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Sample records for alkali halide clusters

  1. Photoelectron Spectroscopy of Alkali-Halide Cluster Anions Containing Excess Electrons

    NASA Astrophysics Data System (ADS)

    Fatemi, Darius James

    1995-01-01

    We have obtained photoelectron spectra for alkali -halide clusters containing excess electrons. These measurements demonstrate that the mode of electron accommodation and the cluster configuration depend on the sizes of the atomic ions comprising the aggregate. We also report on the role of the source temperature in determining the structures observed for a cluster. Photoelectron measurements of metal-rich alkali -halide clusters (MX)_{n}M _{m}^-(m >=q 2) suggest that the metallic and ionic components within each of these systems are separated from each other. This behavior is evident for n = 3,5 in clusters of cesium chloride and for n = 3,7,8,9 for sodium iodide clusters. We also studied the mixed species (NaI) _{n}Na_{m} OH^- and(NaI)_ {n}H_2O ^-. The (NaI)_{n} Na_{m}OH ^- clusters appear to contain the OH ^- ion in the same way a halogen anion would be accommodated. Photoelectron spectra of(NaI) _{n}H_2O ^- are consistent with adsorption of a water molecule on an edge of an ionic lattice.

  2. Excess-electron and excess-hole states of charged alkali halide clusters

    NASA Astrophysics Data System (ADS)

    Honea, Eric C.; Homer, Margie L.; Whetten, R. L.

    1990-12-01

    Charged alkali halide clusters from a He-cooled laser vaporization source have been used to investigate two distinct cluster states corresponding to the excess-electron and excess-hole states of the crystal. The production method is UV-laser vaporization of an alkali metal rod into a halogen-containing He flow stream, resulting in variable cluster composition and cooling sufficient to stabilize weakly bound forms. Detection of charged clusters is accomplished without subsequent ionization by pulsed-field time-of-flight mass spectrometry of the skimmed cluster beam. Three types of positively charged sodium fluoride cluster are observed, each corresponding to a distinct physical situation: NanF+n-1 (purely ionic form), Nann+1F+n-1 (excess-electron form), and NanF+n (excess-hole form). The purely ionic clusters exhibit an abundance pattern similar to that observed in sputtering and fragmentation experiments and are explained by the stability of completed cubic microlattice structures. The excess-electron clusters, in contrast, exhibit very strong abundance maxima at n = 13 and 22, corresponding to the all-odd series (2n + 1 = jxkxl;j,k,l odd). Their high relative stability is explained by the ease of Na(0) loss except when the excess electron localizes in a lattice site to complete a cuboid structure. These may correspond to the internal F-center state predicted earlier. A localized electron model incorporating structural simulation results as account for the observed pattern. The excess-hole clusters, which had been proposed as intermediates in the ionization-induced fragmentation of neutral AHCs, exhibit a smaller variation in stability, indicating that the hole might not be well localized.

  3. Adsorption on Alkali Halides.

    NASA Astrophysics Data System (ADS)

    Urzua Duran, Gilberto Antonio

    1995-01-01

    Using a variety of interionic potentials, I have computed the configurations of adsorbed alkali halides monomers on the (001) surface of selected alkali halides crystals. In the majority of cases studied it is found that the monomer adsorbs perpendicular to the surface with the cation sitting nearly on top of the surface anion. In about ten percent of the cases though the monomer adsorbs tilted from the vertical. In these cases the ion that is closer to the surface can be the cation or the anion. The effect of polarization forces is found to be important. In order to discuss the effects of surface retaxation with adsorbates, I have evaluated the surface relaxation of the alkali halide crystals, using a shell model for the interionic forces. It is found that surface relaxation and rumpling are generally small, especially when the van der Waals forces are included. A theory of the effect of substrate vibrations on the binding of an adsorbed atom is developed. At T = 0 the binding energy is D_0-E, where D_0 is the surface well depth (classical binding energy) and E is the quantum correction. For several simple models, it is found that E is surprisingly model-independent. We compare D _0-E with the binding energies to a rigid substrate, D_0-E_{rs}, and to a vibrationally averaged substrate, D _0-E_{va}. We prove that E_{va}>=q E>=q E_ {rs} and that similar relations hold at finite temperature for the free energy of binding. In most cases E_{rs} is better than E_{va} as an approximation to E.

  4. Alkali metal and alkali earth metal gadolinium halide scintillators

    DOEpatents

    Bourret-Courchesne, Edith; Derenzo, Stephen E.; Parms, Shameka; Porter-Chapman, Yetta D.; Wiggins, Latoria K.

    2016-08-02

    The present invention provides for a composition comprising an inorganic scintillator comprising a gadolinium halide, optionally cerium-doped, having the formula A.sub.nGdX.sub.m:Ce; wherein A is nothing, an alkali metal, such as Li or Na, or an alkali earth metal, such as Ba; X is F, Br, Cl, or I; n is an integer from 1 to 2; m is an integer from 4 to 7; and the molar percent of cerium is 0% to 100%. The gadolinium halides or alkali earth metal gadolinium halides are scintillators and produce a bright luminescence upon irradiation by a suitable radiation.

  5. The Additive Coloration of Alkali Halides

    ERIC Educational Resources Information Center

    Jirgal, G. H.; and others

    1969-01-01

    Describes the construction and use of an inexpensive, vacuum furnace designed to produce F-centers in alkali halide crystals by additive coloration. The method described avoids corrosion or contamination during the coloration process. Examination of the resultant crystals is discussed and several experiments using additively colored crystals are…

  6. Mass spectrometry of oligopeptides in the presence of large amounts of alkali halides using desorption/ionization induced by neutral cluster impact.

    PubMed

    Portz, André; Baur, Markus; Gebhardt, Christoph R; Dürr, Michael

    2016-06-01

    Oligopeptides in the presence of large amounts of salt were desorbed and ionized using desorption/ionization induced by neutral clusters (DINeC) for further analysis by means of mass spectrometry (MS). Using oligopeptides in alkali halide solutions as a model system, DINeC was shown to yield clear and fragmentation free mass spectra of the biomolecules even from environments with a large excess of salt. The results were traced back to a phase separation between salt and biomolecules during sample preparation. The ratio between alkali metal complexes [M+A](+) and bare biomolecules [M+H](+) was controlled using different preparation schemes. DINeC was applied to the products of a tryptic digest of bovine serum albumin in the presence of sodium chloride; the results of a mass fingerprint analysis did not show a major difference for the spectra with and without salt in the original solution. The metal-ion/peptide interaction was further investigated by means of tandem-MS. PMID:26825286

  7. Ionic alkali halide XUV laser feasibility study

    SciTech Connect

    Yang, T.T.; Gylys, V.T.; Bower, R.D.; Harris, D.G.; Blauer, J.A.; Turner, C.E.; Hindy, R.N.

    1989-11-10

    The objective of this work is to assess the feasibility of a select set of ionic alkali halide XUV laser concepts by obtaining the relevant kinetic and spectroscopic parameters required for a proof-of-principle and conceptual design. The proposed lasers operate in the 80--200 nm spectral region and do not require input from outside radiation sources for their operation. Frequency up-conversion and frequency mixing techniques and therefore not considered in the work to be described. An experimental and theoretical study of a new type of laser operating in the extreme ultraviolet wavelength region has been conducted. The lasing species are singly ionized alkali halide molecules such as Rb{sup 2+}F{sub {minus}}, Rb{sup 2+}Br{sup {minus}} and Cs{sup 2+}F{sup {minus}}. These species are similar in electronic structure to the rare gas halide excimers, such as XeF and Krf, except that the ionic molecules emit at wavelengths of 80--200 nm, much shorter than the conventional rare-gas halide excimer laser. The radiative lifetime of these molecules are typically near 1 ns, which is about an order of magnitude shorter than that for rare-gas halide systems. The values of the cross section for stimulated emission are on the order of 1 {times} 10{sup {minus}16}cm{sup 2}. Because of the fundamental similarity to existing UV lasers, these systems show promise as a high power, efficient XUV lasers. 55 refs., 50 figs., 5 tabs.

  8. A new polarizable force field for alkali and halide ions

    SciTech Connect

    Kiss, Péter T.; Baranyai, András

    2014-09-21

    We developed transferable potentials for alkali and halide ions which are consistent with our recent model of water [P. T. Kiss and A. Baranyai, J. Chem. Phys. 138, 204507 (2013)]. Following the approach used for the water potential, we applied Gaussian charge distributions, exponential repulsion, and r{sup −6} attraction. One of the two charges of the ions is fixed to the center of the particle, while the other is connected to this charge by a harmonic spring to express polarization. Polarizability is taken from quantum chemical calculations. The repulsion between different species is expressed by the combining rule of Kong [J. Chem. Phys. 59, 2464 (1972)]. Our primary target was the hydration free energy of ions which is correct within the error of calculations. We calculated water-ion clusters up to 6 water molecules, and, as a crosscheck, we determined the density and internal energy of alkali-halide crystals at ambient conditions with acceptable accuracy. The structure of hydrated ions was also discussed.

  9. A new polarizable force field for alkali and halide ions

    NASA Astrophysics Data System (ADS)

    Kiss, Péter T.; Baranyai, András

    2014-09-01

    We developed transferable potentials for alkali and halide ions which are consistent with our recent model of water [P. T. Kiss and A. Baranyai, J. Chem. Phys. 138, 204507 (2013)]. Following the approach used for the water potential, we applied Gaussian charge distributions, exponential repulsion, and r-6 attraction. One of the two charges of the ions is fixed to the center of the particle, while the other is connected to this charge by a harmonic spring to express polarization. Polarizability is taken from quantum chemical calculations. The repulsion between different species is expressed by the combining rule of Kong [J. Chem. Phys. 59, 2464 (1972)]. Our primary target was the hydration free energy of ions which is correct within the error of calculations. We calculated water-ion clusters up to 6 water molecules, and, as a crosscheck, we determined the density and internal energy of alkali-halide crystals at ambient conditions with acceptable accuracy. The structure of hydrated ions was also discussed.

  10. Relation between the electroforming voltage in alkali halide-polymer diodes and the bandgap of the alkali halide

    SciTech Connect

    Bory, Benjamin F.; Wang, Jingxin; Janssen, René A. J.; Meskers, Stefan C. J.; Gomes, Henrique L.; De Leeuw, Dago M.

    2014-12-08

    Electroforming of indium-tin-oxide/alkali halide/poly(spirofluorene)/Ba/Al diodes has been investigated by bias dependent reflectivity measurements. The threshold voltages for electrocoloration and electroforming are independent of layer thickness and correlate with the bandgap of the alkali halide. We argue that the origin is voltage induced defect formation. Frenkel defect pairs are formed by electron–hole recombination in the alkali halide. This self-accelerating process mitigates injection barriers. The dynamic junction formation is compared to that of a light emitting electrochemical cell. A critical defect density for electroforming is 10{sup 25}/m{sup 3}. The electroformed alkali halide layer can be considered as a highly doped semiconductor with metallic transport characteristics.

  11. Electro-optic contribution to Raman scattering from alkali halides

    SciTech Connect

    Mahan, G.D.; Subbaswamy, K.R.

    1986-06-15

    The electro-optic contributions to second-order Raman scattering and field-induced first-order scattering from alkali halides are calculated explicitly in terms of the ionic hyperpolarizability coefficients. The relevant local-field corrections are evaluated. Illustrative numerical results are presented.

  12. Cohesive Energy-Lattice Constant and Bulk Modulus-Lattice Constant Relationships: Alkali Halides, Ag Halides, Tl Halides

    NASA Technical Reports Server (NTRS)

    Schlosser, Herbert

    1992-01-01

    In this note we present two expressions relating the cohesive energy, E(sub coh), and the zero pressure isothermal bulk modulus, B(sub 0), of the alkali halides. Ag halides and TI halides, with the nearest neighbor distances, d(sub nn). First, we show that the product E(sub coh)d(sub 0) within families of halide crystals with common crystal structure is to a good approximation constant, with maximum rms deviation of plus or minus 2%. Secondly, we demonstrate that within families of halide crystals with a common cation and common crystal structure the product B(sub 0)d(sup 3.5)(sub nn) is a good approximation constant, with maximum rms deviation of plus or minus 1.36%.

  13. Interfacial tension in immiscible mixtures of alkali halides.

    PubMed

    Lockett, Vera; Rukavishnikova, Irina V; Stepanov, Victor P; Tkachev, Nikolai K

    2010-02-01

    The interfacial tension of the liquid-phase interface in seven immiscible reciprocal ternary mixtures of lithium fluoride with the following alkali halides: CsCl, KBr, RbBr, CsBr, KI, RbI, and CsI was measured using the cylinder weighing method over a wide temperature range. It was shown that for all mixtures the interfacial tension gradually decreases with growing temperature. The interfacial tension of the reciprocal ternary mixtures at a given temperature increases both with the alkali cation radius (K(+) < Rb(+) < Cs(+)) and with the radius of the halogen anion (Cl(-) < Br(-) < I(-)). PMID:20094678

  14. Alkali Halide Microstructured Optical Fiber for X-Ray Detection

    NASA Technical Reports Server (NTRS)

    DeHaven, S. L.; Wincheski, R. A.; Albin, S.

    2014-01-01

    Microstructured optical fibers containing alkali halide scintillation materials of CsI(Na), CsI(Tl), and NaI(Tl) are presented. The scintillation materials are grown inside the microstructured fibers using a modified Bridgman-Stockbarger technique. The x-ray photon counts of these fibers, with and without an aluminum film coating are compared to the output of a collimated CdTe solid state detector over an energy range from 10 to 40 keV. The photon count results show significant variations in the fiber output based on the materials. The alkali halide fiber output can exceed that of the CdTe detector, dependent upon photon counter efficiency and fiber configuration. The results and associated materials difference are discussed.

  15. Alkali halide microstructured optical fiber for X-ray detection

    SciTech Connect

    DeHaven, S. L. E-mail: russel.a.wincheski@nasa.gov; Wincheski, R. A. E-mail: russel.a.wincheski@nasa.gov; Albin, S.

    2015-03-31

    Microstructured optical fibers containing alkali halide scintillation materials of CsI(Na), CsI(Tl), and NaI(Tl) are presented. The scintillation materials are grown inside the microstructured fibers using a modified Bridgman-Stockbarger technique. The x-ray photon counts of these fibers, with and without an aluminum film coating are compared to the output of a collimated CdTe solid state detector over an energy range from 10 to 40 keV. The photon count results show significant variations in the fiber output based on the materials. The alkali halide fiber output can exceed that of the CdTe detector, dependent upon photon counter efficiency and fiber configuration. The results and associated materials difference are discussed.

  16. Volcanic Origin of Alkali Halides on Io

    NASA Technical Reports Server (NTRS)

    Schaefer, L.; Fegley, B., Jr.

    2003-01-01

    The recent observation of NaCl (gas) on Io confirms our earlier prediction that NaCl is produced volcanically. Here we extend our calculations by modeling thermochemical equilibrium of O, S, Li, Na, K, Rb, Cs, F, Cl, Br, and I as a function of temperature and pressure in a Pele-like volcanic gas with O/S/Na/Cl/K = 1.518/1/0.05/0.04/0.005 and CI chondritic ratios of the other (as yet unobserved) alkalis and halogens. For reference, the nominal temperature and pressure for Pele is 1760 plus or minus 210 K and 0.01 bars based on Galileo data and modeling.

  17. Electronic excitation in bulk and nanocrystalline alkali halides.

    PubMed

    Bichoutskaia, Elena; Pyper, Nicholas C

    2012-11-14

    The lowest energy excitations in bulk alkali halides are investigated by considering five different excited state descriptions. It is concluded that excitation transfers one outermost halide electron in the fully ionic ground state to the lowest energy vacant s orbital of one closest cation neighbour to produce the excited state termed dipolar. The excitation energies of seven salts were computed using shell model description of the lattice polarization produced by the effective dipole moment of the excited state neutral halogen-neutral metal pair. Ab initio uncorrelated short-range inter-ionic interactions computed from anion wavefunctions adapted to the in-crystal environment were augmented by short-range electron correlation contributions derived from uniform electron-gas density functional theory. Dispersive attractions including wavefunction overlap damping were introduced using reliable semi-empirical dispersion coefficients. The good agreement between the predicted excitation energies and experiment provides strong evidence that the excited state is dipolar. In alkali halide nanocrystals in which each ionic plane contains only four ions, the Madelung energies are significantly reduced compared with the bulk. This predicts that the corresponding intra-crystal excitation energies in the nanocrystals, where there are two excited states depending on whether the halide electron is transferred to a cation in the same or in the neighbouring plane, will be reduced by almost 2 eV. For such an encapsulated KI crystal, it has been shown that the greater polarization in the excited state of the bulk crystal causes these reductions to be lowered to a 1.1 eV-1.5 eV range for the case of charge transfer to a neighbouring plane. For intra-plane charge transfer the magnitude of the polarization energy is further reduced thus causing the excitation in these encapsulated materials to be only 0.2 eV less than in the bulk crystal. PMID:23163361

  18. A new mechanism for radiation damage processes in alkali halides

    NASA Astrophysics Data System (ADS)

    Dubinko, V. I.; Turkin, A. A.; Vainshtein, D. I.; den Hartog, H. W.

    1999-12-01

    We present a theory of radiation damage formation in alkali halides based on a new mechanism of dislocation climb, which involves the production of VF centers (self-trapped hole neighboring a cation vacancy) as a result of the absorption of H centers of dislocation lines. We consider the evolution of all experimentally observed extended defects: metal colloids, gas bubbles, and vacancy voids. Voids are shown to arise and grow large due to the reaction between F and VF centers at the surface of halogen bubbles. Voids can ignite a back reaction between the radiolytic products resulting in decomposition of the irradiated material.

  19. Potential function and dissociation energy of alkali halide

    NASA Astrophysics Data System (ADS)

    Srivastava, Abhay P.; Pandey, Anjani K.; Pandey, Brijesh K.

    2016-05-01

    Dissociation energy of some alkali halides have been calculated by using different interaction potential function such as Born-Mayer, Varshani-Shukla and L5 potential model. The theoretical calculation is compared with experimental values. The Result shows that the values of dissociation energy as calculated by using different potential models have an equal amount of deviation with experimental values. The above said deviation with experimental values can be explained by consideration of rotational-vibrational coupling between the constituents of molecules in the limelight of molecular spectroscopy. Findings of present work suggest that the existing potential model need to be reviewed in view of the correction factors solely depending on the rotational, vibrational and electronic coupling between the constituents of molecules.

  20. Fabrication of alkali halide UV photocathodes by pulsed laser deposition

    SciTech Connect

    Brendel', V M; Bukin, V V; Garnov, Sergei V; Bagdasarov, V Kh; Denisov, N N; Garanin, Sergey G; Terekhin, V A; Trutnev, Yurii A

    2012-12-31

    A technique has been proposed for the fabrication of atmospheric corrosion resistant alkali halide UV photocathodes by pulsed laser deposition. We produced photocathodes with a highly homogeneous photoemissive layer well-adherent to the substrate. The photocathodes were mounted in a vacuum photodiode, and a tungsten grid was used as an anode. Using pulsed UV lasers, we carried out experiments aimed at evaluating the quantum efficiency of the photocathodes. With a dc voltage applied between the photocathode and anode grid, we measured a shunt signal proportional to the total charge emitted by the cathode exposed to UV laser light. The proposed deposition technique enables one to produce photocathodes with photoemissive layers highly uniform in quantum efficiency, which is its main advantage over thin film growth by resistive evaporation. (laser technologies)

  1. Fabrication of alkali halide UV photocathodes by pulsed laser deposition

    NASA Astrophysics Data System (ADS)

    Brendel', V. M.; Bukin, V. V.; Garnov, Sergei V.; Bagdasarov, V. Kh; Denisov, N. N.; Garanin, Sergey G.; Terekhin, V. A.; Trutnev, Yurii A.

    2012-12-01

    A technique has been proposed for the fabrication of atmospheric corrosion resistant alkali halide UV photocathodes by pulsed laser deposition. We produced photocathodes with a highly homogeneous photoemissive layer well-adherent to the substrate. The photocathodes were mounted in a vacuum photodiode, and a tungsten grid was used as an anode. Using pulsed UV lasers, we carried out experiments aimed at evaluating the quantum efficiency of the photocathodes. With a dc voltage applied between the photocathode and anode grid, we measured a shunt signal proportional to the total charge emitted by the cathode exposed to UV laser light. The proposed deposition technique enables one to produce photocathodes with photoemissive layers highly uniform in quantum efficiency, which is its main advantage over thin film growth by resistive evaporation.

  2. Solvent-averaged potentials for alkali-, earth alkali-, and alkylammonium halide aqueous solutions

    NASA Astrophysics Data System (ADS)

    Hess, Berk; van der Vegt, Nico F. A.

    2007-12-01

    We derive effective, solvent-free ion-ion potentials for alkali-, earth alkali-, and alkylammonium halide aqueous solutions. The implicit solvent potentials are parametrized to reproduce experimental osmotic coefficients. The modeling approach minimizes the amount of input required from atomistic (force field) models, which usually predict large variations in the effective ion-ion potentials at short distances. For the smaller ion species, the reported potentials are composed of a Coulomb and a Weeks-Chandler-Andersen term. For larger ions, we find that an additional, attractive potential is required at the contact minimum, which is related to solvent degrees of freedom that are usually not accounted for in standard electrostatics models. The reported potentials provide a simple and accurate force field for use in molecular dynamics and Monte Carlo simulations of (poly-)electrolyte systems.

  3. Efficient destruction of CF4 through in situ generation of alkali metals from heated alkali halide reducing mixtures.

    PubMed

    Lee, Myung Churl; Choi, Wonyong

    2002-03-15

    Perfluorocarbons (PFCs) are the most potent green house gases that are very recalcitrant at destruction. An effective way of converting PFCs using hot solid reagents into safe products has been recently introduced. By investigating the thermal reductive destruction of tetrafluoromethane (CF4) we provided new insight and more physicochemical consideration on this novel process. The complete destruction of CF4was successfully achieved by flowing the gas through a heated reagent bed (400-950 degrees C) that contained powder mixtures of alkali halides, CaO, and Si. The silicon acted as a reducing agent of alkali halides for the in-situ production of alkali metals, and the calcium oxide played the role of a halide ion acceptor. The absence of any single component in this ternary mixture drastically reduced the destruction efficiency of CF4. The CF4 destruction efficiencies with the solid reagent containing the alkali halide, MX, increased in the order of Li approximately Na < K < Cs for alkali cations and I < Br < Cl < F for halide anions. This trend agreed with the endothermicity of the alkali metal generation reaction: the higher the endothermicity, the lower the destruction efficiency. Alkali metal generation was indirectly detected by monitoring H2 production from its reaction with water. The production of alkali metals increased with NaF, KF, and CsF in this order. The CsF/CaO/Si system exhibited the complete destruction of CF4 at as low as 600 degrees C. The solid product analysis by X-ray diffraction (XRD) showed the formation of CaF2 and the depletion of Si with black carbon particles formed in the solid reagent residue. No CO/CO2 and toxic HF and SiF4 formation were detected in the exhaust gas. PMID:11944694

  4. Investigating Metallization in Shock-Compressed Alkali Halides

    NASA Astrophysics Data System (ADS)

    Diamond, M. R.; Ali, S. J.; Eggert, J.; Jeanloz, R.; Collins, G. W.; McWilliams, R. S.

    2014-12-01

    Laser-shock compression on four alkali halides has been used to probe the transition from insulating to metallic states, a high-pressure transition in chemical bonding that has fundamental implications for planetary formation and structure. Collectively, pressures up to 450 GPa were explored across a total of fourteen single-crystal samples of CsI, CsBr, KBr and NaCl. Velocity interferometry (VISAR) was used to record shock velocities and reflectivities at 532 nm during decaying shock compression. The data show up to three-fold increases in density as well as significant increases in optical reflectivity in response to high pressures and temperatures. Using a Drude model to estimate conductivities from the measured reflectivities, we investigate the onset of metallic conductivities for each compound. Ionic salts are simple model systems amenable to first-principles theory and serve as analog materials for predicting whether specific chemical constituents can reside in the rocky mantles or metallic cores of planets. A key objective is to disentangle the complementary roles of temperature and compression in transforming ionic into metallic bonding. Furthermore, at high pressures CsI becomes analogous to Xe: they are isoelectronic and follow matching equations of state. Therefore, studies on CsI can inform understanding of noble-gas geochemistry at conditions deep inside planets (e.g., the likelihood of Xe solubility in planetary mantles or cores). Our experiments were conducted using the Janus laser of the Jupiter Laser Facility at Lawrence Livermore National Laboratory.

  5. Strong Turbulence in Alkali Halide Negative Ion Plasmas

    NASA Astrophysics Data System (ADS)

    Sheehan, Daniel

    1999-11-01

    Negative ion plasmas (NIPs) are charge-neutral plasmas in which the negative charge is dominated by negative ions rather than electrons. They are found in laser discharges, combustion products, semiconductor manufacturing processes, stellar atmospheres, pulsar magnetospheres, and the Earth's ionosphere, both naturally and man-made. They often display signatures of strong turbulence^1. Development of a novel, compact, unmagnetized alkali halide (MX) NIP source will be discussed, it incorporating a ohmically-heated incandescent (2500K) tantulum solenoid (3cm dia, 15 cm long) with heat shields. The solenoid ionizes the MX vapor and confines contaminant electrons, allowing a very dry (electron-free) source. Plasma densities of 10^10 cm-3 and positive to negative ion mass ratios of 1 <= fracm_+m- <= 20 are achievable. The source will allow tests of strong turbulence theory^2. 1 Sheehan, D.P., et al., Phys. Fluids B5, 1593 (1993). 2 Tsytovich, V. and Wharton, C.W., Comm. Plasma Phys. Cont. Fusion 4, 91 (1978).

  6. Reflectivities of Four Shock-Compressed Alkali Halides

    NASA Astrophysics Data System (ADS)

    Diamond, M. R.; McWilliams, R. S.; Eggert, J.; Jeanloz, R.; Ali, S. J.; Collins, G. W.

    2015-12-01

    Laser-shock compression on four alkali halides has been used to probe the transition from insulating to metallic states, a high-pressure transition in chemical bonding that has fundamental implications for planetary formation and structure. Collectively, pressures up to 450 GPa and densities up to three-fold compression were explored across a total of fourteen single-crystal samples of CsI, CsBr, KBr and NaCl. Velocity interferometry was used to record shock velocities and reflectivities at 532 nm during decaying shock compression. The data show up to 40% (or higher) reflectivity, corresponding to notable electrical conductivities, in response to high pressures and temperatures. Furthermore, band-gap closure, dependent on density, can be examined from the reflectivity data. Ionic salts are simple model systems amenable to first-principles theory and serve as analog materials for predicting whether specific chemical constituents can reside in the rocky mantles or metallic cores of planets. A key objective is to disentangle the complementary roles of temperature and compression in transforming ionic into metallic bonding. Furthermore, at high pressures CsI becomes analogous to Xe: they are isoelectronic and follow matching equations of state. Therefore, studies on CsI could inform understanding of noble-gas geochemistry at conditions deep inside planets.

  7. Graphitic cage transformation by electron-beam-induced catalysis with alkali-halide nanocrystals

    NASA Astrophysics Data System (ADS)

    Fujita, Jun-ichi; Tachi, Masashi; Ito, Naoto; Murakami, Katsuhisa; Takeguchi, Masaki

    2016-05-01

    We found that alkali-halide nanocrystals, such as KCl and NaCl, have strong catalytic capability to form graphitic carbon cages from amorphous carbon shells under electron beam irradiation. In addition to the electron beam irradiation strongly inducing the decomposition of alkali-halide nanocrystals, graphene fragments were formed and linked together to form the final product of thin graphitic carbon cages after the evaporation of alkali-halide nanocrystals. The required electron dose was approximately 1 to 20 C/cm2 at 120 keV at room temperature, which was about two orders of magnitude smaller than that required for conventional beam-induced graphitization. The “knock-on” effect of primary electrons strongly induced the decomposition of the alkali-halide crystal inside the amorphous carbon shell. However, the strong ionic cohesion quickly reformed the crystal into thin layers inside the amorphous shell. The bond excitation induced by the electron beam irradiation seemed to enhance strongly the graphitization at the interface between the outer amorphous carbon shell and the inner alkali-halide crystal.

  8. Theoretical and experimental investigation of force imaging at the atomic scale on alkali halide crystals

    NASA Astrophysics Data System (ADS)

    Shluger, A. L.; Wilson, R. Mark; Williams, R. T.

    1994-02-01

    Assuming a model tip (Si4O10H10) as a reasonable representation of the surface of a Si3N4 cantilever stylus having a hydrogen-terminated asperity and a broader load-bearing base, we investigate the interaction of an atomic force microscope (AFM) with an alkali halide crystal by quantum chemical methods. Structural relaxation of the sample during engagement is allowed, and defect formation is investigated. Force curves above cation and anion positions are calculated, determining maximum sustainable loads and indicating a basis for atomic contrast. Experiments using a Si3N4 cantilever for AFM imaging of 12 alkali halide and alkaline earth fluoride crystals in air and desiccated helium are reported, in the widest AFM survey of such materials to date. Adsorbed water is shown to significantly enhance the observation of atomic periodicity on ionic halide samples, and rapid surface diffusion on alkali halide crystals is illustrated as it affects prospects for defect investigations. Observations of step edges and point-defect candidates at atomic scale are reported. The theoretical and experimental results are discussed together in the effort to provide a quantum-mechanical model for observations of alkali halide samples at atomic resolution, and to examine a possible basis for atomic resolution in the presence of long-range attractive forces.

  9. UV laser-induced desorption mechanism analyzed through two-layer alkali halide samples.

    PubMed

    Fernández-Lima, F A; Ponciano, C R; da Silveira, E F

    2008-05-01

    Time of flight-mass spectrometry (TOF-MS) is used to analyze positive and negative desorbed ions generated by UV laser ablation of several alkali (X) halide (Y) salts. Most of the observed desorbed cluster ions have the structure (XY)(n)X(+) or (XY)(n)Y(-). Their desorption yields decrease as exp(-kn), where k approximately 2 for both series, suggesting that the neutral component (XY)(n) plays the dominant role in the desorption process. Mass spectrum measurements were performed for compound samples in which two salts (out of CsI, RbI, KBr, KCl and KI) are homogeneously mixed or disposed in two superposed layers. The detection of small new ion species and large cluster ions of the original salts supports the scenario that the uppermost layers are completely atomized while deep layers are emitted colder and fragmented: It is proposed that ns-pulsed laser induced desorption of ionic salts occurs via two sequential mechanisms: (1) ejection of cations and anions in the hot plume, followed by recombination into new cluster ions and (2) ejection of relatively cold preformed species originated from deep layers or from periphery of the irradiated region. PMID:18095386

  10. Electro-optic contribution to field-induced Raman scattering in alkali halides

    SciTech Connect

    Subbaswamy, K.R.; Mahan, G.D.

    1985-10-15

    The electro-optic contribution to the field-induced first-order Raman scattering cross section in alkali halide crystals is calculated using measured values for hyperpolarizabilities. The electro-optic contribution is much larger than the previously reported atomic displacement contribution. The results cast some doubt on the accuracy of the reported hyperpolarizability values.

  11. Size distributions and geometries of alkali halide nanoclusters probed using ESI FT-ICR mass spectrometry and quantum chemistry

    NASA Astrophysics Data System (ADS)

    Lemke, K.; Sadjadi, S.; Seward, T.

    2010-12-01

    The structures and energetic properties of ionic alkali metal halide clusters play a significant role in our understanding of aqueous geochemical processes such as salt dissolution, precipitation and neutralization reactions. Mass spectrometric and quantum chemical studies of such systems offer new opportunities to study the size-dependent evolution of cluster structures, the occurrence of magic number species as well as their fundamental properties. The work here presents new results for the stability, abundance and structure of pure [Na(NaClm)]+ , [K(KCl)m]+ and mixed [Na(NaCl)p(KCl)q]+ metal halide clusters with m<23 and p+q<14, respectively, using ultra-high resolution Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR/MS) in combination with the Gn and CBS-x multistep ab initio methods. Ion-cluster experiments were conducted on a modified 7T Bruker FT-ICR/MS equipped with electrospray ionization (ESI) sources and a custom-designed solvent gas inlet interface. In ESI FT-ICR/MS experiments performed with solutions containing NaCl and KCl salts (1mM; 80/20 CH3CN/H2O), singly and doubly charged salt clusters were generated up to a cluster size of [Na(NaCl)22]+, [K(KCl)17]+ and [K2(KCl)21,23]2+, respectively, including “magic number” clusters that correspond to the completed cluster cuboids with the dimensions 3x3x1 (m=4), 3x3x2+3 (m=10) 3x3x3 (m=13) and 3x3x5 (m=22) (see Figure). On the other hand, no pure clusters except [K(KCl)1-3]+ were generated when alkali halides were electrosprayed from 1mM NaCl/KCl solutions. Instead, mixed [Na(NaCl)p(KCl)q]+ clusters are generated up to p+q=14, which are the largest mixed alkali halide clusters yet generated in mass spectrometric experiments, including a suite of ionic species that are generated via CH3CN fragmentation and charge transfer in [Na(CH3CN)n]+ to yield the clusters [Na(NaCN)(CH3CN)n-1]+. We describe our ESI FT-ICR/MS experiments and discuss ion cluster abundances and extent of clustering

  12. Resonance-Raman-scattering spectroscopy for the halogen-molecular-ion centers in alkali halides

    NASA Astrophysics Data System (ADS)

    Suzuki, T.; Tanimura, K.; Itoh, N.

    1993-10-01

    We have measured the Raman scattering in resonance with the bonding-to-antibonding transitions of two types of dihalogen-molecular-ion centers in alkali halides, the VK and H centers; the molecular ion occupies two adjacent halogen sites in the former and a single halogen site in the latter. It is found that the stretching-vibration frequency of the molecular ion is higher by more than 30% for the H center than for the VK center. The hardening is ascribed to the bond tightening due to the Madelung potential. Although the Raman line due to the stretching vibration consists of a single line in most alkali halides, two closely lying lines are observed for the H centers in alkali halides with small alkali-metal to halogen radius ratio and also for the VK center in NaCl. The paired-line structure is ascribed to the coupling of the stretching vibration of the halogen molecular ion with the lattice.

  13. Refined potentials for rare gas atom adsorption on rare gas and alkali-halide surfaces

    NASA Technical Reports Server (NTRS)

    Wilson, J. W.; Heinbockel, J. H.; Outlaw, R. A.

    1985-01-01

    The utilization of models of interatomic potential for physical interaction to estimate the long range attractive potential for rare gases and ions is discussed. The long range attractive force is calculated in terms of the atomic dispersion properties. A data base of atomic dispersion parameters for rare gas atoms, alkali ion, and halogen ions is applied to the study of the repulsive core; the procedure for evaluating the repulsive core of ion interactions is described. The interaction of rare gas atoms on ideal rare gas solid and alkali-halide surfaces is analyzed; zero coverage absorption potentials are derived.

  14. Theory of metal atom-water interactions and alkali halide dimers

    NASA Technical Reports Server (NTRS)

    Jordan, K. D.; Kurtz, H. A.

    1982-01-01

    Theoretical studies of the interactions of metal atoms with water and some of its isoelectronic analogs, and of the properties of alkali halides and their aggregates are discussed. Results are presented of ab initio calculations of the heats of reaction of the metal-water adducts and hydroxyhydrides of Li, Be, B, Na, Mg, and Al, and of the bond lengths and angles an; the heats of reaction for the insertion of Al into HF, H2O, NH3, H2S and CH3OH, and Be and Mg into H2O. Calculations of the electron affinities and dipole moments and polarizabilities of selected gas phase alkali halide monomers and dimers are discussed, with particular attention given to results of calculations of the polarizability of LiF taking into account electron correlation effects, and the polarizability of the dimer (LiF)2.

  15. Reactions between cold methyl halide molecules and alkali-metal atoms

    SciTech Connect

    Lutz, Jesse J.; Hutson, Jeremy M.

    2014-01-07

    We investigate the potential energy surfaces and activation energies for reactions between methyl halide molecules CH{sub 3}X (X = F, Cl, Br, I) and alkali-metal atoms A (A = Li, Na, K, Rb) using high-level ab initio calculations. We examine the anisotropy of each intermolecular potential energy surface (PES) and the mechanism and energetics of the only available exothermic reaction pathway, CH{sub 3}X + A → CH{sub 3} + AX. The region of the transition state is explored using two-dimensional PES cuts and estimates of the activation energies are inferred. Nearly all combinations of methyl halide and alkali-metal atom have positive barrier heights, indicating that reactions at low temperatures will be slow.

  16. Development of processes for the production of solar grade silicon from halides and alkali metals

    NASA Technical Reports Server (NTRS)

    Dickson, C. R.; Gould, R. K.

    1980-01-01

    High temperature reactions of silicon halides with alkali metals for the production of solar grade silicon in volume at low cost were studied. Experiments were performed to evaluate product separation and collection processes, measure heat release parameters for scaling purposes, determine the effects of reactants and/or products on materials of reactor construction, and make preliminary engineering and economic analyses of a scaled-up process.

  17. Theoretical analysis of the kinetics of low-temperature defect recombination in alkali halide crystals

    NASA Astrophysics Data System (ADS)

    Kuzovkov, V. N.; Popov, A. I.; Kotomin, E. A.; Moskina, A. M.; Vasilchenko, E.; Lushchik, A.

    2016-07-01

    We analyzed carefully the experimental kinetics of the low-temperature diffusion-controlled F, H center recombination in a series of irradiated alkali halides and extracted the migration energies and pre-exponential parameters for the hole H centers. The migration energy for the complementary electronic F centers in NaCl was obtained from the colloid formation kinetics observed above room temperature. The obtained parameters were compared with data available from the literature.

  18. Temperature Dependence of Interatomic Separation and Bulk Modulus for Alkali Halides

    NASA Astrophysics Data System (ADS)

    Liu, Quan

    2016-07-01

    The values of interatomic separation r with the change of temperature T for seven alkali halides have been investigated with the help of an isobaric equation of state. The calculated results are used to predict the values of bulk modulus at different temperatures. The results are compared with the available experimental data and other theoretical results and are further discussed in view of recent research in the field of high temperature physics.

  19. Alkali metal/halide thermal energy storage systems performance evaluation

    NASA Technical Reports Server (NTRS)

    Phillips, W. M.; Stearns, J. W.

    1986-01-01

    A pseudoheat-pipe heat transfer mechanism has been demonstrated effective in terms of both total heat removal efficiency and rate, on the one hand, and system isothermal characteristics, on the other, for solar thermal energy storage systems of the kind being contemplated for spacecraft. The selection of appropriate salt and alkali metal substances for the system renders it applicable to a wide temperature range. The rapid heat transfer rate obtainable makes possible the placing of the thermal energy storage system around the solar receiver canister, and the immersing of heat transfer fluid tubes in the phase change salt to obtain an isothermal heat source.

  20. Metal Hydride and Alkali Halide Opacities in Extrasolar Giant Planets and Cool Stellar Atmospheres

    NASA Technical Reports Server (NTRS)

    Weck, Philippe F.; Stancil, Phillip C.; Kirby, Kate; Schweitzer, Andreas; Hauschildt, Peter H.

    2006-01-01

    The lack of accurate and complete molecular line and continuum opacity data has been a serious limitation to developing atmospheric models of cool stars and Extrasolar Giant Planets (EGPs). We report our recent calculations of molecular opacities resulting from the presence of metal hydrides and alkali halides. The resulting data have been included in the PHOENIX stellar atmosphere code (Hauschildt & Baron 1999). The new models, calculated using spherical geometry for all gravities considered, also incorporate our latest database of nearly 670 million molecular lines, and updated equations of state.

  1. Zintl cluster chemistry in the alkali-metal-gallium systems

    SciTech Connect

    Henning, R.

    1998-03-27

    Previous research into the alkali-metal-gallium systems has revealed a large variety of networked gallium deltahedra. The clusters are analogues to borane clusters and follow the same electronic requirements of 2n+2 skeletal electrons for closo-deltahedra. This work has focused on compounds that do not follow the typical electron counting rules. The first isolated gallium cluster was found in Cs{sub 8}Ga{sub 11}. The geometry of the Ga{sub 11}{sup 7{minus}} unit is not deltahedral but can be described as a penta-capped trigonal prism. The reduction of the charge from a closo-Ga{sub 11}{sup 13{minus}} to Ga{sub 11}{sup 7{minus}} is believed to be the driving force of the distortion. The compound is paramagnetic because of an extra electron but incorporation of a halide atom into the structure captures the unpaired electron and forms a diamagnetic compound. A second isolated cluster has been found in Na{sub 10}Ga{sub 10}Ni where the tetra-capped trigonal prismatic gallium is centered by nickel. Stabilization of the cluster occurs through Ni-Ga bonding. A simple two-dimensional network occurs in the binary K{sub 2}Ga{sub 3} Octahedra are connected through four waist atoms to form a layered structure with the potassium atoms sitting between the layers. Na{sub 30.5}Ga{sub 60{minus}x}Ag{sub x} is nonstoichiometric and needs only a small amount of silver to form (x {approximately} 2--6). The structure is composed of three different clusters which are interconnected to form a three-dimensional structure. The RbGa{sub 3{minus}x}Au{sub x} system is also nonstoichiometric with a three-dimensional structure composed of Ga{sub 8} dodecahedra and four-bonded gallium atoms. Unlike Na{sub 30.5}Ga{sub 60{minus}x}Ag{sub x}, the RbGa{sub 3} binary is also stable. The binary is formally a Zintl phase but the ternary is not. Some chemistry in the alkali-metal-indium system also has been explored. A new potassium-indium binary is discussed but the structure has not been completely

  2. Molecular dispersion energy parameters for alkali and halide ions in aqueous solution.

    PubMed

    Reiser, S; Deublein, S; Vrabec, J; Hasse, H

    2014-01-28

    Thermodynamic properties of aqueous solutions containing alkali and halide ions are determined by molecular simulation. The following ions are studied: Li(+), Na(+), K(+), Rb(+), Cs(+), F(-), Cl(-), Br(-), and I(-). The employed ion force fields consist of one Lennard-Jones (LJ) site and one concentric point charge with a magnitude of ±1 e. The SPC/E model is used for water. The LJ size parameter of the ion models is taken from Deublein et al. [J. Chem. Phys. 136, 084501 (2012)], while the LJ energy parameter is determined in the present study based on experimental self-diffusion coefficient data of the alkali cations and the halide anions in aqueous solutions as well as the position of the first maximum of the radial distribution function of water around the ions. On the basis of these force field parameters, the electric conductivity, the hydration dynamics of water molecules around the ions, and the enthalpy of hydration is predicted. Considering a wide range of salinity, this study is conducted at temperatures of 293.15 and 298.15 K and a pressure of 1 bar. PMID:25669552

  3. Molecular dispersion energy parameters for alkali and halide ions in aqueous solution

    SciTech Connect

    Reiser, S.; Deublein, S.; Hasse, H.; Vrabec, J.

    2014-01-28

    Thermodynamic properties of aqueous solutions containing alkali and halide ions are determined by molecular simulation. The following ions are studied: Li{sup +}, Na{sup +}, K{sup +}, Rb{sup +}, Cs{sup +}, F{sup −}, Cl{sup −}, Br{sup −}, and I{sup −}. The employed ion force fields consist of one Lennard-Jones (LJ) site and one concentric point charge with a magnitude of ±1 e. The SPC/E model is used for water. The LJ size parameter of the ion models is taken from Deublein et al. [J. Chem. Phys. 136, 084501 (2012)], while the LJ energy parameter is determined in the present study based on experimental self-diffusion coefficient data of the alkali cations and the halide anions in aqueous solutions as well as the position of the first maximum of the radial distribution function of water around the ions. On the basis of these force field parameters, the electric conductivity, the hydration dynamics of water molecules around the ions, and the enthalpy of hydration is predicted. Considering a wide range of salinity, this study is conducted at temperatures of 293.15 and 298.15 K and a pressure of 1 bar.

  4. Alkali Halide Interfacial Behavior in a Sequence of Charged Slit Pores

    SciTech Connect

    Wander, Matthew C; Shuford, Kevin L

    2011-01-01

    In this paper, a variety of alkali halide, aqueous electrolyte solutions in contact with charged, planar-graphite slit-pores are simulated using classical molecular dynamics. Size trends in structure and transport properties are examined by varying the choice of ions among the alkali metal and halide series. As with the uncharged pores, system dynamics are driven by changes in water hydration behavior and specifically by variations in the number of hydrogen bonds per water molecule. Overall, the larger ions diffuse more rapidly under high surface charge conditions than the smaller ions. In particular, for the 1 nmslit, ion diffusivity increased by a factor of 4 compared to the uncharged case. Finally, a quantitative fit to the interfacial charge structure is presented, which confirms the presence of two distinct types of layers in an aqueous interface. This model indicates that the chemistry of the interface is able to create a small interfacial potential, and it shows how water molecules can rotate to increase charge separation in response to a surface potential.

  5. Multiple neutral alkali halide attachments onto oligosaccharides in electrospray ionization mass spectrometry

    NASA Astrophysics Data System (ADS)

    Striegel, André M.; Timpa, Judy D.; Piotrowiak, Piotr; Cole, Richard B.

    1997-03-01

    Oligosaccharides perform essential functions in a variety of biological and agricultural processes. Recent approaches to characterization of these molecules by mass spectrometry have utilized mainly soft-ionization methods such as electrospray ionization (ESI) and thermospray (TS), as well as fast atom bombardment (FAB). The behavior of a series of maltooligosaccharides with [alpha]-(1 --> 4) linkages, maltose (G2) through maltoheptaose (G7), under ESI conditions, has been investigated here. The oligosaccharides were dissolved in N,N-dimethylacetamide containing lithium chloride (DMAc/LiCl) prior to analysis by ESI-MS. A highly unusual feature, evident in all mass spectra obtained using this solvent system, was the presence of multiple [`]neutral' salt attachments onto lithium adducts of the sugars. Resultant ions took the form of [Gx + Li + nLiCl+, where n may reach a value as high as eight. Compared to LiCl, the propensity for alkali halide attachment using other alkali chlorides or lithium halides was greatly reduced. An investigation of this phenomenon is presented in which the organic and inorganic portions of the employed solvent were systematically varied, and semi-empirical computer modeling was performed to better understand lithium coordination by the sugars.

  6. Alkali Halide Interfacial Behavior in a Sequence of Charged Slit Pores

    SciTech Connect

    Wander, Matthew C. F.; Shuford, Kevin L.

    2011-12-01

    In this paper, a variety of alkali halide, aqueous electrolyte solutions in contact with charged, planar-graphite slit-pores are simulated using classical molecular dynamics. Size trends in structure and transport properties are examined by varying the choice of ions among the alkali metal and halide series. As with the uncharged pores, system dynamics are driven by changes in water hydration behavior and specifically by variations in the number of hydrogen bonds per water molecule. Overall, the larger ions diffuse more rapidly under high surface charge conditions than the smaller ions. In particular, for the 1 nm slit, ion diffusivity increased by a factor of 4 compared to the uncharged case. Finally, a quantitative fit to the interfacial charge structure is presented, which confirms the presence of two distinct types of layers in an aqueous interface. This model indicates that the chemistry of the interface is able to create a small interfacial potential, and it shows how water molecules can rotate to increase charge separation in response to a surface potential.

  7. Alkali Metal Halide Salts as Interface Additives to Fabricate Hysteresis-Free Hybrid Perovskite-Based Photovoltaic Devices.

    PubMed

    Wang, Lili; Moghe, Dhanashree; Hafezian, Soroush; Chen, Pei; Young, Margaret; Elinski, Mark; Martinu, Ludvik; Kéna-Cohen, Stéphane; Lunt, Richard R

    2016-09-01

    A new method was developed for doping and fabricating hysteresis-free hybrid perovskite-based photovoltaic devices by using alkali metal halide salts as interface layer additives. Such salt layers introduced at the perovskite interface can provide excessive halide ions to fill vacancies formed during the deposition and annealing process. A range of solution-processed halide salts were investigated. The highest performance of methylammonium lead mixed-halide perovskite device was achieved with a NaI interlayer and showed a power conversion efficiency of 12.6% and a hysteresis of less than 2%. This represents a 90% improvement compared to control devices without this salt layer. Through depth-resolved mass spectrometry, optical modeling, and photoluminescence spectroscopy, this enhancement is attributed to the reduction of iodide vacancies, passivation of grain boundaries, and improved hole extraction. Our approach ultimately provides an alternative and facile route to high-performance and hysteresis-free perovskite solar cells. PMID:27532662

  8. Silicon Halide-alkali Metal Flames as a Source of Solar Grade Silicon

    NASA Technical Reports Server (NTRS)

    Olson, D. B.; Gould, R. K.

    1979-01-01

    A program is presented which was aimed at determining the feasibility of using high temperature reactions of alkali metals and silicon halides to produce low cost solar-grade silicon. Experiments are being conducted to evaluate product separation and collection processes, measure heat release parameters for scaling purposes, and determine the effects of the reactants and/or products on materials of reactor construction. During the current reporting period, the results of heat release experiments were used to design and construct a new type of thick-wall graphite reactor to produce larger quantities of silicon. A reactor test facility was constructed. Material compatibility tests were performed for Na in contact with graphite and several coated graphites. All samples were rapidly degraded at T = 1200K, while samples retained structural strength at 1700K. Pyrolytic graphite coatings cracked and separated from substances in all cases.

  9. Ion Segregation and Deliquescence of Alkali Halide Nanocrystals on SiO2

    NASA Astrophysics Data System (ADS)

    Arima, Kenta; Jiang, Peng; Lin, Deng-Sung; Verdaguer, Albert; Salmeron, Miquel

    2009-08-01

    The adsorption of water on alkali halide (KBr, KCl, KF, NaCl) nanocrystals on SiO2 and their deliquescence was investigated as a function of relative humidity (RH) from 8% to near saturation by scanning polarization force microscopy. At low humidity, water adsorption solvates ions at the surface of the crystals and increases their mobility. This results in a large increase in the dielectric constant, which is manifested in an increase in the electrostatic force and in an increase in the apparent height of the nanocrystals. Above 58% RH, the diffusion of ions leads to Ostwald ripening, where larger nanocrystals grow at the expense of the smaller ones. At the deliquescence point, droplets were formed. For KBr, KCl, and NaCl, the droplets exhibit a negative surface potential relative to the surrounding region, which is indicative of the preferential segregation of anions to the air/solution interface.

  10. Role of excitons in electron- and photon-stimulated desorption of neutrals from alkali halides.

    PubMed

    Alexandrov, A; Piacentini, M; Zema, N; Felici, A C; Orlando, T M

    2001-01-15

    Low-energy (5-15 eV) electron- and photon-stimulated desorption of KI(100) yields I2P3/2 and 2P1/2 with hyperthermal (0.3 eV) and thermal velocity components. The desorption threshold for both components is 5.3 eV and is correlated with the gamma3/2-exciton long-wavelength edge. Exciton decay at the surface directly produces I2P3/2 and 2P1/2 with hyperthermal velocity and is in competition with self-trapping. Spin memory of the gamma-exciton hole-component is also evident in the hyperthermal channel. An exciton mediated desorption mechanism is presented which is general in alkali halides. PMID:11177874

  11. Ab initio perspective on the Mollwo-Ivey relation for F centers in alkali halides

    NASA Astrophysics Data System (ADS)

    Tiwald, Paul; Karsai, Ferenc; Laskowski, Robert; Gräfe, Stefanie; Blaha, Peter; Burgdörfer, Joachim; Wirtz, Ludger

    2015-10-01

    We revisit the well-known Mollwo-Ivey relation that describes the "universal" dependence of the absorption energies of F-type color centers on the lattice constant a of alkali-halide crystals, Eabs∝a-n. We perform both state-of-the-art ab initio quantum chemistry and post-DFT calculations of F-center absorption spectra. By "tuning" independently the lattice constant and the atomic species we show that the scaling with the lattice constant alone (keeping the elements fixed) would yield n =2 in agreement with the "particle-in-the-box" model. Keeping the lattice constant fixed and changing the atomic species enables us to quantify the ion-size effects which are shown to be responsible for the exponent n ≈1.8 .

  12. Studies of Non-Proportionality in Alkali Halide and Strontium Iodide Scintillators Using SLYNCI

    SciTech Connect

    Ahle, L; Bizarri, G; Boatner, L; Cherepy, N J; Choong, W; Moses, W W; Payne, S A; Shah, K; Sheets, S; Sturm, B W

    2009-05-05

    Recently a collaboration of LLNL and LBNL has constructed a second generation Compton coincidence instrument to study the non-proportionality of scintillators [1-3]. This device, known as SLYNCI (Scintillator Light-Yield Non-proportionality Characterization Instrument), has can completely characterize a sample with less than 24 hours of running time. Thus, SLYNCI enables a number of systematic studies of scintillators since many samples can be processed in a reasonable length of time. These studies include differences in nonproportionality between different types of scintillators, different members of the same family of scintillators, and impact of different doping levels. The results of such recent studies are presented here, including a study of various alkali halides, and the impact of europium doping level in strontium iodide. Directions of future work area also discussed.

  13. Studies of non-proportionality in alkali halide and strontium iodide scintillators using SLYNCI

    SciTech Connect

    Ahle, Larry; Bizarri, Gregory; Boatner, Lynn; Cherepy, Nerine J.; Choong, Woon-Seng; Moses, William W.; Payne, Stephen A.; Shah, Kanai; Sheets, Steven; Sturm, Benjamin, W.

    2010-10-14

    Recently a collaboration of LLNL and LBNL has constructed a second generation Compton coincidence instrument to study the non-proportionality of scintillators. This device, known as SLYNCI (Scintillator Light-Yield Non-proportionality Characterization Instrument), has can completely characterize a sample with less than 24 hours of running time. Thus, SLYNCI enables a number of systematic studies of scintillators since many samples can be processed in a reasonable length of time. These studies include differences in nonproportionality between different types of scintillators, different members of the same family of scintillators, and impact of different doping levels. The results of such recent studies are presented here, including a study of various alkali halides, and the impact of europium doping level in strontium iodide. Directions of future work area also discussed.

  14. Ion Segregation and Deliquescence of Alkali Halide Nanocrystals on SiO2

    SciTech Connect

    Arima, Kenta; Jiang, Peng; Lin, Deng-Sung; Verdaguer, Albert; Salmeron, Miquel

    2009-08-11

    The adsorption of water on alkali halide (KBr, KCl, KF, NaCl) nanocrystals on SiO{sub 2} and their deliquescence was investigated as a function of relative humidity (RH) from 8% to near saturation by scanning polarization force microscopy. At low humidity, water adsorption solvates ions at the surface of the crystals and increases their mobility. This results in a large increase in the dielectric constant, which is manifested in an increase in the electrostatic force and in an increase in the apparent height of the nanocrystals. Above 58% RH, the diffusion of ions leads to Ostwald ripening, where larger nanocrystals grow at the expense of the smaller ones. At the deliquescence point, droplets were formed. For KBr, KCl, and NaCl, the droplets exhibit a negative surface potential relative to the surrounding region, which is indicative of the preferential segregation of anions to the air/solution interface.

  15. Density functional studies on hydrogen-bonded clusters of hydrogen halides and the interaction on halide anions

    NASA Astrophysics Data System (ADS)

    Nirmala, V.; Kolandaivel, P.

    Density functional theory (DFT) calculations have been performed to study the structures and stability of X-·(HX)n=2-5 clusters where X = F, Cl, Br at B3LYP/6-311++G** level of theory. The presence of halide ions in these clusters disintegrates the hydrogen halide clusters. All the hydrogen halides are then hydrogen bonded to the centrally placed halide ions, thereby forming multiple hydrogen bonds. The interaction energies have been corrected for the basis set superposition error (BSSE) using Boy's counterpoise correction method. Evidence for the destruction of hydrogen bonds in hydrogen halide clusters due to the presence of halide ions is further obtained from topological analysis and natural bond orbital analysis. The chemical hardness and chemical potential have been calculated for all the anion clusters. The above analysis reveals that hydrogen bonding in these systems is not an essentially electrostatic interaction. The nature of the stabilization interactions operative in these multiple hydrogen-bonded clusters has been explained in terms of many-body contribution to interaction energies. From these studies, an attempt has been made to understand the nature of the molecular properties resulting from different electronegativities of the halogens.

  16. Silicon halide-alkali metal flames as a source of solar grade silicon

    NASA Technical Reports Server (NTRS)

    Olsen, D. B.; Miller, W. J.

    1979-01-01

    The feasibility of using alkali metal-silicon halide diffusion flames to produce solar-grade silicon in large quantities and at low cost is demonstrated. Prior work shows that these flames are stable and that relatively high purity silicon can be produced using Na + SiCl4 flames. Silicon of similar purity is obtained from Na + SiF4 flames although yields are lower and product separation and collection are less thermochemically favored. Continuous separation of silicon from the byproduct alkali salt was demonstrated in a heated graphite reactor. The process was scaled up to reduce heat losses and to produce larger samples of silicon. Reagent delivery systems, scaled by a factor of 25, were built and operated at a production rate of 0.5 kg Si/h. Very rapid reactor heating rates are observed with wall temperatures reaching greater than 2000 K. Heat release parameters were measured using a cooled stainless steel reactor tube. A new reactor was designed.

  17. Chemistry of alkali cation exchanged faujasite and mesoporous NaX using alkyl halides and phosphates

    NASA Astrophysics Data System (ADS)

    Lee, Min-Hong

    The purpose of this work was to increase the reactivity of Faujasite X (NaX) zeolite toward the reactive decontamination of materials subject to nucleophilic attack by means of zeolite cation optimization and by means of the synthesis of mesoporous Faujasite X. Primary alkyl halides and trialkyl phosphates have been the test materials on which the cation-optimized and mesoporous zeolites have been tested. In the alkali cation optimization work, reactions of methyl iodide and 1-chloropropane with alkali metal cation exchanged Faujasite zeolite X were investigated at room temperature. The reactivity of the framework and the product formation were shown to depend on zeolite framework counter-cation. A quantitative study of zeolite product formation has been carried out, primarily using solid-state NMR spectroscopy. Large alkali cations showed preference toward substitution chemistry. In contrast, alkyl halide exposed LiX and NaX zeolites underwent both substitution and elimination. Subsequently introduced water molecules led to hydrolysis of framework species that was sensitive to framework counter-cation. The mesoporous NaX zeolites work undertakes to test whether an improvement in surface chemical reactivity can be achieved by introducing mesopores into the already reactive nucleophilic microporous NaX zeolite. Incorporation of the polydiallyl dimethyl ammonium chloride (PDADMAC) template and the formation of mesopores in Faujasite X zeolite (NaX) were successful and well-characterized. The mesopores are proposed to have occurred from incorporation of the cationic PDADMAC polymer into the zeolite by compensating zeolite framework charge. Subsequent sodium cation exchange of calcined mesoporous NaX was shown to restore the chemical reactivity characteristic of as-synthesized NaX. Trialkyl organophosphorous compounds underwent substitution reactions. The reactivity of both microporous and mesoporous Faujasite zeolite X and the product formation was shown to depend on

  18. Physics of solid and liquid alkali halide surfaces near the melting point

    NASA Astrophysics Data System (ADS)

    Zykova-Timan, T.; Ceresoli, D.; Tartaglino, U.; Tosatti, E.

    2005-10-01

    This paper presents a broad theoretical and simulation study of the high-temperature behavior of crystalline alkali halide surfaces typified by NaCl(100), of the liquid NaCl surface near freezing, and of the very unusual partial wetting of the solid surface by the melt. Simulations are conducted using two-body rigid-ion Born-Mayer-Huggins-Fumi-Tosi (BMHFT) potentials, with full treatment of long-range Coulomb forces. After a preliminary check of the description of bulk NaCl provided by these potentials, which seems generally good even at the melting point, we carry out a new investigation of solid and liquid surfaces. Solid NaCl(100) is found in this model to be very anharmonic and yet exceptionally stable when hot. It is predicted by a thermodynamic integration calculation of the surface free energy that NaCl(100) should be a well-ordered, nonmelting surface, metastable even well above the melting point. By contrast, the simulated liquid NaCl surface is found to exhibit large thermal fluctuations and no layering order. In spite of that, it is shown to possess a relatively large surface free energy. The latter is traced to a surface entropy deficit, reflecting some kind of surface short-range order. We show that the surface short-range order is most likely caused by the continuous transition of the bulk ionic melt into the vapor, made of NaCl molecules and dimers rather than of single ions. Finally, the solid-liquid interface free energy is derived through Young's equation from direct simulation of partial wetting of NaCl(100) by a liquid droplet. The resulting interface free energy is large, in line with the conspicuous solid-liquid 27% density difference. A partial wetting angle near 50° close to the experimental value of 48° is obtained in the process. It is concluded that three elements, namely, the exceptional anharmonic stability of the solid (100) surface, the molecular short-range order at the liquid surface, and the costly solid-liquid interface, all

  19. Silicon halide-alkali metal flames as a source of solar grade silicon

    NASA Technical Reports Server (NTRS)

    Olson, D. B.; Miller, W. J.; Gould, R. K.

    1980-01-01

    The feasibility of using continuous high-temperature reactions of alkali metals and silicon halides to produce silicon in large quantities and of suitable purity for use in the production of photovoltaic solar cells was demonstrated. Low pressure experiments were performed demonstrating the production of free silicon and providing experience with the construction of reactant vapor generators. Further experiments at higher reagent flow rates were performed in a low temperature flow tube configuration with co-axial injection of reagents and relatively pure silicon was produced. A high temperature graphite flow tube was built and continuous separation of Si from NaCl was demonstrated. A larger scaled well stirred reactor was built. Experiments were performed to investigate the compatability of graphite based reactor materials of construction with sodium. At 1100 to 1200 K none of these materials were found to be suitable. At 1700 K the graphites performed well with little damage except to coatings of pyrolytic graphite and silicon carbide which were damaged.

