination bond linkages in bis-porphyrin scaffolds is also presented. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. Accelerated electron exchange between U4+ and UO22+ by foreign metal ions

    Obanawa, Heiichiro; Onitsuka, Hatsuki; Takeda, Kunihiko

    1990-01-01

    The rate constant of U 4+ -UO 2 2+ electron exchange (k et ) was increased by more than 100 times in the presence of various metal ions. The larger rate constant was observed for the smaller difference of the standard reduction potential strength between metal ion and UO 2 2+ ion (Δμ θ e ). Detailed investigation of the electron exchange reaction in the presence of Mo 5+ suggested that the mechanism of the electron transfer reaction catalyzed by metal ions is the outer-sphere type independent of U-Clcomplex ions. (author)

  5. Gas-Phase Energetics of Actinide Oxides: An Assessment of Neutral and Cationic Monoxides and Dioxides from Thorium to Curium

    Marçalo, Joaquim; Gibson, John K.

    2009-09-01

    An assessment of the gas-phase energetics of neutral and singly and doubly charged cationic actinide monoxides and dioxides of thorium, protactinium, uranium, neptunium, plutonium, americium, and curium is presented. A consistent set of metal-oxygen bond dissociation enthalpies, ionization energies, and enthalpies of formation, including new or revised values, is proposed, mainly based on recent experimental data and on correlations with the electronic energetics of the atoms or cations and with condensed-phase thermochemistry.

  6. Metallic vapor supplying by the electron bombardment for a metallic ion production with an ECR ion source

    Kitagawa, Atsushi; Sasaki, Makoto; Muramatsu, Masayuki [National Inst. of Radiological Sciences, Chiba (Japan); Jincho, Kaoru; Sasaki, Noriyuki; Sakuma, Tetsuya; Takasugi, Wataru; Yamamoto, Mitsugu [Accelerator Engineering Corporation, Chiba (Japan)

    2001-11-19

    To produce the metallic ion beam for the injection into the Heavy Ion Medical Accelerator in Chiba (HIMAC) at the National Institute of Radiological Sciences (NIRS), a new gas supply method has been developed for an 18 GHz ECR ion source (NIRS-HEC). A metallic target rod at a high positive potential is melted by the electron bombardment technique. The evaporated gas with a maximum flow rate of 50A/sec is supplied into the ECR plasma in case of Fe metal. (author)

  7. Metallic vapor supplying by the electron bombardment for a metallic ion production with an ECR ion source

    Kitagawa, Atsushi; Sasaki, Makoto; Muramatsu, Masayuki; Jincho, Kaoru; Sasaki, Noriyuki; Sakuma, Tetsuya; Takasugi, Wataru; Yamamoto, Mitsugu

    2001-01-01

    To produce the metallic ion beam for the injection into the Heavy Ion Medical Accelerator in Chiba (HIMAC) at the National Institute of Radiological Sciences (NIRS), a new gas supply method has been developed for an 18 GHz ECR ion source (NIRS-HEC). A metallic target rod at a high positive potential is melted by the electron bombardment technique. The evaporated gas with a maximum flow rate of 50A/sec is supplied into the ECR plasma in case of Fe metal. (author)

  8. Cation radicals of xanthophylls.

    Galinato, Mary Grace I; Niedzwiedzki, Dariusz; Deal, Cailin; Birge, Robert R; Frank, Harry A

    2007-10-01

    Carotenes and xanthophylls are well known to act as electron donors in redox processes. This ability is thought to be associated with the inhibition of oxidative reactions in reaction centers and light-harvesting pigment-protein complexes of photosystem II (PSII). In this work, cation radicals of neoxanthin, violaxanthin, lutein, zeaxanthin, beta-cryptoxanthin, beta-carotene, and lycopene were generated in solution using ferric chloride as an oxidant and then studied by absorption spectroscopy. The investigation provides a view toward understanding the molecular features that determine the spectral properties of cation radicals of carotenoids. The absorption spectral data reveal a shift to longer wavelength with increasing pi-chain length. However, zeaxanthin and beta-cryptoxanthin exhibit cation radical spectra blue-shifted compared to that of beta-carotene, despite all of these molecules having 11 conjugated carbon-carbon double bonds. CIS molecular orbital theory quantum computations interpret this effect as due to the hydroxyl groups in the terminal rings selectively stabilizing the highest occupied molecular orbitals of preferentially populated s-trans-isomers. The data are expected to be useful in the analysis of spectral results from PSII pigment-protein complexes seeking to understand the role of carotene and xanthophyll cation radicals in regulating excited state energy flow, in protecting PSII reaction centers against photoinhibition, and in dissipating excess light energy absorbed by photosynthetic organisms but not used for photosynthesis.

  9. Pseudoclassical approach to electron and ion density correlations in simple liquid metals

    Vericat, F.; Tosi, M.P.; Pastore, G.

    1986-04-01

    Electron-electron and electron-ion structural correlations in simple liquid metals are treated by using effective pair potentials to incorporate quantal effects into a pseudoclassical description of the electron fluid. An effective pair potential between simultaneous electron density fluctuations is first constructed from known properties of the degenerate jellium model, which are the plasmon sum rule, the Kimball-Niklasson relation and Yasuhara's values of the electron pair distribution function at contact. An analytic expression is thereby obtained in the Debye-Hueckel approximation for the electronic structure factor in jellium over a range of density appropriate to metals, with results which compare favourably with those of fully quantal evaluations. A simple pseudoclassical model is then set up for a liquid metal: this involves a model of charged hard spheres for the ion-ion potential and an empty core model for the electron-ion potential, the Coulombic tails being scaled as required by the relation between the long-wavelength partial structure factors and the isothermal compressibility of the metal. The model is solved analytically by a pseudoclassical linear response treatment of the electron-ion coupling and numerical results are reported for partial structure factors in liquid sodium and liquid beryllium. Contact is made for the latter system with data on the electron-electron structure factor in the crystal from inelastic X-ray scattering experiments of Eisenberger, Marra and Brown. (author)

  10. Recent Advancements in Liquid Metal Flexible Printed Electronics: Properties, Technologies, and Applications

    Xuelin Wang

    2016-11-01

    Full Text Available This article presents an overview on typical properties, technologies, and applications of liquid metal based flexible printed electronics. The core manufacturing material—room-temperature liquid metal, currently mainly represented by gallium and its alloys with the properties of excellent resistivity, enormous bendability, low adhesion, and large surface tension, was focused on in particular. In addition, a series of recently developed printing technologies spanning from personal electronic circuit printing (direct painting or writing, mechanical system printing, mask layer based printing, high-resolution nanoimprinting, etc. to 3D room temperature liquid metal printing is comprehensively reviewed. Applications of these planar or three-dimensional printing technologies and the related liquid metal alloy inks in making flexible electronics, such as electronical components, health care sensors, and other functional devices were discussed. The significantly different adhesions of liquid metal inks on various substrates under different oxidation degrees, weakness of circuits, difficulty of fabricating high-accuracy devices, and low rate of good product—all of which are challenges faced by current liquid metal flexible printed electronics—are discussed. Prospects for liquid metal flexible printed electronics to develop ending user electronics and more extensive applications in the future are given.

  11. Non-equilibrium thermionic electron emission for metals at high temperatures

    Domenech-Garret, J. L.; Tierno, S. P.; Conde, L.

    2015-08-01

    Stationary thermionic electron emission currents from heated metals are compared against an analytical expression derived using a non-equilibrium quantum kappa energy distribution for the electrons. The latter depends on the temperature decreasing parameter κ ( T ) , which decreases with increasing temperature and can be estimated from raw experimental data and characterizes the departure of the electron energy spectrum from equilibrium Fermi-Dirac statistics. The calculations accurately predict the measured thermionic emission currents for both high and moderate temperature ranges. The Richardson-Dushman law governs electron emission for large values of kappa or equivalently, moderate metal temperatures. The high energy tail in the electron energy distribution function that develops at higher temperatures or lower kappa values increases the emission currents well over the predictions of the classical expression. This also permits the quantitative estimation of the departure of the metal electrons from the equilibrium Fermi-Dirac statistics.

  12. Study of the nanostructure of Gum Metal using energy-filtered transmission electron microscopy

    Yano, T.; Murakami, Y.; Shindo, D.; Kuramoto, S.

    2009-01-01

    The nanostructure of Gum Metal, which has many anomalous mechanical properties, was investigated using transmission electron microscopy with energy filtering. A precise analysis of the weak diffuse electron scattering that was observed in the electron diffraction patterns of the Gum Metal specimen revealed that Gum Metal contains a substantial amount of the nanometer-sized ω phase. The morphology of the ω phase appeared to have a correlation with the faulting in the {2 1 1} planes, which are one of the characteristic lattice imperfections of the Gum Metal specimen. It is likely that the nanometer-sized ω phase may be a type of obstacle related to the restriction of the dislocation movement, which has been a significant problem in research on Gum Metal

  13. Reconfigurable electronics using conducting metal-organic frameworks

    Allendorf, Mark D.; Talin, Albert Alec; Leonard, Francois; Stavila, Vitalie

    2017-07-18

    A device including a porous metal organic framework (MOF) disposed between two terminals, the device including a first state wherein the MOF is infiltrated by a guest species to form an electrical path between the terminals and a second state wherein the electrical conductivity of the MOF is less than the electrical conductivity in the first state. A method including switching a porous metal organic framework (MOF) between two terminals from a first state wherein a metal site in the MOF is infiltrated by a guest species that is capable of charge transfer to a second state wherein the MOF is less electrically conductive than in the first state.

  14. SEM evaluation of metallization on semiconductors. [Scanning Electron Microscope

    Fresh, D. L.; Adolphsen, J. W.

    1974-01-01

    A test method for the evaluation of metallization on semiconductors is presented and discussed. The method has been prepared in MIL-STD format for submittal as a proposed addition to MIL-STD-883. It is applicable to discrete devices and to integrated circuits and specifically addresses batch-process oriented defects. Quantitative accept/reject criteria are given for contact windows, other oxide steps, and general interconnecting metallization. Figures are provided that illustrate typical types of defects. Apparatus specifications, sampling plans, and specimen preparation and examination requirements are described. Procedures for glassivated devices and for multi-metal interconnection systems are included.

  15. Electron spin resonance and electron spin echo modulation studies of Cu(II) ions in the aluminosilicate chabazite: A comparison of Cu(II) cation location and adsorbate interaction with isostructural silicoaluminophosphate-34

    Zamadics, M.; Kevan, L.

