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Sample records for al br cl

  1. Synthesis in ionic liquids : [Bi{sub 2}Te{sub 2}Br](AlCl{sub 4}), a direct gap semiconductor with a cationic framework.

    SciTech Connect

    Biswas, K.; Zhang, Q.; Chung, I.; Song, J.-H.; Androulaksi, J.; Freeman, A. J.; Kanatzidis, M. G.; Materials Science Division; Northwestern Univ.

    2010-01-01

    The Lewis acidic ionic liquid EMIMBr-AlCl{sub 3} (EMIM = 1-ethyl-3-methylimidazolium) allows a novel synthetic route to the semiconducting layered metal chalcogenides halide [Bi{sub 2}Te{sub 2}Br](AlCl{sub 4}) and its Sb analogue. [Bi{sub 2}Te{sub 2}Br](AlCl{sub 4}) is a direct band gap, strongly anisotropic semiconductor and consists of cationic infinite layers of [Bi{sub 2}Te{sub 2}Br]{sup +} and [AlCl{sub 4}]{sup -} anions inserted between the layers.

  2. A new method for distinguishing between Al 2X 6 (X=Cl, Br) conformers based on ab initio calculated nuclear quadrupole coupling constants

    NASA Astrophysics Data System (ADS)

    Hadipour, N. L.; Elmi, F.

    2003-03-01

    Nuclear quadrupole coupling constants ( χ) of 27Al, 35Cl and 81Br in AlX 3 monomers as well as Al 2X 6 (X=Cl, Br) dimers are calculated at the RHF/6-311G* and B 3LYP/6-311G* levels, using G AUSSIAN 98 package. Correlations are made between χ and dihedral angles θ, of Al 2X 6. These θs are produced through the ring puckering motions about the hinge line which joins the two bridge halogens (X b). Nuclear quadrupole coupling constants of 35Cl, 81Br and 27Al are used as probes for monitoring the departure of the symmetry of Al 2X 6 from a high symmetry point group D 2h to a lower one. The χs of chlorine nuclei of AlCl 3 differ significantly from those of Al 2Cl 6. These differences appear negligible for AlBr 3 in comparison to Al 2Br 6. This work demonstrates the considerable sensitivity of nuclear quadrupole resonance in distinguishing between Al 2X 6 conformers. This is in comparison to the usage of energy differences which is customarily employed.

  3. Czochralski growth of the mixed halides BaBrCl and BaBrCl:Eu

    NASA Astrophysics Data System (ADS)

    Yan, Z.; Shalapska, T.; Bourret, E. D.

    2016-02-01

    We present results from the growth of BaBrCl and BaBrCl:Eu single crystals, using the Czochralski method. Cubic inch crack-free crystals of both undoped and 5% Eu doped BaBrCl were obtained. The BaBr2-BaCl2 phase diagram was acquired by differential thermal analysis revealing that the system forms a solid solution at all concentrations with no significant separation between the solidus and liquidus curves. Details of the Czochralski process used to prevent cracking are presented. The scintillation performance of the Czochralski grown crystals is presented.

  4. Chalcogenide chemistry in ionic liquids: nonlinear optical wave-mixing properties of the double-cubane compound [Sb{sub 7}S{sub 8}Br{sub 2}](AlCl{sub 4}){sub 3}.

    SciTech Connect

    Zhang, Q.; Chung, I.; Jang, J. I.; Ketterson, J. B.; Kanatzidis, M. G.

    2009-07-06

    The new cation [Sb{sub 7}S{sub 8}Br{sub 2}]{sup 3+} has a double-cubane structure and forms as the [AlCl{sub 4}]{sup -} salt from the ionic liquid EMIMBr-AlCl{sub 3} (EMIM = 1-ethyl-3-methylimidazolium) at 165 C. The compound is noncentrosymmetric with space group P2{sub 1}2{sub 1}2{sub 1} and exhibits second-harmonic and difference-frequency nonlinear optical response across a wide range of the visible and near-infrared regions.

  5. Kinetics and product studies of the reaction ClO + BrO using flash photolysis-ultraviolet absorption

    NASA Technical Reports Server (NTRS)

    Sander, Stanley P.; Friedl, Randall R.

    1989-01-01

    The reaction between BrO and ClO was studied over the pressure range 50-700 torr and temperature range 220-400 K, using the flash photolysis-ultraviolet absorption method described by Watson et al. (1979). In order to investigate the mechanism of the BrO + ClO reaction, the product branch reactions Br + Cl2O yielding ClO + BrCl and Cl2O + h(nu) yielding products were examined. The rate constant for the overall reaction and the Arrhenius expression for the Br + Cl2O reaction are given, as well as the quantum yield for the production of atomic oxygen from the Cl2O photolysis.

  6. Crystal structures of hydrates of simple inorganic salts. III. Water-rich aluminium halide hydrates: AlCl3 · 15H2O, AlBr3 · 15H2O, AlI3 · 15H2O, AlI3 · 17H2O and AlBr3 · 9H2O.

    PubMed

    Schmidt, Horst; Hennings, Erik; Voigt, Wolfgang

    2014-09-01

    Water-rich aluminium halide hydrate structures are not known in the literature. The highest known water content per Al atom is nine for the perchlorate and fluoride. The nonahydrate of aluminium bromide, stable pentadecahydrates of aluminium chloride, bromide and iodide, and a metastable heptadecahydrate of the iodide have now been crystallized from low-temperature solutions. The structures of these hydrates were determined and are discussed in terms of the development of cation hydration spheres. The pentadecahydrate of the chloride and bromide are isostructural. In AlI(3) · 15H2O, half of the Al(3+) cations are surrounded by two complete hydration spheres, with six H2O in the primary and 12 in the secondary. For the heptadecahydrate of aluminium iodide, this hydration was found for every Al(3+). PMID:25186362

  7. Studies of ClO and BrO reactions important in the polar stratosphere: Kinetics and mechanism of the ClO+BrO and ClO+ClO reactions

    NASA Technical Reports Server (NTRS)

    Friedl, Randall R.; Sander, Stanley P.

    1988-01-01

    The reactions, BrO + ClO yields Br + ClOO (1a) yields Br + OClO (1b) yields BrCl + O2 (1c) and ClO + ClO yields Cl + CiOO (2a) yields Cl + OClO (2b) yields Cl2 + O2 (2c) yields (ClO)2 (2d) have assumed new importance in explaining the unusual springtime depletion of ozone observed in the Antarctic stratosphere. The mechanisms of these reactions involve the formation of metastable intermediates which subsequently decompose through several energetically allowed products providing the motivation to study these reactions using both the discharge flow-mass spectrometric and flash photolysis - ultraviolet absorption techniques. These methods have also been used to explore aspects of the kinetics and spectroscopy of the ClO dimer.

  8. Compositional superlattices based on PtCl/PtBr MX materials

    SciTech Connect

    Saxena, A.; Huang, X.Z.; Bishop, A.R.

    1992-01-01

    We consider theoretically a novel class of compositional superlattices consisting of alternating layers of quasi-one-dimensional (QlD) MX (halogen-bridged, transition metal) chain materials. In particular, we have studied a superlattice based on the PtCl/PtBr unit where the Peierls band gap for PtCl is [approximately]2.4 eV and [approximately]1.5 eV for PtBr. We have calculated electronic properties, optical absorption and vibrational properties (e.g. Raman spectrum) of an MX superlattice using a discrete, two-band, tight-binding Peierls-Hubbard model. The electronic band structure reveals a typical subband structure and varies with the relative lengths of the constituent PtCl and PtBr units. The MX superlattice can be thought of as an analog of a GaAs/GaAl[sub x]As[sub 1-x] compositional superlattice but with the added feature that the optical, transport and various other physical properties are modified due to presence of nonlinear excitations (e.g. polarons) in the doped samples.

  9. Br/Cl partitioning in chloride minerals in the Burns formation on Mars

    NASA Astrophysics Data System (ADS)

    Marion, G. M.; Catling, D. C.; Kargel, J. S.

    2009-04-01

    Within Gusev Crater and Meridiani Planum on Mars, the Mars exploration rovers have found Br concentrations in soils and rocks in the hundreds of ppm range. Relative to Earth compositions, these are high Br concentrations. Because of low Br concentrations on Earth, Br largely precipitates from seawater as a minor constituent in halite crystals rather than as a separate phase mineral. This is also likely to be the case for Mars. But given that the surface chemistries on Mars are significantly different than on Earth, minerals other than halite could serve as sinks for Br. The specific objectives of this paper were to (1) incorporate Br solution phase chemistries into the FREZCHEM model, (2) integrate the Siemann-Schramm Br/Cl mineral model into FREZCHEM, and (3) apply this mineral model to Br/Cl partitioning in Burns formation rocks as an indicator of past environments in the Meridiani Planum region of Mars. We showed that: (1) a molar-based model for Br substitution into halite and bischofite provided a better fit to experimental data than the standard mass-based model; (2) the concentrations of all of the soluble salts (mainly of Na, Mg, Ca, Cl, Br, and SO 4) in the Burns formation, except for Ca, were significantly related to stratigraphic depth; (3) the likely precipitation of Ca as gypsum on Mars precluded Ca precipitating as a CaCl 2 salt and thus impacts the possible minimum eutectic brine temperatures relevant to the Burns formation; (4) bischofite (MgCl 2ṡ6H 2O) was a much more important sink for Br than halite; (5) Br/Cl patterns in the Burns formation, and within the three formation layers, argued in support of salt upwelling through groundwater evaporation; and (6) the high concentrations of Br in the surface layers of the Burns formation suggested that there was little water leaching and removal of soluble phases from the upper part of the stratigraphic succession.

  10. Molecular dynamics simulations of Si etching in Cl- and Br-based plasmas: Cl{sup +} and Br{sup +} ion incidence in the presence of Cl and Br neutrals

    SciTech Connect

    Nakazaki, Nobuya Takao, Yoshinori; Eriguchi, Koji; Ono, Kouichi

    2015-12-21

    Classical molecular dynamics (MD) simulations have been performed for Cl{sup +} and Br{sup +} ions incident on Si(100) surfaces with Cl and Br neutrals, respectively, to gain a better understanding of the ion-enhanced surface reaction kinetics during Si etching in Cl- and Br-based plasmas. The ions were incident normally on surfaces with translational energies in the range E{sub i} = 20–500 eV, and low-energy neutrals of E{sub n} = 0.01 eV were also incident normally thereon with the neutral-to-ion flux ratio in the range Γ{sub n}{sup 0}/Γ{sub i}{sup 0} = 0–100, where an improved Stillinger--Weber potential form was employed for the interatomic potential concerned. The etch yields and thresholds presently simulated were in agreement with the experimental results previously reported for Si etching in Cl{sub 2} and Br{sub 2} plasmas as well as in Cl{sup +}, Cl{sub 2}{sup +}, and Br{sup +} beams, and the product stoichiometry simulated was consistent with that observed during Ar{sup +} beam incidence on Si in Cl{sub 2}. Moreover, the surface coverage of halogen atoms, halogenated layer thickness, surface stoichiometry, and depth profile of surface products simulated for Γ{sub n}{sup 0}/Γ{sub i}{sup 0} = 100 were in excellent agreement with the observations depending on E{sub i} reported for Si etching in Cl{sub 2} plasmas. The MD also indicated that the yield, coverage, and surface layer thickness are smaller in Si/Br than in Si/Cl system, while the percentage of higher halogenated species in product and surface stoichiometries is larger in Si/Br. The MD further indicated that in both systems, the translational energy distributions of products and halogen adsorbates desorbed from surfaces are approximated by two Maxwellians of temperature T{sub 1} ≈ 2500 K and T{sub 2} ≈ 7000–40 000 K. These energy distributions are discussed in terms of the desorption or evaporation from hot spots formed through chemically enhanced physical

  11. Al/Cl2 molten salt battery

    NASA Technical Reports Server (NTRS)

    Giner, J.

    1972-01-01

    Molten salt battery has been developed with theoretical energy density of 5.2 j/kg (650 W-h/lb). Battery, which operates at 150 C, can be used in primary mode or as rechargeable battery. Battery has aluminum anode and chlorine cathode. Electrolyte is mixture of AlCl3, NaCl, and some alkali metal halide such as KCl.

  12. Fractionation of Cl/Br during fluid phase separation in magmatic-hydrothermal fluids

    NASA Astrophysics Data System (ADS)

    Seo, Jung Hun; Zajacz, Zoltán

    2016-06-01

    Brine and vapor inclusions were synthesized to study Cl/Br fractionation during magmatic-hydrothermal fluid phase separation at 900 °C and pressures of 90, 120, and 150 MPa in Li/Na/K halide salt-H2O systems. Laser ablation ICP-MS microanalysis of high-density brine inclusions show an elevated Cl/Br ratio compared to the coexisting low-density vapor inclusions. The degree of Cl/Br fractionation between vapor and brine is significantly dependent on the identity of the alkali metal in the system: stronger vapor partitioning of Br occurs in the Li halide-H2O system compared to the systems of K and Na halide-H2O. The effect of the identity of alkali-metals in the system is stronger compared to the effect of vapor-brine density contrast. We infer that competition between alkali-halide and alkali-OH complexes in high-temperature fluids might cause the Cl/Br fractionation, consistent with the observed molar imbalances of alkali metals compared to halides in the analyzed brine inclusions. Our experiments show that the identity of alkali metals controls the degrees of Cl/Br fractionation between the separating aqueous fluid phases at 900 °C, and suggest that a significant variability in the Cl/Br ratios of magmatic fluids can arise in Li-rich systems.

  13. Origin of halides (Cl- and Br-) and of their stable isotopes (d37Cl and d81Br) at the Tournemire URL (France) - Experimental and numerical approach

    NASA Astrophysics Data System (ADS)

    Bachir-Bey, Nassim; Matray, Jean-Michel

    2014-05-01

    This work is part of research conducted by the Institute of Radiological and Nuclear Safety (IRSN) on the geological disposal of High-Level and Intermediate-Level Long-Lived (HL-ILLL) radioactive waste in deep clayrocks. In France, the choice of the potential host rock for the geological storage is focused on the Callovian-Oxfordian (COx) of Meuse/Haute-Marne from its low permeability, capacity for self- sealing, high sorption and ability to radionuclide (RN) transport by diffusion. IRSN, which plays an expert role for ASN has its own underground research laboratory in a clayrock which has strong analogies to the COx. This is the Toarcian/Domerian clayrock located at Tournemire in southern Aveyron in France. The purpose of this study was to assess the transfer of RN in the Tournemire clayrock through the study of halides contents and of their stable isotopes (Cl-, Br-, Cl-/Br-, d37Cl, d81Br). The approach used was multiple and consisted for halides to: 1) Assess their stock in different fractions of the rock by applying several techniques including i) alkaline fusion for their total stock, ii) leaching to access their stock in porewater and to mineral phases sensitive to dissolution iii) cubic diffusion for their stock in porewater, 2) Get their diffusive transport parameters of a selection of samples from the upper Toarcian by cubic diffusion experiments modelled using the Hytec transport code developed by Mines ParisTech and 3) Model their transport after palaeohydrogeological known changes of the Tournemire massif. The experimental approach, conducted at the LAME lab, did not lead to an operational protocol for the alkaline fusion due to an incomplete rock dissolution. Leaching was used to characterize the concentrations of halides in the fractions of pore water and of minerals sensitive to dissolution. The results show levels of halides much higher than those of pore water with very low Cl/Br ratios likely resulting from the dissolution of mineral species. The

  14. Geochemistry of the Halogens (I, Br, Cl) and Evolution of the Seawater During the Archean

    NASA Astrophysics Data System (ADS)

    Avice, G.; Marty, B.; Burgess, R.; Goldsmith, S. L.

    2015-12-01

    Halogens (I, Cl, Br) on Earth are depleted relative to the results of the condensation sequence of elements from the solar nebula [1]. The cause of this depletion remains unknown but might be related to loss from impacts or to the presence of an hidden reservoir (e.g. core). The presence of fluid inclusions in hydrothermal quartz of various ages is an opportunity to follow the evolution of the composition of the atmosphere (N, noble gases) through time [2] but also of halogens in seawater (their main reservoir). Such studies may help to constrain what is the origin of these volatile elements on Earth. For this purpose, we analysed quartz from hydrothermal veins and pods of various localities and ages (e.g. Barberton Greenstone Belt (South Africa; 3.2 Ga), Fortescue Group (Australia; 2.7 Ga)) by crushing and step-heating following the extended Ar-Ar method [3]. In Barberton and Fortescue Gp. quartz, a hydrothermal component characterized by excess 40Ar (40ArE) and closely associated with chlorine is clearly identified from crushing and step-heating results and permits to define a 40ArE/Cl used to correct Ar-Ar data for this contribution. In the case of Barberton, the correction for the hydrothermal component leads to an approximate formation age of the quartz of 3.2 (+/- 0.1) Ga. In Barberton quartz, halogens elemental ratios obtained during crushing and step-heating experiments are highly enriched in iodine and bromine (I/Cl=2-7x10-4; Br/Cl=4-10x10-3) relative to modern seawater. These results are similar to those found in a previous study of Barberton fluid inclusions [3] and can be interpreted as indicators that organic carbon was not sufficiently abundant at this time and/or this location to efficiently pump Br and I during sediment burial. Iodine and bromine, in Fortescue Gp. quartz, are less enriched suggesting that, in that case, organic activity already acted as pump for these elements. [1] Sharp & Draper (2013) EPSL, 369-370, p. 71-77 [2] Pujol et al. (2011

  15. Reaction cross sections and thermal rate constant for Cl(-) + CH3BrClCH3 + Br(-) from J-dependent quantum scattering calculations.

    PubMed

    Hennig, Carsten; Schmatz, Stefan

    2016-07-20

    Employing dimensionality-reduced time-independent quantum scattering theory and summation over all possible total angular momentum states, initial-state selected reaction cross sections for the exothermic gas-phase bimolecular nucleophilic substitution (SN2) reaction Cl(-) + CH3BrClCH3 + Br(-) have been calculated. The carbon-halogen bonds and the rotation of the methyl halides are taken into account. In agreement with previous calculations for J = 0, initial rotational motion of CH3Br decreases the reaction probability and consequently the cross sections. The experimentally obtained thermal rate constant for 300 K is reproduced within the experimental error. For lower temperatures, it is calculated to be below the experimental values but shows the same strong increase for T → 0. PMID:27381461

  16. Theoretical investigation of structural properties of CuCl, CuBr and CuI compounds under hydrostatic pressure

    SciTech Connect

    Louhibi-Fasla, S.; Djabri, H. Rekab; Achour, H.; Kefif, K.

    2013-12-16

    We have applied a recent version of the full potential linear muffin-tin orbitals method (FPLMTO) to study the structural properties of copper halides CuX (X=Cl, Br, I) under high pressure using the generalized gradient approximation (GGA) for the exchange and correlation potential by Perdew et al. Results are given for lattice parameters, bulk modulus and its first derivatives in the wurtzite(B4), zinc-blende (B3), CsCl (B2), rock-salt (B1), and PbO (B10) structures. The results of these calculations are compared with the available theoretical and experimental data.

  17. Br-Cl-Na systematics in Illinois basin fluids: Constraints on fluid origin and evolution

    SciTech Connect

    Walter, L.M.; Huston, T.J. ); Stueber, A.M. )

    1990-04-01

    The authors present here bromide, chloride, and sodium data for fluids from reservoirs of Ordovician through Pennsylvania age in the Illinois basic which suggest that remnant marine fluids contribute significantly to fluid Cl budgets. Cl/Br and NaBr ratios for Ordovician through Devonian formation fluids are relatively uniform and near those for seawater, despite greater than a factor of ten range in Cl concentration. In contrast, fluids from Mississippian and Pennsylvanian reservoirs, separated from older reservoirs by the New Albany Shale Group, have more variable fluid Cl/Br and Na/Br ratios, most of which are significantly greater then those of seawater. The 1:1 stoichiometry of Cl and Na increases for Mississippian and Pennsylvanian formation fluids is consistent with halite dissolution. Nevertheless, Br systematics and mass-balance considerations indicate that he overall Cl budget of Illinois basin formation fluids appears to be more significantly influenced by the contribution from subaerially evaporated seawater than by halite dissolution.

  18. Chalcogen- and halogen-bonds involving SX2 (X = F, Cl, and Br) with formaldehyde.

    PubMed

    Mo, Lixin; Zeng, Yanli; Li, Xiaoyan; Zhang, Xueying; Meng, Lingpeng

    2016-07-01

    The capacity of SX2 (X = F, Cl, and Br) to engage in different kinds of noncovalent bonds was investigated by ab initio calculations. SCl2 (SBr2) has two σ-holes upon extension of Cl (Br)-S bonds, and two σ-holes upon extension of S-Cl (Br) bonds. SF2 contains only two σ-holes upon extension of the F-S bond. Consequently, SCl2 and SBr2 form chalcogen and halogen bonds with the electron donor H2CO while SF2 forms only a chalcogen bond, i.e., no F···O halogen bond was found in the SF2:H2CO complex. The S···O chalcogen bond between SF2 and H2CO is the strongest, while the strongest halogen bond is Br···O between SBr2 and H2CO. The nature of these two types of noncovalent interaction was probed by a variety of methods, including molecular electrostatic potentials, QTAIM, energy decomposition, and electron density shift maps. Termolecular complexes X2S···H2CO···SX'2 (X = F, Cl, Br, and X' = Cl, Br) were constructed to study the interplay between chalcogen bonds and halogen bonds. All these complexes contained S···O and Cl (Br)···O bonds, with longer intermolecular distances, smaller values of electron density, and more positive three-body interaction energies, indicating negative cooperativity between the chalcogen bond and the halogen bond. In addition, for all complexes studied, interactions involving chalcogen bonds were more favorable than those involving halogen bonds. Graphical Abstract Molecular electrostatic potential and contour map of the Laplacian of the electron density in Cl2S···H2CO···SCl2 complex. PMID:27342252

  19. Kinetics and product studies of the reaction ClO + BrO using discharge-flow mass spectrometry

    NASA Technical Reports Server (NTRS)

    Friedl, Randall R.; Sander, Stanley P.

    1989-01-01

    The kinetics and product branching ratios of the reaction between ClO and BrO were studied at 1 torr pressure over the temperature range 220-400 K, using the method of discharge-flow mass spectrometry. Three product channels were identified and quantified: Br + ClOO, Br + OClO, and BrCl + O2, indicating that the reaction mechanism of ClO + BrO involves metastable intermediates. The overall reaction rate coefficient and the rate coefficients for the three channel reactions are given.

  20. Energetic Diagrams and Structural Properties of Monohaloacetylenes HC≡CX (X = F, Cl, Br).

    PubMed

    Khiri, D; Hochlaf, M; Chambaud, G

    2016-08-01

    Highly correlated electronic wave functions within the Multi Reference Configuration Interaction (MRCI) approach are used to study the stability and the formation processes of the monohaloacetylenes HCCX and monohalovinylidenes C2HX (X = F, Cl, Br) in their electronic ground state. These tetra-atomics can be formed through the reaction of triatomic fragments C2F, C2Cl, and C2Br with a hydrogen atom or of C2H with halogen atoms via barrierless reactions, whereas the reactions between the diatomics [C2 + HX] need to overcome barriers of 1.70, 0.89, and 0.58 eV for X = F, Cl, and Br. It is found that the linear HCCX isomers, in singlet symmetry, are more stable than the singlet C2HX iso-forms by 1.995, 2.083, and 1.958 eV for X = F, Cl, and Br. The very small isomerization barriers from iso to linear forms are calculated 0.067, 0.044, and 0.100 eV for F, Cl, and Br systems. The dissociation energies of the HCCX systems (without ZPE corrections), resulting from the breaking of the CX bond, are calculated to be 5.647, 4.691, and 4.129 eV for X = F, Cl, Br, respectively. At the equilibrium geometry of the X(1)Σ(+) state of HCCX, the vertical excitation energies in singlet and triplet symmetries are all larger than the respective dissociation energies. Stable excited states are found only as (3)A', (3)A″, and (1)A″ monohalovinylidene structures. PMID:27415415

  1. Four-dimensional quantum study on exothermic complex-forming reactions: Cl{sup -}+CH{sub 3}Br{yields}ClCH{sub 3}+Br{sup -}

    SciTech Connect

    Hennig, Carsten; Schmatz, Stefan

    2005-06-15

    The exothermic gas-phase bimolecular nucleophilic substitution (S{sub N}2) reaction Cl{sup -}+CH{sub 3}Br ({upsilon}{sub 1}{sup '},{upsilon}{sub 2}{sup '},{upsilon}{sub 3}{sup '}){yields}ClCH{sub 3} ({upsilon}{sub 1},{upsilon}{sub 2},{upsilon}{sub 3})+Br{sup -} and the corresponding endothermic reverse reaction have been studied by time-independent quantum scattering calculations in hyperspherical coordinates on a coupled-cluster potential-energy surface. The dimensionality-reduced model takes four degrees of freedom into account [Cl-C and C-Br stretching modes (quantum numbers {upsilon}{sub 3}{sup '} and {upsilon}{sub 3}); totally symmetric modes of the methyl group, i.e., C-H stretching ({upsilon}{sub 1}{sup '} and {upsilon}{sub 1}) and umbrella bending vibrations ({upsilon}{sub 2}{sup '} and {upsilon}{sub 2})]. Diagonalization of the Hamiltonian was performed employing the Lanczos algorithm with a variation of partial reorthogonalization. A narrow grid in the total energy was employed so that long-living resonance states could be resolved and extracted. While excitation of the reactant umbrella bending mode already leads to a considerable enhancement of the reaction probability, its combination with vibrational excitation of the broken C-Br bond, (0, 1, 1), results in a strong synergic effect that can be rationalized by the similarity with the classical transitional normal mode. Exciting the C-H stretch has a non-negligible effect on the reaction probability, while for larger translational energies this mode follows the expected spectatorlike behavior. Combination of C-Br stretch and symmetric C-H, (1,0,1), stretch does not show a cooperative effect. Contrary to the spectator mode concept, energy originally stored in the C-H stretching mode is by no means conserved, but almost completely released in other modes of the reaction products. Products are most likely formed in states with a high degree of excitation in the new C-Cl bond, while the internal modes of

  2. Long-term CH3Br and CH3Cl flux measurements in temperate salt marshes

    NASA Astrophysics Data System (ADS)

    Blei, E.; Heal, M. R.; Heal, K. V.

    2010-08-01

    Fluxes of CH3Br and CH3Cl and their relationship with potential drivers such as sunlight, temperature and soil moisture, were monitored at fortnightly to monthly intervals for more than two years at two contrasting temperate salt marsh sites in Scotland. Manipulation experiments were conducted to further investigate possible links between drivers and fluxes. Mean (± 1 sd) annually and diurnally-weighted net emissions from the two sites were found to be 300 ± 44 ng m-2 h-1 for CH3Br and 662 ± 266 ng m-2 h-1 for CH3Cl. A tentative scale-up indicates that salt marshes account for 0.5-3.2% and 0.05-0.33%, respectively, of currently-estimated total global production of these two gases, in line with previous findings from this and other research groups, but consistently lower than past global scale-up estimates from Southern Californian salt marshes. Fluxes followed both seasonal and diurnal trends with highest fluxes during summer days and lowest (negative) fluxes during winter nights. Statistical analysis generally did not demonstrate a strong link between temperature or sunlight levels and methyl halide fluxes, although it is likely that temperatures have a weak direct influence on emissions, and both certainly have indirect influence via the annual and daily cycles of the vegetation. CH3Cl flux magnitudes from different measurement locations depended on the plant species enclosed whereas such dependency was not discernible for CH3Br fluxes. In 14 out of 19 collars CH3Br and CH3Cl net fluxes were significantly correlated. The CH3Cl/CH3Br net-emission mass ratio was 2.2, a magnitude lower than mass ratios of global methyl halide budgets (~22) or emissions from tropical rainforests (~60). This is likely due to preference for CH3Br production by the relatively high bromine content in the salt marsh plant material.

  3. Rechargeable Al/Cl2 battery with molten AlCl4/-/ electrolyte.

    NASA Technical Reports Server (NTRS)

    Holleck, G. L.; Giner, J.; Burrows, B.

    1972-01-01

    A molten salt system based on Al- and Cl2 carbon electrodes, with an AlCl3 alkali chloride eutectic as electrolyte, offers promise as a rechargeable, high energy density battery which can operate at a relatively low temperature. Electrode kinetic studies showed that the electrode reactions at the Al anode were rapid and that the observed passivation phenomena were due to the formation at the electrode surface of a solid salt layer resulting from concentration changes on anodic or cathodic current flow. It was established that carbon electrodes were intrinsically active for chlorine reduction in AlCl3-alkali chloride melts. By means of a rotating vitreous carbon disk electrode, the kinetic parameters were determined.

  4. Radiative forcing calculations for CH{sub 3}Cl and CH{sub 3}Br

    SciTech Connect

    Grossman, A.S.; Grant, K.E.; Blass, W.E.; Wuebbles, D.J.

    1997-06-01

    Methyl chloride, CH{sub 3}Cl, and methyl bromide, CH{sub 3}Br, are particularly important in the global atmosphere as major natural sources of chlorine and bromine to the stratosphere. The production of these gases is dominated by natural sources, but smaller, important anthropogenic sources, such as agricultural fumigation and/or biomass burning, also exist. As absorbers of infrared radiation these gases are of interest for their potential effect on the tropospheric energy balance as well as for chemical interactions. In this study we estimate the radiative forcing and Global Warming Potentials (GWPs) of CH{sub 3}Cl and CH{sub 3}Br. Our calculations use an infrared radiative transfer model based on the correlated k-distribution algorithm for band absorption. Radiative forcing values of 0.0047W/m{sup 2} per part per billion by volume (ppbv) for CH{sub 3}Cl in the troposphere and 0.0049W/m{sup 2} per ppbv for CH{sub 3}Br in the troposphere were obtained. On a per molecule basis the radiative forcing values are about 2{percent} of the forcing of CFC-11 and about 270 times the forcing of CO{sub 2}. GWPs for these gases are about 8 for CH{sub 3}Cl and about 4 for CH{sub 3}Br (100 year time integration, CO{sub 2}=1). These results indicate that while CH{sub 3}Cl and CH{sub 3}Br have direct GWPs similar to that of CH{sub 4}, the current emission rates are too low to contribute meaningfully to atmospheric greenhouse heating effects.{copyright} 1997 American Geophysical Union

  5. Long-term CH3Br and CH3Cl flux measurements in temperate salt marshes

    NASA Astrophysics Data System (ADS)

    Blei, E.; Heal, M. R.; Heal, K. V.

    2010-11-01

    Fluxes of CH3Br and CH3Cl and their relationship with potential drivers such as sunlight, temperature and soil moisture, were monitored at fortnightly to monthly intervals for more than two years at two contrasting temperate salt marsh sites in Scotland. Manipulation experiments were conducted to further investigate possible links between drivers and fluxes. Fluxes followed both seasonal and diurnal trends with highest fluxes during summer days and lowest (negative) fluxes during winter nights. Mean (± 1 sd) annually and diurnally-weighted net emissions from the two sites were found to be 300 ± 44 ng m-2 h-1 for CH3Br and 662 ± 266 ng m-2 h-1 for CH3Cl. The fluxes from this work are similar to findings from this and other research groups for salt marshes in cooler, higher latitude climates, but lower than values from salt marshes in the Mediterranean climate of southern California. Statistical analysis generally did not demonstrate a strong link between temperature or sunlight levels and methyl halide fluxes, although it is likely that temperatures have a weak direct influence on emissions, and both certainly have indirect influence via the annual and daily cycles of the vegetation. CH3Cl flux magnitudes from different measurement locations depended on the plant species enclosed whereas such dependency was not discernible for CH3Br fluxes. In 14 out of 18 collars with vegetation CH3Br and CH3Cl net fluxes were significantly positively correlated. The CH3Cl/CH3Br net-emission mass ratio was 2.2, a magnitude lower than mass ratios of global methyl halide budgets (~22) or emissions from tropical rainforests (~60). This is likely due to preference for CH3Br production by the relatively high bromine content in the salt marsh plant material. Extrapolation based solely on data from this study yields salt marsh contributions of 0.5-3.2% and 0.05-0.33%, respectively, of currently-estimated total global production of CH3Br and CH3Cl, but actual global contributions likely

  6. Observations of Cl2, Br2, and I2 in coastal marine air

    NASA Astrophysics Data System (ADS)

    Finley, B. D.; Saltzman, E. S.

    2008-11-01

    Cl2, Br2, and I2 were measured in coastal Pacific air from 2 to 29 January 2006. Air was sampled at 10 m over the sea surface near the end of Scripps Pier (La Jolla, California). The measurements were made using atmospheric pressure chemical ionization with tandem mass spectrometry (APCI/MS/MS). Over the course of this study, Cl2, Br2, and I2 levels ranged from below detection limits of 1.0, 0.5, and 0.2 ppt, respectively, to maxima of 26, 19, and 8 ppt, respectively. Mean dihalogen levels for the study period were 2.3 ± 1 ppt for Cl2, 2.3 ± 0.4 ppt for Br2, and 0.7 ± 0.1 ppt for I2 (expressed as geometric mean ±1 geometric standard error). The mixed dihalogens BrCl, ICl, and IBr had geometric mean levels below 0.3 ± 1 ppt and never exceeded their detection limits of 0.5 ppt. Consistent patterns of diurnal variability were observed for Cl2 and I2, with Cl2 maxima during daytime and I2 appearing almost exclusively at night. The detection of I2 appeared to be related to the passage of air over nearby kelp beds. The observed dihalogen levels suggest that (1) chlorine atom oxidation of hydrocarbons makes a significant contribution to the formation of ozone and (2) halogen atom oxidation of airborne mercury contributes to mercury deposition in polluted coastal air.

  7. REACTION AND DEACTIVATION OF HCl (v = 1, 2) BY Cl, Br, AND H ATOMS

    SciTech Connect

    Macdonald, R.G.; Moore, C.Bradley

    1980-02-01

    Total decay rates for HCl(v = 2, 1) were measured in the range 294 - 439 K for Cl, 295 - 390 K for Br, and at 296 K for H. HCl(v = 2) was produced directly by pulsed laser excitation of the overtone. The fraction of HCl(v = 2) relaxed to HCl(v = 1) was determined. For HCl(v = 2) + Cl, relaxation gave entirely HCl(v = 1) within an experimental uncertainty of ± 10%, the total relaxation rate was large, k/v = 5 {Angstrom}{sup 2} , and rates varied only slightly with temperature. For Br + HCl(v = 2) reaction to HBr(v = 0) + Cl is exoergic by about kT. Relaxation to HCl(v = 1) is the dominant process. Reaction contributes roughly 17% and 34% to the loss of HCl(v = 2) at 295 and 390 K, respectively. In constrast to the result for Br and for O (reported previously) H + HCl(v = 2) gives 65% H{sub 2} + Cl and only 35% HCl(v = 1) +H. For HCl(v = 1) + H Cl, O the vibrational excitation energy is greater than the activation energy for reaction. The relaxation rates are between 1/2 and 1/3 of the A values for the measured thermal exchange rates Aexp(-{Delta}E{sub act}/RT). For HCl(v = 1) + Br, well below threshold, the rate is some 20 times less than for HCl(v = 1) + Cl. The rate for HCl(v = 2) + Br, just above reaction threshold is not dramatically larger. The ratios of vibrational relaxation rates for HCl(v = 2) vs HCl(v = 1) are 5.0 ± 1.3, 4.2 ± 0.4, and 5.0 ± 1.3 for O, Cl, and Br, respectively. Any first order linear perturbation treatment gives rates proportional to v; the data scale more closely as v{sup 2}.

  8. Kinetics and products of the BrO + ClO reaction

    SciTech Connect

    Poulet, G.; Lancar, I.T.; Laverdet, G.; Le Bras, G. )

    1990-01-11

    The overall rate constant of the BrO + ClO reaction has been measured by the discharge flow mass spectrometry method. The value found at 298 K is k{sub 1} = (1.13 {plus minus} 0.15) {times} 10{sup {minus}11} cm{sup 3} molecule{sup {minus}1} s{sup {minus}1}. Branching ratios for two of the three reaction channels were determined from the direct measurements of OClO and BrCl and were found to be (0.43 {plus minus} 0.10) and (0.12 {plus minus} 0.05), respectively. These results are compared with recent literature data and their implication for the polar ozone stratospheric chemistry is discussed.

  9. Kinetics of the BrO + ClO reaction and implications for stratospheric ozone

    NASA Technical Reports Server (NTRS)

    Hills, Alan J.; Cicerone, Ralph J.; Calvert, Jack G.; Birks, John W.

    1987-01-01

    The first direct measurements of the rate constant and product distribution of the BrO + ClO reaction as a function of temperature is reported. It is shown that this reaction could account for a large fraction of the springtime ozone depletion over Antarctica and provide a source of chlorine dioxide of sufficient magnitude to explain the recent measurements of this species in the Antarctic atmosphere, provided that the stratosphere contains a sufficient quantity of bromine.

  10. Mutual neutralization of He+ with the anions Cl-, Br-, I-, and SF6-

    NASA Astrophysics Data System (ADS)

    Wiens, Justin P.; Shuman, Nicholas S.; Miller, Thomas M.; Viggiano, Albert A.

    2016-05-01

    Mutual neutralization (MN) rate coefficients kMN for He+ with the anions Cl-, Br-, I-, and SF6- are reported from 300 to 500 K. The measured rate coefficients may contain a contribution from transfer ionization, i.e., double ionization of the anion. The large rate coefficient for He+ + SF6- (2.4 × 10-7 cm3 s-1 at 300 K) is consistent with earlier polyatomic MN results found to have a reduced mass dependence of μ-1/2. Neutralization of He+ by the atomic halides follows the trend observed earlier for Ne+, Ar+, Kr+, and Xe+ neutralized by atomic halides, kMN (Cl-) < kMN (Br-) < kMN (I-). Only an upper limit could be measured for the neutralization of He+ by Cl-. Predictions of the rate coefficients from a previously proposed simple model of atomic-atomic MN results are consistent with the present He+-halide rate coefficients. The temperature dependences are modestly negative for Br- and I-, while that for SF6- is small or negligible.

  11. Corrosion of type 316 stainless steel in molten LiF-LiCl-LiBr

    SciTech Connect

    Tortorelli, P.F.; DeVan, J.H.; Keiser, J.R.

    1981-01-01

    The properties of LiF-LiCl-LiBr salt make it attractive as a solvent for extracting tritium from a fusion reactor lithium blanket. Consequently, the corrosion of type 316 stainless steel by flowing (about 15 mm/s) LiF-LiCl-LiBr at a maximum temperature of 535/sup 0/C was studied to determine whether compatibility with the structural material would be limiting in such a system. The corrosion rate was found to be low (<2 ..mu..m/year) except immediately after the addition of a small amount of lithium metal to the salt. The lithium addition increased the corrosion rate to approx. 13.5 ..mu..m/year at 535/sup 0/C (approximately that of type 316 stainless steel exposed to lithium flowing at a similar velocity). At the proposed operating temperature (less than or equal to approx. 535/sup 0/C), however, it appears that type 316 stainless steel has acceptable compatibility with the tritium-processing salt LiF-LiCl-LiBr for use with a lithium blanket.

  12. Electronic properties of PbCl2 and PbBr2 using Compton scattering technique.

    PubMed

    Ahmed, G; Sharma, Y; Ahuja, B L

    2009-06-01

    We present the electron momentum densities of PbCl(2) and PbBr(2) using 661.65 keV gamma-rays from 20 Ci (137)Cs source. To supplement our experimental investigations, we also report energy bands, density of states, Mulliken's population and Compton profiles of PbCl(2) and PbBr(2) using linear combination of atomic orbitals within Hartree-Fock and density functional theories. The energy bands are also computed employing full potential linearized augmented plane wave (FP-LAPW) method. Compton profiles are also analyzed in terms of equal-valence-electron-density scale. It shows that PbCl(2) is more covalent than PbBr(2), which is in agreement with the Mulliken's population analysis. It is seen that the Hartree-Fock and density functional theory based Compton line shapes show similar type of deviations from the experimental data. The luminescence properties of these halides are explained on the basis of energy band and density of states. PMID:19269187

  13. Mutual neutralization of He(+) with the anions Cl(-), Br(-), I(-), and SF6 (.).

    PubMed

    Wiens, Justin P; Shuman, Nicholas S; Miller, Thomas M; Viggiano, Albert A

    2016-05-28

    Mutual neutralization (MN) rate coefficients kMN for He(+) with the anions Cl(-), Br(-), I(-), and SF6 (-) are reported from 300 to 500 K. The measured rate coefficients may contain a contribution from transfer ionization, i.e., double ionization of the anion. The large rate coefficient for He(+) + SF6 (-) (2.4 × 10(-7) cm(3) s(-1) at 300 K) is consistent with earlier polyatomic MN results found to have a reduced mass dependence of μ(-1/2). Neutralization of He(+) by the atomic halides follows the trend observed earlier for Ne(+), Ar(+), Kr(+), and Xe(+) neutralized by atomic halides, kMN (Cl(-)) < kMN (Br(-)) < kMN (I(-)). Only an upper limit could be measured for the neutralization of He(+) by Cl(-). Predictions of the rate coefficients from a previously proposed simple model of atomic-atomic MN results are consistent with the present He(+)-halide rate coefficients. The temperature dependences are modestly negative for Br(-) and I(-), while that for SF6 (-) is small or negligible. PMID:27250308

  14. Laser cooling of MgCl and MgBr in theoretical approach

    SciTech Connect

    Wan, Mingjie; Shao, Juxiang; Huang, Duohui; Yang, Junsheng; Cao, Qilong; Jin, Chengguo; Wang, Fanhou; Gao, Yufeng

    2015-07-14

    Ab initio calculations for three low-lying electronic states (X{sup 2}Σ{sup +}, A{sup 2}Π, and 2{sup 2}Π) of MgCl and MgBr molecules, including spin-orbit coupling, are performed using multi-reference configuration interaction plus Davidson correction method. The calculations involve all-electronic basis sets and Douglas–Kroll scalar relativistic correction. Spectroscopic parameters well agree with available theoretical and experimental data. Highly diagonally distributed Franck-Condon factors f{sub 00} for A{sup 2}Π{sub 3/2,1/2} (υ′ = 0) → X{sup 2}Σ{sup +}{sub 1/2} (υ″ = 0) are determined for both MgCl and MgBr molecules. Suitable radiative lifetimes τ of A{sup 2}Π{sub 3/2,1/2} (υ′ = 0) states for rapid laser cooling are also obtained. The proposed laser drives A{sup 2}Π{sub 3/2} (υ′ = 0) → X{sup 2}Σ{sup +}{sub 1/2} (υ″ = 0) transition by using three wavelengths (main pump laser λ{sub 00}; two repumping lasers λ{sub 10} and λ{sub 21}). These results indicate the probability of laser cooling MgCl and MgBr molecules.

  15. Structure of equimolar LiCl-AlCl3 melt by neutron scattering

    NASA Astrophysics Data System (ADS)

    Biggin, S.; Cummings, S.; Enderby, J. E.; Blander, M.

    The structure of LiAlCl4 has been investigated by neutron diffraction of isotopically enriched samples. The lithium contribution to the scattering has been removed by using a null scattering sample, of Li-6 and Li-7. We have derived three partial structure factors S/sub AlAl/(k), S/sub ClCl/(k) and S/sub AlCl/(k) and their Fourier transforms, the partial radial distribution functions (rdf's), g/sub ij/(r). The first peaks in g/sub AlAl/(r), g/sub ClCl/(r) and g/sub AlCl/(r) are at 5.6, 3.51, and 2.13 A, respectively. The coordination numbers obtained by integrating to the first minima are about 6, 6, and 4, respectively. As anticipated, the existence of extremely well defined AlCl4(-) tetrahedra has been established, with little if any Al-Cl-Al bridging between tetrahedra in this melt. The results are similar to those predicted from molecular dynamical calculations on model systems.

  16. First-principles thermochemistry for the combustion of a TiCl4 and AlCl3 mixture.

    PubMed

    Shirley, Raphael; Liu, Yaoyao; Totton, Tim S; West, Richard H; Kraft, Markus

    2009-12-10

    AlCl(3) is added in small quantities to TiCl(4) fed to industrial reactors during the combustion synthesis of titanium dioxide nanoparticles in order to promote the rutile crystal phase. Despite the importance of this process, a detailed mechanism including AlCl(3) is still not available. This work presents the thermochemistry of many of the intermediates in the early stages of the mechanism, computed using quantum chemistry. The enthalpies of formation and thermochemical data for AlCl, AlO, AlOCl, AlOCl(2), AlO(2), AlO(2)Cl, AlOCl(3), AlO(2)Cl(2), AlO(3)ClTi, AlO(2)Cl(2)Ti, AlO(2)Cl(4)Ti, AlOCl(5)Ti, AlO(2)Cl(3)Tia (isomer-a), AlO(3)Cl(2)Ti, AlO(2)Cl(5)Ti, AlOCl(4)Ti, AlO(2)Cl(3)Tib (isomer-b), AlCl(7)Ti, AlCl(6)Ti, Al(2)Cl(6), Al(2)O(2)Cl, Al(2)O(2)Cl(3), Al(2)O(3)Cl(2), Al(2)O(2)Cl(2), Al(2)OCl(4), Al(2)O(3), and Al(2)OCl(3) were calculated using density functional theory (DFT). A full comparison between a number of methods is made for one of the important species, AlOCl, to validate the use of DFT and gauge the magnitude of errors involved with this method. Finally, equilibrium calculations are performed to try to identify which intermediates are likely to be most prevalent in the high temperature industrial process and as a first attempt to characterize the nucleation process. PMID:19888740

  17. Kinetics and product studies of the BrO + ClO reaction - Implications for Antarctic chemistry

    NASA Technical Reports Server (NTRS)

    Sander, Stanley P.; Friedl, Randall R.

    1988-01-01

    Discharge flow-mass spectrometry and flash photolysis-UV spectrometry were used to investigate the reaction of ClO with BrO over the temperature range of 220-400 K and the pressure range of 1-760 Torr. Rate constants were determined for: (1) Br + ClOO, (2) Br + OClO, and (3) BrCl + O2. It is found that the rate constants for the overall reaction and each reaction branch are inversely dependent on temperature and independent of pressure. For temperatures found in the Antarctic stratosphere, the rate coefficients for the channels yielding ClOO and OClO are a factor of 2-3 larger than previously estimated.

  18. Investigating the properties of infrared PCFs based on AgCl-AgBr, AgBr-TlI, AgCl-AgBr-AgI(TlI) crystals theoretically and experimentally

    NASA Astrophysics Data System (ADS)

    Korsakov, A. S.; Zhukova, L. V.; Vrublevsky, D. S.; Korsakova, E. A.

    2014-12-01

    For operating at the CO2 laser wavelength (10.6 μm), we manufactured single- and double-layered infrared (IR) fibers, as well as those with an enlarged mode field diameter, obtained via extrusion from Ag(Cl) x Br1 - x (0 < x < 1), Ag1 - x Tl x Br1 - x I x (0 < x ≤ 0.08), Ag1 - x Tl x Cl y I z Br1 - y - z (0.003 ≤ x ≤ 0.040; 0.066 ≤ y ≤ 0.246; 0.004 ≤ z ≤ 0.048) crystals. We calculated their fundamental characteristics at 10.6 μm and conducted computer simulation of their structure and mode field beforehand. Optical and mechanical characteristics of IR crystals and fibers, such as transmission range, refractive indices, and durability, were also determined, with the dependence of varying monadic thallium iodide content on them being shown as well. In particular, we demonstrated that the increase of thallium iodide content in the initial silver chloride bromide widens the transparency range to 40 μm and improves the rupture strength up to 200 MPa, which is due to the decrease in average fiber grain size up to 95 nm—nanocrystalline size. Using a CCD camera for the far field investigation at 10.6 μm, we showed the single mode of the fibers obtained.

  19. Airborne Instruments for the In Situ Detection of ClONO2, NO2, ClO, and BrO in the Stratosphere

    NASA Technical Reports Server (NTRS)

    Anderson, James G.

    1999-01-01

    The objective of the research supported by this grant was the development of a new instrument to both further the technology of small, lightweight instruments for robotic aircraft and to achieve the ability to detect ClONO2, NO2, ClO and BrO from the NASA ER-2 aircraft. All of these objectives were accomplished.

  20. Specific oxidation pattern of soluble starch with TEMPO-NaBr-NaClO system.

    PubMed

    Hao, Jie; Lu, Jiaojiao; Xu, Naiyu; Linhardt, Robert J; Zhang, Zhenqing

    2016-08-01

    Oxidized starch, one of the most important starch derivatives, has many different properties and applications. Currently, there are two ways to produce oxidized starch, through specific and nonspecific oxidation. Specific oxidation using the stable nitroxyl radical, 2,2,6,6-tetramethyl preparidinloxy (TEMPO), with NaBr and NaClO can produce oxidized starches with different properties under good quality control. In the current study, we examine the products of specifically oxidized starch. As the amount of oxidant and the temperature, two critical factors impacting the oxidation of starch were thoroughly investigated. Analysis of the molecular weight (MW), degree of oxidization (DO) and the detailed structures of corresponding products was accomplished using gel permeation chromatography with multi-angle laser light scattering (GPC-MALLS), infrared (IR) spectroscopy, nuclear magnetic resonance (NMR) spectroscopy, and quadrapole time-of-flight mass spectrometry (Q/TOF-MS). According to the analytical results, the oxidation patterns of starch treated with specific oxidant TEMPO-NaBr-NaClO were established. When high amounts of oxidant was applied, more glucose residues within starch were oxidized to glucuronic acids (higher DO) and substantial degradation to starch oligosaccharides was observed. By selecting a reaction temperature of 25°C a high DO could be obtained for a given amount of oxidant. The reducing end sugar residue within oxidized starch was itself oxidized and ring opened in all TEMPO-NaBr-NaClO reactions. Furthermore, extra oxidant generated additional novel structures in the reducing end residues of some products, particularly in low temperature reactions. PMID:27112871

  1. Structure and bonding of [(SIPr)AgX] (X = Cl, Br, I and OTf).

    PubMed

    Wong, Valerie H L; White, Andrew J P; Hor, T S Andy; Hii, King Kuok Mimi

    2015-12-28

    A series of iso-structural complexes [(SIPr)AgX] (X = Cl, Br, I, OTf; SIPr = 1,3-bis(2,6-diisopropylphenyl)imidazolidene) were synthesised, including the first example of a N-heterocyclic carbene silver(I) complex containing an O-bound triflate. Bond Energy Dissociation and Natural Orbitals for Chemical Valence bond analyses (BEDA & ETS-NOCV) revealing a significant NHC → M σ-back-donation, which influences the stability and sigma-donicity of these complexes. PMID:26489888

  2. The matrix-isolated molecular complexes CO/XF (X=Cl,Br,I) and the molecular structure of FC(O)Br

    SciTech Connect

    Garcia, Placido; Willner, Helge; Oberhammer, Heinz; Francisco, Joseph S.

    2004-12-15

    FC(O)Br has been synthesized, and its IR spectrum in the gas phase and isolated in an Ar matrix, as well as, its Raman spectrum in the solid state at -196 deg. C has been analyzed. Its molecular structure has been determined and its UV has been measured. FC(O)Br and FC(O)Cl has been photodissociated in an argon matrix at 17 K with a 193 nm laser. The photolysis produces CO and XF which recombine to form CO/XF complexes. The formation of complexes are followed by the shift of the normal vibration modes with respect to CO and XF isolated in argon matrix. In the case of FC(O)Br, three isomers are identified, OC{center_dot}{center_dot}{center_dot}BrF, OC{center_dot}{center_dot}{center_dot}FBr, and CO{center_dot}{center_dot}{center_dot}BrF, whereas for FC(O)Cl only one isomer is observed, OC{center_dot}{center_dot}{center_dot}ClF. High level quantum chemical calculations are used to help the assignment of the different isomers.

  3. Temperature dependence of the rate constant and product channels for the BrO + ClO reaction

    SciTech Connect

    Hills, A.J.; Cicerone, R.J.; Calvert, J.G.; Birks, J.W.

    1988-04-07

    The authors have measured the rate constant for the reactions BrO + ClO ..-->.. Br + OClO (6a), BrO + ClO ..-->.. Br + Cl + O/sub 2/ (6b), and BrO + ClO ..-->.. BrCl + O/sub 2/ (6c) over the temperature range 241-408 K and found k/sub 6/ = (8.2 +/- 1.0) x 10/sup -12/ cm/sup 3/ molecule/sup -1/ s/sup -1/ independent of temperature. Measurement of the individual product branching ratios yielded values for channels 6a, 6b, and 6c equal to 0.55 +/- 0.10, 0.45 +/- 0.10, and < 0.02, respectively. Measurements of ozone in the stratosphere over Antarctica have shown that the springtime ozone column has fallen 40% from 1960 to 1985. The reaction above could account for a large fraction of the springtime ozone hole reported recently, provided that at least 20 ppt of total inorganic bromine is present, and it may provide a source of chlorine dioxide of sufficient magnitude to explain the recent measurements of this species in the Antarctica stratosphere.

  4. The Electrochemical Co-reduction of Mg-Al-Y Alloys in the LiCl-NaCl-MgCl2-AlF3-YCl3 Melts

    NASA Astrophysics Data System (ADS)

    Li, Mei; Liu, Yaochen; Han, Wei; Wang, Shanshan; Zhang, Milin; Yan, Yongde; Shi, Weiqun

    2015-04-01

    The electrochemical formation of Mg-Al-Y alloys was studied in the LiCl-NaCl-MgCl2 melts by the addition of AlF3 and YCl3 on a molybdenum electrode at 973 K (700 °C). In order to reduce the volatilization of salt solvent in the electrolysis process, the volatile loss of LiCl-NaCl-MgCl2 and LiCl-KCl-MgCl2 melts was first measured in the temperature range from 873 K to 1023 K (600 °C to 750 °C). Then, the electrochemical behaviors of Mg(II), Al(III), Y(III) ions and alloy formation processes were investigated by cyclic voltammetry, chronopotentiometry, and open circuit chronopotentiometry. The cyclic voltammograms indicate that the under-potential deposition of magnesium and yttrium on pre-deposited Al leads to formation of Mg-Al and Al-Y intermetallic compounds. The Mg-Al-Y alloys were prepared by galvanostatic electrolysis in the LiCl-NaCl-MgCl2-AlF3-YCl3 melts and characterized by X-ray diffraction and scanning electron microscopy with energy dispersive spectrometry. Composition of the alloys was analyzed by inductively coupled plasma-atomic emission spectrometer, and current efficiency was also determined by the alloy composition.

  5. Speciation in the AlCl3/SO2Cl2 catholyte system.

    SciTech Connect

    Boyle, Timothy J.; Ingersoll, David T.; Tallant, David Robert; Andrews, Nicholas L.; Rodriguez, Mark Andrew; Alam, Todd Michael

    2005-02-01

    The fundamental chemical behavior of the AlCl{sub 3}/SO{sub 2}Cl{sub 2} catholyte system was investigated using {sup 27}Al NMR spectroscopy, Raman spectroscopy, and single-crystal X-ray diffraction. Three major Al-containing species were found to be present in this catholyte system, where the ratio of each was dependent upon aging time, concentration, and/or storage temperature. The first species was identified as [Cl{sub 2}Al({mu}-Cl)]{sub 2} in equilibrium with AlCl{sub 3}. The second species results from the decomposition of SO{sub 2}Cl{sub 2} which forms Cl{sub 2}(g) and SO{sub 2}(g). The SO{sub 2}(g) is readily consumed in the presence of AlCl{sub 3} to form the crystallographically characterized species [Cl{sub 2}Al({mu}-O{sub 2}SCl)]{sub 2} (1). For 1, each Al is tetrahedrally (T{sub d}) bound by two terminal Cl and two {mu}-O ligands whereas, the S is three-coordinated by two {mu}-O ligands and one terminal Cl. The third molecular species also has T{sub d}-coordinated Al metal centers but with increased oxygen coordination. Over time it was noted that a precipitate formed from the catholyte solutions. Raman spectroscopic studies show that this gel or precipitate has a component that was consistent with thionyl chloride. We have proposed a polymerization scheme that accounts for the precipitate formation. Further NMR studies indicate that the precipitate is in equilibrium with the solution.

  6. Electronic structures and geometries of the XF{sub 3} (X = Cl, Br, I, At) fluorides

    SciTech Connect

    Sergentu, Dumitru-Claudiu; Amaouch, Mohamed; Pilmé, Julien; Galland, Nicolas; Maurice, Rémi

    2015-09-21

    The potential energy surfaces of the group 17 XF{sub 3} (X = Cl, Br, I, At) fluorides have been investigated for the first time with multiconfigurational wave function theory approaches. In agreement with experiment, bent T-shaped C{sub 2v} structures are computed for ClF{sub 3}, BrF{sub 3}, and IF{sub 3}, while we predict that an average D{sub 3h} structure would be experimentally observed for AtF{sub 3}. Electron correlation and scalar relativistic effects strongly reduce the energy difference between the D{sub 3h} geometry and the C{sub 2v} one, along the XF{sub 3} series, and in the X = At case, spin-orbit coupling also slightly reduces this energy difference. AtF{sub 3} is a borderline system where the D{sub 3h} structure becomes a minimum, i.e., the pseudo-Jahn-Teller effect is inhibited since electron correlation and scalar-relativistic effects create small energy barriers leading to the global C{sub 2v} minima, although both types of effects interfere.

  7. Halide coordination of perhalocyclohexasilane Si6X12 (X=Cl or Br).

    PubMed

    Dai, Xuliang; Choi, Seok-Bong; Braun, Christopher W; Vaidya, Pooja; Kilina, Svetlana; Ugrinov, Angel; Schulz, Douglas L; Boudjouk, Philip

    2011-05-01

    The addition of halide anions (X' = Cl(-), Br(-), or I(-)) to perhalocyclohexasilane Si(6)X(12) (X = Cl or Br) led to the formation of complexes comprising [Si(6)X(12)X'(2)](2-) dianions. An upfield shift in the (29)Si NMR spectra was noted upon coordination, and structural determination by X-ray crystallography showed that the dianions adopt an "inverse sandwich" structure where the six cyclic silicon atoms form a planar hexagon with the two halide anions X' located on the 6-fold axis equally disposed above and below the plane of the Si(6) ring. Additionally, these apical X' atoms are within the van der Waals bonding distance to the silicon ring atoms, indicating a strong interaction between X' and silicon atoms. These results detail crystallographic variations within the halogen series providing further insight into the nature of the Lewis acid sites above and below the Si(6)X(12) ring, where interactions with hard Lewis bases such as halide anions are observed. Interestingly, the stereochemistry of the silicon atoms in [Si(6)X(12)X'(2)](2-) is not affected much by the size or electronegativity of the halogen atoms. PMID:21462954

  8. High temperature crystal structures and superionic properties of SrCl{sub 2}, SrBr{sub 2}, BaCl{sub 2} and BaBr{sub 2}

    SciTech Connect

    Hull, Stephen; Norberg, Stefan T.; Ahmed, Istaq; Eriksson, Sten G.; Mohn, Chris E.

    2011-11-15

    The structural properties of the binary alkaline-earth halides SrCl{sub 2}, SrBr{sub 2}, BaCl{sub 2} and BaBr{sub 2} have been investigated from ambient temperature up to close to their melting points, using the neutron powder diffraction technique. Fluorite-structured SrCl{sub 2} undergoes a gradual transition to a superionic phase at 900-1100 K, characterised by an increasing concentration of anion Frenkel defects. At a temperature of 920(3) K, the tetragonal phase of SrBr{sub 2} undergoes a first-order transition to a cubic fluorite phase. This high temperature phase shows the presence of extensive disorder within the anion sublattice, which differs from that found in superionic SrCl{sub 2}. BaCl{sub 2} and BaBr{sub 2} both adopt the cotunnite crystal structure under ambient conditions. BaCl{sub 2} undergoes a first-order structural transition at 917(5) K to a disordered fluorite-structured phase. The relationship between the (disordered) crystal structures and the ionic conductivity behaviour is discussed and the influence of the size of the mobile anion on the superionic behaviour is explored. - Graphical abstract: Anomalous behaviour of the lattice expansion of SrCl{sub 2} at temperatures of {approx}1000 K is associated with the gradual transition to a superionic phase, whilst SrBr{sub 2} undergoes a first-order structural transition ({beta}{yields}{alpha}) to a fluorite-structured superionic phase at 920(3) K. Highlights: > Anomalous behaviour of the lattice expansion of SrCl{sub 2} occurs at temperatures {approx}1000 K. > Crystal structure of {beta}-SrBr{sub 2} is described in detail. > On heating, SrBr{sub 2} and BaCl{sub 2} transform to a fluorite-structured superionic phase. > Temperature dependence of the BaCl{sub 2} and BaBr{sub 2} structures is presented. > Nature of the superionic phases within the alkaline-earth halides is discussed.

  9. Experimental characterization of C-X···Y-C (X = Br, I; Y = F, Cl) halogen-halogen bonds.

    PubMed

    Hauchecorne, Dieter; Herrebout, Wouter A

    2013-11-14

    Using FTIR and Raman spectroscopy, we investigated the formation of halogen bonded complexes of the trifluorohalomethanes CF3Cl, CF3Br, and CF3I with the halomethanes CH3F and CH3Cl and the haloethanes C2H5F and C2H5Cl dissolved in liquid krypton. For CF3Br and CF3I, evidence was found for the formation of C-X···F and C-X···Cl halogen bonded 1:1 complexes. Using spectra recorded at different temperatures, we determined the complexation enthalpies for the complexes to be -7.0(3) kJ mol(-1) for CF3Br·CH3F, -7.6(1) kJ mol(-1) for CF3I·CH3F, -5.9(2) kJ mol(-1) for CF3Br·CH3Cl, -8.3(3) kJ mol(-1) for CF3I·CH3Cl, -7.1(1) kJ mol(-1) for CF3Br·C2H5F, -8.7(2) kJ mol(-1) for CF3I·C2H5F, -6.5(2) kJ mol(-1) for CF3Br·C2H5Cl, and -8.8(3) kJ mol(-1) for CF3I·C2H5Cl. For all halogen bonded complexes with a fluorine-electron donor, a blue shift ranging from +0.6 to +1.5 cm(-1) was observed for the C-X stretching mode. The results from the cyrospectroscopic study are compared with ab initio calculations at the MP2/aug-cc-pVDZ(-PP) level. PMID:24128324

  10. Lead-Free MA2CuCl(x)Br(4-x) Hybrid Perovskites.

    PubMed

    Cortecchia, Daniele; Dewi, Herlina Arianita; Yin, Jun; Bruno, Annalisa; Chen, Shi; Baikie, Tom; Boix, Pablo P; Grätzel, Michael; Mhaisalkar, Subodh; Soci, Cesare; Mathews, Nripan

    2016-02-01

    Despite their extremely good performance in solar cells with efficiencies approaching 20% and the emerging application for light-emitting devices, organic-inorganic lead halide perovskites suffer from high content of toxic, polluting, and bioaccumulative Pb, which may eventually hamper their commercialization. Here, we present the synthesis of two-dimensional (2D) Cu-based hybrid perovskites and study their optoelectronic properties to investigate their potential application in solar cells and light-emitting devices, providing a new environmental-friendly alternative to Pb. The series (CH3NH3)2CuCl(x)Br(4-x) was studied in detail, with the role of Cl found to be essential for stabilization. By exploiting the additional Cu d-d transitions and appropriately tuning the Br/Cl ratio, which affects ligand-to-metal charge transfer transitions, the optical absorption in this series of compounds can be extended to the near-infrared for optimal spectral overlap with the solar irradiance. In situ formation of Cu(+) ions was found to be responsible for the green photoluminescence of this material set. Processing conditions for integrating Cu-based perovskites into photovoltaic device architectures, as well as the factors currently limiting photovoltaic performance, are discussed: among them, we identified the combination of low absorption coefficient and heavy mass of the holes as main limitations for the solar cell efficiency. To the best of our knowledge, this is the first demonstration of the potential of 2D copper perovskite as light harvesters and lays the foundation for further development of perovskite based on transition metals as alternative lead-free materials. Appropriate molecular design will be necessary to improve the material's properties and solar cell performance filling the gap with the state-of-the-art Pb-based perovskite devices. PMID:26756860

  11. Comparison of the Properties of SnCl(3)(-) and SnBr(3)(-) Complexes of Platinum(II).

    PubMed

    Nelson, John H.; Wilson, William L.; Cary, Lewis W.; Alcock, Nathaniel W.; Clase, Howard J.; Jas, Gouri S.; Ramsey-Tassin, Lori; Kenney, John W.

    1996-02-14

    The complexes M(3)[Pt(SnX(3))(5)] (M = Bu(4)N(+), PhCH(2)PPh(3)(+); X = Cl, Br), cis-M(2)[PtX(2)(SnX(3))(2)] (M = Bu(4)N(+), PhCH(2)PPh(3)(+), CH(3)PPh(3)(+), Pr(4)N(+); X = Cl, Br), and [PhCH(2)PPh(3)](2)[PtBr(3)(SnBr(3))] have been prepared and characterized by (119)Sn and (195)Pt NMR, far-infrared, and electronic absorption and emission spectroscopies. In acetone solutions the [Pt(SnX(3))(5)](3)(-) ions retain their trigonal bipyramidal structures but are stereochemically nonrigid as evidenced by (119)Sn and (195)Pt NMR spectroscopy. For [Pt(SnCl(3))(5)](3)(-) spin correlation is preserved between 183 and 363 K establishing that the nonrigidity is due to intramolecular tin site exchange, probably via Berry pseudorotation. Whereas, [Pt(SnCl(3))(5)](3)(-) does not undergo loss of SnCl(3)(-) or SnCl(2) to form either [Pt(SnCl(3))(4)](2)(-) or [PtCl(2)(SnCl(3))(2)](2)(-), [Pt(SnBr(3))(5)](3)(-) is not stable in acetone solution in the absence of excess SnBr(2) and forms [PtBr(2)(SnBr(3))(2)](2)(-) and [PtBr(3)(SnBr(3))](2)(-) by loss of SnBr(2). Similarly, [PtCl(2)(SnCl(3))(2)](2)(-) is stable in acetone at ambient temperatures but disproportionates at elevated temperatures and [PtBr(2)(SnBr(3))(2)](2)(-) loses SnBr(2) in acetone to form [PtBr(3)(SnBr(3))](2)(-). The crystal structures of methyltriphenylphosphonium cis-dibromobis(tribromostannyl)platinate(II) and benzyltriphenylphosphonium tribromo(tribromostannyl)platinate(II) have been determined. Both compounds crystallize in the triclinic space group P&onemacr; in unit cells with a = 12.293(16) Å, b = 12.868(6) Å, c = 25.047(8) Å, alpha = 96.11(3) degrees, beta = 91.06(3) degrees, gamma = 116.53(3) degrees, rho(calc) = 2.30 g cm(-)(3), Z = 3 and with a = 11.046(7) Å, b = 14.164(9) Å, c = 22.549(10) Å, alpha = 89.44(4) degrees, beta = 83.32(5) degrees, gamma = 68.31(5) degrees, rho(calc) = 1.893 g cm(-)(3), Z = 2, respectively. Least-squares refinements converged at R = 0.057 and 0.099 for 4048 and 4666

  12. Matrix-isolation and computational study of the HXeY⋯H2O complexes (Y = Cl, Br, and I).

    PubMed

    Tsuge, Masashi; Berski, Sławomir; Räsänen, Markku; Latajka, Zdzisław; Khriachtchev, Leonid

    2014-01-28

    The HXeY⋯H2O complexes (Y = Cl, Br, and I) are studied theoretically and experimentally. The calculations at the CCSD(T)/def2-TZVPPD level of theory predict two stable structures for Y = Cl and Br and one structure for Y = I, with interaction energies up to about -7 kcal mol(-1). In the experiments, we have identified several infrared absorption bands originating from the H-Xe stretching mode of these complexes in a xenon matrix. The monomer-to-complex frequency shifts of this mode are up to +82 cm(-1) (Y = Cl), +101 cm(-1) (Y = Br), and +138 cm(-1) (Y = I), i.e., the shift is smaller for more strongly bound molecules. Based on the agreement of the experimental and theoretical results, the observed bands are assigned to the most stable planar structure with an O-H⋯Y-Xe hydrogen bond. PMID:25669539

  13. Calorimetric determination of the thermoneutral potential for Li/BrCl in SOCl2 (BCX) cells

    NASA Technical Reports Server (NTRS)

    Darcy, Eric C.; Kalu, Eric E.; White, Ralph E.

    1991-01-01

    Proliferation of lithium cells into large modular battery packs are projected for future space applications. Assuring battery design safety while maintaining high energy density requires accurate and precise knowledge of the thermal parameters of the battery cell. Specifically, the thermoneutral potential was determined using heat conduction calorimetry on Li/BrCl in SOCl2 (BCX) DD-cells and compared to measurements obtained on Li/SOCl2 D-cells. Over 20 to 60 C, the Li/BCX cells were found to have a thermoneutral potential significantly higher (near 4.0 volts) than that for the Li/SOCl2 cells tested. The higher heat generation measured during discharge reflects the higher electrochemical polarization observed with the BCX cells.

  14. LiCl dehumidifier LiBr absorption chiller hybrid air conditioning system with energy recovery

    SciTech Connect

    Ko, S.M.

    1980-06-03

    This invention relates to a hybrid air conditioning system that combines a solar powered LiCl dehumidifier with a LiBr absorption chiller. The desiccant dehumidifier removes the latent load by absorbing moisture from the air, and the sensible load is removed by the absorption chiller. The desiccant dehumidifier is coupled to a regenerator and the desiccant in the regenerator is heated by solar heated hot water to drive the moisture therefrom before being fed back to the dehumidifier. The heat of vaporization expended in the desiccant regenerator is recovered and used to partially preheat the driving fluid of the absorption chiller, thus substantially improving the overall COP of the hybrid system. 4 figs.

  15. Crystal growth of HfS 2 by chemical vapour transport with halogen (Cl, Br, I)

    NASA Astrophysics Data System (ADS)

    Fiechter, S.; Eckert, K.

    1988-05-01

    Single crystals of HfS 2 have been prepared by chemical vapour transport (CVT) with halogen. Depending on the transporting agent added, exergonic or endergonic transport was observed. Employing 0.5 mg/cm 3 chlorine or bromine in evacuated and sealed quartz ampoules, exergonic transport occurs. In a temperature gradient from 850 to 870 K transparent reddish-orange crystal platelets of pseudohexagonal shape (10×10×0.05 mm3) were obtained. Endergonic transport, found with iodine as transporting agent, first starts at higher temperatures (1270-1220 K). A thermochemical study of the vapour phase composition revealed that gaseous HfHal 4 and HfHal 3 ( Hal = Cl, Br) are responsible for the exergonic transport observed. Because of the higher stability of HfS 2 against iodine, CVT first starts at elevated temperatures. In the vapour phase Hfl and Hfl 2 dominate and effect a reversal of the transport direction.

  16. LiCl Dehumidifier LiBr absorption chiller hybrid air conditioning system with energy recovery

    DOEpatents

    Ko, Suk M.

    1980-01-01

    This invention relates to a hybrid air conditioning system that combines a solar powered LiCl dehumidifier with a LiBr absorption chiller. The desiccant dehumidifier removes the latent load by absorbing moisture from the air, and the sensible load is removed by the absorption chiller. The desiccant dehumidifier is coupled to a regenerator and the desiccant in the regenerator is heated by solar heated hot water to drive the moisture therefrom before being fed back to the dehumidifier. The heat of vaporization expended in the desiccant regenerator is recovered and used to partially preheat the driving fluid of the absorption chiller, thus substantially improving the overall COP of the hybrid system.

  17. The reduction of chlorine on carbon in AlCl3-KCl-NaCl melts

    NASA Technical Reports Server (NTRS)

    Holleck, G. L.

    1971-01-01

    Using a rotating vitreous carbon disk electrode, the kinetic parameters for chlorine reduction in an AlCl3-KCl-NaCl (57.5-12.5-30 mol percent) melt were determined. It was found that the reduction of chlorine occurs according to two paths, with the first step probably being rate-determining.

  18. Groundwater nitrate contamination and use of Cl/Br ratio for source appointment.

    PubMed

    Samantara, M K; Padhi, R K; Satpathy, K K; Sowmya, M; Kumaran, P

    2015-02-01

    Source appointment for groundwater nitrate contamination is critical in prioritizing effective strategy for its mitigation. Here, we assessed the use of Cl/Br ratio and statistical correlation of hydro-chemical parameters to identify the nitrate source to the groundwater. A total of 228 samples from 19 domestic wells distributed throughout the study area were collected during June 2011-May 2012 and analyzed for various physicochemical parameters. Study area was divided into three spatial zones based on demographic features, viz., northern, southern, and central part. Nitrate concentration in 57 % of samples exceeded the prescribed safe limit for drinking stipulated by the World Health Organization (WHO) and Bureau of Indian standards (BIS). The central part of the study area showed elevated nitrate concentration ranging from below detection limit (BDL) to 263.5 mg/l as NO3 (-) and demonstrated high attenuation within the immediate vicinity thereby restricting diffusion of the nitrate to the adjacent parts. Resolution of correlation matrix as statistical indicator for nitrate contamination was poor. Seventy-seven percent of samples with high nitrate concentration (>45 mg/l as NO3 (-)) showed strong association with high Cl/Br mass ratio (350-900), indicating mixing of sewage and septic tank effluents with groundwater as a primary source for the nitrate in the studied area. Nitrate level during monsoon (BDL, 229.9 mg/l as NO3 (-)), post-monsoon (BDL, 263.5 mg/l as NO3 (-)), and pre-monsoon (0.5-223.1 mg/l as NO3 (-)) indicated additional contribution of surface leaching to groundwater. PMID:25638054

  19. Airborne Instruments for the In Situ Detection of ClONO2, NO2, ClO, and BrO in the Stratosphere

    NASA Technical Reports Server (NTRS)

    Anderson, James G.

    1999-01-01

    The objective of the research was the development of a new small, lightweight instrument for the detection of ClONO2, NO2, ClO, and BrO, carried aboard a robotic aircraft, specifically the NASA ER-2. The schematic of the instrument is shown. Some of the observations which this instrument is designed to make are discussed. The observations of the instrument during the Photochemistry of Ozone Loss in the Arctic Region in Summer (POLARIS) mission are also reviewed.

  20. Dissociative adsorption of CH{sub 3}X (X = Br and Cl) on a silicon(100) surface revisited by density functional theory

    SciTech Connect

    Wang, Chen-Guang; Huang, Kai E-mail: wji@ruc.edu.cn; Ji, Wei E-mail: wji@ruc.edu.cn

    2014-11-07

    During the dissociative adsorption on a solid surface, the substrate usually participates in a passive manner to accommodate fragments produced upon the cleavage of the internal bond(s) of a (transient) molecular adsorbate. This simple picture, however, neglects the flexibility of surface atoms. Here, we report a Density Functional Theory study to revisit our early studies of the dissociative adsorption of CH{sub 3}X (X = Br and Cl) on Si(100). We have identified a new reaction pathway, which involves a flip of a silicon dimer; this new pathway agrees better with experiments. For our main exemplar of CH{sub 3}Br, insights have been gained using a simple model that involves a three-atom reactive center, Br-C-Si. When the silicon dimer flips, the interaction between C and Si in the Br-C-Si center is enhanced, evident in the increased energy-split of the frontier orbitals. We also examine how the dissociation dynamics of CH{sub 3}Br is altered on a heterodimer (Si-Al, Si-P, and Si-Ge) in a Si(100) surface. In each case, we conclude, on the basis of computed reaction pathways, that no heterodimer flipping is involved before the system transverses the transition state to dissociative adsorption.

  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. Temporal behavior of NO laser emission from the photodissociation of ClNO and BrNO

    SciTech Connect

    del Barrio, J.I.; Rebato, J.R.; Tablas, F.M.G.

    1986-06-15

    We have studied the temporal behavior of the NO laser emission produced from the photodissociation of ClNO and BrNO. No J shifting has been observed except in the 7..-->..6 band of /sup 2/Pi/sub 3//sub ///sub 2/ from ClNO. In both cases laser starts from an intermediate lasing vibrational level, triggering higher and lower transitions that end with the lowest observed band.

  3. The origin of the conductivity maximum in molten salts. II. SnCl2 and HgBr2.

    PubMed

    Aravindakshan, Nikhil P; Kuntz, Colin M; Gemmell, Kyle E; Johnson, Keith E; East, Allan L L

    2016-09-01

    The phenomenon of electrical conductivity maxima of molten salts versus temperature during orthobaric (closed-vessel) conditions is further examined via ab initio simulations. Previously, in a study of molten BiCl3, a new theory was offered in which the conductivity falloff at high temperatures is due not to traditional ion association, but to a rise in the activation energy for atomic ions hopping from counterion to counterion. Here this theory is further tested on two more inorganic melts which exhibit conductivity maxima: another high-conducting melt (SnCl2, σmax = 2.81 Ω(-1) cm(-1)) and a low-conducting one (HgBr2, σmax = 4.06 × 10(-4) Ω(-1) cm(-1)). First, ab initio molecular dynamics simulations were performed and again appear successful in reproducing the maxima for both these liquids. Second, analysis of the simulated liquid structure (radial distributions, species concentrations) was performed. In the HgBr2 case, a very molecular liquid like water, a clear Grotthuss chain of bromide transfers was observed in simulation when seeding the system with a HgBr(+) cation and HgBr3 (-) anion. The first conclusion is that the hopping mechanism offered for molten BiCl3 is simply the Grotthuss mechanism for conduction, applicable not just to H(+) ions, but also to halide ions in post-transition-metal halide melts. Second, it is conjectured that the conductivity maximum is due to rising activation energy in network-covalent (halide-bridging) melts (BiCl3, SnCl2, PbCl2), but possibly a falling Arrhenius prefactor (collision frequency) for molecular melts (HgBr2). PMID:27609001

  4. Evaluation of production samples of the scintillators LaBr3:Ce andLaCl3:Ce

    SciTech Connect

    Choong, Woon-Seng; Derenzo, Stephen E.; Moses, William W.

    2005-09-15

    We report on the evaluation of the performance of two recently developed scintillator materials, LaCl{sub 3}:Ce and LaBr{sub 3}:Ce, at the task of gamma ray spectroscopy. Their performance is compared to a standard scintillator used for gamma ray spectroscopy--a 25 mm diameter 25 mm tall cylinder of NaI:Tl. We measure the pulse height, energy resolution, and full-energy efficiency of production LaBr{sub 3}:Ce and LaCl{sub 3}:Ce scintillation crystals of different sizes and geometries for a variety of gamma-ray energies. Using production rather than specially selected crystals will establish whether immediate large-scale use is feasible. The crystal is excited by gamma rays from one of six isotopic sources ({sup 125}I, {sup 241}Am, {sup 57}Co, {sup 22}Na, {sup 137}Cs, and {sup 60}Co) placed 15 cm away from the scintillator. Our measurements show that both LaCl{sub 3} and LaBr{sub 3} outperform NaI:Tl in almost all cases. They outperform NaI:Tl at all energies for the photopeak fraction and counting rate measurements, and for energy resolution at higher energies (above 200 keV for LaCl{sub 3} and 75 keV for LaBr{sub 3}). The performance of production crystals is excellent and these scintillators should be considered for immediate use in systems where stopping power and energy resolution are crucial.

  5. Convenient recycling of 3D AgX/graphene aerogels (X = Br, Cl) for efficient photocatalytic degradation of water pollutants.

    PubMed

    Fan, Yingying; Ma, Weiguang; Han, Dongxue; Gan, Shiyu; Dong, Xiandui; Niu, Li

    2015-07-01

    3D AgX/graphene aerogel (GA) composites (X = Br, Cl) are synthesized. Not only is the photocatalytic performance increased in comparison with pristine AgX, but also the photocatalytic cycling process is facilitated just using tweezers Thus, the comprehensive performance of the AgX/GA composites provides robust support for future industrial applications of the photocatalyst. PMID:25994835

  6. Estimation of S, F, Br, Cl, and P Fluxes at Mid Ocean Ridges

    NASA Astrophysics Data System (ADS)

    Kagoshima, T.; Sano, Y.; Takahata, N.; Jung, J.; Amakawa, H.; Kumagai, H.

    2011-12-01

    It is known that superficial volatile elements have been accumulated by degassing from the solid Earth. Studies that use noble gases as tracers have been conducted to investigate the degassing history of the Earth, which suggests that the significant degassing occurred in the early Earth. C and N fluxes were well documented in literatures. In order to estimate the other fluxes of volatile elements from mantle, we measured S, F, Br, Cl, and P concentrations trapped in vesicles in mid-ocean ridge basalts (MORBs) and back-arc basin basalts (BABBs). Highly reactive elements such as sulfur and fluorine in the sample were extracted into the alkali solution at the crushing: crush leaching. We selected fresh glassy aliquots from MORBs and BABBs and put them in a crusher with an iron ball and 1-2 cm^{3} of 4M aqueous sodium hydroxide. Then, we crushed the samples with the solution kept frozen at the liquid nitrogen temperature to avoid the adhesion of the solution to the inside of the crusher. After crushing, we froze the solution again, and introduced volatiles in the gas phase into the purification vacuum line. At first, we removed volatile elements except He and Ne by a U-tube and activated charcoals at the temperature of liquid nitrogen and hot Ti-getters. We measured ^{4}He/^{20}Ne ratio of the gas by a quadrupole mass spectrometer and removed Ne by a cryogenic charcoal trap at 40K. Then, the He fraction was introduced into VG5400 mass spectrometer and the ^{3}He/^{4}He ratio was measured. Immediately after the sample analysis, we measured HESJ (He standard of Japan; 20.4 R_{A}) for calibration. For sulfur measurement, 1-2 cm^{3} of 30% hydrogen peroxide were added into the filtered sodium hydroxide solutions. Thus all sulfur compounds were quantified as sulfate ions and F, Br, Cl, and P were measured by ion chromatography (Dionex-320). We collected fine powders of basalt glass by filtering through a stainless steel sieve and measured their weight to estimate the

  7. Halogen (F, Cl, Br, I) behaviour in subducting slabs: A study of lawsonite blueschists in western Turkey

    NASA Astrophysics Data System (ADS)

    Pagé, Lilianne; Hattori, Keiko; de Hoog, Jan C. M.; Okay, Aral I.

    2016-05-01

    We examined the F, Cl, Br and I abundance of minimally retrogressed lawsonite blueschists from the Tavsanli Zone in northwest Turkey to evaluate the behaviour of halogens in subduction zones, and to determine the role coexisting high pressure minerals may play in transporting the halogens to the Earth's mantle. The blueschists contain sodic amphibole and lawsonite, with variable amounts of phengite and chlorite, and minor apatite. A positive correlation between Cl, Br and I contents in bulk rocks suggests their overall coherent behaviour in subduction zones, although high ratios of I/Cl and Br/Cl compared to altered oceanic crust indicate that Cl is preferentially lost relative to Br and I before or during blueschist metamorphism. Iodine and F are enriched relative to altered oceanic crust, suggesting incorporation from marine sediments. In situ analyses of minerals in thin sections reveal F preferentially concentrates in apatite (avg. 3.13 wt%), over phengite (482 ppm), lawsonite (avg. 413 ppm) and Na-amphibole (257 ppm). Chlorine also preferentially resides in apatite (138 ppm), followed by equal partitioning between phengite (59 ppm) and Na-amphibole (56 ppm), and lower concentrations in lawsonite (27 ppm). Upon apatite decomposition at a depth of ∼200 km, F may redistribute into lawsonite and phengite in slabs, whilst Cl is likely expelled to the overlying mantle wedge. Given the stability of lawsonite and phengite to a depth of 280-300 km in cold subduction zones, they may transport F beyond subarc depths, contributing to the high F in magmas derived from the deep mantle.

  8. Na/beta-alumina/NaAlCl4, Cl2/C circulating cell

    NASA Astrophysics Data System (ADS)

    Cherng, Jing-Yih; Bennion, Douglas N.

    1987-09-01

    A study was made of a high specific energy battery based on a sodium negative electrode and a chlorine positive electrode with molten AlCl3-NaCl electrolyte and a solid beta alumina separator. The basic performance of a Na beta-alumina NaAlCl4, Cl2/C circulating cell at 200 C was demonstrated. This cell can be started at 150 C. The use of melting sodium chloroaluminate electrolyte overcomes some of the material problems associated with the high working temperatures of present molten salt systems, such as Na/S and LiAl/FeS, and retains the advantages of high energy density and relatively efficient electrode processes. Preliminary investigations were conducted on a sodium-chlorine static cell, material compability, electrode design, wetting, and theoretical calculations to assure a better chance of success before assembling a Na/Cl2 circulating cell. Mathematical models provide a theoretical explanation for the performance of the NaCl2 battery. The results of mathematical models match the experimental results very well. According to the result of the mathematical modeling, an output at 180 mA/sq cm and 3.2 V can be obtained with optimized cell design.

  9. Na/beta-alumina/NaAlCl4, Cl2/C circulating cell

    NASA Technical Reports Server (NTRS)

    Cherng, Jing-Yih; Bennion, Douglas N.

    1987-01-01

    A study was made of a high specific energy battery based on a sodium negative electrode and a chlorine positive electrode with molten AlCl3-NaCl electrolyte and a solid beta alumina separator. The basic performance of a Na beta-alumina NaAlCl4, Cl2/C circulating cell at 200 C was demonstrated. This cell can be started at 150 C. The use of melting sodium chloroaluminate electrolyte overcomes some of the material problems associated with the high working temperatures of present molten salt systems, such as Na/S and LiAl/FeS, and retains the advantages of high energy density and relatively efficient electrode processes. Preliminary investigations were conducted on a sodium-chlorine static cell, material compability, electrode design, wetting, and theoretical calculations to assure a better chance of success before assembling a Na/Cl2 circulating cell. Mathematical models provide a theoretical explanation for the performance of the NaCl2 battery. The results of mathematical models match the experimental results very well. According to the result of the mathematical modeling, an output at 180 mA/sq cm and 3.2 V can be obtained with optimized cell design.