  20. Physics of solid and liquid alkali halide surfaces near the melting point

    NASA Astrophysics Data System (ADS)

    Zykova-Timan, Tatyana; Ceresoli, Davide; Tartaglino, Ugo; Tosatti, Erio

    2006-03-01

    NaCl (and other alkali halide) crystal surfaces have the peculiar property of repelling their own melt. As a result they let themselves be wetted only partially by their own liquid at the melting point TM. We recently investigated the physical reasons for this unusual behavior. We found them through theory and molecular dynamics simulation to stem from the conspiracy of three factors. First, the solid NaCl(100) surface is exceptionally anharmonic,but also exceptionally stable. It can in fact survive even well above the melting point, for unlike most other surfaces it does not spontaneously melt. Second, the solid-liquid interface is very costly, due to a 27% density difference between solid and liquid. Third, the surface tension of liquid NaCl is relatively high. This last feature is due to an unexpected entropy deficit, that can in turn be traced to incipient molecular charge order in the outermost regions of the molten salt surface[1,2].[1] T. Zykova-Timan, D. Ceresoli, U. Tartaglino, E. Tosatti, Phys. Rev. Lett. 94, 176105 (2005) [2] T. Zykova-Timan, D. Ceresoli, U. Tartaglino, E. Tosatti, J. Chem. Phys. 123, 164701 (2005)

  1. Dynamics of nuclear wave packets at the F center in alkali halides

    NASA Astrophysics Data System (ADS)

    Koyama, Takeshi; Suemoto, Tohru

    2011-07-01

    The F center in alkali halides is a well-known prototype of a strongly coupled localized electron-phonon system. This colour center is one of the long studied targets in the field of photophysics because it is simple but rich in variety. Steady-state spectroscopy, such as modulation spectroscopy and Raman scattering spectroscopy, has elucidated the strength of the electron-phonon coupling in the (meta-)stable state, i.e. the ground state and the relaxed excited state. Picosecond spectroscopy has improved understanding of the state mixing in the transient state. Owing to recent developments of ultrafast lasers with pulse widths shorter than oscillation periods of phonons, it has been possible to perform real-time observation of lattice vibration, and the understanding of the transient state has been remarkably expanded. In this paper, we review early and present studies on dynamics of electron-phonon coupling at the F center, especially recent real-time observations on the dynamics of nuclear wave packets in the excited state of the F center in KI, KBr, KCl and RbCl. These real-time observations reveal (i) spatial extension of the electronic wave function of a trapped electron, (ii) the difference between the coupled phonons in the ground state and the excited state, (iii) diabatic transition between the adiabatic potential energy surfaces and (iv) anharmonicity of the potential energy surface.

  2. Surface Spectroscopy Studies of the Reactive Uptake of Ozone on Alkali Halides

    NASA Astrophysics Data System (ADS)

    Newberg, J. T.; Hemminger, J. C.

    2003-12-01

    Heterogeneous reactions in the atmosphere have attracted a lot of attention. In particular, reactions involving sea-salt in the form of aerosol droplets, particles, and/or sea-ice have been implicated to significantly affect the chemistry and composition of the marine boundary layer. For example, highly reactive chlorine and bromine atoms resulting from the oxidation of sea-salt halides (Cl- and Br-) have been implicated in tropospheric ozone depletion in the arctic and in lower latitude marine regions, as well as the deposition of mercury. While the heterogeneous processing of sea-salt has been studied extensively in laboratory, field and model studies, the mechanistic details behind the release of gas-phase halogens remains unclear and has sparked some interests. Recently there has been attention focused on the interaction of important atmospheric oxidants (e.g., OH and O3) with halides that reside at the air-particle interface of sea-salt. Such chemical interactions at the surface of particles may lead to unique chemical transformations that can alter current views of known chemical processing of sea-salt particles. There are several laboratory investigations which have investigated the surface reactivity of salts by measuring the reactive loss and/or formation of gas-phase species, indicating that reactions at the interface likely play an important role in aerosol chemistry. The efficacy of such surface-phase chemistry has yet to be elucidated with surface spectroscopy studies. X-ray photoelectron spectroscopy (XPS) is a surface spectroscopy technique with submonolayer resolution. Using XPS, we have investigated changes in the surface chemistry of various alkali halide salts upon exposure to ozone in an ultra-high vacuum (UHV) instrument. Salt samples were either freshly cleaved single crystals which were prepared from a melt, or purified salt crystals/powders pressed into pellets. Upon exposure to ozone, oxygen on the salt surfaces was monitored by measuring

  3. Optical properties of alkali halide crystals from all-electron hybrid TD-DFT calculations

    SciTech Connect

    Webster, R. Harrison, N. M.; Bernasconi, L.

    2015-06-07

    We present a study of the electronic and optical properties of a series of alkali halide crystals AX, with A = Li, Na, K, Rb and X = F, Cl, Br based on a recent implementation of hybrid-exchange time-dependent density functional theory (TD-DFT) (TD-B3LYP) in the all-electron Gaussian basis set code CRYSTAL. We examine, in particular, the impact of basis set size and quality on the prediction of the optical gap and exciton binding energy. The formation of bound excitons by photoexcitation is observed in all the studied systems and this is shown to be correlated to specific features of the Hartree-Fock exchange component of the TD-DFT response kernel. All computed optical gaps and exciton binding energies are however markedly below estimated experimental and, where available, 2-particle Green’s function (GW-Bethe-Salpeter equation, GW-BSE) values. We attribute this reduced exciton binding to the incorrect asymptotics of the B3LYP exchange correlation ground state functional and of the TD-B3LYP response kernel, which lead to a large underestimation of the Coulomb interaction between the excited electron and hole wavefunctions. Considering LiF as an example, we correlate the asymptotic behaviour of the TD-B3LYP kernel to the fraction of Fock exchange admixed in the ground state functional c{sub HF} and show that there exists one value of c{sub HF} (∼0.32) that reproduces at least semi-quantitatively the optical gap of this material.

  4. Simple electrolyte solutions: Comparison of DRISM and molecular dynamics results for alkali halide solutions

    PubMed Central

    Joung, In Suk; Luchko, Tyler; Case, David A.

    2013-01-01

    Using the dielectrically consistent reference interaction site model (DRISM) of molecular solvation, we have calculated structural and thermodynamic information of alkali-halide salts in aqueous solution, as a function of salt concentration. The impact of varying the closure relation used with DRISM is investigated using the partial series expansion of order-n (PSE-n) family of closures, which includes the commonly used hypernetted-chain equation (HNC) and Kovalenko-Hirata closures. Results are compared to explicit molecular dynamics (MD) simulations, using the same force fields, and to experiment. The mean activity coefficients of ions predicted by DRISM agree well with experimental values at concentrations below 0.5 m, especially when using the HNC closure. As individual ion activities (and the corresponding solvation free energies) are not known from experiment, only DRISM and MD results are directly compared and found to have reasonably good agreement. The activity of water directly estimated from DRISM is nearly consistent with values derived from the DRISM ion activities and the Gibbs-Duhem equation, but the changes in the computed pressure as a function of salt concentration dominate these comparisons. Good agreement with experiment is obtained if these pressure changes are ignored. Radial distribution functions of NaCl solution at three concentrations were compared between DRISM and MD simulations. DRISM shows comparable water distribution around the cation, but water structures around the anion deviate from the MD results; this may also be related to the high pressure of the system. Despite some problems, DRISM-PSE-n is an effective tool for investigating thermodynamic properties of simple electrolytes. PMID:23387564

  5. a Study of Two Electron Defect Systems in Alkali Halide Crystals

    NASA Astrophysics Data System (ADS)

    Zhang, Chang Gang

    1993-01-01

    The structures of two electron defect systems in alkali halide crystals are studied. The systems which have been studied include: two electrons localized at an anion vacancy (F^'-centre); positronium self-trapped at an anion vacancy (Fe ^+-centre); positron self-trapped at a cation vacancy (F_{rm anti} -centre); positronium self-trapped at an interstice; and positronium in a Bloch state. An improved version of the extended-ion method which is based on the one electron Hartree-Fock approximation is used to perform these calculations. Its main feature is the exclusive use of floating 1s Gaussian functions as basis. For the multi-electron defect systems, the calculation of matrix elements of two electron interaction terms is a most difficult problem. We developed an effective approach to treat this interaction approximately. The correlation effect of defect electrons is partly accounted for by properly arranged Gaussian basis. The binding energy, thermal dissociation energy, and transition energy between ground state and excited state are calculated for F ^'-centres. A defect model with negative-U properties was introduced to interpret the deeply bound F^'-centre. Calculations of positron binding energies are made for Fe^+ -centres and F_{rm anti }-centres. In addition, we evaluate the angular correlation and lifetime of an annihilated electron-positron pair for Fe^+-centres, localized positronium and Bloch state positronium. The observed phenomena such as the transition of positronium from Bloch state to localized state, and the crystallographic effect are examined theoretically. The calculated results regarding various properties of crystals are in reasonably good agreement with experiment.

  6. Liquid madelung energy and schottky defect energy related to liquid structure and melting temperature for alkali halides

    SciTech Connect

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

    1985-01-01

    Motivated by the work of Reiss et al. in which the melting temperature T /SUB m/ of alkali halides is correlated with Coulomb energy, we consider the cohesive energy W of ionic melts and Schottky defect energy E /SUB s/ in the hot crystal, relative to the thermal energy k /SUB B/ T /SUB m/ . It is shown here that is accurately approximated by the liquid Madelung energy and hence that W/k /SUB B/ T /SUB m/ relates to the charge-charg direct correlation function c /SUB QQ/ (r) at r = 0. The existence of a ''Madelung constant'' for the liquid at T /SUB m/ is thereby demonstrated through the alkali halide series. An estimate of the ratio E /SUB s/ /k /SUB B/ T /SUB m/ i then considered; the basic additional ingredient being argued to be the static dielectric constant of the solid. Th BarrDawson-Lidiard empirical correlation between E /SUB s/ and k /SUB B/ T /SUB m/ can be understood in this way.

  7. Universal scaling of potential energy functions describing intermolecular interactions. II. The halide-water and alkali metal-water interactions

    SciTech Connect

    Werhahn, Jasper C.; Akase, Dai; Xantheas, Sotiris S.

    2014-08-14

    The scaled versions of the newly introduced [S. S. Xantheas and J. C. Werhahn, J. Chem. Phys.141, 064117 (2014)] generalized forms of some popular potential energy functions (PEFs) describing intermolecular interactions – Mie, Lennard-Jones, Morse, and Buckingham exponential-6 – have been used to fit the ab initio relaxed approach paths and fixed approach paths for the halide-water, X-(H2O), X = F, Cl, Br, I, and alkali metal-water, M+(H2O), M = Li, Na, K, Rb, Cs, interactions. The generalized forms of those PEFs have an additional parameter with respect to the original forms and produce fits to the ab initio data that are between one and two orders of magnitude better in the χ2 than the original PEFs. They were found to describe both the long-range, minimum and repulsive wall of the respective potential energy surfaces quite accurately. Overall the 4-parameter extended Morse (eM) and generalized Buckingham exponential-6 (gBe-6) potentials were found to best fit the ab initio data for these two classes of ion-water interactions. Finally, the fitted values of the parameter of the (eM) and (gBe-6) PEFs that control the repulsive wall of the potential correlate remarkably well with the ionic radii of the halide and alkali metal ions.

  8. Low-Energy Grazing Ion-Scattering from Alkali-Halide Surfaces: A Novel Approach to C-14 Detection

    SciTech Connect

    Meyer, Fred W; Galutschek, Ernst; Hotchkis, Michael

    2009-01-01

    Carbon-14 labeled compounds are widely used in the pharmaceutical industry, e.g., as tracers to determine the fate of these compounds in vivo. Conventional accelerator mass spectrometry (AMS) is one approach that offers sufficiently high sensitivity to avoid radiological waste and contamination issues in such studies, but requires large, expensive facilities that are usually not solely dedicated to this task. At the ORNL Multicharged Ion Research Facility (MIRF) we are exploring a small size, low cost alternative to AMS for biomedical 14C tracer studies that utilizes ECR-ion-source-generated keV-energy-range multicharged C beams grazingly incident on an alkali halide target, where efficient negative ion production by multiple electron capture takes place. By using C ion charge states of +3 or higher, the molecular isobar interference at mass 14, e.g. 12CH2 and 13CH, is eliminated. The negatively charged ions in the beam scattered from the alkali halide surface are separated from other scattered charge states by two large acceptance ({approx}15 msr) stages of electrostatic analysis. The N-14 isobar interference is thus removed, since N does not support a stable negative ion. Initial results for C-14 detection obtained using C-14 enriched CO2 from ANSTO will be described.

  9. Integrating 2-D position sensitive X-ray detectors with low-density alkali halide storage targets

    NASA Astrophysics Data System (ADS)

    Haubold, H.-G.; Hoheisel, W.; Hiller, P.

    1986-05-01

    For the use in scattering experiments with synchrotron radiation, integrating position sensitive X-ray detectors are discussed. These detectors store the photon number equivalent charge (PNEC) in low-density alkali halide targets. Performance tests are given for a detector which uses a Gd 2O 2S fluorescence screen for X-ray detection and the low-density KCl storage target of a television SEC vidicon tube for photon integration. Rather than directly by X-rays, this target is charged by 6 keV electrons from the image intensifier section of the vidicon. Its excellent storage capability allows measurements of extremely high-contrast, high-flux X-ray patterns with the same accuracy as achieved with any single photon detection system if the discussed readout techniques are applied.

  10. Development of processes for the production of solar grade silicon from halides and alkali metals, phase 1 and phase 2

    NASA Technical Reports Server (NTRS)

    Dickson, C. R.; Gould, R. K.; Felder, W.

    1981-01-01

    High temperature reactions of silicon halides with alkali metals for the production of solar grade silicon are described. Product separation and collection processes were evaluated, measure heat release parameters for scaling purposes and effects of reactants and/or products on materials of reactor construction were determined, and preliminary engineering and economic analysis of a scaled up process were made. The feasibility of the basic process to make and collect silicon was demonstrated. The jet impaction/separation process was demonstrated to be a purification process. The rate at which gas phase species from silicon particle precursors, the time required for silane decomposition to produce particles, and the competing rate of growth of silicon seed particles injected into a decomposing silane environment were determined. The extent of silane decomposition as a function of residence time, temperature, and pressure was measured by infrared absorption spectroscopy. A simplistic model is presented to explain the growth of silicon in a decomposing silane enviroment.

  11. Self-assembly of Alkali-uranyl-peroxide Clusters

    SciTech Connect

    Nyman, May; Rodriquez, Mark A.; Campana, Charles F.

    2010-08-11

    The hexavalent uranium specie, uranyl triperoxide, UO2(O2)34-, has been shown recently to behave like high oxidation-state d0 transition-metals, self-assembling into polyoxometalate-like clusters that contain up to 60 uranyl cations bridged by peroxide ligands. There has been much less focus on synthesis and structural characterization of salts of the monomeric UO2(O2)34- building block of these clusters. However, these could serve as water-soluble uranyl precursors for both clusters and materials, and also be used as simple models to study aqueous behavior by experiment and modeling. The countercation is of utmost importance to the assembly of these clusters, and Li+ has proven useful for the crystallization of many of the known cluster geometries to date. We present in this paper synthesis and structural characterization of two monomeric lithium uranyl-peroxide salts, Li4[UO2(O2)3]·10H2O (1) and [UO2(O2)3]12[(UO2(OH)4)Li16(H2O)28]3·Li6[H2O]26 (2). They were obtained from aqueous-alcohol solutions rather than the analogous aqueous solutions from which lithium uranyl-peroxide clusters are crystallized. Rapid introduction of the alcohol gives the structure of (1) whereas slow diffusion of alcohol results in crystallization of (2). (2) is an unusual structure featuring uranyl-centered alkali clusters that are linked into ring and spherical arrangements via [UO2(O2)3] anions. Furthermore, partial substitution of Rb or Cs into the synthesis results in formation of (2) with substitution of these larger alkalis into the uranyl-centered clusters. We surmise that the slow crystallization allows for direct bonding of alkali metals to the

  12. Solubility of alkali metal halides in the ionic liquid [C4C1im][OTf].

    PubMed

    Kuzmina, O; Bordes, E; Schmauck, J; Hunt, P A; Hallett, J P; Welton, T

    2016-06-28

    The solubilities of the metal halides LiF, LiCl, LiBr, LiI, NaF, NaCl, NaBr, NaI, KF, KCl, KBr, KI, RbCl, CsCl, CsI, were measured at temperatures ranging from 298.15 to 378.15 K in the ionic liquid 1-butyl-3-methylimidazolium trifluoromethanesulfonate ([C4C1im][OTf]). Li(+), Na(+) and K(+) salts with anions matching the ionic liquid have also been investigated to determine how well these cations dissolve in [C4C1im][OTf]. This study compares the influence of metal cation and halide anion on the solubility of salts within this ionic liquid. The highest solubility found was for iodide salts, and the lowest solubility for the three fluoride salts. There is no outstanding difference in the solubility of salts with matching anions in comparison to halide salts. The experimental data were correlated employing several phase equilibria models, including ideal mixtures, van't Hoff, the λh (Buchowski) equation, the modified Apelblat equation, and the non-random two-liquid model (NRTL). It was found that the van't Hoff model gave the best correlation results. On the basis of the experimental data the thermodynamic dissolution parameters (ΔH, ΔS, and ΔG) were determined for the studied systems together with computed gas phase metathesis parameters. Dissolution depends on the energy difference between enthalpies of fusion and dissolution of the solute salt. This demonstrates that overcoming the lattice energy of the solid matrix is the key to the solubility of inorganic salts in ionic liquids. PMID:27264676

  13. Low-frequency modes of aqueous alkali halide solutions: an ultrafast optical Kerr effect study.

    PubMed

    Heisler, Ismael A; Mazur, Kamila; Meech, Stephen R

    2011-03-01

    A detailed picture of aqueous solvation of ions is central to the understanding of diverse phenomena in chemistry and biology. In this work, we report polarization resolved THz time domain measurements of the Raman spectral density of a wide range of aqueous salt solutions. In particular, the isotropic Raman spectral density reveals the frequency of the hydrogen bond formed between the halide ion and water. The frequency of this mode is measured for the series Cl(-), Br(-), and I(-) as a function of concentration, cation size, and charge. The frequencies extrapolated to zero concentration permit an estimation of the force constant of the mode, which is found to decrease with increasing halide mass and to be similar to the force constant associated with the water-water hydrogen bond. This result is consistent with recent calculations. The extrapolation of the frequency of the chloride hydrogen bond to zero concentration reveals a dependence of the frequency on the nature of the cation. This is ascribed to an interaction between the solvated anion and cation even at the lowest concentration studied here (<0.15 M). It is suggested that this behavior reflects the influence of the electric field of the cation on the hydrogen bond of an adjacent anion. Such interactions should be taken into account when modeling experimental data recorded at concentrations of ions in excess of 0.1 M. These measurements of the isotropic Raman spectral density are compared with those for the anisotropic response, which reflects the frequencies of the full range of hydrogen bonds in aqueous salt solutions. The anisotropic spectral density recovered can be modeled in terms of a concentration-dependent population of water-water H-bonds with a frequency unaffected by the ions, the halide-water hydrogen bonds, and a low-frequency collision-induced contribution. PMID:21291185

  14. EPR study of electron bombarded alkali- and alkaline-earth halide crystal surfaces

    NASA Technical Reports Server (NTRS)

    Fryburg, G. C.; Lad, R. A.

    1975-01-01

    An EPR study of electron bombarded LiF, NaCl, KCl, CaF2 and BaF2 polycrystalline surfaces has shown that small metal particles are formed on the surfaces of the crystals. Identification was made from CESR signals. The symmetric line-shape of the signals, even at 77 K, indicated that the particles were less than 0.5 micron in diameter. Signals due to F centers were observed in LiF but not in the other halides. Implications to metal deposition are considered.

  15. Lattice model calculation of elastic and thermodynamic properties at high pressure and temperature. [for alkali halides in NaCl lattice

    NASA Technical Reports Server (NTRS)

    Demarest, H. H., Jr.

    1972-01-01

    The elastic constants and the entire frequency spectrum were calculated up to high pressure for the alkali halides in the NaCl lattice, based on an assumed functional form of the inter-atomic potential. The quasiharmonic approximation is used to calculate the vibrational contribution to the pressure and the elastic constants at arbitrary temperature. By explicitly accounting for the effect of thermal and zero point motion, the adjustable parameters in the potential are determined to a high degree of accuracy from the elastic constants and their pressure derivatives measured at zero pressure. The calculated Gruneisen parameter, the elastic constants and their pressure derivatives are in good agreement with experimental results up to about 600 K. The model predicts that for some alkali halides the Grunesen parameter may decrease monotonically with pressure, while for others it may increase with pressure, after an initial decrease.

  16. Ca-Fe and Alkali-Halide Alteration of an Allende Type B CAI: Aqueous Alteration in Nebular or Asteroidal Settings

    NASA Technical Reports Server (NTRS)

    Ross, D. K.; Simon, J. I.; Simon, S. B.; Grossman, L.

    2012-01-01

    Ca-Fe and alkali-halide alteration of CAIs is often attributed to aqueous alteration by fluids circulating on asteroidal parent bodies after the various chondritic components have been assembled, although debate continues about the roles of asteroidal vs. nebular modification processes [1-7]. Here we report de-tailed observations of alteration products in a large Type B2 CAI, TS4 from Allende, one of the oxidized subgroup of CV3s, and propose a speculative model for aqueous alteration of CAIs in a nebular setting. Ca-Fe alteration in this CAI consists predominantly of end-member hedenbergite, end-member andradite, and compositionally variable, magnesian high-Ca pyroxene. These phases are strongly concentrated in an unusual "nodule" enclosed within the interior of the CAI (Fig. 1). The Ca, Fe-rich nodule superficially resembles a clast that pre-dated and was engulfed by the CAI, but closer inspection shows that relic spinel grains are enclosed in the nodule, and corroded CAI primary phases interfinger with the Fe-rich phases at the nodule s margins. This CAI also contains abundant sodalite and nepheline (alkali-halide) alteration that occurs around the rims of the CAI, but also penetrates more deeply into the CAI. The two types of alteration (Ca-Fe and alkali-halide) are adjacent, and very fine-grained Fe-rich phases are associated with sodalite-rich regions. Both types of alteration appear to be replacive; if that is true, it would require substantial introduction of Fe, and transport of elements (Ti, Al and Mg) out of the nodule, and introduction of Na and Cl into alkali-halide rich zones. Parts of the CAI have been extensively metasomatized.

  17. Interaction of wide band gap single crystals with 248 nm excimer laser radiation. XII. The emission of negative atomic ions from alkali halides

    SciTech Connect

    Kimura, Kenichi; Langford, S. C.; Dickinson, J. T.

    2007-12-01

    Many wide band gap materials yield charged and neutral emissions when exposed to sub-band-gap laser radiation at power densities below the threshold for optical breakdown and plume formation. In this work, we report the observation of negative alkali ions from several alkali halides under comparable conditions. We observe no evidence for negative halogen ions, in spite of the high electron affinities of the halogens. Significantly, the positive and negative alkali ions show a high degree of spatial and temporal overlap. A detailed study of all the relevant particle emissions from potassium chloride (KCl) suggests that K{sup -} is formed by the sequential attachment of two electrons to K{sup +}.

  18. Shallow electron traps in alkali halide crystals: Mollwo-Ivey relations of the optical absorption bands

    NASA Astrophysics Data System (ADS)

    Ziraps, Valters

    2001-03-01

    Evidences are given that two classes of the transient IR- absorption bands: (a) with max. at 0.27-0.36 eV in NaCl, KCl, KBr, KI and RbCl (due to shallow electron traps according G. Jacobs or due to bound polarons according E.V. Korovkin and T.A. Lebedkina) and (b) with max. at 0.15-0.36 eV in NaI, NaBr, NaCl:I, KCl:I, RbCl:I and RbBr:I (due to on-center STE localized at iodine dimer according M. Hirai and collaborators) are caused by the same defect- atomic alkali impurity center [M+]c0e- (electron e- trapped by a substitutional smaller size alkali cation impurity [M+]c0). The Mollwo-Ivey plots (for the transient IR-absorption bands) of the zero-phonon line energy E0 (for NaCl, KCl, KBr, RbCl and NaBr, KCl:I) and/or the low-energy edge valued E0 (for NaI, RbCl:I, RbBr:I) versus anion-cation distance (d) evidence that two types of the [M+]c0e- centers are predominant: (a) [Na+]c0e- in the KX and RbX host crystals with the relation E0approximately equals 6.15/d2.74, (b) [Li+]c03- in the NaX host crystals - E0approximately equals 29.4/d4.72. The Mollwo-Ivey relation E0approximately equals 18.36/d(superscript 2.70 is fulfilled as well for the F' band in NaCl, KCl, KBr, KI, RbCl, RbI if we use the F' center optical binding energy values E0.

  19. Temperature-dependent solubilities and mean ionic activity coefficients of alkali halides in water from molecular dynamics simulations.

    PubMed

    Mester, Zoltan; Panagiotopoulos, Athanassios Z

    2015-07-28

    The mean ionic activity coefficients of aqueous KCl, NaF, NaI, and NaCl solutions of varying concentrations have been obtained from molecular dynamics simulations following a recently developed methodology based on gradual insertions of salt molecules [Z. Mester and A. Z. Panagiotopoulos, J. Chem. Phys. 142, 044507 (2015)]. The non-polarizable ion models of Weerasinghe and Smith [J. Chem. Phys. 119, 11342 (2003)], Gee et al. [J. Chem. Theory Comput. 7, 1369 (2011)], Reiser et al. [J. Chem. Phys. 140, 044504 (2014)], and Joung and Cheatham [J. Phys. Chem. B 112, 9020 (2008)] were used along with the extended simple point charge (SPC/E) water model [Berendsen et al., J. Phys. Chem. 91, 6269 (1987)] in the simulations. In addition to the chemical potentials in solution used to obtain the activity coefficients, we also calculated the chemical potentials of salt crystals and used them to obtain the solubility of these alkali halide models in SPC/E water. The models of Weerasinghe and Smith [J. Chem. Phys. 119, 11342 (2003)] and Gee et al. [J. Chem. Theory Comput. 7, 1369 (2011)] provide excellent predictions of the mean ionic activity coefficients at 298.15 K and 1 bar, but significantly underpredict or overpredict the solubilities. The other two models generally predicted the mean ionic activity coefficients only qualitatively. With the exception of NaF for which the solubility is significantly overpredicted, the model of Joung and Cheatham predicts salt solubilities that are approximately 40%-60% of the experimental values. The models of Reiser et al. [J. Chem. Phys. 140, 044504 (2014)] make good predictions for the NaCl and NaI solubilities, but significantly underpredict the solubilities for KCl and NaF. We also tested the transferability of the models to temperatures much higher than were used to parametrize them by performing simulations for NaCl at 373.15 K and 1 bar, and at 473.15 K and 15.5 bar. All models overpredict the drop in the values of mean ionic

  20. Temperature-dependent solubilities and mean ionic activity coefficients of alkali halides in water from molecular dynamics simulations

    NASA Astrophysics Data System (ADS)

    Mester, Zoltan; Panagiotopoulos, Athanassios Z.

    2015-07-01

    The mean ionic activity coefficients of aqueous KCl, NaF, NaI, and NaCl solutions of varying concentrations have been obtained from molecular dynamics simulations following a recently developed methodology based on gradual insertions of salt molecules [Z. Mester and A. Z. Panagiotopoulos, J. Chem. Phys. 142, 044507 (2015)]. The non-polarizable ion models of Weerasinghe and Smith [J. Chem. Phys. 119, 11342 (2003)], Gee et al. [J. Chem. Theory Comput. 7, 1369 (2011)], Reiser et al. [J. Chem. Phys. 140, 044504 (2014)], and Joung and Cheatham [J. Phys. Chem. B 112, 9020 (2008)] were used along with the extended simple point charge (SPC/E) water model [Berendsen et al., J. Phys. Chem. 91, 6269 (1987)] in the simulations. In addition to the chemical potentials in solution used to obtain the activity coefficients, we also calculated the chemical potentials of salt crystals and used them to obtain the solubility of these alkali halide models in SPC/E water. The models of Weerasinghe and Smith [J. Chem. Phys. 119, 11342 (2003)] and Gee et al. [J. Chem. Theory Comput. 7, 1369 (2011)] provide excellent predictions of the mean ionic activity coefficients at 298.15 K and 1 bar, but significantly underpredict or overpredict the solubilities. The other two models generally predicted the mean ionic activity coefficients only qualitatively. With the exception of NaF for which the solubility is significantly overpredicted, the model of Joung and Cheatham predicts salt solubilities that are approximately 40%-60% of the experimental values. The models of Reiser et al. [J. Chem. Phys. 140, 044504 (2014)] make good predictions for the NaCl and NaI solubilities, but significantly underpredict the solubilities for KCl and NaF. We also tested the transferability of the models to temperatures much higher than were used to parametrize them by performing simulations for NaCl at 373.15 K and 1 bar, and at 473.15 K and 15.5 bar. All models overpredict the drop in the values of mean ionic

  1. Assignment of photoelectron spectra of halide-water clusters: Contrasting patterns of delocalization in Dyson orbitals

    NASA Astrophysics Data System (ADS)

    Dolgounitcheva, O.; Zakrzewski, V. G.; Ortiz, J. V.

    2013-04-01

    Ab initio electron propagator calculations in various self-energy approximations provide accurate assignments of peaks observed in the photoelectron spectra of complexes that comprise a fluoride or chloride anion and two or three water molecules. More than one minimum structure is found in all four cases. When the halide anion is Cl-, the first three final states may be described as quasi-degenerate 2P chlorine atoms coordinated to water molecules. Higher final states consist of a chloride anion juxtaposed to a positive charge that is delocalized over the water molecules. For the clusters with fluoride anions, most of the final states correspond to Dyson orbitals that are delocalized over the F and O nuclei. A variety of F-O σ and π bonding and antibonding patterns are evident in the Dyson orbitals. The assignment of low-lying spectral peaks to halide p orbital vacancies or to delocalized solvent orbitals is more valid for the chloride clusters than for the fluoride clusters, where a delocalized picture arises from strong bonding interactions between F 2p and H2O 1b1 orbitals.

  2. Interionic Force Model for Pentahalide Molecules and Higher Niobium-Based Halide Clusters

    NASA Astrophysics Data System (ADS)

    Önem, Z. Çiçek; Akdeniz, Z.; Tosi, M. P.

    2002-12-01

    Molecular bound states tend to become progressively more stable in the melts of polyvalent metal halides as the nominal valence of the metal increases. We examine in this work the case of pentavalent metal halides. First we propose a simple ionic model for the binding in several pentahalide clusters: the chlorides of Nb, Ta, Sb, and Mo and the bromides of Nb and Ta. The molecular monomers of these compounds have a D3h trigonal-bipyramidal structure in the ground state, and we make use of data on equatorial bond lengths and breathing mode frequencies in the vapour to determine the main force-law parameters of the metal ion. We also find that the C4v square-pyramidal structure is mechanically unstable against transformation into the D3h shape.We then consider higher molecular clusters, i. e. the dimers of Nb pentahalides and the bound states formed by NbCl5 with the chlorides of Cs, Al, Ga, and Sb. We propose structural models for all these stable clusters and compare their calculated vibrational frequencies with the available data from vibrational spectroscopy of mixed melts.

  3. Study on influence of growth conditions on position and shape of crystal/melt interface of alkali lead halide crystals at Bridgman growth

    NASA Astrophysics Data System (ADS)

    Král, Robert

    2012-12-01

    Suitable conditions for growth of high quality single crystals of ternary alkali lead halides prepared by a Bridgman method were explored using direct observation of a crystal/melt interface when pulling an ampoule out of a furnace, deliberated striations' induction and measurement of a temperature field in the filled ampoule in the vertical Bridgman arrangement, as model compounds lead chloride and ternary rubidium lead bromide were used. By direct observation only position of the crystal/melt interface was markedly determined, while by induced striations both the position and the shape of the interface were visualized but their contrast had to be intensified by adding admixtures. Performed temperature measurements in the filled ampoule brought both a view of temperature field in the 3D radial symmetry and basic data for comparison of a real temperature field with those obtained by projected modeling.

  4. Chloroaluminate ionic liquids as reagents for isolating soluble hexanuclear zirconium halide cluster compounds.

    PubMed

    Sun, D; Hughbanks, T

    2000-05-01

    Ambient-temperature chloroaluminate molten salts, mixtures of aluminum trichloride (AlCl3) and 1-ethyl-3-methylimidazolium chloride (ImCl), have been used as solvents to excise and isolate centered hexanuclear zirconium halide clusters from their solid-state precursors. Cluster compounds synthesized via high-temperature reactions, KZr6CCl15 and Li2Zr6MnCl15, were dissolved into basic molten salts at 100-110 degrees C. The C-centered cluster compound, Im4Zr6CCl18, was isolated in 70% yield, and the Mn-centered cluster compound, Im5Zr6MnCl18.C7H(8).2CH3CN, was isolated in 54% yield. Im5Zr6BCl18 is efficiently oxidized by ferrocenium tetrafluoroborate, and one-electron-oxidized B-centered cluster, [(Zr6B)Cl18]4-, was isolated in 90% yield as the salt Im4Zr6BCl18. PMID:11428116

  5. Theoretical estimation of solvation parameters and interfacial tension of clusters of potassium halides in aqueous solutions

    NASA Astrophysics Data System (ADS)

    Polak, W.; Sangwal, K.

    1996-03-01

    Using the model of the formation of ionic clusters, an analytical equation valid for the equilibrium concentration of solute in the solution is derived. Employing Boltzmann statistics in conjunction with the experimental values of the equilibrium concentration of KF, KCl, KBr and KI electrolytes in aqueous solution at 25°C, the above analytical equation is used to compute the best values of the dielectric permittivity of the solvation shell for the K + ion and four anions separately. These values of the dielectric permittivity of the solvation shells are then used to compute adsorption energy of water molecules on the {100} surface of regular clusters and their surface tension in the solution as functions of type of the salt, its concentration and cluster size. It is found that both the average adsorption energy and the interfacial tension of regular clusters composed of i ions can be approximated by a linear function of i - {1}/{2} for different concentrations of all the investigated potassium halides, and that, depending on the concentration of the solutions, the surface tension of regular clusters in solutions can increase or decrease with their size.

  6. Structure and photoabsorption properties of cationic alkali dimers solvated in neon clusters.

    PubMed

    Zanuttini, D; Douady, J; Jacquet, E; Giglio, E; Gervais, B

    2010-11-01

    We present a theoretical investigation of the structure and optical absorption of M(2)(+) alkali dimers (M=Li,Na,K) solvated in Ne(n) clusters for n=1 to a few tens Ne atoms. For all these alkali, the lowest-energy isomers are obtained by aggregation of the first Ne atoms at the extremity of the alkali molecule. This particular geometry, common to other M(2)(+)-rare gas clusters, is intimately related to the shape of the electronic density of the X  (2)Σ(g)(+) ground state of the bare M(2)(+) molecules. The structure of the first solvation shell presents equilateral Ne(3) and capped pentagonal Ne(6) motifs, which are characteristic of pure rare gas clusters. The size and geometry of the complete solvation shell depend on the alkali and were obtained at n=22 with a D(4h) symmetry for Li and at n=27 with a D(5h) symmetry for Na. For K, our study suggests that the closure of the first solvation shell occurs well beyond n=36. We show that the atomic arrangement of these clusters has a profound influence on their optical absorption spectrum. In particular, the XΣ transition from the X  (2)Σ(g)(+) ground state to the first excited (2)Σ(u)(+) state is strongly blueshifted in the Frank-Condon area. PMID:21054047

  7. Theoretical study of mixed LiLnX4 (Ln = La, Dy; X = F, Cl, Br, I) rare earth/alkali halide complexes.

    PubMed

    Groen, C P; Oskam, A; Kovács, A

    2000-12-25

    The structure, bonding and vibrational properties of the mixed LiLnX4 (Ln = La, Dy; X = F, Cl, Br, I) rare earth/alkali halide complexes were studied using various quantum chemical methods (HF, MP2 and the Becke3-Lee-Yang-Parr exchange-correlation density functional) in conjunction with polarized triple-zeta valence basis sets and quasi-relativistic effective core potentials for the heavy atoms. Our comparative study indicated the superiority of MP2 theory while the HF and B3-LYP methods as well as less sophisticated basis sets failed for the correct energetic relations. In particular, f polarization functions on Li and X proved to be important for the Li...X interaction in the complexes. From the three characteristic structures of such complexes, possessing 1-(C3v), 2-(C2v), or 3-fold coordination (C3v) between the alkali metal and the bridging halide atoms, the bi- and tridentate forms are located considerably lower on the potential energy surface then the monodentate isomer. Therefore only the bi- and tridentate isomers have chemical relevance. The monodentate isomer is only a high-lying local minimum in the case of X = F. For X = Cl, Br, and I this structure is found to be a second-order saddle point. The bidentate structure was found to be the global minimum for the systems with X = F, Cl, and Br. However, the relative stability with respect to the tridentate structure is very small (1-5 kJ/mol) for the heavier halide derivatives and the relative order is reversed in the case of the iodides. The energy difference between the three structures and the dissociation energy decrease in the row F to I. The ionic bonding in the complexes was characterized by natural charges and a topological analysis of the electron density distribution according to Bader's theorem. Variation of the geometrical and bonding characteristics between the lanthanum and dysprosium complexes reflects the effect of "lanthanide contraction". The calculated vibrational data indicate that

  8. A different view of structure-making and structure-breaking in alkali halide aqueous solutions through x-ray absorption spectroscopy.

    PubMed

    Waluyo, Iradwikanari; Nordlund, Dennis; Bergmann, Uwe; Schlesinger, Daniel; Pettersson, Lars G M; Nilsson, Anders

    2014-06-28

    X-ray absorption spectroscopy measured in transmission mode was used to study the effect of alkali and halide ions on the hydrogen-bonding (H-bonding) network of water. Cl(-) and Br(-) are shown to have insignificant effect on the structure of water while I(-) locally weakens the H-bonding, as indicated by a sharp increase of the main-edge feature in the x-ray absorption spectra. All alkali cations act as structure-breakers in water, weakening the H-bonding network. The spectral changes are similar to spectra of high density ices where the 2nd shell has collapsed due to a break-down of the tetrahedral structures, although here, around the ions, the breakdown of the local tetrahedrality is rather due to non-directional H-bonding to the larger anions. In addition, results from temperature-dependent x-ray Raman scattering measurements of NaCl solution confirm the H-bond breaking effect of Na(+) and the effect on the liquid as similar to an increase in temperature. PMID:24985653

  9. A different view of structure-making and structure-breaking in alkali halide aqueous solutions through x-ray absorption spectroscopy

    NASA Astrophysics Data System (ADS)

    Waluyo, Iradwikanari; Nordlund, Dennis; Bergmann, Uwe; Schlesinger, Daniel; Pettersson, Lars G. M.; Nilsson, Anders

    2014-06-01

    X-ray absorption spectroscopy measured in transmission mode was used to study the effect of alkali and halide ions on the hydrogen-bonding (H-bonding) network of water. Cl- and Br- are shown to have insignificant effect on the structure of water while I- locally weakens the H-bonding, as indicated by a sharp increase of the main-edge feature in the x-ray absorption spectra. All alkali cations act as structure-breakers in water, weakening the H-bonding network. The spectral changes are similar to spectra of high density ices where the 2nd shell has collapsed due to a break-down of the tetrahedral structures, although here, around the ions, the breakdown of the local tetrahedrality is rather due to non-directional H-bonding to the larger anions. In addition, results from temperature-dependent x-ray Raman scattering measurements of NaCl solution confirm the H-bond breaking effect of Na+ and the effect on the liquid as similar to an increase in temperature.

  10. Multi-electron dissociative ionization of clusters under picosecond and femtosecond laser irradiation: the case of alkyl-halide clusters.

    PubMed

    Karras, Gabriel; Kosmidis, Constantine

    2012-09-21

    The multi-electron dissociative ionization (MEDI) of alkyl-halide clusters induced by 35 ps (at 266, 532 and 1064 nm) and 20 fs (at 400 and 800 nm) laser pulses is reported. In most cases, the MEDI of clusters is observed at substantially lower laser intensities than those reported for the monomer molecules, while the fragment ions are released with higher kinetic energies. From the comparative analysis of the experimental data, is concluded that the increase of molecular chain and/or the presence of a lighter halogen (I, Br, Cl) in the molecular skeleton results in the increase of the laser intensity thresholds for the appearance of the singly and multiply charged fragment ions. As far as the angular distributions of the ejected ions are concerned, they are found to be dependent on the laser pulse duration. For the observed experimental data, a physical mechanism is proposed, based on the combined action of the laser and the electric field created within the clusters after their single ionization. PMID:22859215

  11. Stability and structure of cluster ions: Halide ions with CO2

    NASA Astrophysics Data System (ADS)

    Hiraoka, Kenzo; Mizuse, Susumu; Yamabe, Shinichi

    1987-09-01

    Thermodynamic data, ΔH0n-1,n and ΔS0n-1,n, for clustering reactions of halide ions with CO2 were measured with a pulsed electron-beam high-pressure mass spectrometer. The large value of -ΔH00,1 (32.3 kcal/mol) and a sudden decrease of -ΔH01,2 (7.3 kcal/mol) for reaction F-(CO2)n-1+CO2=F-(CO2)n indicate the formation of the core ion, not F-ṡCO2, but FCO-2, i.e., FCO-2 is the fluoroformate ion. The measured binding energies -ΔH0n-1,n for the clusters F-(CO2)n were reproduced satisfactorily by the ab initio MO calculations. The FCO-2 ion is attacked successively and electrostatically by five CO2 molecules to form the first solvation shell. The two oxygen atoms in the core ion FCO-2 are able to accept four CO2 molecules as ligands. The bonding of CI-, Br-, and I- to CO2 is found to be mainly electrostatic.

  12. Complete-velocity-range description of negative-ion conversion of neutral atoms on an alkali-metal-halide surface under grazing geometry

    NASA Astrophysics Data System (ADS)

    Zhou, Hu; Zhou, Wang; Zhang, Meixiao; Zhou, Lihua; Ma, Yulong; Wang, Guangyi; Wu, Yong; Li, Bowen; Chen, Ximeng

    2016-06-01

    We propose a simple theoretical approach to consider negative-ion conversion of neutral atoms grazing on alkali-metal-halide crystal surfaces over the complete velocity range. The conversion process is viewed as a series of successive binary collisions between the projectile and the negatively charged sites on the surface along their trajectories due to localization of valence-band electrons at the anionic sites of the crystal. Conversion from F0 to F- via grazing scattering in LiF(100) and KI(100) is demonstrated with this model, which incorporates the key factors of image interaction and Mott-Littleton polarization interaction for electron capture. It also incorporates the decrease in the electron affinity due to Coulomb barrier tunneling of large-velocity negative ions to the vacuum level near surface anion sites. The pronounced differences in the efficiency of F- formation at LiF(100) and KI(100) surfaces are well explained by the proposed model. The relative efficiency and related saturation of the negative-ion formation for LiF and KI crystals compare well with experimental results.

  13. Band-structure calculations of noble-gas and alkali halide solids using accurate Kohn-Sham potentials with self-interaction correction

    SciTech Connect

    Li, Y.; Krieger, J.B. ); Norman, M.R. ); Iafrate, G.J. )

    1991-11-15

    The optimized-effective-potential (OEP) method and a method developed recently by Krieger, Li, and Iafrate (KLI) are applied to the band-structure calculations of noble-gas and alkali halide solids employing the self-interaction-corrected (SIC) local-spin-density (LSD) approximation for the exchange-correlation energy functional. The resulting band gaps from both calculations are found to be in fair agreement with the experimental values. The discrepancies are typically within a few percent with results that are nearly the same as those of previously published orbital-dependent multipotential SIC calculations, whereas the LSD results underestimate the band gaps by as much as 40%. As in the LSD---and it is believed to be the case even for the exact Kohn-Sham potential---both the OEP and KLI predict valence-band widths which are narrower than those of experiment. In all cases, the KLI method yields essentially the same results as the OEP.

  14. Cluster harvesting by successive reduction of a metal halide with a nonconventional reduction agent: a benefit for the exploration of metal-rich halide systems.

    PubMed

    Ströbele, Markus; Mos, Agnieszka; Meyer, Hans-Jürgen

    2013-06-17

    The preparation of thermally labile compounds is a great temptation in chemistry which requires a careful selection of reaction media and reaction conditions. With a new scanning technique denoted here as Cluster Harvesting, a whole series of metal halide compounds is detected by differential thermal analysis (DTA) in fused silica tubes and structurally characterized by X-ray powder diffraction. Experiments of the reduction of tungsten hexahalides with elemental antimony and iron are presented. A cascade of six compounds is identified during the reduction with antimony, and five compounds or phases are monitored following the reduction with iron. The crystal structure of Fe2W2Cl10 is reported, and two other phases in the Fe-W-Cl system are discussed. PMID:23718691

  15. Halide binding and inhibition of laccase copper clusters: the role of reorganization energy.

    PubMed

    Kepp, Kasper P

    2015-01-20

    Laccase-like proteins are multicopper oxidases involved in several biological and industrial processes. Their application is commonly limited due to inhibition by fluoride and chloride, and as-isolated proteins are often substantially activated by heat, suggesting that multiple redox states can complicate characterization. Understanding these processes at the molecular level is thus desirable but theoretically unexplored. This paper reports systematic calculations of geometries, reorganization energies, and ionization energies for all partly oxidized states of the trinuclear copper clusters in realistic models with ∼200 atoms. Corrections for scalar-relativistic effects, dispersion, and thermal effects were estimated. Fluoride, chloride, hydroxide, or water was bound to the T2 copper site of the oxidized resting state, and the peroxo intermediate was also computed for reference. Antiferromagnetic coupling, assigned oxidation states, and general structures were consistent with known spectroscopic data. The computations show that (i) ligands bound to the T2 site substantially increase the reorganization energy of the second reduction of the resting state and reduce the redox potentials, providing a possible mechanism for inhibition; (ii) the reorganization energy is particularly large for F(-) but also high for Cl(-), consistent with the experimental tendency of inhibition; (iii) reduction leads to release of Cl(-) from the T2 site, suggesting a mechanism for heat/reduction activation of laccases by dissociation of inhibiting halides or hydroxide from T2. PMID:25532722

  16. Characterization of an Alkali- and Halide-Resistant Laccase Expressed in E. coli: CotA from Bacillus clausii

    PubMed Central

    Brander, Søren; Mikkelsen, Jørn D.; Kepp, Kasper P.

    2014-01-01

    The limitations of fungal laccases at higher pH and salt concentrations have intensified the search for new extremophilic bacterial laccases. We report the cloning, expression, and characterization of the bacterial cotA from Bacillus clausii, a supposed alkalophilic ortholog of cotA from B. subtilis. Both laccases were expressed in E. coli strain BL21(DE3) and characterized fully in parallel for strict benchmarking. We report activity on ABTS, SGZ, DMP, caffeic acid, promazine, phenyl hydrazine, tannic acid, and bilirubin at variable pH. Whereas ABTS, promazine, and phenyl hydrazine activities vs. pH were similar, the activity of B. clausii cotA was shifted upwards by ∼0.5–2 pH units for the simple phenolic substrates DMP, SGZ, and caffeic acid. This shift is not due to substrate affinity (KM) but to pH dependence of catalytic turnover: The kcat of B. clausii cotA was 1 s−1 at pH 6 and 5 s−1 at pH 8 in contrast to 6 s−1 at pH 6 and 2 s−1 at pH 8 for of B. subtilis cotA. Overall, kcat/KM was 10-fold higher for B. subtilis cotA at pHopt. While both proteins were heat activated, activation increased with pH and was larger in cotA from B. clausii. NaCl inhibited activity at acidic pH, but not up to 500–700 mM NaCl in alkaline pH, a further advantage of the alkali regime in laccase applications. The B. clausii cotA had ∼20 minutes half-life at 80°C, less than the ∼50 minutes at 80°C for cotA from B. subtilis. While cotA from B. subtilis had optimal stability at pH∼8, the cotA from B. clausii displayed higher combined salt- and alkali-resistance. This resistance is possibly caused by two substitutions (S427Q and V110E) that could repel anions to reduce anion-copper interactions at the expense of catalytic proficiency, a trade-off of potential relevance to laccase optimization. PMID:24915287

  17. Characterization of an alkali- and halide-resistant laccase expressed in E. coli: CotA from Bacillus clausii.

    PubMed

    Brander, Søren; Mikkelsen, Jørn D; Kepp, Kasper P

    2014-01-01

    The limitations of fungal laccases at higher pH and salt concentrations have intensified the search for new extremophilic bacterial laccases. We report the cloning, expression, and characterization of the bacterial cotA from Bacillus clausii, a supposed alkalophilic ortholog of cotA from B. subtilis. Both laccases were expressed in E. coli strain BL21(DE3) and characterized fully in parallel for strict benchmarking. We report activity on ABTS, SGZ, DMP, caffeic acid, promazine, phenyl hydrazine, tannic acid, and bilirubin at variable pH. Whereas ABTS, promazine, and phenyl hydrazine activities vs. pH were similar, the activity of B. clausii cotA was shifted upwards by ~0.5-2 pH units for the simple phenolic substrates DMP, SGZ, and caffeic acid. This shift is not due to substrate affinity (K(M)) but to pH dependence of catalytic turnover: The k(cat) of B. clausii cotA was 1 s⁻¹ at pH 6 and 5 s⁻¹ at pH 8 in contrast to 6 s⁻¹ at pH 6 and 2 s⁻¹ at pH 8 for of B. subtilis cotA. Overall, k(cat)/K(M) was 10-fold higher for B. subtilis cotA at pH(opt). While both proteins were heat activated, activation increased with pH and was larger in cotA from B. clausii. NaCl inhibited activity at acidic pH, but not up to 500-700 mM NaCl in alkaline pH, a further advantage of the alkali regime in laccase applications. The B. clausii cotA had ~20 minutes half-life at 80°C, less than the ~50 minutes at 80°C for cotA from B. subtilis. While cotA from B. subtilis had optimal stability at pH~8, the cotA from B. clausii displayed higher combined salt- and alkali-resistance. This resistance is possibly caused by two substitutions (S427Q and V110E) that could repel anions to reduce anion-copper interactions at the expense of catalytic proficiency, a trade-off of potential relevance to laccase optimization. PMID:24915287

  18. Pre- and initial stages of epitaxy in alkali halide systems. II. Interaction of molecular beams of CsCl with (100) surfaces of NaCl

    NASA Astrophysics Data System (ADS)

    Dabringhaus, H.; Haag, M.

    The interaction of molecular beams of CsCl with (100) surfaces of NaCl is studied for crystal temperatures between 560 and 620 K and for molecular beam fluxes between 2 × 10 7 and 2 × 10 13 cm -2 s -1 by measurements of transient and steady state desorption fluxes, by static SIMS, and by electron microscopy. Also for the large Cs + ions a fast cation exchange Cs + ⇌ Na + between CsCl molecules adsorbed on the terrace and the outermost surface layer of the NaCl crystal is observed. The results for undersaturation are interpreted by incorporation of Cs + ions in the outermost surface layer of the NaCl crystal and by adsorption of CsCl molecules at the monatomic steps on the surface. The outermost surface layer proves to have a maximum capacity for Cs + of 2.4 × 10 11 cm -2. The residence time of Cs + ions in the outermost surface layer is determined as τ0 = 1.6 × 10 -12 exp(1.49 (eV)/ kT), the time for desorption of CsCl molecules from the monatomic steps as τ1 = 2.9 × 10 -14 exp(1.60 (eV)/ kT). By experiments with an additional NaCl flux onto the surface it is shown that τ0 is the time for a back-exchange of Cs + ions from the outermost surface layer against Na + from NaCl admolecules. For supersaturation the growth of polymorphic CsCl islands is observed. In the first growth stages these islands show the NaCl-type structure, while for later growth stages the CsCl type structure is found. A comparative discussion of all studied alkali halide systems shows that the different results can be attributed to the different radii of guest and host cation and to lattice misfits, respectively.

  19. Alkali halide-assisted penetration of neostigmine across excised human skin: a combination of structured water disruption and a Donnan-like effect.

    PubMed

    Michael-Baruch, E; Shiri, Y; Cohen, S

    1994-08-01

    The penetration of neostigmine across excised human skin mounted in flow-through diffusion cells, delivered from a 0.28 M aqueous solution, was below detection limits. The presence of either NaCl or LiCl in the donor solution caused significant fluxes of neostigmine, with permeability coefficients (Kp's) in the range of 10(-6) cm min-1. Paradoxically, low concentrations of NaCl or LiCl (0.25 and 0.5 M) were more effective in this respect than the 1 M solution, which was the least effective concentration in the range of 0.25-3 M. Thus, the dependence of the experimental Kp values on inorganic ion concentration followed a biphasic course, suggesting the participation of two distinctive mechanisms in the penetration-enhancement process. The early phase corresponding to 0.25 and 0.5 M NaCl or LiCl is being partly ascribed to a decrease in the viscosity of lamellar water caused by the influx of the respective hydrated ions, hydration of LiCl or NaCl being more extensive at low alkali halide concentration that at higher ones (reference cited). The late phase corresponding to 2 and 3 M LiCl and NaCl is partly ascribed to a Donnan-like effect whereby the presence of a large excess of poorly diffusible common ion (Na+ or Li+) enhances the partitioning into the skin of the more diffusible ion, in this case neostigmine cation. The presence of inorganic ions at different concentrations had no effect on the partial molal volume of neostigmine bromide (Vi infinity = 223.5 cm3 mol-1), which was practically the same for all concentrations of either LiCl and NaCl.(ABSTRACT TRUNCATED AT 250 WORDS) PMID:7983588

  20. Ab Initio Molecular Dynamics of Dimerization and Clustering in Alkali Metal Vapors.

    PubMed

    Chaban, Vitaly V; Prezhdo, Oleg V

    2016-06-30

    Alkali metals are known to form dimers, trimers, and tetramers in their vapors. The mechanism and regularities of this phenomenon characterize the chemical behavior of the first group elements. We report ab initio molecular dynamics (AIMD) simulations of the alkali metal vapors and characterize their structural properties, including radial distribution functions and atomic cluster size distributions. AIMD confirms formation of Men, where n ranges from 2 to 4. High pressure sharply favors larger structures, whereas high temperature decreases their fraction. Heavier alkali metals maintain somewhat larger fractions of Me2, Me3, and Me4, relative to isolated atoms. A single atom is the most frequently observed structure in vapors, irrespective of the element and temperature. Due to technical difficulties of working with high temperatures and pressures in experiments, AIMD is the most affordable method of research. It provides valuable understanding of the chemical behavior of Li, Na, K, Rb, and Cs, which can lead to development of new chemical reactions involving these metals. PMID:27294399

  1. Structure and Dynamics of Tunneling and Laser - Defects in Alkali Halides as Studied by a Behavior Type Analysis of the Polarized Raman Scattering.

    NASA Astrophysics Data System (ADS)

    Joosen, Wim M. C.

    It is demonstrated that proper analysis of polarized Raman spectra of defects in alkali halides by means of the Behavior Type (BT) method allows a detailed description of defect dynamics. The recently developed BT method provides a systematic procedure to distinguish, among the 125 Raman -active modes of the 33 possible point groups of a defect in a cubic lattice, the Raman modes which are consistent with the polarized Raman data, from those which are not. The efficiency of the BT method was shown in the interpretation of the low frequency Raman mode at 43 cm ^{-1} of the Li ^+ off-center impurity in KCl, which was attributed to a collective motion of the surrounding chlorine ions. This experimental finding inspired us to calculate the time dependent phonon autocorrelation function of a coupled spin-phonon system, which explains the anomalous isotope shift of the low frequency mode. We also studied the hydrogen-tagged Li ^+ center in KCl, which performs a correlated tunneling motion and put forward a defect model, in which the Li^+ ion and the hydrogen atom are both accommodated on the same cation site and displaced along <111> in opposite directions. There is no preferential molecular bond of any consequence between them. Our picture modifies the model based on electron spin resonance measurements, in which the H^{0}Li ^+ center is considered as a (LiH) ^+ molecular system. The Tl^0(1) defect is the first laser-center of the atomic type investigated with the Raman technique. The polarized Raman spectra, were excited in the third optical band of Tl^0 (1) and show that this transition is broadened by A_1-modes of the C_ {rm 4v} defect symmetry. We distinguished an induced first order spectrum, shown to be characteristic for the KCl lattice, and a low frequency vibration at about 30 cm^{-1}, which reflects the motion of the thallium atom along the fourfold axis. The Tl^+Tl^0 (1) center provided a first test-case for the extended BT method for resonant Raman

  2. Electrolytic systems and methods for making metal halides and refining metals

    SciTech Connect

    Holland, Justin M.; Cecala, David M.

    2015-05-26

    Disclosed are electrochemical cells and methods for producing a halide of a non-alkali metal and for electrorefining the halide. The systems typically involve an electrochemical cell having a cathode structure configured for dissolving a hydrogen halide that forms the halide into a molten salt of the halogen and an alkali metal. Typically a direct current voltage is applied across the cathode and an anode that is fabricated with the non-alkali metal such that the halide of the non-alkali metal is formed adjacent the anode. Electrorefining cells and methods involve applying a direct current voltage across the anode where the halide of the non-alkali metal is formed and the cathode where the non-alkali metal is electro-deposited. In a representative embodiment the halogen is chlorine, the alkali metal is lithium and the non-alkali metal is uranium.

  3. From T2,2@Bmmim to Alkali@T2,2@Bmmim Ivory Ball-like Clusters: Ionothermal Syntheses, Precise Doping, and Photocatalytic Properties.

    PubMed

    Du, Cheng-Feng; Li, Jian-Rong; Zhang, Bo; Shen, Nan-Nan; Huang, Xiao-Ying

    2015-06-15

    Presented here are the syntheses, structures, and properties of an In-Sn-Se compound based on a ternary super-supertetrahedral T2,2 cluster nested by Bmmim cations and two of its alkali-doped quaternary analogues. By means of a one-pot ionothermal method, an alkali metal ion (Cs(+) or Rb(+)) could be precisely doped into the central cavity of the cluster, forming an alkali@T2,2@Bmmim quaternary cluster. Remarkably, the undoped compound exhibited excellent stability and visible light photodegradation ability over a wide range of pH, especially in acidic conditions. PMID:26034842

  4. Solid-state NMR/NQR and first-principles study of two niobium halide cluster compounds.

    PubMed

    Perić, Berislav; Gautier, Régis; Pickard, Chris J; Bosiočić, Marko; Grbić, Mihael S; Požek, Miroslav

    2014-01-01

    Two hexanuclear niobium halide cluster compounds with a [Nb6X12](2+) (X=Cl, Br) diamagnetic cluster core, have been studied by a combination of experimental solid-state NMR/NQR techniques and PAW/GIPAW calculations. For niobium sites the NMR parameters were determined by using variable Bo field static broadband NMR measurements and additional NQR measurements. It was found that they possess large positive chemical shifts, contrary to majority of niobium compounds studied so far by solid-state NMR, but in accordance with chemical shifts of (95)Mo nuclei in structurally related compounds containing [Mo6Br8](4+) cluster cores. Experimentally determined δiso((93)Nb) values are in the range from 2,400 to 3,000 ppm. A detailed analysis of geometrical relations between computed electric field gradient (EFG) and chemical shift (CS) tensors with respect to structural features of cluster units was carried out. These tensors on niobium sites are almost axially symmetric with parallel orientation of the largest EFG and the smallest CS principal axes (Vzz and δ33) coinciding with the molecular four-fold axis of the [Nb6X12](2+) unit. Bridging halogen sites are characterized by large asymmetry of EFG and CS tensors, the largest EFG principal axis (Vzz) is perpendicular to the X-Nb bonds, while intermediate EFG principal axis (Vyy) and the largest CS principal axis (δ11) are oriented in the radial direction with respect to the center of the cluster unit. For more symmetrical bromide compound the PAW predictions for EFG parameters are in better correspondence with the NMR/NQR measurements than in the less symmetrical chlorine compound. Theoretically predicted NMR parameters of bridging halogen sites were checked by (79/81)Br NQR and (35)Cl solid-state NMR measurements. PMID:24581866

  5. An extended basis set {ital ab} {ital initio} study of alkali metal cation--water clusters

    SciTech Connect

    Feller, D.; Glendening, E.D.; Woon, D.E.; Feyereisen, M.W.

    1995-09-01

    Ionic clusters comprised of a single alkali metal cation and up to eight water molecules were studied at the Hartree--Fock and correlated levels of theory using the correlation consistent sequence of basis sets. Estimates of the degree of convergence in the computed properties with respect to the complete basis set limit were facilitated by the underlying systematic manner in which the correlation consistent sets approach completeness. In favorable cases, improved property values could be obtained by fitting finite basis set results with a simple analytical expression in order to extrapolate to the complete basis set limit. The sensitivity of structures and binding energies were analyzed with regard to the inclusion of valence and core-valence correlation recovery at the MP2, MP4, and CCSD(T) levels of theory. The replacement of metal core electrons and the introduction of relativistic contributions via effective core potentials was compared to corresponding all-electron results. {copyright} {ital 1995} {ital American} {ital Institute} {ital of} {ital Physics}.

  6. Study of the stabilization energies of halide-water clusters: An application of first-principles interaction potentials based on a polarizable and flexible model

    SciTech Connect

    Ayala, Regla; Martinez, Jose M.; Pappalardo, Rafael R.; Sanchez Marcos, Enrique

    2004-10-15

    The aim of this work is to compute the stabilization energy E{sub stab}(n) of [X(H{sub 2}O){sub n}]{sup -} (X{identical_to}F, Br, and I for n=1-60) clusters from Monte Carlo simulations using first-principles ab initio potentials. Stabilization energy of [X(H{sub 2}O){sub n}]{sup -} clusters is defined as the difference between the vertical photodeachment energy of the cluster and the electron affinity of the isolated halide. On one hand, a study about the relation between cluster structure and the E{sub stab}(n) value, as well as the dependence of the latter with temperature is performed, on the other hand, a test on the reliability of our recently developed first-principles halide ion-water interaction potentials is carried out. Two different approximations were applied: (1) the Koopmans' theorem and (2) calculation of the difference between the interaction energy of [X(H{sub 2}O){sub n}]{sup -} and [X(H{sub 2}O){sub n}] clusters using the same ab initio interaction potentials. The developed methodology allows for using the same interaction potentials in the case of the ionic and neutral clusters with the proviso that the charge of the halide anion was switched off in the latter. That is, no specific parametrization of the interaction potentials to fit the magnitude under study was done. The good agreement between our predicted E{sub stab}(n) and experimental data allows us to validate the first-principles interaction potentials developed elsewhere and used in this study, and supports the fact that this magnitude is mainly determined by electrostatic factors, which can be described by our interaction potentials. No relation between the value of E{sub stab}(n) and the structure of clusters has been found. The diversity of E{sub stab}(n) values found for different clusters with similar interaction energy indicates the need for statistical information to properly estimate the stabilization energy of the halide anions. The effect of temperature in the prediction of

  7. Tug of war between AO-hybridization and aromaticity in dictating structures of Li-doped alkali clusters

    NASA Astrophysics Data System (ADS)

    Alexandrova, Anastassia N.