    1992-01-01

    This study focuses on Cu(II) ions exchanged in the aluminosilicate zeolite chabazite. The various Cu(II) species formed after dehydration, rehydration, and exposure to adsorbates are characterized by electron spin resonance and electron spin echo modulation spectroscopies. These results are interpreted in terms of Cu(II) ion location and adsorbate interaction. The results of this study are compared to the results found earlier for SAPO-34, chabazite's structural analog from the silicoaluminophosphate group. In a hydrated sample of chabazite the Cu(II) ions are found to be in a near octahedral environment coordinated to three nonequivalent water molecules and three framework oxygens. The most probable location of the Cu(II) ion in a hydrated sample is above the plane of the six-membered ring slightly displaced into the ellipsoidal cavity. A somewhat similar location and coordination is found for Cu(II) ions in H-SAPO-34. A feature common to both CuH-chabazite and CuH-SAPO-34 is the generation of two distinct Cu(II) species upon dehydration. It is found that Cu(II) cations in chabazite interact with the various adsorbate molecules in a similar manner as Cu(II) cation in H-chabazite and three molecules of ethanol and three propanol molecules. Only the Cu(II) ions located in the hexagonal rings after dehydration were found to complex with ethylene. The differences observed in the interaction of the Cu(II) in with water, propanol, and ehtylene between SAPO-34 and chabazite can be related to the differing cation densities of these two materials. 32 refs., 7 figs., 21 tabs

  16. Energy modulation of nonrelativistic electrons in an optical near field on a metal microslit

    R., Ishikawa; Jongsuck, Bae; K., Mizuno

    2001-01-01

    Energy modulation of nonrelativistic electrons with a laser beam using a metal microslit as an interaction circuit has been investigated. An optical near field is induced in the proximity of the microslit by illumination of the laser beam. The electrons passing close to the slit are accelerated or decelerated by an evanescent wave contained in the near field whose phase velocity is equal to the velocity of the electrons. The electron-evanescent wave interaction in the microslit has been analy...

  17. 2-(1,3-Dithiolan-2-ylidene)-5-(1,3-dithian-2-ylidene)-1,3,4,6- tetrathiapentalene(DHDA-TTP), a hybrid of BDH-TTP and BDA-TTP, and its metallic cation-radical salts.

    Yamada, Jun-ichi; Watanabe, Maki; Toita, Takashi; Akutsu, Hiroki; Nakatsuji, Shin'ichi; Nishikawa, Hiroyuki; Ikemoto, Isao; Kikuchi, Koichi

    2002-05-21

    The synthesis and electrochemical properties of the DHDA-TTP donor, a hybrid of 2,5-bis(1,3-dithiolan-2-ylidene)-1,3,4,6-tetrathiapentalene (BDH-TTP) and 2,5-bis(1,3-dithian-2-ylidene)-1,3,4,6-tetrathiapentalene (BDA-TTP), has been investigated, and its ability to form metallic cation-radical salts is elucidated.

  18. Development of high current electron source using photoemission from metals with ultrashort laser pulses

    Tsang, T.; Srinivasan-Rao, T.; Fischer, J.

    1990-10-01

    We summarize the studies of photoemission from metal photocathodes using picosecond pulses in the UV (4.66 eV) wavelength and femtosecond laser pulses in the visible (2 eV) wavelengths. To achieve high current density yield from metal photocathodes, multiphoton photoemission using femtosecond laser pulses are suggested. Electron yield improvement incorporating surface photoemission and surface plasmon resonance in metals and metal films are demonstrated. We examine the possibility of the nonlinear photoemission process overtaking the linear process, and identity some possible complexity. To extract the large amount of electrons free of space charge, a pulsed high voltage is designed; the results of the preliminary test are presented. Finally, for the first time, the width of the electron temporal profiles are measured, utilizing the nonlinear photoelectric effect, to below 100 fsec time regime. The results indicated that the electron pulse duration follows the laser pulses and are not limited by the material. 8 refs., 15 figs

  19. Bioleaching of metals from electronic scrap by moderately thermophilic acidophilic bacteria

    Ilyas, Sadia; Anwar, Munir A.; Niazi, Shahida B.; Ghauri, M. Afzal

    The present work was aimed at studying the bioleachability of metals from electronic scrap by the selected moderately thermophilic strains of acidophilic chemolithotrophic and acidophilic heterotrophic bacteria. These included Sulfobacillus thermosulfidooxidans and an unidentified acidophilic

  20. Liquid alkali metals and alkali-based alloys as electron-ion plasmas

    Tosi, M.P.

    1981-06-01

    The article reviews the theory of thermodynamic and structural properties of liquid alkali metals and alkali-based alloys, within the framework of linear screening theory for the electron-ion interactions. (author)

  1. Electronic structures and magnetic/optical properties of metal phthalocyanine complexes

    Baba, Shintaro; Suzuki, Atsushi, E-mail: suzuki@mat.usp.ac.jp; Oku, Takeo [Department of Materials Science, The University of Shiga Prefecture. 2500 Hassaka, Hikone, Shiga 522-8533 (Japan)

    2016-02-01

    Electronic structures and magnetic / optical properties of metal phthalocyanine complexes were studied by quantum calculations using density functional theory. Effects of central metal and expansion of π orbital on aromatic ring as conjugation system on the electronic structures, magnetic, optical properties and vibration modes of infrared and Raman spectra of metal phthalocyanines were investigated. Electron and charge density distribution and energy levels near frontier orbital and excited states were influenced by the deformed structures varied with central metal and charge. The magnetic parameters of chemical shifts in {sup 13}C-nuclear magnetic resonance ({sup 13}C-NMR), principle g-tensor, A-tensor, V-tensor of electric field gradient and asymmetry parameters derived from the deformed structures with magnetic interaction of nuclear quadruple interaction based on electron and charge density distribution with a bias of charge near ligand under crystal field.

  2. Electronic excitations in metallic systems: from defect annihilation to track formation

    Dunlop, A.; Lesueur, D.

    1991-01-01

    This paper presents an overview of the effects of high electronic energy deposition in metallic targets irradiated with GeV heavy ions. The main result of these investigations is that high electronic excitations lead to various and sometimes conflicting effects according to the nature of the target: - partial annealing of the defects induced by elastic collisions, - creation of additional disorder, - phase transformation (tracks formation and amorphization), - anisotropic growth. These different effects of high electronic energy deposition in metallic targets are probably manifestations at various degrees of the same basic energy transfer process between the excited electrons and the target atoms. Up to now no theoretical model explains these effects. 24 refs

  3. Electronic structure of the 3d metals. An investigation by L-shell-photoionisation

    Richter, T.S.

    2007-12-03

    The 3d transition metal elements from Sc to Cu have been investigated by both photo electron emission and photo absorption. Experimental spectra in the 2p energy range are discussed based on atomic multiplet models and Hartree- Fock calculations. The samples have been evaporated from an electron bombardment crucible and excited/ionized by monochromatized synchrotron radiation. Fundamental effects and the main interactions which govern the electronic structure of the 3d metal atoms are covered. Common spectral features and trends in the series are discussed as well as the importance of many body electron correlation effects. (orig.)

  4. Role of Metal Cations on the corrosion behaviour of 8090-T851 in a pH 2.0 solution

    Murthy, K.S.N.; Ambat, Rajan; Dwarakadasa, E.S.

    1994-01-01

    The influence of cations such as Cu2+, Al3+ and Li+ on the corrosion behaviour of 8090-T851(Al-Li) alloy in a pH 2.0 HCl solution was investigated by weight loss and polarisation techniques. Weight loss experiments showed that the effect of cation is a strong function of its nature...

  5. Competitive/co-operative interactions in acid base sandwich: role of cation vs. substituents.

    Kalpana, Ayyavoo; Akilandeswari, Lakshminarayanan

    2017-11-15

    The cation-π interaction can be envisaged as a lewis acid base interaction, and it is in line with Pearson's acid base concept. The critical examination of interactions between the π-acids (alkali metal cations - Li + , Na + and alkaline earth metal cations Mg 2+ , Ca 2+ ) on one face and tripodal Cr(CO) 3 moiety on the other π face of substituted arenes demonstrates the role of cation and substitutents in manipulating the interactions between them. The interaction of the two π acids on both faces of arene is not expectedly additive, rather it shows either depreciation of interaction energy revealing the competition of acids toward the base or enhancement of interaction energy denoting a cooperative effect. Among the metal cations under study, Mg 2+ shows a cooperative gesture. Although the substituents play a meek role, they unfailingly exert their electronic effects and are amply documented by excellent correlation of various parameters with the Hammett constant σ m . The elusive switching of λ max from the UV to IR region on binding Mg 2+ with substituted arene-Cr(CO) 3 complex is a characteristic clue that TDDFT can help design the ionic sensors for Mg 2+ cations.

  6. Nonequilibrium electron energy-loss kinetics in metal clusters

    Guillon, C; Fatti, N D; Vallee, F

    2003-01-01

    Ultrafast energy exchanges of a non-Fermi electron gas with the lattice are investigated in silver clusters with sizes ranging from 4 to 26 nm using a femtosecond pump-probe technique. The results yield evidence for a cluster-size-dependent slowing down of the short-time energy losses of the electron gas when it is strongly athermal. A constant rate is eventually reached after a few hundred femtoseconds, consistent with the electron gas internal thermalization kinetics, this behaviour reflecting evolution from an individual to a collective electron-lattice type of coupling. The timescale of this transient regime is reduced in small nanoparticles, in agreement with speeding up of the electron-electron interactions with size reduction. The experimental results are in quantitative agreement with numerical simulations of the electron kinetics.

  7. Hot-electron-based solar energy conversion with metal-semiconductor nanodiodes

    Lee, Young Keun; Lee, Hyosun; Lee, Changhwan; Hwang, Euyheon; Park, Jeong Young

    2016-06-01

    Energy dissipation at metal surfaces or interfaces between a metal and a dielectric generally results from elementary excitations, including phonons and electronic excitation, once external energy is deposited to the surface/interface during exothermic chemical processes or an electromagnetic wave incident. In this paper, we outline recent research activities to develop energy conversion devices based on hot electrons. We found that photon energy can be directly converted to hot electrons and that hot electrons flow through the interface of metal-semiconductor nanodiodes where a Schottky barrier is formed and the energy barrier is much lower than the work function of the metal. The detection of hot electron flow can be successfully measured using the photocurrent; we measured the photoyield of photoemission with incident photons-to-current conversion efficiency (IPCE). We also show that surface plasmons (i.e. the collective oscillation of conduction band electrons induced by interaction with an electromagnetic field) are excited on a rough metal surface and subsequently decay into secondary electrons, which gives rise to enhancement of the IPCE. Furthermore, the unique optical behavior of surface plasmons can be coupled with dye molecules, suggesting the possibility for producing additional channels for hot electron generation.

  8. Heat transport and electron cooling in ballistic normal-metal/spin-filter/superconductor junctions

    Kawabata, Shiro; Vasenko, Andrey S.; Ozaeta, Asier; Bergeret, Sebastian F.; Hekking, Frank W.J.