  10. Subduction-related halogens (Cl, Br and I) and H2O in magmatic glasses from Southwest Pacific Backarc Basins

    NASA Astrophysics Data System (ADS)

    Kendrick, Mark A.; Arculus, Richard J.; Danyushevsky, Leonid V.; Kamenetsky, Vadim S.; Woodhead, Jon D.; Honda, Masahiko

    2014-08-01

    Submarine magmatic glasses from the Manus, Woodlark, North Fiji and Lau backarc basins in the Southwest Pacific, and Volcano A on the volcanic front of the Tonga Arc adjacent to the Lau Basin, were investigated to characterise the Cl, Br and I elemental budgets in subduction systems. In particular we seek to determine the extent of variability in the Br/Cl and I/Cl ratios of backarc basin basalts (BABB) and evaluate if these ratios could improve constraints on the source of subducted volatile components in backarc basins worldwide. The selected glasses represent variably evolved melts of boninite, basalt, basaltic-andesite, dacite and rhyolite composition and were selected from spreading centres and seamounts located at varying distances from the associated arcs. In general the strongest subduction signatures (e.g. Ba/Nb of 100-370) occur in the samples closest to the arcs and lower more MORB-like Ba/Nb of <16 are found in the more distal samples. The glasses investigated have extremely variable halogen concentrations (e.g. 3-4200 ppm Cl), with the highest concentrations in enriched glasses with the most evolved compositions. As observed in previous studies, the K/Cl, Br/Cl and I/Cl ratios of glasses from individual settings do not vary as a function of MgO and are considered representative of the magma sources because these ratios are not easily altered by partial melting or fractional crystallisation. Systematic variations in these ratios between basins can therefore be related to mixing of halogens from different sources including: (i) the mantle wedge which has MORB-like Br/Cl and I/Cl; (ii) a subduction-derived slab fluid with estimated salinity of ∼4-10 wt% salts and variable I/Cl; and (iii) brines characterised by salinities of 55±15 wt% salts and Br/Cl slightly higher than seawater, that are sometimes assimilated in crustal magma chambers. The slab fluids enriching the Woodlark Basin, North Fiji Basin and the Fonualei Spreading Centre of the Lau Basin

  11. Compression icing of room-temperature NaX solutions (X = F, Cl, Br, I).

    PubMed

    Zeng, Qingxin; Yan, Tingting; Wang, Kai; Gong, Yinyan; Zhou, Yong; Huang, Yongli; Sun, Chang Q; Zou, Bo

    2016-05-18

    In situ Raman spectroscopy revealed that transiting H2O/NaX (∼64) solutions into an ice VI phase and then into an ice VII phase at a temperature of 298 K requires excessive pressures with respect to pure water. The increase of the critical pressures varies with the solute type in the Hofmeister series order: X = I > Br > Cl > F ∼ 0. The results suggest that the solute hydration creates electric fields that lengthen and soften the O:H nonbond and meanwhile shorten and stiffen the H-O bond through O-O Coulomb repulsion. Compression, however, does the opposite to solute electrification upon the O:H-O bond relaxation. Therefore, compression of the aqueous solutions recovers the electrification-deformed O:H-O bond first and then proceeds to the phase transitions, which requires excessive energy for the same sequence of phase transitions. Ice exclusion of solute disperses the frequencies of characteristic phonons and the critical pressures with unlikely new bond formation. PMID:27156887

  12. Simulation of the resonance Raman spectra for 5-halogenated (F, Cl, and Br) uracils.

    PubMed

    Sun, Shuai; Brown, Alex

    2015-04-30

    The resonance Raman spectra of the 5-halogenated (F, Cl, and Br) uracils are simulated via the Herzberg-Teller (HT) short-time dynamics formalism. The gradient of the S1 excited state is computed at the CAMB3LYP/aug-cc-pVTZ level of theory in the conductor-like polarizable continuum model for water (C-PCM, H2O), based on the equilibrium geometry determined using PBE0/aug-cc-pVTZ in H2O (C-PCM). The simulated resonance Raman spectra show good agreement with the experimental spectra in terms of both peak positions and intensities. The differences between the resonance Raman spectra of the three 5-halogenated uracils, caused by the effect of halogen substitution, are examined in terms of ground-state normal-mode eigenvectors and excited-state Cartesian gradients, according to the HT formalism. The differences in the normal-mode eigenvectors and excited-state Cartesian gradients between 5-fluorouracil and 5-chlorouracil are used to interpret the dissimilarity between their resonance Raman spectra. Meanwhile, the similarity between the spectra of 5-chlorouracil and 5-bromouracil is explained by the correspondence between their normal modes and excited-state gradients. PMID:25856119

  13. Vacuum-UV negative photoion spectroscopy of CF3Cl, CF3Br, and CF3I

    NASA Astrophysics Data System (ADS)

    Simpson, M. J.; Tuckett, R. P.; Dunn, K. F.; Hunniford, C. A.; Latimer, C. J.

    2009-05-01

    Using synchrotron radiation, negative ions are detected by mass spectrometry following vacuum-UV photoexcitation of trifluorochloromethane (CF3Cl), trifluorobromomethane (CF3Br), and trifluoroiodomethane (CF3I). The anions F-, X-, F2-, FX-, CF-, CF2-, and CF3- are observed from all three molecules, where X =Cl, Br, or I, and their ion yields recorded in the range of 8-35 eV. With the exception of Br- and I-, the anions observed show a linear dependence of signal with pressure, showing that they arise from unimolecular ion-pair dissociation. Dissociative electron attachment, following photoionization of CF3Br and CF3I as the source of low-energy electrons, is shown to dominate the observed Br- and I- signals, respectively. Cross sections for ion-pair formation are put onto an absolute scale by calibrating the signal strengths with those of F- from both SF6 and CF4. These anion cross sections are normalized to vacuum-UV absorption cross sections, where available, and the resulting quantum yields are reported. Anion appearance energies are used to calculate upper limits to 298 K bond dissociation energies for Do(CF3-X), which are consistent with literature values. We report new data for Do(CF2I+-F)≤2.7±0.2 eV and ΔfH298o(CF2I+)≤(598±22) kJ mol-1. No ion-pair formation is observed below the ionization energy of the parent molecule for CF3Cl and CF3Br, and only weak signals (in both I- and F-) are detected for CF3I. These observations suggest that neutral photodissociation is the dominant exit channel to Rydberg state photoexcitation at these lower energies.

  14. Synthesis and Crystal Structures of Hg 6Sb 5Br 7, Hg 6As 4BiCl 7, and Hg 6Sb 4BiBr 7, Built of a Polycationic Mercury-Pnictide Framework with Trapped Anions

    NASA Astrophysics Data System (ADS)

    Beck, Johannes; Hedderich, Sylvia; Neisel, Udo

    2000-11-01

    Hg6Sb5Br7, Hg6As4BiCl7, and Hg6Sb4BiBr7 were prepared from stoichiometric mixtures of Hg2X2, HgX2 (X=Cl, Br), As, Sb, and Bi in sealed, evacuated glass ampoules in temperature gradients 260→240°C for Hg6Sb5Br7, 340→320°C for Hg6As4BiCl7, and 290→270°C for Hg6Sb4BiBr7. All compounds crystallize in the cubic space group Paoverline3 with Z=4 and the lattice constants a=13.003(1) Å for Hg6Sb5Br7, a=12.178(2) Å for Hg6As4BiCl7, and a=12.998(4) Å for Hg6Sb4BiBr7. The structures have been solved based on single-crystal X-ray diffraction data and refined to R(F)=0.0431, 666 Fo for Hg6Sb5Br7, R(F)=0.0478, 690 Fo for Hg6As4BiCl7, and R(F)=0.0444, 840 Fo for Hg6Sb4BiBr7 with 30 parameters for each refinement. The structures are characterized by a three-dimensional polycationic framework of pnictide dumb-bells (As-As distance 2.43 Å, Sb-Sb distance 2.78 Å), each connected by six mercury atoms to six neighbored As2/Sb2 groups. There are two different cages in the framework; one type is occupied by nearly regular MX6 octahedra (M=Sb,Bi; X=Cl, Br), the other by halide ions. The three compounds crystallize closely related to Cd7P4Cl6, which contains a similar polycationic framework of P2 dumb-bells connected by Cd, but with only one type of cage occupied by octahedral [CdCl6]4- ions. The interactions between the atoms of the polycationic framework and the anions are very weak. The observed diamagnetism of all three compounds is in agreement with the ionic formulas (Hg6Sb4)4+[SbBr6]3-Br-, (Hg6As4)4+[BiCl6]3-Cl-, and (Hg6Sb4)4+[BiBr6]3-Br-.

  15. Syntheses and structure of hydrothermally prepared CsNiX{sub 3} (X=Cl, Br, I)

    SciTech Connect

    Raw, Adam D.; Ibers, James A.; Poeppelmeier, Kenneth R.

    2012-08-15

    During reinvestigation of the hydrothermal synthesis reported earlier of the compound cesium nickel phosphide, 'CsNiP', we arrived at a new route to the synthesis of the cesium nickel halide compounds CsNiX{sub 3} (X=Cl, Br, I). The method has also been shown to extend to cobalt and iron compounds. Single crystals of these compounds were synthesized in phosphoric acid in sealed autoclaves. Their structures were determined by single-crystal X-ray diffraction methods. The compounds crystallize in the hexagonal space group P6{sub 3}/mmc in the BaNiO{sub 3} structure type. The synthetic method and the resultant crystallographic details for CsNiCl{sub 3} are essentially identical with those reported earlier for the synthesis and structure of 'CsNiP'. - Graphical abstract: The CsNiX{sub 3} (X=Cl, Br, I) structure. Cesium is blue, nickel is in dark green polyhedra, halide is brown. Highlights: Black-Right-Pointing-Pointer A hydrothermal approach to single crystal growth of cesium transition-metal halides. Black-Right-Pointing-Pointer Reexamination of 'CsNiP' to determine its composition as CsNiCl{sub 3}. Black-Right-Pointing-Pointer X-ray single-crystal structures of CsNiBr{sub 3} and CsNiI{sub 3}.

  16. Na-Cl-Br systematics of fluid inclusions from Mississippi Valley-type deposits, Appalachian Basin: Constraints on solute origin and migration paths

    SciTech Connect

    Kesler, S.E.; Martini, A.M.; Appold, M.S.; Walter, L.M.; Huston, T.J.; Furman, F.C.

    1996-01-01

    This study evaluated Na-Cl-Br systematics of fluid inclusion-hosted brines in Mississippi Valley-type (MVT) deposits from the Appalachian Basin. Unlike other geochemical tracers such as lead and strontium isotopes which constrain metal sources, Na-Cl-Br systematics identify sources of brine salinity. Saline formation waters can vary systematically within and between basins with regard to their Na-Cl-Br compositions depending on the importance of halite dissolution relative to retention of subaerially evaporated seawater for the halogen budget. Oil field brine compositions from the Illinois and Appalachian basins are quite distinct in their Na-Cl-Br systematics. Compositions of saline fluid inclusions in MVT deposits generally are consistent with these regional differences. These results shed new light on the extent of regional flow systems and on the geochemical evolution of saline fluids responsible for mineralization. Nearly all fluid inclusions analyzed from the Appalachian MVT deposits have Na/Br and Cl/Br ratios less than modern seawater, consistent with ratios observed in marine brines involved in halite precipitation. The Na-Cl-Br systematics of the brines responsible for Appalachian MVT deposits may be inherited from original marine brines refluxed into the porous carbonate shelf sediments that host these deposits. The Cl/Br and Na/Br ratios of most fluid inclusion-hosted brines from Appalachian MVT sphalerites and fluorites fall into two compositional groups, one from the Lower Cambrian paleoaquifer and another from the Lower Ordovician paleoaquifer. Leachates from most MVT barite deposits form a third compositional group having lower Na/Br and Cl/Br ratios than the other two. Appalachian MVT leachate compositions differ significantly from those in MVT deposits in the Cincinnati arch-midcontinent region suggesting that these two MVT provinces formed from brines of different origin or flow path. 59 refs., 8 figs., 2 tabs.

  17. Optical pump-probe processes in Nd3+-doped KPb2Br5, RbPb2Br5, and KPb2Cl5

    NASA Astrophysics Data System (ADS)

    Rademaker, Katja; Payne, Stephen A.; Huber, Günter; Isaenko, Ludmila I.; Osiac, Eugen

    2005-12-01

    Recently, laser activity has been achieved in the low-phonon-energy, moisture-resistant bromide host crystals: neodymium-doped potassium lead bromide (Nd3+:KPb2Br5) and rubidium lead bromide (Nd3+:RbPb2Br5). Laser activity at 1.07 μm was observed for both crystalline materials. Laser operation at the new wavelengths of 1.18 and 0.97 μm resulting from the 4F5/2+2H9/2-->4IJ transitions (J=13/2 and 11/2) in Nd:RbPb2Br5 was achieved for the first time in a solid-state laser material. We present cw pump-probe spectra and discuss excited-state absorption and reabsorption processes due to the long-lived lower laser levels, as well as possible depopulation mechanisms feasible for more efficient laser operation in these crystals. The bromides are compared with potassium lead chloride (Nd3+:KPb2Cl5).

  18. Lattice dynamics in perovskite halides CsSn X3 with X = I , Br , Cl

    NASA Astrophysics Data System (ADS)

    Huang, Ling-yi; Lambrecht, Walter R. L.

    2014-11-01

    The first-principles linear response method is used within the local-density approximation to calculate the full phonon band structures and phonon density of states (DOS) of CsSn X3 (X =Cl , Br, or I) in different phases. The relations between soft phonon modes and phase transitions are investigated. We find soft phonon modes only in the cubic and tetragonal phases, not in the orthorhombic and monoclinic phases. A dispersionless soft phonon branch spreads from the k point M to R in the Brillouin zone of the cubic phase. The lower symmetry tetragonal phase results from the condensation of the soft phonon mode at the k point M . Furthermore, the condensation of the soft phonon mode at the k point Z in the Brillouin zone of tetragonal phase results in the orthorhombic γ phase. To facilitate comparison with experimental data, we calculate infrared spectra for the cubic phase. At this point only a limited comparison with experimental data is possible. We find that the calculated modes agree with the available experimental data when we assign the second and third calculated modes to the experimental first and second modes. The lowest calculated mode is at a frequency where the phonon DOS has a maximum value. So the strong phonon-phonon interaction results in short phonon lifetime or strong broadening, which could explain why this mode has not been observed. Our first-principles calculated IR spectra show that the third observed mode in IR absorption is actually the highest longitudinal optical (LO) rather than transverse optical mode. We show, furthermore, that a strong LO-plasmon coupling may be expected in these materials and can explain observed Raman data for CsSnI3.

  19. Laser microprobe analyses of Cl, Br, I, and K in fluid inclusions: Implications for sources of salinity in some ancient hydrothermal fluids

    USGS Publications Warehouse

    Böhlke, J.K.; Irwin, J.J.

    1992-01-01

    The relative concentrations of Cl, Br, I, and K in fluid inclusions in hydrothermal minerals were measured by laser microprobe noble gas mass spectrometry on irradiated samples containing 10-10 to 10-8 L of fluid. Distinctive halogen signatures indicate contrasting sources of fluid salinity in fluid inclusions from representative "magmatic" (St. Austell), "metamorphic" (Alleghany), and "geothermal" (Creede, Salton Sea) aqueous systems. Br/Cl mol ratios are lowest at Salton Sea (0.27-0.33 ?? 10-3), where high salinities are largely due to halite dissolution; intermediate at St. Austell (0.85 ?? 10-3), possibly representative of magmatic volatiles; and highest (near that of seawater) at Creede (1.5-2.1 ?? 10-3) and Alleghany (1.2-2.4 ?? 10-3), where dissolved halogens probably were leached from volcanic and (or) nonevaporitic sedimentary rocks. I C1 mol ratios are lowest (near that of seawater) at Creede (1-14 ?? 10-6), possibly because organisms scavenged I during low temperature recharge; intermediate at Salton Sea (24-26 ?? 10-6) and St. Austell (81?? 10-6); and highest at Alleghany (320-940 ?? 10-6), probably because the fluids interacted with organic-rich sediments at high temperatures before being trapped. K Cl mol ratios indicate disequilibrium with respect to hypothetical feldspathic alkali-Al-silicate mineral buffers at fluid inclusion trapping temperatures at Creede, and large contributions of (Na, K)-bicarbonate to total fluid ionic strength at Alleghany. Significant variations in Cl/Br/I/K ratios among different fluid inclusion types are correlated with previously documented mineralization stages at Creede, and with the apparent oxidation state of dissolved carbon at Alleghany. The new data indicate that Cl/ Br/I ratios in hydrothermal fluid inclusions vary by several orders of magnitude, as they do in modern surface and ground waters. This study demonstrates that halogen signatures of fluid inclusions determined by microanalysis yield important

  20. Protic anions [H(B12X12)]- (X = F, Cl, Br, I) that act as Brønsted acids in the gas phase.

    PubMed

    Jenne, Carsten; Keßler, Mathias; Warneke, Jonas

    2015-04-01

    The acidity of protic cations and neutral molecules has been studied extensively in the gas phase, and the gas-phase acidity has been established previously as a very useful measure of the intrinsic acidity of neutral and cationic compounds. However, no data for any anionic acids were available prior to this study. The protic anions [H(B12X12)](-) (X = F, Cl, Br, I) are expected to be the most acidic anions known to date. Therefore, they were investigated in this study with respect to their ability to protonate neutral molecules in the gas phase by using a combination of mass spectrometry and quantum-chemical calculations. For the first time it was shown that in the gas phase protic anions are also able to protonate neutral molecules and thus act as Brønsted acids. According to theoretical calculations, [H(B12I12)](-) is the most acidic gas-phase anion, whereas in actual protonation experiments [H(B12Cl12)](-) is the most potent gas-phase acidic anion for the protonation of neutral molecules. This discrepancy is explained by ion pairing and kinetic effects. PMID:25735766

  1. The effect of F, Cl and Br doping on the growth and structural properties of sprayed ? films

    NASA Astrophysics Data System (ADS)

    Agashe, Chitra; S, S., Major

    1996-12-01

    The effect of halogen (F, Cl and Br) doping on growth kinetics and structural properties of spray pyrolytically deposited tin dioxide 0022-3727/29/12/008/img2 films was studied in detail. The strengths of the halo-acids and hence the electronegativities of the halogens played an important role in governing the reaction processes which controlled the growth kinetics of the films. F doping affected the growth rate of a film the least, whereas Cl and Br doping reduced the growth rate to an increasing extent. The structural properties were less affected by doping. The films were polycrystalline and remained highly textured along the [200] direction irrespective of the dopant as well as of the doping level. The grain size remained essentially the same regardless of the dopant.

  2. FT-Raman spectra of cis-bis(thiourea)tellurium(II) halides (Cl -, Br -, I -) and thiocyanate

    NASA Astrophysics Data System (ADS)

    Alía, J. M.; Edwards, H. G. M.; García-Navarro, F. J.

    1999-09-01

    The FT-Raman spectra of some cis-bis(thiourea)tellurium(II) coordination compounds [Te(tu) 2Cl 2, Te(tu) 2Br 2, Te(tu) 2I 2 and Te(tu) 2(SCN) 2] are reported. The observed spectral modifications affect all the Raman active modes of thiourea and can be interpreted as the result of a strong coordination between the Te(II) ion and the sulphur atom of thiourea that weakens the CS bond and subsequently strengthens the C-N bonds. The Raman bands assigned to (TeS) stretching are located at 266+253 cm -1 (thiocyanate), 276+262 cm -1 (chloride), 258+250 cm -1 (bromide) and 232 cm -1 (iodide). The corresponding wave numbers for (TeX) stretching are: 162 cm -1 for (TeCl) and (TeSCN), 150 cm -1 for (TeBr) and 139 cm -1 for (TeI).

  3. n-type doping in Cu2O with F, Cl, and Br: A first-principles study

    NASA Astrophysics Data System (ADS)

    Bai, Qiong; Wang, Weichao; Zhang, Qiming; Tao, Meng

    2012-01-01

    The n-type doping in the cuprous oxide (Cu2O) synthesized from an acidic solution environment has been studied by the first-principles calculations. The dopants of F, Cl, and Br in substitution of an O atom have low formation energies. They present an n-type conduction behavior with donor levels below but close to the bottom of the conduction bands. The Cl dopant has the shallowest donor level among the three halogens. The results are in good agreement with the very recent experimental results.

  4. Bi3+ Luminescence in ABiO2Cl (A = Sr, Ba) and BaBiO2Br

    SciTech Connect

    Porter-Chapman, Yetta D.; Bourret-Courchesne, Edith E.; Derenzo,Stephen E.

    2007-01-18

    Trivalent bismuth luminescence is reported in three Sillenbismuth oxyhalide phases, SrBiO2Cl, BaBiO2Cl, and BaBiO2Br. Thesecompounds exhibit Bi 6s6->6 s2 emission under UV and X-ray radiation.At room temperature, BaBiO2Cl shows the most intense light emission, withspectral and decay properties similar to those found in Bi4Ge3O12 (BGO).At low temperatures, each phase show an increase in the photoluminescenceintensities and a narrowing of the emission peaks. In contrast to thetemperature dependence of BGO, X-ray excited luminescence intensities ofall three phases remain relatively constant throughout the temperaturerange 10 - 295 K. This result indicates that the Sillen phases undergoless thermal quenching than BGO. The low temperature and room temperatureradio-luminescence decay times were determined from pulsed x-raymeasurements. At room temperature, SrBiO2Cl exhibits faster decays thanBGO, while, BaBiO2Cl and BaBiO2Br have decay times similar toBGO.

  5. Nonlinear-optical susceptibility of hilgardite-like borates MBOX(M=Pb,Ca,Sr,Ba; X=Cl,Br)

    NASA Astrophysics Data System (ADS)

    Plachinda, Paul A.; Dolgikh, Valery A.; Stefanovich, Sergey Yu.; Berdonosov, Petr S.

    2005-10-01

    Usage of non-centrosymmetric boron oxide derivative crystals as nonlinear elements may be a key solution of pressing problem of obtaining powerful radiation at shorter wavelengths via frequency multiplication of solid state laser radiations. It is shown that Pb 2B 5O 9Br and some other members of hilgardite-like borohalogenides demonstrate in powder form, high non-linear optical activity in the SHG experiments. An attempt is made using the Philips-Van Vechten-Levine-Xue bond theory to calculate second-order nonlinear coefficients for isostructural to mineral hilhardite noncentrosymmetric crystals MBOX with M=Pb, Sr, Ba, Eu, Ca and X=Cl, Br. Theoretically obtained values of nonlinear optical coefficients d only partly correlate with the results of SHG measurements. In particular, the experiments distinctively show sharp increase of nonlinear activity along the series Ca < Sr < Ba < Pb and Cl < Br of metal boro-halogenides, while theoretical estimations give substantially more slack composition dependences. Analysis of contribution of different boron-oxygen bonds to optical nonlinearities of the compounds reveals important role of planar BO 3 triangles, though this factor is yet unable to explain enormously high SHG output from Pb 2B 5O 9Br.

  6. Density functional study on chirospectra of hydrogen-bonded systems X- (H2O)3 (X = F, Cl, Br, I)

    NASA Astrophysics Data System (ADS)

    Mang, Chao-Yong; Li, Zhen-Gui; Wu, Ke-Chen

    2010-04-01

    This paper calculates the molecular structures, infrared, Raman, circular dichroism spectra and optical rotatory powers of some hydrogen-bonded supramolecular systems as a cyclic water trimer, (H2O)3 and its pyramidal halide complexes, X- (H2O)3 (X = F, Cl, Br, I) with the gradient-corrected density functional theory method at the B3LYP/6-311++G(2d,2p) and B3LYP/Aug-cc-pVTZ levels. It finds that the complexation of halide anions with the water trimer can efficiently modulate the chirally optical behaviors. The calculated vibrational circular dichroism spectrum illuminates that the vibrational rotational strength of S(+)-(H2O)3 mostly originates from the O-H rocking modes, whereas chirality of S(-)-X- (H2O)3 (X = F, Cl, Br, I) has its important origin in the O-H stretching modes. The calculated optical rotatory power demonstrates that S(+)-(H2O)3 and S(+)-F-(H2O)3 are positively chiral, whereas S(-)-X-(H2O)3 (X = Cl, Br, I) are negatively chiral. With the polarizable continuum model, calculated bulk solvent effect in the solvents water and carbontetrachloride and argon shows that the positive chirality of S(+)-(H2O)3 is enhanced and the negative chirality of S(-)-X-(H2O)3 (X = Cl, Br, I) and the positive chirality of S(+)-F-(H2O)3 are reduced with an augmentation of the solvent dielectric constant.

  7. Rate constants for the reactions of OH with CH3Cl, CH2Cl2, CHCl3, and CH3Br

    NASA Technical Reports Server (NTRS)

    Hsu, K.-J.; Demore, W. B.

    1994-01-01

    Rate constants for the reactions of OH with CH3Cl, CH2Cl2, CHCl3, and CH3Br have been measured by a relative rate technique in which the reaction rate of each compound was compared to that of HFC-152a (CH3CHF2) and (for CH2Cl2) HFC-161 (CH3CH2F). Using absolute rate constants for HFC-152a and HFC-161, which we have determined relative to those for CH4, CH3CCl3, and C2H6, temperature dependent rate constants of both compounds were derived. The derived rate constant for CH3Br is in good agreement with recent absolute measurements. However, for the chloromethanes all the rate constants are lower at atmospheric temperatures than previously reported, especially for CH2Cl2 where the present rate constant is about a factor of 1.6 below the JPL 92-20 value. The new rate constant appears to resolve a discrepancy between the observed atmospheric concentrations and those calculated from the previous rate constant and estimated release rates.

  8. The effects of CaCl2 and CaBr2 on the reproduction of Daphnia magna Straus.

    PubMed

    Mažuran, Neda; Hršak, Vladimir; Kovačević, Goran

    2015-06-01

    Concentrated CaCl2 and CaBr2 salt solutions of densities up to 2.3 kg L-1 are regularly used to control hydrostatic pressure in oil wells during special operations in the exploration and production of natural gas and crude oil. Various concentrations of high density salts are frequently left in mud pits near the drilling site as waste, polluting fresh and ground waters by spillage and drainage. The toxic effects of these salts have already been observed. This study investigated the effects of CaCl2 and CaBr2 on water flea Daphnia magna Straus in a 21-day reproduction test. The three tested concentrations of CaCl2 (240, 481, and 1925 mg L-1) caused a significant dose-response decrease of reproduction (p<0.001). With CaBr2 (533 and 1066 mg L-1), only aborted eggs were produced, demonstrating the embryotoxicity of the substance. The results suggest that high concentrations of the tested chemicals are harmful to Daphnia's reproduction and could reduce its abundance. PMID:26110475

  9. Photochemistry in a dense manifold of electronic states: Photodissociation of CH{sub 2}ClBr

    SciTech Connect

    Valero, Rosendo; Truhlar, Donald G.

    2012-09-14

    We report electronically nonadiabatic dynamics calculations including spin-orbit coupling for the photodissociation of CH{sub 2}ClBr to yield Cl({sup 2}P{sub 3/2}), Cl({sup 2}P{sub 1/2}), Br({sup 2}P{sub 3/2}), and Br({sup 2}P{sub 1/2}). The potential energy is a 24 Multiplication-Sign 24 matrix (divided up here into four 6 Multiplication-Sign 6 blocks in a first approximation to the problem), in a spin-coupled fully diabatic representation obtained by combining the spin-free fourfold way with single-center spin-orbit coupling constants. The spin-free calculations are carried out by multiconfiguration quasidegenerate perturbation theory, and the fully diabatic potentials including spin-orbit coupling are fit to a matrix reactive force field. The dynamics are carried out by the coherent switches with decay of mixing method in the diabatic representation. The results show qualitative agreement with experiment.

  10. Photochemistry in a dense manifold of electronic states: Photodissociation of CH{sub 2}ClBr

    SciTech Connect

    Valero, Rosendo; Truhlar, Donald G.

    2012-12-14

    We report electronically nonadiabatic dynamics calculations including spin-orbit coupling for the photodissociation of CH{sub 2}ClBr to yield Cl({sup 2}P{sub 3/2}), Cl({sup 2}P{sub 1/2}), Br({sup 2}P{sub 3/2}), and Br({sup 2}P{sub 1/2}). The potential energy is a 24 Multiplication-Sign 24 matrix (divided up here into four 6 Multiplication-Sign 6 blocks in a first approximation to the problem), in a spin-coupled fully diabatic representation obtained by combining the spin-free fourfold way with single-center spin-orbit coupling constants. The spin-free calculations are carried out by multiconfiguration quasidegenerate perturbation theory, and the fully diabatic potentials including spin-orbit coupling are fit to a matrix reactive force field. The dynamics are carried out by the coherent switches with decay of mixing method in the diabatic representation. The results show qualitative agreement with experiment.

  11. Caveats for poly(methimazolyl)borate chemistry: the novel inorganic heterocycles [H2C(mt)2BR2]Cl (mt = methimazolyl; BR2 = BH2, BH(mt), 9-BBN).

    PubMed

    Crossley, Ian R; Hill, Anthony F; Humphrey, Elizabeth R; Smith, Matthew K; Tshabang, Never; Willis, Anthony C

    2004-08-21

    Whilst frequently used for reactions of poly(methimazolyl)borates, dichloromethane is not an innocent solvent, but rather slowly forms heterocyclic salts [H(2)C(mt)(2)BR(2)]Cl, three examples of which (BR(2) = BH(2), BH(mt), 9-borabicyclononyl) have been structurally characterised to confirm the unprecedented B(NCS)(2)C connectivity. PMID:15306929

  12. A preliminary investigation for an Al/AlCl3-NaCl/FeS2 secondary cell

    NASA Astrophysics Data System (ADS)

    Koura, N.

    1980-07-01

    The development of an Al/AlCl3-NaCl/FeS2 cell as a potential candidate for advanced secondary cells is investigated, considering that aluminum has a negative potential and a high theoretical capacity, and the system has a low melting point and is stable as molten salt not in the presence of air or moisture. Discharge curves at various temperatures showed a high plateau at about 0.9 V and a low plateau at about 0.6 V; it was also shown that the more the current density increased, the greater was the high plateau capacity. In addition, FeS was detected from the FeS2 electrode discharged up to 0.65 V, and Al2S3 was detected up to 0.20 V by X-ray analysis.

  13. Airborne Instruments for the In Situ Detection of ClONO2, NO2, ClO, and BrO in the Stratosphere

    NASA Technical Reports Server (NTRS)

    Anderson, James G.; Cohen, Ronald C.

    1996-01-01

    Design and construction of an in situ sensor for the detection of stratospheric ClONO2, ClO, BrO, and NO2, was conceived as a two-year program. The experiment has two novel components: a resistive silicon thermal dissociation heater used to fragment ClONO2 into ClO and NO2 and a laser-induced fluorescence sensor for N02. These two new components are integrated into an experiment that uses technology developed in our labs for the ER-2 ClO and ER-2 HO(X) instruments. During the first year we reconstructed our laboratory prototypes for ClONO2 and NO2 detection and made substantial improvements in the calibration apparatus. Results from these laboratory experiments have been used to refine the design of the flight instrument. During this year we began the design of all of the long-lead items required to produce a flight instrument: including the design and fabrication of the air flow system used to direct stratospheric air to our halogen sensors, design and prototyping of an aircraft-compatible thermal dissociation heater, and development and test of a new high powered laser system. Finally, we have designed and released for fabrication several subsystems.

  14. Freeze-dried PVP-Ag+ precursors to novel AgBr/AgCl-Ag hybrid nanocrystals for visible-light-driven photodegradation of organic pollutants

    NASA Astrophysics Data System (ADS)

    Chen, Deliang; Chen, Qianqian; Zhang, Wenjie; Ge, Lianfang; Shao, Gang; Fan, Bingbing; Lu, Hongxia; Zhang, Rui; Yang, Daoyuan; Shao, Guosheng

    2015-04-01

    AgBr/AgCl-Ag nanocrystals with various molar Br-to-Ag ratios (RBr/Ag = 0, 1/3, 1/2, 2/3, 1) and different photoreduction times (0-20 min) were synthesized via stepwise liquid-solid reactions using the freeze-dried PVP-Ag+ hybrid as the Ag source, followed by a photoreduction reaction. The AgBr/AgCl-Ag7.5(1:2) nanocrystals obtained take on a spherical morphology with a particle-size range of 58 ± 15 nm. The photocatalytic performance of AgBr/AgCl-Ag nanocrystals was evaluated by photodegrading organic dyes, 4-chlorophenol and isopropanol under artificial visible light (λ ⩾ 420 nm, 100 mW cm-2). For the decomposition of rhodamine B, the AgBr/AgCl-Ag7.5(1:2) nanocrystals has a photodegradation rate of ∼0.87 min-1, ∼159 times higher than that (∼0.0054 min-1) of TiO2 (P25), whereas the AgCl-Ag and AgBr-Ag nanocrystals have photodegradation rates of 0.35 min-1 and 0.45 min-1, respectively. The efficient separation of photogenerated electron-hole pairs in the ternary system consisting of AgBr, AgCl and Ag species plays a key role in the enhancement of photocatalytic performance.

  15. Electrochemistry of selenium in a basic AlCl{sub 3}-NaCl melt

    SciTech Connect

    Matsunaga, M.; Morimitsu, M.; Hosokawa, K.

    1995-09-01

    Sodium/molten-salt secondary batteries composed of a liquid sodium and chloroaluminate melt have been widely studied for electric vehicle and load-leveling applications. The authors have been interested in developing new cathode materials to be used in this type of battery. The electrochemical reactions of selenium species in a basic AlCl{sub 3}-NaCl melt has been studied by measuring EMF of an Na/SeCl{sub 4} cell. The reaction mechanism between elemental and tetravalent selenium consists of at least four electrochemical steps, including intermediates such as Se{sup 2+}, Se{sub 2}{sup 2+}, and Se{sub 8}{sup 2+}. The reaction sequence from Se{sup 4+} to Se{sub 8}{sup 2+} is discussed. The formal potential for each reaction is also determined.

  16. Trace-element compositions and Br/Cl ratios of fluid inclusions in the Tsushima granite, Japan: Significance for formation of granite-derived fluids

    NASA Astrophysics Data System (ADS)

    Kurosawa, Masanori; Sasa, Kimikazu; Shin, Ki-Choel; Ishii, Satoshi

    2016-06-01

    Fluid inclusions in quartz samples from a miarolitic cavity, two quartz veins, and a hydrothermal ore vein in the Tsushima granite, Japan, were analyzed by particle-induced X-ray emission to examine the chemistry and process of formation of hydrothermal fluids in an island-arc granite. Most of the inclusions were polyphase or vapor, and there were smaller numbers of two-phase aqueous inclusions. The inclusions contained Cl, K, Ca, Ti, Mn, Fe, Cu, Zn, Ge, Br, Rb, Sr, Ba, and Pb. For each inclusion, there was a strong positive correlation between Cl content and contents of other elements identified. Concentration ranges for most elements (other than Rb and Ge) in polyphase inclusions from the miarolitic cavity were comparable to those from cavities in alkaline granites; those from the ore vein were comparable to large-scale continental hydrothermal ore deposits. The lower Rb and higher Ge contents in the polyphase inclusions of the Tsushima granite may be characteristic of hydrothermal fluids from calc-alkaline granites in an island-arc setting. Br/Cl ratios (by weight) for the vapor and two-phase inclusions were 0.0013-0.0030 and differed among the three geological settings. Br/Cl ratios of polyphase inclusions increased with increasing Cl content in single-crystal and polycrystalline quartz, and high values of more than 0.0100 were found. The high Br/Cl ratios and the differences among the geological settings sampled may be due to pressure dependences of partitioning of Cl and Br between fluid and magma during fluid segregation and between liquid and vapor during boiling. Using a simple model based on these dependences, we calculated Br/Cl ratios greater than 0.01 in brine generated at pressures <0.89 kbar. Differences in Br/Cl ratios in polyphase and vapor inclusions from each geological setting were attributed to mixing between two end-member fluids: a high Br/Cl fluid generated at low pressure and a low Br/Cl fluid generated at high pressure. Br/Cl ratios of

  17. Comparison of the directionality of the halogen, hydrogen, and lithium bonds between HOOOH and XF (X = Cl, Br, H, Li).

    PubMed

    Liu, Lixun; Meng, Lingpeng; Zhang, Xueying; Zeng, Yanli

    2016-03-01

    Detailed electrostatic potential (ESP) analyses were performed to compare the directionality of halogen bonds with those of hydrogen bonds and lithium bonds. To do this, the interactions of HOOOH with the molecules XF (X = Cl, Br, H, Li) were investigated. For each molecule, the percentage of the van der Waals (vdW) molecular surface that intersected with the ESP surface was used to roughly quantify the directionality of the halogen/hydrogen/lithium bond associated with the molecule. The size of the region of intersection was found to increase in the following order: ClF < BrF < HF < LiF. The maximum ESP in the region of intersection, V S, max, was observed to become more positive according to the sequence ClF < BrF < HF < LiF. For ClF and BrF, the positive electrostatic potential was concentrated in a very small region of the vdW molecular surface. On the other hand, for HF and LiF, the positive electrostatic potential was more diffusely scattered across the vdW surface than for ClF and BrF. Also, the optimized geometries of the dipolymers HOOOH··· XF (X = Cl, Br, H, Li) indicated that halogen bonds are more directional than hydrogen bonds and lithium bonds, consistent with the results of ESP analyses. PMID:26847451

  18. Structure modeling and growing AgClхBr1-х, Ag1-xTlxBr1-xIx, and Ag1-xTlxClyIzBr1-y-z crystals for infrared fiber optics

    NASA Astrophysics Data System (ADS)

    Korsakov, Alexandr; Zhukova, Liya; Korsakova, Elena; Zharikov, Evgenii

    2014-01-01

    In this paper we describe the aggregate technology of producing variable composition crystals, based on the solid solutions of silver and Tl+-doped halides for creating infrared photonic crystal fibers in the spectral range of 2-40 μm by extruding, we also produce all the necessary equipment. We specified the minimum melting point position for the AgCl-AgBr phase diagram. We also investigated the fundamental physical properties of new crystals and fibers: transmission losses, transmission range, refraction index, hardness, and density.

  19. Tracing recharge to aquifers beneath an Asian megacity with Cl/Br and stable isotopes: the example of Dhaka, Bangladesh

    NASA Astrophysics Data System (ADS)

    Hoque, M. A.; McArthur, J. M.; Sikdar, P. K.; Ball, J. D.; Molla, T. N.

    2014-06-01

    Dhaka, the capital of Bangladesh, is home to a population of 15 million people, whose water supply is 85% drawn from groundwater in aquifers that underlie the city. Values of Cl/Br >500 are common in groundwater beneath western Dhaka in areas <3 km from the river, and in rivers and sewers around and within the city. The study shows that groundwater beneath western Dhaka is strongly influenced by infiltration of effluent from leaking sewers and unsewered sanitation, and by river-bank infiltration from the Turag-Buriganga river system which bounds the western limit of the city. River-bank infiltration from other rivers around Dhaka is minor. Values of Cl/Br and Cl concentrations reveal that 23 % of wells sampled in Dhaka are influenced by saline connate water in amounts up to 1%. This residual natural salinity compromises the use of electrical conductivity of groundwater as a method for defining pathways of recharge by contaminated surface waters. Concentrations of As, B, Ba, Cd, Cu, F, Ni, NO3, Pb, Sb, Se and U in groundwater samples are less than WHO health-based guideline values for drinking water.

  20. Kinetics of the Reactions of O((sup 3)P) and Cl((sup 2)P) with HBr and Br2

    NASA Technical Reports Server (NTRS)

    Nicovich, J. M.; Wine, P. H.

    1997-01-01

    A laser flash photolysis-resonance fluorescence technique has been employed to study the kinetics of reactions (1)-(4) as a function of temperature. (1) O((sup 3)P) + Br2 yields BrO + Br((sup 2)P(sub 3/2)) at 255-350 K; (2) Cl((sup 2)P) + Br2 yields BrCl + Br((sup 2)P(sub 3/2)) at 298-401 K; (3) O((sup 3)P) + HBr yields OH + Br((sup 2)P(sub J)) at 250-402 K; (4) Cl((sup 2)P) + HBr yields HCl + Br((sup 2)P(sub J)) at 257-404 K. In all cases, the concentration of the excess reagent, i.e, HBr or Br2, was measured in situ in the slow flow system by UV-visible photometry. Heterogeneous dark reactions between XBr (X equals H or Br) and the photolytic precursors for Cl((sup 2)P) and O((sup 3)P) (Cl2 and O3, respectively) were avoided by injecting minimal amounts of precursor into the reaction mixture immediately upstream from the reaction zone. The following Arrhenius expressions summarize our results (errors are 2 sigma and represent precision only, units are cu cm/(molecule.s): k(sub 1) = (1.76 +/- 0.80) x 10(exp -11 exp[(40 +/- 100)/T]; k(sub 2) = (2.40 +/- 1.25) x 12(exp -10) exp[-(144 +/- 176)/T]; k(sub 3) = (5.11 +/- 2.82) x 10(exp -12) exp[-(1450 +/- 160)/T]; k(sub 4) = (2.25 +/- 0.56) x 10(exp -11) exp[-(400 +/- 80)/T]. The consistency (or lack thereof) of our results with those reported in previous kinetics and dynamics studies of reactions (1)-(4) is discussed.

  1. Diurnal variation of O3, ClO, HOCl, HO2, and BrO observed by JEM/SMILES

    NASA Astrophysics Data System (ADS)

    Suzuki, Makoto; Mitsuda, Chihiro; Manago, Naohiro; Imai, Koji; Sakazaki, Takatoshi; Ozeki, Hiroyuki; Nishimoto, Eriko; Naito, Yoko; Akiyoshi, Hidehary; Kinnison, Douglas; Sano, Takuki; Shiotani, Masato

    2013-04-01

    SMILES; Superconducting Submillimeter-Wave Limb Emission Sounder is a 4 K cooled 625-650 GHz limb sounder to observe O3, HCl, ClO, HO2, HOCl, BrO, HNO3, and O3 isotopes. SMILES had been operated on the International Space Station from Oct. 12, 2009 to Apr. 21, 2010. Since ISS is 51° inclined orbit, 30-45 days SMILES zonal mean could provide diurnal variation of chemical species in the stratosphere and mesosphere. Diurnal variation of O3, ClO, HOCl, HO2, and BrO are compared with two nudged CGCM calculations (SD-WACCM; Specified-dynamics WACCM, and MIROC) and satellite observations. Diurnal variation of O3 agreed with SD-WACCM over 50-82 km, but small peak in the morning (7 am local time) is apparent for the SMILES but not for the SD-WACCM at 70 km. Diurnal variation of ClO agreed quite well between SMILES L2 ver. 2.2 and SD-WACCM from 19 to 76 km altitude region. But nighttime ClO value of SMILES L2 ver. 2,2 above 50 km is less than SD-WACCM (70%), which is not clearly explained by the SMILES retrieval issue or our current knowledge of chemical kinetics. Diurnal variation of HOCl also agreed quite nicely from 31 to 76 km. SMILES HOCl retrieval is difficult since it is strongly affected by nearby O3 isotope and O3 hot band lines, as well as very strong HCl line. The nighttime build up of HOCl observed SMILES at 44-68 km are nicely reproduced by the SD-WACCM calculation using JPL2006 chemical kinetics dataset. But chemical kinetics calculation using SMILES ClO, HO2, and HOCl at 35-45 km altitude supported much faster reaction rate of ClO + HO2 given by JPL2010. HO2 diurnal variation also agreed with SD-WACCM from 24 to 72 km. Above 76 km, SMILES L2 ver. 2.2 needs modification of a priori and its co-variance, and we will get better agreement with model calculations. SMILES L2 ver. 2.2 also shows night time bias due to AOS (Acousto-Optics Spectrometer) characteristics. SMILES Band C BrO observation is strongly interfered by overlapping O3 isotope lines, and it is

  2. On the chain lenth in Ox, HOx, NOx, ClOx and BrOx cycles in the middle atmosphere

    NASA Astrophysics Data System (ADS)

    Larin, Igor; Kuskov, Michael

    2013-04-01

    Analysis of chain mechanisms of ozone depletion in Ox, HOx, NOx, ClOx and BrOx cycles has been performed. The carried out analysis has allowed to get analytical expression for calculation of the rate of limiting stage of chain prolongation, as well as chain breaking and chain length in cycles specified. It has been shown, that the correct estimation of ozone depletion in the chain processes is possible only through definition of the rate of limiting stage with taking into account of all reactions of chain prolongation, instead of the unique reaction possessing the least rate as it usually became earlier. It has been shown also, that choice of one reaction means ignoring a chain character of the process and leads to overestimate of real rate of ozone destruction. The role of null chain processes in the cycles specified above has been considered. It has been shown, that these processes play defining role in formation of families of odd oxygen, nitrogen, chlorine and bromine. By means of methods developed, data of IPCC scenario RCP 4.5, and two-dimensional model Socrates the rate of ozone destruction and chain length in Ox, HOx, NOx, ClOx and BrOx cycles for modeling conditions of April 2013 at 50 N and height diapason 15-120 km has been calculated. It has been shown, that in the middle stratosphere ozone destruction is due mainly to NOx cycle, whereas in the mesosphere and low thermosphere it is due mainly HOx one. It has been also shown that ClOx and BrOx have the greatest chain length in the upper stratosphere which exceeds 106 and HOx cycle in the low thermosphere has a chain length exceeding 1011.

  3. In situ quantification of Br and Cl in minerals and fluid inclusions by LA-ICP-MS: a powerful tool to identify fluid sources

    USGS Publications Warehouse

    Hammerli, Johannes; Rusk, Brian; Spandler, Carl; Emsbo, Poul; Oliver, Nicholas H.S.

    2013-01-01

    Bromine and chlorine are important halogens for fluid source identification in the Earth's crust, but until recently we lacked routine analytical techniques to determine the concentration of these elements in situ on a micrometer scale in minerals and fluid inclusions. In this study, we evaluate the potential of in situ Cl and Br measurements by LA-ICP-MS through analysis of a range of scapolite grains with known Cl and Br concentrations. We assess the effects of varying spot sizes, variable plasma energy and resolve the contribution of polyatomic interferences on Br measurements. Using well-characterised natural scapolite standards, we show that LA-ICP-MS analysis allows measurement of Br and Cl concentrations in scapolite, and fluid inclusions as small as 16 μm in diameter and potentially in sodalite and a variety of other minerals, such as apatite, biotite, and amphibole. As a demonstration of the accuracy and potential of Cl and Br analyses by LA-ICP-MS, we analysed natural fluid inclusions hosted in sphalerite and compared them to crush and leach ion chromatography Cl/Br analyses. Limit of detection for Br is ~8 μg g−1, whereas relatively high Cl concentrations (> 500 μg g−1) are required for quantification by LA-ICP-MS. In general, our LA-ICP-MS fluid inclusion results agree well with ion chromatography (IC) data. Additionally, combined cathodoluminescence and LA-ICP-MS analyses on natural scapolites within a well-studied regional metamorphic suite in South Australia demonstrate that Cl and Br can be quantified with a ~25 μm resolution in natural minerals. This technique can be applied to resolve a range of hydrothermal geology problems, including determining the origins of ore forming brines and ore deposition processes, mapping metamorphic and hydrothermal fluid provinces and pathways, and constraining the effects of fluid–rock reactions and fluid mixing.

  4. Magnetic Torque Studies of π-d System κ-(BDH-TTP)2FeX4 (X = Br, Cl)

    NASA Astrophysics Data System (ADS)

    Sugii, Kaori; Takai, Kazuyuki; Tsuchiya, Satoshi; Uji, Shinya; Terashima, Taichi; Akutsu, Hiroki; Wada, Atsushi; Ichikawa, Shun; Yamada, Jun-ichi; Enoki, Toshiaki

    2014-02-01

    Systematic measurements of the magnetic torque of organic π-d conductors κ-(BDH-TTP)2FeX4 (X = Br, Cl) have been performed to investigate the magnetic properties. The Fe 3d spins of both salts show antiferromagnetic (AF) orders at low temperatures. A simple two-sublattice model is found to well reproduce the essential features of the torque data in the AF states. The exchange interaction and anisotropic parameter of the ligand field obtained by the simulations are consistent with previous experimental results.

  5. Allylic and Allenic Halide Synthesis via NbCl5- and NbBr5-Mediated Alkoxide Rearrangements

    PubMed Central

    Ravikumar, P. C.; Yao, Lihua; Fleming, Fraser F.

    2009-01-01

    Addition of NbCl5, or NbBr5, to a series of magnesium, lithium, or potassium allylic or propargylic alkoxides directly provides allylic or allenic halides. Halogenation formally occurs through a metalla-halo-[3,3] rearrangement although concerted, ionic, and direct displacement mechanisms appear to operate competitively. Transposition of the olefin is equally effective for allylic alkoxides prepared by nucleophilic addition, deprotonation, or reduction. Experimentally, the niobium pentahalide halogenations are rapid, afford essentially pure E-allylic or allenic halides after extraction, and are applicable to a range of aliphatic and aromatic alcohols, aldehydes, and ketones. PMID:19739606

  6. Allylic and allenic halide synthesis via NbCl(5)- and NbBr(5)-mediated alkoxide rearrangements.

    PubMed

    Ravikumar, P C; Yao, Lihua; Fleming, Fraser F

    2009-10-01

    Addition of NbCl(5) or NbBr(5) to a series of magnesium, lithium, or potassium allylic or propargylic alkoxides directly provides allylic or allenic halides. Halogenation formally occurs through a metalla-halo-[3,3] rearrangement, although concerted, ionic, and direct displacement mechanisms appear to operate competitively. Transposition of the olefin is equally effective for allylic alkoxides prepared by nucleophilic addition, deprotonation, or reduction. Experimentally, the niobium pentahalide halogenations are rapid, afford essentially pure (E)-allylic or -allenic halides after extraction, and are applicable to a range of aliphatic and aromatic alcohols, aldehydes, and ketones. PMID:19739606

  7. Ring-strain release in neutral and dicationic 7,8,17,18-tetra-bromo-5,10,15,20-tetra-phenyl-porphyrin: crystal structures of C44H26Br4N4 and C44H28Br4N4 (2+)·2ClO4 (-)·3CH2Cl2.

    PubMed

    Scheidt, W Robert; Duval, Hugues F; Oliver, Allen G

    2016-06-01

    Two porphyrin complexes were studied to determine the effects of protonation on ring deformation within the porphyrin. The porphyrin 7,8,17,18-tetra-bromo-5,10,15,20-tetra-phenyl-porphyrin, C44H26Br4N4, was selected because the neutral species is readily doubly protonated to yield a dication, which was crystallized here with perchlorate counter-ions as a di-chloro-methane tris-olvate, C44H28Br4N4 (2+)·2ClO4 (-)·3CH2Cl2. The centrosymmetric neutral species is observed to have a mild 'ruffling' of the pyrrole rings and is essentially planar throughout; intra-molecular N-H⋯N hydrogen bonds occur. In contrast, the dication exhibits considerable deformation, with the pyrrole rings oriented well out of the plane of the porphyrin, resulting in a 'saddle' conformation of the ring. The charged species forms N-H⋯O hydrogen bonds to the perchlorate anions, which lie above and below the plane of the porphyrin ring. Distortions to the planarity of the pyrrole rings in both cases are very minor. The characterization of the neutral species represents a low-temperature redetermination of the previous room-temperature analyses [Zou et al. (1995 ▸). Acta Cryst. C51, 760-761; Rayati et al. (2008 ▸). Polyhedron, pp. 2285-2290], which showed disorder and physically unrealistic displacement parameters. PMID:27308051

  8. Reaction of atomic bromine with acetylene and loss rate of atmospheric acetylene due to reaction with OH, Cl, O, and Br

    NASA Technical Reports Server (NTRS)

    Payne, W. A.; Nava, D. F.; Brunning, J.; Stief, L. J.

    1986-01-01

    The first-order, diffusion, and bimolecular rate constants for the reaction Br + C2H2 yields C2H3Br are evaluated. The rate constants are measured at 210, 248, 298, and 393 K and at pressures between 15-100 torr Ar using flash photolysis combined with time-resolved detection of atomic bromine via Br resonance radiation. It is observed that the reaction is not affected by pressure or temperature and the bimolecular constant = (4.0 + or - 0.8) x 10 to the -15th cu cm/sec with an error of two standard deviations. The C2H2 + Br reaction rates are compared with reactions of C2H2 with Cl, OH, NH2, and H. The loss rates for atmospheric C2H2 for reactions with OH, Cl, O, and Br are calculated as a function of altitude.

  9. Silicene/germanene on MgX2 (X = Cl, Br, and I) for Li-ion battery applications

    NASA Astrophysics Data System (ADS)

    Zhu, Jiajie; Chroneos, Alexander; Schwingenschlögl, Udo

    2016-03-01

    Silicene is a promising electrode material for Li-ion batteries due to its high Li capacity and low Li diffusion barrier. Germanene is expected to show a similar performance due to its analogous structural and electronic properties. However, the performance of both the materials will be determined by the substrate, since freestanding configurations are unstable. We propose Si/MgX2 and Ge/MgX2 (X = Cl, Br, and I) as suitable hybrid structures, based on first-principles calculations. We find that Li will not cluster and that the Li capacity is very high (443 and 279 mA h g-1 for silicene and germanene on MgCl2, respectively). Sandwich structures can be used to further enhance the performance. Low diffusion barriers of less than 0.3 eV are predicted for all the hybrid structures.

  10. Silicene/germanene on MgX2 (X = Cl, Br, and I) for Li-ion battery applications.

    PubMed

    Zhu, Jiajie; Chroneos, Alexander; Schwingenschlögl, Udo

    2016-03-24

    Silicene is a promising electrode material for Li-ion batteries due to its high Li capacity and low Li diffusion barrier. Germanene is expected to show a similar performance due to its analogous structural and electronic properties. However, the performance of both the materials will be determined by the substrate, since freestanding configurations are unstable. We propose Si/MgX2 and Ge/MgX2 (X = Cl, Br, and I) as suitable hybrid structures, based on first-principles calculations. We find that Li will not cluster and that the Li capacity is very high (443 and 279 mA h g(-1) for silicene and germanene on MgCl2, respectively). Sandwich structures can be used to further enhance the performance. Low diffusion barriers of less than 0.3 eV are predicted for all the hybrid structures. PMID:26976115

  11. On the vibrational spectra and structural parameters of some XN 3 molecules (X=H, F, Cl, Br)

    NASA Astrophysics Data System (ADS)

    Shen, Shiyu; Durig, James R.

    2003-12-01

    Ab initio calculations with full electron correlation by the perturbation method to second order and hybrid density functional theory calculations by the B3LYP method utilizing the 6-31G* and 6-311+G** basis sets have been carried out for the XN 3 molecules (X=H, F, Cl, Br). From these calculations, force constants, infrared intensities, Raman activities, depolarization ratios, vibrational frequencies, and structural parameters have been determined. These calculations support the assignment of the HN 3 and DN 3 out-of-plane bending modes (ν 6, A″) at 602 and 591 cm -1, respectively, which was proposed [J. Chem. Phys. 44 (1966) 4108] earlier and show the recent assignments at 637 and 638 cm -1 [J. Mol. Struct. (Theochem) 434 (1998) 1], respectively, for these modes are in error. Also the usually used frequency of 588 cm -1 for ν 6 for the HN 3 from nitrogen matrix studies for comparison to ab initio predicted values is also clearly in error. The predicted intensity of ν 6 is only 0.2-0.6 km/mol which is 10 3 times less than the stronger bands which explains why it is so weak in the nitrogen matrix compared to its intensity in the gas phase where it drastically increased by Coriolis coupling with ν 5. For ClN 3 there is extensive coupling of the N 3 deformation at 719 cm -1 with the Cl-N stretch at 545 cm -1 where the latter mode is 71% Cl-N stretch. For BrN 3 the coupling is mainly between the N 3 deformation (682 cm -1) and the BrNN bend which is predicted in the 180 cm -1 region. The predicted force constants for FN 3 are compared to those obtained earlier from frequency and distortion data. By combining previously reported rotational constants for HN 3, FN 3 and ClN 3 with the ab initio MP2/6-311+G** predicted parameters, adjusted r0 parameters have been obtained for all three molecules. The structural parameters for hydrazoic acid are: r(H-N), 1.015(5); r(N 1N 2), 1.243(5); r(N 2N 3), 1.134(2)Å; ∠HN 1N 2, 108.8(5); ∠N 1N 2N 3, 171.8(5)°. It is

  12. The synthesis and structural characterisation of Ru-Sn based derivatives bearing asymmetric X 2ClSn - (X=Br and F) anions

    NASA Astrophysics Data System (ADS)

    de Moura, E. M.; Siebald, H. G. L.; de Lima, G. M.; Porto, A. O.; Rodarte de Moura, C. V.; Horner, M.

    2003-09-01

    Four remarkable ruthenium-tin based derivatives [Ru(η 5-Cp)(PPh 3) 2SnF 2Cl] (1), [Ru(η 5-Cp)(PPh 3) 2SnBr 2Cl] (2), [Ru(η 5-Cp)(dppe)SnF 2Cl] (3) and [Ru(η 5-Cp)(dppe)SnBr 2Cl] (4), Cp=C 5H 5, were obtained by reacting [Ru(η 5-Cp)(PPh 3) 2Cl] or [Ru(η 5-Cp)(dppe)Cl] with SnX 2 {X=F or Br}, respectively. They were studied by i.r. NMR ( 1H, 13C, 31P and 119Sn) and 119Sn-Mössbauer spectroscopies. Additionally, (1) and (4) were structurally authenticated by X-ray crystallography and the results were as follows: (1) orthorhombic, Pbca, V=15181.7(12) Å 3 and Z=8; (4) monoclinic, P2 1/ n, V=3503.74(8) Å 3 and Z=4. All compounds exist as formulated only in the solid sate, in solution they re-distribute in a mixture of species such as [Ru(η 5-Cp)(PPh 3) 2SnF nCl 3- n] and [Ru(η 5-Cp)(dppe)SnBr nCl 3- n] {n=0,1,2, and 3}, as revealed by variable temperature 119Sn NMR experiments.

  13. Photoelectron imaging of atomic chlorine and bromine following photolysis of CH{sub 2}BrCl

    SciTech Connect

    Hua Linqiang; Shen Huan; Hu Changjin; Zhang Bing

    2008-12-28

    Photoionization of chlorine and bromine atoms following photodissociation of CH{sub 2}BrCl was studied in the wavelength range of 231-238 nm by photoelectron imaging technique. Final state-specific speed and angular distributions of the photoelectron were recorded. Analysis of relative branching ratios to different levels of Cl{sup +} and Br{sup +} revealed that the final ion level distributions are generally dominated by the preservation of the ion-core configuration of the intermediate resonant state. Some J{sub c} numbers of the intermediate states were newly assigned according to this regulation. The configuration interaction between resonant states and the autoionization in the continuum were also believed to play an important role in the ionization process since some ions that deviate from the regulation mentioned ahead were observed. The angular distributions of the electrons were found to be well characterized by {beta}{sub 2} and {beta}{sub 4}, although the ionization process of chlorine and bromine atoms involves three photons.

  14. First-principles study of rock-salt AgCl xBr 1-x alloys

    NASA Astrophysics Data System (ADS)

    Amrani, B.; El Haj Hassan, F.; Zoaeter, M.

    2007-06-01

    We present first-principles calculations of the structural, electronic and thermodynamic properties of rock-salt AgCl xBr 1-x alloys by application of the full potential linearized augmented plane wave (FP-LAPW) method. We use both Perdew-Burke-Ernzerhof and Engel-Vosko generalized gradient approximations of the exchange-correlation energy that are based on the optimization of total energy and corresponding potential, respectively. The effect of composition on lattice constants, bulk modulus, cohesive energy, bond ionicity, band gap and effective mass was investigated. These parameters were found to depend nonlinearly on alloy composition x, except the lattice parameter, which follows Vegard's law. The microscopic origins of the gap bowing were explained by using the approach of Zunger and co-workers; we have concluded that the band gap energy bowing was mainly caused by the chemical charge-transfer effect, while the volume deformation and the structural relaxation contribute to the gap bowing parameter at smaller magnitude. On the other hand, the thermodynamic stability of AgCl xBr 1-x was investigated by calculating the excess enthalpy of mixing Δ Hm as well as the phase diagram.

  15. Infrared Absorption Study of Ca2- xNaxCuO2X2 (X=Cl, Br)

    NASA Astrophysics Data System (ADS)

    Hasegawa, Takumi; Ogita, Norio; Kondo, Toshihisa; Zenitani, Yuji; Kawashima, Hirokazu; Suzuki, Teruhiko; Akimitsu, Jun; Udagawa, Masayuki

    2006-09-01

    IR-active phonon spectra of Ca2- xNaxCuO2X2 (X=Cl, Br) have been measured by a CsI powder method in the energy region between 250 and 4000 cm-1 at room temperature. Two absorption peaks with the Eu symmetry have been clearly observed for the undoped crystals of Ca2CuO2Cl2 and Ca2CuO2Br2. However, the observed two peaks disappear for the Na-doped superconducting samples. From the comparison of the highest-energy Eu phonon, which is the Cu-O stretching vibration, the interaction of the Cu-O bond along the CuO2 plane for the T-structure is stronger by 20 % than that of the T'-structure in the 2-1-4 family. To understand the effect of the apical ions, first-principles calculations of the Eu phonon energy for T- and T'-structure La2CuO4 is performed and the preliminary results agree with the experimental tendency.

  16. Periodicity, Electronic Structures, and Bonding of Gold Tetrahalides [AuX4]- (X = F, Cl, Br, I, At, Uus).

    PubMed

    Li, Wan-Lu; Li, Yong; Xu, Cong-Qiao; Wang, Xue-Bin; Vorpagel, Erich; Li, Jun

    2015-12-01

    Systematic theoretical and experimental investigations have been performed to understand the periodicity, electronic structures, and bonding of gold halides using tetrahalide [AuX4](-) anions (X = F, Cl, Br, I, At, Uus). The [AuX4](-) (X = Cl, Br, I) anions were experimentally produced in the gas phase, and their negative-ion photoelectron spectra were obtained, exhibiting rich and well-resolved spectral peaks. As expected, Au-X bonds in such series contain generally increasing covalency when halogen ligands become heavier. We calculated the adiabatic electron detachment energies as well as vertical electron detachment energies using density functional theory methods with scalar relativistic and spin-orbit coupling effects. The computationally simulated photoelectron spectra are in good agreement with the experimental ones. Our results show that the trivalent Au(III) oxidation state becomes progressively less stable while Au(I) tends to be preferred when the halides become heavier along the Periodic Table. This series of molecules provides an example for manipulating the oxidation state of metals in complexes through ligand design. PMID:26550845

  17. C-S barrier and vibrational analyses of (halocarbonyl)sulfenyl halides XCO-SX (X = F, Cl, and Br).

    PubMed

    Badawi, Hassan M

    2004-09-01

    The structural stability of (halocarbonyl)sulfenyl halides XCO-SX (X is F, Cl, and Br) was investigated by DFT-B3LYP and ab initio MP2 calculations using 6-311 + G(**) basis set. From the calculations the molecules were found to exist predominantly in the trans conformation (two halogen atoms are trans to each other). Full energy optimizations were carried out for the minima and the transition states (TS) at the two levels, from which the rotational barriers about C-S bond in the three molecules were calculated to be about 12-13 kcal mol(-1). The vibrational frequencies of (fluorocarbonyl)sulfenyl fluoride (FCO-SF), (chlorocarbonyl)-sulfenyl chloride (ClCO-SCl), and (bromocarbonyl)-sulfenyl bromide (BrCO-SBr) were computed at the DFT-B3LYP level and the vibrational assignments for the normal modes of the stable forms of the compounds were made on the basis of normal coordinate calculations and experimental data of the chloride. PMID:15294247

  18. Crystal structures and thermal behavior of bis[dibenzyldimethylammonium]CuBr 4, bis[dibenzyldimethylammonium]CuCl 4 and bis[dimethyldi(2-phenylethyl)ammonium]CuBr 4 crystallized from acetonitrile and dilute HX (X=Cl or Br) solutions

    NASA Astrophysics Data System (ADS)

    Busi, Sara; Lahtinen, Manu; Valkonen, Jussi; Rissanen, Kari

    2006-08-01

    Bis[dibenzyldimethylammonium]CuBr 4, bis[dibenzyldimethylammonium]CuCl 4 and bis[dimethyldi(2-phenylethyl)ammonium]CuBr 4 were crystallized from acetonitrile and/or dilute HX solutions. Five different kinds of single crystals were obtained. In the case of bis[dibenzyldimethylammonium]CuX 4 (X=Br or Cl), the acetonitrile molecules cocrystallized into the crystal structure when acetonitrile solution was used. As a result, the isomorphic structures of Bis[dibenzyldimethylammonium]CuX 4·0.5 CH 3CN (X=Br or Cl) in monoclinic space group P2 1/ n were obtained. When a dilute HX solution was used, the bis[dibenzyldimethylammonium]CuX 4 (X=Br or Cl) crystallized without solvent molecules. The formed crystals were not isomorphous with each other as the tetrabromocuprate structure crystallized in triclinic space group and the tetrachlorocuprate structure in monoclinic space group. The third compound, bis[di(2-phenylethyl)dimethylammonium]CuBr 4, crystallized without solvent molecules from an acetonitrile solution and no measurable single crystals were obtained from a dilute HX solution. Elemental analysis and powder diffraction analysis were performed to verify the structural similarities of all formed single crystals. The powder diffraction measurements also showed that the compounds have the same structure at room temperature and at a temperature of -100 °C. The thermal behaviour of the compounds was studied by using TG/DTA and DSC measurements; the compounds decomposed in two stages. No phase transitions were observed between room temperature and the melting point. In addition, these crystals showed to be very stable in the air at room temperature as they could be kept in the air for several weeks without any marks of the decomposition.

  19. Matrix infrared spectra and density functional calculations for new iso-halomethanes: CHCl2-Cl, CHFCl-Cl, CFCl2-Cl, CHBr2-Br, and CBr3-Br in solid argon.

    PubMed

    Cho, Han-Gook; Andrews, Lester

    2013-08-01

    Laser ablation of transition metals for reactions with halocarbons to produce new metal bearing molecules also exposed these samples to laser plume radiation and its resulting photochemistry. Investigations with CCl4 also produced several known neutral and charged intermediate species, including the iso-tetrachloromethane CCl3-Cl observed in previous work and identified by the Maier group. CHCl2-Cl, CHFCl-Cl, and CFCl2-Cl, photoisomers of CHCl3, CHFCl2, and CFCl3, were also identified in matrix IR spectra. The new C-X bonds are shorter than those of the reactants, and the Cl atom that is weakly bonded to the residual Cl atom forms an unusually strong C-Cl bond. NBO analysis reveals substantial C═Cl double-bond character, and the weak Cl···Cl bond is largely ionic. Therefore, the CHX2-X species can be represented as HXC═X(δ+)···X(δ-). Ionic properties are revealed for CCl3-Cl, which has an average C-Cl bond length near the median for the CCl3 radical and cation and a natural charge of +0.49 for the CCl3 subunit. IRC computations reproduce smooth interconversion between the reactants and products, and the transition state is energetically close to the product, which is consistent with its disappearance on visible irradiation. PMID:23802623

  20. Electronic properties of PbX₃CH₃NH₃ (X = Cl, Br, I) compounds for photovoltaic and photocatalytic applications.

    PubMed

    Melissen, Sigismund Teunis Alexander George; Labat, Frédéric; Sautet, Philippe; Le Bahers, Tangui

    2015-01-21

    Since the discovery of their excellent performance as the light-absorbing semiconducting component in photovoltaic cells, the PbX3CH3NH3 (X = I, Br, Cl) perovskites have received renewed attention. The five polymorphs stable above 200 K - the tetragonal phases for X = I, Br, Cl and the cubic phases for X = I, Br - were studied using periodic DFT calculations involving hybrid functionals (PBE0 and HSE), employing Gaussian-type orbitals as well as plane waves and including relativistic effects (spin-orbit coupling). The influence of the halogen substitution and of the crystal phase on these properties is analysed by comparing the properties obtained in this study to the experimental ones and to the theoretical ones computed using other methods. We show that an accurate treatment of these systems requires the description of dispersion forces and spin-orbit coupling. The different time scales for the electronic and vibrational components of the polarizability inspire the hypothesis that several interfacial charge transfer mechanisms are encountered in the working principle of the photovoltaic devices involving these perovskite materials. The heavy elements in the structure (Pb, I) play a major role in the high polarizability and the low effective charge carrier masses and hence in the low exciton binding energies and the high charge mobility. This systematic work on the PbX3CH3NH3 family offers to theoreticians an overview of the landscape of quantum chemical methods to enable a reasonable choice of methodology for studying these systems. PMID:25483273

  1. Bromine enrichment in the near-surface region of Br-doped NaCl single crystals diagnosed by Rutherford backscattering spectrometry.

    PubMed

    Hess, M; Krieger, U K; Marcolli, C; Huthwelker, T; Ammann, M; Lanford, W A; Peter, Th

    2007-05-24

    Bromine released from sea-salt aerosols and seawater ice is known for its high chemical reactivity. Previous studies have suggested that its availability to the gas-phase could be enhanced by segregation processes increasing Br concentration on the aerosol surface as compared to the bulk. However, little is known about the composition within the near-surface region, that is, the outermost approximately 100 monolayers. We used Rutherford backscattering spectrometry (RBS) to measure Br concentration profiles to a depth of about 750 nm of Br-doped NaCl single crystals to characterize the thermodynamics and kinetics of Br segregation to the near-surface region in moist air. These experiments were carried out on cleavage planes of melt-grown and of annealed solution-grown crystals at room temperature and relative humidities (RH) too low for formation of a stable liquid phase. Segregation of Br was below the detection limit on melt-grown crystals with Br/Cl = 0.01. In the case of annealed solution-grown crystals with Br/Cl = 0.002, average segregations of (0.24 +/- 0.11) x 10(15) and (0.42 +/- 0.12) x 10(15) Br atoms cm-2 were observed at 50% and 65% RH, respectively. No segregation was found at 20% RH. The observed Br segregation can be explained by the formation of an adsorbed liquid layer (depending on crystal surface properties and relative humidity) and preferential, diffusion-limited dissolution of Br into this layer according to the partition coefficient of Br between aqueous and solid NaCl. The thickness of the adsorbed liquid layer, which depends on crystal surface geometry and on relative humidity, can be estimated to range from 4 to at most 59 nm on the basis of measured Br concentrations and partition coefficients. Applying this concept of partitioning to natural sea salt suggests a Br/Cl molar ratio of up to 0.2 in adsorbed surface water of crystallized natural aerosol particles compared to about 0.0015 in seawater. This would have a major impact on

  2. Estudio comparativo de las moléculas isovalentes de interés atmosférico CF3Cl y CF3Br y sus correspondientes halógenos aislados Cl y Br.

    NASA Astrophysics Data System (ADS)

    Mayor, E.; Velasco, A. M.; Martín, I.; Lavín, C.

    Los estados Rydberg moleculares han suscitado en los últimos años un creciente interés entre los espectroscopistas experimentales, motivado en parte por el desarrollo de nuevas técnicas espectroscópicas capaces de investigar estos estados altamente excitados electrónicamente. Los procesos de fotoabsorción que implican estados Rydberg en los derivados halogenados del metano son de gran importancia, debido a su abundancia en la atmósfera y a sus implicaciones medioambientales. Por ello, la obtención de datos relativos a sus fuerzas de oscilador es de gran interés. En este trabajo se aborda el estudio de dichas propiedades para las moléculas isovalentes CF3Cl y CF3Br. Ambas moléculas presentan idéntica estructura electrónica para el estado fundamental por lo que se espera que sus espectros Rydberg presenten grandes similitudes, en ausencia de perturbaciones. Por ello y dada la escasez de datos relativos a fuerzas de oscilador, hemos establecido la corrección de nuestros resultados en base a las analogías esperadas en las intensidades espectrales correspondientes a transiciones análogas. Por otro lado, Novak y col. [1] han encontrado experimentalmente un marcado carácter atómico en el espectro correspondiente a estas moléculas, siendo muy similar a los de los átomos de Cl y Br. Por ello en el presente trabajo, además de establecer la comparación entre ambas moléculas hemos buscado las similitudes con sus respectivos halógenos. Los cálculos relativos a las especies moleculares se han realizado utilizando la Metodología Molécular de Orbítales de Defecto Cuántico (MQDO) [2], mientras que para el estudio de los átomos de Cl y Br se empleó la versión relativista del método (RQDO) [3].

  3. Electrolytic LiCl precipitation from LiCl-KCl melt in porous Li-Al anodes

    NASA Astrophysics Data System (ADS)

    Vallet, C. E.; Heatherly, D. E.; Heatherly, L., Jr.; Braunstein, J.

    1983-12-01

    Composition gradients such as those predicted to occur during discharge of porous Li-Al negative electrodes of Li/S batteries with LiCl-KCl eutectic electrolyte were generated and measured in the LiCl-KCl anolyte of an electrolysis cell with Li-Al electrodes. Precipitation of lithium chloride during electrolysis was observed by two-dimensional scanning of electrolyte composition in the front part of quenched porous Li-Al anode sections using SEM/EDX. The distribution of sites of increased or decreased LiCl concentration, LiCl saturation and precipitation was mapped. Cathodic regions were observed near the cell walls. Preliminary results of analysis by Auger spectroscopy confirm LiCl precipitation in the porous anode.

  4. Threshold energies for the reactions Oh- + Ch3X yields Ch30H + X- (X = Cl, Br) measured by tandem mass spectrometry: Deprotonation energies (acidities) of Ch3Cl and Ch3Br. (Reannouncement with new availability information)

    SciTech Connect

    Hierl, P.M.; Henchman, M.J.; Paulson, J.F.

    1992-12-31

    In a tandem mass spectrometer, a beam of OH{sup {minus}} ions was reacted with methyl chloride and methyl bromide at collision energies in the range 0.2 < ET < 5 eV. For both of the methyl halides, excitation functions, sigma (ET), were measured for the two competing channels, endoergic proton transfer and exoergic nucleophilic displacement: OH{sup {minus}} + CH3X yields H20 + CH2X yields CH3OH + X{sup {minus}}. The threshold energies estimated for the proton transfer reactions are used to derive energies of deprotonation for CH3Cl and CH3Br of 1672 + or - 10 and 1660 + or - lO kJmol{sup {minus}1} respectively.

  5. Electronic structure and optical properties of Cs 2 AX2 ' X 4 (A=Ge,Sn,Pb; X',X=Cl,Br,I)

    NASA Astrophysics Data System (ADS)

    Wang, Guangtao; Wang, Dongyang; Shi, Xianbiao

    2015-12-01

    We studied the crystal structures, electronic structures and optical properties of Cs 2 AX2 ' X 4 (A=Ge,Sn,Pb; X', X=Cl, Br, I) compounds using the first-principles calculation. Our optimized structures agree well with experimental and theoretical results. Band structure calculations, using the modified Becke-Johnson (mBJ) potential method, indicate that these compounds (with the exception of Cs 2 PbX2 ' I 4 ) are semiconductors with the direct band gap ranging from 0.36 to 4.09 eV. We found the compounds Cs2GeBr2I4, Cs2GeCl2I4, Cs2GeI2Br4, Cs2SnI6, and Cs2SnBr2I4 may be good candidates for lead-free solar energy absorber materials.

  6. Structure of the ambient temperature alkali metal molten salt AlCl3/LiSCN

    NASA Astrophysics Data System (ADS)

    Lee, Yi-Chia; Price, David L.; Curtiss, Larry A.; Ratner, Mark A.; Shriver, Duward F.

    2001-03-01

    The structure of the ambient temperature alkali metal molten salt system LiSCN/AlCl3 1:1 adduct was investigated by neutron diffraction, which demonstrates that the aluminum atom is surrounded by three chlorine atoms and one nitrogen atom, indicating the existence of the AlCl3NCS- anion, in which the NCS- coordinates to the Al center through nitrogen. Molecular orbital calculations using ab initio methods are also performed to study the optimized structures of the AlCl3NCS- and its isomer, AlCl3SCN-. The results are consistent with the neutron diffraction data and indicate that AlCl3NCS- is the major anionic complex in the 1:1 LiSCN/AlCl3 adduct.

  7. Room-temperature and gram-scale synthesis of CsPbX3 (X = Cl, Br, I) perovskite nanocrystals with 50-85% photoluminescence quantum yields.

    PubMed

    Wei, Song; Yang, Yanchun; Kang, Xiaojiao; Wang, Lan; Huang, Lijian; Pan, Daocheng

    2016-05-26

    All inorganic CsPbX3 (X = Cl, Br, I) perovskite nanocrystals (PNCs) with 50-85% photoluminescence quantum yields and tunable emission in the range of 440-682 nm have been successfully synthesized at room temperature in open air. This facile strategy enables us to prepare gram-scale CsPbBr3 NCs with a PLQY approaching 80%. PMID:27180872

  8. Coordination Chemistry of Diiodine and Implications for the Oxidation Capacity of the Synergistic Ag(+) /X2 (X=Cl, Br, I) System.

    PubMed

    Malinowski, Przemysław J; Himmel, Daniel; Krossing, Ingo

    2016-08-01

    The synergistic Ag(+) /X2 system (X=Cl, Br, I) is a very strong, but ill-defined oxidant-more powerful than X2 or Ag(+) alone. Intermediates for its action may include [Agm (X2 )n ](m+) complexes. Here, we report on an unexpectedly variable coordination chemistry of diiodine towards this direction: (A)Ag-I2 -Ag(A), [Ag2 (I2 )4 ](2+) (A(-) )2 and [Ag2 (I2 )6 ](2+) (A(-) )2 ⋅(I2 )x≈0.65 form by reaction of Ag(A) (A=Al(OR(F) )4 ; R(F) =C(CF3 )3 ) with diiodine (single crystal/powder XRD, Raman spectra and quantum-mechanical calculations). The molecular (A)Ag-I2 -Ag(A) is ideally set up to act as a 2 e(-) oxidant with stoichiometric formation of 2 AgI and 2 A(-) . Preliminary reactivity tests proved this (A)Ag-I2 -Ag(A) starting material to oxidize n-C5 H12 , C3 H8 , CH2 Cl2 , P4 or S8 at room temperature. A rough estimate of its electron affinity places it amongst very strong oxidizers like MF6 (M=4d metals). This suggests that (A)Ag-I2 -Ag(A) will serve as an easily in bulk accessible, well-defined, and very potent oxidant with multiple applications. PMID:27411163

  9. Mössbauer Spectroscopic Studies of (Me2NH2)2SnX6 (X = Cl or Br) and Their Related Complexes

    NASA Astrophysics Data System (ADS)

    Katada, Motomi; Afroj, Dilara; Yamauchi, Takashi; Kawata, Satoshi

    2002-07-01

    The temperature dependence in the 119Sn Mössbauer spectral area for {(CH3)2NH2}2SnCl6 was found to be almost linear, although a phase transition of the complex has been suggested by IR, 35Cl NQR and NMRstudies, while an anomaly in the temperature dependence for {(CH3)2NH2}2SnBr6 was found at 235 K, which is close to the phase transition temperature 253 K determined by 89Br NQR. These differences are attributable to molecular motion of the dimethylammonium ion in the complexes. The X-ray powder diffraction pattern of {(CH3)2NH2}2SnCl6 did not change near the phase transition point, but that of {(CH3)2NH2}2SnBr6 changed at 108 - 123 K and 233 - 253 K

  10. Excitons and energy transport in crystals KPb 2Cl 5 and RbPb 2Br 5

    NASA Astrophysics Data System (ADS)

    Pustovarov, V. A.; Ogorodnikov, I. N.; Omelkov, S. I.; Smirnov, A. A.; Yelisseyev, A. P.

    2005-05-01

    A complex investigation of the dynamics of electronic excitations and energy transport in the KPb 2Cl 5 (KPC) and RbPb 2Br 5 (RPB) crystals was performed by means of low-temperature time-resolved vacuum ultraviolet optical luminescence spectroscopy with time resolution under selective excitation with synchrotron radiation. Data on the kinetics of the photoluminescence (PL) decay, time-resolved PL spectra (2-6.2 eV), and time-resolved PL excitation spectra (4-24 eV) at 7-300 K were obtained for the first time. The intrinsic PL bands at 2.4 (KPC) and 2.05 eV (RPB) were attributed to the radiative annihilation of the triplet excitons. This rare-earth (Pr, Er, Nd, Ho) doped crystals exhibit the characteristic luminescence of the appropriate activators. This paper discusses the electronic excitation dynamics and energy transport in these crystals.

  11. A High Resolution Phoswich Detector: LaBr3(Ce) Coupled With LaCl3(Ce)

    NASA Astrophysics Data System (ADS)

    Carmona-Gallardo, M.; Borge, M. J. G.; Briz, J. A.; Gugliermina, V.; Perea, A.; Tengblad, O.; Turrión, M.

    2010-04-01

    An innovative solution for the forward end-cap CALIFA calorimeter of R3B is under investigation consisting of two scintillation crystals, LaBr3 and LaCl3, stacked together in a phoswich configuration with one readout only. This dispositive should be capable of a good determination of the energy of protons and gamma radiation. This composite detector allows to deduce the initial energy of charged particles by ΔE1+ΔE2 identification. For gammas, the simulations show that there is a high probability that the first interaction occurs inside the scintillator at few centimeters, with a second layer, the rest of the energy is absorbed, or it can be used as veto event in case of no deposition in the first layer. One such a detector has been tested at the Centro de MicroAnálisis de Materiales (CMAM) in Madrid. Good resolution and time signal separation have been achieved.

  12. Theoretical study of intermolecular interactions in CB4H8-HOX (X=F, Cl, Br, I) complexes.

    PubMed

    Derikvand, Zohreh; Zabardasti, Abedien; Azadbakht, Azadeh

    2015-11-01

    The molecular aggregation based on intermolecular interactions between CB4H8 and HOX (X=F, Cl, Br and I) with particular emphasis on their bonding characteristics have been investigated using second order Moller-Plesset perturbation (MP2) method with aug-cc-pVDZ basis set. Different kinds of interactions including hydrogen bond (HB; H⋯O, XH; H⋯X), dihydrogen bond (DiHB; H⋯H) and non-classical B-B⋯H interactions were found between CB4H8 and HOX molecules. The structures of complexes have been analyzed using AIM and natural bond orbital methodologies. Good correlations have been found between the interaction energies (SE), the second-order perturbation energies E((2)), and the charge transfer qCT in the studied systems. PMID:26103431

  13. Cooperative effects in FH/Li⋯HCCX⋯OH2 complexes (X = F, Cl, Br, H)

    NASA Astrophysics Data System (ADS)

    McDowell, Sean A. C.; Buckingham, A. David

    2015-02-01

    The dimers with general formula FH/FLi⋯HCCX and HCCX⋯OH2, and the trimers FH⋯HCCX⋯OH2 (X = F, Cl, Br, H), were optimized computationally to stable structures. These model systems derive their strength from a combination of H⋯π (or Li⋯π) electrostatic interactions in the T-shaped FH/FLi⋯HCCX dimers and halogen bonding between the X and the O atom of H2O (or CH⋯O hydrogen-bonding in HCCH complexes). These cooperative interactions in the trimer clusters yield a non-additive energy which enhances the stability by between 7% and 10%. The variation in the interaction energies, as well as other selected properties, for different X is rationalized and discussed.

  14. Quantitative assessment of the multiplicity of carbon-halogen bonds: carbenium and halonium ions with F, Cl, Br, and I.

    PubMed

    Kalescky, Robert; Zou, Wenli; Kraka, Elfi; Cremer, Dieter

    2014-03-13

    CX (X = F, Cl, Br, I) and CE bonding (E = O, S, Se, Te) was investigated for a test set of 168 molecules using the local CX and CE stretching force constants k(a) calculated at the M06-2X/cc-pVTZ level of theory. The stretching force constants were used to derive a relative bond strength order (RBSO) parameter n. As alternative bond strength descriptors, bond dissociation energies (BDE) were calculated at the G3 level or at the two-component NESC (normalized elimination of the small component)/CCSD(T) level of theory for molecules with X = Br, I or E = Se, Te. RBSO values reveal that both bond lengths and BDE values are less useful when a quantification of the bond strength is needed. CX double bonds can be realized for Br- or I-substituted carbenium ions where as suitable reference the double bond of the corresponding formaldehyde homologue is used. A triple bond cannot be realized in this way as the diatomic CX(+) ions with a limited π-donor capacity for X are just double-bonded. The stability of halonium ions increases with the atomic number of X, which is reflected by a strengthening of the fractional (electron-deficient) CX bonds. An additional stability increase of up to 25 kcal/mol (X = I) is obtained when the X(+) ion can form a bridged halonium ion with ethene such that a more efficient 2-electron-3-center bonding situation is created. PMID:24555526

  15. Relativistic effects on the nuclear magnetic resonance shielding of FX (X = F, Cl, Br, I, and At) molecular systems.

    PubMed

    Gómez, Sergio S; Aucar, Gustavo A

    2011-05-28

    We present ab inito full four-component and spin-free calculations of the NMR shielding parameter, σ, in the FX (X = F, Cl, Br, I and At) molecular systems. A different expression that overcomes the traditional non-relativistic (NR) approximation used to calculate the relationship between spin-rotation constants and the paramagnetic terms of σ(p) are given. Large deviations from NR results are obtained for σ(X; X = I and At) and for σ(F; FAt). σ(∥)(p)(I; FI) is zero within the NR approach but -447.4 parts per million from our calculations. The electronic origin of relativistic corrections are analyzed. All passive SO contributions are obtained as a difference between full four-component calculations and spin-free ones. Considering relativistic effects on the anisotropy, we obtain a deviation of 10% for I and 25% for At. σ(∥)(SO)(X) is always negative and σ(∥)(SF)(X) is always positive; the passive SO becomes larger than the SF one for X = Br, I, and At. Both σ(∥)(SO)(X) and σ(⊥)(SO)(X) have a functional dependence such as a Z(X)(b) being the exponent 3.5 and 3.65, respectively. The passive SO contribution to the anisotropy has a similar functional dependence with an exponent of 3.60, meaning that its perpendicular component is larger than its corresponding parallel component. PMID:21639447

  16. Extremely Na and Cl Rich Chondrule Al3509 from the Allende Meteorite

    NASA Astrophysics Data System (ADS)

    Wasserburg, G. J.; Hutcheon, I. D.; Aleon, J.; Ramon, E. C.; Krot, A. N.; Nagashima, K.; Brearley, A. J.

    2011-03-01

    This Ca-Al-rich chondrule is not a replacement product. It has ~10% Na and ~1% Cl. Large excesses of 36S were found uncorrelated with Cl and 26Al/27Al < 3 x 10^-6. It represents the fluid responsible for late alteration in volatile-rich outer layers prior to formation of Allende.

  17. Structural and energetic properties of closed shell XF(n) (X = Cl, Br, and I; n = 1-7) and XO(n)F(m) (X = Cl, Br, and I; n = 1-3; m = 0-6) molecules and ions leading to stability predictions for yet unknown compounds.