    2012-04-01

    Hybridization of atomic orbitals is a widely appreciated phenomenon in organic chemistry. Here, we demonstrate that hybridization also can dramatically impact the shapes of small all-alkali metal clusters, and oppose σ-aromaticity in defining cluster shapes. The valence-iso-electronic LiNa4- and LiK4- clusters adopt different global minimum structures: LiNa4- is a planar C2v (1A1) species distorted from the perfect pentagon, and LiK4- is a planar square D4h (1A1g) species with Li being in the centre. This effect is rooted in the different degrees of the 2s-2p hybridization in Li in response to binding to Na versus K.

  8. Heat capacity of molten halides.

    PubMed

    Redkin, Alexander A; Zaikov, Yurii P; Korzun, Iraida V; Reznitskikh, Olga G; Yaroslavtseva, Tatiana V; Kumkov, Sergey I

    2015-01-15

    The heat capacities of molten salts are very important for their practical use. Experimental investigation of this property is challenging because of the high temperatures involved and the corrosive nature of these materials. It is preferable to combine experimental investigations with empirical relationships, which allows for the evaluation of the heat capacity of molten salt mixtures. The isobaric molar heat capacities of all molten alkali and alkaline-earth halides were found to be constant for each group of salts. The value depends on the number of atoms in the salt, and the molar heat capacity per atom is constant for all molten halide salts with the exception of the lithium halides. The molar heat capacities of molten halides do not change when the anions are changed. PMID:25530462

  9. Oxidation of hydrogen halides to elemental halogens

    DOEpatents

    Rohrmann, Charles A.; Fullam, Harold T.

    1985-01-01

    A process for oxidizing hydrogen halides having substantially no sulfur impurities by means of a catalytically active molten salt is disclosed. A mixture of the subject hydrogen halide and an oxygen bearing gas is contacted with a molten salt containing an oxidizing catalyst and alkali metal normal sulfates and pyrosulfates to produce an effluent gas stream rich in the elemental halogen and substantially free of sulfur oxide gases.

  10. Accurate van der Waals coefficients between fullerenes and fullerene-alkali atoms and clusters: Modified single-frequency approximation

    NASA Astrophysics Data System (ADS)

    Tao, Jianmin; Mo, Yuxiang; Tian, Guocai; Ruzsinszky, Adrienn

    2016-08-01

    Long-range van der Waals (vdW) interaction is critically important for intermolecular interactions in molecular complexes and solids. However, accurate modeling of vdW coefficients presents a great challenge for nanostructures, in particular for fullerene clusters, which have huge vdW coefficients but also display very strong nonadditivity. In this work, we calculate the coefficients between fullerenes, fullerene and sodium clusters, and fullerene and alkali atoms with the hollow-sphere model within the modified single-frequency approximation (MSFA). In the MSFA, we assume that the electron density is uniform in a molecule and that only valence electrons in the outmost subshell of atoms contribute. The input to the model is the static multipole polarizability, which provides a sharp cutoff for the plasmon contribution outside the effective vdW radius. We find that the model can generate C6 in excellent agreement with expensive wave-function-based ab initio calculations, with a mean absolute relative error of only 3 % , without suffering size-dependent error. We show that the nonadditivities of the coefficients C6 between fullerenes and C60 and sodium clusters Nan revealed by the model agree remarkably well with those based on the accurate reference values. The great flexibility, simplicity, and high accuracy make the model particularly suitable for the study of the nonadditivity of vdW coefficients between nanostructures, advancing the development of better vdW corrections to conventional density functional theory.

  11. Fission of multiply charged alkali clusters in helium droplets - approaching the Rayleigh limit.

    PubMed

    Renzler, Michael; Harnisch, Martina; Daxner, Matthias; Kranabetter, Lorenz; Kuhn, Martin; Scheier, Paul; Echt, Olof

    2016-04-21

    Electron ionization of helium droplets doped with sodium, potassium or cesium results in doubly and, for cesium, triply charged cluster ions. The smallest observable doubly charged clusters are Na9(2+), K11(2+), and Cs9(2+); they are a factor two to three smaller than reported previously. The size of sodium and potassium dications approaches the Rayleigh limit nRay for which the fission barrier is calculated to vanish, i.e. their fissilities are close to 1. Cesium dications are even smaller than nRay, implying that their fissilities have been significantly overestimated. Triply charged cesium clusters as small as Cs19(3+) are observed; they are a factor 2.6 smaller than previously reported. Mechanisms that may be responsible for enhanced formation of clusters with high fissilities are discussed. PMID:27035406

  12. Molecular compressibility of some halides in alcohols

    NASA Technical Reports Server (NTRS)

    Serban, C.; Auslaender, D.

    1974-01-01

    After measuring ultrasonic velocity and density, the molecular compressibility values from Wada's formula were calculated, for alkali metal halide solutions in methyl, ethyl, butyl, and glycol alcohol. The temperature and concentration dependence were studied, finding deviations due to the hydrogen bonds of the solvent.

  13. Computation of methodology-independent single-ion solvation properties from molecular simulations. IV. Optimized Lennard-Jones interaction parameter sets for the alkali and halide ions in water

    SciTech Connect

    Reif, Maria M.; Huenenberger, Philippe H.

    2011-04-14

    The raw single-ion solvation free energies computed from atomistic (explicit-solvent) simulations are extremely sensitive to the boundary conditions and treatment of electrostatic interactions used during these simulations. However, as shown recently [M. A. Kastenholz and P. H. Huenenberger, J. Chem. Phys. 124, 224501 (2006); M. M. Reif and P. H. Huenenberger, J. Chem. Phys. 134, 144103 (2010)], the application of appropriate correction terms permits to obtain methodology-independent results. The corrected values are then exclusively characteristic of the underlying molecular model including in particular the ion-solvent van der Waals interaction parameters, determining the effective ion size and the magnitude of its dispersion interactions. In the present study, the comparison of calculated (corrected) hydration free energies with experimental data (along with the consideration of ionic polarizabilities) is used to calibrate new sets of ion-solvent van der Waals (Lennard-Jones) interaction parameters for the alkali (Li{sup +}, Na{sup +}, K{sup +}, Rb{sup +}, Cs{sup +}) and halide (F{sup -}, Cl{sup -}, Br{sup -}, I{sup -}) ions along with either the SPC or the SPC/E water models. The experimental dataset is defined by conventional single-ion hydration free energies [Tissandier et al., J. Phys. Chem. A 102, 7787 (1998); Fawcett, J. Phys. Chem. B 103, 11181] along with three plausible choices for the (experimentally elusive) value of the absolute (intrinsic) hydration free energy of the proton, namely, {Delta}G{sub hyd} {sup O-minus} [H{sup +}]=-1100, -1075 or -1050 kJ mol{sup -1}, resulting in three sets L, M, and H for the SPC water model and three sets L{sub E}, M{sub E}, and H{sub E} for the SPC/E water model (alternative sets can easily be interpolated to intermediate {Delta}G{sub hyd} {sup O-minus} [H{sup +}] values). The residual sensitivity of the calculated (corrected) hydration free energies on the volume-pressure boundary conditions and on the effective

  14. Oligomeric rare-earth-metal halide clusters. Three structures built of (Y{sub 16}Z{sub 4})Br{sub 36} units (Z = Ru, Ir)

    SciTech Connect

    Steinward, S.J.; Corbett, J.D.

    1996-11-20

    Suitable reactions in sealed Nb tubing at 850-950 {degrees}C gave good yields of a family of oligomeric cluster phases that were characterized by single-crystal X-ray diffraction means. The basic Y{sub 16}Z{sub 4} units ({approximately}{bar 4} symmetry) can be derived from 2+2 condensation of centered Y{sub 6}Br{sub 12}Z-type clusters or as tetracapped truncated tetrahedra Y{sub 16} that are centered by a large tetrahedral Z{sub 4}. These are surrounded by 36 bromine atoms which bridge edges or cap faces of the Y{sub 16}Z{sub 4} nuclei and, in part, bridge to metal atoms in other clusters. The principal bonding appears to be Y-Z and Y-Br, with weaker Y-Y ({bar d} {approximately} 3.70 {angstrom}) and negligible Z-Z interactions. The phase Y{sub 16}Br{sub 20}Ru{sub 4} (P4{sub 2}/nnm, Z = 2; a = 11.662(1) {angstrom}, c = 16.992 (2) {angstrom}) is isostructural with Y{sub 16}I{sub 20}Ru{sub 4} and with the new Sc{sub 16-} Br{sub 20}Z{sub 4} (Z = Fe, Os). Syntheses only in the presence of Ir and ABr-YBr{sub 3} fluxes (A = K-Cs) produce Y{sub 16-} Br{sub 24}Ir{sub 4} (Fddd, Z = 8; a = 11.718(3) {angstrom}, b = 22.361(7) {angstrom}, c = 44.702(2) {angstrom}), in which the electron-richer Ir interstitials are compensated by four additional bromine atoms and altered bridging between macroclusters. Larger amounts of YBr{sub 3} yield a third example, Y{sub 20}Br{sub 36}Ir{sub 4} (Y{sub 16}Br{sub 24}Ir{sub 4}{center_dot}4YBr{sub 3}, I4{sub 1}a, Z = 4; a = 12.699(1) {angstrom}, c = 45.11- (1){angstrom}). Here infinite zigzag chains of YBr{sub 6/2} octahedra that share cis edges lie between and bridge to the Y{sub 16}Ir{sub 4} clusters. All of these phases contain 60-electron, closed-shell macroclusters. Y{sub 16}Br{sub 20}Ru{sub 4} and Y{sub 20}Br{sub 36}ir{sub 4} were found to exhibit temperature-independent (Van Vleck) paramagnetism with values typical of those found for other rare-earth-metal, zirconium, niobium, and tantalum cluster halides.

  15. The Silver Halides

    ERIC Educational Resources Information Center

    Sahyun, M. R. V.

    1977-01-01

    Illustrates the type of fractional bonding for solid silver halides. Treats the silver halides as electron excess compounds, and develops a model of a localized bonding unit that may be iterated in three dimensions to describe the bulk phase. (MLH)

  16. Prediction of the fate of Hg and other contaminants in soil around a former chlor-alkali plant using Fuzzy Hierarchical Cross-Clustering approach.

    PubMed

    Frenţiu, Tiberiu; Ponta, Michaela; Sârbu, Costel

    2015-11-01

    An associative simultaneous fuzzy divisive hierarchical algorithm was used to predict the fate of Hg and other contaminants in soil around a former chlor-alkali plant. The algorithm was applied on several natural and anthropogenic characteristics of soil including water leachable, mobile, semi-mobile, non-mobile fractions and total Hg, Al, Ba, Ca, Cr, Cu, Fe, K, Li, Mg, Mn, Na, Sr, Zn, water leachable fraction of Cl(-), NO3(-) and SO4(2)(-), pH and total organic carbon. The cross-classification algorithm provided a divisive fuzzy partition of the soil samples and associated characteristics. Soils outside the perimeter of the former chlor-alkali plant were clustered based on the natural characteristics and total Hg. In contaminated zones Hg speciation becomes relevant and the assessment of species distribution is necessary. The descending order of concentration of Hg species in the test site was semi-mobile>mobile>non-mobile>water-leachable. Physico-chemical features responsible for similarities or differences between uncontaminated soil samples or contaminated with Hg, Cu, Zn, Ba and NO3(-) were also highlighted. Other characteristics of the contaminated soil were found to be Ca, sulfate, Na and chloride, some of which with influence on Hg fate. The presence of Ca and sulfate in soil induced a higher water leachability of Hg, while Cu had an opposite effect by forming amalgam. The used algorithm provided an in-deep understanding of processes involving Hg species and allowed to make prediction of the fate of Hg and contaminants linked to chlor-alkali-industry. PMID:26057390

  17. Metal-halide mixtures for latent heat energy storage

    NASA Technical Reports Server (NTRS)

    Chen, K.; Manvi, R.

    1981-01-01

    Alkali metal and alkali halide mixtures are identified which may be suitable for thermal energy storage at temperatures above 600 C. The use of metal-halides is appropriate because of their tendency to form two immiscible melts with a density difference, which reduces scale formation and solidification on heat transfer surfaces. Also, the accumulation of phase change material along the melt interface is avoided by the self-dispersing characteristic of some metal-halides, in particular Sr-SrCl2, Ba-BaCl2, and Ba-BaBr2 mixtures. Further advantages lie in their high thermal conductivities, ability to cope with thermal shock, corrosion inhibition, and possibly higher energy densities.

  18. Spin-orbit coupling in the dissociative excitation of alkali atoms at the surface of rare gas clusters: A theoretical study

    NASA Astrophysics Data System (ADS)

    Gervais, B.; Zanuttini, D.; Douady, J.

    2016-05-01

    We analyze the role of the spin-orbit (SO) coupling in the dissociative dynamics of excited alkali atoms at the surface of small rare gas clusters. The electronic structure of the whole system is deduced from a one-electron model based on core polarization pseudo-potentials. It allows us to obtain in the same footing the energy, forces, and non-adiabatic couplings used to simulate the dynamics by means of a surface hopping method. The fine structure state population is analyzed by considering the relative magnitude of the SO coupling ξ, with respect to the spin-free potential energy. We identify three regimes of ξ-values leading to different evolution of adiabatic state population after excitation of the system in the uppermost state of the lowest np 2P shell. For sufficiently small ξ, the final population of the J = /1 2 atomic states, P /1 2 , grows up linearly from P /1 2 = /1 3 at ξ = 0 after a diabatic dynamics. For large values of ξ, we observe a rather adiabatic dynamics with P /1 2 decreasing as ξ increases. For intermediate values of ξ, the coupling is extremely efficient and a complete transfer of population is observed for the set of parameters associated to NaAr3 and NaAr4 clusters.

  19. Spin-orbit coupling in the dissociative excitation of alkali atoms at the surface of rare gas clusters: A theoretical study.

    PubMed

    Gervais, B; Zanuttini, D; Douady, J

    2016-05-21

    We analyze the role of the spin-orbit (SO) coupling in the dissociative dynamics of excited alkali atoms at the surface of small rare gas clusters. The electronic structure of the whole system is deduced from a one-electron model based on core polarization pseudo-potentials. It allows us to obtain in the same footing the energy, forces, and non-adiabatic couplings used to simulate the dynamics by means of a surface hopping method. The fine structure state population is analyzed by considering the relative magnitude of the SO coupling ξ, with respect to the spin-free potential energy. We identify three regimes of ξ-values leading to different evolution of adiabatic state population after excitation of the system in the uppermost state of the lowest np (2)P shell. For sufficiently small ξ, the final population of the J=12 atomic states, P12, grows up linearly from P12=13 at ξ = 0 after a diabatic dynamics. For large values of ξ, we observe a rather adiabatic dynamics with P12 decreasing as ξ increases. For intermediate values of ξ, the coupling is extremely efficient and a complete transfer of population is observed for the set of parameters associated to NaAr3 and NaAr4 clusters. PMID:27208949

  20. Formation of Metal Clusters or Nitrogen-Bridged Adducts by Reaction of a Bis(amino)stannylene with Halides of Two-Valent Transition Metals.

    PubMed

    Veith, Michael; Müller, Alice; Stahl, Lothar; Nötzel, Martin; Jarczyk, Maria; Huch, Volker

    1996-06-19

    When the cyclic bis(amino)stannylene Me(2)Si(NtBu)(2)Sn is allowed to react with metal halides MX(2) (M = Cr, Fe, Co, Zn; X = Cl, Br [Zn]) adducts of the general formula [Me(2)Si(NtBu)(2)Sn.MX(2)](n) are obtained. The compounds are generally dimeric (n = 2) except the ZnBr(2) adduct, which is monomeric in benzene. The crystal structures of [Me(2)Si(NtBu)(2)Sn.CoCl(2)](2) (triclinic, space group &Pmacr;1; a = 8.620(9) Å, b = 9.160(9) Å, c = 12.280(9) Å, alpha = 101.2(1) degrees, beta = 97.6(1) degrees, gamma = 105.9(1) degrees, Z = 1) and of [Me(2)Si(NtBu)(2)Sn.ZnCl(2)](2) (monoclinic, space group P2(1)/c; a = 8.156(9) Å, b = 16.835(12) Å, c = 13.206(9) Å, beta = 94.27(6) degrees, Z = 2) were determined by X-ray diffraction techniques. The two compounds form similar polycyclic, centrosymmetrical assemblies of metal atoms bridged by chlorine or nitrogen atoms. While in the case of the cobalt compound Co is pentacoordinated by three chlorine and two nitrogen atoms, in the zinc derivative Zn is almost tetrahedrally coordinated by three chlorine atoms and one nitrogen atom. The iron derivative [Me(2)Si(NtBu)(2)Sn.FeCl(2)](2) seems to be isostructural with the cobalt compound as can be deduced from the crystal data (triclinic, a = 8.622(7) Å, b = 9.158(8) Å, c = 12.353(8) Å, alpha = 101.8(1) degrees, beta = 96.9(1) degrees, gamma = 105.9(1) degrees, Z = 1). If NiBr(2), PdCl(2), or PtCl(2) is combined with the stannylene, the reaction product is totally different: 4 equiv of the stannylene are coordinating per metal halide, forming the molecular compound [Me(2)Si(NtBu)(2)Sn](4)MX(2), which crystallizes with half a mole of benzene per molecular formula. The crystal structures of [Me(2)Si(NtBu)(2)Sn](4).NiBr(2).(1)/(2)C(6)H(6) (tetragonal, space group I4(1)/a, a = b = 43.86(4) Å, c = 14.32(2) Å, Z = 16) and [Me(2)Si(NtBu)(2)Sn](4).PdCl(2).(1)/(2)C(6)H(6) (tetragonal, space group I4(1)/a, a = b = 43.99(4) Å, c = 14.318(14) Å, Z = 16) reveal the two compounds to

  1. Quantum Theoretical Study of KCl and LiCl Clusters

    NASA Astrophysics Data System (ADS)

    Koetter, Ted; Hira, Ajit; Salazar, Justin; Jaramillo, Danelle

    2014-03-01

    This research focuses on the theoretical study of molecular clusters to examine the chemical properties of small KnClnandLinCln clusters (n = 2 - 20). The potentially important role of these molecular species in biochemical and medicinal processes is well known. This work applies the hybrid ab initio methods of quantum chemistry to derive the different alkali-halide (MnHn) geometries. Of particular interest is the competition between hexagonal ring geometries and rock salt structures. Electronic energies, rotational constants, dipole moments, and vibrational frequencies for these geometries are calculated. Magic numbers for cluster stability are identified and are related to the property of cluster compactness. Mapping of the singlet, triplet, and quintet, potential energy surfaces is performed. Calculations were performed to examine the interactions of these clusters with some atoms and molecules of biological interest, including O, O2, and Fe. Potential design of new medicinal drugs is explored.

  2. Alkali Bee

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The alkali bee, Nomia melanderi, is native to deserts and semi-arid desert basins of the western United States. It is a very effective and manageable pollinator for the production of seed in alfalfa (=lucerne) and some other crops, such as onion. It is the world’s only intensively managed ground-n...

  3. Oxidation of hydrogen halides to elemental halogens with catalytic molten salt mixtures

    DOEpatents

    Rohrmann, Charles A.

    1978-01-01

    A process for oxidizing hydrogen halides by means of a catalytically active molten salt is disclosed. The subject hydrogen halide is contacted with a molten salt containing an oxygen compound of vanadium and alkali metal sulfates and pyrosulfates to produce an effluent gas stream rich in the elemental halogen. The reduced vanadium which remains after this contacting is regenerated to the active higher valence state by contacting the spent molten salt with a stream of oxygen-bearing gas.

  4. Metal-halide mixtures for latent heat energy storage

    NASA Technical Reports Server (NTRS)

    Chen, K.; Manvi, R.

    1981-01-01

    Some candidates for alkali metal and alkali halide mixtures suitable for thermal energy storage at temperatures 600 C are identified. A solar thermal system application which offer advantages such as precipitation of salt crystals away from heat transfer surfaces, increased thermal conductivity of phase change materials, corrosion inhibition, and a constant monotectic temperature, independent of mixture concentrations. By using the lighters, metal rich phase as a heat transfer medium and the denser, salt rich phase as a phase change material for latent heat storage, undesirable solidification on the heat transfer surface may be prevented, is presented.

  5. Correspondence between ion-cluster and bulk thermodynamics: on the validity of the cluster pair approximation

    SciTech Connect

    Vlcek, Lukas; Chialvo, Ariel; Simonson, J Michael {Mike}

    2013-01-01

    Molecular models and experimental estimates based on the cluster pair approximation (CPA) provide inconsistent predictions of absolute single-ion hydration properties. To understand the origin of this discrepancy we used molecular simulations to study the transition between hydration of alkali metal and halide ions in small aqueous clusters and bulk water. The results demonstrate that the assumptions underlying the CPA are not generally valid as a result of a significant shift in the ion hydration free energies (~15 kJ/mol) and enthalpies (~47 kJ/mol) in the intermediate range of cluster sizes. When this effect is accounted for, the systematic differences between models and experimental predictions disappear, and the value of absolute proton hydration enthalpy based on the CPA gets in closer agreement with other estimates.

  6. Bio-conventional bleaching of kadam kraft-AQ pulp by thermo-alkali-tolerant xylanases from two strains of Coprinellus disseminatus for extenuating adsorbable organic halides and improving strength with optical properties and energy conservation.

    PubMed

    Lal, Mohan; Dutt, Dharm; Tyagi, C H

    2012-04-01

    Two novel thermo-alkali-tolerant crude xylanases namely MLK-01 (enzyme-A) and MLK-07 (enzyme-B) from Coprinellus disseminatus mitigated kappa numbers of Anthocephalus cadamba kraft-AQ pulps by 32.5 and 34.38%, improved brightness by 1.5 and 1.6% and viscosity by 5.75 and 6.47% after (A)XE(1) and (B)XE(1)-stages, respectively. The release of reducing sugars and chromophores was the highest during prebleaching of A. cadamba kraft-AQ pulp at enzyme doses of 5 and 10 IU/g, reaction times 90 and 120 min, reaction temperatures 75 and 65°C and consistency 10% for MLK-01 and MLK-07, respectively. MLK-07 was more efficient than MLK01 in terms of producing pulp brightness, improving mechanical strength properties and reducing pollution load. MLK-01 and MLK-07 reduced AOX by 19.51 and 42.77%, respectively at 4% chlorine demands with an increase in COD and colour due to removal of lignin carbohydrates complexes. A. cadamba kraft-AQ pulps treated with xylanases from MLK-01 to MLK-07 and followed by CEHH bleaching at half chlorine demand (2%) showed a drastic reduction in brightness with slight improvement in mechanical strength properties compared to pulp bleached at 4% chlorine demand. MLK-01 reduced AOX, COD and colour by 43.83, 39.03 and 27.71% and MLK-07 by 38.34, 40.48 and 30.77%, respectively at half chlorine demand compared to full chlorine demand (4%). pH variation during prebleaching of A. cadamba kraft-AQ pulps with strains MLK-01 and MLK-07 followed by CEHH bleaching sequences showed a decrease in pulp brightness, AOX, COD and colour with an increase in mechanical strength properties, pulp viscosity and PFI revolutions to get a beating level of 35 ± 1 °SR at full chlorine demand. PMID:22805918

  7. Application of Ion Mobility-Mass Spectrometry to the Study of Ionic Clusters: Investigation of Cluster Ions with Stable Sizes and Compositions

    PubMed Central

    Ohshimo, Keijiro; Komukai, Tatsuya; Takahashi, Tohru; Norimasa, Naoya; Wu, Jenna Wen Ju; Moriyama, Ryoichi; Koyasu, Kiichirou; Misaizu, Fuminori

    2014-01-01

    Stable cluster sizes and compositions have been investigated for cations and anions of ionic bond clusters such as alkali halides and transition metal oxides by ion mobility-mass spectrometry (IM-MS). Usually structural information of ions can be obtained from collision cross sections determined in IM-MS. In addition, we have found that stable ion sizes or compositions were predominantly produced in a total ion mass spectrum, which was constructed from the IM-MS measurement. These stable species were produced as a result of collision induced dissociations of the ions in a drift cell. We have confirmed this result in the sodium fluoride cluster ions, in which cuboid magic number cluster ions were predominantly observed. Next the stable compositions, which were obtained for the oxide systems of the first row transition metals, Ti, Fe, and Co, are characteristic for each of the metal oxide cluster ions. PMID:26819887

  8. Vitrification of IFR and MSBR halide salt reprocessing wastes

    SciTech Connect

    Siemer, D.D.

    2013-07-01

    Both of the genuinely sustainable (breeder) nuclear fuel cycles (IFR - Integral Fast Reactor - and MSBR - Molten Salt Breeder Reactor -) studied by the USA's national laboratories would generate high level reprocessing waste (HLRW) streams consisting of a relatively small amount ( about 4 mole %) of fission product halide (chloride or fluoride) salts in a matrix comprised primarily (about 95 mole %) of non radioactive alkali metal halide salts. Because leach resistant glasses cannot accommodate much of any of the halides, most of the treatment scenarios previously envisioned for such HLRW have assumed a monolithic waste form comprised of a synthetic analog of an insoluble crystalline halide mineral. In practice, this translates to making a 'substituted' sodalite ('Ceramic Waste Form') of the IFR's chloride salt-based wastes and fluoroapatite of the MSBR's fluoride salt-based wastes. This paper discusses my experimental studies of an alternative waste management scenario for both fuel cycles that would separate/recycle the waste's halide and immobilize everything else in iron phosphate (Fe-P) glass. It will describe both how the work was done and what its results indicate about how a treatment process for both of those wastes should be implemented (fluoride and chloride behave differently). In either case, this scenario's primary advantages include much higher waste loadings, much lower overall cost, and the generation of a product (glass) that is more consistent with current waste management practices. (author)

  9. Process for oxidation of hydrogen halides to elemental halogens

    DOEpatents

    Lyke, Stephen E.

    1992-01-01

    An improved process for generating an elemental halogen selected from chlorine, bromine or iodine, from a corresponding hydrogen halide by absorbing a molten salt mixture, which includes sulfur, alkali metals and oxygen with a sulfur to metal molar ratio between 0.9 and 1.1 and includes a dissolved oxygen compound capable of reacting with hydrogen halide to produce elemental halogen, into a porous, relatively inert substrate to produce a substrate-supported salt mixture. Thereafter, the substrate-supported salt mixture is contacted (stage 1) with a hydrogen halide while maintaining the substrate-supported salt mixture during the contacting at an elevated temperature sufficient to sustain a reaction between the oxygen compound and the hydrogen halide to produce a gaseous elemental halogen product. This is followed by purging the substrate-supported salt mixture with steam (stage 2) thereby recovering any unreacted hydrogen halide and additional elemental halogen for recycle to stage 1. The dissolved oxygen compound is regenerated in a high temperature (stage 3) and an optical intermediate temperature stage (stage 4) by contacting the substrate-supported salt mixture with a gas containing oxygen whereby the dissolved oxygen compound in the substrate-supported salt mixture is regenerated by being oxidized to a higher valence state.

  10. Theoretical Study of NaCl and LiCl Clusters

    NASA Astrophysics Data System (ADS)

    Ortiz, Bridget; Hira, Ajit; McKeough, James; Koetter, Ted

    This research is a Quantum Mechanical study of molecular clusters that examines the chemical properties of small NanCln and LinCln clusters (n = 2 - 20). The potentially important role of these molecular species in biochemical and medicinal processes is well known. This work applies the hybrid ab initio methods to derive the different alkali-halide (MnHn) geometries. Of particular interest is the competition between hexagonal ring geometries and rock salt structures. Electronic energies, rotational constants, dipole moments, and vibrational frequencies for these geometries are calculated. Magic numbers for cluster stability are identified and are related to the property of cluster compactness. Mapping of the singlet, triplet, and quintet, potential energy surfaces is performed. Calculations were performed to examine the interactions of these clusters with some atoms and molecules of biological interest, including O, O2, and Fe. Potential design of new medicinal drugs is explored. We will also investigate model and material dependence of the results.

  11. Skylab experiments on semiconductors and alkali halides. [single crystal growth

    NASA Technical Reports Server (NTRS)

    Lundquist, C. A.

    1974-01-01

    The space processing experiments performed during the Skylab missions included one on single crystal growth of germanium selenide and telluride, one on pure and doped germanium crystals, two on pure and doped indium antimonide, one on gallium-indium-antimony systems, and one on a sodium chloride-sodium fluoride eutectic. In each experiment, three ampoules of sample were processed in the multipurpose electric furnace within the Skylab Materials Processing Facility. All were successful in varying degrees and gave important information about crystal growth removed from the effects of earth surface gravity.

  12. Cold ablation driven by localized forces in alkali halides.

    PubMed

    Hada, Masaki; Zhang, Dongfang; Pichugin, Kostyantyn; Hirscht, Julian; Kochman, Michał A; Hayes, Stuart A; Manz, Stephanie; Gengler, Regis Y N; Wann, Derek A; Seki, Toshio; Moriena, Gustavo; Morrison, Carole A; Matsuo, Jiro; Sciaini, Germán; Miller, R J Dwayne

    2014-01-01

    Laser ablation has been widely used for a variety of applications. Since the mechanisms for ablation are strongly dependent on the photoexcitation level, so called cold material processing has relied on the use of high-peak-power laser fluences for which nonthermal processes become dominant; often reaching the universal threshold for plasma formation of ~1 J cm(-2) in most solids. Here we show single-shot time-resolved femtosecond electron diffraction, femtosecond optical reflectivity and ion detection experiments to study the evolution of the ablation process that follows femtosecond 400 nm laser excitation in crystalline sodium chloride, caesium iodide and potassium iodide. The phenomenon in this class of materials occurs well below the threshold for plasma formation and even below the melting point. The results reveal fast electronic and localized structural changes that lead to the ejection of particulates and the formation of micron-deep craters, reflecting the very nature of the strong repulsive forces at play. PMID:24835317

  13. Calculations of hyper-Raman tensor components of alkali halides

    NASA Astrophysics Data System (ADS)

    de Landa Castillo-Alvarado, Fray; Kucharczyk, Wlotek

    1998-03-01

    Calculations of hyper-Raman tensor components of NaCl,KCl and KBr crystals based on the bond polizability approach are presented. The results obtained are in good agreement whit experimental data reported previously in literature. A week cubic anisotropy of the hyper-Raman tensor is found. For LO mode our results predict the lattice deformation contribution to hyper-Raman scattering to be comparable whit the electro-optic contribution.

  14. Calculations of hyper-Raman tensor components of alkali halides

    NASA Astrophysics Data System (ADS)

    Kucharczyk, W.; Castillo Alvarado, F. L.

    1999-01-01

    Calculations of hyper-Raman scattering by the zone-centre optical phonons in NaCl, KCl and KBr crystals based on the bond polarizability approach are presented. The results obtained for the hyper-Raman tensor components are in agreement with experimental data reported previously in literature. A weak cubic anisotropy of the hyper-Raman tensor is found. For the LO mode our results predict the lattice and electro-optic contributions to hyper-Raman scattering to be of the same order of magnitude.

  15. Alkali metal nitrate purification

    DOEpatents

    Fiorucci, Louis C.; Morgan, Michael J.

    1986-02-04

    A process is disclosed for removing contaminants from impure alkali metal nitrates containing them. The process comprises heating the impure alkali metal nitrates in solution form or molten form at a temperature and for a time sufficient to effect precipitation of solid impurities and separating the solid impurities from the resulting purified alkali metal nitrates. The resulting purified alkali metal nitrates in solution form may be heated to evaporate water therefrom to produce purified molten alkali metal nitrates suitable for use as a heat transfer medium. If desired, the purified molten form may be granulated and cooled to form discrete solid particles of purified alkali metal nitrates.

  16. High Biomass Specific Methyl Halide Production Rates of Selected Coastal Marsh Plants and its Relationship to Halide Content

    NASA Astrophysics Data System (ADS)

    Manley, S. L.; Wang, N.; Cicerone, R. J.

    2002-12-01

    Salt tolerant coastal marsh plants (halophytes) have previously been shown to be globally significant producers of methyl chloride (MeCl) and methyl bromide (MeBr). While halophytes are known for their high salt content, there are few reports of their halide content. Our studies have attempted to quantify biomass specific methyl halide (MeX) production from these plants and relate it to tissue halide levels. MeCl, MeBr and MeI production rates and tissue chloride, bromide and iodide concentrations from selected coastal marsh plants were measured for nearly a year. Certain halophyte species (i.e. Batis and Frankenia) have very high summer biomass specific production rates for MeX (e.g. Frankenia: 1 ug MeCl /gfwt/hr; 80 ng MeBr/gfwt/hr; 8 ng MeI/gfwt/hr). These rates of MeCl and MeBr production are much higher than those from other coastal marsh plants or seaweeds. Plant halide levels remain high throughout the year, while MeX production peaks at a high level in mid summer falling to low winter rates. This implies a linkage to plant growth. Higher levels of chloride and bromide were seen in the fleshy marsh plants such as Batis (saltwort, approximately 20 percent dry wt chloride, 0.4 percent dry wt bromide) and Salicornia (pickleweed) than in the others such as Frankenia (alkali heath) approx 7 percent dry wt chloride, 0.1 percent dry wt bromide) or Spartina (cordgrass). No such trend was seen for iodide, which ranged from 4 - 10 ppm. Calculations show the daily halide losses from MeX production are far less than the variability in tissue halide content. MeX production removes a small fraction of the total tissue halide from these plants suggesting that MeX production is not a mechanism used by these species to control internal halide levels. Saltwort cell-free extracts incubated with bromide or iodide in the presence of S-adenosyl-L-methionine (SAM) produced the corresponding MeX. MeBr production was inhibited by caffeic acid the substrate of lignin-specific O

  17. Milk-alkali syndrome

    MedlinePlus

    ... this page: //medlineplus.gov/ency/article/000332.htm Milk-alkali syndrome To use the sharing features on this page, please enable JavaScript. Milk-alkali syndrome is a condition in which there ...

  18. Novel studies on the formation and chemical reactivity of compound clusters and their precursors in the gas and liquid phase

    NASA Astrophysics Data System (ADS)

    Bradshaw, James Adam Ferguson

    Presented are four separate and unique studies on molecular and nanoscale systems: Atmospheric hydration and aggregation of NaCl clusters, highly water-soluble aurous-thiolate oligomers, water-soluble gold clusters from aurous-thiolate oligomer precursors, and gold iodide clusters. Adsorption of water on cationic and anionic sodium chloride clusters is investigated to elucidate active sites of molecular interaction as well as primary aggregate formation kinetics. Considered an exceptionally abundant atmospheric species, experiments are conducted to further quantify gas phase chemistry and hydration/solvation of alkali halides. Currently the most soluble of all known gold-thiolates, para-mercaptobenzoic acid-based (pMBA) aurous-thiolate oligomers are investigated and physical and chemical properties quantified. Solubility, structural conformation, and poly-dispersity of higher homologs are observed with the goal of further applications in clusters research, medical and biomedical, and industry. Gold thiolate clusters, synthesized using pMBA-based oligomers, are investigated through reductive formation in solution. UV-VIS and UV-VIS-NIR spectroscopy is undertaken to assign structures based on predictions of the HOMO-LUMO gap and other electronic transitions. Gold iodide is investigated in relation to the common thiolate-halide analogy. Synthesis and characterization of a solid precursor as well as anion and cation cluster formation is presented as part of an ongoing collaboration.

  19. PREPARATION OF HALIDES OF PLUTONIUM

    DOEpatents

    Garner, C.S.; Johns, I.B.

    1958-09-01

    A dry chemical method is described for preparing plutonium halides, which consists in contacting plutonyl nitrate with dry gaseous HCl or HF at an elevated temperature. The addition to the reaction gas of a small quantity of an oxidizing gas or a reducing gas will cause formation of the tetra- or tri-halide of plutonium as desired.

  20. Halide laser glasses

    SciTech Connect

    Weber, M.J.

    1982-01-14

    Energy storage and energy extraction are of prime importance for efficient laser action and are affected by the line strengths and linewidths of optical transitions, excited-state lifetimes, nonradiative decay processes, spectroscopic inhomogeneities, nonlinear refractive index, and damage threshold. These properties are all host dependent. To illustrate this, the spectroscopic properties of Nd/sup 3 +/ have been measured in numerous oxide, oxyhalide, and halide glasses. A table summarizes the reported ranges of stimulated emission cross sections, peak wavelengths, linewidths, and radiative lifetimes associated with the /sup 4/F/sub 3/2/ ..-->.. /sup 4/I/sub 11/2/ lasing transition.

  1. METHOD OF PREPARING METAL HALIDES

    DOEpatents

    Hendrickson, A.V.

    1958-11-18

    The conversion of plutonium halides from plutonium peroxide can be done by washing the peroxide with hydrogen peroxide, drying the peroxide, passing a dry gaseous hydrohalide over the surface of the peroxide at a temperature of about lOO icient laborato C until the reaction rate has stabillzed, and then ralsing the reaction temperature to between 400 and 600 icient laborato C until the conversion to plutonium halide is substantially complete.

  2. Actinide halide complexes

    DOEpatents

    Avens, L.R.; Zwick, B.D.; Sattelberger, A.P.; Clark, D.L.; Watkin, J.G.

    1992-11-24

    A compound is described of the formula MX[sub n]L[sub m] wherein M is a metal atom selected from the group consisting of thorium, plutonium, neptunium or americium, X is a halide atom, n is an integer selected from the group of three or four, L is a coordinating ligand selected from the group consisting of aprotic Lewis bases having an oxygen-, nitrogen-, sulfur-, or phosphorus-donor, and m is an integer selected from the group of three or four for monodentate ligands or is the integer two for bidentate ligands, where the sum of n+m equals seven or eight for monodentate ligands or five or six for bidentate ligands. A compound of the formula MX[sub n] wherein M, X, and n are as previously defined, and a process of preparing such actinide metal compounds are described including admixing the actinide metal in an aprotic Lewis base as a coordinating solvent in the presence of a halogen-containing oxidant.

  3. Actinide halide complexes

    DOEpatents

    Avens, Larry R.; Zwick, Bill D.; Sattelberger, Alfred P.; Clark, David L.; Watkin, John G.

    1992-01-01

    A compound of the formula MX.sub.n L.sub.m wherein M is a metal atom selected from the group consisting of thorium, plutonium, neptunium or americium, X is a halide atom, n is an integer selected from the group of three or four, L is a coordinating ligand selected from the group consisting of aprotic Lewis bases having an oxygen-, nitrogen-, sulfur-, or phosphorus-donor, and m is an integer selected from the group of three or four for monodentate ligands or is the integer two for bidentate ligands, where the sum of n+m equals seven or eight for monodentate ligands or five or six for bidentate ligands, a compound of the formula MX.sub.n wherein M, X, and n are as previously defined, and a process of preparing such actinide metal compounds including admixing the actinide metal in an aprotic Lewis base as a coordinating solvent in the presence of a halogen-containing oxidant, are provided.

  4. Solid state cell with alkali metal halo-alkali thiocyanate electrolyte

    SciTech Connect

    Rao, B. M.; Silbernagel, B. G.

    1980-02-26

    A novel electrochemical cell is disclosed utilizing: (A) an anode which contains an alkali metal as an anode-active material; (B) a cathode and (C) an electrolyte comprising an electrolytically effective amount of one or more compounds having the formula: (Ax)ma'scn wherein a is an alkali metal, X is a halogen, a' is an alkali metal and 0.1 < or = N < or = 10. Preferred systems include lithium-containing anodes, lithium-containing electrolytes and cathodes which contain cathode-active material selected from the group consisting of cathode-active sulfurs, halogens, halides, chromates, phosphates, oxides and chalcogenides, especially those chalcogenides of the empirical formula mzm wherein M is one or more metals selected from the group consisting of iron, titanium, zirconium, hafnium, niobium, tantalum and vanadium, Z is one or more chalcogens selected from the group consisting of oxygen, sulfur, selenium and tellurium, and M is a numerical value between about 1.8 and about 3.2.

  5. Elucidation of transport mechanism and enhanced alkali ion transference numbers in mixed alkali metal-organic ionic molten salts.

    PubMed

    Chen, Fangfang; Forsyth, Maria

    2016-07-28

    Mixed salts of Ionic Liquids (ILs) and alkali metal salts, developed as electrolytes for lithium and sodium batteries, have shown a remarkable ability to facilitate high rate capability for lithium and sodium electrochemical cycling. It has been suggested that this may be due to a high alkali metal ion transference number at concentrations approaching 50 mol% Li(+) or Na(+), relative to lower concentrations. Computational investigations for two IL systems illustrate the formation of extended alkali-anion aggregates as the alkali metal ion concentration increases. This tends to favor the diffusion of alkali metal ions compared with other ionic species in electrolyte solutions; behavior that has recently been reported for Li(+) in a phosphonium ionic liquid, thus an increasing alkali transference number. The mechanism of alkali metal ion diffusion via this extended coordination environment present at high concentrations is explained and compared to the dynamics at lower concentrations. Heterogeneous alkali metal ion dynamics are also evident and, somewhat counter-intuitively, it appears that the faster ions are those that are generally found clustered with the anions. Furthermore these fast alkali metal ions appear to correlate with fastest ionic liquid solvent ions. PMID:27375042

  6. Radiochemical synthesis of pure anhydrous metal halides

    NASA Technical Reports Server (NTRS)

    Philipp, W. H.; Marsik, S. J.; May, C. E.

    1973-01-01

    Method uses radiation chemistry as practical tool for inorganic preparations and in particular deposition of metals by irradiation of their aqueous metal salt solutions with high energy electrons. Higher valence metal halide is dissolved in organic liquid and exposed to high energy electrons. This causes metal halide to be reduced to a lower valence metal halide.

  7. Preparation of cerium halide solvate complexes

    DOEpatents

    Vasudevan, Kalyan V; Smith, Nickolaus A; Gordon, John C; McKigney, Edward A; Muenchaussen, Ross E

    2013-08-06

    Crystals of a solvated cerium(III) halide solvate complex resulted from a process of forming a paste of a cerium(III) halide in an ionic liquid, adding a solvent to the paste, removing any undissolved solid, and then cooling the liquid phase. Diffusing a solvent vapor into the liquid phase also resulted in crystals of a solvated cerium(III) halide complex.

  8. Alkali metal ionization detector

    DOEpatents

    Bauerle, James E.; Reed, William H.; Berkey, Edgar

    1978-01-01

    Variations in the conventional filament and collector electrodes of an alkali metal ionization detector, including the substitution of helical electrode configurations for either the conventional wire filament or flat plate collector; or, the substitution of a plurality of discrete filament electrodes providing an in situ capability for transferring from an operationally defective filament electrode to a previously unused filament electrode without removing the alkali metal ionization detector from the monitored environment. In particular, the helical collector arrangement which is coaxially disposed about the filament electrode, i.e. the thermal ionizer, provides an improved collection of positive ions developed by the filament electrode. The helical filament design, on the other hand, provides the advantage of an increased surface area for ionization of alkali metal-bearing species in a monitored gas environment as well as providing a relatively strong electric field for collecting the ions at the collector electrode about which the helical filament electrode is coaxially positioned. Alternatively, both the filament and collector electrodes can be helical. Furthermore, the operation of the conventional alkali metal ionization detector as a leak detector can be simplified as to cost and complexity, by operating the detector at a reduced collector potential while maintaining the sensitivity of the alkali metal ionization detector adequate for the relatively low concentration of alkali vapor and aerosol typically encountered in leak detection applications.

  9. Atomic forces between noble gas atoms, alkali ions, and halogen ions for surface interactions

    NASA Technical Reports Server (NTRS)

    Wilson, J. W.; Outlaw, R. A.; Heinbockel, J. H.

    1988-01-01

    The components of the physical forces between noble gas atoms, alkali ions, and halogen ions are analyzed and a data base developed from analysis of the two-body potential data, the alkali-halide molecular data, and the noble gas crystal and salt crystal data. A satisfactory global fit to this molecular and crystal data is then reproduced by the model to within several percent. Surface potentials are evaluated for noble gas atoms on noble gas surfaces and salt crystal surfaces with surface tension neglected. Within this context, the noble gas surface potentials on noble gas and salt crystals are considered to be accurate to within several percent.

  10. Correlation of structure and solid state emission properties of anionic copper(I) halide complexes

    NASA Astrophysics Data System (ADS)

    Nurtaeva, Aliya Kamidollovna

    The correlation of emission properties with structural characteristics of solid state copper (I) halide complexes, supported by ab initio calculations, has been the focus of this work. Twenty-four new anionic Cu (I)---iodide complexes with alkali and alkaline earth metals complexed crown ethers as cations have been synthesized and characterized by single crystal diffraction. The complexes belong to 4 different groups: (1) Cu2I 42-, (2) Cu4I6 2-, (3) polymeric CupIq-(q-p) species and (4) simple iodides. The first two groups emit at room temperature when excited in the ultraviolet. The wavelength of maximum emission varies with the symmetry elements present in the crystalline cluster. Four different Cu2I42-rhombs were seen: (1) flat with a center of symmetry---452--453 nm; (2) bent---675 nm (640 nm---shoulder); (3) 2/m symmetry---479 nm and (4) a mixture of flat and bent---474--478 (with long wavelength tail). Ab initio calculations identified the electronic transition, responsible for excitation of the centrosymmetric cluster Cu2I4 2- to be: 26 (Au) → 29 or 31 (Ag) followed by reemission to the ground state. For the bent cluster the corresponding electron transition are HOMO (26) → LUMO (27) for excitation and HOMO (26) → LUMO (27) for emission. The energy gap between these neighboring orbitals is smaller than that for complexes of type I, which explains the relative position of bands in luminescence spectra. Mixed complexes (type 4), containing both types of Cu2I42- units, possess an asymmetrical emission band comprised of both type 1 and type 2 bands. Three hexaiodotetracuprates(I), emitting at 519--524 nm, possess a crystallographic center of symmetry in the center of disordered cluster. While the disorder results in centrosymmetric species, the emitting tetrahedron Cu4I6 is not centrosymmetric. There are no forbidden transitions for this motif. Nine polymeric species (Cu2I3-, Cu 4I6-2 and Cu5I7 -2) are non-emitting at both ambient and low temperature

  11. Apparatus enables accurate determination of alkali oxides in alkali metals

    NASA Technical Reports Server (NTRS)

    Dupraw, W. A.; Gahn, R. F.; Graab, J. W.; Maple, W. E.; Rosenblum, L.

    1966-01-01

    Evacuated apparatus determines the alkali oxide content of an alkali metal by separating the metal from the oxide by amalgamation with mercury. The apparatus prevents oxygen and moisture from inadvertently entering the system during the sampling and analytical procedure.

  12. Development of Halide and Oxy-Halides for Isotopic Separations

    SciTech Connect

    Leigh R. Martin; Aaron T. Johnson; Jana Pfeiffer; Martha R. Finck

    2014-10-01

    The goal of this project was to synthesize a volatile form of Np for introduction into mass spectrometers at INL. Volatile solids of the 5f elements are typically those of the halides (e.g. UF6), however fluorine is highly corrosive to the sensitive internal components of the mass separator, and the other volatile halides exist as several different stable isotopes in nature. However, iodide is both mono-isotopic and volatile, and as such presents an avenue for creation of a form of Np suitable for introduction into the mass separator. To accomplish this goal, the technical work in the project sought to establish a novel synthetic route for the conversion NpO2+ (dissolved in nitric acid) to NpI3 and NpI4.

  13. Alkalis and Skin.

    PubMed

    Greenwood, John E; Tan, Jin Lin; Ming, Justin Choong Tzen; Abell, Andrew D

    2016-01-01

    The aim of this editorial is to provide an overview of the chemical interactions occurring in the skin of our patients on contact with alkaline agents. Strongly basic alkali is highly aggressive and will readily hydrolyze (or cleave) key biological molecules such as lipids and proteins. This phenomenon is known as saponification in the case of lipids and liquefactive denaturation for peptides and proteins. A short section on current first-aid concepts is included. A better understanding of the basic science behind alkali burns will make us better teachers and provide an insight into the urgency needed in treating these common and dangerous chemical injuries. PMID:26182072

  14. The effect of low solublility organic acids on the hygroscopicity of sodium halide aerosols

    NASA Astrophysics Data System (ADS)

    Miñambres, L.; Méndez, E.; Sánchez, M. N.; Castaño, F.; Basterretxea, F. J.

    2014-02-01

    In order to accurately assess the influence of fatty acids on the hygroscopic and other physicochemical properties of sea salt aerosols, hexanoic, octanoic or lauric acid together with sodium halide salts (NaCl, NaBr and NaI) have been chosen to be performed in this study. The hygroscopic properties of sodium halide submicrometer particles covered with organic acids have been examined by Fourier-transform infrared spectroscopy in an aerosol flow cell. Covered particles were generated by flowing atomized sodium halide particles (either dry or aqueous) through a heated oven containing the gaseous acid. The obtained results indicate that gaseous organic acids easily nucleate onto dry and aqueous sodium halide particles. On the other hand, Scanning Electron Microscopy (SEM) images indicate that lauric acid coating on NaCl particles makes them to aggregate in small clusters. The hygroscopic behaviour of covered sodium halide particles in deliquescence mode shows different features with the exchange of the halide ion: whereas the organic covering has little effect in NaBr particles, NaCl and NaI covered particles change their deliquescence relative humidities, with different trends observed for each of the acids studied. In efflorescence mode, the overall effect of the organic covering is to retard the loss of water in the particles. It has been observed that the presence of gaseous water in heterogeneously nucleated particles tends to displace the cover of hexanoic acid to energetically stabilize the system.

  15. The effect of low solubility organic acids on the hygroscopicity of sodium halide aerosols

    NASA Astrophysics Data System (ADS)

    Miñambres, L.; Méndez, E.; Sánchez, M. N.; Castaño, F.; Basterretxea, F. J.

    2014-10-01

    In order to accurately assess the influence of fatty acids on the hygroscopic and other physicochemical properties of sea salt aerosols, hexanoic, octanoic or lauric acid together with sodium halide salts (NaCl, NaBr and NaI) have been chosen to be investigated in this study. The hygroscopic properties of sodium halide sub-micrometre particles covered with organic acids have been examined by Fourier-transform infrared spectroscopy in an aerosol flow cell. Covered particles were generated by flowing atomized sodium halide particles (either dry or aqueous) through a heated oven containing the gaseous acid. The obtained results indicate that gaseous organic acids easily nucleate onto dry and aqueous sodium halide particles. On the other hand, scanning electron microscopy (SEM) images indicate that lauric acid coating on NaCl particles makes them to aggregate in small clusters. The hygroscopic behaviour of covered sodium halide particles in deliquescence mode shows different features with the exchange of the halide ion, whereas the organic surfactant has little effect in NaBr particles, NaCl and NaI covered particles experience appreciable shifts in their deliquescence relative humidities, with different trends observed for each of the acids studied. In efflorescence mode, the overall effect of the organic covering is to retard the loss of water in the particles. It has been observed that the presence of gaseous water in heterogeneously nucleated particles tends to displace the cover of hexanoic acid to energetically stabilize the system.

  16. Alkali metal ion battery with bimetallic electrode

    SciTech Connect

    Boysen, Dane A; Bradwell, David J; Jiang, Kai; Kim, Hojong; Ortiz, Luis A; Sadoway, Donald R; Tomaszowska, Alina A; Wei, Weifeng; Wang, Kangli

    2015-04-07

    Electrochemical cells having molten electrodes having an alkali metal provide receipt and delivery of power by transporting atoms of the alkali metal between electrode environments of disparate chemical potentials through an electrochemical pathway comprising a salt of the alkali metal. The chemical potential of the alkali metal is decreased when combined with one or more non-alkali metals, thus producing a voltage between an electrode comprising the molten the alkali metal and the electrode comprising the combined alkali/non-alkali metals.

  17. Methods of recovering alkali metals

    DOEpatents

    Krumhansl, James L; Rigali, Mark J

    2014-03-04

    Approaches for alkali metal extraction, sequestration and recovery are described. For example, a method of recovering alkali metals includes providing a CST or CST-like (e.g., small pore zeolite) material. The alkali metal species is scavenged from the liquid mixture by the CST or CST-like material. The alkali metal species is extracted from the CST or CST-like material.

  18. 40 CFR 721.4095 - Quaternary ammonium alkyltherpropyl trialkylamine halides.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... trialkylamine halides. 721.4095 Section 721.4095 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.4095 Quaternary ammonium alkyltherpropyl trialkylamine halides. (a... generically as quaternary ammonium alkyltherpropyl trialkylamine halides (PMNs...

  19. TRANSURANIC METAL HALIDES AND A PROCESS FOR THE PRODUCTION THEREOF

    DOEpatents

    Fried, S.

    1951-03-20

    Halides of transuranic elements are prepared by contacting with aluminum and a halogen, or with an aluminum halide, a transuranic metal oxide, oxyhalide, halide, or mixture thereof at an elevated temperature.

  20. Chlor-Alkali Technology.

    ERIC Educational Resources Information Center

    Venkatesh, S.; Tilak, B. V.

    1983-01-01

    Chlor-alkali technology is one of the largest electrochemical industries in the world, the main products being chlorine and caustic soda (sodium hydroxide) generated simultaneously by the electrolysis of sodium chloride. This technology is reviewed in terms of electrochemical principles and manufacturing processes involved. (Author/JN)

  1. Hydrothermal alkali metal recovery process

    DOEpatents

    Wolfs, Denise Y.; Clavenna, Le Roy R.; Eakman, James M.; Kalina, Theodore

    1980-01-01

    In a coal gasification operation or similar conversion process carried out in the presence of an alkali metal-containing catalyst wherein solid particles containing alkali metal residues are produced, alkali metal constituents are recovered from the particles by treating them with a calcium or magnesium-containing compound in the presence of water at a temperature between about 250.degree. F. and about 700.degree. F. and in the presence of an added base to establish a pH during the treatment step that is higher than would otherwise be possible without the addition of the base. During the treating process the relatively high pH facilitates the conversion of water-insoluble alkali metal compounds in the alkali metal residues into water-soluble alkali metal constituents. The resultant aqueous solution containing water-soluble alkali metal constituents is then separated from the residue solids, which consist of the treated particles and any insoluble materials formed during the treatment step, and recycled to the gasification process where the alkali metal constituents serve as at least a portion of the alkali metal constituents which comprise the alkali metal-containing catalyst. Preferably, the base that is added during the treatment step is an alkali metal hydroxide obtained by water washing the residue solids produced during the treatment step.

  2. Simple model potential and model wave functions for (H-alkali)+ and (alkali-alkali)+ ions

    NASA Astrophysics Data System (ADS)

    Patil, S. H.; Tang, K. T.

    2000-07-01

    A simple model potential is proposed to describe the interaction of a valence electron with the alkali core, which incorporates the correct asymptotic behavior in terms of dipolar polarizabilities, and the short-range exchange effects in terms of a hard core adjusted to give the correct energy for the valence electron. Based on this potential, simple wave functions are developed to describe the (H-alkali)+ and (alkali-alkali)+ ions. These wave functions exhibit some important structures of the ions, and provide a universal description of the properties of all (H-alkali)+ and (alkali-alkali)+ ions, in particular, the equilibrium separations of the nuclei and the corresponding dissociation energies. They also allow us to calculate the dipolar polarizabilities of Li2+, Na2+, K2+, Rb2+, and Cs2+.

  3. Multiple-Wavelength Metal/Halide Laser

    NASA Technical Reports Server (NTRS)

    Nerheim, N. M.

    1984-01-01

    Single device produces multiple lasing lines. Laser capable of producing many lasing lines has several reservoirs of halide lasant mixed with chlorides of copper, manganese and iron. Convection-control technique possible to rapidly change from one metal halide to another at maximum energy.

  4. Alkali-vapor lasers

    NASA Astrophysics Data System (ADS)

    Zweiback, J.; Komashko, A.; Krupke, W. F.

    2010-02-01

    We report on the results from several of our alkali laser systems. We show highly efficient performance from an alexandrite-pumped rubidium laser. Using a laser diode stack as a pump source, we demonstrate up to 145 W of average power from a CW system. We present a design for a transversely pumped demonstration system that will show all of the required laser physics for a high power system.

  5. The effects of dissolved halide anions on hydrogen bonding in liquid water.

    PubMed

    Smith, Jared D; Saykally, Richard J; Geissler, Phillip L

    2007-11-14

    It is widely believed that the addition of salts to water engenders structural changes in the hydrogen-bond network well beyond the adjacent shell of solvating molecules. Classification of many ions as "structure makers" and "structure breakers" has been based in part on corresponding changes in the vibrational spectra (Raman and IR). Here we show that changes in O-H vibrational spectra induced by the alkali halides in liquid water result instead from the actions of ions' electric fields on adjacent water molecules. Computer simulations that accurately reproduce our experimental measurements suggest that the statistics of hydrogen-bond strengths are only weakly modified beyond this first solvation shell. PMID:17958418

  6. Hygroscopicity Evaluation of Halide Scintillators

    SciTech Connect

    Zhuravleva, M; Stand, L; Wei, H; Hobbs, C. L.; Boatner, Lynn A; Ramey, Joanne Oxendine; Burger, Arnold; Rowe, E; Bhattacharya, P.; Tupitsyn, E; Melcher, Charles L

    2014-01-01

    A collaborative study of relative hygroscopicity of anhydrous halide scintillators grown at various laboratories is presented. We have developed a technique to evaluate moisture sensitivity of both raw materials and grown crystals, in which the moisture absorption rate is measured using a gravimetric analysis. Degradation of the scintillation performance was investigated by recording gamma-ray spectra and monitoring the photopeak position, count rate and energy resolution. The accompanying physical degradation of the samples exposed to ambient atmosphere was photographically recorded as well. The results were compared with ben

  7. Modification of alkali metals on silicon-based nanoclusters: An enhanced nonlinear optical response

    NASA Astrophysics Data System (ADS)

    Li, Xiaojun; Han, Quan; Yang, Xiaohui; Song, Ruijuan; Song, Limei

    2016-08-01

    Structures, chemical stabilities and nonlinear optical properties of alkali metals-adsorbed niobium-doped silicon (M@SinNb+) clusters are investigated using the DFT methods. The alkali metals prefer energetically to be attached as bridged bond rather than M-Si single bond in most of optimized structures. Adsorption of alkali metals on doped silicon clusters gradually enhances their chemical stabilities with increasing cluster size. Noteworthily, the first hyperpolarizabilities (βtot) of the M@SinNb+ clusters, obtained by using the long-range corrected CAM-B3LYP functional, are large enough to establish their strong nonlinear optical behavior, especially for M@Si9Nb+ (M = Li, Na, and K), and the enhanced βtot ordering by alkali metals is Na > K > Li.

  8. Impurity segregation in zone-refined precursors for crystalline halide scintillators

    NASA Astrophysics Data System (ADS)

    Swider, S.; Lam, S.; Motakef, S.; Donohoe, E.; Coers, L.; Taylor, S.; Spencer, S.

    2015-06-01

    Successful growth of halide scintillator crystals depends on a supply of ultra-high purity (UHP) precursor materials. Metallic interstitials and substitutions may provide traps that quench luminescence. Oxygen impurities can create competing compounds within a matrix, such as oxyhalides, that disrupt crystallinity and nucleate cracks. Using mass spectroscopy and oxygen combustion analysis, we analyzed impurities in SrI2, EuI2, and YCl3 precursors before and after zone refining. The data show most alkali and alkali earth impurities segregated easily. However, with the exception of iron, many transition metals were incorporated into the solid. Reliable oxygen measurements proved difficult to achieve. Additional oxygen was measured in nitrates and sulfates, via ion chromatography. Zone refining reduced the overall impurity content, but levels remained above a 10 ppm target.

  9. Shallow halogen vacancies in halide optoelectronic materials

    DOE PAGESBeta

    Shi, Hongliang; Du, Mao -Hua

    2014-11-05

    Halogen vacancies (VH) are usually deep color centers (F centers) in halides and can act as major electron traps or recombination centers. The deep VH contributes to the typically poor carrier transport properties in halides. However, several halides have recently emerged as excellent optoelectronic materials, e.g., CH3NH3PbI3 and TlBr. Both CH3NH3PbI3 and TlBr have been found to have shallow VH, in contrast to commonly seen deep VH in halides. In this paper, several halide optoelectronic materials, i.e., CH3NH3PbI3, CH3NH3SnI3 (photovoltaic materials), TlBr, and CsPbBr3, (gamma-ray detection materials) are studied to understand the material chemistry and structure that determine whether VHmore » is a shallow or deep defect in a halide material. It is found that crystal structure and chemistry of ns2 ions both play important roles in creating shallow VH in halides such as CH3NH3PbI3, CH3NH3SnI3, and TlBr. The key to identifying halides with shallow VH is to find the right crystal structures and compounds that suppress cation orbital hybridization at VH, such as those with long cation-cation distances and low anion coordination numbers, and those with crystal symmetry that prevents strong hybridization of cation dangling bond orbitals at VH. Furthermore, the results of this paper provide insight and guidance to identifying halides with shallow VH as good electronic and optoelectronic materials.« less

  10. Shallow halogen vacancies in halide optoelectronic materials

    NASA Astrophysics Data System (ADS)

    Shi, Hongliang; Du, Mao-Hua

    2014-11-01

    Halogen vacancies (VH ) are usually deep color centers (F centers) in halides and can act as major electron traps or recombination centers. The deep VH contributes to the typically poor carrier transport properties in halides. However, several halides have recently emerged as excellent optoelectronic materials, e.g., C H3N H3Pb I3 and TlBr. Both C H3N H3Pb I3 and TlBr have been found to have shallow VH , in contrast to commonly seen deep VH in halides. In this paper, several halide optoelectronic materials, i.e., C H3N H3Pb I3 , C H3N H3Sn I3 (photovoltaic materials), TlBr, and CsPbB r3 (gamma-ray detection materials) are studied to understand the material chemistry and structure that determine whether VH is a shallow or deep defect in a halide material. It is found that crystal structure and chemistry of n s2 ions both play important roles in creating shallow VH in halides such as C H3N H3Pb I3 , C H3N H3Sn I3 , and TlBr. The key to identifying halides with shallow VH is to find the right crystal structures and compounds that suppress cation orbital hybridization at VH , such as those with large cation-cation distances and low anion coordination numbers and those with crystal symmetry that prevents strong hybridization of cation dangling bond orbitals at VH . The results of this paper provide insight and guidance to identifying halides with shallow VH as good electronic and optoelectronic materials.

