Synthesis, Structure, and Li-Ion Conductivity of LiLa(BH4)3X, X = Cl, Br, I

DEFF Research Database (Denmark)

GharibDoust, Seyed Hosein Payandeh; Brighi, Matteo; Sadikin, Yolanda

2017-01-01

In this work, a new type of addition reaction between La(BH4)3 and LiX, X = Cl, Br, I, is used to synthesize LiLa(BH4)3Cl and two new compounds LiLa(BH4)3X, X = Br, I. This method increases the amounts of LiLa(BH4)3X and the sample purity. The highest Li-ion conductivity is observed for LiLa(BH4...... with increasing lattice parameter, that is, increasing size of the halide ion in the structure. Thus, we conclude that the sizes of both windows are important for the lithium ion conduction in LiLa(BH4)3X compounds. The lithium ion conductivity is measured over one to three heating cycles and with different...

Spin splitting in band structures of BiTeX (X=Cl, Br, I) monolayers

Science.gov (United States)

Hvazdouski, D. C.; Baranava, M. S.; Stempitsky, V. R.

2018-04-01

In systems with breaking of inversion symmetry a perpendicular electric field arises that interacts with the conduction electrons. It may give rise to electron state splitting even without influence of external magnetic field due to the spin-orbital interaction (SOI). Such a removal of the spin degeneracy is called the Rashba effect. Nanostructure with the Rashba effect can be part of a spin transistor. Spin degeneracy can be realized in a channel from a material of this type without additive of magnetic ions. Lack of additive increases the charge carrier mobility and reliability of the device. Ab initio simulations of BiTeX (X=Cl, Br, I) monolayers have been carried out using VASP wherein implemented DFT method. The study of this structures is of interest because such sort of structures can be used their as spin-orbitronics materials. The crystal parameters of BiTeCl, BiTeBr, BiTeI have been determined by the ionic relaxation and static calculations. It is necessary to note that splitting of energy bands occurs in case of SOI included. The values of the Rashba coefficient aR (in the range from 6.25 to 10.00 eV·Å) have high magnitudes for spintronics materials. Band structure of monolayers structures have ideal Rashba electron gas, i.e. there no other energy states near to Fermi level except Rashba states.

Theoretical study and rate constant calculation for the reactions of SH (SD) with Cl2, Br2, and BrCl.

Science.gov (United States)

Wang, Li; Liu, Jing-Yao; Li, Ze-Sheng; Sun, Chia-Chung

2005-01-30

The mechanisms of the SH (SD) radicals with Cl2 (R1), Br2 (R2), and BrCl (R3) are investigated theoretically, and the rate constants are calculated using a dual-level direct dynamics method. The optimized geometries and frequencies of the stationary points are calculated at the MP2/6-311G(d,p) and MPW1K/6-311G(d,p) levels. Higher-level energies are obtained at the approximate QCISD(T)/6-311++G(3df, 2pd) level using the MP2 geometries as well as by the multicoefficient correlation method based on QCISD (MC-QCISD) using the MPW1K geometries. Complexes with energies less than those of the reactants or products are located at the entrance or the exit channels of these reactions, which indicate that the reactions may proceed via an indirect mechanism. The enthalpies of formation for the species XSH/XSD (X = Cl and Br) are evaluated using hydrogenation working reactions method. By canonical variational transition-state theory (CVT), the rate constants of SH and SD radicals with Cl2, Br2, and BrCl are calculated over a wide temperature range of 200-2000 K at the a-QCISD(T)/6-311++G(3df, 2pd)//MP2/6-311G(d, p) level. Good agreement between the calculated and experimental rate constants is obtained in the measured temperature range. Our calculations show that for SH (SD) + BrCl reaction bromine abstraction (R3a or R3a') leading to the formation of BrSH (BrSD) + Cl in a barrierless process dominants the reaction with the branching ratios for channels 3a and 3a' of 99% at 298 K, which is quite different from the experimental result of k3a'/k3' = 54 +/- 10%. Negative activation energies are found at the higher level for the SH + Br2 and SH + BrCl (Br-abstraction) reactions; as a result, the rate constants show a slightly negative temperature dependence, which is consistent with the determination in the literature. The kinetic isotope effects for the three reactions are "inverse". The values of kH/kD are 0.88, 0.91, and 0.69 at room temperature, respectively, and they increase

Ternary rare-earth halides of the A2MX5 type (A = K, In, NH4, Rb, Cs; X = Cl, Br, I)

International Nuclear Information System (INIS)

Meyer, G.; Soose, J.; Moritz, A.; Vitt, V.; Holljes, T.

1985-01-01

Ternary rare-earth (=M) chlorides, bromides, and iodides In 2 MCl 5 , (NH 4 ) 2 MCl 5 , Rb 2 MCl 5 , Cs 2 MCl 5 , CsRbMCl 5 , K 2 MBr 5 , Rb 2 MBr 5 , K 2 MI 5 , and Rb 2 MI 5 have been synthesized. Single crystals of In 2 PrCl 5 , Rb 2 PrCl 5 , K 2 PrBr 5 , and K 2 PrI 5 were grown and the structures refined. The other halides were characterized by X-ray powder patterns. They are isotypic either with K 2 PrCl 5 (orthorhombic, Pnma, Z = 4, hexagonal arrangement of chains of edge-connected polyhedra [PrX 7 ]) or with Cs 2 DyCl 5 (orthorhombic, Pbnm, Z = 4, hexagonal arrangement of cis-corner-connected octahedra [DyCl 6 ]) which may be discriminated in structure field diagrams. The thermal expansion was investigated for Cs 2 LuCl 5 and Rb 2 PrX 5 (X = Cl, Br, I). (author)

Electronic structure and magnetic ordering of the semiconducting chromium trihalides CrCl3, CrBr3, and CrI3

KAUST Repository

Wang, Hao

2011-03-01

We present results from an electronic structure investigation of the chromium halides CrCl3, CrBr3, and CrI3, as obtained by the linearized augmented plane wave method of density functional theory. Our interest focuses on the chloride. While all three halides display strong ferromagnetic coupling within the halide-Cr-halide triple layers, our emphasis is on differences in the interlayer magnetic coupling. In agreement with experimental results, our calculations indicate ferromagnetic ordering for CrBr3 as well as CrI3. The antiferromagnetic state of CrCl3 can be reproduced by introducing an on-site electron-electron repulsion. However, we observe that the ground state depends critically on the specific approach used. Our results show that a low temperature structural phase transition from monoclinic to trigonal is energetically favourable for CrCl3. © 2011 IOP Publishing Ltd.

Deviation from the <i>trans> -Effect in Ligand-Exchange Reactions of Zeise’s Ions PtCl₃(C₂H₄)^- with Heavier Halides (Br^–, I^- )

Energy Technology Data Exchange (ETDEWEB)

Hou, Gao-Lei [Physical; Govind, Niranjan [Environmental; Xantheas, Sotiris S. [Advanced; Department; Wang, Xue-Bin [Physical

2018-01-16

Four new Zeise’s family ions with mixed-halide ligands, i.e., PtCl_nX_3-n(C₂H₄)^- (X = Br, I; n = 1, 2), were synthesized via ligand-exchange reactions of KX salts with KPtCl₃(C₂H₄) in aqueous solutions, and were detected in vacuum via electrospray ionization mass spectrometry. Their photoelectron spectra reveal a series of well-resolved spectral peaks with their electron binding energies (EBEs) decreasing with increasing halide size, with I having a much stronger effect than Br, i.e., 4.57 (–Cl₃) > 4.56 (–Cl₂Br) > 4.53 (–ClBr₂) > 4.34 (–Cl₂I) > 4.30 eV (–ClI₂). Ab initio electronic structure calculations including spin-orbit coupling (SOC) predict that the cis- and trans-isomers are nearly isoenergetic with the cis-isomer for –Cl₂X, and the trans-isomer for –ClX₂ slightly favored, respectively. Excited-state spectra calculated with time-dependent density functional theory (TDDFT), and their comparison with the observed ones, suggest that for each species, both the cis- and trans-configurations coexist in the experiments and contribute to the observed spectra, a fact that clearly violates the prediction of the widely accepted trans-effect, which suggests that only one isomer would have formed.

Formation of new halogenothiocarbonylsulfenyl halides, XC(S)SY, through photochemical matrix reactions starting from CS2 and a dihalogen molecule XY (XY=Cl2, Br2, or BrCl).

Science.gov (United States)

Tobón, Yeny A; Romano, Rosana M; Védova, Carlos O Della; Downs, Anthony J

2007-05-28

Isolation of a dihalogen molecule XY (XY=Cl2, Br2, or BrCl) with CS2 in a solid Ar matrix at about 15 K leads, by broad-band UV-vis photolysis (200ClCS*, Cl*...SCS, CCl4, *CCl3, :CCl2, SCl2, SCBr2, CBr4, *CBr3, BrC(S)Cl, BrCCl3, and :CBrCl, the following new molecules have also been identified as products of the various photoreactions: syn-ClC(S)SCl, anti-ClC(S)SCl, syn-BrC(S)SBr, anti-BrC(S)SBr, syn-ClC(S)SBr, anti-ClC(S)SBr, syn-BrC(S)SCl, anti-BrC(S)SCl, ClC(S)S*, BrCS*, and Br*...SCS. The IR spectra of these hitherto unknown species have been interpreted with reference to the predictions of ab initio (HF and MP2) and density functional theory (DFT) calculations. The results are analyzed in relation to the reaction pathways accessed by matrix photolysis.

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

Science.gov (United States)

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

Contributions of BrCl, Br2, BrOCl, Br2O, and HOBr to regiospecific bromination rates of anisole and bromoanisoles in aqueous solution.

Science.gov (United States)

Sivey, John D; Bickley, Mark A; Victor, Daniel A

2015-04-21

When bromide-containing waters are chlorinated, conventional wisdom typically assumes HOBr is the only active brominating agent. Several additional and often-overlooked brominating agents (including BrCl, Br2, BrOCl, Br2O) can form in chlorinated waters, albeit at generally lower concentrations than HOBr. The extent to which these additional brominating agents influence bromination rates of disinfection byproduct precursors is, however, poorly understood. Herein, the influence of BrCl, Br2, BrOCl, Br2O, and HOBr toward rates of sequential bromination of anisole was quantified. Conditions affecting bromine speciation (e.g., pH, concentrations of chloride, bromide, and chlorine) were varied, and regiospecific second-order rate constants were calculated for reactions of each brominating agent with anisole, 2-bromoanisole, and 4-bromoanisole. The regioselectivity of anisole bromination changed with pH, consistent with the participation of more than one brominating agent. Under conditions representative of chlorinated drinking water, contributions to bromination rates decreased as BrCl > BrOCl > HOBr > Br2O (Br2 negligible). The second-order rate constant determined for net bromination of anisole by HOBr is up to 3000-times less than reported in previous studies (which assumed HOBr was the only active brominating agent). Accordingly, models that assume HOBr is the only kinetically relevant brominating agent in solutions of free bromine may be insufficient for reactions involving modestly nucleophilic organic compounds.

Charge transfer and relativistic effects in the low-lying electronic states of CuCl, CuBr and CuI

NARCIS (Netherlands)

Sousa, C; de Jong, W.A.; Broer, R.; Nieuwpoort, WC

1997-01-01

The spectral transitions and the character of the low-lying excited states of the copper halides, CuX (X = Cl, Br, I) are studied by means of two different relativistic computational approaches. One is based on the CASSCF/CASPT2 approach with operators accounting for scalar relativistic effects

Chemical vapour transport of pyrite (FeS 2) with halogen (Cl, Br, I)

Science.gov (United States)

Fiechter, S.; Mai, J.; Ennaoui, A.; Szacki, W.

1986-12-01

A systematic study of chemical vapour transport (CVT) of pyrite with halogen, hydrogen halides and ammonium halides as transporting agents has shown that the transport with chlorine and bromine in a temperature gradient Δ T = 920-820 K yields the highest transport rates (˜6 mg/h) with crystals up to 5 mm edge length. Computing thermochemical equilibria and flux functions in the system Fe-S-Hal (Hal = Cl, Br, I) it has been confirmed that the transport velocity of pyrite is limited by the concentration of FeHal 2 in the vapour phase, the equilibrium position between FeHal 2(g) and FeHal 3(g) and the flux directions of the iron gas species.

Superconducting nitride halides MNX (M = Ti, Zr, Hf; X = Cl, Br, I)

Energy Technology Data Exchange (ETDEWEB)

Schurz, Christian M.; Shlyk, Larysa; Schleid, Thomas; Niewa, Rainer [Stuttgart Univ. (Germany). Inst. fuer Anorganische Chemie

2011-07-01

Two different polymorphs of the metal nitride halides MNX (M = Ti, Zr, Hf; X = Cl, Br, I) are known to crystallize in layered structures. The two crystal structures differ in the way {sub {infinity}}{sup 2}{l_brace}X[M{sub 2}N{sub 2}]X{r_brace} slabs are stacked along the c-axes. Metal atoms and/or organic molecules can be intercalated into the van-der-Waals gap between these layers. After such an electron-doping via intercalation the prototypic band insulators change into superconductors with moderate high critical temperatures T{sub c} up to 25.5 K. This review gathers information on synthesis routes, structural characteristics and properties of the prototypic nitride halides and the derivatives after electron-doping with a focus on superconductivity. (orig.)

First-principles investigations on the mechanical, thermal, electronic, and optical properties of the defect perovskites Cs2Sn X 6 ( X = Cl, Br, I)

International Nuclear Information System (INIS)

Huang Hai-Ming; Jiang Zhen-Yi; Luo Shi-Jun

2017-01-01

The mechanical properties, thermal properties, electronic structures, and optical properties of the defect perovskites Cs 2 Sn X 6 ( X = Cl, Br, I) were investigated by first-principles calculation using PBE and HSE06 hybrid functional. The optic band gaps based on HSE06 are 3.83 eV for Cs 2 SnCl 6 , 2.36 eV for Cs 2 SnBr 6 , and 0.92 eV for Cs 2 SnI 6 , which agree with the experimental results. The Cs 2 SnCl 6 , Cs 2 SnBr 6 , and Cs 2 SnI 6 are mechanically stable and they are all anisotropic and ductile in nature. Electronic structures calculations show that the conduction band consists mainly of hybridization between the halogen p orbitals and Sn 5s orbitals, whereas the valence band is composed of the halogen p orbitals. Optic properties indicate that these three compounds exhibit good optical absorption in the ultraviolet region, and the absorption spectra red shift with the increase in the number of halogen atoms. The defect perovskites are good candidates for probing the lead-free and high power conversion efficiency of solar cells. (paper)

A simple access to pure thorium(IV) halides (ThCl{sub 4}, ThBr{sub 4}, and ThI{sub 4})

Energy Technology Data Exchange (ETDEWEB)

Deubner, H. Lars; Rudel, Stefan Sebastian; Kraus, Florian [Fachbereich Chemie, Philipps-Universitaet Marburg (Germany)

2017-12-13

In this work we present a facile, lab scale synthesis for thorium tetrahalides ThX{sub 4} (X = Cl, Br, and I). The reaction between the easily available ThO{sub 2} and AlX{sub 3} (X = Cl, Br, and I) and a subsequent in situ chemical vapor transport (CVT) leads to a product of high purity, which is obtained in the form of crystals or large aggregates of crystals. Their identity and purity was evidenced by X-ray powder diffraction and IR spectroscopy. The usage of ThO{sub 2} avoids, unlike earlier syntheses, the utilization of scarcely available thorium metal or of other reactants, such as CCl{sub 4}, which leads to impurities. Furthermore, the reaction tolerates even less pure ThO{sub 2}. (copyright 2017 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

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

Science.gov (United States)

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.

Crystal and molecular structure of new fullerides (Ph4P)2C60Hal (Hal = Br, I) and (Ph4As)2C60Cl

International Nuclear Information System (INIS)

Gritsenko, V.V.; D'yachenko, O.A.; Shilov, G.V.; Spitsyn, N.G.; Yagubskij, E h.B.

1997-01-01

New stable on air fullerides (Ph 4 P) 2 C 60 Hal (Hal = Br, I) and (Ph 4 As) 2 C 60 Cl were synthesized and their crystal structure were determined. On the basis of their relative crystallochemical analysis fullerides obtained were shown to be isostructural. They are described by general formula (Ph 4 X) 2 C 60 Hal (X = H, As; Hal = Cl, Br, I) and crystallized in triclinic system. Anions C 60 - and Hal - occupy the centre-symmetrical positions, cations (PH 4 P) + and (Ph 4 As) + occupy the general positions. The main parameters of molecular structure are presented

Electronic structure and magnetic ordering of the semiconducting chromium trihalides CrCl3, CrBr3, and CrI3

KAUST Repository

Wang, Hao; Eyert, Volker; Schwingenschlö gl, Udo

2011-01-01

for CrBr3 as well as CrI3. The antiferromagnetic state of CrCl3 can be reproduced by introducing an on-site electron-electron repulsion. However, we observe that the ground state depends critically on the specific approach used. Our results show that a

Benzonitrile: Electron affinity, excited states, and anion solvation

Science.gov (United States)

Dixon, Andrew R.; Khuseynov, Dmitry; Sanov, Andrei

2015-10-01

We report a negative-ion photoelectron imaging study of benzonitrile and several of its hydrated, oxygenated, and homo-molecularly solvated cluster anions. The photodetachment from the unsolvated benzonitrile anion to the X ˜ 1 A 1 state of the neutral peaks at 58 ± 5 meV. This value is assigned as the vertical detachment energy (VDE) of the valence anion and the upper bound of adiabatic electron affinity (EA) of benzonitrile. The EA of the lowest excited electronic state of benzonitrile, a ˜ 3 A 1 , is determined as 3.41 ± 0.01 eV, corresponding to a 3.35 eV lower bound for the singlet-triplet splitting. The next excited state, the open-shell singlet A ˜ 1 A 1 , is found about an electron-volt above the triplet, with a VDE of 4.45 ± 0.01 eV. These results are in good agreement with ab initio calculations for neutral benzonitrile and its valence anion but do not preclude the existence of a dipole-bound state of similar energy and geometry. The step-wise and cumulative solvation energies of benzonitrile anions by several types of species were determined, including homo-molecular solvation by benzonitrile, hydration by 1-3 waters, oxygenation by 1-3 oxygen molecules, and mixed solvation by various combinations of O2, H2O, and benzonitrile. The plausible structures of the dimer anion of benzonitrile were examined using density functional theory and compared to the experimental observations. It is predicted that the dimer anion favors a stacked geometry capitalizing on the π-π interactions between the two partially charged benzonitrile moieties.

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

Science.gov (United States)

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. Copyright © 2016 Elsevier B.V. All rights reserved.

Quantitative interpretation of Cl, Br and I porewater concentration profiles in lake sediments of Loch Lomond, Scotland

International Nuclear Information System (INIS)

Falck, W.E.; Hooker, P.J.

1991-01-01

One of the four natural analogue sites being investigated by the British Geological Survey is Loch Lomond, Scotland. Naturally occurring halogen elements (Cl, Br and I) have been migrating from a thin marine horizon into overlying freshwater deposits by a diffusion process which has been occurring for at least 5 400 years. This report summarizes the main findings accumulated since 1983 when the work was first begun, and provides a modelling interpretation of the measured concentration-depth profiles using a new numerical code called Diagen. The release rates of I and Br from the organic matter association in the shallow buried marine layer are very slow; subsequent anion movement by diffusion is affected by tortuosity differences in the sediments rather than by chemical reaction with the sediments. The bulk of the evidence supports conservative transport of iodide, bromide and chloride anions towards the sediment/loch interface. The report discusses some implications of the findings

Reactivity of BrCl, Br₂, BrOCl, Br₂O, and HOBr toward dimethenamid in solutions of bromide + aqueous free chlorine.

Science.gov (United States)

Sivey, John D; Arey, J Samuel; Tentscher, Peter R; Roberts, A Lynn

2013-02-05

HOBr, formed via oxidation of bromide by free available chlorine (FAC), is frequently assumed to be the sole species responsible for generating brominated disinfection byproducts (DBPs). Our studies reveal that BrCl, Br(2), BrOCl, and Br(2)O can also serve as brominating agents of the herbicide dimethenamid in solutions of bromide to which FAC was added. Conditions affecting bromine speciation (pH, total free bromine concentration ([HOBr](T)), [Cl(-)], and [FAC](o)) were systematically varied, and rates of dimethenamid bromination were measured. Reaction orders in [HOBr](T) ranged from 1.09 (±0.17) to 1.67 (±0.16), reaching a maximum near the pK(a) of HOBr. This complex dependence on [HOBr](T) implicates Br(2)O as an active brominating agent. That bromination rates increased with increasing [Cl(-)], [FAC](o) (at constant [HOBr](T)), and excess bromide (where [Br(-)](o)>[FAC](o)) implicate BrCl, BrOCl, and Br(2), respectively, as brominating agents. As equilibrium constants for the formation of Br(2)O and BrOCl (aq) have not been previously reported, we have calculated these values (and their gas-phase analogues) using benchmark-quality quantum chemical methods [CCSD(T) up to CCSDTQ calculations plus solvation effects]. The results allow us to compute bromine speciation and hence second-order rate constants. Intrinsic brominating reactivity increased in the order: HOBr ≪ Br(2)O Br(2) < BrCl. Our results indicate that species other than HOBr can influence bromination rates under conditions typical of drinking water and wastewater chlorination.

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

Science.gov (United States)

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. IC1">IC1 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. KCl">KCl 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

Study of Cytotoxic Effects of Benzonitrile Pesticides

OpenAIRE

Lovecka, Petra; Thimova, Marketa; Grznarova, Petra; Lipov, Jan; Knejzlik, Zdenek; Stiborova, Hana; Nindhia, Tjokorda Gde Tirta; Demnerova, Katerina; Ruml, Tomas

2015-01-01

The benzonitrile herbicides bromoxynil, chloroxynil, dichlobenil, and ioxynil have been used actively worldwide to control weeds in agriculture since 1970s. Even though dichlobenil is prohibited in EU since 2008, studies addressing the fate of benzonitrile herbicides in the environment show that some metabolites of these herbicides are very persistent. We tested the cytotoxic effects of benzonitrile herbicides and their microbial metabolites using two human cell lines, Hep G2 and HEK293T, rep...

A high quality and quantity hybrid perovskite quantum dots (CsPbX3, X= Cl, Br and I) powders synthesis via ionic displacement

Science.gov (United States)

Yin, Yuhang; Luan, Weiling; Zhang, Chengxi; Yang, Fuqian

2017-12-01

Recently, all-inorganic perovskites CsPbX3 (X= Cl, Br and I) quantum dots (QDs) have drawn great attentions because of their PL spectra tunable over the whole visible spectral region (400-700 nm) and adjustable bandgap, which revealed a promising potential on the field of photoelectronic devices, such as solar cells, LEDs and sensors. In this paper, CsPbX3 QDs and hybrid QDs, CsPbClxBr3-x and CsPbBrxI3-x were synthesized via one-step and two-step methods comparably. The optical bandgaps of CsPbCl3, CsPbBr3, and CsPbI3, were calculated as 3.08, 2.36, and 1.73eV, respectively, based on the Tauc’s equation and UV absorption spectra. Ionic displacement and phase transformation occurred during the mixing process were found based on the monitoring of PL spectra and HRTEM characterization. The long-term stability, dried, high quality and two-dimensional hybrid CsPbBrxI3-x QDs powders could be achieved via the two-step method. Polar solution inductions were used to wash and purify the CsPbX3 QDs, which help obtain of various compositions and well crystallize all-inorganic perovskites QDs powders.

The liquid–liquid coexistence curves of {benzonitrile + n-pentadecane} and {benzonitrile + n-heptadecane} in the critical region

International Nuclear Information System (INIS)

Chen, Zhiyun; Bai, Yongliang; Yin, Tianxiang; An, Xueqin; Shen, Weiguo

2012-01-01

Highlights: ► Coexistence curves of (benzonitrile + n-pentadecane) and (benzonitrile + n-heptadecane) were measured. ► The values of the critical exponent β are consistent with that predicted by the 3D-Ising model. ► The coexistence curves are well described by the critical crossover model. ► The asymmetry of the diameters of the coexistence curves were discussed by the complete scaling theory. - Abstract: Liquid + liquid coexistence curves for the binary solutions of {benzonitrile + n-pentadecane} and {benzonitrile + n-heptadecane} have been measured in the critical region. The critical exponent β and the critical amplitudes have been deduced and the former is consistent with the theoretic prediction. It was found that the coexistence curves may be well described by the crossover model proposed by Gutkowski et al. The asymmetries of the diameters of the coexistence curves were also discussed in the frame of the complete scaling theory.

A study on the redox, spectroscopic, and photophysical characteristics of a series of octahedral hexamolybdenum(ii) clusters: [{Mo6X8}Y6]2- (X, Y = Cl, Br, or I).

Science.gov (United States)

Akagi, Soichiro; Fujii, Sho; Kitamura, Noboru

2018-01-23

We report a systematic study on the redox, spectroscopic, and photophysical properties of a series of [{Mo 6 X 8 }Y 6 ] 2- (X, Y = Cl, Br, or I. 1-9). All of the [{Mo 6 X 8 }Y 6 ] 2- clusters show intense and long-lived phosphorescence in both CH 3 CN and crystalline phases at 298 K. We found that the emission quantum yields (Φ em ) of 1-9 increase in the sequences X = Cl Br Br Br < Cl for given {Mo 6 X 8 } 4+ -core clusters. The present data demonstrate that arbitrary combinations of X and Y in [{Mo 6 X 8 }Y 6 ] 2- could tune τ em and Φ em in the ranges of 85-300 μs and 0.09-0.47, respectively. Both capping (X) and terminal ligand (Y) effects on the photophysical properties of the clusters are discussed on the basis of the energy gap (i.e., emission energy) dependence of the nonradiative decay rate constant.

Permanent electric dipole moments of PtX (X = H, F, Cl, Br, and I) by the composite approach

Science.gov (United States)

Deng, Dan; Lian, Yongqin; Zou, Wenli

2017-11-01

Using the FPD composite approach of Peterson et. al. we calculate the permanent electric dipole moments of PtX (X = H, F, Cl, Br, and I) at the equilibrium geometries of their ground states. The dipole moment of PtF is estimated to be 3.421 Debye, being very close to the experimental value of 3.42(6) Debye. This research also suggests the ordering of dipole moments of PtX being proportional to the electronegativity of X.

Phase Transitions in CsSnCl3 and CsPbBr3 An NMR and NQR Study

Science.gov (United States)

Sharma, Surendra; Weiden, Norbert; Weiss, Alarich

1991-04-01

The phase transitions in CsSnCl3 and CsPbBr3 have been studied by X-ray powder diffraction, by 81Br-NQR and by 'H-, 119Sn-, and 113Cs-NMR. At room temperature in air CsSnCl3 forms a hydrate which can be dehydrated to the monoclinic phase II of CsSnCl3. The high temperature phase I has the Perovskite structure, as the X-ray and NMR experiments show. The three phases of CsPbBr3, known from literature, have been corroborated. The results are discussed in the framework of the group ABX3, A = alkalimetal ion, B = IV main group ion, and X = Halogen ion

La5M3X (M=Sn, Bi; X=Cl, Br, I): exploring the limit of the Mn5Si3-type hosting lattice

International Nuclear Information System (INIS)

Zheng Chong; Mattausch, Hansjuergen; Simon, Arndt

2002-01-01

Three new compounds add to the family of the Mn 5 Si 3 type host-guest lattice. These are La 5 Sn 3 X (X=Cl, Br, I) synthesized from stoichiometric mixtures of La, LaX 3 and Sn heated under Ar atmosphere in sealed Ta ampoules at 850-990 deg. C for 13-62 days. La 5 Sn 3 X crystallize in the space group P6 3 /mcm (No. 193) with lattice parameters a=9.603(1) A, 9.637(1) A and 9.673(1) A; c=6.890(1) A, 6.931(1) A and 6.987(1) A, respectively, for X=Cl, Br and I. Computational analysis using both the extended Hueckel and the local density functional methods showed that the Sn and La site acts as electron reservoir, providing electrons to the interstitials as necessary. This gives rise to a metallic behavior. Susceptibility and conductivity measurements confirmed these predictions. The single crystal structure of La 5 Bi 3 Br is also reported

Modeling study of vibrational photochemical isotope enrichment. [HBr + Cl/sub 2/; HCl + Br/sub 2/

Energy Technology Data Exchange (ETDEWEB)

Badcock, C.C.; Hwang, W.C.; Kalsch, J.F.

1978-09-29

Chemical kinetic modeling studies of vibrational-photochemical isotope enrichment have been performed on two systems: Model (I), H/sup 79/Br(H/sup 81/Br) + Cl/sub 2/ and, Model (II), H/sup 37/Cl(H/sup 35/Cl) + Br. Pulsed laser excitation was modeled to the first excited vibrational level of H/sup 79/Br in Model I and the first and second excited vibrational levels of both HCl isotopes in Model II. These are prototype systems of exoergic (Model I) and endoergic (Model II) reactions. The effects on enrichment of varying the external parameters (pressure, laser intensity) and the internal parameters (rate constants for V-V exchange and excited-state reactions) were examined. Studies of these prototype systems indicate that a favorable reaction for enrichment, with isotopically-specific excitation and a significantly accelerated vibrationally-excited-state reaction should have the following properties: the reaction from v = 0 should be only moderately exoergic, and the most favorable coreactant should be a polyatomic species, such as alkyl radical. Direct excitation of the reacting vibrational level is at least an order of magnitude more favorable for enrichment than is population by energy transfer. Enrichment of the minor isotope by these processes is more effective than is major isotope enrichment. Within limits, increased laser intensity is beneficial. However, for sequential excitation of a second vibrational level, major isotope enrichment can be diminished by high populations of the first vibrational level.

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

KAUST Repository

Zhu, Jiajie

2016-03-15

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. © The Royal Society of Chemistry 2016.

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

KAUST Repository

Zhu, Jiajie; Chroneos, Alexander; Schwingenschlö gl, Udo

2016-01-01

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. © The Royal Society of Chemistry 2016.

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

Energy Technology Data Exchange (ETDEWEB)

Tanley, Simon W. M.; Starkey, Laurina-Victoria; Lamplough, Lucinda; Kaenket, Surasek; Helliwell, John R., E-mail: john.helliwell@manchester.ac.uk [University of Manchester, Brunswick Street, Manchester M13 9PL (United Kingdom)

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’.

Theoretical study on the molecular structure and vibrational properties, NBO and HOMO-LUMO analysis of the POX3 (X = F, Cl, Br, I) series of molecules

Science.gov (United States)

Galván, Jorge E.; Gil, Diego M.; Lanús, Hernán E.; Altabef, Aida Ben

2015-02-01

The fourth member of the series of compounds of the type POX3 with X = I was synthesized and characterized by infrared spectroscopy. The geometrical parameters and vibrational properties of POX3 (X = F, Cl, Br, I) molecules were investigated theoretically by means DFT and ab initio methods. Available geometrical and vibrational data were used together with theoretical calculations in order to obtain a set of scaled force constants. The observed trends in geometrical parameters are analyzed and compared with those obtained in a previous work for the VOX3 (X = F, Cl, Br, I) series of compounds. NBO analysis was performed in order to know the hyper-conjugative interactions that favor one structure over another. The molecular properties such as ionization potential, electron affinity, electronegativity, chemical potential, chemical hardness, softness and global electrophilicity index have been deduced from HOMO-LUMO analysis.

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

Science.gov (United States)

Protesescu, Loredana; Yakunin, Sergii; Bodnarchuk, Maryna I; Krieg, Franziska; Caputo, Riccarda; Hendon, Christopher H; Yang, Ruo Xi; Walsh, Aron; Kovalenko, Maksym V

2015-06-10

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.

Absorption of water vapour in the falling film of water-(LiBr + LiI + LiNO{sub 3} + LiCl) in a vertical tube at air-cooling thermal conditions

Energy Technology Data Exchange (ETDEWEB)

Bourouis, Mahmoud; Valles, Manel; Medrano, Marc; Coronas, Alberto [Centro de Innovacion Tecnologica en Revalorizacion Energetica y Refrigeracion, CREVER, Universitat Rovira i Virgili, Autovia de Salou, s/n, 43006, Tarragona (Spain)

2005-05-01

In air-cooled water-LiBr absorption chillers the working conditions in the absorber and condenser are shifted to higher temperatures and concentrations, thereby increasing the risk of crystallisation. To develop this technology, two main problems are to be addressed: the availability of new salt mixtures with wider range of solubility than water-LiBr, and advanced absorber configurations that enable to carry out simultaneously an appropriate absorption process and an effective air-cooling. One way of improving the solubility of LiBr aqueous solutions is to add other salts to create multicomponent salt solutions. The aqueous solution of the quaternary salt system (LiBr + LiI + LiNO{sub 3} + LiCl) presents favourable properties required for air-cooled absorption systems: less corrosive and crystallisation temperature about 35 K lower than that of water-LiBr.This paper presents an experimental study on the absorption of water vapour over a wavy laminar falling film of an aqueous solution of (LiBr + LiI + LiNO{sub 3} + LiCl) on the inner wall of a water-cooled smooth vertical tube. Cooling water temperatures in the range 30-45 C were selected to simulate air-cooling thermal conditions. The results are compared with those obtained in the same experimental set-up with water-LiBr solutions.The control variables for the experimental study were: absorber pressure, solution Reynolds number, solution concentration and cooling water temperature. The parameters considered to assess the absorber performance were: absorber thermal load, mass absorption flux, degree of subcooling of the solution leaving the absorber, and the falling film heat transfer coefficient.The higher solubility of the multicomponent salt solution makes possible the operation of the absorber at higher salt concentration than with the conventional working fluid water-LiBr. The absorption fluxes achieved with water-(LiBr + LiI + LiNO{sub 3} + LiCl) at a concentration of 64.2 wt% are around 60 % higher than

The study of structural, elastic, electronic and optical properties of CsYx I(1 − x(Y = F, Cl, Br using density functional theory

Directory of Open Access Journals (Sweden)

Mian Shabeer Ahmad

2017-04-01

Full Text Available The structural, electronic, elastic and optical properties of CsYx I(1 − x(Y = F, Cl, Br are investigated using full potential linearized augmented plane wave (FP-LAPW method within the generalized gradient approximation (GGA. The ground state properties such as lattice constant (ao and bulk modulus (K have been calculated. The mechanical properties including Poisson’s ratio (σ, Young’s modulus (E, anisotropy factor (A and shear modulus (G were also calculated. The results of these calculations are comparable with the reported experimental and theoretical values. The ductility of CsYx I(1 − x was analyzed using Pugh’s rule (B/G ratio and Cauchy’s pressure (C12−C44. Our results revealed that CsF is the most ductile among the CsYxI(1 − x(Y = F, Cl, Br compounds. The incremental addition of lighter halogens (Yx slightly weakens the strength of ionic bond in CsYxI(1 − x. Moreover, the optical transitions were found to be direct for binary and ternary CsYxI(1 − x. We hope that this study will be helpful in designing binary and ternary Cs halides for optoelectronic applications.

Optical spectroscopy and Fermi surface studies of BiTeCl and BiTeBr

Science.gov (United States)

Martin, Catalin; Suslov, A. V.; Buvaev, S.; Hebard, A. F.; Bugnon, Philippe; Berger, Helmuth; Magrez, Arnaud; Tanner, D. B.

2014-03-01

The observation of a large bulk Rashba effect in the non-centrosymmetric semiconductors BiTeX(X=Cl, Br, I) has stimulated the interest in these sys- tems, as promising candidates for studying spin related phenomena and for the realization of spin devices. Here we present a comparative study of the electronic properties of BiTeCl and BiTeBr, determined from temperature dependent infrared spectroscopy and Shubnikov-de Haas oscillations. In par- ticular, we compare the angle dependence of quantum oscillations between the two compounds and discuss possible differences between the topology of their Fermi surfaces. Supported by NSF Cooperative Agreement DMR-1157490 to the National High Magnetic Field Laboratory.

What is the best bonding model of the (σ-H-BR) species bound to a transition metal? Bonding analysis in complexes [(H)2Cl(PMe3)2M(σ-H-BR)] (M = Fe, Ru, Os).