    2015-01-01

    We investigate electron cooling based on a clean normal-metal/spin-filter/superconductor junction. Due to the suppression of the Andreev reflection by the spin-filter effect, the cooling power of the system is found to be extremely higher than that for conventional normal-metal/nonmagnetic-insulator/superconductor coolers. Therefore we can extract large amount of heat from normal metals. Our results strongly indicate the practical usefulness of the spin-filter effect for cooling detectors, sensors, and quantum bits

  9. Heat transport and electron cooling in ballistic normal-metal/spin-filter/superconductor junctions

    Kawabata, Shiro, E-mail: s-kawabata@aist.go.jp [Electronics and Photonics Research Institute (ESPRIT), National Institute of Advanced Industrial Science and Technology (AIST), Tsukuba, Ibaraki 305-8568 (Japan); Vasenko, Andrey S. [LPMMC, Université Joseph Fourier and CNRS, 25 Avenue des Martyrs, BP 166, 38042 Grenoble (France); Ozaeta, Asier [Centro de Física de Materiales (CFM-MPC), Centro Mixto CSIC-UPV/EHU, Manuel de Lardizabal 5, E-20018 San Sebastián (Spain); Bergeret, Sebastian F. [Centro de Física de Materiales (CFM-MPC), Centro Mixto CSIC-UPV/EHU, Manuel de Lardizabal 5, E-20018 San Sebastián (Spain); Donostia International Physics Center (DIPC), Manuel de Lardizabal 5, E-20018 San Sebastián (Spain); Hekking, Frank W.J. [LPMMC, Université Joseph Fourier and CNRS, 25 Avenue des Martyrs, BP 166, 38042 Grenoble (France)

    2015-06-01

    We investigate electron cooling based on a clean normal-metal/spin-filter/superconductor junction. Due to the suppression of the Andreev reflection by the spin-filter effect, the cooling power of the system is found to be extremely higher than that for conventional normal-metal/nonmagnetic-insulator/superconductor coolers. Therefore we can extract large amount of heat from normal metals. Our results strongly indicate the practical usefulness of the spin-filter effect for cooling detectors, sensors, and quantum bits.

  10. High pressure metallization of Mott Insulators: Magnetic, structural and electronic properties

    Pasternak, M.P.; Hearne, G.; Sterer, E.; Taylor, R.D.; Jeanloz, R.

    1993-01-01

    High pressure studies of the insulator-metal transition in the (TM)I 2 (TM = V, Fe, Co and Ni) compounds are described. Those divalent transition-metal iodides are structurally isomorphous and classified as Mott Insulators. Resistivity, X-ray diffraction and Moessbauer Spectroscopy were employed to investigate the electronic, structural, and magnetic properties as a function of pressure both on the highly correlated and on the metallic regimes

  11. Spin flip inelastic scattering in electron energy loss spectroscopy of a ferromagnetic metal

    Bocchetta, C.J.; Tosatti, E.; Yin, S.

    1986-11-01

    A model ferromagnetic metal is used to calculate the spin-polarization which occurs during inelastic electron-metal scattering with the production of an electron-hole pair. The polarization is found to have contributions from unequal spin-flip as well as non-flip energy loss rates. Our results indicate an asymmetry of the order of a few percent with parameters roughly modelling iron. (author)

  12. Dosimetric impact of a CT metal artefact suppression algorithm for proton, electron and photon therapies

    Wei Jikun; Sandison, George A; Hsi, W-C; Ringor, Michael; Lu Xiaoyi

    2006-01-01

    Accurate dose calculation is essential to precision radiation treatment planning and this accuracy depends upon anatomic and tissue electron density information. Modern treatment planning inhomogeneity corrections use x-ray CT images and calibrated scales of tissue CT number to electron density to provide this information. The presence of metal in the volume scanned by an x-ray CT scanner causes metal induced image artefacts that influence CT numbers and thereby introduce errors in the radiation dose distribution calculated. This paper investigates the dosimetric improvement achieved by a previously proposed x-ray CT metal artefact suppression technique when the suppressed images of a patient with bilateral hip prostheses are used in commercial treatment planning systems for proton, electron or photon therapies. For all these beam types, this clinical image and treatment planning study reveals that the target may be severely underdosed if a metal artefact-contaminated image is used for dose calculations instead of the artefact suppressed one. Of the three beam types studied, the metal artefact suppression is most important for proton therapy dose calculations, intermediate for electron therapy and least important for x-ray therapy but still significant. The study of a water phantom having a metal rod simulating a hip prosthesis indicates that CT numbers generated after image processing for metal artefact suppression are accurate and thus dose calculations based on the metal artefact suppressed images will be of high fidelity

  13. Transmission electron microscope examination of rare-gas bubbles in metals: analysis of observed contrast effects

    Levy, V.

    1964-01-01

    Metallic samples containing rare gas bubbles have been examined by transmission electron microscopy. The different features of the contrast patterns of the bubbles have been explained by the dynamical theory of contrast, assuming that the bubble behaves as a hole in the metal. Experimental results are in good agreement with the theory. (author) [fr

  14. Theoretical study of the influence of cation vacancies on the catalytic properties of vanadium antimonate

    Messina, S.; Juan, A.; Larrondo, S.; Irigoyen, B.; Amadeo, N.

    2008-01-01

    We have theoretically studied the influence of antimony and vanadium cation vacancies in the electronic structure and reactivity of vanadium antimonate, using molecular orbital methods. From the analysis of the electronic properties of the VSbO 4 crystal structure, we can infer that both antimony and vanadium vacancies increase the oxidation state of closer V cations. This would indicate that, in the rutile-type VSbO 4 phase the Sb and V cations defects stabilize the V in a higher oxidation state (V 4+ ). Calculations of the adsorption energy for different toluene adsorption geometries on the VSbO 4 (1 1 0) surface have also been performed. The oxidation state of Sb, V and O atoms and the overlap population of metal-oxygen bonds have been evaluated. Our results indicate that the cation defects influence in the toluene adsorption reactions is slight. We have computed different alternatives for the reoxidation of the VSbO 4 (1 1 0) surface active sites which were reduced during the oxygenated products formation. These calculations indicate that the V cations in higher oxidation state (V 4+ ) are the species, which preferentially incorporate lattice oxygen to the reduced Sb cations. Thus, the cation defects would stabilize the V 4+ species in the VSbO 4 structure, determining its ability to provide lattice oxygen as a reactant

  15. Chemical activation of molecules by metals: Experimental studies of electron distributions and bonding

    Lichtenberger, D.L.

    1991-10-01

    The formal relationship between measured molecular ionization energies and thermodynamic bond dissociation energies has been developed into a single equation which unifies the treatment of covalent bonds, ionic bonds, and partially ionic bonds. This relationship has been used to clarify the fundamental thermodynamic information relating to metal-hydrogen, metal-alkyl, and metal-metal bond energies. We have been able to obtain a direct observation and measurement of the stabilization energy provided by the agostic interaction of the C-H bond with the metal. The ionization energies have also been used to correlate the rates of carbonyl substitution reactions of (η 5 -C 5 H 4 X)Rh(CO) 2 complexes, and to reveal the electronic factors that control the stability of the transition state. The extent that the electronic features of these bonding interactions transfer to other chemical systems is being investigated in terms of the principle of additivity of ligand electronic effects. Specific examples under study include metal- phosphines, metal-halides, and metallocenes. Especially interesting has been the recent application of these techniques to the characterization of the soccer-ball shaped C 60 molecule, buckminsterfullerene, and its interaction with a metal surface. The high-resolution valence ionizations in the gas phase reveal the high symmetry of the molecule, and studies of thin films of C 60 reveal weak intermolecular interactions. Scanning tunneling and atomic force microscopy reveal the arrangement of spherical molecules on gold substrates, with significant delocalization of charge from the metal surface. 21 refs

  16. Inductive crystal field control in layered metal oxides with correlated electrons

    Balachandran, P. V.; Cammarata, A.; Rondinelli, J. M.; Nelson-Cheeseman, B. B.; Bhattacharya, A.

    2014-01-01

    We show that the NiO 6 crystal field energies can be tailored indirectly via heterovalent A cation ordering in layered (La,A)NiO 4 Ruddlesden–Popper (RP) oxides, where A = Sr, Ca, or Ba, using density functional calculations. We leverage as a driving force the electrostatic interactions between charged [LaO] 1+ and neutral [AO] 0 planes to inductively tune the Ni–O bond distortions, without intentional doping or epitaxial strain, altering the correlated d-orbital energies. We use this strategy to design cation ordered LaCaNiO 4 and LaBaNiO 4 with distortions favoring enhanced Ni e g orbital polarization, and find local electronic structure signatures analogous to those in RP La-cuprates, i.e., parent phases of the high-temperature superconducting oxides

  17. Inductive crystal field control in layered metal oxides with correlated electrons

    Balachandran, P. V.; Cammarata, A.; Rondinelli, J. M., E-mail: jrondinelli@nortwestern.edu [Department of Materials Science and Engineering, Drexel University, Philadelphia, Pennsylvania 19104 (United States); Nelson-Cheeseman, B. B. [School of Engineering, University of St. Thomas, St. Paul, Minnesota 55105 (United States); Materials Science Division, Argonne National Laboratory, Argonne, Illinois 60439 (United States); Bhattacharya, A. [Materials Science Division, Argonne National Laboratory, Argonne, Illinois 60439 (United States); Center for Nanoscale Materials, Argonne National Laboratory, Argonne, Illinois 60439 (United States)

    2014-07-01

    We show that the NiO{sub 6} crystal field energies can be tailored indirectly via heterovalent A cation ordering in layered (La,A)NiO{sub 4} Ruddlesden–Popper (RP) oxides, where A = Sr, Ca, or Ba, using density functional calculations. We leverage as a driving force the electrostatic interactions between charged [LaO]{sup 1+} and neutral [AO]{sup 0} planes to inductively tune the Ni–O bond distortions, without intentional doping or epitaxial strain, altering the correlated d-orbital energies. We use this strategy to design cation ordered LaCaNiO{sub 4} and LaBaNiO{sub 4} with distortions favoring enhanced Ni e{sub g} orbital polarization, and find local electronic structure signatures analogous to those in RP La-cuprates, i.e., parent phases of the high-temperature superconducting oxides.

  18. Magnetic collimation and metal foil filtering for electron range and fluence modulation

    Phaisangittisakul, N.; D'Souza, W.D.; Ma Lijun

    2004-01-01

    We investigated the use of magnetically collimated electron beams together with metal filters for electron fluence and range modulation. A longitudinal magnetic field collimation method was developed to reduce skin dose and to improve the electron beam penumbra. Thin metal foils were used to adjust the energies of magnetically collimated electrons. The effects for different types of foils such as Al, Be, Cu, Pb, and Ti were studied using Monte Carlo calculations. An empirical pencil beam dose calculation model was developed to calculate electron dose distributions under magnetic collimation and foil modulation. An optimization method was developed to produce conformal dose distributions for simulated targets such as a horseshoe-shaped target. Our results show that it is possible to produce an electron depth dose enhancement peak using similar techniques of producing a spread-out Bragg peak. In conclusion, our study demonstrates new aspects of using magnetic collimation and foil filtration for producing fluence and range modulated electron dose distributions

  19. Electron transfer reactions of metal complexes in solution

    Sutin, N.

    1977-01-01

    A few representative electron-transfer reactions are selected and their kinetic parameters compared with the predictions of activated complex models. Since Taube has presented an elegant treatment of intramolecular electron-transfer reactions, emphasis is on bimolecular reactions. The latter electron-transfer reactions are more complicated to treat theoretically since the geometries of their activated complexes are not as well known as for the intramolecular case. In addition in biomolecular reactions, the work required to bring the two reactants together needs to be calculated. Since both reactants generally carry charges this presents a non-trivial problem at the ionic strengths usually used to study bimolecular electron transfer

  20. Electron radiation damage of metals and nature of point defects by high voltage electron microscopy

    Kiritani, M.