    PubMed

    Thanthiriwatte, K Sahan; Vasiliu, Monica; Dixon, David A; Christe, Karl O

    2012-10-15

    Atomization energies at 0 K and heats of formation at 0 and 298 K were predicted for the closed shell compounds XF, XF(2)(-), XF(2)(+), XF(3), XF(4)(-), XF(4)(+), XF(5), XF(6)(-), XF(6)(+) (X = Cl and Br) and XO(+), XOF, XOF(2)(-), XOF(2)(+), XOF(3), XOF(4)(-), XOF(4)(+), XOF(5), XOF(6)(-), XO(2)(+), XO(2)F, XO(2)F(2)(-), XO(2)F(2)(+), XO(2)F(3), XO(2)F(4)(-), XO(3)(+), XO(3)F, XO(3)F(2)(-) (X = Cl, Br, and I) using a composite electronic structure approach based on coupled cluster CCSD(T) calculations extrapolated to the complete basis set limit with additional corrections. The calculated heats of formation are in good agreement with the available experimental data. The calculated heats of formation were used to predict fluoride affinities, fluorine cation affinities, and F(2) binding energies. On the basis of our results, BrOF(5) and BrO(2)F(3) are predicted to be stable against spontaneous loss of F(2) and should be able to be synthesized, whereas BrF(7), ClF(7), BrOF(6)(-), and ClOF(6)(-) are unstable by a very wide margin. The stability of ClOF(5) is a borderline case. Although its F(2) loss is predicted to be exothermic by 4.4 kcal/mol, it may have a sufficiently large barrier toward decomposition and be preparable. This situation would resemble ClO(2)F(3) which was successfully synthesized in spite of being unstable toward F(2) loss by 3.3 kcal/mol. On the other hand, the ClOF(4)(+) and BrOF(4)(+) cations are less likely to be preparable with F(2) loss exothermicities of -17.5 and -9.3 kcal/mol, respectively. On the basis of the F(-) affinities of ClOF (45.4 kcal/mol), BrOF (58.7 kcal/mol), and BrO(2)F(3) (65.7 kcal/mol) and their predicted stabilities against loss of F(2), the ClOF(2)(-), BrOF(2)(-), and BrO(2)F(4)(-) anions are excellent targets for synthesis. Our previous failure to prepare the ClO(2)F(4)(-) anion can be rationalized by the predicted high exothermicity of -17.4 kcal/mol for the loss of F(2). PMID:23009656

  18. Cl/Br ratios and chlorine isotope evidences for groundwater salinization and its impact on groundwater arsenic, fluoride and iodine enrichment in the Datong basin, China.

    PubMed

    Li, Junxia; Wang, Yanxin; Xie, Xianjun

    2016-02-15

    In order to identify the salinization processes and its impact on arsenic, fluoride and iodine enrichment in groundwater, hydrogeochemical and environmental isotope studies have been conducted on groundwater from the Datong basin, China. The total dissolved solid (TDS) concentrations in groundwater ranged from 451 to 8250 mg/L, and 41% of all samples were identified as moderately saline groundwater with TDS of 3000-10,000 mg/L. The results of groundwater Cl concentrations, Cl/Br molar ratio and Cl isotope composition suggest that three processes including water-rock interaction, surface saline soil flushing, and evapotranspiration result in the groundwater salinization in the study area. The relatively higher Cl/Br molar ratio in groundwater from multiple screening wells indicates the contribution of halite dissolution from saline soil flushed by vertical infiltration to the groundwater salinization. However, the results of groundwater Cl/Br molar ratio model indicate that the effect of saline soil flushing practice is limited to account for the observed salinity variation in groundwater. The plots of groundwater Cl vs. Cl/Br molar ratio, and Cl vs δ(37)Cl perform the dominant effects of evapotranspiration on groundwater salinization. Inverse geochemical modeling results show that evapotranspiration may cause approximately 66% loss of shallow groundwater to account for the observed hydrochemical pattern. Due to the redox condition fluctuation induced by irrigation activities and evapotranspiration, groundwater salinization processes have negative effects on groundwater arsenic enrichment. For groundwater iodine and fluoride enrichment, evapotranspiration partly accounts for their elevation in slightly saline water. However, too strong evapotranspiration would restrict groundwater fluoride concentration due to the limitation of fluorite solubility. PMID:26657361

  19. Analytical investigation of AlCl[3]/SO[2]Cl[2] catholyte materials for secondary fuze reserve batteries.

    SciTech Connect

    Butler, Paul Charles; Rodriguez, Mark Andrew; Segall, Judith M.; Malizia, Louis A., Jr.; Cherry, Brian Ray; Andrews, Nicholas L.; Clark, Nancy H.; Alam, Todd Michael; Ingersoll, David T.; Tallant, David Robert; Simpson, Regina Lynn; Boyle, Timothy J.; Garcia, Manuel Joseph

    2004-05-01

    Exploration of the fundamental chemical behavior of the AlCl{sub 3}/SO{sub 2}Cl{sub 2} catholyte system for the ARDEC Self-Destruct Fuze Reserve Battery Project under accelerated aging conditions was completed using a variety of analytical tools. Four different molecular species were identified in this solution, three of which are major. The relative concentrations of the molecular species formed were found to depend on aging time, initial concentrations, and storage temperature, with each variable affecting the kinetics and thermodynamics of this complex reaction system. We also evaluated the effect of water on the system, and determined that it does not play a role in dictating the observed molecular species present in solution. The first Al-containing species formed was identified as the dimer [Al({mu}-Cl)Cl{sub 2}]{sub 2}, and was found to be in equilibrium with the monomer, AlCl{sub 3}. The second species formed in the reaction scheme was identified by single crystal X-ray diffraction studies as [Cl{sub 2}Al({mu}-O{sub 2}SCl)]{sub 2} (I), a scrambled AlCl{sub 3}{center_dot}SO{sub 2} adduct. The SO{sub 2}(g) present, as well as CL{sub 2}(g), was formed through decomposition of SO{sub 2}CL{sub 2}. The SO{sub 2}(g) generated was readily consumed by AlCl{sub 3} to form the adduct 1 which was experimentally verified when 1 was also isolated from the reaction of SO{sub 2}(g) and AlCl {sub 3}. The third species found was tentatively identified as a compound having the general formula {l_brace}[Al(O)Cl{sub 2}][OSCl{sub 2}]{r_brace}{sub n}. This was based on {sup 27}Al NMR data that revealed a species with tetrahedrally coordinated Al metal centers with increased oxygen coordination and the fact that the precipitate, or gel, that forms over time was shown by Raman spectroscopic studies to possess a component that is consistent with SOCl{sub 2}. The precursor to the precipitate should have similar constituents, thus the assignment of {l_brace}[Al(O)Cl{sub 2}][OSCl{sub 2

  20. Ring-strain release in neutral and dicationic 7,8,17,18-tetra­bromo-5,10,15,20-tetra­phenyl­porphyrin: crystal structures of C44H26Br4N4 and C44H28Br4N4 2+·2ClO4 −·3CH2Cl2

    PubMed Central

    Scheidt, W. Robert; Duval, Hugues F.; Oliver, Allen G.

    2016-01-01

    Two porphyrin complexes were studied to determine the effects of protonation on ring deformation within the porphyrin. The porphyrin 7,8,17,18-tetra­bromo-5,10,15,20-tetra­phenyl­porphyrin, C44H26Br4N4, was selected because the neutral species is readily doubly protonated to yield a dication, which was crystallized here with perchlorate counter-ions as a di­chloro­methane tris­olvate, C44H28Br4N4 2+·2ClO4 −·3CH2Cl2. The centrosymmetric neutral species is observed to have a mild ‘ruffling’ of the pyrrole rings and is essentially planar throughout; intra­molecular N—H⋯N hydrogen bonds occur. In contrast, the dication exhibits considerable deformation, with the pyrrole rings oriented well out of the plane of the porphyrin, resulting in a ‘saddle’ conformation of the ring. The charged species forms N—H⋯O hydrogen bonds to the perchlorate anions, which lie above and below the plane of the porphyrin ring. Distortions to the planarity of the pyrrole rings in both cases are very minor. The characterization of the neutral species represents a low-temperature redetermination of the previous room-temperature analyses [Zou et al. (1995 ▸). Acta Cryst. C51, 760–761; Rayati et al. (2008 ▸). Polyhedron, pp. 2285–2290], which showed disorder and physically unrealistic displacement parameters. PMID:27308051

  1. Further Analysis of Boiling Points of Small Molecules, CH[subscript w]F[subscript x]Cl[subscript y]Br[subscript z

    ERIC Educational Resources Information Center

    Beauchamp, Guy

    2005-01-01

    A study to present specific hypothesis that satisfactorily explain the boiling point of a number of molecules, CH[subscript w]F[subscript x]Cl[subscript y]Br[subscript z] having similar structure, and then analyze the model with the help of multiple linear regression (MLR), a data analysis tool. The MLR analysis was useful in selecting the…

  2. Quantum chemical investigation of linear hydrogen bonding in ONCCN···HX (X = F, Cl, Br) dimers

    NASA Astrophysics Data System (ADS)

    Varadwaj, Pradeep R.

    Linear hydrogen bonding formed between the nitrogen end of cyanogen-N-oxide (ONCCN) and hydrogen halides HX (X = F, Cl, Br) has been observed in their ground ? states. The order of agreement of energetic stabilities between the correlated functionals used in this calculation is: B3LYP < PBE0 < PBE < PW91 in conjunction with the 6-311++G(3df,3pd) basis set. Analysis of various parameters describing the existence of H-bonds in these dimers follows the conventional trend: ONCCN···HF > ONCCN···HCl > ONCCN···HBr in the series, except H-bond lengths and static dipole polarizabilities which are in reverse order. The atomic charges obtained from the Mulliken and natural population analysis is used to assess the charge transfer effects that accompany the dimer formation. It is found from the investigation that the dimers having highest binding energy are accompanied by the highest transfer of charge. The 14N nuclear quadrupole coupling constants of the monomer ON1CCN2 are found to be decreased upon complection and in the series it increases from F through Br. We observed enhancements in the values of the dimer dipole moment and intrinsic dipole polarizabilities compared with the sum of the monomer values by intermolecular electrical interaction. Investigation reveals vibrational spectral shifts of HX and CN stretching modes similar to the conventional red-shifted H-bonded dimers; for the former case, the infrared band intensity increases significantly. Finally, the new vibrational modes originated from the intermolecular interaction are outlined.

  3. Coupled evolution of BrOx-ClOx-HOx-NOx chemistry during bromine-catalyzed ozone depletion events in the arctic boundary layer

    NASA Astrophysics Data System (ADS)

    Evans, M. J.; Jacob, D. J.; Atlas, E.; Cantrell, C. A.; Eisele, F.; Flocke, F.; Fried, A.; Mauldin, R. L.; Ridley, B. A.; Wert, B.; Talbot, R.; Blake, D.; Heikes, B.; Snow, J.; Walega, J.; Weinheimer, A. J.; Dibb, J.

    2003-02-01

    Extensive chemical characterization of ozone (O3) depletion events in the Arctic boundary layer during the TOPSE aircraft mission in March-May 2000 enables analysis of the coupled chemical evolution of bromine (BrOx), chlorine (ClOx), hydrogen oxide (HOx) and nitrogen oxide (NOx) radicals during these events. We project the TOPSE observations onto an O3 chemical coordinate to construct a chronology of radical chemistry during O3 depletion events, and we compare this chronology to results from a photochemical model simulation. Comparison of observed trends in ethyne (oxidized by Br) and ethane (oxidized by Cl) indicates that ClOx chemistry is only active during the early stage of O3 depletion (O3 > 10 ppbv). We attribute this result to the suppression of BrCl regeneration as O3 decreases. Formaldehyde and peroxy radical concentrations decline by factors of 4 and 2 respectively during O3 depletion and we explain both trends on the basis of the reaction of CH2O with Br. Observed NOx concentrations decline abruptly in the early stages of O3 depletion and recover as O3 drops below 10 ppbv. We attribute the initial decline to BrNO3 hydrolysis in aerosol, and the subsequent recovery to suppression of BrNO3 formation as O3 drops. Under halogen-free conditions we find that HNO4 heterogeneous chemistry could provide a major NOx sink not included in standard models. Halogen radical chemistry in the model can produce under realistic conditions an oscillatory system with a period of 3 days, which we believe is the fastest oscillation ever reported for a chemical system in the atmosphere.

  4. An evaporated seawater origin for the ore-forming brines in unconformity-related uranium deposits (Athabasca Basin, Canada): Cl/Br and δ 37Cl analysis of fluid inclusions

    NASA Astrophysics Data System (ADS)

    Richard, Antonin; Banks, David A.; Mercadier, Julien; Boiron, Marie-Christine; Cuney, Michel; Cathelineau, Michel

    2011-05-01

    Analyses of halogen concentration and stable chlorine isotope composition of fluid inclusions from hydrothermal quartz and carbonate veins spatially and temporally associated with giant unconformity-related uranium deposits from the Paleoproterozoic Athabasca Basin (Canada) were performed in order to determine the origin of chloride in the ore-forming brines. Microthermometric analyses show that samples contain variable amounts of a NaCl-rich brine (Cl concentration between 120,000 and 180,000 ppm) and a CaCl 2-rich brine (Cl concentration between 160,000 and 220,000 ppm). Molar Cl/Br ratios of fluid inclusion leachates range from ˜100 to ˜900, with most values between 150 and 350. Cl/Br ratios below 650 (seawater value) indicate that the high salinities were acquired by evaporation of seawater. Most δ 37Cl values are between -0.6‰ and 0‰ (seawater value) which is also compatible with a common evaporated seawater origin for both NaCl- and CaCl 2-rich brines. Slight discrepancies between the Cl concentration, Cl/Br, δ 37Cl data and seawater evaporation trends, indicate that the evaporated seawater underwent secondary minor modification of its composition by: (i) mixing with a minor amount of halite-dissolution brine or re-equilibration with halite during burial; (ii) dilution in a maximum of 30% of connate and/or formation waters during its migration towards the base of the Athabasca sandstones; (iii) leaching of chloride from biotites within basement rocks and (iv) water loss by hydration reactions in alteration haloes linked to uranium deposition. The chloride in uranium ore-forming brines of the Athabasca Basin has an unambiguous dominantly marine origin and has required large-scale seawater evaporation and evaporite deposition. Although the direct evidence for evaporative environments in the Athabasca Basin are lacking due to the erosion of ˜80% of the sedimentary pile, Cl/Br ratios and δ 37Cl values of brines have behaved conservatively at the basin

  5. Mass-Dependent and -Independent Fractionation of Mercury Isotope during Gas-Phase Oxidation of Elemental Mercury Vapor by Atomic Cl and Br.

    PubMed

    Sun, Guangyi; Sommar, Jonas; Feng, Xinbin; Lin, Che-Jen; Ge, Maofa; Wang, Weigang; Yin, Runsheng; Fu, Xuewu; Shang, Lihai

    2016-09-01

    This study presents the first measurement of Hg stable isotope fractionation during gas-phase oxidation of Hg(0) vapor by halogen atoms (Cl(•), Br(•)) in the laboratory at 750 ± 1 Torr and 298 ± 3 K. Using a relative rate technique, the rate coefficients for Hg(0)+Cl(•) and Hg(0)+Br(•) reactions are determined to be (1.8 ± 0.5) × 10(-11) and (1.6 ± 0.8) × 10(-12) cm(3) molecule(-1) s(-1), respectively. Results show that heavier isotopes are preferentially enriched in the remaining Hg(0) during Cl(•) initiated oxidation, whereas being enriched in the product during oxidation by Br(•). The fractionation factors for (202)Hg/(198)Hg during the Cl(•) and Br(•) initiated oxidations are α(202/198) = 0.99941 ± 0.00006 (2σ) and 1.00074 ± 0.00014 (2σ), respectively. A Δ(199)Hg/Δ(201)Hg ratio of 1.64 ± 0.30 (2σ) during oxidation of Hg(0) by Br atoms suggests that Hg-MIF is introduced by the nuclear volume effect (NVE). In contrast, the Hg(0) + Cl(•) reaction produces a Δ(199)Hg/Δ(201)Hg-slope of 1.89 ± 0.18 (2σ), which in addition to a high degree of odd-mass-number isotope MIF suggests impacts from MIF effects other than NVE. This reaction also exhibits significant MIF of (200)Hg (Δ(200)Hg, up to -0.17‰ in the reactant) and is the first physicochemical process identified to trigger (200)Hg anomalies that are frequently detected in atmospheric samples. PMID:27501307

  6. Synthesis and structure of fullerene halides in the C{sub 60}-(TiCl{sub 4} + Br{sub 2}) system: Molecular structures of (C{sub 60}Cl{sub 5}){sub 2}, C{sub 60}X{sub 6}, C{sub 60}X{sub 8}, and C{sub 60}X{sub 24}(X = Cl, Br)

    SciTech Connect

    Troyanov, S. I. Burtsev, A. V.; Kemnitz, E.

    2009-03-15

    The reactions in the C{sub 60}-(TiCl{sub 4} + Br{sub 2}) system have been performed in ampoules at elevated temperatures. The molecular structure of the fullerene halides (C{sub 60}Cl{sub 5}){sub 2}, C{sub 60}X{sub 6}, C{sub 60}X{sub 8}, and C{sub 60}X{sub 24} (X = Cl, Br) has been determined and refined using single-crystal X-ray diffraction. It has been established that an increase in the bromine concentration results in an increase in the number of halogen atoms attached to the fullerene cage and in an increase in the relative fraction of bromine atoms in mixed halogen derivatives from almost pure chlorides (C{sub 60}Cl{sub 5}){sub 2} and C{sub 60}Cl{sub 6} to halides C{sub 60}X{sub 8} and C{sub 60}X{sub 24} with a high relative bromine content.

  7. 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.

  8. 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.

  9. Structural phase transitions of ionic layered PbFX (X = Cl{sup −}or Br{sup –}) compounds under high pressure

    SciTech Connect

    Sorb, Y.A. Sornadurai, D.

    2015-05-15

    The PbFX (X = Cl{sup –}or Br{sup –}) compounds crystallize in tetragonal structure with space group P4/nmm. High pressure X-ray diffraction studies carried out on PbFCl compound reveals that it undergoes pressure induced structural transitions at ∼18 GPa and ∼38 GPa to orthorhombic and monoclinic (P2{sub 1}/m) phases respectively. Like PbFCl, a similar phase transition from tetragonal to orthorhombic phase is observed in PbFBr at intermediate pressure. These phase transitions seem to be similar to the transitions involving other matlockite structure compounds such as BaFX (X = Cl{sup –}, Br{sup –}or I{sup –}). PbFCl has a larger structural stability range compared to BaFCl and is attributed to the large anisotropic coordination of the Pb{sup 2+} and Cl{sup –}ions.

  10. Vibrational spectra, isolated CH stretching frequencies and CH bond lengths in CH 3OCH 2X compounds (XF, Cl, Br, I)

    NASA Astrophysics Data System (ADS)

    McKean, D. C.; Torto, I.; Morrisson, A. R.

    1983-05-01

    Infrared and Raman spectra are reported for CH 3OCH 2X, CHD 2OCD 2X, CD 3OCHDX (XF, Cl, Br, I) and for CH 3OCD 2Cl and CD 3OCH 2Cl, in various phases. νCHis values are obtained which enable CH bond lengths and dissociation energies to be predicted. The changes in bond lengths from Me 2O to MeOCH 2X and from MeOCH 2F to MeOCH 2Cl are in good agreement with those calculated ab initio and in radical disagreement with microwave-based values. The effect of halogen is to strengthen all the CH bonds present, especially that lying parallel to the CX one. All major features in the spectra are explained if only the gauche skeletal conformer exists in the phases studied. However, two transient bands in solid films of CH 3OCH 2F may indicate the presence of a metastable trans conformer phase. Secure assignments for CH 3OCH 2Cl are based on the CH 3OCD 2Cl and CD 3OCH 2Cl spectra and extended by analogy to most of the vibrations of the F, Br and I compounds.

  11. The sources and evolution of mineralising fluids in iron oxide-copper-gold systems, Norrbotten, Sweden: Constraints from Br/Cl ratios and stable Cl isotopes of fluid inclusion leachates

    NASA Astrophysics Data System (ADS)

    Gleeson, S. A.; Smith, M. P.

    2009-10-01

    We have analysed the halogen concentrations and chlorine stable isotope composition of fluid inclusion leachates from three spatially associated Fe-oxide ± Cu ± Au mineralising systems in Norrbotten, Sweden. Fluid inclusions in late-stage veins in Fe-oxide-apatite deposits contain saline brines and have a wide range of Br/Cl molar ratios, from 0.2 to 1.1 × 10 -3 and δ 37Cl values from -3.1‰ to -1.0‰. Leachates from saline fluid inclusions from the Greenstone and Porphyry hosted Cu-Au prospects have Br/Cl ratios that range from 0.2 to 0.5 × 10 -3 and δ 37Cl values from -5.6‰ to -1.3‰. Finally, the Cu-Au deposits hosted by the Nautanen Deformation Zone (NDZ) have Br/Cl molar ratios from 0.4 to 1.1 × 10 -3 and δ 37Cl values that range from -2.4‰ to +0.5‰, although the bulk of the data fall within 0‰ ± 0.5‰. The Br/Cl ratios of leachates are consistent with the derivation of salinity from magmatic sources or from the dissolution of halite. Most of the isotopic data from the Fe-oxide-apatite and Greenstone deposits are consistent with a mantle derived source of the chlorine, with the exception of the four samples with the most negative values. The origin of the low δ 37Cl values in these samples is unknown but we suggest that there may have been some modification of the Cl-isotope signature due to fractionation between the mineralising fluids and Cl-rich silicate assemblages found in the alteration haloes around the deposits. If such a process has occurred then a modified crustal source of the chlorine for all the samples cannot be ruled out although the amount of fractionation necessary to generate the low δ 37Cl values would be significantly larger. The source of Cl in the NDZ deposits has a crustal signature, which suggests the Cl in this system may be derived from (meta-) evaporites or from input from crustal melts such as granitic pegmatites of the Lina Suite.

  12. In Situ Detection of OH, HO2, ClO, BrO, NO2, ClONO2, BrONO2, ClOOCl, H2O, and O3 from the ER2

    NASA Technical Reports Server (NTRS)

    Anderson, James G.

    2001-01-01

    We review here the scientific progress that has emerged during the period January 1, 1998 through March 31, 2001. Results from the Sage III Ozone Loss and Validation Experiment (SOLVE) and Photochemistry of Ozone Loss in the Arctic Region in Summer (POLARIS) mission, and continuing work on prior missions, taken in order, including radical control of ozone on the northern hemisphere stratosphere, evolution of NO2 over the arctic winter and its effects on reactive chlorine, and the first measurements of ClOOCl in the stratosphere.

  13. Strongly visible-light responsive plasmonic shaped AgX:Ag (X = Cl, Br) nanoparticles for reduction of CO2 to methanol

    NASA Astrophysics Data System (ADS)

    An, Changhua; Wang, Jizhuang; Jiang, Wen; Zhang, Meiyu; Ming, Xijuan; Wang, Shutao; Zhang, Qinhui

    2012-08-01

    Plasmonic shaped AgX:Ag (X = Cl, Br) nanoparticles have been synthesized by a facile and versatile glycerol-mediated solution route. The as-prepared AgX:Ag nanoparticles exhibit regular shapes, i.e., cube-tetrapod-like AgCl:Ag nanoparticles and AgBr:Ag nanoplates. Compared with the pristine AgX, AgX:Ag nanocomposites display stronger absorption in the visible region due to the surface plasmon resonance of silver nanoparticles. The calculation of bandgaps and band positions indicates the as-achieved AgX:Ag nanoparticles can be used as a class of potential photocatalyst for the reduction of CO2. For example, reduction of CO2 under visible light irradiation with the assistance of the anisotropic AgX:Ag nanoparticles yields as much as 100 μmol methanol in the products. Furthermore, the AgX:Ag nanoparticles can maintain its structure and activity after 3 runs of reactions. Therefore, the present route opens an avenue to acquire plasmonic photocatalysts for conversion of CO2 into useful organic compounds.Plasmonic shaped AgX:Ag (X = Cl, Br) nanoparticles have been synthesized by a facile and versatile glycerol-mediated solution route. The as-prepared AgX:Ag nanoparticles exhibit regular shapes, i.e., cube-tetrapod-like AgCl:Ag nanoparticles and AgBr:Ag nanoplates. Compared with the pristine AgX, AgX:Ag nanocomposites display stronger absorption in the visible region due to the surface plasmon resonance of silver nanoparticles. The calculation of bandgaps and band positions indicates the as-achieved AgX:Ag nanoparticles can be used as a class of potential photocatalyst for the reduction of CO2. For example, reduction of CO2 under visible light irradiation with the assistance of the anisotropic AgX:Ag nanoparticles yields as much as 100 μmol methanol in the products. Furthermore, the AgX:Ag nanoparticles can maintain its structure and activity after 3 runs of reactions. Therefore, the present route opens an avenue to acquire plasmonic photocatalysts for conversion of CO2

  14. Corrosion of Sn-Co alloy in alkaline media and the effect of Cl - and Br - ions

    NASA Astrophysics Data System (ADS)

    Refaey, S. A. M.

    1999-05-01

    Sn-Co electrodeposits alloy of approximate composition 80% Sn-20% Co (wt%) can be obtained from a gluconate bath as single phase CoSn 2, which is similar in appearance to decorative chromium. The potentiodynamic and cyclic voltammogram techniques were used to study the corrosion behaviour of CoSn 2 in sodium borate solutions (Na 2B 4O 7) at pH=9.6. The effect of different factors such as concentration of borate ions, pH, potential scan rate, successive cyclic voltammetry, and progressive addition of halide ions (Cl - and Br -) on the electrochemical behaviour of CoSn 2 alloys are discussed. The observed corrosion resistance of electrodeposited CoSn 2 alloy is due to the formation of a thin passive film, which is examined by X-ray spectroscopy and believed to be mainly tin and cobalt oxides. The voltammograms involve four anodic peaks, the first and second of which correspond to the formation of SnO and SnO 2 and the third and fourth related to the formation of cobalt oxides. SEM examination confirms that pitting corrosion takes place in presence of borax and is increased by adding halide ions.

  15. Theoretical insight into the interaction between SnX2 (X = H, F, Cl, Br, I) and benzene.

    PubMed

    Matczak, Piotr

    2016-09-01

    For a series of five model complexes composed of a singlet SnX2 molecule (X = H, F, Cl, Br, I) and a benzene molecule, the first-principles calculations of their energetics and the analysis of their electron density topology have been performed. The CCSD(T)/CBS interaction energy between SnX2 and C6H6 fall into the range between -10.0 and -11.2 kcal/mol, which indicates that the complexes are rather weakly bound. The relevant role of electrostatic and dispersion contributions to the interaction energy between SnX2 and C6H6 is highlighted in the results obtained from the symmetry-adapted perturbation theory (SAPT). The electron density topological analysis has been carried out using the quantum theory of atoms in molecules (QTAIM) and the noncovalent interactions (NCI) visualization index. Both QTAIM and NCI prove the closed-shell, noncovalent and attractive character of the interaction. A very small charge transfer from C6H6 to SnX2 has been detected. The formation of the five complexes is accompanied by the electron density deformations that are spatially restricted mostly to the region around the Sn atom and its adjacent C atom. The results presented in this work shed some light on the nature of the interactions associated with crystalline structural motifs involving low-valent tin complexed with neutral aryl rings. PMID:27525639

  16. Pressure dependence of band-gap and phase transitions in bulk CuX (X = Cl, Br, I)

    NASA Astrophysics Data System (ADS)

    Azhikodan, Dilna; Nautiyal, Tashi; Sharma, S.

    2016-05-01

    Usually a phase transition, in theoretical studies, is explored or verified by studying the total energy as a function of the volume considering various plausible phases. The intersection point, if any, of the free energy vs. volume curves for the different phases is then the indicator of the phase transition(s). The question is, can the theoretical study of a single phase alone indicate a phase transition? i.e. can we look beyond the phase under consideration through such a study? Using density-functional theory, we report a novel approach to suggest phase transition(s) through theoretical study of a single phase. Copper halides have been engaged for this study. These are direct band-gap semiconductors, with zinc blende structure at ambient conditions, and are reported to exhibit many phase transitions. We show that the study of volume dependence of energy band-gap in a single phase facilitates looking beyond the phase under consideration. This, when translated to pressures, reflects the phase transition pressures for CuX (X = Cl, Br, I) with an encouraging accuracy. This work thus offers a simple, yet reliable, approach based on electronic structure calculations to investigate new semiconducting materials for phase changes under pressure.

  17. The nature of inter- and intramolecular interactions in F2OXe(…)HX (X= F, Cl, Br, I) complexes.

    PubMed

    Makarewicz, Emilia; Lundell, Jan; Gordon, Agnieszka J; Berski, Slawomir

    2016-06-01

    Electronic structure of the XeOF2 molecule and its two complexes with HX (X= F, Cl, Br, I) molecules have been studied in the gas phase using quantum chemical topology methods: topological analysis of electron localization function (ELF), electron density, ρ(r), reduced gradient of electron density |RDG(r)| in real space, and symmetry adapted perturbation theory (SAPT) in the Hilbert space. The wave function has been approximated by the MP2 and DFT methods, using APF-D, B3LYP, M062X, and B2PLYP functionals, with the dispersion correction as proposed by Grimme (GD3). For the Xe-F and Xe=O bonds in the isolated XeOF2 molecule, the bonding ELF-localization basins have not been observed. According to the ELF results, these interactions are not of covalent nature with shared electron density. There are two stable F2OXe(…)HF complexes. The first one is stabilized by the F-H(…)F and Xe(…)F interactions (type I) and the second by the F-H(…)O hydrogen bond (type II). The SAPT analysis confirms the electrostatic term, Eelst ((1)) and the induction energy, Eind ((2)) to be the major contributors to stabilizing both types of complexes. PMID:27146283

  18. Parameterization of the DFTB3 method for Br, Ca, Cl, F, I, K, and Na in organic and biological systems.

    PubMed

    Kubillus, Maximilian; Kubař, Tomáš; Gaus, Michael; Řezáč, Jan; Elstner, Marcus

    2015-01-13

    We present an extension to the recent 3OB parametrization of the Density Functional Tight Binding Model DFTB31,2 for biological and organic systems. Parameters for the halogens F, Cl, Br, and I have been developed for use in covalently bound systems and benchmarked on a test set of 106 molecules (the ‘OrgX’ set), using bonding distances, bonding angles, atomization energies, and vibrational frequencies to assess the performance of the parameters. Additional testing has been done with the X40 set of 40 supramolecular systems containing halogens,3 adding a simple correction for the halogen bonds that are strongly overbound in DFTB3. Furthermore, parameters for Ca, K, and Na as counterions in biological systems have been created. To benchmark geometries as well as ligand binding energies a test set ‘BioMe’ of 210 molecules has been created that cover coordination to various functional groups frequently occurring in biological systems. The new DFTB3/3OB parameter set outperforms DFT calculations with a double-ζ basis set in terms of energies and can reproduce DFT geometries, with some minor deviations in bond distances and angles due to the use of a minimal basis set. PMID:26889515

  19. Synthesis and single-crystal structure determination of the zinc nitride halides Zn2NX (X=Cl, Br, I)

    NASA Astrophysics Data System (ADS)

    Liu, Xiaohui; Wessel, Claudia; Pan, Fangfang; Dronskowski, Richard

    2013-07-01

    A series of zinc nitride halides, Zn2NX (X=Cl, Br, I), has been synthesized from solid-liquid reactions of zinc nitride with the respective zinc halides under vacuum, and their crystal structures were determined using single-crystal and powder X-ray diffraction. While Zn2NCl and Zn2NBr crystallize in the acentric orthorhombic space group Pna21, Zn2NI adopts the centrosymmetric space group Pnma; Zn2NCl and Zn2NBr can be considered to belong to the anti-β-NaFeO2 type, and Zn2NI is closely related. Each N3- is tetrahedrally coordinated by zinc atoms, and the X- anions are located in the vacancies of the framework formed by corner-sharing [NZn4] tetrahedra. According to TGA/DTA analyses, the Zn2NX compounds exhibit good thermal stability. The electronic structure has been analyzed by employing density-functional theory and the HSE06 hybrid functional.

  20. Molecular Dynamics Analysis of Ion Incident Energy and Angle Dependences of Si etching with Cl, Br, and HBr beams

    NASA Astrophysics Data System (ADS)

    Nakazaki, Nobuya; Tsuda, Hirotaka; Takao, Yoshinori; Eriguchi, Koji; Ono, Kouichi

    2011-10-01

    Profile anomalies and surface roughness are now critical issues to be resolved in the plasma etching of nanometer-scale microelectronic devices, which in turn requires a better understanding of the effects of the ion incident angle on surface reaction kinetics. For example, the line edge and line width roughness of feature sidewalls and the roughness of bottom surfaces of the feature are assumed to be caused by the angular distribution of incident ions onto feature surfaces. This paper presents a classical molecular dynamics (MD) simulation of Si(100) etching by Cl+, Br+, and HBr+ ion beams with different incident energies (Ei = 20-300 eV) and angles (θ = 0°-90°), where an improved Stillinger-Weber interatomic potential model is used for Si/halogen interactions. The results indicated that the surface reaction kinetics exhibit a characteristic of the ion-enhanced etching at lower energies, where the etch yield is maximum at normal incidence, while a characteristics of the physical sputtering at higher energies, where the yield is maximum at off-normal incidence.

  1. The origin of disorder in CH 3 HgX (X = Cl, Br and I) crystals investigated by temperature dependent Raman spectroscopy

    NASA Astrophysics Data System (ADS)

    Mohaček-Grošev, V.; Kirin, D.

    2001-03-01

    Methyl-mercury(II) halides CH3HgX (X = Cl, Br and I) were studied by means of temperature dependent Raman spectroscopy from 10 K to 410 K. In addition to the previously reported soft phonons, new changes in the low frequency spectra were observed at T 70 K in CH3HgBr and at T 100 K in CH3HgI. The bandwidths of the two internal modes in CH3HgBr, the CH3 symmetric stretching band and the C-Hg-Br bending band, rise towards a local maximum at T 50 K as the temperature is raised from 10 K to 300 K. On the other hand the bandwidths of the two corresponding modes in CH3HgI crystals monotonously increase with temperature, obeying an Arrhenius law. Besides the three phonon modes present in the Raman spectra of CH3HgCl at room temperature, the fourth phonon band that has been observed at temperatures below 245 K might correspond to the freezing of methyl librations. The huge bandwidth of the C-Hg-Br bending mode could suggest the presence of additional weak bonding of a mercury atom with bromine atoms from other molecules, thus inducing positional disorder.

  2. Fast Anion-Exchange in Highly Luminescent Nanocrystals of Cesium Lead Halide Perovskites (CsPbX3, X = Cl, Br, I)

    PubMed Central

    2015-01-01

    Postsynthetic chemical transformations of colloidal nanocrystals, such as ion-exchange reactions, provide an avenue to compositional fine-tuning or to otherwise inaccessible materials and morphologies. While cation-exchange is facile and commonplace, anion-exchange reactions have not received substantial deployment. Here we report fast, low-temperature, deliberately partial, or complete anion-exchange in highly luminescent semiconductor nanocrystals of cesium lead halide perovskites (CsPbX3, X = Cl, Br, I). By adjusting the halide ratios in the colloidal nanocrystal solution, the bright photoluminescence can be tuned over the entire visible spectral region (410–700 nm) while maintaining high quantum yields of 20–80% and narrow emission line widths of 10–40 nm (from blue to red). Furthermore, fast internanocrystal anion-exchange is demonstrated, leading to uniform CsPb(Cl/Br)3 or CsPb(Br/I)3 compositions simply by mixing CsPbCl3, CsPbBr3, and CsPbI3 nanocrystals in appropriate ratios. PMID:26207728

  3. Fast Anion-Exchange in Highly Luminescent Nanocrystals of Cesium Lead Halide Perovskites (CsPbX3, X = Cl, Br, I).

    PubMed

    Nedelcu, Georgian; Protesescu, Loredana; Yakunin, Sergii; Bodnarchuk, Maryna I; Grotevent, Matthias J; Kovalenko, Maksym V

    2015-08-12

    Postsynthetic chemical transformations of colloidal nanocrystals, such as ion-exchange reactions, provide an avenue to compositional fine-tuning or to otherwise inaccessible materials and morphologies. While cation-exchange is facile and commonplace, anion-exchange reactions have not received substantial deployment. Here we report fast, low-temperature, deliberately partial, or complete anion-exchange in highly luminescent semiconductor nanocrystals of cesium lead halide perovskites (CsPbX3, X = Cl, Br, I). By adjusting the halide ratios in the colloidal nanocrystal solution, the bright photoluminescence can be tuned over the entire visible spectral region (410-700 nm) while maintaining high quantum yields of 20-80% and narrow emission line widths of 10-40 nm (from blue to red). Furthermore, fast internanocrystal anion-exchange is demonstrated, leading to uniform CsPb(Cl/Br)3 or CsPb(Br/I)3 compositions simply by mixing CsPbCl3, CsPbBr3, and CsPbI3 nanocrystals in appropriate ratios. PMID:26207728

  4. Structural and Spectroscopic Characterizations of Amide-AlCl3-Based Ionic Liquid Analogues.

    PubMed

    Hu, Pengcheng; Zhang, Rui; Meng, Xianghai; Liu, Haiyan; Xu, Chunming; Liu, Zhichang

    2016-03-01

    Several amide-AlCl3-based ionic liquid (IL) analogues were synthesized through a one-step method using three different structure amides as donor molecules. The effects of the steric and inductive effects of the methyl group substituted on the N atom on the asymmetric splitting of AlCl3 and the coordination site of the amide were investigated by (27)Al NMR, Raman, in situ IR, and UV-vis spectra for these IL analogues. Bidentate coordination through both the O and N atoms was dominant in the N-methylacetamide-AlCl3- and N,N-dimethylacetamide-AlCl3-based IL analogues because of the inductive effect of the methyl group. By contrast, the acetamide-AlCl3-based IL analogue presented mainly in the form of monodentate coordination via the O atom. Compared with monodentate coordination, bidentate coordination was favorable to the asymmetric splitting of AlCl3 with the same amide-AlCl3 molar ratio. Under the influence of the steric and inductive effects of the methyl group, the ionic species percentages in these IL analogues ranked in the following order: N-methylacetamide > N,N-dimethylacetamide > acetamide. PMID:26848508

  5. The halogen (F, Cl, Br, I) and H2O systematics of Samoan lavas: Assimilated-seawater, EM2 and high-3He/4He components

    NASA Astrophysics Data System (ADS)

    Kendrick, Mark A.; Jackson, Matthew G.; Hauri, Erik H.; Phillips, David

    2015-01-01

    The Samoan mantle plume samples two or more mantle components including an extreme EM2 composition with 87Sr/86Sr > 0.720 and a primitive component with high 3He/4He. The high 87Sr/86Sr melts have a unique potential to constrain the composition of the EM2 mantle end-member that is commonly attributed to subduction recycling. However, a previous study of H2O, CO2, S, F and Cl in Samoan glasses was hampered by the presence of unresolved assimilated sea water. The current study builds on the earlier work by extending the volatile database to include the trace halogens Br and I, and reporting new volatile data for additional glasses with 87Sr/86Sr up to 0.7125 and 3He/4He up to 15 Ra (Ra is the atmospheric 3He/4He ratio of 1.39 ×10-6). The selected glasses with MgO of 4.0 to 6.5 wt.% have CO2 concentrations of 4 to 200 ppm that reflect degassing of CO2 on the seafloor. The glasses contain 0.7-1.9 wt.% H2O, 880-1870 ppm F, 490-1790 ppm Cl, 1.9-7.2 ppm Br, 19-130 ppb I and 0.6-1.7 wt.% K. Correlations between the concentrations of these elements suggest the melts retain H2O concentrations close to pre-degassing values and demonstrate the melts have been variably affected by assimilation of seawater-derived brines. The brines are indicated to have had salinities of 55 ± 15 wt.% salt, F/Cl ratios close to seawater (e.g. <0.0001), Br/Cl ratios ∼ 40% higher than seawater, and I/Cl ratios ten times the seawater value. It is calculated the melts assimilated brine fractions of 0 to 0.45 wt.%, which contributed up to ∼30% of the total H2O and up to ∼70% of the total Cl in the melts. After accounting for the effects of brine assimilation, the Samoan melts are suggested to have a fairly constant magmatic Cl/K of 0.05 ± 0.2, which is lower than the median MORB value. Assimilation-corrected H2O/Ce values are not correlated with 87Sr/86Sr, but the sample with the highest 87Sr/86Sr of 0.7125 has an assimilation-corrected H2O/Ce of 83 ± 3, that is significantly lower than

  6. Quality Structures, Vibrational Frequencies, and Thermochemistry of the Products of Reaction of BrHg(•) with NO2, HO2, ClO, BrO, and IO.

    PubMed

    Jiao, Yuge; Dibble, Theodore S

    2015-10-22

    Quantum chemical calculations have been carried out to investigate the structures, vibrational frequencies, and thermochemistry of the products of BrHg(•) reactions with atmospherically abundant radicals Y(•) (Y = NO2, HO2, ClO, BrO, or IO). The coupled cluster method with single and double excitations (CCSD), combined with relativistic effective core potentials, is used to determine the equilibrium geometries and harmonic vibrational frequencies of BrHgY species. The BrHg-Y bond energies are refined using CCSD with a noniterative estimate of the triple excitations (CCSD(T)) combined with core-valence correlation consistent basis sets. We also assess the performances of various DFT methods for calculating molecular structures and vibrational frequencies of BrHgY species. We attempted to estimate spin-orbit coupling effects on bond energies computed by comparing results from standard and two-component spin-orbit density functional theory (DFT) but obtained unphysical results. The results of the present work will provide guidance for future studies of the halogen-initiated chemistry of mercury. PMID:26401599

  7. New low-dimensional molecular conductors: α''-(BEDO-TTF)2Cl.3H2O and θ-(BDH-TTP)2(Br0.67Cl0.33).3H2O

    NASA Astrophysics Data System (ADS)

    Zorina, L. V.; Simonov, S. V.; Khasanov, S. S.; Shibaeva, R. P.

    2011-10-01

    X-ray single-crystal diffraction studies of two new molecular conductors α''-(BEDO-TTF)2Cl.3H2O and θ-(BDH-TTP)2(Br0.67Cl0.33).3H2O are reported. Both crystals have a layered structure in which conducting layers of organic BEDO-TTF or BDH-TTP π-electron donors are separated by complex anion layers. The anion layers consist of honeycomb networks of Cl- (Br-) halogen anions and water molecules, which are stable owing to the formation of hydrogen bonds. Calculations of the electron band structure of these crystals show that metallic conductivity is to be expected in the organic α''-(BEDO-TTF) and θ-(BDH-TTP) layers.

  8. First Principle Quantum Description of the Energetics Associated with LaBr3, LaCl3, and Ce Doped Scintillators

    SciTech Connect

    Michael E. McIlwain; Da Gao; Nick Thompson

    2007-12-01

    Considerable interest is given to the excellent scintillation properties of cerium doped lanthanum chloride (LaCl3) and lanthanum bromide (LaBr3). The scintillation efficiencies are much greater than other materials, even those containing cerium. This high efficiency is attributed to the high mobility of electrons and holes, unique placement of the cerium 5d states within the band gap, and energy of the band gap. To better understand the scintillation process and better define the nature of the Self Trapped Exciton (STE) within these unique scintillation materials, density functional theory (DFT), and Ab-inito (HF-MP2) calculations are reported. DFT calculations have yielded a qualitative description of the orbital composition and energy distribution of the band structure in the crystalline material. MP2 and single configuration interaction calculations have provided quantitative values for the band gap and provided energies for the possible range of excited states created following hole and electron creation. Based on this theoretical treatment, one possible description of the STE is the combination of Vk center (Br2-1) and LaBr+1 species that recombine to form a distorted geometry LaBr3* (triplet state). Depending on the distance between the LaBr and Br2, the STE emission band can be reproduced.

  9. Kinetic studies of the BrO + ClO cross-reaction over the range T = 246-314 K.

    PubMed

    Ferracci, Valerio; Rowley, David M

    2014-01-21

    The kinetics of the atmospherically important gas phase radical reaction between BrO and ClO have been studied over the temperature range T = 246-314 K by means of laser flash photolysis coupled with UV absorption spectroscopy. Charge-coupled-device (CCD) detection allowed simultaneous monitoring of both free radicals and the OClO product using 'differential' spectroscopy, which minimised interference from underlying UV absorbing species. In this way, the total rate coefficient for BrO + ClO → products (1) was measured, along with that for the OClO producing channel of this process BrO + ClO → OClO + Br (1c). These reaction rate coefficients are described by the Arrhenius expressions: k1/cm(3) molecule(-1) s(-1) = (2.5 ± 2.2) × 10(-12) exp[(630 ± 240)/T] and k(1c)/cm(3) molecule(-1) s(-1) = (4.6 ± 3.0) × 10(-12) exp[(280 ± 180)/T], where errors are 2σ, statistical only. An extensive sensitivity analysis was performed to quantify the potential additional systematic uncertainties in this work arising from uncertainties in secondary chemistry, absorption cross-sections and precursor concentrations. This analysis identified the reactions of initial and secondarily generated bromine atoms (specifically Br + O3 and Br + Cl2O) as particularly important, along with the reversible combination of ClO with OClO forming Cl2O3. Potential uncertainty in this latter process was used to define the lowest temperature of the present study. Results from this work indicate larger absolute values for k1 and k(1c) than those reported in previous studies, but a weaker negative temperature dependence for k(1c) than previously observed, resulting in a branching ratio for with a positive temperature dependence, in disagreement with previous studies. is the principal source of OClO in the polar stratosphere and is commonly used in atmospheric models as an indicator of stratospheric bromine chemistry. Thus these measurements might lead to a reinterpretation of modelled

  10. Kinetics of the Reactions of Cl((sup 2)P(sub J)) and Br((sup 2)P(sub 3/2)) with O3

    NASA Technical Reports Server (NTRS)

    Nicovich, J. M.; Kreutter, K. D.; Wine, P. H.

    1997-01-01

    A laser flash photolysis-resonance fluorescence technique has been employed to study the kinetics of the important stratospheric reactions Cl((sup 2)P(sub J)) + O3 yields ClO + O2 and Br((sup 2)P(sub 3/2)) + O3 yields BrO + O2 as a function of temperature. The temperature dependence observed for the Cl((sup 2)P(sub J)) + O3 reaction is nonArrhenius, but can be adequately described by the following two Arrhenius expressions (units are cu cm/(molecule.s), errors are 2 sigma and represent precision only): k(sub 1)(T) = (1.19 +/- 0.21) x 10(exp -11) exp[(-33 +/- 37)/T] for T = 189-269 K and k(sub 1)(T) = (2.49 +/- 0.38) x 10(exp -11) exp[(-233 +/- 46)/T] for 269-385 K. At temperatures below 230 K, the rate coefficients determined in this study are faster than any reported previously. Incorporation of our values for k(sub 1)(T) into stratospheric models would increase calculated ClO levels and decrease calculated HCI levels; hence the calculated efficiency of ClO catalyzed ozone destruction would increase. The temperature dependence observed for the Br((sup 2)P(sub 3/2)) + O3 reaction is adequately described by the following Arrhenius expression (units are cu cm/(molecule.s), errors are 2 sigma and represent precision only): k(sub 2)(T) = (1.50 +/- 0.16) x 10(exp -11)exp[(-775 +/- 30)/T for 195-392 K. While not in quantitative agreement with Arrhenius parameters reported in most previous studies, our results almost exactly reproduce the average of all earlier studies and therefore will not affect the choice of k(sub 2)(T) for use in modeling stratospheric BrO2 chemistry.

  11. Kinetic smog-chamber studies on halogen activation from a simulated salt pan, using dry and wet NaCl/NaBr surfaces

    NASA Astrophysics Data System (ADS)

    Bleicher, Sergej; Balzer, Natalja; Zetzsch, Cornelius; Buxmann, Joelle; Platt, Ulrich

    2010-05-01

    Field experiments and laboratory studies have shown that atomic Br and Cl are released from sea-salt aerosol and saline soils. This halogen release is based on the uptake of gaseous HOX by aqueous, acidified salt surfaces. Br and Cl play an important role in atmospheric ozone depletion and the destruction of hydrocarbons. Furthermore, Secondary Organic Aerosol (SOA) and HUmic LIke Substances (HULIS) may take part in these reaction cycles by halogenation and production of volatile organic halogen compounds. Aerosol smog-chamber facilities (coolable to -25°C) enable us to simulate the halogen release mechanism under arctic tropospheric conditions. Mechanistic and kinetic studies are carried out to investigate the influence of SOA and HULIS on halogen cycles and to determine halogenated gaseous and solid organic products. The present laboratory measurements study halogen activation from salt surfaces, which are similar to typical salt pan environments. In these experiments we placed different artificial salt mixtures with NaCl/NaBr ratios up to 300:1 on a Teflon pan located in a Teflon chamber with a volume of 3.5 m3. Under clean air conditions we inject ozone and a mixture of non-methane hydrocarbons with well-known reactivities against OH and Cl and irradiated the chamber with a solar simulator. Beside the usual observing instruments like an ozone monitor and a gas chromatograph we used Differential Optical Absorption Spectroscopy (DOAS) in a White cell with a light path up to 320 m to observe various gas-phase species including BrO radicals. A dry air / dry salt pan environment showed no ozone depletion and no halogen activation. At relative humidity above 50%, a rapid ozone depletion (4.7 h half-life) was observed, which is much faster than for pure NaCl under the same conditions (77 h). Furthermore, the mixed salt was acidified with H2SO4 to a pH value of 4.3, no difference in ozone depletion and halogen activation was observed at this point. The DOAS

  12. The role of reduction extent of graphene oxide in the photocatalytic performance of Ag/AgX (X = Cl, Br)/rGO composites and the pseudo-second-order kinetics reaction nature of the Ag/AgBr system.

    PubMed

    Gao, Weiyin; Ran, Chenxin; Wang, Minqiang; Li, Le; Sun, Zhongwang; Yao, Xi

    2016-07-21

    Although reduced graphene oxide (rGO)-based photocatalyst composites have been intensively developed during the past few years, the influence of reduction extent of rGO on the photocatalytic performance of the rGO-based composite has virtually not been investigated due to some technical limitations, such as the poor water dispersibility of rGO and low reduction selectivity of the hydrothermal method, which make it difficult to control the reduction extent of rGO in these composites. Herein, we used a facile room-temperature method to synthesize Ag/AgX (X = Cl, Br)/rGO photocatalyst composites as a model to study the effect of reduction extent of rGO on the photocatalytic performance of the photocatalyst. It was found that the photocatalytic activities of both Ag/AgCl/PrGO and Ag/AgBr/PrGO systems had an optimized threshold of the reduction extent of photoreduced GO (PrGO). More importantly, due to the different conductive band values of AgCl and AgBr, the optimized thresholds in the two systems were at different PrGO reduction extents, based on which we proposed that the favorable energy band matching between AgX and PrGO in the two systems played a crucial role in obtaining high photocatalysis performance. Besides, the photocatalytic reaction of the Ag/AgBr based system was confirmed to be a pseudo-second-order kinetics reaction rather than pseudo-first-order kinetics reaction. The new insights presented in this work provided useful information on the design and development of a more sophisticated photocatalyst, and can also be applied to many other applications. PMID:27332751

  13. Use of CO2 laser and AgClBr infrared transmitting fibers for tympanoplasty: experiments on animal models

    NASA Astrophysics Data System (ADS)

    Zilker, Zeev; Daykhovsky, Leon; Nageris, Ben I.; Feinmesser, R.; Papaioannou, Thanassis; Ravid, Avi; Kariv, Naam; Katzir, Abraham

    1999-06-01

    One of the most common ear disease is Chronic Otitis Media that leads to a tympanic membrane perforation. The treatment of this condition is by a surgical procedure, tympanoplasty that is often done under local or general anesthesia. During this procedure an autologous fascia is applied to close the perforation. Commonly, fixation of the fascia is achieved mostly by Gel-Form. During the last several years various fascia fixation techniques were suggested. These included a welding procedure based on using an Argon laser. The disadvantages of the latter is that the visible Argon laser is not absorbed well by the relatively thin tympanic membrane and the fascia. It does not lead to strong weld and it may heat the middle of the ear, causing neural hearing loss. The CO2 laser IR radiation is much more suitable for welding of these thin tissues, because of its very high absorption in tissues. There is still a need to deliver this radiation to the weld site using a thin and flexible optical fiber. In this work we have welded fascia on the tympanic membranes of guinea pigs using a CO2 laser. Holes of diameter 2-3 mm were punctured in the membranes and apiece of fascia was placed on the holes. Laser power of the order of 0.5W was delivered to the fascia using an IR transmitting AgClBr fiber. In experiments done on 11 animals and CO2 laser welding was successfully done on in 15 years. The success of these preliminary studies in the animal models shows that CO2 laser tympanoplasty could be a very valuable surgical technique.

  14. Heterogeneous reaction HOCl + HBr {r_arrow} BrCl + H{sub 2}O on ice films

    SciTech Connect

    Chu, L.; Chu, L.T.

    1999-02-11

    Heterogeneous reactions on the surface of polar stratospheric clouds (PSCs) are critical to an understanding of the annual appearance of the Antarctic ozone hole. The heterogeneous reaction HOCl + HBr(s) {r_arrow} BrCl + H{sub 2}O(s) on the ice surface at 189 and 220 K has been investigated in a flow reactor interfaced with a differentially pumped quadrupole mass spectrometer. Pseudo first-order decay of HOCl over the HBr-treated ice surfaces has been determined under the condition of P{sub HOCl} < P{sub HBr}. For the HBr partial pressure in the range of 1.1 {times} 10{sup {minus}7} to 6.6 {times} 10{sup {minus}5} Torr, the reaction probability ({gamma}{sub g}) was determined in the range of 0.06 to 0.38 at 189 K. The reaction probability is in the range of 0.01 to 0.07 at 220 K for HBr partial pressure from 7.2 {times} 10{sup {minus}7} to 1.3 {times} 10{sup {minus}5} Torr. The reaction probability was found to be strongly dependent on the ice surface temperature. The reaction probability is higher at the lower temperature than that at the warmer temperature and a mechanistic explanation is provided. The true reaction probabilities ({gamma}{sub t}) of the reaction were calculated using a pore diffusion model. The kinetic analysis indicates that the heterogeneous reaction of HOCl + HBr may follow the Eley-Rideal type of mechanism. Also, the heat of uptake of HOCl on ice was determined to be about {minus}8.5 {+-} 2 kcal/mol.

  15. Computational study of non-covalent interactions in oxirane…XF complexes (X = H, F, Cl, Br, Li) and their F-/Li-substituted analogues

    NASA Astrophysics Data System (ADS)

    McDowell, Sean A. C.; Holder, Zandel L.

    2015-12-01

    A computational study found oxirane…XF (X = H, Cl, Br, F, Li) dimers to be energetically stable, with their interaction energies increasing with the magnitude of the XF dipole moment in the order XF = LiF > BrF ∼ HF > ClF > F2. Their relative stabilities roughly correlate with the amount of charge transferred from the lone pairs on the O atom of oxirane to the antibonding σ* orbital of XF. However, the most strongly bound dimer, oxirane…LiF, is stabilised by the largest dipole but involves the smallest charge transfer. The variation in the strength of the oxirane…XF interaction was subsequently investigated by the sequential substitution of the protons on oxirane by either electron-donating Li or electron-withdrawing F atoms.

  16. A comparative study of model halogen-bonded, π-hole-bonded and cationic complexes involving NCX AND H2O (X = F, Cl, Br)

    NASA Astrophysics Data System (ADS)

    McDowell, Sean A. C.; Joseph, Jerelle A.

    2015-01-01

    A MP2/6-311+ +G(d,p) study of NCX (X = F, Cl, Br) has shown that it is possible to attach an electrophile (H+, Be2+) to the positive halogen X surface of NCX. The stability and properties of model halogen-bonded and π-hole carbon-bonded NCX/H2O complexes were found to be significantly affected by H+ or Be2+ cationic attachment at the N atom. The halogen-bonded complexes are destabilised by binding at the N, while an attached proton enhances the binding in the π-hole bonded dimers. For the attached Be2+, an unusual complex was obtained with the NCF subunit, whereas the complexes containing Cl and Br were destabilised by the interaction.

  17. FTIR and Raman spectra and fundamental frequencies of 5-halosubstituted uracils: 5-X-uracil (X = F, Cl, Br and I)

    NASA Astrophysics Data System (ADS)

    Singh, J. S.

    2012-02-01

    FTIR and Raman spectra of 5-halosubstituted uracils (5-X-uracil; X = F, Cl, Br and I) were recorded in the region 200-4000 cm -1. Assuming under the Cs point group, the distribution of normal mode of vibrations between the two species as planar (a') and non-planar (a″) are given by 21a' + 9a″, of which also correspond to the 30 modes of uracil moiety and the electro negativity of halogen group substitution causes some where mixing/shifting in their modes with other modes. The ring breathing and kekule stretching modes are observed in lower magnitudes compared to those of uracil which could be due to mass effect of halogen atom in place of the hydrogen atom. The C-X (X = F, Cl, Br and I) stretching frequency is distinctly separated from the CH/NH ring stretching frequencies on the pyrimidine ring. All other bands have also been assigned different fundamentals/overtones/combinations.

  18. A theoretical simulation of the resonant Raman spectroscopy of the H2O⋯Cl2 and H2O⋯Br2 halogen-bonded complexes.

    PubMed

    Franklin-Mergarejo, Ricardo; Rubayo-Soneira, Jesús; Halberstadt, Nadine; Janda, Kenneth C; Apkarian, V Ara

    2016-02-01

    The resonant Raman spectra of the H2O⋯Cl2 and H2O⋯Br2 halogen-bonded complexes have been studied in the framework of a 2-dimensional model previously used in the simulation of their UV-visible absorption spectra using time-dependent techniques. In addition to the vibrational progression along the dihalogen mode, a progression is observed along the intermolecular mode and its combination with the intramolecular one. The relative intensity of the inter to intramolecular vibrational progressions is about 15% for H2O⋯Cl2 and 33% for H2O⋯Br2. These results make resonant Raman spectra a potential tool for detecting the presence of halogen bonded complexes in condensed phase media such as clathrates and ice. PMID:26851921

  19. Infrared multiphoton induced isomerization and dissociation of FCN, ClCN, and BrCN in liquid Ar: A classical simulation study

    SciTech Connect

    Zhang Ming; Gong Jiangbin; Ma Ao; Rice, Stuart A.

    2007-10-14

    We report the results of classical mechanics simulations of infrared multiphoton induced control of isomerization of FCN, ClCN, and BrCN in liquid Ar, using ab initio potential energy and dipole moment surfaces for the XCN molecules. The field induced isomerization and fragmentation dynamics of these molecules are found to be different from that of HCN in liquid Ar. In particular, the scheme that provides complete controlled conversion of HCN to CNH in liquid Ar fails to generate complete conversion of XCN to CNX in liquid Ar for X=F,Cl,Br. It is suggested that the sources of the differences in behavior arise from differences in the spectra of vibrational nonlinear resonances in HCN and XCN and to the occurrence of monodromy in the dynamics of the XCN molecules.

  20. On the electrochemical formation of Pu-Al alloys in molten LiCl-KCl

    NASA Astrophysics Data System (ADS)

    Mendes, E.; Malmbeck, R.; Nourry, C.; Souček, P.; Glatz, J.-P.

    2012-01-01

    Properties of Pu-Al alloys were investigated in connection with development of pyrochemical methods for reprocessing of spent nuclear fuel. Electroseparation techniques in molten LiCl-KCl are being developed in ITU to group-selectively recover actinides from the mixture with fission products. In the process, actinides are electrochemically reduced on solid aluminium cathodes, forming solid actinide-aluminium alloys. This article is focused on electro-chemical characterisation of Pu-Al alloys in molten LiCl-KCl, on electrodeposition of Pu on solid Al electrodes and on determination of chemical composition and structure of the formed alloys. Cyclic voltammetry and chronopotentiometry were used to study Pu-Al alloys in the temperature range 400-550 °C. Pu is reduced to metal in one reduction step Pu 3+/Pu 0 on an inert W electrode. On a reactive Al electrode, the reduction of Pu 3+ to Pu 0 occurs at a more positive potential due to formation of Pu-Al alloys. The open circuit potential technique was used to identify the alloys formed. Stable deposits were obtained by potentiostatic electrolyses of LiCl-KCl-PuCl 3 melts on Al plates. XRD and SEM-EDX analyses were used to characterise the alloys, which were composed mainly of PuAl 4 with some PuAl 3. In addition, the preparation of PuCl 3 containing salt by carbochlorination of PuO 2 is described.

  1. Recognition of a novel type X═N-Hal···Hal (X = C, S, P; Hal = F, Cl, Br, I) halogen bonding.

    PubMed

    Gushchin, Pavel V; Kuznetsov, Maxim L; Haukka, Matti; Kukushkin, Vadim Yu

    2013-04-01

    The chlorination of the eight-membered platinum(II) chelates [PtCl2{NH═C(NR2)N(Ph)C(═NH)N(Ph)C(NR2)═NH}] (R = Me (1); R2 = (CH2)5 (2)) with uncomplexed imino group with Cl2 gives complexes bearing the ═N-Cl moiety [PtCl4{NH═C(NR2)N(Ph)C(═NCl)N(Ph)C(NR2)═NH}] (R = Me (3); R2 = (CH2)5 (4)). X-ray study for 3 revealed a novel type intermolecular halogen bonding ═N-Cl···Cl(-), formed between the Cl atom of the chlorinated imine and the chloride bound to the platinum(IV) center. The processing relevant structural data retrieved from the Cambridge Structural Database (CSDB) shows that this type of halogen bonding is realized in 18 more molecular species having X═N-Hal moieties (X = C, P, S, V, W; Hal = Cl, Br, I), but this weak ═N-Hal···Hal(-) bonding was totally neglected in the previous works. The presence of the halogen bonding in 3 was confirmed by theoretical calculations at the density functional theory (DFT, M06-2X) level, and its nature was analyzed. PMID:23469756

  2. The Role of Spin-Orbit Coupling in the Double-Ionization Photoelectron Spectra of XCN(2+) (X = Cl, Br, and I).

    PubMed

    Manna, Soumitra; Mishra, Sabyashachi

    2016-03-10

    The photoelectron spectra of XCN(2+) (X = Cl, Br, and I) were calculated employing ab initio electronic structure methods with high-level electron correlation and explicit treatment of spin-orbit coupling. Twelve scalar-relativistic excited states of the dicationic systems, calculated from state-averaged CASSCF/MRCI calculations, were used as the electronic basis to evaluate spin-orbit eigenstates. While the spin-orbit effects in ClCN(2+) are found to be negligible, the electronic spectroscopy of BrCN(2+) and ICN(2+) is significantly influenced by interstate spin-orbit coupling. Several electronic degeneracies are lifted, and many unexpected accidental degeneracies occurred due to the spin-orbit coupling. In particular, the spin-orbit interactions between X̃ (3)Σ(-)-b̃ (1)Σ(+), Ã (3)Π-c̃ (1)Π, B̃ (3)Δ-ã (1)Δ, and C̃ (3)Σ(+)-d̃ (1)Σ(-) are found to be strong in BrCN(2+) and ICN(2+). By careful analysis of the effect of spin-orbit coupling parameters and the spin-orbit eigenstate composition, an assignment of the hitherto unidentified experimental photoelectron bands of BrCN(2+) and ICN(2+) is presented. PMID:26881722

  3. Syntheses, crystal structures, and optical properties of Pb{sub 6}B{sub 3}O{sub 10}X (X=F, Cl, Br)

    SciTech Connect

    Dong, Lingyun; Pan, Shilie; Wu, Hongping; Su, Xin; Yu, Hongwei; Wang, Ying; Chen, Zhaohui; Huang, Zhenjun; Yang, Zhihua

    2013-08-15

    A series of lead-containing halogen oxyborates, Pb{sub 6}B{sub 3}O{sub 10}X (X=F, Cl, Br), have been grown by high-temperature solution method and their crystal structures were determined by single-crystal X-ray diffraction. They are isostructural and crystallize in the space group Pbcm of the orthorhombic crystal system. The crystal structures are dominated by one-dimensional {sub ∞}[(Pb{sub 4}O)(BO{sub 3}){sub 3}] “Zig-Zag”-chains, while the remaining Pb atoms and X (X=F, Cl, Br) atoms are filled to balance the charge. Compared with the previously reported compound Pb{sub 4}O(BO{sub 3}){sub 2} (the molecular formula Pb{sub 4}O(BO{sub 3}){sub 2} can be regarded as Pb{sub 6}B{sub 3}O{sub 10.5}) with the space group Aba2, the structures of Pb{sub 6}B{sub 3}O{sub 10}X (X=F, Cl, Br) are completely different from that of Pb{sub 4}O(BO{sub 3}){sub 2}. IR spectroscopy, UV–vis-NIR diffuse reflectance spectroscopy, thermal analysis, and theoretical calculations were also performed on the reported materials. Highlights: • A new family of lead-containing halogen oxyborates, Pb{sub 6}B{sub 3}O{sub 10}X (X=F, Cl, Br), have been grown by high-temperature solution method. • Owing to the introduction of X atoms into Pb{sub 4}O(BO{sub 3}){sub 2}, the structures of Pb{sub 6}B{sub 3}O{sub 10}X are completely different. • The crystal structures are dominated by one-dimensional {sub ∞}[(Pb{sub 4}O)(BO{sub 3}){sub 3}] “Zig-Zag”-chains.

  4. Two-Inch-Sized Perovskite CH3 NH3 PbX3 (X = Cl, Br, I) Crystals: Growth and Characterization.

    PubMed

    Liu, Yucheng; Yang, Zhou; Cui, Dong; Ren, Xiaodong; Sun, Jiankun; Liu, Xiaojing; Zhang, Jingru; Wei, Qingbo; Fan, Haibo; Yu, Fengyang; Zhang, Xu; Zhao, Changming; Liu, Shengzhong Frank

    2015-09-16

    Two-inch-sized perovskite crystals, CH3 NH3 PbX3 (X=I, Br, Cl), with high crystalline quality are prepared by a solution-grown strategy. The availability of large perovskite crystals is expected to transform its broad applications in photovoltaics, optoelectronics, lasers, photodetectors, LEDs, etc., just as crystalline silicon has done in revolutionizing the modern electronics and photovoltaic industries. PMID:26247401

  5. Reactivity of anthracene in liquid SbCl/sub 3/-AlCl/sub 3/-N-(1-Butyl)Pyridinium chlrodie mixtures

    SciTech Connect

    Zingg, S.P.; Dworkin, A.S.; Soerlie, M.; Chapman, D.M.; Buchanan, A.C. III; Smith, G.P.

    1984-07-01

    Mixtures of SbCl/sub 3/ and N-(1-butyl)pyridinium chloride (BPCl) containing 75-87 mole % SbCl/sub 3/ and SbCl/sub 3/-AlCl/sub 3/-BPCl mixtures containing 60 mole % of SbCl/sub 3/ and 16-23 mole % of AlCl/sub 3/ were found to be liquid at 25/sup 0/C. Results of studies to determine to what extent SbCl/sub 3/ diluted by 25 mole % BPAlCl/sub 4/ at ambient temperature retains the catalytic properties that SbCl/sub 3/ displays at elevated temperatures for a variety of hydrogen redistribution reactions are reported. Anthracene was chosen as the hydrogen-transfer substrate, because of the extensive research on its reactivity in SbCl/sub 3/-rich high-melting mixtures. Fundamental differences in the two systems due to the fact that in the SbCl/sub 3/-rich melts, SbCl/sub 2//sup +/ is the Lewis acid and has an additional redox functionality, whereas, in the chloroaluminate melt, this acidity resides in Al/sub 2/Cl/sub 7//sup -/, which has no redox functionality are related to the catalytic activity. The role of impurities in these mixtures was investigated with results that are relevant to earlier investigations of liquid AlCl/sub 3/-BPCl mixtures. An improved procedure for purifying BPCl is described.

  6. LIBS-based detection of As, Br, C, Cl, P, And S in the VUV spectral region in a Mars atmosphere.

    SciTech Connect

    Radziemski, Leon J.,; Cremers, D. A.; Benelli, K. M.; Khoo, C.; Harris, R. D.

    2005-01-01

    Several elements important to planetary geology (e.g. Br, C, Cl, P, S) and the human exploration of Mars (e.g. toxic elements such as As) have strong emission lines in the purge and vacuum ultraviolet (VUV) spectral region (100 to 200 nm). This spectral region has not been extensively studied using geological samples. Prior LIBS work by others examined sulfide mineral indentification and Cl/C and Br/C ratio determinations in organic materials. We studied emissions from the LIBS plasma in this region using a sample chamber filled with 7 torr (930 Pa) of CO{sub 2} to simulate the Martian atmosphere. Lower pressures were also used to evaluate the effect of residual CO{sub 2} on the spectra. The effects of time delay and laser energy on LIBS detection at reduced pressure were examined. The effect of ambient CO{sub 2} on the detection of C in soil was also evaluated. Lines useful for the spectrochemical analysis of As, Br, C, Cl, P, and S were determined, calibration curves prepared, and limits of detection determined for these elements. The experiments reported here were aimed at in-situ (closeup) analysis rather than stand-off detection at many meters.

  7. Computationally efficient methodology to calculate C-H and C-X (X = F, Cl, and Br) bond dissociation energies in haloalkanes

    SciTech Connect

    McGivern, W.S.; Derecskei-Kovacs, A.; North, S.W.; Francisco, J.S.

    2000-01-20

    A computationally efficient method for calculating C-H and C-X (X = F, Cl, and Br) bond dissociation energies in haloalkanes has been developed by determining correction factors to MP2/cc-pVtz energies. Corrections for basis set effects were determined by the difference in bond dissociation energies calculated at the MP2/cc-pVtz and MP2/cc-pV5z levels, and correlation effects were corrected by calculating the difference in energies at the MP2/cc-pVtz and CCSD(T)/cc-pVtz levels. Subsequent corrections for the spin-orbit energy of the atomic fragment and zero-point energy were applied to give a final bond dissociation energy. The correction factors were determined using CH{sub 4}, CH{sub 3}F, CH{sub 3}Cl, and CH{sub 3}Br and are found to yield bond dissociation energies in excellent agreement with experimental results. This correction may also be broadly applied to multihalogen compounds, as shown in calculations of the C-H and C-X bond dissociation energies of CH{sub 2}X{sub 2} and CHX{sub 3} (X = F, Cl, and Br) compounds, which accurately reproduce experimental values.

  8. Synergistic photocatalytic inactivation mechanisms of bacteria by graphene sheets grafted plasmonic AgAgX (X = Cl, Br, I) composite photocatalyst under visible light irradiation.

    PubMed

    Xia, Dehua; An, Taicheng; Li, Guiying; Wang, Wanjun; Zhao, Huijun; Wong, Po Keung

    2016-08-01

    By coupling graphene sheet and plasmonic photocatalysis technologies, a series of AgAgX/RGOs (X = Cl, Br, I; RGO = reduced graphene oxide) composites were prepared and found to be efficient antimicrobial agents for water disinfection upon visible light. Attributed to the efficient charge transfer by RGO sheets, the optimum AgAgBr/0.5% RGO could completely inactivate 2 × 10(7) cfu mL(-1) of Escherichia coli within 8 min, much faster than bare AgAgBr within 35 min. The synergistic antimicrobial mechanism of AgAgBr/0.5% RGO was studied by Ag(+) ions release evaluation, radical scavengers study, and radical determination. The enhanced photocatalytic activity of irradiated AgAgBr/0.5% RGO originated from the synergistic activities of its three components including Ag, AgBr and RGO, and the proposed mechanisms contained enhanced attraction by RGO followed by two pathways: primary oxidative stress caused by plasma induced reactive species like H2O2 and bactericidal effect of released Ag(+) ions. Furthermore, characterization of E. coli cells using SEM, fluorescent microscopy, and cytoplasmic substance leakage illustrated that VL irradiated AgAgBr/0.5% RGO could not only cause metabolic dysfunction but also destroy the cell envelope and biomolecular, while irradiated Ag(+) ions play a differential bactericidal action with a limited metabolic injury and no cell-membrane damage. The present work provides an efficient water disinfection technology and also opens a new idea in studying the antimicrobial mechanism of plasmonic photocatalyst. PMID:27155987

  9. Waste-water impacts on groundwater: Cl/Br ratios and implications for arsenic pollution of groundwater in the Bengal Basin and Red River Basin, Vietnam.

    PubMed

    McArthur, J M; Sikdar, P K; Hoque, M A; Ghosal, U

    2012-10-15

    Across West Bengal and Bangladesh, concentrations of Cl in much groundwater exceed the natural, upper limit of 10 mg/L. The Cl/Br mass ratios in groundwaters range up to 2500 and scatter along mixing lines between waste-water and dilute groundwater, with many falling near the mean end-member value for waste-water of 1561 at 126 mg/L Cl. Values of Cl/Br exceed the seawater ratio of 288 in uncommon NO(3)-bearing groundwaters, and in those containing measurable amounts of salt-corrected SO(4) (SO(4) corrected for marine salt). The data show that shallow groundwater tapped by tube-wells in the Bengal Basin has been widely contaminated by waste-water derived from pit latrines, septic tanks, and other methods of sanitary disposal, although reducing conditions in the aquifers have removed most evidence of NO(3) additions from these sources, and much evidence of their additions of SO(4). In groundwaters from wells in palaeo-channel settings, end-member modelling shows that >25% of wells yield water that comprises ≥10% of waste-water. In palaeo-interfluvial settings, only wells at the margins of the palaeo-interfluvial sequence contain detectable waste water. Settings are identifiable by well-colour survey, owner information, water composition, and drilling. Values of Cl/Br and faecal coliform counts are both inversely related to concentrations of pollutant As in groundwater, suggesting that waste-water contributions to groundwater in the near-field of septic-tanks and pit-latrines (within 30 m) suppress the mechanism of As-pollution and lessen the prevalence and severity of As pollution. In the far-field of such sources, organic matter in waste-water may increase groundwater pollution by As. PMID:22960402

  10. Four new chalcohalides, NaBa{sub 2}SnS{sub 4}Cl, KBa{sub 2}SnS{sub 4}Cl, KBa{sub 2}SnS{sub 4}Br and CsBa{sub 2}SnS{sub 4}Cl: Syntheses, crystal structures and optical properties

    SciTech Connect

    Li, Chao; Feng, Kai; Tu, Heng; Yao, Jiyong; Wu, Yicheng

    2015-07-15

    Four new chalcohalides, namely NaBa{sub 2}SnS{sub 4}Cl, KBa{sub 2}SnS{sub 4}Cl, KBa{sub 2}SnS{sub 4}Br, and CsBa{sub 2}SnS{sub 4}Cl, have been synthesized by the conventional high temperature solid-state reactions. They crystallize in three different space groups: space group I4/mcm for NaBa{sub 2}SnS{sub 4}Cl and KBa{sub 2}SnS{sub 4}Cl, Pnma for KBa{sub 2}SnS{sub 4}Br, and P2{sub 1}/c for CsBa{sub 2}SnS{sub 4}Cl. In all four compounds, the X{sup −} halide anions are only connected to six alkali metal or Ba cations, and the Sn atoms are only tetrahedrally enjoined to four S atoms. However, the M–X–Ba pseudo layers and the SnS{sub 4} tetrahedra are arranged in different ways in the three structural types, which demonstrates the interesting effect of ionic radii on the crystal structures. UV–vis–NIR spectroscopy measurements indicate that NaBa{sub 2}SnS{sub 4}Cl, KBa{sub 2}SnS{sub 4}Cl, KBa{sub 2}SnS{sub 4}Br, and CsBa{sub 2}SnS{sub 4}Cl have band gaps of 2.28, 2.30, 1.95, and 2.06 eV, respectively. - Graphical abstract: A new series of chalcohalides, NaBa{sub 2}SnS{sub 4}Cl, KBa{sub 2}SnS{sub 4}Cl, KBa{sub 2}SnS{sub 4}Br and CsBa{sub 2}SnS{sub 4}Cl have been obtained. They present three different space groups: NaBa{sub 2}SnS{sub 4}Cl and KBa{sub 2}SnS{sub 4}Cl in space group I4/mcm, KBa{sub 2}SnS{sub 4}Br in Pnma and CsBa{sub 2}SnS{sub 4}Cl in space group P2{sub 1}/c. UV–vis–NIR spectroscopy measurements indicate that NaBa{sub 2}SnS{sub 4}Cl, KBa{sub 2}SnS{sub 4}Cl, KBa{sub 2}SnS{sub 4}Br and CsBa{sub 2}SnS{sub 4}Cl have band gaps of 2.28, 2.30 1.95, and 2.06 eV, respectively. - Highlights: • Four new chalcohalides, NaBa{sub 2}SnS{sub 4}Cl, KBa{sub 2}SnS{sub 4}Cl, KBa{sub 2}SnS{sub 4}Br and CsBa{sub 2}SnS{sub 4}Cl were obtained. • They adopt three different structures owing to different ionic radii and elemental electronegativity. • NaBa{sub 2}SnS{sub 4}Cl, KBa{sub 2}SnS{sub 4}Cl, KBa{sub 2}SnS{sub 4}Br and CsBa{sub 2}SnS{sub 4}Cl have band gaps

  11. Theoretical Study of Electronic Properties of X-Doped (X = F, Cl, Br, I) VO2 Nanoparticles for Thermochromic Energy-Saving Foils.

    PubMed

    Ren, Qinghua; Wan, Jinyu; Gao, Yanfeng

    2014-11-20

    First-principles density functional theory (DFT) electronic structure calculations were carried out for the model halogen-doped VO2 (M1 phase) to evaluate the effect of halogen (X = F, Cl, Br, I) doping on the band edges. The model structures of X-doped VO2 with X at V site or O site were constructed on the basis of 96-atom 2 × 2 × 2 supercell of monoclinic M1 phase of VO2. Our results showed that the band gap Eg2 for Cl-doped VO2 at O1 site (0.51 eV) is smaller than that of F-doped VO2 at O1 site (0.61 eV) and that of pure VO2 (0.78 eV). We also investigated the substitution of chlorine, bromine, and iodine for vanadium in VO2, where the band gaps Eg2 are 0.40, 0.45, and 0.37 eV for Cl-, Br-, and I-doped VO2 at V site, respectively. The Cl-doped VO2 at V site is the best one for achieving good VO2 thermochromic energy-saving foils. PMID:25353175

  12. Broad Wavelength Tunable Robust Lasing from Single-Crystal Nanowires of Cesium Lead Halide Perovskites (CsPbX3, X = Cl, Br, I).

    PubMed

    Fu, Yongping; Zhu, Haiming; Stoumpos, Constantinos C; Ding, Qi; Wang, Jue; Kanatzidis, Mercouri G; Zhu, Xiaoyang; Jin, Song

    2016-08-23

    Lead halide perovskite nanowires (NWs) are emerging as a class of inexpensive semiconductors with broad bandgap tunability for optoelectronics, such as tunable NW lasers. Despite exciting progress, the current organic-inorganic hybrid perovskite NW lasers suffer from limited tunable wavelength range and poor material stability. Herein, we report facile solution growth of single-crystal NWs of inorganic perovskite CsPbX3 (X = Br, Cl) and their alloys [CsPb(Br,Cl)3] and a low-temperature vapor-phase halide exchange method to convert CsPbBr3 NWs into perovskite phase CsPb(Br,I)3 alloys and metastable CsPbI3 with well-preserved perovskite crystal lattice and NW morphology. These single crystalline NWs with smooth end facets and subwavelength dimensions are ideal Fabry-Perot cavities for NW lasers. Optically pumped tunable lasing across the entire visible spectrum (420-710 nm) is demonstrated at room temperature from these NWs with low lasing thresholds and high-quality factors. Such highly efficient lasing similar to what can be achieved with organic-inorganic hybrid perovskites indicates that organic cation is not essential for light emission application from these lead halide perovskite materials. Furthermore, the CsPbBr3 NW lasers show stable lasing emission with no measurable degradation after at least 8 h or 7.2 × 10(9) laser shots under continuous illumination, which are substantially more robust than their organic-inorganic counterparts. The Cs-based perovskites offer a stable material platform for tunable NW lasers and other nanoscale optoelectronic devices. PMID:27437566

  13. A coordinatively flexible hexadentate ligand gives structurally isomeric complexes M2(L)X3 (M = Cu, Zn; X = Br, Cl).

    PubMed

    Wegeberg, Christina; McKee, Vickie; McKenzie, Christine J

    2016-01-01

    Polypyridyl multidentate ligands based on ethylenediamine backbones are important metal-binding agents with applications in biomimetics and homogeneous catalysis. The seemingly hexadentate tpena ligand [systematic name: N,N,N'-tris(pyridin-2-ylmethyl)ethylenediamine-N'-acetate] reacts with zinc chloride and zinc bromide to form trichlorido[μ-N,N,N'-tris(pyridin-2-ylmethyl)ethylenediamine-N'-acetato]dizinc(II), [Zn2(C22H24N5O2)Cl3], and tribromido[μ-N,N,N'-tris(pyridin-2-ylmethyl)ethylenediamine-N'-acetato]dizinc(II), [Zn2Br3(C22H24N5O2)]. One Zn(II) ion shows the anticipated N5O coordination in an irregular six-coordinate site and is linked by an anti carboxylate bridge to a tetrahedral ZnX3 (X = Cl or Br) unit. In contrast, the Cu(II) ions in aquatribromido[μ-N,N,N'-tris(pyridin-2-ylmethyl)ethylenediamine-N'-acetato]dicopper(II)-tribromido[μ-N,N,N'-tris(pyridin-2-ylmethyl)ethylenediamine-N'-acetato]dicopper(II)-water (1/1/6.5) [Cu2Br3(C22H24N5O2)][Cu2Br3(C22H24N5O2)(H2O)]·6.5H2O, occupy two tpena-chelated sites, one a trigonal bipyramidal N3Cl2 site and the other a square-planar N2OCl site. In all three cases, electrospray ionization mass spectra were dominated by a misleading ion assignable to [M(tpena)](+) (M = Zn(2+) and Cu(2+)). PMID:26742830

  14. Potential groundwater age tracer found: Halon-1301 (CF3Br), as previously identified as CFC-13 (CF3Cl)

    NASA Astrophysics Data System (ADS)

    Beyer, Monique; van der Raaij, Rob; Morgenstern, Uwe; Jackson, Bethanna

    2014-09-01

    Groundwater dating using anthropogenic and natural tracer substances is a powerful tool for understanding groundwater dynamics for improved management of groundwater resources. Due to limitations in individual dating methods, often multiple tracers are used to reduce ambiguities. It is commonly accepted that there is a need for further complementary age tracers, in addition to current ones (e.g., tritium, SF6, and CFCs). We propose a potential new groundwater age tracer, Halon-1301 (CF3Br), which can easily be determined using gas chromatography with an attached electron capture detector (GC/ECD) developed by Busenberg and Plummer (2008). Its peak was noted by Busenberg and Plummer (2008), but they believed it to be CFC-13 (CF3Cl) at that time. We performed rigorous tests on gases containing or excluding Halon-1301 and CFC-13 and modern water samples and concluded that the two compounds have extremely similar retention times. Additionally, we found that the ECD response of CFC-13 is far too low to be detected in groundwater or air using standard volumes and sampling techniques. However, the peak areas and concentrations Busenberg and Plummer (2008) reported are in line with what would be expected for Halon-1301. Thus, we are confident that the peak formerly identified as CFC-13 is actually Halon-1301. Busenberg agrees with our findings. We further suggest that Halon-1301 has potential as a (complementary) age tracer, due to its established atmospheric history, and could hypothetically be used to date groundwater recharged in the 1970s or onward. We discuss known relevant properties, such as solubility and stability of Halon-1301 in the context of how these effect its potential application as a groundwater age tracer. Some open questions remain concerning how conservative Halon-1301 is—is it subject to degradation, retardation, and/or local contamination in groundwater. We are confident that Halon-1301 possesses important tracer relevant properties, but further

  15. Ab initio molecular orbital study of XO{sub 2}{sup +} (X = F, Cl, Br, I) systems

    SciTech Connect

    Alcami, M.; Mo, O.; Yanez, M.; Cooper, I.L.

    1999-04-15

    The depletion of stratospheric ozone has resulted in an increasing interest in the study of the possible reaction mechanisms responsible for its depletion. The structures and relative stabilities of the cationic forms of the halogen dioxides have been studied by means of ab initio molecular orbital calculations. For fluorine- and chlorine-containing compounds the geometries and the harmonic vibrational frequencies of all possible isomers were calculated at the QCISD/6-311+G(2d) level of theory. For bromine- and iodine-containing compounds the effective core-potential basis sets of Hay and Wadt, modified to include a set of diffuse functions and two sets of polarization functions, were employed. For all systems the final energies were obtained at the QCISD(T)/6-311+G(3df) level of theory. In addition, multiconfiguration-based methods have also been used. The relative stabilities of structures XOO{sup +} and OXO{sup +} are greatly reduced relative to those observed for the corresponding neutral species. In fact, for Cl and I derivatives, the lowest energy isomer corresponds to the symmetric OXO{sup +} open-chain species. The corresponding cyclic structures arise as local minima on the respective potential energy surfaces, but they lie much higher in energy than the OXO{sup +} open-chain form or the XOO{sup +} isomer. There are significant differences in bonding between XOO{sup +} and OXO{sup +}, the X-O interaction in OXO{sup +} being more covalent than in XOO{sup +}. There are also trends along the series that reflect the pronounced disparity between the electron affinity of F{sup +} and those of the heavier atoms of the group. FOO{sup +} species can be viewed as F({sup 2}P)-O{sub 2}{sup +} complexes, whereas XOO{sup +}(X = Br, I) species can be regarded as X{sup +}({sup 3}P)-O{sub 2} complexes. The OXO{sup +} open-chain species have an electron charge distribution similar to that of the ozone molecule, reflecting the same number of valence electrons in each case.

  16. Eu(2+)-Activated Alkaline-Earth Halophosphates, M5(PO4)3X:Eu(2+) (M = Ca, Sr, Ba; X = F, Cl, Br) for NUV-LEDs: Site-Selective Crystal Field Effect.