Science.gov (United States)

Pandey, Krishna K

2012-03-21

Density Functional Theory calculations have been performed for the σ-hydroboryl complexes of iron, ruthenium and osmium [(H)(2)Cl(PMe(3))(2)M(σ-H-BR)] (M = Fe, Ru, Os; R = OMe, NMe(2), Ph) at the BP86/TZ2P/ZORA level of theory in order to understand the interactions between metal and HBR ligands. The calculated geometries of the complexes [(H)(2)Cl(PMe(3))(2)Ru(HBNMe(2))], [(H)(2)Cl(PMe(3))(2)Os(HBR)] (R = OMe, NMe(2)) are in excellent agreement with structurally characterized complexes [(H)(2)Cl(P(i)Pr(3))(2)Os(σ-H-BNMe(2))], [(H)(2)Cl(P(i)Pr(3))(2)Os{σ-H-BOCH(2)CH(2)OB(O(2)CH(2)CH(2))}] and [(H)(2)Cl(P(i)Pr(3))(2)Os(σ-H-BNMe(2))]. The longer calculated M-B bond distance in complex [(H)(2)Cl(PMe(3))(2)M(σ-H-BNMe(2))] are due to greater B-N π bonding and as a result, a weaker M-B π-back-bonding. The B-H2 bond distances reveal that (i) iron complexes contain bis(σ-borane) ligand, (ii) ruthenium complexes contain (σ-H-BR) ligands with a stretched B-H2 bond, and (iii) osmium complexes contain hydride (H2) and (σ-H-BR) ligands. The H-BR ligands in osmium complexes are a better trans-directing ligand than the Cl ligand. Values of interaction energy, electrostatic interaction, orbital interaction, and bond dissociation energy for interactions between ionic fragments are very large and may not be consistent with M-(σ-H-BR) bonding. The EDA as well as NBO and AIM analysis suggest that the best bonding model for the M-σ-H-BR interactions in the complexes [(H)(2)Cl(PMe(3))(2)M(σ-H-BR)] is the interaction between neutral fragments [(H)(2)Cl(PMe(3))(2)M] and [σ-H-BR]. This becomes evident from the calculated values for the orbital interactions. The electron configuration of the fragments which is shown for C in Fig. 1 experiences the smallest change upon the M-σ-H-BR bond formation. Since model C also requires the least amount of electronic excitation and geometry changes of all models given by the ΔE(prep) values, it is clearly the most appropriate choice of

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

Energy Technology Data Exchange (ETDEWEB)

Leblanc, Nicolas [Laboratoire MOLTECH-Anjou, UMR-CNRS 6200, Universite d' Angers 2 Bd Lavoisier, 49045 Angers (France); Mercier, Nicolas, E-mail: nicolas.mercier@univ-angers.fr [Laboratoire MOLTECH-Anjou, UMR-CNRS 6200, Universite d' Angers 2 Bd Lavoisier, 49045 Angers (France); Allain, Magali; Toma, Oksana [Laboratoire MOLTECH-Anjou, UMR-CNRS 6200, Universite d' Angers 2 Bd Lavoisier, 49045 Angers (France); Auban-Senzier, Pascale; Pasquier, Claude [Laboratoire de Physique des Solides, UMR-CNRS 8502, Bat. 510,Universite Paris Sud, 91405 Orsay (France)

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

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

Energy Technology Data Exchange (ETDEWEB)

Yan, Mingquan, E-mail: yanmq@pku.edu.cn; Li, Mingyang; Han, Xuze

2016-08-15

Highlights: • Additions of KI and KIO{sub 3}-fortified table salt cause I-THMs to increase. • CHCl{sub 2}I is the predominant I-THM formed in the presence of KIO{sub 3}-fortified table salt. • >90% of CHCl{sub 2}I is removed by heating, but concentrations of the other I-THMs increase. • Additions of KI or KIO{sub 3}-fortified salt increase the cytotoxicity due to I-THM formed. • Heating causes cytotoxicity to decrease for KIO{sub 3}-fortified salt but increase for KI. - Abstract: 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 KIO{sub 3}-fortified salt, total I-THM concentrations increased with increasing iodine concentration, while total Cl/Br-THM concentrations decreased. CHCl{sub 2}I, CHBrClI, CHBrI{sub 2}, CHBr{sub 2}I and CHI{sub 3} were formed in the presence of KI salt, while only CHCl{sub 2}I was formed in the presence of KIO{sub 3} salt. CHCl{sub 2}I 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 KIO{sub 3}-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.

Protonation Reaction of Benzonitrile Radical Anion and Absorption of Product

DEFF Research Database (Denmark)

Holcman, Jerzy; Sehested, Knud

1975-01-01

The rate constant for the protonation of benzonitrile radical anions formed in pulse radiolysis of aqueous benzonitrile solutions is (3.5 ± 0.5)× 1010 dm3 mol–1 s–1. A new 270 nm absorption band is attributed to the protonated benzonitrile anion. The pK of the protonation reaction is determined t...

PbCl2-tuned inorganic cubic CsPbBr3(Cl) perovskite solar cells with enhanced electron lifetime, diffusion length and photovoltaic performance

Science.gov (United States)

Li, Bo; Zhang, Yanan; Zhang, Luyuan; Yin, Longwei

2017-08-01

Inorganic CsPbBr3 perovskite is arousing great interest following after organic-inorganic hybrid halide perovskites, and is found as a good candidate for photovoltaic devices for its prominent photoelectric property and stability. Herein, we for the first time report on PbCl2-tuned inorganic Cl-doped CsPbBr3(Cl) perovskite solar cells with adjustable crystal structure and Cl doping for enhanced carrier lifetime, extraction rate and photovoltaic performance. The effect of PbCl2 on the morphologies, structures, optical, and photovoltaic performance of CsPbBr3 perovskite solar cells is investigated systemically. Compared with orthorhombic CsPbBr3, cubic CsPbBr3 demonstrates a significant improvement for electron lifetime (from 6.7 ns to 12.3 ns) and diffusion length (from 69 nm to 197 nm), as well as the enhanced electron extraction rate from CsPbBr3 to TiO2. More importantly, Cl doping benefits the further enhancement of carrier lifetime (14.3 ns) and diffusion length (208 nm). The Cl doped cubic CsPbBr3(Cl) perovskite solar cell exhibits a Jsc of 8.47 mA cm-2 and a PCE of 6.21%, superior to that of pure orthorhombic CsPbBr3 (6.22 mA cm-2 and 3.78%). The improvement of photovoltaic performance can be attributed to enhanced carrier lifetime, diffusion length and extraction rates, as well as suppressed nonradiative recombination.

Crystal-field analysis of U3+ ions in K2LaX5 (X=Cl, Br or I) single crystals

Science.gov (United States)

Karbowiak, M.; Edelstein, N.; Gajek, Z.; Drożdżyński, J.

1998-11-01

An analysis of low temperature absorption spectra of U3+ ions doped in K2LaX5 (X=Cl, Br or I) single crystals is reported. The energy levels of the U3+ ion in the single crystals were assigned and fitted to a semiempirical Hamiltonian representing the combined atomic and crystal-field interactions at the Cs symmetry site. An analysis of the nephelauxetic effect and crystal-field splittings in the series of compounds is also reported.

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

Science.gov (United States)

Khiri, D; Hochlaf, M; Chambaud, G

2016-08-04

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.

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

Science.gov (United States)

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.

Polymorphism in 2-X-adamantane derivatives (X = Cl, Br).

Science.gov (United States)

Negrier, Philippe; Barrio, María; Tamarit, Josep Ll; Mondieig, Denise

2014-08-14

The polymorphism of two 2-X-adamantane derivatives, X = Cl, X = Br, has been studied by X-ray powder diffraction and normal- and high-pressure (up to 300 MPa) differential scanning calorimetry. 2-Br-adamantane displays a low-temperature orthorhombic phase (space group P212121, Z = 4) and a high-temperature plastic phase (Fm3̅m, Z = 4) from 277.9 ± 1.0 K to the melting point at 413.4 ± 1.0 K. 2-Cl-adamantane presents a richer polymorphic behavior through the temperature range studied. At low temperature it displays a triclinic phase (P1̅, Z = 2), which transforms to a monoclinic phase (C2/c, Z = 8) at 224.4 ± 1.0 K, both phases being ordered. Two high-temperature orientationally disordered are found for this compound, one hexagonal (P63/mcm, Z = 6) at ca. 241 K and the highest one, cubic (Fm3̅m, Z = 4), being stable from 244 ± 1.0 K up to the melting point at 467.5 ± 1.0 K. No additional phase appears due to the increase in pressure within the studied range. The intermolecular interactions are found to be weak, especially for the 2-Br-adamantane compound for which the Br···Br as well as C-Br···H distances are larger than the addition of the van der Waals radii, thus confirming the availability of this compound for building up diamondoid blocks.

Lasagna-type arrays with halide-nitromethane cluster filling. The first recognition of the Hal(-)···HCH2NO2 (Hal = Cl, Br, I) hydrogen bonding.

Science.gov (United States)

Gushchin, Pavel V; Kuznetsov, Maxim L; Wang, Qian; Karasik, Andrey A; Haukka, Matti; Starova, Galina L; Kukushkin, Vadim Yu

2012-06-21

The previously predicted ability of the methyl group of nitromethane to form hydrogen bonding with halides is now confirmed experimentally based on X-ray data of novel nitromethane solvates followed by theoretical ab initio calculations at the MP2 level of theory. The cationic (1,3,5-triazapentadiene)Pt(II) complexes [Pt{HN=C(NC(5)H(10))N(Ph)C(NH(2))=NPh}(2)](Cl)(2), [1](Hal)(2) (Hal = Cl, Br, I), and [Pt{HN=C(NC(4)H(8)O)N(Ph)C(NH(2))=NPh}(2)](Cl)(2), [2](Cl)(2), were crystallized from MeNO(2)-containing systems providing nitromethane solvates studied by X-ray diffraction. In the crystal structure of [1][(Hal)(2)(MeNO(2))(2)] (Hal = Cl, Br, I) and [2][(Cl)(2)(MeNO(2))(2)], the solvated MeNO(2) molecules occupy vacant spaces between lasagna-type layers and connect to the Hal(-) ion through a weak hydrogen bridge via the H atom of the methyl thus forming, by means of the Hal(-)···HCH(2)NO(2) contact, the halide-nitromethane cluster "filling". The quantum-chemical calculations demonstrated that the short distance between the Hal(-) anion and the hydrogen atom of nitromethane in clusters [1][(Hal)(2)(MeNO(2))(2)] and [2][(Cl)(2)(MeNO(2))(2)] is not just a consequence of the packing effect but a result of the moderately strong hydrogen bonding.

Copper(I), silver(I) and gold(I) halide complexes with the dithioformamidinium dihalides

Science.gov (United States)

Peyronel, Giorgio; Malavasi, Wanda; Pignedoli, Anna

Some copper(I), silver(I) and gold(I) halide complexes with the dithioformamidinium dihalides (Tu 2X 2) were prepared and studied by infrared spectroscopy and conductometry: 3CuX.2Tu 2X 2(XCl,I), CuBr.Tu 2Br 2, 4CuBr.3.5Tu 2Br 2.MeOH, 2CuBr.Tu 2Br 2.0.66EtOH, 3CuI.2Tu 2I 2, 2AgCl.2.5Tu 2Cl 2, 3AgCl.2Tu 2Cl 2.0.5EtOH, 3AgCl.Tu 2Cl 2, 2AgBr.2Tu 2Br 2.0.5Tu 2(NO 3) 2.H 2O, AgBr.Tu 2Br 2, 4AgBr.Tu 2Br 2, 4AgI.0.5Tu 2I 2.EtOH, AuCl.1.5Tu 2Cl 2, 4AuCl.3.5Tu 2Cl 2.2DMF, AuBr.4Tu 2Br 2, AuBr.2Tu 2Br 2.1.5DMF, AuI.5Tu 2I 2, AuI.Tu 2I 2. A decrease of the ν(NH), δ(NH 2) and ν(CN 2) frequencies and an increase of the ν(CS) frequencies indicate an N-coordination of the dithioformamidinium cation to the metal ions; ν(MN) and ν(MX) frequencies are tentatively assigned in the far-infrared spectra.

Resonance Raman Spectra of the Transient Cl2 and Br2 Radical Anions

DEFF Research Database (Denmark)

Wilbrandt, Robert Walter; Jensen, Niels-Henrik; Sillesen, Alfred Hegaard

1984-01-01

The resonance Raman spectra of the short-lived radical anions ClImage 2− and BrImage − in aqueous solution are reported. The observed wavenumbers of 279 cm−1 for ClImage − and 177 cm−1 for BrImage − are about 10% higher than those published for the corresponding species isolated in solid argon ma...

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

Science.gov (United States)

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

Molecular structure and vibrational spectra of MHal3 (M = Sc, Y, La, Lu; Hal = F, Cl, Br, I): ab initio calculations by the CISD+Q method

International Nuclear Information System (INIS)

Solomonik, V.G.; Marochko, O.Yu.

2000-01-01

Structure and vibrational spectra of MHal 3 molecules (M = Sc, Y, La, Lu; Hal = F, Cl, Br, I) are studied by the CISD+Q method. It is ascertained that equilibrium configuration of nuclei in all the molecules, except LaF 3 , is plane (D 3h symmetry), while that of LaF 3 molecule - pyramidal (C 3c symmetry). Results of the calculations are compared with previously published experimental data. Band reference in IR spectra of ScBr 3 , YF 3 and YCl 3 molecules has been corrected [ru

Structural and electronic properties of silicene on MgX2 (X = Cl, Br, and I)

KAUST Repository

Zhu, Jiajie

2014-07-23

Silicene is a monolayer of Si atoms in a two-dimensional honeycomb lattice, being expected to be compatible with current Si-based nanoelectronics. The behavior of silicene is strongly influenced by the substrate. In this context, its structural and electronic properties on MgX2 (X = Cl, Br, and I) have been investigated using first-principles calculations. Different locations of the Si atoms are found to be energetically degenerate because of the weak van der Waals interaction with the substrates. The Si buckling height is below 0.55 Å, which is close to the value of free-standing silicene (0.49 Å). Importantly, the Dirac cone of silicene is well preserved on MgX2 (located slightly above the Fermi level), and the band gaps induced by the substrate are less than 0.1 eV. Application of an external electric field and stacking can be used to increase the band gap. © 2014 American Chemical Society.

Raman spectra of Pm2O3, PmF3, PmCl3, PmBr3 and PmI3

International Nuclear Information System (INIS)

Wilmarth, W.R.; Peterson, J.R.

1988-01-01

Raman spectral data are presented for the sesquioxide and the trihalides (F, Cl, Br and I) of promethium. The Raman spectra of these lanthanide compounds are reported for the first time and are compared with those of the homologous lanthanide compounds. Tentative symmetry assignments have been made for the observed Raman-active bands based on factor group analysis of their respective crystal structures and comparisons with the assigned Raman spectra of other lanthanide compounds. The characteristic band patterns of the Raman phonon spectra have been found to be very useful in determining the crystal structure of the respective promethium compounds. (author)

Cs _1–<i>x> Rb _<i>x> PbCl ₃ and Cs _1–<i>x> Rb _<i>x> PbBr ₃ Solid Solutions: Understanding Octahedral Tilting in Lead Halide Perovskites

Energy Technology Data Exchange (ETDEWEB)

Linaburg, Matthew R.; McClure, Eric T.; Majher, Jackson D.; Woodward, Patrick M.

2017-04-03

The structures of the lead halide perovskites CsPbCl3 and CsPbBr3 have been determined from X-ray powder diffraction data to be orthorhombic with Pnma space group symmetry. Their structures are distorted from the cubic structure of their hybrid analogs, CH3NH3PbX3 (X = Cl, Br), by tilts of the octahedra (Glazer tilt system a–b+a–). Substitution of the smaller Rb+ for Cs+ increases the octahedral tilting distortion and eventually destabilizes the perovskite structure altogether. To understand this behavior, bond valence parameters appropriate for use in chloride and bromide perovskites have been determined for Cs+, Rb+, and Pb2+. As the tolerance factor decreases, the band gap increases, by 0.15 eV in Cs1–xRbxPbCl3 and 0.20 eV in Cs1–xRbxPbBr3, upon going from x = 0 to x = 0.6. The band gap shows a linear dependence on tolerance factor, particularly for the Cs1–xRbxPbBr3 system. Comparison with the cubic perovskites CH3NH3PbCl3 and CH3NH3PbBr3 shows that the band gaps of the methylammonium perovskites are anomalously large for APbX3 perovskites with a cubic structure. This comparison suggests that the local symmetry of CH3NH3PbCl3 and CH3NH3PbBr3 deviate significantly from the cubic symmetry of the average structure.

Polymeric anionic networks using dibromine as a crosslinker; the preparation and crystal structure of [(C4H9)4N]2[Pt2Br10].(Br2)7 and [(C4H9)4N]2[PtBr4Cl2].(Br2)6.

Science.gov (United States)

Berkei, Michael; Bickley, Jamie F; Heaton, Brian T; Steiner, Alexander

2002-09-21

The reaction of M[PtX3(CO)] (M+ = [(C4H9)4N]+, X = Br, Cl) with an excess of Br2 gives the new platinum(IV) salts, [(C4H9)4N]2[Pt2Br10].(Br2)7, 1, and [(C4H9)4N]2[PtBr4Cl2].(Br2)6, 2, which, in the solid state, contain strong Br Br interactions resulting in the formation of polymeric networks; they could provide useful solid storage reservoirs for elemental bromine.

Study of Cytotoxic Effects of Benzonitrile Pesticides

Science.gov (United States)

Lovecka, Petra; Thimova, Marketa; Grznarova, Petra; Lipov, Jan; Knejzlik, Zdenek; Stiborova, Hana; Nindhia, Tjokorda Gde Tirta; Demnerova, Katerina; Ruml, Tomas

2015-01-01

The benzonitrile herbicides bromoxynil, chloroxynil, dichlobenil, and ioxynil have been used actively worldwide to control weeds in agriculture since 1970s. Even though dichlobenil is prohibited in EU since 2008, studies addressing the fate of benzonitrile herbicides in the environment show that some metabolites of these herbicides are very persistent. We tested the cytotoxic effects of benzonitrile herbicides and their microbial metabolites using two human cell lines, Hep G2 and HEK293T, representing liver and kidneys as potential target organs in humans. The cell viability and proliferation were determined by MTT test and RTCA DP Analyzer system, respectively. The latter allows real-time monitoring of the effect of added substances. As the cytotoxic compounds could compromise cell membrane integrity, the lactate dehydrogenase test was performed as well. We observed high toxic effects of bromoxynil, chloroxynil, and ioxynil on both tested cell lines. In contrast, we determined only low inhibition of cell growth in presence of dichlobenil and microbial metabolites originating from the tested herbicides. PMID:26339609

Electronic structure of f1 actinide complexes. Pt. 3. Quasi-relativistic density functional calculations of the optical transition energies of PaX62-(X=F,Cl,Br,I)

International Nuclear Information System (INIS)

Kaltsoyannis, N.

1998-01-01

For pt.II see J. Organomet. Chem., vol.528, p.19, 1997. The four f→f transition energies of the single 5f-based electron of PaX 6 2- (X=F, Cl, Br, I) have been calculated using quasi-relativistic local density functional theory. Excellent agreement ( -1 ) between theory and experiment is obtained for PaCl 6 2- , PaBr 6 2- and PaI 6 2- by variation of the value of α in the Xα exchange-only functional. In contrast, more sophisticated calculational methods including non-local corrections fail to reproduce the experiments well. The PaF 6 2- results are less impressive (up to 1000 cm -1 discrepancy), possibly due to non-aufbau orbital occupations for certain values of α. The values of α employed lie in the range 0.79-0.85, somewhat higher than the most widely used value of 0.7. The theoretical basis for using such values is discussed. (orig.)

Energikravene i BR15

DEFF Research Database (Denmark)

Kragh, Jesper; Aggerholm, Søren

2015-01-01

Bygningsreglement 2015 – BR15 – gælder fra 1. januar 2016 med en overgangsfase frem til 1. juli 2016. Det bygger videre på BR10 og de tidligere udmeldte krav til nybyggeriet frem mod 2020. I denne kvikguide får du hurtigt overblik over, hvordan du sikrer, at de bygninger, du er med til at opføre...... eller renovere, lever op til BR15’s energikrav. Disse krav findes primært i reglementets kapitel 7 om energiforbrug og i kapitel 8 om installationer samt i kapitel 6 om indeklima....

Resistance to {gamma} irradiation of LaBr{sub 3}:Ce and LaCl{sub 3}:Ce single crystals

Energy Technology Data Exchange (ETDEWEB)

Normand, S. [CEA-Recherche Technologique, DETECS/SSTM CE Saclay F-91191 Gif Sur Yvette Cedex (France)]. E-mail: stephane.normand@cea.fr; Iltis, A. [Saint-Gobain Crystals, 104 Route de Larchant, 77140 St Pierre les Nemours (France); Bernard, F. [Saint-Gobain Crystals, 104 Route de Larchant, 77140 St Pierre les Nemours (France); Domenech, T. [CEA-Recherche Technologique, DETECS/SSTM CE Saclay F-91191 Gif Sur Yvette Cedex (France); Delacour, P. [CEA-Recherche Technologique, DETECS/SSTM CE Saclay F-91191 Gif Sur Yvette Cedex (France)

2007-03-11

LaBr{sub 3}:Ce (Brillance 380) and LaCl{sub 3}:Ce (Brillance 350) both exhibit a very good energy resolution and energy linearity response. They are also more sensitive to {gamma}-rays than NaI(Tl) detectors, due to their higher density. The aim of this work is to determine the behaviour of those new single crystals in comparison with NaI(Tl) under severe {gamma}-ray irradiation. Therefore we have irradiated three 25 by 25 mm cylinder crystals encapsulated in air-tight aluminium housing with {sup 60}Co beam. Crystals were tested as stand-alone material not to test the impact of radiation to our photomultiplier tube (PMT). Only encapsulated crystals (alone, without PMTs) were irradiated during several periods to achieve the final 3.4 kGy integrated dose. Intermediate measurements of {sup 137}Cs spectrum were done in order to evaluate the impact of the dose on the studied crystal performances. The radiation hardness of LaBr{sub 3}:Ce and LaCl{sub 3}:Ce was then compared to NaI(Tl). We show in this paper that up to 3.4 kGy no permanent modification of the energy resolution nor colour change is observed for LaBr{sub 3}:Ce and LaCl{sub 3}:Ce crystals. The light output also seems quite stable. This is in stark contrast with the behaviour of NaI:Tl which exhibits continuously decreasing light output, colour change and worsening of energy resolution for doses above 5 Gy.

Comprehensive ab initio calculation and simulation on the low-lying electronic states of TlX (X = F, Cl, Br, I, and At).

Science.gov (United States)

Zou, Wenli; Liu, Wenjian

2009-03-01

The low-lying electronic states of TlX (X=F, Cl, Br, I, and At) are investigated using the configuration interaction based complete active space third-order perturbation theory [CASPT3(CI)] with spin-orbit coupling accounted for. The potential energy curves and the corresponding spectroscopic constants are reported. The results are grossly in good agreement with the available experimental data. The absorption spectra are simulated as well to reassign the experimental bands. The present results are also useful for guiding future experimental measurements.

Structure and bonding of transition metal-boryl compounds. Theoretical study of [(PH3)2(CO)ClOs-BR2] and [(PH3)2(CO)2ClOs-BR2] (BR2 = BH2, BF2, B(OH)2, B(OCH=CHO), Bcat).

Science.gov (United States)

Giju, K T; Bickelhaupt, F M; Frenking, G

2000-10-16

Quantum chemical DFT calculations using the B3LYP functionals have been carried out for the electronically unsaturated 16 VE five-coordinate osmium boryl-complexes [(PH3)2(CO)ClOs-BR2] and the 18 VE six-coordinate complexes [(PH3)2(CO)2ClOs-BR2] with BR2 = BH2, BF2, B(OH)2, B(OHC=CHO), and Bcat (cat = catecholate O2C6H4). The bonding situation of the Os-BR2 bond was analyzed with the help of the NBO partitioning scheme. The Os-B bond dissociation energies of the 16 VE complexes are very high, and they do not change very much for the different boryl ligands. The 18 VE complexes have only slightly lower bond energies than the 16 VE species. The Os-B bond in both classes of compounds is provided by a covalent sigma-bond which is polarized toward osmium and by strong charge attraction. Os-->B pi-donation is not important for the Os-B binding interactions, except for the Os-BH2 complexes. The stability of the boryl complexes [Os]-BR2 comes mainly from BB pi-donation. The intraligand charge distribution of the BR2 group changes little when the Os-B bond is formed, except for BH2. The CO ligand in [(PH3)2(CO)2ClOs-BR2] which is trans to BR2 has a relatively weak bond to the osmium atom.

NQR and X-ray crystal structure studies of cadmium halide complexes: [C(NH2)3]CdI3 and [4-ClC6H5NH3]3CdBr5

International Nuclear Information System (INIS)

Gesing, Thorsten M.; Lork, Enno; Terao, Hiromitsu; Ishihara, Hideta

2016-01-01

The crystal structures of [C(NH 2 ) 3 ]CdI 3 (1) and [4-ClC 6 H 5 NH 3 ] 3 CdBr 5 (2) have been determined at 100 K: monoclinic, Cc, a = 828.75(3) pm, b = 1615.31(5) pm, c = 810.64(3) pm, and β = 106.5820(10) for 1; monoclinic, P2 1 /c, a = 1486.93(5) pm, b = 794.31(3) pm, c = 2290.59(7) pm, and β = 99.6830(10) for 2. The structure of 1 has an infinite chain of anions consisting of [CdI 4 ] tetrahedra sharing two corners. The structure of 2 has an infinite chain of anions consisting of [CdBr 6 ] octahedra sharing two corners in cis positions. In both structures, isolated cations are connected to the anion chains through weak hydrogen bonds Cd-X..H to result in three-dimensional network structures. In accordance with the crystal structures, three 127 I (m = ±1/2 <-> m = ±3/2), five 81 Br, and three 35 Cl nuclear quadrupole resonance (NQR) lines were observed for 1 and 2. The NQR spectra reflect the anion chain structures and their weak hydrogen bonds. The MO calculations of the models [Cd 5 I 16 ] 6- for 1 and [Cd 3 Br 16 ] 10- for 2 estimate only about half the values for the NQR frequencies but give accurate electric field gradient directions.

(Ferrocenylmethylamino) Benzonitrile and 3-(Ferrocenylmethylamino)

African Journals Online (AJOL)

2016-01-01

Jan 1, 2016 ... (ferrocenylmethylamino)benzonitrile (3FMAB) were successfully synthesised and their binding parameters with DPPH radical were determined using spectrophotometrical technics. The results indicated chemical interaction of DPPH radical with 3FMAB and electrostatic interaction of 2FMAB and Ascorbic ...

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

Science.gov (United States)

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

2013-04-04

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.

Electric Multipole Moments and (HyperPolarizability of X–C≡C–X, X = F, Cl, Br and I

Directory of Open Access Journals (Sweden)

Demetrios Xenides

2003-04-01

Full Text Available Abstract: We have calculated self-consistent field (SCF and second-order Møller-Plesset perturbation theory (MP2 for the dihaloethynes X–C≡C–X, X = F, Cl, Br and I. All calculations have been performed with carefully optimized, flexible basis sets of gaussiantype functions. Our best values for the quadrupole moment (Θ/ea02 are -0.6524 (FCCF, 3.6612 (ClCCCl, 5.8143 (BrCCBr and 8.3774 (ICCI. The dipole polarizability is strongly anisotropic. For the mean (α /e2a02Eh-1 and the anisotropy (Δα/e2a02Eh-1 we obtain 23.58 and 15.09 (FCCF, 51.75 and 48.30 (ClCCCl, 66.53 and 60.04 (BrCCBr, 93.79 and 78.91 (ICCI. The mean dipole hyperpolarizability (γ /e4a04Eh-3 increases rapidly as 2932 (FCCF, 9924 (ClCCCl, 17409 (BrCCBr and 35193 (ICCI. The transversal component of the hyperpolarizability is larger than the longitudinal one for FCCF, γxxxx > γzzzz but this is reversed for the other molecules in the series. Difluoroethyne is less (hyperpolarizable than ethyne.

Synthesis of iridacarborane halide complexes [(η-9-SMe2-7,8-C2B9H10)IrX2]2 (X=Cl, Br, I)

International Nuclear Information System (INIS)

Kudinov, A.R.; Perekalin, D.S.; Petrovskij, P.V.

2001-01-01

By interaction between Na[9-SMe 2 -7,8-C 2 B 9 H 10 ] and [(Cod)IrCl] 2 (Cod - cycloocta-1,5-diene) iridium complex (η-9-SMe 2 -7,8-C 2 B 9 H 10 )Ir(Cod), which under the action of anhydrous hydrohalogenic acids HX (X=Cl, Br, I) yields iridacarborane halide complexes [(η-9-SMe 2 -7,8-C 2 B 9 H 10 )IrX 2 ] 2 , being analogs of cyclopentadienyl complexes [(C 5 Me 5 )IrX 2 ] 2 . The complexes prepared were characterized on the basis of data of elementary analysis and 1 H, 11 B NMR spectra [ru

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

International Nuclear Information System (INIS)

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 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 ( 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 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

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)

Science.gov (United States)

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.

Mass transfer performance comparison of two commonly used liquid desiccants: LiBr and LiCl aqueous solutions

International Nuclear Information System (INIS)

Liu, X.H.; Yi, X.Q.; Jiang, Y.

2011-01-01

Mass transfer performance of two commonly used liquid desiccants, LiBr aqueous solution and LiCl aqueous solution, is compared in this paper on the basis of the same solution temperature and surface vapor pressure. According to the analysis of the analytical solutions of heat and mass transfer processes, the key performance influencing factors are heat capacity ratio of air to desiccant m * and mass transfer unit NTU m . The heat capacities of the two liquid desiccants are about the same at same volumetric flow rate, and LiBr solution has higher density and smaller specific heat capacity. The variance of mass transfer unit with different operating conditions and liquid desiccants are derived based on the experimental results. In the condition of the same desiccant mass flow rate, the dehumidification performance of LiCl solution is better, and the regeneration performance of LiBr solution is a little better or almost the same as that of LiCl solution. In the condition of the same desiccant volumetric flow rate, the dehumidification performance of LiCl solution is a little better or about the same compared with LiBr solution, and the regeneration performance of LiBr solution is better. The COPs of the liquid desiccant systems using these two desiccants are similar; while LiCl solution costs 18% lower than LiBr solution at current Chinese price.

Chemical effects of nuclear transformations in mixed crystals. 7. Chemical effects of the 35Cl(n,γ)36Cl nuclear reaction in K2ReCl6-K2ReBr6 mixed crystals

International Nuclear Information System (INIS)

Mueller, H.; Diefallah, E.H.M.; Martin, S.

1981-01-01

The solid-state reactions occurring during the moderation of recoiling 36 Cl, produced by the (n,γ) reaction, have been studied in K 2 ReCl 6 -K 2 ReBr 6 mixed crystals. The main reaction products are Re 36 ClCl 5 2- , Re 36 ClBr 5 2- , and 36 Cl - , but the more intimately mixed species Re 36 ClCl/sub n/Br/sub 5-n/ 2- (n = 1, 2, 3, 4) are found in significant amounts. The production of the different recoil-labeled species can be explained by elementary impact models: 6% of the recoils do not leave their original lattice site (primary retetion); between 6% and 23%, dependent upon the mixed-crystal composition, appear as interstitials; 31 to 48% give rise to direct displacement reactions of one halide ligand; and 40% produce larger disruption by substitution of at least two halide ligands. The results have been compared with Roessler's 38 Cl recoil experiments

Growth mechanism of NaClO 3 and NaBrO 3 crystals from aqueous ...

Indian Academy of Sciences (India)

A study of growth rates of NaClO3 and NaBrO3 has been carried out using a small growth cell by in situ observation. Normal growth rates of {100} faces of NaClO3 and {111} faces of NaBrO3 along ⟨ 110 ⟩ direction are measured under relatively high supersaturation ranging from 3–8%. In the initial stages of growth, {100}, ...

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

Energy Technology Data Exchange (ETDEWEB)

Kesler, S.E.; Martini, A.M.; Appold, M.S.; Walter, L.M.; Huston, T.J. [Univ. of Michigan, Ann Arbor, MI (United States); Furman, F.C. [Univ. of Missouri, Rolla, MO (United States)

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.

Reduction of substituted benzonitrile pesticides

Czech Academy of Sciences Publication Activity Database

Sokolová, Romana; Hromadová, Magdaléna; Fiedler, Jan; Pospíšil, Lubomír; Giannarelli, S.; Valášek, Michal

2008-01-01

Roč. 622, č. 2 (2008), s. 211-218 ISSN 1572-6657 R&D Projects: GA AV ČR IAA400400505; GA MŠk OC 140; GA MŠk LC510 Institutional research plan: CEZ:AV0Z40400503; CEZ:AV0Z40550506 Keywords : benzonitrile pesticides * polarography * voltammetry Subject RIV: CG - Electrochemistry Impact factor: 2.484, year: 2008

Specific non-bonding contacts in the crystal structure of [Mo3(μ3-S)(μ-S2)3(S2CNEt2)3]Cl0.53Br0.47 solid solution

International Nuclear Information System (INIS)

Virovets, A.V.; Volkov, O.V.

2000-01-01

Solid solution [Mo 3 S 7 (dtc) 3 ]Cl 0.53 Br 0.47 (dtc diethyl-dithiocarbamate) featuring the following parameters of monoclinic all: a = 14.541(2), b = 12.407(2), c = 18.117(2) A, β = 90.032(9) deg, sp.gr. P2 1 /n, Z = 4, d cal = 2.107 g/cm 3 , was studied by the method of X-ray diffraction analysis. Formation of ionic pairs with axial contact 3S ax ...Br, its length 3.028-3.105 A, in the compound structure was ascertained. For compounds [Mo 3 S 7 (dtc) 3 ] Hal (Hal = Cl, Br, I) a regular growth in S...Hal distances in the series Cl-Br-I was pointed out, meanwhile the distances remained shorted than the van-der-Waals sums of sulfur and halogen radii [ru

A study of the atmospherically important reactions between dimethyl selenide (DMSe) and molecular halogens (X2 = Cl2, Br2, and I2) with ab initio calculations.

Science.gov (United States)

Rhyman, Lydia; Armata, Nerina; Ramasami, Ponnadurai; Dyke, John M

2012-06-14

The atmospherically relevant reactions between dimethyl selenide (DMSe) and the molecular halogens (X(2) = Cl(2), Br(2), and I(2)) have been studied with ab initio calculations at the MP2/aug-cc-pVDZ level of theory. Geometry optimization calculations showed that the reactions proceed from the reagents to the products (CH(3)SeCH(2)X + HX) via three minima, a van der Waals adduct (DMSe:X(2)), a covalently bound intermediate (DMSeX(2)), and a product-like complex (CH(3)SeCH(2)X:HX). The computed potential energy surfaces are used to predict what molecular species are likely to be observed in spectroscopic experiments such as gas-phase photoelectron spectroscopy and infrared matrix isolation spectroscopy. It is concluded that, for the reactions of DMSe with Cl(2) and Br(2), the covalent intermediate should be seen in spectroscopic experiments, whereas, in the DMSe + I(2) reaction, the van der Waals adduct DMSe:I(2) should be observed. Comparison is made with previous related calculations and experiments on dimethyl sulfide (DMS) with molecular halogens. The relevance of the results to atmospheric chemistry is discussed. The DMSeX(2) and DMSe:X(2) intermediates are likely to be reservoirs of molecular halogens in the atmosphere which will lead on photolysis to ozone depletion.

Partial structures in molten AgBr

Energy Technology Data Exchange (ETDEWEB)

Ueno, Hiroki [Department of Condensed Matter Chemistry and Physics, Faculty of Sciences, Kyushu University, 4-2-1 Ropponmatsu, Chuo-ku, Fukuoka 810-8560 (Japan)], E-mail: ueno@gemini.rc.kyushu-u.ac.jp; Tahara, Shuta [Faculty of Pharmacy, Niigata University of Pharmacy and Applied Life Science, Higashijima, Akiha-ku, Niigata 956-8603 (Japan); Kawakita, Yukinobu [Department of Physics, Faculty of Sciences, Kyushu University, 4-2-1 Ropponmatsu, Chuo-ku, Fukuoka 810-8560 (Japan); Kohara, Shinji [Research and Utilization Division, Japan Synchrotron Radiation Research Institute (JASRI, SPring-8), 1-1-1 Koto, Sayo-cho, Sayo-gun, Hyogo 679-5198 (Japan); Takeda, Shin' ichi [Department of Physics, Faculty of Sciences, Kyushu University, 4-2-1 Ropponmatsu, Chuo-ku, Fukuoka 810-8560 (Japan)

2009-02-21

The structure of molten AgBr has been studied by means of neutron and X-ray diffractions with the aid of structural modeling. It is confirmed that the Ag-Ag correlation has a small but well-defined first peak in the partial pair distribution function whose tail penetrates into the Ag-Br nearest neighbor distribution. This feature on the Ag-Ag correlation is intermediate between that of molten AgCl (non-superionic melt) and that of molten AgI (superionic melt). The analysis of Br-Ag-Br bond angle reveals that molten AgBr preserves a rocksalt type local ordering in the solid phase, suggesting that molten AgBr is clarified as non-superionic melt like molten AgCl.

Growth of PbX2 and CsPbX3 (X = Cl, Br) mesoscopic phases in alkali halide host lattices

Science.gov (United States)

Polak, K.; Nitsch, K.; Nikl, M.

Formation of PbCl2 and CsPbBr3 microphases in NaCl and CsBr respectively is studied using mainly an absorption spectroscopy. The absorption of NaCl: Pb crystal was investigated as a function of annealing temperature and duration of thermal treatment. Changes in the position and shape of the exciton band were studied in CsBr: Pb absorption spectrum. The results showed that the shape of CsPbBr3 microcrystals is far from a spherical one. The microcrystals probably grow as highly elongated discs.