  11. Cross-Electrophile Coupling of Vinyl Halides with Alkyl Halides.

    PubMed

    Johnson, Keywan A; Biswas, Soumik; Weix, Daniel J

    2016-05-23

    An improved method for the reductive coupling of aryl and vinyl bromides with alkyl halides that gave high yields for a variety of substrates at room temperature with a low (2.5 to 0.5 mol %) catalyst loading is presented. Under the optimized conditions, difficult substrates, such as unhindered alkenyl bromides, can be coupled to give the desired olefins with minimal diene formation and good stereoretention. These improved conditions also worked well for aryl bromides. For example, a gram-scale reaction was demonstrated with 0.5 mol % catalyst loading, whereas reactions at 10 mol % catalyst loading completed in as little as 20 minutes. Finally, a low-cost single-component pre-catalyst, (bpy)NiI2 (bpy=2,2'-bipyridine) that is both air- and moisture-stable over a period of months was introduced. PMID:27017436

  12. New halide-centered discrete Ag(I)(8) cubic clusters containing diselenophosphate ligands, [Ag(8)(X)[Se(2)P(OR)(2)](6)](PF(6)) (X = Cl, Br; R = Et, Pr, (i)Pr): syntheses, structures, and DFT calculations.

    PubMed

    Liu, C W; Haia, Hsien-Chung; Hung, Chiu-Mine; Santra, Bidyut Kumar; Liaw, Ben-Jie; Lin, Zhenyang; Wang, Ju-Chun

    2004-07-12

    Six clusters Ag(8)(micro(8)-X)[Se(2)P(OR)(2)](6)(PF(6)) (R = Et, X = Cl, 1a, X = Br, 1b; R = Pr, X = Cl, 2a, X = Br, 2b; R = (i)Pr, X = Cl, 3a, X = Br, 3b) were isolated from the reaction of [Ag(CH(3)CN)(4)](PF(6)), NH(4)[Se(2)P(OR)(2)], and Bu(4)NX in a molar ratio of 4:3:1 in CH(2)X(2). Positive FAB mass spectra show m/z peaks at 2573.2 for 1a, 2617.3 for 1b, 2740.9 for 2a, 2786.9 for 2b, 2742.3 for 3a, and 2787.0 for 3b due to respective molecular cation, (M - PF(6))(+). (31)P NMR spectra of 1a-3b display a singlet at delta 82.3, 81.5, 82.9, 81.7, 76.3, and 75.8 ppm with a set of satellites (J(PSe) = 661, 664, 652, 652, 656, and 656 Hz, respectively). The X-ray structure (1a-2b) consists of a discrete cationic cluster in which eight silver ions are linked by six diselenophosphate ligands and a central micro(8)-Cl or micro(8)-Br ion with a noncoordinating PF(6)(-) anion. The shape of the molecule is a halide-centered distorted Ag(8) cubic cluster. The dsep ligand exhibits a tetrametallic tetraconnective (micro(2), micro(2)) coordination pattern, and each caps on a square face of the cube. Each silver atom of the cube is coordinated by three selenium atoms and the central chloride or bromide ion. Additionally, molecular orbital calculations at the B3LYP level of the density functional theory have been carried out to study the Ag-micro(8)-X (X = Cl, Br) interactions for cluster cations [Ag(8)(micro(8)-X)[Se(2)P(OR)(2)](6)](+). Calculations show very weak bonding interactions exist between micro(8)-X and Ag atoms of the cube. PMID:15236560

  13. PROCESS OF RECOVERING ALKALI METALS

    DOEpatents

    Wolkoff, J.

    1961-08-15

    A process is described of recovering alkali metal vapor by sorption on activated alumina, activated carbon, dehydrated zeolite, activated magnesia, or Fuller's earth preheated above the vaporization temperature of the alkali metal and subsequent desorption by heating the solvent under vacuum. (AEC)

  14. Preparation of alkali metal dispersions

    NASA Technical Reports Server (NTRS)

    Rembaum, A.; Landel, R. F. (Inventor)

    1968-01-01

    A method is described for producing alkali metal dispersions of high purity. The dispersions are prepared by varying the equilibrium solubility of the alkali metal in a suitable organic solvent in the presence of aromatic hydrocarbons. The equilibrium variation is produced by temperature change. The size of the particles is controlled by controlling the rate of temperature change.

  15. Purification of alkali metal nitrates

    DOEpatents

    Fiorucci, Louis C.; Gregory, Kevin M.

    1985-05-14

    A process is disclosed for removing heavy metal contaminants from impure alkali metal nitrates containing them. The process comprises mixing the impure nitrates with sufficient water to form a concentrated aqueous solution of the impure nitrates, adjusting the pH of the resulting solution to within the range of between about 2 and about 7, adding sufficient reducing agent to react with heavy metal contaminants within said solution, adjusting the pH of the solution containing reducing agent to effect precipitation of heavy metal impurities and separating the solid impurities from the resulting purified aqueous solution of alkali metal nitrates. The resulting purified solution of alkali metal nitrates may be heated to evaporate water therefrom to produce purified molten alkali metal nitrate suitable for use as a heat transfer medium. If desired, the purified molten form may be granulated and cooled to form discrete solid particles of alkali metal nitrates.

  16. Toxicity of organometal halide perovskite solar cells

    NASA Astrophysics Data System (ADS)

    Babayigit, Aslihan; Ethirajan, Anitha; Muller, Marc; Conings, Bert

    2016-03-01

    In the last few years, the advent of metal halide perovskite solar cells has revolutionized the prospects of next-generation photovoltaics. As this technology is maturing at an exceptional rate, research on its environmental impact is becoming increasingly relevant.

  17. Hydrogen Halides on Jupiter and Saturn

    NASA Astrophysics Data System (ADS)

    Showman, Adam P.

    2001-07-01

    The quest to detect gaseous HCl, HBr, and HF in the atmospheres of Jupiter and Saturn has led to a tentative detection of 1 ppb HCl near Saturn's cloud deck. The detection is puzzling because, while these hydrogen halides may be present several scale heights below the clouds, they are expected to react with ammonia to form solid ammonium halide salts in the upper troposphere. I show that the loss timescale for condensation of gaseous hydrogen halides onto particles is ˜10 3-10 5 s for realistic cloud densities and particle sizes, which is much less than the ˜10 8 s residence time of upper tropospheric air. The hydrogen halides can only survive transport up to the cloud layer if less than 1 in 10 6 of their collisions with particle surfaces leads to condensation, which is unlikely. Even in the absence of foreign particles, homogeneous nucleation would probably prevent supersaturations in excess of a few hundred, which is ˜10 20-10 40 times too low to explain the observation. These calculations therefore suggest that hydrogen halides cannot exist at part-per-billion levels in the upper troposphere. The interplanetary source of halogens is also too low to produce detectable quantities of hydrogen halides except perhaps at pressures less than 1 mbar. A possible detection of chlorine by the Galileo probe at pressures exceeding 9 bars on Jupiter may be consistent with the equilibrium abundance of gaseous HCl or NH 4Cl.

  18. Physiological Evaluation of Alkali-Salt Tolerance of Thirty Switchgrass (Panicum virgatum) Lines.

    PubMed

    Hu, Guofu; Liu, Yiming; Zhang, Xunzhong; Yao, Fengjiao; Huang, Yan; Ervin, Erik H; Zhao, Bingyu

    2015-01-01

    Soil salt-alkalization is a major limiting factor for crop production in many regions. Switchgrass (Panicum virgatum L.) is a warm-season C4 perennial rhizomatous bunchgrass and a target lignocellulosic biofuel species. The objective of this study was to evaluate relative alkali-salt tolerance among 30 switchgrass lines. Tillers of each switchgrass line were transplanted into pots filled with fine sand. Two months after transplanting, plants at E5 developmental stage were grown in either half strength Hoagland's nutrient solution with 0 mM Na+ (control) or half strength Hoagland's nutrient solution with 150 mM Na+ and pH of 9.5 (alkali-salt stress treatment) for 20 d. Alkali-salt stress damaged cell membranes [higher electrolyte leakage (EL)], reduced leaf relative water content (RWC), net photosynthetic rate (Pn), stomatal conductance (gs), and transpiration rate (Tr). An alkali-salt stress tolerance trait index (ASTTI) for each parameter was calculated based on the ratio of the value under alkali-salt stress and the value under non-stress conditions for each parameter of each line. Relative alkali-salt tolerance was determined based on principal components analysis and cluster analysis of the physiological parameters and their ASTTI values. Significant differences in alkali-salt stress tolerance were found among the 30 lines. Lowland lines TEM-SEC, Alamo, TEM-SLC and Kanlow were classified as alkali-salt tolerant. In contrast, three lowland lines (AM-314/MS-155, BN-13645-64) and two upland lines (Caddo and Blackwell-1) were classified as alkali-salt sensitive. The results suggest wide variations exist in alkali-salt stress tolerance among the 30 switchgrass lines. The approach of using a combination of principal components and cluster analysis of the physiological parameters and related ASTTI is feasible for evaluating alkali-salt tolerance in switchgrass. PMID:26146987

  19. Dimming of metal halide lamps

    NASA Technical Reports Server (NTRS)

    Schurer, Kees

    1994-01-01

    We ran some tests on the effect of dimming of metal halide (MH) lamps upon the stability and the spectral quality of the light output. Lamps used were a new Philips lamp HPI-T 250W, a similar Philips lamp with a few thousand burning hours and a new Osram lamp HQI-T 250W/D. The ballast was a BBC type DJ 250/2KS, the starter a BAS TORGI type MZN 250 SE and the dimmer an Elstrom Control System type ERHQ-T 250. Power was derived from a Philips stabilizer, type PE 1602. Lamp output was monitored with a PAR meter. Spectra were taken at 100% and at 50% output as measured with the PAR meter. Lamps were allowed to stabilize at any setting for 30 minutes before measurements were made. Lamp manufacturers advise against dimming for fear of poor stability and intolerable changes of the spectrum. However, none of the lamps showed a decrease in stability, no flicker or wandering of the discharge, and the changes of the spectrum were not negligible, but certainly not dramatic. Lamps of either manufacture retain their white color, relative peak heights of spectral lines did shift, but no gaps in the spectrum occurred. Spectra taken at 50% with 30 minutes intervals coincided. Differences between the new and the older Philips lamp were noticeable, but not really significant.

  20. Photokeratitis Linked to Metal Halide Bulbs in Two Gymnasiums - Philadelphia, Pennsylvania, 2011 and 2013.

    PubMed

    Finn, Lauren E; Gutowski, Jennifer; Alles, Steve; Mirowitz, Naomi; Johnson, Caroline; Osterhoudt, Kevin C; Patel, Ami

    2016-01-01

    In December 2011 and December 2013, the Philadelphia Department of Public Health (PDPH) received separate reports of clusters of photokeratitis linked to gymnasium events. Photokeratitis, a painful eye condition resulting from unprotected exposure to ultraviolet radiation, has previously been linked to metal halide lamps with broken outer envelopes (1,2). To investigate the cause of these clusters and further characterize patients with photokeratitis, PDPH administered questionnaires to potentially exposed persons, established a case definition, and conducted environmental assessments of both gymnasiums. Because event attendee registration information was available, a cohort study was conducted to evaluate the 2011 cluster of 242 persons who met the photokeratitis case definition. A case-series investigation was conducted to evaluate the 2013 cluster of 20 persons who met the photokeratitis case definition for that event. These investigations indicated that Type R metal halide bulbs with broken outer envelopes found in both gymnasiums were the probable cause of the photokeratitis. The Food and Drug Administration has made a number of recommendations regarding the use of metal halide bulbs in facilities where bulbs are at elevated risk for breaking, such as schools and indoor sports facilities (3). Because Type R metal halide lamps do not self-extinguish once the outer envelope is broken, these bulbs should be removed from settings with a high risk for outer envelope rupture, such as gymnasiums, or should be placed within enclosed fixtures. In instances where these bulbs cannot be exchanged for self-extinguishing lamps, Type R lamps with a broken outer envelope should be replaced immediately to limit exposure to ultraviolet radiation. A broken outer envelope can be detected by the presence of glass on the floor, or visual examination of the bulb when the power is turned off. A broken outer envelope is difficult to detect when the lamp is emitting light. PMID

  1. Upgrading platform using alkali metals

    SciTech Connect

    Gordon, John Howard

    2014-09-09

    A process for removing sulfur, nitrogen or metals from an oil feedstock (such as heavy oil, bitumen, shale oil, etc.) The method involves reacting the oil feedstock with an alkali metal and a radical capping substance. The alkali metal reacts with the metal, sulfur or nitrogen content to form one or more inorganic products and the radical capping substance reacts with the carbon and hydrogen content to form a hydrocarbon phase. The inorganic products may then be separated out from the hydrocarbon phase.

  2. The Remarkable Reactivity of Aryl Halides with Nucleophiles

    ERIC Educational Resources Information Center

    Bunnett, Joseph F.

    1974-01-01

    Discusses the reactivity of aryl halides with nucleophilic or basic reagents, including nucleophilic attacks on carbon, hydrogen, halogen, and arynes. Suggestions are made concerning revisions of the sections on aryl halide chemistry courses and the corresponding chapters in textbooks. (CC)

  3. Shallow halogen vacancies in halide optoelectronic materials

    SciTech Connect

    Shi, Hongliang; Du, Mao -Hua

    2014-11-05

    Halogen vacancies (VH) are usually deep color centers (F centers) in halides and can act as major electron traps or recombination centers. The deep VH contributes to the typically poor carrier transport properties in halides. However, several halides have recently emerged as excellent optoelectronic materials, e.g., CH3NH3PbI3 and TlBr. Both CH3NH3PbI3 and TlBr have been found to have shallow VH, in contrast to commonly seen deep VH in halides. In this paper, several halide optoelectronic materials, i.e., CH3NH3PbI3, CH3NH3SnI3 (photovoltaic materials), TlBr, and CsPbBr3, (gamma-ray detection materials) are studied to understand the material chemistry and structure that determine whether VH is a shallow or deep defect in a halide material. It is found that crystal structure and chemistry of ns2 ions both play important roles in creating shallow VH in halides such as CH3NH3PbI3, CH3NH3SnI3, and TlBr. The key to identifying halides with shallow VH is to find the right crystal structures and compounds that suppress cation orbital hybridization at VH, such as those with long cation-cation distances and low anion coordination numbers, and those with crystal symmetry that prevents strong hybridization of cation dangling bond orbitals at VH. Furthermore, the results of this paper provide insight and guidance to identifying halides with shallow VH as good electronic and optoelectronic materials.

  4. Imaging of hydrogen halides photochemistry on argon and ice nanoparticles

    NASA Astrophysics Data System (ADS)

    Poterya, V.; Lengyel, J.; Pysanenko, A.; Svrčková, P.; Fárník, M.

    2014-08-01

    The photodissociation dynamics of HX (X = Cl, Br) molecules deposited on large ArN and (H2O)N, bar{N}≈ 102-103, clusters is investigated at 193 nm using velocity map imaging of H and Cl photofragments. In addition, time-of-flight mass spectrometry after electron ionization complemented by pickup cross section measurements provide information about the composition and structure of the clusters. The hydrogen halides coagulate efficiently to generate smaller (HX)n clusters on ArN upon multiple pickup conditions. This implies a high mobility of HX molecules on argon. On the other hand, the molecules remain isolated on (H2O)N. The photodissociation on ArN leads to strong H-fragment caging manifested by the fragment intensity peaking sharply at zero kinetic energy. Some of the Cl-fragments from HCl photodissociation on ArN are also caged, while some of the fragments escape the cluster directly without losing their kinetic energy. The images of H-fragments from HX on (H2O)N also exhibit a strong central intensity, however, with a different kinetic energy distribution which originates from different processes: the HX acidic dissociation followed by H3O neutral hydronium radical formation after the UV excitation, and the slow H-fragments stem from subsequent decay of the H3O. The corresponding Cl-cofragment from the photoexcitation of the HCl.(H2O)N is trapped in the ice nanoparticle.

  5. An insight into liquid water networks through hydrogen bonding halide anion: Stimulated Raman scattering

    NASA Astrophysics Data System (ADS)

    Wang, Shenghan; Fang, Wenhui; Li, Tianyu; Li, Fangfang; Sun, Chenglin; Li, Zuowei; Huang, Yuxin; Men, Zhiwei

    2016-04-01

    We have studied the interaction between water molecules and halide anions and acquired the influence of concentration by the spontaneous Raman spectrum. The results agreed well with the previous researches. To explore further, the stimulated Raman scattering of a halide-water binary solution is measured to study the nature of the hydrogen bonding between water molecules and halogen anions. Under the effect of laser-induced plasma, the OH stretching vibration spectra of aqueous solutions of halogen ions pretty exhibit different trend compared with that of spontaneous Raman spectrum. The frequency shifts of water OH vibration show different values and directions with adding different halide anions. The red shift of F-- and Cl--water molecule clusters is due to the process of charge transfer, whereas the blue shift of Br-- and I--water molecule cluster is due to polarization effect without charge transfer. The results demonstrate that F- and Cl- slightly weaken the hydrogen bond (HB), whereas Br- and I- enhance HB in the water cluster. The decrease of concentration of halogen ions aqueous solution can weaken the effect on the HB.

  6. 40 CFR 721.575 - Substituted alkyl halide.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Substituted alkyl halide. 721.575... Substances § 721.575 Substituted alkyl halide. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as substituted alkyl halide (PMN P-83-1222)...

  7. Method for recovering hydrocarbons from molten metal halides

    DOEpatents

    Pell, Melvyn B.

    1979-01-01

    In a process for hydrocracking heavy carbonaceous materials by contacting such carbonaceous materials with hydrogen in the presence of a molten metal halide catalyst to produce hydrocarbons having lower molecular weights and thereafter recovering the hydrocarbons so produced from the molten metal halide, an improvement comprising injecting into the spent molten metal halide, a liquid low-boiling hydrocarbon stream is disclosed.

  8. Interactions between halide anions and a molecular hydrophobic interface.

    PubMed

    Rankin, Blake M; Hands, Michael D; Wilcox, David S; Fega, K Rebecca; Slipchenko, Lyudmila V; Ben-Amotz, Dor

    2013-01-01

    Interactions between halide ions (fluoride and iodide) and t-butyl alcohol (TBA) dissolved in water are probed using a recently developed hydration-shell spectroscopic technique and theoretical cluster and liquid calculations. High ignal-to-noise Raman spectroscopic measurements are combined with multivariate curve resolution (Raman-MCR) to reveal that while there is little interaction between aqueous fluoride ions and TBA, iodide ions break down the tetrahedral hydration-shell structure of TBA and produce a red-shift in its CH stretch frequency, in good agreement with the theoretical effective fragment potential (EFP) molecular dynamics simulations and hybrid quantum/EFP frequency calculations. The results imply that there is a significantly larger probability of finding iodide than fluoride in the first hydration shell of TBA, although the local iodide concentration is apparently not as high as in the surrounding bulk aqueous NaI solution. PMID:23795504

  9. Recent advances in technetium halide chemistry.

    PubMed

    Poineau, Frederic; Johnstone, Erik V; Czerwinski, Kenneth R; Sattelberger, Alfred P

    2014-02-18

    Transition metal binary halides are fundamental compounds, and the study of their structure, bonding, and other properties gives chemists a better understanding of physicochemical trends across the periodic table. One transition metal whose halide chemistry is underdeveloped is technetium, the lightest radioelement. For half a century, the halide chemistry of technetium has been defined by three compounds: TcF6, TcF5, and TcCl4. The absence of Tc binary bromides and iodides in the literature was surprising considering the existence of such compounds for all of the elements surrounding technetium. The common synthetic routes that scientists use to obtain binary halides of the neighboring elements, such as sealed tube reactions between elements and flowing gas reactions between a molecular complex and HX gas (X = Cl, Br, or I), had not been reported for technetium. In this Account, we discuss how we used these routes to revisit the halide chemistry of technetium. We report seven new phases: TcBr4, TcBr3, α/β-TcCl3, α/β-TcCl2, and TcI3. Technetium tetrachloride and tetrabromide are isostructural to PtX4 (X = Cl or Br) and consist of infinite chains of edge-sharing TcX6 octahedra. Trivalent technetium halides are isostructural to ruthenium and molybdenum (β-TcCl3, TcBr3, and TcI3) and to rhenium (α-TcCl3). Technetium tribromide and triiodide exhibit the TiI3 structure-type and consist of infinite chains of face-sharing TcX6 (X = Br or I) octahedra. Concerning the trichlorides, β-TcCl3 crystallizes with the AlCl3 structure-type and consists of infinite layers of edge-sharing TcCl6 octahedra, while α-TcCl3 consists of infinite layers of Tc3Cl9 units. Both phases of technetium dichloride exhibit new structure-types that consist of infinite chains of [Tc2Cl8] units. For the technetium binary halides, we studied the metal-metal interaction by theoretical methods and magnetic measurements. The change of the electronic configuration of the metal atom from d(3) (Tc

  10. The electronic structure of alkali aurides. A four-component Dirac-Kohn-Sham study.

    PubMed

    Belpassi, Leonardo; Tarantelli, Francesco; Sgamellotti, Antonio; Quiney, Harry M

    2006-04-01

    Spectroscopic constants, including dissociation energies, harmonic and anharmonic vibrational frequencies, and dipole moments, are calculated for the complete alkali auride series (LiAu, NaAu, KAu, RbAu, CsAu). The four-component formulation of relativistic density functional theory has been employed in this study, using the G-spinor basis sets implemented recently in the program BERTHA. The performance of four standard nonrelativistic density functionals employed is investigated by comparing the results with the best available theoretical and experimental data. The present work provides the first theoretical predictions on the molecular properties of RbAu. The intermetallic bond that occurs in the alkali auride series is highly polar and is characterized by a large charge transfer from the alkali metals to gold. The extent of this electron transfer has been investigated using several different charge analysis methods, enabling us to reach some general conclusions on their relative performance. We further report a detailed analysis of the topological properties of relativistic electron density in the bonding region, discussing the features of this approach which characterize the nature of the chemical bond. We have also computed the fully relativistic density for the alkali halides MBr and MI (M = Li, Na, K, Rb, and Cs). The comparative study shows that, on the basis of several topological properties and the variation in bond lengths, the gold atom behaves similarly to a halogen intermediate between Br and I. PMID:16571062

  11. Hydrothermal alkali metal catalyst recovery process

    DOEpatents

    Eakman, James M.; Clavenna, LeRoy R.

    1979-01-01

    In a coal gasification operation or similar conversion process carried out in the presence of an alkali metal-containing catalyst wherein solid particles containing alkali metal residues are produced, alkali metal constituents are recovered from the particles primarily in the form of water soluble alkali metal formates by treating the particles with a calcium or magnesium-containing compound in the presence of water at a temperature between about 250.degree. F. and about 700.degree. F. and in the presence of added carbon monoxide. During the treating process the water insoluble alkali metal compounds comprising the insoluble alkali metal residues are converted into water soluble alkali metal formates. The resultant aqueous solution containing water soluble alkali metal formates is then separated from the treated particles and any insoluble materials formed during the treatment process, and recycled to the gasification process where the alkali metal formates serve as at least a portion of the alkali metal constituents which comprise the alkali metal-containing catalyst. This process permits increased recovery of alkali metal constituents, thereby decreasing the overall cost of the gasification process by reducing the amount of makeup alkali metal compounds necessary.

  12. Alkali Halide Opacity in Brown Dwarf and Cool Stellar Atmospheres: A Study of Lithium Chloride

    NASA Astrophysics Data System (ADS)

    Kirby, K.; Weck, P. F.; Schweitzer, A.; Stancil, P. C.; Hauschildt, P. H.

    2003-12-01

    Recent thermochemical equilibrium calculations have revealed the important role played by lithium chloride in the lithium chemistry of cool dwarf atmospheres (K. Lodders 1999, ApJ 519, 793). Indeed, LiCl appears to be the dominant Li-bearing gas over an extended domain of the (P,T) diagram, typically for temperatures below 1500 K. LiCl has a large dipole moment in its ground electronic state which can give rise to intense rovibrational line spectra. In addition, LiCl can make dipole transitions to several low-lying unbound excited states, causing dissociation of the molecule. For these reasons, LiCl may be a significant source of line and continuum opacity in brown dwarf and cool stellar atmospheres. In this work, we report calculations of complete lists of line oscillator strengths and photodissociation cross sections for the low-lying electronic states of LiCl. We have performed single- and double-excitation configuration interaction calculations using the ALCHEMY ab initio package (Mc Lean et al. 1991, MOTECC 91, Elsevier, Leiden) and obtained the potential curves and the corresponding dipole transition moment functions between the X 1Σ ^+ ground state and the B 1Σ ^+ and A 1Π excited states. The resulting line oscillator strengths and molecular photodissociation cross sections have been included in the PHOENIX stellar atmosphere code (Hauschildt & Baron 1999, J. Comput. App. Math. 102, 41). The new models, calculated using spherical geometry for all gravities considered, also incorporate our latest database of nearly 670 million molecular lines, and updated equations of state (EOS). This work was supported in part by NSF grants AST-9720704 and AST-0086246, NASA grants NAG5-8425, NAG5-9222, and NAG5-10551 as well as NASA/JPL grant 961582.

  13. Elastic properties of alpha quartz and the alkali halides based on an interatomic force model.

    NASA Technical Reports Server (NTRS)

    Weidner, D. J.; Simmons, G.

    1972-01-01

    A two-body central-force atomic model can be used to describe accurately the elastic properties of alpha quartz if the nontetrahedral O:O forces are included. The strength of the Si:O interaction has little effect on the bulk modulus. The technique is sufficiently general to allow calculations of the elastic properties of a specified structure under arbitrary pressure from a complete description of the interatomic forces. The elastic constants for the NaCl structure and the CsCl structure are examined. Our model includes two-body, central, anion-anion, anion-cation, and electrostatic interactions.

  14. The aluminum electrode in AlCl3-alkali-halide melts

    NASA Technical Reports Server (NTRS)

    Holleck, G. L.; Giner, J.

    1972-01-01

    Passivation phenomena were observed upon cathodic and anodic polarization of the Al electrode in AlCl3-KCl-NaCl melts between 100 and 160 C. They are caused by formation of a solid salt layer at the electrode surface resulting from concentration changes upon current flow. The anodic limiting currents increased with temperature and with decreasing AlCl3 content of the melt. Current voltage curves obtained on a rotating aluminum disk showed a linear relationship between the anodic limiting current and 1/sq root of 2 pi (rps). Upon cathodic polarization dentrite formation occurs at the Al electrode. The activation overvoltage in AlCl3-KCl-NaCl (57.5-12.5-20 mol%) was determined by galvanostatic current step methods. An apparent exchange current density of 270 mA/cm2 at 130 C and a double layer capacity of 40 plus or minus 10 microfarad/cm2 were measured.

  15. The aluminum electrode in AlCl3-alkali-halide melts.

    NASA Technical Reports Server (NTRS)

    Holleck, G. L.; Giner, J.

    1972-01-01

    Passivation phenomena have been observed upon cathodic and anodic polarization of the Al electrode in AlCl3-KCl-NaCl melts between 100 and 160 C. They are caused by formation of a solid salt layer at the electrode surface resulting from concentration changes upon current flow. The anodic limiting currents increased with temperature and with decreasing AlCl3 content of the melt. Current voltage curves obtained on a rotating aluminum disk showed a linear relationship between the anodic limiting current and omega to the minus 1/2 power. Upon cathodic polarization, dendrite formation occurs at the Al electrode. The activation overvoltage in AlCl3-KCl-NaCl was determined by galvanostatic current step methods. An apparent exchange current density of 270 mA/sq cm at 130 C and a double layer capacity of 40 plus or minus 10 microfarad/sq cm were measured.

  16. Extreme ultraviolet quantum efficiency of opaque alkali halide photocathodes on microchannel plates

    NASA Technical Reports Server (NTRS)

    Siegmund, O. H. W.; Everman, E.; Vallerga, J. V.; Lampton, M.

    1988-01-01

    Comprehensive measurements are presented for the quantum detection efficiency (QDE) of the microchannel plate materials CsI, KBr, KCl, and MgF2, over the 44-1800 A wavelength range. QDEs in excess of 40 percent are achieved by several materials in specific wavelength regions of the EUV. Structure is noted in the wavelength dependence of the QDE that is directly related to the valence-band/conduction-band gap energy and the onset of atomic-like resonant transitions. A simple photocathode model allows interpretation of these features, together with the QDE efficiency variation, as a function of illumination angle.

  17. Is surface layering of aqueous alkali halides determined by ion pairing in the bulk solution?

    NASA Astrophysics Data System (ADS)

    Brandes, Eva; Stage, Christiane; Motschmann, Hubert; Rieder, Julian; Buchner, Richard

    2014-11-01

    This contribution aims to elucidate the connection between ion-ion-solvent interactions in the bulk of aqueous electrolyte solutions and the properties of their liquid-air interface. In particular, we were interested in the conditions under which ion pairs form at the surface and whether this is linked to ion pairing in the bulk. For this reason different combinations of hard (Cl-, Li+) and soft ions (I-, Cs+) were investigated. Ion hydration and possible ion association in the bulk was probed with dielectric relaxation spectroscopy. This technique monitors the cooperative reorientation of the dipolar solvent molecules and detects all ion-pair species possibly present in the solution. At the interface, the formation of contact ion pairs was investigated by infrared-visible-sum frequency spectroscopy (SFG). This nonlinear optical technique possesses an inherent surface specificity and can be used for the characterization of interfacial water. The intensity of the SFG-active vibrational stretching modes depends on the number of oriented water molecules. The electric field at the surface of a charged aqueous interface aligns the water dipoles, which in turn increases the SFG response. Hence, the enhancement of the oscillator strengths of the water vibrational modes can be used to draw some conclusions on the strengths and geometrical extension of the electric field. The formation of ion pairs at the interface reduces the intensity of the band associated with hydrogen-bonded water. The underlying theory is presented. The combined data show that there are no contact ion pairs in the bulk of the fluid and—at best—only small amounts of solvent shared ion pairs. On the other hand, the combination of hard/hard or soft/soft ions leads to the formation of ion pairs at the liquid-air interface.

  18. Properties of alkali-halide salt solutions about polarizable nanoparticle solutes for different ion models

    NASA Astrophysics Data System (ADS)

    Wynveen, Aaron; Bresme, Fernando

    2010-10-01

    We investigate the distributions of various salts about large hydrophobic polarizable solutes in aqueous electrolyte solutions. The solutes are modeled as nanometer-sized cylindrical objects, a scale relevant to biomolecules and nanomaterials, and particularly high aspect ratio nanoparticles. Interactions, including image charge forces arising from the finite polarizability of the solute, between explicit solvent/ions and the solute are computed explicitly using a molecular dynamics simulation methodology we have recently introduced. Comparisons are made between several salt species and different models of the force fields for each ionic component of the salt. We find evidence that both small cations, Li+, and large anions, I-, adsorb at hydrophobic interfaces. Our results indicate that the ion structure about the solute is strongly dependent on the force field investigated, suggesting that ion selectivity is quite sensitive to the respective parameters defining the ion's size and binding energy as well as to the polarizability of the solute.

  19. Dipole-driven self-organization of zwitterionic molecules on alkali halide surfaces.

    PubMed

    Nony, Laurent; Bocquet, Franck; Para, Franck; Chérioux, Frédéric; Duverger, Eric; Palmino, Frank; Luzet, Vincent; Loppacher, Christian

    2012-01-01

    We investigated the adsorption of 4-methoxy-4'-(3-sulfonatopropyl)stilbazolium (MSPS) on different ionic (001) crystal surfaces by means of noncontact atomic force microscopy. MSPS is a zwitterionic molecule with a strong electric dipole moment. When deposited onto the substrates at room temperature, MSPS diffuses to step edges and defect sites and forms disordered assemblies of molecules. Subsequent annealing induces two different processes: First, at high coverage, the molecules assemble into a well-organized quadratic lattice, which is perfectly aligned with the <110> directions of the substrate surface (i.e., rows of equal charges) and which produces a Moiré pattern due to coincidences with the substrate lattice constant. Second, at low coverage, we observe step edges decorated with MSPS molecules that run along the <110> direction. These polar steps most probably minimize the surface energy as they counterbalance the molecular dipole by presenting oppositely charged ions on the rearranged step edge. PMID:22497002

  20. Dipole-driven self-organization of zwitterionic molecules on alkali halide surfaces

    PubMed Central

    Nony, Laurent; Bocquet, Franck; Para, Franck; Chérioux, Frédéric; Duverger, Eric; Palmino, Frank; Luzet, Vincent

    2012-01-01

    Summary We investigated the adsorption of 4-methoxy-4′-(3-sulfonatopropyl)stilbazolium (MSPS) on different ionic (001) crystal surfaces by means of noncontact atomic force microscopy. MSPS is a zwitterionic molecule with a strong electric dipole moment. When deposited onto the substrates at room temperature, MSPS diffuses to step edges and defect sites and forms disordered assemblies of molecules. Subsequent annealing induces two different processes: First, at high coverage, the molecules assemble into a well-organized quadratic lattice, which is perfectly aligned with the <110> directions of the substrate surface (i.e., rows of equal charges) and which produces a Moiré pattern due to coincidences with the substrate lattice constant. Second, at low coverage, we observe step edges decorated with MSPS molecules that run along the <110> direction. These polar steps most probably minimize the surface energy as they counterbalance the molecular dipole by presenting oppositely charged ions on the rearranged step edge. PMID:22497002

  1. Electronic line-up in light-emitting diodes with alkali-halide/metal cathodes

    NASA Astrophysics Data System (ADS)

    Brown, T. M.; Friend, R. H.; Millard, I. S.; Lacey, D. J.; Butler, T.; Burroughes, J. H.; Cacialli, F.

    2003-05-01

    The electronic nature of metal-semiconductor contacts is a fundamental issue in the understanding of semiconductor device physics, because such contacts control charge injection, and therefore play a major role in determining the electron/hole population in the semiconductor itself. This role is particularly important for organic semiconductors as they are generally used in their pristine, undoped form. Here, we review our progress in the understanding of the energy level line-up in finished, blue-emitting, polyfluorene-based light-emitting diodes, which exploit LiF and CsF thin films in combination with Ca and Al to obtain cathodes with low injection barriers. We have used electroabsorption measurements, as they allow the noninvasive determination of the built-in potential when changing the cathode. This provides precious experimental information on the alteration of the polymer/cathode interfacial energy level line-up. The latter is found to depend strongly on the electrode work function. Thus, the Schottky-Mott model for the energy level alignment is found to be a better first-order approximation than those models where strong pinning or large interface dipoles determine the alignment (e.g., Bardeen model), except for electrodes that extensively react with the polymer, and introduce deep gap states. In addition, we show results that validate the approximation of rigid tilting of polymer energy levels with bias (for biases for which no significant injection of carriers occurs). To investigate further the consequences of the electronic line-up on device operation, we complemented the electroabsorption measurements with characterization of the emissive and transport properties of the light-emitting diodes, and confirmed that the cathodic barrier lowering in CsF/Ca/Al and LiF/Ca/Al electrodes leads to the best improvements in electron injection. We found that luminance and overall current are greatly affected by the barrier-reducing cathodes, indicating a truly bipolar transport, with comparable electron and hole currents. We also found significant indications of CsF/Ca/Al cathodes strongly reacting with the polymer, which is suggestive of CsF dissociation and diffusion in the bulk of the polymer.

  2. Vibration-Resistant Support for Halide Lamps

    NASA Technical Reports Server (NTRS)

    Kiss, J.

    1987-01-01

    Lamp envelope protected against breakage. Old and new mounts for halide arc lamp sealed in housing with parabolic refector and quartz window. New version supports lamp with compliant garters instead of rigid brazed joint at top and dimensionally unstable finger stock at bottom.

  3. Electric properties of stannous and stannic halides: How good are the experimental values?

    NASA Astrophysics Data System (ADS)

    Kalugina, Yulia N.; Thakkar, Ajit J.

    2015-04-01

    Coupled-cluster calculations are reported for the electric and vibrational properties of the stannous halides SnX2 and stannic halides SnX4 with X = F, Cl, Br, and I. Comparison with experiment, where available, is made. Our best values of the static mean dipole polarizability for SnF2, SnCl2, SnBr2, and SnI2, are 39.98, 71.93, 91.37, and 125.8 atomic units, respectively. Our best values of the static mean dipole polarizability for SnF4, SnCl4, SnBr4, and SnI4, are 32.82, 93.04, 126.9, and 191.2 atomic units, respectively.

  4. Electrolytic method to make alkali alcoholates using ion conducting alkali electrolyte/separator

    DOEpatents

    Joshi, Ashok V.; Balagopal, Shekar; Pendelton, Justin

    2011-12-13

    Alkali alcoholates, also called alkali alkoxides, are produced from alkali metal salt solutions and alcohol using a three-compartment electrolytic cell. The electrolytic cell includes an anolyte compartment configured with an anode, a buffer compartment, and a catholyte compartment configured with a cathode. An alkali ion conducting solid electrolyte configured to selectively transport alkali ions is positioned between the anolyte compartment and the buffer compartment. An alkali ion permeable separator is positioned between the buffer compartment and the catholyte compartment. The catholyte solution may include an alkali alcoholate and alcohol. The anolyte solution may include at least one alkali salt. The buffer compartment solution may include a soluble alkali salt and an alkali alcoholate in alcohol.

  5. The calcium-alkali syndrome.

    PubMed

    Arroyo, Mariangeli; Fenves, Andrew Z; Emmett, Michael

    2013-04-01

    The milk-alkali syndrome was a common cause of hypercalcemia, metabolic alkalosis, and renal failure in the early 20th century. It was caused by the ingestion of large quantities of milk and absorbable alkali to treat peptic ulcer disease. The syndrome virtually vanished after introduction of histamine-2 blockers and proton pump inhibitors. More recently, a similar condition called the calcium-alkali syndrome has emerged as a common cause of hypercalcemia and alkalosis. It is usually caused by the ingestion of large amounts of calcium carbonate salts to prevent or treat osteoporosis and dyspepsia. We describe a 78-year-old woman who presented with weakness, malaise, and confusion. She was found to have hypercalcemia, acute renal failure, and metabolic alkalosis. Upon further questioning, she reported use of large amounts of calcium carbonate tablets to treat recent heartburn symptoms. Calcium supplements were discontinued, and she was treated with intravenous normal saline. After 5 days, the calcium and bicarbonate levels normalized and renal function returned to baseline. In this article, we review the pathogenesis of the calcium-alkali syndrome as well as the differences between the traditional and modern syndromes. PMID:23543983

  6. Theoretical characterization of dihydrogen adducts with halide anions

    NASA Astrophysics Data System (ADS)

    Vitillo, Jenny G.; Damin, Alessandro; Zecchina, Adriano; Ricchiardi, Gabriele

    2006-06-01

    The interaction between a hydrogen molecule and the halide anions F-, Cl-, Br-, and I- has been studied at different levels of theory and with different basis sets. The most stable configurations of the complexes have a linear geometry, while the t-shaped complexes are saddle points on the potential energy surface, opposite to what is observed for alkali cations. An electrostatic analysis conducted on the resulting adducts has highlighted the predominance of the electrostatic term in the complexation energy and, in particular, of the quadrupole- and dipole-polarizability dependent contributions. Another striking difference with respect to the positive ions, is the fact that although the binding energies have similar values (ranging between 25 and 3kJ/mol for F- and I-, respectively), the vibrational shift of the ν˜H-H and in general the perturbation of the hydrogen molecule in complexes are much greater in the complexes with anions (Δν˜H-H ranges between -720 and -65cm-1). Another difference with respect to the interaction with cations is a larger charge transfer from the anion to the hydrogen molecule. The Δν˜ is the result of the cooperative role of the electrostatics and of the charge transfer in the interaction. The correlation between binding energies and vibrational shift is far from linear, contrary to what is observed for cation complexes, in accordance with the higher polarizability and dynamic polarizability of the molecule along the molecular axis. The observed correlation may be valuable in the interpretation of spectra and thermodynamic properties of adsorbed H2 in storage materials.

  7. Transport of Soil Halides through Rice Paddies: A Viable Mechanism for Rapid Dispersion of the Soil Halide Reservoir

    NASA Astrophysics Data System (ADS)

    Redeker, K. R.; Manley, S.; Wang, N.; Cicerone, R.

    2002-05-01

    On short time scales (1-10 years) soil halide concentrations have been assumed to be primarily driven by leaching and deposition processes. Recent results however, have shown that terrestrial plants volatilize soil halides in the form of methyl halides. Emissions of methyl chloride, methyl bromide and methyl iodide represent major pathways for delivery of inorganic halogen radicals to the atmosphere. Inorganic halogen radicals destroy ozone in the stratosphere and modify the oxidative capacity of the lower atmosphere. We have previously shown that rice paddies emit methyl halides and that emissions depend on growth stage of the rice plant as well as field water management. We show here that rice grown in a greenhouse at UCI is capable of volatilizing and/or storing up to 30%, 5%, and 10% of the available chloride, bromide and iodide within the top meter of soil. The percent of plant tissue halide volatilized as methyl halide over the course of the season is calculated to be 0.05%, 0.25% and 85.0% for chloride, bromide and iodide. We compare our greenhouse soil halide concentrations to other commercial rice fields around the world and estimate the e-folding time for soil halides within each region. We suggest that rice agriculture is the driving removal mechanism for halides within rice paddies and that terrestrial plants play a larger role in global cycling of halides than previously estimated.

  8. Imaging of hydrogen halides photochemistry on argon and ice nanoparticles.

    PubMed

    Poterya, V; Lengyel, J; Pysanenko, A; Svrčková, P; Fárník, M

    2014-08-21

    The photodissociation dynamics of HX (X = Cl, Br) molecules deposited on large ArN and (H2O)N, N̄ ≈ 10(2)-10(3), clusters is investigated at 193 nm using velocity map imaging of H and Cl photofragments. In addition, time-of-flight mass spectrometry after electron ionization complemented by pickup cross section measurements provide information about the composition and structure of the clusters. The hydrogen halides coagulate efficiently to generate smaller (HX)n clusters on ArN upon multiple pickup conditions. This implies a high mobility of HX molecules on argon. On the other hand, the molecules remain isolated on (H2O)N. The photodissociation on ArN leads to strong H-fragment caging manifested by the fragment intensity peaking sharply at zero kinetic energy. Some of the Cl-fragments from HCl photodissociation on ArN are also caged, while some of the fragments escape the cluster directly without losing their kinetic energy. The images of H-fragments from HX on (H2O)N also exhibit a strong central intensity, however, with a different kinetic energy distribution which originates from different processes: the HX acidic dissociation followed by H3O neutral hydronium radical formation after the UV excitation, and the slow H-fragments stem from subsequent decay of the H3O. The corresponding Cl-cofragment from the photoexcitation of the HCl·(H2O)N is trapped in the ice nanoparticle. PMID:25149788

  9. Imaging of hydrogen halides photochemistry on argon and ice nanoparticles

    SciTech Connect

    Poterya, V. Lengyel, J.; Pysanenko, A.; Svrčková, P.; Fárník, M.

    2014-08-21

    The photodissociation dynamics of HX (X = Cl, Br) molecules deposited on large Ar{sub N} and (H{sub 2}O){sub N}, N{sup ¯}≈ 10{sup 2}–10{sup 3}, clusters is investigated at 193 nm using velocity map imaging of H and Cl photofragments. In addition, time-of-flight mass spectrometry after electron ionization complemented by pickup cross section measurements provide information about the composition and structure of the clusters. The hydrogen halides coagulate efficiently to generate smaller (HX){sub n} clusters on Ar{sub N} upon multiple pickup conditions. This implies a high mobility of HX molecules on argon. On the other hand, the molecules remain isolated on (H{sub 2}O){sub N}. The photodissociation on Ar{sub N} leads to strong H-fragment caging manifested by the fragment intensity peaking sharply at zero kinetic energy. Some of the Cl-fragments from HCl photodissociation on Ar{sub N} are also caged, while some of the fragments escape the cluster directly without losing their kinetic energy. The images of H-fragments from HX on (H{sub 2}O){sub N} also exhibit a strong central intensity, however, with a different kinetic energy distribution which originates from different processes: the HX acidic dissociation followed by H{sub 3}O neutral hydronium radical formation after the UV excitation, and the slow H-fragments stem from subsequent decay of the H{sub 3}O. The corresponding Cl-cofragment from the photoexcitation of the HCl·(H{sub 2}O){sub N} is trapped in the ice nanoparticle.

  10. Flame inhibition by hydrogen halides - Some spectroscopic measurements

    NASA Technical Reports Server (NTRS)

    Lerner, N. R.; Cagliostro, D. E.

    1973-01-01

    The far-ultraviolet absorption spectrum of an air-propane diffusion flame inhibited with hydrogen halides has been studied. Plots of the absorption of light by hydrogen halides as a function of position in the flame and also as a function of the amount of hydrogen halide added to the flame have been obtained. The hydrogen halides are shown to be more stable on the fuel side of the reaction zone than they are on the air side. Thermal diffusion is seen to be important in determining the concentration distribution of the heavier hydrogen halides in diffusion flames. The relationship between the concentration distribution of the hydrogen halides in the flame and the flame inhibition mechanism is discussed.

  11. Morphology-Controlled Synthesis of Organometal Halide Perovskite Inverse Opals.

    PubMed

    Chen, Kun; Tüysüz, Harun

    2015-11-01

    The booming development of organometal halide perovskites in recent years has prompted the exploration of morphology-control strategies to improve their performance in photovoltaic, photonic, and optoelectronic applications. However, the preparation of organometal halide perovskites with high hierarchical architecture is still highly challenging and a general morphology-control method for various organometal halide perovskites has not been achieved. A mild and scalable method to prepare organometal halide perovskites in inverse opal morphology is presented that uses a polystyrene-based artificial opal as hard template. Our method is flexible and compatible with different halides and organic ammonium compositions. Thus, the perovskite inverse opal maintains the advantage of straightforward structure and band gap engineering. Furthermore, optoelectronic investigations reveal that morphology exerted influence on the conducting nature of organometal halide perovskites. PMID:26376773

  12. Lanthanide-halide based humidity indicators

    DOEpatents

    Beitz, James V.; Williams, Clayton W.

    2008-01-01

    The present invention discloses a lanthanide-halide based humidity indicator and method of producing such indicator. The color of the present invention indicates the humidity of an atmosphere to which it is exposed. For example, impregnating an adsorbent support such as silica gel with an aqueous solution of the europium-containing reagent solution described herein, and dehydrating the support to dryness forms a substance with a yellow color. When this substance is exposed to a humid atmosphere the water vapor from the air is adsorbed into the coating on the pore surface of the silica gel. As the water content of the coating increases, the visual color of the coated silica gel changes from yellow to white. The color change is due to the water combining with the lanthanide-halide complex on the pores of the gel.

  13. EVALUATION OF METHODS FOR THE DETERMINATION OF TOTAL ORGANIC HALIDE IN WATER AND WASTE

    EPA Science Inventory

    Various methods for the determination of total organic halides (TOX) in groundwater and in waste oil samples have been evaluated. Of three inorganic halide species generation approaches and three inorganic halide determinative techniques evaluated for groundwater analyses, one co...

  14. Progress in Understanding Alkali-Alkali Spin Relaxation

    NASA Astrophysics Data System (ADS)

    Erickson, Christopher J.; Happer, William; Chann, Bien; Kadlecek, Stephen; Anderson, L. W.; Walker, Thad G.

    2000-06-01

    In extensive experiments we have shown that a spin interaction with a relatively long correlation time causes much of the spin relaxation in very dense alkali-metal vapors. The spin relaxation is affected by the pressure of the helium or nitrogen buffer gas, although there is little dependence at pressures above one atmosphere. There are substantial differences in the relaxation rates for different isotopes of the same element, for example ^87Rb and ^85Rb. We have completed extensive modeling of how singlet and triplet dimers and doublet trimers of the alkali-metal atoms could cause spin relaxation in dense alkali-metal vapors. In the case of doublet trimers or triplet dimers, we assume the main coupling to the nuclear spins is through the Fermi Contact interaction with the unpaired electrons. Spin loss to the rotation of the molecule is assumed to occur through the electronic spin-rotation and spin-axis (dipole-dipole) interactions for the triplet dimers. For the singlet dimers, we assume that the nuclear spins couple directly to the rotational angular momentum of the molecule through the electric quadrupole interaction. We account for all of the total nuclear spin states that occur for the dimers and trimers. We have also considered the possibility that the collisional breakup and formation rates of the dimers or trimers could saturate with increasing buffer gas pressure. Such saturation occurs in many other unimolecular reactions and is often ascribed to breakup through activated states.

  15. Interpulse kinetics in copper and copper halide lasers

    NASA Technical Reports Server (NTRS)

    Harstad, K. G.

    1983-01-01

    The various rate processes that govern the interpulse relaxation in metal vapor and metal halide vapor lasers are considered. Computer calculations indicate that the rapid metastable levels relaxation observed in copper and copper halide laser experiments requires the existence of a relatively small resonance in the cross section for metastable excitation or deexcitation near threshold. The accurate calculation of interpulse relaxation requires knowledge of rate constants presently not well known; this is especially so for metal halide lasers.

  16. Process and composition for drying of gaseous hydrogen halides

    DOEpatents

    Tom, Glenn M.; Brown, Duncan W.

    1989-08-01

    A process for drying a gaseous hydrogen halide of the formula HX, wherein X is selected from the group consisting of bromine, chlorine, fluorine, and iodine, to remove water impurity therefrom, comprising: contacting the water impurity-containing gaseous hydrogen halide with a scavenger including a support having associated therewith one or more members of the group consisting of: (a) an active scavenging moiety selected from one or more members of the group consisting of: (i) metal halide compounds dispersed in the support, of the formula MX.sub.y ; and (ii) metal halide pendant functional groups of the formula -MX.sub.y-1 covalently bonded to the support, wherein M is a y-valent metal, and y is an integer whose value is from 1 to 3; (b) corresponding partially or fully alkylated compounds and/or pendant functional groups, of the metal halide compounds and/or pendant functional groups of (a); wherein the alkylated compounds and/or pendant functional groups, when present, are reactive with the gaseous hydrogen halide to form the corresponding halide compounds and/or pendant functional groups of (a); and M being selected such that the heat of formation, .DELTA.H.sub.f of its hydrated halide, MX.sub.y.(H.sub.2 O).sub.n, is governed by the relationship: .DELTA.H.sub.f .gtoreq.n.times.10.1 kilocalories/mole of such hydrated halide compound wherein n is the number of water molecules bound to the metal halide in the metal halide hydrate. Also disclosed is an appertaining scavenger composition and a contacting apparatus wherein the scavenger is deployed in a bed for contacting with the water impurity-containing gaseous hydrogen halide.

  17. Molecular dynamics simulations of the surface tension and structure of salt solutions and clusters.

    PubMed

    Sun, Lu; Li, Xin; Hede, Thomas; Tu, Yaoquan; Leck, Caroline; Ågren, Hans

    2012-03-15

    Sodium halides, which are abundant in sea salt aerosols, affect the optical properties of aerosols and are active in heterogeneous reactions that cause ozone depletion and acid rain problems. Interfacial properties, including surface tension and halide anion distributions, are crucial issues in the study of the aerosols. We present results from molecular dynamics simulations of water solutions and clusters containing sodium halides with the interatomic interactions described by a conventional force field. The simulations reproduce experimental observations that sodium halides increase the surface tension with respect to pure water and that iodide anions reach the outermost layer of water clusters or solutions. It is found that the van der Waals interactions have an impact on the distribution of the halide anions and that a conventional force field with optimized parameters can model the surface tension of the salt solutions with reasonable accuracy. PMID:22352372

  18. Lanthanide doped strontium-barium cesium halide scintillators

    SciTech Connect

    Bizarri, Gregory; Bourret-Courchesne, Edith; Derenzo, Stephen E.; Borade, Ramesh B.; Gundiah, Gautam; Yan, Zewu; Hanrahan, Stephen M.; Chaudhry, Anurag; Canning, Andrew

    2015-06-09

    The present invention provides for a composition comprising an inorganic scintillator comprising an optionally lanthanide-doped strontium-barium, optionally cesium, halide, useful for detecting nuclear material.

  19. Positron-alkali atom scattering

    NASA Technical Reports Server (NTRS)

    Mceachran, R. P.; Horbatsch, M.; Stauffer, A. D.; Ward, S. J.

    1990-01-01

    Positron-alkali atom scattering was recently investigated both theoretically and experimentally in the energy range from a few eV up to 100 eV. On the theoretical side calculations of the integrated elastic and excitation cross sections as well as total cross sections for Li, Na and K were based upon either the close-coupling method or the modified Glauber approximation. These theoretical results are in good agreement with experimental measurements of the total cross section for both Na and K. Resonance structures were also found in the L = 0, 1 and 2 partial waves for positron scattering from the alkalis. The structure of these resonances appears to be quite complex and, as expected, they occur in conjunction with the atomic excitation thresholds. Currently both theoretical and experimental work is in progress on positron-Rb scattering in the same energy range.

  20. Alkali metal/sulfur battery

    DOEpatents

    Anand, Joginder N.

    1978-01-01

    Alkali metal/sulfur batteries in which the electrolyte-separator is a relatively fragile membrane are improved by providing means for separating the molten sulfur/sulfide catholyte from contact with the membrane prior to cooling the cell to temperatures at which the catholyte will solidify. If the catholyte is permitted to solidify while in contact with the membrane, the latter may be damaged. The improvement permits such batteries to be prefilled with catholyte and shipped, at ordinary temperatures.

  1. Superconductivity in alkali metal fullerides

    NASA Astrophysics Data System (ADS)

    Murphy, D. W.; Rosseinsky, M. J.; Haddon, R. C.; Ramirez, A. P.; Hebard, A. F.; Tycko, R.; Fleming, R. M.; Dabbagh, G.

    1991-12-01

    The recent synthesis of macroscopic quantities of spherical molecular carbon compounds, commonly called fullerenes, has stimulated a wide variety of studies of the chemical and physical properties of this novel class of compounds. We discovered that the smallest of the known fullerenes, C 60, could be made conducting and superconducting by reaction with alkali metals. In this paper, an overview of the motivation for these discoveries and some recent results are presented.

  2. Alkali metal sources for OLED devices

    NASA Astrophysics Data System (ADS)

    Cattaneo, Lorena; Longoni, Giorgio; Bonucci, Antonio; Tominetti, Stefano

    2005-07-01

    In OLED organic layers electron injection is improved by using alkali metals as cathodes, to lower work function or, as dopants of organic layer at cathode interface. The creation of an alkali metal layer can be accomplished through conventional physical vapor deposition from a heated dispenser. However alkali metals are very reactive and must be handled in inert atmosphere all through the entire process. If a contamination takes place, it reduces the lithium deposition rate and also the lithium total yield in a not controlled way. An innovative alkali metal dispensing technology has been developed to overcome these problems and ensure OLED alkali metal cathode reliability. The alkali Metal dispenser, called Alkamax, will be able to release up to a few grams of alkali metals (in particular Li and Cs) throughout the adoption of a very stable form of the alkali metal. Lithium, for example, can be evaporated "on demand": the evaporation could be stopped and re-activated without losing alkali metal yield because the metal not yet consumed remains in its stable form. A full characterization of dispensing material, dispenser configuration and dispensing process has been carried out in order to optimize the evaporation and deposition dynamics of alkali metals layers. The study has been performed applying also inside developed simulations tools.

  3. Making and Breaking of Lead Halide Perovskites.

    PubMed

    Manser, Joseph S; Saidaminov, Makhsud I; Christians, Jeffrey A; Bakr, Osman M; Kamat, Prashant V

    2016-02-16

    A new front-runner has emerged in the field of next-generation photovoltaics. A unique class of materials, known as organic metal halide perovskites, bridges the gap between low-cost fabrication and exceptional device performance. These compounds can be processed at low temperature (typically in the range 80-150 °C) and readily self-assemble from the solution phase into high-quality semiconductor thin films. The low energetic barrier for crystal formation has mixed consequences. On one hand, it enables inexpensive processing and both optical and electronic tunability. The caveat, however, is that many as-formed lead halide perovskite thin films lack chemical and structural stability, undergoing rapid degradation in the presence of moisture or heat. To date, improvements in perovskite solar cell efficiency have resulted primarily from better control over thin film morphology, manipulation of the stoichiometry and chemistry of lead halide and alkylammonium halide precursors, and the choice of solvent treatment. Proper characterization and tuning of processing parameters can aid in rational optimization of perovskite devices. Likewise, gaining a comprehensive understanding of the degradation mechanism and identifying components of the perovskite structure that may be particularly susceptible to attack by moisture are vital to mitigate device degradation under operating conditions. This Account provides insight into the lifecycle of organic-inorganic lead halide perovskites, including (i) the nature of the precursor solution, (ii) formation of solid-state perovskite thin films and single crystals, and (iii) transformation of perovskites into hydrated phases upon exposure to moisture. In particular, spectroscopic and structural characterization techniques shed light on the thermally driven evolution of the perovskite structure. By tuning precursor stoichiometry and chemistry, and thus the lead halide charge-transfer complexes present in solution, crystallization

  4. Mechanism and Selectivity in Nickel-Catalyzed Cross-Electrophile Coupling of Aryl Halides with Alkyl Halides

    PubMed Central

    Biswas, Soumik; Weix, Daniel J.

    2013-01-01

    The direct cross-coupling of two different electrophiles, such as an aryl halide with an alkyl halide, offers many advantages over conventional cross-coupling methods that require a carbon nucleophile. Despite its promise as a versatile synthetic strategy, a limited understanding of the mechanism and origin of cross selectivity has hindered progress in reaction development and design. Herein, we shed light on the mechanism for the nickel-catalyzed cross-electrophile coupling of aryl halides with alkyl halides and demonstrate that the selectivity arises from an unusual catalytic cycle that combines both polar and radical steps to form the new C-C bond. PMID:23952217

  5. Intermolecular interactions and proton transfer in the hydrogen halide-superoxide anion complexes.

    PubMed

    Lee, Sebastian J R; Mullinax, J Wayne; Schaefer, Henry F

    2016-02-17

    The superoxide radical anion O2(-) is involved in many important chemical processes spanning different scientific disciplines (e.g., environmental and biological sciences). Characterizing its interaction with various substrates to help elucidate its rich chemistry may have far reaching implications. Herein, we investigate the interaction between O2(-) (X[combining tilde] (2)Πg) and the hydrogen halides (X[combining tilde] (1)Σ) with coupled-cluster theory. In contrast to the short (1.324 Å) hydrogen bond formed between the HF and O2(-) monomers, a barrierless proton transfer occurs for the heavier hydrogen halides with the resulting complexes characterized as long (>1.89 Å) hydrogen bonds between halide anions and the HO2 radical. The dissociation energy with harmonic zero-point vibrational energy (ZPVE) for FHO2(-) (X[combining tilde] (2)A'') → HF (X[combining tilde] (1)Σ) + O2(-) (X[combining tilde] (2)Πg) is 31.2 kcal mol(-1). The other dissociation energies with ZPVE for X(-)HO2 (X[combining tilde] (2)A'') → X(-) (X[combining tilde] (1)Σ) + HO2 (X[combining tilde] (2)A'') are 25.7 kcal mol(-1) for X = Cl, 21.9 kcal mol(-1) for X = Br, and 17.9 kcal mol(-1) for X = I. Additionally, the heavier hydrogen halides can form weak halogen bonds H-XO2(-) (X[combining tilde] (2)A'') with interaction energies including ZPVE of -2.3 kcal mol(-1) for HCl, -8.3 kcal mol(-1) for HBr, and -16.7 kcal mol(-1) for HI. PMID:26852733

  6. Regenerable activated bauxite adsorbent alkali monitor probe

    DOEpatents

    Lee, Sheldon H. D.

    1992-01-01

    A regenerable activated bauxite adsorber alkali monitor probe for field applications to provide reliable measurement of alkali-vapor concentration in combustion gas with special emphasis on pressurized fluidized-bed combustion (PFBC) off-gas. More particularly, the invention relates to the development of a easily regenerable bauxite adsorbent for use in a method to accurately determine the alkali-vapor content of PFBC exhaust gases.

  7. Regenerable activated bauxite adsorbent alkali monitor probe

    DOEpatents

    Lee, S.H.D.

    1992-12-22

    A regenerable activated bauxite adsorber alkali monitor probe for field applications to provide reliable measurement of alkali-vapor concentration in combustion gas with special emphasis on pressurized fluidized-bed combustion (PFBC) off-gas. More particularly, the invention relates to the development of a easily regenerable bauxite adsorbent for use in a method to accurately determine the alkali-vapor content of PFBC exhaust gases. 6 figs.

  8. Controlling Metal-Halide Vapor Density in Lasers

    NASA Technical Reports Server (NTRS)

    Pivirotto, T. J.

    1984-01-01

    Streams of buffer gas convect and dilute metal-halide vapor. Technique uses flow of buffer gas through reservoir, which contains heated metal halide, to convect vapors into discharge tube. Second stream of buffer gas dilutes vapor. Final vapor density in laser tube controlled and changed by adjusting either one or both of buffer gas flow rates.

  9. [Emissions of methyl halides from coastal salt marshes: A review].