    PubMed

    Kim, Donghyeon; Kim, Sung-Chul; Bae, Jong-Seong; Kim, Sungyun; Kim, Seung-Joo; Park, Jung-Chul

    2016-09-01

    Eu(2+)-activated M5(PO4)3X (M = Ca, Sr, Ba; X = F, Cl, Br) compounds providing different alkaline-earth metal and halide ions were successfully synthesized and characterized. The emission peak maxima of the M5(PO4)3Cl:Eu(2+) (M = Ca, Sr, Ba) compounds were blue-shifted from Ca to Ba (454 nm for Ca, 444 nm for Sr, and 434 nm for Ba), and those of the Sr5(PO4)3X:Eu(2+) (X = F, Cl, Br) compounds were red-shifted along the series of halides, F → ClBr (437 nm for F, 444 nm for Cl, and 448 nm for Br). The site selectivity and occupancy of the activator ions (Eu(2+)) in the M5(PO4)3X:Eu(2+) (M = Ca, Sr, Ba; X = F, Cl, Br) crystal lattices were estimated based on theoretical calculation of the 5d → 4f transition energies of Eu(2+) using LCAO. In combination with the photoluminescence measurements and theoretical calculation, it was elucidated that the Eu(2+) ions preferably enter the fully oxygen-coordinated sites in the M5(PO4)3X:Eu(2+) (M = Ca, Sr, Ba; X = F, Cl, Br) compounds. This trend can be well explained by "Pauling's rules". These compounds may provide a platform for modeling a new phosphor and application in the solid-state lighting field. PMID:27494550

  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. X-ray photoelectron spectroscopy of fast-frozen hematite colloids in aqueous solutions. 5. Halide ion (F-, Cl-, Br-, I-) adsorption.

    PubMed

    Shimizu, Kenichi; Shchukarev, Andrey; Kozin, Philipp A; Boily, Jean-François

    2013-02-26

    Halide anion (F(-), Cl(-), Br(-), and I(-)) adsorption and its impact on sodium adsorption at the hematite/water interface were studied by cryogenic X-ray photoelectron spectroscopy (XPS). Measurements were carried out on frozen, centrifuged wet hematite pastes that were previously equilibrated in 50 mM electrolytic solutions in the pH 2-11 range. XPS-derived halide ion surface loadings decreased in the order F(-) > I(-) ≈ Cl(-) > Br(-), whereas sodium loadings were in the order Na(F) > Na(I) > Na(Br) > Na(Cl). The greater sodium loadings in NaF and in NaI resulted from larger anion loadings in these systems. Bromide ion had the lowest loading among all halide ions despite having a charge-to-size ratio that is intermediate between those of Cl(-) and I(-). This unexpected result may have arisen from specific properties of the hematite/water interface, such as water structure and electric double layer thickness. Fluoride ion adsorption proceeded via the formation of hydrogen bonds with the surface hydroxo groups (e.g., ≡Fe-OH(2)···F(-) or ≡Fe-OH···F(-)). Surface-bound fluoride ions exert a greater charge-screening effect than the other halide anions, as demonstrated by considerably small zeta potential values. Fe-F bond formation was excluded as a possible interfacial process as the F 1s peak binding energy (684.2 eV) was more comparable to that of NaF (684.6 eV) than FeF(3) (685.4 eV). Overall, these findings motivate further refinements of existing thermodynamic adsorption models for predicting the ionic composition of hematite particle surfaces contacted with sodium halide aqueous solutions. PMID:23347248

  19. Influence of irrigation practices on arsenic mobilization: Evidence from isotope composition and Cl/Br ratios in groundwater from Datong Basin, northern China

    NASA Astrophysics Data System (ADS)

    Xie, Xianjun; Wang, Yanxin; Su, Chunli; Li, Junxia; Li, Mengdi

    2012-03-01

    SummaryEnvironment isotopes (δ18O and δ2H) and Cl/Br ratios in groundwater have been used to trace groundwater recharge and geochemical processes for arsenic contamination in Datong Basin. The arsenic concentrations of groundwater samples ranged from 0.4 to 434.9 μg/L with the average of 51.2 μg/L, which exceeded China's drinking water standard (10 μg/L). All the groundwater samples are plotted on or close to the meteoric water line of the δ18O vs. δ2H plot, indicating their meteoric origin. The relationship between δ18O values and Cl/Br ratios and Cl concentrations demonstrate that leaching and mixing are the dominant processes affecting the distribution of high arsenic groundwater in this area. The observed non-linearity in the trend between δ18O and arsenic concentration is due to combined effects of mixing and leaching. The similarity of the trend in Cl/Br ratios and δ18O values for high arsenic groundwater demonstrate that extensive leaching of irrigation return and salt flushing water flow could be the dominant process driving arsenic mobilization in the groundwater system. Moreover, the long term irrigation practice can cause the drastic change of the biogeochemical and redox condition of in the aquifer system, which in turn promotes the mobilization of arsenic. Therefore, groundwater pumping for irrigation in this area of waterborne endemic arsenic poisoning should be under strict control to protect groundwater quality in this area.

  20. An ab initio investigation of the ground and low-lying singlet and triplet electronic states of XNO{sub 2} and XONO (X = Cl, Br, and I)

    SciTech Connect

    Peterson, Kirk A.; Francisco, Joseph S.

    2014-01-28

    A systematic ab initio treatment of the nitryl halides (XNO{sub 2}) and the cis- and trans- conformers of the halide nitrites (XONO), where X = Cl, Br, and I, have been carried out using highly correlated methods with sequences of correlation consistent basis sets. Equilibrium geometries and harmonic frequencies have been accurately calculated in all cases at the explicitly correlated CCSD(T)-F12b level of theory, including the effects of core-valence correlation for the former. Where experimental values are available for the equilibrium structures (ClNO{sub 2} and BrNO{sub 2}), the present calculations are in excellent agreement; however, the X-O distances are slightly too long by about 0.01 Å due to missing multireference effects. Accurate predictions for the iodine species are made for the first time. The vertical electronic excitation spectra have been calculated using equation-of-motion coupled cluster methods for the low-lying singlet states and multireference configuration interaction for both singlet and triplet states. The latter also included the effects of spin-orbit coupling to provide oscillator strengths for the ground state singlet to excited triplet transitions. While for ClNO{sub 2} the transitions to excited singlet states all occur at wavelengths shorter than 310 nm, there is one longer wavelength singlet transition in BrNO{sub 2} and two in the case of INO{sub 2}. The long wavelength tail in the XNO{sub 2} species is predicted to be dominated by transitions to triplet states. In addition to red-shifting from X = Cl to I, the triplet transitions also increase in oscillator strength, becoming comparable to many of the singlet transitions in the case of INO{sub 2}. Hence in particular, the latter species should be very photolabile. Similar trends are observed and reported for the halogen nitrites, many of which for the first time.

  1. Nanocrystals of Cesium Lead Halide Perovskites (CsPbX3, X = Cl, Br, and I): Novel Optoelectronic Materials Showing Bright Emission with Wide Color Gamut

    PubMed Central

    2015-01-01

    Metal halides perovskites, such as hybrid organic–inorganic CH3NH3PbI3, are newcomer optoelectronic materials that have attracted enormous attention as solution-deposited absorbing layers in solar cells with power conversion efficiencies reaching 20%. Herein we demonstrate a new avenue for halide perovskites by designing highly luminescent perovskite-based colloidal quantum dot materials. We have synthesized monodisperse colloidal nanocubes (4–15 nm edge lengths) of fully inorganic cesium lead halide perovskites (CsPbX3, X = Cl, Br, and I or mixed halide systems Cl/Br and Br/I) using inexpensive commercial precursors. Through compositional modulations and quantum size-effects, the bandgap energies and emission spectra are readily tunable over the entire visible spectral region of 410–700 nm. The photoluminescence of CsPbX3 nanocrystals is characterized by narrow emission line-widths of 12–42 nm, wide color gamut covering up to 140% of the NTSC color standard, high quantum yields of up to 90%, and radiative lifetimes in the range of 1–29 ns. The compelling combination of enhanced optical properties and chemical robustness makes CsPbX3 nanocrystals appealing for optoelectronic applications, particularly for blue and green spectral regions (410–530 nm), where typical metal chalcogenide-based quantum dots suffer from photodegradation. PMID:25633588

  2. Brightly Luminescent and Color-Tunable Colloidal CH3NH3PbX3 (X = Br, I, Cl) Quantum Dots: Potential Alternatives for Display Technology.

    PubMed

    Zhang, Feng; Zhong, Haizheng; Chen, Cheng; Wu, Xian-gang; Hu, Xiangmin; Huang, Hailong; Han, Junbo; Zou, Bingsuo; Dong, Yuping

    2015-04-28

    Organometal halide perovskites are inexpensive materials with desirable characteristics of color-tunable and narrow-band emissions for lighting and display technology, but they suffer from low photoluminescence quantum yields at low excitation fluencies. Here we developed a ligand-assisted reprecipitation strategy to fabricate brightly luminescent and color-tunable colloidal CH3NH3PbX3 (X = Br, I, Cl) quantum dots with absolute quantum yield up to 70% at room temperature and low excitation fluencies. To illustrate the photoluminescence enhancements in these quantum dots, we conducted comprehensive composition and surface characterizations and determined the time- and temperature-dependent photoluminescence spectra. Comparisons between small-sized CH3NH3PbBr3 quantum dots (average diameter 3.3 nm) and corresponding micrometer-sized bulk particles (2-8 μm) suggest that the intense increased photoluminescence quantum yield originates from the increase of exciton binding energy due to size reduction as well as proper chemical passivations of the Br-rich surface. We further demonstrated wide-color gamut white-light-emitting diodes using green emissive CH3NH3PbBr3 quantum dots and red emissive K2SiF6:Mn(4+) as color converters, providing enhanced color quality for display technology. Moreover, colloidal CH3NH3PbX3 quantum dots are expected to exhibit interesting nanoscale excitonic properties and also have other potential applications in lasers, electroluminescence devices, and optical sensors. PMID:25824283

  3. Extremely NA and CL Rich Chondrule AL3509 from the Allende Meteorite

    SciTech Connect

    Wasserburg, G J; Hutcheon, I D; Aleon, J; Ramon, E C; Krot, A N; Nagashima, K; Brearley, A J

    2011-04-07

    We report on the mineralogy, petrology, chemistry, oxygen isotopes, {sup 26}Al-{sup 26}Mg and {sup 36}Cl-{sup 36}S isotope systematics of the Allende chondrule Al3509 discovered and described by [1] and [2]. This spherical object ({approx}1cm {phi}) contains {approx}10% Na and 1% Cl, and nearly pure {sup 129}Xe [({sup 129}Xe/{sup 127}I) = 1.1 x 10{sup -4} (3)]. This high enrichment in halogens makes it of interest in searching for radiogenic {sup 36}S from {sup 36}Cl (t{sub 1/2} {approx} 0.3 Ma) decay. While there is strong evidence for the presence of {sup 36}Cl in sodalite and wadalite in CV CAIs [4,5], some sodalites show no evidence for excesses of {sup 36}S ({sup 36}S*). In contrast, high inferred initial {sup 36}Cl/{sup 35}Cl = 2 x 10{sup -5} has been found in wadalite from the Allende CAI AJEF [5]. The observed {sup 36}S excesses in sodalite are not correlated with radiogenic {sup 26}Mg, decay product of {sup 26}Al (t{sub 1/2} {approx} 0.72 Ma) [4]. From the inferred initial {sup 36}Cl/{sup 35}Cl ratios and consideration of both AGB and SNe stellar sources, {sup 36}Cl must be the product of charged particle irradiation within the early solar system. However, neither the specific nuclear production mechanism nor the irradiation site have been identified. Both sodalite and wadalite are found as late stage alteration products of CAIs together with grossular, monticellite, Al-rich pyroxene, wollastonite, nepheline, ferroan olivine, and ferroan pyroxenes. This late-stage alteration has been found to extensively change some CAIs in Allende, but clear residues of spinel, hibonite and Wark-Lovering rims are recognizable remnants of the original CAIs. The nature of the widespread volatile alteration process as well as that of the fluid phase remain controversial.

  4. Technical note: Interference of Br{sup {minus}}, BrO{sub 3}{sup {minus}}, and ClO{sub 3}{sup {minus}} with DOX determination

    SciTech Connect

    Symons, J.M.; Xia, R.

    1995-08-01

    In the dissolved organic halogen (DOX) water quality analytic test, prior to combustion, the granular activated carbon (GAC) on which the DOX is adsorbed is washed with a sodium nitrate solution designed to remove any inorganic chloride that may have also adsorbed to the GAC. Thus, a potential positive interference is removed. This study investigated the effectiveness of the nitrate wash in eliminating possible interferences from bromide, bromate, and chlorate ions. No interference was detected from bromate or chlorate ion, but a small positive interference of about 12 {micro}g Cl{sup {minus}}/L per mg/L of bromide ion was found in the presence of background organic matter.

  5. Monocapped tris(dioxime) complexes of technetium(III): Synthesis and structural characterization of TcX(dioxime) sub 3 B-R (X = Cl, Br; dioxime = dimethylglyoxime, cyclohexanedione dioxime; R = CH sub 3 , C sub 4 H sub 9 )

    SciTech Connect

    Treher, E.N.; Francesconi, L.C.; Gougoutas, J.Z.; Malley, M.F.; Nunn, A.D. )

    1989-09-06

    Monocapped boronic acid adducts of technetium tris(dioxime) complexes (BATO), TcX(dioximeH){sub 2}(dioxime)B-R, where X = Cl or Br, dioxime = cyclohexanedione dioxime or dimethylglyoxime, and R = methyl or butyl, have been prepared by template synthesis starting with pertechnetate and stannous ion, (N(C{sub 4}H{sub 9}){sub 4})(TcOCl{sub 4}), or M{sub 2}(TcX{sub 6}) (M = NH{sub 4}, K; X = Cl, Br). These seven-coordinate Tc(III) compounds are the first examples of tris(dioxime) complexes in which one and only one oxygen of each of the three dioximes is joined to a common cap atom (boron). The crystal structures of three of the BATO complexes have been determined and are reported. The three dioxime oxygens on the uncapped end of the molecule are intramolecularly hydrogen bonded to two bridging protons. A halogen occupies the seventh coordination site. 34 refs., 4 figs., 8 tabs.

  6. Room-temperature scintillation properties of cerium-doped REOX (RE=Y, La, Gd, and Lu; X=F, Cl, Br, and I)

    SciTech Connect

    Eagleman, Yetta; Bourret-Courchesne, Edith; Derenzo, Stephen

    2010-12-10

    The scintillation properties of cerium-doped oxyhalides following the general formula REOX (RE=Y, La, Gd, and Lu; X=F, Cl, Br, and I) are reported. These materials were synthesized under dry conditions as microcrystalline powders from conventional solid state reactions. The room temperature X-ray excited emission and scintillation decay curves were measured and analyzed for each material. Additionally, the hygroscopic nature of the oxychlorides and oxybromides was compared to that of their corresponding rare earth halides. The yttrium, lanthanum, and gadolinium oxychlorides, and all of the oxybromides and oxyiodides are found to be activated by Ce{sup 3+}. GdOBr doped with 0.5% Ce{sup 3+} has the highest light output with a relative luminosity of about one-half that of LaBr{sub 3}: Ce{sup 3+}. It displays a single exponential decay of 30 ns.

  7. Behaviour of I/Br/Cl-THMs and their projected toxicities under simulated cooking conditions: Effects of heating, table salt and residual chlorine.

    PubMed

    Yan, Mingquan; Li, Mingyang; Han, Xuze

    2016-08-15

    This study examined the effects of heating, residual chlorine and concentration of table salt on the generation of iodine-, bromine- and chlorine-containing trihalomethanes (THMs) under simulated cooking conditions. In the case of addition of either KI- or KIO3-fortified salt, total I-THM concentrations increased with increasing iodine concentration, while total Cl/Br-THM concentrations decreased. CHCl2I, CHBrClI, CHBrI2, CHBr2I and CHI3 were formed in the presence of KI salt, while only CHCl2I was formed in the presence of KIO3 salt. CHCl2I was unstable under cooking conditions, and >90% of this DBP was removed during heating, which in some cases increased the concentrations of the other I-THMs. The calculated cytotoxicity increased with addition of KI- or KIO3-fortified salt due to the generation of I-THMs, whose impact on the cytotoxicity at room temperature was equal to or five times higher, respectively, than the cytotoxicity of the simultaneously formed Cl/Br-THMs for the cases of salts. Heating decreased the cytotoxicity, except for the case of addition of KI salt, in which the calculated cytotoxicity of I-THMs increased above 150% as the temperature was increased up to 100°C. The reported results may have important implications for epidemiologic exposure assessments and, ultimately, for public health protection. PMID:27107240

  8. Photoluminescent mixed ligand complexes of CuX (X = Cl, Br, I) with PPh3 and a polydentate imino-pyridyl ligand - Syntheses, structural variations and catalytic property

    NASA Astrophysics Data System (ADS)

    Ghorai, Anupam; Mondal, Jahangir; Patra, Goutam K.

    2015-10-01

    Three ternary copper(I) complexes [CuI2Cl2(L1)(PPh3)4] (1), [CuI2Br2(L1) (PPh3)4] (2) and [CuI2(μ-I)2 (μ-L1) (PPh3)2]n (3) have been prepared by reactions of CuX (X = Cl, Br and I) with PPh3 and the polydentate imino-pyridyl ligand L1. These complexes have been characterized by elemental analysis, IR, UV-Vis, NMR and X-ray crystallography. From single crystal structural analysis it has been found that complexes 1 and 2 are homo-dinuclear having non-bridging halide ions whereas complex 3 is a 1-D zig-zag co-ordination polymer containing bridged iodide ions. Complexes 1, 2 and 3 are photoluminescent at room temperature in chloroform whereas ligand L1 is non-emissive. The E½ values of the CuIsbnd CuII couple of 1, 2 and 3 are 0.98 V, 0.92 V and 0.42 V respectively (vs Ag/AgCl in 1 M KCl, scan rate 100 mV s-1). All three complexes function as effective catalysts for the synthesis of 2-substituted benzoxazoles.

  9. Structural, Electronic, and Optical Properties of BiOX1-xYx (X, Y = F, Cl, Br, and I) Solid Solutions from DFT Calculations.

    PubMed

    Zhao, Zong-Yan; Liu, Qing-Lu; Dai, Wen-Wu

    2016-01-01

    Six BiOX1-xYx (X, Y = F, Cl, Br, and I) solid solutions have been systematically investigated by density functional theory calculations. BiOCl1-xBrx, BiOBr1-xIx, and BiOCl1-xIx solid solutions have very small bowing parameters; as such, some of their properties increase almost linearly with increasing x. For BiOF1-xYx solid solutions, the bowing parameters are very large and it is extremely difficult to fit the related calculated data by a single equation. Consequently, BiOX1-xYx (X, Y = Cl, Br, and I) solid solutions are highly miscible, while BiOF1-xYx (Y = Cl, Br, and I) solid solutions are partially miscible. In other words, BiOF1-xYx solid solutions have miscibility gaps or high miscibility temperature, resulting in phase separation and F/Y inhomogeneity. Comparison and analysis of the calculated results and the related physical-chemical properties with different halogen compositions indicates that the parameters of BiOX1-xYx solid solutions are determined by the differences of the physical-chemical properties of the two halogen compositions. In this way, the large deviation of some BiOX1-xYx solid solutions from Vegard's law observed in experiments can be explained. Moreover, the composition ratio of BiOX1-xYx solid solutions can be measured or monitored using optical measurements. PMID:27549344

  10. Transfer of Organic br and cl from the Biosphere to the Atmosphere during Meteorite Impacts: Implications for the Stratospheric Ozone Layer

    NASA Astrophysics Data System (ADS)

    Kourtidis, Kostas

    2010-05-01

    Following the Cretaceous / Tertiary (K/T) meteoritic impact some 65 Myr ago, large portions of aboveground terrestrial biomass were burned. As a result, large amounts of various trace gases were injected to the atmosphere, inducing a wide range of effects on climate and ecosystems. Here, it is commented on the emission to the atmosphere of methyl bromide (CH3Br) and methyl chloride (CH3Cl) from extensive biomass burning that followed the impact. Based on reported biomass burning emission rates, it is estimated that their emissions from global fires resulted in tropospheric mixing ratios of around 20-65.8 ppbv organic Cl and 110-390 pptv organic Br. The above calculated mixing ratios of active chlorine and bromine are more than an order of magnitude their present, anthropogenically perturbed level and, although the ocean ultimately might absorb them, we calculate here that they could still remain in the stratosphere for many years, substantially affecting the ozone layer. This would have lead to very serious increases in short wavelength UV radiation reaching the lowermost atmosphere. While impacts such as the K/T one occur at intervals of 107 yrs, more frequent, less massive events could ignite a smaller portion of the global forests. If one-tenth of the forests ignited during the K/T event are burned, CH3Cl and CH3Br levels might rise by 3.6-12 times and 1.1-3.9 times their present level, respectively, leading still to global ozone-hole conditions.

  11. Synthetic cannabinoid JWH-018 and its halogenated derivatives JWH-018-Cl and JWH-018-Br impair Novel Object Recognition in mice: Behavioral, electrophysiological and neurochemical evidence.

    PubMed

    Barbieri, M; Ossato, A; Canazza, I; Trapella, C; Borelli, A C; Beggiato, S; Rimondo, C; Serpelloni, G; Ferraro, L; Marti, M

    2016-10-01

    It is well known that an impairment of learning and memory function is one of the major physiological effects caused by natural or synthetic cannabinoid consumption in rodents, nonhuman primates and in humans. JWH-018 and its halogenated derivatives (JWH-018-Cl and JWH-018-Br) are synthetic CB1/CB2 cannabinoid agonists, illegally marketed as "Spice" and "herbal blend" for their Cannabis-like psychoactive effects. In the present study the effects of acute exposure to JWH-018, JWH-018-Cl, JWH-018-Br (JWH-018-R compounds) and Δ(9)-THC (for comparison) on Novel Object Recognition test (NOR) has been investigated in mice. Moreover, to better characterize the effects of JWH-018-R compounds on memory function, in vitro electrophysiological and neurochemical studies in hippocampal preparations have been performed. JWH-018, JWH-018-Cl and JWH-018-Br dose-dependently impaired both short- and long-memory retention in mice (respectively 2 and 24 h after training session). Their effects resulted more potent respect to that evoked by Δ(9)-THC. Moreover, in vitro studies showed as JWH-018-R compounds negatively affected electrically evoked synaptic transmission, LTP and aminoacid (glutamate and GABA) release in hippocampal slices. Behavioral, electrophysiological and neurochemical effects were fully prevented by CB1 receptor antagonist AM251 pretreatment, suggesting a CB1 receptor involvement. These data support the hypothesis that synthetic JWH-018-R compounds, as Δ(9)-THC, impair cognitive function in mice by interfering with hippocampal synaptic transmission and memory mechanisms. This data outline the danger that the use and/or abuse of these synthetic cannabinoids may represent for the cognitive process in human consumer. PMID:27346209

  12. Structural, Electronic, and Optical Properties of BiOX1−xYx (X, Y = F, Cl, Br, and I) Solid Solutions from DFT Calculations

    PubMed Central

    Zhao, Zong-Yan; Liu, Qing-Lu; Dai, Wen-Wu

    2016-01-01

    Six BiOX1−xYx (X, Y = F, Cl, Br, and I) solid solutions have been systematically investigated by density functional theory calculations. BiOCl1−xBrx, BiOBr1−xIx, and BiOCl1−xIx solid solutions have very small bowing parameters; as such, some of their properties increase almost linearly with increasing x. For BiOF1−xYx solid solutions, the bowing parameters are very large and it is extremely difficult to fit the related calculated data by a single equation. Consequently, BiOX1−xYx (X, Y = Cl, Br, and I) solid solutions are highly miscible, while BiOF1−xYx (Y = Cl, Br, and I) solid solutions are partially miscible. In other words, BiOF1−xYx solid solutions have miscibility gaps or high miscibility temperature, resulting in phase separation and F/Y inhomogeneity. Comparison and analysis of the calculated results and the related physical–chemical properties with different halogen compositions indicates that the parameters of BiOX1−xYx solid solutions are determined by the differences of the physical–chemical properties of the two halogen compositions. In this way, the large deviation of some BiOX1−xYx solid solutions from Vegard’s law observed in experiments can be explained. Moreover, the composition ratio of BiOX1−xYx solid solutions can be measured or monitored using optical measurements. PMID:27549344

  13. Fenugreek seeds, a hepatoprotector forage crop against chronic AlCl3 toxicity

    PubMed Central

    2013-01-01

    Background Having considered how bioavailable aluminium (Al) may affect ecological systems and animals living there, especially cattle, and in search for a preventive dietary treatment against Al toxicity, we aimed to test the protective role of fenugreek seeds against chronic liver injury induced by aluminum chloride (AlCl3) in Wistar rats. Results Five months of AlCl3 oral exposure (500 mg/kg bw i.g for one month then 1600 ppm via drinking water) caused liver atrophy, an inhibition of aspartate transaminase (AST), alanine transaminase (ALT) and glutamyl transpeptidase (GGT), an enhancement of both lipid peroxidation and lactate dehydrogenase (LDH) activity and an increase of total protein level in liver. Moreover, histopathological and histochemical examinations revealed moderate alterations in the hepatic parenchyma in addition to a disrupted iron metabolism. Co-administration of fenugreek seed powder (FSP) at 5% in pellet diet during two months succeeded to antagonize the harmful effects of AlCl3 by restoring all tested parameters. Conclusion This study highlighted the hepatotoxicity of AlCl3 through biochemical and histological parameters in one hand and the hepatoprotective role of fenugreek seeds on the other hand. Thus this work could be a pilot study which will encourage farmers to use fenugreek seeds as a detoxifying diet supplement for domestic animals. PMID:23363543

  14. Effects of Al2O3 phase and Cl component on dehydrogenation of propane

    NASA Astrophysics Data System (ADS)

    Liu, Jie; Liu, Changcheng; Ma, Aizeng; Rong, Junfeng; Da, Zhijian; Zheng, Aiguo; Qin, Ling

    2016-04-01

    The effects of two Al2O3 phases, γ- and θ-Al2O3, and Cl component on the performances of Pt-Al2O3 catalysts in the dehydrogenation of propane were investigated in this work. The catalysts were systematically characterized by various techniques, such as scanning transmission electron microscopy (STEM), temperature-programmed desorption with ammonia as probe molecules (NH3-TPD) and temperature-programmed oxidation (TPO). The characterizations and catalytic results show that: (i) the pore structures and acid properties of the two Al2O3 phases can change the quantity, location and property of the carbon deposition, (ii) the existence of Cl plays a significant role on the agglomeration of Pt particles and carbon deposition, which further influence the catalytic performances of Pt-Al2O3 catalysts with different support phases for propane dehydrogenation.

  15. Reactivity of anthracene in liquid SbCl/sub 3/-AlCl/sub 3/-N-(1-BUTYL)pyridinium chloride mixtures

    SciTech Connect

    Zingg, S.P.; Buchanan, A.C.; Chapman, D.M.; Dworkin, A.S.; Smith, G.P.; Sorlie, M.

    1983-05-01

    Mixtures of SbCl/sub 3/ and N-(1-butyl)pyridinium chloride (BPCl) containing 75-87 mol % SbCl/sub 3/ and SbCl/sub 3/-AlCl/sub 3/-BPCl mixtures containing 60 mol % SbCl/sub 3/ and 17-24 mol % BPCl were found to be liquid at 25/sup 0/C. Dilute solutions of anthracene were stable in ternary mixtures containing 18 mol % AlCl/sub 3/, but in mixtures containing 22-24 mol % AlCl/sub 3/, anthracene reacted under the influence of the solvent, which behaved as both oxidant and H-transfer catalyst. The oxidized product was protonated anthracene, which was stable in this melt. The source of protons was provided by hydrogen-liberating Scholl condensations combined with the reduction of Sb(III). A part of the hydrogen from Scholl reactions reacted with anthracene to form 9,10-dihydroanthracene. By contrast, a liquid mixture without SbCl/sub 3/, AlCl/sub 3/-BPCl (2:1 mole ratio), proved to be a much less active H-transfer catalyst than the SbCl/sub 3/-rich liquids even though it is a stronger Lewis acid, and it did not induce protonation beyond a trace attributable to protic impurities.

  16. Reactivity of anthracene in liquid SbCl/sub 3/-AlCl/sub 3/-N-(1-butyl)pyridinium chloride mixtures

    SciTech Connect

    Zingg, S.P.; Dworkin, A.S.; Sorlie, M.; Chapman, D.M.; Buchanan, A.C. III; Smith, G.P.

    1983-01-01

    Mixtures of SbCl/sub 3/ and N-(1-butyl)pyridinium chloride (BPCl) containing 75 to 87 mol % SbCl/sub 3/ and SbCl/sub 3/-AlCl/sub 3/-BPCl mixtures containing 60 mol % SbCl/sub 3/ and 17 to 24 mol % BPCl were found to be liquid at 25/sup 0/C. Dilute solutions of anthracene were stable in ternary mixtures containing 18 mol % AlCl/sub 3/, but in mixtures containing 22 to 24 mol % AlCl/sub 3/, anthracene reacted under the influence of the solvent, which behaved as both oxidant and H-transfer catalyst. The oxidized product was protonated anthracene, which was stable in this melt. The source of protons was provided by hydrogen-liberating Scholl condensations combined with the reduction of Sb(III). A part of the hydrogen from Scholl reactions reacted with anthracene to form 9,10-dihydroanthracene. By contrast, a liquid mixture without SbCl/sub 3/, AlCl/sub 3/-BPCl (2:1 mole ratio), proved to be a much less active H-transfer catalyst than the SbCl/sub 3/-rich liquids even though it is a stronger Lewis acid, and it did not induce protonation beyond a trace attributable to protic impurities.

  17. Molten salt electrolytes. I. experimental and theoretical studies of Lil/AlCl{sub 3}.

    SciTech Connect

    Lee, Y.-C.; Kolafa, J.; Curtiss, L. A.; Ratner, M. A.; Shriver, D. F.; Materials Science Division; Northwestern Univ.; Inst. of Chemical Process Fundamentals

    2001-06-08

    Molten LiI/AlCl3 with different molar ratios of LiI to AlCl{sub 3} were prepared and characterized by Raman spectroscopy, thermal analysis, and impedance measurements. The LiI/AlCl{sub 3} adducts melt at 70-80 C and the Raman spectrum indicates that a variety of haloaluminates exist in the system. The 1:1 adduct has the highest ionic conductivity, 2x10{sup -6} S/cm at 25 C, and the conductivity increases dramatically as the temperature is increased. Molecular dynamics (MD) simulations suggest that several haloaluminates are present in the adducts. Ab initio calculations were carried out on the species that were predicted by MD simulations and these results were compared with Raman spectra, and good agreement was obtained. Several-ns-long MD simulations allowed us to study the conductivity and relaxation processes in the 1:1 and 1:2 melts at higher temperatures.

  18. NMR shielding and spin–rotation constants of {sup 175}LuX (X = {sup 19}F, {sup 35}Cl, {sup 79}Br, {sup 127}I) molecules

    SciTech Connect

    Demissie, Taye B.

    2015-12-31

    This presentation demonstrates the relativistic effects on the spin-rotation constants, absolute nuclear magnetic resonance (NMR) shielding constants and shielding spans of {sup 175}LuX (X = {sup 19}F, {sup 35}Cl, {sup 79}Br, {sup 127}I) molecules. The results are obtained from calculations performed using density functional theory (non-relativistic and four-component relativistic) and coupled-cluster calculations. The spin-rotation constants are compared with available experimental values. In most of the molecules studied, relativistic effects make an order of magnitude difference on the NMR absolute shielding constants.

  19. Parity violation in nuclear magnetic resonance frequencies of chiral tetrahedral tungsten complexes NWXYZ (X, Y, Z = H, F, Cl, Br or I)

    SciTech Connect

    Nahrwold, Sophie Berger, Robert; Schwerdtfeger, Peter

    2014-01-14

    Density functional theory within the two-component quasi-relativistic zeroth-order regular approximation (ZORA) is used to predict parity violation shifts in {sup 183}W nuclear magnetic resonance shielding tensors of chiral, tetrahedrally bonded tungsten complexes of the form NWXYZ (X, Y, Z = H, F, Cl, Br or I), as well as for the heavier systems NWHAtF and NWH(117)F for comparison. The calculations reveal that sub-mHz accuracy is required to detect such tiny effects in this class of compounds, and that parity violation effects are very sensitive to the choice of ligands.

  20. Self-assembly of [UO2X4]2- (X=Cl, Br) dianions with γ substituted pyridinium cations: Structural systematics and fluorescence properties

    NASA Astrophysics Data System (ADS)

    Surbella, Robert G.; Andrews, Michael B.; Cahill, Christopher L.

    2016-04-01

    Room temperature self-assembly of [UO2X4]2- (X=Cl, Br) with γ substituted pyridinium cations has resulted in the formation of twelve compounds that were studied via single crystal X-ray diffraction and fluorescence spectroscopy. Systematic variation of electron donating groups on the pyridinium species is shown to influence the presence and/or strength of various supramolecular synthons, including hydrogen bonding and pi interactions. Combinations of such non-covalent interactions (NCIs) have given rise to a range of supramolecular assemblies, and are shown to influence uranyl emission by way of second sphere coordination to equatorial ligands.

  1. Theoretical Study of Low-Lying Electronic States of PtX (X = F, Cl, Br, and I) Including Spin-Orbit Coupling.

    PubMed

    Zou, Wenli; Suo, Bingbing

    2016-08-18

    The low-lying electronic states of platinum ions (Pt(+)) and platinum monohalides (PtX; X = F, Cl, Br, and I) are calculated using the multireference configuration interaction method with relativistic effective core potentials. The spin-orbit coupling is taken into account through the perturbative state-interaction approach. For the Ω states of PtX below 35000 cm(-1), the potential energy curves and the corresponding spectroscopic constants are reported. It is found that the lowest Ω = 3/2 state is the ground one for the four species of PtX. Overall, the theoretical results are in reasonable agreement with the available experimental data. PMID:27463417

  2. NMR shielding and spin-rotation constants of 175LuX (X = 19F, 35Cl, 79Br, 127I) molecules

    NASA Astrophysics Data System (ADS)

    Demissie, Taye B.

    2015-12-01

    This presentation demonstrates the relativistic effects on the spin-rotation constants, absolute nuclear magnetic resonance (NMR) shielding constants and shielding spans of 175LuX (X = 19F, 35Cl, 79Br, 127I) molecules. The results are obtained from calculations performed using density functional theory (non-relativistic and four-component relativistic) and coupled-cluster calculations. The spin-rotation constants are compared with available experimental values. In most of the molecules studied, relativistic effects make an order of magnitude difference on the NMR absolute shielding constants.

  3. Electronic structure, optical properties and bonding in alkaline earth halo-fluoride scintillators: BaClF, BaBrF and BaIF

    SciTech Connect

    Yedukondalu, N.; Babu, K. Ramesh; Bheemalingam, Ch.; Singh, David J; Vaitheeswaran, G.; Kanchana, V.

    2011-01-01

    We report first-principles studies of the structural, electronic, and optical properties of the alkaline-earth halofluorides, BaXF (X = Cl, Br, and I), including pressure dependence of structural properties. The band structures show clear separation of the halogen p derived valence bands into higher binding energy F and lower binding energy X derived manifolds reflecting the very high electronegativity of F relative to the other halogens. Implications of this for bonding and other properties are discussed. We find an anisotropic behavior of the structural parameters especially of BaIF under pressure. The optical properties on the other hand are almost isotropic, in spite of the anisotropic crystal structures.

  4. Comment on "Destabilization of the halogen bond in complexes of protonated NCX (X = F, Cl, Br) molecules" [Chem. Phys. Lett. 603 (2014) 37-40

    NASA Astrophysics Data System (ADS)

    McDowell, Sean A. C.; Joseph, Jerelle A.; Buckingham, A. David

    2015-02-01

    A computational study at various levels of theory was undertaken for protonated NCX (X = F, Cl, Br) complexes, which were previously characterized using the MP2/6-311++G(d,p) procedure. It is shown that the apparent destabilization of the halogen bond in some of these complexes is due to a basis set deficiency. The protonated species were re-optimized at MP2/6-311++G(2df,2pd) and found to be more strongly bound than their unprotonated counterparts. These new results suggest that only H+NCF⋯F- may be considered to be destabilized, since no local minimum was found.

  5. UV-VIS Absorption Spectra of Molten AgCl and AgBr and of their Mixtures with Group I and II Halide Salts

    NASA Astrophysics Data System (ADS)

    Greening, Giorgio G. W.

    2015-10-01

    The UV-VIS absorption spectra of (Ag1-X[Li-Cs, Ba]X)Cl and of (Ag1-X[Na, K, Cs]X)Br at 823 K at the concentrations X=0.0, 0.1, 0.2 have been measured. The findings show that on adding the respective halides to molten silver chloride and silver bromide, shifts of the fundamental absorption edge to shorter wavelengths result. A correlation between the observed shifts and the expansion of the silver sub-lattice is found, which is valid for both silver halide systems studied in this work.

  6. Reactivity of anthracene in liquid SbCl/sub 3/-AlCl/sub 3/-N-(1-butyl)pyridinium chloride mixtures

    SciTech Connect

    Zingg, S.P.; Buchanan, A.C.; Chapman, D.M.; Dworkin, A.S.; Smith, G.P.; Sorlie, M.

    1984-07-01

    Mixtures of SbCl/sub 3/ and N-(l-butyl)pyridinium chloride (BPCl) containing 75-87 m/o (mole percent) SbCl/sub 3/ and SbCl/sub 3/AlCl/sub 3/-BPCl mixtures containing 60 m/o SbCl/sub 3/ and 16-23 m/o AlCl/sub 3/ were found to be liquid at 25/sup 0/C. Dilute solutions of anthracene were stable in ternary mixtures containing 18 m/o AlCl/sub 3/, but in mixtures containing 22-24 m/o AlCl/sub 3/, anthracene reacted under the influence of the solvent, which behaved as both oxidant and H-transfer catalyst. The oxidized product was protonated anthracene, which was stable in this melt. The source of protons was provided by hydrogen liberating Scholl condensations combined with the reduction of Sb(III). A part of the hydrogen from Scholl reactions reacted with anthracene to form 9,10-dihydroanthracene. By contrast, a liquid mixture without SbCl/sub 3/, AlCl/sub 3/-BPCl (2:1 mole ratio) proved to be a much less active H-transfer catalyst than the SbCl/sub 3/-rich liquids even though it is a stronger Lewis acid, and it did not induce protonation beyond a trace attributable to protic impurities. The role of impurities in these mixtures was investigated with results that are relevant to earlier investigations of liquid AlCl/sub 3/-BPCl mixtures. An improved procedure for purifying BPCl is described.

  7. Novel sodium aluminium borohydride containing the complex anion [Al(BH4,Cl)4]-.

    PubMed

    Lindemann, Inge; Ferrer, Roger Domènech; Dunsch, Lothar; Cerný, Radovan; Hagemann, Hans; D'Anna, Vincenza; Filinchuk, Yaroslav; Schultz, Ludwig; Gutfleisch, Oliver

    2011-01-01

    The synthesis of a novel alkali-metal aluminium borohydride NaAl(BH4)xCl4-x from NaBH4 and AlCl3 using a solid state metathesis reaction is described. Structure determination was carried out using synchrotron powder diffraction data and vibrational spectroscopy. An orthorhombic structure (space group Pmn2(1)) is formed which contains Na+ cations and complex [Al(BH4,Cl)4]- anions. Due to the high chlorine content (1 < or = x < or = 1.43) the hydrogen density of the borohydride is only between 2.3 and 3.5 wt.% H2 in contrast to the expected 14.6 wt.% for chlorine free NaAl(BH4)4. The decomposition of NaAl(BH4)xCl4-x is observed in the target range for desorption at about 90 degrees C by differential scanning calorimetry (DSC), in situ Raman spectroscopy and synchrotron powder X-ray diffraction. Thermogravimetric analysis (TG) shows extensive mass loss indicating the loss of H2 and B2H6 at about 90 degrees C followed by extensive weight loss in the form of chloride evaporation. PMID:22455071

  8. Ion imaging studies of Cl(2P3/2) fragments arising in the visible photolysis of BrCl: Measurement of orientation, alignment, and alignment-free anisotropy parameters

    NASA Astrophysics Data System (ADS)

    Wouters, Eloy R.; Beckert, Marco; Russell, Lucy J.; Rosser, Keith N.; Orr-Ewing, Andrew J.; Ashfold, Michael N. R.; Vasyutinskii, Oleg S.

    2002-08-01

    The photodissociation dynamics of jet-cooled BrCl molecules have been investigated at four different wavelengths in the range 425-485 nm by high-resolution velocity map ion imaging. Four images of the Cl(2P3/2) atomic fragments are recorded at each photolysis wavelength with the probe laser polarization, respectively, linearly aligned and vertical (i.e., perpendicular to the detection axis), right circularly polarized, horizontally linearly polarized (i.e., parallel to the detection axis) and left circularly polarized on successive laser shots, thereby ensuring automatic mutual self-normalization. Appropriate linear combinations of these images allow quantification of the angular momentum alignment of the Cl(2P3/2)o fragments [i.e., the correlation between their recoil velocity (v) and their electronic angular momentum (J)] in terms of the alignment anisotropy parameters s2, alpha2, eta2, and gamma2, and determination of the "alignment-free" recoil anisotropy parameter, beta0, as a function of parent excitation wavelength. Both incoherent and coherent contributions to the alignment are identified, with both simultaneous parallel and perpendicular excitations to the B 3Pi(0+) and C 1Pi(1 states and excitations to the Omega]=[plus-or-minus1 components of the C state contributing to the latter. The deduced values of the alignment-free beta parameters indicate (wavelength dependent) contributions from both parallel and perpendicular parent absorptions in this wavelength range. Such a conclusion accords with approximate deconvolutions of the parent absorption spectrum that are currently available, and with determinations of the orientation parameter gamma1' obtained by fitting the difference image obtained when using left and right circularly polarized radiation to probe the ground state Cl atoms arising in the 480.63 nm photodissociation of BrCl when the photolysis laser radiation is polarized linearly at 45deg to the detection axis.

  9. Rate Constants for the Reactions of OH with CH(sub 3)Cl, CH(sub 2) C1(sub 2), CHC1(sub 3)and CH(sub 3)Br

    NASA Technical Reports Server (NTRS)

    Hsu, H-J.; DeMore, W.

    1994-01-01

    Rate constants for the reactions of OH with CH3C1, CH2Cl2, CHCl3 and CH3Br have been measured by a relative rate technique in which the reaction rate of each compound was compared to that of HFC-152a (CH3CHF2)and for CH2Cl2, HFC-161 (CH3CH2F).

  10. Facile formation of Ag{sub 2}WO{sub 4}/AgX (X = Cl, Br, I) hybrid nanorods with enhanced visible-light-driven photoelectrochemical properties

    SciTech Connect

    Li, Jingjing; Yu, Caiyun; Zheng, Changcheng; Etogo, Atangana; Xie, Yunlong; Zhong, Yijun; Hu, Yong

    2015-01-15

    Highlights: • Ag{sub 2}WO{sub 4}/AgX hybrid nanorods were prepared by a facile in-situ anion exchange reaction. • Ag{sub 2}WO{sub 4} nanorods and different X{sup −} ions were reacted in water at room temperature. • The hybrids possess significantly enhanced photoelectrochemical properties. • Ag{sub 2}WO{sub 4}/AgBr hybrids exhibit the highest photocatalytic activity among three samples. • The active species tests were also investigated to confirm photocatalytic mechanism. - Abstract: In this work, we demonstrated a general strategy for the preparation of a series of uniform Ag{sub 2}WO{sub 4}/AgX (X = Cl, Br, I) hybrid nanorods by a facile in-situ anion exchange reaction occurring at room temperature between pregrown Ag{sub 2}WO{sub 4} nanorods and different X{sup −} ions in water. Compared with Ag{sub 2}WO{sub 4} nanorods, further investigation has revealed that the as-prepared hybrid nanorods possess significantly enhanced photocurrent response and photocatalytic activity in degrading methyl orange (MO) under visible-light irradiation. In particular, the Ag{sub 2}WO{sub 4}/AgBr hybrid nanorods exhibit the highest photocatalytic activity among the three kinds of samples. The active species tests indicate that superoxide anion radicals and photogenerated holes are responsible for the enhanced photocatalytic performance.

  11. Diurnal variation of BrO, HO2, HOCl, ClO, and O3 in the range from stratosphere to lower ionosphere observed by SMILES

    NASA Astrophysics Data System (ADS)

    Kasai, Yasuko; Sagawa, Hideo; Kuribayashi, Kouta

    A good understanding of halogen and hydrogen chemistry is required to understand Earth’s upper atmosphere above stratosphere. The abundance of these highly reactive species varies widely (within the parts per billion to parts per trillion range) on a day-to-day timescale due to photochemical reactions induced by sunlight. Until now, however, it has been difficult to accurately estimate their abundances and behavior. The Superconducting Submillimeter-Wave Limb-Emission Sounder (SMILES) is an atmospheric observation instrument with unprecedented sensitivity to monitor atmospheric minor compositions. SMILES is the first global environment observation instrument in the Japanese Experiment Module onboard the International Space Station (ISS). This mission is a joint project of the National Institute of Information and Communications Technology (NICT) and the Japan Aerospace Exploration Agency. The observation frequency bands of SMILES range from 624.32-626.32GHz to 649.12-650.32GHz. This range allows us to obtain vertical profiles of several atmospheric constituents simultaneously. We measure the abundance of O3 and its isotopic compositions, and of hydrochloric acid (HCl), ClO, HOCl, HO2, hydrogen peroxide (H2O2), BrO, acetonitrile (CH3CN), nitric acid (HNO3), water vapor, and ice clouds. The non-sun-synchronized orbit of the ISS gives us the opportunity to observe the diurnal variation of the species we measure. We performed atmospheric limb observations between 12 October 2009 and 21 April 2010. With the successful observations, we found that the amplitude of diurnal variations for halogen and hydrogen radicals (i.e., ClO, HOCl, HO2, and BrO) are quite large. Within one day, the abundance of BrO in the stratosphere and mesosphere varies from 0 to 16 parts per trillion. This comprises more than 80% of the total stratospheric bromine inventory. The results from SMILES represent the first studies of atmospheric composition diurnal variation using short-lived radical

  12. Strongly visible-light responsive plasmonic shaped AgX:Ag (X = Cl, Br) nanoparticles for reduction of CO2 to methanol.

    PubMed

    An, Changhua; Wang, Jizhuang; Jiang, Wen; Zhang, Meiyu; Ming, Xijuan; Wang, Shutao; Zhang, Qinhui

    2012-09-21

    Plasmonic shaped AgX:Ag (X = Cl, Br) nanoparticles have been synthesized by a facile and versatile glycerol-mediated solution route. The as-prepared AgX:Ag nanoparticles exhibit regular shapes, i.e., cube-tetrapod-like AgCl:Ag nanoparticles and AgBr:Ag nanoplates. Compared with the pristine AgX, AgX:Ag nanocomposites display stronger absorption in the visible region due to the surface plasmon resonance of silver nanoparticles. The calculation of bandgaps and band positions indicates the as-achieved AgX:Ag nanoparticles can be used as a class of potential photocatalyst for the reduction of CO(2). For example, reduction of CO(2) under visible light irradiation with the assistance of the anisotropic AgX:Ag nanoparticles yields as much as 100 μmol methanol in the products. Furthermore, the AgX:Ag nanoparticles can maintain its structure and activity after 3 runs of reactions. Therefore, the present route opens an avenue to acquire plasmonic photocatalysts for conversion of CO(2) into useful organic compounds. PMID:22869008

  13. Structures, properties and nature of DMSO-XY (XY=ClF and BrF) complexes: redshift and blueshift of S=O stretch.

    PubMed

    Li, Qing-Zhong; Xu, Wen-Rui; Li, Ran; Liu, Xiao-Feng; Li, Wen-Zuo; Cheng, Jian-Bo

    2012-11-01

    The DMSO-XY (XY=ClF and BrF) complexes have been investigated with quantum chemical calculations. In general, two minima complexes were found, one with an O···X halogen bond and the other one with a S···X halogen bond. The former is more stable than the latter. Additionally, one first order saddle point complex was also observed. The interaction energies in the S complexes suffer a prominent influence from the calculation methods. At the CCSD(T)/aug-cc-pVDZ level, the interaction energies are calculated to be -9.19 and -12.73 kcal/mol for the Cl and Br global minima, respectively. Both complexes have also been evidenced to be stable at room temperature. The SO stretch vibration exhibits a red shift at the global minimum but a blue shift at the local minimum, whereas the CSC and CH stretch vibrations move to high frequency in both cases. The energy decomposition analyses indicate that the electrostatic interaction plays a dominant role in stabilizing these halogen-bonded complexes. PMID:22858607

  14. Relevance of weak intermolecular forces on the supramolecular structure of free or DMSO solvated 5-(4-X-benzylidene)rhodanines (X = F, Cl, Br, I)

    NASA Astrophysics Data System (ADS)

    Casas, José S.; Castaño, M. Victoria; Couce, María D.; Sánchez, Agustín; Sordo, José; Torres, M. Dolores; Vázquez, Saulo A.; Vázquez-López, Ezequiel M.

    2016-09-01

    The rhodanines of the title (Xp-Rhod, X = F, Cl, Br, I) were synthesized and characterized in solid state and in solution. The crystal structures of the four compounds show different supramolecular organizations. In the F-, Cl- and Br-derivatives, a R22(8) (CSNH)2 ring forms via Nsbnd H⋯S hydrogen bonds between two neighbouring molecules to give dimers. The I-derivative is also dimeric, but exhibits R22(8) (CONH)2 rings. The two type of dimers are associated in a variety of structures through hydrogen bonding, π-stacking, Csbnd H⋯π interactions and halogen bonding. These interactions were analysed from a crystallographic point of view and their relative relevance was explored using DFT calculations. The effect produced on all these interactions by the incorporation of DMSO molecules to the lattice was analysed by comparing the crystal structures of Xp-Rhod compounds and those of corresponding Xp-RhodṡDMSO solvates.

  15. Theoretical study on the substitution reactions of the germylenoid H2GeLiF with SiH3X (X = F, Cl, Br).

    PubMed

    Zhang, Gongxiao; Qi, Yuhua; Xu, Chongjuan

    2016-06-01

    The substitution reactions of H2GeLiF (G) with SiH3X (X = F, Cl, Br) were investigated using calculations performed at the QCISD/6-311++G (d, p)//B3LYP/6-311+G (d, p) level of theory. The results led to the following conclusions. (i) The substitutions are nucleophilic reactions. There are two substitution paths, I and II, which both lead to the germane H2GeFSiH3. The enantiomers of this germane are obtained via these two paths if an H in SiH3X is replaced with a different group or atom. (ii) Both substitution pathways show the same order of barrier heights (SiH3F > SiH3Cl > SiH3Br). The difference between the bond energies of Li-X and Si-X may explain the precedence among the substitution reactions of G with SiH3X. Path I has a lower activation barrier than path II, indicating that path I is more favorable. (iii) Comparison between the relevant insertion and substitution reactions shows that substitutions are more favorable and that the substitution product H2GeFSiH3 predominates over the insertion product. (iv) The substitution reactions of H2GeLiF with SiH3X are exothermic. PMID:27179805

  16. Diurnal variation climatology of short-lived at atmospheric compositions (ClO, BrO, HO2 and HOCl) derived from SMILES NICT data

    NASA Astrophysics Data System (ADS)

    Kreyling, Daniel; Sagawa, Hideo; Kasai, Yasuko

    2013-04-01

    We present a diurnal variation climatology for short-lived at atmospheric compositions, such as ClO, BrO, HO2 and HOCl, as well as for longer life time species, like O3 and HCl from observations of unprecedented sensitivity with the Superconducting SubMIllimeter wave Limb-Emission Sounder (SMILES), which is installed on the Japanese Experiment Module (JEM) at the International Space Station (ISS). With its non sun synchronous orbit, SMILES measurements comprise observations at all local times. The target altitude range is between lower stratosphere and mesopause. Differences in diurnal variation chemistry of strato-, and mesospheric BrO and ClO of the diurnal climatology are presented. The data employed is produced by the SMILES level 2 retrieval algorithm version 2.1.5 at the National Institute of Information and Communications Technology (NICT). The SMILES climatology data sets are available via the SMILES data distribution homepage in NICT at https://smiles-p6.nict.go.jp/products/research_latitude-longitude.jsf

  17. Comparison of π-hole tetrel bonding with σ-hole halogen bonds in complexes of XCN (X = F, Cl, Br, I) and NH3.

    PubMed

    Nziko, Vincent de Paul N; Scheiner, Steve

    2016-02-01

    In addition to the standard halogen bond formed when NH3 approaches XCN (X = F, Cl, Br, I) along its molecular axis, a perpendicular approach is also possible, toward a π-hole that is present above the X-C bond. MP2/aug-cc-pVDZ calculations indicate the latter geometry is favored for X = F, and the σ-hole structure is preferred for the heavier halogens. The π-hole structure is stabilized by charge transfer from the NH3 lone pair into the π*(CN) antibonding orbital, and is characterized by a bond path from the N of NH3 to the C atom of XCN, a form of tetrel bond. The most stable 2 : 1 NH3/XCN heterotrimer for X = F and Cl is cyclic and contains a tetrel bond augmented by a pair of NHN H-bonds. For X = Br and I, the favored trimer is noncyclic, stabilized by a tetrel and a halogen bond. PMID:26750543

  18. Four-mode quantum calculations of resonance states in complex-forming bimolecular reactions: Cl{sup -}+CH{sub 3}Br

    SciTech Connect

    Schmatz, Stefan

    2005-06-15

    The vibrational resonance states of the complexes formed in the nucleophilic bimolecular substitution (S{sub N}2) reaction Cl{sup -}+CH{sub 3}Br{yields}ClCH{sub 3}+Br{sup -} were calculated by means of the filter diagonalization method employing a coupled-cluster potential-energy surface and a Hamiltonian that incorporates an optical potential and is formulated in Radau coordinates for the carbon-halogen stretching modes. The four-dimensional model also includes the totally symmetric vibrations of the methyl group (C-H stretch and umbrella bend). The vast majority of bound states and many resonance states up to the first overtone of the symmetric stretching vibration in the exit channel complex have been calculated, analyzed, and assigned four quantum numbers. The resonances are classified into entrance channel, exit channel, and delocalized states. The resonance widths fluctuate over six orders of magnitude. In addition to a majority of Feshbach-type resonances there are also exceedingly long-lived shape resonances, which are associated with the entrance channel and can only decay by tunneling. The state-selective decay of the resonances was studied in detail. The linewidths of the resonances, and thus the coupling to the energetic continuum, increase with excitation in any mode. Due to the strong mixing of the many progressions in the intermolecular stretching modes of the intermediate complexes, this increase as a function of the corresponding quantum numbers is not monotonic, but exhibits pronounced fluctuations.

  19. FTIR and Raman spectra and fundamental frequencies of 5-halosubstituted uracils: 5-X-uracil (X=F, Cl, Br and I).

    PubMed

    Singh, J S

    2012-02-15

    FTIR and Raman spectra of 5-halosubstituted uracils (5-X-uracil; X=F, Cl, Br and I) were recorded in the region 200-4000cm(-1). Assuming under the C(s) point group, the distribution of normal mode of vibrations between the two species as planar (a') and non-planar (a″) are given by 21a'+9a″, of which also correspond to the 30 modes of uracil moiety and the electro negativity of halogen group substitution causes some where mixing/shifting in their modes with other modes. The ring breathing and kekule stretching modes are observed in lower magnitudes compared to those of uracil which could be due to mass effect of halogen atom in place of the hydrogen atom. The C-X (X=F, Cl, Br and I) stretching frequency is distinctly separated from the CH/NH ring stretching frequencies on the pyrimidine ring. All other bands have also been assigned different fundamentals/overtones/combinations. PMID:22169026

  20. Magnetization and Specific Heat Investigations of the Bose Glass: Br-doped NiCl2-4SC(NH2)2

    NASA Astrophysics Data System (ADS)

    Weickert, Franziska; Miclea, Corneliu; Movshovich, Roman; Zapf, Vivien; Yu, Rong; Roscilde, Tommaso

    2012-02-01

    NiCl2-4SC(NH2)2 (DTN) is an insulating material, which shows field induced XY-AFM order between Hc1 = 2.1 T and Hc2 = 12.6 T. In boson language, the ground state of DTN can be described as a Mott insulator, and the ordered state as a Bose-Einstein condensation of magnons. Bond disorder is introduced by substituting Br atoms on Cl positions, which simultaneously changes the super exchange interaction along the c-direction on a local scale and leads to a Mott-glass ground state in zero field. Furthermore, the system develops a gapless Bose glass for magnetic fields 0 < H < Hc1 and H > Hc2, followed by a Mott insulating state above the saturation field Hsat. Note, that the critical fields Hc1,2 and Hsat are shifted compared to those of pure DTN. In this talk, we report on measurements of the magnetization and specific heat at very low temperatures between 50 mK and 3 K in high magnetic fields up to 14 T on an 8% Br-doped single crystal DTN. We compare our data with the local gap model, which reduces the low-temperature and low-field behavior to those of an ensemble of individual three level systems with local magnetization MS = 0, ±1 and a finite energy gap for H = 0.

  1. New approach to the fast screening of plant oil samples for F-, Cl-, Br- and S-organic compounds on the trace level.

    PubMed

    Chivarzin, M E; Revelsky, I A; Nikoshina, A V; Buldyzkova, A N; Chepeliansky, D A; Revelsky, A I; Buriak, A K

    2016-04-01

    The fast method of the simultaneous determination of F(-), Cl(-), Br(-) and SO4(2-) anions in the deionized water on the trace level by ion chromatography using thorough cleaning of respective water containers, 10 μM NaHCO3 water solution as eluent, short Metrohm (50 × 4 mm) separation column and a large water volume injection is proposed. Calculated detection limits are 10(-9)-10(-8)% depending on the element. The method for the fast screening of plant oil samples for the total fluorine-, chlorine-, bromine- and sulfur-organic compounds content (calculated for the respective elements) on the trace level is developed. It is based on the high temperature combustion of oil sample in oxygen flow, absorption of the conversion products in deionized water and whole absorbate volume analysis for F(-), Cl(-), Br(-) and SO4(2-) anions, corresponding to the respective elements, using the developed method of these anions analysis by ion chromatography. The samples of soya, olive, sunflower and cotton seed oil were analyzed. The method detection limits (for 1mg sample) were 2 × 10(-6)%, 2 × 10(-6)%, 5 × 10(-6)% and 5 × 10(-6)% for fluorine, chlorine, bromine and sulfur, respectively. The relative standard deviation was ≤ 15%. The method gives the compressed information about the total content of all target and nontarget fluorine-, chlorine-, bromine- and sulfur-organic compounds in plant oils. PMID:26838388

  2. Behavior of Al2O3 and SiO2 with heating in a Cl2 + CO stream

    NASA Technical Reports Server (NTRS)

    Shchetinin, L. K.

    1984-01-01

    Differential thermal analysis (DTA) and Thermogravimetric analysis (TGA) were used to study the chlorination of alpha-Al2O3, gamma-Al2O3 and amorphous SiO2 in a Cl + CO stream, for the preparation of AlCl3 and SiCl4. The chlorination starting temperatures were 235 deg for Al2O3 and 680 deg for SiO2. The chlorination of alpha- and gamma-Al2O3 takes place via the formation of AlOCl as an intermediate product, and its subsequent dissociation at 480 to 560 deg, according to 3AlOCl yields AlCl3 + Al2O3. The chlorination activation energies are given for the three oxides.

  3. Antiperovskite Chalco-Halides Ba3(FeS4)Cl, Ba3(FeS4)Br, and Ba3(FeSe4)Br with Spin Super-Super Exchange

    PubMed Central

    Zhang, Xian; Liu, Kai; He, Jian-Qiao; Wu, Hui; Huang, Qing-Zhen; Lin, Jian-Hua; Lu, Zhong-Yi; Huang, Fu-Qiang

    2015-01-01

    Perovskite-related materials have received increasing attention for their broad applications in photovoltaic solar cells and information technology due to their unique electrical and magnetic properties. Here we report three new antiperovskite chalco-halides: Ba3(FeS4)Cl, Ba3(FeS4)Br, and Ba3(FeSe4)Br. All of them were found to be good solar light absorbers. Remarkably, although the shortest Fe-Fe distance exceeds 6 Å, an unexpected anti-ferromagnetic phase transition near 100 K was observed in their magnetic susceptibility measurement. The corresponding complex magnetic structures were resolved by neutron diffraction experiments as well as investigated by first-principles electronic structure calculations. The spin-spin coupling between two neighboring Fe atoms along the b axis, which is realized by the Fe-S···S-Fe super-super exchange mechanism, was found to be responsible for this magnetic phase transition. PMID:26525136

  4. Structure and stability of noble gas bound EX3+ compounds (E = C, Ge, Sn, Pb; X = H, F, Cl, Br).

    PubMed

    Pan, Sudip; Moreno, Diego; Ghosh, Sreyan; Chattaraj, Pratim K; Merino, Gabriel

    2016-01-15

    It has been analyzed at the MP2/def2-QZVPPD level whether EX3+ (E = C-Pb; X = H, F-Br) can bind noble gas atoms. Geometrical and electronic structures, dissociation energy values, thermochemical parameters, natural bond order, electron density, and energy decomposition analyses highlight the possibility of such noble gas bound EX3+ compounds. Except He and Ne, the other heavier congeners of this family make quite strong bonds with E. In fact, the dissociations of Ar-Rn bound analogues turn out to be endergonic in nature at 298 K, except in the cases of ArGe Cl3+, Ar/KrGeBr3+, and ArSnBr3+. GeH3+ and EF3+ (E = Ge-Pb) can even bind two Ng atoms with reasonably high dissociation energy. As the pz orbital of the E center in EX3+ plays a crucial role in its binding with the noble gas atoms, the effect of the π back-bonding causing X → E electron transfer ought to be properly understood. Due to the larger back-donation, the Ng binding ability of EX3+ gradually decreases along F to Br. EH2+ and the global minimum HE(+…) H2 (E = Sn, Pb) complexes are also able to bind Ar-Rn atoms quite effectively. The NgE bonds in Ar-Rn bound CH3+, GeH3+, and EF3+ (E = Ge-Pb) and Xe/RnE bonds in NgECl3+ and NgEBr3+ (E = Ge, Sn) are mainly of covalent type. PMID:26132752

  5. The 1988 Arctic Survey, Diurnal Study (Sunrise and Sunset) and Peak Altitude (22 km) Flights for the In Situ Detection of ClO and BrO from the NASA ER-2 Aircraft

    NASA Technical Reports Server (NTRS)

    Anderson, James G.

    1996-01-01

    Two critical areas of research were addressed successfully by this research. The first involves NASA ER-2 airborne observations of ClO and BrO radical destruction of ozone within the arctic vortex. The second involves the analysis of diurnal variations in ClO, to test the production and loss rates of ClO that constitutes the test for coupling reactions between the chlorine and nitrogen systems. We discuss results from this research in order.

  6. Using Halogens (Cl, Br, F, I) and Stable Isotopes of Water (δ18O, δ2H) to Trace Hydrological and Biogeochemical Processes in Prairie Wetlands

    NASA Astrophysics Data System (ADS)

    Levy, Z. F.; Lu, Z.; Mills, C. T.; Goldhaber, M. B.; Rosenberry, D. O.; Mushet, D.; Siegel, D. I.; Fiorentino, A. J., II; Gade, M.; Spradlin, J.

    2014-12-01

    Prairie pothole wetlands are ubiquitous features of the Great Plains of North America, and important habitat for amphibians and migratory birds. The salinity of proximal wetlands varies highly due to groundwater-glacial till interactions, which influence wetland biota and associated ecosystem functions. Here we use halogens and stable isotopes of water to fingerprint hydrological and biogeochemical controls on salt cycling in a prairie wetland complex. We surveyed surface, well, and pore waters from a groundwater recharge wetland (T8) and more saline closed (P1) and open (P8) basin discharge wetlands in the Cottonwood Lake Study Area (ND) in August/October 2013 and May 2014. Halogen concentrations varied over a broad range throughout the study area (Cl = 2.2 to 170 mg/L, Br = 13 to 2000 μg/L, F = < 30 (MDL) to 740 μg/L, I = 1 to 538 μg/L). The Cl/Br molar ratios were higher (171 to 574) at the recharge wetland, indicating meteoric sources, and had a tighter and lower range (33 to 320) at the down-gradient sites. The Cl/I molar ratios of waters throughout the site had a wide range (32 to 26,000). Lowest values occurred at the upgradient shore of P1 (32 to 43) due to low Cl concentrations and the center of P1 (196 to 213) where pore water of weathered till underlying 1.2 m of organic-rich sediment and silty clay soil is enriched in I to ~500 µg/L. Stable isotopes of water showed that evaporation-enriched pond water (δ18O = -9.5 to -2.71 ‰) mixes with shallow groundwater in the top 0.6 m of fringing wetland soils and 1.2 m of the substrate in the center of P1. Our results suggest endogenous sources for Br and I within the prairie landscape that may be controlled by biological mechanisms or weathering of shale from glacial till.

  7. Temperature induced changes on the structure and the dynamics of the ``tetrahedral'' glasses and melts of ZnCl2 and ZnBr2

    NASA Astrophysics Data System (ADS)

    Yannopoulos, S. N.; Kalampounias, A. G.; Chrissanthopoulos, A.; Papatheodorou, G. N.

    2003-02-01

    Glassy, supercooled, and molten ZnCl2 and ZnBr2 have been studied by Raman spectroscopy over the broad temperature range -196 to 800 °C in an effort to follow in detail the structural changes caused by temperature variation. A systematic study has also been undertaken for the corresponding crystalline polymorphs showing that each material exists in only one crystalline phase if water traces are not present. The reduced isotropic and anisotropic Raman spectra of the ZnCl2 and ZnBr2 glasses and melts are isomorphous. Unusually drastic changes of the relative intensities of particular bands occur with temperature in the reduced isotropic spectra. A comparison between the spectral features of crystals, glasses, and melts has revealed that the network structure of the glasses and melts consists of ZnX4/2 (X=Br,Cl) tetrahedra bound to each other by apex- and edge-bridged halides. The substructure of the glass/melt is formed by mixing a variety of tetrahedra participating in "open," "cluster," and "chain" networks which are bound to each other by bridged halides. The boundaries of the substructure involve neutral or charged terminal halide bonds with zinc of an average threefold coordination. Temperature rise breaks up the substructure to smaller fragments, increases the number of terminal bonds, and rearranges the apex- and edge-bridging networks. The good glass-forming ability of the ZnX2 melts is attributed to the existence and mixing of the three topologically different networks within the substructure. Our data of ZnCl2 are in qualitative agreement with molecular dynamics simulations as regards the frequency distribution of vibrational modes. However, simulations are not able to correctly predict polarization properties in the glass and the melt. The low-frequency Raman spectra reveal the presence of the Boson peak in both glasses, which interestingly persists, well resolved, also into the normal liquid state above the melting point. The spectra in the region of the

  8. Geometrical structure of CH 3ClX(μ-Cl) 2XClCH 3(X = Al, Ga): experimental versus ab initio calculations

    NASA Astrophysics Data System (ADS)

    Mains, Gilbert J.; Bock, Charles W.; Trachtman, Mendel; Mastryukov, Vladimir S.

    1992-11-01

    The GAUSSIAN90 set of programs is used to obtain geometry optimizations of CH 3ClX(μ-Cl) 2XClCH 3 (X = Al, Ga), which exhibit cis/trans isomerization. The results are compared with experimental data.

  9. Electrochemical Codeposition of Al-Li-Mg Alloys at Solid Aluminum Electrode from LiCl-KCl-MgCl2 Molten Salt System

    NASA Astrophysics Data System (ADS)

    Ye, Ke; Zhang, Mi Lin; Chen, Ye; Han, Wei; de Yan, Yong; Cao, Peng

    2010-06-01

    The electrochemical codeposition of Mg and Li at an aluminium electrode in LiCl-KCl (50:50 wt pct) melts containing different concentrations of MgCl2 at 893 K (620 °C) to form Al-Li-Mg alloys was investigated. Cyclic voltammograms showed that the potential of Li metal deposition at an Al electrode, before the addition of MgCl2, is more positive than that of Li metal deposition at an Mo electrode, which indicated the formation of an Al-Li alloy. The underpotential deposition of magnesium at an aluminium electrode leads to the formation of Al-Mg alloys, and the succeeding underpotential deposition of lithium on predeposited Al-Mg alloys leads to the formation of Al-Li-Mg alloys. Chronopotentiometric measurements indicated that the codeposition of Mg and Li occurs at current densities lower than -0.668 A cm-2 in LiCl-KCl-MgCl2 (8 wt pct) melts at an aluminium electrode. The chronoamperometric studies indicated that the onset potential for the codeposition of Mg and Li is -2.000 V, and the codeposition of Mg and Li at an aluminium electrode is formed into Al-Li-Mg alloys when the applied potentials are more negative than -2.000 V. X-ray diffraction and inductively coupled plasma analysis indicated that Al-Li-Mg alloys with different lithium and magnesium contents were prepared via potentiostatic and galvanostatic electrolysis. The microstructure of typical dual phases of the Al-Li-Mg alloy was characterized by an optical microscope and by scanning electron microscopy. The analysis of energy dispersive spectrometry showed that the elements of Al and Mg distribute homogeneously in the Al-Li-Mg alloy. The lithium and magnesium contents of Al-Li-Mg alloys can be controlled by MgCl2 concentrations and by electrolytic parameters.

  10. Mechanistic Study on the Formation of Cl-/Br-/I-Trihalomethanes during Chlorination/Chloramination Combined with a Theoretical Cytotoxicity Evaluation.

    PubMed

    Allard, Sebastien; Tan, Jace; Joll, Cynthia A; von Gunten, Urs

    2015-09-15

    Chlorination followed by chloramination can be used to mitigate the formation of potentially toxic iodinated disinfection byproducts (I-DBPs) while controlling the formation of regulated chloro-bromo-DBPs (Cl-/Br-DBPs). Water samples containing dissolved organic matter (DOM) isolates were subjected to 3 disinfection scenarios: NH2Cl, prechlorination followed by ammonia addition, and HOCl alone. A theoretical cytotoxicity evaluation was carried out based on the trihalomethanes (THMs) formed. This study demonstrates that the presence of bromide not only enhances the yield and rate of iodate formation, it also increases the formation of brominated I-THM precursors. A shift in the speciation from CHCl2I to the more toxic CHBr2I, as well as increased iodine incorporation in THMs, was observed in the presence of bromide. For low bromide concentrations, a decrease in I-THM formation and theoretical cytotoxicity was achieved only for high prechlorination times, while for high bromide concentrations, a short prechlorination time enabled the full conversion of iodide to iodate. For low DOM concentrations or DOM with low reactivity, Br-/I-THMs were preferentially formed for short prechlorination times, inducing high cytotoxicity. However, for high chlorine exposures, the cytotoxicity induced by the formation of regulated THMs might outweigh the benefit of I-THM mitigation. For high DOM concentrations or DOM with higher reactivity, mixed I-THMs were formed together with high concentrations of regulated THMs. In this case, based on the cytotoxicity of the THMs formed, the use of NH2Cl is recommended. PMID:26280905

  11. Structures, spectroscopic studies and solid-state thermal transformations of coordination polymers from P 4Se 3 and CuX (X=Cl, Br, I)

    NASA Astrophysics Data System (ADS)

    Biegerl, Andreas; Gröger, Christian; Kalbitzer, Hans R.; Pfitzner, Arno; Wachter, Joachim; Weihrich, Richard; Zabel, Manfred

    2011-07-01

    The formation of coordination polymers (CuCl)P 4Se 3 ( 1), (CuBr) 3(P 4Se 3) 2 ( 2), (CuI) 3(P 4Se 3) 2 ( 3) and (CuI)P 4Se 3 ( 4), from solutions of copper(I) halides and P 4Se 3 by diffusion methods has been studied. The new compounds were characterized by X-ray crystallography, solid-state 31P MAS NMR and Raman spectroscopy. Theoretical studies on the DFT level in the crystalline phase allowed the unequivocal assignment of the recorded Raman shifts between 200 and 480 cm -1. The structure of 1 consists of a 2D network of castellated [CuCl] n chains and bidentate P 4Se 3 molecules. The 3D network of 2 comprises [CuBr] n chains, which are linked by tridentate P 4Se 3 molecules. Compound 3 is a three-dimensional polymer composed of four-membered (CuI) 2 rings and castellated [CuI] n chains, which are linked by tridentate P 4Se 3 molecules involving two basal and the apical P atoms. Thermal conversion of 1 at 230 °C gives (CuCl) 3(P 4Se 3) 2 ( 5), which is isostructural with 2. The thermal conversion of (CuI) 3P 4S 3, which was studied for comparison gave at 371 °C (CuI) 3P 4S 4, Cu 3PS 4 and small amounts of Cu 6PS 5I.

  12. Electrochemical and spectroscopic studies of the chloro and oxochloro complex formation of Nb(V) and Ta(V) in NaCl-AlCl3 melts.

    PubMed

    von Barner, J H; Bjerrum, N J

    2005-12-26

    The equilibrium constant for the chloro complex formation of Nb(V) NbCl6-<--->NbCl5+Cl- (i) in NaCl-AlCl3 melts at 175 degrees C was found to be pKi = 2.86(5). The oxochloro complex formation of Nb(V) and Ta(V) in NaCl-AlCl3 melts at 175 degrees C could be explained by the following equilibria: MOCl4- <-->MOCl3+Cl- (ii) MOCl3<-->MOCl2(+)+Cl- (iii) where M = Nb and Ta. The equilibrium constants determined by potentiometric measurements with chlorine-chloride electrodes were, for M = Nb, pKii = 2.21(4) and pKiii = 3.95(5) and, for M = Ta, pKii = 2.743(15) and pKiii = 4.521(13). NbCl6- has two bands in the UV-vis region, a strong one at 34.7 x 10(3) cm-1 and a weaker one at 41.6 x 10(3) cm-1. The MOCl4- complexes showed in the case of Nb(V) absorption bands at 32.7 and 42.9 x 10(3) cm-1 and in the case of Ta(V) at 38.6 and 48.1 x 10(3) cm-1. PMID:16363855

  13. Visible-light-driven photocatalysts Ag/AgCl dispersed on mesoporous Al2O3 with enhanced photocatalytic performance.

    PubMed

    Feng, Zhouzhou; Yu, Jiajie; Sun, Dongping; Wang, Tianhe

    2016-10-15

    In this paper, Ag/AgCl and Ag/AgCl/Al2O3 photocatalysts were synthesized via a precipitation reaction between NaCl and CH3COOAg or Ag(NH3)2NO3, wherein Ag/AgCl was immobilized into mesoporous Al2O3 medium. The Ag/AgCl-based nanostructures were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), photoluminescence (PL) spectra, and so on. The photocatalysts displayed excellent photocatalytic activity for the degradations of methyl orange (MO) and methylene blue (MB) pollutants under visible light irradiation. The Ag/AgCl(CH3COOAg)/Al2O3 sample exhibited the best photocatalytic performance, degrading 99% MO after 9min of irradiation, which was 1.1 times, 1.22 times and 1.65 times higher than that of Ag/AgCl(Ag(NH3)2NO3)/Al2O3, Ag/AgCl(CH3COOAg) and Ag/AgCl(Ag(NH3)2NO3) photocatalyst, respectively. Meanwhile, Ag/AgCl(CH3COOAg)/Al2O3 also showed excellent capability of MB degradation. Compared to the data reported for Ag/AgCl/TiO2, the Ag/AgCl/Al2O3 prepared in this work exhibited a good performance for the degradation of methyl orange (MO). The results suggest that the dispersion of Ag/AgCl on mesoporous Al2O3 strongly affected their photocatalytic activities. O2(-), OH radicals and Cl(0) atoms are main active species during photocatalysis. PMID:27442145

  14. Behavior of BaBr2, BaI2, and BaCl2 at high pressure as analogs to SiO2.

    NASA Astrophysics Data System (ADS)

    Smart, T. J.; Stackhouse, S.; Diamond, M. R.; Godwal, B. K.; Jeanloz, R.

    2015-12-01

    Motivated by the expectation that giant and supergiant planets likely contain rocky components in their cores, we study analogs of the archetypal rock constituent, SiO2. The crystal structures of SiO2 under ultra-high pressures, greater than feasible experimental conditions, are believed to be documented by the high pressure structural sequence of AX2 compounds. Experimental and theoretical work agree on a high pressure transition to the cotunnite (orthorhombic) phase, with first-principles theory predicting that SiO2 transforms to the cotunnite structure at 750 GPa. However, the existence of a postcotunnite (monoclinic) phase as the final high pressure polymorph, suggested by X-ray diffraction (XRD) experiments on ambient pressure cotunnite-structured AX2 compounds (e.g. PbCl2, SnCl2), has been challenged by density-functional theory (DFT) computations. This disagreement could perhaps be due to sensitivity in diamond-anvil cell (DAC) experiments to pressure gradients; conversely, it could perhaps arise from limitations of DFT. This study further explores both the experimental and theoretical sides of this debate, with an aim to resolve this discrepancy. We present synchrotron XRD data on the AX2 compounds BaCl2, BaBr2, and BaI2, compressed up to 70 GPa at room temperature in a DAC. Here we compare our experimentally observed crystallography and equations of state with results from our DFT simulations.

  15. 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

  16. Infrared Spectroscopic Study of ClCN Adsorption on Clean and Triethylenediamine-Precovered y-Al2O3

    SciTech Connect

    Kim, S.; Sorescu, D.C.; Yates, J., Jr.

    2007-12-13

    The effect of triethylenediamine (TEDA) (also named 1,4-diazabicyclo [2.2.2]octane, DABCO) on the adsorption of ClCN on a y-Al2O3 absorbent has been investigated. Both Fourier transform infrared (FTIR) and theoretical studies indicate that no direct interaction between amine groups of TEDA and ClCN molecules takes place. Instead, we found that TEDA competes with ClCN for active surface sites on y-Al2O3. In addition, the adsorption behavior of cyanogen chloride (ClCN) on a clean y-Al2O3 surface has been studied. The sequence of the thermally activated processes of diffusion, adsorption, desorption, and decomposition of ClCN molecules on the clean y-Al2O3 surface following icelike ClCN layer formation at lower temperature was observed. One of the decomposition products, Al-NCO, was assigned by using an Al-18OH labeled surface for reaction with ClCN. In addition, Al-CN and Al2-OCN species were also detected upon ClCN decomposition. Good correlation of the calculated vibrational frequencies for the adsorbed species with experimental data is found.

  17. Mössbauer spectroscopic studies of (n-C n H2 n +1NH3)2SnX6 ( n=0-4; X = Cl or Br) and their related complexes

    NASA Astrophysics Data System (ADS)

    Katada, M.; Yoneyama, M.; Nakai, S.; Kawata, S.; Sano, H.

    1994-12-01

    Complexes of the type (n-C n H2 n +1NH3)2SnX6 (0≤ n≤ 4 and X=Cl or Br) have been investigated with a variety of physico-chemical techniques. The structural phase transitions were found in some of these complexes. The temperature dependence of the Mössbauer spectral absorption area for (C2H5NH3)2SnCl6 and (C2H5NH3)2SnBr6 changed sharply at phase transition temperatures. The temperature dependences for (n-C4H9NH3)2SnCl6 and (n-C4H9NH3)2SnBr6 decreased gradually with an increase in temperature. The correlation between the temperature dependence of the spectral absorption area and the motion of n-C n H2 n+1NH3 + ions is discussed.

  18. Advanced treatment of stabilized landfill leachate after biochemical process with hydrocalumite chloride (Ca/Al-Cl LDH).

    PubMed

    Chen, Hua; Sun, Ying; Ruan, Xiuxiu; Yu, Ying; Zhu, Minying; Zhang, Jia; Zhou, Jizhi; Xu, Yunfeng; Liu, Jianyong; Qian, Guangren

    2016-06-01

    This study investigated the effectiveness of Ca/Al-Cl LDH for the treatment of stabilized landfill leachate. Experiments were performed including different dosage of Ca/Al-Cl LDH and comparison with different reagents, such as CaCl2 and AlCl3. As a result, Ca/Al-Cl LDH efficiently removed organic matters in stabilized landfill leachate with the maximum removal (59.41% COD, 62.06% DOC and 70.56% UV254) at the dose of 30g/L. According to UV254 and EEM, it is remarkable that the formation of Ca/Al-LDH has a greater beneficial to organic removal than other reagents, especially for fulvic acid-like and humic acid-like compounds. Moreover, the removal of fulvic acid-like compounds was much better than humic acid-like compounds. The previous compounds had more carboxylic groups, thus had a better removal selectivity. PMID:26920626

  19. Study of formation of ZnCl/sub 2/-NaCl//gamma/-Al/sub 2/O/sub 3/ and ZnCl/sub 2/-KCl//gamma/-Al/sub 2/O/sub 3/ catalytic systems

    SciTech Connect

    Glazunova, E.D.; Kurlyandskaya, I.I.; Boevskaya, E.A.; Solomonik, I.G.; Danyushevskii, V.Ya.; Golosman, E.Z.; Yakerson, V.I.

    1988-04-01

    X-ray phase analysis and thermal analysis have been used in an investigation of the structure and phase composition of catalytic systems consisting of ZnCl/sub 2/-NaCl and ZnCl/sub 2/-KCl on /gamma/-Al/sub 2/O/sub 3/ support, and also the genesis of these systems under the influence of temperature. It has been shown that the systems contain excess agglomerated salt phases, two-dimensional structures that are cross-linked to the surface, and bulk structures formed by insertion of metal ions into the crystal lattice of the support. At high temperatures, the sodium and potassium chlorides on the surface exist for the most part in isolation from the zinc-containing salt phases. Changes in the composition and structure of the zinc-containing phases play the predominant role in forming the catalytic systems. No melting effects have been found in these catalytic systems.

  20. Ligand effects due to resonance character in LAuCCH(-) (L = F, Cl, Br, I, CCH) complexes: an NBO/NRT analysis.

    PubMed

    Zhang, Guiqiu; Wang, Hui; Yue, Huanjing; Li, Hong; Zhang, Shengnan; Fu, Lei

    2015-06-01

    The organogold complexes of LAuCCH(-) (L = F, Cl, Br, I, CCH) were investigated using natural bond orbital/natural resonance theory (NBO/NRT) methods. The NBO/NRT results strongly support the general resonance-type three-center-four-electron (3c/4e) picture of LAuCCH: L(-): Au-CCH ↔ L-Au :CCH(-), arising from hyperconjugation interactions. The sums of ionic and covalent contributions to both L-Au and Au-CCH bonds are all slightly larger than that due to the additional π-back bonding within the 3c/4e hyperbonded triad. This complementary relationship between L-Au and Au-CCH bond orders implies a competing relationship between the ancillary ligand and CCH around the gold atom. We discuss the ligand effects in the LAuCCH(-) series on the basis of this competing relationship. PMID:26026301

  1. Low-dimensional charge transport of the ferroic NH 2(C 2H 5) 4CoCl 2Br 2 nanocrystals

    NASA Astrophysics Data System (ADS)

    Tkaczyk, S. W.; Kityk, I. V.; Rudyk, V.; Kapustianyk, V.

    2010-06-01

    DC-conductivity of the nanocomposites consisting of ferroic nanocrystals NH 2(C 2H 5) 4CoCl 2Br 2 (TEA-CCB) incorporated into the polymer PMMA matrices is investigated. The investigations are performed for different number of nanocrystallite chromophores and thickness of the samples. The thickness of the nanocomposite films was varied within 0.44-0.48 μm. The measurements were done at different temperatures and different applied voltages. As a dominant mechanism thermoemission was considered, which is determined by temperature of the samples.. The gold electrodes were used as principle electrodes. The observed phenomena were explained within a framework of hopping between the trapping levels and possible contribution of self-trapped excitons.

  2. Nature of the band gap of halide perovskites ABX3 (A = CH3NH3, Cs; B = Sn, Pb; X = Cl, Br, I): First-principles calculations

    NASA Astrophysics Data System (ADS)

    Yuan, Ye; Xu, Run; Xu, Hai-Tao; Hong, Feng; Xu, Fei; Wang, Lin-Jun

    2015-11-01

    The electronic structures of cubic structure of ABX3(A=CH3NH3, Cs; B=Sn, Pb; X=Cl, Br, I) are analyzed by density functional theory using the Perdew-Burke-Ernzerhof exchange-correlation functional and using the Heyd-Scuseria-Ernzerhof hybrid functional. The valence band maximum (VBM) is found to be made up by an antibonding hybridization of B s and X p states, whereas bands made up by the π antibonding of B p and X p states dominates the conduction band minimum (CBM). The changes of VBM, CBM, and band gap with ion B and X are then systematically summarized. The natural band offsets of ABX3 are partly given. We also found for all the ABX3 perovskite materials in this study, the bandgap increases with an increasing lattice parameter. This phenomenon has good consistency with the experimental results. Project supported by the National Natural Science Foundation of China (Grant No. 11375112).