    1975-01-01

    The formation of point defect clusters by electron irradiation in a variety of metals (Al, Au, Cu, Fe, Ni, Mo, Pt, W) in a wide range of temperatures 10 to 1000 0 K are observed. A unified explanation is given for their nucleation and growth from the viewpoint of the migration and interaction of point defects. The effect of free surfaces and other permanent sinks are examined. Analysis of the systematic variation of the nucleation of interstitial clustered defects lead to confirm the free migration of interstitials with fairly small activation energies. Their apparent values obtained from the impurity sensitive nucleation at medium temperatures are 0.08 (Al), 0.19 (Au), 0.26 (Fe), 0.18 (Mo) and 0.21 eV (W), and their values obtained from low temperature irradiation are 0.03 (Al), 0.04 (Au) and 0.05 eV (Mo). The trapping of interstitials by foreign atoms and heterogeneous effects on nucleation of interstitial clusters are discussed

  1. Transferred metal electrode films for large-area electronic devices

    Yang, Jin-Guo; Kam, Fong-Yu; Chua, Lay-Lay

    2014-01-01

    The evaporation of metal-film gate electrodes for top-gate organic field-effect transistors (OFETs) limits the minimum thickness of the polymer gate dielectric to typically more than 300 nm due to deep hot metal atom penetration and damage of the dielectric. We show here that the self-release layer transfer method recently developed for high-quality graphene transfer is also capable of giving high-quality metal thin-film transfers to produce high-performance capacitors and OFETs with superior dielectric breakdown strength even for ultrathin polymer dielectric films. Dielectric breakdown strengths up to 5–6 MV cm −1 have been obtained for 50-nm thin films of polystyrene and a cyclic olefin copolymer TOPAS ® (Zeon). High-quality OFETs with sub-10 V operational voltages have been obtained this way using conventional polymer dielectrics and a high-mobility polymer semiconductor poly[2,5-bis(3-tetradecylthiophene-2-yl)thieno[3,2-b]thiophene-2,5-diyl]. The transferred metal films can make reliable contacts without damaging ultrathin polymer films, self-assembled monolayers and graphene, which is not otherwise possible from evaporated or sputtered metal films

  2. Sequential injection chromatography with post-column reaction/derivatization for the determination of transition metal cations in natural water samples.

    Horstkotte, Burkhard; Jarošová, Patrícia; Chocholouš, Petr; Sklenářová, Hana; Solich, Petr

    2015-05-01

    In this work, the applicability of Sequential Injection Chromatography for the determination of transition metals in water is evaluated for the separation of copper(II), zinc(II), and iron(II) cations. Separations were performed using a Dionex IonPAC™ guard column (50mm×2mm i.d., 9 µm). Mobile phase composition and post-column reaction were optimized by modified SIMPLEX method with subsequent study of the concentration of each component. The mobile phase consisted of 2,6-pyridinedicarboxylic acid as analyte-selective compound, sodium sulfate, and formic acid/sodium formate buffer. Post-column addition of 4-(2-pyridylazo)resorcinol was carried out for spectrophotometric detection of the analytes׳ complexes at 530nm. Approaches to achieve higher robustness, baseline stability, and detection sensitivity by on-column stacking of the analytes and initial gradient implementation as well as air-cushion pressure damping for post-column reagent addition were studied. The method allowed the rapid separation of copper(II), zinc(II), and iron(II) within 6.5min including pump refilling and aspiration of sample and 1mmol HNO3 for analyte stacking on the separation column. High sensitivity was achieved applying an injection volume of up to 90µL. A signal repeatability of<2% RSD of peak height was found. Analyte recovery evaluated by spiking of different natural water samples was well suited for routine analysis with sub-micromolar limits of detection. Copyright © 2015 Elsevier B.V. All rights reserved.

  3. Delayed electron emission in strong-field driven tunnelling from a metallic nanotip in the multi-electron regime

    Yanagisawa, Hirofumi; Schnepp, Sascha; Hafner, Christian; Hengsberger, Matthias; Kim, Dong Eon; Kling, Matthias F.; Landsman, Alexandra; Gallmann, Lukas; Osterwalder, Jürg

    2016-01-01

    Illuminating a nano-sized metallic tip with ultrashort laser pulses leads to the emission of electrons due to multiphoton excitations. As optical fields become stronger, tunnelling emission directly from the Fermi level becomes prevalent. This can generate coherent electron waves in vacuum leading to a variety of attosecond phenomena. Working at high emission currents where multi-electron effects are significant, we were able to characterize the transition from one regime to the other. Specifically, we found that the onset of laser-driven tunnelling emission is heralded by the appearance of a peculiar delayed emission channel. In this channel, the electrons emitted via laser-driven tunnelling emission are driven back into the metal, and some of the electrons reappear in the vacuum with some delay time after undergoing inelastic scattering and cascading processes inside the metal. Our understanding of these processes gives insights on attosecond tunnelling emission from solids and should prove useful in designing new types of pulsed electron sources. PMID:27786287

  4. Electron-phonon coupling in the rare-earth metals

    Skriver, Hans Lomholt; Mertig, I.

    1990-01-01

    -phonon parameters were calculated within the Gaspari-Gyorffy formulation. For the heavier rare earths Gd–Tm spin polarization was included both in the band-structure calculations and in the treatment of the electron-phonon coupling to take into account the spin splitting of the conduction electrons induced by the 4...

  5. Azobenzenes as light-controlled molecular electronic switches in nanoscale metal-molecule-metal junctions.

    Mativetsky, Jeffrey M; Pace, Giuseppina; Elbing, Mark; Rampi, Maria A; Mayor, Marcel; Samorì, Paolo

    2008-07-23

    Conductance switching associated with the photoisomerization of azobenzene-based (Azo) molecules was observed in nanoscopic metal-molecule-metal junctions. The junctions were formed by using a conducting atomic force microscope (C-AFM) approach, where a metallic AFM tip was used to electrically contact a gold-supported Azo self-assembled monolayer. The measured 30-fold increase in conductance is consistent with the expected decrease in tunneling barrier length resulting from the conformational change of the Azo molecule.

  6. Electronic Structure of Rare-Earth Metals. II. Positron Annihilation

    Williams, R. W.; Mackintosh, Allan

    1968-01-01

    of Loucks shows that the independent-particle model gives a good first approximation to the angular distribution, although correlation effects probably smear out some of the structure. The angular distributions from the heavy rare-earth metals are very similar to that from Y and can be understood....... In the spiral phase of Ho, the structure in the c-axis distribution is much reduced, indicating that the Fermi surface is substantially modified by the magnetic ordering, as expected. The photon distribution from the equiatomic Ho-Er alloy is very similar to those from the constituent metals, although...

  7. Hydrogen Bonding, (1)H NMR, and Molecular Electron Density Topographical Characteristics of Ionic Liquids Based on Amino Acid Cations and Their Ester Derivatives.

    Rao, Soniya S; Bejoy, Namitha Brijit; Gejji, Shridhar P

    2015-08-13

    Amino acid ionic liquids (AAILs) have attracted significant attention in the recent literature owing to their ubiquitous applications in diversifying areas of modern chemistry, materials science, and biosciences. The present work focuses on unraveling the molecular interactions underlying AAILs. Electronic structures of ion pairs consisting of amino acid cations ([AA(+)], AA = Gly, Ala, Val, Leu, Ile, Pro, Ser, Thr) and their ester substituted derivatives [AAE(+)] interacting with nitrate anion [NO3(-)] have been obtained from the dispersion corrected M06-2x density functional theory. The formation of ion pair is accompanied by the transfer of proton from quaternary nitrogen to anion facilitated via hydrogen bonding. The [Ile], [Pro], [Ser], and [Thr] and their esters reveal relatively strong inter- as well as intramolecular hydrogen-bonding interactions. Consequently, the hierarchy in binding energies of [AA][NO3] ion pairs and their ester analogues turns out to be [Gly] > [Ala] > [Ser] ∼ [Val] ∼ [Ile] > [Leu] ∼ [Thr] > [Pro]. The work underlines how the interplay of intra- as well as intermolecular hydrogen-bonding interactions in [AA]- and [AAE]-based ILs manifest in their infrared and (1)H NMR spectra. Substitution of -OCH3 functional group in [AA][NO3] ILs lowers the melting point attributed to weaker hydrogen-bonding interactions, making them suitable for room temperature applications. As opposed to gas phase structures, the presence of solvent (DMSO) does not bring about any proton transfer in the ion pairs or their ester analogues. Calculated (1)H NMR chemical shifts of the solvated structures agree well with those from experiment. Correlations of decomposition temperatures in [AA]- and [AAE]-based ILs with binding energies and electron densities at the bond critical point(s) in molecular electron density topography, have been established.

  8. Detection of heavy-metal ions using liquid crystal droplet patterns modulated by interaction between negatively charged carboxylate and heavy-metal cations.

    Han, Gyeo-Re; Jang, Chang-Hyun

    2014-10-01

    Herein, we demonstrated a simple, sensitive, and rapid label-free detection method for heavy-metal (HM) ions using liquid crystal (LC) droplet patterns on a solid surface. Stearic-acid-doped LC droplet patterns were spontaneously generated on an n-octyltrichlorosilane (OTS)-treated glass substrate by evaporating a solution of the nematic LC, 4-cyano-4'-pentylbiphenyl (5CB), dissolved in heptane. The optical appearance of the droplet patterns was a dark crossed texture when in contact with air, which represents the homeotropic orientation of the LC. This was caused by the steric interaction between the LC molecules and the alkyl chains of the OTS-treated surface. The dark crossed appearance of the acid-doped LC patterns was maintained after the addition of phosphate buffered saline (PBS) solution (pH 8.1 at 25°C). The deprotonated stearic-acid molecules self-assembled through the LC/aqueous interface, thereby supporting the homeotropic anchoring of 5CB. However, the optical image of the acid-doped LC droplet patterns incubated with PBS containing HM ions appeared bright, indicating a planar orientation of 5CB at the aqueous/LC droplet interface. This dark to bright transition of the LC patterns was caused by HM ions attached to the deprotonated carboxylate moiety, followed by the sequential interruption of the self-assembly of the stearic acid at the LC/aqueous interface. The results showed that the acid-doped LC pattern system not only enabled the highly sensitive detection of HM ions at a sub-nanomolar concentration but it also facilitated rapid detection (<10 min) with simple procedures. Copyright © 2014 Elsevier B.V. All rights reserved.

  9. Chemical potential pinning due to equilibrium electron transfer at metal/C60-doped polymer interfaces

    Heller, C. M.; Campbell, I. H.; Smith, D. L.; Barashkov, N. N.; Ferraris, J. P.