    PubMed

    Xie, Wen-xia; Zhao, Quan-sheng; Cui, Yu-qian; Du, Hui-na; Ye, Si-yuan

    2015-11-01

    Methyl halides are the major carrier of halogens in the atmosphere, and they play an important role in tropospheric and stratospheric ozone depletion. Meanwhile, methyl halides can act as greenhouse gases in the atmosphere, and they are also environmentally significant because of their toxicity. Coastal salt marshes, the important intertidal ecosystems at the land-ocean interface, have been considered to be a large potential natural source of methyl halides. In this paper, the research status of the natural source or sink of methyl halides, the mechanisms of their emission from coastal salt marshes and affecting factors were summarized. In view of this, the following research fields need to be strengthened in the future: 1) Long time-scale and large region-range researches about the emission of methyl halides and the evaluation of their source and sink function, 2) Accurate quantification of contribution rates of different plant species and various biological types to fluxes of methyl halides, 3) Further researches on effects of the tidal fluctuation process and flooding duration on methyl halides emission, 4) Effects of the global change and human activities on methyl halides emission. PMID:26915215

  10. How specific halide adsorption varies hydrophobic interactions.

    PubMed

    Stock, Philipp; Müller, Melanie; Utzig, Thomas; Valtiner, Markus

    2016-03-01

    Hydrophobic interactions (HI) are driven by the water structure around hydrophobes in aqueous electrolytes. How water structures at hydrophobic interfaces and how this influences the HI was subject to numerous studies. However, the effect of specific ion adsorption on HI and hydrophobic interfaces remains largely unexplored or controversial. Here, the authors utilized atomic force microscopy force spectroscopy at well-defined nanoscopic hydrophobic interfaces to experimentally address how specific ion adsorption of halide ions as well as NH4 (+), Cs(+), and Na(+) cations alters interaction forces across hydrophobic interfaces. Our data demonstrate that iodide adsorption at hydrophobic interfaces profoundly varies the hydrophobic interaction potential. A long-range and strong hydration repulsion at distances D > 3 nm, is followed by an instability which could be explained by a subsequent rapid ejection of adsorbed iodides from approaching hydrophobic interfaces. In addition, the authors find only a weakly pronounced influence of bromide, and as expected no influence of chloride. Also, all tested cations do not have any significant influence on HI. Complementary, x-ray photoelectron spectroscopy and quartz-crystal-microbalance with dissipation monitoring showed a clear adsorption of large halide ions (Br(-)/I(-)) onto hydrophobic self-assembled monolayers (SAMs). Interestingly, iodide can even lead to a full disintegration of SAMs due to specific and strong interactions of iodide with gold. Our data suggest that hydrophobic surfaces are not intrinsically charged negatively by hydroxide adsorption, as it was generally believed. Hydrophobic surfaces rather interact strongly with negatively charged large halide ions, leading to a surface charging and significant variation of interaction forces. PMID:26753786

  11. Ultraviolet absorption spectra of mercuric halides.

    NASA Technical Reports Server (NTRS)

    Templet, P.; Mcdonald, J. R.; Mcglynn, S. P.; Kendrow, C. H.; Roebber, J. L.; Weiss, K.

    1972-01-01

    The gas phase transitions of the mercuric halides were observed in the UV region by operating at temperatures above 400 K and at vapor pressures on the order of 0.5 mm. Spectral features exhibited by the chloride, bromide, and iodide of mercury correlate energetically with bands previously designated as intermolecular charge transfer transitions. The solution spectra of mercuric iodide and deep color of the crystals (if not due to some solid state interactions) indicate that this molecule may also have longer wavelength transitions.

  12. Raman spectra of hydroxide-halide melts

    NASA Astrophysics Data System (ADS)

    Zakiriyanova, I. D.; Khokhlov, V. A.

    2012-08-01

    The Raman spectra of molten binary mixtures based on sodium hydroxide and containing (mol %) 35 NaCl, 30 NaBr, and 30 NaI have been recorded at various temperatures. An increase in the vibrational frequency and the force constant of the O-H bond is detected under isothermal conditions upon a variation of the anionic composition of a melt in the series I → Br → Cl. Based on the experimental data, the viscosity of the hydroxide-halide melts is estimated.

  13. Alkali-Metal Spin Maser.

    PubMed

    Chalupczak, W; Josephs-Franks, P

    2015-07-17

    Quantum measurement is a combination of a read-out and a perturbation of the quantum system. We explore the nonlinear spin dynamics generated by a linearly polarized probe beam in a continuous measurement of the collective spin state in a thermal alkali-metal atomic sample. We demonstrate that the probe-beam-driven perturbation leads, in the presence of indirect pumping, to complete polarization of the sample and macroscopic coherent spin oscillations. As a consequence of the former we report observation of spectral profiles free from collisional broadening. Nonlinear dynamics is studied through exploring its effect on radio frequency as well as spin noise spectra. PMID:26230788

  14. Structural, dynamical, and transport properties of the hydrated halides: How do At(-) bulk properties compare with those of the other halides, from F(-) to I(-)?

    PubMed

    Réal, Florent; Gomes, André Severo Pereira; Guerrero Martínez, Yansel Omar; Ayed, Tahra; Galland, Nicolas; Masella, Michel; Vallet, Valérie

    2016-03-28

    The properties of halides from the lightest, fluoride (F(-)), to the heaviest, astatide (At(-)), have been studied in water using a polarizable force-field approach based on molecular dynamics (MD) simulations at the 10 ns scale. The selected force-field explicitly treats the cooperativity within the halide-water hydrogen bond networks. The force-field parameters have been adjusted to ab initio data on anion/water clusters computed at the relativistic Möller-Plesset second-order perturbation theory level of theory. The anion static polarizabilities of the two heaviest halides, I(-) and At(-), were computed in the gas phase using large and diffuse atomic basis sets, and taking into account both electron correlation and spin-orbit coupling within a four-component framework. Our MD simulation results show the solvation properties of I(-) and At(-) in aqueous phase to be very close. For instance, their first hydration shells are structured and encompass 9.2 and 9.1 water molecules at about 3.70 ± 0.05 Å, respectively. These values have to be compared to the F(-), Cl(-), and Br(-) ones, i.e., 6.3, 8.4, and 9.0 water molecules at 2.74, 3.38, and 3.55 Å, respectively. Moreover our computations predict the solvation free energy of At(-) in liquid water at ambient conditions to be 68 kcal mol(-1), a value also close the I(-) one, about 70 kcal mol(-1). In all, our simulation results for I(-) are in excellent agreement with the latest neutron- and X-ray diffraction studies. Those for the At(-) ion are predictive, as no theoretical or experimental data are available to date. PMID:27036467

  15. Structural, dynamical, and transport properties of the hydrated halides: How do At- bulk properties compare with those of the other halides, from F- to I-?

    NASA Astrophysics Data System (ADS)

    Réal, Florent; Severo Pereira Gomes, André; Guerrero Martínez, Yansel Omar; Ayed, Tahra; Galland, Nicolas; Masella, Michel; Vallet, Valérie

    2016-03-01

    The properties of halides from the lightest, fluoride (F-), to the heaviest, astatide (At-), have been studied in water using a polarizable force-field approach based on molecular dynamics (MD) simulations at the 10 ns scale. The selected force-field explicitly treats the cooperativity within the halide-water hydrogen bond networks. The force-field parameters have been adjusted to ab initio data on anion/water clusters computed at the relativistic Möller-Plesset second-order perturbation theory level of theory. The anion static polarizabilities of the two heaviest halides, I- and At-, were computed in the gas phase using large and diffuse atomic basis sets, and taking into account both electron correlation and spin-orbit coupling within a four-component framework. Our MD simulation results show the solvation properties of I- and At- in aqueous phase to be very close. For instance, their first hydration shells are structured and encompass 9.2 and 9.1 water molecules at about 3.70 ± 0.05 Å, respectively. These values have to be compared to the F-, Cl-, and Br- ones, i.e., 6.3, 8.4, and 9.0 water molecules at 2.74, 3.38, and 3.55 Å, respectively. Moreover our computations predict the solvation free energy of At- in liquid water at ambient conditions to be 68 kcal mol-1, a value also close the I- one, about 70 kcal mol-1. In all, our simulation results for I- are in excellent agreement with the latest neutron- and X-ray diffraction studies. Those for the At- ion are predictive, as no theoretical or experimental data are available to date.

  16. 10 CFR 429.54 - Metal halide lamp ballasts and fixtures.

    Code of Federal Regulations, 2012 CFR

    2012-01-01

    ... 10 Energy 3 2012-01-01 2012-01-01 false Metal halide lamp ballasts and fixtures. 429.54 Section... CONSUMER PRODUCTS AND COMMERCIAL AND INDUSTRIAL EQUIPMENT Certification § 429.54 Metal halide lamp ballasts... are applicable to metal halide lamp ballasts; and (2) For each basic model of metal halide...

  17. 10 CFR 429.54 - Metal halide lamp ballasts and fixtures.

    Code of Federal Regulations, 2014 CFR

    2014-01-01

    ... 10 Energy 3 2014-01-01 2014-01-01 false Metal halide lamp ballasts and fixtures. 429.54 Section... CONSUMER PRODUCTS AND COMMERCIAL AND INDUSTRIAL EQUIPMENT Certification § 429.54 Metal halide lamp ballasts... are applicable to metal halide lamp ballasts; and (2) For each basic model of metal halide...

  18. 10 CFR 429.54 - Metal halide lamp ballasts and fixtures.

    Code of Federal Regulations, 2013 CFR

    2013-01-01

    ... 10 Energy 3 2013-01-01 2013-01-01 false Metal halide lamp ballasts and fixtures. 429.54 Section... CONSUMER PRODUCTS AND COMMERCIAL AND INDUSTRIAL EQUIPMENT Certification § 429.54 Metal halide lamp ballasts... are applicable to metal halide lamp ballasts; and (2) For each basic model of metal halide...

  19. Methyl halide production associated with kelp

    NASA Technical Reports Server (NTRS)

    Dastoor, Minoo N.; Manley, Steven L.

    1985-01-01

    Methyl halides (MeX) are important trace constituents of the atmosphere because they, mostly MeCl, have a major impact on the atmospheric ozone layer. Also, MeCl may account for 5 pct. of the total Cl budget and MeI may have a central role in the biogeochemical cycling of iodine. High MeI concentrations were found in seawater from kelp beds and it has been suggested that MeI is produced by kelps and that MeI and MeBr along with numerous other halocarbons were released by non-kelp marine macroalgae. The objective was to determine if kelps (and other seaweeds) are sources of MeX and to assess their contribution to the estimated global source strength (EGSS) of MeX. Although the production of MeX appears to be associated with kelp, microbes involved with kelp degradation also produce MeX. Microbial MeX production may be of global significance. The microbial MeX production potential, assuming annual kelp production equals kelp degradation and 100 pct. conversion of kelp halides to MeX, is approx. 2 x the EGSS. This is not achieved but indicates that microbial production of MeX may be of global significance.

  20. Finding new perovskite halides via machine learning

    DOE PAGESBeta

    Pilania, Ghanshyam; Balachandran, Prasanna V.; Kim, Chiho; Lookman, Turab

    2016-04-26

    Advanced materials with improved properties have the potential to fuel future technological advancements. However, identification and discovery of these optimal materials for a specific application is a non-trivial task, because of the vastness of the chemical search space with enormous compositional and configurational degrees of freedom. Materials informatics provides an efficient approach toward rational design of new materials, via learning from known data to make decisions on new and previously unexplored compounds in an accelerated manner. Here, we demonstrate the power and utility of such statistical learning (or machine learning, henceforth referred to as ML) via building a support vectormore » machine (SVM) based classifier that uses elemental features (or descriptors) to predict the formability of a given ABX3 halide composition (where A and B represent monovalent and divalent cations, respectively, and X is F, Cl, Br, or I anion) in the perovskite crystal structure. The classification model is built by learning from a dataset of 185 experimentally known ABX3 compounds. After exploring a wide range of features, we identify ionic radii, tolerance factor, and octahedral factor to be the most important factors for the classification, suggesting that steric and geometric packing effects govern the stability of these halides. As a result, the trained and validated models then predict, with a high degree of confidence, several novel ABX3 compositions with perovskite crystal structure.« less

  1. Finding New Perovskite Halides via Machine learning

    NASA Astrophysics Data System (ADS)

    Pilania, Ghanshyam; Balachandran, Prasanna V.; Kim, Chiho; Lookman, Turab

    2016-04-01

    Advanced materials with improved properties have the potential to fuel future technological advancements. However, identification and discovery of these optimal materials for a specific application is a non-trivial task, because of the vastness of the chemical search space with enormous compositional and configurational degrees of freedom. Materials informatics provides an efficient approach towards rational design of new materials, via learning from known data to make decisions on new and previously unexplored compounds in an accelerated manner. Here, we demonstrate the power and utility of such statistical learning (or machine learning) via building a support vector machine (SVM) based classifier that uses elemental features (or descriptors) to predict the formability of a given ABX3 halide composition (where A and B represent monovalent and divalent cations, respectively, and X is F, Cl, Br or I anion) in the perovskite crystal structure. The classification model is built by learning from a dataset of 181 experimentally known ABX3 compounds. After exploring a wide range of features, we identify ionic radii, tolerance factor and octahedral factor to be the most important factors for the classification, suggesting that steric and geometric packing effects govern the stability of these halides. The trained and validated models then predict, with a high degree of confidence, several novel ABX3 compositions with perovskite crystal structure.

  2. Process for the disposal of alkali metals

    DOEpatents

    Lewis, Leroy C.

    1977-01-01

    Large quantities of alkali metals may be safely reacted for ultimate disposal by contact with a hot concentrated caustic solution. The alkali metals react with water in the caustic solution in a controlled reaction while steam dilutes the hydrogen formed by the reaction to a safe level.

  3. The alkali metals: 200 years of surprises.

    PubMed

    Dye, James L

    2015-03-13

    Alkali metal compounds have been known since antiquity. In 1807, Sir Humphry Davy surprised everyone by electrolytically preparing (and naming) potassium and sodium metals. In 1808, he noted their interaction with ammonia, which, 100 years later, was attributed to solvated electrons. After 1960, pulse radiolysis of nearly any solvent produced solvated electrons, which became one of the most studied species in chemistry. In 1968, alkali metal solutions in amines and ethers were shown to contain alkali metal anions in addition to solvated electrons. The advent of crown ethers and cryptands as complexants for alkali cations greatly enhanced alkali metal solubilities. This permitted us to prepare a crystalline salt of Na(-) in 1974, followed by 30 other alkalides with Na(-), K(-), Rb(-) and Cs(-) anions. This firmly established the -1 oxidation state of alkali metals. The synthesis of alkalides led to the crystallization of electrides, with trapped electrons as the anions. Electrides have a variety of electronic and magnetic properties, depending on the geometries and connectivities of the trapping sites. In 2009, the final surprise was the experimental demonstration that alkali metals under high pressure lose their metallic character as the electrons are localized in voids between the alkali cations to become high-pressure electrides! PMID:25666067

  4. Tellurite glass as a waste form for mixed alkali-chloride waste streams: Candidate materials selection and initial testing

    NASA Astrophysics Data System (ADS)

    Riley, Brian J.; Rieck, Bennett T.; McCloy, John S.; Crum, Jarrod V.; Sundaram, S. K.; Vienna, John D.

    2012-05-01

    Tellurite glasses have historically been shown to host large concentrations of halides. They are here considered for the first time as a waste form for immobilizing chloride wastes, such as may be generated in the proposed molten alkali salt electrochemical separations step in nuclear fuel reprocessing. Key properties of several tellurite glasses are determined to assess acceptability as a chloride waste form. TeO2 glasses with other oxides (PbO, Al2O3 + B2O3, WO3, P2O5, or ZnO) were fabricated with and without 10 mass% of a simulated (non-radioactive) mixed alkali, alkaline-earth, and rare earth chloride waste. Measured chemical durability is compared for the glasses, as determined by the product consistency test (PCT), a common standardized chemical durability test often used to validate borosilicate glass waste forms. The glass with the most promise as a waste form is the TeO2-PbO system, as it offers good halide retention, a low sodium release (by PCT) comparable with high-level waste silicate glass waste forms, and a high storage density.

  5. Method of handling radioactive alkali metal waste

    DOEpatents

    Wolson, Raymond D.; McPheeters, Charles C.

    1980-01-01

    Radioactive alkali metal is mixed with particulate silica in a rotary drum reactor in which the alkali metal is converted to the monoxide during rotation of the reactor to produce particulate silica coated with the alkali metal monoxide suitable as a feed material to make a glass for storing radioactive material. Silica particles, the majority of which pass through a 95 mesh screen or preferably through a 200 mesh screen, are employed in this process, and the preferred weight ratio of silica to alkali metal is 7 to 1 in order to produce a feed material for the final glass product having a silica to alkali metal monoxide ratio of about 5 to 1.

  6. Method of handling radioactive alkali metal waste

    DOEpatents

    Wolson, R.D.; McPheeters, C.C.

    Radioactive alkali metal is mixed with particulate silica in a rotary drum reactor in which the alkali metal is converted to the monoxide during rotation of the reactor to produce particulate silica coated with the alkali metal monoxide suitable as a feed material to make a glass for storing radioactive material. Silica particles, the majority of which pass through a 95 mesh screen or preferably through a 200 mesh screen, are employed in this process, and the preferred weight ratio of silica to alkali metal is 7 to 1 in order to produce a feed material for the final glass product having a silica to alkali metal monoxide ratio of about 5 to 1.

  7. BEAM EXPOSURE DEPENDENCE AND MECHANISMS OF PHOTON-STIMULATED DESORPTION FROM ALKALI FLUORIDES

    SciTech Connect

    Parks, C.C.; Shirley, D.A.; Loubriel, G.

    1983-11-01

    Photon-stimulated desorption experiments were performed on the (001) face of LiF for photon energies near the F(2s) and Li(ls) edges (from 37 to 72 eV). There are structures in the F{sup +} yield above the F(2s) edge which are absent in the Li{sup +} spectrum, differences in detail in the Li{sup +} and F{sup +} yields near the Li(1s) edge, and considerable broadening of the desorption yields as compared to the bulk photoabsorption spectrum. The first observation of a strong x-ray, and visible, beam exposure dependence of ion yields from LiF and NaF is also presented. These results are discussed in terms of electronic and defect properties of alkali halides.

  8. Adsorption of hydrated halide ions on charged electrodes: Molecular dynamics simulation

    NASA Astrophysics Data System (ADS)

    Glosli, James N.; Philpott, Michael R.

    1993-04-01

    Constant temperature molecular dynamics has been used to simulate the adsorption of hydrated halide ion X(-) = F(-), Cl(-), Br(-), and I(-), and lithium ion Li(+) on a flat uniformly charged surfaces. The simulations were done with either 214 water molecules and two ions (Li(+) and X(-)) in a box 2.362 nm deep or with 430 water molecules and the two ions in a box 4.320 nm deep. The boxes were periodically replicated in the xy directions. The magnitude of the surface charge on the box end was + or - 0.11 c/nm(sup 2), corresponding to an electric field of 2 x 10(exp 7) V/cm. The lateral dimensions of the simulation cell were 1.862 nm x 1.862 nm (x times y) in each case. All of the water molecules and ions interacted with the end walls via a weak 9 - 3 potential. The ST2 water model and parameters optimized for alkali halides interacting with the model ST2 water molecule were used in the calculations. Common practices of truncating the interactions at a finite distance (0.82 nm) and switching off Coulomb interactions at small distances were followed. The temperature was set at T = 2.411 kJ/mole (290 K). Some of the properties calculated were: distribution density profiles for ions and water across the gap important for comparisons iwth Gouy-Chapman theory, adsorbed ion-water pair correlation functions, the number of water molecules in the first and second hydration shells of the ions as a function of time. The time spent by a water molecule in the hydration shell was calculated to be approximately ten times longer for lithium than any other ion. The correlation between distance from the electrode and hydration number was studied and generally found to be pronounced for the larger anions.

  9. Halide-Substituted Electronic Properties of Organometal Halide Perovskite Films: Direct and Inverse Photoemission Studies.

    PubMed

    Li, Chi; Wei, Jian; Sato, Mikio; Koike, Harunobu; Xie, Zhong-Zhi; Li, Yan-Qing; Kanai, Kaname; Kera, Satoshi; Ueno, Nobuo; Tang, Jian-Xin

    2016-05-11

    Solution-processed perovskite solar cells are attracting increasing interest due to their potential in next-generation hybrid photovoltaic devices. Despite the morphological control over the perovskite films, quantitative information on electronic structures and interface energetics is of paramount importance to the optimal photovoltaic performance. Here, direct and inverse photoemission spectroscopies are used to determine the electronic structures and chemical compositions of various methylammonium lead halide perovskite films (MAPbX3, X = Cl, Br, and I), revealing the strong influence of halide substitution on the electronic properties of perovskite films. Precise control over halide compositions in MAPbX3 films causes the manipulation of the electronic properties, with a qualitatively blue shift along the I → Br → Cl series and showing the increase in ionization potentials from 5.96 to 7.04 eV and the change of transport band gaps in the range from 1.70 to 3.09 eV. The resulting light absorption of MAPbX3 films can cover the entire visible region from 420 to 800 nm. The results presented here provide a quantitative guide for the analysis of perovskite-based solar cell performance and the selection of optimal carrier-extraction materials for photogenerated electrons and holes. PMID:27101940

  10. Unraveling the Role of Monovalent Halides in Mixed-Halide Organic-Inorganic Perovskites.

    PubMed

    Deepa, Melepurath; Ramos, F Javier; Shivaprasad, S M; Ahmad, Shahzada

    2016-03-16

    The performance of perovskite solar cells is strongly influenced by the composition and microstructure of the perovskite. A recent approach to improve the power conversion efficiencies utilized mixed-halide perovskites, but the halide ions and their roles were not directly studied. Unraveling their precise location in the perovskite layer is of paramount importance. Here, we investigated four different perovskites by using X-ray photoelectron spectroscopy, and found that among the three studied mixed-halide perovskites, CH3 NH3 Pb(I0.74 Br0.26 )3 and CH3 NH3 PbBr3-x Clx show peaks that unambiguously demonstrate the presence of iodide and bromide in the former, and bromide and chloride in the latter. The CH3 NH3 PbI3-x Clx perovskite shows anomalous behavior, the iodide content far outweighs that of the chloride; a small proportion of chloride, in all likelihood, resides deep within the TiO2 /absorber layer. Our study reveals that there are many distinguishable structural differences between these perovskites, and that these directly impact the photovoltaic performances. PMID:26717046

  11. Vibrational Spectroscopy of Sodium Halide and Hydrogen Halide Aqueous Solutions: Application to Atmospheric Aerosol Chemistry

    NASA Astrophysics Data System (ADS)

    Levering, L. M.; Liu, D.; Allen, H. C.

    2003-12-01

    Heterogeneous reactions on the surfaces of atmospheric aerosols play an important role in atmospheric chemistry. These reactions are capable of converting alkyl and hydrogen halides (common constituents of marine boundary aerosols) into active halogen compounds. Fundamental questions still remain concerning surface species and reaction mechanisms pertaining to marine boundary aerosols. The first step in beginning to understand these heterogeneous reactions is to determine how ions in solution affect the structure of water at the interface. Vibrational sum frequency generation spectroscopy is used to examine the air-liquid interface of sodium halide and hydrogen halide (i.e. strong acid) solutions. In addition, comparison of the bulk water structure to that of the interface is accomplished using Raman spectroscopy. The hydrogen-bonding environment at the surface of NaCl is found to be similar to that of the air-water interface. In contrast, the interfacial water structure of NaBr, HCl, and HBr solutions is significantly altered from that of neat water. In the bulk, NaCl, NaBr, HCl, and HBr solutions disturb the hydrogen-bonding network of neat water. A comparison between the corresponding salts and acids show that the salts produce greater disorder (i.e. less coupling of the water symmetric stretching modes) in the bulk water structure.

  12. Alkali burns from wet cement.

    PubMed Central

    Peters, W. J.

    1984-01-01

    When water is added to the dry materials of Portland cement calcium hydroxide is formed; the wet cement is caustic (with a pH as high as 12.9) and can produce third-degree alkali burns after 2 hours of contact. Unlike professional cement workers, amateurs are usually not aware of any danger and may stand or kneel in the cement for long periods. As illustrated in a case report, general physicians may recognize neither the seriousness of the injury in its early stages nor the significance of a history of prolonged contact with wet cement. All people working with cement should be warned about its dangers and advised to immediately wash and dry the skin if contact does occur. Images Fig. 1 PMID:6561052

  13. Aqueous Copper(II) Photoinduced Polymerization of Acrylates: Low Copper Concentration and the Importance of Sodium Halide Salts.

    PubMed

    Jones, Glen R; Whitfield, Richard; Anastasaki, Athina; Haddleton, David M

    2016-06-15

    Photoinduced metal-mediated radical polymerization is a rapidly developing technique which allows for the synthesis of macromolecules with defined molecular weight and narrow molecular weight distributions, although typically exhibiting significant limitations in aqueous media. Herein we demonstrate that the presence of alkali metal halide salts, in conjunction with low copper concentration and UV irradiation, allows for the controlled polymerization of water-soluble acrylates in aqueous media, yielding narrow molecular weight distributions and high conversions. Despite the aqueous environment which typically compromises polymer end group fidelity, chain extensions have also been successfully performed and different degrees of polymerization were targeted. Importantly, no conversion was observed in the absence of UV light and the polymerization could be switched "on" and "off" upon demand, as demonstrated by intermittent light and dark periods and thus allowing access to spatiotemporal control. PMID:27184213

  14. Passive particle dosimetry. [silver halide crystal growth

    NASA Technical Reports Server (NTRS)

    Childs, C. B.

    1977-01-01

    Present methods of dosimetry are reviewed with emphasis on the processes using silver chloride crystals for ionizing particle dosimetry. Differences between the ability of various crystals to record ionizing particle paths are directly related to impurities in the range of a few ppm (parts per million). To understand the roles of these impurities in the process, a method for consistent production of high purity silver chloride, and silver bromide was developed which yields silver halides with detectable impurity content less than 1 ppm. This high purity silver chloride was used in growing crystals with controlled doping. Crystals were grown by both the Czochalski method and the Bridgman method, and the Bridgman grown crystals were used for the experiments discussed. The distribution coefficients of ten divalent cations were determined for the Bridgman crystals. The best dosimeters were made with silver chloride crystals containing 5 to 10 ppm of lead; other impurities tested did not produce proper dosimeters.

  15. Metal halide perovskites for energy applications

    NASA Astrophysics Data System (ADS)

    Zhang, Wei; Eperon, Giles E.; Snaith, Henry J.

    2016-06-01

    Exploring prospective materials for energy production and storage is one of the biggest challenges of this century. Solar energy is one of the most important renewable energy resources, due to its wide availability and low environmental impact. Metal halide perovskites have emerged as a class of semiconductor materials with unique properties, including tunable bandgap, high absorption coefficient, broad absorption spectrum, high charge carrier mobility and long charge diffusion lengths, which enable a broad range of photovoltaic and optoelectronic applications. Since the first embodiment of perovskite solar cells showing a power conversion efficiency of 3.8%, the device performance has been boosted up to a certified 22.1% within a few years. In this Perspective, we discuss differing forms of perovskite materials produced via various deposition procedures. We focus on their energy-related applications and discuss current challenges and possible solutions, with the aim of stimulating potential new applications.

  16. Integrating Sphere Alkali-Metal Vapor Cells

    NASA Astrophysics Data System (ADS)

    McGuyer, Bart; Ben-Kish, Amit; Jau, Yuan-Yu; Happer, William

    2010-03-01

    An integrating sphere is an optical multi-pass cavity that uses diffuse reflection to increase the optical path length. Typically applied in photometry and radiometry, integrating spheres have previously been used to detect trace gases and to cool and trap alkali-metal atoms. Here, we investigate the potential for integrating spheres to enhance optical absorption in optically thin alkali-metal vapor cells. In particular, we consider the importance of dielectric effects due to a glass container for the alkali-metal vapor. Potential applications include miniature atomic clocks and magnetometers, where multi-passing could reduce the operating temperature and power consumption.

  17. Alkali Silicate Vehicle Forms Durable, Fireproof Paint

    NASA Technical Reports Server (NTRS)

    Schutt, John B.; Seindenberg, Benjamin

    1964-01-01

    The problem: To develop a paint for use on satellites or space vehicles that exhibits high resistance to cracking, peeling, or flaking when subjected to a wide range of temperatures. Organic coatings will partially meet the required specifications but have the inherent disadvantage of combustibility. Alkali-silicate binders, used in some industrial coatings and adhesives, show evidence of forming a fireproof paint, but the problem of high surface-tension, a characteristic of alkali silicates, has not been resolved. The solution: Use of a suitable non-ionic wetting agent combined with a paint incorporating alkali silicate as the binder.

  18. Diode pumped alkali vapor fiber laser

    DOEpatents

    Payne, Stephen A.; Beach, Raymond J.; Dawson, Jay W.; Krupke, William F.

    2007-10-23

    A method and apparatus is provided for producing near-diffraction-limited laser light, or amplifying near-diffraction-limited light, in diode pumped alkali vapor photonic-band-gap fiber lasers or amplifiers. Laser light is both substantially generated and propagated in an alkali gas instead of a solid, allowing the nonlinear and damage limitations of conventional solid core fibers to be circumvented. Alkali vapor is introduced into the center hole of a photonic-band-gap fiber, which can then be pumped with light from a pump laser and operated as an oscillator with a seed beam, or can be configured as an amplifier.

  19. Diode pumped alkali vapor fiber laser

    DOEpatents

    Payne, Stephen A.; Beach, Raymond J.; Dawson, Jay W.; Krupke, William F.

    2006-07-26

    A method and apparatus is provided for producing near-diffraction-limited laser light, or amplifying near-diffraction-limited light, in diode pumped alkali vapor photonic-band-gap fiber lasers or amplifiers. Laser light is both substantially generated and propagated in an alkali gas instead of a solid, allowing the nonlinear and damage limitations of conventional solid core fibers to be circumvented. Alkali vapor is introduced into the center hole of a photonic-band-gap fiber, which can then be pumped with light from a pump laser and operated as an oscillator with a seed beam, or can be configured as an amplifier.

  20. Advancements in flowing diode pumped alkali lasers

    NASA Astrophysics Data System (ADS)

    Pitz, Greg A.; Stalnaker, Donald M.; Guild, Eric M.; Oliker, Benjamin Q.; Moran, Paul J.; Townsend, Steven W.; Hostutler, David A.

    2016-03-01

    Multiple variants of the Diode Pumped Alkali Laser (DPAL) have recently been demonstrated at the Air Force Research Laboratory (AFRL). Highlights of this ongoing research effort include: a) a 571W rubidium (Rb) based Master Oscillator Power Amplifier (MOPA) with a gain (2α) of 0.48 cm-1, b) a rubidium-cesium (Cs) Multi-Alkali Multi-Line (MAML) laser that simultaneously lases at both 795 nm and 895 nm, and c) a 1.5 kW resonantly pumped potassium (K) DPAL with a slope efficiency of 50%. The common factor among these experiments is the use of a flowing alkali test bed.

  1. Electronic and Ionic Transport Dynamics in Organolead Halide Perovskites.

    PubMed

    Li, Dehui; Wu, Hao; Cheng, Hung-Chieh; Wang, Gongming; Huang, Yu; Duan, Xiangfeng

    2016-07-26

    Ion migration has been postulated as the underlying mechanism responsible for the hysteresis in organolead halide perovskite devices. However, the electronic and ionic transport dynamics and how they impact each other in organolead halide perovskites remain elusive to date. Here we report a systematic investigation of the electronic and ionic transport dynamics in organolead halide perovskite microplate crystals and thin films using temperature-dependent transient response measurements. Our study reveals that thermally activated ionic and electronic conduction coexist in perovskite devices. The extracted activation energies suggest that the electronic transport is easier, but ions migrate harder in microplates than in thin films, demonstrating that the crystalline quality and grain boundaries can fundamentally modify electronic and ionic transport in perovskites. These findings offer valuable insight on the electronic and ionic transport dynamics in organolead halide perovskites, which is critical for optimizing perovskite devices with reduced hysteresis and improved stability and efficiency. PMID:27315525

  2. Alkali metal for ultraviolet band-pass filter

    NASA Technical Reports Server (NTRS)

    Mardesich, Nick (Inventor); Fraschetti, George A. (Inventor); Mccann, Timothy A. (Inventor); Mayall, Sherwood D. (Inventor); Dunn, Donald E. (Inventor); Trauger, John T. (Inventor)

    1993-01-01

    An alkali metal filter having a layer of metallic bismuth deposited onto the alkali metal is provided. The metallic bismuth acts to stabilize the surface of the alkali metal to prevent substantial surface migration from occurring on the alkali metal, which may degrade optical characteristics of the filter. To this end, a layer of metallic bismuth is deposited by vapor deposition over the alkali metal to a depth of approximately 5 to 10 A. A complete alkali metal filter is described along with a method for fabricating the alkali metal filter.

  3. Alkali Metal Handling Practices at NASA MSFC

    NASA Technical Reports Server (NTRS)

    Salvail, Patrick G.; Carter, Robert R.

    2002-01-01

    NASA Marshall Space Flight Center (MSFC) is NASA s principle propulsion development center. Research and development is coordinated and carried out on not only the existing transportation systems, but also those that may be flown in the near future. Heat pipe cooled fast fission cores are among several concepts being considered for the Nuclear Systems Initiative. Marshall Space Flight Center has developed a capability to handle high-purity alkali metals for use in heat pipes or liquid metal heat transfer loops. This capability is a low budget prototype of an alkali metal handling system that would allow the production of flight qualified heat pipe modules or alkali metal loops. The processing approach used to introduce pure alkali metal into heat pipe modules and other test articles are described in this paper.

  4. Alkali-metal intercalation in carbon nanotubes

    NASA Astrophysics Data System (ADS)

    Béguin, F.; Duclaux, L.; Méténier, K.; Frackowiak, E.; Salvetat, J. P.; Conard, J.; Bonnamy, S.; Lauginie, P.

    1999-09-01

    We report on successful intercalation of multiwall (MWNT) and single wall (SWNT) carbon nanotubes with alkali metals by electrochemical and vapor phase reactions. A LiC10 compound was produced by full electrochemical reduction of MWNT. KC8 and CsC8-MWNT first stage derivatives were synthesized in conditions of alkali vapor saturation. Their identity periods and the 2×2 R 0° alkali superlattice are comparable to their parent graphite compounds. The dysonian shape of KC8 EPR line and the temperature-independent Pauli susceptibility are both characteristic of a metallic behavior, which was confirmed by 13C NMR anisotropic shifts. Exposure of SWNT bundles to alkali vapor led to an increase of the pristine triangular lattice from 1.67 nm to 1.85 nm and 1.87 nm for potassium and rubidium, respectively.

  5. Alkali metal intercalates of molybdenum disulfide.

    NASA Technical Reports Server (NTRS)

    Somoano, R. B.; Hadek, V.; Rembaum, A.

    1973-01-01

    Study of some of the physicochemical properties of compounds obtained by subjecting natural molybdenite and single crystals of molybdenum disulfide grown by chemical vapor transport to intercalation with the alkali group of metals (Li, Na, K, Rb, and Cs) by means of the liquid ammonia technique. Reported data and results include: (1) the intercalation of the entire alkali metal group, (2) stoichiometries and X-ray data on all of the compounds, and (3) superconductivity data for all the intercalation compounds.

  6. Superconductivity in alkali-doped C60

    NASA Astrophysics Data System (ADS)

    Ramirez, Arthur P.

    2015-07-01

    Superconductivity in alkali-doped C60 (A3C60, A = an alkali atom) is well described by an s-wave state produced by phonon mediated pairing. Moderate coupling of electrons to high-frequency shape-changing intra-molecular vibrational modes produces transition temperatures (Tc) up to 33 K in single-phase material. The good understanding of pairing in A3C60 offers a paradigm for the development of new superconducting materials.

  7. Desulfurizing Coal With an Alkali Treatment

    NASA Technical Reports Server (NTRS)

    Ravindram, M.; Kalvinskas, J. J.

    1987-01-01

    Experimental coal-desulfurization process uses alkalies and steam in fluidized-bed reactor. With highly volatile, high-sulfur bituminous coal, process removed 98 percent of pyritic sulfur and 47 percent of organic sulfur. Used in coal liquefaction and in production of clean solid fuels and synthetic liquid fuels. Nitrogen or steam flows through bed of coal in reactor. Alkalies react with sulfur, removing it from coal. Nitrogen flow fluidizes bed while heating or cooling; steam is fluidizing medium during reaction.

  8. Analysis of the physical atomic forces between noble gas atoms, alkali ions and halogen ions

    NASA Technical Reports Server (NTRS)

    Wilson, J. W.; Heinbockel, J. H.; Outlaw, R. A.

    1986-01-01

    The physical forces between atoms and molecules are important in a number of processes of practical importance, including line broadening in radiative processes, gas and crystal properties, adhesion, and thin films. The components of the physical forces between noble gas atoms, alkali ions, and halogen ions are analyzed and a data base for the dispersion forces is developed from the literature based on evaluations with the harmonic oscillator dispersion model for higher order coefficients. The Zener model of the repulsive core is used in the context of the recent asymptotic wave functions of Handler and Smith; and an effective ionization potential within the Handler and Smith wave functions is defined to analyze the two body potential data of Waldman and Gordon, the alkali-halide molecular data, and the noble gas crystal and salt crystal data. A satisfactory global fit to this molecular and crystal data is then reproduced by the model to within several percent. Surface potentials are evaluated for noble gas atoms on noble gas and salt crystal surfaces with surface tension neglected. Within this context, the noble gas surface potentials on noble gas and salt crystals are considered to be accurate to within several percent.

  9. Alkali metal crystalline polymer electrolytes.

    PubMed

    Zhang, Chuhong; Gamble, Stephen; Ainsworth, David; Slawin, Alexandra M Z; Andreev, Yuri G; Bruce, Peter G

    2009-07-01

    Polymer electrolytes have been studied extensively because uniquely they combine ionic conductivity with solid yet flexible mechanical properties, rendering them important for all-solid-state devices including batteries, electrochromic displays and smart windows. For some 30 years, ionic conductivity in polymers was considered to occur only in the amorphous state above Tg. Crystalline polymers were believed to be insulators. This changed with the discovery of Li(+) conductivity in crystalline poly(ethylene oxide)(6):LiAsF(6). However, new crystalline polymer electrolytes have proved elusive, questioning whether the 6:1 complex has particular structural features making it a unique exception to the rule that only amorphous polymers conduct. Here, we demonstrate that ionic conductivity in crystalline polymers is not unique to the 6:1 complex by reporting several new crystalline polymer electrolytes containing different alkali metal salts (Na(+), K(+) and Rb(+)), including the best conductor poly(ethylene oxide)(8):NaAsF(6) discovered so far, with a conductivity 1.5 orders of magnitude higher than poly(ethylene oxide)(6):LiAsF(6). These are the first crystalline polymer electrolytes with a different composition and structures to that of the 6:1 Li(+) complex. PMID:19543313

  10. New gas phase inorganic ion cluster species and their atmospheric implications

    NASA Technical Reports Server (NTRS)

    Maerk, T. D.; Peterson, K. I.; Castleman, A. W., Jr.

    1980-01-01

    Recent experimental laboratory observations, with high-pressure mass spectroscopy, have revealed the existence of previously unreported species involving water clustered to sodium dimer ions, and alkali metal hydroxides clustered to alkali metal ions. The important implications of these results concerning the existence of such species are here discussed, as well as how from a practical aspect they confirm the stability of certain cluster species proposed by Ferguson (1978) to explain masses recently detected at upper altitudes using mass spectrometric techniques.

  11. New gas phase inorganic ion cluster species and their atmospheric implications

    NASA Astrophysics Data System (ADS)

    Maerk, T. D.; Peterson, K. I.; Castleman, A. W., Jr.

    1980-06-01

    Recent experimental laboratory observations, with high-pressure mass spectroscopy, have revealed the existence of previously unreported species involving water clustered to sodium dimer ions, and alkali metal hydroxides clustered to alkali metal ions. The important implications of these results concerning the existence of such species are here discussed, as well as how from a practical aspect they confirm the stability of certain cluster species proposed by Ferguson (1978) to explain masses recently detected at upper altitudes using mass spectrometric techniques.

  12. Effects of Halide Ions on the Carbamidocyclophane Biosynthesis in Nostoc sp. CAVN2

    PubMed Central

    Preisitsch, Michael; Heiden, Stefan E.; Beerbaum, Monika; Niedermeyer, Timo H. J.; Schneefeld, Marie; Herrmann, Jennifer; Kumpfmüller, Jana; Thürmer, Andrea; Neidhardt, Inga; Wiesner, Christoph; Daniel, Rolf; Müller, Rolf; Bange, Franz-Christoph; Schmieder, Peter; Schweder, Thomas; Mundt, Sabine

    2016-01-01

    In this study, the influence of halide ions on [7.7]paracyclophane biosynthesis in the cyanobacterium Nostoc sp. CAVN2 was investigated. In contrast to KI and KF, supplementation of the culture medium with KCl or KBr resulted not only in an increase of growth but also in an up-regulation of carbamidocyclophane production. LC-MS analysis indicated the presence of chlorinated, brominated, but also non-halogenated derivatives. In addition to 22 known cylindrocyclophanes and carbamidocyclophanes, 27 putative congeners have been detected. Nine compounds, carbamidocyclophanes M−U, were isolated, and their structural elucidation by 1D and 2D NMR experiments in combination with HRMS and ECD analysis revealed that they are brominated analogues of chlorinated carbamidocyclophanes. Quantification of the carbamidocyclophanes showed that chloride is the preferably utilized halide, but incorporation is reduced in the presence of bromide. Evaluation of the antibacterial activity of 30 [7.7]paracyclophanes and related derivatives against selected pathogenic Gram-positive and Gram-negative bacteria exhibited remarkable effects especially against methicillin- and vancomycin-resistant staphylococci and Mycobacterium tuberculosis. For deeper insights into the mechanisms of biosynthesis, the carbamidocyclophane biosynthetic gene cluster in Nostoc sp. CAVN2 was studied. The gene putatively coding for the carbamoyltransferase has been identified. Based on bioinformatic analyses, a possible biosynthetic assembly is discussed. PMID:26805858

  13. Color silver halide hologram production and mastering

    NASA Astrophysics Data System (ADS)

    Bjelkhagen, Hans I.; Huang, Qiang

    1997-04-01

    Color reflection holograms recorded with the Denisyuk geometry have been demonstrated by the recently formed HOLOS Corporation in New Hampshire. The Slavich red-green-blue (RGB) sensitized ultra-high resolution silver halide emulsion was used for the hologram recording. The employed laser wavelengths were 647 nm, 532 nm, and 476 nm, generated by an argon ion, a frequency doubled Nd:YAG, and a krypton ion laser, respectively. A beam combination mechanism with dichroic filters enabled a simultaneous RGB exposure, which made the color balance and overall exposure energy easy to control as well as simplifying the recording procedure. HOLOS has been producing limited edition color holograms in various sizes from 4' X 5' to 12' X 16'. A 30 foot long optical table and high power lasers will enable HOLOS to record color holograms up to the size of one meter square in the near future. Various approaches have been investigated in generating color hologram masters which have sufficiently high diffraction efficiency to contact copy the color images onto photopolymer materials. A specially designed test object including the 1931 CIE chromaticity diagram, a rainbow ribbon cable, pure yellow dots, and a cloisonne elephant was used for color recording experiments. In addition, the Macbeth Color Checker chart was used. Both colorimetric evaluation and scattering noise measurements were performed using the PR-650 Photo Research SpectraScan SpectraCalorimeter.

  14. Charge carrier mobility in hybrid halide perovskites

    PubMed Central

    Motta, Carlo; El-Mellouhi, Fedwa; Sanvito, Stefano

    2015-01-01

    The charge transport properties of hybrid halide perovskites are investigated with a combination of density functional theory including van der Waals interaction and the Boltzmann theory for diffusive transport in the relaxation time approximation. We find the mobility of electrons to be in the range 5–10 cm2V−1s−1 and that for holes within 1–5 cm2V−1s−1, where the variations depend on the crystal structure investigated and the level of doping. Such results, in good agreement with recent experiments, set the relaxation time to about 1 ps, which is the time-scale for the molecular rotation at room temperature. For the room temperature tetragonal phase we explore two possible orientations of the organic cations and find that the mobility has a significant asymmetry depending on the direction of the current with respect to the molecular axis. This is due mostly to the way the PbI3 octahedral symmetry is broken. Interestingly we find that substituting I with Cl has minor effects on the mobilities. Our analysis suggests that the carrier mobility is probably not a key factor in determining the high solar-harvesting efficiency of this class of materials. PMID:26235910

  15. Genetic Control of Methyl Halide Production in Arabidopsis

    NASA Astrophysics Data System (ADS)

    Rhew, R. C.; Ostergaard, L.; Saltzman, E. S.; Yanofsky, M. F.

    2003-12-01

    Methyl chloride and methyl bromide are the primary carriers of natural chlorine and bromine to the stratosphere where they catalyze the destruction of ozone, whereas methyl iodide influences aerosol formation and ozone loss in the troposphere. Methyl bromide is also an agricultural fumigant whose use is scheduled to be phased out by international agreement. Despite the economic and environmental importance of these methyl halides, their natural sources and biological production mechanisms are poorly understood. Currently identified sources include oceans, biomass burning, industrial and agricultural use, fuel combustion, salt marshes, wetlands, rice paddies, certain terrestrial plants and fungi, and abiotic processes. We demonstrate that the model plant Arabidopsis thaliana produces and emits methyl halides and that the enzyme primarily responsible for the production is encoded by the HARMLESS TO OZONE LAYER (HOL) gene located on chromosome II. In mutant plants that have a disruption of the HOL gene, methyl halide production is largely eliminated. A phylogenetic analysis using the HOL gene suggests that the ability to produce methyl halides is widespread among vascular plants. This approach provides a genetic basis for understanding and predicting patterns of methyl halide production by plants.

  16. Halide Perovskites: Poor Man's High-Performance Semiconductors.

    PubMed

    Stoumpos, Constantinos C; Kanatzidis, Mercouri G

    2016-07-01

    Halide perovskites are a rapidly developing class of medium-bandgap semiconductors which, to date, have been popularized on account of their remarkable success in solid-state heterojunction solar cells raising the photovoltaic efficiency to 20% within the last 5 years. As the physical properties of the materials are being explored, it is becoming apparent that the photovoltaic performance of the halide perovskites is just but one aspect of the wealth of opportunities that these compounds offer as high-performance semiconductors. From unique optical and electrical properties stemming from their characteristic electronic structure to highly efficient real-life technological applications, halide perovskites constitute a brand new class of materials with exotic properties awaiting discovery. The nature of halide perovskites from the materials' viewpoint is discussed here, enlisting the most important classes of the compounds and describing their most exciting properties. The topics covered focus on the optical and electrical properties highlighting some of the milestone achievements reported to date but also addressing controversies in the vastly expanding halide perovskite literature. PMID:27174223

  17. Two Dimensional Organometal Halide Perovskite Nanorods with Tunable Optical Properties.

    PubMed

    Aharon, Sigalit; Etgar, Lioz

    2016-05-11

    Organo-metal halide perovskite is an efficient light harvester in photovoltaic solar cells. Organometal halide perovskite is used mainly in its "bulk" form in the solar cell. Confined perovskite nanostructures could be a promising candidate for efficient optoelectronic devices, taking advantage of the superior bulk properties of organo-metal halide perovskite, as well as the nanoscale properties. In this paper, we present facile low-temperature synthesis of two-dimensional (2D) lead halide perovskite nanorods (NRs). These NRs show a shift to higher energies in the absorbance and in the photoluminescence compared to the bulk material, which supports their 2D structure. X-ray diffraction (XRD) analysis of the NRs demonstrates their 2D nature combined with the tetragonal 3D perovskite structure. In addition, by alternating the halide composition, we were able to tune the optical properties of the NRs. Fast Fourier transform, and electron diffraction show the tetragonal structure of these NRs. By varying the ligands ratio (e.g., octylammonium to oleic acid) in the synthesis, we were able to provide the formation mechanism of these novel 2D perovskite NRs. The 2D perovskite NRs are promising candidates for a variety of optoelectronic applications, such as light-emitting diodes, lasing, solar cells, and sensors. PMID:27089497

  18. High-spin multiplicities in ferromagnetic ground states of supramolecular halide complexes based on the gadolinium chloride

    NASA Astrophysics Data System (ADS)

    Paduani, C.

    2016-03-01

    Calculations using density functional theory are performed to study supramolecular assemblage of high spin halide complexes based on the gadolinium chloride. With the addition of Cl atoms to both Gd and B in number that exceeds their formal valence by 1 the calculated vertical detachment energy increases to 6.08 and 5.57 eV in GdCl4 and BCl4, respectively, indicating superhalogen behavior. By using BCl4 and GdCl4 clusters as building blocks to decorate the Gd atom the vertical detachment energy increases to 7.12 and 7.70 eV in the anionic clusters Gd(BCl4)4- and Gd(GdCl4)4-, respectively, which is indicative of hyperhalogen behavior. High spin multiplicities in the ferromagnetic state are observed for these clusters indicating therein outstanding paramagnetic response.

  19. Regeneration of zinc halide catalyst used in the hydrocracking of polynuclear hydrocarbons

    DOEpatents

    Gorin, Everett

    1978-01-01

    Improved recovery of spent molten zinc halide hydro-cracking catalyst is achieved in the oxidative vapor phase regeneration thereof by selective treatment of the zinc oxide carried over by the effluent vapors from the regeneration zone with hydrogen halide gas under conditions favoring the reaction of the zinc oxide with the hydrogen halide, whereby regenerated zinc halide is recovered in a solids-free state with little loss of zinc values.

  20. Adsorption of halide ions from aqueous solutions at a Cd(0 0 0 1) electrode surface: quantum chemical modelling and experimental study

    NASA Astrophysics Data System (ADS)

    Nazmutdinov, Renat R.; Zinkicheva, Tamara T.; Probst, Michael; Lust, Karmen; Lust, Enn

    2005-03-01

    Adsorption of the halide ions X (X = Cl -, Br -, I -) at a cadmium monocrystalline face (0 0 0 1) from aqueous solutions has been studied by the impedance spectroscopy. Analysis of the impedance data does not predict specific adsorption for Cl - and shows that the Gibbs adsorption energy increases from Br - to I - in accordance with the decrease of the hydration energy of anions. The adsorption of halide ions and their atomic forms on a Cd(0 0 0 1) electrode at the potential of zero charge (pzc) has been studied with the use of the cluster model. The quantum chemical calculations were performed at the DFT and the SCF levels involving the hydrated species X -(H 2O) 3 and X -(H 2O) 6 besides the bare anions. The effective distance-dependent solvation energy of halide ions constructed on the basis of molecular dynamics simulations was used to build the adsorption terms. For all three halides contact adsorption was found to be the most favourable state. The partial charge transfer (PCT) from the adsorbed species to the metal was analysed in terms of the Anderson-Newns model. A combined consideration of the solvation and PCT effects enables prediction of the experimentally observed metal-ion interaction order (Cl - < Br - < I -).

  1. 10 CFR 431.322 - Definitions concerning metal halide lamp ballasts and fixtures.

    Code of Federal Regulations, 2010 CFR

    2010-01-01

    ... 10 Energy 3 2010-01-01 2010-01-01 false Definitions concerning metal halide lamp ballasts and... FOR CERTAIN COMMERCIAL AND INDUSTRIAL EQUIPMENT Metal Halide Lamp Ballasts and Fixtures § 431.322 Definitions concerning metal halide lamp ballasts and fixtures. Ballast efficiency means, in the case of...

  2. 10 CFR 431.322 - Definitions concerning metal halide lamp ballasts and fixtures.

    Code of Federal Regulations, 2012 CFR

    2012-01-01

    ... 10 Energy 3 2012-01-01 2012-01-01 false Definitions concerning metal halide lamp ballasts and fixtures. 431.322 Section 431.322 Energy DEPARTMENT OF ENERGY ENERGY CONSERVATION ENERGY EFFICIENCY PROGRAM FOR CERTAIN COMMERCIAL AND INDUSTRIAL EQUIPMENT Metal Halide Lamp Ballasts and Fixtures § 431.322 Definitions concerning metal halide...

  3. 10 CFR 431.322 - Definitions concerning metal halide lamp ballasts and fixtures.

    Code of Federal Regulations, 2013 CFR

    2013-01-01

    ... 10 Energy 3 2013-01-01 2013-01-01 false Definitions concerning metal halide lamp ballasts and fixtures. 431.322 Section 431.322 Energy DEPARTMENT OF ENERGY ENERGY CONSERVATION ENERGY EFFICIENCY PROGRAM FOR CERTAIN COMMERCIAL AND INDUSTRIAL EQUIPMENT Metal Halide Lamp Ballasts and Fixtures § 431.322 Definitions concerning metal halide...

  4. 10 CFR 431.322 - Definitions concerning metal halide lamp ballasts and fixtures.

    Code of Federal Regulations, 2011 CFR

    2011-01-01

    ... 10 Energy 3 2011-01-01 2011-01-01 false Definitions concerning metal halide lamp ballasts and fixtures. 431.322 Section 431.322 Energy DEPARTMENT OF ENERGY ENERGY CONSERVATION ENERGY EFFICIENCY PROGRAM FOR CERTAIN COMMERCIAL AND INDUSTRIAL EQUIPMENT Metal Halide Lamp Ballasts and Fixtures § 431.322 Definitions concerning metal halide...

  5. 40 CFR 721.10181 - Halide salt of an alkylamine (generic).

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Halide salt of an alkylamine (generic... Specific Chemical Substances § 721.10181 Halide salt of an alkylamine (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as halide salt...

  6. 40 CFR 721.10181 - Halide salt of an alkylamine (generic).

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Halide salt of an alkylamine (generic... Specific Chemical Substances § 721.10181 Halide salt of an alkylamine (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as halide salt...

  7. 40 CFR 721.10181 - Halide salt of an alkylamine (generic).

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Halide salt of an alkylamine (generic... Specific Chemical Substances § 721.10181 Halide salt of an alkylamine (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as halide salt...

  8. 40 CFR 721.10181 - Halide salt of an alkylamine (generic).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Halide salt of an alkylamine (generic... Specific Chemical Substances § 721.10181 Halide salt of an alkylamine (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as halide salt...

  9. Alkali metal adsorption on Al(111)

    NASA Astrophysics Data System (ADS)

    Andersen, J. N.; Lundgren, E.; Nyholm, R.; Qvarford, M.

    1993-06-01

    The submonolayer adsorption of Na, K, Rb, and Cs on the Al(111) surface at 100 K and at room temperature is investigated by high resolution core level spectroscopy and low energy electron diffraction. It is found that the first alkali atoms on the surface adsorb at surface defects. At higher coverages, up to approximately one third of the maximum submonolayer coverage, alkali atoms adsorbed at defects coexist with a dispersed phase. At higher coverages island formation is found to occur for the majority of the systems. It is argued that all of the ordered structures formed at room temperature involve a disruption of the Al(111) surface in contrast to the situation at 100 K where the alkali atoms adsorb as adatoms.

  10. SAFE Alkali Metal Heat Pipe Reliability

    NASA Astrophysics Data System (ADS)

    Reid, Robert S.

    2003-01-01

    Alkali metal heat pipes are among the best understood and tested of components for first generation space fission reactors. A flight reactor will require production of a hundred or more heat pipes with assured reliability over a number of years. To date, alkali metal heat pipes have been built mostly in low budget development environments with little formal quality assurance. Despite this, heat pipe test samples suggest that high reliability can be achieved with the care justified for space flight qualification. Fabrication procedures have been established that, if consistently applied, ensure long-term trouble-free heat pipe operation. Alkali metal heat pipes have been successfully flight tested in micro gravity and also have been shown capable of multi-year operation with no evidence of sensitivity to fast neutron fluence up to 1023 n/cm2. This represents 50 times the fluence of the proposed Safe Affordable Fission Engine (SAFE-100) heat pipe reactor core.

  11. Diode pumped alkali lasers (DPALs): an overview

    NASA Astrophysics Data System (ADS)

    Krupke, William F.

    2008-05-01

    The concept of power-scalable, high beam-quality diode pumped alkali lasers was introduced in 2003 [Krupke, US Patent No. 6,643,311; Opt. Letters, 28, 2336 (2003)]. Since then several laboratory DPAL devices have been reported on, confirming many of the spectroscopic, kinetic, and laser characteristics projected from literature data. This talk will present an overview of the DPAL concept, summarize key relevant properties of the cesium, rubidium, and potassium alkali vapor gain media so-far examined, outline power scaling considerations, and highlight results of published DPAL laboratory experiments.

  12. Alkali metal vapors - Laser spectroscopy and applications

    NASA Technical Reports Server (NTRS)

    Stwalley, W. C.; Koch, M. E.

    1980-01-01

    The paper examines the rapidly expanding use of lasers for spectroscopic studies of alkali metal vapors. Since the alkali metals (lithium, sodium, potassium, rubidium and cesium) are theoretically simple ('visible hydrogen'), readily ionized, and strongly interacting with laser light, they represent ideal systems for quantitative understanding of microscopic interconversion mechanisms between photon (e.g., solar or laser), chemical, electrical and thermal energy. The possible implications of such understanding for a wide variety of practical applications (sodium lamps, thermionic converters, magnetohydrodynamic devices, new lasers, 'lithium waterfall' inertial confinement fusion reactors, etc.) are also discussed.

  13. Ultrafast time-resolved spectroscopy of lead halide perovskite films

    NASA Astrophysics Data System (ADS)

    Idowu, Mopelola A.; Yau, Sung H.; Varnavski, Oleg; Goodson, Theodore

    2015-09-01

    Recently, lead halide perovskites which are organic-inorganic hybrid structures, have been discovered to be highly efficient as light absorbers. Herein, we show the investigation of the excited state dynamics and emission properties of non-stoichiometric precursor formed lead halide perovskites grown by interdiffusion method using steady-state and time-resolved spectroscopic measurements. The influence of the different ratios of the non-stoichiometric precursor solution was examined. The observed photoluminescence properties were correlated with the femtosecond transient absorption measurements.

  14. Thermodynamic reactivity, growth and characterization of mercurous halide crystals

    NASA Technical Reports Server (NTRS)

    Singh, N. B.; Gottlieb, M.; Henningsen, T.; Hopkins, R. H.; Mazelsky, R.; Singh, M.; Glicksman, M. E.; Paradies, C.

    1992-01-01

    Thermodynamic calculations were carried out for the Hg-X-O system (X = Cl, Br, I) to identify the potential sources of contamination and relative stability of oxides and oxy-halide phases. The effect of excess mercury vapor pressure on the optical quality of mercurous halide crystal was studied by growing several mercurous chloride crystals from mercury-rich composition. The optical quality of crystals was examined by birefringence interferometry and laser scattering studies. Crystals grown in slightly mercury-rich composition showed improved optical quality relative to stoichiometric crystals.

  15. Thallous halide materials for use in cryogenic applications

    NASA Technical Reports Server (NTRS)

    Lawless, William N. (Inventor)

    1981-01-01

    Thallous halides, either alone or in combination with other ceramic materials, are used in cryogenic applications such as heat exchange material for the regenerator section of a closed-cycle cryogenic refrigeration section, as stabilizing coatings for superconducting wires, and as dielectric insulating materials. The thallous halides possess unusually large specific heats at low temperatures, have large thermal conductivities, are nonmagnetic, and are nonconductors of electricity. They can be formed into a variety of shapes such as spheres, bars, rods, or the like and can be coated onto substrates.

  16. Boron and aluminum halides under pressure - polymerization and chemical transformations

    NASA Astrophysics Data System (ADS)

    Yao, Yansun

    2013-06-01

    High-pressure phase transitions of boron and aluminum halides have been theoretically studied. At low pressure, crystals of the familiar monomers (BX3) and dimers (Al2X6) are the structures of choice. While the higher oligomers as well as three dimensional infinite polymers are unstable at ambient pressure, they are stabilized by application of external pressure, taking advantage of the extra orbitals made accessible by the increased coordination. Several new crystal structures of boron and aluminum halides have been predicted at high pressures. Calculated x-ray diffraction patterns and Raman spectra of these phases are in good agreement with available experimental data.

  17. Applications of Raman scattering spectroscopy to halide glasses

    NASA Astrophysics Data System (ADS)

    Bendow, B.; Banerjee, P. K.; Drexhage, M. G.

    1983-04-01

    Polarized Raman scattering spectroscopy is a useful tool for investigating fundamental vibrational properties, structure and bonding, origins of IR edge absorption, and dispersion of the IR refractive index. In this paper, the application of Raman spectroscopy to halide glasses and, in particular, heavy metal fluoride glasses, is described. The spectra of the latter differ substantially from those of simple oxide, halide or chalcogenide glasses and, moreover, display a wide range of vibrational characteristics, depending on composition. In combination with infrared spectroscopy, useful guidelines can be developed for tailoring glass compositions for specific applications.

  18. Alkali-aggregate reaction in concrete containing high-alkali cement and granite aggregate

    SciTech Connect

    Owsiak, Z

    2004-01-01

    The paper discusses results of the research into the influence of high-alkali Portland cement on granite aggregate. The deformation of the concrete structure occurred after 18 months. The research was carried out by means of a scanning electron microscope equipped with a high-energy dispersive X-ray analyzer that allowed observation of unpolished sections of concrete bars exhibiting the cracking pattern typical of the alkali-silica reaction. Both the microscopic observation and the X-ray elemental analysis confirm the presence of alkali-silica gel and secondary ettringite in the cracks.

  19. Recovery of alkali metal constituents from catalytic coal conversion residues

    DOEpatents

    Soung, W.Y.

    In a coal gasification operation (32) or similar conversion process carried out in the presence of an alkali metal-containing catalyst wherein particles containing alkali metal residues are produced, alkali metal constituents are recovered from the particles by contacting them with water or an aqueous solution to remove water-soluble alkali metal constituents and produce an aqueous solution enriched in said constituents. The aqueous solution thus produced is then contacted with carbon dioxide to precipitate silicon constituents, the pH of the resultant solution is increased, preferably to a value in the range between about 12.5 and about 15.0, and the solution of increased pH is evaporated to increase the alkali metal concentration. The concentrated aqueous solution is then recycled to the conversion process where the alkali metal constituents serve as at least a portion of the alkali metal constituents which comprise the alkali metal-containing catalyst.