Insights into the catalytic activity of [Pd(NHC)(cin)Cl] (NHC = IPr, IPrCl, IPrBr) complexes in the Suzuki-Miyaura reaction

KAUST Repository

Nolan, Steven Patrick; Izquierdo, Frederic; Zinser, Caroline; Minenkov, Yury; Cordes, David; Slawin, Alexandra; Cavallo, Luigi; Nahra, Fady; Cazin, Catherine

2017-01-01

The influence of C4,5-halogenation on palladium N-heterocyclic carbene complexes and their activity in the Suzuki-Miyaura reaction have been investigated. Two [Pd(NHC)(cin)Cl] complexes bearing IPrCl and IPrBr ligands were synthesized. After

Novel germanetellones: XYGe=Te (X, Y = H, F, Cl, Br, I and CN) - structures and energetics. Comparison with the first synthetic successes.

Science.gov (United States)

Jaufeerally, Naziah B; Abdallah, Hassan H; Ramasami, Ponnadurai; Schaefer, Henry F

2014-03-14

No stable germanetellone was described until Tbt(Dis)Ge=Te and Tbt(Tip)Ge=Te (Tbt = 2,4,6-tris[bis(trimethylsilyl)methyl]phenyl, Dis = bis(trimethylsilyl)methyl and Tip = 2,4,6-triisopropylphenyl) were reported in 1997. Following these initial experiments, there has arisen considerable interest in Ge[double bond, length as m-dash]Te systems. An obvious question is: why have the simple XYGe=Te (X, Y = H, F, Cl, Br, I and CN) molecules not yet been isolated? In view of the present situation, theoretical information may be of great help for further advances in germanetellone chemistry. A systematic investigation of the XYGe=Te molecules is carried out using the second order Møller-Plesset perturbation theory (MP2) and density functional theory (DFT). The structures and energetics, including ionization potentials (IPad and IPad(ZPVE)), four different forms of neutral-anion separations (EAad, EAad(ZPVE), VEA and VDE) and the singlet-triplet gaps, are reported. The electronegativity (χ) reactivity descriptor for the halogens (F, Cl, Br and I) and the natural charge separations of the Ge=Te moiety are used to assess the interrelated properties of germanetellone and its derivatives. The results are analyzed, discussed and compared with analogous studies of telluroformaldehyde, silanetellone and their derivatives. The thermodynamic viabilities of some of the novel germanetellones have also been evaluated in terms of the bond dissociation enthalpies of Tbt(Dis)Ge=Te and Tbt(Tip)Ge=Te. The simple mono-substituted germanetellones appear to be slightly more thermodynamically favored than Tbt(Dis)Ge=Te and Tbt(Tip)Ge=Te, since the bond dissociation enthalpies of these kinetically stabilized germanetellones are about 28 and 51 kcal mol(-1) lower, respectively.

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

Energy Technology Data Exchange (ETDEWEB)

Demissie, Taye B. [Centre for Theoretical and Computational Chemistry Department of Chemistry, UiT – The Arctic University of Norway, N-9037 Tromsø (Norway)

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.

Theoretical investigation of potential energy surface and bound states for the van der Waals complex Ar–BrCl dimer

Energy Technology Data Exchange (ETDEWEB)

Zheng, Rui [School of Mathematics and Information Science, North China University of Water Resources and Electric Power, Zhengzhou (China); Key Laboratory of Magnetic Resonance in Biological Systems, State Key Laboratory of Magnetic Resonance and Atomic and Molecular Physics, Wuhan Centre for Magnetic Resonance, Wuhan Institute of Physics and Mathematics, Chinese Academy of Sciences, Wuhan (China); Li, Song, E-mail: lsong@yangtzeu.edu.cn [School of Physics and Optoelectronic Engineering, Yangtze University, Jingzhou (China); Chen, Shan-Jun; Chen, Yan [School of Physics and Optoelectronic Engineering, Yangtze University, Jingzhou (China); Zheng, Li-Min [Key Laboratory of Magnetic Resonance in Biological Systems, State Key Laboratory of Magnetic Resonance and Atomic and Molecular Physics, Wuhan Centre for Magnetic Resonance, Wuhan Institute of Physics and Mathematics, Chinese Academy of Sciences, Wuhan (China)

2015-09-08

Highlights: • A two-dimensional potential for Ar–BrCl is constructed at the CCSD(T) level. • The PES is characterized by three minima and two saddle points between them. • Bound state calculations were carried out for the complex. - Abstract: The intermolecular potential energy surface (PES) of the ground electronic state for the Ar–BrCl dimer is constructed at the CCSD(T) level with the aug-cc-pVQZ basis set and mid-bond functions. The PES is characterized by three minima and two saddle points. The global minimum corresponding to a collinear Ar–BrCl configuration, which has been observed experimentally, is located at R = 4.10 Å and θ = 2.5° with a well depth of −285.207 cm{sup −1}. A nearly T-shaped structure and an anti-linear Ar–ClBr geometry is also predicted. The bound state calculations are preformed to study intermolecular vibrational modes, rotational levels and average structures for the complex. Our transition frequencies, spectroscopic constants and average structures for all isotopomers of the collinear isomer agree well with experimental data. We have also provided pure rotational transitional frequencies for both nearly T-shaped and anti-linear isomers. These results are significant for further experimental investigations of the Ar–BrCl dimer.

Tunable White-Light Emission in Single-Cation-Templated Three-Layered 2D Perovskites (CH ₃ CH ₂ NH ₃ ) ₄ Pb ₃ Br _10–<i>x> Cl _<i>x>

Energy Technology Data Exchange (ETDEWEB)

Mao, Lingling; Wu, Yilei; Stoumpos, Constantinos C.; Traore, Boubacar [Institut; Katan, Claudine [Institut; Even, Jacky [Fonctions; Wasielewski, Michael R.; Kanatzidis, Mercouri G.

2017-08-16

Two-dimensional (2D) hybrid halide perovskites come as a family (B)₂(A)_n-1PbnX_3n+1 (B and A= cations; X= halide). These perovskites are promising semiconductors for solar cells and optoelectronic applications. Among the fascinating properties of these materials is white-light emission, which has been mostly observed in single-layered 2D lead bromide or chloride systems (n = 1), where the broad emission comes from the transient photoexcited states generated by self-trapped excitons (STEs) from structural distortion. Here we report a multilayered 2D perovskite (n = 3) exhibiting a tunable white-light emission. Ethylammonium (EA+) can stabilize the 2D perovskite structure in EA₄Pb₃Br_10–xCl_x (x = 0, 2, 4, 6, 8, 9.5, and 10) with EA⁺ being both the A and B cations in this system. Because of the larger size of EA, these materials show a high distortion level in their inorganic structures, with EA4Pb3Cl10 having a much larger distortion than that of EA₄Pb₃Br₁₀, which results in broadband white-light emission of EA₄Pb₃Cl₁₀ in contrast to narrow blue emission of EA4Pb3Br10. The average lifetime of the series decreases gradually from the Cl end to the Br end, indicating that the larger distortion also prolongs the lifetime (more STE states). The band gap of EA₄Pb₃Br_10–xCl_x ranges from 3.45 eV (x = 10) to 2.75 eV (x = 0), following Vegard’s law. First-principles density functional theory calculations (DFT) show that both EA₄Pb₃Cl₁₀ and EA₄Pb₃Br₁₀ are direct band gap semiconductors. The color rendering index (CRI) of the series improves from 66 (EA₄Pb₃Cl₁₀) to 83 (EA₄Pb₃Br_0.5Cl_9.5), displaying high tunability and versatility of the

Radiation-induced reactions of Cl-, CO32-, and Br- in seawater, - Model calculation of gamma radiolysis of seawater

International Nuclear Information System (INIS)

Hata, Kuniki; Hanawa, Satoshi; Kasahara, Shigeki; Muroya, Yusa; Katsumura, Yosuke

2012-09-01

Gamma-radiolysis of seawater has been simulated to estimate the concentrations of radiolysis products. Although gas products such as H 2 , O 2 and H 2 O 2 in irradiated pure water quickly attain the steady state with very low concentrations, the products in seawater monotonically increase with dose. It was found that H 2 is produced almost linearly with dose, and corresponding G-value was 4.4 x 10 -8 mol J -1 . As similar result was obtained from the calculation of 8 x 10 -4 mol dm -3 NaBr solution, the origin of the linear increase in seawater was attributable to be the reactions of Br - . According to the sensitivity analysis, three reactions, 1: Br - + ·OH → BrOH· - , 2: BrOH· - → Br - + ·OH, and 3: BrOH· - → Br· + OH - , determined the concentrations of the products. The presence of Cl - and HCO 3 - in seawater hardly affected the concentrations of the radiolysis products. Oxyanions derived from Cl - and Br - were not obtained at observable concentration. (authors)

Crystal structures of palladium(II) ternary complexes of 5-x-2-aminobenzoic acid with 1,10-phenanthroline and their interaction with calf thymus DNA (where X=Cl, Br and I).

Science.gov (United States)

Wang, Yue; Okabe, Nobuo; Odoko, Mamiko

2005-10-01

The crystal structures of a series of three palladium(II) ternary complexes of 5-halogeno-2-aminobenzoic acid (5-X-AB, where X=Cl, Br and I) with 1,10-phenanthroline [Pd(5-Cl-AB)(phen)] (1), [Pd(5-Br-AB)(phen)] (2) and [Pd(5-I-AB)(phen)] (3) have been determined, and their coordination geometries and the crystal architecture characterized. All of the complexes are an isostructure in which each Pd(II) atom has basically similar square planar coordination geometry. The substitute halogen group at 5-position of AB plays an important role in producing the coordination bonds of the carboxylate and amino groups in which the carboxylate O atom and the amino N atom act as the negative monodentate ligand atoms. The coordination bond distances of O-Pd increase in the order 1<2<3, while those of N-Pd decrease in the same order. The binding of the complexes to the calf thymus DNA has also been studied by the fluorescence method. Each of the complexes shows high binding propensity to DNA which can be reflected as the relative order 1<2<3.

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

Science.gov (United States)

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.

MAPbI2.9-xBrxCl0.1 hybrid halide perovskites: Shedding light on the effect of chloride and bromide ions on structural and photoluminescence properties

Science.gov (United States)

Atourki, Lahoucine; Vega, Erika; Marí, Bernabé; Mollar, Miguel; Ait Ahsaine, Hassan; Bouabid, Khalid; Ihlal, Ahmed

2016-12-01

The optical and structural properties of CH3NH3PbI3 can be adjusted by introducing other extrinsic ions such as chloride and bromide. In this work, mixed bromide iodide lead perovskites with a 10% fraction of chloride were prepared from methylamine, lead nitrate and the corresponding hydro acid (X = I, Br, Cl). The effect of bromide and chloride incorporation on different properties of perovskite thin film was investigated. The Pawley fit method indicates the formation of the iodide halide MAPbI3 Pm-3 m cubic phase for x = 0 and the tetragonal P4/mmm phase for x ≥ 0.3. All deposited films showed a strong absorbance in the UV-vis range. The band gap values were estimated from absorbance measurements. It was found that the onset of the absorption edge for MAPbI2.9-xBrxCl0.1 thin film perovskites ranges between 1.60 and 1.80 eV. Moreover, it was found that both Cl and Br affect the PL emission of the mixed halide lead perovskite, the MAPbI2.9-xBrxCl0.1 films displayed intermediate values from 730 nm (MAPbI2.2Br0.7Cl0.1) to 770 nm (MAPbI2.6Br0.3Cl0.1).

High Br- Content CsPb(Cl yBr1- y)3 Perovskite Nanocrystals with Strong Mn2+ Emission through Diverse Cation/Anion Exchange Engineering.

Science.gov (United States)

Li, Fei; Xia, Zhiguo; Pan, Caofeng; Gong, Yue; Gu, Lin; Liu, Quanlin; Zhang, Jin Z

2018-04-11

The unification of tunable band edge (BE) emission and strong Mn 2+ doping luminescence in all-inorganic cesium lead halide perovskite nanocrystals (NCs) CsPbX 3 (X = Cl and Br) is of fundamental importance in fine tuning their optical properties. Herein, we demonstrate that benefiting from the differentiation of the cation/anion exchange rate, ZnBr 2 and preformed CsPb 1- x Cl 3 : xMn 2+ NCs can be used to obtain high Br - content Cs(Pb 1- x- z Zn z )(Cl y Br 1- y ) 3 : xMn 2+ perovskite NCs with strong Mn 2+ emission, and the Mn 2+ substitution ratio can reach about 22%. More specifically, the fast anion exchange could be realized by the soluble halide precursors, leading to anion exchange within a few seconds as observed from the strong BE emission evolution, whereas the cation exchange instead generally required at least a few hours; moreover, their exchange mechanism and dynamics process have been evaluated. The Mn 2+ emission intensity could be further varied by controlling the replacement of Mn 2+ by Zn 2+ with prolonged ion exchange reaction time. White light emission of the doped perovskite NCs via this cation/anion synergistic exchange strategy has been realized, which was also successfully demonstrated in a prototype white light-emitting diode (LED) device based on a commercially available 365 nm LED chip.

TeX4 (X = F, Cl, Br) as Lewis acids--complexes with soft thio- and seleno-ether ligands.

Science.gov (United States)

Hector, Andrew L; Jolleys, Andrew; Levason, William; Reid, Gillian

2012-08-28

TeF(4) reacts with OPR(3) (R = Me or Ph) in anhydrous CH(2)Cl(2) to give the colourless, square based pyramidal 1 : 1 complexes [TeF(4)(OPR(3))] only, in which the OPR(3) is coordinated basally in the solid state, (R = Me: d(Te-O) = 2.122(2) Å; R = Ph: d(Te-O) = 2.1849(14) Å). Variable temperature (19)F{(1)H}, (31)P{(1)H} and (125)Te{(1)H} NMR spectroscopic studies strongly suggest this is the low temperature structure in solution, although the systems are dynamic. The much softer donor ligands SMe(2) and SeMe(2) show a lower affinity for TeF(4), although unstable, yellow products with spectroscopic features consistent with [TeF(4)(EMe(2))] are obtained by the reaction of TeF(4) in neat SMe(2) or via reaction in CH(2)Cl(2) with SeMe(2). TeX(4) (X = F, Cl or Br) causes oxidation and halogenation of TeMe(2) to form X(2)TeMe(2). The Br(2)TeMe(2) hydrolyses in trace moisture to form [BrMe(2)Te-O-TeMe(2)Br], the crystal structure of which has been determined. TeX(4) (X = Cl or Br) react with the selenoethers SeMe(2), MeSe(CH(2))(3)SeMe or o-C(6)H(4)(SeMe)(2) (X = Cl) in anhydrous CH(2)Cl(2) to give the distorted octahedral monomers trans-[TeX(4)(SeMe(2))(2)], cis-[TeX(4){MeSe(CH(2))(3)SeMe}] and cis-[TeCl(4){o-C(6)H(4)(SeMe)(2)}], which have been characterised by IR, Raman and multinuclear NMR ((1)H, (77)Se{(1)H} and (125)Te{(1)H}) spectroscopy, and via X-ray structure determinations of representative examples. Tetrahydrothiophene (tht) can form both 1 : 1 and 1 : 2 Te : L complexes. For X = Br, the former has been shown to be a Br-bridged dimer, [Br(3)(tht)Te(μ-Br)(2)TeBr(3)(tht)], by crystallography with the tht ligands anti, whereas the latter are trans-octahedral monomers. Like its selenoether analogue, MeS(CH(2))(3)SMe forms distorted octahedral cis-chelates, [TeX(4){MeS(CH(2))(3)SMe}], whereas the more rigid o-C(6)H(4)(SMe)(2) unexpectedly forms a zig-zag chain polymer in the solid state, [TeCl(4){o-C(6)H(4)(SMe)(2)}](n), in which the dithioether adopts an

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

Science.gov (United States)

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.

17β-estradiol as precursors of Cl/Br-DBPs in the disinfection process of different water samples.

Science.gov (United States)

Shao, Yanan; Pan, Zihan; Rong, Chuan; Wang, Yinghui; Zhu, Hongxiang; Zhang, Yuanyuan; Yu, Kefu

2018-05-21

During chlorine disinfection process, reactions between the disinfectant and 17β-estradiol (E2) lead to the formation of halogenated disinfection byproducts (DBPs) which can be a risk to both ecosystem and human health. The degradation and transformation products of E2 in sodium hypochlorite (NaClO) disinfection processes of different water samples were investigated. The reaction kinetics research showed that the degradation rates of E2 were considerably dependent on the initial pH value and the types of water samples. In fresh water, synthetic marine aquaculture water and seawater, the reaction rate constant was 0.133 min -1 , 2.067 min -1 and 2.592 min -1 , respectively. The reasons for the above phenomena may be due to the different concentrations of bromide ions (Br - ) in these three water samples which could promote the reaction between NaClO and E2. Furthermore, Br - could also cause the formation of brominated DBPs (Br-DBPs). The main DBPs, reaction centers and conceivable reaction pathways were explored. Seven halogenated DBPs have been observed including three chlorinated DBPs (Cl-DBPs) and four Br-DBPs. The active sites of E2 were found to be the pentabasic cyclic ring and the ortho position of the phenol moiety as well as C9-C10 position. The identified Cl/Br-DBPs were also confirmed in actual marine aquaculture water from a shrimp pond. The comparison of bio-concentration factors (BCF) values based on calculation of EPI-suite showed that the toxicities of the Br-DBPs were stronger than that of their chloride analogues. The absorbable organic halogens (AOX) analysis also suggested that the DBPs produced in the marine aquaculture water were more toxic than that in the fresh water system. Copyright © 2018 Elsevier Ltd. All rights reserved.

Bonding in d9 complexes derived from EPR: Application to CuCl2-4, CuBr2-4, and CdCl2:Cu2+

Science.gov (United States)

Aramburu, J. A.; Moreno, M.

1985-12-01

In this work are reported the theoretical expressions for the [g], hyperfine, and superhyperfine (shf) tensors of a d9 square-planar complex within a molecular orbital (MO) scheme. These expressions include contributions arising from crystal field and charge transfer excitations calculated up to third and second order perturbations, respectively. This makes the present framework more general than those previously used. Through those expressions we have derived from the experimental EPR and optical data the MO coefficients corresponding to the valence b1g(x2-y2), b2g(xy), and eg(xz,yz) levels and also the core polarization contribution K to the hyperfine tensor for the systems CuCl2-4, CuBr2-4, and CdCl2:Cu2+. The 3d charge obtained for CuCl2-4 is equal to 0.61, 0.83, and 0.85 for the antibonding 3b1g, 2b2g, and 2eg levels, respectively. These figures are much closer to the Xα results by Bencini and Gatteschi [J. Am. Chem. Soc. 105, 5535 (1983)] than to those by Desjardins et al. [J. Am. Chem. Soc. 105, 4590 (1983)]. The σ and π covalency for CuBr2-4 are both higher than for CuCl2-4 in accord to the lower electronegativity for bromine. However, only for the antibonding 3b1g level of CuBr2-4 have we obtained an electronic charge lying mainly on ligands. The covalency of CdCl2:Cu2+ is smaller than that found for CuCl2-4, a fact associated to a higher metal-ligand distance for the former. Evidence of this statement are also given from the analysis of crystal-field spectra and isotropic shf constant. The values of K derived for CuCl2-4 (128.1×10-4 cm-1), CuBr2-4 (103.6×10-4 cm-1), and CdCl2:Cu2+ (123.9×10-4 cm-1) point out the dependence of K on the equatorial covalency but also on the existence of axial ligands. The [g] tensor of CuBr2-4 is dominated by the charge transfer contribution while the crystal field one is negative. Finally an analysis of the importance of each one of the involved contributions to the spin-Hamiltonian parameters is reported for the

Semiconducting perovskites (2-XC6H4C2H4NH3)2SnI4 (X = F, Cl, Br): steric interaction between the organic and inorganic layers.

Science.gov (United States)

Xu, Zhengtao; Mitzi, David B; Dimitrakopoulos, Christos D; Maxcy, Karen R

2003-03-24

Two new semiconducting hybrid perovskites based on 2-substituted phenethylammonium cations, (2-XC(6)H(4)C(2)H(4)NH(3))(2)SnI(4) (X = Br, Cl), are characterized and compared with the previously reported X = F compound, with a focus on the steric interaction between the organic and inorganic components. The crystal structure of (2-ClC(6)H(4)C(2)H(4)NH(3))(2)SnI(4) is solved in a disordered subcell [C2/m, a = 33.781(7) A, b = 6.178(1) A, c = 6.190(1) A, beta = 90.42(3)(o), and Z = 2]. The structure is similar to the known (2-FC(6)H(4)C(2)H(4)NH(3))(2)SnI(4) structure with regard to both the conformation of the organic cations and the bonding features of the inorganic sheet. The (2-BrC(6)H(4)C(2)H(4)NH(3))(2)SnI(4) system adopts a fully ordered monoclinic cell [P2(1)/c, a = 18.540(2) A, b = 8.3443(7) A, c = 8.7795(7) A, beta = 93.039(1)(o), and Z = 2]. The organic cation adopts the anti conformation, instead of the gauche conformation observed in the X = F and Cl compounds, apparently because of the need to accommodate the additional volume of the bromo group. The steric effect of the bromo group also impacts the perovskite sheet, causing notable distortions, such as a compressed Sn-I-Sn bond angle (148.7(o), as compared with the average values of 153.3 and 154.8(o) for the fluoro and chloro compounds, respectively). The optical absorption features a substantial blue shift (lowest exciton peak: 557 nm, 2.23 eV) relative to the spectra of the fluoro and chloro compounds (588 and 586 nm, respectively). Also presented are transport properties for thin-film field-effect transistors (TFTs) based on spin-coated films of the two hybrid semiconductors.

Dielectric Study of the Phase Transitions in [P(CH3)4]2CuY4 (Y = Cl, Br)

Science.gov (United States)

Gesi, Kazuo

2002-05-01

Phase transitions in [P(CH3)4]2CuY4 (Y = Cl, Br) have been studied by dielectric measurements. In [P(CH3)4]2CuCl4, a slight break and a discontinuous jump on the dielectric constant vs. temperature curve are seen at the normal-incommensurate and the incommensurate-commensurate phase transitions, respectively. A small peak of dielectric constant along the b-direction exists just above the incommensurate-to-commensurate transition temperature. The anisotropic dielectric anomalies of [P(CH3)4]2CuBr4 at phase transitions were measured along the three crystallographic axes. The pressure-temperature phase diagram of [P(CH3)4]2CuCl4 was determined. The initial pressure coefficients of the normal-to-incommensurate and the incommensurate-to-commensurate transition temperatures are 0.19 K/MPa and 0.27 K/MPa, respectively. The incommensurate phase in [P(CH3)4]2CuCl4 disappears at a triple point which exists at 335 MPa and 443 K. The stability and the pressure effects of the incommensurate phases are much different among the four [Z(CH3)4]2CuY4 crystals (Z = N, P; Y = Cl, Br).

Formation of methane versus benzene in the reactions of (C{sub 5}Me{sub 5}){sub 2}Th(CH{sub 3}){sub 2} with [CH{sub 3}PPh{sub 3}]X (X=Cl, Br, I) yielding thorium-carbene or thorium-ylide complexes

Energy Technology Data Exchange (ETDEWEB)

Rungthanaphatsophon, Pokpong; Behrle, Andrew C.; Barnes, Charles L.; Walensky, Justin R. [Department of Chemistry, University of Missouri, Columbia, MO (United States); Bathelier, Adrien; Castro, Ludovic; Maron, Laurent [Toulouse Univ. and CNRS, INSA, UPS, CNRS, UMR, UMR 5215, LPCNO (France)

2017-10-09

The reaction of (C{sub 5}Me{sub 5}){sub 2}Th(CH{sub 3}){sub 2} with the phosphonium salts [CH{sub 3}PPh{sub 3}]X (X=Cl, Br, I) was investigated. When X=Br and I, two equivalents of methane are liberated to afford (C{sub 5}Me{sub 5}){sub 2}Th[CHPPh{sub 3}]X, rare terminal phosphorano-stabilized carbenes with thorium. These complexes feature the shortest thorium-carbon bonds (∼2.30 Aa) reported to date, and electronic structure calculations show some degree of multiple bonding. However, when X=Cl, only one equivalent of methane is lost with concomitant formation of benzene from an unstable phosphorus(V) intermediate, yielding (C{sub 5}Me{sub 5}){sub 2}Th[κ{sup 2}-(C,C{sup '})-(CH{sub 2})(CH{sub 2})PPh{sub 2}]Cl. Density functional theory (DFT) investigations of the reaction energy profiles for [CH{sub 3}PPh{sub 3}]X, X=Cl and I showed that in the case of iodide, thermodynamics prevents the production of benzene and favors formation of the carbene. (copyright 2017 Wiley-VCH Verlag GmbH and Co. KGaA, Weinheim)

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

Science.gov (United States)

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.

Synthesis and the crystal and molecular structures of (H3L . Cl)[CoCl4] and H2L[CuBr4] (L is 2,4,6-Tri(N,N-dimethylamino)methylphenol)

International Nuclear Information System (INIS)

Kovalchukova, O. V.; Stash, A. I.; Strashnova, S. B.; Romashkina, E. P.; Zaitsev, B. E.

2010-01-01

The complex compounds (H 3 L . Cl)[CoCl 4 ] (I) and H 2 L[CuBr 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 3 L 3+ cation exists as the cis tautomer. In compound II, the H 2 L 2+ dication exists as the trans isomer. In the crystal structure, the dications are arranged in layers via hydrogen bonds.

Speciation analysis of 129I in seawater by carrier-free AgI-AgCl coprecipitation and accelerator mass spectrometric measurement

DEFF Research Database (Denmark)

Luo, Maoyi; Hou, Xiaolin; He, Chaohui

2013-01-01

A rapid and simple method was developed for speciation analysis of 129I in seawater by selective coprecipitation of carrier-free iodide and accelerator mass spectrometry (AMS) measurement of 129I. Iodide was separated from seawater and other species of iodine by coprecipitation of AgI with Ag2SO3......, AgCl, and AgBr by addition of only 100 mg/L Ag+ and 0.3 mmol/L NaHSO3 at pH 4.2-5.5. The separation efficiency of iodide was more than 95%, and crossover between 129IO3- and 129I- fractions is less than 3%. Iodate and total inorganic iodine were converted to iodide by use of NaHSO3 at pH 1......-2 and then separated by the same method as for iodide. Ag2SO3 in the coprecipitate was removed by washing with 3 mol/L HNO3 and the excess AgCl and AgBr was removed by use of diluted NH3, and finally a 1-3 mg precipitate was obtained for AMS measurement of 129I. The recovery of iodine species in the entire procedure...

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

Science.gov (United States)

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.

NQR and X-ray crystal structure studies of cadmium halide complexes: [C(NH{sub 2}){sub 3}]CdI{sub 3} and [4-ClC{sub 6}H{sub 5}NH{sub 3}]{sub 3}CdBr{sub 5}

Energy Technology Data Exchange (ETDEWEB)

Gesing, Thorsten M.; Lork, Enno [Bremen Univ. (Germany). MAPEX Center for Material and Processes; Terao, Hiromitsu [Tokushima Univ. (Japan). Faculty of Integrated Arts and Sciences; Ishihara, Hideta [Saga Univ. (Japan). Faculty of Culture and Education

2016-05-01

The crystal structures of [C(NH{sub 2}){sub 3}]CdI{sub 3} (1) and [4-ClC{sub 6}H{sub 5}NH{sub 3}]{sub 3}CdBr{sub 5} (2) have been determined at 100 K: monoclinic, Cc, a = 828.75(3) pm, b = 1615.31(5) pm, c = 810.64(3) pm, and β = 106.5820(10) for 1; monoclinic, P2{sub 1}/c, a = 1486.93(5) pm, b = 794.31(3) pm, c = 2290.59(7) pm, and β = 99.6830(10) for 2. The structure of 1 has an infinite chain of anions consisting of [CdI{sub 4}] tetrahedra sharing two corners. The structure of 2 has an infinite chain of anions consisting of [CdBr{sub 6}] octahedra sharing two corners in cis positions. In both structures, isolated cations are connected to the anion chains through weak hydrogen bonds Cd-X..H to result in three-dimensional network structures. In accordance with the crystal structures, three {sup 127}I (m = ±1/2 <-> m = ±3/2), five {sup 81}Br, and three {sup 35}Cl nuclear quadrupole resonance (NQR) lines were observed for 1 and 2. The NQR spectra reflect the anion chain structures and their weak hydrogen bonds. The MO calculations of the models [Cd{sub 5}I{sub 16}]{sup 6-} for 1 and [Cd{sub 3}Br{sub 16}]{sup 10-} for 2 estimate only about half the values for the NQR frequencies but give accurate electric field gradient directions.

Hybridization of Single Nanocrystals of Cs4PbBr6 and CsPbBr3

OpenAIRE

Weerd, Chris de; Lin, Junhao; Gomez, Leyre; Fujiwara, Yasufumi; Suenaga, Kazutomo; Gregorkiewicz, Tom

2017-01-01

Nanocrystals of all-inorganic cesium lead halide perovskites (CsPbX3, X = Cl, Br, I) feature high absorption and efficient narrow-band emission which renders them promising for future generation of photovoltaic and optoelectronic devices. Colloidal ensembles of these nanocrystals can be conveniently prepared by chemical synthesis. However, in the case of CsPbBr3, its synthesis can also yield nanocrystals of Cs4PbBr6 and the properties of the two are easily confused. Here, we investigate in de...

ANTIMONY HALIDES AND HgX2 (X = Cl, Br AMINE ADDUCTS: SYNTHESIS AND INFRARED STUDY

Directory of Open Access Journals (Sweden)

NDONGO GUEYE

2013-12-01

Full Text Available Eight new SbF3, SbCl5 and HgX2 (X = Cl, Br amine adducts have been synthesized and their infrared study carried out. Discrete structures have been suggested on the basis of elemental analysis and infrared data, the coordination number of antimony varying from five to nine, while the environment around Hg is tetrahedral.

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

Directory of Open Access Journals (Sweden)

Wouter A. Herrebout

2013-06-01

Full Text Available 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 (CF3I2.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.

Study of ammonia dynamics in mixed crystals K1-x(NH4)xHal (Hal = Cl, Br, I) by the inelastic neutron scattering

International Nuclear Information System (INIS)

Natkanets, I.; Smirnov, L.S.; Solov'ev, A.I.; )

1997-01-01

The investigation of the dynamics of ammonium ion in the disordered α-phase of mixed crystals K 1-x (NH 4 ) x Hal (Hal = Cl, Br, I) is carried out by the inelastic incoherent neutron scattering (IINS) method. IINS spectra are measured in the 2-200 meV energy range and the 10-300 K temperature range by the time-of-flight method. The generalized densities of phonon states are defined in the single-phonon approximation. It is found out that the libration mode of ammonium ion has the weak concentration dependence. Resonant modes are observed at low temperature for all concentration range of the existence of the disordered α-phase. The broadening of resonant modes at the expensive of the jump rotation diffusion of ammonium ions takes place at temperature above 10 K [ru

Thermodynamic Study of Solid-Liquid Equilibrium in NaCl-NaBr-H2O System at 288.15 K

Science.gov (United States)

Li, Dan; Meng, Ling-zong; Deng, Tian-long; Guo, Ya-fei; Fu, Qing-Tao

2018-06-01

The solubility data, composition of the solid solution and refractive indices of the NaCl-NaBr-H2O system at 288.15 K were studied with the isothermal equilibrium dissolution method. The solubility diagram and refractive index diagram of this system were plotted at 288.15 K. The solubility diagram consists of two crystallization zones for solid solution Na(Cl,Br) · 2H2O and Na(Cl,Br), one invariant points cosaturated with two solid solution and two univariant solubility isothermal curves. On the basis of Pitzer and Harvie-Weare (HW) chemical models, the composition equations and solubility equilibrium constant equations of the solid solutions at 288.15 K were acquired using the solubility data, the composition of solid solutions, and binary Pitzer parameters. The solubilities calculated using the new method combining the equations are in good agreement with the experimental data.

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.

Science.gov (United States)

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. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Crystallographic Investigations into Properties of Acentric Hybrid Perovskite Single Crystals NH(CH3)3SnX3(X = Cl, Br)

KAUST Repository

Dang, Yangyang

2016-10-11

The hybrid perovskites with special optoelectronic properties have attracted more attention to the scientific and industrial applications. However, because of the toxicity and instability of lead complexes, there is interest in finding a nontoxic substitute for the lead in the halides perovskites and solving the ambiguous crystal structures and phase transition of NH(CH3)3SnX3 (X = Cl, Br). Here, we report the bulk crystal growths and different crystal morphologies of orthorhombic hybrid perovskites NH(CH3)3SnX3 (X = Cl, Br) in an ambient atmosphere by bottom-seeded solution growth (BSSG) method. More importantly, detailed structural determination and refinements, phase transition, band gap, band structure calculations, nonlinear optical (NLO) properties, XPS, thermal properties, and stability of NH(CH3)3SnX3 (X = Cl, Br) single crystals are demonstrated. NH(CH3)3SnCl3 single crystal undergoes reversible structural transformation from orthorhombic space group Cmc21 (no. 36) to monoclinic space group Cc (no. 9) and NH(CH3)3SnBr3 belongs to the orthorhombic space group Pna21 (no. 33) by DSC, single-crystal X-ray diffraction and temperature-dependent SHG measurements, which clarify the former results. These results should pave the way for further studies of these materials in optoelectronics.

Magic Angle Spinning 207 Pb and low temperature deuterium NMR as a tool for studying local order and dynamics in CH 3 NH 3 PbX 3 (X=Cl, Br, I) hybrid perovskites

OpenAIRE

Roiland , Claire; trippé-Allard , gaelle; Jemli , K; Alonso , C; ameline , jean-claude; Gautier , Regis; Le Pollès , Laurent; Deleporte , Emmanuelle; Even , Jacky; Katan , Claudine

2016-01-01

National audience; Presenting high solar energy conversion efficiencies (>21%), hybrid perovskites APbX 3 (A is a small organic cation, X=Cl, Br, I) have recently become one of the most promising material in the field of photovoltaic devices. Meanwhile, fundamental understanding of what makes these preovskites so smart for photovoltaics remains limited. More then three decades ago, Wasylishen et al. had already revealed the interest of deuterium NMR to investigate the temperature behaviour an...

Insights into the catalytic activity of [Pd(NHC)(cin)Cl] (NHC = IPr, IPrCl, IPrBr) complexes in the Suzuki-Miyaura reaction

KAUST Repository

Nolan, Steven Patrick

2017-09-06

The influence of C4,5-halogenation on palladium N-heterocyclic carbene complexes and their activity in the Suzuki-Miyaura reaction have been investigated. Two [Pd(NHC)(cin)Cl] complexes bearing IPrCl and IPrBr ligands were synthesized. After determining electronic and steric properties of these ligands, their properties were compared to those of [Pd(IPr)(cin)Cl]. The three palladium complexes were studied using DFT calculations to delineate their behaviour in the activation step leading to the putative 12-electron active catalyst. Experimentally, their catalytic activity in the Suzuki-Miyaura reaction involving a wide range of coupling partners (30 entries) at low catalyst loading was studied.

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

Science.gov (United States)

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

2016-09-06

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.

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

Science.gov (United States)

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.

A dansyl group modified SBA-15 INHIBIT logic gate with [Hg2+ and Cl-] or [Hg2+ and Br-] as inputs

Science.gov (United States)

Wang, Xiaoyu; Yang, Honglei

2013-07-01

We developed a SBA-15-based INHIBIT logic gate (DA-SBA-15) which was prepared by covalent immobilization of a dansylamide derivative into the channels of the mesoporous silica material (SBA-15) via (3-aminopropyl)triethoxysilane (APTES) groups. A series of characteristic results proved that the fluorescent ligand was successfully grafted into the mesopores of SBA-15. The fluorescent characterization revealed excellent selectivity of DA-SBA-15 to the Hg2+ ion. Moreover, DA-SBA-15 can be considered as a selective fluorescent probe for Cl- and Br-. The fluorescent changes of DA-SBA-15 upon the addition of ions (Hg2+, Cl- and Br-) were utilized as an INH logic gate at the molecular level, using [Hg2+ and Cl-] or [Hg2+ and Br-] as chemical inputs and the fluorescence intensity signal as output.