    1997-04-01

    We report electroabsorption measurements of the built-in electrostatic potential in metal/C60-doped polymer/metal structures to investigate chemical potential pinning due to equilibrium electron transfer from a metal contact to the electron acceptor energy level of C60 molecules in the polymer film. The built-in potentials of a series of structures employing thin films of both undoped and C60-doped poly[2-methoxy, 5-(2'-ethyl-hexyloxy)-1,4-phenylene vinylene] (MEH-PPV) were measured. For undoped MEH-PPV, which has an energy gap of about 2.4 eV, the maximum built-in potential is about 2.1 eV, whereas for C60-doped MEH-PPV the maximum built-in potential decreases to 1.5 eV. Electron transfer to the C60 molecules close to the metal interface pins the chemical potential of the metal contact near the electron acceptor energy level of C60 and decreases the built-in potential of the structure. From the systematic dependence of the built-in potential on the metal work function we find that the electron acceptor energy level of C60 in MEH-PPV is about 1.7 eV above the hole polaron energy level of MEH-PPV.

  10. A pulsed electron injector using a metal photocathode irradiated by an excimer laser

    Kauppila, T.J.; Builta, L.A.; Crutcher, J.K.; Elliott, J.C.; Moir, D.C.

    1987-01-01

    The hot cathode of an electron gun is replaced by a metallic photocathode driven by an excimer laser. The current, current density, and emittance of the 500-kV electron beam produced by the photoelectron source are presented. In addition, the temperature of the photocathode is varied to study the possibility of a hybrid source

  11. Metal-Organic Frameworks as Active Materials in Electronic Sensor Devices.

    Campbell, Michael G; Dincă, Mircea

    2017-05-12

    In the past decade, advances in electrically conductive metal-organic frameworks (MOFs) and MOF-based electronic devices have created new opportunities for the development of next-generation sensors. Here we review this rapidly-growing field, with a focus on the different types of device configurations that have allowed for the use of MOFs as active components of electronic sensor devices.

  12. Exchange corrections to the bulk plasmon cross section of slow electrons in metals

    Yin, S.; Goodman, B.; Tosatti, E.

    1981-08-01

    We present a calculation of the simplest exchange correction to the low-energy electron cross section for plasmon creation in a free-electron-like metal with the density of Al. The resulting cancellation effect is found to be much too small to account for the anomalous delayed onset of plasmon losses, found in core level photo emission for Al. (author)

  13. The kinetics of low-temperature electron-phonon relaxation in a metallic film following instantaneous heating of the electrons

    Bezuglyi, A.I.; Shklovskii, V.A.

    1997-01-01

    The theoretical analysis of experiments on pulsed laser irradiation of metallic films sputtered on insulating supports is usually based on semiphenomenological dynamical equations for the electron and phonon temperatures, an approach that ignores the nonuniformity and the nonthermal nature of the phonon distribution function. In this paper we discuss a microscopic model that describes the dynamics of the electron-phonon system in terms of kinetic equations for the electron and phonon distribution functions. Such a model provides a microscopic picture of the nonlinear energy relaxation of the electron-phonon system of a rapidly heated film. We find that in a relatively thick film the energy relaxation of electrons consists of three stages: the emission of nonequilibrium phonons by 'hot' electrons, the thermalization of electrons and phonons due to phonon reabsorption, and finally the cooling of the thermalized electron-phonon system as a result of phonon exchange between film and substrate. In thin films, where there is no reabsorption of nonequilibrium phonons, the energy relaxation consists of only one stage, the first. The relaxation dynamics of an experimentally observable quantity, the phonon contribution to the electrical conductivity of the cooling film, is directly related to the dynamics of the electron temperature, which makes it possible to use the data of experiments on the relaxation of voltage across films to establish the electron-phonon and phonon-electron collision times and the average time of phonon escape from film to substrate

  14. Electron dynamics in metals and semiconductors in strong THz fields

    Jepsen, Peter Uhd

    2017-01-01

    Semiconductors and metals respond to strong electric fields in a highly nonlinear fashion. Using single-cycle THz field transients it is possible to investigate this response in regimes not accessible by transport-based measurements. Extremely high fields can be applied without material damage...

  15. Electronic Contributions to the Phonon Damping in Metals

    Johnson, Rune

    1968-07-15

    An imaginary part of the dielectric matrix is derived based on a first order perturbation expansion of the valence electron states in a local potential model of the crystal. The results are used to estimate the electronic contributions to the phonon damping in aluminum and lead. The corrections which have been obtained are of the same order of magnitude at small phonon momenta as the damping earlier calculated for the free electrons. However, the discrepancies between the theoretical and experimental results still remain. The major contribution to damping seems to originate in anharmonic effects, even at 80 deg K.

  16. Presence and Character of the 5f Electrons in the Actinide Metals

    Johansson, B.; Skriver, Hans Lomholt; Mårtensson, N.

    1980-01-01

    The sensitivity of the Image level binding energy to the occupation of the 5f orbital is pointed out and used to demonstrate the presence of 5f electrons in the uranium metal. It is suggested that the valence band spectrum of uranium might contain satellites originating from excitations...... to localized 5f-electron configurations. Different kinds of core-hole screenings are discussed for the actinide metals as well as the difference between inner and outer core electron ionizations. Finally, the question of itinerant versus localized 5f behaviour is treated by means of a total energy comparison...

  17. Limitations in cooling electrons using normal-metal-superconductor tunnel junctions.

    Pekola, J P; Heikkilä, T T; Savin, A M; Flyktman, J T; Giazotto, F; Hekking, F W J

    2004-02-06

    We demonstrate both theoretically and experimentally two limiting factors in cooling electrons using biased tunnel junctions to extract heat from a normal metal into a superconductor. First, when the injection rate of electrons exceeds the internal relaxation rate in the metal to be cooled, the electrons do not obey the Fermi-Dirac distribution, and the concept of temperature cannot be applied as such. Second, at low bath temperatures, states within the gap induce anomalous heating and yield a theoretical limit of the achievable minimum temperature.

  18. A metal-ion NMR investigation of the antibiotic facilitated transport of monovalent cations through the walls of phospholipid vesicles. II. Sulfur-33 NMR

    Buster, D.C.

    1988-01-01

    A technique has been developed to investigate the antibiotic facilitated transmembrane transport of monovalent cations using 23 Na and 7 Li Nuclear Magnetic Resonance spectroscopy. The initial portion of this thesis outlines the production and characterization of a model lipid system amenable to the NMR detection of cation transport. Large unilamellar vesicles (LUV) have been prepared from a 4:1 mixture of phosphatidylcholine and phosphatidylglycerol. The presence of the anionic chemical shift reagent dysprosium (III) tripolyphosphate, either inside or outside of the vesicles, allows for the spectroscopic separation of the NMR resonances arising from the inter- and extravesicular cation pools. The cation transporting properties of the channel-forming pentadecapeptide, gramicidin D, have been studied using the NMR technique

  19. Rational design of metal-organic electronic devices: A computational perspective

    Chilukuri, Bhaskar

    Organic and organometallic electronic materials continue to attract considerable attention among researchers due to their cost effectiveness, high flexibility, low temperature processing conditions and the continuous emergence of new semiconducting materials with tailored electronic properties. In addition, organic semiconductors can be used in a variety of important technological devices such as solar cells, field-effect transistors (FETs), flash memory, radio frequency identification (RFID) tags, light emitting diodes (LEDs), etc. However, organic materials have thus far not achieved the reliability and carrier mobility obtainable with inorganic silicon-based devices. Hence, there is a need for finding alternative electronic materials other than organic semiconductors to overcome the problems of inferior stability and performance. In this dissertation, I research the development of new transition metal based electronic materials which due to the presence of metal-metal, metal-pi, and pi-pi interactions may give rise to superior electronic and chemical properties versus their organic counterparts. Specifically, I performed computational modeling studies on platinum based charge transfer complexes and d 10 cyclo-[M(mu-L)]3 trimers (M = Ag, Au and L = monoanionic bidentate bridging (C/N~C/N) ligand). The research done is aimed to guide experimental chemists to make rational choices of metals, ligands, substituents in synthesizing novel organometallic electronic materials. Furthermore, the calculations presented here propose novel ways to tune the geometric, electronic, spectroscopic, and conduction properties in semiconducting materials. In addition to novel material development, electronic device performance can be improved by making a judicious choice of device components. I have studied the interfaces of a p-type metal-organic semiconductor viz cyclo-[Au(mu-Pz)] 3 trimer with metal electrodes at atomic and surface levels. This work was aimed to guide the device

  20. The effect of atoms excited by electron beam on metal evaporation

    Xie Guo Feng; Ying Chun Tong

    2002-01-01

    In atomic vapor laser isotope separation (AVLIS), the metal is heated to melt by electron beams. The vapor atoms may be excited by electrons when flying through the electron beam. The excited atoms may be deexcited by inelastic collision during expansion. The electronic energy transfers translational energy. In order to analyse the effect of reaction between atoms and electron beams on vapor physical parameters, such as density, velocity and temperature, direct-simulation Monte Carlo method (DSMC) is used to simulate the 2-D gadolinium evaporation from long and narrow crucible. The simulation results show that the velocity and temperature of vapor increase, and the density decreases

  1. Regeneration of β-Carotene from Radical Cation by Eugenol, Isoeugenol, and Clove Oil in the Marcus Theory Inverted Region for Electron Transfer.

    Chang, Hui-Ting; Cheng, Hong; Han, Rui-Min; Wang, Peng; Zhang, Jian-Ping; Skibsted, Leif H

    2017-02-01

    The rate of regeneration of β-carotene by eugenol from the β-carotene radical cation, an initial bleaching product of β-carotene, was found by laser flash photolysis and transient absorption spectroscopy to be close to the diffusion limit in chloroform/methanol (9:1, v/v), with a second-order rate constant (k 2 ) of 4.3 × 10 9 L mol -1 s -1 at 23 °C. Isoeugenol, more reducing with a standard reduction potential of 100 mV lower than eugenol, was slower, with k 2 = 7.2 × 10 8 L mol -1 s -1 . Regeneration of β-carotene following photobleaching was found 50% more efficient by eugenol, indicating that, for the more reducing isoeugenol, the driving force exceeds the reorganization energy for electron transfer significantly in the Marcus theory inverted region. For eugenol/isoeugenol mixtures and clove oil, kinetic control by the faster eugenol determines the regeneration, with a thermodynamic backup of reduction equivalent through eugenol regeneration by the more reducing isoeugenol for the mixture. Clove oil, accordingly, is a potential protector of provitamin A for use in red palm oils.

  2. Chemical reactivity of cation-exchanged zeolites

    Pidko, E.A.

    2008-01-01

    Zeolites modified with metal cations have been extensively studied during the last two decades because of their wide application in different technologically important fields such as catalysis, adsorption and gas separation. Contrary to the well-understood mechanisms of chemical reactions catalyzed by Brønsted acid sites in the hydrogen forms of zeolites, the nature of chemical reactivity, and related, the structure of the metal-containing ions in cation-exchanged zeolites remains the subject...