  20. Local reactivity descriptors to predict the strength of Lewis acid sites in alkali cation-exchanged zeolites

    NASA Astrophysics Data System (ADS)

    Deka, Ramesh Ch.; Kinkar Roy, Ram; Hirao, Kimihiko

    2004-05-01

    Lewis acidity of alkali cation-exchanged zeolite is studied using local reactivity descriptors based on hard-soft acid-base (HSAB) concept. The local softness for nucleophilic attack ( sx+), local softness for electrophilic attack ( sx-) and their ratio, which is called `relative electrophilicity' ( sx+/ sx-), are calculated for the exchanged cations and Lewis acidity of the cations is found to decrease in the order: Li + > Na + > K + > Rb + > Cs +. Calculated blue shift of CO vibrational frequency (Δ ν) and interaction energy of CO molecule with alkali cation-exchanged zeolite clusters vary linearly with sx+/ sx- values.

  1. Ab initio interaction potentials and scattering lengths for ultracold mixtures of metastable helium and alkali-metal atoms

    NASA Astrophysics Data System (ADS)

    Kedziera, Dariusz; Mentel, Łukasz; Żuchowski, Piotr S.; Knoop, Steven

    2015-06-01

    We have obtained accurate ab initio +4Σ quartet potentials for the diatomic metastable triplet helium+alkali-metal (Li, Na, K, Rb) systems, using all-electron restricted open-shell coupled cluster singles and doubles with noniterative triples corrections CCSD(T) calculations and accurate calculations of the long-range C6 coefficients. These potentials provide accurate ab initio quartet scattering lengths, which for these many-electron systems is possible, because of the small reduced masses and shallow potentials that result in a small amount of bound states. Our results are relevant for ultracold metastable triplet helium+alkali-metal mixture experiments.

  2. Salts of alkali metal anions and process of preparing same

    DOEpatents

    Dye, James L.; Ceraso, Joseph M.; Tehan, Frederick J.; Lok, Mei Tak

    1978-01-01

    Compounds of alkali metal anion salts of alkali metal cations in bicyclic polyoxadiamines are disclosed. The salts are prepared by contacting an excess of alkali metal with an alkali metal dissolving solution consisting of a bicyclic polyoxadiamine in a suitable solvent, and recovered by precipitation. The salts have a gold-color crystalline appearance and are stable in a vacuum at -10.degree. C. and below.

  3. Quantum efficiencies of imaging detectors with alkali halide photocathodes. I - Microchannel plates with separate and integral CsI photocathodes

    NASA Technical Reports Server (NTRS)

    Carruthers, George R.

    1987-01-01

    Measurements and comparisons have been made of the quantum efficiencies of microchannel plate (MCP) detectors in the far-UV (below 2000-A) wavelength range using CsI photocathodes (a) deposited on the front surfaces of microchannel plates and (b) deposited on solid substrates as opaque photocathodes with the resulting photoelectrons input to microchannel plates. The efficiences were measured in both pulse-counting and photodiode modes of operation. Typical efficiencies are about 15 percent at 1216 A for a CsI-coated MCP compared with 65 percent for an opaque CsI photocathode MCP detector. Special processing has yielded an efficiency as high as 20 percent for a CsI-coated MCP. This may possibly be further improved by optimization of the tilt angle of the MCP channels relative to the front face of the MCP and incident radiation. However, at present there still remains a factor of at least 3 quantum efficiency advantage in the separate opaque CsI photocathode configuration.

  4. Cocrystallization of certain 4f and 5f elements in the bivalent state with alkali metal halides

    SciTech Connect

    Mikheev, N.B.; Kamenskaya, A.M.; Veleshko, I.E.; Kulyukhin, S.A.

    1987-01-01

    The cocrystallization of Fm/sup 2 +/, Es/sup 2 +/, Cf/sup 2 +/, Am/sup 2 +/, Yb/sup 2 +/, Eu/sup 2 +/ and Sr/sup 2 +/ with NaCl, KCl and KBr in tetrahydrofuran (THF), hexamethylphosphorotriamide (HMPA), and ethanol has been studied. It is shown that in water-ethanol medium An/sup 2 +/ cocrystallize with KCl by the formation of anomalous mixed crystals and Ln/sup 2 +/ do not cocrystallize. In HMPA neither Ln/sup 2 +/ nor An/sup 2 +/ are observed to transfer into the KBr solid phase, while in THF both Ln/sup 2 +/ and An/sup 2 +/ cocrystallize with NaCl. The change in the behavior on Ln/sup 2 +/ and An/sup 2 +/ cocrystallize with a change from one solvent to another is caused by the difference in the effective ionic radii of these elements, which arises from the large nephelauxetic effect for An/sup 2 +/ as well as by the different solvating power of these solvents.

  5. The interaction energies and polarizabilities of sodium fluoride, sodium chloride, and some alkali and halide ions pairs

    NASA Astrophysics Data System (ADS)

    Bounds, David G.; Hinchliffe, Alan

    1982-02-01

    Ab initio SCF pair potentials and polarizabilities for NaF, NaCl, F 2-2, Na 2-2, K 2-2, FCl 2-, LiNa 2+, LiK 2+, presented. Together with results reported previously, these values form a complete and consistent set of energy and polarizability data on the fluorides and chlorides of lithium, sodium and potassium.

  6. On the 2 s-like relaxed excited state of the F center in alkali halide crystals

    NASA Astrophysics Data System (ADS)

    Panov, V. G.; Varaksin, A. N.; Sobolev, A. B.

    2008-06-01

    The energy and spectroscopic characteristics of the first excited 2 s-like electron state of the F center are presented according to the calculations performed in the framework of the variational model proposed by Gourary and Adrian. The relaxation of the crystal lattice in the vicinity of the excited F center is described. The problem of the spatial propagation of the F center is discussed. The results obtained for the 2 p and 2 s states of the F center are compared with each other and with the relevant experimental data.

  7. Faraday rotation density measurements of optically thick alkali metal vapors

    NASA Astrophysics Data System (ADS)

    Vliegen, E.; Kadlecek, S.; Anderson, L. W.; Walker, T. G.; Erickson, C. J.; Happer, William

    2001-03-01

    We investigate the measurement of alkali number densities using the Faraday rotation of linearly polarized light. We find that the alkali number density may be reliably extracted even in regimes of very high buffer gas pressure, and very high alkali number density. We have directly verified our results in potassium using absorption spectroscopy on the second resonance (4 2S→5 2P).

  8. 40 CFR 721.1878 - Alkali metal alkyl borohydride (generic).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Alkali metal alkyl borohydride... Specific Chemical Substances § 721.1878 Alkali metal alkyl borohydride (generic). (a) Chemical substance... alkali metal alkyl borohydride (PMN P-00-1089) is subject to reporting under this section for...

  9. 40 CFR 721.1878 - Alkali metal alkyl borohydride (generic).

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Alkali metal alkyl borohydride... Specific Chemical Substances § 721.1878 Alkali metal alkyl borohydride (generic). (a) Chemical substance... alkali metal alkyl borohydride (PMN P-00-1089) is subject to reporting under this section for...

  10. 40 CFR 721.1878 - Alkali metal alkyl borohydride (generic).

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Alkali metal alkyl borohydride... Specific Chemical Substances § 721.1878 Alkali metal alkyl borohydride (generic). (a) Chemical substance... alkali metal alkyl borohydride (PMN P-00-1089) is subject to reporting under this section for...

  11. 40 CFR 721.1878 - Alkali metal alkyl borohydride (generic).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Alkali metal alkyl borohydride... Specific Chemical Substances § 721.1878 Alkali metal alkyl borohydride (generic). (a) Chemical substance... alkali metal alkyl borohydride (PMN P-00-1089) is subject to reporting under this section for...

  12. 40 CFR 721.4660 - Alcohol, alkali metal salt.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Alcohol, alkali metal salt. 721.4660... Substances § 721.4660 Alcohol, alkali metal salt. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance generically identified as alcohol, alkali metal salt (PMN P-91-151)...

  13. 40 CFR 721.4660 - Alcohol, alkali metal salt.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Alcohol, alkali metal salt. 721.4660... Substances § 721.4660 Alcohol, alkali metal salt. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance generically identified as alcohol, alkali metal salt (PMN P-91-151)...

  14. 40 CFR 721.4660 - Alcohol, alkali metal salt.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Alcohol, alkali metal salt. 721.4660... Substances § 721.4660 Alcohol, alkali metal salt. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance generically identified as alcohol, alkali metal salt (PMN P-91-151)...

  15. 40 CFR 721.4660 - Alcohol, alkali metal salt.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Alcohol, alkali metal salt. 721.4660... Substances § 721.4660 Alcohol, alkali metal salt. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance generically identified as alcohol, alkali metal salt (PMN P-91-151)...

  16. 40 CFR 721.4660 - Alcohol, alkali metal salt.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Alcohol, alkali metal salt. 721.4660... Substances § 721.4660 Alcohol, alkali metal salt. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance generically identified as alcohol, alkali metal salt (PMN P-91-151)...

  17. 40 CFR 721.5278 - Substituted naphthalenesulfonic acid, alkali salt.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ..., alkali salt. 721.5278 Section 721.5278 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.5278 Substituted naphthalenesulfonic acid, alkali salt. (a) Chemical... as a substituted naphthalenesulfonic acid, alkali salt (PMN P-95-85) is subject to reporting...

  18. 40 CFR 721.8900 - Substituted halogenated pyridinol, alkali salt.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ..., alkali salt. 721.8900 Section 721.8900 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.8900 Substituted halogenated pyridinol, alkali salt. (a) Chemical... as substituted halogenated pyridinols, alkali salts (PMNs P-88-1271 and P-88-1272) are subject...

  19. 40 CFR 721.5278 - Substituted naphthalenesulfonic acid, alkali salt.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ..., alkali salt. 721.5278 Section 721.5278 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.5278 Substituted naphthalenesulfonic acid, alkali salt. (a) Chemical... as a substituted naphthalenesulfonic acid, alkali salt (PMN P-95-85) is subject to reporting...

  20. 40 CFR 721.8900 - Substituted halogenated pyridinol, alkali salt.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ..., alkali salt. 721.8900 Section 721.8900 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.8900 Substituted halogenated pyridinol, alkali salt. (a) Chemical... as substituted halogenated pyridinols, alkali salts (PMNs P-88-1271 and P-88-1272) are subject...

  1. 40 CFR 721.5278 - Substituted naphthalenesulfonic acid, alkali salt.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ..., alkali salt. 721.5278 Section 721.5278 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.5278 Substituted naphthalenesulfonic acid, alkali salt. (a) Chemical... as a substituted naphthalenesulfonic acid, alkali salt (PMN P-95-85) is subject to reporting...

  2. 40 CFR 721.5278 - Substituted naphthalenesulfonic acid, alkali salt.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ..., alkali salt. 721.5278 Section 721.5278 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.5278 Substituted naphthalenesulfonic acid, alkali salt. (a) Chemical... as a substituted naphthalenesulfonic acid, alkali salt (PMN P-95-85) is subject to reporting...

  3. 40 CFR 721.5278 - Substituted naphthalenesulfonic acid, alkali salt.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ..., alkali salt. 721.5278 Section 721.5278 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.5278 Substituted naphthalenesulfonic acid, alkali salt. (a) Chemical... as a substituted naphthalenesulfonic acid, alkali salt (PMN P-95-85) is subject to reporting...

  4. Structural Characterization of Methanol Substituted Lanthanum Halides

    PubMed Central

    Boyle, Timothy J.; Ottley, Leigh Anna M.; Alam, Todd M.; Rodriguez, Mark A.; Yang, Pin; Mcintyre, Sarah K.

    2010-01-01

    The first study into the alcohol solvation of lanthanum halide [LaX3] derivatives as a means to lower the processing temperature for the production of the LaBr3 scintillators was undertaken using methanol (MeOH). Initially the de-hydration of {[La(µ-Br)(H2O)7](Br)2}2 (1) was investigated through the simple room temperature dissolution of 1 in MeOH. The mixed solvate monomeric [La(H2O)7(MeOH)2](Br)3 (2) compound was isolated where the La metal center retains its original 9-coordination through the binding of two additional MeOH solvents but necessitates the transfer of the innersphere Br to the outersphere. In an attempt to in situ dry the reaction mixture of 1 in MeOH over CaH2, crystals of [Ca(MeOH)6](Br)2 (3) were isolated. Compound 1 dissolved in MeOH at reflux temperatures led to the isolation of an unusual arrangement identified as the salt derivative {[LaBr2.75•5.25(MeOH)]+0.25 [LaBr3.25•4.75(MeOH)]−0.25} (4). The fully substituted species was ultimately isolated through the dissolution of dried LaBr3 in MeOH forming the 8-coordinated [LaBr3(MeOH)5] (5) complex. It was determined that the concentration of the crystallization solution directed the structure isolated (4 concentrated; 5 dilute) The other LaX3 derivatives were isolated as [(MeOH)4(Cl)2La(µ-Cl)]2 (6) and [La(MeOH)9](I)3•MeOH (7). Beryllium Dome XRD analysis indicated that the bulk material for 5 appear to have multiple solvated species, 6 is consistent with the single crystal, and 7 was too broad to elucidate structural aspects. Multinuclear NMR (139La) indicated that these compounds do not retain their structure in MeOD. TGA/DTA data revealed that the de-solvation temperatures of the MeOH derivatives 4 – 6 were slightly higher in comparison to their hydrated counterparts. PMID:20514349

  5. Computational studies of solid-state alkali conduction in rechargeable alkali-ion batteries

    DOE PAGESBeta

    Deng, Zhi; Mo, Yifei; Ong, Shyue Ping

    2016-03-25

    The facile conduction of alkali ions in a crystal host is of crucial importance in rechargeable alkali-ion batteries, the dominant form of energy storage today. In this review, we provide a comprehensive survey of computational approaches to study solid-state alkali diffusion. We demonstrate how these methods have provided useful insights into the design of materials that form the main components of a rechargeable alkali-ion battery, namely the electrodes, superionic conductor solid electrolytes and interfaces. We will also provide a perspective on future challenges and directions. Here, the scope of this review includes the monovalent lithium- and sodium-ion chemistries that aremore » currently of the most commercial interest.« less

  6. Alkali resistant optical coatings for alkali lasers and methods of production thereof

    DOEpatents

    Soules, Thomas F; Beach, Raymond J; Mitchell, Scott C

    2014-11-18

    In one embodiment, a multilayer dielectric coating for use in an alkali laser includes two or more alternating layers of high and low refractive index materials, wherein an innermost layer includes a thicker, >500 nm, and dense, >97% of theoretical, layer of at least one of: alumina, zirconia, and hafnia for protecting subsequent layers of the two or more alternating layers of high and low index dielectric materials from alkali attack. In another embodiment, a method for forming an alkali resistant coating includes forming a first oxide material above a substrate and forming a second oxide material above the first oxide material to form a multilayer dielectric coating, wherein the second oxide material is on a side of the multilayer dielectric coating for contacting an alkali.

  7. Terahertz radiation in alkali vapor plasmas

    SciTech Connect

    Sun, Xuan; Zhang, X.-C.

    2014-05-12

    By taking advantage of low ionization potentials of alkali atoms, we demonstrate terahertz wave generation from cesium and rubidium vapor plasmas with an amplitude nearly one order of magnitude larger than that from nitrogen gas at low pressure (0.02–0.5 Torr). The observed phenomena are explained by the numerical modeling based upon electron tunneling ionization.

  8. Purification and Characterization of an Extracellular, Thermo-Alkali-Stable, Metal Tolerant Laccase from Bacillus tequilensis SN4

    PubMed Central

    Sondhi, Sonica; Sharma, Prince; Saini, Shilpa; Puri, Neena; Gupta, Naveen

    2014-01-01

    A novel extracellular thermo-alkali-stable laccase from Bacillus tequilensis SN4 (SN4LAC) was purified to homogeneity. The laccase was a monomeric protein of molecular weight 32 KDa. UV-visible spectrum and peptide mass fingerprinting results showed that SN4LAC is a multicopper oxidase. Laccase was active in broad range of phenolic and non-phenolic substrates. Catalytic efficiency (kcat/Km) showed that 2, 6-dimethoxyphenol was most efficiently oxidized by the enzyme. The enzyme was inhibited by conventional inhibitors of laccase like sodium azide, cysteine, dithiothreitol and β-mercaptoethanol. SN4LAC was found to be highly thermostable, having temperature optimum at 85°C and could retain more than 80% activity at 70°C for 24 h. The optimum pH of activity for 2, 6-dimethoxyphenol, 2, 2′-azino bis[3-ethylbenzthiazoline-6-sulfonate], syringaldazine and guaiacol was 8.0, 5.5, 6.5 and 8.0 respectively. Enzyme was alkali-stable as it retained more than 75% activity at pH 9.0 for 24 h. Activity of the enzyme was significantly enhanced by Cu2+, Co2+, SDS and CTAB, while it was stable in the presence of halides, most of the other metal ions and surfactants. The extracellular nature and stability of SN4LAC in extreme conditions such as high temperature, pH, heavy metals, halides and detergents makes it a highly suitable candidate for biotechnological and industrial applications. PMID:24871763

  9. Purification and characterization of an extracellular, thermo-alkali-stable, metal tolerant laccase from Bacillus tequilensis SN4.

    PubMed

    Sondhi, Sonica; Sharma, Prince; Saini, Shilpa; Puri, Neena; Gupta, Naveen

    2014-01-01

    A novel extracellular thermo-alkali-stable laccase from Bacillus tequilensis SN4 (SN4LAC) was purified to homogeneity. The laccase was a monomeric protein of molecular weight 32 KDa. UV-visible spectrum and peptide mass fingerprinting results showed that SN4LAC is a multicopper oxidase. Laccase was active in broad range of phenolic and non-phenolic substrates. Catalytic efficiency (kcat/Km) showed that 2, 6-dimethoxyphenol was most efficiently oxidized by the enzyme. The enzyme was inhibited by conventional inhibitors of laccase like sodium azide, cysteine, dithiothreitol and β-mercaptoethanol. SN4LAC was found to be highly thermostable, having temperature optimum at 85°C and could retain more than 80% activity at 70°C for 24 h. The optimum pH of activity for 2, 6-dimethoxyphenol, 2, 2'-azino bis[3-ethylbenzthiazoline-6-sulfonate], syringaldazine and guaiacol was 8.0, 5.5, 6.5 and 8.0 respectively. Enzyme was alkali-stable as it retained more than 75% activity at pH 9.0 for 24 h. Activity of the enzyme was significantly enhanced by Cu2+, Co2+, SDS and CTAB, while it was stable in the presence of halides, most of the other metal ions and surfactants. The extracellular nature and stability of SN4LAC in extreme conditions such as high temperature, pH, heavy metals, halides and detergents makes it a highly suitable candidate for biotechnological and industrial applications. PMID:24871763

  10. Hyaline membrane disease, alkali, and intraventricular haemorrhage.

    PubMed Central

    Wigglesworth, J S; Keith, I H; Girling, D J; Slade, S A

    1976-01-01

    The relation between intraventricular haemorrhage (IVH) and hyaline membrane disease (HMD) was studied in singletons that came to necropsy at Hammersmith Hospital over the years 1966-73. The incidence of IVH in singleton live births was 3-22/1000 and of HMD 4-44/1000. Although the high figures were partily due to the large number of low birthweight infants born at this hospital, the incidence of IVH in babies weighing 1001-1500 g was three times as great as that reported in the 1658 British Perinatal Mortality Survey. Most IVH deaths were in babies with HMD, but the higher frequency of IVH was not associated with any prolongation of survival time of babies who died with HMD as compared with the 1958 survey. IVH was seen frequently at gestations of up to 36 weeks in babies with HMD but was rare above 30 weeks' gestation in babies without HMD. This indicated that factors associated with HMD must cause most cases of IVH seen at gestations above 30 weeks. Comparison of clinical details in infants with HMD who died with or without IVH (at gestations of 30-37 weeks) showed no significant differences between the groups other than a high incidence of fits and greater use of alkali therapy in the babies with IVH. During the 12 hours when most alkali therapy was given, babies dying with IVD received a mean total alkali dosage of 10-21 mmol/kg and those dying without IVH 6-34 mmol/kg (P less than 0-001).There was no difference in severity of hypoxia or of metabolic acidosis between the 2 groups. Babies who died with HMD and germinal layer haemorrhage (GLH) without IVH had received significantly more alkali than those who died with HMD alone, whereas survivors of severe respiratory distress syndrome had received lower alkali doses than other groups. It is suggested that the greatly increased death rate from IVH in babies with HMD indicates some alteration of management of HMD (since 1958) as a causative factor. Liberal use of hypertonic alkali solutions is the common factor

  11. 40 CFR 721.10698 - Polyfluorinated alkyl halide (generic).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Polyfluorinated alkyl halide (generic). 721.10698 Section 721.10698 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) TOXIC SUBSTANCES CONTROL ACT SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical Substances §...

  12. Kinetic Studies of the Solvolysis of Two Organic Halides

    ERIC Educational Resources Information Center

    Duncan, J. A.; Pasto, D. J.

    1975-01-01

    Describes an undergraduate organic chemistry laboratory experiment which utilizes the solvolysis of organic halides to demonstrate first and second order reaction kinetics. The experiment also investigates the effect of a change of solvent polarity on reaction rate, common-ion and noncommon-ion salt effects, and the activation parameters of a…

  13. Method for calcining nuclear waste solutions containing zirconium and halides

    DOEpatents

    Newby, Billie J.

    1979-01-01

    A reduction in the quantity of gelatinous solids which are formed in aqueous zirconium-fluoride nuclear reprocessing waste solutions by calcium nitrate added to suppress halide volatility during calcination of the solution while further suppressing chloride volatility is achieved by increasing the aluminum to fluoride mole ratio in the waste solution prior to adding the calcium nitrate.

  14. Methyl halide emission estimates from domestic biomass burning in Africa

    NASA Astrophysics Data System (ADS)

    Mead, M. I.; Khan, M. A. H.; White, I. R.; Nickless, G.; Shallcross, D. E.

    Inventories of methyl halide emissions from domestic burning of biomass in Africa, from 1950 to the present day and projected to 2030, have been constructed. By combining emission factors from Andreae and Merlet [2001. Emission of trace gases and aerosols from biomass burning. Global Biogeochemical Cycles 15, 955-966], the biomass burning estimates from Yevich and Logan [2003. An assessment of biofuel use and burning of agricultural waste in the developing world. Global Biogeochemical Cycles 17(4), 1095, doi:10.1029/2002GB001952] and the population data from the UN population division, the emission of methyl halides from domestic biomass usage in Africa has been estimated. Data from this study suggest that methyl halide emissions from domestic biomass burning have increased by a factor of 4-5 from 1950 to 2005 and based on the expected population growth could double over the next 25 years. This estimated change has a non-negligible impact on the atmospheric budgets of methyl halides.

  15. Students' Understanding of Alkyl Halide Reactions in Undergraduate Organic Chemistry

    ERIC Educational Resources Information Center

    Cruz-Ramirez de Arellano, Daniel

    2013-01-01

    Organic chemistry is an essential subject for many undergraduate students completing degrees in science, engineering, and pre-professional programs. However, students often struggle with the concepts and skills required to successfully solve organic chemistry exercises. Since alkyl halides are traditionally the first functional group that is…

  16. On the Boiling Points of the Alkyl Halides.

    ERIC Educational Resources Information Center

    Correia, John

    1988-01-01

    Discusses the variety of explanations in organic chemistry textbooks of a physical property of organic compounds. Focuses on those concepts explaining attractive forces between molecules. Concludes that induction interactions play a major role in alkyl halides and other polar organic molecules and should be given wider exposure in chemistry texts.…

  17. Semiempirical and DFT Investigations of the Dissociation of Alkyl Halides

    ERIC Educational Resources Information Center

    Waas, Jack R.

    2006-01-01

    Enthalpy changes corresponding to the gas phase heats of dissociation of 12 organic halides were calculated using two semiempirical methods, the Hartree-Fock method, and two DFT methods. These calculated values were compared to experimental values where possible. All five methods agreed generally with the expected empirically known trends in the…

  18. CO2 electrochemical reduction via adsorbed halide anions

    NASA Astrophysics Data System (ADS)

    Ogura, Kotaro; Salazar-Villalpando, Maria D.

    2011-01-01

    The electrochemical reduction of CO2 was studied utilizing halide ions as electrolytes, specifically, aqueous solutions of KCl, KBr, KI. Electrochemical experiments were carried out in a laboratory-made, divided H-type cell. The working electrode was a copper mesh, while the counter and reference electrodes were a Pt wire and an Ag/AgCl electrode, respectively. The results of our work suggest a reaction mechanism for the electrochemical reduction of CO2 where the presence of Cu-X as the catalytic layer facilitates the electron transfer from the electrode to CO2. Electron-transfer to CO2 may occur via the X- ad(Br-, Cl-, I-)-C bond, which is formed by the electron flow from the specifically adsorbed halide anion to the vacant orbital of CO2. The stronger the adsorption of the halide anion to the electrode, the more strongly CO2 is restrained, resulting in higher CO2 reduction current. Furthermore, it is suggested that specifically adsorbed halide anions could suppress the adsorption of protons; leading to a higher hydrogen overvoltage. These effects may synergistically mitigate the over potential necessary for CO2 reduction, and thus increase the rate of electrochemical CO2 reduction.

  19. Physics and chemistry of alkali-silica reactions

    SciTech Connect

    Diamond, S.; Barneyback, R.S. Jr.; Struble, L.J.

    1981-01-01

    The philosophy underlying recent research on alkali-silica reactions is reviewed and illustrations of recent results are provided. It has been possible to follow the kinetics of the chemical reaction between dissolved alkalis and opal in mortars by monitoring the rate at which alkalis are removed from the pore solutions of reacting mortars. Studies of the expansion behavior of synthetic alkali silica gels under controlled conditions were carried out and show no obvious correlation to chemical composition. The alkali reaction in mortars was found to produce changes in the appearance of opal grains documentable by the use of a scanning electron microscope.

  20. Calcium-Alkali Syndrome in the Modern Era

    PubMed Central

    Patel, Ami M.; Adeseun, Gbemisola A.; Goldfarb, Stanley

    2013-01-01

    The ingestion of calcium, along with alkali, results in a well-described triad of hypercalcemia, metabolic alkalosis, and renal insufficiency. Over time, the epidemiology and root cause of the syndrome have shifted, such that the disorder, originally called the milk-alkali syndrome, is now better described as the calcium-alkali syndrome. The calcium-alkali syndrome is an important cause of morbidity that may be on the rise, an unintended consequence of shifts in calcium and vitamin D intake in segments of the population. We review the pathophysiology of the calcium-alkali syndrome. PMID:24288027

  1. Silver-halide/organic-composite structures: Toward materials with multiple photographic functionalities

    SciTech Connect

    Bringley, Joseph F. . E-mail: joseph.bringley@kodak.com; Rajeswaran, Manju; Olson, Leif P.; Liebert, Nancy M.

    2005-10-15

    We report the synthesis and structure of the novel silver-halide-based organic-inorganic hybrids Ag{sub 2}Br{sub 6}(PPD){sub 2}, Ag{sub 2}Br{sub 6}(CD-2){sub 2}.H{sub 2}O, Ag{sub 2}Br{sub 4}(TMBD), and Ag{sub 2}I{sub 6}(CD-2){sub 2}.H{sub 2}O. 1,4-phenylenediammonium hexabromodiargentate(I) [Ag{sub 2}Br{sub 6}(PPD){sub 2}] crystals are monoclinic (P2{sub 1}/n), with unit-cell dimensions, a=10.1915(3)A, b=7.7562(2)A, c=12.4340(5)A and {beta}=93.109(1){sup o}. N,N-diethyl-2-methyl-1,4-benzenediammonium hexabromodiargentate(I) monohydrate [Ag{sub 2}Br{sub 6}(CD-2){sub 2}.H{sub 2}O] crystals are monoclinic (space group P2{sub 1}/c) with a=10.8434(2)A, b=11.4293(2)A, c=14.3729(1)A, and {beta}=96.153(1){sup o}. N,N,N',N'-tetramethyl-1,4-benzenediammonium tetrabromodiargentate(I) [Ag{sub 2}Br{sub 4}(TMBD)] crystals are orthorhombic (space group Pbcn) with a=17.0030(6)A, b=6.6163(2)A, and c=15.9762(6)A. N,N-diethyl-2-methyl-1,4-benzenediammonium hexaiododiargentate(I) monohydrate, [Ag{sub 2}I{sub 6}(CD-2){sub 2}.H{sub 2}O], are monoclinic (C2/c), with unit-cell dimensions, a=21.4691(4)A, b=12.1411(2)A, c=14.3102(2)A, and {beta}=98.657(1){sup o}. The novel structures are members of a class of silver-halide-based organic-inorganic hybrids based upon the assembly of [Ag{sub a}X{sub b}]{sup n-} clusters and protonated organoamines in aqueous mineral acids. The clusters display short intracluster Ag-Ag distances, and computational methods are used to evaluate intracluster Ag-Ag bonding. The diverse stoichiometries and cluster connectivities observed suggest a rich compositional and structural chemistry based upon the general assembly method. We have extended the methodology to include a silver-halide-organoamonium chemistry in which the organic moiety is chosen to serve a specific photographic function and demonstrate the first examples of such materials. The methodology allows for the direct assembly of [Ag{sub a}X{sub b}]{sup n-} clusters with commercial photographic color

  2. Alkali metal recovery from carbonaceous material conversion process

    DOEpatents

    Sharp, David W.; Clavenna, LeRoy R.; Gorbaty, Martin L.; Tsou, Joe M.

    1980-01-01

    In a coal gasification operation or similar conversion process carried out in the presence of an alkali metal-containing catalyst wherein solid particles containing alkali metal residues are produced in the gasifier or similar reaction zone, alkali metal constitutents are recovered from the particles by withdrawing and passing the particles from the reaction zone to an alkali metal recovery zone in the substantial absence of molecular oxygen and treating the particles in the recovery zone with water or an aqueous solution in the substantial absence of molecular oxygen. The solution formed by treating the particles in the recovery zone will contain water-soluble alkali metal constituents and is recycled to the conversion process where the alkali metal constituents serve as at least a portion of the alkali metal constituents which comprise the alkali metal-containing catalyst. Preventing contact of the particles with oxygen as they are withdrawn from the reaction zone and during treatment in the recovery zone avoids the formation of undesirable alkali metal constituents in the aqueous solution produced in the recovery zone and insures maximum recovery of water-soluble alkali metal constituents from the alkali metal residues.

  3. Alkali element background reduction in laser ICP-MS

    NASA Astrophysics Data System (ADS)

    Magee, C. W., Jr.; Norris, C. A.

    2014-11-01

    Alkali backgrounds in laser ablation ICP-MS analyses can be enhanced by electron-induced ionization of alkali contamination on the skimmer cone, reducing effective detection limits for these elements. Traditionally, this problem is addressed by isolating analyses of high alkali materials onto a designated cone set, or by operating the ICP-MS in a "soft extraction" mode, which reduces the energy of electrons repelled into the potentially contaminated sampling cone by the extraction field. Here we present a novel approach, where we replace the traditional alkali glass tuning standards with synthetic low-alkali glass reference materials. Using this vitreous tuning solution, we find that this approach reduces the amount of alkali contamination produced, halving backgrounds for the heavy alkali elements without any change to analytical procedures. Using segregated cones is still the most effective method for reducing lithium backgrounds, but since the procedures are complimentary both can easily be applied to the routine operations of an analytical lab.

  4. Alkali element background reduction in laser ICP-MS

    NASA Astrophysics Data System (ADS)

    Magee, C. W., Jr.; Norris, C. A.

    2015-03-01

    Alkali backgrounds in laser ablation ICP-MS analyses can be enhanced by electron-induced ionisation of alkali contamination on the skimmer cone, reducing effective detection limits for these elements. Traditionally, this problem is addressed by isolating analyses of high-alkali materials onto a designated cone set, or by operating the ICP-MS in a "soft extraction" mode, which reduces the energy of electrons repelled into the potentially contaminated sampling cone by the extraction field. Here we present a novel approach, where we replace the traditional alkali glass tuning standards with synthetic low-alkali glass reference materials. Using this vitreous tuning solution, we find that this approach reduces the amount of alkali contamination produced, halving backgrounds for the heavy alkali elements without any change to analytical procedures. Using segregated cones is still the most effective method for reducing lithium backgrounds, but since the procedures are complimentary, both can easily be applied to the routine operations of an analytical lab.

  5. Developments in alkali-metal atomic magnetometry

    NASA Astrophysics Data System (ADS)

    Seltzer, Scott Jeffrey

    Alkali-metal magnetometers use the coherent precession of polarized atomic spins to detect and measure magnetic fields. Recent advances have enabled magnetometers to become competitive with SQUIDs as the most sensitive magnetic field detectors, and they now find use in a variety of areas ranging from medicine and NMR to explosives detection and fundamental physics research. In this thesis we discuss several developments in alkali-metal atomic magnetometry for both practical and fundamental applications. We present a new method of polarizing the alkali atoms by modulating the optical pumping rate at both the linear and quadratic Zeeman resonance frequencies. We demonstrate experimentally that this method enhances the sensitivity of a potassium magnetometer operating in the Earth's field by a factor of 4, and we calculate that it can reduce the orientation-dependent heading error to less than 0.1 nT. We discuss a radio-frequency magnetometer for detection of oscillating magnetic fields with sensitivity better than 0.2 fT/ Hz , which we apply to the observation of nuclear magnetic resonance (NMR) signals from polarized water, as well as nuclear quadrupole resonance (NQR) signals from ammonium nitrate. We demonstrate that a spin-exchange relaxation-free (SERF) magnetometer can measure all three vector components of the magnetic field in an unshielded environment with comparable sensitivity to other devices. We find that octadecyltrichlorosilane (OTS) acts as an anti-relaxation coating for alkali atoms at temperatures below 170°C, allowing them to collide with a glass surface up to 2,000 times before depolarizing, and we present the first demonstration of high-temperature magnetometry with a coated cell. We also describe a reusable alkali vapor cell intended for the study of interactions between alkali atoms and surface coatings. Finally, we explore the use of a cesium-xenon SERF comagnetometer for a proposed measurement of the permanent electric dipole moments (EDMs

  6. Effect of alkali lignins with different molecular weights from alkali pretreated rice straw hydrolyzate on enzymatic hydrolysis.

    PubMed

    Li, Yun; Qi, Benkun; Luo, Jianquan; Wan, Yinhua

    2016-01-01

    This study investigated the effect of alkali lignins with different molecular weights on enzymatic hydrolysis of lignocellulose. Different alkali lignins fractions, which were obtained from cascade ultrafiltration, were added into the dilute acid pretreated (DAP) and alkali pretreated (AP) rice straws respectively during enzymatic hydrolysis. The results showed that the addition of alkali lignins enhanced the hydrolysis and the enhancement for hydrolysis increased with increasing molecular weights of alkali lignins, with maximum enhancement being 28.69% for DAP and 20.05% for AP, respectively. The enhancement was partly attributed to the improved cellulase activity, and filter paper activity increased by 18.03% when adding lignin with highest molecular weight. It was found that the enhancement of enzymatic hydrolysis was correlated with the adsorption affinity of cellulase on alkali lignins, and the difference in surface charge and hydrophobicity of alkali lignins were responsible for the difference in affinity between cellulase and lignins. PMID:26496216

  7. Spectroscopic effects of disorder and vibrational localization in mixed-halide metal-halide chain solids

    SciTech Connect

    Love, S.P.; Scott, B.; Worl, L.A.; Huckett, S.C.; Saxena, A.; Huang, X.Z.; Bishop, A.R.; Swanson, B.I.

    1993-02-01

    Resonance Raman techniques, together with lattice-dynamics and Peierls-Hubbard modelling, are used to explore the electronic and vibrational dynamics of the quasi-one-dimensional metal-halogen chain solids [Pt(en){sub 2}][R(en){sub 2}X{sub 2}](ClO{sub 4}){sub 4}, (en = C{sub 2}H{sub 8}N{sub 2} and X=Cl, Br), abbreviated ``PLX.`` The mixed-halide materials PtCl{sub 1-x}Br{sub x} and PtCl{sub 1-x}I{sub x} consist of long mixed chains with heterojunctions between segments of the two constituent materials. Thus, in addition to providing mesoscale modulation of the chain electronic states, they serve as prototypes for elucidating the properties to be expected for macroscopic heterojunctions of these highly nonlinear materials. Once a detailed understanding of the various local vibrational modes occurring in these disordered solids is developed, the electronic structure of the chain segments and junctions can be probed by tuning the Raman excitation through their various electronic resonances.

  8. Matrix isolation infrared spectra of hydrogen halide and halogen complexes with nitrosyl halides

    NASA Technical Reports Server (NTRS)

    Allamandola, Louis J.; Lucas, Donald; Pimentel, George C.

    1982-01-01

    Matrix isolation infrared spectra of nitrosyl halide (XNO) complexes with HX and X2 (X = Cl, Br) are presented. The relative frequency shifts of the HX mode are modest (ClNO H-Cl, delta-nu/nu = -0.045; BrNO H-Br, delta-nu/nu = -0.026), indicating weak hydrogen bonds 1-3 kcal/mol. These shifts are accompanied by significant shifts to higher frequencies in the XN-O stretching mode (CIN-O HCl, delta-nu/nu = +0.016; BrN-O HBr, delta-nu/nu = +0.011). Similar shifts were observed for the XN-O X2 complexes (ClN-O Cl2, delta-nu/nu = +0.009; BrN-O-Br2, delta-nu/nu = +0.013). In all four complexes, the X-NO stretching mode relative shift is opposite in sign and about 1.6 times that of the NO stretching mode. These four complexes are considered to be similar in structure and charge distribution. The XN-O frequency shift suggests that complex formation is accompanied by charge withdrawal from the NO bond ranging from about .04 to .07 electron charges. The HX and X2 molecules act as electron acceptors, drawing electrons out of the antibonding orbital of NO and strengthening the XN-O bond. The implications of the pattern of vibrational shifts concerning the structure of the complexes are discussed.

  9. Removal of Retired Alkali Metal Test Systems

    SciTech Connect

    BREHM, W.F.

    2003-01-01

    This paper describes the successful effort to remove alkali metals, alkali metal residues, and piping and structures from retired non-radioactive test systems on the Hanford Site. These test systems were used between 1965 and 1982 to support the Fast Flux Test Facility and the Liquid Metal Fast Breeder Reactor Program. A considerable volume of sodium and sodium-potassium alloy (NaK) was successfully recycled to the commercial sector; structural material and electrical material such as wiring was also recycled. Innovative techniques were used to safely remove NaK and its residues from a test system that could not be gravity-drained. The work was done safely, with no environmental issues or significant schedule delays.

  10. Removal of Retired Alkali Metal Test Systems

    SciTech Connect

    Brehm, W. F.; Church, W. R.; Biglin, J. W.

    2003-02-26

    This paper describes the successful effort to remove alkali metals, alkali metal residues, and piping and structures from retired non-radioactive test systems on the Hanford Site. These test systems were used between 1965 and 1982 to support the Fast Flux Test Facility and the Liquid Metal Fast Breeder Reactor Program. A considerable volume of sodium and sodium-potassium alloy (NaK) was successfully recycled to the commercial sector; structural material and electrical material such as wiring was also recycled. Innovative techniques were used to safely remove NaK and its residues from a test system that could not be gravity-drained. The work was done safely, with no environmental issues or significant schedule delays.

  11. Geopolymers and Related Alkali-Activated Materials

    NASA Astrophysics Data System (ADS)

    Provis, John L.; Bernal, Susan A.

    2014-07-01

    The development of new, sustainable, low-CO2 construction materials is essential if the global construction industry is to reduce the environmental footprint of its activities, which is incurred particularly through the production of Portland cement. One type of non-Portland cement that is attracting particular attention is based on alkali-aluminosilicate chemistry, including the class of binders that have become known as geopolymers. These materials offer technical properties comparable to those of Portland cement, but with a much lower CO2 footprint and with the potential for performance advantages over traditional cements in certain niche applications. This review discusses the synthesis of alkali-activated binders from blast furnace slag, calcined clay (metakaolin), and fly ash, including analysis of the chemical reaction mechanisms and binder phase assemblages that control the early-age and hardened properties of these materials, in particular initial setting and long-term durability. Perspectives for future research developments are also explored.

  12. Quantum magnetism of alkali Rydberg atoms

    NASA Astrophysics Data System (ADS)

    Malinovskaya, Svetlana; Liu, Gengyuan

    2016-05-01

    We discuss a method to control dynamics in many-body spin states of 87Rb Rydberg atoms. The method permits excitation of cold gases and form ordered structures of alkali atoms. It makes use of a two-photon excitation scheme with circularly polarized and linearly chirped pulses. The method aims for controlled quantum state preparation in large ensembles. It is actual for experiments studding the spin hopping dynamics and realization of quantum random walks.

  13. Alkali Metal Heat Pipe Life Issues

    NASA Technical Reports Server (NTRS)

    Reid, Robert S.

    2004-01-01

    One approach to space fission power system design is predicated on the use of alkali metal heat pipes, either as radiator elements, thermal management components, or as part of the core primary heat-transfer system. This synopsis characterizes long-life core heat pipes. References are included where more detailed information can be found. Specifics shown here are for demonstrational purposes and do not necessarily reflect current Project Prometheus point designs.

  14. Alkali metal protective garment and composite material

    SciTech Connect

    Ballif, J.L.; Yuan, W.W.

    1980-09-16

    A protective garment and composite material providing satisfactory heat resistance and physical protection for articles and personnel exposed to hot molten alkali metals, such as sodium are described. Physical protection is provided by a continuous layer of nickel foil. Heat resistance is provided by an underlying backing layer of thermal insulation. Overlying outer layers of fireproof woven ceramic fibers are used to protect the foil during storage and handling.

  15. Alkali metal protective garment and composite material

    SciTech Connect

    Ballif, III, John L.; Yuan, Wei W.

    1980-01-01

    A protective garment and composite material providing satisfactory heat resistance and physical protection for articles and personnel exposed to hot molten alkali metals, such as sodium. Physical protection is provided by a continuous layer of nickel foil. Heat resistance is provided by an underlying backing layer of thermal insulation. Overlying outer layers of fireproof woven ceramic fibers are used to protect the foil during storage and handling.

  16. Study of superconducting state parameters of alkali alkali binary alloys by a pseudopotential

    NASA Astrophysics Data System (ADS)

    Vora, Aditya M.

    2006-12-01

    A detailed study of the superconducting state parameters (SSP) viz. electron-phonon coupling strength λ, Coulomb pseudopotential μ∗, transition temperature TC, isotope effect exponent α and effective interaction strength N OV of ten alkali-alkali binary alloys i.e. Li 1- xNa x, Li 1- xK x, Li 1- xRb x, Li 1- xCs x, Na 1- xK x, Na 1- xRb x, Na 1- xCs x, K 1- xRb x, K 1- xCs x and Rb 1- xCs x are made within the framework of the model potential formalism and employing the pseudo-alloy-atom (PAA) model for the first time. We use the Ashcroft’s empty core (EMC) model potential for evaluating the superconducting properties of alkali alloys. Five different forms of local field correction functions viz. Hartree (H), Taylor (T), Ichimaru-Utsumi (IU), Farid et al. (F) and Sarkar et al. (S) are used to incorporate the exchange and correlation effects. A considerable influence of various exchange and correlation functions on λ and μ∗ is found from the present study. Reasonable agreement with the theoretical values of the SSP of pure components is found (corresponding to the concentration x = 0 or 1). It is also concluded that nature of the SSP strongly depends on the value of the atomic volume Ω0 of alkali-alkali binary alloys.

  17. Transport properties of alkali metal doped fullerides

    SciTech Connect

    Yadav, Daluram Yadav, Nishchhal

    2015-07-31

    We have studied the intercage interactions between the adjacent C{sub 60} cages and expansion of lattice due to the intercalation of alkali atoms based on the spring model to estimate phonon frequencies from the dynamical matrix for the intermolecular alkali-C{sub 60} phonons. We considered a two-peak model for the phonon density of states to investigate the nature of electron pairing mechanism for superconducting state in fullerides. Coulomb repulsive parameter and the electron phonon coupling strength are obtained within the random phase approximation. Transition temperature, T{sub c}, is obtained in a situation when the free electrons in lowest molecular orbital are coupled with alkali-C{sub 60} phonons as 5 K, which is much lower as compared to reported T{sub c} (20 K). The superconducting pairing is mainly driven by the high frequency intramolecular phonons and their effects enhance it to 22 K. The importance of the present study, the pressure effect and normal state transport properties are calculated within the same model leading superconductivity.

  18. Transport properties of alkali metal doped fullerides

    NASA Astrophysics Data System (ADS)

    Yadav, Daluram; Yadav, Nishchhal

    2015-07-01

    We have studied the intercage interactions between the adjacent C60 cages and expansion of lattice due to the intercalation of alkali atoms based on the spring model to estimate phonon frequencies from the dynamical matrix for the intermolecular alkali-C60 phonons. We considered a two-peak model for the phonon density of states to investigate the nature of electron pairing mechanism for superconducting state in fullerides. Coulomb repulsive parameter and the electron phonon coupling strength are obtained within the random phase approximation. Transition temperature, Tc, is obtained in a situation when the free electrons in lowest molecular orbital are coupled with alkali-C60 phonons as 5 K, which is much lower as compared to reported Tc (20 K). The superconducting pairing is mainly driven by the high frequency intramolecular phonons and their effects enhance it to 22 K. The importance of the present study, the pressure effect and normal state transport properties are calculated within the same model leading superconductivity.

  19. Ion Pairing in Alkali Nitrate Electrolyte Solutions.

    PubMed

    Xie, Wen Jun; Zhang, Zhen; Gao, Yi Qin

    2016-03-10

    In this study, we investigate the thermodynamics of alkali nitrate salt solutions, especially the formation of contact ion pairs between alkali cation and nitrate anion. The ion-pairing propensity shows an order of LiNO3 < NaNO3 < KNO3. Such results explain the salt activity coefficients and suggest that the empirical "law of matching water affinity" is followed by these alkali nitrate salt solutions. The spatial patterns of contact ion pairs are different in the three salt solutions studied here: Li(+) forms the contact ion pair with only one oxygen of the nitrate while Na(+) and K(+) can also be shared by two oxygens of the nitrate. In reproducing the salt activity coefficient using Kirkwood-Buff theory, we find that it is essential to include electronic polarization for Li(+) which has a high charge density. The electronic continuum correction for nonpolarizable force field significantly improves the agreement between the calculated activity coefficients and their experimental values. This approach also improves the performance of the force field on salt solubility. From these two aspects, this study suggests that electronic continuum correction can be a promising approach to force-field development for ions with high charge densities. PMID:26901167

  20. Methods and Mechanisms for Cross-Electrophile Coupling of Csp(2) Halides with Alkyl Electrophiles.

    PubMed

    Weix, Daniel J

    2015-06-16

    Cross-electrophile coupling, the cross-coupling of two different electrophiles, avoids the need for preformed carbon nucleophiles, but development of general methods has lagged behind cross-coupling and C-H functionalization. A central reason for this slow development is the challenge of selectively coupling two substrates that are alike in reactivity. This Account describes the discovery of generally cross-selective reactions of aryl halides and acyl halides with alkyl halides, the mechanistic studies that illuminated the underlying principles of these reactions, and the use of these fundamental principles in the rational design of new cross-electrophile coupling reactions. Although the coupling of two different electrophiles under reducing conditions often leads primarily to symmetric dimers, the subtle differences in reactivity of aryl halides and alkyl halides with nickel catalysts allowed for generally cross-selective coupling reactions. These conditions could also be extended to the coupling of acyl halides with alkyl halides. These reactions are exceptionally functional group tolerant and can be assembled on the benchtop. A combination of stoichiometric and catalytic studies on the mechanism of these reactions revealed an unusual radical-chain mechanism and suggests that selectivity arises from (1) the preference of nickel(0) for oxidative addition to aryl halides and acyl halides over alkyl halides and (2) the greater propensity of alkyl halides to form free radicals. Bipyridine-ligated arylnickel intermediates react with alkyl radicals to efficiently form, after reductive elimination, new C-C bonds. Finally, the resulting nickel(I) species is proposed to regenerate an alkyl radical to carry the chain. Examples of new reactions designed using these principles include carbonylative coupling of aryl halides with alkyl halides to form ketones, arylation of epoxides to form β-aryl alcohols, and coupling of benzyl sulfonate esters with aryl halides to form

  1. Methods and Mechanisms for Cross-Electrophile Coupling of Csp2 Halides with Alkyl Electrophiles

    PubMed Central

    2016-01-01

    Conspectus Cross-electrophile coupling, the cross-coupling of two different electrophiles, avoids the need for preformed carbon nucleophiles, but development of general methods has lagged behind cross-coupling and C–H functionalization. A central reason for this slow development is the challenge of selectively coupling two substrates that are alike in reactivity. This Account describes the discovery of generally cross-selective reactions of aryl halides and acyl halides with alkyl halides, the mechanistic studies that illuminated the underlying principles of these reactions, and the use of these fundamental principles in the rational design of new cross-electrophile coupling reactions. Although the coupling of two different electrophiles under reducing conditions often leads primarily to symmetric dimers, the subtle differences in reactivity of aryl halides and alkyl halides with nickel catalysts allowed for generally cross-selective coupling reactions. These conditions could also be extended to the coupling of acyl halides with alkyl halides. These reactions are exceptionally functional group tolerant and can be assembled on the benchtop. A combination of stoichiometric and catalytic studies on the mechanism of these reactions revealed an unusual radical-chain mechanism and suggests that selectivity arises from (1) the preference of nickel(0) for oxidative addition to aryl halides and acyl halides over alkyl halides and (2) the greater propensity of alkyl halides to form free radicals. Bipyridine-ligated arylnickel intermediates react with alkyl radicals to efficiently form, after reductive elimination, new C–C bonds. Finally, the resulting nickel(I) species is proposed to regenerate an alkyl radical to carry the chain. Examples of new reactions designed using these principles include carbonylative coupling of aryl halides with alkyl halides to form ketones, arylation of epoxides to form β-aryl alcohols, and coupling of benzyl sulfonate esters with aryl

  2. Gaseous NH3 Confers Porous Pt Nanodendrites Assisted by Halides.

    PubMed

    Lu, Shuanglong; Eid, Kamel; Li, Weifeng; Cao, Xueqin; Pan, Yue; Guo, Jun; Wang, Liang; Wang, Hongjing; Gu, Hongwei

    2016-01-01

    Tailoring the morphology of Pt nanocrystals (NCs) is of great concern for their enhancement in catalytic activity and durability. In this article, a novel synthetic strategy is developed to selectively prepare porous dendritic Pt NCs with different structures for oxygen reduction reaction (ORR) assisted by NH3 gas and halides (F(-), Cl(-), Br(-)). The NH3 gas plays critical roles on tuning the morphology. Previously, H2 and CO gas are reported to assist the shape control of metallic nanocrystals. This is the first demonstration that NH3 gas assists the Pt anisotropic growth. The halides also play important role in the synthetic strategy to regulate the formation of Pt NCs. As-made porous dendritic Pt NCs, especially when NH4F is used as a regulating reagent, show superior catalytic activity for ORR compared with commercial Pt/C catalyst and other previously reported Pt-based NCs. PMID:27184228

  3. Gaseous NH3 Confers Porous Pt Nanodendrites Assisted by Halides

    PubMed Central

    Lu, Shuanglong; Eid, Kamel; Li, Weifeng; Cao, Xueqin; Pan, Yue; Guo, Jun; Wang, Liang; Wang, Hongjing; Gu, Hongwei

    2016-01-01

    Tailoring the morphology of Pt nanocrystals (NCs) is of great concern for their enhancement in catalytic activity and durability. In this article, a novel synthetic strategy is developed to selectively prepare porous dendritic Pt NCs with different structures for oxygen reduction reaction (ORR) assisted by NH3 gas and halides (F−, Cl−, Br−). The NH3 gas plays critical roles on tuning the morphology. Previously, H2 and CO gas are reported to assist the shape control of metallic nanocrystals. This is the first demonstration that NH3 gas assists the Pt anisotropic growth. The halides also play important role in the synthetic strategy to regulate the formation of Pt NCs. As-made porous dendritic Pt NCs, especially when NH4F is used as a regulating reagent, show superior catalytic activity for ORR compared with commercial Pt/C catalyst and other previously reported Pt-based NCs. PMID:27184228

  4. Gaseous NH3 Confers Porous Pt Nanodendrites Assisted by Halides

    NASA Astrophysics Data System (ADS)

    Lu, Shuanglong; Eid, Kamel; Li, Weifeng; Cao, Xueqin; Pan, Yue; Guo, Jun; Wang, Liang; Wang, Hongjing; Gu, Hongwei

    2016-05-01

    Tailoring the morphology of Pt nanocrystals (NCs) is of great concern for their enhancement in catalytic activity and durability. In this article, a novel synthetic strategy is developed to selectively prepare porous dendritic Pt NCs with different structures for oxygen reduction reaction (ORR) assisted by NH3 gas and halides (F‑, Cl‑, Br‑). The NH3 gas plays critical roles on tuning the morphology. Previously, H2 and CO gas are reported to assist the shape control of metallic nanocrystals. This is the first demonstration that NH3 gas assists the Pt anisotropic growth. The halides also play important role in the synthetic strategy to regulate the formation of Pt NCs. As-made porous dendritic Pt NCs, especially when NH4F is used as a regulating reagent, show superior catalytic activity for ORR compared with commercial Pt/C catalyst and other previously reported Pt-based NCs.

  5. Large methyl halide emissions from south Texas salt marshes

    NASA Astrophysics Data System (ADS)

    Rhew, R. C.; Whelan, M. E.; Min, D.-H.

    2014-06-01

    Coastal salt marshes are natural sources of methyl chloride (CH3Cl) and methyl bromide (CH3Br) to the atmosphere, but measured emission rates vary widely by geography. Here we report large methyl halide fluxes from subtropical salt marshes of south Texas. Sites with the halophytic plant, Batis maritima, emitted methyl halides at rates that are orders of magnitude greater than sites containing other vascular plants or macroalgae. B. maritima emissions were generally highest at midday; however, diurnal variability was more pronounced for CH3Br than CH3Cl, and surprisingly high nighttime CH3Cl fluxes were observed in July. Seasonal and intra-site variability were large, even taking into account biomass differences. Overall, these subtropical salt marsh sites show much higher emission rates than temperate salt marshes at similar times of the year, supporting the contention that low-latitude salt marshes are significant sources of CH3Cl and CH3Br.

  6. Large methyl halide emissions from south Texas salt marshes

    NASA Astrophysics Data System (ADS)

    Rhew, R. C.; Whelan, M. E.; Min, D.-H.

    2014-11-01

    Coastal salt marshes are natural sources of methyl chloride (CH3Cl) and methyl bromide (CH3Br) to the atmosphere, but measured emission rates vary widely by geography. Here we report large methyl halide fluxes from subtropical salt marshes of south Texas. Sites with the halophytic plant, Batis maritima, emitted methyl halides at rates that are orders of magnitude greater than sites containing other vascular plants or macroalgae. B. maritima emissions were generally highest at midday; however, diurnal variability was more pronounced for CH3Br than CH3Cl, and surprisingly high nighttime CH3Cl fluxes were observed in July. Seasonal and intra-site variability were large, even taking into account biomass differences. Overall, these subtropical salt marsh sites show much higher emission rates than temperate salt marshes at similar times of the year, supporting the contention that low-latitude salt marshes are significant sources of CH3Cl and CH3Br.

  7. Oxidative alkoxylation of phosphine in alcohol solutions of copper halides

    NASA Astrophysics Data System (ADS)

    Polimbetova, G. S.; Borangazieva, A. K.; Ibraimova, Zh. U.; Bugubaeva, G. O.; Keynbay, S.

    2016-08-01

    The phosphine oxidation reaction with oxygen in alcohol solutions of copper (I, II) halides is studied. Kinetic parameters, intermediates, and by-products are studied by means of NMR 31Р-, IR-, UV-, and ESR- spectroscopy; and by magnetic susceptibility, redox potentiometry, gas chromatography, and elemental analysis. A reaction mechanism is proposed, and the optimum conditions are found for the reaction of oxidative alkoxylation phosphine.

  8. Copper-catalyzed arylation of alkyl halides with arylaluminum reagents

    PubMed Central

    Shrestha, Bijay

    2015-01-01

    Summary We report a Cu-catalyzed coupling between triarylaluminum reagents and alkyl halides to form arylalkanes. The reaction proceeds in the presence of N,N,N’,N’-tetramethyl-o-phenylenediamine (NN-1) as a ligand in combination with CuI as a catalyst. This catalyst system enables the coupling of primary alkyl iodides and bromides with electron-neutral and electron-rich triarylaluminum reagents and affords the cross-coupled products in good to excellent yields. PMID:26734088

  9. Copper-catalyzed arylation of alkyl halides with arylaluminum reagents.

    PubMed

    Shrestha, Bijay; Giri, Ramesh

    2015-01-01

    We report a Cu-catalyzed coupling between triarylaluminum reagents and alkyl halides to form arylalkanes. The reaction proceeds in the presence of N,N,N',N'-tetramethyl-o-phenylenediamine (NN-1) as a ligand in combination with CuI as a catalyst. This catalyst system enables the coupling of primary alkyl iodides and bromides with electron-neutral and electron-rich triarylaluminum reagents and affords the cross-coupled products in good to excellent yields. PMID:26734088

  10. Organolead Halide Perovskites for Low Operating Voltage Multilevel Resistive Switching.

    PubMed

    Choi, Jaeho; Park, Sunghak; Lee, Joohee; Hong, Kootak; Kim, Do-Hong; Moon, Cheon Woo; Park, Gyeong Do; Suh, Junmin; Hwang, Jinyeon; Kim, Soo Young; Jung, Hyun Suk; Park, Nam-Gyu; Han, Seungwu; Nam, Ki Tae; Jang, Ho Won

    2016-08-01

    Organolead halide perovskites are used for low-operating-voltage multilevel resistive switching. Ag/CH3 NH3 PbI3 /Pt cells exhibit electroforming-free resistive switching at an electric field of 3.25 × 10(3) V cm(-1) for four distinguishable ON-state resistance levels. The migration of iodine interstitials and vacancies with low activation energies is responsible for the low-electric-field resistive switching via filament formation and annihilation. PMID:27192161

  11. Lasing in robust cesium lead halide perovskite nanowires

    PubMed Central

    Eaton, Samuel W.; Lai, Minliang; Gibson, Natalie A.; Wong, Andrew B.; Dou, Letian; Ma, Jie; Wang, Lin-Wang; Leone, Stephen R.; Yang, Peidong

    2016-01-01

    The rapidly growing field of nanoscale lasers can be advanced through the discovery of new, tunable light sources. The emission wavelength tunability demonstrated in perovskite materials is an attractive property for nanoscale lasers. Whereas organic–inorganic lead halide perovskite materials are known for their instability, cesium lead halides offer a robust alternative without sacrificing emission tunability or ease of synthesis. Here, we report the low-temperature, solution-phase growth of cesium lead halide nanowires exhibiting low-threshold lasing and high stability. The as-grown nanowires are single crystalline with well-formed facets, and act as high-quality laser cavities. The nanowires display excellent stability while stored and handled under ambient conditions over the course of weeks. Upon optical excitation, Fabry–Pérot lasing occurs in CsPbBr3 nanowires with an onset of 5 μJ cm−2 with the nanowire cavity displaying a maximum quality factor of 1,009 ± 5. Lasing under constant, pulsed excitation can be maintained for over 1 h, the equivalent of 109 excitation cycles, and lasing persists upon exposure to ambient atmosphere. Wavelength tunability in the green and blue regions of the spectrum in conjunction with excellent stability makes these nanowire lasers attractive for device fabrication. PMID:26862172

  12. Quantum Size Effect in Organometal Halide Perovskite Nanoplatelets.

    PubMed

    Sichert, Jasmina A; Tong, Yu; Mutz, Niklas; Vollmer, Mathias; Fischer, Stefan; Milowska, Karolina Z; García Cortadella, Ramon; Nickel, Bert; Cardenas-Daw, Carlos; Stolarczyk, Jacek K; Urban, Alexander S; Feldmann, Jochen

    2015-10-14

    Organometal halide perovskites have recently emerged displaying a huge potential for not only photovoltaic, but also light emitting applications. Exploiting the optical properties of specifically tailored perovskite nanocrystals could greatly enhance the efficiency and functionality of applications based on this material. In this study, we investigate the quantum size effect in colloidal organometal halide perovskite nanoplatelets. By tuning the ratio of the organic cations used, we can control the thickness and consequently the photoluminescence emission of the platelets. Quantum mechanical calculations match well with the experimental values. We find that not only do the properties of the perovskite, but also those of the organic ligands play an important role. Stacking of nanoplatelets leads to the formation of minibands, further shifting the bandgap energies. In addition, we find a large exciton binding energy of up to several hundreds of meV for nanoplatelets thinner than three unit cells, partially counteracting the blueshift induced by quantum confinement. Understanding of the quantum size effects in perovskite nanoplatelets and the ability to tune them provide an additional method with which to manipulate the optical properties of organometal halide perovskites. PMID:26327242

  13. Lasing in robust cesium lead halide perovskite nanowires.

    PubMed

    Eaton, Samuel W; Lai, Minliang; Gibson, Natalie A; Wong, Andrew B; Dou, Letian; Ma, Jie; Wang, Lin-Wang; Leone, Stephen R; Yang, Peidong

    2016-02-23

    The rapidly growing field of nanoscale lasers can be advanced through the discovery of new, tunable light sources. The emission wavelength tunability demonstrated in perovskite materials is an attractive property for nanoscale lasers. Whereas organic-inorganic lead halide perovskite materials are known for their instability, cesium lead halides offer a robust alternative without sacrificing emission tunability or ease of synthesis. Here, we report the low-temperature, solution-phase growth of cesium lead halide nanowires exhibiting low-threshold lasing and high stability. The as-grown nanowires are single crystalline with well-formed facets, and act as high-quality laser cavities. The nanowires display excellent stability while stored and handled under ambient conditions over the course of weeks. Upon optical excitation, Fabry-Pérot lasing occurs in CsPbBr3 nanowires with an onset of 5 μJ cm(-2) with the nanowire cavity displaying a maximum quality factor of 1,009 ± 5. Lasing under constant, pulsed excitation can be maintained for over 1 h, the equivalent of 10(9) excitation cycles, and lasing persists upon exposure to ambient atmosphere. Wavelength tunability in the green and blue regions of the spectrum in conjunction with excellent stability makes these nanowire lasers attractive for device fabrication. PMID:26862172

  14. Deciphering Halogen Competition in Organometallic Halide Perovskite Growth

    DOE PAGESBeta

    Keum, Jong Kahk; Ovchinnikova, Olga S.; Chen, Shiyou; Du, Mao-Hua; Ivanov, Ilia N; Rouleau, Christopher; Geohegan, David B.; Xiao, Kai

    2016-03-01

    Organometallic halide perovskites (OHPs) hold great promise for next-generation, low-cost optoelectronic devices. During the chemical synthesis and crystallization of OHP thin films a major unresolved question is the competition between multiple halide species (e.g. I-, Cl-, Br-) in the formation of the mixed halide perovskite crystals. Whether Cl- ions are successfully incorporated into the perovskite crystal structure or alternatively, where they are located, is not yet fully understood. Here, in situ X-ray diffraction measurements of crystallization dynamics are combined with ex situ TOF-SIMS chemical analysis to reveal that Br- or Cl- ions can promote crystal growth, yet reactive I- ionsmore » prevent them from incorporating into the lattice of the final perovskite crystal structure. The Cl- ions are located in the grain boundaries of the perovskite films. These findings significantly advance our understanding of the role of halogens during synthesis of hybrid perovskites, and provide an insightful guidance to the engineering of high-quality perovskite films, essential for exploring superior-performance and cost-effective optoelectronic devices.« less

  15. Environmental controls over methyl halide emissions from rice paddies

    NASA Astrophysics Data System (ADS)

    Redeker, K. R.; Cicerone, R. J.