Phase diagram of pressure-induced superconductor β-(BDA-TTP)2MX4 (M=Fe, Ga and X=Cl, Br) with localized magnetic moments

Science.gov (United States)

Choi, E. S.; Graf, D.; Tokumoto, T.; Brooks, J. S.; Yamada, Jun-Ichi

2007-03-01

We have investigated transport and magnetization properties of β-(BDA-TTP)2MX4 (M=Fe, Ga and X=Cl, Br) as a function of pressure, temperature and magnetic field. The title material undergoes metal-insulator transitions above 100 K at ambient pressure. The insulating phase is suppressed with pressure and superconductivity eventually appears above Pc= 4.5 kbar (X=Cl) and 13 kbar (X=Br). The general temperature-pressure (TP) phase diagram is similar each other, while higher pressure is required for X=Br compounds to suppress the insulating state and induce the superconductivity. Pressure dependent DC magnetization studies on β-(BDA-TTP)2FeCl4 compound revealed that the AFM ordering persist well above Pc. In spite of similarity of phase diagram between M=Fe and M=Ga compounds, magnetoresistance results show distinct behaviors, which indicates the magnetic interaction with the conduction electrons are still effective. The comparison between X=Cl and X=Br compounds suggests the anion-size effect rather than the existence of localized magnetic moments plays more important role in determining the ground state.

Lattice potential energies and thermochemical properties of triethylammonium halides (Et3NHX) (X = Cl, Br, and I)

International Nuclear Information System (INIS)

Liu Yupu; Tan Zhicheng; Di Youying; Xing Yiting; Zhang Peng

2012-01-01

Highlights: ► The crystal structures of (Et 3 NHX) (X = Cl, Br, and I) were determined. ► Lattice potential energies and ionic radius of the common cation were obtained. ► Molar enthalpies of dissolution at infinite dilution were derived. ► Relative partial molar enthalpies were derived. ► Hydration enthalpy of Et 3 NH + was calculated. - Abstract: A series of triethylammonium halides (Et 3 NHCl, Et 3 NHBr, and Et 3 NHI) was synthesized. The crystal structures of the three compounds were characterized by X-ray crystallography. The lattice potential energies and ionic radius of the common cation of the three compounds were obtained from crystallographic data. Molar enthalpies of dissolution of the compounds at various values of molality were measured in the double-distilled water at T = 298.150 K by means of an isoperibol solution-reaction calorimeter. According to Pitzer’s theory, the values of molar enthalpies of dissolution at infinite dilution and Pitzer’s parameters of the compounds were obtained. The values of apparent relative molar enthalpies, relative partial molar enthalpies of the solvent and the compounds at different molalities were derived from the experimental values of molar enthalpies of dissolution of the compounds. Finally, hydration enthalpy of the common cation Et 3 NH + was calculated to be ΔH + = −(150.386 ± 4.071) kJ · mol −1 by designing a thermochemical cycle.

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

Science.gov (United States)

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 = 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.

Pyrolysis studies of PP/PE/PS/PVC/HIPS-Br plastics mixed with PET and dehalogenation (Br, Cl) of the liquid products

Energy Technology Data Exchange (ETDEWEB)

Bhaskar, Thallada; Kaneko, Jun; Muto, Akinori; Sakata, Yusaku [Department of Applied Chemistry, Faculty of Engineering, Okayama University, 3-1-1 Tsushima Naka, 700-8530 Okayama (Japan); Jakab, Emma [Research Laboratory of Materials and Environmental Chemistry, Chemical Research Center, Hungarian Academy of Sciences, P.O. Box 17, H-1525 Budapest (Hungary); Matsui, Toshiki [Toda Kogyo Co. Ltd., Hiroshima 739-0652 (Japan); Uddin, Md. Azhar [Process Safety and Environment Protection Group, School of Engineering, The University of Newcastle, Callaghan, NSW 2308 (Australia)

2004-08-01

Pyrolysis of polypropylene (PP)/polyethylene (PE)/polystyrene (PS)/poly(vinyl chloride) (PVC)/high impact polystyrene with brominated flame retardant (HIPS-Br) plastics mixed with poly(ethylene terephthalate) (PET) was performed at 430C under atmospheric pressure using a semi-batch operation. The presence of PET in the pyrolysis mixture of PP/PE/PS/PVC/HIPS-Br affected significantly the formation of decomposition products and the decomposition behavior of the plastic mixture. We observed the following effects of PET on the pyrolysis of PP/PE/PS/PVC/HIPS-Br mixed plastics: (1) the yield of liquid product decreased and the formation of gaseous products increased; (2) a waxy residue was formed in addition to the solid carbon residue; (3) the formation of SbBr{sub 3} was not detected in liquid products; (4) the yield of chlorinated branched alkanes increased as well as vinyl bromide and ethyl bromide were formed. The use of calcium carbonate carbon composite (Ca-C) completely removed the chlorine and bromine content from the liquid products during PP/PE/PS/PVC/HIPS-Br pyrolysis, however in the presence of PET, the catalytic experiment (Ca-C, 8g) yielded liquid products containing 310ppm of Br and 20ppm of Cl. In addition, the Ca-C increased the yield of liquid products about 3-6wt.%, as well as enhanced the gaseous product evolution and decreased the yield of residue. The halogen free liquid hydrocarbons can be used as a feedstock in a refinery or as a fuel.

Theoretical descriptions of novel triplet germylenes M1-Ge-M2-M3 (M1 = H, Li, Na, K; M2 = Be, Mg, Ca; M3 = H, F, Cl, Br).

Science.gov (United States)

Kassaee, Mohamad Zaman; Ashenagar, Samaneh

2018-02-06

In a quest to identify new ground-state triplet germylenes, the stabilities (singlet-triplet energy differences, ΔE S-T ) of 96 singlet (s) and triplet (t) M 1 -Ge-M 2 -M 3 species were compared and contrasted at the B3LYP/6-311++G**, QCISD(T)/6-311++G**, and CCSD(T)/6-311++G** levels of theory (M 1  = H, Li, Na, K; M 2  = Be, Mg, Ca; M 3  = H, F, Cl, Br). Interestingly, F-substituent triplet germylenes (M 3  = F) appear to be more stable and linear than the corresponding Cl- or Br-substituent triplet germylenes (M 3  = Cl or Br). Triplets with M 1  = K (i.e., the K-Ge-M 2 -M 3 series) seem to be more stable than the corresponding triplets with M 1  = H, Li, or Na. This can be attributed to the higher electropositivity of potassium. Triplet species with M 3  = Cl behave similarly to those with M 3  = Br. Conversely, triplets with M 3  = H show similar stabilities and linearities to those with M 3  = F. Singlet species of formulae K-Ge-Ca-Cl and K-Ge-Ca-Br form unexpected cyclic structures. Finally, the triplet germylenes M 1 -Ge-M 2 -M 3 become more stable as the electropositivities of the α-substituents (M 1 and M 2 ) and the electronegativity of the β-substituent (M 3 ) increase.

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

Energy Technology Data Exchange (ETDEWEB)

Li, Junxia; Wang, Yanxin, E-mail: yx.wang@cug.edu.cn; 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{sup 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. - Highlights: • Natural high arsenic, fluoride and iodine groundwater co-occur with saline water. �

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

International Nuclear Information System (INIS)

Li, Junxia; Wang, Yanxin; Xie, Xianjun

2016-01-01

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"3"7Cl 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. - Highlights: • Natural high arsenic, fluoride and iodine groundwater co-occur with saline water. • Groundwater

Understanding the insight into the mechanisms and dynamics of the Cl-initiated oxidation of (CH3)3CC(O)X and the subsequent reactions in the presence of NO and O2 (X = F, Cl, and Br).

Science.gov (United States)

Bai, Feng-Yang; Lv, Shuang; Ma, Yuan; Liu, Chun-Yu; He, Chun-Fang; Pan, Xiu-Mei

2017-03-01

In this work, the density functional and high-level ab initio theories are adopted to investigate the mechanisms and kinetics of reaction of (CH 3 ) 3 CC(O)X (X = F, Cl, and Br) with atomic chlorine. Rate coefficients for the reactions of chlorine atom with (CH 3 ) 3 CC(O)F (k 1 ), (CH 3 ) 3 CC(O)Cl (k 2 ), and (CH 3 ) 3 CC(O)Br (k 3 ) are calculated using canonical variational transition state theory coupled with small curvature tunneling method over a wide range of temperatures from 250 to 1000 K. The dynamic calculations are performed by the variational transition state theory with the interpolated single-point energies method at the CCSD(T)/aug-cc-pVDZ//B3LYP/6-311++G(d,p) level of theory. Computed rate constant is in good line with the available experimental value. The rate constants for the title reactions are in this order: k 1 Br) are estimated, and it shows that (CH 3 ) 3 CC(O)F have larger GWP value than that of (CH 3 ) 3 CC(O)Cl and (CH 3 ) 3 CC(O)Br. Due to the presence of Cl and Br atoms, the environmental impact of (CH 3 ) 3 CC(O)Cl and (CH 3 ) 3 CC(O)Br may be given more concerns. Copyright © 2016 Elsevier Ltd. All rights reserved.

Formation of T-shaped versus charge-transfer molecular adducts in the reactions between bis(thiocarbonyl) donors and Br2 and I2.

Science.gov (United States)

Mancini, Annalisa; Aragoni, M Carla; Bricklebank, Neil; Castellano, Carlo; Demartin, Francesco; Isaia, Francesco; Lippolis, Vito; Pintus, Anna; Arca, Massimiliano

2013-03-01

The reactions of 4,5,6,7-tetrathiocino-[1,2-b:3,4-b']-1,3,8,10-tetrasubstituted-diimidazolyl-2,9-dithiones (R(2),R'(2)-todit; 1: R=R'=Et; 2: R=R'=Ph; 3: R=Et, R'=Ph) with Br(2) exclusively afforded 1:1 and 1:2 "T-shaped" adducts, as established by FT-Raman spectroscopy and single-crystal X-ray diffraction in the case of complex 1·2Br(2). On the other hand, the reactions of compounds 1-3 with molecular I(2) provided charge-transfer (CT) "spoke" adducts, among which the solvated species 3·2I(2)·(1-x)I(2)·xCH(2)Cl(2) (x=0.94) and (3)(2)·7I(2)·xCH(2)Cl(2), (x=0.66) were structurally characterized. The nature of all of the reaction products was elucidated based on elemental analysis and FT-Raman spectroscopy and supported by theoretical calculations at the DFT level. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Spin-Orbit Effect on the Molecular Properties of TeXn (X = F, Cl, Br, and I; n = 1, 2, and 4): A Density Functional Theory and Ab Initio Study.

Science.gov (United States)

Moon, Jiwon; Kim, Joonghan

2016-09-29

Density functional theory (DFT) and ab initio calculations, including spin-orbit coupling (SOC), were performed to investigate the spin-orbit (SO) effect on the molecular properties of tellurium halides, TeXn (X = F, Cl, Br, and I; n = 1, 2, and 4). SOC elongates the Te-X bond and slightly reduces the vibrational frequencies. Consideration of SOC leads to better agreement with experimental values. Møller-Plesset second-order perturbation theory (MP2) seriously underestimates the Te-X bond lengths. In contrast, B3LYP significantly overestimates them. SO-PBE0 and multireference configuration interactions with the Davidson correction (MRCI+Q), which include SOC via a state-interaction approach, give the Te-I bond length of TeI2 that matches the experimental value. On the basis of the calculated thermochemical energy and optimized molecular structure, TeI4 is unlikely to be stable. The use of PBE0 including SOC is strongly recommended for predicting the molecular properties of Te-containing compounds.

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

Science.gov (United States)

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.

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

Science.gov (United States)

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].

Thermodynamic investigations of the quasi-2d triangular Heisenberg antiferromagnet Cs{sub 2}CuCl{sub 2}Br{sub 2}

Energy Technology Data Exchange (ETDEWEB)

Tutsch, Ulrich; Postulka, Lars; Wolf, Bernd; Lang, Michael; Well, Natalija van; Ritter, Franz; Krellner, Cornelius; Assmus, Wolf [Physikalisches Institut, Goethe-University Frankfurt (Germany)

2015-07-01

The system Cs{sub 2}CuCl{sub 4-x}Br{sub x} (0 ≤ x ≤ 4) is a quasi-two-dimensional Heisenberg antiferromagnet with a triangular in-plane arrangement of the spin-spin couplings. The ratio J{sup '}/J of the corresponding coupling constants determines the degree of frustration in the system and has been found to be 0.34 (x = 0) and 0.74 (x = 4) for the border compounds. One may ask whether for some intermediate Br concentration an even higher degree of frustration can be reached. Indeed, some indications have been reported by Ono et al. Here, we present specific heat C and susceptibility χ measurements below 1 K in magnetic fields B up to 13.5 T for the intermediate compound Cs{sub 2}CuCl{sub 2}Br{sub 2}, which, due to site-selective substitution, shows a well-ordered halide sublattice. Indications for an antiferromagnetic transition are observed around 90 mK for B = 0. A small field of B = 0.14 T is sufficient to fully suppress this anomaly. Taking into account the high saturation field of about 20 T, extrapolated from χ(T = const, B) scans at low temperatures, this small ordered region in the B-T plane clearly indicates a high degree of frustration in Cs{sub 2}CuCl{sub 2}Br{sub 2}.

Greatly enhanced flux pinning properties of fluorine-free metal-organic decomposition YBCO films by co-addition of halogens (Cl, Br) and metals (Zr, Sn, Hf)

Science.gov (United States)

Motoki, Takanori; Ikeda, Shuhei; Nakamura, Shin-ichi; Honda, Genki; Nagaishi, Tatsuoki; Doi, Toshiya; Shimoyama, Jun-ichi

2018-04-01

Additive-free YBCO films, as well as those with halogen (X) added, metal (M) added and (X, M) co-added, have been prepared by the fluorine-free metal-organic decomposition method on SrTiO3(100) single crystalline substrates, where X = Cl, Br and M = Zr, Sn, Hf. It was revealed that the addition of both Cl and Br to the starting solution resulted in the generation of oxyhalide, Ba2Cu3O4 X 2, in the YBCO films, and that the oxyhalide was found to promote the bi-axial orientation of the YBCO crystals. By adding a decent amount of Cl or Br, highly textured YBCO films with high J c were reproducibly obtained, even when an impurity metal, M, was co-added, while the addition of M without X did not greatly improve J c owing to the poor bi-axial orientation of the YBCO crystals. Our results suggest that the addition of Br more effectively enhances J c than the addition of Cl. The pinning force density at 40 K in 4.8 T reached ˜55 GN m-3 with the co-addition of (Br, M). This value is much larger than that of the pure YBCO film, reaching ˜17 GN m-3.

Neutron diffraction study of structural changes in ammonium halides ND4Br and ND4Cl under high pressure

International Nuclear Information System (INIS)

Balagurov, A.M.; Kozlenko, D.P.; Savenko, B.N.; Glazkov, V.P.; Somenkov, V.A.

1997-01-01

Structural changes in ammonium halides ND 4 Br and ND 4 Cl at pressures up to 45 kbar and up to 35 kbar, respectively, have been studied with the DN-12 diffractometer at the IBR-2 pulsed reactor. For both systems, the equation of state and the position parameter of deuterium atoms as functions of pressure were obtained. The obtained equations of state are nearly the same as the ones for the nondeuterated systems NH 4 Br and NH 4 Cl obtained by the piston displacement technique. It was found that the order - disorder phase transition from the phase in which the ammonium tetrahedra are randomly oriented (CsCl-type cubic structure, space group Pm3m) into the phase in which the ammonium tetrahedra are oriented in parallel (CsCl-type cubic structure, space group P4 bar 3m), occurs at equal critical value of the position parameter u=0.153 ± 0.002 in both systems. It appears to be valid for all of the ammonium halides, and, possibly, for other similar compounds. (author)

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.

Science.gov (United States)

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. Copyright © 2015. Published by Elsevier B.V.

Scattering of electrons by alkali-halide molecules: LiBr and CsCl

International Nuclear Information System (INIS)

Vukovic, L.; Zuo, M.; Shen, G.F.; Stumpf, B.; Bederson, B.

1989-01-01

We have investigated small-angle electron scattering by highly polar molecules. Recoil experiments are performed at 5 and 20 eV for electrons scattered by LiBr and CsCl, within the shadow of the unscattered molecular beam. Low-angular-range scattering described by the Born approximation for rotating dipoles, combined with different theories for intermediate- and high-angle scattering, are compared with our results. Evaluated total scattering cross sections as well as momentum-transfer and viscosity cross sections are given. A general two-dimensional analysis of the recoil experiment is presented

Cd4As2Br3

Directory of Open Access Journals (Sweden)

Mohammed Kars

2014-03-01

Full Text Available Single crystals of Cd4As2Br3 (tetracadmium biarsenide tribromide were grown by a chemical transport reaction. The structure is isotypic with the members of the cadmium and mercury pnictidohalides family with general formula M4A2X3 (M = Cd, Hg; A = P, As, Sb; X = Cl, Br, I and contains two independent As atoms on special positions with site symmetry -3 and two independent Cd atoms, of which one is on a special position with site symmetry -3. The Cd4As2Br3 structure consists of AsCd4 tetrahedra sharing vertices with isolated As2Cd6 octahedra that contain As–As dumbbells in the centre of the octahedron. The Br atoms are located in the voids of this three-dimensional arrangement and bridge the different polyhedra through Cd...Br contacts.

Magnetism of CuCl{sub 2}·2D{sub 2}O and CuCl{sub 2}·2H{sub 2}O, and of CuBr{sub 2}·6H{sub 2}O

Energy Technology Data Exchange (ETDEWEB)

DeFotis, G.C., E-mail: gxdefo@wm.edu [Department of Chemistry, College of William and Mary, Williamsburg, VA 23187 (United States); Hampton, A.S.; Van Dongen, M.J.; Komatsu, C.H.; Benday, N.S.; Davis, C.M. [Department of Chemistry, College of William and Mary, Williamsburg, VA 23187 (United States); Hays, K.; Wagner, M.J. [Department of Chemistry, George Washington University, Washington, D.C. 20052 (United States)

2017-07-15

Highlights: • CuCl{sub 2}·2D{sub 2}O is examined magnetically and compared with CuCl{sub 2}·2H{sub 2}O. • Slightly lower magnetic characteristic temperatures occur for deuterated dihydrate. • The new compound CuBr{sub 2}·6H{sub 2}O is examined magnetically. • Unexpected relationships appears between magnetic behaviors of CuBr{sub 2}·6H{sub 2}O and CuBr{sub 2}. • Two alternative monoclinic unit cells can account for diffraction data on CuBr{sub 2}·6H{sub 2}O. - Abstract: The magnetic properties of little examined CuCl{sub 2}·2D{sub 2}O are studied and compared with those of CuCl{sub 2}·2H{sub 2}O. New CuBr{sub 2}·6H{sub 2}O is also examined. Susceptibility maxima appear for chlorides at 5.35 and 5.50 K, in the above order, with estimated antiferromagnetic ordering at 4.15 and 4.25 K. Curie-Weiss fits yield g of 2.210 and 2.205, and Weiss θ of −6.0 and −4.7 K, respectively, in χ{sub M} = C/(T − θ). One-dimensional Heisenberg model fits to susceptibilities, including interchain exchange in a mean-field approximation, are performed. Interchain exchange is significant but much weaker than intrachain. The bromide hexahydrate strongly differs magnetically from any chloride hydrate, but exhibits notable similarities and differences compared to previously studied CuBr{sub 2}. A broad susceptibility maximum occurs near 218 K, only 4% lower than for CuBr{sub 2}, but with almost twice the magnitude. Powder X-ray diffraction data for CuBr{sub 2}·6H{sub 2}O may be best accounted for by a monoclinic unit cell that is metrically orthorhombic. The volume per formula unit is consistent with trends in metal ionic radii. However, an alternative monoclinic cell with 5% smaller volume more readily rationalizes the magnetism.

Ruthenium Dioxide Catalysts for the Selective Oxidation of Benzylamine to Benzonitrile: Investigating the Effect of Ruthenium Loading on Physical and Catalytic Properties

DEFF Research Database (Denmark)

Nordvang, Emily Catherine; Schill, Leonhard; Riisager, Anders

2017-01-01

The oxidative dehydrogenation of benzylamine to benzonitrile was studied in batch and continuous flow processes using ruthenium dioxide catalysts with varying ruthenium loadings. Increased conversions were observed in the continuous flow process compared with the batch process (up to 100% in the ......The oxidative dehydrogenation of benzylamine to benzonitrile was studied in batch and continuous flow processes using ruthenium dioxide catalysts with varying ruthenium loadings. Increased conversions were observed in the continuous flow process compared with the batch process (up to 100......% in the flow process compared with up to 92% in the batch process), with increased selectivity to benzonitrile (82 and 65%, respectively) and benzonitrile yields (84 and 58%, respectively). The major by-product was N-benzylidenebenzylamine. The ruthenium loading in the catalyst was successfully optimised...... and the most active catalyst had a ruthenium loading of 2.5-3.5 wt%....

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

Science.gov (United States)

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 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.

Hybridization of Single Nanocrystals of Cs4PbBr6 and CsPbBr3.

Science.gov (United States)

Weerd, Chris de; Lin, Junhao; Gomez, Leyre; Fujiwara, Yasufumi; Suenaga, Kazutomo; Gregorkiewicz, Tom

2017-09-07

Nanocrystals of all-inorganic cesium lead halide perovskites (CsPbX 3 , X = Cl, Br, I) feature high absorption and efficient narrow-band emission which renders them promising for future generation of photovoltaic and optoelectronic devices. Colloidal ensembles of these nanocrystals can be conveniently prepared by chemical synthesis. However, in the case of CsPbBr 3 , its synthesis can also yield nanocrystals of Cs 4 PbBr 6 and the properties of the two are easily confused. Here, we investigate in detail the optical characteristics of simultaneously synthesized green-emitting CsPbBr 3 and insulating Cs 4 PbBr 6 nanocrystals. We demonstrate that, in this case, the two materials inevitably hybridize, forming nanoparticles with a spherical shape. The actual amount of these Cs 4 PbBr 6 nanocrystals and nanohybrids increases for synthesis at lower temperatures, i.e., the condition typically used for the development of perovskite CsPbBr 3 nanocrystals with smaller sizes. We use state-of-the-art electron energy loss spectroscopy to characterize nanoparticles at the single object level. This method allows distinguishing between optical characteristics of a pure Cs 4 PbBr 6 and CsPbBr 3 nanocrystal and their nanohybrid. In this way, we resolve some of the recent misconceptions concerning possible visible absorption and emission of Cs 4 PbBr 6 . Our method provides detailed structural characterization, and combined with modeling, we conclusively identify the nanospheres as CsPbBr 3 /Cs 4 PbBr 6 hybrids. We show that the two phases are independent of each other's presence and merge symbiotically. Herein, the optical characteristics of the parent materials are preserved, allowing for an increased absorption in the UV due to Cs 4 PbBr 6 , accompanied by the distinctive efficient green emission resulting from CsPbBr 3 .

Neutron scattering study of MnX2 (X = Br, I)

International Nuclear Information System (INIS)

Sato, Taku; Kadowaki, Hiroaki.

1993-01-01

Successive magnetic phase transitions in MnX 2 (X = Br, I), found by bulk measurements, are studied by neutron scattering experiments. There occur two (T N1 = 2.32K, T N2 = 2.17K) and three (T N1 = 3.95K, T N2 = 3.8K, T N3 = 3.45K) phase transitions in MnBr 2 and MnI 2 , respectively. We have found that magnetic structures of the both compounds in the intermediate temperature phases (MnBr 2 : T N1 > T > T N2 ; MnI 2 : T N1 > T > T N3 ) are transverse sinusoidally-modulated structures with incommensurate wave-vectors which vary as a function of temperature. As the temperature is lowered into the lowest temperature phases, the magnetic structures change via first order transition into ↑↑↓↓ and a helical structure for MnBr 2 and MnI 2 , respectively, which were determined by previous experiments. The successive phase transitions in MnBr 2 are accounted for quantitatively using a mean field approximation of a Hamiltonian consisting of exchange interactions up to third inter- and third intra-layer neighbor sites and the dipolar interaction. (author)

UV-VIS absorption spectra of molten AgCl and AgBr and of their mixtures with group I and II halide salts

Energy Technology Data Exchange (ETDEWEB)

Greening, Giorgio G.W. [Technische Universitaet Darmstadt (Germany). Eduard-Zintl-Institut fuer Anorganische und Physikalische Chemie

2015-07-01

The UV-VIS absorption spectra of (Ag{sub 1-X}[Li-Cs, Ba]{sub X})Cl and of (Ag{sub 1-X}[Na, K, Cs]{sub 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.

In-Plane Angular Effect of Magnetoresistance of Quasi-One-Dimensional Organic Metals, (DMET) 2AuBr 2 and (TMTSF) 2ClO 4

Science.gov (United States)

Yoshino, Harukazu; Saito, Kazuya; Nishikawa, Hiroyuki; Kikuchi, Koichi; Kobayashi, Keiji; Ikemoto, Isao

1997-08-01

Comparative study is presented for the in-plane angular effect of magnetoresistance of quasi-one-dimensional organic conductors, (DMET)2AuBr2 and (TMTSF)2ClO4. The magnetoresistance for the magnetic and electrical fields parallel and perpendicular to the most conducting plane, respectively, was measured at 4.2 K and up to 7.0 T. (DMET)2AuBr2 shows an anomalous hump in the field-orientation dependence of the magnetoresistance for the magnetic field nearly parallel to the most conducting axis and this is very similar to what previously reported for (DMET)2I3. Weak anomaly was detected for the magnetoresistance of (TMTSF)2ClO4 in the Relaxed state, while no anomaly was observed in the SDW phase in the Quenched state. By comparing the numerical angular derivatives of the magnetoresistance, it is shown that the anomaly in the in-plane angular effect continuously develops from zero magnetic field and is closely related to the quasi-one-dimensional Fermi surface. A simple method is proposed to estimate the anisotropy of the transfer integral from the width of the hump anomaly.

Biotransformation of benzonitrile herbicides via the nitrile hydratase-amidase pathway in rhodococci.

Science.gov (United States)

Veselá, Alicja B; Pelantová, Helena; Sulc, Miroslav; Macková, Martina; Lovecká, Petra; Thimová, Markéta; Pasquarelli, Fabrizia; Pičmanová, Martina; Pátek, Miroslav; Bhalla, Tek Chand; Martínková, Ludmila

2012-12-01

The aim of this work was to determine the ability of rhodococci to transform 3,5-dichloro-4-hydroxybenzonitrile (chloroxynil), 3,5-dibromo-4-hydroxybenzonitrile (bromoxynil), 3,5-diiodo-4-hydroxybenzonitrile (ioxynil) and 2,6-dichlorobenzonitrile (dichlobenil); to identify the products and determine their acute toxicities. Rhodococcus erythropolis A4 and Rhodococcus rhodochrous PA-34 converted benzonitrile herbicides into amides, but only the former strain was able to hydrolyze 2,6-dichlorobenzamide into 2,6-dichlorobenzoic acid, and produced also more of the carboxylic acids from the other herbicides compared to strain PA-34. Transformation of nitriles into amides decreased acute toxicities for chloroxynil and dichlobenil, but increased them for bromoxynil and ioxynil. The amides inhibited root growth in Lactuca sativa less than the nitriles but more than the acids. The conversion of the nitrile group may be the first step in the mineralization of benzonitrile herbicides but cannot be itself considered to be a detoxification.

Stable Chloro- and Bromoxenate Cage Anions; [X3(XeO3)3]3- and [X4(XeO3)4]4- (X = Cl or Br).

Science.gov (United States)

Goettel, James T; Haensch, Veit G; Schrobilgen, Gary J

2017-06-28

The number of isolable compounds which contain different noble-gas-element bonds is limited for xenon and even more so for krypton. Examples of Xe-Cl bonds are rare, and prior to this work, no Xe-Br bonded compound had been isolated in macroscopic quantities. The syntheses, isolation, and characterization of the first compounds to contain Xe-Br bonds and their chlorine analogues are described in the present work. The reactions of XeO 3 with [N(CH 3 ) 4 ]Br and [N(C 2 H 5 ) 4 ]Br have provided two bromoxenate salts, [N(C 2 H 5 ) 4 ] 3 [Br 3 (XeO 3 ) 3 ] and [N(CH 3 ) 4 ] 4 [Br 4 (XeO 3 ) 4 ], in which the cage anions have Xe-Br bond lengths that range from 3.0838(3) to 3.3181(8) Å. The isostructural chloroxenate anions (Xe-Cl bond lengths, 2.9316(2) to 3.101(4) Å) were synthesized by analogy with their bromine analogues. The bromo- and chloroxenate salts are stable in the atmosphere at room temperature and were characterized in the solid state by Raman spectroscopy and low-temperature single-crystal X-ray diffraction, and in the gas phase by quantum-chemical calculations. They are the only known examples of cage anions that contain a noble-gas element. The Xe-Br and Xe-Cl bonds are very weakly covalent and can be viewed as σ-hole interactions, similar to those encountered in halogen bonding. However, the halogen atoms in these cases are valence electron lone pair donors, and the σ* Xe-O orbitals are lone pair acceptors.

A hybrid material based on [Mo6Br14]2- inorganic cluster units and [BEDO-TTF]+ organic monocationic radicals: Synthesis, structure and properties of (BEDO-TTF)2Mo6Br14(PhCN)4

International Nuclear Information System (INIS)

Kirakci, Kaplan; Hosoda, Hidemasa; Cordier, Stephane; Perrin, Christiane; Saito, Gunzi

2006-01-01

The first charge transfer salt based on non- dimerized [BEDO-TTF] + monocationic radical (BEDO-TTF=bis(ethylenedioxy)tetrathiafulvalene) associated with [Mo 6 Br 14 ] 2- cluster anions has been synthesized by conventional electro-oxidation and characterized by single crystal X-ray diffraction, UV-VIS-NIR absorption and magnetic susceptibility measurements. (BEDO-TTF) 2 Mo 6 Br 14 (PhCN) 4 crystallizes in the monoclinic system, space group P2 1 /n, a=10.414(4)A, b=21.711(7)A, c=15.958(5)A, β=93.65(3) o , V=3601(2)A 3 , Z=2, R 1 =0.0578, wR 2 =0.0731. The structure of this hybrid compound is built up from a [BEDO-TTF] + and PhCN (benzonitrile) organic framework in which are hosted the [Mo 6 Br 14 ] 2- inorganic cluster units. It results in non- dimerized [BEDO-TTF] + cations that exhibit a paramagnetic behavior characteristic of one unpaired electron

Microhardness studies on as-grown faces of NaClO3 and NaBrO3 ...

Indian Academy of Sciences (India)

Unknown

studies are made on as-grown faces of these crystals at various loads. Typical cracks are ... crystals is around 1⋅6 suggesting that these are moderately harder samples. ... the values of elastic constants (C44) and are found to be close to the experimental results. ..... the structure of NaClO3 and NaBrO3 is not as simple as.

Hydrolysis of benzonitrile herbicides by soil actinobacteria and metabolite toxicity

Czech Academy of Sciences Publication Activity Database

Veselá, Alicja Barbara; Franc, M.; Pelantová, Helena; Kubáč, David; Vejvoda, Vojtěch; Šulc, Miroslav; Bhalla, T. C.; Macková, M.; Lovecká, P.; Janů, P.; Demnerová, K.; Martínková, Ludmila

2011-01-01

Roč. 22, č. 6 (2011), s. 761-770 ISSN 0923-9820 R&D Projects: GA MPO FT-TA5/043; GA MŠk OC09046; GA MŠk(CZ) LC06010; GA AV ČR IAA500200708; GA ČR GD305/09/H008 Institutional research plan: CEZ:AV0Z50200510 Keywords : nitrilase * benzonitrile herbicides * chloroxynil Subject RIV: CE - Biochemistry Impact factor: 2.017, year: 2011

Hydrolysis of benzonitrile herbicides by soil actinobacteria and metabolite toxicity

Czech Academy of Sciences Publication Activity Database

Veselá, Alicja Barbara; Franc, M.; Pelantová, Helena; Kubáč, David; Vejvoda, Vojtěch; Šulc, Miroslav; Bhalla, T. C.; Macková, M.; Lovecká, P.; Janů, P.; Demnerová, K.; Martínková, Ludmila

2010-01-01

Roč. 21, č. 5 (2010), s. 761-770 ISSN 0923-9820 R&D Projects: GA MPO FT-TA5/043; GA MŠk OC09046; GA MŠk(CZ) LC06010; GA AV ČR IAA500200708; GA ČR GD305/09/H008 Institutional research plan: CEZ:AV0Z50200510 Keywords : Benzonitrile herbicides * nitrilase * Chloroxynil Subject RIV: EE - Microbiology, Virology Impact factor: 2.012, year: 2010

Is the 'Bromine Explosion' generated from the reaction BrO HO2 alone?

Science.gov (United States)

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

A Study of Acid-Base Equilibria in Acetonitrile Systems of 2-Halo(Cl,Br,I-4-nitropicoline(3,5,6 N-oxides

Directory of Open Access Journals (Sweden)

Lech Chmurzynski

1999-03-01

Full Text Available An attempt has been made to determine potentiometrically (1 acid dissociation constants of cations obtained by protonation of nine trisubstituted pyridine N-oxides, namely 2-halo(Cl, Br and I-4-nitropicoline N-oxides with the methyl group at positions 3, 5, and 6, as well as (2 the cationic homoconjugation constants of these cationic acids with conjugated N-oxides in acetonitrile. On the basis of the substitution effect, variations of the acid dissociation constants of the trisubstituted pyridine N-oxide cations are discussed. The determined pKa values of the protonated 2-halo-4-nitropicoline N-oxides are compared with the previously determined equilibrium constants of the cationic acids conjugated with the mono- and disubstituted pyridine N-oxides in acetonitrile. Further, based on the pKa values of the protonated 2-halo-4-nitropicoline N-oxides in acetonitrile, supplemented with correlations between pKa’s of the protonated mono- and disubstituted pyridine N-oxides in acetonitrile and water, the pKa's of the acids conjugated with the trisubstituted N-oxides studied in aqueous solutions have been estimated. Moreover, it has been concluded that the cationic homoconjugation constants cannot be determined by potentiometric titration in acetonitrile solutions of the 2-halo-4-nitropicoline N-oxide systems.

Biotransformation of benzonitrile herbicides via the nitrile hydratase-amidase pathway in rhodococci

Czech Academy of Sciences Publication Activity Database

Veselá, Alicja Barbara; Pelantová, Helena; Šulc, Miroslav; Macková, M.; Lovecká, P.; Thimová, P.; Pasquarelli, F.; Pičmanová, Martina; Pátek, Miroslav; Bhalla, T. C.; Martínková, Ludmila

2012-01-01

Roč. 39, č. 12 (2012), s. 1811-1819 ISSN 1367-5435 R&D Projects: GA MŠk OC09046; GA ČR(CZ) GAP504/11/0394; GA ČR GD305/09/H008 Keywords : Nitrile hydratase * Amidase * Benzonitrile herbicides Subject RIV: EE - Microbiology, Virology Impact factor: 2.321, year: 2012

Kinetics and Products of the Reactions of Fluorine Atoms with ClNO and Br2 from 295 to 950 K.

Science.gov (United States)

Bedjanian, Yuri

2017-11-09

The kinetics and products of the reactions of F atoms with Br 2 and ClNO have been studied in a flow reactor coupled with an electron impact ionization mass spectrometer at nearly 2 Torr total pressure of helium and over a wide temperature range, T = 295-950 K. The rate constant of the reaction F + ClNO → products (1) was determined under pseudo-first order conditions, monitoring the kinetics of F atom consumption in excess of ClNO. The measured temperature independent rate constant, k 1 = (1.29 ± 0.13) × 10 -10 cm 3 molecule -1 s -1 (T = 299-950 K), was found to be in excellent agreement with the only previous low temperature study which allowed to recommend the value of k 1 in an extended temperature range, 228-950 K. FCl and Cl atoms were observed as the reactions products (corresponding to two reaction pathways: Cl-atom abstraction and replacement with fluorine atom, respectively) with the independent of temperature, in the range 295-948 K, yields of 0.68 ± 0.10 and 0.32 ± 0.05, respectively. Rate constant of the reaction F + Br 2 (2), k 2 = (1.28 ± 0.20) × 10 -10 cm 3 molecule -1 s -1 , determined using both absolute and relative rate methods, was found to be independent of temperature at T = 299-940 K.

First-principles study of electronic and optical properties of lead-free double perovskites Cs2NaBX6 (B = Sb, Bi; X = Cl, Br, I)

Science.gov (United States)

Zhao, Shuai; Yamamoto, Kumiko; Iikubo, Satoshi; Hayase, Shuzi; Ma, Tingli

2018-06-01

Organolead halide perovskite is regarded as the most promising light-harvesting material for next-generation solar cells; however, the intrinsic instability and toxicity of lead are still of great concern. Bismuth is ecofriendly and has electronic properties similar to those of lead, which has gradually attracted interest for optoelectronic applications. However, the valence state of bismuth is different from that of lead, eliminating the possibility of replacing lead by bismuth in organolead halide perovskites. To address this matter, one feasible strategy is to construct B-site double perovskites by the combination of Bi3+ and B+ in 1:1 ratio. In this work, lead-free halide double perovskites of the form Cs2NaBX6 (B = Sb, Bi; X = Cl, Br, I) were investigated by first-principles calculations. The electronic properties, optical absorption coefficients, and thermodynamic stability of these compounds were investigated to ascertain their potential application in solar energy conversion. The results provide theoretical support for the exploration of lead-free perovskite materials in potential optoelectronic applications.