  3. SMILES zonal and diurnal variation climatology of stratospheric and mesospheric trace gasses: O3, HCl, HNO3, ClO, BrO, HOCl, HO2, and temperature

    NASA Astrophysics Data System (ADS)

    Kreyling, Daniel; Sagawa, Hideo; Wohltmann, Ingo; Lehmann, Ralph; Kasai, Yasuko

    2013-10-01

    We present a climatology of the diurnal variation of short-lived atmospheric compounds, such as ClO, BrO, HO2, and HOCl, as well as longer-lived species: O3, the hydrogen chloride isotopes H35Cl and H37Cl, and HNO3. Measurements were taken by the Superconducting Submillimeter-wave Limb-Emission Sounder (SMILES). This spectrally resolving radiometer, with very low observation noise and altitude range from the lower stratosphere to the lower thermosphere (20-100km), was measuring vertical profiles of absorption spectra along a non-sun-synchronous orbit, thus observing at all local times. We used the retrieved volume mixing ratio profiles to compile climatologies that are a function of pressure, a horizontal coordinate (latitude or equivalent latitude), and a temporal coordinate (solar zenith angle or local solar time). The main product presented are climatologies with a high resolution of the temporal coordinate (diurnal variation climatologies). In addition, we provide climatologies with a high resolution of the horizontal coordinate (zonal climatologies).The diurnal variation climatologies are based on data periods of 2 months and the zonal climatologies on monthly data periods. Consideration of the SMILES time-space sampling patterns with respect to the averaging coordinates is a key issue for climatology creation, especially in case of diurnal variation climatologies. Biases induced by inhomogeneous sampling are minimized by carefully choosing the size of averaging bins. The sampling biases of the diurnal variation climatology of ClO and BrO are investigated in a comparison of homogeneously sampled model data versus SMILES-sampled model data from the stratospheric Lagrangian chemistry and transport model Alfred Wegener Institute Lagrangian Chemisrty/Transport System. In most cases, the relative sampling error is in the range of 0-20%. The strongest impact of sampling biases is found where the species' temporal gradients are strongest (mostly at sunrise and sunset

  4. Synthesis and structure of the ternary and quaternary strontium nitride halides, Sr{sub 2}N(X, X') (X, X'=Cl, Br, I)

    SciTech Connect

    Bowman, Amy; Smith, Ronald I.; Gregory, Duncan H. . E-mail: Duncan.Gregory@Nottingham.ac.uk

    2006-01-15

    A number of new, layered nitride mixed halides have been synthesised in the quaternary phase systems Sr-N-Cl-Br and Sr-N-Br-I. The variation in structure with composition has been investigated by powder X-ray and powder neutron diffraction techniques and the structure of strontium nitride iodide, Sr{sub 2}NI, has been determined for the first time (rhombohedral space group R-3m, a=4.0103(1)A, c=23.1138(2)A, Z=3). A continuous solid solution exists between Sr{sub 2}NCl and Sr{sub 2}NBr with intermediate compounds adopting the same anti-{alpha}-NaFeO{sub 2} structure (rhombohedral space group R-3m) as the ternary end members. A similar smooth and linear relationship between structure and composition is seen from Sr{sub 2}NBr to Sr{sub 2}NI and hence cubic close packing of metal-nitrogen layers is adopted regardless of halide, X (X'). While nitride and halide anions occupy distinct crystallographic sites, there is no ordering of the halides in the quaternary materials irrespective of stoichiometry or temperature (between 3 and 673K)

  5. Ternary and quaternary layered nitride halides, Ca{sub 2}N(X,X') (X,X'=Cl, Br, I): Evolution of structure with composition

    SciTech Connect

    Bowman, Amy; Smith, Ronald I.; Gregory, Duncan H. . E-mail: Duncan.Gregory@Nottingham.ac.uk

    2005-06-15

    The quaternary systems Ca-N-Cl-Br and Ca-N-Br-I have been investigated resulting in the synthesis of a number of new layered nitride mixed halides. The evolution of structure with composition has been investigated by powder X-ray and powder neutron diffraction techniques. A continuous solid solution exists between Ca{sub 2}NCl and Ca{sub 2}NBr with intermediate compounds adopting the same anti- {alpha}-NaFeO{sub 2} structure (rhombohedral space group R3-bar m) as the ternary end members. A phase transition occurs in the Ca{sub 2}NBr{sub 1-y}I{sub y} system between y=0.7 and y=0.8 corresponding to a switch from cubic close packing to hexagonal close packing of metal-nitrogen layers and corresponding adoption of the anti-{beta}-RbScO{sub 2} (filled anti-CdI{sub 2}) structure (hexagonal space group P6{sub 3}/mmc). While nitride and halide anions occupy distinct crystallographic sites, there is no ordering of halides in quaternary materials irrespective of stoichiometry or structure type. All the nitride halides show temperature independent paramagnetic behaviour between 2 and 300K.

  6. High-pressure Raman studies on laurionite-type hydroxides Ba(OD)X (X = Cl, Br, I) and Sr(OD) 2

    NASA Astrophysics Data System (ADS)

    Jung, C.; Lutz, H. D.

    1996-07-01

    High-pressure Raman studies on Sr(OD) 2 and laurionite-type barium hydroxide halides Ba(OD)Cl, Ba(OD)Br, and Ba(OD)I were performed under hydrostatic compression up to 5 GPa using a diamond anvil cell. The pressure evolution of the OD stretching vibrations of the isostructural Ba(OD)X and Sr(OD) 2 is discussed with respect to the different behaviours of the respective hydrogen bond systems. The OD stretching modes slightly increase ( {dν OD}/{dp } = 4 cm-1 GPa -1) with increase in pressure if the respective ions are not involved in hydrogen bonds as in the case of Ba(OD)I and OD(2) of Sr(OD) 2 (lattice repulsion effect). The wavenumbers of OD stretching modes of ions involved in hydrogen bonds, as OD(1) of Sr(OD) 2, decrease due to a strengthening of the respective bonds with increasing pressure. A discontinuous decrease of νOD is observed for Ba(OD)Br indicating transition from a weakly hydrogen-bonded structure to a more strongly bonded one via reorientation of the OD - ions. In the case of Sr(OD) 2, it is confirmed that one of two crystallographically different hydroxide ions is involved in hydrogen bonding but the other is not.

  7. Relativistic four- and two-component calculations of parity violation effects in chiral tungsten molecules of the form NWXYZ (X, Y, Z = H, F, Cl, Br, or I).

    PubMed

    Figgen, Detlev; Saue, Trond; Schwerdtfeger, Peter

    2010-06-21

    Parity violation (PV) effects to the electronic ground state structure for a series of chiral tungsten molecules of the type NWXYZ (X, Y, Z = H, F, Cl, Br, or I) are compared using four- (Dirac) and two- (X2C) component relativistic Hartree-Fock and density functional theories. The results show the computationally more affordable two-component X2C approach yields accurate results for all molecules investigated. The PV energy differences between the two enantiomers range from as little as 0.4 Hz for NWClBrI to 140 Hz for NWHClI using a generalized gradient approximation including exact exchange (B3LYP). The W-N stretching mode in these molecules lies in the experimentally favorable CO(2) laser frequency range, and we therefore investigated PV effects in vibrational transitions using a single normal mode analysis. Here the PV frequency shift between the two enantiomers ranges from 1.6 mHz for NWFBrI to 710 mHz for NWHClI. Thus these types of molecules could be useful for the future detection of PV effects in chiral molecules. PMID:20572708

  8. Ab initio molecular dynamics study of polarization effects on ionic hydration in aqueous AlCl3 solution

    NASA Astrophysics Data System (ADS)

    Ikeda, Takashi; Hirata, Masaru; Kimura, Takaumi

    2003-12-01

    The solvation shell structure and dynamics of Al3+ and Cl- in an aqueous solution of 0.8 M AlCl3 are studied under ambient conditions by using an ab initio molecular dynamics method. The solvation structures obtained from our ab initio simulations are in good agreement with the experimental ones for both Al3+ and Cl-. A detailed analysis of intramolecular geometry of hydration waters and dipole moments of the ingredients shows that the polarization has substantial effects on the structures and dynamics of both the cation and anion hydration shells. Implications for metal hydrolysis of Al3+ will also be given.

  9. Insight into the substitution reactions of silylenoid H2SiLiF with GeH3X (X = F, Cl, Br): a theoretical study.

    PubMed

    Yan, Bingfei; Li, Wenzuo; Xiao, Cuiping; Li, Qingzhong; Cheng, Jianbo

    2015-04-01

    The unique substitution reactions of the three-membered-ring silylenoid H2SiLiF with GeH3X (X = F, Cl, Br) were investigated using ab initio and density functional theory calculations. All stationary points on the potential energy surfaces were optimized at the B3LYP/6-311 + G (d, p) level of theory and the QCISD method was then used to calculate the single-point energies. Theoretical calculations predicted that the substitution reactions of H2SiLiF with GeH3X proceed via two reaction paths (I and II), while forming the same product H2FSi-GeH3. In either pathway, there is one precursor complex (Q), one transition state (TS), and one intermediate (IM) connecting the reactants and products. The substitution reaction barriers of H2SiLiF with GeH3X for path I (48.49, 42.71, and 38.71 kJ mol(-1)) decreased with the increase for the same-family element X from up to down in the periodic table, whereas the substitution barriers for path II (6.51, 22.04, and 23.62 kJ mol(-1)) increased with the increase in atomic number of X (X = F, Cl, Br). Path II was more favorable than path I. All the substitution reactions of H2SiLiF with GeH3X were exothermic. The elucidation of the unique mechanism of these substitution reactions suggests a new reaction mode of silicon-germanium bond formation. PMID:25754138

  10. Theoretical and Synthetic Study on the Existence, Structures, and Bonding of the Halide-Bridged [B2X7](-) (X = F, Cl, Br, I) Anions.

    PubMed

    Bertocco, Philipp; Bolli, Christoph; Correia Bicho, Bruno A; Jenne, Carsten; Erken, Berrin; Laitinen, Risto S; Seeger, Helene A; Takaluoma, Teemu T

    2016-04-01

    While hydrogen bridging is very common in boron chemistry, halogen bridging is rather rare. The simplest halogen-bridged boron compounds are the [B2X7](-) anions (X = F, Cl, Br, I), of which only [B2F7](-) has been reported to exist experimentally. In this paper a detailed theoretical and synthetic study on the [B2X7](-) anions is presented. The structures of [B2X7](-) anions have been calculated at the MP2/def2-TZVPP level of theory, and their local minima have been shown to be of C2 symmetry in all cases. The bonding situation varies significantly between the different anions. While in [B2F7](-) the bonding is mainly governed by electrostatics, the charge is almost equally distributed over all atoms in [B2I7](-) and additional weak iodine···iodine interactions are observed. This was shown by an atoms in molecules (AIM) analysis. The thermodynamic stability of the [B2X7](-) anions was estimated in all phases (gas, solution, and solid state) based on quantum-chemical calculations and estimations of the lattice enthalpies using a volume-based approach. In the gas phase the formation of [B2X7](-) anions from [BX4](-) and BX3 is favored in accord with the high Lewis acidity of the BX3 molecules. In solution and in the solid state only [B2F7](-) is stable against dissociation. The other three anions are borderline cases, which might be detectable under favorable conditions. However, experimental attempts to identify [B2X7](-) (X = Cl, Br, I) anions in solution by (11)B NMR spectroscopy and to prepare stable [PNP][B2X7] salts failed. PMID:26977788

  11. Five-coordinate complexes [FeX(depe)(2)]BPh(4), X = Cl, Br: electronic structure and spin-forbidden reaction with N(2).

    PubMed

    Franke, Oliver; Wiesler, Beatrix E; Lehnert, Nicolai; Näther, Christian; Ksenofontov, Vadim; Neuhausen, Jörg; Tuczek, Felix

    2002-07-01

    The bonding of N(2) to the five-coordinate complexes [FeX(depe)(2)](+), X = Cl (1a) and Br (1b), has been investigated with the help of X-ray crystallography, spectroscopy, and quantum-chemical calculations. Complexes 1a and 1b are found to have an XP(4) coordination that is intermediate between square-pyramidal and trigonal-bipyramidal. Mössbauer and optical absorption spectroscopy coupled with angular overlap model (AOM) calculations reveal that 1a and 1b have (3)B(1) ground states deriving from a (xz)(1)(z(2))(1) configuration. The zero-field splitting for this state is found to be 30-35 cm(-1). In contrast, the analogous dinitrogen complexes [FeX(N(2))(depe)(2)](+), X = Cl (2a) and Br (2b), characterized earlier are low-spin (S = 0; Wiesler, B. E.; Lehnert, N.; Tuczek, F.; Neuhausen, J.; Tremel, W. Angew. Chem, Int. Ed. 1998, 37, 815-817). N(2) bonding and release in these systems are thus spin-forbidden. It is shown by density functional theory (DFT) calculations of the chloro complex that the crossing from the singlet state (ground state of 2a) to the triplet state (ground state of 1a) along the Fe-N coordinate occurs at r(C) = 2.4 A. Importantly, this intersystem crossing lowers the enthalpy calculated for N(2) release by 10-18 kcal/mol. The free reaction enthalpy Delta G degrees for this process is calculated to be 4.7 kcal/mol, which explains the thermal instability of N(2) complex 2a with respect to the loss of N(2). The differences in reactivity of analogous trans hydrido systems are discussed. PMID:12079469

  12. Ce53Fe12S90X3 (X = Cl, Br, I): the first rare-earth transition-metal sulfide halides.

    PubMed

    Mills, Allison M; Ruck, Michael

    2006-06-26

    The compounds Ce53Fe12S90X3 (X = Cl, Br, I), which represent the first examples of rare-earth transition-metal sulfide halides, were prepared using the reactive-flux method, through reaction of Ce2S3, FeS, or Fe and S in a CeX3 flux at 1320 K. Their structures were determined by single-crystal X-ray diffraction. The compounds are isostructural, crystallizing in the trigonal space group Rm with Z = 1 [Ce53Fe12S90Cl3, a = 13.9094(9) A, c = 21.604(2) A, V = 3619.7(4) A3; Ce(53)Fe(12)S(90)Br(3), a = 13.916(1) A, c = 21.824(2) A, V = 3660.0(5) A3; Ce53Fe12S90I3, a = 13.863(3) A, c = 21.944(6) A, V = 3652(2) A3]. The structure adopted is a stuffed variant of the La52Fe12S90 structure type. Fe2S9 dimers of face-sharing octahedra are linked by face- and vertex-sharing capped CeS6 trigonal prisms, forming a three-dimensional framework containing cuboctahedral cavities of two sizes. The smaller cavities accommodate alternative sites for disordered cerium atoms. The larger cavities, which remain empty in the parent structure, are filled by halogen atoms in Ce53Fe12S90X3. Alternatively, the structure can be described as a 9-fold superstructure of the Mn5Si3 structure type (P6(3)/mcm), with a = a' and c = 3c'. Temperature-dependent magnetic susceptibility measurements suggest that Ce53Fe12S90I3 may order antiferromagnetically at low temperatures. PMID:16780341

  13. Antiferromagnetism in a Family of S = 1 Square Lattice Coordination Polymers NiX2(pyz)2 (X = Cl, Br, I, NCS; pyz = Pyrazine).

    PubMed

    Liu, Junjie; Goddard, Paul A; Singleton, John; Brambleby, Jamie; Foronda, Francesca; Möller, Johannes S; Kohama, Yoshimitsu; Ghannadzadeh, Saman; Ardavan, Arzhang; Blundell, Stephen J; Lancaster, Tom; Xiao, Fan; Williams, Robert C; Pratt, Francis L; Baker, Peter J; Wierschem, Keola; Lapidus, Saul H; Stone, Kevin H; Stephens, Peter W; Bendix, Jesper; Woods, Toby J; Carreiro, Kimberly E; Tran, Hope E; Villa, Cecelia J; Manson, Jamie L

    2016-04-01

    The crystal structures of NiX2(pyz)2 (X = Cl (1), Br (2), I (3), and NCS (4)) were determined by synchrotron X-ray powder diffraction. All four compounds consist of two-dimensional (2D) square arrays self-assembled from octahedral NiN4X2 units that are bridged by pyz ligands. The 2D layered motifs displayed by 1-4 are relevant to bifluoride-bridged [Ni(HF2)(pyz)2]EF6 (E = P, Sb), which also possess the same 2D layers. In contrast, terminal X ligands occupy axial positions in 1-4 and cause a staggered packing of adjacent layers. Long-range antiferromagnetic (AFM) order occurs below 1.5 (Cl), 1.9 (Br and NCS), and 2.5 K (I) as determined by heat capacity and muon-spin relaxation. The single-ion anisotropy and g factor of 2, 3, and 4 were measured by electron-spin resonance with no evidence for zero-field splitting (ZFS) being observed. The magnetism of 1-4 spans the spectrum from quasi-two-dimensional (2D) to three-dimensional (3D) antiferromagnetism. Nearly identical results and thermodynamic features were obtained for 2 and 4 as shown by pulsed-field magnetization, magnetic susceptibility, as well as their Néel temperatures. Magnetization curves for 2 and 4 calculated by quantum Monte Carlo simulation also show excellent agreement with the pulsed-field data. Compound 3 is characterized as a 3D AFM with the interlayer interaction (J⊥) being slightly stronger than the intralayer interaction along Ni-pyz-Ni segments (J(pyz)) within the two-dimensional [Ni(pyz)2](2+) square planes. Regardless of X, J(pyz) is similar for the four compounds and is roughly 1 K. PMID:27002487

  14. Formation of the Si-B bond: insertion reactions of silylenes into B-X(X = F, Cl, Br, O, and N) bonds.

    PubMed

    Geng, Bing; Xu, Chongjuan; Chen, Zhonghe

    2016-06-01

    The insertion reactions of the silylene H2Si with H2BXHn-1 (X = F, Cl, Br, O, N; n = 1, 1, 1, 2, 3) have been studied by DFT and MP2 methods. The calculations show that the insertions occur in a concerted manner, forming H2Si(BH2)(XHn-1). The essences of H2Si insertions with H2BXHn-1 are the transfers of the σ electrons on the Si atom to the positive BH2 group and the electrons of X into the empty p orbital on the Si atom in H2Si. The order of reactivity in vacuum shows the barrier heights increase for the same-family element X from up to down and the same-row element X from right to left in the periodic table. The energies relating to the B-X bond in H2BXHn-1, and the bond energies of Si-X and Si-B in H2Si(BH2)(XHn-1) may determine the preference of insertions of H2Si into B-X bonds for the same-column element X or for the same-row element X. The insertion reactions in vacuum are similar to those in solvents, acetone, ether, and THF. The barriers in vacuum are lower than those in solvents and the larger polarities of solvents make the insertions more difficult to take place. Both in vacuum and in solvents, the silylene insertions are thermodynamically exothermic. Graphical Abstract The insertion process of H2Si and H2BXHn-1(X = F, Cl, Br, O, and N; n = 1, 1 , 1, 2, 3). PMID:27184004

  15. Absorption characteristics of anions (I-, Br-, and Te2-) into zeolite in molten LiCl-KCl eutectic salt

    NASA Astrophysics Data System (ADS)

    Uozumi, Koichi; Sugihara, Kei; Kinoshita, Kensuke; Koyama, Tadafumi; Tsukada, Takeshi; Terai, Takayuki; Suzuki, Akihiro

    2014-04-01

    The behaviors of anion fission product (FP) elements to be absorbed into zeolite in molten LiCl-KCl eutectic salt were studied using iodine, bromine, and tellurium. First, the type-A zeolite was selected as the most suitable type of zeolite among type-A, type-X, and type-Y zeolites through experiments in which zeolites were heated together with LiCl-KCl-KI salt. As the next step, experiments in which the type-A zeolite was immersed in molten LiCl-KCl salt containing various concentrations of iodine, bromine, or tellurium were performed. The degree of absorption of the anion FP elements was evaluated using the separation factor (SF) value versus chlorine. Although the SF values for iodine and tellurium were higher than 1.0, which meant that these elements were absorbed into the type-A zeolite more intensively than chlorine in the salt, the corresponding value for bromine was approximately 1.0. The effects of coexisting cation FPs were also examined using cesium, strontium, and neodymium, and it was revealed that the SF values for iodine were less than those in the case without cation addition. On the other hand, the SF values for tellurium were not affected by the coexistence of cesium and strontium. Finally, the feasibility of the present pyroprocess flowsheet was evaluated by calculating the inventory of each anion FP in an electrorefiner based on the obtained SF values instead of temporary values for the anion FPs absorption, which were set due to lack of experimental data.

  16. Experimental and theoretical studies of LiI/AlCl{sub 3} molten salt system.

    SciTech Connect

    Lee, Y. C.; Kolafa, J. P.; Curtiss, L. A.; Ratner, M. A.; Schriver, D. F.; Northwestern Univ.; Inst. of Chemical Process Fundamentals

    2001-01-01

    Molten LiI/AlCl{sub 3} with different molar ratios of LiI to AlCl{sub 3} were prepared and characterized by Raman spectroscopy, thermal analysis, and impedance measurements. The LiI/AlCl{sub 3} adducts melt at 70-80 {sup o}C and the Raman spectrum indicates that a variety of haloaluminates exist in the system. The 1:1 adduct has the highest ionic conductivity, 2 x 10{sup -6} S/cm at 25 {sup o}C, and the conductivity increases dramatically as the temperature is increased. Molecular dynamics (MD) simulations suggest that several haloaluminates are present in the adducts. Ab initio calculations were carried out on the species that were predicted by MD simulations and these results were compared with Raman spectra, and good agreement was obtained. Several-ns-long MD simulations allowed us to study the conductivity and relaxation processes in the 1:1 and 1:2 melts at higher temperatures.

  17. Effect of AlCl3 concentration on nanoparticle removal by coagulation.

    PubMed

    Zhang, Lizhu; Mao, Jingchun; Zhao, Qing; He, Shaobo; Ma, Jun

    2015-12-01

    In recent years, engineered nanoparticles, as a new group of contaminants emerging in natural water, have been given more attention. In order to understand the behavior of nanoparticles in the conventional water treatment process, three kinds of nanoparticle suspensions, namely multi-walled carbon nanotube-humic acid (MWCNT-HA), multi-walled carbon nanotube-N,N-dimethylformamide (MWCNT-DMF) and nanoTiO2-humic acid (TiO2-HA) were employed to investigate their coagulation removal efficiencies with varying aluminum chloride (AlCl3) concentrations. Results showed that nanoparticle removal rate curves had a reverse "U" shape with increasing concentration of aluminum ion (Al(3+)). More than 90% of nanoparticles could be effectively removed by an appropriate Al(3+) concentration. At higher Al(3+) concentration, nanoparticles would be restabilized. The hydrodynamic particle size of nanoparticles was found to be the crucial factor influencing the effective concentration range (ECR) of Al(3+) for nanoparticle removal. The ECR of Al(3+) followed the order MWCNT-DMF>MWCNT-HA>TiO2-HA, which is the reverse of the nanoparticle size trend. At a given concentration, smaller nanoparticles carry more surface charges, and thus consume more coagulants for neutralization. Therefore, over-saturation occurred at relatively higher Al(3+) concentration and a wider ECR was obtained. The ECR became broader with increasing pH because of the smaller hydrodynamic particle size of nanoparticles at higher pH values. A high ionic strength of NaCl can also widen the ECR due to its strong potential to compress the electric double layer. It was concluded that it is important to adjust the dose of Al(3+) in the ECR for nanoparticle removal in water treatment. PMID:26702973

  18. Electrodeposition of Mg-Li-Al-La Alloys on Inert Cathode in Molten LiCl-KCl Eutectic Salt

    NASA Astrophysics Data System (ADS)

    Han, Wei; Chen, Qiong; Sun, Yi; Jiang, Tao; Zhang, Milin

    2011-12-01

    Electrochemical preparation of Mg-Li-Al-La alloys on inert electrodes was investigated in LiCl-KCl melt at 853 K (580 °C). Cyclic voltammograms (CVs) and square wave voltammograms (SWVs) show that the existence of AlCl3 or AlF3 could promote La deposition on an active Al substrate, which is predeposited on inert electrodes. All electrochemical tests show that the reduction of La3+ is a one-step reduction process with three electrons exchanged. The reduction of La(III)→La(0) occurred at -2.04 V, and the underpotential deposition (UPD) of La was detected at -1.55 V ( vs Ag/AgCl). The same phenomena concerning La UPD were observed on two inert cathodes, W and Mo. In addition, Mg-Li-Al-La alloys were obtained by galvanostatic electrolysis on the W cathode from La2O3 in LiCl-KCl-MgCl2-KF melts with aluminum as the anode. X-ray diffraction (XRD) measurements indicated that various phases like the Al2La, Al12Mg17, and βLi phase (LiMg/Li3Mg7) existed in the Mg-Li-Al-La alloys. The distribution of Mg, Al, and La in Mg-Li-Al-La alloys from the analysis of a scan electron micrograph (SEM) and energy dispersive spectrometry (EDS) indicated that the elements Mg, Al, and La distributed homogeneously in the alloys.

  19. Relativistic effects on nuclear magnetic shieldings of CHnX4-n and CHXYZ (X, Y, Z = H, F, Cl, Br, I)

    NASA Astrophysics Data System (ADS)

    Melo, Juan I.; Maldonado, Alejandro F.; Aucar, Gustavo A.

    2012-12-01

    Nuclear magnetic shieldings of both carbon and hydrogen atoms of haluro methyl molecules are highly influenced by the substitution of one or more hydrogen by halogen heavy atoms. We applied the linear response elimination of small components, LRESC, formalism to calculate such shieldings and learn whether including only few terms is enough for getting quantitative reproduction of the total shieldings or not. First, we discuss the contribution of all leading relativistic corrections to σ(C), in CHX2I molecular models with X = H, F, and Cl, and show that spin-orbit (SO) effects are the main ones. After adding the SO effects to the non-relativistic (NR) results, we obtain ˜ 97% (93%) of the total LRESC values for σ(C) (σ(H)). The magnitude of SO terms increases when the halogen atom becomes heavier. In this case, such contributions to σ(C) can be extrapolated as a function of Z, the halogen atomic number. Furthermore, when paramagnetic spin-orbit (PSO) contributions are also considered, we obtain results that are within 1% of the total LRESC value. Then we study in detail the main electronic mechanisms involved to contribute C and H shieldings on CHnX4 - n (n = 1, 3), and CHXYZ (X, Y, Z = F, Cl, Br, I) model compounds. The pattern of σ(C) for all series of compounds follows a normal halogen dependence (NHD), though with different rate of increase. A special family of compounds is that of CHF2X for which σnr(C) follows an inverse halogen dependence though the total shielding have a NHD due to the SO contributions. For the series CH3X (X = F, Cl, Br and I), we found that σSO ˜ Z_X^{2.53}. Another important finding of this work is the logarithmic dependence of σSO(C) with the substituent atomic number: ln σSO(C) = A_X + a_X Z_Y for both family of compounds CH2XY and CHX2Y. We also performed four-component calculations using the spin-free Hamiltonian to obtain SO contributions within a four-component framework.

  20. Optical absorption and luminescence spectroscopy of U{sup 3+} in K{sub 2}La{ital X}{sub 5} ({ital X}=Cl,Br,I)

    SciTech Connect

    Andres, H.P.; Kraemer, K.; Guedel, H.

    1996-08-01

    The title compounds were synthesized and high-resolution absorption and luminescence spectra measured in the near-infrared, VIS, and near UV regions. The visible absorption spectra are dominated by very intense 5{ital f}{r_arrow}6{ital d} bands overlapping with {ital f}-{ital f} transitions. The onset of the first {ital f}-{ital d} absorption is shifted from 46000 cm{sup {minus}1} in K{sub 2}LaCl{sub 5}:Nd{sup 3+} to 15000 cm{sup {minus}1} in K{sub 2}LaCl{sub 5}:U{sup 3+}. Crystal-field splittings in corresponding {sup 2{ital S}+1}{ital L}{sub {ital J}} multiplets are greater by typically a factor of 2 in the U{sup 3+} doped crystal, thus reflecting the larger extension and stronger interaction of the 5{ital f} electrons with the ligands. {ital f}-{ital f} transitions are typically two orders of magnitude more intense in K{sub 2}LaCl{sub 5}:U{sup 3+} than in K{sub 2}LaCl{sub 5}:Nd{sup 3+}. Along the halide series K{sub 2}La{ital X}{sub 5}:U{sup 3+} ({ital X}=Cl,Br,I) the differences in the position of corresponding {ital f}-{ital d} and {ital f}-{ital f} transitions, crystal-field splittings, vibronic intensities, and excited-state lifetimes can be explained with the increasing covalency, the decreasing phonon energies, the increasing electron-phonon coupling, and the increasing U-{ital X} distances. The {ital f}-{ital d} excited states provide a nonradiative bypass of some {ital f}-{ital f} excited states in the case of all these halide lattices. The excited-state dynamics are determined by a delicate interplay of radiative and nonradiative relaxation processes, they are strongly dependent on the nature of {ital X}. Multiphonon relaxation processes are least competitive in the iodide due to the very low value of 106 cm{sup {minus}1} for the highest-energy phonons. A cross-relaxation mechanism determines the dynamics of the iodide at room temperature. {copyright} {ital 1996 The American Physical Society.}

  1. Increased photovoltaic performance by the optimized TiClI4 and AlCl3 surface treatment in dye-sensitized solar cells.

    PubMed

    Oh, Ju Hee; Kim, Dae-Hwan; Lee, Sang-Ju; Kwak, Giseop; Han, Yoon Soo

    2014-12-01

    The surface of TiO2 photoelectrodes coated on F-doped SnO2 (FTO) was modified by soaking it in a TiCl4:AlCl3 mixed aqueous solution with various molar ratios, and then calcining to produce the TiCl4:AlCl3-treated TiO2 photoelectrode (Ti:Al-TiO2/FTO). The highest power conversion efficiency (PCE) was obtained from dye-sensitized solar cells (DSSC) with Ti:Al(5:5)-TiO2/FTO, which was prepared from the mixed solution with the molar ratio of 5:5 (TiCi4:AlCl3). PCE of DSSC with Ti:Al (5:5)-TiO2/FTO was improved by ca. 19.6%, compared to that of the reference device with Ti:Al (10:0)-TiO2/FTO (i.e., TiO2-coated TiO2/FTO) due to an enhancement in both short-circuit photocurrent (J(sc)) and open-circuit voltage (V(oc)). A series of measurements such as UV-visible absorption, electrochemical impedance, open circuit voltage decay and dark current revealed that the increase in J(sc) was attributed to the improvement of electron collection efficiency by a prolonged electron lifetime, and the suppression of the charge recombination between injected electrons and I3(-) ions was found to increase the V(oc) value of the device with Ti:Al(5:5)-TiO2/FTO. PMID:25971045

  2. Plasma-surface interactions during Si etching in Cl- and Br-based plasmas: An empirical and atomistic study

    NASA Astrophysics Data System (ADS)

    Tsuda, Hirotaka; Nagaoka, Tatsuya; Miyata, Hiroki; Takao, Yoshinori; Eriguchi, Koji; Ono, Kouichi

    2009-10-01

    Nanometer-scale control of Si etching in Cl2- and HBr-containing plasmas is indispensable in the fabrication of gate electrodes and shallow trench isolation. There are profile anomalies of sidewalls such as tapering, bowing, footing (or corner rounding), and notching, which largely affect the critical dimension. There are also anomalies of bottom surfaces such as microtrenching and roughness (or residues), which affect the bottom uniformity, and lead to recess and damage in gate fabrication. Atomic-scale cellular model (ASCeM) based on the Monte Carlo method has been developed to simulate plasma-surface interactions and the profile evolution during etching, including passivation layer formation, and also ion reflection and penetration on feature surfaces. We have also studied atomistic plasma-surface interactions by classical molecular dynamics (MD) simulation, where an improved Stillinger-Weber interatomic potential was newly developed. The numerical results were compared with etching experiments and also with surface diagnostics including in-situ Fourier-transform-infrared reflection absorption spectroscopy (FTIR-RAS), to reveal the origin of profile anomalies on feature surfaces during etching, and then to achieve the precise control of etched profiles.

  3. Hydrogen generation from Al-NiCl2/NaBH4 mixture affected by lanthanum metal.

    PubMed

    Sun, Wen Qiang; Fan, Mei-Qiang; Fei, Yong; Pan, Hua; Wang, Liang Liang; Yao, Jun

    2012-01-01

    The effect of La on Al/NaBH(4) hydrolysis was elaborated in the present paper. Hydrogen generation amount increases but hydrogen generation rate decreases with La content increasing. There is an optimized composition that Al-15 wt% La-5 wt% NiCl(2)/NaBH(4) mixture (Al-15 wt% La-5 wt% NiCl(2)/NaBH(4) weight ratio, 1 : 3) has 126 mL g(-1 )min(-1) maximum hydrogen generation rate and 1764 mL g(-1) hydrogen generation amount within 60 min. The efficiency is 88%. Combined with NiCl(2), La has great effect on NaBH(4) hydrolysis but has little effect on Al hydrolysis. Increasing La content is helpful to decrease the particle size of Al-La-NiCl(2) in the milling process, which induces that the hydrolysis byproduct Ni(2)B is highly distributed into Al(OH)(3) and the catalytic reactivity of Ni(2)B/Al(OH)(3) is increased therefore. But hydrolysis byproduct La(OH)(3) deposits on Al surface and leads to some side effect. The Al-La-NiCl(2)/NaBH(4) mixture has good stability in low temperature and its hydrolytic performance can be improved with increasing global temperature. Therefore, the mixture has good safety and can be applied as on board hydrogen generation material. PMID:22619596

  4. Hydrogen Generation from Al-NiCl2/NaBH4 Mixture Affected by Lanthanum Metal

    PubMed Central

    Qiang Sun, Wen; Fan, Mei-Qiang; Fei, Yong; Pan, Hua; Wang, Liang Liang; Yao, Jun

    2012-01-01

    The effect of La on Al/NaBH4 hydrolysis was elaborated in the present paper. Hydrogen generation amount increases but hydrogen generation rate decreases with La content increasing. There is an optimized composition that Al-15 wt% La-5 wt% NiCl2/NaBH4 mixture (Al-15 wt% La-5 wt% NiCl2/NaBH4 weight ratio, 1 : 3) has 126 mL g−1 min−1 maximum hydrogen generation rate and 1764 mL g−1 hydrogen generation amount within 60 min. The efficiency is 88%. Combined with NiCl2, La has great effect on NaBH4 hydrolysis but has little effect on Al hydrolysis. Increasing La content is helpful to decrease the particle size of Al-La-NiCl2 in the milling process, which induces that the hydrolysis byproduct Ni2B is highly distributed into Al(OH)3 and the catalytic reactivity of Ni2B/Al(OH)3 is increased therefore. But hydrolysis byproduct La(OH)3 deposits on Al surface and leads to some side effect. The Al-La-NiCl2/NaBH4 mixture has good stability in low temperature and its hydrolytic performance can be improved with increasing global temperature. Therefore, the mixture has good safety and can be applied as on board hydrogen generation material. PMID:22619596

  5. Metal-Metal Bonding in Trinuclear, Mixed-Valence [Ti3X12](4-) (X = F, Cl, Br, I) Face-Shared Complexes.

    PubMed

    Hewage, Jinasena W; Cavigliasso, Germán; Stranger, Robert

    2015-11-16

    Metal-metal bonding in structurally characterized In4Ti3Br12, comprising linear, mixed-valence d(1)d(2)d(1) face-shared [Ti3Br12](4-) units with a Ti-Ti separation of 3.087 Å and strong antiferromagnetic coupling (Θ = -1216 K), has been investigated using density functional theory. The antiferromagnetic configuration, in which the single d electron on each terminal Ti(III) (d(1)) metal center is aligned antiparallel to the two electrons occupying the central Ti(II) (d(2)) metal site, is shown to best agree with the reported structural and magnetic data and is consistent with an S = 0 ground state in which two of the four metal-based electrons are involved in a two-electron, three-center σ bond between the Ti atoms (formal Ti-Ti bond order of ∼0.5). However, the unpaired spin densities on the Ti sites indicate that while the metal-metal σ interaction is strong, the electrons are not fully paired off and consequently dominate the ground state antiferromagnetic coupling. The same overall partially delocalized bonding regime is predicted for the other three halide [Ti3X12](4-) (X = F, Cl, I) systems with the metal-metal bonding becoming weaker as the halide group is descended. The possibility of bond-stretch isomerism was also examined where one isomer has a symmetric structure with identical Ti-Ti bonds while the other is unsymmetric with one short and one long Ti-Ti bond. Although calculations indicate that the latter form is more stable, the barrier to interconversion between equivalent unsymmetric forms, where the short Ti-Ti bond is on one side of the trinuclear unit or the other, is relatively small such that at room temperature only the averaged (symmetric) structure is likely to be observed. PMID:26523831

  6. A comparison of experimental and DFT calculations of ¹⁹⁵Pt NMR shielding trends for [PtX(n)Y(6-n)](2-) (X, Y = Cl, Br, F and I) anions.

    PubMed

    Burger, Marga R; Kramer, J; Chermette, H; Koch, Klaus R

    2010-12-01

    A comparison between experimental and calculated gas-phase as well as the conductor-like screening model DFT (195)Pt chemical shifts of a series of octahedral [PtX(6-n)Y(n)](2-) complexes for X = Cl, Br, F, I was carried out to assess the accuracy of computed NMR shielding and to gain insight into the dominant σ(dia), σ(para) and σ(SO) shielding contributions. The discrepancies between the experimental and the DFT-calculated (195)Pt chemical shifts vary for these complexes as a function of the coordinated halide ions, the largest being obtained for the fluorido-chlorido and fluorido-bromido complexes, while negligible discrepancies are found for the [PtCl(6-n)Br(n)](2-) series; the discrepancies are somewhat larger where a significant deviation from the ideal octahedral symmetry such as for the geometric cis/trans or fac/mer isomers of [PtF(6-n)Cl(n)](2-) and [PtF(6-n)Br(n)](2-) may be expected. The discrepancies generally increase in the order [PtCl(6-n)Br(n)](2-) < [PtBr(6-n)I(n)](2-) < [PtCl(6-n)I(n)](2-) < [PtF(6-n)Br(n)](2-) ≈ [PtF(6-n)Cl(n)](2-), and show a striking correlation with the increase in electronegativity difference Δχ between the two halide ligands (X(-) and Y(-)) bound to Pt(IV) for these anions: 0.09 < 0.52 < 0.63 < 1.36 ≈ 1.27, respectively. The computed (195)Pt sensitivity to Pt-X bond displacement, ∂(δ(195)Pt)/∂(ΔPt-X), of these complexes is very large and depends on the halide ion, decreasing from 24 800, 18 300, 15 700 to 12 000 ppm/Å for [PtF(6)](2-), [PtCl(6)](2-), [PtBr(6)](2-) and [PtI(6)](2-), respectively. PMID:21104761

  7. Kinetics study of the reactions of NO with FO, ClO, BrO, and IO at 298 K

    NASA Technical Reports Server (NTRS)

    Ray, G. W.; Watson, R. T.

    1981-01-01

    The kinetics of the four considered reactions were studied by means of the discharge flow/mass spectrometric technique. The discharge flow/mass spectrometer has been described by Sander et al. (1981). The flow velocity in the investigation was varied in the range from 750 to 2100 cm/s, while total pressures in the range from 1.0 torr to 2.1 torr were employed. The results of the study are compared to the values of current literature. With minor exceptions, the new results are in excellent agreement with the data of the previous studies. It is pointed out that the reported results will have a minimal impact on the predictions of atmospheric photochemical model calculations as they have confirmed prior expectations.

  8. Multicomponent diffusion of a suite of tracers (HTO, Cl, Br, I, Na, Sr, Cs) in a single sample of Opalinus Clay

    NASA Astrophysics Data System (ADS)

    Appelo, C. A. J.; Van Loon, L. R.; Wersin, P.

    2010-02-01

    Diffusion experiments with HTO, 36Cl -, Br -, I -, 22Na +, 85Sr 2+ and 134Cs + at trace concentrations in a single sample of Opalinus Clay are modeled with PHREEQC's multicomponent diffusion module. The model is used first in a classical approach to derive accessible porosities, geometrical factors (the ratio of pore tortuosity and constrictivity) and sorption behavior of the individual tracers assuming that the clay is homogeneous. The accessible porosity for neutral species and cations is obtained from HTO, the anion exclusion volume from 36Cl - and Br -, and the cation exchange capacity from 22Na +. The homogeneous model works well for tritium, the anions and 22Na +. However, the 85Sr 2+ and 134Cs + experiments show an early arrival of the tracer and a front-form that suggest a dual porosity structure. A model with 10% dead-end pores, containing 19% of the total exchange capacity, can satisfactorily calculate all the experimental data. The Cs + diffusion model builds on a 3-site exchange model, constructed from batch sorption data. The excellent agreement of modeled and measured data contradicts earlier reports that the exchange capacity for Cs + would be smaller in diffusion than in batch experiments. The geometrical factors for the anions are 1.5 times larger than for HTO, and for the cations 2-4 times smaller than for HTO. The different behavior is explained by a tripartite division of the porespace in free porewater, diffuse double layer (DDL) water, and interlayer water in montmorillonite. Differences between estimated and observed geometrical factors for cations are attributed to increased ion-pairing of the divalent cations in DDL water as a result of the low relative dielectric permittivity. Interlayer and/or surface diffusion contributes significantly to the diffusive flux of Cs + but is negligible for the other solutes. The geometrical factors for anions are higher than estimated, because pore constrictions with overlapping double layers force the

  9. Synthesis and single-crystal structure determination of the zinc nitride halides Zn{sub 2}NX (X=Cl, Br, I)

    SciTech Connect

    Liu, Xiaohui; Wessel, Claudia; Pan, Fangfang; Dronskowski, Richard

    2013-07-15

    A series of zinc nitride halides, Zn{sub 2}NX (X=Cl, Br, I), has been synthesized from solid–liquid reactions of zinc nitride with the respective zinc halides under vacuum, and their crystal structures were determined using single-crystal and powder X-ray diffraction. While Zn{sub 2}NCl and Zn{sub 2}NBr crystallize in the acentric orthorhombic space group Pna2{sub 1}, Zn{sub 2}NI adopts the centrosymmetric space group Pnma; Zn{sub 2}NCl and Zn{sub 2}NBr can be considered to belong to the anti-β-NaFeO{sub 2} type, and Zn{sub 2}NI is closely related. Each N{sup 3−} is tetrahedrally coordinated by zinc atoms, and the X{sup −} anions are located in the vacancies of the framework formed by corner-sharing [NZn{sub 4}] tetrahedra. According to TGA/DTA analyses, the Zn{sub 2}NX compounds exhibit good thermal stability. The electronic structure has been analyzed by employing density-functional theory and the HSE06 hybrid functional. - Graphical abstract: Zn{sub 2}NCl, Zn{sub 2}NBr, and Zn{sub 2}NI have been synthesized, and their crystal structures (Cl and Br phases: Pna2{sub 1}; I phase: Pnma) have been determined from XRD; the direct band gap of Zn{sub 2}NCl is theoretically (HSE06 hybrid functional) predicted as 3.7 eV. - Highlights: • Zn{sub 2}NCl, Zn{sub 2}NBr, and Zn{sub 2}NI have been synthesized from solid–liquid reactions. • The crystal structures of Zn{sub 2}NCl, Zn{sub 2}NBr, and Zn{sub 2}NI have been determined from single-crystal X-ray diffraction. • Zn{sub 2}NCl and Zn{sub 2}NBr crystallize in the acentric space group Pna2{sub 1} whereas Zn{sub 2}NI adopts the centrosymmetric space group Pnma. • Zn{sub 2}NCl and Zn{sub 2}NBr are stable up to 750 °C whereas Zn{sub 2}NI decays at 600 °C already. • The direct band gap of Zn{sub 2}NCl is theoretically predicted as 3.7 eV using the HSE06 hybrid functional.

  10. Calculation of the electron affinities of the second row atoms: Al--Cl

    SciTech Connect

    Woon, D.E.; Dunning, T.H. Jr. )

    1993-09-01

    The electron affinities (EAs) of aluminum through chlorine have been calculated with multireference single and double excitation configuration interaction calculations (MRSD-CI) with the augmented correlation consistent basis sets of Woon and Dunning [J. Chem. Phys. [bold 98], 1358 (1993)]. The orbital space for the complete active space (CAS) wave functions is systematically expanded beyond the Hartree--Fock wave function by inclusion of additional [ital s], [ital p], and [ital d] orbitals. This approach provides a well balanced treatment of the neutral and ionic charge states and led to accurate EAs for hydrogen and the first row atoms [R. A. Kendall, T. H. Dunning, Jr., and R. J. Harrison, J. Chem. Phys. [bold 96], 6796 (1992)]. The best MRSD-CI values for the EAs (in eV) of the second row atoms are Al, 0.440; Si, 1.413; P, 0.689; S, 2.023; and Cl, 3.606. Inclusion of spin--orbit effects in the calculated EAs yields (experimental values in parentheses): Al, 0.437 (0.441); Si, 1.395 (1.385); P, 0.700 (0.746); S, 2.019 (2.077); and Cl, 3.570 (3.613). The amenability of the correlation consistent basis sets for extrapolating to the complete basis set limit has also been exploited in this work. The neutral and anion energies are extrapolated separately in order to account for the different convergence rates in the energies of the two species. The extrapolated values of the EAs, including an empirical spin--orbit correction, are Al, 0.438; Si, 1.395; P, 0.713; S, 2.047; and Cl, 3.596. Additional calculations suggest that the remaining error is a measure of the residual imbalance in the MRSD-CI treatments of the neutral and anion. Extrapolated EAs for the first row atoms are also reported.

  11. New ionic liquids based on complexation of dipropylsulfide and AlCl3 for electrochodeposition of aluminum

    DOE PAGESBeta

    Fang, Youxing; Jiang, Xueguang; Dai, Sheng; Sun, Xiao-Guang

    2015-01-01

    A new kind of ionic liquid based on complexation of dipropyl sulfide (DPS) and AlCl3 has been prepared. The equivalent concentration of AlCl3 in the ionic liquid is as high as 2.3 M. More importantly, it is highly fluidic and exhibits an ambient ionic conductivity of 1.25 x 10-4 S cm-1. This new ionic liquid can be successfully used as an electrolyte for electrodeposition of aluminum.

  12. Crystalline Al1 - x Ti x phases in the hydrogen cycled NaAlH4 + 0.02TiCl3 system

    NASA Astrophysics Data System (ADS)

    Pitt, M. P.; Vullum, P. E.; Sørby, M. H.; Emerich, H.; Paskevicius, M.; Buckley, C. E.; Gray, E. MacA.; Walmsley, J. C.; Holmestad, R.; Hauback, B. C.

    2013-03-01

    The hydrogen (H) cycled planetary milled (PM) NaAlH4 + 0.02TiCl3 system has been studied by high resolution synchrotron X-ray diffraction and transmission electron microscopy during the first 10 H cycles. After the first H absorption, we observe the formation of four nanoscopic crystalline (c-) Ti-containing phases embedded on the NaAlH4 surface, i.e. Al2Ti, Al3Ti, Al82Ti18 and Al89Ti11, with 100% of the originally added Ti atoms accounted for. Al2Ti and Al3Ti are observed morphologically as a mechanical couple on the NaAlH4 surface, with a moderately strained interface. Electron diffraction shows that the Al82Ti18 phase retains some ordering from the L12 structure type, with the observation of forbidden (100) ordering reflections in the fcc Al82Ti18 lattice. After 2 H cycles the NaAlH4 + 0.02TiCl3 system displays only two crystalline Ti-containing phases, Al3Ti and Al89Ti11. After 10 H cycles, the Al89Ti11 is completely converted to Al85Ti15. Al89Ti11, Al85Ti15 and Al3Ti do not display any ordering reflections, and they are modeled in the A1 structure type. Quantitative phase analysis indicates that the Al3Ti proportion continues to increase with further H cycles. The formation of Ti-poor Al1 - x Ti x (x < 0.25) phases in later H cycles is detrimental to hydrogenation kinetics, compared to the starting Ti-richer near-surface Al2Ti/NaAlH4 interface present during the first absorption of hydrogen.

  13. Theoretical study of the nuclear spin-molecular rotation coupling for relativistic electrons and non-relativistic nuclei. II. Quantitative results in HX (X=H,F,Cl,Br,I) compounds

    NASA Astrophysics Data System (ADS)

    Aucar, I. Agustín; Gómez, Sergio S.; Melo, Juan I.; Giribet, Claudia C.; Ruiz de Azúa, Martín C.

    2013-04-01

    In the present work, numerical results of the nuclear spin-rotation (SR) tensor in the series of compounds HX (X=H,F,Cl,Br,I) within relativistic 4-component expressions obtained by Aucar et al. [J. Chem. Phys. 136, 204119 (2012), 10.1063/1.4721627] are presented. The SR tensors of both the H and X nuclei are discussed. Calculations were carried out within the relativistic Linear Response formalism at the Random Phase Approximation with the DIRAC program. For the halogen nucleus X, correlation effects on the non-relativistic values are shown to be of similar magnitude and opposite sign to relativistic effects. For the light H nucleus, by means of the linear response within the elimination of the small component approach it is shown that the whole relativistic effect is given by the spin-orbit operator combined with the Fermi contact operator. Comparison of "best estimate" calculated values with experimental results yield differences smaller than 2%-3% in all cases. The validity of "Flygare's relation" linking the SR tensor and the NMR nuclear magnetic shielding tensor in the present series of compounds is analyzed.

  14. Theoretical study of the nuclear spin-molecular rotation coupling for relativistic electrons and non-relativistic nuclei. II. Quantitative results in HX (X = H,F,Cl,Br,I) compounds.

    PubMed

    Aucar, I Agustín; Gómez, Sergio S; Melo, Juan I; Giribet, Claudia C; Ruiz de Azúa, Martín C

    2013-04-01

    In the present work, numerical results of the nuclear spin-rotation (SR) tensor in the series of compounds HX (X = H,F,Cl,Br,I) within relativistic 4-component expressions obtained by Aucar et al. [J. Chem. Phys. 136, 204119 (2012)] are presented. The SR tensors of both the H and X nuclei are discussed. Calculations were carried out within the relativistic Linear Response formalism at the Random Phase Approximation with the DIRAC program. For the halogen nucleus X, correlation effects on the non-relativistic values are shown to be of similar magnitude and opposite sign to relativistic effects. For the light H nucleus, by means of the linear response within the elimination of the small component approach it is shown that the whole relativistic effect is given by the spin-orbit operator combined with the Fermi contact operator. Comparison of "best estimate" calculated values with experimental results yield differences smaller than 2%-3% in all cases. The validity of "Flygare's relation" linking the SR tensor and the NMR nuclear magnetic shielding tensor in the present series of compounds is analyzed. PMID:23574208

  15. Frustration and Dzyaloshinsky-Moriya anisotropy in the kagome francisites Cu3Bi (SeO3)2 O2X (X = Br , Cl )

    NASA Astrophysics Data System (ADS)

    Rousochatzakis, Ioannis; Richter, Johannes; Zinke, Ronald; Tsirlin, Alexander A.

    2015-01-01

    We investigate the antiferromagnetic canting instability of the spin-1/2 kagome ferromagnet, as realized in the layered cuprates Cu3Bi (SeO3)2 O2X (X = Br , Cl ). While the local canting can be explained in terms of competing exchange interactions, the direction of the ferrimagnetic order parameter fluctuates strongly even at short distances on account of frustration which gives rise to an infinite ground state degeneracy at the classical level. In analogy with the kagome antiferromagnet, the accidental degeneracy is fully lifted only by nonlinear 1 /S corrections, rendering the selected uniform canted phase very fragile even for spins-1/2, as shown explicitly by coupled-cluster calculations. To account for the observed ordering, we show that the minimal description of these systems must include the microscopic Dzyaloshinsky-Moriya interactions, which we obtain from density-functional band-structure calculations. The model explains all qualitative properties of the kagome francisites, including the detailed nature of the ground state and the anisotropic response under a magnetic field. The predicted magnon excitation spectrum and quantitative features of the magnetization process call for further experimental investigations of these compounds.

  16. Resonance Character of Copper/Silver/Gold Bonding in Small Molecule⋅⋅⋅M-X (X=F, Cl, Br, CH3, CF3) Complexes.

    PubMed

    Zhang, Guiqiu; Yue, Huanjing; Weinhold, Frank; Wang, Hui; Li, Hong; Chen, Dezhan

    2015-08-01

    The resonance character of Cu/Ag/Au bonding is investigated in B⋅⋅⋅M-X (M=Cu, Ag, Au; X=F, Cl, Br, CH3, CF3; B=CO, H2O, H2S, C2H2, C2H4) complexes. The natural bond orbital/natural resonance theory results strongly support the general resonance-type three-center/four-electron (3c/4e) picture of Cu/Ag/Au bonding, B:M-X↔B(+) -M:X(-) , which mainly arises from hyperconjugation interactions. On the basis of such resonance-type bonding mechanisms, the ligand effects in the more strongly bound OC⋅⋅⋅M-X series are analyzed, and distinct competition between CO and the axial ligand X is observed. This competitive bonding picture directly explains why CO in OC⋅⋅⋅Au-CF3 can be readily replaced by a number of other ligands. Additionally, conservation of the bond order indicates that the idealized relationship bB⋅⋅⋅M +bMX =1 should be suitably generalized for intermolecular bonding, especially if there is additional partial multiple bonding at one end of the 3c/4e hyperbonded triad. PMID:26083320

  17. Structure, stability, and nature of bonding in carbon monoxide bound EX3+ complexes (E = group 14 element; X = H, F, Cl, Br, I).

    PubMed

    Ghara, Manas; Pan, Sudip; Kumar, Anand; Merino, Gabriel; Chattaraj, Pratim K

    2016-09-15

    A density functional theory study is performed to predict the structures and stability of carbon monoxide (CO) bound EX3+ (E = C, Si, Ge, Sn, Pb; X = H, F, Cl, Br, I) complexes. The possibility of bonding through both C- and O-sides of CO is considered. Thermochemical analysis reveals that all the dissociation processes producing CO and EX3+ are endothermic in nature whereas most of the dissociation reactions are endergonic in nature at room temperature. The nature of bonding in EC/O bonds is analyzed via Wiberg bond index, natural population analysis, electron density, and energy decomposition analyses in conjunction with natural orbitals for chemical valence scheme. In comparison to CO stretching frequency ( ν∼CO) in free CO, while a red shift is noted in O-side binding, the C-side binding results in a blue shift in ν∼CO. The relative change in ν∼CO values in CO bound EX3+ complexes on changing either E or X is scrutinized and possible explanation is provided in terms of polarization in the σ- and π-orbitals and the relative strength of C→E or O→E σ-donation and E→C or E→O π-back-donation. © 2016 Wiley Periodicals, Inc. PMID:27425405

  18. Origin of selenium-gold interaction in F2CSe⋯AuY (Y = CN, F, Cl, Br, OH, and CH3): Synergistic effects

    NASA Astrophysics Data System (ADS)

    Guo, Xin; Yang, Yu-Ping; Li, Qing-Zhong; Li, Hai-Bei

    2016-03-01

    Selenium-gold interaction plays an important role in crystal materials, molecular self-assembly, and pharmacochemistry involving gold. In this paper, we unveiled the mechanism and nature of selenium-gold interaction by studying complexes F2CSe⋯AuY (Y = CN, F, Cl, Br, OH, and CH3). The results showed that the formation of selenium-gold interaction is mainly attributed to the charge transfer from the lone pair of Se atom to the Au—Y anti-bonding orbital. Energy decomposition analysis indicated that the polarization energy is nearly equivalent to or exceeds the electrostatic term in the selenium-gold interaction. Interestingly, the chalcogen-gold interaction becomes stronger with the increase of chalcogen atomic mass in F2CX⋯AuCN (X = O, S, Se, and Te). The cyclic ternary complexes are formed with the introduction of NH3 into F2CSe⋯AuY, in which selenium-gold interaction is weakened and selenium-nitrogen interaction is strengthened due to the synergistic effects.

  19. FT-IR, FT-Raman and DFT study of 3,3'-bis (trifluoromethyl) benzophenone and its biological activity with other halogen (Cl, Br) atoms.

    PubMed

    Mahalakshmi, G; Balachandran, V

    2014-04-24

    The FT-IR and FT-Raman spectra of 3,3'-bis (trifluoromethyl) benzophenone (TFMBP) were recorded and analyzed. Natural bond orbital analysis on TFMBP, 3,3'-bis (trichloromethyl) benzophenone (TCMBP) and 3,3'-bis (tribromomethyl) benzophenone (TBMBP) has been carried out for various intramolecular interactions that are responsible for the stabilization of the molecule. HOMO-LUMO energy gap of the halogen substitution (Cl, Br) has been computed with the help of density functional theory. The statistical thermodynamic functions (heat capacity, entropy, vibrational partition function and Gibbs energy) were obtained for the range of temperature 100-1000 K. The polarizability, first hyperpolarizability, anisotropy polarizability invariant has been computed using quantum chemical calculations. The infrared and Raman spectra were also predicted from the calculated intensities. Comparison of the experimental and theoretical spectra values provides important information about the ability of the computational method to describe the vibrational modes. UV-VIS spectral analyses of TFMBP have been researched by theoretical calculations. In order to understand electronic transitions of the compound, TD-DFT calculations on electronic absorption spectra in gas phase and solvent (DMSO and Chloroform) were performed. The calculated frontier orbital energies, absorption wavelengths (λ), oscillator strengths (ƒ) and excitation energies (E) for gas phase and solvent (water and methanol) are also illustrated. PMID:24503154

  20. Direct evaluation of the hyperconjugative interactions in 1,1,1-trihaloethane (CH3CX3, X = F, Cl, and Br).

    PubMed

    Chen, Zhenhua; Corminboeuf, Clémence; Mo, Yirong

    2014-08-01

    Following the computational strategy proposed by Mulliken in 1939 ( J. Chem. Phys. 1939, 7 (5), 339-352), when the concept of hyperconjugation was coined, we evaluated the hyperconjugative stabilization energy in 1,1,1-trihaloethane using the block-localized wave function (BLW) method. The BLW method is the simplest and most efficient variant of ab initio valence bond (VB) theory and can derive the strictly electron-localized state wave function self-consistently. The latter serves as a reference for the quantification of the electron delocalization effect in terms of the resonance theory. Computations show that the overall hyperconjugative interactions in 1,1,1-trihaloethane, dominated by σ(CH) → σ'(CX) with minor contribution from σ(CX) → σ'(CH), ranges from 9.59 to 7.25 kcal/mol in the staggered structures and decreases in the order Br > Cl > F. This is in accord with the (1)H NMR spectra of CH3CX3. Notably, the hyperconjugation effect accounts for 35-40% of the rotation barriers in these molecules, which are dominated by the conventional steric repulsion. This is consistent with the recent findings with 1,2-difluoroethane (Freitas, Bühl, and O'Hagan. Chem. Comm. 2012, 48, 2433-2435) that the variation of (1)J(CF) with the FCCF torsional angle cannot be well explained by the hyperconjugation model PMID:24041308

  1. Enhanced surface modification engineering (H, F, Cl, Br, and NO{sub 2}) of CdS nanowires with and without surface dangling bonds

    SciTech Connect

    Zeng, Yijie; Xing, Huaizhong Lu, Aijiang; Wang, Chunrui; Xu, Xiaofeng; Huang, Yan; Chen, Xiaoshuang E-mail: xschen@mail.sitp.ac.cn; Wang, Jiqing E-mail: xschen@mail.sitp.ac.cn

    2015-08-07

    Semiconductor nanowires (NWs) can be applied in gas sensing and cell detection, but the sensing mechanism is not clearly understood. In this study, surface modification effect on the electronic properties of CdS NWs for different diameters with several species (H, F, Cl, Br, and NO{sub 2}) is investigated by first principles calculations. The surface dangling bonds and halogen elements are chosen to represent the environment of the surface. Halogen passivation drastically changes the band gaps due to the strong electronegativity and the energy level of halogen atoms. Density of states analysis indicates that valence band maximum (VBM) of halogen-passivated NWs is formed by the p states of halogen atoms, while VBM of H-passivated NWs is originated from Cd 4d and S 3p orbitals. To illustrate that surface modification can be applied in gas sensing, NO{sub 2}-absorbed NWs with different coverage are calculated. Low coverage of NO{sub 2} introduces a deep p-type dopant-like level, while high coverage introduces a shallow n-type dopant-like level into the band structure. The transformation is due to that at low coverage the adsorption is chemical while at high coverage is physical. These findings might promote the understanding of surface modification effect and the sensing mechanism of NWs as gas sensors.

  2. Atomiclike ionization and fragmentation of a series of CH{sub 3}-X (X: H, F, Cl, Br, I, and CN) by an intense femtosecond laser

    SciTech Connect

    Tanaka, Michinori; Murakami, Masanao; Yatsuhashi, Tomoyuki; Nakashima, Nobuaki

    2007-09-14

    Methane derivatives of CH{sub 3}-X (X: H, F, Cl, Br, I, and CN) were ionized and fragmented by an intense femtosecond laser with a 40 fs pulse at 0.8 {mu}m in intensities of 10{sup 13}-10{sup 15} W cm{sup -2}. The curves of the ionization yields of CH{sub 3}-X versus laser intensities have been found to be fitted with an atomic ionization theory (the theory of Perelomov, Popov, and Terent'ev) that has been established to reproduce experimental results well for rare gas atoms. The saturation intensities have been reproduced within a factor of 1.6 of the calculated ones. For molecules with low ionization potentials such as amines, another atomic ionization theory (the theory of Ammosov, Delone, and Krainov) reproduced the saturation intensities. The atomiclike ionization behavior of molecules indicates that the fragmentation occurs after the ionization. The fragmentation mechanisms after the ionization of some molecular ions are discussed.

  3. FT-IR, Raman and DFT study of 2-amino-5-fluorobenzoic acid and its biological activity with other halogen (Cl, Br) substitution

    NASA Astrophysics Data System (ADS)

    Xavier, T. S.; Hubert, Joe I.

    2011-07-01

    The Fourier-transform Raman and infrared spectra of 2-amino-5-fluoro benzoic acid has been recorded and analyzed. The optimized geometry of the other halogen substitution (Cl, Br) have been computed with the help of density functional theory. The detailed interpretation of vibrational spectra of 2-amino-5-fluoro benzoic acid have performed in terms of potential energy distribution analysis. Natural bond orbital analysis on 2-amino-5-fluoro benzoic acid, 2-amino-5-chloro benzoic acid and 2-amino-5-bromo benzoic acid has been carried out for various intramolecular interactions that are responsible for the stabilization of the molecule. The p Ka values of 2-amino-5-fluoro benzoic acid, 2-amino-5-chloro benzoic acid and 2-amino-5-bromo benzoic acid are computed using MOPAC and it is related with HOMO-LUMO energy difference obtained from Gaussian 03 software. The biological activity of 2-amino-5-fluoro benzoic acid has been predicted based on these values. The inhibition activity of 2-amino-5-bromo benzoic acid with the protein tyrosine kinase 3LQ8 is simulated by using Autodock software.

  4. FT-IR, Raman and DFT study of 2-amino-5-fluorobenzoic acid and its biological activity with other halogen (Cl, Br) substitution.

    PubMed

    Xavier, T S; Joe, I Hubert

    2011-07-01

    The Fourier-transform Raman and infrared spectra of 2-amino-5-fluoro benzoic acid has been recorded and analyzed. The optimized geometry of the other halogen substitution (Cl, Br) have been computed with the help of density functional theory. The detailed interpretation of vibrational spectra of 2-amino-5-fluoro benzoic acid have performed in terms of potential energy distribution analysis. Natural bond orbital analysis on 2-amino-5-fluoro benzoic acid, 2-amino-5-chloro benzoic acid and 2-amino-5-bromo benzoic acid has been carried out for various intramolecular interactions that are responsible for the stabilization of the molecule. The pKa values of 2-amino-5-fluoro benzoic acid, 2-amino-5-chloro benzoic acid and 2-amino-5-bromo benzoic acid are computed using MOPAC and it is related with HOMO-LUMO energy difference obtained from Gaussian 03 software. The biological activity of 2-amino-5-fluoro benzoic acid has been predicted based on these values. The inhibition activity of 2-amino-5-bromo benzoic acid with the protein tyrosine kinase 3LQ8 is simulated by using Autodock software. PMID:21497545

  5. Conformational stability and normal coordinate analyses for 1-halovinyl azides CH2=CX-NNN (X is F, Cl and Br).

    PubMed

    Badawi, Hassan M; Förner, Wolfgang; Al-Ghamdi, Khalid S

    2003-12-01

    The conformational behavior of 1-halovinyl azides CH2=CX-NNN (X=F, Cl and Br) were investigated by DFT-B3LYP and ab initio MP2 calculations with the 6-311++G** basis set. The molecules were predicted to exist predominantly in the trans (the vinyl CH2=CH- and the azide -NNN groups are trans to each other) conformation. The relative energy between cis and trans were calculated to decrease in order: bromide>chloride>fluoride. Full optimization was performed at the ground and transition states in the molecule at both MP2 and B3LYP levels. The barrier to internal rotation around the C-N single bond in the three molecules was calculated to be about 4-5 kcal mol(-1). The vibrational frequencies were computed at the DFT-B3LYP level and the calculated infrared and Raman spectra of the cis- trans mixture of the three molecules were plotted. Complete vibrational assignments were made on the basis of normal coordinate calculations for both stable conformers of the three molecules. PMID:12720114

  6. Synthesis, crystal structures, magnetic properties, and lattice dynamics of Ba2XCu(OH)[V2O7] with X=Cl, Br

    NASA Astrophysics Data System (ADS)

    Sun, Kewen; Litvinchuk, Alexander P.; Tapp, Joshua; Möller, Angela

    2016-04-01

    We have synthesized Ba2XCu(OH)[V2O7] with X=Cl, Br by hydrothermal methods. The isotypic structures (Pnma, Z=4, a≈15.1 Å, b≈6.1 Å, c≈9.6 Å) contain distorted hexagonal layers of Ba and X in a BN-type arrangement. Each halide is further coordinated by one out-of plane Ba atom in an alternate up-down fashion resulting in an overall 3+ ∞ 2[Ba2 X ] structural feature. The planar Ba-X hexagonal rings are centered by divanadate groups in an eclipsed orientation. Edge-sharing chains of 5- ∞ 1[CuO2/2(OH)2/2O2/1 ] complement the structure. The magnetic properties are associated with the magnetic Cu2+ ions and can be described as an antiferromagnetic quasi 1D S=1/2 Heisenberg system. Confirmation is obtained from both magnetic and specific heat measurements. Furthermore, lattice dynamics are studied by DFT methods, IR, and Raman spectroscopy.

  7. Molecular orbital analysis of the inverse halogen dependence of nuclear magnetic shielding in LaX₃, X = F, Cl, Br, I.

    PubMed

    Moncho, Salvador; Autschbach, Jochen

    2010-12-01

    The NMR nuclear shielding tensors for the series LaX(3), with X = F, Cl, Br and I, have been computed using two-component relativistic density functional theory based on the zeroth-order regular approximation (ZORA). A detailed analysis of the inverse halogen dependence (IHD) of the La shielding was performed via decomposition of the shielding tensor elements into contributions from localized and delocalized molecular orbitals. Both spin-orbit and paramagnetic shielding terms are important, with the paramagnetic terms being dominant. Major contributions to the IHD can be attributed to the La-X bonding orbitals, as well as to trends associated with the La core and halogen lone pair orbitals, the latter being related to X-La π donation. An 'orbital rotation' model for the in-plane π acceptor f orbital of La helps to rationalize the significant magnitude of deshielding associated with the in-plane π donation. The IHD goes along with a large increase in the shielding tensor anisotropy as X becomes heavier, which can be associated with trends for the covalency of the La-X bonds, with a particularly effective transfer of spin-orbit coupling induced spin density from iodine to La in LaI(3). PMID:20586110

  8. New k-phase materials, k-(ET) sub 2 Cu(N(CN) sub 2 )X: X = Cl, Br and I: The synthesis, structure and superconductivity above 11 K in the Cl ( Tc = 12. 8 K, 0. 3 kbar) and Br( Tc = 11. 6 K) salts

    SciTech Connect

    Wang, H.H.; Carlson, K.D.; Geiser, U.; Kini, A.M.; Schultz, A.J.; Williams, J.M.; Montgomery, L.K.; Kwok, W.K.; Welp, U.; Vandervoort, K.G.; Boryschuk, S.J.; Strieby Crouch, A.V.; Kommers, J.M.; Watkins, D.M. ); Schirber, J.E.; Overmyer, D.L. ); Jung, D.; Novoa, J.J.; Whangbo, M.H. )

    1990-01-01

    The syntheses, structures, selected physical properties, and band electronic structures of three copper (I) dicyanamide halide salts of bis(ethylenedithio)tetrathiafulvalene ({kappa}-(ET){sub 2}Cu(N(CN){sub 2})X, where X = Cl, Br, and I) are discussed. X-ray crystallographic studies demonstrate that the three derivatives are isostructural. The bromide salt is an ambient pressure superconductor with an inductive onset at 11.6 K and a resistive onset at 12.5 K. {kappa}-(ET){sub 2}Cu(N(CN){sub 2})Cl exhibits the highest reported superconducting transition temperature ({Tc} = 12.8 K, 0.3 kbar) for an organic superconductor, once a semiconductor-semiconductor transition (42 K) is suppressed. The application of GE varnish or Apiezon N grease to crystals of {kappa}-(ET){sub 2}Cu(N(CN){sub 2})Cl provides sufficient stress to induce superconductivity at ambient pressure.'' Crystals of the iodide remain metallic to {approximately}150 K, where they become weakly semiconductive. No sign of superconductivity was detected at pressures (hydrostatic and shearing) up to 5.2 kbar and at temperatures as low as 1.1 K. The band electronic structures of the three salts are essentially identical. The differences in superconducting properties are explained in terms of differences in lattice softness, which are strongly influenced by short C-H{hor ellipsis}donor and C-H{hor ellipsis}anion contacts. 17 refs., 2 figs.

  9. Electrical, dielectric and electrochemical measurements of bulk aluminum phthalocyanine chloride (AlPcCl)

    NASA Astrophysics Data System (ADS)

    Soliman, I. M.; El-Nahass, M. M.; Mansour, Y.

    2016-01-01

    AC conductivity and the related dielectric properties of bulk aluminum phthalocyanine chloride (AlPcCl) have been studied over a temperature range (303-403 K) and frequency range (42-106 Hz). The universal power law σac (ω)=Aωs has been used to investigate dependence of AC conductivity on frequency. The variation of the frequency exponent (s) with temperature was analyzed in terms of different conduction mechanisms; the predominant conduction mechanism was found to be the correlated barrier hopping (CBH) model. The barrier height was calculated by using (CBH) model, it was found to be 1.41 eV. Dependence of σac (ω) on temperature refers to a linear increase with increasing temperature at different frequencies. The density of states N (EF) was calculated to be equal 4.11×1019 cm-3 using Elliott model. It has been found that AC activation energy decreases with increasing frequency. Dielectric values were analyzed using complex permittivity and complex electric modulus for bulk AlPcCl at different temperatures. The obtained value of HOMO-LUMO energy gap was found to be 1.48 eV.

  10. Characterization of ultraviolet excited Br*-radical etching of InGaAs/InAlAs material system

    NASA Astrophysics Data System (ADS)

    Habibi, Soheil; Tanaka, Jun; Hattori, Hideki; Totsuka, Masahiro; Matsumoto, Satoru

    1996-04-01

    Dry selective photochemical etching of InGaAs/InAlAs material system, in HBr gas excited by a 172 nm excimer lamp, has been characterized. The etching is thought to be due to the formation of reactive Br*-radicals which are photocreated in the gas phase and then diffused into the solid semiconductor to create volatile products. The etching is temperature sensitive with best etching results at 50-110° C. Atomic force microscope and scanning electron microscope pictures reveal that the surface morphology at this temperature range is smooth and fine. Auger electron spectroscopy and x-ray photoelectron spectroscopy measurements show that at low temperatures the etch products are primarily salts of bromide and are in the liquid phase and thus remain at the surface and a desorption process stops further etching. At slightly elevated temperature range, the creation of oxides and deposition of bromine compounds reduces the etch rate and causes the surface quality to deteriorate. Etching at higher pressure range increases the etch rate of InGaAs but results in surface quality deterioration.

  11. Thermal evolution of the Cl(-)-LiAl(2) layered double hydroxide: a multinuclear MAS NMR and XRD perspective.

    PubMed

    Hou, X; Kirkpatrick, R J

    2001-12-01

    Layered double hydroxides (LDHs) with a cation composition of LiAl(2) have a wide range of potential applications as catalysts, catalyst supports, and precursors for refractory oxide materials, including several industrially important lithium aluminate phases. The understanding of the calcination behavior of this group of LDH phases is essential to advancing these applications, and the research described here focuses on the thermal decomposition and structural evolution of LiAl(2)(OH)(6)Cl.nH(2)O in the temperature range of 20-1100 degrees C. (27)Al, (35)Cl, and (6,7)Li magic angle spinning nuclear magnetic resonance spectroscopy, powder X-ray diffraction, thermal analysis (including thermogravimetric and differential scanning calorimetry), and compositional analysis provide a highly consistent picture of the thermally induced phase formation and transformations of this LDH. The loss of the surface and interlayer water can begin as low as room temperature, depending on the relative humidity. Beginning at about 300 degrees C, the simultaneous volatilization of H(2)O and HCl and the exsolution of crystalline LiCl result in the formation of amorphous Li-Al-O-OH. By at least 500 degrees C, volumes with the structures of alpha-LiAlO(2) and LiAl(5)O(8) appear, and these phases become progressively more ordered with increasing temperature. LiCl begins to volatilize by 850 degrees C and is present only in trace amounts above ca. 1000 degrees C. alpha-LiAlO(2) converts to gamma-LiAlO(2) between 970 and 1100 degrees C. Because of the delithiation due to LiCl volatilization, the final products are dominated by LiAl(5)O(8), in contrast to the calcination products of previously studied LiAl(2) LDHs which are dominated by LiAlO(2). PMID:11720493

  12. COMBINING COSMOGENIC BE, C, AL AND CL - Quantifying depth of glacial erosion and timing of deglaciation

    NASA Astrophysics Data System (ADS)

    Wirsig, C.; Ivy-Ochs, S.; Akcar, N.; Alfimov, V.; Kämpfer, C.; Schlüchter, C.

    2012-04-01

    Over the course of the next years, we are aiming to combine signals of cosmogenic Be-10, C-14, Al-26 and Cl-36 to constrain depth and rate of glacial erosion at several study sites in the Alps and to determine the timing of local deglaciation. Within this suite of nuclides, the system of Be is the best understood. It is routinely used and often combined with Al for various applications in Quaternary Geology, i.e. dating rock avalanches. Cl-36 is an important addition due to its unique depth profile: complicated production pathways cause the maximum concentration not to form at the top of the rock, but at a depth of some centimetres [1]. Furthermore, extending the suite by in-situ produced C-14 is crucial. Its short half-live enables the detection of brief periods of ice coverage that could not be noticed in the other nuclides. Measurement of in-situ produced C-14 in bedrock is not trivial, but has been achieved with reliable results [2]. Concentration-depth profiles for all of these nuclides can be modelled for diverse scenarios of past ice coverage. If the local Quaternary history is known independently, (glacial) erosion rates can be determined. As a first study site, Grueben glacier in the Grimsel region was chosen. The area was recently mapped in detail by C. Kämpfer allowing to draw robust conclusions based on field observations. Here we will present and discuss exposure ages of four bedrock samples taken to be analysed this winter for a first assessment of the local situation and to identify promising sites for intense examination in the future. [1] Alfimov and Ivy-Ochs, Quat. Geochr. 4, 2009 [2] Hippe et. al., Quat. Geochr. 4, 2009

  13. High-resolution aluminum-27 solid-state magic-angle sample-spinning nuclear magnetic resonance spectroscopic study of AlCl sub 3 -tetrahydrofuran complexes

    SciTech Connect

    Han, Oc Hee; Oldfield, E. )

    1990-09-19

    The authors have obtained {sup 27}Al solid-state nuclear magnetic resonance (NMR) spectra of several AlCl{sub 3}-THF complexes, using magic-angle sample-spinning (MASS) NMR at high field. The authors results suggest that the isotropic chemical shifts ({delta}{sub i}) occur in relatively well defined regions for 4-, 5-, and 6-coordinate species (AlCl{sub 4}{sup {minus}}, {approximately} 103 ppm; AlCl{sub 3}{center dot}THF, {approximately} 99 ppm; trans-AlCl{sub 3}{center dot}2THF, {approximately} 60 ppM; trans-(AlCl{sub 2}(THF){sub 4}){sup +}, {approximately} 14 ppM), as found previously with aluminum oxo compounds. They also find that theoretically calculated average nuclear quadrupole coupling constants (e{sup 2}qQ/h) (trans-(AlCl{sub 2}(THF){sub 4}){sup +}, {approximately} 6.3 MHz; trans-AlCl{sub 3}{center dot}2THF, {approximately} 4.6 MHz; AlCl{sub 3}{center dot}THF, {approximately} 3.0 MHz; AlCl{sub 4}{sup {minus}}, 0 MHz) are in good accord with experimentally determined nuclear quadrupole coupling constants, determined from computer simulations of the MASS NMR spectra (trans-(AlCl{sub 2}(THF){sub 4}){sup +}, 6.4 MHz; trans-AlCl{sub 3}{center dot}2THF, 4.9 MHz; AlCl{sub 3}{center dot}THF, 4.7 MHz; AlCl{sub 4}{sup {minus}}, 0.3 MHz). Both {sup 27}Al {delta}{sub i} and e{sup 2}qQ/h determinations appear to be useful as probes of structure in these systems, and thus offer a facile means of monitoring various solid-state reactions. 14 refs., 3 figs., 3 tabs.

  14. Synergistic effect and mechanisms of compound bioflocculant and AlCl3 salts on enhancing Chlorella regularis harvesting.

    PubMed

    Zhang, Chaofan; Wang, Xiansheng; Wang, Yao; Li, Yunbao; Zhou, Dandan; Jia, Yanwu

    2016-06-01

    The high energy input required for harvesting microalgae means that commercial production of microalgal biodiesel is economically unfeasible. In this study, we investigated the flocculation efficiency and synergistic mechanisms of novel coupled flocculants, AlCl3 and compound bioflocculants (CBF), to overcome this difficulty. AlCl3 flocculation was found to be very sensitive to pH, and flocculation efficiency increased from 55 to 95 % when pH increased from 4 to 10. CBF was environmental friendly, less reliant on pH, but had a relatively low flocculation of 75 % in optimum conditions. The harvesting efficiency of Chlorella regularis can achieve a satisfactory level of 96.77 % even in neutral conditions, with a CBF dosage of 0.26 g/L, AlCl3 dosage of 0.18 g/L, and coagulant aid (CaCl2) dosage of 0.12 g/L. Interestingly, compared with the use of single flocculant, the dosage of CBF, AlCl3, and coagulant aid (CaCl2) were reduced by about 52, 49, and 66 %, respectively. Besides, the aluminum (Al) ion content of the supernatant decreased significantly to a residue of only 0.03 mg/L, therefore meeting the downstream process needs easily. Patching and bridging played key roles in coupled flocculant flocculation, in which AlCl3 mainly carried out the electrical neutralization. This work provides new insight into an efficient, economical, and environmentally friendly protocol for microalgae harvesting. PMID:27102131

  15. RECONCILE Airborne ClOx Measurements and the ClO/ClOOCl Equilibrium Constant

    NASA Astrophysics Data System (ADS)

    Stroh, Fred; Grooß, Jens-Uwe; Heinecke, Florian; Suminska, Olga; von Hobe, Marc; Volk, Michael; Wegner, Tobias

    2013-04-01

    ClOx (denoting mainly ClO and its peroxide dimer ClOOCl) chemistry is driving the ClO dimer and ClO-BrO catalytic ozone destruction cycles leading to the ozone hole phenomena in southern and northern high latitudes. HALOX is an in-situ instrument to measure ClO and ClO dimer by the technique of thermal dissociation (of the dimer) followed by chemical conversion and resonance fluorescence (CCRF) detection of the halogen atoms. The instrument was installed onboard the high-flying research aircraft M55 Geophysica during the RECONCILE Arctic field campaign in early 2010. While results for the ClO dimer, ClOOCl, photolysis derived from the sunrise evolution of ClO during a self-match flight have been recently published by Suminska-Ebersoldt et al. (Atmosph. Chem. Phys. 12, 1353-1365, 2012) we now present ClO dimer data which could only be derived after thorough laboratory calibrations of the thermolysis efficiency of the HALOX inlet heater element. Details of the calibration setup and the procedure are presented and preliminary results for the ClO/ClOOCl equilibrium constant are derived and discussed.

  16. Effect of trace amounts of NaCl vapor on high-temperature oxidation of TiAl

    SciTech Connect

    Hara, M.; Kitagawa, Y.

    1999-08-01

    The effect of trace amounts of NaCl vapor on the high-temperature oxidation of TiAl was examined by thermogravimetry and analysis of the scale formed on TiAl. The mass gain due to oxidation at 1273 K in O{sub 2} with trace amounts of NaCl vapor was far lower than that in pure O{sub 2} without NaCl vapor. This low mass gain in the atmosphere with trace amounts of NaCl vapor resulted from the saturation behavior of mass gain during the initial period of oxidation. It was found from X-ray photoemission spectroscopy (XPS) analyses of the specimen surface that the oxide film formed during the initial period in the atmosphere with trace amounts of NaCl vapor consisted of dense Al{sub 2}O{sub 3}, thus, the low oxidation rate of TiAl was attributed to a protective oxide film of dense Al{sub 2}O{sub 3}.

  17. Librational modes of the water molecules in barium and strontium halide monohydrates, MX 2 · 1H 2O (M = Ba, Sr; X = Cl, Br, I)

    NASA Astrophysics Data System (ADS)

    Lutz, H. D.; Christian, H.

    1983-09-01

    The IR and Raman spectra of the isotypic alkaline earth halide monohydrates, MX 2 · 1H 2O, with M = Sr, Ba and X = Cl, Br, I, and of deuterated samples are presented for the range 200-700 cm -1 and discussed in terms of normal modes, assignment, coupling, correlation with structure data, and temperature dependence of both the H 2O (D 2O) and the HDO librational modes. The normal modes of the out-of-plane librations of HDO molecules are of the wagging and twisting type rather than H and D out-of-plane vibrations [4], at least for water molecules with C2v or nearly C2v symmetry. Thus the observed H 2O/HDO isotopic shifts can be used as a criterion for assigning the H 2O librations. The librational modes of the halide monohydrates (with tetrahedrally coordinated water oxygen atoms) are found in the order ν Rγ ≫ ν Rt ≫ ν Rr. The intensities of the IR and Raman spectra are in the order Rγ ≫ Rr ≫ Rt (or ˜ Rt in the case of strongly distorted H 2O molecules) and Rt ≫ Rr ≫ Rγ, respectively. Correlations of the H 2O librational modes with structural or bonding data are restricted by frequency shifts due to vibrational coupling and by the fact that the oxygen and the hydrogen atoms of the water molecules are generally affected in a different manner by bond interactions. However, in the case of the twisting vibrations, there are clear correlations with both the size of the metal ions, i.e. increase of ν Rt with decreasing size, and the intermolecular bonding of the hydrogen atoms, as shown by the OH stretching frequencies, i.e. increase of ν Rt with decreasing ν OH.

  18. Determination of molecular stopping cross section of 12C, 16O, 28Si, 35Cl, 58Ni, 79Br, and 127I in silicon nitride

    NASA Astrophysics Data System (ADS)

    Barradas, N. P.; Bergmaier, A.; Mizohata, K.; Msimanga, M.; Räisänen, J.; Sajavaara, T.; Simon, A.

    2015-10-01

    Silicon nitride is a technologically important material in a range of applications due to a combination of important properties. Ion beam analysis techniques, and in particular, heavy ion elastic recoil detection analysis can be used to determine the stoichiometry of silicon nitride films, which often deviates from the ideal Si3N4, as well as the content of impurities such as hydrogen, even in the presence of other materials or in a matrix containing heavier elements. Accurate quantification of IBA results depends on the basic data used in the data analysis. Quantitative depth profiling relies on the knowledge of the stopping power cross sections of the materials studied for the ions involved, which in the case of HI-ERDA is both the primary beam, and the recoiled species. We measured the stopping cross section of 12C, 16O, 28Si, 35Cl, 58Ni, 79Br, and 127I in a well-characterised silicon nitride membrane. The measurements were made by independent groups utilising different experimental setups and methods. In some cases there is extensive overlap of the energy range in different experiments, allowing a comparison of the different results. The four independent data sets reported in this work are in excellent agreement with each other, in the cases where similar energy ranges were measured. On the other hand, the data are in most cases higher than calculations made with the interpolative schemes SRIM and MSTAR together with the Bragg rule. Better agreement is found with MSTAR in some of the cases studied. This work is a significant extension of the heavy ion stopping power data base for silicon nitride.

  19. Photoelectron spectroscopy of aqueous solutions: Streaming potentials of NaX (X = Cl, Br, and I) solutions and electron binding energies of liquid water and X{sup −}

    SciTech Connect

    Kurahashi, Naoya; Horio, Takuya; Suzuki, Toshinori; Karashima, Shutaro; Suzuki, Yoshi-Ichi; Tang, Ying; Abulimiti, Bumaliya; Ogi, Yoshihiro; Oura, Masaki

    2014-05-07

    The streaming potentials of liquid beams of aqueous NaCl, NaBr, and NaI solutions are measured using soft X-ray, He(I), and laser multiphoton ionization photoelectron spectroscopy. Gaseous molecules are ionized in the vicinity of liquid beams and the photoelectron energy shifts are measured as a function of the distance between the ionization point and the liquid beam. The streaming potentials change their polarity with concentration of electrolytes, from which the singular points of concentration eliminating the streaming potentials are determined. The streaming currents measured in air also vanish at these concentrations. The electron binding energies of liquid water and I{sup −}, Br{sup −}, and Cl{sup −} anions are revisited and determined more accurately than in previous studies.

  20. A theoretical simulation of the resonant Raman spectroscopy of the H2O⋯Cl2 and H2O⋯Br2 halogen-bonded complexes

    NASA Astrophysics Data System (ADS)

    Franklin-Mergarejo, Ricardo; Rubayo-Soneira, Jesús; Halberstadt, Nadine; Janda, Kenneth C.; Apkarian, V. Ara

    2016-02-01

    The resonant Raman spectra of the H2O⋯Cl2 and H2O⋯Br2 halogen-bonded complexes have been studied in the framework of a 2-dimensional model previously used in the simulation of their UV-visible absorption spectra using time-dependent techniques. In addition to the vibrational progression along the dihalogen mode, a progression is observed along the intermolecular mode and its combination with the intramolecular one. The relative intensity of the inter to intramolecular vibrational progressions is about 15% for H2O⋯Cl2 and 33% for H2O⋯Br2. These results make resonant Raman spectra a potential tool for detecting the presence of halogen bonded complexes in condensed phase media such as clathrates and ice.

  1. Laser cooling of the AlCl molecule with a three-electronic-level theoretical model

    NASA Astrophysics Data System (ADS)

    Wan, Mingjie; Yuan, Di; Jin, Chengguo; Wang, Fanhou; Yang, Yujie; Yu, You; Shao, Juxiang

    2016-07-01

    Feasibility of laser-cooling AlCl molecule is investigated using ab initio quantum chemistry. Potential energy curves, permanent dipole moments, and transition dipole moments for the X1Σ+, a3Π, and A1Π states are studied based on multi-reference configuration interaction plus Davidson corrections (MRCI+Q) method with ACVQZ basis set, spin-orbit coupling effects are considered at the MRCI+Q level. Highly diagonally distributed Franck-Condon factors (f00 = 0.9988 and f11 = 0.9970) and branching ratios (R00 = 0.9965, R01 = 2.85 × 10-3, R02 = 6.35 × 10-4, and R03 = 2.05 × 10-6) for the A 1 Π 1 ( ν ' = 0 ) → X 1 Σ0 + + ( ν ″ = 0 ) transition are determined. A sufficiently radiative lifetime τ (A1Π1) = 4.99 ns is predicted for rapid laser cooling. The proposed cooling wavelength is deep in the ultraviolet region at λ00 = 261.75 nm. Total emission rates for the a 3 Π 0 + → X 1 Σ0 + + , a 3 Π 1 → X 1 Σ0 + + , A1Π1 → a3Π0+, and A1Π1 → a3Π1 transitions are particularly small (˜10 s-1-650 s-1). The calculated vibrational branching loss ratio to the intermediate a3Π0+ and a3Π1 states can be negligible. The results imply the probability of laser cooling AlCl molecule with three-electronic-level.