    2004-03-01

    This paper examines primary controlling factors that affect methyl halide emissions from rice paddy ecosystems. Observations of four cultivars under multiple growth conditions during studies in commercial fields and the University of California, Irvine, greenhouse lead to the conclusion that daily emissions of methyl halides are primarily determined by the growth stage of the rice plant, with the exception that methyl chloride emissions show no clear seasonal pattern. Methyl chloride emissions appear to be more from the paddy water and/or soil as opposed to the plants; however, in soils with high chloride content, these emissions appear to peak during the reproductive phase. Strong secondary influences include air temperature, soil halide concentration, and soil pore water saturation. The cultivars studied had statistically separate seasonally integrated emissions. Irradiant light and aboveground biomass appear to have little effect on emissions. Emissions of methyl chloride, methyl bromide, and methyl iodide are estimated to be 3.5, 2.3, and 48 mg/m2/yr, or 5.3, 3.5, and 72 Gg/yr, from rice paddies globally.

  16. Deciphering Halogen Competition in Organometallic Halide Perovskite Growth.

    PubMed

    Yang, Bin; Keum, Jong; Ovchinnikova, Olga S; Belianinov, Alex; Chen, Shiyou; Du, Mao-Hua; Ivanov, Ilia N; Rouleau, Christopher M; Geohegan, David B; Xiao, Kai

    2016-04-20

    Organometallic halide perovskites (OHPs) hold great promise for next-generation, low-cost optoelectronic devices. During the chemical synthesis and crystallization of OHP thin films, a major unresolved question is the competition between multiple halide species (e.g., I(-), Cl(-), Br(-)) in the formation of the mixed-halide perovskite crystals. Whether Cl(-) ions are successfully incorporated into the perovskite crystal structure or, alternatively, where they are located is not yet fully understood. Here, in situ X-ray diffraction measurements of crystallization dynamics are combined with ex situ TOF-SIMS chemical analysis to reveal that Br(-) or Cl(-) ions can promote crystal growth, yet reactive I(-) ions prevent them from incorporating into the lattice of the final perovskite crystal structure. The Cl(-) ions are located in the grain boundaries of the perovskite films. These findings significantly advance our understanding of the role of halogens during synthesis of hybrid perovskites and provide an insightful guidance to the engineering of high-quality perovskite films, essential for exploring superior-performing and cost-effective optoelectronic devices. PMID:26931634

  17. Insights from the Adsorption of Halide Ions on Graphene Materials.

    PubMed

    Zhu, Chang; Yang, Gang

    2016-08-18

    Graphene has recently found applications in a wide range of fields. Density functional calculations show that halide ions can be adsorbed on pristine graphene, but only F(-) has an appreciable binding energy (-97.0 kJ mol(-1) ). Graphene materials, which are mainly electron donors, can be made strong electron acceptors by edge functionalization with F atoms. The binding strengths of halide ions are greatly enhanced by edge functionalization and show direct proportionality with the degree of functionalization Θ and increased charge transfer. In contrast, the adsorption strengths of metal ions on pristine graphene are clearly superior to those of halide ions but decline substantially with increasing degree of edge functionalization, and for Θ=100 %, the binding energies of -95.7, -44.8, and -25.9 kJ mol(-1) that are calculated for Li(+) , Na(+) , and K(+) , respectively, are obviously inferior to that of F(-) (-186.3 kJ mol(-1) ). Thus, the electronic properties of graphene are fundamentally regulated by edge functionalization, and the preferential adsorption of certain metal ions or anions can be facilely realized by choice of an appropriate degree of functionalization. Adsorbed metal ions and anions behave differently on gradual addition of water molecules, and their binding strengths remain substantial when graphene materials are in the pristine and highly edge functionalized states, respectively. PMID:27127939

  18. Depth profile of halide anions under highly charged biological membrane

    NASA Astrophysics Data System (ADS)

    Sung, Woongmo; Wang, Wenjie; Lee, Jonggwan; Vaknin, David; Kim, Doseok

    2015-03-01

    Halide ion (Cl- and I-) distribution under a cationic Langmuir monolayer consisting of 1,2-dipalmitoyl-3 trimethylammonium-propane (DPTAP) molecules was investigated by vibrational sum-frequency generation (VSFG) and X-ray spectroscopy. From VSFG spectra, it was observed that large halide anions (I-) screen surface charge more efficiently so that interfacial water alignment becomes more randomized. On the other hand, number density of ions directly measured by X-ray fluorescence spectroscopy at grazing incidence angle reveals that the ion densities within 6 ~ 8 nm are the same for both I- and Cl-. Since the observed ion densities in both cases are almost equal to the charge density of the DPTAP monolayer, we propose that larger halide anions are attracted closer to the surface making direct binding with the charged headgroups of the molecules in the monolayer, accomplishing charge neutrality in short distance. This direct adsorption of anions also disturbs the monolayer structure both in terms of the conformation of alkyl chains and the vertical configuration of the monolayer, with iodine having the stronger effect. Our study shows that the length scale that ions neutralize a charged interface varies significantly and specifically even between monovalent ions.

  19. Iodomethane-Mediated Organometal Halide Perovskite with Record Photoluminescence Lifetime.

    PubMed

    Xu, Weidong; McLeod, John A; Yang, Yingguo; Wang, Yimeng; Wu, Zhongwei; Bai, Sai; Yuan, Zhongcheng; Song, Tao; Wang, Yusheng; Si, Junjie; Wang, Rongbin; Gao, Xingyu; Zhang, Xinping; Liu, Lijia; Sun, Baoquan

    2016-09-01

    Organometallic lead halide perovskites are excellent light harvesters for high-efficiency photovoltaic devices. However, as the key component in these devices, a perovskite thin film with good morphology and minimal trap states is still difficult to obtain. Herein we show that by incorporating a low boiling point alkyl halide such as iodomethane (CH3I) into the precursor solution, a perovskite (CH3NH3PbI3-xClx) film with improved grain size and orientation can be easily achieved. More importantly, these films exhibit a significantly reduced amount of trap states. Record photoluminescence lifetimes of more than 4 μs are achieved; these lifetimes are significantly longer than that of pristine CH3NH3PbI3-xClx films. Planar heterojunction solar cells incorporating these CH3I-mediated perovskites have demonstrated a dramatically increased power conversion efficiency compared to the ones using pristine CH3NH3PbI3-xClx. Photoluminescence, transient absorption, and microwave detected photoconductivity measurements all provide consistent evidence that CH3I addition increases the number of excitons generated and their diffusion length, both of which assist efficient carrier transport in the photovoltaic device. The simple incorporation of alkyl halide to enhance perovskite surface passivation introduces an important direction for future progress on high efficiency perovskite optoelectronic devices. PMID:27529636

  20. Extensive and Highly Accurate Line Lists for Hydrogen Halides

    NASA Astrophysics Data System (ADS)

    Li, G.; Bernath, P. F.; Gordon, I. E.; Rothman, L. S.; Richard, C.; Le Roy, R. J.; Coxon, J. A.; Hajigeorgiou, P.

    2011-06-01

    New dipole moment functions (DMF) for the ground X 1Σ+ electronic states of the hydrogen halides (HF, HCl, HBr, HI) have been obtained using a direct fit approach that fits the best available and appropriately weighted experimental line intensity data for individual ro-vibrational transitions. Combining the newly developed (taking into account the most recent experiments) empirical potential energy functions and the DMFs, line positions and line intensities of the hydrogen halides and their isotopologues have been calculated numerically using program LEVEL. In addition, new semi-empirical algorithms for assigning line-shape parameters for these species have been developed. Using these improvements, new line lists for hydrogen halides were created to update the HITRAN spectroscopic database. These new lists are more accurate and significantly more extensive than those included in the current version of the database (HITRAN2008). R.J. Le Roy, ``LEVEL 8.0, 2007'', University of Waterloo Chemical Physics Research Report CP-663 (2007); see http://leroy.uwaterloo.ca/programs/. L.S. Rothman, I.E. Gordon, A. Barbe, D.C. Benner, P.F. Bernath, et al., ``The HITRAN 2008 Molecular Spectroscopic Database,'' JQSRT 110, 532-572 (2009).

  1. Contributions to the mixed-alkali effect in molecular dynamics simulations of alkali silicate glasses

    NASA Astrophysics Data System (ADS)

    Lammert, Heiko; Heuer, Andreas

    2005-12-01

    The mixed-alkali effect in the cation dynamics in silicate glasses is analyzed via molecular dynamics simulations. Observations suggest a description of the dynamics in terms of stable sites mostly specific to one ionic species. As main contributions to the mixed-alkali slow down longer residence times and an increased probability of correlated backjumps are identified. The slow down is related to the limited accessibility of foreign sites. The mismatch experienced in a foreign site is stronger and more retarding for the larger ions, the smaller ions can be temporarily accommodated. Also correlations between unlike as well as like cations are demonstrated that support cooperative behavior.

  2. Method for the safe disposal of alkali metal

    DOEpatents

    Johnson, Terry R.

    1977-01-01

    Alkali metals such as those employed in liquid metal coolant systems can be safely reacted to form hydroxides by first dissolving the alkali metal in relatively inert metals such as lead or bismuth. The alloy thus formed is contacted with a molten salt including the alkali metal hydroxide and possibly the alkali metal carbonate in the presence of oxygen. This oxidizes the alkali metal to an oxide which is soluble within the molten salt. The salt is separated and contacted with steam or steam-CO.sub.2 mixture to convert the alkali metal oxide to the hydroxide. These reactions can be conducted with minimal hydrogen evolution and with the heat of reaction distributed between the several reaction steps.

  3. Indirect detection of halide ions via fluorescence quenching of quinine sulfate in microcolumn ion chromatography.

    PubMed

    Takeuchi, Toyohide; Sumida, Junichi

    2004-06-01

    Halide ions could be visualized via fluorescence quenching in microcolumn ion chromatography. The fluorescence of quinine sulfate, which was contained in an acidic eluent, was quenched by halide ions. The observed fluorescence quenching values increased in this order: iodide, bromide, and chloride. The present detection system was relatively sensitive to halide ions except for fluoride: other anions gave smaller signals than halide ions. The present detection system provided quantitative information, so it could be applied to the determination of chloride in water samples. PMID:15228124

  4. Method for producing hydrocarbon fuels from heavy polynuclear hydrocarbons by use of molten metal halide catalyst

    DOEpatents

    Gorin, Everett

    1979-01-01

    In a process for hydrocracking heavy polynuclear carbonaceous feedstocks to produce lighter hydrocarbon fuels by contacting the heavy feedstocks with hydrogen in the presence of a molten metal halide catalyst, thereafter separating at least a substantial portion of the carbonaceous material associated with the reaction mixture from the spent molten metal halide and thereafter regenerating the metal halide catalyst, an improvement comprising contacting the spent molten metal halide catalyst after removal of a major portion of the carbonaceous material therefrom with an additional quantity of hydrogen is disclosed.

  5. Systematic analysis of the unique band gap modulation of mixed halide perovskites.

    PubMed

    Kim, Jongseob; Lee, Sung-Hoon; Chung, Choong-Heui; Hong, Ki-Ha

    2016-02-14

    Solar cells based on organic-inorganic hybrid metal halide perovskites have been proven to be one of the most promising candidates for the next generation thin film photovoltaic cells. Mixing Br or Cl into I-based perovskites has been frequently tried to enhance the cell efficiency and stability. One of the advantages of mixed halides is the modulation of band gap by controlling the composition of the incorporated halides. However, the reported band gap transition behavior has not been resolved yet. Here a theoretical model is presented to understand the electronic structure variation of metal mixed-halide perovskites through hybrid density functional theory. Comparative calculations in this work suggest that the band gap correction including spin-orbit interaction is essential to describe the band gap changes of mixed halides. In our model, both the lattice variation and the orbital interactions between metal and halides play key roles to determine band gap changes and band alignments of mixed halides. It is also presented that the band gap of mixed halide thin films can be significantly affected by the distribution of halide composition. PMID:26791587

  6. Determination of the common and rare alkalies in mineral analysis

    USGS Publications Warehouse

    Wells, R.C.; Stevens, R.E.

    1934-01-01

    Methods are described which afford a determination of each member of the alkali group and are successful in dealing with the quantities of the rare alkalies found in rocks and minerals. The procedures are relatively rapid and based chiefly on the use of chloroplatinic acid, absolute alcohol and ether, and ammonium sulfate. The percentages of all the alkalies found in a number of minerals are given.

  7. Environmental mercury contamination around a chlor-alkali plant

    SciTech Connect

    Lodenius, M.; Tulisalo, E.

    1984-04-01

    The chlor-alkali industry is one of the most important emitters of mercury. This metal is effectively spread from chlor-alkali plants into the atmosphere and it has been reported that only a few percent of the mercury emissions are deposited locally the major part spreading over very large areas. The purpose of this investigation was to study the spreading of mercury up to 100 km from a chlor-alkali plant using three different biological indicators.

  8. Basicity of the framework oxygen atom of alkali and alkaline earth-exchanged zeolites: a hard soft acid base approach

    NASA Astrophysics Data System (ADS)

    Deka, Ramesh Ch; Kinkar Roy, Ram; Hirao, Kimihiko

    2000-12-01

    The basicity of framework oxygen atoms of alkali and alkaline earth-exchanged zeolites has been studied using reactivity descriptors based on a local hard-soft acid-base (HSAB) concept. We have calculated the `local softness' and the `relative nucleophilicity' values of the framework oxygen atoms of zeolite clusters as the measure of basicity. The local softness and relative nucleophilicity appear to be more reliable descriptors to predict the experimental basicity trend, compared to the negative charge on the oxygen atom.

  9. Electrochemical devices utilizing molten alkali metal electrode-reactant

    DOEpatents

    Hitchcock, D.C.; Mailhe, C.C.; De Jonghe, L.C.

    1985-07-10

    Electrochemical cells are provided with a reactive metal to reduce the oxide of the alkali metal electrode-reactant. Cells employing a molten alkali metal electrode, e.g., sodium, in contact with a ceramic electrolyte, which is a conductor of the ions of the alkali metal forming the electrode, exhibit a lower resistance when a reactive metal, e.g., vanadium, is allowed to react with and reduce the alkali metal oxide. Such cells exhibit less degradation of the electrolyte and of the glass seals often used to joining the electrolyte to the other components of the cell under cycling conditions.

  10. Electrochemical devices utilizing molten alkali metal electrode-reactant

    DOEpatents

    Hitchcock, David C.; Mailhe, Catherine C.; De Jonghe, Lutgard C.

    1986-01-01

    Electrochemical cells are provided with a reactive metal to reduce the oxide of the alkali metal electrode-reactant. Cells employing a molten alkali metal electrode, e.g., sodium, in contact with a ceramic electrolyte, which is a conductor of the ions of the alkali metal forming the electrode, exhibit a lower resistance when a reactive metal, e.g., vanadium, is allowed to react with and reduce the alkali metal oxide. Such cells exhibit less degradation of the electrolyte and of the glass seals often used to joining the electrolyte to the other components of the cell under cycling conditions.

  11. Abiotic Formation of Methyl Halides in the Terrestrial Environment

    NASA Astrophysics Data System (ADS)

    Keppler, F.

    2011-12-01

    Methyl chloride and methyl bromide are the most abundant chlorine and bromine containing organic compounds in the atmosphere. Since both compounds have relatively long tropospheric lifetimes they can effectively transport halogen atoms from the Earth's surface, where they are released, to the stratosphere and following photolytic oxidation form reactive halogen gases that lead to the chemical destruction of ozone. Methyl chloride and methyl bromide account for more than 20% of the ozone-depleting halogens delivered to the stratosphere and are predicted to grow in importance as the chlorine contribution to the stratosphere from anthropogenic CFCs decline. Today methyl chloride and methyl bromide originate mainly from natural sources with only a minor fraction considered to be of anthropogenic origin. However, until as recently as 2000 most of the methyl chloride and methyl bromide input to the atmosphere was considered to originate from the oceans, but investigations in recent years have clearly demonstrated that terrestrial sources such as biomass burning, wood-rotting fungi, coastal salt marshes, tropical vegetation and organic matter degradation must dominate the atmospheric budgets of these trace gases. However, many uncertainties still exist regarding strengths of both sources and sinks, as well as the mechanisms of formation of these naturally occurring halogenated gases. A better understanding of the atmospheric budget of both methyl chloride and methyl bromide is therefore required for reliable prediction of future ozone depletion. Biotic and abiotic methylation processes of chloride and bromide ion are considered to be the dominant pathways of formation of these methyl halides in nature. In this presentation I will focus on abiotic formation processes in the terrestrial environment and the potential parameters that control their emissions. Recent advances in our understanding of the abiotic formation pathway of methyl halides will be discussed. This will

  12. Secondary nucleation of gibbsite crystals from synthetic Bayer liquors: effect of alkali metal ions

    NASA Astrophysics Data System (ADS)

    Li, Jun; Prestidge, Clive A.; Addai-Mensah, Jonas

    2000-11-01

    The effect of alkali metal ions (Na + versus K +) on secondary nucleation of gibbsite ( γ-Al(OH) 3) from synthetic Bayer liquors has been investigated under seeded, isothermal, batch crystallisation conditions. The nucleation kinetics showed a fourth-order dependence upon Al(III) relative supersaturation and a strong temperature effect. An activation energy of 132 kJ mol -1, which was independent of alkali metal ion, was calculated. Secondary nucleation and subsequent crystal growth rates however, were greater in sodium than in potassium aluminate solution. The Arrhenius, pre-exponential factor was at least three times larger in sodium than in potassium aluminate solutions at equivalent crystal surface area, similar supersaturation and temperature. The results indicated that secondary nucleation of Al(OH) 3 is a chemical reaction-controlled process which is alkali metal ion-mediated. Na + ions provide a more favourable pathway than potassium ions for the formation of Al(III)-containing clusters, higher collision frequency between the species and crystal surface, and faster growth of potential secondary nuclei in the solutions.

  13. Electrodes For Alkali-Metal Thermoelectric Converters

    NASA Technical Reports Server (NTRS)

    Williams, Roger M.; Wheeler, Bob L.; Jeffries-Nakamura, Barbara; Lamb, James L.; Bankston, C. Perry; Cole, Terry

    1989-01-01

    Combination of thin, porous electrode and overlying collector grid reduces internal resistance of alkali-metal thermoelectric converter cell. Low resistance of new electrode and grid boosts power density nearly to 1 W/cm2 of electrode area at typical operating temperatures of 1,000 to 1,300 K. Conductive grid encircles electrode film on alumina tube. Bus wire runs along tube to collect electrical current from grid. Such converters used to transform solar, nuclear, and waste heat into electric power.

  14. High power diode pumped alkali vapor lasers

    NASA Astrophysics Data System (ADS)

    Zweiback, J.; Krupke, B.

    2008-05-01

    Diode pumped alkali lasers have developed rapidly since their first demonstration. These lasers offer a path to convert highly efficient, but relatively low brightness, laser diodes into a single high power, high brightness beam. General Atomics has been engaged in the development of DPALs with scalable architectures. We have examined different species and pump characteristics. We show that high absorption can be achieved even when the pump source bandwidth is several times the absorption bandwidth. In addition, we present experimental results for both potassium and rubidium systems pumped with a 0.2 nm bandwidth alexandrite laser. These data show slope efficiencies of 67% and 72% respectively.

  15. Cathode architectures for alkali metal / oxygen batteries

    SciTech Connect

    Visco, Steven J; Nimon, Vitaliy; De Jonghe, Lutgard C; Volfkovich, Yury; Bograchev, Daniil

    2015-01-13

    Electrochemical energy storage devices, such as alkali metal-oxygen battery cells (e.g., non-aqueous lithium-air cells), have a cathode architecture with a porous structure and pore composition that is tailored to improve cell performance, especially as it pertains to one or more of the discharge/charge rate, cycle life, and delivered ampere-hour capacity. A porous cathode architecture having a pore volume that is derived from pores of varying radii wherein the pore size distribution is tailored as a function of the architecture thickness is one way to achieve one or more of the aforementioned cell performance improvements.

  16. Water in the hydration shell of halide ions has significantly reduced Fermi resonance and moderately enhanced Raman cross section in the OH stretch regions.

    PubMed

    Ahmed, Mohammed; Singh, Ajay K; Mondal, Jahur A; Sarkar, Sisir K

    2013-08-22

    Water in the presence of electrolytes plays an important role in biological and industrial processes. The properties of water, such as the intermolecular coupling, Fermi resonance (FR), hydrogen-bonding, and Raman cross section were investigated by measuring the Raman spectra in the OD and OH stretch regions in presence of alkali halides (NaX; X = F, Cl, Br, I). It is observed that the changes in spectral characteristics by the addition of NaX in D2O are similar to those obtained by the addition of H2O in D2O. The spectral width decreases significantly by the addition of NaX in D2O (H2O) than that in the isotopically diluted water. Quantitative estimation, on the basis of integrated Raman intensity, revealed that the relative Raman cross section, σ(H)/σ(b) (σ(H) and σ(b) are the average Raman cross section of water in the first hydration shell of X(-) and in bulk, respectively), in D2O and H2O is higher than those in the respective isotopically diluted water. These results suggest that water in the hydration shell has reduced FR and intermolecular coupling compared to those in bulk. In the isotopically diluted water, the relative Raman cross section increases with increase in size of the halide ions (σ(H)/σ(b) = 0.6, 1.1, 1.5, and 1.9 for F(-), Cl(-), Br(-), and I(-), respectively), which is assignable to the enhancement of Raman cross section by charge transfer from halide ions to the hydrating water. Nevertheless, the experimentally determined σ(H)/σ(b) is lower than the calculated values obtained on the basis of the energy of the charge transfer state of water. The weak enhancement of σ(H)/σ(b) signifies that the charge transfer transition in the hydration shell of halide ions causes little change in the OD (OH) bond lengths of hydrating water. PMID:23895453

  17. (abstract) Fundamental Mechanisms of Electrode Kinetics and Alkali Metal Atom Transport at the Alkali Beta'-Alumina/Porous Electrode/Alkali Metal Vapor Three Phase Boundary

    NASA Technical Reports Server (NTRS)

    Williams, R. M.; Jeffries-Nakamura, B.; Ryan, M. A.; Underwood, M. L.; O'Connor, D.; Kisor, A.; Kikkert, S. K.

    1993-01-01

    The mechanisms of electrode kinetics and mass transport of alkali metal oxidation and alkali metal cation reduction at the solid electrolyte/porous electrode boundary as well as alkali metal transport through porous metal electrodes has important applications in optimizing device performance in alkali metal thermal to electric converter (AMTEC) cells which are high temperature, high current density electrochemical cells. Basic studies of these processes also affords the opportunity to investigate a very basic electrochemical reaction over a wide range of conditions; and a variety of mass transport modes at high temperatures via electrochemical techniques. The temperature range of these investigations covers 700K to 1240K; the alkali metal vapor pressures range from about 10(sup -2) to 10(sup 2) Pa; and electrodes studied have included Mo, W, Mo/Na(sub 2)MoO(sub 4), W/Na(sub 2)WO(sub 4), WPt(sub x), and WRh(sub x) (1.0 < x < 6.0 ) with Na at Na-beta'-alumina, and Mo with K at K-beta'-alumina. Both liquid metal/solid electrolyte/alkali metal vapor and alkali metal vapor/solid electrolyte/vapor cells have been used to characterize the reaction and transport processes. We have previously reported evidence of ionic, free molecular flow, and surface transport of sodium in several types of AMTEC electrodes.

  18. Superconductivity in alkali metal intercalated iron selenides.

    PubMed

    Krzton-Maziopa, A; Svitlyk, V; Pomjakushina, E; Puzniak, R; Conder, K

    2016-07-27

    Alkali metal intercalated iron selenide superconductors A x Fe2-y Se2 (where A  =  K, Rb, Cs, Tl/K, and Tl/Rb) are characterized by several unique properties, which were not revealed in other superconducting materials. The compounds crystallize in overall simple layered structure with FeSe layers intercalated with alkali metal. The structure turned out to be pretty complex as the existing Fe-vacancies order below ~550 K, which further leads to an antiferromagnetic ordering with Néel temperature fairly above room temperature. At even lower temperatures a phase separation is observed. While one of these phases stays magnetic down to the lowest temperatures the second is becoming superconducting below ~30 K. All these effects give rise to complex relationships between the structure, magnetism and superconductivity. In particular the iron vacancy ordering, linked with a long-range magnetic order and a mesoscopic phase separation, is assumed to be an intrinsic property of the system. Since the discovery of superconductivity in those compounds in 2010 they were investigated very extensively. Results of the studies conducted using a variety of experimental techniques and performed during the last five years were published in hundreds of reports. The present paper reviews scientific work concerning methods of synthesis and crystal growth, structural and superconducting properties as well as pressure investigations. PMID:27248118

  19. Durability of Alkali Activated Blast Furnace Slag

    NASA Astrophysics Data System (ADS)

    Ellis, K.; Alharbi, N.; Matheu, P. S.; Varela, B.; Hailstone, R.

    2015-11-01

    The alkali activation of blast furnace slag has the potential to reduce the environmental impact of cementitious materials and to be applied in geographic zones where weather is a factor that negatively affects performance of materials based on Ordinary Portland Cement. The scientific literature provides many examples of alkali activated slag with high compressive strengths; however research into the durability and resistance to aggressive environments is still necessary for applications in harsh weather conditions. In this study two design mixes of blast furnace slag with mine tailings were activated with a potassium based solution. The design mixes were characterized by scanning electron microscopy, BET analysis and compressive strength testing. Freeze-thaw testing up to 100 freeze-thaw cycles was performed in 10% road salt solution. Our findings included compressive strength of up to 100 MPa after 28 days of curing and 120 MPa after freeze-thaw testing. The relationship between pore size, compressive strength, and compressive strength after freeze-thaw was explored.

  20. Superconductivity in alkali metal intercalated iron selenides

    NASA Astrophysics Data System (ADS)

    Krzton-Maziopa, A.; Svitlyk, V.; Pomjakushina, E.; Puzniak, R.; Conder, K.

    2016-07-01

    Alkali metal intercalated iron selenide superconductors A x Fe2‑y Se2 (where A  =  K, Rb, Cs, Tl/K, and Tl/Rb) are characterized by several unique properties, which were not revealed in other superconducting materials. The compounds crystallize in overall simple layered structure with FeSe layers intercalated with alkali metal. The structure turned out to be pretty complex as the existing Fe-vacancies order below ~550 K, which further leads to an antiferromagnetic ordering with Néel temperature fairly above room temperature. At even lower temperatures a phase separation is observed. While one of these phases stays magnetic down to the lowest temperatures the second is becoming superconducting below ~30 K. All these effects give rise to complex relationships between the structure, magnetism and superconductivity. In particular the iron vacancy ordering, linked with a long-range magnetic order and a mesoscopic phase separation, is assumed to be an intrinsic property of the system. Since the discovery of superconductivity in those compounds in 2010 they were investigated very extensively. Results of the studies conducted using a variety of experimental techniques and performed during the last five years were published in hundreds of reports. The present paper reviews scientific work concerning methods of synthesis and crystal growth, structural and superconducting properties as well as pressure investigations.

  1. Unconventional Superconductivity of Alkali-doped Fullerenes

    NASA Astrophysics Data System (ADS)

    Potocnik, Anton; Krajnc, Andraz; Jeglic, Peter; Prassides, Kosmas; Rosseinsky, Matthew J.; Arcon, Denis

    2014-03-01

    The superconductivity of the alkali-doped fullerenes (A3C60, A = alkali metal) has been so far discussed within the standard theory of superconductivity developed by Bardeen, Cooper and Shrieffer (BCS), even thought, they exhibit relatively high critical temperatures (up to Tc = 32 K). However, after our recent high-pressure measurements on Cs3C60 such description became questionable. We have shown that the superconducting phase of A3C60, in fact, borders the antiferromagnetic insulating phase (AFI), commonly observed for high-temperature superconductors like cuprates or pnictides. In addition, we also increased the maximal Tc to 38 K. To investigate this peculiar superconductivity close to the border with AFI state we employed nuclear magnetic resonance technique on Cs3-xRbxC60 and on Cs3C60 at various high pressures. Our results could not be correctly explained either by the standard BCS or the extended BCS that includes electron-electron repulsion interaction - the Migdal-Eliashberg theory. Far better agreement is obtained by the Dynamical Mean Field Theory. Due to similarity with other unconventional superconductors these results could also be relevant to other unconventional high-temperature superconductors.

  2. Decalcification resistance of alkali-activated slag.

    PubMed

    Komljenović, Miroslav M; Baščarević, Zvezdana; Marjanović, Nataša; Nikolić, Violeta

    2012-09-30

    This paper analyses the effects of decalcification in concentrated 6M NH(4)NO(3) solution on mechanical and microstructural properties of alkali-activated slag (AAS). Portland-slag cement (CEM II/A-S 42.5 N) was used as a benchmark material. Decalcification process led to a decrease in strength, both in AAS and in CEM II, and this effect was more pronounced in CEM II. The decrease in strength was explicitly related to the decrease in Ca/Si atomic ratio of C-S-H gel. A very low ratio of Ca/Si ~0.3 in AAS was the consequence of coexistence of C-S-H(I) gel and silica gel. During decalcification of AAS almost complete leaching of sodium and tetrahedral aluminum from C-S-H(I) gel also took place. AAS showed significantly higher resistance to decalcification in relation to the benchmark CEM II due to the absence of portlandite, high level of polymerization of silicate chains, low level of aluminum for silicon substitution in the structure of C-S-H(I), and the formation of protective layer of polymerized silica gel during decalcification process. In stabilization/solidification processes alkali-activated slag represents a more promising solution than Portland-slag cement due to significantly higher resistance to decalcification. PMID:22818592

  3. Dynamics of reactive ultracold alkali polar molecules

    NASA Astrophysics Data System (ADS)

    Quéméner, Goulven; Bohn, John; Petrov, Alexander; Kotochigova, Svetlana

    2011-05-01

    Recently, ultracold polar molecules of KRb have been created. These molecules are chemically reactive and their lifetime in a trap is limited. However, their lifetime increases when they are loaded into a 1D optical lattice in the presence of an electric field. These results naturally raise the question of manipulating ultracold collisions of other species of alkali dimer molecules, with an eye toward both novel stereochemistry, as well as suppressing unwanted reactions, to enable condensed matter applications. In this talk, we report on a comparative study between the bi-alkali polar molecules of LiNa, LiK, LiRb, LiCs which have been predicted to be reactive. We compute the isotropic C6 coefficients of these systems and we predict the elastic and reactive rate coefficients when an electric field is applied in a 1D optical lattice. We will discuss the efficacy of evaporative cooling for each species. This work was supported by a MURI-AFOSR grant.

  4. Artificial Synapses: Organometal Halide Perovskite Artificial Synapses (Adv. Mater. 28/2016).

    PubMed

    Xu, Wentao; Cho, Himchan; Kim, Young-Hoon; Kim, Young-Tae; Wolf, Christoph; Park, Chan-Gyung; Lee, Tae-Woo

    2016-07-01

    A synapse-emulating electronic device based on organometal halide perovskite thin films is described by T.-W. Lee and co-workers on page 5916. The device successfully emulates important characteristics of a biological synapse. This work extends the application of organometal halide perovskites to bioinspired electronic devices, and contributes to the development of neuromorphic electronics. PMID:27442971

  5. EPA (ENVIRONMENTAL PROTECTION AGENCY) METHOD STUDY 32: METHOD 450.1 - TOTAL ORGANIC HALIDES (TOX)

    EPA Science Inventory

    The report describes the interlaboratory method study that was performed to evaluate interim Method 450.1 for total organic halides (TOX). In the method, a measured volume of water is passed through two columns in series each containing 40 mg of activated charcoal. Organic halide...

  6. Aryl-triazole foldamers incorporating a pyridinium motif for halide anion binding in aqueous media.

    PubMed

    Shang, Jie; Zhao, Wei; Li, Xichen; Wang, Ying; Jiang, Hua

    2016-03-15

    Aryl-triazole oligomers incorporating a pyridinium motif have been synthesized from their pyridine precursors. Anion binding studies show that methylation of the pyridine units can significantly enhance the halide anion affinities of the folded oligomers so that the foldamers are capable of binding halide anions in aqueous solutions. PMID:26933696

  7. 75 FR 5544 - Energy Conservation Program: Energy Conservation Standards for Metal Halide Lamp Fixtures: Public...

    Federal Register 2010, 2011, 2012, 2013, 2014

    2010-02-03

    ... public meeting and availability of the Framework Document in the Federal Register (74 FR 69036) for... for Metal Halide Lamp Fixtures: Public Meeting and Availability of the Framework Document AGENCY... conservation standards for certain metal halide lamp fixtures. This document announces that the period...

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

    DOEpatents

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

    1973-03-06

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

  9. THE DETERMINATION OF TOTAL ORGANIC HALIDE IN WATER: AN INTERLABORATORY COMPARATIVE STUDY OF TWO METHODS

    EPA Science Inventory

    Total organic halide (TOX) analyzers are commonly used to measure the amount of dissolved halogenated organic byproducts in disinfected waters. Because of the lack of information on the identity of disinfection byproducts, rigorous testing of the dissolved organic halide (DOX) pr...

  10. THE DETERMINATION OF TOTAL ORGANIC HALIDE IN WATER: A COMPARATIVE STUDY OF TWO INSTRUMENTS

    EPA Science Inventory

    Total organic halide (TOX) analyzers are commonly used to measure the amount of dissolved halogenated organic byproducts in disinfected waters. ecause of the lack of information on the identity of disinfection byproducts, rigorous testing of the dissolved organic halide (DOX) pro...

  11. 40 CFR 721.8900 - Substituted halogenated pyridinol, alkali salt.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ..., alkali salt. 721.8900 Section 721.8900 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.8900 Substituted halogenated pyridinol, alkali salt. (a) Chemical..., chemical destruction and carbon adsorption. (iv) Release to water. Requirements as specified in § 721.90...

  12. Formation of lysinoalanine in egg white under alkali treatment.

    PubMed

    Zhao, Yan; Luo, Xuying; Li, Jianke; Xu, Mingsheng; Tu, Yonggang

    2016-03-01

    To investigate the formation mechanism of lysinoalanine (LAL) in eggs during the alkali treatment process, NaOH was used for the direct alkali treatment of egg white, ovalbumin, and amino acids; in addition, the amount of LAL formed during the alkali treatment process was measured. The results showed that the alkali treatment resulted in the formation of LAL in the egg white. The LAL content increased with increasing pH and temperature, with the LAL content first increasing and then leveling off with increasing time. The amount of LAL formed in the ovalbumin under the alkali treatment condition accounted for approximately 50.51% to 58.68% of the amount of LAL formed in the egg white. Thus, the LAL formed in the ovalbumin was the main source for the LAL in the egg white during the alkali treatment process. Under the alkali treatment condition, free L-serine, L-cysteine, and L-cystine reacted with L-lysine to form LAL; therefore, they are the precursor amino acids of LAL formed in eggs during the alkali treatment process. PMID:26772660

  13. Recovery of alkali metal constituents from catalytic coal conversion residues

    DOEpatents

    Soung, Wen Y.

    1984-01-01

    In a coal gasification operation (32) or similar conversion process carried out in the presence of an alkali metal-containing catalyst wherein particles containing alkali metal residues are produced, alkali metal constituents are recovered from the particles by contacting them (46, 53, 61, 69) with water or an aqueous solution to remove water-soluble alkali metal constituents and produce an aqueous solution enriched in said constituents. The aqueous solution thus produced is then contacted with carbon dioxide (63) to precipitate silicon constituents, the pH of the resultant solution is increased (81), preferably to a value in the range between about 12.5 and about 15.0, and the solution of increased pH is evaporated (84) to increase the alkali metal concentration. The concentrated aqueous solution is then recycled to the conversion process (86, 18, 17) where the alkali metal constituents serve as at least a portion of the alkali metal constituents which comprise the alkali metal-containing catalyst.

  14. 40 CFR 721.4740 - Alkali metal nitrites.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... defined in 40 CFR 721.3) containing amines. (b) ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Alkali metal nitrites. 721.4740... Substances § 721.4740 Alkali metal nitrites. (a) Chemical substances and significant new use subject...

  15. 40 CFR 721.4740 - Alkali metal nitrites.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... defined in 40 CFR 721.3) containing amines. (b) ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Alkali metal nitrites. 721.4740... Substances § 721.4740 Alkali metal nitrites. (a) Chemical substances and significant new use subject...

  16. 40 CFR 721.4740 - Alkali metal nitrites.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... defined in 40 CFR 721.3) containing amines. (b) ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Alkali metal nitrites. 721.4740... Substances § 721.4740 Alkali metal nitrites. (a) Chemical substances and significant new use subject...

  17. 40 CFR 721.4740 - Alkali metal nitrites.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... defined in 40 CFR 721.3) containing amines. (b) ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Alkali metal nitrites. 721.4740... Substances § 721.4740 Alkali metal nitrites. (a) Chemical substances and significant new use subject...

  18. Self-discharge in bimetallic cells containing alkali metal

    NASA Technical Reports Server (NTRS)

    Foster, M. S.; Hesson, J. C.; Shimotake, H.

    1969-01-01

    Theoretical analysis of thermally regenerative bimetallic cells with alkali metal anodes shows a relation between the current drawn and the rate of discharge under open-circuit conditions. The self-discharge rate of the cell is due to the dissolution and ionization of alkali metal atoms in the fused-salt electrolyte

  19. COMPLEX FLUORIDES OF PLUTONIUM AND AN ALKALI METAL

    DOEpatents

    Seaborg, G.T.

    1960-08-01

    A method is given for precipitating alkali metal plutonium fluorides. such as KPuF/sub 5/, KPu/sub 2/F/sub 9/, NaPuF/sub 5/, and RbPuF/sub 5/, from an aqueous plutonium(IV) solution by adding hydrogen fluoride and alkali-metal- fluoride.

  20. 40 CFR 721.4740 - Alkali metal nitrites.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... CONTROL ACT SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.4740 Alkali metal nitrites. (a) Chemical substances and significant new use subject to reporting. (1) The category of chemical substances which are nitrites of the alkali metals (Group IA in...

  1. 40 CFR 721.1878 - Alkali metal alkyl borohydride (generic).

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ...) TOXIC SUBSTANCES CONTROL ACT SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.1878 Alkali metal alkyl borohydride (generic). (a) Chemical substance... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Alkali metal alkyl...

  2. Method for producing hydrocarbon fuels and fuel gas from heavy polynuclear hydrocarbons by the use of molten metal halide catalysts

    DOEpatents

    Gorin, Everett

    1979-01-01

    In a process for hydrocracking heavy polynuclear carbonaceous feedstocks to produce lighter hydrocarbon fuels by contacting the heavy feedstocks with hydrogen in the presence of a molten metal halide catalyst in a hydrocracking zone, thereafter separating at least a major portion of the lighter hydrocarbon fuels from the spent molten metal halide and thereafter regenerating the spent molten metal halide by incinerating the spent molten metal halide by combustion of carbon and sulfur compounds in the spent molten metal halide in an incineration zone, the improvement comprising: (a) contacting the heavy feedstocks and hydrogen in the presence of the molten metal halide in the hydrocracking zone at reaction conditions effective to convert from about 60 to about 90 weight percent of the feedstock to lighter hydrocarbon fuels; (b) separating at least a major portion of the lighter hydrocarbon fuels from the spent molten metal halide; (c) contacting the spent molten metal halide with oxygen in a liquid phase gasification zone at a temperature and pressure sufficient to vaporize from about 25 to about 75 weight percent of the spent metal halide, the oxygen being introduced in an amount sufficient to remove from about 60 to about 90 weight percent of the carbon contained in the spent molten metal halide to produce a fuel gas and regenerated metal halide; and (d) incinerating the spent molten metal halide by combusting carbon and sulfur compounds contained therein.

  3. Unified mechanism of alkali and alkaline earth catalyzed gasification reactions of carbon by CO2 and H2O

    USGS Publications Warehouse

    Chen, S.G.; Yang, R.T.

    1997-01-01

    From molecular orbital calculations, a unified mechanism is proposed for the gasification reactions of graphite by CO2 and H2O, both uncatalyzed and catalyzed by alkali and alkaline earth catalysts. In this mechanism, there are two types of oxygen intermediates that are bonded to the active edge carbon atoms: an in-plane semiquinone type, Cf(O), and an off-plane oxygen bonded to two saturated carbon atoms that are adjacent to the semiquinone species, C(O)Cf(O). The rate-limiting step is the decomposition of these intermediates by breaking the C-C bonds that are connected to Cf(O). A new rate equation is derived for the uncatalyzed reactions, and that for the catalyzed reactions is readily available from the proposed mechanism. The proposed mechanism can account for several unresolved experimental observations: TPD and TK (transient kinetics) desorption results of the catalyzed systems, the similar activation energies for the uncatalyzed and catalyzed reactions, and the relative activities of the alkali and alkaline earth elements. The net charge of the edge carbon active site is substantially changed by gaining electron density from the alkali or alkaline earth element (by forming C-O-M, where M stands for metal). The relative catalytic activities of these elements can be correlated with their abilities of donating electrons and changing the net charge of the edge carbon atom. As shown previously (Chen, S. G.; Yang, R. T. J. Catal. 1993, 141, 102), only clusters of the alkali compounds are active. This derives from the ability of the clusters to dissociate CO2 and H2O to form O atoms and the mobility of the dissociated O atoms facilitated by the clusters.

  4. Effects of alkali treatments on Ag nanowire transparent conductive films

    NASA Astrophysics Data System (ADS)

    Kim, Sunho; Kang, Jun-gu; Eom, Tae-yil; Moon, Bongjin; Lee, Hoo-Jeong

    2016-06-01

    In this study, we employ various alkali materials (alkali metals with different base strengths, and ammonia gas and solution) to improve the conductivity of silver nanowire (Ag NW)-networked films. The alkali treatment appears to remove the surface oxide and improve the conductivity. When applied with TiO2 nanoparticles, the treatment appears more effective as the alkalis gather around wire junctions and help them weld to each other via heat emitted from the reduction reaction. The ammonia solution treatment is found to be quick and aggressive, damaging the wires severely in the case of excessive treatment. On the other hand, the ammonia gas treatment seems much less aggressive and does not damage the wires even after a long exposure. The results of this study highlight the effectiveness of the alkali treatment in improving of the conductivity of Ag NW-networked transparent conductive films.

  5. Performance of Straight Steel Fibres Reinforced Alkali Activated Concrete

    NASA Astrophysics Data System (ADS)

    Faris, Meor Ahmad; Bakri Abdullah, Mohd Mustafa Al; Nizar Ismail, Khairul; Muniandy, Ratnasamy; Putra Jaya, Ramadhansyah

    2016-06-01

    This paper focus on the performance of alkali activated concrete produced by using fly ash activated by sodium silicate and sodium hydroxide solutions. These alkali activated concrete were reinforced with straight steel fibres with different weight percentage starting from 0 % up to 5 %. Chemical composition of raw material in the production alkali activated concrete which is fly ash was first identified by using X-ray fluorescence. Results reveal there have an effect of straight steel fibres inclusion to the alkali activated concrete. Highest compressive strength of alkali activated concrete which is 67.72 MPa was obtained when 3 % of straight fibres were added. As well as flexural strength, highest flexural strength which is 6.78 MPa was obtained at 3 % of straight steel fibres inclusions.

  6. Methyl Halide Production by Periphyton Mats from the Florida Everglades

    NASA Astrophysics Data System (ADS)

    Raffel, A.; Jones, R. D.; Rice, A. L.; Scully, N. M.

    2012-12-01

    Methyl chloride and methyl bromide are trace gases with both natural and anthropogenic origins. Once generated these gases transport chlorine and bromine into the stratosphere, where they play an important role in atmospheric chemistry by participating in ozone depleting catalytic cycles. Coastal wetlands are one location where methyl halide emissions have been proposed to be elevated due to high primary production and ionic halogens. This region also provides a unique study environment due to salt water intrusions which occur during storm or low marsh water level-high tide events. The purpose of this research was to determine how varying concentrations of salinity affect methyl halide production originating from periphyton mats within the Florida Everglades. Florida Everglades periphyton (25 g/L) were exposed to continuous 12 hour dark/light cycles in varying concentrations of salt water (0, 0.1, 1.0, and 10‰). All water samples were analyzed to determine the concentration and production rate of methyl chloride and methyl bromide in periphyton samples using a gas chromatograph coupled with an electron capture detector. The concentration of methyl chloride increased by approximately 3.4 and 60 pM over a 0 to 72 hour range for 1‰ and 10 ‰ treatments respectively, and reached a steady state concentration after 24 hours. There was no significant production of methyl bromide for all treatments. These studies will be used to gain a better understanding of methyl halide production from periphyton mats in simulated natural conditions. This research was supported by the National Science Foundation Chemical Oceanography Program Award No. 1029710.

  7. New generation of medium wattage metal halide lamps and spectroscopic tools for their diagnostics

    NASA Astrophysics Data System (ADS)

    Dunaevsky, A.; Tu, J.; Gibson, R.; Steere, T.; Graham, K.; van der Eyden, J.

    2010-11-01

    A new generation of ceramic metal halide high intensity discharge (HID) lamps has achieved high efficiencies by implementing new design concepts. The shape of the ceramic burner is optimized to withstand high temperatures with minimal thermal stress. Corrosion processes with the ceramic walls are slowed down via adoption of non-aggressive metal halide chemistry. Light losses over life due to tungsten deposition on the walls are minimized by maintaining a self-cleaning chemical process, known as tungsten cycle. All these advancements have made the new ceramic metal halide lamps comparable to high pressure sodium lamps for luminous efficacy, life, and maintenance while providing white light with high color rendering. Direct replacement of quartz metal halide lamps and systems results in the energy saving from 18 up to 50%. High resolution spectroscopy remains the major non-destructive tool for the ceramic metal halide lamps. Approaches to reliable measurements of relative partial pressures of the arc species are discussed.

  8. Impact of the organic halide salt on final perovskite composition for photovoltaic applications

    SciTech Connect

    Moore, David T.; Sai, Hiroaki; Wee Tan, Kwan; Estroff, Lara A.; Wiesner, Ulrich

    2014-08-01

    The methylammonium lead halide perovskites have shown significant promise as a low-cost, second generation, photovoltaic material. Despite recent advances, however, there are still a number of fundamental aspects of their formation as well as their physical and electronic behavior that are not well understood. In this letter we explore the mechanism by which these materials crystallize by testing the outcome of each of the reagent halide salts. We find that components of both salts, lead halide and methylammonium halide, are relatively mobile and can be readily exchanged during the crystallization process when the reaction is carried out in solution or in the solid state. We exploit this fact by showing that the perovskite structure is formed even when the lead salt's anion is a non-halide, leading to lower annealing temperature and time requirements for film formation. Studies into these behaviors may ultimately lead to improved processing conditions for photovoltaic films.

  9. Accurate potential energy, dipole moment curves, and lifetimes of vibrational states of heteronuclear alkali dimers

    SciTech Connect

    Fedorov, Dmitry A.; Varganov, Sergey A.; Derevianko, Andrei

    2014-05-14

    We calculate the potential energy curves, the permanent dipole moment curves, and the lifetimes of the ground and excited vibrational states of the heteronuclear alkali dimers XY (X, Y = Li, Na, K, Rb, Cs) in the X{sup 1}Σ{sup +} electronic state using the coupled cluster with singles doubles and triples method. All-electron quadruple-ζ basis sets with additional core functions are used for Li and Na, and small-core relativistic effective core potentials with quadruple-ζ quality basis sets are used for K, Rb, and Cs. The inclusion of the coupled cluster non-perturbative triple excitations is shown to be crucial for obtaining the accurate potential energy curves. A large one-electron basis set with additional core functions is needed for the accurate prediction of permanent dipole moments. The dissociation energies are overestimated by only 14 cm{sup −1} for LiNa and by no more than 114 cm{sup −1} for the other molecules. The discrepancies between the experimental and calculated harmonic vibrational frequencies are less than 1.7 cm{sup −1}, and the discrepancies for the anharmonic correction are less than 0.1 cm{sup −1}. We show that correlation between atomic electronegativity differences and permanent dipole moment of heteronuclear alkali dimers is not perfect. To obtain the vibrational energies and wave functions the vibrational Schrödinger equation is solved with the B-spline basis set method. The transition dipole moments between all vibrational states, the Einstein coefficients, and the lifetimes of the vibrational states are calculated. We analyze the decay rates of the vibrational states in terms of spontaneous emission, and stimulated emission and absorption induced by black body radiation. In all studied heteronuclear alkali dimers the ground vibrational states have much longer lifetimes than any excited states.

  10. Accurate potential energy, dipole moment curves, and lifetimes of vibrational states of heteronuclear alkali dimers

    NASA Astrophysics Data System (ADS)

    Fedorov, Dmitry A.; Derevianko, Andrei; Varganov, Sergey A.

    2014-05-01

    We calculate the potential energy curves, the permanent dipole moment curves, and the lifetimes of the ground and excited vibrational states of the heteronuclear alkali dimers XY (X, Y = Li, Na, K, Rb, Cs) in the X1Σ+ electronic state using the coupled cluster with singles doubles and triples method. All-electron quadruple-ζ basis sets with additional core functions are used for Li and Na, and small-core relativistic effective core potentials with quadruple-ζ quality basis sets are used for K, Rb, and Cs. The inclusion of the coupled cluster non-perturbative triple excitations is shown to be crucial for obtaining the accurate potential energy curves. A large one-electron basis set with additional core functions is needed for the accurate prediction of permanent dipole moments. The dissociation energies are overestimated by only 14 cm-1 for LiNa and by no more than 114 cm-1 for the other molecules. The discrepancies between the experimental and calculated harmonic vibrational frequencies are less than 1.7 cm-1, and the discrepancies for the anharmonic correction are less than 0.1 cm-1. We show that correlation between atomic electronegativity differences and permanent dipole moment of heteronuclear alkali dimers is not perfect. To obtain the vibrational energies and wave functions the vibrational Schrödinger equation is solved with the B-spline basis set method. The transition dipole moments between all vibrational states, the Einstein coefficients, and the lifetimes of the vibrational states are calculated. We analyze the decay rates of the vibrational states in terms of spontaneous emission, and stimulated emission and absorption induced by black body radiation. In all studied heteronuclear alkali dimers the ground vibrational states have much longer lifetimes than any excited states.

  11. Volatile species in halide-activated-diffusion coating packs

    NASA Technical Reports Server (NTRS)

    Bianco, Robert; Rapp, Robert A.; Jacobson, Nathan S.

    1992-01-01

    An atmospheric pressure sampling mass spectrometer was used to identify the vapor species generated in a halide-activated cementation pack. Pack powder mixtures containing a Cr-Al binary masteralloy powder, an NH4Cl activator salt, and either ZrO2 or Y2O3 (or neither) were analyzed at 1000 C. Both the equilibrium calculations for the pack and mass spectrometer results indicated that volatile AlCl(x) and CrCl(y) species were generated by the pack powder mixture; in packs containing the reactive element oxide, volatile ZrCl(z) and YCl(w) species were formed by the conversion of their oxide sources.

  12. Silylaryl Halides Can Replace Triflates as Aryne Precursors.

    PubMed

    Mesgar, Milad; Daugulis, Olafs

    2016-08-01

    Silylaryl bromides and iodides can be prepared in one step from commercially available starting materials. Arynes can be generated from these compounds under conditions nearly identical to those employed for silylaryl triflates. Three distinct transformations, ortho-arylation of N-tritylanilines, intermolecular addition of arynes to amides, and reaction of ureas with arynes, were shown to be successful for the new aryne precursors. The main advantage of silylaryl halides relative to silyl aryl triflates is their one-step preparation from commercially available starting materials. PMID:27415183

  13. Heavy ion passive dosimetry with silver halide single crystals

    NASA Technical Reports Server (NTRS)

    Childs, C. B.; Parnell, T. A.

    1972-01-01

    A method of detecting radiation damage tracks due to heavy particles in large single crystals of the silver halides is described. The tracks, when made visible with a simple electrical apparatus, appear similar to tracks in emulsions. The properties of the crystals, the technique of printing out the tracks, and evidence concerning the threshold energy for registering particles indicates that this method may find application in heavy ion dosimetry. The method has been found to be sensitive to stopping He nuclei and relativistic M group cosmic rays. Some impurities strongly influence the printout of the tracks, and the effects of these impurities are discussed.

  14. Optical Properties of Photovoltaic Organic-Inorganic Lead Halide Perovskites.

    PubMed

    Green, Martin A; Jiang, Yajie; Soufiani, Arman Mahboubi; Ho-Baillie, Anita

    2015-12-01

    Over the last several years, organic-inorganic lead halide perovskites have rapidly emerged as a new photovoltaic contender. Although energy conversion efficiency above 20% has now been certified, improved understanding of the material properties contributing to these high performance levels may allow the progression to even higher efficiency, stable cells. The optical properties of these new materials are important not only to device design but also because of the insight they provide into less directly accessible properties, including energy-band structures, binding energies, and likely impact of excitons, as well as into absorption and inverse radiative recombination processes. PMID:26560862

  15. Thermal conductivity of halide solid solutions: measurement and prediction.

    PubMed

    Gheribi, Aïmen E; Poncsák, Sándor; St-Pierre, Rémi; Kiss, László I; Chartrand, Patrice

    2014-09-14

    The composition dependence of the lattice thermal conductivity in NaCl-KCl solid solutions has been measured as a function of composition and temperature. Samples with systematically varied compositions were prepared and the laser flash technique was used to determine the thermal diffusivity from 373 K to 823 K. A theoretical model, based on the Debye approximation of phonon density of state (which contains no adjustable parameters) was used to predict the thermal conductivity of both stoichiometric compounds and fully disordered solid solutions. The predictions obtained with the model agree very well with our measurement. A general method for predicting the thermal conductivity of different halide systems is discussed. PMID:25217938

  16. Ferroelectricity and Rashba-type band splittings in metal halides

    NASA Astrophysics Data System (ADS)

    Kim, Minsung; Im, Jino; Freeman, Arthur; Ihm, Jisoon; Jin, Hosub

    2014-03-01

    In this study, we investigate Rashba-type band splittings in metal halides. We use a minimal tight-binding model and first principles calculations based on density functional theory to understand the electronic structures of the materials. We find that different types of Rashba bands occur in the conduction and valence band edges in terms of the angular momentum textures. Also, the characteristics of the band splittings will be discussed in connection with the ferroelectric property. Department of Physics and Astronomy, Seoul National University, Seoul 151-747, Korea.

  17. "XA6" octahedra influencing the arrangement of anionic groups and optical properties in inverse-perovskite [B6O10]XA3 (X = Cl, Br; A = alkali metal).

    PubMed

    Yang, Zhihua; Lei, Bing-Hua; Yang, Bin; Pan, Shilie

    2016-06-01

    Exploring the effect of microscopic units, which set up the perovsikte framework, is of importance for material design. In this study, a series of borate halides with inverse-perovskite structures [B6O10]XA3 (X = Cl, Br; A = alkali metal) have been studied. It was revealed that the distortion and volume of XA6 octahedra influence the arrangement of anionic groups, which leads to the flexibility of the perovskite-related framework and differences in optical properties. Under the structural control scheme, the structure of Rb3B6O10Cl was predicted. The stability of the predicted structure was confirmed by an ab initio density functional theory-based method. The calculation shows Rb3B6O10Cl has a short UV cutoff edge of less than 200 nm, a moderate birefringence and a large second harmonic generation response. PMID:27211304

  18. Diversity and Mechanisms of Alkali Tolerance in Lactobacilli▿

    PubMed Central

    Sawatari, Yuki; Yokota, Atsushi

    2007-01-01

    We determined the maximum pH that allows growth (pHmax) for 34 strains of lactobacilli. High alkali tolerance was exhibited by strains of Lactobacillus casei, L. paracasei subsp. tolerans, L. paracasei subsp. paracasei, L. curvatus, L. pentosus, and L. plantarum that originated from plant material, with pHmax values between 8.5 and 8.9. Among these, L. casei NRIC 1917 and L. paracasei subsp. tolerans NRIC 1940 showed the highest pHmax, at 8.9. Digestive tract isolates of L. gasseri, L. johnsonii, L. reuteri, L. salivarius subsp. salicinius, and L. salivarius subsp. salivarius exhibited moderate alkali tolerance, with pHmax values between 8.1 and 8.5. Dairy isolates of L. delbrueckii subsp. bulgaricus, L. delbrueckii subsp. lactis, and L. helveticus exhibited no alkali tolerance, with pHmax values between 6.7 and 7.1. Measurement of the internal pH of representative strains revealed the formation of transmembrane proton gradients (ΔpH) in a reversed direction (i.e., acidic interior) at alkaline external-pH ranges, regardless of their degrees of alkali tolerance. Thus, the reversed ΔpH did not determine alkali tolerance diversity. However, the ΔpH contributed to alkali tolerance, as the pHmax values of several strains decreased with the addition of nigericin, which dissipates ΔpH. Although neutral external-pH values resulted in the highest glycolysis activity in the presence of nigericin regardless of alkali tolerance, substantial glucose utilization was still detected in the alkali-tolerant strains, even in a pH range of between 8.0 and 8.5, at which the remaining strains lost most activity. Therefore, the alkali tolerance of glycolysis reactions contributes greatly to the determination of alkali tolerance diversity. PMID:17449704

  19. Adsorption of hydrated halide ions on charged electrodes. Molecular dynamics simulation

    NASA Astrophysics Data System (ADS)

    Glosli, James N.; Philpott, Michael R.

    1993-06-01

    Constant temperature molecular dynamics has been used to simulate the adsorption of hydrated halide ions X-=F-, Cl-, Br- and I-, and lithium ion Li+ on flat uniformly charged surfaces. The simulations were done with either 214 water molecules and two ions (Li+ and X-) in a box 2.362 nm deep or with 430 water molecules and the two ions in a box 4.320 nm deep. The boxes were periodically replicated in the xy directions. The magnitude of the surface charge on the box ends was ±0.11 e/(nm)2, corresponding to an electric field of 2×107 V/cm. The lateral dimensions of the simulation cell were 1.862 nm×1.862 nm (x×y) in each case. All of the water molecules and ions interacted with the end walls via a weak 9-3 potential. The Stillinger ST2 water model and parameters optimized for alkali halides interacting with the model ST2 water molecule were used in the calculations. Common particles of truncating the interactions at a finite distance (0.82 nm) and switching off Coulomb interactions at small distances were followed. The temperature was set at T=2.411 kJ/mol (290 K). Some of the properties calculated were distribution density profiles for ions and water across the gap important for comparisons with Gouy-Chapman theory, adsorbed ion-water pair correlation functions, and the number of water molecules in the first and second hydration shells of the ions as a function of time. The time spent by a water molecule in the hydration shell was calculated to be approximately ten times longer for lithium than any other ion. The correlation between distance from the electrode and hydration number was studied and generally found to be pronounced for the larger anions. Comparison of the dynamics of the common ion Li+ for different anions revealed the subtle influence of a transcell interaction in the 2.362 nm thick film. In the given field, the smallest ions Li+ and F- remained fully solvated at all times. Chloride behaved quite differently. Part of the time this ion was far

  20. Construction of copper halide-triiron selenide carbonyl complexes: synthetic, electrochemical, and theoretical studies.