Importance of halogen···halogen contacts for the structural and magnetic properties of CuX2(pyrazine-N,N′-dioxide)(H2O)2 (X = Cl and Br).

Science.gov (United States)

Schlueter, John A; Park, Hyunsoo; Halder, Gregory J; Armand, William R; Dunmars, Cortney; Chapman, Karena W; Manson, Jamie L; Singleton, John; McDonald, Ross; Plonczak, Alex; Kang, Jinhee; Lee, Chaghoon; Whangbo, Myung-Hwan; Lancaster, Tom; Steele, Andrew J; Franke, Isabel; Wright, Jack D; Blundell, Stephen J; Pratt, Francis L; deGeorge, Joseph; Turnbull, Mark M; Landee, Christopher P

2012-02-20

The structural and magnetic properties of the newly crystallized CuX(2)(pyzO)(H(2)O)(2) (X = Cl, Br; pyzO = pyrazine-N,N'-dioxide) coordination polymers are reported. These isostructural compounds crystallize in the monoclinic space group C2/c with, at 150 K, a = 17.0515(7) Å, b = 5.5560(2) Å, c = 10.4254(5) Å, β = 115.400(2)°, and V = 892.21(7) Å(3) for X = Cl and a = 17.3457(8) Å, b = 5.6766(3) Å, c = 10.6979(5) Å, β = 115.593(2)°, and V = 950.01(8) Å(3) for X = Br. Their crystal structure is characterized by one-dimensional chains of Cu(2+) ions linked through bidentate pyzO ligands. These chains are joined together through OH···O hydrogen bonds between the water ligands and pyzO oxygen atoms and Cu-X···X-Cu contacts. Bulk magnetic susceptibility measurements at ambient pressure show a broad maximum at 7 (Cl) and 28 K (Br) that is indicative of short-range magnetic correlations. The dominant spin exchange is the Cu-X···X-Cu supersuperexchange because the magnetic orbital of the Cu(2+) ion is contained in the CuX(2)(H(2)O)(2) plane and the X···X contact distances are short. The magnetic data were fitted to a Heisenberg 1D uniform antiferromagnetic chain model with J(1D)/k(B) = -11.1(1) (Cl) and -45.9(1) K (Br). Magnetization saturates at fields of 16.1(3) (Cl) and 66.7(5) T (Br), from which J(1D) is determined to be -11.5(2) (Cl) and -46.4(5) K (Br). For the Br analog the pressure dependence of the magnetic susceptibility indicates a gradual increase in the magnitude of J(1D)/k(B) up to -51.2 K at 0.84 GPa, suggesting a shortening of the Br···Br contact distance under pressure. At higher pressure X-ray powder diffraction data indicates a structural phase transition at ∼3.5 GPa. Muon-spin relaxation measurements indicate that CuCl(2)(pyzO)(H(2)O)(2) is magnetically ordered with T(N) = 1.06(1) K, while the signature for long-range magnetic order in CuBr(2)(pyzO)(H(2)O)(2) was much less definitive down to 0.26 K. The results for the Cu

Cs_7Sm_1_1[TeO_3]_1_2Cl_1_6 and Rb_7Nd_1_1[TeO_3]_1_2Br_1_6, the new tellurite halides of the tetragonal Rb_6LiNd_1_1[SeO_3]_1_2Cl_1_6 structure type

International Nuclear Information System (INIS)

Charkin, Dmitri O.; Black, Cameron; Downie, Lewis J.; Sklovsky, Dmitry E.; Berdonosov, Peter S.; Olenev, Andrei V.; Zhou, Wuzong; Lightfoot, Philip; Dolgikh, Valery A.

2015-01-01

Two new rare-earth – alkali – tellurium oxide halides were synthesized by a salt flux technique and characterized by single-crystal X-ray diffraction. The structures of the new compounds Cs_7Sm_1_1[TeO_3]_1_2Cl_1_6 (I) and Rb_7Nd_1_1[TeO_3]_1_2Br_1_6 (II) (both tetragonal, space group I4/mcm) correspond to the sequence of [MLn_1_1(TeO_3)_1_2] and [M_6X_1_6] layers and bear very strong similarities to those of known selenite analogs. We discuss the trends in similarities and differences in compositions and structural details between the Se and Te compounds; more members of the family are predicted. - Graphical abstract: Two new rare-earth – alkali – tellurium oxide halides were predicted and synthesized. - Highlights: • Two new rare-earth – alkali – tellurium oxide halides were synthesized. • They adopt slab structure of rare earth-tellurium-oxygen and CsCl-like slabs. • The Br-based CsCl-like slabs have been observed first in this layered family.

Photon Reabsorption in Mixed CsPbCl3:CsPbI3 Perovskite Nanocrystal Films for Light-Emitting Diodes

KAUST Repository

Davis, Nathaniel J. L. K.

2017-01-24

Cesium lead halide nanocrystals, CsPbX3 (X = Cl, Br, I), exhibit photoluminescence quantum efficiencies approaching 100% without the core–shell structures usually used in conventional semiconductor nanocrystals. These high photoluminescence efficiencies make these crystals ideal candidates for light-emitting diodes (LEDs). However, because of the large surface area to volume ratio, halogen exchange between perovskite nanocrystals of different compositions occurs rapidly, which is one of the limiting factors for white-light applications requiring a mixture of different crystal compositions to achieve a broad emission spectrum. Here, we use mixtures of chloride and iodide CsPbX3 (X = Cl, I) perovskite nanocrystals where anion exchange is significantly reduced. We investigate samples containing mixtures of perovskite nanocrystals with different compositions and study the resulting optical and electrical interactions. We report excitation transfer from CsPbCl3 to CsPbI3 in solution and within a poly(methyl methacrylate) matrix via photon reabsorption, which also occurs in electrically excited crystals in bulk heterojunction LEDs.

Vapor pressures and isopiestic molalities of concentrated CaCl2(aq), CaBr2(aq), and NaCl(aq) to T = 523 K

International Nuclear Information System (INIS)

Gruszkiewicz, Miroslaw S.; Simonson, John M.

2005-01-01

The Oak Ridge National Laboratory high-temperature isopiestic apparatus was outfitted with precise pressure gauges to allow for direct vapor pressure measurements. Vapor pressures over concentrated solutions of CaCl 2 (aq), and CaBr 2 (aq) were measured at temperatures between (380.15 and 523.15) K in the range of water activities between 0.2 and 0.85. Isopiestic molalities were used to determine osmotic coefficients at the conditions where NaCl reference standard solutions remained undersaturated. The main goal of this work was to improve the accuracy of isopiestic comparisons based on the calcium chloride reference standard. Osmotic coefficients for CaCl 2 (aq) and CaBr 2 (aq) calculated from both isopiestic and direct vapor pressure results were combined with the literature data and used to build general thermodynamic models based on a variant of extended Pitzer ion-interaction equations and valid at the saturation pressure of water. While these empirical models approach the accuracy of the experimental data in a wider range of concentrations and temperatures than any previously published equations, considerable amounts of accurate data and a substantial effort are required in order to obtain a satisfactory representation using power series-based virial equations. The effect of experimental uncertainties on the accuracy of the direct vapor pressure results is discussed, including in particular the error caused by the presence in the apparatus of a small amount of CO 2 . The substantial decrease of the solubility product of CaCO 3 in concentrated chloride solutions at temperatures above 423 K is a serious defect of calcium chloride as a water activity reference standard

Exergetic and energetic comparison of LiCl-H_2O and LiBr-H_2O working pairs in a solar absorption cooling system

International Nuclear Information System (INIS)

Bellos, Evangelos; Tzivanidis, Christos; Antonopoulos, Kimon A.

2016-01-01

Highlights: • Two working pairs (LiCl-H_2O and LiBr-H_2O) are examined in a solar absorption chiller. • The examined single effect absorption chiller is driven by flat plate collectors. • The system is analyzed energetically and energetically for 3 ambient temperatures. • LiCl-H_2O performs better than LiBr-H_2O in all the examined cases. • The optimum operating temperature is lower for the case of pair LiCl-H_2O. - Abstract: The objective of this study is to investigate the use of an alternative working pair in a solar absorption cooling system. LiCl-H_2O is the new examined pair and it is compared energetically and exegetically with the conventional pair LiBr-H_2O, which is the most usual in air-conditioning applications. The simplest solar cooling system is analyzed in order to focus in the comparison between these working fluids. Specifically, flat plate collectors, coupled with a storage tank, feed the single effect absorption chiller which produces 250 kW cooling at 10 °C. The two pairs are examined parametrically for various heat source temperature levels and for three ambient temperature levels (25 °C, 30 °C and 35 °C). The minimization of the collecting area, which means maximum exergetic efficiency, is the optimization goal in every case. The final results show that LiCl-H_2O pair performs better in all cases by giving greater exergetic efficiency. More specifically, about 8% lower collecting area is required to cover the demanded cooling load with this working pair. Another interesting result is that the optimum heat source temperature for the LiCl-H_2O is roughly lower than the respective for the LiBr-H_2O. The system is analyzed in steady state with the commercial software Engineering Equator Solver (EES).

Oxidation of cyclic amines by molybdenum(II and tungsten(II halocarbonyls, [M(CO4X2]2 (M = Mo, W; X = Cl, Br

Directory of Open Access Journals (Sweden)

H.M. Mbuvi

2013-05-01

Full Text Available The molybdenum(II and tungsten(II halocarbonyls, [M(CO4X2]2 (M = Mo, W; X = Cl, Br react with a large excess of the nitrogen bases, 1-methylpyrrolidine, 1-methylpiperidine, 1-ethylpiperidine and 2-ethylpiperidine to give aminecarbonyl complexes of the type M(CO3L3 (L= alkylamine. Excess piperidine reacts with the tungsten halocarbonyls, [W(CO4X2]2 (X = Cl, Br, to give the trans isomer of the complex, W(CO3(C5H11N3. The halogens were recovered as the amminium salts, amine, HX. The oxidized amine dimerized to form a yellow product which was recovered as an oily liquid but in very small amounts. However, in the reaction between Mo(CO4Br2 and 1-ethylpiperidine, a yellow crystalline solid, with a melting point of 224 oC was recovered in sufficient amounts for elemental analysis, melting point and spectral data. Its mass spectrum showed a molecular ion peak at m+/z = 222, a clear evidence that the oxidized amine dimerizes. The cyclic dibasic amine piperazine, C4H10N2 is not, however, oxidized by these halocarbonyls but rather it reacts by substituting some CO groups to form products of the type, M(CO3(C4H10N22X2 (M = Mo, W; X = Cl, Br. Products were characterized by elemental analysis, IR, UV, 1H NMR and mass spectrometry.

Quantum Chemical Examination of the Sequential Halogen Incorporation Scheme for the Modeling of Speciation of I/Br/Cl-Containing Trihalomethanes.

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Zhang, Chenyang; Li, Maodong; Han, Xuze; Yan, Mingquan

2018-02-20

The recently developed three-step ternary halogenation model interprets the incorporation of chlorine, bromine, and iodine ions into natural organic matter (NOM) and formation of iodine-, bromine-, and chlorine-containing trihalomethanes (THMs) based on the competition of iodine, bromine, and chlorine species at each node of the halogenation sequence. This competition is accounted for using the dimensionless ratios (denoted as γ) of kinetic rates of reactions of the initial attack sites or halogenated intermediates with chlorine, bromine, and iodine ions. However, correlations between the model predictions made and mechanistic aspects of the incorporation of halogen species need to be ascertained in more detail. In this study, quantum chemistry calculations were first used to probe the formation mechanism of 10 species of Cl-/Br-/I- THMs. The HOMO energy (E HOMO ) of each mono-, bi-, or trihalomethanes were calculated by B3LYP method in Gaussian 09 software. Linear correlations were found to exist between the logarithms of experimentally determined kinetic preference coefficients γ reported in prior research and, on the other hand, differences of E HOMO values between brominated/iodinated and chlorinated halomethanes. One notable exception from this trend was that observed for the incorporation of iodine into mono- and di-iodinated intermediates. These observations confirm the three-step halogen incorporation sequence and the factor γ in the statistical model. The combined use of quantum chemistry calculations and the ternary sequential halogenation model provides a new insight into the microscopic nature of NOM-halogen interactions and the trends seen in the behavior of γ factors incorporated in the THM speciation models.

An empirical, quantitative approach to predict the reactivity of some substituted aromatic compounds towards reactive radical species (Cl2-*, Br2-*, *NO2, SO3-*, SO4-*) in aqueous solution.

Science.gov (United States)

Minero, Claudio; Maurino, Valter; Pelizzetti, Ezio; Vione, Davide

2006-07-01

The Hammett approach, applied to the reaction of various classes of aromatic compounds with the radicals Cl2-*, Br2-*, *NO2, SO3-*, and SO4-* yielded good predictive models, supported by high values of the correlation coefficient r2 in the case of phenols with Cl2-* and of phenolates with *NO2 and SO3-*. Lower but statistically significant correlation coefficients could be obtained for benzoates with Cl2-*, phenolates with Br2-*, and benzoates and anisoles with SO4-*.

Crystallographic Investigations into Properties of Acentric Hybrid Perovskite Single Crystals NH(CH3)3SnX3(X = Cl, Br)

KAUST Repository

Dang, Yangyang; Zhong, Cheng; Zhang, Guodong; Ju, Dianxing; Wang, Lei; Xia, Shengqing; Xia, Haibing; Tao, Xutang

2016-01-01

substitute for the lead in the halides perovskites and solving the ambiguous crystal structures and phase transition of NH(CH3)3SnX3 (X = Cl, Br). Here, we report the bulk crystal growths and different crystal morphologies of orthorhombic hybrid perovskites

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

International Nuclear Information System (INIS)

Michael E. McIlwain; Da Gao; Nick Thompson

2007-01-01

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-initio (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

Substitution and Redox Chemistry of [Bu(4)N](2)[Ta(6)Cl(12)(OSO(2)CF(3))(6)].

Science.gov (United States)

Prokopuk, Nicholas; Kennedy, Vance O.; Stern, Charlotte L.; Shriver, Duward F.

1998-09-21

Two sequential electrochemical reductions occur for the cluster anion [Ta(6)Cl(12)(OSO(2)CF(3))(6)](2)(-) at 0.89 and 0.29 V vs Ag/AgCl, with the generation [Ta(6)Cl(12)(OSO(2)CF(3))(6)](3)(-) and [Ta(6)Cl(12)(OSO(2)CF(3))(6)](4)(-). Chemical reduction of [Ta(6)Cl(12)(OSO(2)CF(3))(6)](2)(-) by ferrocene produces [Ta(6)Cl(12)(OSO(2)CF(3))(6)](3)(-) with the concomitant shift of the nu(SO(2)) stretch from 1002 to 1018 cm(-)(1). Reaction of [Bu(4)N](2)[Ta(6)Cl(12)(OSO(2)CF(3))(6)] (1) with [Bu(4)N]X (X = Cl, Br, I, NCS) occurs by reduction and substitution, yielding [Bu(4)N](3)[Ta(6)Cl(12)X(6)], where the clusters with X = Br, I, and NCS are new. Spectroscopic (IR and UV-vis) evidence indicates that the reduced cluster core {Ta(6)Cl(12)}(2+) is produced in reaction mixtures of 1 with the halide and pseudohalide ions. Concomitant substitution of the triflate ligands of 1 by X(-) occurs and the rates for the overall reduction and substitution increase in the order X(-) = Cl(-) < Br(-) < NCS(-) < I(-) < CN(-). Reduction of 1 with ferrocene followed by addition of [Bu(4)N]O(2)CCH(3) produces the new cluster [Ta(6)Cl(12)(O(2)CCH(3))(6)](3)(-) isolated as the tetrabutylammonium salt. Cyclic voltammetry and UV-vis spectroscopy on the new clusters [Bu(4)N](3)[Ta(6)Cl(12)X(6)] (X = Br, I, NCS, and O(2)CCH(3)) are reported. Crystal data for [Bu(4)N](3)[Ta(6)Cl(12)(NCS)(6)].CH(2)Cl(2): monoclinic, space group, P2(1)/c (No. 14); a = 25.855(6) Å, b = 21.843(6) Å, c = 16.423(3) Å; beta = 100.03(2) degrees; V = 9133(3) Å(3); Z = 4.

Rotationally adiabatic pair interactions of para- and ortho-hydrogen with the halogen molecules F2, Cl2, and Br2.

Science.gov (United States)

Berg, Matthias; Accardi, Antonio; Paulus, Beate; Schmidt, Burkhard

2014-08-21

The present work is concerned with the weak interactions between hydrogen and halogen molecules, i.e., the interactions of pairs H2-X2 with X = F, Cl, Br, which are dominated by dispersion and quadrupole-quadrupole forces. The global minimum of the four-dimensional (4D) coupled cluster with singles and doubles and perturbative triples (CCSD(T)) pair potentials is always a T shaped structure where H2 acts as the hat of the T, with well depths (De) of 1.3, 2.4, and 3.1 kJ/mol for F2, Cl2, and Br2, respectively. MP2/AVQZ results, in reasonable agreement with CCSD(T) results extrapolated to the basis set limit, are used for detailed scans of the potentials. Due to the large difference in the rotational constants of the monomers, in the adiabatic approximation, one can solve the rotational Schrödinger equation for H2 in the potential of the X2 molecule. This yields effective two-dimensional rotationally adiabatic potential energy surfaces where pH2 and oH2 are point-like particles. These potentials for the H2-X2 complexes have global and local minima for effective linear and T-shaped complexes, respectively, which are separated by 0.4-1.0 kJ/mol, where oH2 binds stronger than pH2 to X2, due to higher alignment to minima structures of the 4D-pair potential. Further, we provide fits of an analytical function to the rotationally adiabatic potentials.

Tunable CsPbBr3/Cs4PbBr6 phase transformation and their optical spectroscopic properties.

Science.gov (United States)

Chen, Xiao; Chen, Daqin; Li, Junni; Fang, Gaoliang; Sheng, Hongchao; Zhong, Jiasong

2018-04-24

As a novel type of promising materials, metal halide perovskites are a rising star in the field of optoelectronics. On this basis, a new frontier of zero-dimensional perovskite-related Cs4PbBr6 with bright green emission and high stability has attracted an enormous amount of attention, even though its photoluminescence still requires to clarification. Herein, the controllable phase transformation between three-dimensional CsPbBr3 and zero-dimensional Cs4PbBr6 is easily achieved in a facile ligand-assisted supersaturated recrystallization synthesis procedure via tuning the amount of surfactants, and their unique optical properties are investigated and compared in detail. Both Cs4PbBr6 and CsPbBr3 produce remarkably intense green luminescence with quantum yields up to 45% and 80%, respectively; however, significantly different emitting behaviors are observed. The fluorescence lifetime of Cs4PbBr6 is much longer than that of CsPbBr3, and photo-blinking is easily detected in the Cs4PbBr6 product, proving that the zero-dimensional Cs4PbBr6 is indeed a highly luminescent perovskite-related material. Additionally, for the first time, tunable emissions over the visible-light spectral region are demonstrated to be achievable via halogen composition modulations in the Cs4PbX6 (X = Cl, Br, I) samples. Our study brings a simple method for the phase control of CsPbBr3/Cs4PbBr6 and demonstrates the intrinsic luminescence nature of the zero-dimensional perovskite-related Cs4PbX6 products.

Static and dynamic magnetic properties of two synthetic francisites Cu3La(SeO3)2O2X (X = Br and Cl)

Science.gov (United States)

Markina, M. M.; Zakharov, K. V.; Zvereva, E. A.; Denisov, R. S.; Berdonosov, P. S.; Dolgikh, V. A.; Kuznetsova, E. S.; Olenev, A. V.; Vasiliev, A. N.

2017-04-01

The formation of long-range magnetic order at low temperatures was established in francisite—type compounds Cu3La(SeO3)2O2X (X = Br and Cl) through measurements of magnetic susceptibility, magnetization, specific heat and X-band electron spin resonance. The significantly enhanced critical index p = 1.0 ± 0.1 in Cu3La(SeO3)2Br and p = 0.8 ± 0.1 in Cu3La(SeO3)2Cl in the temperature dependence of the width of ESR signal evidence the reduced dimensionality of the kagome-type francisite's magnetic subsystem. Under action of external magnetic field, the presumably non-collinear six-sublattices antiferromagnetic structure of these compounds experiences the first-order metamagnetic transformation. The B- T magnetic phase diagrams were established from the positions of singularities in temperature and field dependences of thermodynamic properties. Contrary to pristine mineral Cu3Bi(SeO3)2Cl, no signature of structural phase transition was detected.

Cs/CsPbX3 (X = Br, Cl) epitaxial heteronanocrystals with magic-angle stable/metastable grain boundary

Science.gov (United States)

Zhang, Yumeng; Fan, Baolu; Wu, Wenhui; Fan, Jiyang

2017-05-01

Metal-semiconductor heteronanostructures are crucial building blocks of nanoscale electronic and optoelectronic devices. However, the lattice misfit remains a challenge in constructing heteronanostructures. Perovskite nanocrystals are superior candidates for constructing nanodevices owing to excellent optical, ferroelectric, and superconducting properties. We report the epitaxial growth of lattice-matched Cs/CsPbBr3 metal-semiconductor heteronanocrystals in a liquid medium. The well-crystallized ultrathin Cs layers grow epitaxially on the surfaces of colloidal CsPbBr3 nanocrystals, forming heteronanocrystals with interface diameters of several nanometers. Most of them are pseudomorphic with coherent interfaces free from dislocations, and the others exhibit discrete high-angle grain boundaries. The model based on the calculation of the elastic potential energy of the epilayer and analysis of the near-coincidence sites explains well the experimental result. The analysis shows that the excellent lattice match between the metal and the semiconductor ensures the ideal epitaxial-growth of both Cs/CsPbBr3 and Cs/CsPbCl3 heteronanocrystals. Such metal/semiconductor heteronanocrystals pave the way for developing perovskite-based nanodevices.

NMR espectroscopic parameters of HX and Si (Sn)X{sub 4} (X = H, F, Cl, Br and I) and SnBr{sub 4-n}I{sub n} model compounds

Energy Technology Data Exchange (ETDEWEB)

Maldonado, Alejandro F.; Gimenez, Carlos A. [Physics Department, Natural and Exact Science Faculty, Northeastern University of Argentina and Institute of Modelling and Innovation on Technology, IMIT Avda Libertad 5460, W3404AAS Corrientes (Argentina); Aucar, Gustavo A., E-mail: gaa@unne.edu.ar [Physics Department, Natural and Exact Science Faculty, Northeastern University of Argentina and Institute of Modelling and Innovation on Technology, IMIT Avda Libertad 5460, W3404AAS Corrientes (Argentina)

2012-02-20

Graphical abstract: Optimized fully relativistic calculations of NMR J-couplings (HBr, HI), chemical shifts (Si, Sn) and absolute shielding for reference compounds of heavy atoms (Si, Sn) are given. Highlights: Black-Right-Pointing-Pointer In this article we show a procedure to get accurate NMR {sigma}{sup Ref} of Si and Sn. Black-Right-Pointing-Pointer Calculations of {sigma} on more than three heavy-atom-containing molecules are given. Black-Right-Pointing-Pointer Our results are closer to {delta}{sup exp} than previous calculations for SnX{sub 4} (X = H, Cl, Br, I). Black-Right-Pointing-Pointer Optimized basis sets were considered for full R and NR calculations of NMR J and {sigma}. Black-Right-Pointing-Pointer Relativistic effects enlarge electron correlation effects on J-couplings. - Abstract: The NMR spectroscopic parameters are largely influenced by relativistic effects. They are highly dependent on the electronic behavior inside the spatial regions occupied by nuclei. Full relativistic calculations of indirect nuclear spin-spin couplings at random phase level of approach (RPA) in the title compounds with reoptimized Dyall cVTZ basis sets are given. A comparison with the results of calculations with other basis sets that are mostly used within the non-relativistic (NR) domain is presented. We analyzed the dependence of that couplings with the speed of light over the whole range of values, from the full relativistic to the NR regimes. Within this last regime, calculations at the second-order level of approach (SOPPA) indicated that electron correlation effects may not be as important for nuclear magnetic shieldings, but they must be included with care for J-coupling calculations. From these calculations, we determined that relativity enlarges the electron correlation effects of the J-couplings of HBr and HI. Because the results of nuclear magnetic shielding calculations within polarization propagators at the RPA level were reliable, we were able to show a new

Imaging the Dynamics of CH2BrI Photodissociation in the Near Ultraviolet Region.

Science.gov (United States)

Pan, Changen; Zhang, Yi; Lee, Joseph D; Kidwell, Nathanael M

2018-04-19

The photodissociation dynamics of jet-cooled CH 2 BrI were investigated in the near-ultraviolet (UV) region from 280-310 nm using velocity map imaging. We report the translational and internal energy distributions of the CH 2 Br radical and ground state I ( 2 P 3/2 ) or spin-orbit excited I ( 2 P 1/2 ) fragments determined by velocity map imaging of the ionized iodine fragments following 2 + 1 resonance-enhanced multiphoton ionization of the nascent neutral iodine products. The velocity distributions indicate that most of the available energy is partitioned into the internal energy of the CH 2 Br radical with only modest translational excitation imparted to the cofragments, which is consistent with a simple impulsive model. Furthermore, from extrapolation of the velocity distribution results, the first determination of the C-I bond dissociation energy of CH 2 BrI is presented in this work to be D 0 = 16 790 ± 590 cm -1 . The ion images appear anisotropic, indicative of a prompt dissociation, and the derived anisotropy parameters are consistently positive. Additionally, the angular distributions report on the electronic excited state dynamics, which validate recent works characterizing the electronic states responsible for the first absorption band of CH 2 BrI. In the current work, photolysis of CH 2 BrI on the red edge of the absorption spectrum reveals an additional channel producing I ( 2 P 3/2 ) fragments.

Photochemistry of xenon-halogen Van der Waals complexes (X2 = Cl2, Br2, I2): evidence for the intermediate states in the (Xe-X2)*→ XeX* + X reaction

International Nuclear Information System (INIS)

Boivineau, Michel

1987-01-01

This research thesis addresses the reactivity of excited states of xenon-halogen Van der Waals complexes (Cl 2 , Br 2 , I 2 ) submitted to a multi-photonic excitation. The objective of this study is, by means of a specific experimental approach, to highlight the R*+ X 2 *- to better understand the reaction mechanism, and to study the reactivity of rare gas/halogen systems depending on the halogen nature. After having reported a bibliographical study on each studied system, the author describes the experimental system, reports and discusses experimental results obtained on the different complex systems (chlorine-, bromine- or iodine-based). He finally comments a possible and original application of these works in the development of an excimer laser with a new active medium (the rare gas/halogen Van der Waals complex) which would allow a continuous operation and an easy discharge production [fr

BiOCl{sub x}Br{sub y}I{sub z} (x + y + z = 1) solid solutions with controllable band gap and highly enhanced visible light photocatalytic performances

Energy Technology Data Exchange (ETDEWEB)

Sun, Xiuguo; Zhang, Yangyang; Li, Chunmei; Zhang, Zhifeng; Peng, Zheng; Si, Huayan; Zhang, Jianmin [School of Materials Science and Engineering, Shijiazhuang Tiedao University, Shijiazhuang 050043 (China); Li, Yanting, E-mail: yantingcn@stdu.edu.cn [School of Materials Science and Engineering, Shijiazhuang Tiedao University, Shijiazhuang 050043 (China); Hebei Provincial Key Laboratory of Traffic Engineering materials, Shijiazhuang Tiedao University, Shijiazhuang 050043 (China)

2015-07-25

Highlights: • BiOCl{sub x}Br{sub y}I{sub z} solid solutions were prepared by hydrolysis method. • Band gap of the solid solutions can be controllable by adjusting the molar ratio of halogen ions. • The samples show higher visible light photocatalytic activity than pure BiOX. • Orbital diversification of VB is beneficial to separating the holes and electrons effectively. • The mechanisms are discussed by active species trapping and band theory. - Abstract: A series of BiOCl{sub x}Br{sub y}I{sub z} solid solutions with controllable band gap and highly enhanced visible light photocatalytic performances were synthesized by a simple hydrolysis method. The samples were characterized by X-ray powder diffraction, UV–vis diffuse reflectance spectra, scanning electron microscope, high-resolution transmission electron microscopy and Brunauer–Emmett–Teller analysis. By adjusting the molar ratio of halogen ions, the band gap of BiOCl{sub x}Br{sub y}I{sub z} could be controllable to the suitable value for a photocatalytic reaction. Especially, BiOCl{sub x}Br{sub y}I{sub z} with a 1:1:2 molar ratio of Cl, Br to I showed the highest visible light photocatalytic activity for the degradation of methyl orange than individual BiOX systems. The degradation efficiency could reach over 90% within 60 min. The possible mechanism of photogenerated carrier transfer and higher photocatalytic activity was analyzed by active species trapping and energy band theory.

Lattice and Valence Electronic Structures of Crystalline Octahedral Molybdenum Halide Clusters-Based Compounds, Cs2[Mo6X14] (X = Cl, Br, I), Studied by Density Functional Theory Calculations.

Science.gov (United States)

Saito, Norio; Cordier, Stéphane; Lemoine, Pierric; Ohsawa, Takeo; Wada, Yoshiki; Grasset, Fabien; Cross, Jeffrey S; Ohashi, Naoki

2017-06-05

The electronic and crystal structures of Cs 2 [Mo 6 X 14 ] (X = Cl, Br, I) cluster-based compounds were investigated by density functional theory (DFT) simulations and experimental methods such as powder X-ray diffraction, ultraviolet-visible spectroscopy, and X-ray photoemission spectroscopy (XPS). The experimentally determined lattice parameters were in good agreement with theoretically optimized ones, indicating the usefulness of DFT calculations for the structural investigation of these clusters. The calculated band gaps of these compounds reproduced those experimentally determined by UV-vis reflectance within an error of a few tenths of an eV. Core-level XPS and effective charge analyses indicated bonding states of the halogens changed according to their sites. The XPS valence spectra were fairly well reproduced by simulations based on the projected electron density of states weighted with cross sections of Al K α , suggesting that DFT calculations can predict the electronic properties of metal-cluster-based crystals with good accuracy.

Vapor pressures and isopiestic molalities of concentrated CaCl{sub 2}(aq), CaBr{sub 2}(aq), and NaCl(aq) to T = 523 K

Energy Technology Data Exchange (ETDEWEB)

Gruszkiewicz, Miroslaw S. [Oak Ridge National Laboratory, Chemical Sciences Division, P.O. Box 2008, Building 4500S MS-6110, Oak Ridge, TN 37831-6110 (United States)]. E-mail: gruszkiewicz@ornl.gov; Simonson, John M. [Oak Ridge National Laboratory, Chemical Sciences Division, P.O. Box 2008, Building 4500S MS-6110, Oak Ridge, TN 37831-6110 (United States)]. E-mail: simonsonjm@ornl.gov

2005-09-15

The Oak Ridge National Laboratory high-temperature isopiestic apparatus was outfitted with precise pressure gauges to allow for direct vapor pressure measurements. Vapor pressures over concentrated solutions of CaCl{sub 2}(aq), and CaBr{sub 2}(aq) were measured at temperatures between (380.15 and 523.15) K in the range of water activities between 0.2 and 0.85. Isopiestic molalities were used to determine osmotic coefficients at the conditions where NaCl reference standard solutions remained undersaturated. The main goal of this work was to improve the accuracy of isopiestic comparisons based on the calcium chloride reference standard. Osmotic coefficients for CaCl{sub 2}(aq) and CaBr{sub 2}(aq) calculated from both isopiestic and direct vapor pressure results were combined with the literature data and used to build general thermodynamic models based on a variant of extended Pitzer ion-interaction equations and valid at the saturation pressure of water. While these empirical models approach the accuracy of the experimental data in a wider range of concentrations and temperatures than any previously published equations, considerable amounts of accurate data and a substantial effort are required in order to obtain a satisfactory representation using power series-based virial equations. The effect of experimental uncertainties on the accuracy of the direct vapor pressure results is discussed, including in particular the error caused by the presence in the apparatus of a small amount of CO{sub 2}. The substantial decrease of the solubility product of CaCO{sub 3} in concentrated chloride solutions at temperatures above 423 K is a serious defect of calcium chloride as a water activity reference standard.

Thermolysis of salts of [ReCl6]2- and [ReBr6]2- anions

International Nuclear Information System (INIS)

Gubanov, A.I.; Korenev, S.V.; Gromilov, S.A.; Shubin, Yu.V.

2003-01-01

Thermal decomposition of the [Pd(NH 3 ) 4 ][ReG 6 ], [Pt(NH 3 ) 4 ][ReG 6 ], (NH 4 ) 2 [ReG 6 ] complexes, where G = Cl, Br, was studied in the inert atmosphere. Certain regularities of the thermolysis were established. Finished products of the thermolysis of binary complexes in the inert atmosphere were demonstrated to be two-phase systems containing two solid solutions - one on the basis of the platinum (palladium) fcc-lattice, another - on the basis of the rhenium hcp lattice. One-phase solid palladium - rhenium solutions were established to be obtained during reduction of the studied complexes in the hydrogen atmosphere [ru

Structure of the mercury(II mixed-halide (Br/Cl complex of 2,2′-(5-tert-butyl-1,3-phenylenebis(1-pentyl-1H-benzo[d]imidazole

Directory of Open Access Journals (Sweden)

Varsha Rani

2017-03-01

Full Text Available The mercury(II complex of 2,2′-(5-tert-butyl-1,3-phenylenebis(1-pentyl-1H-benzimidazole, namely catena-poly[[dihalogenidomercury(II]-μ-2,2′-(5-tert-butyl-1,3-phenylenebis(1-pentyl-1H-benzimidazole-κ2N3:N3′], [HgBr1.52Cl0.48(C34H42N4], 2, has a polymeric structure bridging via the N atoms from the benzimidazole moieties of the ligand. The compound crystallizes in the orthorhombic space group Pca21 and is a racemic twin [BASF = 0.402 (9]. The geometry around the HgII atom is distorted tetrahedral, with the HgII atom coordinated to two N atoms, one Br atom, and a fourth coordination site is occupied by a mixed halide (Br/Cl. For the two ligands in the asymmetric unit, there is disorder with one of the two tert-butyl groups and benzimidazole moieties showing twofold disorder, with occupancy factors of 0.57 (2:0.43 (2 for the tert-butyl group and 0.73 (3:0.27 (3 for the benzimidazole group. In addition, there is threefold disorder for two of the four n-pentyl groups, with occupancy factors of 0.669 (4:0.177 (4:0.154 (4 and 0.662 (4:0.224 (4:0.154 (4, respectively. The molecules form a one-dimensional helical polymer propagating in the b-axis direction. The helices are held together by intra-strand C—H...Br and C—H...Cl interactions. Each strand is further linked by inter-strand C—H...Br and C—H...Cl interactions. In addition, there are weak C—H...N inter-strand interactions which further stabilize the structural arrangement.

PuBr3-type as high pressure modification of rare earth trihalides LnX3 (X = Cl, Br, I)

International Nuclear Information System (INIS)

Beck, H.P.; Gladrow, E.

1983-01-01

High pressure experiments in a belt-type apparatus were performed on rare earth trichlorides, -bromides and -iodides. The results underline the importance of the PuBr 3 -type arrangement. The range of existence of this structure type is considerably increased under pressure. X-ray high temperature investigations at ambient pressure on the quenched high pressure phases show a marked correlation between the transformation pressures, which rise with smaller cations, and the temperatures at which the high pressure phases are reconverted to the thermodynamically stable ones. (author)

Comparative study of α and β-ThBr4: structure and luminescence. Spectroscopy of U4+ in α-ThBr4

International Nuclear Information System (INIS)

Simoni, E.

1988-05-01

UV absorption of β-ThBr 4 : presents a plain absorption front and for the same temperature the threshold energy has the same value than the threshold energy of excitation function and photocurrent peak. Emission intensity and lifetime decrease when temperature increases from 300 K to 400K (extinction temperature). Results are interpreted either by molecular orbital levels of the ThBr 8 4- cluster or either by conduction and valence bands of the matrix above. Absorption and emission spectra of U 4+ in α-ThBr 4 (where U 4+ has a S 4 symmetry) between 300 K and 4.2 K allow indexation of 30 levels. Spectroscopic parameters are calculated in D 2d and S 4 symmetry. Comparison of these parameters with those of U 4+ in β-ThBr 4 and β-ThCl 4 shows that crystal field force is practically the same in the three matrices but the structure transformation from β to α has more influence on B q k than ligand change from Br - to Cl - . Owing to very low phonon energy, fluorescence spectra of U 4+ is easy to observe in α-ThBr 4 as it is in β-ThBr 4 and ThCl 4 [fr

35Cl, sup(79,81)Br NQR spectra of chalcogenide molybdenum (5) complexes

International Nuclear Information System (INIS)

Fokina, Z.A.; Kuznetsov, S.I.; Timoshchenko, N.I.; Kolesnichenko, V.L.; Bryukhova, E.V.; Semin, G.K.