  2. Conformational Properties of 1-Halogenated-1-Silacyclohexanes, C5H10SiHX (X = Cl, Br, I): Gas Electron Diffraction, Low-Temperature NMR, Temperature-Dependent Raman Spectroscopy, and Quantum-Chemical Calculations.

    PubMed

    Wallevik, Sunna Ó; Bjornsson, Ragnar; Kvaran, Agúst; Jonsdottir, Sigridur; Arnason, Ingvar; Belyakov, Alexander V; Kern, Thomas; Hassler, Karl

    2013-12-01

    The molecular structures of axial and equatorial conformers of cyclo-C5H10SiHX (X = Cl, Br, I) as well as the thermodynamic equilibrium between these species was investigated by means of gas electron diffraction, dynamic nuclear magnetic resonance, temperature-dependent Raman spectroscopy, and quantum-chemical calculations applying CCSD(T), MP2, and DFT methods. According to the experimental and calculated results, all three compounds exist as a mixture of two chair conformers of the six-membered ring. The two chair forms of Cs symmetry differ in the axial or equatorial position of the X atom. In all cases, the axial conformer is preferred over the equatorial one. When the experimental uncertainties are taken into account, all of the experimental and theoretical results for the conformational energy (E axial - E equatorial) fit into a remarkably narrow range of -0.50 ± 0.15 kcal mol(-1). It was found by NBO analysis that the axial conformers are unfavorable in terms of steric energy and conjugation effects and that they are stabilized mainly by electrostatic interactions. The conformational energies for C6H11X and cyclo-C5H10SiHX (X = F, Cl, Br, I, At) were compared using CCSD(T) calculations. In both series, fluorine is predicted to have a lower conformational preference (cyclohexane equatorial, silacyclohexane axial) than Cl, Br, and I. It is predicted that astatine would behave very similarly to Cl, Br, and I within each series. PMID:24353364

  3. Conformational Properties of 1-Halogenated-1-Silacyclohexanes, C5H10SiHX (X = Cl, Br, I): Gas Electron Diffraction, Low-Temperature NMR, Temperature-Dependent Raman Spectroscopy, and Quantum-Chemical Calculations†

    PubMed Central

    2013-01-01

    The molecular structures of axial and equatorial conformers of cyclo-C5H10SiHX (X = Cl, Br, I) as well as the thermodynamic equilibrium between these species was investigated by means of gas electron diffraction, dynamic nuclear magnetic resonance, temperature-dependent Raman spectroscopy, and quantum-chemical calculations applying CCSD(T), MP2, and DFT methods. According to the experimental and calculated results, all three compounds exist as a mixture of two chair conformers of the six-membered ring. The two chair forms of Cs symmetry differ in the axial or equatorial position of the X atom. In all cases, the axial conformer is preferred over the equatorial one. When the experimental uncertainties are taken into account, all of the experimental and theoretical results for the conformational energy (Eaxial – Eequatorial) fit into a remarkably narrow range of −0.50 ± 0.15 kcal mol–1. It was found by NBO analysis that the axial conformers are unfavorable in terms of steric energy and conjugation effects and that they are stabilized mainly by electrostatic interactions. The conformational energies for C6H11X and cyclo-C5H10SiHX (X = F, Cl, Br, I, At) were compared using CCSD(T) calculations. In both series, fluorine is predicted to have a lower conformational preference (cyclohexane equatorial, silacyclohexane axial) than Cl, Br, and I. It is predicted that astatine would behave very similarly to Cl, Br, and I within each series. PMID:24353364

  4. Transparent CH3NH3SnCl3/Al-ZnO p-n heterojunction diode

    NASA Astrophysics Data System (ADS)

    Kumar, Sunil; Ansari, Mohd. Zubair; Khare, Neeraj

    2016-05-01

    A p-type Organic inorganic tin chloride (CH3NH3SnCl3) perovskite thin film has been synthesized by solution method. An n-type 1% Al doped ZnO (AZO) film has been deposited on FTO substrate by ultrasonic assisted chemical vapor deposition technique. A transparent CH3NH3SnCl3/AZO p-n heterojunction diode has been fabricated by spin coating technique. CH3NH3SnCl3/AZO p-n heterojunction shows 75% transparency in the visible region. I-V characteristic of CH3NH3SnCl3/AZO p-n heterojunction shows rectifying behavior of the diode. The diode parameters calculated as ideality factor η=2.754 and barrier height V= 0.76 eV. The result demonstrates the potentiality of CH3NH3SnCl3/AZO p-n heterojunction for transparent electronics.

  5. High-Altitude Aircraft and Balloon-Borne Observations of OH, HO2, ClO, BrO, NO2, ClONO2, ClOOCl, H2O, and O3 in Earth's Stratosphere

    NASA Technical Reports Server (NTRS)

    Anderson, James G.

    1999-01-01

    Using observations from balloon-borne instruments and aircraft-borne instruments the investigation arrived at the following developments.: (1) Determination of the dominant catalytic cycles that destroy ozone in the lower stratosphere; (2) The partial derivatives of the rate limiting steps are observables in the lower stratosphere; (3) Recognition that the "Low NOx" condition is the regime that holds the greatest potential for misjudgement of Ozone loss rates; (4) Mapping of the Bromine radical contribution to the ozone destruction rate in the lower stratosphere; (5) Observation of OH, HO2 and ClO in the plume of the Concorde SST in the stratosphere; (6) Determination of the diurnal behavior of OH in the lower stratosphere; (7) Observed OH and H02 in the Troposphere and the interrelationship between Ozone and OH, HO2, CO and NO; (8) Analysis of the Catalytic Production of Ozone and Reactions that Couple OH and H02 in the Troposphere; (9) The continuing development of the understanding of the Tropopause temperatures, water vapor mixing ratios, and vertical advection and the mixing in of mid-latitude air; (10) Performed Multiple Tracer Analyses as a diagnostic of water vapor intrusion into the "Middle World" (i.e., the lowermost stratsophere); (11) Flight testing of a new instrument for the In Situ detection of ClON02 from the ER-2; (12) Laser induced fluorescence detection of NO2. There is included an in depth discussion of each of these developments and observations.

  6. A unique case of oxidative addition of interhalogens IX (X=Cl, Br) to organodiselone ligands: nature of the chemical bonding in asymmetric I-Se-X polarised hypervalent systems.

    PubMed

    Juárez-Pérez, Emilio José; Aragoni, M Carla; Arca, Massimiliano; Blake, Alexander J; Devillanova, Francesco A; Garau, Alessandra; Isaia, Francesco; Lippolis, Vito; Núñez, Rosario; Pintus, Anna; Wilson, Claire

    2011-10-01

    The reactivity of the imidazoline-2-selone derivatives 1,1'-methylenebis(3-methyl-4-imidazoline-2-selone) (D1) and 1,2-ethylenebis(3-methyl-4-imidazoline-2-selone) (D2) towards the interhalogens IBr and ICl has been investigated in the solid state with the aim of synthesising "T-shaped" hypervalent chalcogen compounds featuring the extremely rare linear asymmetric I-E-X moieties (E=S, Se; X=Br, Cl). X-ray diffraction analysis and FT-Raman measurements provided a clear indication of the presence in the compounds obtained of discrete molecular adducts containing I-Se-Br and I-Se-Cl hypervalent moieties following a unique oxidative addition of interhalogens IX (X=Cl, Br) to the organoselone ligands. In all asymmetric hypervalent systems isolated, a strong polarisation was observed, with longer bond lengths at the selenium atom involving the most electronegative halogen. A topological electron density analysis on model compounds based on the quantum theory of atoms-in-molecules (QTAIM) and electron localisation function (ELF) established the three-centre-four-electron (3c-4e) nature of the bonding in these very polarised selenium hypervalent systems and new criteria were suggested to define and ascertain the hypervalency of the selenium atoms in these and related halogen and interhalogen adducts. PMID:21953928

  7. A Localized Molecular Orbital Study of the Halogen Substitution Effect on (103)Rh NMR Shielding in [Cp*RhX2]2, Where X = Cl, Br, or I.

    PubMed

    Mirzaeva, Irina V; Mainichev, Dmitry A; Kozlova, Svetlana G

    2016-03-24

    (103)Rh NMR parameters and the bonding structure of three complexes of [Cp*RhX2]2, where X = Cl, Br, or I, have been studied with the help of natural bond orbitals (NBOs) and natural localized molecular orbitals (NLMOs). The complexes of [Cp*RhX2]2, where X = Cl, Br, or I, have similar bonding structures, with the major difference being in the degree of covalency of the Rh-X bonds. The decomposition of (103)Rh NMR shielding into diamagnetic, paramagnetic, and spin-orbit terms shows that normal halogen dependence (NHD) of the (103)Rh NMR shift is defined mostly by the paramagnetic term, with the spin-orbit term being significantly smaller. The decomposition of (103)Rh shielding into spin-free NBO and NLMO contributions shows that (103)Rh shielding is dominated by Rh d-orbital deshielding contributions. We explain the NHD of the (103)Rh NMR shift with the increase in the energies of the virtual antibonding Rh-X orbitals along the X = Cl, Br, and I series. PMID:26927955

  8. Framework solids based on copper(II) halides (Cl/Br) and methylene-bridged bis(1-hydroxybenzotriazole): synthesis, crystal structures, magneto-structural correlation, and density functional theory (DFT) studies.

    PubMed

    Sasmal, Ashok; Shit, Shyamapada; Rizzoli, Corrado; Wang, Hongfeng; Desplanches, Cédric; Mitra, Samiran

    2012-10-01

    A methylene-bridged 1-hydroxybenzotriazole derived ligand L [L = 1, 3-bis(benzotriazol-1-yl)-1,3-dioxapropane] has been synthesized and characterized by spectroscopic and structural methods. Reaction of L with two different copper(II) halides [CuX(2); X = Br, Cl] in an identical condition yields two different compounds of similar compositions, {[Cu(μ-Br)(Br)(μ-L)](2)}(n)·2nH(2)O (1) and {[Cu(μ-Cl)(Cl)(μ-L)](2)}(n)·2nH(2)O (2), both being characterized by various physicochemical techniques. Single crystal X-ray studies reveal that they appear as 2D coordination polymers with similar bridging fashion of L. Low temperature magnetic susceptibility measurements reveal antiferromagnetic and ferromagnetic behaviors for 1 and 2 with magnetic coupling constants J = -15.2 and +1.7 cm(-1), which are in a reasonable agreement with their calculated values (J = -9.79 and +0.68 cm(-1) respectively, for 1 and 2). The role of bridging halides in the structure and magnetic properties of the complexes are investigated, and a possible magneto-structural correlation has been established. Influence of spin density of bridging halides on the magnitude of coupling constants has been discussed with the help of density functional theory (DFT) calculations. PMID:22974283

  9. The origin of inverse absorption bands observed in the far-infrared RAIRS spectra of SnCl 4 and SnBr 4 adsorbed on thin-film SnO 2 surfaces

    NASA Astrophysics Data System (ADS)

    Awaluddin, A.; Pilling, M. J.; Wincott, P. L.; LeVent, S.; Surman, M.; Pemble, M. E.; Gardner, P.

    2002-04-01

    The adsorption of SnCl 4 and SnBr 4 on polycrystalline SnO 2 has been studied using synchrotron radiation based far-infrared reflection absorption infrared spectroscopy FIR-RAIRS. In order to exploit the sensitivity advantages of the buried metal layer method, the SnO 2 is in the form of a thin film deposited on a tungsten foil substrate. Adsorption of SnCl 4 and SnBr 4 on an oxygen sputtered surface at 120 K results in spectra characteristic of condensed multilayers. In addition, both spectra exhibit an inverse absorption band centred at 355 cm -1. Modified 4-layer, wavelength-dependent, Greenler calculations show that this inverse absorption band is induced by the presence of the adsorbate but is characteristic of the SnO 2 layer. The lack of any frequency shift upon changing the adsorbate from SnCl 4 to SnBr 4 rules out the possibility that the inverse absorption band is due to a dipole-forbidden parallel mode of the molecule excited via the interaction with free electron oscillations in the metal, resulting from the radiation induced oscillating electric field just below the surface.

  10. Evidence for Live Cl-36 in Ca-Al-rich Inclusions from the Ningqiang Carbonaceous Chondrite

    NASA Technical Reports Server (NTRS)

    Lin, Y.; Guan, Y.; Leshin, L. A.; Ouyang, Z.; Wang, D.

    2004-01-01

    The short-lived radionuclide Cl-36 decays to either Ar-36 (98.1%, beta(sup -)) or S-36 (1.9%, epsilon and beta(sup +)), with a half life of 3.01 x 10(exp 5) yr. Both the nucleosynthetic and spallation models suggest high initial Cl-36/Cl-35 ratios ((Cl-36/Cl-35)o up to approximately 10(exp -4)) in the early solar system. Previous observed excess Ar-36 in Efremovka matrix has been interpreted to represent a much lower (Cl-36/Cl-35)o ratio of approximately 1 x 10(exp -6). From the observed S-36 excesses in sodalite in calcium aluminum-rich inclusions (CAIs), we report in this study the first direct evidence of the presence of Cl-36 in primitive meteorites. The inferred (Cl-36/Cl-35)o ratios range from approximately 5 x 10(exp -6) to approximately 1 x 10(exp -5).

  11. Corrosion Performance Based on the Microstructural Array of Al-Based Monotectic Alloys in a NaCl Solution

    NASA Astrophysics Data System (ADS)

    Osório, Wislei R.; Freitas, Emmanuelle S.; Garcia, Amauri

    2014-01-01

    The aim of this study is to compare the electrochemical behavior of three monotectic Al-based alloys (Al-Pb, Al-Bi, and Al-In) in a 0.5 M NaCl solution at room temperature. Two distinct microstructure arrays were experimentally obtained for each Al monotectic alloy by using a water-cooled unidirectional solidification system. Results of electrochemical impedance spectroscopy (EIS) plots, potentiodynamic polarization curves, and impedance parameters obtained by an equivalent circuit analysis are discussed. It was found that the Al-Pb alloy has lower corrosion current density, higher polarization resistance, lower relative weight, and cost than the corresponding values of Al-Bi and Al-In alloys. It is also shown that the electrochemical behavior of the three alloys examined are intimately correlated with the scale of the corresponding microstructure, with smaller droplets and spacings (i.e., cell and interphase spacings) being associated with a decrease in the corrosion resistance.

  12. Ibuprofen targets neuronal pentraxins expresion and improves cognitive function in mouse model of AlCl3-induced neurotoxicity

    PubMed Central

    JAMIL, ANUM; MAHBOOB, AAMRA; AHMED, TOUQEER

    2016-01-01

    Aluminum is known to exert neurotoxic effects associated with various neurodegenerative disorders, including Alzheimer's disease (AD). Ibuprofen is a well-known non-steroidal anti-inflammatory drug, which has demonstrated potential efficacy in the treatment of numerous inflammatory and neurodegenerative disorders, including AD. The present study aimed to investigate the protective effects of ibuprofen on cognitive function, and the expression levels of neuronal pentraxins (NPs) and interleukin (IL)-1β in an aluminum chloride (AlCl3)-induced mouse model of neurotoxicity. The effects of ibuprofen (100 mg/kg/day for 12 days) on learning and memory were evaluated in the AlCl3-induced neurotoxic mice using a Morris water maze and open field tests. In addition, ibuprofen was assessed for its effects on the expression levels of NPs and IL-1β in the hippocampus, cortex and amygdala of the brain. Treatment of the AlCl3-treated mice with ibuprofen decreased anxiety levels (6.90±0.34 min) compared with the AlCl3-treated group (1.80±0.29 min), as indicated by the time spent in the central area in an open field test. Furthermore, the expression levels of NP1 (1.32±0.47) and IL-1β (0.99±0.21) were significantly decreased in the hippocampus of mice following ibuprofen treatment, as compared with the AlCl3-treated mice (8.62±1.54 and 7.47±0.53, respectively). In the present study, ibuprofen was able to target novel structures in order to attenuate the inflammation associated with an AlCl3-induced mouse model of neurotoxicity; thus suggesting that ibuprofen may be considered a potential therapeutic option for the treatment of neurodegenerative diseases, including AD. PMID:26893653

  13. Rotational excitation of AlCl induced by its collision with helium: cross sections and collisional rate coefficients

    NASA Astrophysics Data System (ADS)

    Pamboundom, Mama; Tchakoua, Théophile; Nsangou, Mama

    2016-04-01

    In this work, inelastic rotational collision of AlCl with helium was studied. The CCSD(T) method was used for the computation of an accurate two dimensional potential energy surface (PES). In the calculation of the PES, Al-Cl bond was frozen at the experimental value 4.02678 a0. The aug-cc-pVQZ basis sets of Dunning was used throughout the computational process. This basis was completed with a set of 3s3p2d2f1g bond functions placed at mid-distance between the center of mass of AlCl and He atom for a better description of the van der Waals interaction energy. The PES of AlCl-He was found to have a global minimum at (R=8.65 a0, θ=0 degree), a local minimum at (R=7.45 a0, θ=82 degree) and a saddle point at (R=7.9 a0, θ=56 degree). The depths of the minima were 20.2 cm^{-1} and 19.8 cm^{-1} respectively for θ=0 and 84 degrees. The height of the saddle point with respect to the global minimum was 1.3 cm^{-1}. The PES, the result of an analytical fit, was expanded in terms of Legendre polynomials, then used for the evaluation of state-to-state rotational integral cross sections for the collision of AlCl with He in the close coupling approach. The collisional cross sections for the transitions occurring among the 17 first rotational levels of AlCl were calculated for kinetic energies up to 4000 cm^{-1}. Collisional rate coefficients between these rotational levels were computed for low and moderate kinetic temperatures ranging from 30 to 500 K. A propensity rule that favors odd Δ j transitions was found.

  14. EtAlCl2/2,6-Disubstituted Pyridine-Mediated Carboxylation of Alkenes with Carbon Dioxide.

    PubMed

    Tanaka, Shinya; Watanabe, Kota; Tanaka, Yuuki; Hattori, Tetsutaro

    2016-06-01

    α-Arylalkenes and trialkyl-substituted alkenes undergo carboxylation with CO2 in the presence of EtAlCl2 and 2,6-dibromopyridine to afford the corresponding α,β- and/or β,γ-unsaturated carboxylic acids. This reaction is suggested to proceed via the electrophilic substitution of EtAlCl2 with the aid of the base, followed by the carbonation of the resulting ate complex. This reaction can be applied to terminal dialkylalkenes by using a mixture of 2,6-di-tert-butylpyridine and 2,6-dibromopyridine. PMID:27187716

  15. New ionic liquids based on complexation of dipropylsulfide and AlCl3 for electrochodeposition of aluminum

    SciTech Connect

    Fang, Youxing; Jiang, Xueguang; Dai, Sheng; Sun, Xiao-Guang

    2015-01-01

    A new kind of ionic liquid based on complexation of dipropyl sulfide (DPS) and AlCl3 has been prepared. The equivalent concentration of AlCl3 in the ionic liquid is as high as 2.3 M. More importantly, it is highly fluidic and exhibits an ambient ionic conductivity of 1.25 x 10-4 S cm-1. This new ionic liquid can be successfully used as an electrolyte for electrodeposition of aluminum.

  16. Intramolecular coupling of BrO stretching vibrations in solid bromates, infrared and Raman spectroscopic studies on M(BrO3)2.6H2O (M = Mg, Co, Ni, Zn) and Ni(ClO3)2.6H2O.

    PubMed

    Lutz, H D; Suchanek, E

    2000-12-01

    Infrared and Raman spectra of the isostructural cubic halate hexahydrates M(BrO3)2.6H2O (M = Mg, Co, Ni, Zn) and Ni(ClO3)2.6H2O (space group, Pa3; Z = 4) are presented. They are discussed with respect to the strength of the O-H...OXO2 hydrogen bonds (hydrogen bond acceptor capability, synergetic effect) and the order of the BrO stretching modes. In the case of undistorted bromate ions, e.g. at C3 lattice sites, the order of the symmetric (v1) and asymmetric (v3) XO stretching modes is v1 < v3 as for ClO3- but in contrast to IO3- with v1 > v3. The relative order of v1 and v3 of halate ions is mainly governed by the specific masses of the halogen atoms and the angles of the XO3- ions. The latter decrease in the sequence ClO3- (107degrees) > BrO3-> IO3- (< 100 degrees). The Raman scattering intensities of the asymmetric XO stretching modes v3 of the title compounds are unusually low (< 5% those of v1). PMID:11145337

  17. Intramolecular coupling of BrO stretching vibrations in solid bromates, infrared and Raman spectroscopic studies on M(BrO 3) 2·6H 2O (M=Mg, Co, Ni, Zn) and Ni(ClO 3) 2·6H 2O

    NASA Astrophysics Data System (ADS)

    Lutz, H. D.; Suchanek, E.

    2000-12-01

    Infrared and Raman spectra of the isostructural cubic halate hexahydrates M(BrO 3) 2·6H 2O (M=Mg, Co, Ni, Zn) and Ni(ClO 3) 2·6H 2O (space group, Pa3¯; Z=4) are presented. They are discussed with respect to the strength of the OH···O XO 2 hydrogen bonds (hydrogen bond acceptor capability, synergetic effect) and the order of the BrO stretching modes. In the case of undistorted bromate ions, e.g. at C3 lattice sites, the order of the symmetric ( ν1) and asymmetric ( ν3) XO stretching modes is ν1< ν3 as for ClO 3- but in contrast to IO 3- with ν1> ν3. The relative order of ν1 and ν3 of halate ions is mainly governed by the specific masses of the halogen atoms and the angles of the XO 3- ions. The latter decrease in the sequence ClO 3- (107°)>BrO 3->IO 3- (<100°). The Raman scattering intensities of the asymmetric XO stretching modes ν3 of the title compounds are unusually low (<5% those of ν1).

  18. Electronic Structure of ClAlPc/pentacene/ITO Interfaces Studied by Using Soft X-ray Spectroscopy

    SciTech Connect

    Cho, Sang Wan; Lee, Sangho; Kim, Minsoo; Heo, Nari; Lee, Geunjeong; Smith, Kevin E.

    2014-12-06

    The interfacial electronic structure of a bilayer of chloroaluminum phthalocyanine (ClAlPc) and pentacene grown on indium tin oxide (ITO) has been studied using synchrotron-radiation-excited photoelectron spectroscopy. The energy difference between the highest occupied molecular orbital (HOMO) level of the pentacene layer and the lowest unoccupied molecular orbital (LUMO) level of the ClAlPc layer (E HOMO D - E LUMO A ) was determined and compared with that of C60/pentacene bilayers. The E HOMO D - E LUMO A of a heterojunction with ClAlPc was found to be 1.3 eV while that with C60 was 0.9 eV. This difference is discussed in terms of the difference in the ionization energy of each acceptor materials. We also obtained the complete energy level diagrams of both ClAlPc/pentacene/ITO and C60/pentacene/ITO.

  19. Accelerator mass spectrometry with fully stripped 26Al, 63Cl, 41Ca and (su59)Ni ions

    NASA Astrophysics Data System (ADS)

    Faestermann, H.; Kato, K.; Korschinek, G.; Krauthan, P.; Nolte, E.; Rühm, W.; Zerle, L.

    1990-04-01

    The detection system of accelerator mass spectrometry (AMS) with completely stripped ions of 26Al, 36Cl, 41Ca and 59Ni at the Munich accelerator laboratory and measurements with these ions are presented. Detection limits are given. The presented applications are: dating of groundwater of the Milk River aquifer and deduction of the neutron fluence and spectrum of the Hiroshima A-bomb.

  20. Mixed-Halide CH3 NH3 PbI3-x Xx (X=Cl, Br, I) Perovskites: Vapor-Assisted Solution Deposition and Application as Solar Cell Absorbers.

    PubMed

    Sedighi, Rahime; Tajabadi, Fariba; Shahbazi, Saeed; Gholipour, Somayeh; Taghavinia, Nima

    2016-08-01

    There have been recent reports on the formation of single-halide perovskites, CH3 NH3 PbX3 (X=Cl, Br, I), by means of vapor-assisted solution processing. Herein, the successful formation of mixed-halide perovskites (CH3 NH3 PbI3-x Xx ) by means of a vapor-assisted solution method at ambient atmosphere is reported. The perovskite films are synthesized by exposing PbI2 film to CH3 NH3 X (X=I, Br, or Cl) vapor. The prepared perovskite films have uniform surfaces with good coverage, as confirmed by SEM images. The inclusion of chlorine and bromine into the structure leads to a lower temperature and shorter reaction time for optimum perovskite film formation. In the case of CH3 NH3 PbI3-x Clx , the optimum reaction temperature is reduced to 100 °C, and the resulting phases are CH3 NH3 PbI3 (with trace Cl) and CH3 NH3 PbCl3 with a ratio of about 2:1. In the case of CH3 NH3 PbI3-x Brx , single-phase CH3 NH3 PbI2 Br is formed in a considerably shorter reaction time than that of CH3 NH3 PbI3 . The mesostructured perovskite solar cells based on CH3 NH3 PbI3 films show the best optimal power conversion efficiency of 13.5 %, whereas for CH3 NH3 PbI3-x Clx and CH3 NH3 PbI3-x Brx the best recorded efficiencies are 11.6 and 10.5 %, respectively. PMID:27124622

  1. A Br Isotopic Study of Australian Arid Playa Lakes and halophyte vegetation as a monitor of Br transport

    NASA Astrophysics Data System (ADS)

    Schaefer, B. F.

    2014-12-01

    Bromine possesses a chemistry broadly comparable to that of Cl and F, however its heavier mass and lower abundance results in slightly different behaviours in geochemical cycling. For example it is disproportionately enriched in sea water with respect to Cl. Br can be considered to be a "hydrophile" element, and hence its behaviour is in governed by that of water. It possesses two isotopes 79Br (50.686%) and 81Br (49.314%). This study has developed new chemical extraction, and most significantly, new mass spectrometric protocols for Br isotopes on silicates, evaporites and waters using N-TIMS methodologies. Existing CF-IRMS methodologies offer internal precision of ~0.3‰ (1SD, [1]), whereas N-TIMS measurements of laboratory HBr and seawater standards produce external reproducibility of <0.07‰ (1SD) over an 18 month period with internal precision typically <0.06‰ (1SD) on single analyses. This study presents the first high precision, N-TIMS isotopic data on playa lake evaporites, recording a >5‰ variation in solar system 81Br/79Br. Also presented is data from the analysis of the halophylic saltbush (sp Atriplex) adjacent to the lakes to constrain biological fractionation of Br isotopes. Variations of ~4‰ are observed between the lakes with a comparable shift for the leaves of the saltbush. [1] Shouaker-Stash et al., Anal. Chem, 77; p4027-4033, 2005.

  2. Erosion rate study at the Allchar deposit (Macedonia) based on radioactive and stable cosmogenic nuclides (26 Al, 36 Cl, 3 He, and 21 Ne)

    PubMed Central

    Cvetković, V.; Niedermann, S.; Pejović, V.; Amthauer, G.; Boev, B.; Bosch, F.; Aničin, I.; Henning, W. F.

    2016-01-01

    Abstract This paper focuses on constraining the erosion rate in the area of the Allchar Sb‐As‐Tl‐Au deposit (Macedonia). It contains the largest known reserves of lorandite (TlAsS2), which is essential for the LORanditeEXperiment (LOREX), aimed at determining the long‐term solar neutrino flux. Because the erosion history of the Allchar area is crucial for the success of LOREX, we applied terrestrial in situ cosmogenic nuclides including both radioactive (26Al and 36Cl) and stable (3He and 21Ne) nuclides in quartz, dolomite/calcite, sanidine, and diopside. The obtained results suggest that there is accordance in the values obtained by applying 26Al, 36Cl, and 21Ne for around 85% of the entire sample collection, with resulting erosion rates varying from several tens of m/Ma to ∼165 m/Ma. The samples from four locations (L‐8 CD, L1b/R, L1c/R, and L‐4/ADR) give erosion rates between 300 and 400 m/Ma. Although these localities reveal remarkably higher values, which may be explained by burial events that occurred in part of Allchar, the erosion rate estimates mostly in the range between 50 and 100 m/Ma. This range further enables us to estimate the vertical erosion rate values for the two main ore bodies Crven Dol and Centralni Deo. We also estimate that the lower and upper limits of average paleo‐depths for the ore body Centralni Deo from 4.3 Ma to the present are 250–290 and 750–790 m, respectively, whereas the upper limit of paleo‐depth for the ore body Crven Dol over the same geological age is 860 m. The estimated paleo‐depth values allow estimating the relative contributions of 205Pb derived from pp‐neutrino and fast cosmic‐ray muons, respectively, which is an important prerequisite for the LOREX experiment. PMID:27587984

  3. Erosion rate study at the Allchar deposit (Macedonia) based on radioactive and stable cosmogenic nuclides (26Al, 36Cl, 3He, and 21Ne)

    NASA Astrophysics Data System (ADS)

    Pavićević, M. K.; Cvetković, V.; Niedermann, S.; Pejović, V.; Amthauer, G.; Boev, B.; Bosch, F.; Aničin, I.; Henning, W. F.

    2016-02-01

    This paper focuses on constraining the erosion rate in the area of the Allchar Sb-As-Tl-Au deposit (Macedonia). It contains the largest known reserves of lorandite (TlAsS2), which is essential for the LORanditeEXperiment (LOREX), aimed at determining the long-term solar neutrino flux. Because the erosion history of the Allchar area is crucial for the success of LOREX, we applied terrestrial in situ cosmogenic nuclides including both radioactive (26Al and 36Cl) and stable (3He and 21Ne) nuclides in quartz, dolomite/calcite, sanidine, and diopside. The obtained results suggest that there is accordance in the values obtained by applying 26Al, 36Cl, and 21Ne for around 85% of the entire sample collection, with resulting erosion rates varying from several tens of m/Ma to ˜165 m/Ma. The samples from four locations (L-8 CD, L1b/R, L1c/R, and L-4/ADR) give erosion rates between 300 and 400 m/Ma. Although these localities reveal remarkably higher values, which may be explained by burial events that occurred in part of Allchar, the erosion rate estimates mostly in the range between 50 and 100 m/Ma. This range further enables us to estimate the vertical erosion rate values for the two main ore bodies Crven Dol and Centralni Deo. We also estimate that the lower and upper limits of average paleo-depths for the ore body Centralni Deo from 4.3 Ma to the present are 250-290 and 750-790 m, respectively, whereas the upper limit of paleo-depth for the ore body Crven Dol over the same geological age is 860 m. The estimated paleo-depth values allow estimating the relative contributions of 205Pb derived from pp-neutrino and fast cosmic-ray muons, respectively, which is an important prerequisite for the LOREX experiment.

  4. Using Cl/Br ratios and other indicators to assess potential impacts on groundwater quality from septic systems: A review and examples from principal aquifers in the United States

    USGS Publications Warehouse

    Katz, B.G.; Eberts, S.M.; Kauffman, L.J.

    2011-01-01

    A detailed review was made of chemical indicators used to identify impacts from septic tanks on groundwater quality. Potential impacts from septic tank leachate on groundwater quality were assessed using the mass ratio of chloride-bromide (Cl/Br), concentrations of selected chemical constituents, and ancillary information (land use, census data, well depth, soil characteristics) for wells in principal aquifers of the United States. Chemical data were evaluated from 1848 domestic wells in 19 aquifers, 121 public-supply wells in 6 aquifers, and associated monitoring wells in four aquifers and their overlying hydrogeologic units. Based on previously reported Cl/Br ratios, statistical comparisons between targeted wells (where Cl/Br ratios range from 400 to 1100 and Cl concentrations range from 20 to 100 mg/L) and non-targeted wells indicated that shallow targeted monitoring and domestic wells (0.5. mg/L) shallow groundwater from target domestic wells, relative to non-target wells (1.5. mg/L), corresponded to significantly higher potassium, boron, chloride, dissolved organic carbon, and sulfate concentrations, which may also indicate the influence of septic-tank effluent. Impacts on groundwater quality from septic systems were most evident for the Eastern Glacial Deposits aquifer and the Northern High Plains aquifer that were associated with the number of housing units using septic tanks, high permeability of overlying sediments, mostly oxic conditions, and shallow wells. Overall, little or no influence from septic systems were found for water samples from the deeper public-supply wells.The Cl/Br ratio is a useful first-level screening tool for assessing possible septic tank influence in water from shallow wells (<20 m) with the range of 400-1100. The use of this ratio would be enhanced with information on other chloride sources, temporal variability of chloride and bromide concentrations in shallow groundwater, knowledge of septic-system age and maintenance, and the

  5. Using Cl/Br ratios and other indicators to assess potential impacts on groundwater quality from septic systems: A review and examples from principal aquifers in the United States

    NASA Astrophysics Data System (ADS)

    Katz, Brian G.; Eberts, Sandra M.; Kauffman, Leon J.

    2011-02-01

    SummaryA detailed review was made of chemical indicators used to identify impacts from septic tanks on groundwater quality. Potential impacts from septic tank leachate on groundwater quality were assessed using the mass ratio of chloride-bromide (Cl/Br), concentrations of selected chemical constituents, and ancillary information (land use, census data, well depth, soil characteristics) for wells in principal aquifers of the United States. Chemical data were evaluated from 1848 domestic wells in 19 aquifers, 121 public-supply wells in 6 aquifers, and associated monitoring wells in four aquifers and their overlying hydrogeologic units. Based on previously reported Cl/Br ratios, statistical comparisons between targeted wells (where Cl/Br ratios range from 400 to 1100 and Cl concentrations range from 20 to 100 mg/L) and non-targeted wells indicated that shallow targeted monitoring and domestic wells (<20 m depth below land surface) had a significantly ( p < 0.05) higher median percentage of houses with septic tanks (1990 census data) than non-targeted wells. Higher ( p = 0.08) median nitrate-N concentration (3.1 mg/L) in oxic (dissolved oxygen concentrations >0.5 mg/L) shallow groundwater from target domestic wells, relative to non-target wells (1.5 mg/L), corresponded to significantly higher potassium, boron, chloride, dissolved organic carbon, and sulfate concentrations, which may also indicate the influence of septic-tank effluent. Impacts on groundwater quality from septic systems were most evident for the Eastern Glacial Deposits aquifer and the Northern High Plains aquifer that were associated with the number of housing units using septic tanks, high permeability of overlying sediments, mostly oxic conditions, and shallow wells. Overall, little or no influence from septic systems were found for water samples from the deeper public-supply wells. The Cl/Br ratio is a useful first-level screening tool for assessing possible septic tank influence in water from

  6. Theoretical investigation of the addition reaction of the aluminum chlorosilylenoid H2SiAlCl3 with ethylene.

    PubMed

    Zhang, Mingxia; Li, Wenzuo; Liu, Zhenbo; Li, Qingzhong; Cheng, Jianbo

    2016-07-01

    The addition reaction of the aluminum chlorosilylenoid H2SiAlCl3 with ethylene was investigated using the M06-2X and QCISD methods for the first time. The calculated results demonstrate that the addition reaction proceeds via two pathways: path I involves just one transition state, while path II involves two transition states. Path I is more feasible dynamically, as it has a lower barrier height than path II. The effect of the solvent CH2Cl2 was taken into consideration using the PCM model. The results indicated that the addition reaction is less likely to occur in CH2Cl2 solvent than in vacuum. This work has therefore highlighted a new pathway for the synthesis of silicon heterocyclic compounds. Graphical Abstract Relative energies (in kJ·mol(-1)) of the stationary points along the potential energy surfaces of the addition reaction of H2SiAlCl3 with C2H4 (values in parentheses were calculated in CH2Cl2 solvent). PMID:27271163

  7. Expanding Lone Pair···π Interactions to Nonaromatic Systems and Nitrogen Bases: Complexes of C2F3X (X = F, Cl, Br, I) and TMA-d9.

    PubMed

    Geboes, Yannick; De Proft, Frank; Herrebout, Wouter A

    2015-06-01

    The molecular electrostatic potential surface of unsaturated, locally electron-deficient molecules shows a positive region perpendicular to (a part of) the molecular framework. In recent years it has been shown both theoretically and experimentally that molecules are able to form noncovalent interactions with Lewis bases through this π-hole. When studying unsaturated perfluorohalogenated molecules containing a higher halogen atom, a second electropositive region is also observed near the halogen atom. This region, often denoted as a σ-hole, allows the molecules to interact with Lewis bases and form a halogen bond. To experimentally characterize the competition between both these noncovalent interactions, Fourier transform infrared and Raman spectra of liquefied noble gas solutions containing perfluorohalogenated ethylene derivatives (C2F3X; X = F, Cl, Br, or I) and trimethylamine(-d9) were investigated. Analysis of the spectra shows that in mixed solutions of trimethylamine(-d9) and C2F4 or C2F3Cl lone pair···π complex is present, while evidence for halogen-bonded complex is found in solutions containing trimethylamine(-d9) and C2F3Cl, C2F3Br, or C2F3I. For all species observed, complexation enthalpies were determined, the values varying between -4.9(1) and -24.4 kJ mol(-1). PMID:25924188

  8. Tin(IV) halide complexes of AsPh3) The structures of trans-SnCl4(AsPh3)2 and SnBr4(AsPh3).AsPh3.

    PubMed

    Mahon, Mary F; Moldovan, Natalia L; Molloy, Kieran C; Muresan, Alexandra; Silaghi-Dumitrescu, Ioan; Silaghi-Dumitrescu, Luminita

    2004-12-01

    The structures of two 1 : 2 adducts between tin(IV) halides and AsPh(3) have been determined. SnCl(4)(AsPh(3))(2) adopts a six-coordinate geometry at tin in which the two organoarsine donors are mutually trans. In contrast, SnBr(4)(AsPh(3))(2) is five-coordinate at tin and only one arsine is directly bonded to the metal, in an axial site of the trigonal bipyramid. The second AsPh(3) group has a close contact with the axially bound bromine [As...Br: 3.567(3) angstroms], which is a unique structural variation that depicts an intermediate in a halogen-transfer reaction between Group 14 and Group 15 elements. AACVD using SnCl(4)(AsPh(3))(2) generates a film containing SnO(2) and a second crystalline material which is possibly SnCl(2), but which contains no arsenic. PMID:15558128

  9. Molecular Motions in (CH3)3XCl, X = Sn and Pb. NMR Investigations and Crystal Structure Study of (CH3)3PbCl and CH3SnBr3

    NASA Astrophysics Data System (ADS)

    Zhang, Da; Dou, Shi-Qi; Weiss, Alarich

    1991-04-01

    The molecular motion in (CH3)3XCl, X = Sn and Pb has been investigated by measurement of the second moment M2(1H) as function of temperature in the range 95 < T,/K<345. The methyl groups in both compounds rotate freely over the whole temperature range studied. In (CH3)3SnCl the C'3-rotation of (CH3)3Sn-group about the Sn CI axis sets in above 273 K. To explain the NMR and INS results, the crystal structures of (CH3)3PbCl and CH3SnBr3 were determined by single X-ray diffraction. (CH3)3PbCl crystallizes in a monoclinic space group C32-C2, a = 1276.7(3) pm, b = 982.3(3) pm, c = 547.0(2) pm, ß = 91.12(1)°; Z = 4, R = 0.035. CH3SnBr3 crystallizes in an orthorhombic space group D162h-Pnma, a = 643.0(3) pm, b= 1005.3(4) pm, c= 1148.0(4) pm; Z = 4, R =0.057

  10. Behavior of Halogen Bonds of the Y-X⋅⋅⋅π Type (X, Y=F, Cl, Br, I) in the Benzene π System, Elucidated by Using a Quantum Theory of Atoms in Molecules Dual-Functional Analysis.

    PubMed

    Sugibayashi, Yuji; Hayashi, Satoko; Nakanishi, Waro

    2016-08-18

    The nature of halogen bonds of the Y-X-✶-π(C6 H6 ) type (X, Y=F, Cl, Br, and I) have been elucidated by using the quantum theory of atoms in molecules (QTAIM) dual-functional analysis (QTAIM-DFA), which we proposed recently. Asterisks (✶) emphasize the presence of bond-critical points (BCPs) in the interactions in question. Total electron energy densities, Hb (rc ), are plotted versus Hb (rc )-Vb (rc )/2 [=(ħ(2) /8m)∇(2) ρb (rc )] for the interactions in QTAIM-DFA, in which Vb (rc ) are potential energy densities at the BCPs. Data for perturbed structures around fully optimized structures were used for the plots, in addition to those of the fully optimized ones. The plots were analyzed by using the polar (R, θ) coordinate for the data of fully optimized structures with (θp , κp ) for those that contained the perturbed structures; θp corresponds to the tangent line of the plot and κp is the curvature. Whereas (R, θ) corresponds to the static nature, (θp , κp ) represents the dynamic nature of the interactions. All interactions in Y-X-✶-π(C6 H6 ) are classified by pure closed-shell interactions and characterized to have vdW nature, except for Y-I-✶-π(C6 H6 ) (Y=F, Cl, Br) and F-Br-✶-π(C6 H6 ), which have typical hydrogen-bond nature without covalency. I-I-✶-π(C6 H6 ) has a borderline nature between the two. Y-F-✶-π(C6 H6 ) (Y=Br, I) were optimized as bent forms, in which Y-✶-π interactions were detected. The Y-✶-π interactions in the bent forms are predicted to be substantially weaker than those in the linear F-Y-✶-π(C6 H6 ) forms. PMID:27124373

  11. New amide-chloride phases in the Li-Al-N-H-Cl system: formation and hydrogen storage behaviour.

    PubMed

    Fernández Albanesi, L; Garroni, S; Enzo, S; Gennari, F C

    2016-04-01

    New amide-chloride phases were successfully synthesized by mechanical milling of the LiNH2-AlCl3 mixture at a molar ratio of 1 : 0.11 and further heating at 150 °C under argon (0.1 MPa) or under hydrogen pressure (0.7 MPa). Powder X-ray diffraction measurements as a function of milling time increase revealed that the milling of the LiNH2-0.11AlCl3 mixture results in the formation of a FCC solid solution with an excess of LiNH2. Subsequent heating of the LiNH2-0.11AlCl3 sample ball milled for 5 hours at 150 °C under argon or under hydrogen induces the appearance of an amide-chloride phase isostructural with cubic Li4(NH2)3Cl. This Li-Al-N-H-Cl phase transforms progressively into the trigonal phase after prolonged heating at 300 °C under hydrogen pressure. The thermal behaviour of the amide-chloride without and with LiH addition displays dissimilar decomposition pathways. The decomposition of amide-chloride alone involves the formation of ammonia and hydrogen from 120 to 300 °C. Conversely, the amide-chloride material in the presence of LiH only releases hydrogen avoiding the emission of ammonia. The resultant material is able to be rehydrogenated under moderate conditions (300 °C, 0.7 MPa H2), providing a new reversible hydrogen storage system. PMID:26939035

  12. The binding of platinum hexahalides (Cl, Br and I) to hen egg-white lysozyme and the chemical transformation of the PtI{sub 6} octahedral complex to a PtI{sub 3} moiety bound to His15

    SciTech Connect

    Tanley, Simon W. M.; Starkey, Laurina-Victoria; Lamplough, Lucinda; Kaenket, Surasek; Helliwell, John R.

    2014-08-29

    The platinum hexahalides have an octahedral arrangement of six halogen atoms bound to a Pt centre, thus having an octahedral shape that could prove to be useful in interpreting poor electron-density maps. In a detailed characterization, PtI{sub 6} chemically transformed to a square-planar PtI{sub 3} complex bound to the N{sup δ} atom of His15 of HEWL was also observed, which was not observed for PtBr{sub 6} or PtCl{sub 6}. This study examines the binding and chemical stability of the platinum hexahalides K{sub 2}PtCl{sub 6}, K{sub 2}PtBr{sub 6} and K{sub 2}PtI{sub 6} when soaked into pre-grown hen egg-white lysozyme (HEWL) crystals as the protein host. Direct comparison of the iodo complex with the chloro and bromo complexes shows that the iodo complex is partly chemically transformed to a square-planar PtI{sub 3} complex bound to the N{sup δ} atom of His15, a chemical behaviour that is not exhibited by the chloro or bromo complexes. Each complex does, however, bind to HEWL in its octahedral form either at one site (PtI{sub 6}) or at two sites (PtBr{sub 6} and PtCl{sub 6}). As heavy-atom derivatives of a protein, the octahedral shape of the hexahalides could be helpful in cases of difficult-to-interpret electron-density maps as they would be recognisable ‘objects’.

  13. Synthesis, characterization and sorption properties of functionalized Cr-MIL-101-X (X=-F, -Cl, -Br, -CH3, -C6H4, -F2, -(CH3)2) materials

    NASA Astrophysics Data System (ADS)

    Buragohain, Amlan; Couck, Sarah; Van Der Voort, Pascal; Denayer, Joeri F. M.; Biswas, Shyam

    2016-06-01

    Four existing and three new functionalized chromium terephthalates having MIL-101 topology and denoted as Cr-MIL-101-X (existing ones with X=-F, 1-F; -Cl, 2-Cl; -Br, 3-Br; -CH3, 4-CH3; new ones with X=-C6H4, 5-C6H4; -F2, 6-F2, -(CH3)2, 7-(CH3)2) were synthesized under hydrothermal conditions. All the materials except 5-C6H4 could be prepared by a general synthetic route, in which the mixtures of CrO3, H2BDC-X (BDC=1,4-benzenedicarboxylate) linkers, conc. HCl and water with a molar ratio of 1:1:3.9:222.2 were reacted at 180 °C for 144 h. Compared to the 144 h of synthesis time, three of the compounds, namely 1-Cl, 2-Br and 5-C6H4, could be prepared in much shorter reaction times (12-18 h at 180-210 °C). The materials possess high thermal stability up to 270-300 °C in an air atmosphere. The activated compounds exhibit significant porosity (SBET range: 1273-2135 m2 g-1). At 0 °C and 1 bar, the CO2 adsorption capacities of the compounds fall in the 1.7-2.9 mmol g-1 range. Compounds 1-F and 6-F2 showed enhanced CO2 uptake values compared to parent Cr-MIL-101. The benzene adsorption capacities of the compounds lie in the range of 66.2-139.5 molecules per unit cell at 50 °C and p/p0=0.35. The increased benzene uptake value of 1-F compared to un-functionalized Cr-MIL-101 and 4-CH3 suggests that the fluorination has induced more hydrophobicity in Cr-MIL-101 as compared to the methylation.

  14. Competition of C(sp²)-X···O halogen bonding and lone pair···π interactions: cryospectroscopic study of the complexes of C₂F₃X (X = F, Cl, Br, and I) and dimethyl ether.

    PubMed

    Geboes, Yannick; Nagels, Nick; Pinter, Balazs; De Proft, Frank; Herrebout, Wouter A

    2015-03-19

    Inspection of the electrostatic potential of C2F3X (X = F, Cl, Br, and I) revealed a second electropositive region in the immediate vicinity of the C═C double bond apart from the σ hole of chlorine, bromine, and iodine, leading to C(sp(2))-X···Y halogen bonding, through which complexes stabilized by so-called lone pair···π interactions can be formed. Consequently, the experimental studies for the complexes of dimethyl ether with C2F3X (X = F, Cl, Br, and I) not only allowed one to experimentally characterize and rationalize the effects of hybridization on halogen bonding but, for the first time, also allowed the competition of C-X···Y halogen bonding and lone pair···π interactions to be studied at thermodynamic equilibrium. Analysis of the infrared and Raman spectra reveals that in the cryosolutions of dimethyl ether and C2F3I, solely the halogen-bonded complex is present, whereas C2F3Br and C2F3Cl give rise to a lone pair···π bonded complex as well as a halogen-bonded complex. Mixtures of dimethyl ether with C2F4 solely yield a lone pair···π bonded complex. The experimentally derived complexation enthalpies for the halogen bonded complexes are found to be -14.2(5) kJ mol(-1) for C2F3I·DME and -9.3(5) kJ mol(-1) for C2F3Br·DME. For the complexes of C2F3Cl with dimethyl ether, no experimental complexation enthalpy could be obtained, whereas the C2F4·DME complex has a complexation enthalpy of -5.5(3) kJ mol(-1). The observed trends have been rationalized with the aid of an interaction energy decomposition analysis (EDA) coupled to a Natural Orbital for Chemical Valence (NOCV) analysis and also using the noncovalent interaction index method. PMID:25390877

  15. Factors influencing ALS-resistant gene transfer from CL (tm) rice to red rice.

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Red rice (Oryza sativa L.) is hard to control due to its genetic similarity to cultivated rice. Herbicide-resistant Clearfield ™ (CL) rice now offers an excellent option for red rice control. However, sustainability of CL technology at the producers’ level will be dictated by various factors. Promi...

  16. Reply to ''Comment on the 'Energy level analysis of Np/sup 3 +/:LaCl/sub 3/ and Np/sup 3 +/:LaBr/sub 3/' ''

    SciTech Connect

    Carnall, W.T.; Crosswhite, H.; Crosswhite, H.M.; Hessler, J.P.; Edelstein, N.; Conway, J.G.; Shalimoff, G.V.; Sarup, R.

    1981-10-01

    The crystal field parameters in Np/sup 3 +/:Lad/sub 3/ and Np/sup 3 +/:LaBr/sub 3/ are discussed. The arguments of Poon and Newman, regarding the scaling of the crystal field parameters are aknowdged as being correct.(AIP)

  17. Treatment of electrochemical cell components with lithium tetrachloroaluminate (LiAlCl.sub.4) to promote electrolyte wetting

    DOEpatents

    Eberhart, James G.; Battles, James E.

    1980-01-01

    Electrochemical cell components such as interelectrode separators, retaining screens and current collectors are contacted with lithium tetrachloroaluminate prior to contact with molten electrolytic salt to improve electrolyte wetting. The LiAlCl.sub.4 can be applied in powdered, molten or solution form but, since this material has a lower melting point than the electrolytic salt used in high-temperature cells, the powdered LiAlCl.sub.4 forms a molten flux prior to contact by the molten electrolyte when both materials are initially provided in solid form. Components of materials such as boron nitride and other materials which are difficult to wet with molten salts are advantageously treated by this process.

  18. Conversion of glucose into furans in the presence of AlCl3 in an ethanol-water solvent system.

    PubMed

    Yang, Yu; Hu, Changwei; Abu-Omar, Mahdi M

    2012-07-01

    Glucose was converted into furans (5-hydroxymethylfurfural and 5-ethoxymethylfurfural) in the presence of AlCl(3) in an ethanol-water solvent system. The system showed high activity for the conversion of glucose into furans but low activity for the subsequent formation of LAs (levulinic acid and ethyl levulinate). High furans yield of 57% with low LAs yield of 11% can be obtained at 160 °C within 15 min. Glucose-based disaccharides (sucrose, maltose and cellobiose) and polysaccharides (starch but not cellulose) can also be converted to furans effectively under the same condition. AlCl(3) can be used to prepare furans from biomass-derived compounds in ethanol-water, a green solvent system. PMID:22609675

  19. AlCl3-Catalyzed Ring-Expansion Cascades of Bicyclic Cyclobutenamides Involving Highly Strained Cis,Trans-Cycloheptadienone Intermediates

    PubMed Central

    Wang, Xiao-Na; Krenske, Elizabeth H.; Johnston, Ryne C.; Houk, K. N.; Hsung, Richard P.

    2015-01-01

    We report the first experimental evidence for the generation of highly strained cis,trans-cycloheptadienones by electrocyclic ring opening of 4,5-fused cyclobutenamides. In the presence of AlCl3, the cyclobutenamides rearrange to [2.2.1]-bicyclic ketones; DFT calculations provide evidence for a mechanism involving torquoselective 4π-electrocyclic ring opening to a cis,trans-cycloheptadienone followed by a Nazarov-like recyclization and a 1,2-alkyl shift. Similarly, 4,6-fused cyclobutenamides undergo AlCl3-catalyzed rearrangements to [3.2.1]-bicyclic ketones through cis,trans-cyclooctadienone intermediates. The products can be further elaborated via facile cascade reactions to give complex tri- and tetracyclic molecules. PMID:25895058

  20. Cl, P2O5, U and Br associated with mineral separates from a low and a high Ti mare basalt

    NASA Technical Reports Server (NTRS)

    Jovanovic, S.; Reed, G. W., Jr.

    1980-01-01

    Low Ti basalt 12040 and high Ti basalt 75055 have approximately the same Cl/P2O5 ratio; the Cl is that remaining after a hot water leach. Pyroxene, plagioclase and ilmenite minerals separated from the basalts also tend to have this same Cl/P2O5 ratio. This is evidence that these major minerals do not control the ratio since Cl and P would not be expected to partition to the same extent into each mineral. Olivine appears to be a special case. It is proposed that the grains measured contained inclusions with leachable and P2O5-related Cl. Dilute acid leaches of whole rock and separated minerals have the same or nearly the same Cl/P2O5 ratios as the residual samples. Apatite and whitlockite were probably the phases leached. They must be constituents of the mesostasis and are present as microminerals or coatings on major mineral grains. The acid leach results imply little or no partition of Cl and P2O5 into major minerals.

  1. Preparation of Al-La Master Alloy by Thermite Reaction in NaF-NaCl-KCl Molten Salt

    NASA Astrophysics Data System (ADS)

    Jang, Poknam; Li, Hyonmo; Kim, Wenjae; Wang, Zhaowen; Liu, Fengguo

    2015-05-01

    A NaF-NaCl-KCl ternary system containing La2O3 was investigated for the preparation of Al-La master alloy by the thermite reaction method. The solubility of La2O3 in NaF-NaCl-KCl molten salt was determined by the method of isothermal solution saturation. Inductively coupled plasma-optical emission spectroscopy and x-ray diffraction (XRD) analyses were used to consider the content of La2O3 in molten salt and the supernatant composition of molten salt after dissolution of La2O3, respectively. The results showed that the content of NaF had a positive influence on the solubility of La2O3 in NaF-NaCl-KCl molten salts, and the solubility of La2O3 could reach 8.71 wt.% in molten salts of 50 wt.%NaF-50 wt.% (44 wt.%NaCl + 56 wt.%KCl). The XRD pattern of cooling molten salt indicated the formation of LaOF in molten salt, which was probably obtained by the reaction between NaF and La2O3. The kinetic study showed that the thermite reaction was in accord with a first-order reaction model. The main influence factors on La content in the Al-La master alloy product, including molten salt composition, amount of Al, concentration of La2O3, stirring, reduction time and temperature, were investigated by single-factor experimentation. The content of La in the Al-La master alloy could be reached to 10.1 wt.%.

  2. High-Altitude Aircraft and Balloon-Borne Observations of OH, HO2, ClO, BrO, NO2, ClONO2, ClOOCl, H2O, and O3 in Earth`s Stratosphere. Progress report, 1 January-31 December 1995

    SciTech Connect

    Anderson, J.G.

    1996-02-01

    Research executed over calendar year 1995 focused on three primary objectives. The first is the dissection of free radical catalytic cycles. The objective is to determine both the mechanisms for ozone loss in the lower stratosphere, by establishing the hierarchy of rate limiting steps in the nitrogen, halogen, and hydrogen cycles, and to determine the response of the stratosphere to changing levels of NO(sub x), aerosols, etc., by directly observing the partial derivatives of the constituent concentrations. Observations are made from the NASA ER-2 aircraft. The second is to incorporate fast-response water vapor measurements into the ER-2 payload, to obtain high spatial resolution data on water vapor. This is a particularly powerful technique for diagnosing dynamical behavior of the stratosphere when combined with the rapid time-response CO2 observations available on the ER-2. The third objective is the development of a new instrument designed for the ER-2 superpod, which will observe ClONO2 in situ for the first time, and also will observe ClO, BrO, and NO2 simultaneously. The authors present the progress made in each category.

  3. Electrochemical properties of the solvent SbCl/sub 3/-AlCl/sub 3/-N-(1-Butyl)Pyridinium chloride and electrochemical and spectroelectrochemical studies of arene solutes

    SciTech Connect

    Chapman, D.M.; Smith, G.P.; Soerlie, M.; Petrovic, C.; Mamantov, G.

    1984-07-01

    Physical and electrochemical properties are reported for SbCl/sub 3/-AlCl/sub 3/-N-(1-butyl)pyridinium chloride (BPCl) mixtures that are liquid at ambient temperatures; and studies of the electrogeneration and open-circuit decay of some arene radical cations, both in this medium and in SbCl/sub 3/-KCl at elevated temperatures, are described. Specific conductivities, densities, and viscosities of various compositions of SbCl/sub 3/-AlCl/sub 3/-BPCl were measured over the temperature range 24-100/sup 0/C. For a potentiometric titration between the compositions 60:18:22 and 60:22:18 with SbCl/sub 3/ fixed at 60 mole %, the potential of the Sb(III)/Sb(O) couple increased about 0.43V at 27/sup 0/C. The persistence of a series of different arene radical cations in SbCl/sub 3/-BP(AlCl)/sub 4/ is compared with their persistance in molten SbCl/sub 3/-KCl.

  4. Preparation and Electrochemical Characterization of Aluminium Liquid Battery Cells With Two Different Electrolytes (NaCl-BaCl2-AlF3-NaF and LiF-AlF3-BaF2).

    PubMed

    Napast, Viktor; Moškon, Jože; Homšak, Marko; Petek, Aljana; Gaberšček, Miran

    2015-01-01

    The possibility of preparation of operating rechargeable liquid battery cells based on aluminium and its alloys is systematically checked. In all cases we started from aluminium as the negative electrode whereas as the positive electrode three different metals were tested: Pb, Bi and Sn. Two types of electrolytes were selected: Na(3)AlF(6) -AlF(3) - BaCl(2) - NaCl and Li(3)AlF(3) - BaF(2). We show that some of these combinations allowed efficient separation of individual liquid layers. The cells exhibited expected voltages, relatively high current densities and could be charged and discharged several times. The capacities were relatively low (120 mAh in the case of Al-Pb system), mostly due to unoptimised cell construction. Improvements in various directions are possible, especially by hermetically sealing the cells thus preventing salt evaporation. Similarly, solubility of aluminium in alloys can be increased by optimising the composition of positive electrode. PMID:26680707

  5. Heterometallic aggregates of copper(I) with metalloligand Sn(edt)2 (edt = ethane-1,2-dithiolate): syntheses and structures of [Sn(edt)2Cl(mu-I)(mu3-I)(CuPPh3)3], [Sn(edt)2(mu-Br)2(mu3-Br)2(CuPPh3)4], and [{Sn(edt)2}3(mu-OH)3Cu5(PPh3)8][PF6]2.

    PubMed

    Han, Yan-Gong; Xu, Chao; Duan, Taike; Wu, Fang-Hui; Zhang, Qian-Feng; Leung, Wa-Hung

    2009-09-21

    The treatment of a slurry of an equimolar mixture of [Sn(edt)(2)] (edt = ethane-1,2- dithiolate) and [Et(4)N]Cl.xH(2)O with CuI in the presence of PPh(3) gave a tetranuclear compound, [Sn(edt)(2)Cl(mu-I)(mu(3)-I)(CuPPh(3))(3)] (1), which consists of a rectangular-pyramidal [Sn(edt)(2)Cl](-) moiety ligated by three [Cu(PPh(3))](+) fragments via the sulfur atoms of the edt(2-) ligands. The treatment of a slurry of [Sn(edt)(2)] and excess [Et(4)N]Br with [Cu(MeCN)(4)][PF(6)] in the presence of PPh(3) afforded a pentanuclear compound, [Sn(edt)(2)(mu-Br)(2)(mu(3)-Br)(2)(CuPPh(3))(4)] (2), which comprises two [(CuPPh(3))(2)(mu-Br)](+) fragments symmetrically ligating an octahedral trans-[Sn(edt)(2)Br(2)](2-) moiety via the sulfur and bromide atoms. Reaction of [Sn(edt)(2)] with [Cu(MeCN)(4)][PF(6)] and PPh(3) in a mixed MeCN/CH(2)Cl(2) solution yielded a novel octanuclear compound, [{Sn(edt)(2)}(3)(mu-OH)(3)Cu(5)(PPh(3))(8)][PF(6)](2) (3), which may be described as a triangular [{Sn(edt)(2)}(3)(mu-OH)(3)](3-) core chelated by three [Cu(PPh(3))(2)](+) species and capped by two [Cu(PPh(3))](+) species. The luminescent properties of compounds 1, 2, and 3 were investigated in a CH(2)Cl(2) solution at room temperature. Upon excitation at lambda > 360 nm, these compounds are luminescent in CH(2)Cl(2) solution with emissions having maxima at 422, 515, and 494 nm, respectively. PMID:19746999

  6. Communication: Probing the entrance channels of the X + CH{sub 4}{yields} HX + CH{sub 3} (X = F, Cl, Br, I) reactions via photodetachment of X{sup -}-CH{sub 4}

    SciTech Connect

    Cheng Min; Feng Yuan; Du Yikui; Zhu Qihe; Zheng Weijun; Czako, Gabor; Bowman, Joel M.

    2011-05-21

    The entrance channel potentials of the prototypical polyatomic reaction family X + CH{sub 4}{yields} HX + CH{sub 3} (X = F, Cl, Br, I) are investigated using anion photoelectron spectroscopy and high-level ab initio electronic structure computations. The pre-reactive van der Waals (vdW) wells of these reactions are probed for X = Cl, Br, I by photodetachment spectra of the corresponding X{sup -}-CH{sub 4} anion complex. For F-CH{sub 4}, a spin-orbit splitting ({approx}1310 cm{sup -1}) much larger than that of the F atom (404 cm{sup -1}) was observed, in good agreement with theory. This showed that in the case of the F-CH{sub 4} system the vertical transition from the anion ground state to the neutral potentials accesses a region between the vdW valley and transition state of the early-barrier F + CH{sub 4} reaction. The doublet splittings observed in the other halogen complexes are close to the isolated atomic spin-orbit splittings, also in agreement with theory.

  7. Three tetracoordinate Co(II) complexes [Co(biq)X2] (X = Cl, Br, I) with easy-plane magnetic anisotropy as field-induced single-molecule magnets.

    PubMed

    Smolko, L; Černák, J; Dušek, M; Miklovič, J; Titiš, J; Boča, R

    2015-10-28

    Three mononuclear complexes [Co(biq)X2] (biq = 2,2'-biquinoline; X = Cl, Br, I) were prepared by a solvothermal method and characterized by single-crystal X-ray diffraction. In all three complexes the Co(ii) atom is tetrahedrally coordinated by one biq ligand bonded in a chelate manner and two halogenido ligands. Hydrogen bonding interactions (C-HX) along with the π-π interactions contribute to the stability of the formed packing. Magnetic measurements as well as ab initio calculations revealed that the complexes possess a sizable easy-plane magnetic anisotropy (D > 0). They display a superparamagnetic behaviour in an applied external field that culminates between BDC = 0.2-0.3 T. Two relaxation processes are observed; the faster can be analysed in terms of the direct and Orbach processes yielding U/kB = 42.6 K and τ0 = 1.9 × 10(-10) s for X = Cl, U/kB = 39.6 K and τ0 = 1.2 × 10(-10) s for X = Br and U/kB = 57.0 K and τ0 = 3.2 × 10(-13) s for X = I at BDC = 0.2 T. PMID:26391615

  8. A cryospectroscopic infrared and Raman study of the CX⋯π halogen bonding motif: complexes of the CF3Cl, CF3Br, and CF3I with ethyne, propyne and 2-butyne.

    PubMed

    Nagels, Nick; Herrebout, Wouter A

    2015-02-01

    Experimental information on the C-X⋯π halogen bonding motif was obtained by studying the formation of molecular complexes of CF3Cl, CF3Br and CF3I with ethyne, propyne and 2-butyne in liquid krypton, using FTIR and Raman spectroscopy. For CF3Br, experimental evidence was found for the formation of 1:1 complexes with propyne and 2-butyne only, while for CF3I spectroscopic features confirming the existence of the halogen bonded complexes were observed for ethyne, propyne and 2-butyne. In addition, at higher concentrations of CF3I and 2-butyne, weak absorptions due to a 2:1 complex were also observed. The experimental complexation enthalpies, obtained by using spectra recorded at temperatures between 120 K and 140 K, are -5.9(3) kJ mol(-1) for CF3I.ethyne, -5.6(3) kJ mol(-1) for CF3Br.propyne, -8.1(2) kJ mol(-1) for CF3I.propyne, -7.3(2) kJ mol(-1) for CF3Br.2-butyne, -10.9(2) kJ mol(-1) for CF3I.2-butyne and -20.9(7) kJ mol(-1) for (CF3I)2.2-butyne. The experimental study is supported by theoretical data obtained from ab initio calculations at the MP2/aug-cc-pVDZ(-PP) and MP2/aug-cc-pVTZ(-PP) levels, and Monte Carlo Free Energy Perturbation (MC-FEP) simulations. The experimental and theoretical values on the C-X⋯π halogen-bonding motifs studied are compared with previously reported data for the complexes with ethene and propene and with preliminary results obtained for benzene and toluene. PMID:24910010

  9. A cryospectroscopic infrared and Raman study of the Csbnd X⋯π halogen bonding motif: Complexes of the CF3Cl, CF3Br, and CF3I with ethyne, propyne and 2-butyne

    NASA Astrophysics Data System (ADS)

    Nagels, Nick; Herrebout, Wouter A.

    2015-02-01

    Experimental information on the Csbnd X⋯π halogen bonding motif was obtained by studying the formation of molecular complexes of CF3Cl, CF3Br and CF3I with ethyne, propyne and 2-butyne in liquid krypton, using FTIR and Raman spectroscopy. For CF3Br, experimental evidence was found for the formation of 1:1 complexes with propyne and 2-butyne only, while for CF3I spectroscopic features confirming the existence of the halogen bonded complexes were observed for ethyne, propyne and 2-butyne. In addition, at higher concentrations of CF3I and 2-butyne, weak absorptions due to a 2:1 complex were also observed. The experimental complexation enthalpies, obtained by using spectra recorded at temperatures between 120 K and 140 K, are -5.9(3) kJ mol-1 for CF3I.ethyne, -5.6(3) kJ mol-1 for CF3Br.propyne, -8.1(2) kJ mol-1 for CF3I.propyne, -7.3(2) kJ mol-1 for CF3Br.2-butyne, -10.9(2) kJ mol-1 for CF3I.2-butyne and -20.9(7) kJ mol-1 for (CF3I)2.2-butyne. The experimental study is supported by theoretical data obtained from ab initio calculations at the MP2/aug-cc-pVDZ(-PP) and MP2/aug-cc-pVTZ(-PP) levels, and Monte Carlo Free Energy Perturbation (MC-FEP) simulations. The experimental and theoretical values on the Csbnd X⋯π halogen-bonding motifs studied are compared with previously reported data for the complexes with ethene and propene and with preliminary results obtained for benzene and toluene.

  10. C-X···π halogen and C-H···π hydrogen bonding: interactions of CF3X (X = Cl, Br, I or H) with ethene and propene.

    PubMed

    Hauchecorne, Dieter; Nagels, Nick; van der Veken, Benjamin J; Herrebout, Wouter A

    2012-01-14

    Using FTIR and Raman spectroscopy, the formation of halogen bonded complexes of the trifluorohalomethanes CF(3)Cl, CF(3)Br and CF(3)I with ethene and propene dissolved in liquid argon has been investigated. For CF(3)Br and CF(3)I, evidence was found for the formation of C-X···π halogen bonded 1:1 complexes. At a higher ratio of CF(3)I/propene, weak absorptions due to a 2:1 complex were also observed. Using spectra recorded at different temperatures, the complexation enthalpies for the complexes were determined to be -5.3(2) kJ mol(-1) for CF(3)Br·ethene, -7.5(2) kJ mol(-1) for CF(3)I·ethene, -5.6(1) kJ mol(-1) for CF(3)Br·propene, -8.8(1) kJ mol(-1) for CF(3)I·propene and -16.5(6) kJ mol(-1) for (CF(3)I·)(2)propene. The complexation enthalpies of the hydrogen bonded counterparts, with CF(3)H as the Lewis acid, were determined to be -4.6(4) kJ mol(-1) for CF(3)H·ethene and -5.1(2) kJ mol(-1) for CF(3)H·propene. For both hydrogen bonded complexes, a blue shift, by +4.8 and +4.0 cm(-1), respectively, was observed for the C-H stretching mode. The results from the cryospectroscopic study are compared with ab initio calculations at the MP2/aug-cc-pVDZ(-PP) level. PMID:22089664

  11. Exploring the C-X…π halogen bonding motif: an infrared and Raman study of the complexes of CF₃X (X = Cl, Br and I) with the aromatic model compounds benzene and toluene.

    PubMed

    Nagels, Nick; Hauchecorne, Dieter; Herrebout, Wouter A

    2013-01-01

    The formation of halogen bonded complexes formed between the trifluorohalomethanes CF₃Cl, CF₃Br and CF₃I and the Lewis bases benzene and toluene at temperatures below 150K was investigated using FTIR and Raman spectroscopy. Experiments using liquid krypton as solvent show that for both CF₃Br and CF₃I substantial fractions of the monomers can be involved in 1:1 complexes. In addition, weak absorptions illustrating the formation of 2:1 complexes between CF₃I and benzene are observed. Using spectra recorded at temperatures between 120 and 140 K, observed information on the relative stability was obtained for all complexes by determining the complexation enthalpies in solution. The resulting values for CF₃Br.benzene, CF₃I.benzene and (CF₃I)₂.benzene are -6.5(3), -7.6(2) and -14.5(9) kJ mol⁻¹. The values for CF₃Br.toluene and CF₃I.toluene are -6.2(5) and -7.4(5) kJ mol⁻¹. The experimental complexation enthalpies are compared with theoretical data obtained by combining results from MP2/aug-cc-pVDZ(-PP) and MP2/aug-cc-pVTZ(-PP) ab initio calculations, from statistical thermodynamical calculations and from Monte Carlo Free Energy Perturbation simulations. The data are also compared with results derived for other C-X···π halogen bonded complexes involving unsaturated Lewis bases such as ethene and ethyne. PMID:23752468

  12. The single-electrode Peltier heats of Li-Al alloy electrodes in LiCl-KCl eutectic system

    SciTech Connect

    Amezawa, Koji; Ito, Yasuhiko; Tomii, Yoichi )

    1994-11-01

    This paper presents the single-electrode Peltier heat of cathodic (or anodic) reaction of Li-Al alloy electrode in a coexisting phase state, or an intermetallic compound phase state estimated by thermoelectric-power measurement. The thermoelectric-power measurements of Li-Al alloys in various coexisting phase states were carried out with both potentiometric and potential-sweep methods in the LiCl-KCl eutectic system between 673 and 843 K. The values of the thermoelectric power of Li-Al alloys calculated by using thermodynamic literature data were in good agreement with those obtained by experiment. The single-electrode Peltier heat changes drastically with change of its phase state, and it was found that the formation reactions of [beta] (Li[sub 0.5]Al[sub 0.5]) and [gamma] (Li[sub 0.6]Al[sub 0.4]) phases are exothermic, and those of liquid phase from [beta] and [gamma] phase are endothermic. The single-electrode Peltier heat for the cathodic formation reaction of Li-Al alloy in intermetallic compound [gamma] phase is estimated to be exothermic by using the measured values of thermoelectric powers of Li-Al alloys in ([beta] + [gamma]) and ([gamma] + liq.) regions.

  13. Energy level analysis of Np/sup 3 +/:LaCl/sub 3/ and Np/sup 3 +/:LaBr/sub 3/

    SciTech Connect

    Carnall, W.T.; Crosswhite, H.; Crosswhite, H.M.; Hessler, J.P.; Edelstein, N.; Conway, J.G.; Shalimoff, G.V.; Sarup, R.

    1980-05-01

    The polarized absorption and fluorescence spectra of 0.01--5% Np/sup 3 +/ doped into single-crystal LaCl/sub 3/ were measured at moderate and high resolution in the range to 50 000 cm/sup -1/ at 298, 77, and 4 K. The 150 crystal field components identified were fit by a parametrized model which has previously been shown to provide an excellent account of the energy level structures observed for lanthanides doped into LaCl/sub 3/. This constitutes the first successful evaluation of the crystal field interaction for an actinide ion in LaCl/sub 3/ in which J mixing effects were explicitly included. The crystal field parameters for Np/sup 3 +/:LaCl/sub 3/, B/sup 2//sub 0/=163, B/sup 4//sub 0/=-632, B/sup 6//sub 0/=-1625, and B/sup 6//sub 6/=1028, all in cm/sup -1/, were determined to be approximately twice as large as those for the analogous lanthanide, Pm/sup 3 +/:LaCl/sub 3/. From analysis of Zeeman patterns in the fluorescence spectra, the ground state was found to be doubly degenerate, having crystal quantum numbers +- 2 and a parallel splitting factor 0.17 LU (Lorentz unit).

  14. The stability of sodalite in the system NaAlSiO sub 4 -NaCl

    SciTech Connect

    Sharp, Z.D. ); Helffrich, G.R. ); Bohlen, S.R. ); Essene, E.J. )

    1989-08-01

    The reaction sodalite = {beta}-nepheline + NaCl (s) was reversed in solid-medium apparatus and the reaction sodalite = carnegieite + NaCl (l) was reversed at 1 bar (1,649-1,652 K). The experimental reversals between 923 K and 973 K can be fit with a dP/dT of {minus}11 bar/K, suggesting that the excess entropy for sodalite is present only above 923 K. A phase diagram for the NaAlSiO{sub 4}-NaCl system that is consistent with the measured thermochemical data and the experiments between 973 and 1,650 K can be generated if the 61.7 J/mol{center dot}K entropy contribution is included in the S{sup 0}{sub 298} of sodalite. This entropy contribution must be removed below 973 K for the experiments to fit with calculations. Previously unreported thermodynamic data estimated in this study are {Delta}G{sup 0}{sub 298} for sodalite ({minus}12,697 kJ/mol) and carnegieite (NaAlSiO{sub 4}) ({minus}1,958 kJ/mol), S{sup 0}{sub 298} of carnegieite (129.6 J/mol{center dot}K) and compressibility of NaCl{sub liquid} (V{sup P}{sub 298} (cm{sup 3}) = 31.6{center dot}(1 - 24.7{center dot}10{sup {minus}3}{center dot}P + 800{center dot}10{sup {minus}6}{center dot}P{sup 2}))(T in K; P in kbar). Sodalite is a high-temperature, low-pressure phase, stable well above the solidus in sodic silica-undersaturated magmas enriched in NaCl, and its presence constrains NaCl activities in magmas. Estimates of minimum NaCl (l) activities in the Mont St-Hilaire sodalite syenites are 0.05 at 1,073 K and 0.13 at 1,273 K. Density calculations are consistent with the field observations that sodalite phenocrysts will float in a nepheline syenite liquid. This explains the enrichment of sodalite in the upper levels of the sodalite syenites at Mont St.Hilaire and elsewhere.

  15. Ab initio MO Calculations on the Structure and Raman and Infrared Spectra of [Al4O2Cl10]2- Oxide in Chloroaluminate Melts

    NASA Astrophysics Data System (ADS)

    Berg, Rolf W.

    2007-04-01

    The oxide complexation chemistry in molten tetrachloroaluminate salts and ionic liquids is discussed with respect to what possible structures may be formed in addition to [AlCl4]-: [Al2OCl6]2-, [Al3OCl8]-, [Al2O2Cl4]2-, [Al3O2Cl6]- and [Al4O2Cl10]2-. Ab initio molecular orbital calculations are carried out on these various aluminium chloride and oxochloride ions, in assumed isolated gaseous free ionic state, by use of the Gaussian 03W program at the restricted Hartree-Fock (HF) level and with the 6-31+G(d,p) basis set.Without any pre-assumed symmetries and with tight optimization convergence criteria and by using the modified GDIIS algorithm, the model calculations generally converge. The structures and their binding energies are presented. The expected geometries are supported, with one exception perhaps being the [Al2OCl6]2- ion, that gave a linear Al-O-Al bonding system of staggered AlCl3-groups (approximate D3d symmetry), in analogy to the linear Al-O-Al geometry of the analogous [Al2OF6]2- ion, found previously. The calculations include determination of the vibrational harmonic normal modes and the infrared and Raman spectra (vibrational band wavenumbers and intensities), without any empiric adjustments of the harmonic force constants, using constants directly predicted from the Gaussian 03W program. Previously obtained IR absorption and Raman scattering spectra of melts are assigned, by comparing to the ab initio quantum mechanical vibrational analysis results. It is concluded that the small oxide content commonly found in basic and neutral tetrachloroaluminate melts, most probably consists of [Al4O2Cl10]2- ions, and the vibrational spectra are given.

  16. Can the positive aromatic ring be as π-electron donor in π-halogen bond? A MP2 theoretical investigation on the unusual π-halogen bond interaction between three-membered ring (BNN)₃⁺ and X1X2 (X1, X2 = F, Cl, Br).

    PubMed

    Qi, Hai-Tao; Ren, Fu-de; Zhang, Jing-Lin; Wang, Jing-Yu

    2011-05-01

    The unusual π-halogen bond interactions are investigated between (BNN)₃⁺ and X1X2 (X1, X2 = F, Cl, Br) employing MP2 at 6-311 + G(2d) and aug-cc-pVDZ levels according to the "CP (counterpoise) corrected potential energy surface (PES)" method. The order of the π-halogen bond interactions and stabilities of the complexes are obtained to be (BNN)₃⁺... F₂ < (BNN)₃⁺... ClF < (BNN)₃⁺... Cl₂ < (BNN)₃⁺... BrCl < (BNN)₃⁺... Br₂ < (BNN)₃⁺ ... BrF. at MP2/aug-cc-pVDZ level. The analyses of the Mulliken charge transfer, natural bond orbital (NBO), atoms in molecules (AIM) theory and electron density shifts reveal that the nature of the π-halogen bond interaction in the complexes of ClF, BrF and BrCl might partly be charge transfer from the delocalized π-HOMO orbital of (BNN)₃⁺ to X1X2. This result suggests that the positive aromatic ring (BNN)₃⁺ might act as a π-electron donor to form the π-halogen bond. PMID:20607330

  17. Synthesis, structural and optical characterization of APbX3 (A=methylammonium, dimethylammonium, trimethylammonium; X=I, Br, Cl) hybrid organic-inorganic materials

    NASA Astrophysics Data System (ADS)

    Mancini, Alessandro; Quadrelli, Paolo; Amoroso, Giuseppe; Milanese, Chiara; Boiocchi, Massimo; Sironi, Angelo; Patrini, Maddalena; Guizzetti, Giorgio; Malavasi, Lorenzo

    2016-08-01

    In this paper we report the synthesis, the crystal structure and the optical response of APbX3 (A=MA, DMA, and TMA; X=I, Br) hybrid organic-inorganic materials including some new phases. We observe that as the cation group increases in size, the optical absorption edge shifts to higher energies with energy steps which are systematic and independent on the anion. A linear correlation between the optical bad gap and the tolerance factor has been shown for the series of samples investigated.

  18. Electrochemically conductive treatment of TiO2 nanotube arrays in AlCl3 aqueous solution for supercapacitors

    NASA Astrophysics Data System (ADS)

    Zhong, Wenjie; Sang, Shangbin; Liu, Yingying; Wu, Qiumei; Liu, Kaiyu; Liu, Hongtao

    2015-10-01

    Highly ordered TiO2 nanotube arrays (NTAs) with excellent stability and large specific surface area make them competitive using as supercapacitor materials. Improving the conductivity of TiO2 is of great concern for the construction of high-performance supercapacitors. In this work, we developed a novel approach to improve the performance of TiO2 materials, involving the fabrication of Al-doped TiO2 NTAs by a simple electrochemical cathodic polarization treatment in AlCl3 aqueous solution. The prepared Al-doped TiO2 NTAs exhibited excellent electrochemical performances, attributing to the remarkably improved electrical conductivity (i.e., from approx. 10 kΩ to 20 Ω). Further analysis showed that Al3+ ions rather than H+ protons doped into TiO2 lattice cause this high conductivity. A MnO2/Al-TiO2 composite was evaluated by cyclic voltammetry, and achieved the specific capacitance of 544 F g-1, and the Ragone plot of the sample showed a high power density but less reduction of energy density. These results indicate that the MnO2/Al-TiO2 NTAs sample could be served as a promising electrode material for high -performance supercapacitors.

  19. The motley family of polar compounds (MV)[M(X{sub 5-x}X Prime {sub x})] based on anionic chains of trans-connected M{sup (III)}(X,X Prime ){sub 6} octahedra (M=Bi, Sb; X, X Prime =Cl, Br, I) and methylviologen (MV) dications

    SciTech Connect

    Leblanc, Nicolas; Mercier, Nicolas; Allain, Magali; Toma, Oksana; Auban-Senzier, Pascale; Pasquier, Claude

    2012-11-15

    The search for hybrid organic-inorganic materials remains a great challenge in the field of ferroelectrics. Following the discovery of the room temperature ferroelectric material (MV)[BiI{sub 3}Cl{sub 2}] (MV{sup 2+}: methylviologen) exhibiting the highest polarization value in the field of hybrid ferroelectrics, we report here nine new hybrids with the general formulation (MV)[M{sup (III)}X{sub 5-x}X Prime {sub x}] (M=Bi, Sb; X, X Prime =Cl, Br, I): (MV)[BiCl{sub 3.3}Br{sub 1.7}] (1), (MV)[BiCl{sub 1.3}Br{sub 3.7}] (2), (MV)[BiBr{sub 3.2}I{sub 1.8}] (3), (MV)[SbCl{sub 5}] (4), (MV)[SbBr{sub 5}] (5), (MV)[SbCl{sub 3.8}Br{sub 1.2}] (6), (MV)[SbCl{sub 2.4}Br{sub 2.6}] (7), (MV)[SbI{sub 3}Cl{sub 2}] (8) and (MV)[SbBr{sub 3.8}I{sub 1.2}] (9). Depending on the presence of polar chains or not, and on the coupling of polar chains, two types of centrosymmetrical structures [C1] and [C2] and two types of polar structures [P1] and [P2] are defined. (2) undergoes a paraelectric-to-relaxor ferroelectric transition around 100-150 K depending of the frequency showing that the Curie temperature, T{sub C}, of (MV)[BiBr{sub 5}] (243 K) can be modulated by the substitution of Br by Cl. The most interesting family is the [P2] type because the syn coupling of polar chains is in favor of high polarization values, as in (MV)[BiI{sub 3}Cl{sub 2}]. Five of the nine new hybrids, (4), (6-9), which have the [P2] type structure are potential ferroelectrics. - Graphical abstract: The methylviologen haloantimonate (MV)[SbX{sub 5-x}X Prime {sub x}] families (X, X Prime =Cl, Br, I) - [P1] and [P2] are the two kinds of polar structures - and view of the (MV)[SbBr{sub 3.8}I{sub 1.2}] hybrid based on chiral polar chains which are in syn coupling. Highlights: Black-Right-Pointing-Pointer Nine hybrids based on methylviologen and halometalate chains have been discovered. Black-Right-Pointing-Pointer The polar nature of chains is due to the ns{sup 2} stereoactivity of Sb{sup (III)} or Bi{sup (III

  20. Six- and eight-coordinate thio- and seleno-ether complexes of NbF5 and some comparisons with NbCl5 and NbBr5 adducts.

    PubMed

    Jura, Marek; Levason, William; Ratnani, Raju; Reid, Gillian; Webster, Michael

    2010-01-21

    The reaction of RS(CH(2))(2)SR (R = Me, Et or (i)Pr) with NbF(5) produces [NbF(4){RS(CH(2))(2)SR}(2)][NbF(6)] which contain distorted eight-coordinate (dodecahedral) cations and octahedral anions, whereas RSe(CH(2))(2)SeR (R = Me or Bu(n)) form six-coordinate [(NbF(5))(2)(mu-RSe(CH(2))(2)SeR)]. Et(2)S and Me(2)Se (L) also form six-coordinate [NbF(5)(L)], but Me(2)S forms both [NbF(5)(Me(2)S)] and an eight-coordinate cation in [NbF(4)(Me(2)S)(4)][NbF(6)]. MeS(CH(2))(2)SMe forms eight-coordinate cations in [NbX(4){MeS(CH(2))(2)SMe}(2)][NbX(6)] (X = Cl or Br), but other complexes of the heavier halides including [NbX(5)(L)] and [(NbX(5))(2)(mu-L-L)] (L-L = RSe(CH(2))(2)SeR; o-C(6)H(4)(CH(2)SMe)(2) and o-C(6)H(4)(CH(2)SeMe)(2)) contain six-coordinate niobium. The very unstable [NbCl(5)(Me(2)Te)] was characterised spectroscopically, but all other attempts to form telluroether complexes resulted in decomposition, and NbI(5) was reduced even by thioethers. The complexes have been characterised by multinuclear NMR ((1)H, (19)F, (93)Nb, (77)Se or (125)Te), IR and UV/visible spectroscopy, and X-ray crystal structures are reported for [NbF(4){RS(CH(2))(2)SR}(2)][NbF(6)] (R = Me, (i)Pr), [NbF(4)(Me(2)S)(4)][NbF(6)], [NbCl(5)(Me(2)Se)], [NbBr(5)(Me(2)S)], [(NbCl(5))(2){o-C(6)H(4)(CH(2)SMe)(2)}] and [(NbCl(5))(2){MeSe(CH(2))(2)SeMe}]. All the complexes are very moisture sensitive and the fluoride complexes decompose slowly with fluorination of the neutral ligand. PMID:20066233

  1. Oxidation of elemental mercury vapor over gamma-Al2O3 supported CuCl2 catalyst for mercury emissions control

    SciTech Connect

    Liu, Zhouyang; Liu, Xin; Lee, Joo-Youp; Bolin, Trudy B.