    PubMed

    Shieh, Minghuey; Miu, Chia-Yeh; Lee, Chang-Ju; Chen, Wei-Cheng; Chu, Yen-Yi; Chen, Hui-Lung

    2008-12-01

    A new family of CuX-, Cu(2)X(2)-, and Cu(4)X(2)-incorporated mono- or di-SeFe(3)-based carbonyl clusters were constructed and structurally characterized. When the selenium-capped triiron carbonyl cluster [Et(4)N](2)[SeFe(3)(CO)(9)] was treated with 1-3 equiv of CuX in tetrahydrofuran (THF) at low or room temperatures, CuX-incorporated SeFe(3) complexes [Et(4)N](2)[SeFe(3)(CO)(9)CuX] (X = Cl, [Et(4)N](2)[1a]; Br, [Et(4)N](2)[1b]; I, [Et(4)N](2)[1c]), Cu(2)X(2)-incorporated SeFe(3) clusters [Et(4)N](2)[SeFe(3)(CO)(9)Cu(2)X(2)] (X = Cl, [Et(4)N](2)[2a]; Br, [Et(4)N](2)[2b]), and Cu(4)X(2)-linked di-SeFe(3) clusters [Et(4)N](2)[{SeFe(3)(CO)(9)}(2)Cu(4)X(2)] (X = Cl, [Et(4)N](2)[3a]; Br, [PPh(4)](2)[3b]) were obtained, respectively, in good yields. SeFe(3)CuX complexes 1a and 1b were found to undergo cluster expansion to form SeFe(3)Cu(2)X(2) complexes 2a and 2b, respectively, upon the addition of 1 equiv of CuX (X = Cl, Br). Furthermore, complexes 2a and 2b can expand further to form Cu(4)X(2)-linked di-SeFe(3) clusters 3a and 3b, upon treatment with 1 equiv of CuX (X = Cl, Br). [Et(4)N](4)[{SeFe(3)(CO)(9)(CuCl)(2)}(2)] ([Et(4)N](4)[4a]) was produced when the reaction of [Et(4)N](2)[SeFe(3)(CO)(9)] with 2 equiv of CuCl was conducted in THF at 40 degrees C. The Cu(2)Cl(2)-linked di-SeFe(3)CuCl cluster 4a is a dimerization product derived from complex 2a. Further, it is found that complex 4a can convert to the Cu(4)Cl(2)-linked di-SeFe(3) cluster 3a upon treatment with CuCl. The nature, formation, stepwise cluster expansion, and electrochemical properties of these CuX-, Cu(2)X(2)-, and Cu(4)X(2)-incorporated mono- or di-SeFe(3)-based clusters are elucidated in detail by molecular calculations at the B3LYP level of the density functional theory in terms of the effects of selenium, iron, copper halides, and the size of the metal skeleton. PMID:19228023

  1. Elastic properties of alkali-feldspars

    NASA Astrophysics Data System (ADS)

    Waeselmann, N.; Brown, J.; Angel, R. J.; Ross, N.; Kaminsky, W.

    2013-12-01

    New measurements of single crystal elastic moduli for a suite of the alkali feldspars are reported. In order to interpret Earth's seismic structure, knowledge of the elastic properties of constituent minerals is essential. The elasticity of feldspar minerals, despite being the most abundant phase in Earth's crust (estimated to be more than 60%), were previously poorly characterized. All prior seismic and petrologic studies have utilized 50-year-old results, of questionable quality, based on 1-bar measurements on pseudo-single crystals. Alkali-feldspars present a large experimental challenge associated with their structural complexity. In the K-end member (KAlSi3O8) the symmetry is governed by Al/Si ordering, in the Na-end member (NaAlSi3O8) the symmetry is governed by whether or not there is a displacive collapse of the framework independent of the Al/Si ordering. K-feldspars exhibit monoclinic (C2/m) symmetry (necessitating determination of 13 elastic moduli) if disordered and triclinic (C-1) symmetry (21 elastic moduli) if ordered. Exsolution of Na-rich and K-rich phases is ubiquitous in natural samples, making it difficult to find suitable single phase and untwinned samples for study. The small single domain samples selected for this study were previously characterized by x-ray diffraction and microprobe analysis to ensure adequate sample quality. Surface wave velocities were measured on oriented surfaces of natural and synthetic single crystals using impulsively stimulated light scattering. A surface corrugation with a spacing of about 2 microns was impulsively created by the overlap of 100 ps infrared light pulses. The time evolution of the stimulated standing elastic waves was detected by measuring the intensity of diffraction from the surface corrugation of a variably delayed probe pulse. This method allows accurate (better than 0.2%) determination of velocities on samples smaller than 100 microns. The combination of measured surface wave velocities and

  2. CLUSTER CHEMISTRY

    SciTech Connect

    Muetterties, Earl L.

    1980-05-01

    Metal cluster chemistry is one of the most rapidly developing areas of inorganic and organometallic chemistry. Prior to 1960 only a few metal clusters were well characterized. However, shortly after the early development of boron cluster chemistry, the field of metal cluster chemistry began to grow at a very rapid rate and a structural and a qualitative theoretical understanding of clusters came quickly. Analyzed here is the chemistry and the general significance of clusters with particular emphasis on the cluster research within my group. The importance of coordinately unsaturated, very reactive metal clusters is the major subject of discussion.

  3. Monte Carlo simulations of electron thermalization in alkali iodide and alkaline-earth fluoride scintillators

    SciTech Connect

    Wang, Zhiguo; Xie, YuLong; Campbell, Luke W.; Gao, Fei; Kerisit, Sebastien N.

    2012-07-01

    A Monte Carlo model of electron thermalization in inorganic scintillators, which was developed and applied to CsI in a previous publication [Wang et al., J. Appl. Phys. 110, 064903 (2011)], is extended to another material of the alkali halide class, NaI, and to two materials from the alkaline-earth halide class, CaF2 and BaF2. This model includes electron scattering with both longitudinal optical (LO) and acoustic phonons as well as the effects of internal electric fields. For the four pure materials, a significant fraction of the electrons recombine with self-trapped holes and the thermalization distance distributions of the electrons that do not recombine peak between approximately 25 and 50 {per_thousand}nm and extend up to a few hundreds of nanometers. The thermalization time distributions of CaF2, BaF2, NaI, and CsI extend to approximately 0.5, 1, 2, and 7 ps, respectively. The simulations show that the LO phonon energy is a key factor that affects the electron thermalization process. Indeed, the higher the LO phonon energy is, the shorter the thermalization time and distance are. The thermalization time and distance distributions show no dependence on the incident {gamma}-ray energy. The four materials also show different extents of electron-hole pair recombination due mostly to differences in their electron mean free paths (MFPs), LO phonon energies, initial densities of electron-hole pairs, and static dielectric constants. The effect of thallium doping is also investigated for CsI and NaI as these materials are often doped with activators. Comparison between CsI and NaI shows that both the larger size of Cs+ relative to Na+, i.e., the greater atomic density of NaI, and the longer electron mean free path in NaI compared to CsI contribute to an increased probability for electron trapping at Tl sites in NaI versus CsI.

  4. Monte Carlo simulations of electron thermalization in alkali iodide and alkaline-earth fluoride scintillators

    SciTech Connect

    Wang Zhiguo; Gao Fei; Kerisit, Sebastien; Xie Yulong; Campbell, Luke W.

    2012-07-01

    A Monte Carlo model of electron thermalization in inorganic scintillators, which was developed and applied to CsI in a previous publication [Wang et al., J. Appl. Phys. 110, 064903 (2011)], is extended to another material of the alkali halide class, NaI, and to two materials from the alkaline-earth halide class, CaF{sub 2} and BaF{sub 2}. This model includes electron scattering with both longitudinal optical (LO) and acoustic phonons as well as the effects of internal electric fields. For the four pure materials, a significant fraction of the electrons recombine with self-trapped holes and the thermalization distance distributions of the electrons that do not recombine peak between approximately 25 and 50 nm and extend up to a few hundreds of nanometers. The thermalization time distributions of CaF{sub 2}, BaF{sub 2}, NaI, and CsI extend to approximately 0.5, 1, 2, and 7 ps, respectively. The simulations show that the LO phonon energy is a key factor that affects the electron thermalization process. Indeed, the higher the LO phonon energy is, the shorter the thermalization time and distance are. The thermalization time and distance distributions show no dependence on the incident {gamma}-ray energy. The four materials also show different extents of electron-hole pair recombination due mostly to differences in their electron mean free paths (MFPs), LO phonon energies, initial densities of electron-hole pairs, and static dielectric constants. The effect of thallium doping is also investigated for CsI and NaI as these materials are often doped with activators. Comparison between CsI and NaI shows that both the larger size of Cs{sup +} relative to Na{sup +}, i.e., the greater atomic density of NaI, and the longer electron mean free path in NaI compared to CsI contribute to an increased probability for electron trapping at Tl sites in NaI versus CsI.

  5. Fission and dipole resonances in metal clusters

    SciTech Connect

    Martin, T. P.; Billas, I. M. L.; Branz, W.; Heinebrodt, M.; Tast, F.; Malinowski, N.

    1997-06-20

    It is not obvious that metal clusters should behave like atomic nuclei--but they do. Of course the energy and distance scales are quite different. But aside from this, the properties of these two forms of condensed matter are amazingly similar. The shell model developed by nuclear physicists describes very nicely the electronic properties of alkali metal clusters. The giant dipole resonances in the excitation spectra of nuclei have their analogue in the plasmon resonances of metal clusters. Finally, the droplet model describing the fission of unstable nuclei can be successively applied to the fragmentation of highly charged metal clusters. The similarity between clusters and nuclei is not accidental. Both systems consist of fermions moving, nearly freely, in a confined space.

  6. Alkali oxide-tantalum oxide and alkali oxide-niobium oxide ionic conductors

    NASA Technical Reports Server (NTRS)

    Roth, R. S.; Parker, H. S.; Brower, W. S.; Minor, D.

    1974-01-01

    A search was made for new cationic conducting phases in alkali-tantalate and niobate systems. The phase equilibrium diagrams were constructed for the six binary systems Nb2O5-LiNbO3, Nb2O5-NaNbO3, Nb2O5-KNbO3, Ta2O5-NaTaO3, Ta2O5-LiTaO3, and Ta2O5-KTaO3. Various other binary and ternary systems were also examined. Pellets of nineteen phases were evaluated (by the sponsoring agency) by dielectric loss measurements. Attempts were made to grow large crystals of eight different phases. The system Ta2O5-KTaO3 contains at least three phases which showed peaks in dielectric loss vs. temperature. All three contain structures related to the tungsten bronzes with alkali ions in non-stoichiometric crystallographic positions.

  7. Method to reduce particles and defects on unprocessed wafers caused by clusterization and cross contamination from processed wafers

    NASA Astrophysics Data System (ADS)

    Sant, Sanket

    2012-10-01

    One of the leading problems in the semiconductor industry with device scaling is defects and particles. Of this the most important ones are particles that can clusterize (condensate) with exposure to atmosphere. These clusters can be formed by residual halides or halide structures on the wafer surface reacting with surface moisture which is unavoidable. Such clusters can prove detrimental to the processed wafer, but more interestingly can migrate inside the FOUP onto unetched wafers. This migration of clusters can cause micro masking and other defects when these wafers are processed. This reduces the wafer yield and is challenging to resolve as we move towards smaller nodes. In this work, different methods of eliminating cross condensation defects and avoiding cluster formation on processed wafers are discussed. UV, Ozone and heat are the primary candidates explored and the mechanism behind each method is explored and optimized. Impact of each mechanism on wafer yield, part corrosion in a reactor platform and wafer throughput has been studied.

  8. Ion Partitioning at the liquid/vapor interface of a multi-component alkali halidesolution: A model for aqueous sea salt aerosols

    SciTech Connect

    Ghosal, Sutapa; Brown, Matthew A.; Bluhm, Hendrik; Krisch, Maria J.; Salmeron, Miquel; Jungwirth, Pavel; Hemminger, John C.

    2008-12-22

    The chemistry of Br species associated with sea salt ice and aerosols has been implicated in the episodes of ozone depletion reported at Arctic sunrise. However, Br{sup -} is only a minor component in sea salt, which has a Br{sup -}/Cl{sup -} molar ratio of {approx}0.0015. Sea salt is a complex mixture of many different species, with NaCl as the primary component. In recent years experimental and theoretical studies have reported enhancement of the large, more polarizable halide ion at the liquid/vapor interface of corresponding aqueous alkali halide solutions. The proposed enhancement is likely to influence the availability of sea salt Br{sup -} for heterogeneous reactions such as those involved in the ozone depletion episodes. We report here ambient pressure x-ray photoelectron spectroscopy studies and molecular dynamics simulations showing direct evidence of Br{sup -} enhancement at the interface of an aqueous NaCl solution doped with bromide. The experiments were carried out on samples with Br{sup -}/Cl{sup -} ratios in the range 0.1% to 10%, the latter being also the ratio for which simulations were carried out. This is the first direct measurement of interfacial enhancement of Br{sup -} in a multi-component solution with particular relevance to sea salt chemistry.

  9. Alkali differentiation in LL-chondrites

    NASA Astrophysics Data System (ADS)

    Wlotzka, F.; Palme, H.; Spettel, B.; Wanke, H.; Fredriksson, K.; Noonan, A. F.

    1983-04-01

    The Kraehenberg and Bhola LL-group chondrites are heterogeneous agglomerates which contain a variety of lithic fragments and chondrules as well as crystal fragments. Both meteorites contain large, cm-sized fragments with high K enrichments. The K-rich inclusions are fragments of larger rock bodies which crystallized from melts of chondritic parent material that had previously been enriched in K and in heavier alkalies,while also being depleted in Na and metal. It is suggested that the K enrichment occurred as an exchange for Na in feldspars via a vapor phase, whose presence on the chondrite parent body (or bodies) is supported by the recent finding of fluid inclusions in chondritic silicates. Cooling rate considerations indicate that the K-rich rock units could not have been very large, implying that the K-rich materials were locally molten by, for example, impact.

  10. Heat pipes containing alkali metal working fluid

    NASA Technical Reports Server (NTRS)

    Morris, J. F. (Inventor)

    1981-01-01

    A technique for improving high temperature evaporation-condensation heat-transfer devices which have important and unique advantage in terrestrial and space energy processing is described. The device is in the form of a heat pipe comprising a sealed container or envelope which contains a capillary wick. The temperature of one end of the heat pipe is raised by the input of heat from an external heat source which is extremely hot and corrosive. A working fluid of a corrosive alkali metal, such as lithium, sodium, or potassium transfers this heat to a heat receiver remote from the heat source. The container and wick are fabricated from a superalloy containing a small percentage of a corrosion inhibiting or gettering element. Lanthanum, scandium, yttrium, thorium, and hafnium are utilized as the alloying metal.

  11. Comparative alkali washing of simulated radioactive sludge

    SciTech Connect

    Fugate, G.A.; Ensor, D.D.; Egan, B.Z.

    1996-10-01

    The treatment of large volumes of radioactive sludge generated from uranium and plutonium recovery processes is a pressing problem in the environmental restoration currently planned at various U.S. Department of Energy sites. This sludge, commonly stored in underground tanks, is mainly in the form of metal oxides or precipitated metal hydroxides and the bulk of this material is nonradioactive. One method being developed to pretreat this waste takes advantage of the amphoteric character of aluminum and other nonradioactive elements. Previous studies have reported on the dissolution of eleven elements from simulated sludge using NaOH solutions up to 6M. This work provides a comparative study using KOH. The effectiveness of the alkali washing as a treatment method to reduce the bulk of radioactive sludge requiring long term isolation will be discussed.

  12. Two-Dimensional Halide Perovskites: Tuning Electronic Activities of Defects.

    PubMed

    Liu, Yuanyue; Xiao, Hai; Goddard, William A

    2016-05-11

    Two-dimensional (2D) halide perovskites are emerging as promising candidates for nanoelectronics and optoelectronics. To realize their full potential, it is important to understand the role of those defects that can strongly impact material properties. In contrast to other popular 2D semiconductors (e.g., transition metal dichalcogenides MX2) for which defects typically induce harmful traps, we show that the electronic activities of defects in 2D perovskites are significantly tunable. For example, even with a fixed lattice orientation one can change the synthesis conditions to convert a line defect (edge or grain boundary) from electron acceptor to inactive site without deep gap states. We show that this difference originates from the enhanced ionic bonding in these perovskites compared with MX2. The donors tend to have high formation energies and the harmful defects are difficult to form at a low halide chemical potential. Thus, we unveil unique properties of defects in 2D perovskites and suggest practical routes to improve them. PMID:27100910

  13. Oxide Film Aging on Alloy 22 in Halide Containing Solutions

    SciTech Connect

    Rodriguez, Martin A.; Carranza, Ricardo M.; Rebak, Raul B.

    2007-07-01

    Passive and corrosion behaviors of Alloy 22 in chloride and fluoride containing solutions, changing the heat treatment of the alloy, the halide concentration and the pH of the solutions at 90 deg. C, was investigated. The study was implemented using electrochemical techniques, which included open circuit potential monitoring over time, potentiodynamic polarization and electrochemical impedance spectroscopy (EIS) measurements carried out at open circuit and at passivity potentials. Corrosion rates obtained by EIS measurements after 24 h immersion in naturally aerated solutions were below 0.5 {mu}m/year. The corrosion rates were practically independent of solution pH, alloy heat treatment and halide ion nature and concentration. EIS low frequency resistance values increased with applied potential in the passive domain and with polarization time in pH 6 - 1 M NaCl at 90 deg. C. This effect was attributed to an increase in the oxide film thickness and oxide film aging. High frequency capacitance measurements indicated that passive oxide on Alloy 22 presented a double n-type/p-type semiconductor behavior in the passive potential range. (authors)

  14. Tunable Near-Infrared Luminescence in Tin Halide Perovskite Devices.

    PubMed

    Lai, May L; Tay, Timothy Y S; Sadhanala, Aditya; Dutton, Siân E; Li, Guangru; Friend, Richard H; Tan, Zhi-Kuang

    2016-07-21

    Infrared emitters are reasonably rare in solution-processed materials. Recently, research into hybrid organo-lead halide perovskite, originally popular in photovoltaics,1-3 has gained traction in light-emitting diodes (LED) due to their low-cost solution processing and good performance.4-9 The lead-based electroluminescent materials show strong colorful emission in the visible region, but lack emissive variants further in the infrared. The concerns with the toxicity of lead may, additionally, limit their wide-scale applications. Here, we demonstrate tunable near-infrared electroluminescence from a lead-free organo-tin halide perovskite, using an ITO/PEDOT:PSS/CH3NH3Sn(Br1-xIx)3/F8/Ca/Ag device architecture. In our tin iodide (CH3NH3SnI3) LEDs, we achieved a 945 nm near-infrared emission with a radiance of 3.4 W sr(-1) m(-2) and a maximum external quantum efficiency of 0.72%, comparable with earlier lead-based devices. Increasing the bromide content in these tin perovskite devices widens the semiconductor bandgap and leads to shorter wavelength emissions, tunable down to 667 nm. These near-infrared LEDs could find useful applications in a range of optical communication, sensing and medical device applications. PMID:27336412

  15. Two-Dimensional Halide Perovskites: Tuning Electronic Activities of Defects

    NASA Astrophysics Data System (ADS)

    Liu, Yuanyue; Xiao, Hai; Goddard, William A., III

    2016-05-01

    Two-dimensional (2D) halide perovskites are emerging as promising candidates for nano-electronics and optoelectronics. To realize their full potential, it is important to understand the role of those defects that can strongly impact material properties. In contrast to other popular 2D semiconductors (e.g. transition metal dichalcogenides MX2) for which defects typically induce harmful traps, we show that the electronic activities of defects in 2D perovskites are significantly tunable. For example, even with a fixed lattice orientation, one can change the synthesis conditions to convert a line defect (edge or grain boundary) from electron acceptor to inactive site without deep gap states. We show that this difference originates from the enhanced ionic bonding in these perovskites compared with MX2. The donors tend to have high formation energies, and the harmful defects are difficult to form at a low halide chemical potential. Thus we unveil unique properties of defects in 2D perovskites and suggest practical routes to improve them.

  16. Subsurface Ectomycorrhizal Fungi: A New Source of Atmospheric Methyl Halides?

    NASA Astrophysics Data System (ADS)

    Treseder, K. K.; Redeker, K. R.; Allen, M. F.

    2001-12-01

    Incomplete source budgets for methyl halides---compounds that release inorganic halogen radicals which, in turn, catalyze atmospheric ozone depletion---limit our abilities to predict the fate of the stratospheric ozone layer. We tested the ability ectomycorrhizal fungi to produce methyl bromide and methyl iodide. These fungi are abundant in temperate forests, where they colonize tree roots and provide nutrients to their symbiotic plants in exchange for carbon compounds. The observed range of emissions from seven different species in culture is 0.001- to 100-μ g g-1 fungi d-1 for methyl bromide, and 0.5- to 500-μ g g-1 fungi d-1 for methyl iodide. While methyl chloride was not specifically tested, large emissions were observed from several species with little to no emissions observed from others. Further analyses of the effects of substrate concentration, headspace concentration, and temperature were performed on the species Cenococcum geophilum, one of the most abundant ectomycorrhizal fungi. Our results suggest that subsurface fungal emissions may be a significant global source of methyl halides.

  17. Photocrystallographic Observation of Halide-Bridged Intermediates in Halogen Photoeliminations

    PubMed Central

    2015-01-01

    Polynuclear transition metal complexes, which frequently constitute the active sites of both biological and chemical catalysts, provide access to unique chemical transformations that are derived from metal–metal cooperation. Reductive elimination via ligand-bridged binuclear intermediates from bimetallic cores is one mechanism by which metals may cooperate during catalysis. We have established families of Rh2 complexes that participate in HX-splitting photocatalysis in which metal–metal cooperation is credited with the ability to achieve multielectron photochemical reactions in preference to single-electron transformations. Nanosecond-resolved transient absorption spectroscopy, steady-state photocrystallography, and computational modeling have allowed direct observation and characterization of Cl-bridged intermediates (intramolecular analogues of classical ligand-bridged intermediates in binuclear eliminations) in halogen elimination reactions. On the basis of these observations, a new class of Rh2 complexes, supported by CO ligands, has been prepared, allowing for the isolation and independent characterization of the proposed halide-bridged intermediates. Direct observation of halide-bridged structures establishes binuclear reductive elimination as a viable mechanism for photogenerating energetic bonds. PMID:25264809

  18. Controlled in-situ dissolution of an alkali metal

    DOEpatents

    Jones, Jeffrey Donald; Dooley, Kirk John; Tolman, David Donald

    2012-09-11

    A method for the controllable dissolution of one or more alkali metals from a vessel containing a one or more alkali metals and/or one or more partially passivated alkali metals. The vessel preferably comprising a sodium, NaK or other alkali metal-cooled nuclear reactor that has been used. The alkali metal, preferably sodium, potassium or a combination thereof, in the vessel is exposed to a treatment liquid, preferably an acidic liquid, more preferably citric acid. Preferably, the treatment liquid is maintained in continuous motion relative to any surface of unreacted alkali metal with which the treatment liquid is in contact. The treatment liquid is preferably pumped into the vessel containing the one or more alkali metals and the resulting fluid is extracted and optionally further processed. Preferably, the resulting off-gases are processed by an off-gas treatment system and the resulting liquids are processed by a liquid disposal system. In one preferred embodiment, an inert gas is pumped into the vessel along with the treatment liquid.

  19. Ultrasonic coal washing to leach alkali elements from coals.

    PubMed

    Balakrishnan, S; Reddy, V Midhun; Nagarajan, R

    2015-11-01

    Deposition of fly ash particles onto heat-transfer surfaces is often one of the reasons for unscheduled shut-downs of coal-fired boilers. Fouling deposits encountered in convective sections of a boiler are characterized by arrival of ash particles in solidified (solid) state. Fouling is most frequently caused by condensation and chemical reaction of alkali vapors with the deposited ash particles creating a wet surface conducive to collect impacting ash particles. Hence, the amount of alkali elements present in coals, which, in turn, is available in the flue gas as condensable vapors, determines the formation and growth of fouling deposits. In this context, removal of alkali elements becomes vital when inferior coals having high-ash content are utilized for power generation. With the concept of reducing alkali elements present in a coal entering the combustor, whereby the fouling deposits can either be minimized or be weakened due to absence of alkali gluing effect, the ultrasonic leaching of alkali elements from coals is investigated in this study. Ultrasonic water-washing and chemical-washing, in comparison with agitation, are studied in order to estimate the intensification of the alkali removal process by sonication. PMID:26186840

  20. Alkali elemental and potassium isotopic compositions of Semarkona chondrules

    USGS Publications Warehouse

    Alexander, C.M. O'D.; Grossman, J.N.

    2005-01-01

    We report measurements of K isotope ratios in 28 Semarkona chondrules with a wide range of petrologic types and bulk compositions as well as the compositions of CPX-mesostasis pairs in 17 type I Semarkona chondrules, including two chondrules with radial alkali zonation and 19 type II chondrules. Despite the wide range in K/Al ratios, no systematic variations in K isotopic compositions were found. Semarkona chondrules do not record a simple history of Rayleigh-type loss of K. Experimentally determined evaporation rates suggest that considerable alkali evaporation would have occurred during chondrule formation. Nevertheless, based on Na CPX-mesostasis distribution coefficients, the alkali contents of the cores of most chondrules in Semarkona were probably established at the time of final crystallization. However, Na CPX-mesostasis distribution coefficients also show that alkali zonation in type I Semarkona chondrules was produced by entry of alkalis after solidification, probably during parent body alteration. This alkali metasomatism may have gone to completion in some chondrules. Our preferred explanation for the lack of systematic isotopic enrichments, even in alkali depleted type I chondrule cores, is that they exchanged with the ambient gas as they cooled. ?? The Meteoritical Society, 2005.

  1. Formability of ABX3 (X = F, Cl, Br, I) halide perovskites.

    PubMed

    Li, Chonghea; Lu, Xionggang; Ding, Weizhong; Feng, Liming; Gao, Yonghui; Guo, Ziming

    2008-12-01

    In this study a total of 186 complex halide systems were collected; the formabilities of ABX3 (X = F, Cl, Br and I) halide perovskites were investigated using the empirical structure map, which was constructed by Goldschmidt's tolerance factor and the octahedral factor. A model for halide perovskite formability was built up. In this model obtained, for all 186 complex halides systems, only one system (CsF-MnF2) without perovskite structure and six systems (RbF-PbF2, CsF-BeF2, KCl-FeCl2, TlI-MnI2, RbI-SnI2, TlI-PbI2) with perovskite structure were wrongly classified, so its predicting accuracy reaches 96%. It is also indicated that both the tolerance factor and the octahedral factor are a necessary but not sufficient condition for ABX3 halide perovskite formability, and a lowest limit of the octahedral factor exists for halide perovskite formation. This result is consistent with our previous report for ABO3 oxide perovskite, and may be helpful to design novel halide materials with the perovskite structure. PMID:19029699

  2. Using Perovskite Nanoparticles as Halide Reservoirs in Catalysis and as Spectrochemical Probes of Ions in Solution.

    PubMed

    Doane, Tennyson L; Ryan, Kayla L; Pathade, Laxmikant; Cruz, Kevin J; Zang, Huidong; Cotlet, Mircea; Maye, Mathew M

    2016-06-28

    The ability of cesium lead halide (CsPbX3; X = Cl(-), Br(-), I(-)) perovskite nanoparticles (P-NPs) to participate in halide exchange reactions, to catalyze Finkelstein organohalide substitution reactions, and to colorimetrically monitor chemical reactions and detect anions in real time is described. With the use of tetraoctylammonium halide salts as a starting point, halide exchange with the P-NPs was performed to calibrate reactivity, stability, and extent of ion exchange. The exchange of CsPbI3 with Cl(-) or Br(-) causes a significant blue-shift in absorption and photoluminescence, whereas reacting I(-) with CsPbBr3 causes a red-shift of similar magnitudes. With the high local halide concentrations and the facile nature of halide exchange in mind, we then explored the ability of P-NPs to catalyze organohalide exchange in Finkelstein like reactions. Results indicate that the P-NPs serve as excellent halide reservoirs for substitution of organohalides in nonpolar media, leading to not only different organohalide products, but also a complementary color change over the course of the reaction, which can be used to monitor kinetics in a precise manner. The merits of using P-NP as spectrochemical probes for real time assaying is then expanded to other anions which can react with, or result in unique, classes of perovskites. PMID:27149396

  3. Increasing Class C fly ash reduces alkali silica reactivity

    SciTech Connect

    Hicks, J.K.

    2007-07-01

    Contrary to earlier studies, it has been found that incremental additions of Class C fly ash do reduce alkali silica reactivity (ASR), in highly reactive, high alkali concrete mixes. AST can be further reduced by substituting 5% metakaolin or silica fume for the aggregate in concrete mixes with high (more than 30%) Class C fly ash substitution. The paper reports results of studies using Class C fly ash from the Labadie Station plant in Missouri which typically has between 1.3 and 1.45% available alkalis by ASTM C311. 7 figs.

  4. Electrochemical cell utilizing molten alkali metal electrode-reactant

    DOEpatents

    Virkar, Anil V.; Miller, Gerald R.

    1983-11-04

    An improved electrochemical cell comprising an additive-modified molten alkali metal electrode-reactant and/or electrolyte is disclosed. Various electrochemical cells employing a molten alkali metal, e.g., sodium, electrode in contact with a cationically conductive ceramic membrane experience a lower resistance and a lower temperature coefficient of resistance whenever small amounts of selenium are present at the interface of the electrolyte and the molten alkali metal. Further, cells having small amounts of selenium present at the electrolyte-molten metal interface exhibit less degradation of the electrolyte under long term cycling conditions.

  5. i-TTM Model for Ab Initio-Based Ion-Water Interaction Potentials. 1. Halide-Water Potential Energy Functions.

    PubMed

    Arismendi-Arrieta, Daniel J; Riera, Marc; Bajaj, Pushp; Prosmiti, Rita; Paesani, Francesco

    2016-03-01

    New potential energy functions (i-TTM) describing the interactions between halide ions and water molecules are reported. The i-TTM potentials are derived from fits to electronic structure data and include an explicit treatment of two-body repulsion, electrostatics, and dispersion energy. Many-body effects are represented through classical polarization within an extended Thole-type model. By construction, the i-TTM potentials are compatible with the flexible and fully ab initio MB-pol potential, which has recently been shown to accurately predict the properties of water from the gas to the condensed phase. The accuracy of the i-TTM potentials is assessed through extensive comparisons with CCSD(T)-F12, DF-MP2, and DFT data as well as with results obtained with common polarizable force fields for X(-)(H2O)n clusters with X(-) = F(-), Cl(-), Br(-), and I(-), and n = 1-8. By construction, the new i-TTM potentials will enable direct simulations of vibrational spectra of halide-water systems from clusters to bulk and interfaces. PMID:26560189

  6. Low-pressure indium-halide discharges for fluorescent illumination applications

    NASA Astrophysics Data System (ADS)

    Hayashi, Daiyu; Hilbig, Rainer; Körber, Achim; Schwan, Stefan; Scholl, Robert; Boerger, Martin; Huppertz, Maria

    2010-02-01

    Low-pressure gas discharges of molecular radiators were studied for fluorescent lighting applications with a goal of reducing the energy loss due to the large Stokes shift in phosphors of conventional mercury-based fluorescent lamp technology. Indium halides (InCl, InBr, and InI) were chosen as the molecular radiators that generate ultraviolet to blue light emissions. The electrical characteristics and optical emission intensities were measured in discharges containing gaseous indium halides (InCl, InBr, and InI) as molecular radiators. The low-pressure discharges in indium halide vapor showed potential as a highly efficient gas discharge system for fluorescent lighting application.

  7. Vaporisation and thermal decomposition of dialkylimidazolium halide ion ionic liquids.

    PubMed

    Lovelock, Kevin R J; Armstrong, James P; Licence, Peter; Jones, Robert G

    2014-01-28

    Vaporisation and liquid phase thermal decomposition, TD, of two halide ion ionic liquids, 1-octyl-3-methylimidazolium chloride, [C8C1Im]Cl, and 1-octyl-3-methylimidazolium iodide, [C8C1Im]I, are investigated using temperature programmed desorption (TPD) line of sight mass spectrometry (LOSMS) at ultra-high vacuum (UHV). The ability to use MS to distinguish between vaporisation and TD allows the thermodynamics/kinetics of both vaporisation and TD to be investigated within the same experiments. Vaporisation of both halide ion ionic liquids is demonstrated. For both [C8C1Im]Cl and [C8C1Im]I the vapour is shown to be composed of neutral ion pairs (NIPs). The enthalpy of vaporisation at temperature T, ΔvapHT, was experimentally determined as ΔvapH455 = 151 ± 10 kJ mol(-1) for [C8C1Im]Cl and ΔvapH480 = 149 ± 8 kJ mol(-1) for [C8C1Im]I. Extrapolation of ΔvapHT to the reference temperature, 298 K, gave ΔvapH298 = 166 ± 10 kJ mol(-1) for [C8C1Im]Cl and ΔvapH298 = 167 ± 8 kJ mol(-1) for [C8C1Im]I, higher than most ΔvapH298 values measured to date for other [C8C1Im](+)-containing ionic liquids. In addition, predictions of ΔvapH298 for other halide ion ionic liquids are made. Liquid phase TD is shown to proceed via nucleophilic substitution to give two sets of products: 1-octylimidazole and methylhalide, and 1-methylimidazole and 1-octylhalide. The activation energy of TD at a temperature T, Ea,TD,T, is measured for the nucleophilic substitution of [C8C1Im]I to give methyliodide; Ea,TD,480 = 136 ± 15 kJ mol(-1). Ea,TD,T is measured for the nucleophilic substitution of [C8C1Im]Cl to give methylchloride; Ea,TD,455 = 132 ± 10 kJ mol(-1). The fact that ΔvapHT and Ea,TD,T are the same (within error) for both ionic liquids is commented upon, and conclusions are drawn as to the thermal stability of these ionic liquids. PMID:24105256

  8. Electric field-induced softening of alkali silicate glasses

    NASA Astrophysics Data System (ADS)

    McLaren, C.; Heffner, W.; Tessarollo, R.; Raj, R.; Jain, H.

    2015-11-01

    Motivated by the advantages of two-electrode flash sintering over normal sintering, we have investigated the effect of an external electric field on the viscosity of glass. The results show remarkable electric field-induced softening (EFIS), as application of DC field significantly lowers the softening temperature of glass. To establish the origin of EFIS, the effect is compared for single vs. mixed-alkali silicate glasses with fixed mole percentage of the alkali ions such that the mobility of alkali ions is greatly reduced while the basic network structure does not change much. The sodium silicate and lithium-sodium mixed alkali silicate glasses were tested mechanically in situ under compression in external electric field ranging from 0 to 250 V/cm in specially designed equipment. A comparison of data for different compositions indicates a complex mechanical response, which is observed as field-induced viscous flow due to a combination of Joule heating, electrolysis and dielectric breakdown.

  9. The 4843 Alkali Metal Storage Facility Closure Plan

    SciTech Connect

    Not Available

    1991-06-01

    The 4843 AMSF has been used primarily to provide a centralized building to receive and store dangerous and mixed alkali metal waste, including sodium and lithium, which has been generated at the Fast Flux Test Facility and at various other Hanford Site operations that used alkali metals. Most of the dangerous and mixed alkali metal waste received consists of retired equipment from liquid sodium processes. The unit continues to store material. In general, only solid alkali metal waste that is water reactive is stored at the 4843 AMSF. The 4843 AMSF will be closed in a manner consistent with Ecology guidelines and regulations (WAC 173-303-610). The general closure procedure is detailed as follows.

  10. Hall Determination of Atomic Radii of Alkali Metals

    ERIC Educational Resources Information Center

    Houari, Ahmed

    2008-01-01

    I will propose here an alternative method for determining atomic radii of alkali metals based on the Hall measurements of their free electron densities and the knowledge of their crystal structure. (Contains 2 figures.)

  11. Method for intercalating alkali metal ions into carbon electrodes

    DOEpatents

    Doeff, M.M.; Ma, Y.; Visco, S.J.; DeJonghe, L.

    1995-08-22

    A low cost, relatively flexible, carbon electrode for use in a secondary battery is described. A method is provided for producing same, including intercalating alkali metal salts such as sodium and lithium into carbon.

  12. Method for intercalating alkali metal ions into carbon electrodes

    DOEpatents

    Doeff, Marca M.; Ma, Yanping; Visco, Steven J.; DeJonghe, Lutgard

    1995-01-01

    A low cost, relatively flexible, carbon electrode for use in a secondary battery is described. A method is provided for producing same, including intercalating alkali metal salts such as sodium and lithium into carbon.

  13. Electric field-induced softening of alkali silicate glasses

    SciTech Connect

    McLaren, C.; Heffner, W.; Jain, H.; Tessarollo, R.; Raj, R.

    2015-11-02

    Motivated by the advantages of two-electrode flash sintering over normal sintering, we have investigated the effect of an external electric field on the viscosity of glass. The results show remarkable electric field-induced softening (EFIS), as application of DC field significantly lowers the softening temperature of glass. To establish the origin of EFIS, the effect is compared for single vs. mixed-alkali silicate glasses with fixed mole percentage of the alkali ions such that the mobility of alkali ions is greatly reduced while the basic network structure does not change much. The sodium silicate and lithium-sodium mixed alkali silicate glasses were tested mechanically in situ under compression in external electric field ranging from 0 to 250 V/cm in specially designed equipment. A comparison of data for different compositions indicates a complex mechanical response, which is observed as field-induced viscous flow due to a combination of Joule heating, electrolysis and dielectric breakdown.

  14. Effect of cavitation on removal of alkali elements from coal

    NASA Astrophysics Data System (ADS)

    Srivalli, H.; Nirmal, L.; Nagarajan, R.

    2015-12-01

    The main impurities in coal are sulphur, ash and alkali. On combustion, the volatile forms of these impurities are either condensed on the boilers, or emitted in the form of potentially hazardous gases. The alkali elements present in coal help the fly ash particles adhere to boiler surfaces by providing a wet surface on which collection of these particles can take place. Use of ultrasonic techniques in cleaning of coal has stirred interest among researchers in recent times. Extraction of alkali elements by cavitation effect using low-frequency ultrasound, in the presence of reagents (HNO3 and H2O2) is reported in this paper. Powdered coal was dissolved with the reagent and exposed to ultrasonic fields of various frequencies at different time intervals. The treated solution is filtered and tested for alkali levels.

  15. Alkali absorption and citrate excretion in calcium nephrolithiasis

    NASA Technical Reports Server (NTRS)

    Sakhaee, K.; Williams, R. H.; Oh, M. S.; Padalino, P.; Adams-Huet, B.; Whitson, P.; Pak, C. Y.

    1993-01-01

    The role of net gastrointestinal (GI) alkali absorption in the development of hypocitraturia was investigated. The net GI absorption of alkali was estimated from the difference between simple urinary cations (Ca, Mg, Na, and K) and anions (Cl and P). In 131 normal subjects, the 24 h urinary citrate was positively correlated with the net GI absorption of alkali (r = 0.49, p < 0.001). In 11 patients with distal renal tubular acidosis (RTA), urinary citrate excretion was subnormal relative to net GI alkali absorption, with data from most patients residing outside the 95% confidence ellipse described for normal subjects. However, the normal relationship between urinary citrate and net absorbed alkali was maintained in 11 patients with chronic diarrheal syndrome (CDS) and in 124 stone-forming patients devoid of RTA or CDS, half of whom had "idiopathic" hypocitraturia. The 18 stone-forming patients without RTA or CDS received potassium citrate (30-60 mEq/day). Both urinary citrate and net GI alkali absorption increased, yielding a significantly positive correlation (r = 0.62, p < 0.0001), with the slope indistinguishable from that of normal subjects. Thus, urinary citrate was normally dependent on the net GI absorption of alkali. This dependence was less marked in RTA, confirming the renal origin of hypocitraturia. However, the normal dependence was maintained in CDS and in idiopathic hypocitraturia, suggesting that reduced citrate excretion was largely dietary in origin as a result of low net alkali absorption (from a probable relative deficiency of vegetables and fruits or a relative excess of animal proteins).

  16. Rock Degradation by Alkali Metals: A Possible Lunar Erosion Mechanism.

    PubMed

    Naughton, J J; Barnes, I L; Hammond, D A

    1965-08-01

    When rocks melt under ultrahigh-vacuum conditions, their alkali components volatilize as metals. These metal vapors act to comminute polycrystalline rocks to their component minerals. The resultant powder is porous and loosely packed and its characteristics may be compatible with the lunar surface as revealed by the Ranger photographs. If meteorite impact or lunar volcanism has produced vaporization or areas of molten lava, alkali erosion may have given dust of this character in adjacent solid areas. PMID:17747570

  17. Electrochemical cell having an alkali-metal-nitrate electrode

    DOEpatents

    Roche, M.F.; Preto, S.K.

    1982-06-04

    A power-producing secondary electrochemical cell includes a molten alkali metal as the negative-electrode material and a molten-nitrate salt as the positive-electrode material. The molten material in the respective electrodes are separated by a solid barrier of alkali-metal-ion conducting material. A typical cell includes active materials of molten sodium separated from molten sodium nitrate and other nitrates in mixture by a layer of sodium ..beta..'' alumina.

  18. Direct current ballast circuit for metal halide lamp

    NASA Technical Reports Server (NTRS)

    Lutus, P. (Inventor)

    1981-01-01

    A direct current ballast circuit for a two electrode metal halide lamp is described. Said direct current ballast circuit includes a low voltage DC input and a high frequency power amplifier and power transformer for developing a high voltage output. The output voltage is rectified by diodes and filtered by inductor and capacitor to provide a regulated DC output through commutating diodes to one terminal of the lamp at the output terminal. A feedback path from the output of the filter capacitor through the bias resistor to power the high frequency circuit which includes the power amplifier and the power transformer for sustaining circuit operations during low voltage transients on the input DC supply is described. A current sensor connected to the output of the lamp through terminal for stabilizing lamp current following breakdown of the lamp is described.

  19. Metal halide arc discharge lamp having short arc length

    NASA Technical Reports Server (NTRS)

    Muzeroll, Martin E. (Inventor)

    1994-01-01

    A metal halide arc discharge lamp includes a sealed light-transmissive outer jacket, a light-transmissive shroud located within the outer jacket and an arc tube assembly located within the shroud. The arc tube assembly includes an arc tube, electrodes mounted within the arc tube and a fill material for supporting an arc discharge. The electrodes have a spacing such that an electric field in a range of about 60 to 95 volts per centimeter is established between the electrodes. The diameter of the arc tube and the spacing of the electrodes are selected to provide an arc having an arc diameter to arc length ratio in a range of about 1.6 to 1.8. The fill material includes mercury, sodium iodide, scandium tri-iodide and a rare gas, and may include lithium iodide. The lamp exhibits a high color rendering index, high lumen output and high color temperature.

  20. Theory of hydrogen migration in organic-inorganic halide perovskites.

    PubMed

    Egger, David A; Kronik, Leeor; Rappe, Andrew M

    2015-10-12

    Solar cells based on organic-inorganic halide perovskites have recently been proven to be remarkably efficient. However, they exhibit hysteresis in their current-voltage curves, and their stability in the presence of water is problematic. Both issues are possibly related to a diffusion of defects in the perovskite material. By using first-principles calculations based on density functional theory, we study the properties of an important defect in hybrid perovskites-interstitial hydrogen. We show that differently charged defects occupy different crystal sites, which may allow for ionization-enhanced defect migration following the Bourgoin-Corbett mechanism. Our analysis highlights the structural flexibility of organic-inorganic perovskites: successive iodide displacements, combined with hydrogen bonding, enable proton diffusion with low migration barriers. These findings indicate that hydrogen defects can be mobile and thus highly relevant for the performance of perovskite solar cells. PMID:26073061

  1. Enhanced quantum efficiency from hybrid cesium halide/copper photocathodes

    NASA Astrophysics Data System (ADS)

    Kong, Lingmei; Joly, Alan G.; Droubay, Timothy C.; Gong, Yu; Hess, Wayne P.

    2014-04-01

    The quantum efficiency (QE) of Cu is found to increase dramatically when coated by a CsI film and then irradiated by a UV laser. Over three orders of magnitude quantum efficiency enhancement at 266 nm is observed in CsI/Cu(100), indicating potential application in future photocathode devices. Upon laser irradiation, a large work function reduction to a value less than 2 eV is also observed, significantly greater than for similarly treated CsBr/Cu(100). The initial QE enhancement, prior to laser irradiation, is attributed to interface interaction and the intrinsic properties of the Cs halide film. Further QE enhancement following activation is attributed to formation of inter-band states and Cs metal accumulation at the interface induced by laser irradiation.

  2. Evaluation of low melting halide systems for battery applications

    NASA Astrophysics Data System (ADS)

    Mamantov, G.; Perrovic, C.

    1981-03-01

    This three year program involves evaluation of selected low temperature molten salt solvent systems containing inorganic and/or organic chlorides and bromides for battery applications. The research involves determination of the liquidus temperatures, the specific electrical conductivity, and the electrochemical span of selected halide systems. Characterization of the solvent species by Raman spectroscopy, vapor pressure measurements, and the electrochemical study of a few cathode and anode systems will be undertaken for the most promising solvent systems. The research during the second year of this project involved the determination of liquidus temperatures and/or specific electrical conductivities for a number of binary and ternary molten salt systems containing AlCl3, AlBr3, SbCl3, FeCl3, and GaCl3.

  3. Giant photostriction in organic-inorganic lead halide perovskites.

    PubMed

    Zhou, Yang; You, Lu; Wang, Shiwei; Ku, Zhiliang; Fan, Hongjin; Schmidt, Daniel; Rusydi, Andrivo; Chang, Lei; Wang, Le; Ren, Peng; Chen, Liufang; Yuan, Guoliang; Chen, Lang; Wang, Junling

    2016-01-01

    Among the many materials investigated for next-generation photovoltaic cells, organic-inorganic lead halide perovskites have demonstrated great potential thanks to their high power conversion efficiency and solution processability. Within a short period of about 5 years, the efficiency of solar cells based on these materials has increased dramatically from 3.8 to over 20%. Despite the tremendous progress in device performance, much less is known about the underlying photophysics involving charge-orbital-lattice interactions and the role of the organic molecules in this hybrid material remains poorly understood. Here, we report a giant photostrictive response, that is, light-induced lattice change, of >1,200 p.p.m. in methylammonium lead iodide, which could be the key to understand its superior optical properties. The strong photon-lattice coupling also opens up the possibility of employing these materials in wireless opto-mechanical devices. PMID:27044485

  4. Recent progress and challenges of organometal halide perovskite solar cells

    NASA Astrophysics Data System (ADS)

    Yang, Liyan; Barrows, Alexander T.; Lidzey, David G.; Wang, Tao

    2016-02-01

    We review recent progress in the development of organometal halide perovskite solar cells. We discuss different compounds used to construct perovskite photoactive layers, as well as the optoelectronic properties of this system. The factors that affect the morphology of the perovskite active layer are explored, e.g. material composition, film deposition methods, casting solvent and various post-treatments. Different strategies are reviewed that have recently emerged to prepare high performing perovskite films, creating polycrystalline films having either large or small grain size. Devices that are constructed using meso-superstructured and planar architectures are summarized and the impact of the fabrication process on operational efficiency is discussed. Finally, important research challenges (hysteresis, thermal and moisture instability, mechanical flexibility, as well as the development of lead-free materials) in the development of perovskite solar cells are outlined and their potential solutions are discussed.

  5. Active terahertz device based on optically controlled organometal halide perovskite

    NASA Astrophysics Data System (ADS)

    Zhang, Bo; Lv, Longfeng; He, Ting; Chen, Tianji; Zang, Mengdi; Zhong, Liang; Wang, Xinke; Shen, Jingling; Hou, Yanbing

    2015-08-01

    An active all-optical high-efficiency broadband terahertz device based on an organometal halide perovskite (CH3NH3PbI3, MAPbI3)/inorganic (Si) structure is investigated. Spectrally broadband modulation of the THz transmission is obtained in the frequency range from 0.2 to 2.6 THz, and a modulation depth of nearly 100% can be achieved with a low-level photoexcitation power (˜0.4 W/cm2). Both THz transmission and reflection were suppressed in the MAPbI3/Si structure by an external continuous-wave (CW) laser. Enhancement of the charge carrier density at the MAPbI3/Si interface is crucial for photo-induced absorption. The results show that the proposed high-efficiency broadband optically controlled terahertz device based on the MAPbI3/Si structure has been realized.

  6. Mechanical properties of silver halide core/clad IR fibers

    NASA Astrophysics Data System (ADS)

    Shalem, Shaul; German, Alla; Moser, Frank; Katzir, Abraham

    1996-04-01

    We have developed core/clad polycrystalline silver halide optical fibers with a loss of roughly 0.3 dB/m at 10.6 micrometers. Such fibers, with core diameters 0.3 - 0.6 mm and lengths of 1 to 2 meters are capable of continuously delivering output power densities as high as 14 KW/cm2. The fibers were repetitively bent in the plastic and elastic regimes and the optical transmission monitored during bending. The mechanical properties of the core/clad fibers and of the core only fibers are similar. It was also demonstrated that the 'bending' properties of the core/clad fibers are determined by the cladding material. Our investigations suggest that proper design of the core/clad structure may give significant improvement in mechanical properties such as more cycles to optical failure. This will be very important especially for endoscopic laser surgery and other medical applications.

  7. Enhanced Quantum Efficiency From Hybrid Cesium Halide/Copper Photocathode

    SciTech Connect

    Kong, Lingmei; Joly, Alan G.; Droubay, Timothy C.; Gong, Yu; Hess, Wayne P.

    2014-04-28

    The quantum efficiency of Cu is found to increase dramatically when coated by a CsI film and then irradiated by a UV laser. Over three orders of magnitude quantum efficiency enhancement at 266 nm is observed in CsI/Cu(100), indicating potential application in future photocathode devices. Upon laser irradiation, a large work function reduction to a value less than 2 eV is also observed, significantly greater than for similarly treated CsBr/Cu(100). The initial QE enhancement, prior to laser irradiation, is attributed to interface interaction, surface cleanliness and the intrinsic properties of the Cs halide film. Further QE enhancement following activation is attributed to formation of inter-band states and Cs metal accumulation at the interface induced by laser irradiation.

  8. Large Magnetoresistance Effects in Novel Layered Rare Earth Halides

    NASA Astrophysics Data System (ADS)

    Kremer, R. K.; Ryazanov, M.; Simon, A.

    We give a survey of the structures, electric, magnetic and magnetoresistance properties of the two novel low dimensional rare-earth halide systems, GdI2 and GdIHy (2/3 < y ≤ 1). The large magnetoresistance e.ect observed for GdI2 can be understood on the basis of a conventional spin disorder scattering mechanism, however, strongly magni.ed by the structural anisotropy and the special topology of the Fermi surface. Bound magnetic polarons are formed in GdIHy leading to a metal insulator transition below ~ 30 K. The mobility of the magnetic polarons can be e.ectively modi.ed by external magnetic .fields resulting in the large experimentally found magnetoresistance.

  9. Enhanced quantum efficiency from hybrid cesium halide/copper photocathodes

    SciTech Connect

    Kong, Lingmei; Joly, Alan G.; Droubay, Timothy C.; Gong, Yu; Hess, Wayne P.

    2014-04-28

    The quantum efficiency (QE) of Cu is found to increase dramatically when coated by a CsI film and then irradiated by a UV laser. Over three orders of magnitude quantum efficiency enhancement at 266 nm is observed in CsI/Cu(100), indicating potential application in future photocathode devices. Upon laser irradiation, a large work function reduction to a value less than 2 eV is also observed, significantly greater than for similarly treated CsBr/Cu(100). The initial QE enhancement, prior to laser irradiation, is attributed to interface interaction and the intrinsic properties of the Cs halide film. Further QE enhancement following activation is attributed to formation of inter-band states and Cs metal accumulation at the interface induced by laser irradiation.

  10. Fast Photoconductive Responses in Organometal Halide Perovskite Photodetectors.

    PubMed

    Wang, Fei; Mei, Jingjing; Wang, Yunpeng; Zhang, Ligong; Zhao, Haifeng; Zhao, Dongxu

    2016-02-01

    Inorganic semiconductor-based photodetectors have been suffering from slow response speeds, which are caused by the persistent photoconductivity of semiconductor materials. For realizing high speed optoelectronic devices, the organometal halide perovskite thin films were applied onto the interdigitated (IDT) patterned Au electrodes, and symmetrical structured photoconductive detectors were achieved. The detectors were sensitive to the incident light signals, and the photocurrents of the devices were 2-3 orders of magnitude higher than dark currents. The responsivities of the devices could reach up to 55 mA W(1-). Most importantly, the detectors have a fast response time of less than 20 μs. The light and bias induced dipole rearrangement in organometal perovskite thin films has resulted in the instability of photocurrents, and Ag nanowires could quicken the process of dipole alignment and stabilize the photocurrents of the devices. PMID:26796674

  11. Venus: Halide cloud condensation and volatile element inventories

    NASA Technical Reports Server (NTRS)

    Lewis, J. S.; Fegley, B., Jr.

    1982-01-01

    Several Venus cloud condensates, including A12C16 as well as halides, oxides and sulfides of arsenic and antimony, are assessed for their thermodynamic and geochemical plausibility. Aluminum chloride can confidently be ruled out, and condensation of arsenic sulfides on the surface will cause arsenic compounds to be too rare to produce the observed clouds. Antimony may conceivably be sufficiently volatile, but the expected molecular form is gaseous SbS, not the chloride. Arsenic and antimony compounds in the atmosphere will be regulated at very low levels by sulfide precipitation, irrespective of the planetary inventory of As and Sb. Thus the arguments for a volatile-deficient origin for Venus based on the depletion of water and mercury (relative to Earth) cannot be tested by a search for atmospheric arsenic or antimony.

  12. Material Innovation in Advancing Organometal Halide Perovskite Functionality.

    PubMed

    Zheng, Fan; Saldana-Greco, Diomedes; Liu, Shi; Rappe, Andrew M

    2015-12-01

    Organometal halide perovskites (OMHPs) have garnered much attention recently for their unprecedented rate of increasing power conversion efficiency (PCE), positioning them as a promising basis for the next-generation photovoltaic devices. However, the gap between the rapid increasing PCE and the incomplete understanding of the structure-property-performance relationship prevents the realization of the true potential of OMHPs. This Perspective aims to provide a concise overview of the current status of OMHP research, highlighting the unique properties of OMHPs that are critical for solar applications but still not adequately explained. Stability and performance challenges of OMHP solar cells are discussed, calling upon combined experimental and theoretical efforts to address these challenges for pioneering commercialization of OMHP solar cells. Various material innovation strategies for improving the performance and stability of OMHPs are surveyed, showing that the OMHP architecture can serve as a promising and robust platform for the design and optimization of materials with desired functionalities. PMID:26631361

  13. Giant photostriction in organic–inorganic lead halide perovskites

    PubMed Central

    Zhou, Yang; You, Lu; Wang, Shiwei; Ku, Zhiliang; Fan, Hongjin; Schmidt, Daniel; Rusydi, Andrivo; Chang, Lei; Wang, Le; Ren, Peng; Chen, Liufang; Yuan, Guoliang; Chen, Lang; Wang, Junling

    2016-01-01

    Among the many materials investigated for next-generation photovoltaic cells, organic–inorganic lead halide perovskites have demonstrated great potential thanks to their high power conversion efficiency and solution processability. Within a short period of about 5 years, the efficiency of solar cells based on these materials has increased dramatically from 3.8 to over 20%. Despite the tremendous progress in device performance, much less is known about the underlying photophysics involving charge–orbital–lattice interactions and the role of the organic molecules in this hybrid material remains poorly understood. Here, we report a giant photostrictive response, that is, light-induced lattice change, of >1,200 p.p.m. in methylammonium lead iodide, which could be the key to understand its superior optical properties. The strong photon-lattice coupling also opens up the possibility of employing these materials in wireless opto-mechanical devices. PMID:27044485

  14. Giant photostriction in organic-inorganic lead halide perovskites

    NASA Astrophysics Data System (ADS)

    Zhou, Yang; You, Lu; Wang, Shiwei; Ku, Zhiliang; Fan, Hongjin; Schmidt, Daniel; Rusydi, Andrivo; Chang, Lei; Wang, Le; Ren, Peng; Chen, Liufang; Yuan, Guoliang; Chen, Lang; Wang, Junling

    2016-04-01

    Among the many materials investigated for next-generation photovoltaic cells, organic-inorganic lead halide perovskites have demonstrated great potential thanks to their high power conversion efficiency and solution processability. Within a short period of about 5 years, the efficiency of solar cells based on these materials has increased dramatically from 3.8 to over 20%. Despite the tremendous progress in device performance, much less is known about the underlying photophysics involving charge-orbital-lattice interactions and the role of the organic molecules in this hybrid material remains poorly understood. Here, we report a giant photostrictive response, that is, light-induced lattice change, of >1,200 p.p.m. in methylammonium lead iodide, which could be the key to understand its superior optical properties. The strong photon-lattice coupling also opens up the possibility of employing these materials in wireless opto-mechanical devices.

  15. Semiphysical development of holograms recorded in silver halide emulsions

    NASA Astrophysics Data System (ADS)

    Banyasz, Istvan; Belendez, Augusto; Pascual, Inmaculada V.; Fimia, Antonio

    2000-10-01

    In the course of experiments on measurement of the effects of processing on nonlinear characteristics of silver halide holograms recorded in Agfa-gevaert 8E75HD emulsions we found that, under certain circumstances, the AAC developer acted as a semi-physical developer instead of the normal chemical developing action. The developed and fixed holograms were of low optical density (<0.5) and of high diffraction efficiency (up to 15%). Phase contrast microscopy revealed that very clean phase gratings were obtained. This effect of the AAC developer was due to the replacement of one of its components, sodium carbonate of purest grade with that of for analysis grade of the same company.

  16. Theoretical study of the scandium and yttrium halides

    NASA Technical Reports Server (NTRS)

    Langhoff, Stephen R.; Bauschlicher, Charles W., Jr.; Partridge, Harry

    1988-01-01

    The X1Sigma(+) ground states and a3Delta excited states of the diatomic halides of Sc and Y are characterized theoretically, using the SDCI coupled-pair functional method and the state-averaged CASSCF method to determine the spectroscopic constants and related properties. The techniques employed are discussed, and the results are presented in extensive tables. The dissociation energies are given as D0 = 6.00 eV for ScF, 4.55 eV for ScCl, 3.90 eV for ScBr, 6.72 eV for YF, 5.36 eV for YCl, and 4.74 eV for YBr.

  17. Alkali metal yttrium neo-pentoxide double alkoxide precursors to alkali metal yttrium oxide nanomaterials

    DOE PAGESBeta

    Boyle, Timothy J.; Neville, Michael L.; Sears, Jeremiah Matthew; Cramer, Roger

    2016-03-15

    In this study, a series of alkali metal yttrium neo-pentoxide ([AY(ONep)4]) compounds were developed as precursors to alkali yttrium oxide (AYO2) nanomaterials. The reaction of yttrium amide ([Y(NR2)3] where R=Si(CH3)3) with four equivalents of H-ONep followed by addition of [A(NR2)] (A=Li, Na, K) or Ao (Ao=Rb, Cs) led to the formation of a complex series of AnY(ONep)3+n species, crystallographically identified as [Y2Li3(μ3-ONep)(μ3-HONep)(μ-ONep)5(ONep)3(HONep)2] (1), [YNa2(μ3-ONep)4(ONep)]2 (2), {[Y2K3(μ3-ONep)3(μ-ONep)4(ONep)2(ηξ-tol)2][Y4K2(μ4-O)(μ3-ONep)8(ONep)4]•ηx-tol]} (3), [Y4K2(μ4-O)(μ3-ONep)8(ONep)4] (3a), [Y2Rb3(μ4-ONep)3(μ-ONep)6] (4), and [Y2Cs4(μ6-O)(μ3-ONep)6(μ3-HONep)2(ONep)2(ηx-tol)4]•tol (5). Compounds 1–5 were investigated as single source precursors to AYOx nanomaterials following solvothermal routes (pyridine, 185 °C for 24h). The final products after thermal processing weremore » found by powder X-ray diffraction experiments to be Y2O3 with variable sized particles based on transmission electron diffraction. Energy dispersive X-ray spectroscopy studies indicated that the heavier alkali metal species were present in the isolated nanomaterials.« less

  18. Alkali-slag cements for the immobilization of radioactive wastes

    SciTech Connect

    Shi, C.; Day, R.L.

    1996-12-31

    Alkali-slag cements consist of glassy slag and an alkaline activator and can show both higher early and later strengths than Type III Portland cement, if a proper alkaline activator is used. An examination of microstructure of hardened alkali-slag cement pastes with the help of XRD and SEM with EDAX shows that the main hydration product is C-S-H (B) with low C/S ratio and no crystalline substances exist such as Ca(OH){sub 2}, Al (OH){sub 3} and sulphoaluminates. Mercury intrusion tests indicate that hardened alkali-slag cement pastes have a lower porosity than ordinary Portland cement, and contain mainly gel pores. The fine pore structure of hardened alkali-slag cement pastes will restrict the ingress of deleterious substances and the leaching of harmful species such as radionuclides. The leachability of Cs{sup + } from hardened alkali-slag cement pastes is only half of that from hardened Portland cement. From all these aspects, it is concluded that alkali-slag cements are a better solidification matrix than Portland cement for radioactive wastes.

  19. Temperature dependence of elastic properties in alkali borate binary glasses

    NASA Astrophysics Data System (ADS)

    Kawashima, Mitsuru; Matsuda, Yu; Kojima, Seiji

    2011-05-01

    The elastic properties of alkali borate glasses, xM 2O·(100 - x)B 2O 3 (M = Li, Na, K, Rb, Cs, x = 14, 28), have been investigated by Brillouin scattering spectroscopy from room temperature up to 1100 °C. Above the glass transition temperature, Tg, the longitudinal sound velocity, VL, decreases markedly on heating. Such significant changes of the elastic properties result from the breakdown of the glass network above Tg. Alkali borate family with the same x shows the similar behavior in the temperature variations of VL up to around Tg. The absorption coefficient, αL, increases gradually above Tg. With the increase of the size of an alkali ion, the slope of VL just above Tg decreases. Since the fragility is related to the slope, the present results suggest that the fragility of alkali borate glasses increases as the size of alkali ion decreases. Such an alkali dependence of the fragility is discussed on the basis of the fluctuation of the boron coordination number.

  20. Two-phase alkali-metal experiments in reduced gravity

    SciTech Connect

    Antoniak, Z.I.

    1986-06-01

    Future space missions envision the use of large nuclear reactors utilizing either a single or a two-phase alkali-metal working fluid. The design and analysis of such reactors require state-of-the-art computer codes that can properly treat alkali-metal flow and heat transfer in a reduced-gravity environment. A literature search of relevant experiments in reduced gravity is reported on here, and reveals a paucity of data for such correlations. The few ongoing experiments in reduced gravity are noted. General plans are put forth for the reduced-gravity experiments which will have to be performed, at NASA facilities, with benign fluids. A similar situation exists regarding two-phase alkali-metal flow and heat transfer, even in normal gravity. Existing data are conflicting and indequate for the task of modeling a space reactor using a two-phase alkali-metal coolant. The major features of past experiments are described here. Data from the reduced-gravity experiments with innocuous fluids are to be combined with normal gravity data from the two-phase alkali-metal experiments. Analyses undertaken here give every expectation that the correlations developed from this data base will provide a valid representation of alkali-metal heat transfer and pressure drop in reduced gravity.