1984-01-01

The NQR spectra of molybdenum thioselenohalogenides MoS 2 SeX 5 (X=Cl, Br) are studied. A high-frequency doublet and a low-frequency triplet are observed in both spectra, one of the lines in the latter being noticeably higher by frequency than two others. The NKR spectra structure, with accoUnt of data on thermography and IR-spectroscopy, points to the MoS 2 X 3 xSeX 2 strrcture where two halide atoms are bound with a chalcogen atom and three others with Mo, one of the three chalcogen atoms being in trans-position to SeX 2 . Essential splittings in low-frequency triplet take place at the expense of intrasphere effect of coordinated S 2 -2 and SeX 2 groups

Investigation of the magnetic structure of KFeCl3, KFeBr3, Rb2MnCl4, and Rb3Mn2Cl7 compounds with magnetic correlations in one and two dimensions

International Nuclear Information System (INIS)

Gurewitz, E.

1976-12-01

The crystallographic structure of KFeCl 3 and KFeBr 3 consists of (FeCl) - octahedra packed in isolated zigzagging chains. These compounds order antiferromagnetically at Tsub(N) approximately 16 deg K and Tsub(N) approximately 9.5 deg K, respectively. Below Tsub(N) the Fe 2+ magnetic moments within a chain are ferromagnetically coupled, parallel to the chain axis, while the chains are coupled antiferromagnetically. In the temperatures Tsub(N) 3 has magnetic correlations within the chains only, whereas the correlations between the chains are negligible. Moessbauer effect measurements at these temperatures show a distinct hyperfine magnetic splitting, characteristic of relaxation phenomena. Cs 2 MnCl 4 , Rb 2 MnCl 4 and Rb 3 Mn 2 Cl 7 belong to the Asub(n+1)Bsub(n)Xsub(3n+1) family of compounds, with the Dsub(4h)sup(17) space group. These compounds order antiferromagnetically at Tsub(N) approximately 55 deg K for Cs 2 MnCl 4 and Rb 2 MnCl 4 , and Tsub(N) approximately 64.5 deg K for Rb 3 Mn 2 Cl 7 . Below Tsub(N) each Mn 2+ moment is along the c-axis and is coupled antiferromagnetically to the moments of its nearest neighbours (nn). These compounds behave like a two-dimensional antiferromagnet at T >= Tsub(N). Neutron scans of the reciprocal space exhibit rods of reflections along c vectorsup(*). The negligible interactions between next nn sets of MnCl 2 layers, a distance c vector apart, yield both in Rb 2 MnCl 4 and in Rb 3 Mn 2 Cl 7 , two distinctive magnetic structures (polytypes) below Tsub(N). (author)

Two-dimensional H2O-Cl2 and H2O-Br2 potential surfaces: an ab initio study of ground and valence excited electronic states.

Science.gov (United States)

Hernandez-Lamoneda, Ramón; Rosas, Victor Hugo Uc; Uruchurtu, Margarita I Bernal; Halberstadt, Nadine; Janda, Kenneth C

2008-01-10

All electron ab initio calculations for the interaction of H2O with Cl2 and Br2 are reported for the ground state and the lowest triplet and singlet Pi excited states as a function of both the X-X and O-X bond lengths (X = Cl or Br). For the ground state and lowest triplet state, the calculations are performed with the coupled cluster singles, doubles, and perturbative triple excitation level of correlation using an augmented triple-zeta basis set. For the 1Pi state the multireference average quadratic coupled cluster technique was employed. For several points on the potential, the calculations were repeated with the augmented quadruple-zeta basis set. The ground-state well depths were found to be 917 and 1,183 cm-1 for Cl2 and Br2, respectively, with the triple-zeta basis set, and they increased to 982 and 1,273 cm-1 for the quadruple-zeta basis set. At the geometry of the ground-state minimum, the lowest energy state corresponding to the unperturbed 1Pi states of the halogens increases in energy by 637 and 733 cm-1, respectively, relative to the ground-state dissociation limit of the H2O-X2 complex. Adding the attractive ground-state interaction energy to that of the repulsive excited state predicts a blue-shift, relative to that of the free halogen molecules, of approximately 1,600 cm-1 for H2O-Cl2 and approximately 2,000 cm-1 for H2O-Br2. These vertical blue-shifts for the dimers are greater than the shift of the band maximum upon solvation of either halogen in liquid water.

Bond selective photochemistry in CH2BrI through electronic excitation at 210 nm

International Nuclear Information System (INIS)

Butler, L.J.; Hintsa, E.J.; Lee, Y.T.

1986-01-01

To explore the possibility of bond selective photochemistry in an excited electronic state, we have studied the photolysis of CH 2 BrI in a molecular beam at 210 nm. Following the direct local excitation of a repulsive transition on the C--Br bond at 210 nm, the fragments were detected by time-of-flight mass spectrometry. The dominant channel was found to be C--Br fission (60%) releasing an average of 15 kcal/mol into translation with the remainder reacting to form CH 2 +IBr and CH 2 +I+Br. There was no evidence for the primary fission of the C--I bond, making this the first clear example of the selective cleavage of a stronger bond in a molecule over the weakest one

Matrix isolation and theoretical study of the photochemical reactions of C{sub 2}H{sub 3}Br and 1,2-C{sub 2}H{sub 2}Br{sub 2} with CrO{sub 2}Cl{sub 2}

Energy Technology Data Exchange (ETDEWEB)

Lemon, Christine E. [Department of Chemistry, University of Cincinnati, P.O. Box 210172, Cincinnati, OH 45221 (United States); Goldberg, Nicola [Department of Chemistry, University of Cincinnati, P.O. Box 210172, Cincinnati, OH 45221 (United States); Klein-Riffle, Evan T. [Department of Chemistry, University of Cincinnati, P.O. Box 210172, Cincinnati, OH 45221 (United States); Kronberg, Jon K. [Department of Chemistry, University of Cincinnati, P.O. Box 210172, Cincinnati, OH 45221 (United States); Ault, Bruce S. [Department of Chemistry, University of Cincinnati, P.O. Box 210172, Cincinnati, OH 45221 (United States)], E-mail: bruce.ault@uc.edu

2006-08-01

The matrix-isolation technique has been combined with infrared spectroscopy and theoretical calculations to characterize the products of the photochemical reactions of C{sub 2}H{sub 3}Br and 1,2-C{sub 2}H{sub 2}Br{sub 2} with CrO{sub 2}Cl{sub 2}. For these systems, oxygen-atom transfer occurred upon visible-near ultraviolet irradiation, yielding bromoacetaldehyde and CrOCl{sub 2} in the former case and bromoacetyl bromide and CrCl{sub 2}O in the latter. For each system, the products were formed in the same matrix cage and strongly interacted to form a distinct molecular complex. No evidence was obtained for the acetyl bromide derivative in the C{sub 2}H{sub 3}Br system, indicating the occurrence of oxygen-atom attack at the less substituted carbon of vinyl bromide, nor was any evidence obtained for the formation of a possible five-membered metallocycle. Two different modes of interaction were explored computationally: {eta}{sup 1} (end-on) to the oxygen atom and {eta}{sup 2} (side-on) to the C=O bond. Theoretical calculations indicated that the {eta}{sup 1} complex of CH{sub 2}BrCHO-CrCl{sub 2}O was 13 kcal mol{sup -1} more stable than the {eta}{sup 2} complex at the B3LYP/6-311++G(d,2p) level of theory. The binding energy of the {eta}{sup 1} complex was found to be 21 kcal mol{sup -1}, compared to 8 kcal mol{sup -1} for the {eta}{sup 2} complex at this level of theory.

Zn2(TeO3Br2

Directory of Open Access Journals (Sweden)

Mats Johnsson

2008-05-01

Full Text Available Single crystals of dizinc tellurium dibromide trioxide, Zn2(TeO3Br2, were synthesized via a transport reaction in sealed evacuated silica tubes. The compound has a layered crystal structure in which the building units are [ZnO4Br] distorted square pyramids, [ZnO2Br2] distorted tetrahedra, and [TeO3E] tetrahedra (E being the 5s2 lone pair of Te4+ joined through sharing of edges and corners to form layers of no net charge. Bromine atoms and tellurium lone pairs protrude from the surfaces of each layer towards adjacent layers. This new compound Zn2(TeO3Br2 is isostructural with the synthetic compounds Zn2(TeO3Cl2, CuZn(TeO32, Co2(TeO3Br2 and the mineral sophiite, Zn2(SeO3Cl2.

The association between content of the elements S, Cl, K, Fe, Cu, Zn and Br in normal and cirrhotic liver tissue from Danes and Greenlandic Inuit examined by dual hierarchical clustering analysis.

Science.gov (United States)

Laursen, Jens; Milman, Nils; Pind, Niels; Pedersen, Henrik; Mulvad, Gert

2014-01-01

Meta-analysis of previous studies evaluating associations between content of elements sulphur (S), chlorine (Cl), potassium (K), iron (Fe), copper (Cu), zinc (Zn) and bromine (Br) in normal and cirrhotic autopsy liver tissue samples. Normal liver samples from 45 Greenlandic Inuit, median age 60 years and from 71 Danes, median age 61 years. Cirrhotic liver samples from 27 Danes, median age 71 years. Element content was measured using X-ray fluorescence spectrometry. Dual hierarchical clustering analysis, creating a dual dendrogram, one clustering element contents according to calculated similarities, one clustering elements according to correlation coefficients between the element contents, both using Euclidian distance and Ward Procedure. One dendrogram separated subjects in 7 clusters showing no differences in ethnicity, gender or age. The analysis discriminated between elements in normal and cirrhotic livers. The other dendrogram clustered elements in four clusters: sulphur and chlorine; copper and bromine; potassium and zinc; iron. There were significant correlations between the elements in normal liver samples: S was associated with Cl, K, Br and Zn; Cl with S and Br; K with S, Br and Zn; Cu with Br. Zn with S and K. Br with S, Cl, K and Cu. Fe did not show significant associations with any other element. In contrast to simple statistical methods, which analyses content of elements separately one by one, dual hierarchical clustering analysis incorporates all elements at the same time and can be used to examine the linkage and interplay between multiple elements in tissue samples. Copyright © 2013 Elsevier GmbH. All rights reserved.

Synthesis and characterization of novel plasmonic Ag/AgX-CNTs (X = Cl, Br, I) nanocomposite photocatalysts and synergetic degradation of organic pollutant under visible light.

Science.gov (United States)

Shi, Huixian; Chen, Jiangyao; Li, Guiying; Nie, Xin; Zhao, Huijun; Wong, Po-Keung; An, Taicheng

2013-08-14

A series of novel well-defined Ag/AgX (X = Cl, Br, I) loaded carbon nanotubes (CNTs) composite photocatalysts (Ag/AgX-CNTs) were fabricated for the first time via a facile ultrasonic assistant deposition-precipitation method at the room temperature (25 ± 1 °C). X-ray diffraction, X-ray photoelectron spectroscopy, nitrogen adsorption-desorption analysis, scanning electron microscopy, and ultraviolet-visible light absorption spectra analysis were used to characterize the structure, morphology, and optical properties of the as-prepared photocatalysts. Results confirmed the existence of the direct interfacial contact between Ag/AgX nanoparticles and CNTs, and Ag/AgX-CNTs nanocomposites exhibit superior absorbance in the visible light (VL) region owing to the surface plasmon resonance (SPR) of Ag nanoparticles. The fabricated composite photocatalysts were employed to remove 2,4,6-tribromophenol (TBP) in aqueous phase. A remarkably enhanced VL photocatalytic degradation efficiency of Ag/AgX-CNTs nanocomposites was observed when compared to that of pure AgX or CNTs. The photocatalytic activity enhancement of Ag/AgX-CNTs was due to the effective electron transfer from photoexcited AgX and plasmon-excited Ag(0) nanoparticles to CNTs. This can effectively decrease the recombination of electron-hole pairs, lead to a prolonged lifetime of the photoholes that promotes the degradation efficiency.

Preparation of 80Br or 82Br-biomolecules via excitation labelling methods

International Nuclear Information System (INIS)

Wong, S.; Ache, H.J.

1975-01-01

The direct decay-induced 82 Br (or 80 Br) labelling by exposing the solid substrate molecules, such as deoxyuridine, L-tyrosine, guanosine, deoxycytidine, phenylalanine, and acetic acid, to gaseous CF 3 82 /sup m/Br (or CF 3 80 /sup m/Br) was studied. The radiochemical yields of the brominated products are relatively small and range from 1 percent in the case of bromo deoxyuridine to 11 percent for bromoacetic acid. The modification of this technique by adding Cl 2 gas to the reaction mixture improves the yields in several cases drastically (up to 80 percent for bromo-guanosine and bromo-L-tyrosine). Similar improvement can be achieved by exposing crystalline KBrO 3 for some time to CF 3 82 /sup m/Br (or CF 3 80 /sup m/Br) and dissolving subsequently the KBrO 3 in an acidic solution of the substrate. (auth)

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

Science.gov (United States)

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.

Postsynthetic Doping of MnCl2 Molecules into Preformed CsPbBr3 Perovskite Nanocrystals via a Halide Exchange-Driven Cation Exchange.

Science.gov (United States)

Huang, Guangguang; Wang, Chunlei; Xu, Shuhong; Zong, Shenfei; Lu, Ju; Wang, Zhuyuan; Lu, Changgui; Cui, Yiping

2017-08-01

Unlike widely used postsynthetic halide exchange for CsPbX 3 (X is halide) perovskite nanocrystals (NCs), cation exchange of Pb is of a great challenge due to the rigid nature of the Pb cationic sublattice. Actually, cation exchange has more potential for rendering NCs with peculiar properties. Herein, a novel halide exchange-driven cation exchange (HEDCE) strategy is developed to prepare dually emitting Mn-doped CsPb(Cl/Br) 3 NCs via postsynthetic replacement of partial Pb in preformed perovskite NCs. The basic idea for HEDCE is that the partial cation exchange of Pb by Mn has a large probability to occur as a concomitant result for opening the rigid halide octahedron structure around Pb during halide exchange. Compared to traditional ionic exchange, HEDCE is featured by proceeding of halide exchange and cation exchange at the same time and lattice site. The time and space requirements make only MnCl 2 molecules (rather than mixture of Mn and Cl ions) capable of doping into perovskite NCs. This special molecular doping nature results in a series of unusual phenomenon, including long reaction time, core-shell structured mid states with triple emission bands, and dopant molecules composition-dependent doping process. As-prepared dual-emitting Mn-doped CsPb(Cl/Br) 3 NCs are available for ratiometric temperature sensing. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

Science.gov (United States)

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…

Interacting spin-1/2 tetrahedral system Cu2Te2O5X2 (X = Cl, Br)

DEFF Research Database (Denmark)

Jensen, Jens

2009-01-01

Magnetic ordering and excitations of Cu2Te2O5Cl2 are analyzed in terms of a tetramerized spin model for the tetrahedral Cu clusters of spin 1/2. The mean-field model is able to account for the main properties of the incommensurable magnetic structure observed by Zaharko et al. [Phys. Rev. B 73......-dimensional fashion. Preliminary model calculations for the Cu2Te2O5Br2 system lead to the same conclusion. Udgivelsesdato: 7. Januar...

<i>Entre Casandra y Clío:> A propósito del pasado, el presente y el futuro de la filosofía de la historia

Directory of Open Access Journals (Sweden)

Moro Abadía, Óscar

2006-12-01

Full Text Available Taking the publication of the second edition of Concha Roldan’s <i>Entre Casandra y Clío> as reference, this article analyses the philosophy of history from the perspectives of the past, the present and the future. First, the paper examines the current disciplinary crisis in an effort to define the philosophy of history at the beginning of the twenty-first century. Second, the article considers the historical dimension of the debated scientific nature of historical knowledge and includes the current implications of this controversy. Third, the essay explores the ways in which the philosophy of history can play an ethical function.<br>>Tomando como referencia la publicación de la segunda edición del libro de Concha Roldán <i>Entre Casandra y Clío>, el presente artículo examina algunas cuestiones relacionadas con el pasado, el presente y el futuro de la filosofía de la historia. En primer lugar, se analiza la crisis actual que atraviesa la disciplina tratando de determinar cuál puede ser el sentido de la filosofía de la historia en el comienzo del siglo XXI. En segundo lugar, se pasa revista al debate a propósito del carácter científico del conocimiento histórico y se examinan sus implicaciones en la actualidad. En tercer lugar, se intenta determinar la función ética que puede desempeñar la filosofía de la historia.

Zn2(TeO3)Br2

Science.gov (United States)

Zhang, Dong; Johnsson, Mats

2008-01-01

Single crystals of dizinc tellurium dibromide trioxide, Zn2(TeO3)Br2, were synthesized via a transport reaction in sealed evacuated silica tubes. The compound has a layered crystal structure in which the building units are [ZnO4Br] distorted square pyramids, [ZnO2Br2] distorted tetra­hedra, and [TeO3 E] tetra­hedra (E being the 5s 2 lone pair of Te4+) joined through sharing of edges and corners to form layers of no net charge. Bromine atoms and tellurium lone pairs protrude from the surfaces of each layer towards adjacent layers. This new compound Zn2(TeO3)Br2 is isostructural with the synthetic compounds Zn2(TeO3)Cl2, CuZn(TeO3)2, Co2(TeO3)Br2 and the mineral sophiite, Zn2(SeO3)Cl2. PMID:21202162

What dictates which ion, I- or Br-, mediates the growth of cubic Pd nanocrystals?

Science.gov (United States)

Wang, Ze-Hong; Wu, Ya-Jiao; Xue, Huan-Huan; Zhou, Lin-Nan; Geng, Wen-Chao; Yi, Hai-Bo; Li, Yong-Jun

2018-04-25

Cubic Pd nanocrystals (CPNCs) as one of typical nanostructures are generally fabricated using I- or Br- as capping ions. However, which ion, I- or Br-, exclusively mediates the growth of CPNCs in a given reaction system is not well understood. Herein, regardless of I- or Br- as the capping ion, we successfully achieved CPNCs in the same reaction system simply by adjusting the pH. Based on the Finke-Watzky kinetic model, an increase in pH accelerates the overall reduction rate of Pd2+, and the formation of CPNCs only occurs over the range of specific solution reduction rate constants (k1). This kinetically illuminates that the reduction rate of Pd2+ is the physicochemical parameter that determines which ion, I- or Br-, dictates the growth of CPNCs. Also, density functional theory (DFT) calculations further elucidate the dependence of the reduction rate of Pd2+ on pH and the configuration of the activated Pd2+ complex.

Electrical properties and Raman studies of phase transitions in ferroelectric [N(CH3)4]2CoCl2Br2

Science.gov (United States)

Ben Mohamed, C.; Karoui, K.; Bulou, A.; Ben Rhaiem, A.

2018-03-01

The present paper accounted for the synthesis, electric properties and vibrational spectroscopy of [N(CH3)4]2CoCl2Br2. The dielectric spectra were measured in the frequency range 10-1-105 Hz and temperature interval from 223 to 393 K. The dielectical properties confirm the ferroelectric-paraelectric phase transition at 290 K, which is reported by Abdallah Ben Rhaiem et al. (2013). The equivalent circuit based on the Z-View-software was proposed and the conduction mechanisms were determined. The obtained results have been discussed in terms of the correlated barrier hopping model (CBH) in phase I and non-overlapping small polaron tunneling model (NSPT) in phases II and III. Raman spectra as function temperature have been used to characterize the phase transitions and their nature, which indicates a change of the some peak near the transitions phase.

Cs7Sm11[TeO3]12Cl16 and Rb7Nd11[TeO3]12Br16, the new tellurite halides of the tetragonal Rb6LiNd11[SeO3]12Cl16 structure type

Science.gov (United States)

Charkin, Dmitri O.; Black, Cameron; Downie, Lewis J.; Sklovsky, Dmitry E.; Berdonosov, Peter S.; Olenev, Andrei V.; Zhou, Wuzong; Lightfoot, Philip; Dolgikh, Valery A.

2015-12-01

Two new rare-earth - alkali - tellurium oxide halides were synthesized by a salt flux technique and characterized by single-crystal X-ray diffraction. The structures of the new compounds Cs7Sm11[TeO3]12Cl16 (I) and Rb7Nd11[TeO3]12Br16 (II) (both tetragonal, space group I4/mcm) correspond to the sequence of [MLn11(TeO3)12] and [M6X16] layers and bear very strong similarities to those of known selenite analogs. We discuss the trends in similarities and differences in compositions and structural details between the Se and Te compounds; more members of the family are predicted.

Vibrational spectroscopic and theoretical study of 3,5-dimethyl-1-thiocarboxamide pyrazole (L) and the complexes Co2L2Cl4, Cu2L2Cl4 and Cu2L2Br2

International Nuclear Information System (INIS)

Nemcsok, Denes; Kovacs, Attila; Szecsenyi, Katalin Meszaros; Leovac, Vukadin M.

2006-01-01

In the present paper we report a joint experimental and theoretical study of 3,5-dimethyl-1-thiocarboxamide pyrazole (L) and its complexes Co 2 L 2 Cl 4 , Cu 2 L 2 Cl 4 and Cu 2 L 2 Br 2 . DFT computations were used to model the structural and bonding properties of the title compounds as well as to derive a reliable force field for the normal coordinate analysis of L. The computations indicated the importance of hydrogen bonding interactions in stabilising the global minimum structures on the potential energy surfaces. In contrast to the S-bridged binuclear Cu 2 L 2 Br 2 complex found in the crystal, our computations predicted the formation of (CuLBr) 2 dimers in the isolated state stabilized by very strong (53 kJ/mol) N-H...Br hydrogen bonding interactions. On the basis of FT-IR and FT-Raman experiments and the DFT-derived scaled quantum mechanical force field we carried out a complete normal coordinate analysis of L. The FT-IR spectra of the three complexes were interpreted using the present assignment of L, literature data and computed results

Quantum state-to-state dynamics for the quenching process of Br(2P1/2) + H2(v(i) = 0, 1, j(i) = 0).

Science.gov (United States)

Xie, Changjian; Jiang, Bin; Xie, Daiqian; Sun, Zhigang

2012-03-21

Quantum state-to-state dynamics for the quenching process Br((2)P(1/2)) + H(2)(v(i) = 0, 1, j(i) = 0) → Br((2)P(3/2)) + H(2)(v(f), j(f)) has been studied based on two-state model on the recent coupled potential energy surfaces. It was found that the quenching probabilities have some oscillatory structures due to the interference of reflected flux in the Br((2)P(1/2)) + H(2) and Br((2)P(3/2)) + H(2) channels by repulsive potential in the near-resonant electronic-to-vibrational energy transfer process. The final vibrational state resolved integral cross sections were found to be dominated by the quenching process Br((2)P(1/2)) + H(2)(v) → Br((2)P(3/2)) + H(2)(v+1) and the nonadiabatic reaction probabilities for Br((2)P(1/2)) + H(2)(v = 0, 1, j(i) = 0) are quite small, which are consistent with previous theoretical and experimental results. Our calculated total quenching rate constant for Br((2)P(1/2)) + H(2)(v(i) = 0, j(i) = 0) at room temperature is in good agreement with the available experimental data. © 2012 American Institute of Physics

NMR espectroscopic parameters of HX and Si (Sn)X4 (X = H, F, Cl, Br and I) and SnBr4−nIn model compounds

International Nuclear Information System (INIS)

Maldonado, Alejandro F.; Gimenez, Carlos A.; Aucar, Gustavo A.

2012-01-01

Graphical abstract: Optimized fully relativistic calculations of NMR J-couplings (HBr, HI), chemical shifts (Si, Sn) and absolute shielding for reference compounds of heavy atoms (Si, Sn) are given. Highlights: ► In this article we show a procedure to get accurate NMR σ Ref of Si and Sn. ► Calculations of σ on more than three heavy-atom-containing molecules are given. ► Our results are closer to δ exp than previous calculations for SnX 4 (X = H, Cl, Br, I). ► Optimized basis sets were considered for full R and NR calculations of NMR J and σ. ► Relativistic effects enlarge electron correlation effects on J-couplings. - Abstract: The NMR spectroscopic parameters are largely influenced by relativistic effects. They are highly dependent on the electronic behavior inside the spatial regions occupied by nuclei. Full relativistic calculations of indirect nuclear spin–spin couplings at random phase level of approach (RPA) in the title compounds with reoptimized Dyall cVTZ basis sets are given. A comparison with the results of calculations with other basis sets that are mostly used within the non-relativistic (NR) domain is presented. We analyzed the dependence of that couplings with the speed of light over the whole range of values, from the full relativistic to the NR regimes. Within this last regime, calculations at the second-order level of approach (SOPPA) indicated that electron correlation effects may not be as important for nuclear magnetic shieldings, but they must be included with care for J-coupling calculations. From these calculations, we determined that relativity enlarges the electron correlation effects of the J-couplings of HBr and HI. Because the results of nuclear magnetic shielding calculations within polarization propagators at the RPA level were reliable, we were able to show a new and easy procedure to obtain absolute nuclear magnetic shieldings on reference compounds for both Si and Sn nuclei: σ[Si (CH 3 ) 4 ] = 421.28 ± 29.33 ppm

On the electronic structure and thermoelectric properties of BiTeBr and BiTeI single crystals and of BiTeI with the addition of BiI3 and CuI

International Nuclear Information System (INIS)

Kulbachinskii, Vladimir A.; Kytin, Vladimir G.; Kudryashov, Alexey A.; Kuznetsov, Alexei N.; Shevelkov, Andrei V.

2012-01-01

The electronic structures were calculated for BiTeBr and BiTeI using the density-functional theory approach and accounting for the strong spin–orbital interaction. Qualitatively, the band structures for two compounds are similar, showing strong mixing of the p states of all elements in vicinity of the Fermi level, with the band gaps of 0.595 and 0.478 eV for BiTeBr and BiTeI, respectively. The optimized crystal structures show a tendency for the Bi–X (X=Br, I) bond elongation compared to the Bi–Te one. Both compounds are intrinsic n-type semiconductors but display a metallic-like conductivity coupled to rather large thermopower, which is rationalized within the frames of the acoustic phonons scattering model. Because of larger thermopower BiTeBr exhibits a twice higher thermoelectric figure-of-merit near room temperature, ZT=0.17, compared to BiTeI. The addition of 1 mass% of BiI 3 or CuI to BiTeI decreases the mobility of electrons by two orders of magnitude, leading to significantly lower electrical conductivity, but at the same time effectively reduces the thermal conductivity. The prospects of further enhancing the thermoelectric efficiency are briefly discussed. - Graphical abstract: View of the crystal structure of BiTeBr is shown in the figure The optimized crystal structures show a tendency for the Bi–X (X=Br, I) bond elongation compared to the Bi–Te one. The electronic structures were calculated for BiTeBr and BiTeI using the density-functional theory approach and accounting for the strong spin–orbital interaction. Qualitatively, the band structures for two compounds are similar, showing strong mixing of the p states of all elements in vicinity of the Fermi level, with the band gaps of 0.595 and 0.478 eV for BiTeBr and BiTeI, respectively. Both compounds are intrinsic n-type semiconductors but display a metallic-like conductivity coupled to rather large thermopower, which is rationalized within the frames of the acoustic phonons scattering

Corrosion and inhibition of stainless steel pitting corrosion in alkaline medium and the effect of Cl- and Br- anions

International Nuclear Information System (INIS)

Refaey, S.A.M.; Taha, F.; El-Malak, A.M. Abd

2005-01-01

The effect of carbonate anion on the pitting corrosion and inhibition behavior of stainless steel samples (304L SS and 316L SS) has been studied using potentiodynamic and scanning electron microscope (SEM) techniques. The effect of concentration of CO 3 2- ions, pH, potential scanning rate and the composition of stainless steel are discussed. Additions of Cl - and Br - ions into the carbonate solution increase the anodic dissolution of stainless steel and decrease its pitting corrosion resistance. The effect of CO 3 2- anion on the inhibition of chloride and bromide pitting corrosion of the two stainless steel types has been studied also. Pitting corrosion decrease with the increasing of sodium carbonate concentration, i.e. increases the resistance of stainless steels towards the chloride and bromide pitting corrosion. This inhibition effect argued to formation of [Fe,Cr]CO 3 film caused by preferential adsorption of the CO 3 2- ion, leading to instantaneous repair of weak sites for pit nucleation

Ammonia Uptake and Release in the MnX2–NH3 (X = Cl, Br Systems and Structure of the Mn(NH3nX2 (n = 6, 2 Ammines

Directory of Open Access Journals (Sweden)

Duncan H. Gregory

2012-04-01

Full Text Available Hexa-ammine complexes, Mn(NH36X2 (X = Cl, Br, have been synthesized by ammoniation of the corresponding transition metal halide and characterized by Powder X-ray diffraction (PXRD and Raman spectroscopy. The hexa-ammine complexes are isostructural (Cubic, Fm-3m, Z = 4; a = 10.2742(6 Å and 10.527(1 Å for X = Cl, Br respectively. Temperature programmed desorption (TPD demonstrated that ammonia release from Mn(NH36X2 complexes occurred in three stages corresponding to the release of 4, 1 and 1 NH3 equivalents respectively. The chloride and bromide both exhibit a deammoniation onset temperature below 323 K. The di-ammoniates from the first desorption step were isolated during TPD measurements and their crystal structures determined by Rietveld refinement against PXRD data (X = Cl: orthorhombic Cmmm, a = 8.1991(9 Å, b = 8.2498(7 Å, c = 3.8212(4 Å, Z = 2; X = Br: orthorhombic Pbam, a = 6.0109(5 Å, b = 12.022(1 Å, c = 4.0230(2 Å, Z = 2.

Elimination of nonspecific radioactivity from [76Br]bromide in PET study with [76Br]bromodeoxyuridine

International Nuclear Information System (INIS)

Li Lu; Bergstroem, Mats; Fasth, Karl-Johan; Wu Feng; Eriksson, Barbro; Laangstroem, Bengt

1999-01-01

[ 76 Br]Bromodeoxyuridine ([ 76 Br]BrdU) might allow a determination of proliferation in vivo using positron emission tomography (PET), but only with consideration of organ nonspecific radioactivity constituted by [ 76 Br]bromide. A first study assessed the potential of diuretics to eliminate [ 76 Br]bromide. [ 76 Br]Bromide was injected in the vein of rats and different diuretic combinations were given. Urine was collected and radioactivity measured. Torasemide plus sodium chloride gave better 76 Br elimination than the other diuretics. In a second experiment, rats were given [ 76 Br]BrdU. After the radioactivity injection, the rats of the treatment group were given torasemide plus NaCl. At 44 h after the radioactivity injection, the radioactivity concentration and the fraction incorporated into DNA were measured in different organs. Using diuretics, the elimination of [ 76 Br]bromide was increased. The radioactivity decreased 30-50% in most of the organs but the highest radioactivity uptake was found in the organs with more active DNA synthesis. This method may facilitate the use of [ 76 Br]BrdU as a tracer for DNA synthesis using PET

Addition reaction of adamantylideneadamantane with Br2 and 2Br2: a computational study.

Science.gov (United States)

Islam, Shahidul M; Poirier, Raymond A

2008-01-10

Ab initio calculations were carried out for the reaction of adamantylideneadamantane (Ad=Ad) with Br2 and 2Br2. Geometries of the reactants, transition states, intermediates, and products were optimized at HF and B3LYP levels of theory using the 6-31G(d) basis set. Energies were also obtained using single point calculations at the MP2/6-31G(d)//HF/6-31G(d), MP2/6-31G(d)//B3LYP/6-31G(d), and B3LYP/6-31+G(d)//B3LYP/6-31G(d) levels of theory. Intrinsic reaction coordinate (IRC) calculations were performed to characterize the transition states on the potential energy surface. Only one pathway was found for the reaction of Ad=Ad with one Br2 producing a bromonium/bromide ion pair. Three mechanisms for the reaction of Ad=Ad with 2Br2 were found, leading to three different structural forms of the bromonium/Br3- ion pair. Activation energies, free energies, and enthalpies of activation along with the relative stability of products for each reaction pathway were calculated. The reaction of Ad=Ad with 2Br2 was strongly favored over the reaction with only one Br2. According to B3LYP/6-31G(d) and single point calculations at MP2, the most stable bromonium/Br3- ion pair would form spontaneously. The most stable of the three bromonium/Br3- ion pairs has a structure very similar to the observed X-ray structure. Free energies of activation and relative stabilities of reactants and products in CCl4 and CH2ClCH2Cl were also calculated with PCM using the united atom (UA0) cavity model and, in general, results similar to the gas phase were obtained. An optimized structure for the trans-1,2-dibromo product was also found at all levels of theory both in gas phase and in solution, but no transition state leading to the trans-1,2-dibromo product was obtained.

81Br, 37Cl, and 87Sr studies to assess groundwater flow and solute sources in the southwestern Great Artesian Basin, Australia

International Nuclear Information System (INIS)

Gwynne, Rhys; Frape, Shaun; Shouakar-Stash, Orfan; Love, Andy

2013-01-01

The Great Artesian Basin (GAB) is a water source for more than 200,000 residents in central Australia. This study investigates the relationship of bromine and chlorine stable isotopes to groundwater chemistry in a confined aquifer in the southwestern GAB to better understand its flow regime and solute sources. δ 81 Br values range from +0.660/00 near the recharge area to +1.04 0/00, 150 km down gradient, while δ 37 Cl ranges from 00/00 to -2.50/00. While δ 37 Cl decreases with distance from the recharge area, δ 81 Br increases slightly. Bromide in the recharge area is possibly enriched from selective atmospheric processes causing fractionation in marine aerosols during transport. When confined and isolated from the atmosphere, increases in bromide and to a lesser extent strontium concentrations may contribute through water-rock interaction to changes in isotopic signatures along the flow system. 87 Sr/ 86 Sr values range from ∼0.717 near the recharge zone to a depleted 0.708 160 km down gradient. (authors)

Core-dependent and ligand-dependent relativistic corrections to the nuclear magnetic shieldings in MH4-n Y n (n = 0-4; M = Si, Ge, Sn, and Y = H, F, Cl, Br, I) model compounds.

Science.gov (United States)

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

2014-09-01

The nuclear magnetic shieldings of Si, Ge, and Sn in MH(4-n) Y(n) (M = Si, Ge, Sn; Y = F, Cl, Br, I and n = 1-4) molecular systems are highly influenced by the substitution of one or more hydrogens by heavy-halogen atoms. We applied the linear response elimination of small components (LRESC) formalism to calculate those shieldings and learn whether including only a few of the leading relativistic correction terms is sufficient to be able to quantitatively reproduce the full relativistic value. It was observed that the nuclear magnetic shieldings change as the number of heavy halogen substituents and their weights vary, and the pattern of σ(M) generally does not exhibit the normal halogen dependence (NHD) behavior that can be seen in similar molecular systems containing carbon atoms. We also analyzed each relativistic correction afforded by the LRESC method and split them in two: core-dependent and ligand-dependent contributions; we then looked for the electronic mechanisms involved in the different relativistic effects and in the total relativistic value. Based on this analysis, we were able to study the electronic mechanism involved in a recently proposed relativistic effect, the "heavy atom effect on vicinal heavy atom" (HAVHA), in more detail. We found that the main electronic mechanism is the spin-orbit or σ p (T(3)) correction, although other corrections such as σ p (S(1)) and σ p (S(3)) are also important. Finally, we analyzed proton magnetic shieldings and found that, for molecules containing Sn as the central atom, σ(H) decreases as the number of heavy halogen substituents (of the same type: either F, Cl, or Br) increases, albeit at different rates for different halogens. σ(H) only increase as the number of halogen substituents increases if the halogen is iodine.

Structure and luminescence of α and β ThBr4: optical properties of U4+ in α ThBr4

International Nuclear Information System (INIS)

Simoni, E.

1988-05-01

The aim of this work is to understand the comparative structural and intrinsic luminescence properties of the pure matrices α and β - ThBr 4 , and to study the electronic structure by optical spectroscopy of the U 4+ ion in the α-ThBr 4 matrix. 1)Under U.V. excitation, βThBr 4 is intensively fluorescent in the blue-purple and α-ThBr 4 is fluorescent in the red. The main results concerning β-ThBr 4 are the following: -the optical absorption in the U.V. is under the form of a sudden absorption front and for a same temperature, its threshold energy has the same value as the threshold energy of the excitation function and of the photocurrent peak; -the intensity and the life time of the emission decrease when the temperature increases from 300 K until 400 K ( extinction temperature). All the obtained results have been explained either with the molecular orbitals levels of the ThBr 8 4- cluster or with the valence and conduction bands of the pure matrix. 2)The absorption and emission spectra of U 4+ in α-ThBr 4 (in which U 4+ has a point symmetry S 4 ) obtained between 300 K and 4.2 K have allowed to index 30 levels. The calculation of the spectroscopic parameters F k , ξ and B k q has been carried out in symmetry D 2d and S 4 . The comparison of these parameters with those calculated for U 4+ in β-ThBr 4 and β-ThCl 4 show that the global force of the crystalline field is practically the same in the three matrices, but that the structure transformation β→α occurs more on the values of these B k q than on the change of the ligands Br - →Cl - . On the other hand, it has been possible with the α-ThBr 4 matrix, or the β-ThBr 4 and the β-ThCl 4 , to observe the fluorescence spectra of the U 4+ ion (particularly weak phonons energies). (O.M.)