    2015-09-01

    In our previous studies, CuCl2 demonstrated excellent Hg(0) oxidation capability and holds potential for Hg(0) oxidation in coal-fired power plants. In this study, the properties and performances of CuCl2 supported onto gamma-Al2O3 with high surface area were investigated. From various characterization techniques using XPS, XAFS, XRD, TPR, SEM and TGA, the existence of multiple copper species was identified. At low CuCl2 loadings, CuCl2 forms copper aluminate species with gamma-Al2O3 and is inactive for Hg(0) oxidation. At high loadings, amorphous CuCl2 forms onto the gamma-Al2O3 surface, working as a redox catalyst for Hg(0) oxidation by consuming Cl to be converted into CuCl and then being regenerated back into CuCl2 in the presence of O-2 and HCl gases. The 10%(wt) CuCl2/gamma-Al2O3 catalyst showed excellent Hg(0) oxidation performance and SO2 resistance at 140 degrees C under simulated flue gas conditions containing 6%(v) O-2 and 10 ppmv HCl. The oxidized Hg(0) in the form of HgCl2 has a high solubility in water and can be easily captured by other air pollution control systems such as wet scrubbers in coal-fired power plants. The CuCl2/gamma-Al2O3 catalyst can be used as a low temperature Hg(0) oxidation catalyst. (C) 2015 Elsevier B.V. All rights reserved.

  2. Gamma Radiation Monitoring Through Thin Film of ClAlPc Doped With TiO2

    NASA Astrophysics Data System (ADS)

    Roy, M. S.; Gautam, A. K.; Kumar, M.; Prasad, N.; Janu, Y.; Deol, Y. S.; Mishra, R. K.; Choudhary, G. R.; Sadh, A. K.

    2008-04-01

    Chloroaluminum phthalocyanine (ClAlPc) synthesized by adopting focused microwave synthesis approach was doped with nanocrystalline TiO2 (5% by weight) and developed into the thin film sandwiched device having ITO/ClAlPc:TiO2/Ag Schottky configuration by spin coating technique covering 1 cm2 as an active area. The so fabricated device having initial dark current of the order of 0.2 5 m A was exposed to variable dose of gamma radiation ranging from lcGy to 10 Gy at a dose rate of 1 Gy/hour. The experimental observation reveals the generation of localized traps leading to structural disorder within the solid material. Doping with TiO2 enhances the surface area of the film which in tern improves sensitivity of device to wider dose rage. Exposure of the device to variable dose of gamma radiation imparts decrease in forward bias current and capacitance characteristics with increase in radiation dose. Also, absorbance characteristics of the Al Pc: TiO2 was analyzed before & after exposure to radiation which reveals that absorbance decreases with radiation dose leading to decrease in optical band gap.

  3. Mechanism of reaction in NaAlCl4 molten salt batteries with nickel felt cathodes and aluminum anodes. 2: Experimental results and comparison with model calculations

    NASA Astrophysics Data System (ADS)

    Knutz, B. C.; Berg, R. W.; Hjuler, H. A.; Bjerrum, N. J.

    1993-12-01

    The battery systems: Al/NaCl-AlCl3-Al2 X3/Ni-felt (X = S, Se, Te) and the corresponding system without chalcogen have been studied experimentally at 175 C. Charge/discharge experiments, performed on cells with NaCl saturated melts, show that advantages with regard to rate capability and cyclability can be obtained with systems containing dissolved chalcogen compared with the chalcogen-free system. Exchange of chalcogen between cathode and electrolyte during cycling was confirmed by performing gravimetric analysis and Raman spectroscopy of the electrolytes. Cathode reactions were studied by coulometric titrations (performed on cells with slightly acidic NaCl-AlCl3 melts and small amounts of chalcogen) and compared with model calculations. Cells containing chalcogen revealed at least three voltage plateaus during cycling. The lowest plateau is associated with formation/decomposition of essentially Ni(y)S(z) an d Ni(y)Se(z) in the sulfide and selenide system, respectively. Cells containing selenide revealed extra capacity below the Ni(y) Se(z)-plateau, most probably associated with a Al(v)Ni(y)Se(z) compound. On the second plateau of sulfide systems NiCl2 or a Ni(y)S(z) Cl(2y - 2z) compound with y greater than (4.4 +/- 0.2), z is formed during charging. Reduction of the formed compound to Ni takes place via consumption of sodium chloride.

  4. Conversion of xylan, d-xylose and lignocellulosic biomass into furfural using AlCl3 as catalyst in ionic liquid.

    PubMed

    Zhang, Luxin; Yu, Hongbing; Wang, Pan; Dong, Heng; Peng, Xinhong

    2013-02-01

    In order to define a new green catalytic pathway for the production of furfural, the catalyzed conversion of xylan into furfural in 1-butyl-3-methylimidazolium chloride was studied by using mineral acids and metal chlorides as catalysts under microwave irradiation. Amongst these catalysts, AlCl(3) resulted in the highest furfural yield of 84.8% at 170°C for 10s. The effect of AlCl(3) on the conversion efficiency of d-xylose and untreated lignocellulosic biomass was also investigated, the yields of furfural from corncob, grass and pine wood catalyzed by AlCl(3) in [BMIM]Cl were in the range of 16-33%. [BMIM]Cl and AlCl(3) could be recycled for four runs with stable catalytic activity. AlCl(3) is less corrosive than mineral acids, and the use of ionic liquid as reaction medium will no longer generate toxic wastewater, thus this reaction system is more ecologically viable. PMID:23306118

  5. Electrochemical noise Analysis of the Corrosion Behaviors of Al-Zn- In based Alloy in NaCl Solution

    NASA Astrophysics Data System (ADS)

    Ma, Jingling; Wen, Jiuba; Li, Quanan

    The corrosion behaviors of Al-5Zn-0.02In-1Mg-0.05Ti (wt. %) alloy immersion in 3.5% NaCl solution were analyzed using electrochemical noise. At the initial immersion, the potential noise due to the pitting shows small fluctuation of less than 1 mV about 5 s intervals. After 10 h immersion, the potential noise due to the dissolution/precipitation shows larger fluctuation about 5 mV at 10 s intervals. In the later corrosion, the potential noise caused by the uniform corrosion shows the fluctuation about 10 mV at 60 s intervals.

  6. Stress corrosion cracking of a superplastic and nonsuperplastic Zn-22.3Al alloy in 3% NaCl solution

    SciTech Connect

    Yeh, M.S.; Chang, J.C.; Chuang, T.H.

    1999-04-01

    Through appropriate heat treatments, a Zn-22.3wt%Al (Zn-22.3Al) alloy can be prepared in both superplastic and nonsuperplastic specimens. It has been found that the superplastic Zn-22.3Al alloy possesses a very fine microduplex structure, while the nonsuperplastic alloy has a lamellar duplex structure with locally coarsened second phases. The very different microstructures of both specimens result in different corrosion and stress corrosion cracking (SCC) behaviors in 3% NaCl solution. In addition, the fractographs of both the superplastic and nonsuperplastic Zn-22.3Al specimens after SCC tests under various anodic applied potentials have been compared. Through the observations, a mechanism for the SCC in this case was proposed to show that the cracks proceeded with successive processes of oxide film rupture and Zn-Al matrix tearing. Such a mechanism is more evident for the fractography of nonsuperplastic specimens, on which a series of parallel strips inserted with dimple-bands can be obviously found.

  7. Alkaline hydrolysis of dimethyl terephthalate in the presence of [LiAl{sub 2}(OH){sub 6}]Cl.2H{sub 2}O

    SciTech Connect

    Lei Lixu . E-mail: lixu.lei@seu.edu.cn1; Zhang Weifeng; Hu Meng; Zheng Hegen

    2006-11-15

    The alkaline hydrolysis of dimethyl terephthalate (DMT) in the presence of [LiAl{sub 2}(OH){sub 6}]Cl has been investigated to demonstrate a possible application of anion exchange facility of layered double hydroxides (LDHs) to control chemical reactions. The results show that (i) in the alkaline hydrolysis of DMT in the presence of [LiAl{sub 2}(OH){sub 6}]Cl, most of the interlayer Cl{sup -} of [LiAl{sub 2}(OH){sub 6}]Cl is quickly replaced by OH{sup -} in the alkaline solution because the LDH host favors OH{sup -} more; (ii) the alkaline hydrolysis of DMT in the presence of [LiAl{sub 2}(OH){sub 6}]Cl is faster than the reaction of DMT and [LiAl{sub 2}(OH){sub 6}]OH; (iii) The hydrolysis of DMT in a buffer solution of pH{approx}8 takes longer time to reach equilibrium than the alkaline hydrolysis of DMT in the presence of [LiAl{sub 2}(OH){sub 6}]Cl. It is believed that the selective anion exchange chemistry of the LDH plays a key role in storage and controlled release of active reactant, that is, OH{sup -}, thus make the hydrolysis proceeds in a controlled way. - Graphical abstract: XRD patterns of the solid products of the alkaline hydrolysis of dimethyl terephthalate (DMT) in the presence of [LiAl{sub 2}(OH){sub 6}]Cl at 70 deg. C halted at different time, which shows that [LiAl{sub 2}(OH){sub 6}]Cl turns out to be [LiAl{sub 2}(OH){sub 6}]OH, and [LiAl{sub 2}(OH){sub 6}]{sub 2}TP forms gradually. In this reaction, the alkaline hydrolysis of DMT is controlled by replacement of Cl{sup -} in [LiAl{sub 2}(OH){sub 6}]Cl by OH{sup -}, and subsequent replacement of OH{sup -} in [LiAl{sub 2}(OH){sub 6}]OH by terephthalate anion.

  8. Ab initio studies on cyanoacetylenes of astrochemical interest: [Y(Ctbnd C)CN, Y dbnd C2H5, C3H7, C4H9, F, Cl, Br and CN

    NASA Astrophysics Data System (ADS)

    Kodi Ramanah, D.; Surajbali, P.; Rhyman, L.; Alswaidan, I. A.; Fun, H.-K.; Somanah, R.; Ramasami, P.

    2016-01-01

    Theoretical studies were performed on seven potential interstellar and circumstellar substituted cyanoacetylenes, Y(Ctbnd C)CN [Y = C2H5, C3H7, C4H9, F, Cl, Br and CN]. Geometry optimizations were carried out using the DFT/B3LYP, the CCSD and CCSD(T) levels of theory. The cc-pVTZ basis set was used for all atoms. Frequency computations were also carried out at the same level of theory as for the optimization to check the nature of the stationary points. The molecular and spectroscopic parameters of the cyanoacetylenes were computed. An analysis of these parameters is in line with the satisfactory performance of the B3LYP/cc-pVTZ level compared to the golden standard, the CCSD(T) level. The theoretical data reported in this work should facilitate future identifications of these cyanoacetylenes in extraterrestrial locations. Plausible mechanisms for the formation of these molecules have been proposed.

  9. Pb6Ba2(BO3)5X (X = Cl, Br): new borate halides with strong predicted optical anisotropies derived from Pb(2+) and (BO3)(3.).

    PubMed

    Liu, Lu; Zhang, Bingbing; Zhang, Fangfang; Pan, Shilie; Zhang, Fangyuan; Zhang, Xingwen; Dong, Xiaoyu; Yang, Zhihua

    2015-04-21

    Two new borate halides, Pb6Ba2(BO3)5X (X = Cl, Br), have been synthesized by solid-state reactions and their structures determined by single-crystal X-ray diffraction. They are isostructural and feature 3D frameworks composed of alternate stacking of [PbBO] and [PbBOX] layers which are connected by 10-coordinated Ba atoms along the c direction. First-principles calculations show that both compounds have a large birefringence of 0.1582 and 0.1810 at 532 nm, respectively. The large birefringence originates from the strong optical anisotropies of the Pb(2+) cations and (BO3)(3-) groups based on the real-space atom-cutting analysis. The IR and UV-Vis-NIR diffuse reflectance spectroscopy, as well as thermal stability analyses of both compounds, were performed. PMID:25785911

  10. Impact of deformation energy on the hydrogen bonding interactions in gas phase 3-X catechol ⋯ H2O complexes (X = H, F, Cl, Br): The effect of approach of a water molecule

    NASA Astrophysics Data System (ADS)

    Deb, Debojit Kumar; Sarkar, Biplab

    2016-06-01

    The conformations and nature of hydrogen bonding interactions for 3-X catechol ⋯ H2O (X = H, F, Cl, Br) has been investigated by ab initio MP2, CCSD(T), and density functional B3LYP, wB97XD and M06-2X methods. The changes in interaction energies due to deformation of the structures has been studied in detail. The intra- and intermolecular hydrogen bonding interactions due to the different direction of approach of water molecule have been discussed. A detailed natural bond orbital (NBO) analysis and the symmetry-adapted perturbation theory (SAPT) based energy decomposition analysis has been carried out to elucidate interaction strength and properties in these hydrogen bonded systems. The charge transfer percentage (CTP) has been derived which will be universally useful for correlating binding energy, deformation energy and the geometrical parameters such as angles, bond lengths, etc. for other systems as well.

  11. A rapid method for the measurement of sulfur hexafluoride (SF6), trifluoromethyl sulfur pentafluoride (SF5CF3), and Halon 1211 (CF2ClBr) in hydrologic tracer studies

    NASA Astrophysics Data System (ADS)

    Busenberg, Eurybiades; Plummer, L. Niel

    2010-11-01

    A rapid headspace method for the simultaneous laboratory determination of intentionally introduced hydrologic tracers, sulfur hexafluoride (SF6), trifluoromethyl sulfur pentafluoride (SF5CF3), Halon 1211 (CF2ClBr), and other halocarbons in water and gases is described. The high sensitivity of the procedure allows for introduction of minimal tracer mass (a few grams) into hydrologic systems with a large dynamic range of analytical detection (dilutions to 1:108). Analysis times by gas chromatography with electron capture detector are less than 1 min for SF6; about 2 min for SF6 and SF5CF3; and 4 min for SF6, SF5CF3, and Halon 1211. Many samples can be rapidly collected, preserved in stoppered septum bottles, and analyzed at a later time in the laboratory. Examples are provided showing the effectiveness of the gas tracer test studies in varied hydrogeological settings.

  12. A rapid method for the measurement of sulfur hexafluoride (SF6), trifluoromethyl sulfur pentafluoride (SF5CF3), and Halon 1211 (CF2ClBr) in hydrologic tracer studies

    USGS Publications Warehouse

    Busenberg, Eurybiades; Plummer, L. Niel

    2010-01-01

    A rapid headspace method for the simultaneous laboratory determination of intentionally introduced hydrologic tracers, sulfur hexafluoride (SF6), trifluoromethyl sulfur pentafluoride (SF5CF3), Halon 1211 (CF2ClBr), and other halocarbons in water and gases is described. The high sensitivity of the procedure allows for introduction of minimal tracer mass (a few grams) into hydrologic systems with a large dynamic range of analytical detection (dilutions to 1:108). Analysis times by gas chromatography with electron capture detector are less than 1 min for SF6; about 2 min for SF6 and SF5CF3; and 4 min for SF6, SF5CF3, and Halon 1211. Many samples can be rapidly collected, preserved in stoppered septum bottles, and analyzed at a later time in the laboratory. Examples are provided showing the effectiveness of the gas tracer test studies in varied hydrogeological settings.

  13. Conformational Isomerism of trans-[Pt(NH2C6H11)2I2] and the Classical Wernerian Chemistry of [Pt(NH2C6H11)4]X2 (X = Cl, Br, I)1

    PubMed Central

    Johnstone, Timothy C.; Lippard, Stephen J.

    2012-01-01

    X-ray crystallographic analysis of the compound trans-[Pt(NH2C6H11)2I2] revealed the presence of two distinct conformers within one crystal lattice. This compound was studied by variable temperature NMR spectroscopy to investigate the dynamic interconversion between these isomers. The results of this investigation were interpreted using physical (CPK) and computational (molecular mechanics and density functional theory) models. The conversion of the salts [Pt(NH2C6H11)4]X2 into trans-[Pt(NH2C6H11)2X2] (X = Cl, Br, I) was also studied and is discussed here with an emphasis on parallels to the work of Alfred Werner. PMID:23554544

  14. Band Gaps of the Lead-Free Halide Double Perovskites Cs2BiAgCl6 and Cs2BiAgBr6 from Theory and Experiment.

    PubMed

    Filip, Marina R; Hillman, Samuel; Haghighirad, Amir Abbas; Snaith, Henry J; Giustino, Feliciano

    2016-07-01

    The recent discovery of lead-free halide double perovskites with band gaps in the visible represents an important step forward in the design of environmentally friendly perovskite solar cells. Within this new family of semiconductors, Cs2BiAgCl6 and Cs2BiAgBr6 are stable compounds crystallizing in the elpasolite structure. Following the recent computational discovery and experimental synthesis of these compounds, a detailed investigation of their electronic properties is warranted in order to establish their potential as optoelectronic materials. In this work, we perform many-body perturbation theory calculations and obtain high accuracy band gaps for both compounds. In addition, we report on the synthesis of Cs2BiAgBr6 single crystals, which are stable in ambient conditions. From our complementary theoretical and experimental analysis, we are able to assign the indirect character of the band gaps and obtain both experimental and theoretical band gaps of these novel semiconductors that are in close agreement. PMID:27322413

  15. Mutual neutralization of atomic rare-gas cations (Ne{sup +}, Ar{sup +}, Kr{sup +}, Xe{sup +}) with atomic halide anions (Cl{sup −}, Br{sup −}, I{sup −})

    SciTech Connect

    Shuman, Nicholas S.; Miller, Thomas M.; Viggiano, Albert A.; Johnsen, Rainer

    2014-01-28

    We report thermal rate coefficients for 12 reactions of rare gas cations (Ne{sup +}, Ar{sup +}, Kr{sup +}, Xe{sup +}) with halide anions (Cl{sup −}, Br{sup −}, I{sup −}), comprising both mutual neutralization (MN) and transfer ionization. No rate coefficients have been previously reported for these reactions; however, the development of the Variable Electron and Neutral Density Attachment Mass Spectrometry technique makes it possible to measure the difference of the rate coefficients for pairs of parallel reactions in a Flowing Afterglow-Langmuir Probe apparatus. Measurements of 18 such combinations of competing reaction pairs yield an over-determined data set from which a consistent set of rate coefficients of the 12 MN reactions can be deduced. Unlike rate coefficients of MN reactions involving at least one polyatomic ion, which vary by at most a factor of ∼3, those of the atom-atom reactions vary by at least a factor 60 depending on the species. It is found that the rate coefficients involving light rare-gas ions are larger than those for the heavier rare-gas ions, but the opposite trend is observed in the progression from Cl{sup −} to I{sup −}. The largest rate coefficient is 6.5 × 10{sup −8} cm{sup 3} s{sup −1} for Ne{sup +} with I{sup −}. Rate coefficients for Ar{sup +}, Kr{sup +}, and Xe{sup +} reacting with Br{sub 2}{sup −} are also reported.

  16. FT-IR and Raman spectra, ab initio and density functional computations of the vibrational spectra, molecular geometries and atomic charges of uracil and 5-halogenated uracils (5-X-uracils; X=F, Cl, Br, I).

    PubMed

    Singh, J S

    2014-01-01

    Raman (200-4000 cm(-1)) and FT-IR (400-4000 cm(-1)) spectra of uracil and 5-halogenated uracils (5-X-uracils; X=F, Cl, Br, I) have been recorded and analyzed in the range 200-4000 cm(-1). The optimized molecular geometries, atomic polar tensor (APT) charges and vibrational characteristics have been studied theoretically using restricted Hartree-Fock (RHF) and density functional theory (DFT) methods. Ab initio and DFT calculations [using Becke's exchange in conjunction with Lee-Yang-Parr's correlation functional and Becke's three-parameter hybrid method (B3LYP)] were carried out to study the optimized molecular fundamental vibrational frequencies for uracil and 5-halogenated uracils by employing Gaussian-03 program. Gauss View software was used to make the vibrational analysis. Raman and IR spectra have been computed theoretically for the uracil and 5-halogenated molecules. The fundamental vibrational frequencies along with their corresponding intensities in IR and Raman activities and depolarization ratios of the Raman lines have also been calculated using the RHF and DFT methods employing different basis sets. Quantum chemical calculations helped in the reassignments of some fundamental vibrational modes. Most of the B3LYP/6-311++G(**) vibrational frequencies are in excellent agreement with available experimental assignments. The ring breathing and kekule stretching modes are found to lower magnitudes compared to those for uracil which could be due to mass effect of halogen atom in place of the hydrogen atom. The C-X (X=F, Cl, Br, I) stretching frequency is distinctly separated from the CH/NH ring stretching frequencies on the pyrimidine ring. All other bands have also been assigned different fundamentals/overtones/combinations. PMID:24036044

  17. FT-IR and Raman spectra, ab initio and density functional computations of the vibrational spectra, molecular geometries and atomic charges of uracil and 5-halogenated uracils (5-X-uracils; X = F, Cl, Br, I)

    NASA Astrophysics Data System (ADS)

    Singh, J. S.

    2014-01-01

    Raman (200-4000 cm-1) and FT-IR (400-4000 cm-1) spectra of uracil and 5-halogenated uracils (5-X-uracils; X = F, Cl, Br, I) have been recorded and analyzed in the range 200-4000 cm-1. The optimized molecular geometries, atomic polar tensor (APT) charges and vibrational characteristics have been studied theoretically using restricted Hartree-Fock (RHF) and density functional theory (DFT) methods. Ab initio and DFT calculations [using Becke's exchange in conjunction with Lee-Yang-Parr's correlation functional and Becke's three-parameter hybrid method (B3LYP)] were carried out to study the optimized molecular fundamental vibrational frequencies for uracil and 5-halogenated uracils by employing Gaussian-03 program. Gauss View software was used to make the vibrational analysis. Raman and IR spectra have been computed theoretically for the uracil and 5-halogenated molecules. The fundamental vibrational frequencies along with their corresponding intensities in IR and Raman activities and depolarization ratios of the Raman lines have also been calculated using the RHF and DFT methods employing different basis sets. Quantum chemical calculations helped in the reassignments of some fundamental vibrational modes. Most of the B3LYP/6-311++G∗∗ vibrational frequencies are in excellent agreement with available experimental assignments. The ring breathing and kekule stretching modes are found to lower magnitudes compared to those for uracil which could be due to mass effect of halogen atom in place of the hydrogen atom. The C-X (X = F, Cl, Br, I) stretching frequency is distinctly separated from the CH/NH ring stretching frequencies on the pyrimidine ring. All other bands have also been assigned different fundamentals/overtones/combinations.

  18. Synthesis and electrochemistry of ([mu]-oxo)technetium complexes with bipyridine and halide ligands. Crystal structures of ([mu]-O)[X(bpy)[sub 2]Tc][sub 2]X[sub x][center dot]bpy (X = Cl, Br) and ([mu]-O)[Cl(phen)[sub 2]Tc][sub 2]Cl[sub 2

    SciTech Connect

    Jun Lu; Hiller, C.D.; Clarke, M.J. )

    1993-04-14

    Dinuclear [mu]-oxo complexes of technetium, in which the two Tc atoms are in intimate electronic communication, have been synthesized and structurally characterized. ([mu]-O)[X(bpy)[sub 2]Tc][sub 2]X[sub 2][center dot]bpy, where X = Cl (I) and Br (II), are isomorphic and crystallize in the orthorhombic space group. The compound ([mu]-O)[Cl(phen)[sub 2]Tc]Cl[sub 2][center dot]4H[sub 2]O (III) also crystallized in Pbcn. In each structure, the geometry is distorted octahedral around each Tc, with the equatorial ligands on the opposite metal atoms being staggered relative to one another. The bridging oxygen atom sits on a 2-fold symmetry element which bisects the angle formed by the staggered Tc-X bonds. Infrared Tc-O stretching frequencies are in the range 723-730 cm[sup [minus]1]. Halides are easily dissociated from the phenanthroline complexes and an analog, ([mu]-O)[(OH)(phen)[sub 2]Tc][sub 2](PF[sub 6])[sub 2][center dot]6H[sub 2]O, of a ruthenium water oxidation catalyst has been investigated. Cyclic voltammetry revealed three one-electron couples that are independent of pH over a wide range. At low pH, oxidation of ([mu]-O)[(OH)(phen)[sub 2]Tc][sub 2][sup 2+] by O[sub 2] occurs slowly, but is rapid with HNO[sub 3] or H[sub 2]O[sub 2] to give the (III--IV) mixed-valent complex, which exhibits a low energy (IVCT) band at 959 nm. The comproportionation constant for ([mu]-O)[(OH)(phen)[sub 2]Tc][sub 2][sup 2+] + ([mu]-O)[(OH)(phen)[sub 2]Tc][sub 2][sup 4+] [yields] ([mu]-O)[(OH)(phen)[sub 2] Tc][sub 2][sup 3+] is 3.07 [times] 10[sup 10], consistent with close electronic communication between the two technetium atoms. 33 refs., 4 figs., 7 tabs.

  19. A Potentiometric, Spectrophotometric and Pitzer Ion-Interaction Study of Reaction Equilibria in the Aqueous H+-Al3+, H+-Oxalate and H+-Al3+-Oxalate Systems up to 5 mol*dm-3 NaCl

    SciTech Connect

    Boily, Jean F.; Qafoku, Odeta; Felmy, Andrew R.

    2007-12-01

    Aluminium-oxalate complexation was determined in acidic media of aqueous NaCl solutions ranging from 0.1-5.0 mol•dm-3. Complexation in the H+-Al3+ and H+-Oxalate systems was also studied to provide a set of internally consistent thermodynamic data. The ionic strength dependent formation constants describing the stabilities of the Al3+, AlOH2+, Al3(OH)45+, Al13O4(OH)247+, H2L, HL-, L2-, AlL+, AlL2- and AlL33- species (where L is the oxalate ion) was also described using a Pitzer ion interaction model. The derived parameters can be used to predict chemical speciation in the H+-Al3+-Oxalate system in the 0.1-5.0 mol•dm-3 NaCl range.

  20. Synthesis and the crystal and molecular structures of (H{sub 3}L . Cl)[CoCl{sub 4}] and H{sub 2}L[CuBr{sub 4}] (L is 2,4,6-Tri(N,N-dimethylamino)methylphenol)

    SciTech Connect

    Kovalchukova, O. V.; Stash, A. I.; Strashnova, S. B.; Romashkina, E. P.; Zaitsev, B. E.

    2010-05-15

    The complex compounds (H{sub 3}L . Cl)[CoCl{sub 4}] (I) and H{sub 2}L[CuBr{sub 4}] (II), where L is 2,4,6-tri(N,N-dimethylamino)methylphenol, were isolated in the crystalline state and studied by X-ray diffraction. The organic cations were found to be outer-sphere ligands. All three nitrogen atoms of the tertiary amino groups are protonated. In compound I, the H{sub 3}L{sup 3+} cation exists as the cis tautomer. In compound II, the H{sub 2}L{sup 2+} dication exists as the trans isomer. In the crystal structure, the dications are arranged in layers via hydrogen bonds.

  1. Synthesis, characterization, and physical properties of two new magnetic organic metals, [BEDT-TTF]{sub 4}[C(CN){sub 2}CONH{sub 2}]CuX{sub x} (X = Cl and Br{sub 0.77}Cl{sub 0.22})

    SciTech Connect

    Wang, H.H.; Geiser, U.; Kumar, S.K.

    1995-12-31

    Two new BEDT-TTF based charge transfer salts, [BEDT-TTF]{sub 4}[C(CN){sub 2}CONH{sub 2}]CuX{sub 2} (X = Cl and Br{sub 0.77}Cl{sub 0.22}) have been synthesized and characterized with use of X-ray diffraction, Energy Dispersive Spectroscopy (EDS), and Raman spectroscopy. ESR spectroscopy reveals that the anion layer contains 3% of paramagnetic Cu(II) species which exhibit Curie-Weiss behavior with a Weiss constant of {theta} = {minus}2.8 K. Both compounds are metallic below 150 K. AC susceptibility, RF penetration depth, and RF impedance measurements under pressure do not reveal signals of superconductivity.

  2. Time-resolved resonance Raman study of the. delta. delta. * excited state of Re sub 2 Cl sub 8 sup 2 minus and Re sub 2 Br sub 8 sup 2 minus

    SciTech Connect

    Schoonover, J.R.; Dallinger, R.F.; Killough, P.M.; Sattelberger, A.P.; Woodruff, W.H. )

    1991-03-06

    Time-resolved resonance Raman (TR{sup 3}) spectra have been obtained for Re{sub 2}X{sub 8}{sup 2{minus}} (X = Cl, Br) in the A{sub 2u} ({delta}{delta}*) electronically excited state, at ambient temperature in solution. The Tr{sup 3} spectra exhibit Raman peaks that are assigned to the three symmetric vibrations of the excited state: the Re-Re stretch, Re-X stretch, and the Re-Re-X deformation. In addition, a depolarized peak attributed to an asymmetric X-Re-X bend is observed. Comparison of the TR{sub 3} results to single-crystal vibronic spectra reported by others clearly shows the effects of crystal constraints and observation time scale upon the strucutre of the {delta}{delta}* excited state. The TR{sup 3} data, obtained in solution on the nanosecond time scale, indicate that the excited state relaxes to a staggared molecular structure (D{sub 4} or D{sub 4d} symmetry). The vibronic data, obtained on single crystals under cryogenic conditions, are consistent with an eclipsed (D{sub 4h}) structure, similar to that of the ground state. A comparative TR{sup 3} study of quadruply bonded complexes, including both octahalodirhenate ions and Mo{sub 2}(PMe{sub 3}){sub 4}Cl{sub 4} (which is precluded by steric factors from significant torsional distorition about the metal-metal bond), was essential in elucidating the excited-state structures.

  3. Structural (EXAFS) and solution equilibrium studies on the oxotechnetium(V) complexes TcOX/sub 4//sup -/ and TcOX/sub 5//sup 2 -/ (X = Cl, Br)

    SciTech Connect

    Thomas, R.W.; Heeg, M.J.; Elder, R.C.; Deutsch, E.

    1985-05-08

    The equilibrium between the technetium(V) complexes TcOCl/sub 4//sup -/ and TcOCl/sub 5//sup 2 -/ has been investigated in 12 M HCl and in CH/sub 2/Cl/sub 2/ solutions by Raman spectroscopy. In both media the five-coordinate complex is the predominant species, but in the aqueous medium water competes for the sixth coordination site and causes formation of the six-coordinate TcOCl/sub 5//sup 2 -/ anion to be even less favorable. Rate constants for the reaction are given. Procedures are described for generating good yields of either TcOX/sub 4//sup -/ or TcOX/sub 5//sup 2 -/ (X = Cl, Br) salts from the same reaction mixture. The complexes TcOCl/sub 4//sup -/, TcOCl/sub 5//sup 2 -/, TcOBr/sub 4//sup -/, TcOBr/sub 5//sup 2 -/, and TcI/sub 6//sup 2 -/ have been structurally characterized by EXAFS techniques. Observed Tc=O and Tc-X bond lengths are consistent with the known dependence of bond length on coordination number, the established structural trans effect induced by the Tc=O linkage, and existing crystallographic data on TcOCl/sub 4//sup -/ and related molybdenum(V) complexes.

  4. Growth mechanism of atomic-layer-deposited TiAlC metal gate based on TiCl4 and TMA precursors

    NASA Astrophysics Data System (ADS)

    Jinjuan, Xiang; Yuqiang, Ding; Liyong, Du; Junfeng, Li; Wenwu, Wang; Chao, Zhao

    2016-03-01

    TiAlC metal gate for the metal-oxide-semiconductor field-effect-transistor (MOSFET) is grown by the atomic layer deposition method using TiCl4 and Al(CH3)3(TMA) as precursors. It is found that the major product of the TiCl4 and TMA reaction is TiAlC, and the components of C and Al are found to increase with higher growth temperature. The reaction mechanism is investigated by using x-ray photoemission spectroscopy (XPS), Fourier transform infrared spectroscopy (FTIR), and scanning electron microscope (SEM). The reaction mechanism is as follows. Ti is generated through the reduction of TiCl4 by TMA. The reductive behavior of TMA involves the formation of ethane. The Ti from the reduction of TiCl4 by TMA reacts with ethane easily forming heterogenetic TiCH2, TiCH=CH2 and TiC fragments. In addition, TMA thermally decomposes, driving Al into the TiC film and leading to TiAlC formation. With the growth temperature increasing, TMA decomposes more severely, resulting in more C and Al in the TiAlC film. Thus, the film composition can be controlled by the growth temperature to a certain extent. Project supported by the Key Technology Study for 16/14 nm Program of the Ministry of Science and Technology of China (Grant No. 2013ZX02303).

  5. Structures, spectroscopic studies and solid-state thermal transformations of coordination polymers from P{sub 4}Se{sub 3} and CuX (X=Cl, Br, I)

    SciTech Connect

    Biegerl, Andreas; Groeger, Christian; Kalbitzer, Hans R.; Pfitzner, Arno; Wachter, Joachim; Weihrich, Richard; Zabel, Manfred

    2011-07-15

    The formation of coordination polymers (CuCl)P{sub 4}Se{sub 3} (1), (CuBr){sub 3}(P{sub 4}Se{sub 3}){sub 2} (2), (CuI){sub 3}(P{sub 4}Se{sub 3}){sub 2} (3) and (CuI)P{sub 4}Se{sub 3} (4), from solutions of copper(I) halides and P{sub 4}Se{sub 3} by diffusion methods has been studied. The new compounds were characterized by X-ray crystallography, solid-state {sup 31}P MAS NMR and Raman spectroscopy. Theoretical studies on the DFT level in the crystalline phase allowed the unequivocal assignment of the recorded Raman shifts between 200 and 480 cm{sup -1}. The structure of 1 consists of a 2D network of castellated [CuCl]{sub n} chains and bidentate P{sub 4}Se{sub 3} molecules. The 3D network of 2 comprises [CuBr]{sub n} chains, which are linked by tridentate P{sub 4}Se{sub 3} molecules. Compound 3 is a three-dimensional polymer composed of four-membered (CuI){sub 2} rings and castellated [CuI]{sub n} chains, which are linked by tridentate P{sub 4}Se{sub 3} molecules involving two basal and the apical P atoms. Thermal conversion of 1 at 230 deg. C gives (CuCl){sub 3}(P{sub 4}Se{sub 3}){sub 2} (5), which is isostructural with 2. The thermal conversion of (CuI){sub 3}P{sub 4}S{sub 3}, which was studied for comparison gave at 371 deg. C (CuI){sub 3}P{sub 4}S{sub 4}, Cu{sub 3}PS{sub 4} and small amounts of Cu{sub 6}PS{sub 5}I. - Graphical Abstract: New coordination polymers have been prepared and characterized by the reaction of P{sub 4}Se{sub 3} and copper(I) halides solutions under diffusion conditions. Highlights: > Coordination polymers from P{sub 4}Se{sub 3} and copper(I) halide are described. > Solid-state phases are prepared from solution by interdiffusion techniques. > One-, two- and three-dimensional polymers are formed. > Up to three P atoms are involved in coordination to copper. > Application of {sup 31}P MAS NMR spectroscopy.

  6. Thermodynamic properties of antiferromagnetic ordered states of π -d interacting systems of κ -(BETS) 2Fe X4(X =Br ,Cl )

    NASA Astrophysics Data System (ADS)

    Fukuoka, Shuhei; Yamashita, Satoshi; Nakazawa, Yasuhiro; Yamamoto, Takashi; Fujiwara, Hideki; Shirahata, Takashi; Takahashi, Kazuko

    2016-06-01

    The results are presented for systematic heat capacity measurements of π-d interacting systems of κ -(BETS) 2Fe Br4 and κ -(BETS) 2FeC l4 [BETS = bis(ethylenedithio)tetraselenafulvalene] performed under in-plane magnetic fields. We observed sharp thermal anomalies at 2.47 K for κ -(BETS) 2FeB r4 and at 0.47 K for κ -(BETS) 2FeC l4 at 0 T that are associated with antiferromagnetic transitions of the 3 d electrons in the anion layers. From analyses of the magnetic heat capacity data, we indicate that the two compounds show unconventional thermodynamic behaviors inherent in the π-d interacting layered system. In the case of κ -(BETS) 2FeB r4 , a small hump structure was observed in the magnetic heat capacity below the transition temperature when a magnetic field was applied parallel to the a axis. In the case of κ -(BETS) 2FeC l4 , a similar hump structure was observed at 0 T that remained in the data with magnetic fields applied parallel to the a axis. We demonstrate that the temperature dependencies of the magnetic heat capacities scale well by normalizing the temperatures with dominant one-dimensional direct interactions (Jdd/kB) of each compound. The field dependencies of the transition temperatures and the hump structures are elucidated in one simple magnetic field vs temperature (H -T ) phase diagram. These results indicate that the thermodynamic features of both κ-type BETS salts are essentially equivalent, and the observed hump structures are derived from the one-dimensional Jdd interaction characters, which are still influential for magnetic features even in the long-range magnetic ordered states.

  7. Thermoluminescence response of new KCl(X)Br(1-X):EuCl3 sintered phosphors exposed to beta and gamma radiation.

    PubMed

    Bernal, R; Cruz-Zaragoza, E; Cruz-Vázquez, C; Burruel-Ibarra, S E; Rivera-Flores, M J; Barboza-Flores, M

    2006-01-01

    Alkali halides crystals have been the subject of intense research for an understanding of their radiation-induced defects and luminescence properties. They exhibit noteworthy thermoluminescence (TL) properties when exposed to ionising radiation. Currently, these materials are grown employing expensive and rather complicated techniques. In this work, the results on the TL properties of new alkali halides phosphors fabricated by a simple and inexpensive procedure are presented. The samples were made by mixing KCl, KBr and EuCl3 salts, and compressing them at a pressure of 3.2 x 10(7) Pa during 3 min, followed by sintering at 700 degrees C during 24 h under air atmosphere. The dosimetric response of the samples showed an increase with radiation dose in the 1.5-20.0 Gy dose range for beta and gamma radiation. The TL glow curves in sintered samples presented significant differences in their peak structures compared with monocrystalline samples, indicating that the nature of the trapping states and the recombination mechanisms may be different. PMID:16702244

  8. Structural and morphological characterization of Mg0.8Al0.2(OH)2Cl0.2 hydrotalcite produced by mechanochemistry method

    NASA Astrophysics Data System (ADS)

    Fahami, Abbas; Beall, Gary W.

    2016-01-01

    Chlorine intercalated Mg-Al layered double hydroxides (Mg-Al-Cl-LDH) with a chemical formula Mg0.8Al0.2(OH)2Cl0.2 were successfully produced by the one-step mechanochemistry method and subsequent water washing followed by drying in oven for 1 h at 80 °C. The samples were characterized by X-ray diffraction (XRD), Fourier Transform Infrared spectroscopy (FT-IR), field emission scanning electron microscopy (FESEM), energy dispersive spectroscopy (EDS), elemental mapping analysis, transmission electron microscopy (TEM), X-ray fluorescence (XRF), and the differential thermogravimetric analysis (DTGA). Results revealed that the structural characteristics of Mg-Al-Cl-LDH were affected strongly by milling time. At the beginning of milling (up to 1 h), Hydrotalcite (HT) and Brucite were the dominant phases, while the progressive mechanical activation was completed as milling time increased, which resulted in the formation of nanostructured Mg-Al-Cl-LDH. Based on XRD and FTIR data, Mg0.8Al0.2(OH)2Cl0.2 with high purity was obtained at 5 h milling. The interlayer spacing of LDH is also strongly influenced by milling time so that it escalated from 7.737±0.001 to 8.005±0.002 (1-15 h) and then decreased to 7.937±0.001 for 20 h milled sample. Electron microscopic observation displayed that the final product had hexagonal platelet structure with lateral dimension of 20-100 nm. Therefore, the synthesis of Mg0.8Al0.2(OH)2Cl0.2 via mechanochemistry owing to simplicity and versatility can be a promising candidate for use in catalyst carriers, drug delivery, and gene delivery.

  9. Doped-CuCl2/Al2O3 catalysts for ethylene oxychlorination: Influence of additives on the nature of active phase and reducibility

    NASA Astrophysics Data System (ADS)

    Gianolio, D.; Muddada, N. B.; Olsbye, U.; Lamberti, C.

    2012-08-01

    Doped CuCl2/Al2O3 is an industrial catalyst used to produce dichloroethane, key intermediate of the polyvinyl chloride (PVC) chemistry. Using in situ and operando X-ray absorption spectroscopies, combined with laboratory techniques, we succeeded in understanding the nature of the active phase and the role played by most used additives for fluid and fixed beds technologies (LiCl, KCl, CsCl, MgCl2, and LaCl3). Moreover we were able to quantify relative fraction, reducibility and dispersion of Cu-phases adjoining catalytic tests in a pulse reactor. EXAFS and XANES highlighted that all additives contribute more or less efficiently in increasing the fraction of the active species (supported CuCl2). EXAFS directly, UV-vis and IR spectroscopies indirectly proved the formation of mixed salts, when KCl or CsCl are added, so displacing the rate determining step from the CuCl oxidation to the CuCl2 reduction. Fully oxidized catalyst is inactive, so copper in the working catalyst, exhibits a I/II mixed valence state. Coupling the ethylene conversion, measured with a pulse reactor, with XANES spectra collected after interaction with C2H4, we could differentiate the ability of doped samples to be reduced by ethylene. We obtained slightly different results explainable by the different dispersion of the active phase, measured by CO chemisorption.

  10. Measurements of the ClO radical vibrational band intensity and the ClO + ClO + M reaction product

    NASA Technical Reports Server (NTRS)

    Burkholder, James B.; Orlando, John J.; Hammer, Philip D.; Howard, Carleton J.; Goldman, Aaron

    1988-01-01

    There is considerable interest in the kinetics and concentrations of free radicals in the stratosphere. Chlorine monoxide is a critically important radical because of its role in catalytic cycles for ozone depletion. Depletion occurs under a wide variety of conditions including the Antarctic spring when unusual mechanisms such as the BrO sub x/ClO sub x, ClO dimer (Cl sub 2 O sub 2), and ClO sub x/HO sub x cycles are suggested to operate. Infrared spectroscopy is one of the methods used to measure ClO in the stratosphere (Menzies 1979 and 1983; Mumma et al., 1983). To aid the quantification of such infrared measurements, researchers measured the ClO ground state fundamental band intensity.

  11. Structural parameters, vibrational spectra and centrifugal distortion constants of F(CN)C dbnd NX (X = H, F, Cl, Br) and CH 3(Y)C dbnd NH (Y = H, CN)

    NASA Astrophysics Data System (ADS)

    Durig, James R.; Zhou, Sarah Xiaohua; Zhou, Carmen Xiaomin; Durig, Nicole E.

    2010-04-01

    Ab initio calculations with full electron correlation by the perturbation method to second order and hybrid density functional theory calculations by the B3LYP method utilizing a variety of basis sets have been carried out for the F(CN)C dbnd NX (X = H, F, Cl, Br) and CH 3(Y)C dbnd NH (Y = H, CN) molecules. From these calculations, force constants, vibrational frequencies, infrared intensities, Raman activities, depolarization ratios, and structural parameters have been determined and compared to the experimental quantities when available. By combining previously reported rotational constants for F(CN)C dbnd NBr with the ab initio MP2/6-311+G(d) predicted parameters, adjusted r0 parameters have been obtained. The structural parameters are: distances (Å) (N-Br) = 1.865(3); (C dbnd N) = 1.270(3); (C-F) = 1.327(3); (C-C) = 1.437(3); (C tbnd N) = 1.160(3); and angles (°) ∠BrNC = 114.4(5); ∠NCF = 127.4(5); ∠NCC = 119.7(5). These reported parameters have much lower uncertainties than those previously reported from the microwave data. Similar theoretical calculations have been carried out for CH 3(Y)C dbnd NH (Y = H, CN) and r0 structural parameters have been obtained for both the cis and trans conformers of ethylidenimine, CH 3(H)C dbnd NH, and for cis iminopyruvonitrile, CH 3(CN)C dbnd NH utilizing previously reported microwave rotational constants. For CH 3(H)C dbnd NH the determined r0 heavy atom parameters for the cis [trans] form are: distances (Å) (C dbnd N) = 1.276(3) [1.275(3)]; (C-C) = 1.500(3) [1.508(3)]; angles (°) ∠(HN dbnd C) = 109.4(5) [108.8(5)]; ∠(N dbnd CC) = 121.2(5) [127.2(5)]; ∠(HCC) = 116.2(5) [116.4(5)]. Centrifugal distortion constants have been obtained for all of the molecules from the ab initio predicted force constants and the values are compared to the experimentally determined values when available. The results of these studies are compared to the corresponding quantities of some other similar molecules.

  12. Effects of partial anion substitution on the thermoelectric properties of silver(I) chalcogenide halides in the system Ag{sub 5}Q{sub 2}X with Q=Te, Se and S and X=Br and Cl

    SciTech Connect

    Eckstein, Nadine; Nilges, Tom; Decourt, Rodolphe; Bobet, Jean-Louis; Chevalier, Bernard

    2011-04-15

    A selection of mixed conducting silver chalcogenide halides of the general formula Ag{sub 5}Q{sub 2}X with Q=sulfur, selenium and tellurium and X=chlorine and bromine has been investigated due to their thermoelectric properties. Recently, the ternary counterpart Ag{sub 5}Te{sub 2}Cl showed a defined d{sup 10}-d{sup 10} interaction in the disordered cation substructure at elevated temperatures where Ag{sub 5}Te{sub 2}Cl is present in its high temperature {alpha}-phase. A significant drop of the thermal diffusivity has been observed during the {beta}-{alpha} phase transition reducing the values from 0.12 close to 0.08 mm{sup 2} s{sup -1}. At the same transition the thermopower reacts on the increasing silver mobility and jumps towards less negative values. Thermal conductivities, thermopower and thermal diffusivity of selected compounds with various grades of anion substitution in Ag{sub 5}Q{sub 2}X were determined around the silver-order/disorder {beta}-{alpha} phase transition. A formation of attractive interactions could be observed for selenium substituted phases while no effect was detected for bromide and sulfide samples. Depending on the grade and type of substitution the thermopower changes significantly at and after the {beta}-{alpha} phase transition. Thermal conductivities are low reaching values around 0.2-0.3 W m{sup -1} K{sup -1} at 299 K. Partial anion exchange can substantially tune the thermoelectric properties in Ag{sub 5}Q{sub 2}X phases. -- Graphical abstract: A structure section of the {alpha}-Ag{sub 5}Te{sub 2}Cl structure type and the thermopower evolution of Ag{sub 5}Te{sub 2}Cl{sub 0.4}Br{sub 0.6} undergoing a silver ion order/disorder phase transition. Display Omitted Research highlights: > We report on thermoelectric properties of silver(I) chalcogenide halides. > We examine thermopower, thermal diffusivity and thermal behavior. > Silver mobility, phase transitions and order/disorder phenomena are discussed. > Partial anion exchange can

  13. Mechanism of reaction in NaAlCl4 molten salt batteries with nickel felt cathodes and aluminum anodes. 1: Modeling of the battery properties of thermodynamic equilibrium

    NASA Astrophysics Data System (ADS)

    Knutz, B. C.; Hjuler, H. A.; Berg, R. W.; Bjerrum, N. J.

    1993-12-01

    A theoretical description of the thermodynamic properties of the battery systems: Al/NaCl-AlCl3 -Al2X3/Ni-felt (X = S, Se, Te) and the corresponding system without chalcogen has been provided for cells with basic to slightly acidic NaCl-AlCl3 melts containing small amounts of chalcogen. The model developed describes the equilibrium concentrations of constituent species in the electrolyte and equilibrium potentials of the electrodes vs. number of coulombs passed through the cells. For cells without chalcogen curves were calculated under the assumption of NiCl2 formation showing corresponding variation of anode potential, cathode potential, and cell voltage as a function of electrolyte composition. For sulfide containing cells the plateau of lowest potential has been found to be associated with essentially pure nickel sulfide, Ni(y)S(z). A procedure for model fitting to the cathode potential curve-form of the Ni(y)S(z)-plateau is presented. A general equation is proposed for the reaction taking place along the second plateau.

  14. Investigation of electrochemical etch differences in AlGaAs heterostructures using Cl{sub 2} ion beam assisted etching

    SciTech Connect

    Anglin, Kevin Goodhue, William D.; Swint, Reuel B.; Porter, Jeanne

    2015-03-15

    A deeply etched, anisotropic 45° and 90° mirror technology is developed for Al{sub x}Ga{sub 1−x}As heterostructures using a Cl{sub 2} ion beam assisted etching system. When etching vertically, using a conductive low-erosion Ni mask, electrochemical etch differences between layers with various Al mole fractions caused nonuniform sidewall profiles not seen in semi-insulating GaAs test samples. These variations, based on alloy composition, were found to be negligible when etching at a 45°. A Si{sub 3}N{sub 4}-Ni etch mask is designed in order to electrically isolate charge buildup caused by the incoming Ar{sup +} ion beam to the Ni layer, preventing conduction to the underlying epitaxial layers. This modification produced smoothly etched facets, up to 8 μm in depth, enabling fabrication of substrate–surface-emitting slab-coupled optical waveguide lasers and other optoelectronic devices.

  15. Si-Al-Cl-Mg-Ca Aqueous Fluids in Dora-Maira Pyrope: new Contributions for an old Question

    NASA Astrophysics Data System (ADS)

    Ferrando, S.; Frezzotti, M.; Compagnoni, R.

    2007-12-01

    Recent discovery of multiphase solid inclusions (MSI) in peak minerals from ultra-high pressure (UHP) terranes opened up new prospects for understanding the fluid-rock interaction during deep subduction in both crust and mantle. The first report on MSI in UHP rocks was from Dora-Maira (DM; Case Parigi; western Alps) whiteschists, more than ten years ago (Philippot et al, 1995, CMP, 121, 29-44). Nevertheless, the nature of such a fluid, and its role on the origin of the unusual composition of these rocks is still matter of debate. We report data on inclusions in DM UHP pyropes and HP prograde kyanite, part of them from a new sampling site (SSW Case Parigi). Primary MSI (30 micron) are present only in small UHP pyropes (1 - 6 cm) and often show post-entrapment decrepitation. Each MSI contains Mg-chlorite, Na-phlogopite, minor Cl-rich apatite, talc, pyrite, magnesite, Ca-rich chlorides +/- liquid water. Maps of total water concentrations collected in MSI-rich pyropes by infrared synchrotron radiation show gradients that suggest considerable H diffusion from inclusions into the host garnet (Frezzotti et al, 2007, abstract ECROFI XIX). In prograde kyanite, rare fluid inclusions are high salinity brines, containing different salts. Present data indicate that at HP conditions brines were present in the rocks and that at UHP peak aqueous fluids were enriched in Si, Al, Mg, Na, Ca, but still containing significant amounts of Cl, P, S, C. DM whiteschists are commonly considered metasomatic rocks from a granitic protolith. Our data on MSI in UHP pyrope and on rare brines in prograde HP kyanite strongly support metasomatism by external high-Ca-Mg fluids, probably evolved during serpentinite dehydration as proposed by Sharp and Barnes (2004, EPSL, 226, 243-254). Present data support the model of Compagnoni and Hirajima (2001, Lithos, 57, 219-236), who proposed that metasomatic fluids were introduced into the system during prograde metamorphism, channelled along shear zones

  16. Internally consistent thermodynamic data for aqueous species in the system Na-K-Al-Si-O-H-Cl

    NASA Astrophysics Data System (ADS)

    Miron, George D.; Wagner, Thomas; Kulik, Dmitrii A.; Heinrich, Christoph A.

    2016-08-01

    A large amount of critically evaluated experimental data on mineral solubility, covering the entire Na-K-Al-Si-O-H-Cl system over wide ranges in temperature and pressure, was used to simultaneously refine the standard state Gibbs energies of aqueous ions and complexes in the framework of the revised Helgeson-Kirkham-Flowers equation of state. The thermodynamic properties of the solubility-controlling minerals were adopted from the internally consistent dataset of Holland and Powell (2002; Thermocalc dataset ds55). The global optimization of Gibbs energies of aqueous species, performed with the GEMSFITS code (Miron et al., 2015), was set up in such a way that the association equilibria for ion pairs and complexes, independently derived from conductance and potentiometric data, are always maintained. This was achieved by introducing reaction constraints into the parameter optimization that adjust Gibbs energies of complexes by their respective Gibbs energy effects of reaction, whenever the Gibbs energies of reactant species (ions) are changed. The optimized thermodynamic dataset is reported with confidence intervals for all parameters evaluated by Monte Carlo trial calculations. The new thermodynamic dataset is shown to reproduce all available fluid-mineral phase equilibria and mineral solubility data with good accuracy and precision over wide ranges in temperature (25-800 °C), pressure (1 bar to 5 kbar) and composition (salt concentrations up to 5 molal). The global data optimization process adopted in this study can be readily repeated any time when extensions to new chemical elements and species are needed, when new experimental data become available, or when a different aqueous activity model or equation of state should be used. This work serves as a proof of concept that our optimization strategy is feasible and successful in generating a thermodynamic dataset reproducing all fluid-mineral and aqueous speciation equilibria in the Na-K-Al-Si-O-H-Cl system within

  17. ICP-RIE etching of polar, semi-polar and non-polar AlN: comparison of Cl2/Ar and Cl2/BCl3/Ar plasma chemistry and surface pretreatment

    NASA Astrophysics Data System (ADS)

    Shah, Amit P.; Azizur Rahman, A.; Bhattacharya, Arnab

    2015-01-01

    We report a comprehensive investigation of inductively-coupled plasma reactive ion etching (ICP-RIE) of polar (0001) c-plane, semi-polar (11-22) and non-polar (11-20) a-plane AlN epilayers and show that under optimized conditions a combination of BCl3-based surface oxide removal pretreatment and Cl2/Ar ICP etching allows fast etch rates (750 nm min-1) with a smooth surface morphology. We compare samples of different orientation etched in Cl2/Ar and Cl2/BCl3/Ar plasmas, with and without BCl3/Ar ICP pretreatment, and show that the effective removal of surface oxide is a crucial step for reliable ICP-RIE etching of AlN layers. For such pretreated samples, optimization of etch parameters such as RF power, ICP power, and chamber pressure then permit very high etch rates to be obtained with a smooth surface morphology. We also study the effect of varying the BCl3 fraction in BCl3/Cl2/Ar plasmas on the etch rate and surface morphology and find that increasing the BCl3 fraction reduces the etch rate for AlN. However, above 20% BCl3 content, samples with and without pre-treatment show similar etch rates.

  18. Reaction kinetics for the solid state synthesis of the AlH3/MgCl2 nano-composite by mechanical milling.

    PubMed

    Duan, C W; Hu, L X; Sun, Y; Zhou, H P; Yu, H

    2015-09-14

    The process of mechanical milling has been proved to be a cost-effective way to synthesize the AlH3/MgCl2 nano-composite by using MgH2 and AlCl3 as reagents. However, so far there is no comprehensive knowledge of the kinetics of this process. In an effort to predict the reaction progress and optimize the milling parameters, the kinetics of the synthesis of the AlH3/MgCl2 nano-composite by mechanical milling of MgH2 and AlCl3 is experimentally investigated in the present work. The reaction progress or the transformation fraction upon milling for different times is evaluated using the isothermal hydrogen desorption test of the as-milled samples at 220 °C, which is much lower than the threshold temperature for the de-hydriding of the reagent MgH2 but enough for the de-hydriding of the as-synthesized nano-sized AlH3. The effects of milling parameters on the reaction kinetics as well as the underlying mechanism are discussed by referring to the mechanical energy input intensity, the vial temperature and the Gibbs free energy change for the reaction. Furthermore, it is found that the Johnson-Mehl-Avrami (JMA) model can well describe the kinetics theoretically. By fitting the experimental data with the JMA expression, the theoretical kinetics expressions, the equation parameters, and the activation energy are obtained. PMID:26256935

  19. Electrochemical properties of the solvent SbCl/sub 3/-AlCl/sub 3/-N(1-butyl)pyridinium chloride and electrochemical and spectroelectrochemical studies of arene solutes

    SciTech Connect

    Chapman, D.M.; Mamantov, G.; Petrovic, C.; Smith, G.P.; Sorlie, M.

    1984-07-01

    Physical and electrochemical properties are reported for SbCl/sub 3/-AlCl/sub 3/-N-(1-butyl)pyridinium chloride (BPCl) mixtures that are liquid at ambient temperatures, and studies of the electrogeneration and open-circuit decay of some arene radical cations, both in this medium and in SbCl/sub 3/-KCl at elevated temperatures, are described. Specific conductivities, densities, and viscosities of the compositions (m/o (mole percent)) 60:19:21 (basic) and 60:21:19 (acidic) SbCl/sub 3/-AlCl/sub 3/-BPCl were measured over the temperature range 24/sup 0/-100/sup 0/C. For a potentiometric titration between the compositions 60:18:22 and 60:22:18 with SbCl/sub 3/ fixed at 60 m/o, the potential of the Sb(III)/Sb(0) couple increased by 0.43V at 27/sup 0/C. Electrochemical studies showed that perylene (Per), 9,10-dimethylanthracene (DMA), and 9,10diphenylanthracene (DPA) can be reversibly oxidized to their radical cations in a 60:19:21 melt, whereas the oxidation of anthracene (Ant) is irreversible. Spectroelectrochemical studies showed that Per radical cations were stable in this melt, those of DPA decayed very slowly, those of DMA decayed somewhat faster, and those of Ant were too transient to be observed optically. Similar degrees of stability were found for these radical cations in SbCl/sub 3/ containing 1 M KCl at elevated temperatures, and transient spectra of Ant radical cations were observed in this solvent.

  20. X-ray powder diffraction, vibration and thermal studies of [A{sub 0.92}(NH{sub 4}){sub 0.08}]{sub 2}TeCl{sub 4}Br{sub 2} with A = Cs, Rb: Influence of mixed cationic and anionic substitutions

    SciTech Connect

    Aribia, W. Ben; Abdelmouleh, M.; Kabadou, A.; Van Der Lee, A.

    2012-05-15

    Graphical abstract: The structures of [A{sub 0.92}(NH{sub 4}){sub 0.08}]{sub 2}TeCl{sub 4}Br{sub 2} with A = Cs, Rb belong to the tetragonal {beta}-K{sub 2}SnCl{sub 6} structure type. Highlights: Black-Right-Pointing-Pointer The two new compound crystallises in P4/mnc tetragonal space group. Black-Right-Pointing-Pointer The structure is considered as isolated octahedred TeCl{sub 4}Br{sup 2-}. Black-Right-Pointing-Pointer The octahedra connected by ionic and hydrogen bonding through the Cs/Rb or N atoms. Black-Right-Pointing-Pointer A DTA/TGA experiment reveals one endothermic peak at 780 K for these compounds. Black-Right-Pointing-Pointer One endothermic peak is detected at around 213 K by DSC experiment. -- Abstract: The crystal structures of [A{sub 0.92}(NH{sub 4}){sub 0.08}]{sub 2}TeCl{sub 4}Br{sub 2} with A = Cs, Rb have been determined using X-ray powder diffraction techniques. The two compounds crystallize in the tetragonal space group P4/mnc, with the unit cell parameters: a = 7.452(1) Angstrom-Sign , c = 10.544(3) Angstrom-Sign , Z = 2 and a = 7.315(2) Angstrom-Sign , c = 10.354(4) Angstrom-Sign , Z = 2 in the presence of Cs and Rb, respectively. These two compounds have an antifluorite-type arrangement of NH{sub 4}{sup +}/Rb{sup +}/Cs{sup +} and octahedral TeCl{sub 4}Br{sub 2}{sup 2-} anions. The stability of these structure is by ionic and hydrogen bonding contacts: A Midline-Horizontal-Ellipsis Cl, A Midline-Horizontal-Ellipsis Br and N-H Midline-Horizontal-Ellipsis Cl, N-H Midline-Horizontal-Ellipsis Br. The different vibrational modes of these powders were analysed by FTIR and Raman spectroscopic studies. A DTA/TGA experiment reveals one endothermic peak at 780 K implicating the decomposition of the sample. At low temperature, one endothermic peak in thermal behavior is detected at around 213 K by DSC experiment. This transition was confirmed by dielectric measurements.

  1. Absolute NMR shielding scales and nuclear spin–rotation constants in {sup 175}LuX and {sup 197}AuX (X = {sup 19}F, {sup 35}Cl, {sup 79}Br and {sup 127}I)

    SciTech Connect

    Demissie, Taye B. Komorovsky, Stanislav; Repisky, Michal; Ruud, Kenneth; Jaszuński, Michał

    2015-10-28

    We present nuclear spin–rotation constants, absolute nuclear magnetic resonance (NMR) shielding constants, and shielding spans of all the nuclei in {sup 175}LuX and {sup 197}AuX (X = {sup 19}F, {sup 35}Cl, {sup 79}Br, {sup 127}I), calculated using coupled-cluster singles-and-doubles with a perturbative triples (CCSD(T)) correction theory, four-component relativistic density functional theory (relativistic DFT), and non-relativistic DFT. The total nuclear spin–rotation constants determined by adding the relativistic corrections obtained from DFT calculations to the CCSD(T) values are in general in agreement with available experimental data, indicating that the computational approach followed in this study allows us to predict reliable results for the unknown spin–rotation constants in these molecules. The total NMR absolute shielding constants are determined for all the nuclei following the same approach as that applied for the nuclear spin–rotation constants. In most of the molecules, relativistic effects significantly change the computed shielding constants, demonstrating that straightforward application of the non-relativistic formula relating the electronic contribution to the nuclear spin–rotation constants and the paramagnetic contribution to the shielding constants does not yield correct results. We also analyze the origin of the unusually large absolute shielding constant and its relativistic correction of gold in AuF compared to the other gold monohalides.

  2. Absolute NMR shielding scales and nuclear spin-rotation constants in (175)LuX and (197)AuX (X = (19)F, (35)Cl, (79)Br and (127)I).

    PubMed

    Demissie, Taye B; Jaszuński, Michał; Komorovsky, Stanislav; Repisky, Michal; Ruud, Kenneth

    2015-10-28

    We present nuclear spin-rotation constants, absolute nuclear magnetic resonance (NMR) shielding constants, and shielding spans of all the nuclei in (175)LuX and (197)AuX (X = (19)F, (35)Cl, (79)Br, (127)I), calculated using coupled-cluster singles-and-doubles with a perturbative triples (CCSD(T)) correction theory, four-component relativistic density functional theory (relativistic DFT), and non-relativistic DFT. The total nuclear spin-rotation constants determined by adding the relativistic corrections obtained from DFT calculations to the CCSD(T) values are in general in agreement with available experimental data, indicating that the computational approach followed in this study allows us to predict reliable results for the unknown spin-rotation constants in these molecules. The total NMR absolute shielding constants are determined for all the nuclei following the same approach as that applied for the nuclear spin-rotation constants. In most of the molecules, relativistic effects significantly change the computed shielding constants, demonstrating that straightforward application of the non-relativistic formula relating the electronic contribution to the nuclear spin-rotation constants and the paramagnetic contribution to the shielding constants does not yield correct results. We also analyze the origin of the unusually large absolute shielding constant and its relativistic correction of gold in AuF compared to the other gold monohalides. PMID:26520517

  3. Theoretical study on the identity ion pair SN2 reactions of LiX with CH3SX (X=Cl, Br, and I): structure, mechanism, and potential energy surface.

    PubMed

    Ren, Yi; Gai, Jing-Gang; Xiong, Yan; Lee, Kuo-Hsing; Chu, San-Yan

    2007-07-26

    Three archetypal ion pair nucleophilic substitution reactions at the methylsulfenyl sulfur atom LiX+CH3SX-->XSCH3+LiX (X=Cl, Br, and I) are investigated by the modified Gaussian-2 theory. Including lithium cation in the anionic models makes the ion pair reactions proceed along an SN2 mechanism, contrary to the addition-elimination pathway occurring in the corresponding anionic nucleophilic substitution reactions X-+CH3SX-->XSCH3+X-. Two reaction pathways for the ion pair SN2 reactions at sulfur, inversion and retention, are proposed. Results indicate the inversion pathway is favorable for all the halogens. Comparison of the transition structures and energetics for the ion pair SN2 at sulfur with the potential competition ion pair SN2 reactions at carbon LiX+CH3SX-->XCH3+LiXS shows that the SN2 reactions at carbon are not favorable from the viewpoints of kinetics and thermodynamics. PMID:17388388

  4. Absolute NMR shielding scales and nuclear spin-rotation constants in 175LuX and 197AuX (X = 19F, 35Cl, 79Br and 127I)

    NASA Astrophysics Data System (ADS)

    Demissie, Taye B.; Jaszuński, Michał; Komorovsky, Stanislav; Repisky, Michal; Ruud, Kenneth

    2015-10-01

    We present nuclear spin-rotation constants, absolute nuclear magnetic resonance (NMR) shielding constants, and shielding spans of all the nuclei in 175LuX and 197AuX (X = 19F, 35Cl, 79Br, 127I), calculated using coupled-cluster singles-and-doubles with a perturbative triples (CCSD(T)) correction theory, four-component relativistic density functional theory (relativistic DFT), and non-relativistic DFT. The total nuclear spin-rotation constants determined by adding the relativistic corrections obtained from DFT calculations to the CCSD(T) values are in general in agreement with available experimental data, indicating that the computational approach followed in this study allows us to predict reliable results for the unknown spin-rotation constants in these molecules. The total NMR absolute shielding constants are determined for all the nuclei following the same approach as that applied for the nuclear spin-rotation constants. In most of the molecules, relativistic effects significantly change the computed shielding constants, demonstrating that straightforward application of the non-relativistic formula relating the electronic contribution to the nuclear spin-rotation constants and the paramagnetic contribution to the shielding constants does not yield correct results. We also analyze the origin of the unusually large absolute shielding constant and its relativistic correction of gold in AuF compared to the other gold monohalides.

  5. Core-shell Cd0.2Zn0.8S@BiOX (X = Cl, Br and I) microspheres: a family of hetero-structured catalysts with adjustable bandgaps, enhanced stability and photocatalytic performance under visible light irradiation.

    PubMed

    Zhou, Yannan; Wen, Ting; Chang, Binbin; Yang, Baocheng; Wang, Yonggang

    2016-09-21

    Heterostructures consisting of two semiconductors have merited considerable attention in photocatalytic applications due to synergistic effects in complex redox processes. The incorporation of solid solutions into such architectures can further offer extra variability to control the bandgap. In this study, we report the fabrication of a series of core-shell Cd0.2Zn0.8S@BiOX (X = Cl, Br and I) microspheres via a solvothermal route that lead to enhanced photocatalytic performance under visible light irradiation. By optimizing the synthesis conditions, uniform and porous Cd0.2Zn0.8S@BiOX microspheres were achieved. The products were thoroughly characterized by X-ray diffraction studies, scanning electron microscopy, transmission electron microscopy, photoluminescence studies, absorption measurements and the photodegradation of RhB. Remarkably, the electronic structures of Cd0.2Zn0.8S@BiOX composites can be continuously tuned by varying the composition of BiOX to achieve the best catalytic performance under visible light irradiation. Finally, this greatly enhanced visible-light-driven photocatalytic efficiency was observed in the optimized Cd0.2Zn0.8S@BiOI composites when compared to their single-component counterparts, which may be attributed to increased light absorption and improved electron-hole separation. The photocatalytic mechanism has also been proposed based on the experimental evidences and the theoretical band positions of Cd0.2Zn0.8S@BiOI. PMID:27510184

  6. Jet Cooled Laser Induced Fluorescence Spectroscopy of FCH2CH2O and Other Photo-Fragments of XCH2CH2ONO (X=F, Cl, Br, Oh)

    NASA Astrophysics Data System (ADS)

    Chhantyal-Pun, Rabi; Chen, Ming-Wei; Miller, Terry A.

    2011-06-01

    HOCH2CH2O is one of the prototypical hydroxyalkoxy intermediates formed in the OH mediated oxidation of olefins in the atmosphere. Specifically, HOCH2CH2O is produced from NO assisted reduction of HOCH2CH2OO which in turn is formed by the OH mediated oxidation of ethene in the atmosphere. Halogen substituted ethoxy can be a model to study the hydroxy substituted ethoxy. Our group has successfully studied different primary, secondary and unsaturated alkoxy radicals using Laser Induced Fluorescence technique (LIF) coupled with supersonic free jet expansion in the past. In this talk we will present the jet cooled LIF spectrum of FCH2CH2O. FCH2CH2O was produced in the jet by 351nm photodissociation of FCH2CH2ONO. Aided by ab inito calculations and past experiments, we were able to assign our spectrum to different conformers of FCH2CH2O based on the G(±120°) and T(O°) orientations of the OCCF dihedral angle. Besides FCH2CH2O, we also found transitions belonging to HCHO and CH2CHO from FCH2CH2ONO photodissociation. HCHO and CH2CHO were also found in Cl, Br and OH substituted precursors.

  7. Raman and infrared spectra of barium and strontium halide monohydrates, MX2 · 1H2O (M = Ba, Sr; X = Cl, Br, I). A new interpretation of the frequency shiftings of OH stretching modes in solid hydrates

    NASA Astrophysics Data System (ADS)

    Lutz, H. D.; Christian, H.

    The infrared and Raman spectra of the isotypic alkaline earth halide monohydrates, MX2 · 1H2O, with M = Sr, Ba and X = Cl, Br, I, and of deuterated and isotopically dilute samples have been recorded in the H2O stretching and bending mode region. From the temperature dependence of the stretching modes it is shown that bifurcated hydrogen bridges are present in these hydrates. The water molecules are symmetrically bonded in the case of the iodides, possibly caused by dipole-like interactions with adjacent iodide ions, and assymmetrically bonded in the case of the chlorides and bromides due to normal hydrogen bonds, as shown from the absence or presence of splitting of the stretching modes in isotopically dilute samples. The relative Raman intensities of the two H2O stretching modes, {Ivsym}/{Ivasym}, which reveal the amount of intramolecular coupling of the stretching vibrations, give an additional view of the bond structure of the water molecules. The frequency shiftings of the stretching modes of water molecules in solid hydrates are discussed in terms of hydrogen bonds, metal-oxygen interaction and the repulsion potential of the lattice, as shown, for example, by the correlation with the unit cell volumes.

  8. Photoluminescence properties of Yb(2+) ions doped in the perovskites CsCaX3 and CsSrX3 (X = Cl, Br, and I) - a comparative study.

    PubMed

    Suta, Markus; Urland, Werner; Daul, Claude; Wickleder, Claudia

    2016-05-21

    The Yb(2+)-doped perovskite derivatives CsMX3 (M = Ca and Sr; X = Cl, Br, and I) are ideal systems for obtaining a detailed insight into the structure-luminescence relationship of divalent lanthanides. The investigation of the respective photoluminescence properties yielded two emission bands in the violet and blue spectral range for all compounds, which are assigned to the spin-allowed and spin-forbidden 5d-4f transitions, respectively. The impact on their energetic positions is dependent on both the covalency of the Yb(2+)-halide bond and the corresponding bond length in agreement with expectations. The excitation spectra provide a detailed fine structure at low temperatures and can be partly interpreted separating the 4f(13) core from the 5d electron in the excited state. The local crystal field in CsSrI3:Yb(2+) provides a special case due to the trigonal distortion induced by the crystal structure that is clearly evident in the luminescence features of Yb(2+). The structure-property relationship of several spectroscopic key quantities of Yb(2+) in this series of halides is analyzed in detail and parallels the properties of Eu(2+) ions doped in the given perovskites. PMID:26894637

  9. Changes in Phase Composition of NaAlH{sub 4}+FeCl{sub 2} Complex Hydride Exposed to Air

    SciTech Connect

    Roupcova, P.; Schneeweiss, O.

    2010-07-13

    Phase composition in AlNaH{sub 4} doped with FeCl{sub 2} was studied by Moessbauer spectroscopy and X-ray diffraction and stabilities in Ar and air were compared. The results show that the hydride disappeared during the exposition to air. The major sodium alanate hydride traps gaseous impurities and transforms to Na{sub 2}CO{sub 3} and Al(OH){sub 3}.

  10. Catalytic dehydration of carbohydrates suspended in organic solvents promoted by AlCl3 /SiO2 coated with choline chloride.

    PubMed

    Yang, Jie; De Oliveira Vigier, Karine; Gu, Yanlong; Jérôme, François

    2015-01-01

    We show that the coating of choline chloride on silica-supported AlCl3 allows the dehydration of carbohydrates to successfully proceed in low boiling point organic solvents. The concept is based on the in situ formation of a deep eutectic liquid phase on the catalyst surface, thus facilitating the interaction between the solid catalyst and insoluble carbohydrate. PMID:25404114

  11. Effect of LiAlO{sub 2} nanoparticle filler concentration on the electrical properties of PEO–LiClO{sub 4} composite

    SciTech Connect

    Masoud, E.M.; El-Bellihi, A.-A.; Bayoumy, W.A.; Mousa, M.A.

    2013-03-15

    Highlights: ► Structural modification of nano LiAlO{sub 2} filler increased conductivity. ► Good ionic conductivity for (LiAlO{sub 2}){sub 1.5}(PEO){sub 11}(LiClO{sub 4}) at room temperature. ► Nano LiAlO{sub 2} filler enhanced both ion migration and orientation. ► High dielectric properties for (LiAlO{sub 2}){sub 1.5}(PEO){sub 11}(LiClO{sub 4}) at room temperature. - Abstract: Nano-composite polymer electrolytes are receiving attention as potential candidates to be used as electrolyte membranes in lithium polymer batteries and other devices. In this work, polyethylene oxide–LiClO{sub 4} based composite polymer electrolyte was prepared by solution casting method. The effect of LiAlO{sub 2} nanoparticle ceramic filler concentration on the structure and electrical conduction of the composite was studied. Nano-LiAlO{sub 2} was synthesized by sol–gel method. The samples were characterized using X-ray diffraction, Fourier Transmission-Infra Red, Differential Scanning Calorimetry, and tested by dielectric properties, Direct and Alternating current measurements as well as by impedance spectroscopy. All samples showed a behavior referring to an ionic conduction. Generally, the melting temperature of the polymer electrolyte decreased with filler concentration. Both thermal property and filler concentration influenced conductivity value. At room temperature, the highest ionic conductivity was 9.76 × 10{sup −5} ohm{sup −1} cm{sup −1} for sample with a composition of (LiAlO{sub 2}){sub 1.5}(polyethylene oxide){sub 11}(LiClO{sub 4}). All results were correlated and discussed.

  12. Impact of boronate capping groups on biological characteristics of novel (99m)Tc(III) complexes [(99m)TcCl(CDO)(CDOH)2B-R] (CDOH2 = cyclohexanedione dioxime).

    PubMed

    Yang, Yong; Zheng, Yumin; Tomaselli, Elena; Fang, Wei; Liu, Shuang

    2015-02-18

    This study sought to explore the impact of boronate groups on the heart uptake and myocardial retention of novel (99m)Tc(III) complexes [(99m)TcCl(CDO)(CDOH)2B-R] ((99m)Tc-ISboroxime: R = isoxazol-4-yl (IS); (99m)Tc-MPboroxime: R = N-methylpyridinium (MP); (99m)Tc-PAboroxime: R = pyrazol-3-yl (PA); (99m)Tc-PYboroxime: R = pyridin-3-yl (PY); and (99m)Tc-5Uboroxime: R = uracil-5-yl (5U)). All five new (99m)Tc(III) radiotracers were prepared in high yield and high radiochemical purity (RCP = 90-98%), and they remained stable in the kit mixture for >6 h. Biodistribution and imaging (planar and SPECT) studies were carried out using Sprague-Dawley (SD) rats. Planar image quantification was performed to compare their myocardial retention and liver clearance kinetics. It was found that their heart retention and liver clearance curves were best fitted to the biexponential decay function. The initial heart uptake at 0-1 min after injection followed the general ranking order of (99m)Tc-ISboroxime (4.98 ± 1.05%ID) ∼ (99m)Tc-Teboroxime (4.56 ± 0.91%ID) ∼ (99m)Tc-PAboroxime (4.03 ± 1.23%ID) ∼ (99m)Tc-PYboroxime (4.07 ± 0.80%ID) > (99m)Tc-5Uboroxime (3.24 ± 0.67%ID) > (99m)Tc-MPboroxime (2.53 ± 0.65%ID). The fast-phase myocardial retention time followed the general order of (99m)Tc-PAboroxime (3.21 ± 0.29 min) > (99m)Tc-Teboroxime (1.63 ± 0.40 min) ∼ (99m)Tc-PYboroxime (1.57 ± 0.29 min) ∼ (99m)Tc-ISboroxime (1.55 ± 0.32 min) > (99m)Tc-MPboroxime (0.68 ± 0.16 min) > (99m)Tc-5Uboroxime (0.33 ± 0.11 min). (99m)Tc-PAboroxime (3.05 ± 1.10%ID/g) and (99m)Tc-ISboroxime (3.75 ± 0.68%ID/g) had the 2 min initial heart uptake very close to that of (99m)Tc-Teboroxime (3.30 ± 0.50%ID/g). However, the myocardial retention time of (99m)Tc-PAboroxime was significantly longer than that of (99m)Tc-ISboroxime and (99m)Tc-Teboroxime. Even though the best time window is 0-5 min for SPECT image acquisition, high quality SPECT images could be obtained during the first 30 min

  13. Novel bismuth oxophosphate halides [Bi8O8][BiO2](PO4)2X (X=Cl, Br) based on oxocentered 2D blocks and their relationships to the Aurivillius phases

    NASA Astrophysics Data System (ADS)

    Kozin, Michael S.; Aliev, Almaz; Colmont, Marie; Mentré, Olivier; Siidra, Oleg I.; Krivovichev, Sergey V.

    2013-03-01

    Two new bismuth phosphate halides [Bi8O8][BiO2](PO4)2Cl and [Bi8O8][BiO2](PO4)2Br, high-temperature phases have been obtained by the solid-state reaction method. Oa-Bi bonds (Oa—additional oxygen atoms not bonded to P) are the shortest and therefore the strongest in the studied structures, which makes it reasonable to consider the Bi-O substructure consisting of OBi4 tetrahedra and OBi3 triangles as an independent structural unit interacting with X atoms and PO4 tetrahedra through relatively weak Bi-X and Bi-O bonds. The topology of this oxocentered Bi-O structural unit is two-dimensional and obviously related to the [O2Bi2]2+ layer typical for the Aurivillius type compounds. The formula of the oxocentered block is ([O8Bi8][O2Bi])7+ with the first part in square brackets designating the moiety formed by the OBi4 tetrahedra, whereas the second part shows 3-coordinated O atoms and the Bi atoms not participating in the OBi4 tetrahedra. The interlayer in between the oxocentered 2D blocks is occupied by the phosphate groups and halogen atoms which are organized in alternating stripes. In the case of studied bismuth oxyphosphate halides as well as in other previously reported compounds, 'additional' oxygen atoms can be considered as segregation centers for Bi3+ cations. This viewpoint may appear to be useful for design of new schemes and synthetic routes to the bismuth oxysalt compounds with different structural architectures and possible useful applications. The comparison with the similar stairs-like layers in bismuth oxysalt structures is also given.

  14. Monohalogenated ferrocenes C5H5FeC5H4 X (X = Cl, Br and I) and a second polymorph of C5H5FeC5H4I

    PubMed Central

    Romanov, Alexander S.; Mulroy, Joseph M.; Khrustalev, Victor N.; Antipin, Mikhail Yu.; Timofeeva, Tatiana V.

    2009-01-01

    The structures of the three title monosubstituted ferrocenes, namely 1-chloro­ferrocene, [Fe(C5H5)(C5H4Cl)], (I), 1-bromo­ferrocene, [Fe(C5H5)(C5H4Br)], (II), and 1-iodo­ferrocene, [Fe(C5H5)(C5H4I)], (III), were determined at 100 K. The chloro- and bromo­ferrocenes are isomorphous crystals. The new triclinic polymorph [space group P , Z = 4, T = 100 K, V = 943.8 (4) Å3] of iodo­ferrocene, (III), and the previously reported monoclinic polymorph of (III) [Laus, Wurst & Schottenberger (2005 ▶). Z. Kristallogr. New Cryst. Struct. 220, 229–230; space group Pc, Z = 4, T = 100 K, V = 924.9 Å3] were obtained by crystallization from ethanolic solutions at 253 and 303 K, respectively. All four phases contain two independent mol­ecules in the unit cell. The relative orientations of the cyclo­penta­dienyl (Cp) rings are eclipsed and staggered in the independent mol­ecules of (I) and (II), while (III) demonstrates only an eclipsed conformation. The triclinic and monoclinic polymorphs of (III) contain nonbonded inter­molecular I⋯I contacts, causing different packing modes. In the triclinic form of (III), the mol­ecules are arranged in zigzag tetra­mers, while in the monoclinic form the mol­ecules are arranged in zigzag chains along the a axis. Crystallographic data for (III), along with the computed lattice energies of the two polymorphs, suggest that the monoclinic form is more stable. PMID:19893225

  15. Nature of the bonding in the AuNgX (Ng = Ar, Kr, Xe; X = F, Cl, Br, I) molecules. Topological study on electron density and the electron localization function (ELF).

    PubMed

    Makarewicz, Emilia; Gordon, Agnieszka J; Berski, Slawomir

    2015-03-19

    Topological analysis of the electron localization function (ELF) has been carried out for the AuNgX (Ng = Ar, Kr, Xe; X = F, Cl, Br, I) molecules using the wave function approximated by the CCSD, MP2, and DFT(B3LYP, M062X) methods including zero-order regular approximation (ZORA). In the Ng-F bond, the bonding disynaptic attractor V(Ng,F) is missing; therefore, there are no signs of the covalent binding. The nature of the Au-Ng bond depends on the computational method used. Analysis of the ELF carried out for the AuArF and AuXeF molecules, with the wave function approximated by the CCSD and MP2 methods, shows the V(Au,Ng) attractor possibly corresponding to a partially covalent binding between the gold and noble gas atom. However, its very small basin population (<1e) and a very large value of the variance of the basin population suggest that the Au-Ng bond has a very delocalized character. Such bond nature may be related to the charge shift concept with a resonance of the Au(-+)NgX, Au(+-)NgX hybrids. The weakest Au-Ng bond, in terms of the smallest amount of electron density for the V(Au,Ng) basin, is found for the AuKrF molecule with the CCSD method (0.13e). The MP2 method, however, does not yield any V(Au, Ng) population; hence, the covalent Au-Kr bond is not confirmed. Because the V(Au,Ng) attractor is also not observed with the DFT method, the proper characterization of the Au-Ng bond requires proper description of correlation effects. Additional studies on the Au2 and [AuXe](+) molecules, performed at the CCSD and B3LYP levels, exhibit no V(Au,Au) and V(Au,Xe) bonding basins either. PMID:25266645

  16. Anticooperativity of FHF hydrogen bonds in clusters of the type F- × (HF)n, RF × (HF)n and XF × (HF)n, R = alkyl and X = H, Br, Cl, F

    NASA Astrophysics Data System (ADS)

    Kucherov, S. Yu.; Bureiko, S. F.; Denisov, G. S.

    2016-02-01

    Properties of twenty five hydrogen-bonded complexes, namely, F- × (HF)n (n = 1-6), RF × (HF)n (R = t-Bu, i-Pr, Et, Me; n = 1-3), XF × (HF)n (X = H, Br, Cl; n = 1-2), and FF…HF with the hydrogen bond energy varying in a wide range have been calculated using ab initio methods at the MP2/6-31++G** level. For the first time, the energies, geometrical parameters and vibrational frequencies are obtained for the series of clusters, where the bonding character changes from covalent to van der Waals on the variation of proton-acceptor ability of the base, and the energies are in the range of 45-1 kcal/mol. The mutual influence of multiple hydrogen bonds of F…HF type in clusters, in which a fluorine anion or an atom participates in hydrogen bond formation as the acceptor, is systematically investigated. The relative changes in the values of the considered parameters on the sequential addition of an HF molecule (anticooperativity) were determined. It was shown that non-additivity of the interaction is most strongly pronounced in the energy and vibrational frequency values, geometrical parameters of hydrogen bonds are less sensitive to the mutual influence. The anticooperative effect is more pronounced on the hydrogen bridge length R(F...F) than on the geometry of proton donor r(HF). The hydrogen bond formation and the increase of the number n of ligands lead to successive lengthening of the r(XF) bond adjacent to the hydrogen bridge. The length of an XF bond changes stronger on formation of each hydrogen bond than the HF bond length.

  17. Etude structurale et vibrationnelle d'un nouveau composé complexe de cobalt: [Co(imidazole)4Cl]Cl.

    PubMed

    Derbel, Amira; Mhiri, Tahar; Graia, Mohsen

    2015-10-01

    In the title complex, chlorido-tetra-kis-(1H-imidazole-κN (3))cobalt(II) chloride, [CoCl(C3H4N2)4]Cl, the Co(II) cation has a distorted square-pyramidal coordination environment. It is coordinated by four N atoms of four imidazole (Im) groups in the basal plane, and by a Cl atom in the apical position. It is isostructural with [Cu(Im)4Cl]Cl [Morzyk-Ociepa et al. (2012 ▸). J. Mol. Struct. 1028, 49-56] and [Cu(Im)4Br]Br [Hossaini Sadr et al. (2004 ▸). Acta Cryst. E60, m1324-m1326]. In the crystal, the [CoCl(C3H4N2)4](+) cations and Cl(-) anions are linked via N-H⋯Cl hydrogen bonds, forming layers parallel to (010). These layers are linked via C-H⋯Cl hydrogen bonds and C-H⋯π and π-π [inter-centroid distance = 3.794 (2) Å] inter-actions, forming a three-dimensional framework. The IR spectrum shows vibrational bands typical for imidazol groups. The monoclinic unit cell of the title compound emulates an ortho-rhom-bic cell as its β angle is close to 90°. The crystal is twinned, with the refined ratio of twin components being 0.569 (1):0.431 (1). PMID:26594402

  18. Efficient synthesis of Empagliflozin, an inhibitor of SGLT-2, utilizing an AlCl3-promoted silane reduction of a β-glycopyranoside.

    PubMed

    Wang, Xiao-jun; Zhang, Li; Byrne, Denis; Nummy, Larry; Weber, Dirk; Krishnamurthy, Dhileep; Yee, Nathan; Senanayake, Chris H

    2014-08-15

    An efficient production synthesis of the SGLT-2 inhibitor Empagliflozin (5) from acid 1 is described. The key tactical stage involves I/Mg exchange of aryl iodide 2 followed by addition to glucono lactone 3 in THF. Subsequent in situ treatment of the resulting lactol with HCl in MeOH produces β-anomeric methyl glycopyranoside 4 which is, without isolation, directly reduced with Et3SiH mediated by AlCl3 as a Lewis acid in CH2Cl2/MeCN to afford 5 in 50% overall yield. The process was implemented for production on a metric ton scale for commercial launch. PMID:25061799

  19. The formation of surface multilayers at the air-water interface from sodium polyethylene glycol monoalkyl ether sulfate/AlCl(3) solutions: the role of the size of the polyethylene oxide group.