  3. Evidence for single metal two electron oxidative addition and reductive elimination at uranium.

    Gardner, Benedict M; Kefalidis, Christos E; Lu, Erli; Patel, Dipti; McInnes, Eric J L; Tuna, Floriana; Wooles, Ashley J; Maron, Laurent; Liddle, Stephen T

    2017-12-01

    Reversible single-metal two-electron oxidative addition and reductive elimination are common fundamental reactions for transition metals that underpin major catalytic transformations. However, these reactions have never been observed together in the f-block because these metals exhibit irreversible one- or multi-electron oxidation or reduction reactions. Here we report that azobenzene oxidises sterically and electronically unsaturated uranium(III) complexes to afford a uranium(V)-imido complex in a reaction that satisfies all criteria of a single-metal two-electron oxidative addition. Thermolysis of this complex promotes extrusion of azobenzene, where H-/D-isotopic labelling finds no isotopomer cross-over and the non-reactivity of a nitrene-trap suggests that nitrenes are not generated and thus a reductive elimination has occurred. Though not optimally balanced in this case, this work presents evidence that classical d-block redox chemistry can be performed reversibly by f-block metals, and that uranium can thus mimic elementary transition metal reactivity, which may lead to the discovery of new f-block catalysis.

  4. Influence of metallic surface states on electron affinity of epitaxial AlN films

    Mishra, Monu; Krishna, Shibin; Aggarwal, Neha [Advanced Materials and Devices Division, CSIR-National Physical Laboratory, Dr. K.S. Krishnan Marg, New Delhi110012 (India); Academy of Scientific and Innovative Research (AcSIR), CSIR-NPL Campus, Dr. K.S. Krishnan Marg, New Delhi 110012 (India); Gupta, Govind, E-mail: govind@nplindia.org [Advanced Materials and Devices Division, CSIR-National Physical Laboratory, Dr. K.S. Krishnan Marg, New Delhi110012 (India); Academy of Scientific and Innovative Research (AcSIR), CSIR-NPL Campus, Dr. K.S. Krishnan Marg, New Delhi 110012 (India)

    2017-06-15

    The present article investigates surface metallic states induced alteration in the electron affinity of epitaxial AlN films. AlN films grown by plasma-assisted molecular beam epitaxy system with (30% and 16%) and without metallic aluminium on the surface were probed via photoemission spectroscopic measurements. An in-depth analysis exploring the influence of metallic aluminium and native oxide on the electronic structure of the films is performed. It was observed that the metallic states pinned the Fermi Level (FL) near valence band edge and lead to the reduction of electron affinity (EA). These metallic states initiated charge transfer and induced changes in surface and interface dipoles strength. Therefore, the EA of the films varied between 0.6–1.0 eV due to the variation in contribution of metallic states and native oxide. However, the surface barrier height (SBH) increased (4.2–3.5 eV) adversely due to the availability of donor-like surface states in metallic aluminium rich films.

  5. Heavy-Ion-Induced Electronic Desorption of Gas from Metals

    Molvik, A W; Mahner, E; Kireeff Covo, M; Bellachioma, M C; Bender, M; Bieniosek, F M; Hedlund, E; Krämer, A; Kwan, J; Malyshev, O B; Prost, L; Seidl, P A; Westenskow, G; Westerberg, L

    2007-01-01

    During heavy-ion operation in several particle accelerators worldwide, dynamic pressure rises of orders of magnitude were triggered by lost beam ions that bombarded the vacuum chamber walls. This ion-induced molecular desorption, observed at CERN, GSI, and BNL, can seriously limit the ion beam lifetime and intensity of the accelerator. From dedicated test stand experiments we have discovered that heavy-ion-induced gas desorption scales with the electronic energy loss (dEe/dx) of the ions slowing down in matter; but it varies only little with the ion impact angle, unlike electronic sputtering.

  6. Effect of cation competition on cadmium uptake from solution by the earthworm Eisenia fetida.

    Li, L.-Z.; Zhou, D.-M.; Wang, P.; Jin, S.-Y.; Peijnenburg, W.J.G.M.; Reinecke, A.J.; van Gestel, C.A.M.

    2009-01-01

    Metal speciation alone is insufficient to predict metal accumulation in aquatic and terrestrial organisms, because competition between cations can play an important role. In the present study, the effects of competing cations (Ca

  7. Asymmetric cation-binding catalysis

    Oliveira, Maria Teresa; Lee, Jiwoong

    2017-01-01

    The employment of metal salts is quite limited in asymmetric catalysis, although it would provide an additional arsenal of safe and inexpensive reagents to create molecular functions with high optical purity. Cation chelation by polyethers increases the salts' solubility in conventional organic...... solvents, thus increasing their applicability in synthesis. The expansion of this concept to chiral polyethers led to the emergence of asymmetric cation-binding catalysis, where chiral counter anions are generated from metal salts, particularly using BINOL-based polyethers. Alkali metal salts, namely KF...... highly enantioselective silylation reactions in polyether-generated chiral environments, and leading to a record-high turnover in asymmetric organocatalysis. This can lead to further applications by the asymmetric use of other inorganic salts in various organic transformations....

  8. Plasmonically sensitized metal-oxide electron extraction layers for organic solar cells.

    Trost, S; Becker, T; Zilberberg, K; Behrendt, A; Polywka, A; Heiderhoff, R; Görrn, P; Riedl, T

    2015-01-16

    ZnO and TiOx are commonly used as electron extraction layers (EELs) in organic solar cells (OSCs). A general phenomenon of OSCs incorporating these metal-oxides is the requirement to illuminate the devices with UV light in order to improve device characteristics. This may cause severe problems if UV to VIS down-conversion is applied or if the UV spectral range (λ work, silver nanoparticles (AgNP) are used to plasmonically sensitize metal-oxide based EELs in the vicinity (1-20 nm) of the metal-oxide/organic interface. We evidence that plasmonically sensitized metal-oxide layers facilitate electron extraction and afford well-behaved highly efficient OSCs, even without the typical requirement of UV exposure. It is shown that in the plasmonically sensitized metal-oxides the illumination with visible light lowers the WF due to desorption of previously ionosorbed oxygen, in analogy to the process found in neat metal oxides upon UV exposure, only. As underlying mechanism the transfer of hot holes from the metal to the oxide upon illumination with hν < Eg is verified. The general applicability of this concept to most common metal-oxides (e.g. TiOx and ZnO) in combination with different photoactive organic materials is demonstrated.

  9. Electrons and Spin Waves in Heavy Rare Earth Metals

    Mackintosh, A. R.

    1972-01-01

    this understanding on a more quantitative basis. The experimental evidence on the electronic structure of the rare earths is still rather meager but, so far as it goes, is in accord with the detailed description provided by band structure calculations. On the other hand, the experimental study of the magnon...

  10. Pervasive liquid metal based direct writing electronics with roller-ball pen

    Yi Zheng

    2013-11-01

    Full Text Available A roller-ball pen enabled direct writing electronics via room temperature liquid metal ink was proposed. With the rolling to print mechanism, the metallic inks were smoothly written on flexible polymer substrate to form conductive tracks and electronic devices. The contact angle analyzer and scanning electron microscope were implemented to disclose several unique inner properties of the obtained electronics. An ever high writing resolution with line width and thickness as 200 μm and 80 μm, respectively was realized. Further, with the administration of external writing pressure, GaIn24.5 droplets embody increasing wettability on polymer which demonstrates the pervasive adaptability of the roller-ball pen electronics.

  11. Spherical electron momentum density distribution and Bayesian analysis of the renormalization parameter in Li metal

    Dobrzynski, Ludwik

    2000-01-01

    The Bayesian analysis of the spherical part of the electron momentum density was carried out with the goal of finding the best estimation of the spherically averaged renormalization parameter, z , quantifying the discontinuity in the electron momentum density distribution in Li metal. Three models parametrizing the electron momentum density were considered and nuisance parameters integrated out. The analysis show that the most likely value of z following from the data of Sakurai et al is in the range of 0.45-0.50, while 0.55 is obtained for the data of Schuelke et al . In the maximum entropy reconstruction of the spherical part of the electron momentum density three different algorithms were used. It is shown that all of them produce essentially the same results. The paper shows that the accurate Compton scattering experiments are capable of bringing information on this very important Fermiological aspect of the electron gas in a metal. (author)

  12. Synthesis of biocidal polymers containing metal NPs using an electron beam

    Choi, Kwonyong; Kim, Seong-Eun; Kim, Hee-Yeon; Yoon, Jeyong; Lee, Jong-Chan

    2012-01-01

    Metal containing antibacterial polymers were prepared by the polymerization of methylmethacrylate and methacrylic acid with copper or zinc. When the thin film of the polymers coated on a glass was irradiated with an electron beam, nanoparticles were obtained. It was found that these polymers exhibited a potent antibacterial activity against the Gram-negative bacteria, Escherichia coli. The metal containing polymers showed a 99.999% (5.0 logs) reduction in E. coli at a contact time of 12 h. In addition, polymers had a good antifouling effect against marine organisms. - Graphical abstract: Biocidal activity of Cu nanoparticle/polymer composite film against Gram-negative bacteria. Highlights: ► Metal containing antibacterial polymers were prepared with copper. ► Using the electron beam, nanoparticles were obtained. ► It was found that these polymers exhibited potent biocidal activity against E. coli. ► The metal containing polymers showed a 99.999% reduction of E. coli.

  13. NATO International Symposium on the Electronic Structure and Properties of Hydrogen in Metals

    Satterthwaite, C

    1983-01-01

    Hydrogen is the smallest impurity atom that can be implanted in a metallic host. Its small mass and strong interaction with the host electrons and nuclei are responsible for many anomalous and interesting solid state effects. In addition, hydrogen in metals gives rise to a number of technological problems such as hydrogen embrittlement, hydrogen storage, radiation hardening, first wall problems associated with nuclear fusion reactors, and degradation of the fuel cladding in fission reactors. Both the fundamental effects and applied problems have stimulated a great deal of inter­ est in the study of metal hydrogen systems in recent years. This is evident from a growing list of publications as well as several international conferences held in this field during the past decade. It is clear that a fundamental understanding of these problems re­ quires a firm knowledge of the basic interactions between hydrogen, host metal atoms, intrinsic lattice defects and electrons. This understanding is made particularly di...