$\\beta$-delayed neutrons from oriented $^{137,139}$I and $^{87,89}$Br nuclei

CERN Multimedia

We propose a world-first measurement of the angular distribution of $\\beta$‐delayed n and $\\gamma$-radiation from oriented $^{137, 139}$I and $^{87,89}$Br nuclei, polarised at low temperature at the NICOLE facility. $\\beta$­-delayed neutron emission is an increasingly important decay mechanism as the drip line is approached and its detailed understanding is essential to phenomena as fundamental as the r‐process and practical as the safe operation of nuclear power reactors. The experiments offer sensitive tests of theoretical input concerning the allowed and first­‐forbidden $\\beta$‐decay strength, the spin-density of neutron emitting states and the partial wave barrier penetration as a function of nuclear deformation. In $^{137}$I and $^{87}$Br the decay feeds predominantly the ground state of the daughters $^{136}$Xe and $^{86}$Kr whereas in $^{139}$I and $^{89}$Br we will explore the use of n-$\\gamma$- coincidence to study neutron transitions to the first and second excited states in the daughters...

Luminescent manganese-doped CsPbCl3 perovskite quantum dots

NARCIS (Netherlands)

Lin, Chun Che; Xu, Kun Yuan; Wang, Da; Meijerink, A|info:eu-repo/dai/nl/075044986

2017-01-01

Nanocrystalline cesium lead halide perovskites (CsPbX3, X = Cl, Br, and I) form an exciting new class of semiconductor materials showing quantum confinement. The emission color can be tuned over the full visible spectral region making them promising for light‒emitting applications. Further control

Influence of the Li···π Interaction on the H/X···π Interactions in HOLi···C6H6···HOX/XOH (X=F, Cl, Br, I) complexes.

Science.gov (United States)

Zeng, Yanli; Wu, Wenjie; Li, Xiaoyan; Zheng, Shijun; Meng, Lingpeng

2013-06-03

The influences of the Li···π interaction of C6H6···LiOH on the H···π interaction of C6H6···HOX (X=F, Cl, Br, I) and the X···π interaction of C6H6···XOH (X=Cl, Br, I) are investigated by means of full electronic second-order Møller-Plesset perturbation theory calculations and "quantum theory of atoms in molecules" (QTAIM) studies. The binding energies, binding distances, infrared vibrational frequencies, and electron densities at the bond critical points (BCPs) of the hydrogen bonds and halogen bonds prove that the addition of the Li···π interaction to benzene weakens the H···π and X···π interactions. The influences of the Li···π interaction on H···π interactions are greater than those on X···π interactions; the influences of the H···π interactions on the Li···π interaction are greater than X···π interactions on Li···π interaction. The greater the influence of Li···π interaction on H/X···π interactions, the greater the influences of H/X···π interactions on Li···π interaction. QTAIM studies show that the intermolecular interactions of C6H6···HOX and C6H6···XOH are mainly of the π type. The electron densities at the BCPs of hydrogen bonds and halogen bonds decrease on going from bimolecular complexes to termolecular complexes, and the π-electron densities at the BCPs show the same pattern. Natural bond orbital analyses show that the Li···π interaction reduces electron transfer from C6 H6 to HOX and XOH. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Reactions of N2O5 with Salty and Surfactant-Coated Glycerol: Interfacial Conversion of Br- to Br2 Mediated by Alkylammonium Cations.

Science.gov (United States)

Shaloski, Michael A; Gord, Joseph R; Staudt, Sean; Quinn, Sarah L; Bertram, Timothy H; Nathanson, Gilbert M

2017-05-18

Gas-liquid scattering and product-yield experiments are used to investigate reactions of N 2 O 5 with glycerol containing Br - and surfactant ions. N 2 O 5 oxidizes Br - to Br 2 for every solution tested: 2.7 M NaBr, 0.03 M tetrahexylammonium bromide (THABr), 0.03 M THABr + 0.5 M NaBr, 0.03 M THABr + 0.5 M NaCl, 0.03 M THABr + 0.01 M sodium dodecyl sulfate (SDS), and 0.01 M cetyltrimethylammonium bromide (CTABr). N 2 O 5 also reacts with glycerol itself to produce mono- and dinitroglycerin. Surface tension measurements indicate that 0.03 M THABr and 2.7 M NaBr have similar interfacial Br - concentrations, though their bulk Br - concentrations differ by 90-fold. We find that twice as much Br 2 is produced in the presence of THA + , implying that the conversion of Br - to Br 2 is initiated at the interface, perhaps mediated by the charged, hydrophobic pocket within the surface THA + cation. The addition of 0.5 M NaBr, 0.5 M NaCl, or 0.01 M SDS to 0.03 M THABr lowers the Br 2 production rate by 23%, 63%, and 67% of the THABr value, respectively. When CTA + is substituted for THA + , Br 2 production drops to 12% of the THABr value. The generation of Br 2 under such different conditions implies that trace amounts of surface-active alkylammonium ions can catalyze interfacial N 2 O 5 reactions, even when salts and other surfactants are present.

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

Science.gov (United States)

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).

Resonance dielectric dispersion of TEA-CoCl2Br2 nanocrystals incorporated into the PMMA matrix

Science.gov (United States)

Kapustianyk, V.; Shchur, Ya; Kityk, I.; Rudyk, V.; Lach, G.; Laskowski, L.; Tkaczyk, S.; Swiatek, J.; Davydov, V.

2008-09-01

The dielectric properties of TEA-CoCl2Br2 nanocrystals incorporated into the polymethylmethacrylate matrix within the frequency range of 3 × 105-2.6 × 109 Hz in the temperature region of 90-300 K were investigated. The considerable difference in the dielectric spectra of the nanocomposite compared to those of the bulk crystal and the pure polymer matrix was observed. The dielectric dispersion of the composite material reveals a resonance type (resonance frequency was found to be near 1.3 GHz) and may be qualitatively explained as the result of piezoelectric resonance on the nanocrystals. The model interpretation of this phenomenon based on the forced-dumped oscillator is presented.

Sinteza i fizičko-hemijske karakteristike eksploziva hniw (cl-20)

OpenAIRE

Mirjana Anđelković-Lukić

2009-01-01

Novo jedinjenje CL-20 je ciklični nitramin sa najvećom kristalnom gustinom (iznad 2,0 g/cm3) i najsnažniji nenuklearni eksploziv. Opisana je sinteza HNIW ili CL-20 u tri stepena. CL-20 ima najveću gustinu i brzinu detonacije među poznatim eksplozivima, kao i najveću energiju među energetskim dodacima koji se koriste kao dodaci za eksplozive, barute i kompozitna raketna goriva. Prikazani su neki sastavi na bazi CL-20, energetskih polimera, aluminijuma i amonijumperhlorata, ka...

Superconductivity in intercalated and substituted Y2Br2C2

International Nuclear Information System (INIS)

Baecker, M.; Simon, A.; Kremer, R.K.; Mattausch, H.J.; Dronskowski, R.; Rouxel, J.

1996-01-01

Layer compounds of the type Y 2 X 2 C 2 (X=Cl, Br, I) show superconductivity at temperatures between 2.3 and 11.2 K. The transition temperature is related to the tendency of conduction electrons toward pairwise localization in C 2 -π * states at the Fermi level, and changes with the concentration of valence electrons, which is varied by intercalation of Na. (orig.)

Fluorescence Blinking and Photoactivation of All-Inorganic Perovskite Nanocrystals CsPbBr3 and CsPbBr2I.

Science.gov (United States)

Seth, Sudipta; Mondal, Navendu; Patra, Satyajit; Samanta, Anunay

2016-01-21

Study of the emission behavior of all-inorganic perovskite nanocrystals CsPbBr3 and CsPbBr2I as a function of the excitation power employing fluorescence correlation spectroscopy and conventional techniques reveals fluorescence blinking in the microsecond time scale and photoinduced emission enhancement. The observation provides insight into the radiative and nonradiative deactivation pathways of these promising substances. Because both blinking and photoactivation processes are intimately linked to the charge separation efficiency and dynamics of the nanocrystals, these key findings are likely to be helpful in realizing the true potential of these substances in photovoltaic and optoelectronic applications.

$\\beta$-delayed neutrons from oriented $^{137,139}$I and $^{87,89}$Br nuclei

CERN Document Server

Grzywacz, Robert; Stone, Nicholas; Köster, Ulli; Singh, Barlaj; Bingham, Carrol; Gaulard, S; Kolos, Karolina; Madurga, Miguel; Nikolov, J; Otsubo, T; Roccia, S; Veskovic, Miroslav; Walker, Phil; Walters, William

2013-01-01

We propose a world-­‐first measurement of the angular distribution of $\\beta$-­‐delayed n and $\\gamma$- radiation from oriented $^{137, 139}$I and $^{87,89}$Br nuclei, polarised at low temperature at the NICOLE facility. $\\beta$-­‐delayed neutron emission is an increasingly important decay mechanism as the drip line is approached and its detailed understanding is essential to phenomena as fundamental as the r‐process and practical as the safe operation of nuclear power reactors. The experiments offer sensitive tests of theoretical input concerning the allowed and first-­‐forbidden $\\beta$‐decay strength, the spin-­‐density of neutron emitting states and the partial wave barrier penetration as a function of nuclear deformation. In $^{137}$I and $^{87}$Br the decay feeds predominantly the ground state of the daughters $^{136}$Xe and $^{86}$Kr whereas in $^{139}$I and $^{89}$Br we will explore the use of n-$\\gamma$- coincidence to study neutron transitions to the first and second excited state...

An ab initio study on BeX 3- superhalogen anions (X = F, Cl, Br)

Science.gov (United States)

Anusiewicz, Iwona; Skurski, Piotr

2002-06-01

The vertical electron detachment energies (VDE) of 10 BeX 3- (X = F, Cl, Br) anions were calculated at the outer valence Green function (OVGF) level with the 6-311++G(3df) basis sets. The largest vertical electron binding energy was found for BeF 3- system (7.63 eV). All negatively charged species possess the vertical electron detachment energies that are larger than 5.5 eV and thus may be termed superhalogen anions. The strong dependence of the VDE of the BeX 3- species on the ligand-central atom (Be-X) distance and on the partial atomic charge localized on Be was observed and discussed, as well as the other factors that may influence the electronic stability of such anions. In addition, the usefulness of the various theoretical treatments for estimating the VDEs of superhalogen anions was tested and analyzed.

73Ge, 119Sn and 207Pb: general cooperative effects of single atom ligands on the NMR signals observed in tetrahedral [MXnY4-n] (M = Ge, Sn, Pb; 1 ≤ n ≤ 4; X, Y = Cl, Br, I) coordination compounds of heavier XIV group elements.

Science.gov (United States)

Benedetti, M; De Castro, F; Fanizzi, F P

2017-02-28

An inverse linear relationship between 73 Ge, 119 Sn and 207 Pb NMR chemical shifts and the overall sum of ionic radii of coordinated halido ligands has been discovered in tetrahedral [MX n Y 4-n ] (M = Ge, Sn, Pb; 1 ≤ n ≤ 4; X, Y = Cl, Br, I) coordination compounds. This finding is consistent with a previously reported correlation found in octahedral, pentacoordinate and square planar platinum complexes. The effect of the coordinated halido ligands acting on the metal as shielding conducting rings is therefore confirmed also by 73 Ge, 119 Sn and 207 Pb NMR spectroscopy.

The effect of age on Br, Ca, Cl, K, Mg, Mn, and Na mass fraction in pediatric and young adult prostate glands investigated by neutron activation analysis

International Nuclear Information System (INIS)

Zaichick, Vladimir; Zaichick, Sofia

2013-01-01

The effect of age on chemical element mass fractions in intact prostate of 50 apparently healthy 0–30 year old males was investigated by neutron activation analysis with high resolution spectrometry of short-lived radionuclides. Mean values (M±SΕΜ) for mass fraction (mg kg −1 , dry mass basis) of chemical elements before the time of puberty and in the period of puberty and post-puberty were: Br 46.0±6.7, Ca 1151±140, Cl 14572±700, K 10147±700, Mg 771±131, Mn 2.13±0.25, Na 9880±659 and Br 29.0±4.6, Ca 2049±364, Cl 11518±1121, K 13029±542, Mg 1186±134, Mn 1.74±0.16, Na 9887±716, respectively. A tendency of age-related increase in Ca, K, and Mg mass fraction and of age-related decrease in Br mass fraction was observed in period of life from 0 to 30 years. This new data indicates that of the elements studied, only the Ca, K, and Mg mass fraction in prostate tissue is an androgen-dependent parameter

Sinteza i fizičko-hemijske karakteristike eksploziva HNIW (CL-20) / Synthesis and physicochemical properties of the HNIW (CL-20) explosive

OpenAIRE

Mirjana Lukić-Anđelković

2009-01-01

Novo jedinjenje CL-20 je ciklični nitramin sa najvećom kristalnom gustinom (iznad 2,0 g/cm3) i najsnažniji nenuklearni eksploziv. Opisana je sinteza HNIW ili CL-20 u tri stepena. CL-20 ima najveću gustinu i brzinu detonacije među poznatim eksplozivima, kao i najveću energiju među energetskim dodacima koji se koriste kao dodaci za eksplozive, barute i kompozitna raketna goriva. Prikazani su neki sastavi na bazi CL-20, energetskih polimera, aluminijuma i amonijumperhlorata, kao i gustine i brzi...

Structural and thermodynamic characteristics of X2MYH2 compounds (M Al, Ga, In; X = F, Cl, Br, I; Y = N, P, As) - the products of hydrohalogen elimination from X3MYH3 donor-acceptor complexes

International Nuclear Information System (INIS)

Timoshkin, A.Yu.; Suvorov, A.V.; Shefer, G.F.

2001-01-01

Geometrical and thermodynamic characteristics of complexes X 2 MYH 2 (M Al, Ga, In; X = F, Cl, Br, I; Y = N, P, As) were obtained by the method of density functional B3LYP. It is shown that nitrogen complexes X 2 MNH 2 have a plane structure, whereas phosphorus and arsenic complexes are pyramidal. In the process of HX elimination the dissociation energy of M-Y bond is strengthened essentially (by 150-270 kJ/mol), which makes dissociation of X 2 MYH 2 into components quite inefficient from thermodynamic viewpoint even at temperatures of about 1000 deg C. Dimerization enthalpies of X 2 MYH 2 lie in the range 40 (Y = P, As) - 260 (Y=N) kJ/mol. Thus, dimers [X 2 MNH 2 ] 2 can be intermediate products in the processes of nitrides chemical precipitation from gaseous phase of donor-acceptor complexes [ru

Cerium(IV) Tellurite Halides [Ce ₂ Te ₇ O ₁₇ ]X ₂ (X = Cl ^– or Br ^– ): The First Cerium-Containing Cationic Frameworks

Energy Technology Data Exchange (ETDEWEB)

Lin, Jian [Department of Civil; amp, Environmental Engineering & amp, Earth Sciences and Department of Chemistry and Biochemistry, University of Notre Dame, 156 Fitzpatrick Hall, Notre; Diwu, Juan [Department of Civil; amp, Environmental Engineering & amp, Earth Sciences and Department of Chemistry and Biochemistry, University of Notre Dame, 156 Fitzpatrick Hall, Notre; Cross, Justin N. [Department of Civil; amp, Environmental Engineering & amp, Earth Sciences and Department of Chemistry and Biochemistry, University of Notre Dame, 156 Fitzpatrick Hall, Notre; Villa, Eric M. [Department of Civil; amp, Environmental Engineering & amp, Earth Sciences and Department of Chemistry and Biochemistry, University of Notre Dame, 156 Fitzpatrick Hall, Notre; Albrecht-Schmitt, Thomas E. [Department of Chemistry

2012-09-13

Two isotypic cerium tellurite halides with the formulas [Ce2Te7O17]Cl2 and [Ce2Te7O17]Br2 have been synthesized hydrothermally via the reactions of CeCl3 and CeBr3 with TeO2. The structures of these compounds feature a cationic inorganic framework. The CeIV dimers are bound by a novel 3D Te7O176– building unit, forming an unusual hexagonal-bipyramidal environment around CeIV.

Fizičko-hemijske i detonacione karakteristike nitraminskih eksploziva - RDX, HMX i CL-20

OpenAIRE

Anđelković-Lukić Mirjana

2002-01-01

U radu su prikazane fizičko-hemijske i detonacione karakteristike nitraminskih brizantnih eksploziva, heksogena i oktogena, uporedene sa osobinama novog cikličnog nitraminskog eksploziva CL-20. Novi visokobrizantni eksploziv CL-20 postoji u četiri kristalne forme, stabilne na različitim temepraturama. Ima bolje detonacione karakteristike od heksogena i oktogena veću gustinu i brzinu detonacije, all mnogo veću osetljivost na udar i trenje, reda PETN. Zbog toga se ovaj eksploziv flegmatizuje sa...

Elimination of nonspecific radioactivity from [{sup 76}Br]bromide in PET study with [{sup 76}Br]bromodeoxyuridine

Energy Technology Data Exchange (ETDEWEB)

Li Lu; Bergstroem, Mats E-mail: Mats.Bergstroem@pet.uu.se; Fasth, Karl-Johan; Wu Feng; Eriksson, Barbro; Laangstroem, Bengt

1999-10-01

[{sup 76}Br]Bromodeoxyuridine ([{sup 76}Br]BrdU) might allow a determination of proliferation in vivo using positron emission tomography (PET), but only with consideration of organ nonspecific radioactivity constituted by [{sup 76}Br]bromide. A first study assessed the potential of diuretics to eliminate [{sup 76}Br]bromide. [{sup 76}Br]Bromide was injected in the vein of rats and different diuretic combinations were given. Urine was collected and radioactivity measured. Torasemide plus sodium chloride gave better {sup 76}Br elimination than the other diuretics. In a second experiment, rats were given [{sup 76}Br]BrdU. After the radioactivity injection, the rats of the treatment group were given torasemide plus NaCl. At 44 h after the radioactivity injection, the radioactivity concentration and the fraction incorporated into DNA were measured in different organs. Using diuretics, the elimination of [{sup 76}Br]bromide was increased. The radioactivity decreased 30-50% in most of the organs but the highest radioactivity uptake was found in the organs with more active DNA synthesis. This method may facilitate the use of [{sup 76}Br]BrdU as a tracer for DNA synthesis using PET.

Sinteza i fizičko-hemijske karakteristike eksploziva HNIW (CL-20 / Synthesis and physicochemical properties of the HNIW (CL-20 explosive

Directory of Open Access Journals (Sweden)

Mirjana Lukić-Anđelković

2009-04-01

Full Text Available Novo jedinjenje CL-20 je ciklični nitramin sa najvećom kristalnom gustinom (iznad 2,0 g/cm3 i najsnažniji nenuklearni eksploziv. Opisana je sinteza HNIW ili CL-20 u tri stepena. CL-20 ima najveću gustinu i brzinu detonacije među poznatim eksplozivima, kao i najveću energiju među energetskim dodacima koji se koriste kao dodaci za eksplozive, barute i kompozitna raketna goriva. Prikazani su neki sastavi na bazi CL-20, energetskih polimera, aluminijuma i amonijumperhlorata, kao i gustine i brzine njihove detonacije. / The new compound CL-20, a cyclic nitramine with the highest crystal density (over 2.0 g/cm3, is the most powerful non-nuclear explosive. The three-step synthesis of hexanitrohexaazaisowurtzitane (HNIW or CL-20 has been described. The CL-20 has the highest density and the highest detonation velocity among existing explosives as well as the highest energy among existing energetic ingredients for explosives, gun propellants and rocket propellants. Same explosive formulations based on the CL-20, energetic polymers, aluminium and ammoniumperchlorate are presented. Their densities and detonation velocities are also presented.

Fizičko-hemijske i detonacione karakteristike nitraminskih eksploziva - RDX, HMX i CL-20 / Physico-chemical and detonation properties of nitramine explosives: RDX, HMX and CL-20

Directory of Open Access Journals (Sweden)

Mirjana Anđelković-Lukić

2002-11-01

Full Text Available U radu su prikazane fizičko-hemijske i detonacione karakteristike nitraminskih brizantnih eksploziva, heksogena i oktogena, uporedene sa osobinama novog cikličnog nitraminskog eksploziva CL-20. Novi visokobrizantni eksploziv CL-20 postoji u četiri kristalne forme, stabilne na različitim temepraturama. Ima bolje detonacione karakteristike od heksogena i oktogena veću gustinu i brzinu detonacije, all mnogo veću osetljivost na udar i trenje, reda PETN. Zbog toga se ovaj eksploziv flegmatizuje sa polimerima etilenvinilacetatom (EVA i estanom. Da bi se povećale energetske performanse eksploziva i smanjila osetljivost na mehanička dejstva eksplozivu CL-20 dodaju se visokoenergetski materijali, fluoronitrojedinjenja (FEFO. / In this paper the physico-chemical and detonation properties of nitramine high explosives, hexogen and octogen, are presented and compared with a polycyclic nitramine high explosive CL-20. This new high explosive CL-20 exists in four crystalline forms, stable at different temperatures. CL-20 has better detonation properties than hexogen and octogen, higher density and detonation rate, but greater impact and friction sensitivity (of PETN class. So it is necessary to bond this explosive with polymers-ethylenvinil acetat (EVA and estane to reduce sensitivity to mechanical effects. CL-20 can be prepared by adding high energy materials-fluoro-nitro compounds (FEFO as regulators of energy performances.

Efficient blue emission from ambient processed all-inorganic CsPbBr2Cl perovskite cubes

Science.gov (United States)

Paul, T.; Chatterjee, B. K.; Maiti, S.; Besra, N.; Thakur, S.; Sarkar, S.; Chanda, K.; Das, A.; Sardar, K.; Chattopadhyay, K. K.

2018-04-01

The recent resurgence of photovoltaic research has empowered all inorganic perovskite materials to take the center stage thus leading to a plethora of interesting results. Here, via a facile room-temperature synthesis protocol high quality cesium lead halide perovskite (CsPbBr2Cl) cubes has been realized. Surface morphology and crystallinity of the synthesized sample were investigated by FESEM and XRD respectively. To attain detail information of its chemical composition EDX analysis and elemental mapping were carried out. These single crystalline cubes crystallize in orthorhombic phase and exhibit strong photoluminescence emission at 482 nm with narrow FWHM value (˜18nm) and photoluminescence decay time of 10.44 ns. We believe, this facile synthesis protocol will pave the way for realization other perovskite cube and thereby their usage in several optoelectronic arena like as lasing, LEDs and photo detector etc.

Density and adiabatic compressibility of the immiscible molten AgBr+LiCl mixture

Energy Technology Data Exchange (ETDEWEB)

Stepanov, Victor P. [Russian Academy of Sciences, Yekaterinburg (Russian Federation). Inst. of High-Temperature Electrochemistry; Ural Federal Univ., Yekaterinburg (Russian Federation); Kulik, Nina P. [Russian Academy of Sciences, Yekaterinburg (Russian Federation). Inst. of High-Temperature Electrochemistry

2017-07-01

The adiabatic compressibility, β, of the immiscible liquid mixture 0.52 LiCl+0.48 AgBr (the top of the miscibility gap) was experimentally investigated in the temperature range from the melting point to the critical mixing temperature using the sound velocity values, u, measured by the pulse method, and the density quantities, ρ, which were determined using the hydrostatic weight procedure based on the relationship β = u{sup -2}ρ{sup -1}. It is shown that the coefficients of the temperature dependencies for the compressibility and density of the upper and lower equilibrium phases have opposite signs because of the superposition of the intensity of the thermal motion of the ions and the change in the composition of the phases. The differences, Δβ and Δρ, in the magnitudes of the compressibility and density for the equilibrium phases decrease with temperature elevation. The temperature dependencies of the compressibility and density difference are described using the empirical equations Δβ ∼ (T{sub c}-T){sup 0.438} and Δρ ∼ (T{sub c}-T){sup 0.439}.

Design and operation of thermal-convection loops for corrosion measurements in LiF--LiCl--LiBr

International Nuclear Information System (INIS)

Keiser, J.R.; DeVan, J.H.

1979-01-01

Using a most sophisticated design of a thermal-convection loop to study the corrosion behavior of type 316 stainless steel and the salt mixture LiF--LiCl--LiBr is reported. The corrosion rate is being determined as a function of time and temperature through weight change measurements. The maximum corrosion rate measured is about 20 μm/year on removable corrosion specimens. Controlled potential voltammetry has been found to be satisfactory and is being used to monitor the oxidation potential of the salt. Measurements demonstrate the effect on the oxidation potential of impurities introduced during specimen insertion, and techniques should show the effect of a lithium addition on the oxidation potential

Solid state physics and actinide spectroscopy with ThBr4 and ThCl4

International Nuclear Information System (INIS)

Genet, M.

1984-01-01

From the solid state physics to the optical spectroscopy of 5 f elements, we have described in details how ThBr 4 and ThCl 4 are acting an important role in the applied and basic research field. The possible applications are based on the scintillation properties of these crystals while the fundamental aspect is related to their special incommensurate structure which modulates the host properties of these matrices at low temperature. This very small perturbation of bromine atom positions have optical consequences on the absorption and emission of the actinide studied ions which are interpreted in function of the modulated structure parameters determined by inelastic and elastic neutron scattering and by Raman spectroscopy. The structural model proposed shows, for the first time, how the optical properties of the investigated ion are influenced by the sinusoidal displacements of the bromine atoms, leading to an energy continuum in the absorption and reducing the site symmetry from Dsub(2d) to a multisite of D 2 symmetry

Comparison of partial structures of melts of superionic AgI and CuI and non-superionic AgCl

Energy Technology Data Exchange (ETDEWEB)

Kawakita, Yukinobu [Department of Physics, Faculty of Sciences, Kyushu University, 4-2-1 Ropponmatsu, Fukuoka 810-8560 (Japan); Tahara, Shuta [Department of Condensed Matter Chemistry and Physics, Graduate School of Sciences, Kyushu University, 4-2-1 Ropponmatsu, Chuo-ku, Fukuoka 810-8560 (Japan); Fujii, Hiroyuki [Department of Condensed Matter Chemistry and Physics, Graduate School of Sciences, Kyushu University, 4-2-1 Ropponmatsu, Chuo-ku, Fukuoka 810-8560 (Japan); Kohara, Shinji [Research and Utilization Division, Japan Synchrotron Radiation Research Institute (JASRI, SPring-8), 1-1-1 Koto, Sayo-cho, Sayo-gun, Hyogo 679-5198 (Japan); Takeda, Shin' ichi [Department of Physics, Faculty of Sciences, Kyushu University, 4-2-1 Ropponmatsu, Fukuoka 810-8560 (Japan)

2007-08-22

Neutron and high-energy x-ray diffraction analyses of molten AgI have been performed and the partial structures are discussed in detail with the aid of the structural modelling procedure of the reverse Monte Carlo (RMC) technique by comparison with those of molten CuI and AgCl. It is well known that AgI and CuI have a superionic solid phase below the melting point, in which the cations favour a tetrahedral configuration, while solid AgCl has a rock-salt structure with an octahedral environment around both Ag and Cl atoms. Even in the molten states, there is a significant difference between superionic and non-superionic melts. The cation is located on the triangular plain formed by three iodine ions in molten AgCl and CuI, while molten AgCl favours a 90 deg. Cl-Ag-Cl bond angle, which is understood to maintain a similar local environment to that in the solid state. The atomic configurations of the RMC model suggest that the cation distributions in superionic melts of CuI and AgI exhibit large fluctuations, while Ag ions in the non-superionic melts of AgCl are distributed much more uniformly.

Nuclear Magnetic Resonance Reveals Disordered Level-Crossing Physics in the Bose-Glass Regime of the Br-Doped Ni(Cl_{1-x}Br_{x})_{2}-4SC(NH_{2})_{2} Compound at a High Magnetic Field.

Science.gov (United States)

Orlova, Anna; Blinder, Rémi; Kermarrec, Edwin; Dupont, Maxime; Laflorencie, Nicolas; Capponi, Sylvain; Mayaffre, Hadrien; Berthier, Claude; Paduan-Filho, Armando; Horvatić, Mladen

2017-02-10

By measuring the nuclear magnetic resonance (NMR) T_{1}^{-1} relaxation rate in the Br (bond) doped DTN compound, Ni(Cl_{1-x}Br_{x})_{2}-4SC(NH_{2})_{2}(DTNX), we show that the low-energy spin dynamics of its high magnetic field "Bose-glass" regime is dominated by a strong peak of spin fluctuations found at the nearly doping-independent position H^{*}≅13.6  T. From its temperature and field dependence, we conclude that this corresponds to a level crossing of the energy levels related to the doping-induced impurity states. Observation of the local NMR signal from the spin adjacent to the doped Br allowed us to fully characterize this impurity state. We have thus quantified a microscopic theoretical model that paves the way to better understanding of the Bose-glass physics in DTNX, as revealed in the related theoretical study [M. Dupont, S. Capponi, and N. Laflorencie, Phys. Rev. Lett. 118, 067204 (2017).PRLTAO0031-900710.1103/PhysRevLett.118.067204].

Stability and Performance of CsPbI2Br Thin Films and Solar Cell Devices.

Science.gov (United States)

Mariotti, Silvia; Hutter, Oliver S; Phillips, Laurie J; Yates, Peter J; Kundu, Biswajit; Durose, Ken

2018-01-31

In this manuscript, the inorganic perovskite CsPbI 2 Br is investigated as a photovoltaic material that offers higher stability than the organic-inorganic hybrid perovskite materials. It is demonstrated that CsPbI 2 Br does not irreversibly degrade to its component salts as in the case of methylammonium lead iodide but instead is induced (by water vapor) to transform from its metastable brown cubic (1.92 eV band gap) phase to a yellow phase having a higher band gap (2.85 eV). This is easily reversed by heating to 350 °C in a dry environment. Similarly, exposure of unencapsulated photovoltaic devices to water vapor causes current (J SC ) loss as the absorber transforms to its more transparent (yellow) form, but this is also reversible by moderate heating, with over 100% recovery of the original device performance. NMR and thermal analysis show that the high band gap yellow phase does not contain detectable levels of water, implying that water induces the transformation but is not incorporated as a major component. Performances of devices with best efficiencies of 9.08% (V OC = 1.05 V, J SC = 12.7 mA cm -2 and FF = 68.4%) using a device structure comprising glass/ITO/c-TiO 2 /CsPbI 2 Br/Spiro-OMeTAD/Au are presented, and further results demonstrating the dependence of the performance on the preparation temperature of the solution processed CsPbI 2 Br films are shown. We conclude that encapsulation of CsPbI 2 Br to exclude water vapor should be sufficient to stabilize the cubic brown phase, making the material of interest for use in practical PV devices.

Insights into the Halogen Oxidative Addition Reaction to Dinuclear Gold(I) Di(NHC) Complexes

KAUST Repository

Baron, Marco

2016-06-14

Gold(I) dicarbene complexes [Au2(MeIm-Y-ImMe)2](PF6)2(Y=CH2(1), (CH2)2(2), (CH2)4(4), MeIm=1-methylimidazol-2-ylidene) react with iodine to give the mixed-valence complex [Au(MeIm-CH2-ImMe)2AuI2](PF6)2(1 aI) and the gold(III) complexes [Au2I4(MeIm-Y-ImMe)2](PF6)2(2 cIand 4 cI). Reaction of complexes 1 and 2 with an excess of ICl allows the isolation of the tetrachloro gold(III) complexes [Au2Cl4(MeIm-CH2-ImMe)2](PF6)2(1 cCl) and [Au2Cl4(MeIm-(CH2)2-ImMe)2](Cl)2(2 cCl-Cl) (as main product); remarkably in the case of complex 2, the X-ray molecular structure of the crystals also shows the presence of I-Au-Cl mixed-sphere coordination. The same type of coordination has been observed in the main product of the reaction of complexes 3 or 4 with ICl. The study of the reactivity towards the oxidative addition of halogens to a large series of dinuclear bis(dicarbene) gold(I) complexes has been extended and reviewed. The complexes react with Cl2, Br2and I2to give the successive formation of the mixed-valence gold(I)/gold(III) n aXand gold(III) n cX(excluding compound 1 cI) complexes. However, complex 3 affords with Cl2and Br2the gold(II) complex 3 bX[Au2X2(MeIm-(CH2)3-ImMe)2](PF6)2(X=Cl, Br), which is the predominant species over compound 3 cXeven in the presence of free halogen. The observed different relative stabilities of the oxidised complexes of compounds 1 and 3 have also been confirmed by DFT calculations. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Towards a better understanding of the geometrical and orientational aspects of the electronic structure of halogens (F–I) adsorption on graphene

International Nuclear Information System (INIS)

Widjaja, Hantarto; Jiang, Zhong-Tao; Altarawneh, Mohammednoor; Yin, Chun-Yang; Goh, Bee-Min; Mondinos, Nicholas; Dlugogorski, Bogdan Z.

2015-01-01

Graphical abstract: - Highlights: • Examines the orientation (zigzag, armchair) effects of F/Cl/Br/I-adsorbed graphene. • F cases are site-dependent, while Cl/Br/I cases have minimal orientation dependence. • F is adsorbed to graphene at about three times stronger than Cl/Br/I. • To prompt re-examination of elemental-graphene systems to account for orientation. - Abstract: Adding impurities or doping through adsorption is an effective way to modify the properties of graphene-based materials. The capability of making predictions pertinent to the trends of elemental adsorption on graphene is very instrumental towards a better understanding of the more complex adsorption cases. It also affords useful guidelines for fabricating 2-D graphene materials with novel properties. The electronic structure of elemental adsorption on graphene is affected by side of adsorption (single- or double-sided), site of adsorption (i.e. bridge, hollow or top), and the relative orientation of the adsorbed sites (i.e. zigzag or armchair). In this contribution, we apply density functional theory (DFT) calculations to investigate the electronic structures of halogens (F, Cl, Br, I) adsorbed on graphene at lower concentrations spanning 1:6, 1:8 and 1:18 atomic ratios, in order to elucidate effects of adsorption trends. We demonstrate that adsorption of F is merely site-dependent (top). On the contrary, adsorptions of Cl, Br and I display a minimal dependence towards orientation (i.e. the effects of the deployed supercells). Our findings provide a deeper understanding of the elemental adsorption on graphene in terms of geometry which may aid in reexamining previous studies and producing better predictions for future studies, in which the inclusion of orientation is indispensable.

{sup 81}Br, {sup 37}Cl, and {sup 87}Sr studies to assess groundwater flow and solute sources in the southwestern Great Artesian Basin, Australia

Energy Technology Data Exchange (ETDEWEB)

Gwynne, Rhys; Frape, Shaun; Shouakar-Stash, Orfan [University of Waterloo, 200 University Avenue West, Waterloo N2L 3G1 (Canada); Love, Andy [Flinders University, Sturt Road, Bedford Park 5042 (Australia)

2013-07-01

The Great Artesian Basin (GAB) is a water source for more than 200,000 residents in central Australia. This study investigates the relationship of bromine and chlorine stable isotopes to groundwater chemistry in a confined aquifer in the southwestern GAB to better understand its flow regime and solute sources. δ{sup 81}Br values range from +0.660/00 near the recharge area to +1.04 0/00, 150 km down gradient, while δ{sup 37}Cl ranges from 00/00 to -2.50/00. While δ{sup 37}Cl decreases with distance from the recharge area, δ{sup 81}Br increases slightly. Bromide in the recharge area is possibly enriched from selective atmospheric processes causing fractionation in marine aerosols during transport. When confined and isolated from the atmosphere, increases in bromide and to a lesser extent strontium concentrations may contribute through water-rock interaction to changes in isotopic signatures along the flow system. {sup 87}Sr/{sup 86}Sr values range from ∼0.717 near the recharge zone to a depleted 0.708 160 km down gradient. (authors)

Simulation calculations of efficiencies and silicon consumption for CH3NH3PbI3−x−y Brx Cly/crystalline silicon tandem solar cells

International Nuclear Information System (INIS)

Zhang, Lili; Xie, Ziang; Qin, Guogang; Tian, Fuyang

2017-01-01

Much attention has been paid to two-subcell tandem solar cells (TSCs) with crystalline silicon (c-Si) as the bottom cell (TSC-Si). Previous works have pointed out that the optimal band gap, E g , of the top cell material for a TSC-Si is around 1.75 eV. With a tunable E g and better stability than MAPbI 3 (MA  =  CH 3 NH 3 ), MAPbI 3−x−y Br x Cl y is a promising candidate for the top cell material of a TSC-Si. In this work, calculations concerning the E g , refractive index and extinction coefficient of MAPbI 3−x−y Br x Cl y are performed using first-principles calculations including the spin–orbit coupling (SOC) effect. MAPbI 3−x−y Br x Cl y with five sets of x and y , which have a E g around 1.75 eV, are obtained. On this basis, absorption of the perovskite top cell is calculated applying the Lambert–Beer model (LBM) and the transfer matrix model (TMM), respectively. Considering the Auger recombination in the c-Si bottom cell and radiation coupling between the two subcells, the efficiencies for MAPbI 3−x−y Br x Cl y/ c-Si TSCs with the five sets of x and y are calculated. Among them, the MAPbI 2.375 Br 0.5 Cl 0.125 /c-Si TSC achieves the highest efficiency of 35.1% with a 440 nm thick top cell and 50 µ m thick c-Si when applying the LBM. When applying the TMM, the highest efficiency of 32.5% is predicted with a 580 nm thick MAPbI 2.375 Br 0.5 Cl 0.125 top cell and 50 µ m thick c-Si. Compared with the limiting efficiency of 27.1% for a 190 µ m thick c-Si single junction solar cell (SC), the MAPbI 2.375 Br 0.5 Cl 0.125 /c-Si TSC shows a superior performance of high efficiency and low c-Si consumption. (paper)

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

Science.gov (United States)

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.