    PubMed

    Xu, Hui; Penfold, Jeff; Thomas, Robert K; Petkov, Jordan T; Tucker, Ian; Webster, John P R

    2013-09-17

    Neutron reflectivity, NR, and surface tension, ST, have been used to study the surface adsorption properties at the air-water interface of the anionic surfactant sodium polyethylene glycol monododecyl ether sulfate (sodium lauryl ether sulfate, SLES) in the presence of Al(3+) multivalent counterions, by the addition of AlCl3. In the absence of AlCl3 and at low AlCl3 concentrations monolayer adsorption is observed. With increasing AlCl3 concentration, surface multilayer formation is observed, driven by SLES/Al(3+) complex formation. The onset of multilayer formation occurs initially as a single bilayer or a multilayer structure with a limited number of bilayers, N, ≤3, and ultimately at higher AlCl3 concentrations N is large, >20. The evolution in the surface structure is determined by the surfactant and AlCl3 concentrations, and the size of the polyethylene oxide group in the different SLES surfactants studied. From the NR data, approximate surface phase diagrams are constructed, and the evolution of the surface structure with surfactant and electrolyte concentration is shown to be dependent on the size of the polyethylene oxide group. As the polyethylene oxide group increases in size the multilayer formation requires increasingly higher surfactant and AlCl3 concentrations to promote the formation. This is attributed to the increased steric hindrance of the polyethylene oxide group disrupting SLES/Al(3+) complex formation. PMID:23968161

  20. Low to negligible BrO/SO2 ratios at two subduction-zone volcanoes

    NASA Astrophysics Data System (ADS)

    Bobrowski, Nicole; Hörmann, Christoph; Mori, Toshiya; Platt, Ulrich

    2014-05-01

    In July 2013 a measurement campaign took place on Kyushu, Japan, investigating the BrO/SO2 ratio in the plume of Sakurajima and Aso. Multi-Axis-Differential Optical Absorption Spectroscopy (MAX-DOAS) measurements were carried out at four sides on Sakurajima Island, with a maximum distance of about 5 km downwind, and assuming a wind speed of 5 m/s (corresponding to a plume age of about 15 minutes). At Aso measurements took place on the western slope of the active crater and at the crater rim. The MAX-DOAS data of both sites were evaluated for BrO and SO2 slant column densities (SCDs). In the following, BrO/SO2 ratios were calculated to overcome dilution effects and to investigate the BrO formation processes in the ash-laden plume of Sakurajima and the volcanic plume of Aso which is characterized by emissions from a fumarolic area and a mud pool. The BrO/SO2 ratios of the measurement have been below the detection limit for Aso as well as during most of the measurement days at Sakurajima with the only exception on 15th July 2013, when a BrO/SO2 ratio of ~ 1 x 10-5 could be determined. After very high BrO/SO2 ratios at Sakurajima that were reported by C. Lee et al. (2005) our results seem to be unexpected but nevertheless match the general geological settings at both volcanoes. In a recent paper, Shinohara (2013) summarized and compared chlorine emissions from the Japanese volcanic arc with global chlorine emissions from arc volcanoes and pointed out that the volcanic gas emissions in Japan are quite Cl-poor compared to those at other subduction zones. In the recent past it has been found that low chlorine emissions can occur together with nevertheless high bromine emissions (Nyiragongo, Bobrowski et al., 2013). However, looking up Br/Cl ratios (of condensate measurements at fumaroles) of the Japanese arc volcanism summarized in Gerlach, 2004 a comparatively low Br/Cl ratio is added with 6-7 x 10-4 (global arc mean 2 x 10-3) to the already poor chlorine emissions. We

  1. Molecular structures and thermodynamic properties of 12 gaseous cesium-containing species of nuclear safety interest: Cs 2, CsH, CsO, Cs 2O, CsX, and Cs 2X 2 (X = OH, Cl, Br, and I)

    NASA Astrophysics Data System (ADS)

    Badawi, Michael; Xerri, Bertrand; Canneaux, Sébastien; Cantrel, Laurent; Louis, Florent

    2012-01-01

    Ab initio electronic structure calculations at the coupled cluster level with a correction for the triples extrapolated to the complete basis set limit have been made for the estimation of the thermochemical properties of Cs 2, CsH, CsO, Cs 2O, CsX, and Cs 2X 2 (X = OH, Cl, Br, and I). The standard enthalpies of formation and standard molar entropies at 298 K, and the temperature dependence of the heat capacities at constant pressure were evaluated. The calculated thermochemical properties are in good agreement with their literature counterparts. For Cs 2, CsH, CsOH, Cs 2(OH) 2, CsCl, Cs 2Cl 2, CsBr, CsI, and Cs 2I 2, the calculated ΔfH298K∘ values are within chemical accuracy of the most recent experimental values. Based on the excellent agreement observed between our calculated ΔfH298K∘ values and their literature counterparts, the standard enthalpies of formation at 298 K are estimated to be the following: ΔfH298K∘ (CsO) = 17.0 kJ mol -1 and ΔfH298K∘ (Cs 2Br 2) = -575.4 kJ mol -1.

  2. Memory-enhancing effect of aspirin is mediated through opioid system modulation in an AlCl3-induced neurotoxicity mouse model

    PubMed Central

    RIZWAN, SAIMA; IDREES, AYESHA; ASHRAF, MUHAMMAD; AHMED, TOUQEER

    2016-01-01

    Neurodegenerative disorders such as Alzheimers disease (AD) are multifaceted and there are currently a limited number of therapeutic strategies available to treat them. Aspirin is known to act on multiple therapeutic targets and is a successful anti-inflammatory agent in various tissues. The present study aimed to ascertain the performance of aspirin when employed as a therapeutic agent to treat neurodegeneration on novel targets, including opioid system genes, in an AlCl3-induced neurotoxicity mouse model. The effects of two doses of aspirin (5 and 20 mg/kg aspirin for 12 days) were investigated in an AlCl3-induced neurotoxicity mouse model (150 mg/kg AlCl3 for 12 days). Neurological improvements were assessed through different behavioral tests and the effects of aspirin on opioid system gene expression levels were assessed by reverse transcription-polymerase chain reaction. Both doses resulted in improvements in cognitive behavior. A 5 mg/kg dose of aspirin was revealed to be effective for spatial memory improvement (7.14±0.84 sec), whilst a 20 mg/kg dose was superior for improving extinction learning (7.63±4.04%). Aspirin (5 mg/kg) also significantly improved contextual memory (48.05±10.6%) when compared with the AlCl3-treated group (1.49±0.62%; P<0.001). Aspirin was also observed to significantly decrease δ-opioid receptor expression in the cortex (1.09±0.08 and 1.27±0.08, respectively) at both doses (5 and 20 mg/kg) when compared with the AlCl3-treated group (3.69±1.43; P<0.05). Furthermore, aspirin at 5 mg/kg significantly reduced expression of prodynorphin in the cortex (0.57±0.20) when compared with the AlCl3-treated group (1.95±0.84; P<0.05). Notably, the effect of aspirin was significant in the cortex but not in the hippocampus. In summary, aspirin was effective in ameliorating the AD-like symptoms via the modulation of opioid systems. However, additional studies are required to determine the long term effects of aspirin on such conditions. PMID

  3. Crystal structure, thermoelectric and magnetic properties of the type-I clathrate solid solutions Sn 24P 19.3(2)Br xI 8- x (0 ≤ x ≤ 8) and Sn 24P 19.3(2)Cl yI 8- y ( y ≤ 0.8)

    NASA Astrophysics Data System (ADS)

    Zaikina, Julia V.; Schnelle, Walter; Kovnir, Kirill A.; Olenev, Andrei V.; Grin, Yuri; Shevelkov, Andrei V.

    2007-08-01

    A solid solution of the general formula Sn 24P 19.3Cl yI 8- y ( y ≤ 0.8) with a crystal structure of the clathrate-I type (cubic, Pm3¯n) was prepared by a standard ampoule technique and found to be isostructural to the previously discovered Sn 24P 19.3Br xI 8- x ( x = 0-8). The unit cell parameter linearly decreases from 10.954(1) Å for y = 0 to 10.933(1) Å for y = 0.8. Sn 24P 19.3Cl yI 8- y ( y ≤ 0.8) and Sn 24P 19.3Br xI 8- x ( x = 0-8) reveal a non-uniform communal distribution of the halogen atoms inside the cages of different size formed in the clathrate framework. The halogen atoms of smaller size (chlorine for Sn 24P 19.3Cl yI 8- y and bromine for Sn 24P 19.3Br xI 8- x) preferentially occupy the smaller 20-vertex cages. Thereby the chlorine atoms do not show a complete segregation in the smaller cages, but mix with the iodine atoms in both types of cages. The magnetic and thermoelectric properties for Sn 24P 19.3Cl yI 8- y ( y ≤ 0.8) as well as for Sn 24P 19.3Br xI 8- x ( x = 0-8) were investigated. Both solid solutions are diamagnetic semiconductors as expected for Zintl phases. The core diamagnetism of the guest atoms contributes primarily to the diamagnetic susceptibility of the compounds. The band gap in the case of Sn 24P 19.3Br xI 8- x ( x = 0-8) varies from 0.03 eV to 0.14 eV and appears to be a linear function of the guest halogen atom ratios. The lowest value of thermal conductivity, 0.5 W m -1 K -1 at room temperature, is observed for Sn 24P 19.3Br 2I 6 featuring the almost random distribution of the guest bromine and iodine atoms.

  4. Thermodynamic properties and single-electrode Peltier heats of a Li-Al alloy in a LiCl-KCl eutectic melt

    SciTech Connect

    Amezawa, Koji; Yamamoto, Naoichi; Tomii, Yoichi; Ito, Yasuhiko

    1999-03-01

    Thermodynamic properties of a Li-Al alloy in the two-phase ({alpha}Al + {beta}LiAl), ({beta}LiAl + {gamma}Li{sub 3}Al{sub 2}), and ({gamma}Li{sub 3}Al{sub 2} + liquid) regions, and in the single {beta}LiAl phase region were determined from electromotive force measurements in a LiCl-KCl eutectic melt at temperatures from 650 to 76f0 K. From the obtained thermodynamic properties, the single-electrode Peltier heat of a Li-Al alloy electrode was evaluated as a function of the alloy composition. It turned out that the single-electrode Peltier heat of a Li-Al alloy electrode exhibits discontinuities at the compositions of coexisting-single phase boundaries. The change of the single-electrode Peltier heat on a phase boundary was interpreted thermodynamically and was found to follow from thermodynamic data for the single phases and the phase diagram data.

  5. Performance of Al-0.5 Mg-0.02 Ga-0.1 Sn-0.5 Mn as anode for Al-air battery in NaCl solutions

    NASA Astrophysics Data System (ADS)

    Ma, Jingling; Wen, Jiuba; Gao, Junwei; Li, Quanan

    2014-05-01

    In this research, metal-air battery based on Al, Zn, Al-0.5 Mg-0.02 Ga-0.1 Sn and Al-0.5 Mg-0.02 Ga-0.1 Sn-0.5 Mn (wt%) is prepared and the battery performance is investigated by constant current discharge test in 2 mol L-1 NaCl solutions. The characteristics of the anodes after discharge are investigated by electrochemical impedance spectroscopy (EIS), scanning electron microscopy (SEM). The corrosion behavior of the anodes is studied by self-corrosion rate measurement and potentiodynamic polarization measurement. The results show that Al-Mg-Ga-Sn-Mn is more active than Al, Zn and Al-Mg-Ga-Sn anodes. The self-corrosion rate is found to be in the order: Al < Al-Mg-Ga-Sn-Mn < Al-Mg-Ga-Sn < Zn. It has been observed that the Al-air battery based on Al-Mg-Ga-Sn-Mn offers higher operating voltage and anodic utilization than those with others. SEM and EIS results of the alloy are in good agreement with corrosion characteristics.

  6. Synthesis and luminescent properties of Sr3Al2O5Cl2: Eu2+, Dy3+ rod-like nanocrystals

    NASA Astrophysics Data System (ADS)

    Wang, Zhengliang; Zhang, Qiuhan; Rong, Meizhu; Tan, Huiying; Wang, Qin; Zhou, Qiang; Chen, Guo

    2016-08-01

    White long afterglow phosphor with nano-rods, Sr3Al2O5Cl2: Eu2+, Dy3+, has been successfully synthesized by the solid state reaction. Their structure, morphology, scanning electron microscopy, luminescent properties and long afterglow properties were investigated by X-ray diffraction, transmission electron microscopy luminescence spectra and the luminescence decay curve. The obtained phosphor Sr3Al2O5Cl2: Eu2+, Dy3+ exhibits two broad emission bands, which are located at ∼445 nm and ∼590 nm, respectively. White light can be observed from this phosphor with appropriate CIE values (x = 0.357, y = 0.332). The white afterglow duration of this phosphor is about 0.5 h (>0.35 mcd/m2).

  7. 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

  8. Phase behavior and physicochemical properties of sodium octyl sulfate/n-decane/1-hexanol/aqueous AlCl[sub 3] middle-phase microemulsion

    SciTech Connect

    Abe, Masahiko; Yamazaki, Tadao; Ogino, Keizo )

    1992-03-01

    The phase behavior and physicochemical properties of sodium octyl sulfate/n-decane/1-hexanol/aqueous AlCl[sub 3] middle-phase microemulsion have been studied as a function of salinity to develop an experimental investigation for better understanding of the microstructure of a middle-phase microemulsion. The system exhibits a Winsor-type phase transition (Winsor I [leftrightarrow] Winsor III [leftrightarrow] Winsor II) with increasing salinity. Over an appreciable salinity (from 0.50% to 9.2%), the formation of Winsor III, composed of a middle-phase microemulsion in equilibrium with the excess water and oil phases, was observed. It has been observed that as the salinity is increased, the phase volume of the middle-phase microemulsion undergoes a drastic decrease at a specific brine concentration (3.8%). Furthermore, the physicochemical properties such as water content, electrical conductivity, diffusion coefficient, and solubilization of 1-hexanol in the AlCl[sub 3] middle-phase microemulsion all show abrupt changes at this salinity. The drastic change in the phase volume and physicochemical properties at the specific salinity of 3.8% may be attributed to a phase inversion of the AlCl[sub 3] middle-phase microemulsion from oil-rich to water-rich continuous phase with increasing AlCl[sub 3] concentration, which is quite a different behavior from that observed for monovalent and divalent salt systems. Specifically, it may be assumed that a fluctuating structure of bicontinuous type and a liquid crystal structure overcome the droplet structure in the phase equilibrium at a certain salinity during the increase in the trivalent salt concentration. 25 refs., 10 figs.

  9. Effects of Si/Al Ratio on Cu/SSZ-13 NH3-SCR Catalysts: Implications for the active Cu species and the Roles of Brønsted Acidity

    SciTech Connect

    Gao, Feng; Washton, Nancy M.; Wang, Yilin; Kollar, Marton; Szanyi, Janos; Peden, Charles HF

    2015-09-03

    Cu/SSZ-13 catalysts with three Si/Al ratios of 6, 12 and 35 were synthesized with Cu incorporation via solution ion exchange. The implications of varying Si/Al ratios on the nature of the multiple Cu species that can be present in the SSZ-13 zeolite are a major focus of this work, as highlighted by the results of a variety of catalyst characterization and reaction kinetics measurements. Specifically, catalysts were characterized with surface area/pore volume measurements, temperature programmed reduction by H2 (H2-TPR), NH3 temperature programmed desorption (NH3-TPD), and DRIFTS and solid-state nuclear magnetic resonance (NMR) spectroscopies. Catalytic properties were examined using NO oxidation, ammonia oxidation, and standard ammonia selective catalytic reduction (NH3-SCR) reactions on selected catalysts under differential conditions. Besides indicating possible variably active multiple Cu species for these reactions, the measurements are also used to untangle some of the complexities caused by the interplay between redox of Cu ion centers and Brønsted acidity. All three reactions appear to follow a redox reaction mechanism, yet the roles of Brønsted acidity are quite different. For NO oxidation, increasing Si/Al ratio lowers Cu redox barriers, thus enhancing reaction rates. Brønsted acidity appears to play essentially no role for this reaction. For standard NH3-SCR, residual Brønsted acidity plays a significant beneficial role at both low- and high-temperature regimes. For NH3 oxidation, no clear trend is observed suggesting both Cu ion center redox and Brønsted acidity play important and perhaps competing roles. The authors gratefully acknowledge the US Department of Energy (DOE), Energy Efficiency and Renewable Energy, Vehicle Technologies Office for the support of this work. The research described in this paper was performed in the Environmental Molecular Sciences Laboratory (EMSL), a national scientific user facility sponsored by the DOE’s Office of

  10. Intercalation and controlled release of 2,4-dichlorophenoxyacetic acid using rhombohedral [LiAl2(OH)6]Cl·xH2O

    NASA Astrophysics Data System (ADS)

    Ragavan, Anusha; Khan, Aamir I.; O'Hare, Dermot

    2006-05-01

    2,4-Dichlorophenoxyacetic acid (2,4-D) has been fully intercalated into the rhombohedral polymorph of [LiAl2(OH)6]Cl·xH2O ([rhom-Li Al] LDH) by an ion exchange method. The controlled release of 2,4-D from the interlamellar spaces of [rhom-Li Al] LDH has been studied in a phosphate buffer, natural rainwater and deionised water. In buffer solution and rainwater, the intercalated herbicide is exchanged for anions in solution. In contrast, in deionised water the herbicide is released as part of the Li+/herbicide ion pair, leading to the formation of Al(OH)3 and the solvated ions.

  11. Kinetics of NiO and NiCl2 hydrogen reduction as precursors and properties of produced Ni/Al2O3 and Ni-Pd/Al2O3 catalysts.

    PubMed

    Sokić, Miroslav; Kamberović, Željko; Nikolić, Vesna; Marković, Branislav; Korać, Marija; Anđić, Zoran; Gavrilovski, Milorad

    2015-01-01

    The objects of this investigation were the comparative kinetic analysis of the NiO and NiCl2 reduction by hydrogen during an induction period and elimination of the calcination during the synthesis of Ni/Al2O3 catalysts. The effect of temperature and time on NiO and NiCl2 reduction degrees was studied. Avrami I equation was selected as the most favorable kinetic model and used to determine activation energy of the NiO and NiCl2 reduction for the investigated temperature range (623-923 K) and time intervals (1-5 minutes). The investigation enabled reaching conclusions about the reaction ability and rate of the reduction processes. Afterward, Ni/Al2O3 catalysts were obtained by using oxide and chloride precursor for Ni. The catalysts were supported on alumina-based foam and prepared via aerosol route. Properties of the samples before and after low-temperature hydrogen reduction (633 K) were compared. Obtained results indicated that the synthesis of Ni/Al2O3 catalysts can be more efficient if chloride precursor for Ni is directly reduced by hydrogen during the synthesis process, without the calcination step. In addition, Ni-Pd/Al2O3 catalysts with different metal content were prepared by using chloride precursors. Lower reduction temperature was utilized and the chlorides were almost completely reduced at 533 K. PMID:25789335

  12. Kinetics of NiO and NiCl2 Hydrogen Reduction as Precursors and Properties of Produced Ni/Al2O3 and Ni-Pd/Al2O3 Catalysts

    PubMed Central

    Sokić, Miroslav; Kamberović, Željko; Nikolić, Vesna; Marković, Branislav; Korać, Marija; Anđić, Zoran; Gavrilovski, Milorad

    2015-01-01

    The objects of this investigation were the comparative kinetic analysis of the NiO and NiCl2 reduction by hydrogen during an induction period and elimination of the calcination during the synthesis of Ni/Al2O3 catalysts. The effect of temperature and time on NiO and NiCl2 reduction degrees was studied. Avrami I equation was selected as the most favorable kinetic model and used to determine activation energy of the NiO and NiCl2 reduction for the investigated temperature range (623–923 K) and time intervals (1–5 minutes). The investigation enabled reaching conclusions about the reaction ability and rate of the reduction processes. Afterward, Ni/Al2O3 catalysts were obtained by using oxide and chloride precursor for Ni. The catalysts were supported on alumina-based foam and prepared via aerosol route. Properties of the samples before and after low-temperature hydrogen reduction (633 K) were compared. Obtained results indicated that the synthesis of Ni/Al2O3 catalysts can be more efficient if chloride precursor for Ni is directly reduced by hydrogen during the synthesis process, without the calcination step. In addition, Ni-Pd/Al2O3 catalysts with different metal content were prepared by using chloride precursors. Lower reduction temperature was utilized and the chlorides were almost completely reduced at 533 K. PMID:25789335

  13. Is the 'Bromine Explosion' generated from the reaction BrO HO2 alone?

    NASA Astrophysics Data System (ADS)

    Behnke, Wolfgang; Zetzsch, Cornelius

    2010-05-01

    We observed bromine explosions (a fast production of atomic Br and Cl under tropospheric conditions) in various smog chamber experiments in Teflon bags at room temperature at a relative humidity of about 80% in the presence of NaCl/NaBr-aerosol, simulated sunlight and ozone (200 - 400 ppb). Time profiles of ozone and hydrocarbons (HCs: n-butane, 2,2-dimethylbutane, tetramethylbutane and toluene, initially about 2 ppb each) were monitored to determine concentrations and source strengths of OH radicals, atomic Cl and Br and the corresponding time profiles of BrCl and Br2 as their photolytic precursors. The number and size of aerosols are measured as well as their chemical composition (Br-, Cl- and oxalic acid). Full records of raw data from the smog chamber runs are available at www.eurochamp.org for potential users. Chemical box model calculations deliver concentrations of various intermediates, such as aldehydes, HO2 and RO2 radicals and the inorganic halogen compounds ClO, BrO, HOCl and HOBr, where HOBr from O3 + Br- => BrO- + O2 in the aqueous/adsorbed phase induces the following gas-phase/ heterogeneous chain reaction Br + O3 => BrO + O2(1) BrO + HO2 => HOBr + O2(2a) HOBr + (Aerosol) => HOBrad(3) Surface-adsorbed HOBr reacts with Br- or Cl- to produce Br2 or BrCl, both of which are released and photolysed. Formation of Br2 should prevail up to Cl-/Br- -ratios of about 104 (Fickert, S., J.W. Adams, J.N. Crowley, J. Geophys. Res., D104, 23719-23727, 1999). A maximum of this ratio is reached about 30 minutes after the beginning and decreases during the next hours - probably by reaction of Br2 with oxalate and absorption of HBr, formed from the reaction of Br with aldehydes. Parallel to chain reaction (1)-(3) a chain reaction replacing Br by Cl seems possible but can not be realized, since the main sink of atomic Cl is its reaction with hydrocarbons - leading to chain termination - in contrast to atomic Br (ratio of rates: kCl[O3]/kCl[HC] ~ 0.1; kBr[O3]/kBr

  14. Influence of SiC reinforcement particles on the tribocorrosion behaviour of Al-SiCp FGMs in 0.05M NaCl solution

    NASA Astrophysics Data System (ADS)

    Vieira, A. C.; Rocha, L. A.; Mischler, S.

    2011-05-01

    The main aim of this work was to study and understand the influence of SiC particles on the corrosion and tribocorrosion of Al-matrix composite materials. For that, Al-SiCp functionally graded composites were produced by centrifugal casting and different SiCp contents were achieved. Their mechanical properties were improved by age-hardening heat treatments. The tribocorrosion behaviour was studied in 0.05M NaCl solutions using a reciprocating motion tribometer involving an alumina ball sliding against the Al-based samples. Above critical SiC particles' content the matrix alloy surface was found to be protected against wear by SiC particles protruding from the surface. Below this threshold content, the SiC reinforcement was inefficient and the wear rate of the composite was the same as the non-reinforced alloy.

  15. Photoabsorption of the ground state of Ne and of Ne-like Na+, Mg2+, Al3+, Si4+, P5+, S6+, and Cl7+ ions

    NASA Astrophysics Data System (ADS)

    Sakho, I.

    2016-03-01

    Photoabsorption of the 1s2 2s2 2p6 (1S0) ground state of Ne-like ions is presented in this paper. Resonance energies and width of the 2 s 2p6 n p1P1 series of Ne and Ne-like Na+, Mg2+, Al3+, Si4+, P5+, S6+, and Cl7+ ions are reported. Wavelengths of the 2s2 2p6 (1S0) → 2s2 2p5(2P 3 / 2 , 1 / 2) n d transitions in neon-like Na+ ion and of the 2s2 2p6(1S0) → 2 s 2p6 n p1P1 transitions in Ne and in Ne-like Na+, Mg2+, Al3+, Si4+, P5+, S6+, and Cl7+ ions are tabulated. Analysis of the resonances investigated is done in the framework of the LS, jj and JK coupling schemes. All the calculations are made using the Screening constant by unit nuclear charge (SCUNC) formalism. Very good agreement is found between the SCUNC results and various experimental and theoretical literature values and new data for the Ne-like Si4+, P5+, S6+, and Cl7+ ions are listed.

  16. Mechanisms of Tenebrescence and Persistent Luminescence in Synthetic Hackmanite Na8Al6Si6O24(Cl,S)2.

    PubMed

    Norrbo, Isabella; Gluchowski, Pawel; Hyppänen, Iko; Laihinen, Tero; Laukkanen, Pekka; Mäkelä, Jaakko; Mamedov, Fikret; Santos, Hellen S; Sinkkonen, Jari; Tuomisto, Minnea; Viinikanoja, Antti; Lastusaari, Mika

    2016-05-11

    Synthetic hackmanites, Na8Al6Si6O24(Cl,S)2, showing efficient purple tenebrescence and blue/white persistent luminescence were studied using different spectroscopic techniques to obtain a quantified view on the storage and release of optical energy in these materials. The persistent luminescence emitter was identified as impurity Ti(3+) originating from the precursor materials used in the synthesis, and the energy storage for persistent luminescence was postulated to take place in oxygen vacancies within the aluminosilicate framework. Tenebrescence, on the other hand, was observed to function within the Na4(Cl,S) entities located in the cavities of the aluminosilicate framework. The mechanism of persistent luminescence and tenebrescence in hackmanite is presented for the first time. PMID:27088662

  17. Dendrite-Free Aluminum Electrodeposition from AlCl3-1-Ethyl-3-Methyl-Imidazolium Chloride Ionic Liquid Electrolytes

    NASA Astrophysics Data System (ADS)

    Pradhan, Debabrata; Reddy, Ramana G.

    2012-06-01

    A novel, dendrite-free electrorefining of aluminum scrap alloys (A360) was investigated by using a low-temperature AlCl3-1-ethyl-3-methyl-imidazolium chloride (EMIC) ionic liquid electrolyte on copper/aluminum cathodes. The bulk electrodeposition of aluminum was carried out at a fixed voltage of 1.5 V, temperatures 323 K to 383 K (50 °C to 110 °C), stirring rate (0 to 120 rpm), concentration (molar ratio AlCl3:EMIC = 1.25 to 2.0), and electrode surface modification (modified/unmodified). The study investigated the effect of electrode surface modification, cathode materials, temperature, stirring rate, electrolyte concentration, and deposition time on the deposit morphology of aluminum, cathode current density, and their role in production of dendrite-free aluminum deposit, which is essential for decreasing the production cost. The deposits were characterized using scanning electron microscope (SEM), energy-dispersive spectroscopy (EDS), and X-ray diffraction (XRD). It was shown that electrode surface modification, cathode overpotential, and stirring rate play an important role in dendrite-free deposit. Modified electrodes and stirring (60 rpm) eliminate dendritic deposition by reducing cathode overpotential below critical overpotential ( η_{{crt}} ≈ - 0.53V ) for dendrite formation. Pure aluminum (>99 pct) was deposited for all experiments with a current efficiency of 84 to 99 pct and energy consumption of 4.51 to 5.32 kWh/kg Al.

  18. Ozone Depletion Potential of CH3Br

    NASA Technical Reports Server (NTRS)

    Sander, Stanley P.; Ko, Malcolm K. W.; Sze, Nien Dak; Scott, Courtney; Rodriquez, Jose M.; Weisenstein, Debra K.

    1998-01-01

    The ozone depletion potential (ODP) of methyl bromide (CH3Br) can be determined by combining the model-calculated bromine efficiency factor (BEF) for CH3Br and its atmospheric lifetime. This paper examines how changes in several key kinetic data affect BEF. The key reactions highlighted in this study include the reaction of BrO + H02, the absorption cross section of HOBr, the absorption cross section and the photolysis products of BrON02, and the heterogeneous conversion of BrON02 to HOBR and HN03 on aerosol particles. By combining the calculated BEF with the latest estimate of 0.7 year for the atmospheric lifetime of CH3Br, the likely value of ODP for CH3Br is 0.39. The model-calculated concentration of HBr (approximately 0.3 pptv) in the lower stratosphere is substantially smaller than the reported measured value of about I pptv. Recent publications suggested models can reproduce the measured value if one assumes a yield for HBr from the reaction of BrO + OH or from the reaction of BrO + H02. Although the DeAlore et al. evaluation concluded any substantial yield of HBr from BrO + HO2 is unlikely, for completeness, we calculate the effects of these assumed yields on BEF for CH3Br. Our calculations show that the effects are minimal: practically no impact for an assumed 1.3% yield of HBr from BrO + OH and 10% smaller for an assumed 0.6% yield from BrO + H02.

  19. The containment of oil spills in porous media using xanthan/aluminum solutions, gelled by gaseous CO2 or by AlCl3 solutions.

    PubMed

    Gioia, Francesco; Ciriello, Pier Paolo

    2006-12-01

    The gelation in situ of polymers may be a method for temporarily containing organic solvents and other petroleum derived products, which may enter the subsurface. In order to create gels that are neither toxic to humans nor to the ecosystem, we have investigated on the use of the biopolymer xanthan gum with aluminum as a crosslinking agent. Firstly we have considered xanthan/sodium aluminate solutions, which upon preparation are strongly basic and do not gel. The gelation takes place in acid solutions so that Al(III) ions are released, and is instantaneous. Therefore, a special technique must be used for generating the gel structure in situ. The un-gelled solution must be injected and an acid must be added afterwards. We have investigated on the gelling reaction induced by gaseous carbon dioxide, which is an acid gas. The insufflation of CO(2) above the solution generates a layer of gel whose thickness progressively increases as CO(2) diffuses in the polymer solution. Secondly we have investigated on the use of aluminum chloride as the source of Al(III) ions. Also in this case, due to the full availability of Al(III) ions, the gelling reaction would be instantaneous. Therefore, the solution of AlCl(3) must be added on the top of the xanthan solution after its injection. For both gelling systems we have studied both theoretically and experimentally the rate of formation of the gel layer which progressively thickens after the insufflation of CO(2) or after the addition of the AlCl(3) solution. PMID:16935417

  20. Determination of chlorine in food samples via the AlCl molecule using high-resolution continuum source molecular absorption spectrometry in a graphite furnace

    NASA Astrophysics Data System (ADS)

    Fechetia, Miriam; Tognon, André Luiz; da Veiga, Márcia A. M. S.

    2012-05-01

    Determination of chlorine using the molecular absorption of aluminum mono-chloride (AlCl) at the 261.418 nm wavelength was accomplished by high-resolution continuum source molecular absorption spectrometry using a transversely heated graphite tube furnace with an integrated platform. For the analysis, 10 μL of the sample followed by 10 μL of a solution containing Al-Ag-Sr modifier, (1 g L- 1 each), were directly injected onto the platform. A spectral interference due to the use of Al-Ag-Sr as mixed modifier was easily corrected by the least-squares algorithm present in the spectrometer software. The pyrolysis and vaporization temperatures were 500 °C and 2200 °C, respectively. To evaluate the feasibility of a simple procedure for the determination of chlorine in food samples present in our daily lives, two different digestion methods were applied, namely (A) an acid digestion method using HNO3 only at room temperature, and (B) a digestion method with Ag, HNO3 and H2O2, where chlorine is precipitated as a low-solubility salt (AgCl), which is then dissolved with ammonia solution. The experimental results obtained with method B were in good agreement with the certified values and demonstrated that the proposed method is more accurate than method A. This is because the formation of silver chloride prevented analyte losses by volatilization. The limit of detection (LOD, 3σ/s) for Cl in methods A and B was 18 μg g- 1 and 9 μg g- 1, respectively, 1.7 and 3.3 times lower compared to published work using inductively coupled plasma optical emission spectrometry, and absolute LODs were 2.4 and 1.2 ng, respectively.

  1. Solid chemistry of the Zn{sup II}/1,2,4-triazolate/anion system: Separation of 2D isoreticular layers tuned by the terminal counteranions X (X=Cl{sup -}, Br{sup -}, I{sup -}, SCN{sup -})

    SciTech Connect

    Chen Sanping; Sun Shu; Gao Shengli

    2008-12-15

    An array of 2D isoreticular layers, viz. [Zn(atrz)X]{sub {infinity}} (1.X; X=Cl{sup -}, Br{sup -}, I{sup -}; atrz=3-amino-1,2,4-triazole anion), [Zn{sub 4}(atrz){sub 4}(SCN){sub 4}.H{sub 2}O]{sub {infinity}} (1.SCN.H{sub 2}O) and [Zn(trz)X]{sub {infinity}} (2.X; X=Cl{sup -}, Br{sup -}, I{sup -}; trz=1,2,4-triazole anion), have been hydrothermally synthesized and structurally characterized. Compounds 1.X and 1.SCN.H{sub 2}O are constructed from binuclear planar Zn{sub 2}(atrz){sub 2} subunits and exhibit (4,4) topological network when the subunits are simplified as four-connected nodes. Based on changing the terminal counteranions X (X=Cl{sup -}, Br{sup -}, I{sup -}, SCN{sup -}), the average interlayer separations of 1.X and 1.SCN.H{sub 2}O are enlarged, which equal to 5.851, 6.153, 6.651 and 8.292 A, respectively. As a result, H{sub 2}O molecules reside in the spaces between two adjacent layers of 1.SCN.H{sub 2}O. 2 and 1 are the isomorphous structures. In common with 1, the interlayer separations of 2.X are widened with increasing the ion radius. Solid-state luminescence properties and thermogravimetric analyses of 1 and 2 were investigated, respectively. - Graphical Abstract: Based on employing the various terminal counteranions X (X=Cl{sup -}, Br{sup -}, I{sup -}, SCN{sup -}) the average interlayer separations of four 2D isoreticular layer compounds [Zn(atrz)X]{sub {infinity}} are gradually enlarged, which equal to 5.851, 6.153, 6.651 and 8.292 A, respectively. As a result, guest H{sub 2}O molecules reside in the space between two adjacent layers of [Zn{sub 4}(atrz){sub 4}(SCN){sub 4}.H{sub 2}O]{sub {infinity}}.

  2. Crystal structure of Ca{sub 12}Al{sub 14}O{sub 32}Cl{sub 2} and luminescence properties of Ca{sub 12}Al{sub 14}O{sub 32}Cl{sub 2}:Eu{sup 2+}

    SciTech Connect

    Iwata, Tomoyuki; Haniuda, Masahide; Fukuda, Koichiro

    2008-01-15

    The crystal structure of Ca{sub 12}Al{sub 14}O{sub 32}Cl{sub 2} was determined from laboratory X-ray powder diffraction data (CuK{alpha}{sub 1}) using the Rietveld method, with the anisotropic displacement parameters being assigned for all atoms. The crystal structure is cubic (space group I4-bar 3d, Z=2) with lattice dimensions a=1.200950(5) nm and V=1.73211(1) nm{sup 3}. The reliability indices calculated from the Rietveld method were R{sub wp}=8.48% (S=1.21), R{sub p}=6.05%, R{sub B}=1.27% and R{sub F}=1.01%. The validity of the structural model was verified by the three-dimensional electron density distribution, the structural bias of which was reduced as much as possible using the maximum-entropy methods-based pattern fitting (MPF). The reliability indices calculated from the MPF were R{sub B}=0.75% and R{sub F}=0.56%. In the structural model there are one Ca site, two Al sites, two O sites and one Cl site. This compound is isomorphous with Ca{sub 12}Al{sub 10.6}Si{sub 3.4}O{sub 32}Cl{sub 5.4}. Europium-doped sample Ca{sub 12}Al{sub 14}O{sub 32}Cl{sub 2}:Eu{sup 2+} was prepared and the photoluminescence properties were presented. The excitation spectrum consisted of two wide bands, which were located at about 268 and 324 nm. The emission spectrum, when excited at 324 nm, resulted in indigo light with a peak at about 442 nm. - Graphical abstract: A portion of the crystal structure of Ca{sub 12}Al{sub 14}O{sub 32}Cl{sub 2} showing eight-membered AlO{sub 4} rings and Ca-Cl-Ca unit.

  3. Electrochemical Corrosion Behavior of Magnetron-Sputtered Al-Mo Gradient-Coated Steel in 3.5 wt.% NaCl Solution

    NASA Astrophysics Data System (ADS)

    Venugopal, A.; Narayanan, P. Ramesh; Sharma, S. C.; George, Koshy M.

    2016-03-01

    A gradient three-layer Al-Mo coating was deposited on steel using magnetron sputtering method. The corrosion properties of the coating were studied in 3.5 wt.% NaCl solution using electrochemical techniques, whereas the hydrogen-induced cracking (HIC) resistance was examined by constant-load tests using notched tensile specimens. These results were compared with conventional electroplated cadmium-coated steel. The results show that the gradient Al-Mo coating exhibits better corrosion and HIC resistance when compared to electroplated cadmium. This was due to the excellent corrosion resistance of the bottom aluminum-rich layer, while the top Mo-rich layer provided good lubrication properties.

  4. SCC behavior of an Al-3. 7wt%Zn-2. 5wt%Mg alloys before and after welding in 3. 5% NaCl solution

    SciTech Connect

    Liao, C.M. )

    1993-01-01

    The behavior of stress corrosion cracking (SCC) of an overaged Al-3.7wt%Zn-2.5wt%Mg alloy including base metal, weldment, and heat-affected zone (HAZ) in 3.5% NaCl solution was investigated. This Al-Zn-Mg alloy loaded in longitudinal or long transverse direction has good SCC resistance and is maintained even after welding. Welding residual stress alone does not induce the SCC of the weldment. The result of the specially modified type 1 double cantilever beam (DCB) testing shows that the crack can be arrested by the weld metal because of the better SCC resistance of the filler metal ER5183. In addition, a specially designed type 2 DCB testing indicates that the SCC resistance of the HAZ is better than that of the base metal because of the re-overaging of the HAZ during welding.

  5. Moderate temperature sodium cells. V - Discharge reactions and rechargeability of NiS and NiS2 positive electrodes in molten NaAlCl4

    NASA Technical Reports Server (NTRS)

    Abraham, K. M.; Elliot, J. E.

    1984-01-01

    NiS2 and NiS have been characterized as high energy density rechargeable positive electrodes for moderate-temperature Na batteries of the configuration, Na(1)/beta double prime-Al2O3/NaAlCl4(1), NiSx. The batteries operate in the temperature range 170 - 190 C. Positive electrode reactions during discharge/charge cycles have been characterized. Excellent rechargeability of the batteries has been demonstrated by extended cell cycling. A Na/NiS2 cell, operating at 190 C, exceeded 600 deep discharge/charge cycles with practically no capacity deterioration. The feasibility of secondary Na/NiSx batteries with specific energies equal to or greater than 50 Wh/lb and cycle lifes exceeding 1000 deep discharge/charge cycles has been demonstrated.

  6. Molecular modeling of the structure and dynamics of the interlayer species of ZnAlCl layered double hydroxide.

    PubMed

    Pisson, J; Morel, J P; Morel-Desrosiers, N; Taviot-Guého, C; Malfreyt, P

    2008-07-01

    Molecular dynamics simulations of the ZnAl layered double hydroxide containing interlayer chloride anions have been performed in the NpT and Np(zz)T statistical ensembles for metal Zn/Al ratios of 2 and 3. We have monitored the interlayer spacing as a function of the number of intercalated water molecules for each statistical ensemble. We have studied how these profiles are affected by the method of calculation of the charges of the hydroxide layer atoms. Diffusion coefficients of the interlayer water molecules have been calculated for different Zn/Al ratios. The calculation of the chemical potential of the interlayer water molecules has been carried out for three amounts of interlayer water molecules. The calculation showed a qualitative agreement with the bulk water chemical potential within a range of interlayer water molecule contents. PMID:18543873

  7. New Scintillator Materials (K2CeBr5) and (Cs2CeBr5)

    NASA Technical Reports Server (NTRS)

    Hawrami, R.; Volz, M. P.; Batra, A. K.; Aggarwal, M. D.; Roy, U. N.; Groza, M.; Burger, A.; Cherepy, Nerine; Niedermayr, Thomas; Payne, Stephen A.

    2008-01-01

    Cesium cerium bromide (Cs2CeBr5) and potassium cerium bromide (K2CeBr5) are new scintillator materials for X-ray and gamma ray detector applications. Recently halide scintillator materials, such as Ce doped lanthanum bromide has been proved to be very important material for the same purpose. These materials are highly hygroscopic; a search for high light yield non-hygroscopic materials was highly desirable to advance the scintillator technology. In this paper, we are reporting the crystal growth of novel scintillator materials, cesium cerium bromide (Cs2CeBr5) and potassium cerium bromide (K2CeBr5). Crystals were successfully grown from the melt using the vertical Bridgman-Stockbarger technique, in a comparison with the high performance LaBr3 or LaCl3 crystals, cerium based alkali halides crystals, (Cs2CeBr5) and (K2CeBr5) have similar scintillation properties, while being much less hygroscopic. Furthermore, cesium based compounds will not suffer from the self-activity present in potassium and lanthanum compounds. However the Cs2CeBr5 crystals did not grow properly probably due to non-congruent melting or to some phase transition during cooling. Keywords." Scintillator materials; Ce3+; Energy resolution; Light yield; K2CeBr5

  8. Fourier transform infrared spectra in the regions near 1900 and 700 cm -1 and rovibrational analyses of the {ν 1}/{ν 4} and {ν 2}/{ν 5} fundamentals of unstable H 3SnCl, H 3SnBr, and H 3Snl studied as monoisotopic species

    NASA Astrophysics Data System (ADS)

    Bürger, Hans; Betzel, Martina; Schulz, Petra

    1987-01-01

    The IR fundamentals {ν 1}/{ν 4} near 1900 cm -1 and {ν 2}/{ν 5} near 700 cm -1 of the unstable stannyl halides H 3116Sn 35Cl, H 3116Sn 79Br, and H 3116SnI have been studied as monoisotopic species by FT spectroscopy. With a resolution of ˜0.04 cm -1, rotational J and K structure has been resolved at least in part, and rovibrational analyses have been performed. Typically, 500 data of each {a 1}/{e} band have been fitted with σ = 5 × 10 -3 cm -1. Excited state rovibrational parameters complete to second order have been determined. A HOFF-based harmonic force field has been computed, and ground state parameters and ground state geometries have been deduced by combining all presently available data. A strong Coriolis interaction between ν2 and ν5 is revealed, while the interaction between ν1 and ν4 was found to be weak. Perturbations by multiply excited rovibrational levels are important for ν4 of H 3116Sn 79Br, while all other bands (with the exception of a weak local perturbation of ν5 by 2 ν3 in H 3116Sn 35CL) appeared to be unperturbed.

  9. Hydrogen role in stress corrosion cracking process of iron aluminide Fe{sub 3}Al in NaCl solution

    SciTech Connect

    Chiu, H.; Qiao, L.; Mao, X.

    1995-09-01

    The stress corrosion cracking behavior of Fe3AI based intermetallic alloy in 3.5% NaCl solution was studied. The role of hydrogen in the cracking process was also defined. The susceptibility of the alloy to hydrogen embrittlement was first investigated by performing tensile tests in air environment and mineral oil. It was found that ductility increased with increasing strain rate when tested in air, but stayed at a high value when tested in mineral oil. This behavior indicates that the alloy is sensitive to hydrogen embrittlement in air. In 3.5% NaCl solution, the environmental effect was studied by slow strain rate tests that were done at electrochemical potentials ranging from {minus}1,000 mV to 0 mV vs SCE. When tested at anodic potentials, from {minus}500 mV to 0 mV vs SCE, ductility reduced from 8.7% to 3.9%. When tested in cathodic region, from {minus}500 mV to {minus}1,000 mV, the ductility was between 7.3% to 9.1%. Results of tests done on pre-immersed specimens and notched tensile specimens confirmed this material degradation to be caused by stress corrosion cracking (SCC). To identify the mechanism, an electrochemical permeation technique was employed. By measuring the diffusible hydrogen concentration, sensitivity to hydrogen embrittlement has been assessed at different potentials. Anodic dissolution is believed to be the controlling mechanism of the SCC as the alloy is less sensitive to hydrogen embrittlement at anodic potentials. Fracture surfaces were examined under the scanning electron microscope (SEM). Fracture mode was found to be mainly transgranular quasi-cleavage, except the ones tested at anodic potentials on which intergranular fracture area was found near the edge. This intergranular fracture, which increases with increasing anodic potential, is believed to be the stress corrosion cracking area. Pits which corroded intergranularly are the crack initiation sites.

  10. Theoretical study of Pt(PR3)(2)(AlCl3) (R = H, Me, Ph, or Cy) including an unsupported bond between transition metal and non-transition metal elements: geometry, bond strength, and prediction.

    PubMed

    Tsukamoto, Shinya; Sakaki, Shigeyoshi

    2011-08-01

    The molecular structure and the binding energy of Pt(PR(3))(2)(AlCl(3)) (R = H, Me, Ph, or Cy) were investigated by DFT, MP2 to MP4(SDTQ), and CCSD(T) methods. The optimized structure of Pt(PCy(3))(2)(AlCl(3)) (Cy = cyclohexyl) by the DFT method with M06-2X and LC-BLYP functionals agrees well with the experimental one. The MP4(SDTQ) and CCSD(T) methods present similar binding energies (BE) of Pt(PH(3))(2)(AlCl(3)), indicating that these methods provide reliable BE value. The DFT(M06-2X)-calculated BE value is close to the MP4(SDTQ) and CCSD(T)-calculated values, while the other functionals present BE values considerably different from the MP4(SDTQ) and CCSD(T)-calculated values. All computational methods employed here indicate that the BE values of Pt(PMe(3))(2)(AlCl(3)) and Pt(PPh(3))(2)(AlCl(3)) are considerably larger than those of the ethylene analogues. The coordinate bond of AlCl(3) with Pt(PR(3))(2) is characterized to be the σ charge transfer (CT) from Pt to AlCl(3). This complex has a T-shaped structure unlike the well-known Y-shaped structure of Pt(PMe(3))(2)(C(2)H(4)), although both are three-coordinate Pt(0) complex. This T-shaped structure results from important participation of the Pt d(σ) orbital in the σ-CT; because the Pt d(σ) orbital energy becomes lower as the P-Pt-P angle decreases, the T-shaped structure is more favorable for the σ-CT than is the Y-shaped structure. [Co(alcn)(2)(AlCl(3))](-) (alcn = acetylacetoneiminate) is theoretically predicted here as a good candidate for the metal complex, which has an unsupported M-Al bond because its binding energy is calculated to be much larger than that of Pt(PCy(3))(2)(AlCl(3)). PMID:21710982

  11. M{sub 1-x}[W{sub 2}O{sub 2}X{sub 6}] with M=K{sup +}, Tl{sup +}, Ag{sup +}, Hg{sup 2+}, Pb{sup 2+}; X=Cl, Br-A class of mixed valence tungsten (IV,V) compounds with layered structures, W-W bonds and high conductivity

    SciTech Connect

    Beck, Johannes . E-mail: j.beck@uni-bonn.de; Kusterer, Christian; Hoffmann, Rolf-Dieter; Poettgen, Rainer

    2006-08-15

    The crystal structure of WOCl{sub 3}, determined on the basis of powder diffraction data (tetragonal, P4{sub 2}/mnm, a=10.6856(6), c=3.8537(2)), is isotypic to WOI{sub 3} and contains one-dimensional strands of edge-sharing double-octahedral W{sub 2}O{sub 4/2}Cl{sub 6} groups connected via common corners in trans position. A W-W bond of 2.99A is present within the planar W{sub 2}Cl{sub 6} groups. A series of non-stochiometric, mixed valence W(IV,V) compounds M{sub 1-x}[W{sub 2}O{sub 2}Cl{sub 6}] can be obtained from WOCl{sub 3} by reaction with metal halides (TlCl, KCl, PbCl{sub 2}) or by reaction of elemental Hg with WOCl{sub 4}. All were characterized by single crystal structure determinations and EDX measurements (Tl{sub 0.981(2)}[W{sub 2}O{sub 2}Cl{sub 6}]: monoclinic, C2/m, a=12.7050(4), b=3.7797(1), c=10.5651(3)A, {beta}=107.656(1){sup o}; K{sub 0.84(2)}[W{sub 2}O{sub 2}Cl{sub 6}]: monoclinic, C2/m, a=12.812(3), b=3.7779(6), c=10.196(3)A, {beta}=107.422(8){sup o}; Pb{sub 0.549(3)}[W{sub 2}O{sub 2}Cl{sub 6}]: orthorhombic, Immm,a=3.7659(1), b=9.8975(4), c=12.1332(6)A; Hg{sub 0.554(6)}[W{sub 2}O{sub 2}Cl{sub 6}]: monoclinic, C2/m, a=12.8361(8), b=3.7622(3), c=10.2581(9)A, {beta}=113.645(3){sup o}). Two representatives of this family of compounds have already been reported: Na[W{sub 2}O{sub 2}Br{sub 6}] [Y.-Q. Zhang, K. Peters, H.G. von Schnering, Z. Anorg. Allg. Chem. 624 (1998) 1415-1418] and Ag{sub 0.74}[W{sub 2}O{sub 2}Br{sub 6}] [S. Imhaine, C. Perrin, M. Sergent, Mat. Res. Bull. 33 (1998) 927-933]. The Ag containing compound can be obtained from elemental Ag and WOBr{sub 3}. The crystal structure, originally reported in the triclinic system, was redetermined and shown to be monoclinic with space group C2/m (a=13.7338(10), b=3.7769(3), c=10.7954(9)A, {beta}=112.401(3){sup o}). The crystal structures of these compounds are in close relationship to the structure of WOCl{sub 3} and all contain W{sub 2}O{sub 4/2}X{sub 6} (X=Cl, Br) double strands with the mono

  12. Effective n-type doping strategy through codoping SiAl-FN in aluminum nitride

    NASA Astrophysics Data System (ADS)

    Wang, Zhiguo; Li, Jingbo; Qing Fu, Yong

    2014-11-01

    Using a first-principles pseudopotential method, we studied an effective n-type doping strategy through codoping SiAl-XN (X = F, Cl, Br, and I) in aluminum nitride. Results revealed that the donor ionization energy of the SiAl-XN complex is much lower than that of the corresponding isolated SiAl impurity. Theoretically obtained ɛ(+/0) ionization energies are all near the conduction band minimum (CBM), which is only 1.4 meV below the CBM of the SiAl-FN pair. The low ɛ(+/0) ionization energy of the SiAl-XN complex can be explained by the combined repulsion between the X element (X = F, Cl, Br, and I)- and Si donor-induced levels.

  13. Characterization of Ti6Al7Nb alloy foams surface treated in aqueous NaOH and CaCl2 solutions.

    PubMed

    Bütev, Ezgi; Esen, Ziya; Bor, Şakir

    2016-07-01

    Ti6Al7Nb alloy foams having 53-73% porosity were manufactured via evaporation of magnesium space holders. A bioactive 1µm thick sodium hydrogel titanate layer, NaxH2-xTiyO2y+1, formed after 5M NaOH treatment, was converted to crystalline sodium titanate, Na2TiyO2y+1, as a result of post-heat treatment. On the other hand, subsequent CaCl2 treatment of NaOH treated specimens induced calcium titanate formation. However, heat treatment of NaOH-CaCl2 treated specimens led to the loss of calcium and disappearance of the titanate phase. All of the aforementioned surface treatments reduced yield strengths due to the oxidation of the cell walls of the foams, while elastic moduli remained mostly unchanged. Accordingly, equiaxed dimples seen on the fracture surfaces of as-manufactured foams turned into relatively flat and featureless fracture surfaces after surface treatments. On the other hand, Ca- and Na-rich coating preserved their mechanical stabilities and did not spall during fracture. The relation between mechanical properties of foams and macro-porosity fraction were found to obey a power law. The foams with 63 and 73% porosity met the desired biocompatibility requirements with fully open pore structures and elastic moduli similar to that of bone. In vitro tests conducted in simulated body fluid (SBF) showed that NaOH-heat treated surfaces exhibit the highest bioactivity and allow the formation of Ca-P rich phases having Ca/P ratio of 1.3 to form within 5 days. Although Ca-P rich phases formed only after 15 days on NaOH-CaCl2 treated specimens, the Ca/P ratio was closer to that of apatite found in bone. PMID:26807769

  14. Design and Fabrication of a 200N Thrust Rocket Motor Based on NH4ClO4+Al+HTPB as Solid Propellant

    NASA Astrophysics Data System (ADS)

    Wahid, Mastura Ab; Ali, Wan Khairuddin Wan

    2010-06-01

    The development of rocket motor using potassium nitrate, carbon and sulphur mixture has successfully been developed by researchers and students from UTM and recently a new combination for solid propellant is being created. The new solid propellant will combine a composition of Ammonium perchlorate, NH4ClO4 with aluminium, Al and Hydroxyl Terminated Polybutadiene, HTPB as the binder. It is the aim of this research to design and fabricate a new rocket motor that will produce a thrust of 200N by using this new solid propellant. A static test is done to obtain the thrust produced by the rocket motor and analyses by observation and also calculation will be done. The experiment for the rocket motor is successful but the thrust did not achieve its required thrust.

  15. Synthesis and multinuclear ( sup 13 C, sup 77 Se, sup 125 Te, sup 199 Hg) magnetic resonance spectra of adamantane-like anions of mercury(II), ((. mu. -ER) sub 6 (HgX) sub 4 ) sup 2 minus (E = S, Se, Te; X = Cl, Br, I)

    SciTech Connect

    Dean, P.A.W.; Manivannan, V. )

    1990-08-08

    Multinuclear magnetic resonance has been used to characterize the new adamantane-like anions (({mu}-ER){sub 6}(HgX){sub 4}){sup 2{minus}} (ER = SPr{sup n}, SPh, SePh, TePh; X = Cl, Br, I), which are formed in CH{sub 2}Cl{sub 2} and (or) DMF from Hg(ER){sub 2}, HgX{sub 2} and (R{sub 4}N)X in the correct stoichiometric ratio. The products (Et{sub 4}N){sub 2}(({mu}-EPh){sub 6}(HgCl){sub 4}) (E = Se, Te) have been isolated analytically pure. At ambient probe temperature, only the complexities (({mu}-TePh){sub 6}(HgX){sub 4}){sup 2{minus}} are stable to dissociation of the ({mu}-ER){sub 6}Hg{sub 4} core. However, at 213 K, only the core of (({mu}-SPh){sub 6}(HgCl){sub 4}){sup 2{minus}} is measurably dissociated. Overall, the stability of the complexes to dissociation varies with E in the order Te > Se > S. At reduced temperature inversion at Te is slow on the NMR time scale in (({mu}-TePh){sub 6}(HgX){sub 4}){sup 2{minus}}, and these complexes are shown to exist as on predominant configurational isomer or an equilibrium mixture of, probably, two such isomers. Similar behavior is found for (({mu}-SePh){sub 6}(HgX){sub 4}){sup 2{minus}} (X = Cl, Br), which are the first examples of SeR-bridged adamantanoid clusters to exhibit inversion at Se that is slow on the NMR time scale. Metal ({sup 113}Cd, {sup 199}Hg) NMR data for (({mu}-SPr{sup n}){sub 6}(MI){sub 4}){sup 2{minus}}/(({mu}-SPr{sup n}){sub 6}(M{prime}I){sub 4}){sup 2{minus}} (M = Hg, M{prime} = Cd, Zn; M = Zn, M{prime} = Cd) mixtures at 213 K show that an approximately statistical metal redistribution occurs to give (({mu}-SPr{sup n}){sub 6}(MI){sub 4{minus}n}(M{prime}I){sub n}){sup 2{minus}}. 37 refs., 1 fig., 4 tabs.

  16. Hydrogen for X-group exchange in CH3X, X = Cl, Br, I, OMe and NMe2 byMonomeric [1,2,4-(Me3C)3C5H2]2CeH: Experimental and Computational Support for a Carbenoid Mechanism

    SciTech Connect

    Werkema, Evan; Andersen, Richard; Yahia, Ahmed; Maron, Laurent; Eisenstein, Odile

    2009-05-15

    The reaction between [1,2,4-(Me3C)3C5H2]2CeH, referred to as Cp'2CeH, andCH3X where X is Cl, Br, I, OMe and NMe2, are described. The reactions fall intothree distinct classes. Class a, where X = Cl, Br and I rapidly form Cp'2CeX and CH4without formation of identifiable intermediates in the 1H NMR spectra. Class b, whereX = OMe proceeds rapidly to Cp'2Ce(eta2-CH2OMe) and H2 and then to Cp'2CeOMeand CH4. The methoxymethyl derivative is sufficiently stable to be isolated andcharacterized and it is rapidly converted to Cp'2CeOMe in presence of BPh3. Class c,where X = NMe2 does not result in formation of Cp'2CeNMe2, but deuterium labelingexperiments show that H for D exchange occurs in NMe3. Density functionalcalculations DFT(B3PW91) on the reaction of (C5H5)2CeH, referred to as Cp2CeH,and CH3X show that the barrier for alpha-CH activation, resulting in formation ofCp2Ce(eta2-CH2X), proceeds with a relatively low activation barrier (DeltaG++) but thesubsequent ejection of CH2 and trapping by H2 has a higher barrier; the height of thesecond barrier lies in the order F, Cl, Br, I< OMe<< NMe2, consistent with theexperimental studies. The DFT calculations also show that the two-step reaction,which proceeds through a carbenoid intermediate, has a lower barrier than a directone-step sigma bond metathesis mechanism. The reaction of Cp2CeCH2OMe and BPh3 is calculated to be a low barrier process and the ylide, CH2(+)BPh3(-), is a transition state and not an intermediate.

  17. Toward precise QEC values for the superallowed 0+→0+ β decays of T=2 nuclides: The masses of Na20, Al24, P28, and Cl32

    NASA Astrophysics Data System (ADS)

    Wrede, C.; Clark, J. A.; Deibel, C. M.; Faestermann, T.; Hertenberger, R.; Parikh, A.; Wirth, H.-F.; Bishop, S.; Chen, A. A.; Eppinger, K.; García, A.; Krücken, R.; Lepyoshkina, O.; Rugel, G.; Setoodehnia, K.

    2010-05-01

    High-precision measurements of superallowed 0+→0+ β decays of T=2 nuclides such as Mg20, Si24, S28, and Ar32 can contribute to searches for physics beyond the standard model of particle physics if the QEC values are accurate to a few keV or better. As a step toward providing precise QEC values for these decays, the ground-state masses of the respective daughter nuclei Na20, Al24, P28, and Cl32 have been determined by measuring the (He3,t) reactions leading to them with the Ar36(He3,t)K36 reaction as a calibration. A quadrupole-dipole-dipole-dipole (Q3D) magnetic spectrograph was used together with thin ion-implanted carbon-foil targets of Ne20, Mg24, Si28, S32, and Ar36. The masses of Na20 and Cl32 are found to be in good agreement with the values from the 2003 Atomic Mass Evaluation (AME03) [G. Audi, A. H. Wapstra, and C. Thibault, Nucl. Phys. ANUPABL0375-947410.1016/j.nuclphysa.2003.11.003 729, 337 (2003)], and the precision has been improved by a factor of 6 in both cases. The masses of Al24 and P28 are found to be higher than the values from AME03 by 9.5 keV (3.2σ) and 11.5 keV (3.6σ), respectively, and the precision has been improved by a factor of 2.5 in both cases. The new Cl32 mass is used together with the excitation energy of its lowest T=2 level and the mass of Ar32 to derive an improved superallowed QEC value of 6087.3(22) keV for this case. The effects on quantities related to standard-model tests including the β-ν correlation coefficient a and the isospin-symmetry-breaking correction δC are examined for the A=32 case.

  18. Etching Characteristics of ZnO and Al-Doped ZnO in Inductively Coupled Cl2/CH4/H2/Ar and BCl3/CH4/H2/Ar Plasmas

    NASA Astrophysics Data System (ADS)

    Lee, Hack Joo; Kwon, Bong Soo; Kim, Hyun Woo; Kim, Seon Il; Yoo, Dong-Geun; Boo, Jin-Hyo; Lee, Nae-Eung

    2008-08-01

    ZnO and Al-doped ZnO (AZO) were etched in Cl2/CH4/H2/Ar (Cl2-based) and BCl3/CH4/H2/Ar (BCl3-based), inductively coupled plasmas (ICPs) and their etching characteristics were compared by varying the Cl2/(Cl2+CH4) and BCl3/(BCl3+CH4) flow ratios, top electrode power and dc self-bias voltage (Vdc). The etch rates of both ZnO and AZO layers were higher in the Cl2-based chemistry than in the BCl3-based chemistry. The AZO and ZnO etch rates were increased and decreased, respectively, with increasing Cl2 or BCl3 flow ratio. Optical emission measurements of the radical species in the plasma and surface binding states by optical emission spectroscopy (OES) and X-ray photoelectron spectroscopy (XPS), respectively, indicated that, with increasing Cl2 or BCl3 flow ratio; the effective removal of Al in the AZO enhanced the AZO etch rate, whereas the reduced removal of Zn by the Zn(CHx)y products reduced the ZnO etch rate.

  19. Thermal Variance Investigation and Scintillation Mechanisms of Cs2LiLaBr6-xClx:Ce (CLLBC) and Cs2LiYBr6:Ce (CLYB)

    SciTech Connect

    Coupland, Daniel David Schechtman; Budden, Brent Scott; Stonehill, Laura Catherine

    2015-11-23

    We perform an investigation into the scintillation processes and performance of elpasolites Cs2LiLaBr6-xClx:Ce (CLLBC) and Cs2LiYBr6:Ce (CLYB) using a thermal cycle over a range of -20 to +50º C. At 10º increments, we acquire data with both a waveform digitizer and charge-integrating electronics. We identify decay components and evaluate decay times, thermal neutron gamma-equivalent energy (GEE), and pulse shape discrimination (PSD) performance. Results are compared to common Cs2LiYCl6:Ce (CLYC).

  20. Etude structurale et vibrationnelle d’un nouveau composé complexe de cobalt: [Co(imidazole)4Cl]Cl

    PubMed Central

    Derbel, Amira; Mhiri, Tahar; Graia, Mohsen

    2015-01-01

    In the title complex, chlorido­tetra­kis­(1H-imidazole-κN 3)cobalt(II) chloride, [CoCl(C3H4N2)4]Cl, the CoII cation has a distorted square-pyramidal coordination environment. It is coordinated by four N atoms of four imidazole (Im) groups in the basal plane, and by a Cl atom in the apical position. It is isostructural with [Cu(Im)4Cl]Cl [Morzyk-Ociepa et al. (2012 ▸). J. Mol. Struct. 1028, 49–56] and [Cu(Im)4Br]Br [Hossaini Sadr et al. (2004 ▸). Acta Cryst. E60, m1324–m1326]. In the crystal, the [CoCl(C3H4N2)4]+ cations and Cl− anions are linked via N—H⋯Cl hydrogen bonds, forming layers parallel to (010). These layers are linked via C—H⋯Cl hydrogen bonds and C—H⋯π and π–π [inter-centroid distance = 3.794 (2) Å] inter­actions, forming a three-dimensional framework. The IR spectrum shows vibrational bands typical for imidazol groups. The monoclinic unit cell of the title compound emulates an ortho­rhom­bic cell as its β angle is close to 90°. The crystal is twinned, with the refined ratio of twin components being 0.569 (1):0.431 (1). PMID:26594402

  1. The BR eigenvalue algorithm

    SciTech Connect

    Geist, G.A.; Howell, G.W.; Watkins, D.S.

    1997-11-01

    The BR algorithm, a new method for calculating the eigenvalues of an upper Hessenberg matrix, is introduced. It is a bulge-chasing algorithm like the QR algorithm, but, unlike the QR algorithm, it is well adapted to computing the eigenvalues of the narrowband, nearly tridiagonal matrices generated by the look-ahead Lanczos process. This paper describes the BR algorithm and gives numerical evidence that it works well in conjunction with the Lanczos process. On the biggest problems run so far, the BR algorithm beats the QR algorithm by a factor of 30--60 in computing time and a factor of over 100 in matrix storage space.

  2. Energy levels of HoBr 63-

    NASA Astrophysics Data System (ADS)

    Tanner, Peter A.

    1986-12-01

    The excitation, electronic absorption and luminescence spectra of cubic Cs 2NaHoBr 6 have been recorded at temperatures down to that of liquid helium. The detailed spectral analyses enable comparisons to be made of the crystal-field splittings of Russell—Saunders terms with those in Cs 2NaHoCl 6. Under intense 647.1 nm laser excitation, luminescence is observed in the neat material in the spectral region between 17800 and 21750 cm -1.

  3. Pulsed-Field Ultrasonic Experiments in the Quasi-2D Antiferromagnet Cs2CuBr4

    NASA Astrophysics Data System (ADS)

    Wolf, B.; Cong, P. T.; Krüger, N.; Ritter, F.; Assmus, W.; Lang, M.

    2013-03-01

    The magnetic insulators Cs2CuCl4 and Cs2CuBr4 are model systems for a frustrated quasi-two-dimensional triangular-lattice spin-1/2 Heisenberg antiferromagnet with a weak interlayer coupling. The quasi-two-dimensional character manifests itself in a broad maximum at T max in the magnetic susceptibility, which for Cs2CuCl4 has been found to mark the upper bound for a spin-liquid regime (R. Coldea et al. in Phys. Rev. B 68:134424, 2003). Motivated by the observation of characteristic B 2 dependencies in the elastic constants and ultrasound attenuation in the spin-liquid regime for this material, we look for corresponding signatures in the related Cs2CuBr4 compound at low temperatures T≤4.2 K and fields B≤50 T. We observe a softening of the elastic constant up to B s ˜32 T ( B∥ a) and a maximum in the sound attenuation at 0.86 B s . Both quantities exhibit the same characteristic B 2 dependence as found for Cs2CuCl4, suggesting the existence of a spin-liquid phase in Cs2CuBr4 as well.

  4. A novel red phosphor Ca{sub 12}Al{sub 14}O{sub 32}Cl{sub 2}:Eu{sup 3+} for near UV white light-emitting diodes

    SciTech Connect

    Yang, Zhigang; Zhao, Zhengyan; Shi, Yurong; Wang, Yuhua

    2013-10-15

    Graphical abstract: - Highlights: • Novel red phosphor Ca{sub 12}Al{sub 14}O{sub 32}Cl{sub 2}:Eu{sup 3+} was prepared by solid-state reaction. • Excitation spectra suggested an obvious absorption in near-ultraviolet region. • Under 392 nm excitation, the phosphors exhibited a red emission at 614 nm. • Ca{sub 12}Al{sub 14}O{sub 32}Cl{sub 2}:Eu{sup 3+} could be potentially applied in near UV white LEDs. - Abstract: A novel red phosphor Ca{sub 12}Al{sub 14}O{sub 32}Cl{sub 2}:Eu{sup 3+} was synthesized using a solid-state reaction method, and its luminescence characteristics and charge compensators effect (Li{sup +}, Na{sup +}, K{sup +}) were investigated. The excitation spectra showed a obvious absorption in near-ultraviolet region. Under 392 nm excitation, the phosphors exhibited an intense red emission at 614 nm. The Commission Internationale de l’Eclairage (CIE) chromaticity coordinates and quantum efficiency (QE) were (0.65, 0.35) and 62.3%, respectively. The good color saturation, high quantum efficiency and small thermal-quenching properties indicate that Ca{sub 12}Al{sub 14}O{sub 32}Cl{sub 2}:Eu{sup 3+} could be potentially applied in near UV white light-emitting diodes.

  5. Multifunctional effect of Al2O3, SiO2 and CaO on the volatilization of PbO and PbCl2 during waste thermal treatment.

    PubMed

    Wang, Si-Jia; He, Pin-Jing; Shao, Li-Ming; Zhang, Hua

    2016-10-01

    Minerals including Al2O3, SiO2 and CaO are predominant matrixes in waste, and are thought to facilitate lead (Pb) emission control. This study distinguished the inhibition of each mineral on common stable Pb-containing compounds, including highly volatile PbCl2 and less volatile PbO. Al2O3 can lower the volatilization temperature of Pb by 29 °C due to the generation of a eutectic compound and play a minor but non-negligible role in reducing Pb volatilization. The most conspicuous inhibition effect was exerted by SiO2 and a mixture of Al2O3 and SiO2, which completely integrated PbO into the glass phase at 690 °C and prohibited its migration. In contrast, SiO2 had no significant inhibition on volatile PbCl2. CaO inhibited PbO volatilization in the absence of oxygen by controlling its diffusion, while it converted PbO to Ca2PbO4 in the presence of oxygen, thus controlling Pb diffusion and decreasing the Pb volatilization ratio and rate. The influence of CaO on PbCl2 was complex because CaO can convert PbCl2 to PbO with formation of CaCl2, and CaCl2 can also be a Cl-donor for PbO. The roles of mineral matrixes in Pb conversion were shown to be important for Pb emission control. PMID:27434254

  6. MAgnetic stimulation of the brain increase Na+, K+-ATPase activity decreased by injection of AlCl3 into nucleus basalis magnocellularis of rats.

    PubMed

    Jovanova-Nesic, Katica; Eric-Jovicic, Milena; Spector, Novera Herbert

    2006-06-01

    This article reports here on the influence of the static magnetic fields (MFs), locally applied to the brain area, on Na, K-ATPase activity in the rat with lesioned nucleus basalis magnocellularis (NBM) by intracerebral injection of 5 microl, 1% AlCl3 into the nucleus. Two AKMA micromagnets (M) flux density of 60 miliTesla, 5 mm in diameter, were bilaterally implanted with "N" polarity facing down to the cranial bones in the vicinity of the pineal gland (PG), immediately after the lesioning of NBM, during the same operation procedure. Ten days after the lesions of NBM, Na, K-ATPase activity on the erythrocyte membranes in the peripheral blood, measured spectrophotometrically, was completely inhibited. Magnetic stimulation (60 mT) of the brain during the 10 days significantly increased Na, K-ATPase activity on the erythrocyte membranes of rats with lesioned NBM. This results suggests that altered by lesions Na, K-ATPase activity in an experimental model of Alzheimer's disease might be ameliorated by magnetic stimulation of the brain. PMID:16753895

  7. Kinetics of oxidation of Fe-Cr-Al alloy Characterization by electrochemical spectroscopy of impedance in a 3% medium NaCl

    NASA Astrophysics Data System (ADS)

    Chadli, H.; Retima, M.; Khenioui, Y.

    2009-11-01

    The film growths kinetic study developed on the Fe-Cr-Al alloy oxidation under ambient air has been studied due to its tremendous uses in the automobile industry, specifically in catalytic exhaust. In this work, we report on its behavior as a function of various parameters such as the temperature, the oxidation duration, elaboration mode or the substrate nature and geometry. It has been shown that the growth, the morphology or the adherence of the formed layers are strongly affected by these parameters. At high temperature (900-1100 ∘C), the formed protective film for the materials studied in this work is primarily consisted of alumina. Below these temperatures, several phases may coexist, namely, the γ phase and the θ phase. The extension of this alloy application has led us to perform spectroscopic measurements of electrochemical impedance (SEI) in an aqueous environment 3% (NaCl). These measurements have shown that sane coatings preserve excellent insulating properties and the corrosion risks are related to defects in the layers while are formed.

  8. Improving the Photoluminescence Properties of Perovskite CH3NH3PbBr3-xClx Films by Modulating Organic Cation and Chlorine Concentrations.

    PubMed

    Yan, Jun; Zhang, Bing; Chen, Yunlin; Zhang, Ao; Ke, Xiaohan

    2016-05-25

    The photoluminescence (PL) properties of inorganic-organic perovskites can be drastically changed by tuning the halogen composition, especially the Cl content. However, our research demonstrated that in addition to the influence of Cl concentration, the PL emission intensity of CH3NH3PbBr3 strongly depends on the content of CH3NH3Br in the coating solution. The effects of CH3NH3Br and Cl concentrations on the PL properties of CH3NH3PbBr3-xClx were investigated. We found that a strong PL emission intensity of CH3NH3PbBr3 can be obtained from solutions with a high CH3NH3Br concentration. The PL emission intensities of CH3NH3PbBr3-xClx films were enhanced by adjusting the molar ratio of PbBr to PbCl2 only in a highly concentrated CH3NH3Br environment. Moreover, it was found that an optimum CH3NH3Br/PbBr2/PbCl2 ratio in the precursor solutions can be used to obtain the strongest PL emission intensity of CH3NH3PbBr3-xClx films. Further studies revealed that both CH3NH3Br and Cl concentrations significantly influence the CH3NH3PbBr3-xClx films evolution, which affects their PL properties. PMID:27163386

  9. Bee Line BR-1 Racer

    NASA Technical Reports Server (NTRS)

    1926-01-01

    Bee Line BR-1 Racer: The Bee Line BR-1 was a racing aircraft used to compete in the 1922 Pulitzer Air Race. The aircraft and its sister ship, the Bee Line BR-2, came to Langley and the NACA in 1926. The BR-1 is shown in the NACA hangar at Langley Field in early 1926.

  10. Balloon-borne In-Situ Measurements of ClO and ClONO2 in the late 2010/2011 Arctic Polar Vortex: Instrument Calibration and Results

    NASA Astrophysics Data System (ADS)

    Stroh, F.; Heinecke, F.; Afchine, A.; Barthel, J.; Engel, A.; Grooß, J.; von Hobe, M.; Richter, A.; Schönfeld, A.; Suminska, O.; Tan, V.

    2011-12-01

    Since 1995 we have carried out balloon-borne in-situ measurements of ClO and BrO. Lately we have designed an upgraded balloon instrument to additionally measure the ClO dimer and the reservoir species ClONO2. The halogen oxide measurements are carried out employing the chemical conversion resonance fluorescence technique (Brune et al., 1989) in a fast flow through two parallel ducts generated by modified roots blowers. The inlet of one duct is equipped with a dedicated heating element enabling controlled air temperatures in excess of 550K at pressures lower than 50 hPa. This causes the ClO dimer to thermolyze forming two ClO molecules at around 380K as well as additional thermolysis of ClONO2 to ClO and NO2 at around 540K. The ClO generated within the thermolysis is then detected on top of the ambient ClO. Temperature cycling and intercomparisons with the first unheated duct allow the differentiation of the chlorine species. Details of the instrumental setup, instrument calibration, and performance will be discussed. Profiles for ClO and ClONO2 from a flight carried out from ESRANGE near Kiruna, Sweden, on April-01-2011 in the edge region of the degrading arctic vortex will be presented marking the first ClONO2 in-situ measurements above research aircraft altitudes (20km). Brune, W. H., et al., Insitu Observations Of ClO In The Antarctic - Er-2 Aircraft Results From 54-Degrees-S To 72-Degrees-S Latitude, Journal Of Geophysical Research-Atmospheres, 94, 16649-16663, 1989.

  11. CsEuBr3: Crystal structure and its role in the photostimulation of CsBr :Eu2+

    NASA Astrophysics Data System (ADS)

    Hesse, S.; Zimmermann, J.; von Seggern, H.; Ehrenberg, H.; Fuess, H.; Fasel, C.; Riedel, R.

    2006-10-01

    CsBr :Eu2+ has recently been investigated as a photostimulable x-ray storage phosphor with great potential for application in high-resolution image plates. In a recent paper Hackenschmied et al. [J. Appl. Phys. 93, 5109 (2003)] suggested that segregations of CsEuBr3 or Cs4EuBr6 formed within CsBr :Eu2+ during annealing are responsible for an increase in the photostimulated luminescence (PSL) yield. In this work single crystals of CsEuBr3 were prepared by a one step synthesis and identified by x-ray diffraction (XRD) analysis as single phase perovskites. It was concluded that, after preparation, CsEuBr3 degrades in normal atmosphere into at least two phases, one of which is the orthorhombic structure of Cs2EuBr5•10H2O. The XRD powder diffraction pattern of this compound is very similar to that of the segregations observed within CsBr :Eu2+ and reported by Hackenschmied et al. However, the increased PSL yield in CsBr :Eu2+ after annealing cannot be due to the segregations, because the trivalent nature of the europium in the segregations renders them PSL inactive.

  12. Kinetics and mechanism of the gas phase reaction of Cl atoms and OH radicals with bromobenzene

    NASA Astrophysics Data System (ADS)

    Nakano, Y.; Kawasaki, M.; Ponomarev, D. A.; Hurley, M. D.; Wallington, T. J.

    2002-02-01

    Relative rate techniques were used to study the kinetics and mechanism of the reaction of Cl atoms and OH radicals with bromobenzene (C 6H 5Br) in 20-700 Torr of N 2, O 2, or air diluent at 295±2 K. Using the observed rate constant ratios k(C 6H 5Br+Cl)/ k(C 2H 5Cl+Cl)=1.56±0.05 and k(C 6H 5Br+Cl)/ k(C 2H 6+Cl)=0.24±0.01, the C 6H 5Br+Cl rate constant is determined to be k( C6H5Br+ Cl)=(1.32±0.20)×10 -11 cm3 molecule-1 s-1 giving exclusively C 6H 5Cl through a displacement mechanism. Using the observed rate constant ratios k(C 6H 5Br+OH)/ k(C 6H 6+OH)=0.77±0.06 and k(C 6H 5Br+OH)/ k(C 2H 4+OH)=0.11±0.004, the C 6H 5Br+OH rate constant is determined to be k( C6H5Br+ OH)=(9.37±2.04)×10 -13 cm3 molecule-1 s-1. The product expected from a displacement mechanism, phenol, was not observed (<10% yield).

  13. Intense violet-blue-emitting Ba(2)AlB(4)O(9)Cl:Eu(2+) phosphors for applications in fluorescent lamps and ultraviolet-light-emitting diodes.

    PubMed

    Kuo, Te-Wen; Huang, Chien-Hao; Chen, Teng-Ming

    2010-08-01

    We synthesized a violet-blue phosphor Ba(2)AlB(4)O(9)Cl:Eu(2+) with a solid-state reaction. The excitation and emission spectra of this phosphor showed that all were broadband due to 4f(7)-4f(6)d(1) transitions of Eu(2+). The phosphors with different Eu(2+) concentrations presented violet-blue luminescence for ultraviolet [(UV) 250-390nm] excitation. The optimum concentration of Eu(2+) in Ba(2)AlB(4)O(9)Cl:Eu(2+) is determined to be 6mol.%. The luminous efficiency was found to be 8.1lm/W for the violet-blue fluorescent lamp and 3.2lm/W for the violet-blue phosphor-converted light-emitting diode, respectively. Ba(2)AlB(4)O(9)Cl:Eu(2+) would be a promising phosphor for converting the UV radiation to violet-blue emission for a novel high light-conversion efficiency phototherapy illuminator. PMID:20676174

  14. Intramolecular and intermolecular migration of propyl groups in 9-isopropyl-o- and 9-isopropyl-m-carboranes under the action of HCl and AlCl/sub 3/

    SciTech Connect

    Zakharkin, L.I.; Kovredov, A.I.; Ol'shevskaya, V.A.; Vitt, S.V.

    1986-04-20

    Under the action of HCl and AlCl/sub 3/ intramolecular and intermolecular migration of propyl groups occurred in 9-isopropyl-o-carborane and 9-isopropyl-m-carborane in CS/sub 2/ at 20/sup 0/C which was accompanied by isomerization of isopropyl groups into propyl. The action of AlCl/sub 3/ and HCl on 9-isopropyl-o-carborane led to o-carborane, a mixture of disubstituted B,B'-(C/sub 3/H/sub 7/)/sub 2/-o-carboranes, and a mixture of monosubstituted B-(C/sub 3/H/sub 7/)-o-carboranes which consisted of 4-, 8-, and 9-isopropyl-, and 8- and 9-propyl-o-carboranes. On reacting HCl and AlCl/sub 3/ with 9-isopropyl-m-carborane there was formed m-carborane, a mixture of disubstituted B,b'-(C/sub 3/H/sub 7/)/sub 2/-m-carboranes, and a mixture of monosubstituted B-(C/sub 3/H/sub 7/)-m-carboranes consisting of 4-, 5-, and 9-isopropyl-m-, and -, 5-, and 9-propyl-m-carboranes.

  15. Experimental studies on BrO/Br ratios at Stromboli, Etna, Masaya, Gorely and Nyiragongo

    NASA Astrophysics Data System (ADS)

    Bobrowski, Nicole; Wittmer, Julian; Liotta, Marcello; Calabrese, Sergio; Giuffrida, Giovanni; Brusca, Lorenzo; Platt, Ulrich

    2014-05-01

    Since the discovery of BrO in a volcanic plume (Bobrowski et al. 2003) many measurements have been performed as well as modelling to understand the radical chemistry in volcanic plumes, in particular, the interaction between volcanic gas species, released under strongly reduced conditions, and the oxidizing atmosphere. Besides the goal in atmospheric chemistry to better determine the impact of volcanic emission (e.g. reactive bromine) on the local (and maybe global) scale, volcanologists also have an interest to understand if the BrO/SO2 ratios can be used as a monitoring parameter giving further insides in dynamic processes of volcanoes. One of the major advantages when utilizing BrO/SO2 ratios is the relatively easiness of the measurements, which can be taken in a safe distance from volcanic activity accompanied by a good temporal resolution partly even during explosive eruptions. Recently, it has been shown (Lübcke et al., 2013) that already existing automatically running measurement networks can now be used to gain long-term data sets of BrO/SO2 ratios. However, one of the arguments which potentially makes volcanological interpretations difficult is the reactivity of BrO. Therefore it is, of great importance to link the measurements of BrO and gaseous hydrogen bromide to the total emission flux of bromine in order to estimate the pristine gas composition released from magmas. In particular, meteorological influences, trace gas composition of the surrounding atmosphere and the volcanic gas composition can all potentially effect the formation of BrO and might have to be considered. Some of these factors potentially also influence near source in-situ measurement. We need to answer the question: Can we correlate BrO measurements to the total bromine outgassing? Only with this knowledge we can relate changes of the measured gas ratios (BrO/SO2) to the volcanic fluids emitted by the underlying magma and can interpret data as signals from depth, which provide insight

  16. Atmospheric test of the J(BrONO2)/kBrO+NO2 ratio: implications for total stratospheric Bry and bromine-mediated ozone loss

    NASA Astrophysics Data System (ADS)

    Kreycy, S.; Camy-Peyret, C.; Chipperfield, M. P.; Dorf, M.; Feng, W.; Hossaini, R.; Kritten, L.; Werner, B.; Pfeilsticker, K.

    2013-07-01

    We report on time-dependent O3, NO2 and BrO profiles measured by limb observations of scattered skylight in the stratosphere over Kiruna (67.9° N, 22.1° E) on 7 and 8 September 2009 during the autumn circulation turn-over. The observations are complemented by simultaneous direct solar occultation measurements around sunset and sunrise performed aboard the same stratospheric balloon payload. Supporting radiative transfer and photochemical modelling indicate that the measurements can be used to constrain the ratio J(BrONO2)/kBrO+NO2, for which at T = 220 ± 5 K an overall 1.7 (+0.4 -0.2) larger ratio is found than recommended by the most recent Jet Propulsion Laboratory (JPL) compilation (Sander et al., 2011). Sensitivity studies reveal the major reasons are likely to be (1) a larger BrONO2 absorption cross-section σBrONO2, primarily for wavelengths larger than 300 nm, and (2) a smaller kBrO+NO2 at 220 K than given by Sander et al. (2011). Other factors, e.g. the actinic flux and quantum yield for the dissociation of BrONO2, can be ruled out. The observations also have consequences for total inorganic stratospheric bromine (Bry) estimated from stratospheric BrO measurements at high NOx loadings, since the ratio J(BrONO2)/kBrO+NO2 largely determines the stratospheric BrO/Bry ratio during daylight. Using the revised J(BrONO2)/kBrO+NO2 ratio, total stratospheric Bry is likely to be 1.4 ppt smaller than previously estimated from BrO profile measurements at high NOx loadings. This would bring estimates of Bry inferred from organic source gas measurements (e.g. CH3Br, the halons, CH2Br2, CHBr3, etc.) into closer agreement with estimates based on BrO observations (inorganic method). The consequences for stratospheric ozone due to the revised J(BrONO2)/kBrO+NO2 ratio are small (maximum -0.8%), since at high NOx (for which most Bry assessments are made) the enhanced ozone loss by overestimating Bry is compensated for by the suppressed ozone loss due to the underestimation

  17. Photoelectron spectroscopic study of the E ⊗ e Jahn-Teller effect in the presence of a tunable spin-orbit interaction. III. Two-state excitonic model accounting for observed trends in the X~ 2E ground state of CH3X+ (X=F, Cl, Br, I) and CH3Y (Y=O, S)

    NASA Astrophysics Data System (ADS)

    Grütter, M.; Qian, X.; Merkt, F.

    2012-08-01

    Open-shell molecules in doubly degenerate 2E electronic states are subject to the E ⊗ e Jahn-Teller effect and spin-orbit interactions. The rotational structure of the ground vibrational level of the tildeX^+ 2E ground state of CH3F+ has been observed by high-resolution photoelectron spectroscopy. In contrast to what is observed in other members of the isoelectronic families {CH}_3{X}^+ ({X}={Cl, Br, I}) and {CH}_3{Y} ({Y}={O, S}), the spin-orbit interaction does not lead to a splitting of the ground state of CH3F+. Observed trends in the spectra of the tildeX 2E ground states of these molecules are summarized. Whereas certain trends, such as the reduction of the observable effects of the Jahn-Teller interactions and the increase of the spin-orbit splitting with increasing nuclear charge of X and Y are easily understood, other trends are more difficult to explain, such as the much reduced spin-orbit splitting in {CH}_3{F}^+ compared to {CH}_3{O}. A simple two-state excitonic model is used to account for the trends observed within the series of the methyl-halide radical cations and also the similarities and differences between {CH}_3{F}^+ and the isoelectronic {CH}_3{O} radical. Within this model, the electron hole in the 2E ground states of {CH}_3{X}^+ and {CH}_3{Y} is described in terms of contributions from the halogenic (or chalcogenic) px, y orbitals and the pyramidal-methylic (e) orbitals. This model enables a global, semi-quantitative description of the combined effects of the Jahn-Teller and spin-orbit interactions in these molecules and also a simple interpretation of the spin-orbit-coupling reduction factor ζe.

  18. Gas phase complexes of H3NCuF and H3NCuI studied by rotational spectroscopy and ab initio calculations: the effect of X (X = F, Cl, Br, I) in OCCuX and H3NCuX.

    PubMed

    Bittner, Dror M; Stephens, Susanna L; Zaleski, Daniel P; Tew, David P; Walker, Nicholas R; L