  14. Metallic Na formation in NaCl crystals with irradiation of electron or vacuum ultraviolet photon

    Owaki, Shigehiro [Osaka Prefecture Univ., Sakai, Osaka (Japan). Coll. of Integrated Arts and Sciences; Koyama, Shigeko; Takahashi, Masao; Kamada, Masao; Suzuki, Ryouichi

    1997-03-01

    Metallic Na was formed in NaCl single crystals with irradiation of a variety of radiation sources and analyzed the physical states with several methods. In the case of irradiation of 21 MeV electron pulses to the crystal blocks, the optical absorption and lifetime measurement of positron annihilation indicated appearance of Na clusters inside. Radiation effects of electron beam of 30 keV to the crystals in vacuum showed the appearance of not only metallic Na but atomic one during irradiation with Auger electron spectroscopy. Intense photon fluxes in vacuum ultraviolet region of synchrotron radiation were used as another source and an analyzing method of ultraviolet photoelectron spectroscopy. The results showed the metallic Na layered so thick that bulk plasmon can exist. (author)

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

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

    2012-04-13

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

  16. A preliminary categorization of end-of-life electrical and electronic equipment as secondary metal resources

    Oguchi, Masahiro; Murakami, Shinsuke; Sakanakura, Hirofumi; Kida, Akiko; Kameya, Takashi

    2011-01-01

    Highlights: → End-of-life electrical and electronic equipment (EEE) as secondary metal resources. → The content and the total amount of metals in specific equipment are both important. → We categorized 21 EEE types from contents and total amounts of various metals. → Important equipment types as secondary resources were listed for each metal kind. → Collectability and possible collection systems of various EEE types were discussed. - Abstract: End-of-life electrical and electronic equipment (EEE) has recently received attention as a secondary source of metals. This study examined characteristics of end-of-life EEE as secondary metal resources to consider efficient collection and metal recovery systems according to the specific metals and types of EEE. We constructed an analogy between natural resource development and metal recovery from end-of-life EEE and found that metal content and total annual amount of metal contained in each type of end-of-life EEE should be considered in secondary resource development, as well as the collectability of the end-of-life products. We then categorized 21 EEE types into five groups and discussed their potential as secondary metal resources. Refrigerators, washing machines, air conditioners, and CRT TVs were evaluated as the most important sources of common metals, and personal computers, mobile phones, and video games were evaluated as the most important sources of precious metals. Several types of small digital equipment were also identified as important sources of precious metals; however, mid-size information and communication technology (ICT) equipment (e.g., printers and fax machines) and audio/video equipment were shown to be more important as a source of a variety of less common metals. The physical collectability of each type of EEE was roughly characterized by unit size and number of end-of-life products generated annually. Current collection systems in Japan were examined and potentially appropriate collection

  17. Nonlocal Response of Metallic Nanospheres Probed by Light, Electrons, and Atoms

    Christensen, Thomas; Yan, Wei; Raza, Søren

    2014-01-01

    Inspired by recent measurements on individual metallic nanospheres that cannot be explained with traditional classical electrodynamics, we theoretically investigate the effects of nonlocal response by metallic nanospheres in three distinct settings: atomic spontaneous emission, electron energy loss...... blueshifted surface plasmon but also an infinite series of bulk plasmons that have no counterpart in a local-response approximation. We show that these increasingly blueshifted multipole plasmons become spectrally more prominent at shorter probe-to-surface separations and for decreasing nanosphere radii...

  18. Resizing metal-coated nanopores using a scanning electron microscope.

    Chansin, Guillaume A T; Hong, Jongin; Dusting, Jonathan; deMello, Andrew J; Albrecht, Tim; Edel, Joshua B

    2011-10-04

    Electron beam-induced shrinkage provides a convenient way of resizing solid-state nanopores in Si(3) N(4) membranes. Here, a scanning electron microscope (SEM) has been used to resize a range of different focussed ion beam-milled nanopores in Al-coated Si(3) N(4) membranes. Energy-dispersive X-ray spectra and SEM images acquired during resizing highlight that a time-variant carbon deposition process is the dominant mechanism of pore shrinkage, although granular structures on the membrane surface in the vicinity of the pores suggest that competing processes may occur. Shrinkage is observed on the Al side of the pore as well as on the Si(3) N(4) side, while the shrinkage rate is observed to be dependent on a variety of factors. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Magnetic properties of metallic impurities with strongly correlated electrons

    Janiš, Václav; Ringel, Matouš

    2009-01-01

    Roč. 115, č. 1 (2009), s. 30-35 ISSN 0587-4246 R&D Projects: GA ČR GA202/07/0644 Institutional research plan: CEZ:AV0Z10100520 Keywords : And erson impurity * strong electron correlations * spin-polarized solution * three-channel parquet equations * magnetic field Subject RIV: BE - Theoretical Physics Impact factor: 0.433, year: 2009 http://przyrbwn.icm.edu.pl/APP/ABSTR/115/a115-1-5.html

  20. Electron density in non-ideal metal complexes. Pt. 1

    Varghese, J.N.; Maslen, E.N.

    1985-01-01

    The structure of copper sulphate pentahydrate was refined using an accurate set of X-ray data: Msub(r)=249.68, triclinic, Panti 1, a=6.1224(4), b=10.7223(4), c=5.9681(4) A, α=82.35(2), β=107.33(2), γ=102.60(4) 0 , V=364.02(3) A 3 , Z=2, Dsub(x)=2.278 Mg m -3 , Mo Kα, lambda=0.71069 A, μ=3.419 mm -1 , F(000)=254.0, T=298 K, R=0.039 for 7667 reflections. The structural parameters are compared with those obtained by neutron diffraction. The differences between X-ray and neutron positions are related to the hydrogen bonding in the structure. The dominant features in the residual density near the two crystallographically independent Cu atoms result from the redistribution of 3d electrons due to bonding. The density is anisotropic, as expected in view of the Jahn-Teller distortion in the structure. Marked differences in the d-electron distributions for the two Cu atoms correlate with small variations in molecular geometry. Second-nearest-neighbour effects, such as those arising from differently oriented ligating waters, are significant in this structure. Sharp features in the difference density close to the Cu nuclei are similar to those in other Cu 2+ complexes, indicating that the electron density in this region is more reliable than previously believed. (orig.)

  1. Experiments in electron microscopy: from metals to nerves

    Unwin, Nigel

    2015-01-01

    Electron microscopy has advanced remarkably as a tool for biological structure research since the development of methods to examine radiation-sensitive unstained specimens and the introduction of cryo-techniques. Structures of biological molecules at near-atomic resolution can now be obtained from images of single particles as well as crystalline arrays. It has also become possible to analyze structures of molecules in their functional context, i.e. in their natural membrane or cellular setting, and in an ionic environment like that in living tissue. Electron microscopy is thus opening ways to answer definitively questions about physiological mechanisms. Here I recall a number of experiments contributing to, and benefiting from the technical advances that have taken place. I begin—in the spirit of this crystallography series—with some biographical background, and then sketch the path to an analysis by time-resolved microscopy of the opening mechanism of an ion channel (nicotinic acetylcholine receptor). This analysis illustrates how electron imaging can be combined with freeze-trapping to illuminate a transient biological event: in our case, chemical-to-electrical transduction at the nerve-muscle synapse. (invited comment)

  2. Flexible Electronics Powered by Mixed Metal Oxide Thin Film Transistors

    Marrs, Michael

    A low temperature amorphous oxide thin film transistor (TFT) and amorphous silicon PIN diode backplane technology for large area flexible digital x-ray detectors has been developed to create 7.9-in. diagonal backplanes. The critical steps in the evolution of the backplane process include the qualification and optimization of the low temperature (200 °C) metal oxide TFT and a-Si PIN photodiode process, the stability of the devices under forward and reverse bias stress, the transfer of the process to flexible plastic substrates, and the fabrication and assembly of the flexible detectors. Mixed oxide semiconductor TFTs on flexible plastic substrates suffer from performance and stability issues related to the maximum processing temperature limitation of the polymer. A novel device architecture based upon a dual active layer improves both the performance and stability. Devices are directly fabricated below 200 ºC on a polyethylene naphthalate (PEN) substrate using mixed metal oxides of either zinc indium oxide (ZIO) or indium gallium zinc oxide (IGZO) as the active semiconductor. The dual active layer architecture allows for adjustment to the saturation mobility and threshold voltage stability without the requirement of high temperature annealing, which is not compatible with flexible plastic substrates like PEN. The device performance and stability is strongly dependent upon the composition of the mixed metal oxide; this dependency provides a simple route to improving the threshold voltage stability and drive performance. By switching from a single to a dual active layer, the saturation mobility increases from 1.2 cm2/V-s to 18.0 cm2/V-s, while the rate of the threshold voltage shift decreases by an order of magnitude. This approach could assist in enabling the production of devices on flexible substrates using amorphous oxide semiconductors. Low temperature (200°C) processed amorphous silicon photodiodes were developed successfully by balancing the tradeoffs

  3. Energy modulation of nonrelativistic electrons with a CO2 laser using a metal microslit

    Jongsuck, Bae; Ryo, Ishikawa; Sumio, Okuyama; Takashi, Miyajima; Taiji, Akizuki; Tatsuya, Okamoto; Koji, Mizuno

    2000-01-01

    A metal microslit has been used as an interaction circuit between a CO2 laser beam and nonrelativistic free electrons. Evanescent waves which are induced on the slit by illumination of the laser light modulate the energy of electrons passing close to the surface of the slit. The electron-energy change of more than ±5 eV for the 80 keV electron beam has been observed using the 7 kW laser beam at the wavelength of 10.6 μm.

  4. Energy modulation of nonrelativistic electrons with a CO2 laser using a metal microslit

    Bae, Jongsuck; Ishikawa, Ryo; Okuyama, Sumio; Miyajima, Takashi; Akizuki, Taiji; Okamoto, Tatsuya; Mizuno, Koji

    2000-04-01

    A metal microslit has been used as an interaction circuit between a CO2 laser beam and nonrelativistic free electrons. Evanescent waves which are induced on the slit by illumination of the laser light modulate the energy of electrons passing close to the surface of the slit. The electron-energy change of more than ±5 eV for the 80 keV electron beam has been observed using the 7 kW laser beam at the wavelength of 10.6 μm.

  5. Metal-support interactions in electrocatalysis: Hydrogen effects on electron and hole transport at metal-support contacts

    Heller, A.

    1986-01-01

    This paper discusses the effects of hydrogen on electron and hole transport at metal support contacts during electrocatalysis. When hydrogen dissolves in high work function metals such as Pt, Rh or Ru the contact forms between the semiconductor and the hydrogenated metal, which has a work function that is lower than that of the pure metal. Thus by changing the gaseous atmosphere that envelopes metal-substrate contacts, it is possible to reversibly change their diode characteristics. In some cases, such as Pt on n-TiO/sub 2/, Rh on n-TiO/sub 2/ and Ru on n-TiO/sub 2/, it is even possible to reversibly convert Schottky diodes into ohmic contacts by changing the atmosphere from air to hydrogen. In contacts between hydrogen dissolving group VIII metals and semiconducting substrates, one can test for interfacial reaction of the catalysts and the substrate by examining the electrical characteristics of the contacts in air (oxygen) and in hydrogen. In the absence of interfacial reaction, large hydrogen induced variation in the barrier heights is observed and the hydrogenated contacts, approach ideality (i.e. their non-ideality factor is close to unity). When a group VIII metal and a substrate do react, the reaction often produces a phase that blocks hydrogen transport to the interface between the substrate and the reaction product. In this case the hydrogen effect is reduced or absent. Furthermore, because such reaction often introduces defects into the surface of the semiconductor, the contacts have non-ideal diode characteristics

  6. Metal-induced changes in photosynthetic electron transport in poplar Ieaves

    Kralova, K.; Gaplovsky, A.; Masarovicova, E.; Havranek, E.

    2001-01-01

    This study reports the effect of different toxic metals (Cu, Hg and Cd) on dark-induced changes in the photochemical activity of detached poplar leaves that were submersed in solutions of tested metals at different pH level, on the metal accumulation in poplar leaves as well as on fluorescence quenching ability of the tested metals. Cu and Hg inhibited the photosynthetic electron transport (PET) in chloroplast prepared from the leaves of P. nigra and the corresponding IC 50 values were 32.7 and 512.7 μmol dm -3 , respectively. We could not determine the IC 50 value for CdCl 2 due to its very low PET-inhibiting activity. These results are in agreement with previous findings concerning PET inhibition by the studied metals in spinach chloroplasts. The accumulated metal amounts in poplar leaves were determined using radionuclide X-ray fluorescence analysis. The accumulated metal amount increased with the increasing metal concentration and with the decreasing pH value of the applied metal solution. (authors)

  7. Electronic structure of metal phthalocyanines on Ag (100)

    Krull, Cornelius

    2012-01-01

    El uso de moléculas orgánicas en dispositivos tecnológicos ofrece una serie de ventajas: su tamaño (~nm), su capacidad de auto ensamblan dando lugar a la formación de estructuras funcionales, y la posibilidad de adaptar sus propiedades electrónicas y magnéticas a través de los métodos de síntesis molecular. Sin embargo, la implementación de dispositivos orgánicos depende fundamentalmente de la comprensión entre la interacción de las moléculas y los electrodos de metal, así como las interaccio...

  8. Electron spin resonance of radicals and metal complexes

    1993-01-01

    The materials are a collection of extended synopsis of papers presented at the conference sessions. The broad area of magnetic techniques applications has been described as well as their spectra interpretation methods. The ESR, NMR, ENDOR and spin echo were applied for studying the radiation and UV induced radicals in chemical and biological systems. Also in the study of complexes of metallic ions (having the paramagnetic properties) and their interaction with the matrix, the magnetic techniques has been commonly used. They are also very convenient tool for the study of reaction kinetics and mechanism as well as interaction of paramagnetic species with themselves and crystal lattice or with the surface as for thee catalytic processes

  9. Spin-dependent electron emission from metals in the neutralization of He+ ions

    Alducin, M.; Roesler, M.; Juaristi, J.I.; Muino, R. Diez; Echenique, P.M.

    2005-01-01

    We calculate the spin-polarization of electrons emitted in the neutralization of He + ions interacting with metals. All stages of the emission process are included: the spin-dependent perturbation induced by the projectile, the excitation of electrons in Auger neutralization processes, the creation of a cascade of secondaries, and the escape of the electrons through the surface potential barrier. The model allows us to explain in quantitative terms the measured spin-polarization of the yield in the interaction of spin-polarized He + ions with paramagnetic surfaces, and to disentangle the role played by each of the involved mechanisms. We show that electron-electron scattering processes at the surface determine the spin-polarization of the total yield. High energy emitted electrons are the ones providing direct information on the He + ion neutralization process and on the electronic properties of the surface

  10. Energy modulation of nonrelativistic electrons in an optical near field on a metal microslit

    Ishikawa, R.; Bae, J.; Mizuno, K.

    2001-04-01

    Energy modulation of nonrelativistic electrons with a laser beam using a metal microslit as an interaction circuit has been investigated. An optical near field is induced in the proximity of the microslit by illumination of the laser beam. The electrons passing close to the slit are accelerated or decelerated by an evanescent wave contained in the near field whose phase velocity is equal to the velocity of the electrons. The electron-evanescent wave interaction in the microslit has been analyzed theoretically and experimentally. The theory has predicted that electron energy can be modulated at optical frequencies. Experiments performed in the infrared region have verified theoretical predictions. The electron-energy changes of more than ±5 eV with a 10 kW CO2 laser pulse at the wavelength of 10.6 μm has been successfully observed for an electron beam with an energy of less than 80 keV.

  11. Metal-like transport in proteins: A new paradigm for biological electron transfer

    Malvankar, Nikhil; Vargas, Madeline; Tuominen, Mark; Lovley, Derek

    2012-02-01

    Electron flow in biologically proteins generally occurs via tunneling or hopping and the possibility of electron delocalization has long been discounted. Here we report metal-like transport in protein nanofilaments, pili, of bacteria Geobacter sulfurreducens that challenges this long-standing belief [1]. Pili exhibit conductivities comparable to synthetic organic metallic nanostructures. The temperature, magnetic field and gate-voltage dependence of pili conductivity is akin to that of quasi-1D disordered metals, suggesting a metal-insulator transition. Magnetoresistance (MR) data provide evidence for quantum interference and weak localization at room temperature, as well as a temperature and field-induced crossover from negative to positive MR. Furthermore, pili can be doped with protons. Structural studies suggest the possibility of molecular pi stacking in pili, causing electron delocalization. Reducing the disorder increases the metallic nature of pili. These electronically functional proteins are a new class of electrically conductive biological proteins that can be used to generate future generation of inexpensive and environmentally-sustainable nanomaterials and nanolectronic devices such as transistors and supercapacitors. [1] Malvankar et al. Nature Nanotechnology, 6, 573-579 (2011)

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

    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.

  13. Investigation of metal/carbon-related materials for fuel cell applications by electronic structure calculations

    Kong, Ki-jeong [Korea Research Institute of Chemical Technology, P.O.Box 107, Yuseong, Daejeon 305-600 (Korea, Republic of)]. E-mail: kong@krict.re.kr; Choi, Youngmin [Korea Research Institute of Chemical Technology, P.O.Box 107, Yuseong, Daejeon 305-600 (Korea, Republic of); Ryu, Beyong-Hwan [Korea Research Institute of Chemical Technology, P.O.Box 107, Yuseong, Daejeon 305-600 (Korea, Republic of); Lee, Jeong-O [Korea Research Institute of Chemical Technology, P.O.Box 107, Yuseong, Daejeon 305-600 (Korea, Republic of); Chang, Hyunju [Korea Research Institute of Chemical Technology, P.O.Box 107, Yuseong, Daejeon 305-600 (Korea, Republic of)

    2006-07-15

    The potential of carbon-related materials, such as carbon nanotubes (CNTs) and graphite nanofibers (GNFs), supported metal catalysts as an electrode for fuel cell application was investigated using the first-principle electronic structure calculations. The stable binding geometries and energies of metal catalysts are determined on the CNT surface and the GNF edge. The catalyst metal is more tightly bound to the GNF edge than to the CNT surface because of the existence of active dangling bonds of edge carbon atoms. The diffusion barrier of metal atoms on the surface and edge is also obtained. From our calculation results, we have found that high dispersity is achievable for GNF due to high barrier against the diffusion of metal atoms, while CNT appears less suitable. The GNF with a large edge-to-wall ratio is more suitable for the high-performance electrode than perfect crystalline graphite or CNT.

  14. Investigation of metal/carbon-related materials for fuel cell applications by electronic structure calculations

    Kong, Ki-jeong; Choi, Youngmin; Ryu, Beyong-Hwan; Lee, Jeong-O; Chang, Hyunju

    2006-01-01

    The potential of carbon-related materials, such as carbon nanotubes (CNTs) and graphite nanofibers (GNFs), supported metal catalysts as an electrode for fuel cell application was investigated using the first-principle electronic structure calculations. The stable binding geometries and energies of metal catalysts are determined on the CNT surface and the GNF edge. The catalyst metal is more tightly bound to the GNF edge than to the CNT surface because of the existence of active dangling bonds of edge carbon atoms. The diffusion barrier of metal atoms on the surface and edge is also obtained. From our calculation results, we have found that high dispersity is achievable for GNF due to high barrier against the diffusion of metal atoms, while CNT appears less suitable. The GNF with a large edge-to-wall ratio is more suitable for the high-performance electrode than perfect crystalline graphite or CNT

  15. Tool Monitoring and Electronic Event Logging for Sheet Metal Forming Processes

    Gerd Heiserich

    2010-06-01

    Full Text Available This contribution describes some innovative solutions regarding sensor systems for tool monitoring in the sheet metal industry. Autonomous and tamper-proof sensors, which are integrated in the forming tools, can detect and count the strokes carried out by a sheet metal forming press. Furthermore, an electronic event logger for documentary purposes and quality control was developed. Based on this technical solution, new business models such as leasing of sheet metal forming tools can be established for cooperation among enterprises. These models allow usage-based billing for the contractors, taking the effectively produced number of parts into account.

  16. Tuning the electronic structure of graphene through alkali metal and halogen atom intercalation

    Ahmad, Sohail; Miró, Pere; Audiffred, Martha; Heine, Thomas

    2018-04-01

    The deposition, intercalation and co-intercalation of heavy alkali metals and light halogens atoms in graphene mono- and bilayers have been studied using first principles density-functional calculations. Both the deposition and the intercalation of alkali metals gives rise to n-type doping due to the formation of M+-C- pairs. The co-intercalation of a 1:1 ratio of alkali metals and halogens derives into the formation of ionic pairs among the intercalated species, unaltering the electronic structure of the layered material.

  17. Inkjet printing metals on flexible materials for plastic and paper electronics

    Al-Shamery, K.; Raut, N. C.

    2018-01-01

    Inorganic printed electronics is now recognized as an area of tremendous commercial, potential and technical progress. Many research groups are actively involved worldwide in developing metal nanoparticle inks and precursors for printing inorganic/organic materials using different printing....... Besides some examples demonstrating aspects on ink formulation via patterning solid surfaces such as glass and silicon oxide, special emphasis will be placed on compatibility for usage in plastic and paper electronics. Printing of nanoparticles of copper, silver, gold etc. will be discussed...... and will be compared to printing of a variety of metal-organic precursor inks. Finally, a brief account on exemplary applications using the printed inorganic nanoparticles/materials is provided....

  18. Electronic structure and magnetism in transition metals doped 8-hydroxy-quinoline aluminum.

    Baik, Jeong Min; Shon, Yoon; Lee, Seung Joo; Jeong, Yoon Hee; Kang, Tae Won; Lee, Jong-Lam

    2008-10-15

    We report the room-temperature ferromagnetism in transition metals (Co, Ni)-doped 8-hydroxy-quinoline aluminum (Alq3) by thermal coevaporation of high purity metal and Alq3 powders. For 5% Co-doped Alq3, a maximum magnetization of approximately 0.33 microB/Co at 10 K was obtained and ferromagnetic behavior was observed up to 300 K. The Co atoms interact chemically with O atoms and provide electrons to Alq3, forming new states acting as electron trap sites. From this, it is suggested that ferromagnetism may be associated with the strong chemical interaction of Co atoms and Alq3 molecules.

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

    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.

  20. Study of transition metal cations state on the catalyst surface by IR-spectroscopy of adsorbed test-molecules (CO, NO)

    Davydov, A.A.

    1993-01-01

    Using the methods of IR spectroscopy and ESR spectral manifestations of CO and NO in complexes with cations of vanadium in different oxidation degrees and coordination states have been studied. V 5+ cations do not coordinate NO and CO, but coordinate ammonia. Regular decrease of νCO values in V n+ -CO complexes with vanadium oxidation degree decrease has been shown. Spectral manifestation of NO complexes with V 4+ and V 3+ have been followed. The formation of V 4+ -NO, V 3+ -NO and V 3+ (NO) complexes has been established