Investigation on a two-stage solar liquid-desiccant (LiBr) dehumidification system assisted by CaCl2 solution

International Nuclear Information System (INIS)

Xiong, Z.Q.; Dai, Y.J.; Wang, R.Z.

2009-01-01

A two-stage solar powered liquid-desiccant dehumidification system, for which two kinds of desiccant solution (lithium chloride and calcium bromide) are fed to the two dehumidification stages separately, has been studied. In the studied system air moisture (latent) load is separately removed by a pre-dehumidifier using cheap calcium chloride (CaCl 2 ) and a main dehumidifier using stable lithium bromide (LiBr). Side-effect of mixing heat rejected during dehumidification process is considerably alleviated by an indirect evaporative cooling unit added between the two dehumidification stages. The feasibility of high-desiccant concentration difference achieved by reusing desiccant solution to dehumidify air and regenerating desiccant repeatedly is analyzed. By increasing desiccant concentration difference, desiccant storage capacity is effectively explored. It is found that the pre-dehumidification effect of CaCl 2 solution is significant in high ambient humidity condition. Also seen is that the desiccant investment can be decreased by 53%, though the cost of equipments is somewhat increased, and the Tcop and COP of the proposed system can reach 0.97 and 2.13, respectively

Chemical consequences of radioactive decay. 1. Study of 249Cf ingrowth into crystalline 249BkBr3: a new crystalline phase of CfBr3

International Nuclear Information System (INIS)

Young, J.P.; Haire, R.G.; Peterson, J.R.; Ensor, D.D.; Fellows, R.L.

1980-01-01

Spectrophotometric and x-ray powder diffraction methods have been applied to a study of the ingrowth of californium-249 by β - decay of berkelium-249 in crystalline 249 BkBr 3 . It was found that the Cf daughter grows in with the same oxidation state and crystal structure as the parent. Thus, six-coordinate BkBr 3 (AlCl 3 -type monoclinic structure) generates six-coordinate CfBr 3 , and eight-coordinate BkBr 3 (PuBr 3 -type orthorhombic structure) generates eight-coordinate CfBr 3 , a previously unknown form of CfBr 3 . It was also found that the daughter Cf(III) in the BkBr 3 parent compound can be reduced to Cf(II) by treatment with H 2 , as it can in pure CfBr 3 . 5 figures

Highly Emissive Divalent-Ion-Doped Colloidal CsPb1-xMxBr3 Perovskite Nanocrystals through Cation Exchange

NARCIS (Netherlands)

Van der Stam, Ward; Geuchies, Jaco J.; Altantzis, Thomas; Van Den Bos, Karel H.W.; Meeldijk, Johannes D.; Van Aert, Sandra; Bals, Sara; Vanmaekelbergh, Daniel; De Mello Donega, Celso

2017-01-01

Colloidal CsPbX3 (X = Br, Cl, and I) perovskite nanocrystals (NCs) have emerged as promising phosphors and solar cell materials due to their remarkable optoelectronic properties. These properties can be tailored by not only controlling the size and shape of the NCs but also postsynthetic composition

Inter ionic pair potentials for molten copper halides CuX (X=Br, I)

International Nuclear Information System (INIS)

Canan, C.

2004-01-01

In this work, the inter-ionic pair interactions of molten CuBr and Cu I are described with three different form of the rigid ion model potentials (RIM) using i) the functional form originally proposed by Vasishta and Rahman ii) the form used Madden and coworkers which is include the polarization contributions iii) the form parameterizied by Tatlipinar et al. The capability of these potentials have been discussed with each other by calculating the static liquid structure. We present the results of the partial pair distributions for molten CuBr at 810K and for molten Cul at 940K comparing with experimental data. The structural calculations are performed by solving the numerically the hypemetted chain approximate theory of liquids

Dissociative multiple photoionization of Br2, IBr, and I2 in the VUV and X-ray regions: a comparative study of the inner-shell processes involving Br(3d,3p,3s) and I(4d,4p,4s,3d,3p)

International Nuclear Information System (INIS)

Boo, Bong Hyun; Saito, Norio

2002-01-01

Dissociative multiple photoionization of the bromine, the iodine monobromide, and the iodine molecules in the Br(3d,3p,3s) and I(4d,4p,4s,3d,3p) inner-shell regions has been studied by using time-of-flight (TOF) mass spectrometry coupled to synchrotron radiation in the ranges of 90∼978 eV for Br 2 , 60∼133 eV for IBr, and 86∼998 eV for I 2 . Total photoion and photoion-photoion coincidence (PIPICO) yields have been recorded as functions of the photon energy. Here, giant shape resonances have been observed beyond the thresholds of the inner-shells owing to the Br(3d 10 )→Br(3d 9 -f), I(4d 10 )→I(4d 9 -f), and I(3d 10 )→I(3d 9 -f) transitions. The dissociation processes of the multiply charged parent ions have also been evaluated from variations of photoelectron-photoion coincidence (PEPICO) and PIPICO spectra with the photon energy. From each Br(3p 3/2 ) (189.9 eV) and I(4p 3/2 ) threshold (129.9 eV), quintuple ionization of the molecules begins to play important roles in the photoionization, subsequently yielding ion pairs of X 3+ -X 2+ (X=Br, I). From the I(3d 5/2 ) threshold (627.3 eV), loss of six electrons from iodine molecule additionally begins to play a minor role in the multiple photoionization, giving rise to the formation of ion pairs of either I 3+ -I 3+ or I 4+ -I 2+ . A direct comparison of the strengths and the ranges of the I(4d) and Br(3d) giant resonances was successfully made from dissociative photoionization of IBr. Over the entire energy range examined, 60< E<133 eV, biased charge spread relevant to the specific core-hole states of IBr is observed, presumably reflecting the fact that charge localizes mostly in the excited atoms, which can be accounted for mainly by a two step decay via a fast dissociation followed by autoionization upon the VUV absorption

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

Science.gov (United States)

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.

DFT investigation of electronic structures and magnetic properties of halides family MeHal3 (Me=Ti, Mo,Zr,Nb, Ru, Hal=Cl,Br,I) one dimensional structures

Science.gov (United States)

Kuzubov, A. A.; Kovaleva, E. A.; Popova, M. I.; Kholtobina, A. S.; Mikhaleva, N. S.; Visotin, M. A.; Fedorov, A. S.

2017-10-01

Using DFT GGA calculations, electronic structure and magnetic properties of wide family of transition metal trihalides (TMHal3) (Zr, Ti and Nb iodides, Mo, Ru, Ti and Zr bromides and Ti or Zr chlorides) are investigated. These structures consist of transition metal atoms chains surrounded by halides atoms. Chains are connected to each other by weak interactions. All TMHal3 compounds were found to be conductive along chain axis except of MoBr3 which is indirect gap semiconductor. It was shown that NbI3 and MoBr3 have large magnetic moments on metal atoms (1.17 and 1.81 μB, respectively) but other TMHal3 materials have small or zero magnetic moments. For all structures ferromagnetic and anti-ferromagnetic phases have almost the same energies. The causes of these properties are debated.

CsPbBr3 nanocrystal saturable absorber for mode-locking ytterbium fiber laser

Science.gov (United States)

Zhou, Yan; Hu, Zhiping; Li, Yue; Xu, Jianqiu; Tang, Xiaosheng; Tang, Yulong

2016-06-01

Cesium lead halide perovskite nanocrystals (CsPbX3, X = Cl, Br, I) have been reported as efficient light-harvesting and light-emitting semiconductor materials, but their nonlinear optical properties have been seldom touched upon. In this paper, we prepare layered CsPbBr3 nanocrystal films and characterize their physical properties. Broadband linear absorption from ˜0.8 to over 2.2 μm and nonlinear optical absorption at the 1-μm wavelength region are measured. The CsPbBr3 saturable absorber (SA), manufactured by drop-casting of colloidal CsPbBr3 liquid solution on a gold mirror, shows modulation depth and saturation intensity of 13.1% and 10.7 MW/cm2, respectively. With this SA, mode-locking operation of a polarization-maintained ytterbium fiber laser produces single pulses with duration of ˜216 ps, maximum average output power of 10.5 mW, and the laser spectrum is centered at ˜1076 nm. This work shows that CsPbBr3 films can be efficient SA candidates for fiber lasers and also have great potential to become broadband linear and nonlinear optical materials for photonics and optoelectronics.

Realce textural mediante "desbaste iónico" de muestras pulidas de clínker de cemento portland para estudios por microscopía electrónica de "scanning"

Directory of Open Access Journals (Sweden)

Rodríguez Rey, Ángel

1985-06-01

Full Text Available Results of using "ion thinning" techniques as final stage in the preparation of polished samples of portland cement clinker for SEM studies are showed. Under proper conditions, flat and clean surfaces are obtained which allow to discriminate textural facts (grain size, form, etc., hardly to see on conventional polished samples due to the similarities of the secondary electron emission of the clinker minerals.<br>>Se estudian los resultados de la aplicación del "desbaste iónico" como etapa final de la preparación de muestras pulidas de clínker de cemento portland para estudios por microscopía electrónica de "scanning". Se observa que, bajo condiciones apropiadas, se obtienen superficies planas y limpias que permiten distinguir rasgos texturales (tamaño, forma y bordes de grano que, dadas las similares características de emisión de electrones secundarios que poseen los minerales del clínker, son de difícil discriminación en secciones pulidas convencionales.

Luminescent properties of BaCl2-Eu microcrystals embedded in a CsI matrix

International Nuclear Information System (INIS)

Pushak, A.; Vistovskyy, V.; Voloshinovskii, A.; Savchyn, P.; Antonyak, O.; Demkiv, T.; Dacyuk, Yu.; Myagkota, S.; Gektin, A.

2013-01-01

The spectral-luminescent properties of CsI-BaCl 2 (1 mol%)-Eu(0.02 mol%) crystalline system are studied. Europium ion doped BaCl 2 microcrystals embedded in a CsI matrix are revealed on CsI-BaCl 2 (1 mol%)-Eu(0.02 mol%) freshly cleaved surface by the scanning electron microscopy. The size of microcrystals is shown to be within 0.5–5 microns. The luminescent parameters of the BaCl 2 -Eu 2+ microcrystals are shown to be similar to ones of a single crystal analogue. The 4f → 5d absorption transitions in europium ions and the reabsorption of the intrinsic emission of the CsI host are the main excitation mechanisms of europium luminescence in the BaCl 2 microcrystals. -- Highlights: ► The formation of chloride BaCl 2 :Eu microcrystals in the case of BaCl 2 doped CsI crystal has been revealed. ► The observed size of microcrystals at BaCl 2 concentration of 1% is about 0.5–5 μm. ► Majority of Eu 2+ ions in CsI-BaCl 2 -EuCl 3 crystalline system enters into BaCl 2 microcrystals. ► The luminescent parameters of the BaCl 2 :Eu 2+ microcrystals and its bulk analogue are similar

Dynamic [Cl-]i measurement with chloride sensing quantum dots nanosensor in epithelial cells

International Nuclear Information System (INIS)

Wang Yuchi; Mao Hua; Wong, Lid B

2010-01-01

We have synthesized a chloride sensing quantum dots (QD) nanosensor, Cl-QD, for the dynamic measurements of chloride ion concentration in the millimolar range, a sensitivity that is applicable to most physiological intracellular chloride ion concentration ([Cl - ] i ) measurements in epithelial cells. The Cl-QD is synthesized by conjugating an anion receptor, 1-(2-mercapto-ethyl)-3-phenyl-thiourea (MEPTU) to a water soluble CdSe/ZnS QD at an emission wavelength of 620 nm. Upon binding of chloride ions to the Cl-QD, a photo-induced electron transfer mechanism caused the fluorescence of the QD to quench. This resulted in an inversely proportional relationship between the chloride ion concentration and the fluorescence intensity of the Cl-QD. We have utilized this Cl-QD to measure [Cl - ] i in T84 and CF-PAC cultured cells, with either the C1C-2 or CFTR chloride channels being manipulated by pharmacological chloride channel activators and inhibitors. Activations of C1C-2 and CFTR chloride channels in T84 by the respective lubiprostone and genistein caused predictive increases in the fluorescence of the Cl-QD, i.e., a decrease of [Cl - ] i . Conversely, glibenclamide, a chloride channel inhibitor, applied to the CF-PAC cells caused a predictable decrease in the fluorescence of Cl-QD due to the increase of [Cl - ] i . These are the first data in using QD-based chloride ion sensors for dynamic measurements of intracellular chloride ion concentrations in epithelial cells.

Synthesis and characterizations of spherical hollow composed of AgI nanoparticle using AgBr as the precursor

International Nuclear Information System (INIS)

Yang Ming; Zhou Kui

2011-01-01

Hollow spheres of AgI with an average radius of 100-200 nm have been prepared by a simple reaction between AgBr suspension and KI in the presence of gelatin. Gelatin played a decisive role as an inhibitor of the direct attack of I - ions to AgBr surfaces and coagulation of the growing AgI in producing the spherical AgI particles. The products were characterized by X-ray powder diffraction, transmission electron microscopy, UV-vis absorption spectroscopy and X-ray photoelectron spectra techniques. The band gaps are estimated to be 2.95 eV according to the results of optical measurements of the hollow spheres of AgI.

Flash photolysis and pulse radiolysis of the Co(sep)3+-X- (sep = sepulchrate; X = I, Br) systems in aqueous solution

International Nuclear Information System (INIS)

Pina, F.; Maestri, M.; Ballardini, R.; Mulazzani, Q.G.; D'Angelantonio, M.; Balzani, V.

1986-01-01

The Co(sep) 3+ complex (sep = sepulchrate = 1,3,6,8,10,13,16,19-octaazabicyclo[6.6.6]eicosane) in aqueous solution forms ion pairs with the I - and Br - anions, which exhibit a relatively intense charge-transfer absorption. In deoxygenated aqueous solution no net reaction is obtained upon continuous light excitation in the ion-pair charge-transfer bands, but formation of transient species is observed in flash photolysis experiments. For the Co(sep) 3+ -I - system, I 2 - ions are formed that decay in the 50-μs time scale to give I 3 - . The latter species disappears in a time scale of seconds, leading the system back to the preexcitation conditions. For the Co(sep) 3+ -Br - system, only formation of the Br 2 - transient is observed, followed by regeneration of the preexcitation conditions in the 20-μs time scale. In order to elucidate the kinetic aspects of the transient formation and disappearance, pulse radiolysis experiments on the Co(sep) 3+ -I - and Co(sep) 3+ -Br - systems have been carried out. The rate constants of the reactions of Co(sep) 2+ with I 2 - , I 3 - , and Br 2 - have been measured, and a complete picture of the redox processes that follow flash photolysis and pulse radiolysis excitations has been obtained. 5 figures

An ab initio study on MgX3- and CaX3- superhalogen anions (X=F, Cl, Br)

International Nuclear Information System (INIS)

Anusiewicz, Iwona; Sobczyk, Monika; Dabkowska, Iwona; Skurski, Piotr

2003-01-01

The vertical electron detachment energies (VDEs) of twenty MX 3 - (M=Mg, Ca; X=F, Cl, Br) anions were calculated at the OVGF level with the 6-311++G(3df) basis sets. The largest vertical electron binding energy was found for MgF 3 - system (8.793 eV). All negatively charged species possess the VDEs that are larger than 5.9 eV and thus may be termed superhalogen anions. The strong dependence of the VDE of the MX 3 - species on the ligand-central atom (M-X) distance and on the partial atomic charge localized on Mg or Ca was observed and discussed, as well as the other factors that may influence the electronic stability of such anions

An ab initio study on MgX 3- and CaX 3- superhalogen anions (X=F, Cl, Br)

Science.gov (United States)

Anusiewicz, Iwona; Sobczyk, Monika; Dąbkowska, Iwona; Skurski, Piotr

2003-06-01

The vertical electron detachment energies (VDEs) of twenty MX 3- (M=Mg, Ca; X=F, Cl, Br) anions were calculated at the OVGF level with the 6-311++G(3df) basis sets. The largest vertical electron binding energy was found for MgF 3- system (8.793 eV). All negatively charged species possess the VDEs that are larger than 5.9 eV and thus may be termed superhalogen anions. The strong dependence of the VDE of the MX 3- species on the ligand-central atom (M-X) distance and on the partial atomic charge localized on Mg or Ca was observed and discussed, as well as the other factors that may influence the electronic stability of such anions.

Phase-separated CsI-NaCl scintillator grown by the Czochralski method

Science.gov (United States)

Yasui, Nobuhiro; Kobayashi, Tamaki; Ohashi, Yoshihiro; Den, Toru

2014-08-01

A phase-separated CsI-NaCl scintillator with light-guiding properties was grown by the Czochralski method. The CsI-NaCl eutectic phase usually consists of NaCl cylinders in a CsI matrix and contains grain boundaries. However, we have grown composites without grain boundaries by creating a convex solid/liquid interface, selecting a single grain by Dash's neck method, and increasing the diameter of the composite moderately. The good continuous convection flow required for these conditions was achieved by suppressing the drop in the aspect ratio of the melt height to the crucible radius with a double crucible setup. We successfully obtained a CsI-NaCl:Tl composite that was uniform with no grain boundaries greater than 30 mm in diameter.

Etude structurale et vibrationnelle d'un nouveau composé complexe de cobalt: [Co(imidazole)4Cl]Cl.

Science.gov (United States)

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).

Differential diagnosis of thyroid diseases with 131I and 201TlCl scintigraphy

International Nuclear Information System (INIS)

Kumano, Machiko; Ishida, Osamu

1979-01-01

Scintigraphic study with 131 I and 201 TlCl was performed on the differential diagnosis of various kinds of thyroid disease. When thyroid nodules are cold by scintigraphy with 131 I and hot with 201 TlCl, the lesions were proved to be solid tumor, that is, mostly follicular adenoma and carcinoma, and also most probably chronic thyroiditis. Accumulation of 201 TlCl, however, is not observed in cystic lesions, and is very high with high frequency in metastatic lesion of the lymph nodes as well as the thyroid cancer, especially in well differentiated follicular carcinoma. Therefore 201 TlCl was very useful to confirm the metastatic tumors from the thyroid cancer. These features in accumulation of 131 I and 201 TlCl in thyroid disease suggest the imaging technique with 201 TlCl combined with 131 I seem to provide more pathological information on the thyroid and metastatic lesions. (author)

Synthesis and substitution reactions of palladium(II) complexes with 2,2'-Bipyridine and 1,10-Phenanthroline

International Nuclear Information System (INIS)

Zaghal, M. H.; Al-Lawatia, S.

1996-01-01

The complexes cis-[Pd (Nn)CI 2 ] [Nn=2,2'-bipyridine (b py) and 1,10-phenanthroline (phen)] have been prepared via a new method by reacting the benzonitrile complex cis-[Pd(Ph CN) 2 CI 2 ] with the ligands. This method gives the products rapidly, in a pure state and in high yields. The substitution reactions of cis-[Pd(Nn)CI 2 ] (Nn=b py and phen) with Br - and I - have been attempted. The complexes cis-[Pd(Nn)X 2 ] (Nn=b py or phen; X Br, I) have been isolated. The products have been characterized by elemental analysis, conductivity measurements, and infrared, electronics absorption and 1 H NMR spectra. (authors). 26 refs., 1 tab

Experimental and theoretical studies of solvent effects on the hydrogen bonds in homoconjugated cations of substituted 4-halo (Cl, Br) pyridine N-oxide derivatives

International Nuclear Information System (INIS)

Gurzynski, Lukasz; Puszko, Aniela; Makowski, Mariusz; Chmurzynski, Lech

2007-01-01

Hydrogen bond OHO-type bridges formed between six substituted 4-halo (Cl, Br) pyridine N-oxide systems and their simple cations have been investigated by using the potentiometric titration method. The formation constants of these complexes (expressed as lgK BHB + ) have been determined in two non-aqueous aprotic solvents with different polarity, i.e., acetone (AC) and acetonitrile (AN). It has been observed that tri- and tetra-substituted pyridine N-oxides [B] and their cationic acids [BH + ] form stable homocomplexed cations [BHB + ] stabilized by O...H...O bridges in both solvents used. It has been found that the most stable homocomplexed system is formed by 3,5-dimethyl-4-chloropyridine N-oxide (3,5Me 2 4ClPyO). The lgK BHB + values for this compound in acetone and acetonitrile are 3.15 and 2.82, respectively. Furthermore, by using ab initio methods at the RHF and MP2 levels utilizing the Gaussian 6-31++G ** basis set, the energies of formation of the homocomplexed cations and Gibbs free energies have been determined in vacuo. The calculated energy parameters in vacuo have been compared with the cationic homoconjugation constants determined potentiometrically in acetone and acetonitrile to establish a correlation between these magnitudes. Additionally, the results of potentiometric measurements have been used to determine the acidity constants of the conjugate acids of N-oxides

Theory of singlet-ground-state magnetism. Application to field-induced transitions in CsFeCl3 and CsFeBr3

DEFF Research Database (Denmark)

Lindgård, P.-A.; Schmid, B.

1993-01-01

In the singlet ground-state systems CsFeCl3 and CsFeBr3 a large single-ion anisotropy causes a singlet ground state and a doubly degenerate doublet as the first excited states of the Fe2+ ion. In addition the magneteic interaction is anisotropic being much larger along the z axis than perpendicular...... to it. Therefore, these quasi-one-dimensional magnetic model systems are ideal to demonstrate unique correlation effects. Within the framework of the correlation theory we derive the expressions for the excitation spectrum. When a magnetic field is applied parallel to the z axis both substances have...

Theoretical study of the superhyperfine parameters for Cu{sup 2+} in K{sub 2}PdX{sub 4} (X = Cl, Br)

Energy Technology Data Exchange (ETDEWEB)

Wei, L. H.; Wu, S. Y., E-mail: shaoyi_wu@163.com; Zhang, Z. H.; Wang, X. F.; Hu, Y. X. [University of Electronic Science and Technology of China, Department of Applied Physics (China)

2008-01-15

The superhyperfine parameters T{sub j} (j = x, y, z) for Cu{sup 2+} in the square-planar K{sub 2}PdX{sub 4} (X = Cl, Br) are theoretically studied from the perturbation formulas of these parameters for an octahedral 3d{sup 9} cluster, by considering both the contributions from the crystal-field and charge-transfer mechanisms. The related molecular orbital coefficients are determined from the cluster approach in a uniform way. Based on one adjustable proportional factor {rho} for the orbital admixture coefficients, the calculated results of present work show reasonable agreement with the observed values.

A fast and feasible method for Br and I determination in whole egg powder and its fractions by ICP-MS.

Science.gov (United States)

Toralles, Isis Gonçalves; Coelho, Gilberto Silva; Costa, Vanize Cadeira; Cruz, Sandra Meinen; Flores, Erico Marlon Moraes; Mesko, Marcia Foster

2017-04-15

A method for Br and I determination in whole egg powder and its fractions (egg white and yolk) was developed by combining microwave-induced combustion (MIC) and inductively coupled plasma mass spectrometry (ICP-MS). Using the MIC method, 350mg of whole egg powder and its fractions were efficiently digested using 50mmolL -1 NH 4 OH as an absorbing solution. The limits of detection for Br and I using the MIC method followed by ICP-MS determination were 0.039 and 0.015μgg -1 , respectively. Using the proposed method, agreements with the reference values between 97 and 104% for Br and I were obtained by analysis of reference material NIST 8435. Finally, it was possible to observe that Br concentration (4.59-5.29μgg -1 ) was higher than I (0.150-2.28μgg -1 ) for all the evaluated samples. Copyright © 2016 Elsevier Ltd. All rights reserved.

Thermodynamics of the amalgam cells {l_brace}Cs-amalgam|CsX (m)|AgX|Ag{r_brace} (X=Cl, Br, I) and primary medium effects in (methanol+water) (acetonitrile+water), and (1,4-dioxane+water) solvent mixtures

Energy Technology Data Exchange (ETDEWEB)

Falciola, Luigi [Department of Physical Chemistry and Electrochemistry, University of Milan, Via Golgi 19, I-20133 Milan (Italy)]. E-mail: luigi.falciola@unimi.it; Longoni, Giorgio [Department of Physical Chemistry and Electrochemistry, University of Milan, Via Golgi 19, I-20133 Milan (Italy); Mussini, Patrizia R. [Department of Physical Chemistry and Electrochemistry, University of Milan, Via Golgi 19, I-20133 Milan (Italy)]. E-mail: patrizia.mussini@unimi.it; Mussini, Torquato [Department of Physical Chemistry and Electrochemistry, University of Milan, Via Golgi 19, I-20133 Milan (Italy)]. E-mail: torquato.mussini@unimi.it

2006-06-15

The potential difference E of the amalgam cell {l_brace}Cs{sub x}Hg{sub 1-x}|CsX (m)|AgX|Ag{r_brace} (X=Cl, Br, I) has been measured as a function of the mole fraction x{sub Cs} of Cs metal in amalgams and of the molality m of CsX in (methanol+water) (acetonitrile+water), and (1,4-dioxane+water) solvent mixtures containing up to 0.75 mass fraction of the organic component, at the temperature 298.15K. The respective standard molal potential differences E{sub m}{sup o} have been determined together with the relevant activity coefficients {gamma}{sub +}/- as functions of the CsX molality. The found E{sub m}{sup o} values show a parabolic decrease with increasing proportion of the organic component in the solvent mixture. Analysis of the relevant primary medium effects upon CsX shows that the CsX transfer from the standard state in water to the standard state in the (aqueous+organic) mixture is always unfavoured, and the acetonitrile is the least unfavoured co-solvent studied. Analysis of the primary medium effect upon CsI in terms of Feakins and French's theory leads to a primary hydration number close to zero, which is consistent with the results of supplementary EXAFS experiments on Cs{sup +} and I{sup -} in (acetonitrile+water) solvent mixtures.

Ordered distribution of I and Cl in the low-temperature crystal structure of mutnovskite, Pb4As2S6ICl: An X-ray single-crystal study

International Nuclear Information System (INIS)

Bindi, Luca; Garavelli, Anna; Pinto, Daniela; Pratesi, Giovanni; Vurro, Filippo

2008-01-01

To study the temperature-dependent structural changes and to analyze the crystal chemical behavior of the halogens as a function of temperature, a crystal of the recently discovered mineral mutnovskite, ideally Pb 2 AsS 3 (I,Cl,Br), has been investigated by X-ray single-crystal diffraction methods at 300 and 110 K. At room temperature (RT) mutnovskite was confirmed to possess a centrosymmetric structure-type, space group Pnma, while at low temperature (110 K) it adopts a non-centrosymmetric orthorhombic structure-type, space group Pnm2 1 , with a=11.5394(9) A, b=6.6732(5) A, c=9.3454(7) A, V=719.64(9) A 3 and Z=2. Mutnovskite reconverts to the centrosymmetric-type upon returning to RT thus indicating that the phase transition is completely reversible in character. The refinement of the LT-structure leads to a residual factor R=0.0336 for 1827 independent observed reflections [F o >4σ(F o )] and 80 variables. The crystal structure of cooled mutnovskite is topologically identical to that observed at RT and the slight structural changes occurring during the phase transition Pnma→Pnm2 1 are mainly restricted to the coordination polyhedra around Pb. The structure solution revealed that I and Cl are ordered into two specific sites. Indeed, the unique mixed (I,Cl) position in the RT-structure (Wyckoff position 4c) transforms into two 2a Wyckoff positions in the LT-structure hosting I and Cl, respectively. - Graphical abstract: In the crystal structure of mutnovskite at 110 K the two halogens I and Cl are ordered into two specific sites and only slight changes in the coordination environment around Pb atoms occur during the phase transition Pnma→Pnm2 1 from the RT-structure to the LT-structure. Two kinds of layers alternating along a are present in the LT-structure: Layer I contains Cl atoms and [001] columns of Pb1 and Pb4 prisms, layer II contains I atoms and [001] columns of Pb2 and Pb3 prisms

Flexible All-Inorganic Perovskite CsPbBr3 Nonvolatile Memory Device.

Science.gov (United States)

Liu, Dongjue; Lin, Qiqi; Zang, Zhigang; Wang, Ming; Wangyang, Peihua; Tang, Xiaosheng; Zhou, Miao; Hu, Wei

2017-02-22

All-inorganic perovskite CsPbX 3 (X = Cl, Br, or I) is widely used in a variety of photoelectric devices such as solar cells, light-emitting diodes, lasers, and photodetectors. However, studies to understand the flexible CsPbX 3 electrical application are relatively scarce, mainly due to the limitations of the low-temperature fabricating process. In this study, all-inorganic perovskite CsPbBr 3 films were successfully fabricated at 75 °C through a two-step method. The highly crystallized films were first employed as a resistive switching layer in the Al/CsPbBr 3 /PEDOT:PSS/ITO/PET structure for flexible nonvolatile memory application. The resistive switching operations and endurance performance demonstrated the as-prepared flexible resistive random access memory devices possess reproducible and reliable memory characteristics. Electrical reliability and mechanical stability of the nonvolatile device were further tested by the robust current-voltage curves under different bending angles and consecutive flexing cycles. Moreover, a model of the formation and rupture of filaments through the CsPbBr 3 layer was proposed to explain the resistive switching effect. It is believed that this study will offer a new setting to understand and design all-inorganic perovskite materials for future stable flexible electronic devices.

3+ and [Sb13Se16Br2] 5+ - Double and quadruple spiro cubanes from ionic liquids

KAUST Repository

Ahmed, Ejaz

2014-01-08

The reaction of antimony and selenium in the bromine-rich Lewis acidic ionic liquid [BMIm]Br·4.7AlBr3 (BMIm: 1-butyl-3- methylimidazolium) in the presence of a small amount of NbCl5 at 160 °C yielded dark-red crystals of [Sb7Se8Br 2][AlX4]3. For X = Cl0.15(1)Br 0.85(1), the compound is isostructural to [Sb7S 8Br2][AlCl4]3 [P212 121, a = 12.5132(5) Å, b = 17.7394(6) Å, c = 18.3013(6) Å]. For a higher chlorine content, X = Cl 0.58(1)Br0.42(1), a slightly disordered variant with a bisected unit cell is found [P21212, a = 12.3757(3) Å, b = 17.4116(5) Å, c = 9.0420(2) Å]. The [Sb 7Se8Br2]3+ heteropolycation (C 2 symmetry) is a spiro double-cubane with an antimony atom on the shared corner. From this distorted octahedrally coordinated central atom, tricoordinate selenium and antimony atoms alternate in the bonding sequence. The terminal antimony atoms each bind to a bromine atom. Quantum chemical calculations confirm polar covalent Sb-Se bonding within the cubes and indicate three-center, four-electron bonds for the six-coordinate spiro atoms. The calculated charge distribution reflects the electron-donor role of the antimony atoms. The use of a chlorine-rich ionic liquid resulted in the formation of triclinic [Sb13Se16Br2][AlX4] 5 with X = Cl0.80(1)Br0.20(1) [P$\\\\bar {1}$, a = 9.0842(5) Å, b = 19.607(1) Å, c = 21.511(1) Å, α = 64.116(6), β = 79.768(7), γ = 88.499(7)]. The cationic cluster [Sb13Se16Br2]5+ is a bromine-terminated spiro quadruple-cubane. This 31 atom concatenation of four cubes is assumed to be the largest known discrete main group polycation. A similar reaction in a chloride-free system yielded [Sb7Se 8Br2][Sb13Se16Br2] [AlBr4]8. In its monoclinic structure [P2/c, a = 27.214(5) Å, b = 9.383(2) Å, c = 22.917(4) Å, β = 101.68(1)], the two types of polycations alternate in layers along the a axis. In the series [Sb4+3nSe4+4nBr2](2+n)+, these cations are the members with n = 1 and 3. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGa

Investigation of anti-solvent induced optical properties change of cesium lead bromide iodide mixed perovskite (CsPbBr3-xIx) quantum dots.

Science.gov (United States)

Yuan, Lin; Patterson, Robert; Wen, Xiaoming; Zhang, Zhilong; Conibeer, Gavin; Huang, Shujuan

2017-10-15

Cesium lead halide (CsPbX 3 , X=Cl, Br, I) perovskites are a new material system that has attracted a lot of research focus. Its tunable band gap and better thermal stability than organic lead halide perovskite give it the potential for applications in optoelectronic devices such as light-emitting diodes and solar cells. Here we have synthesized CsPbBr 3-x I x perovskite quantum dots (QDs) via a solution process, and then have selected three different anti-solvents to purify the product. A significant effect on optical properties of CsPbBr 3-x I x was found after the centrifugation process. Up to a ∼40nm shift was observed in mixed halide CsPbBr 3-x I x QDs in both absorbance and PL spectra after purification while there was no obvious change in pure CsPbBr 3 when it was subjected to the same purification steps. XPS analysis shows that the Br:I ratio of the CsPbBr 3-x I x QDs had changed as a result of exposure to the anti-solvent, causing the change of the band gap and shift of the spectra. It is also shown that iodine can be removed more easily than bromine during the anti-solvent purification. Ab-initio simulations of small CsPbBr 3-x I x atomic clusters suggest that exposed Cs ions on Cs-terminated facets are the first species to be attacked by hydrophilic molecules, likely dragging halide ions into solution with them to maintain overall charge neutrality in the material. Charge carrier recombination rates were found to be unchanged and all samples maintained a good PL quantum yield which was more than 44%. Copyright © 2017. Published by Elsevier Inc.

Influence of ligand polarizability on the reversible binding of O2 by trans-[Rh(X)(XNC)(PPh3)2] (X = Cl, Br, SC6F5, C2Ph; XNC = xylyl isocyanide). Structures and a kinetic study.

Science.gov (United States)

Carlton, Laurence; Mokoena, Lebohang V; Fernandes, Manuel A

2008-10-06

The complexes trans-[Rh(X)(XNC)(PPh 3) 2] (X = Cl, 1; Br, 2; SC 6F 5, 3; C 2Ph, 4; XNC = xylyl isocyanide) combine reversibly with molecular oxygen to give [Rh(X)(O 2)(XNC)(PPh 3) 2] of which [Rh(SC 6F 5)(O 2)(XNC)(PPh 3) 2] ( 7) and [Rh(C 2Ph)(O 2)(XNC)(PPh 3) 2] ( 8) are sufficiently stable to be isolated in crystalline form. Complexes 2, 3, 4, and 7 have been structurally characterized. Kinetic data for the dissociation of O 2 from the dioxygen adducts of 1- 4 were obtained using (31)P NMR to monitor changes in the concentration of [Rh(X)(O 2)(XNC)(PPh 3) 2] (X = Cl, Br, SC 6F 5, C 2Ph) resulting from the bubbling of argon through the respective warmed solutions (solvent chlorobenzene). From data recorded at temperatures in the range 30-70 degrees C, activation parameters were obtained as follows: Delta H (++) (kJ mol (-1)): 31.7 +/- 1.6 (X = Cl), 52.1 +/- 4.3 (X = Br), 66.0 +/- 5.8 (X = SC 6F 5), 101.3 +/- 1.8 (X = C 2Ph); Delta S (++) (J K (-1) mol (-1)): -170.3 +/- 5.0 (X = Cl), -120 +/- 13.6 (X = Br), -89 +/- 18.2 (X = SC 6F 5), -6.4 +/- 5.4 (X = C 2Ph). The values of Delta H (++) and Delta S (++) are closely correlated (R (2) = 0.9997), consistent with a common dissociation pathway along which the rate-determining step occurs at a different position for each X. Relative magnitudes of Delta H (++) are interpreted in terms of differing polarizabilities of ligands X.

Structure of the fully ferroelectric/fully ferroelastic orthohombic room-temperature phase of cobalt bromine boracite, Co3B7O13Br and nickel chlorine boracite, Ni3B7O13Cl

International Nuclear Information System (INIS)

Kubel, F.; Mao, S.Y.; Schmid, H.

1992-01-01

The X-ray crystal structures of optically controlled single-domain crystals of fully ferroelectric/fully ferroelastic cobalt bromine boracite, Co 3 B 7 O 13 Br (Co-Br) at 298 K [M r = 540.38, orthorhombic, Pca2 1 , a = 8.5614 (2), b = 8.5657 (2), c = 12.1196 (3) A, V = 888.78 (4) A 3 , Z = 4, D x = 4.04 Mg m -3 , λ(Mo Kα) = 0.7107 A, μ = 10.61 mm -1 , F(000) = 1020, R = 7.0, wR = 5.4%, 2824 reflections] and of nickel chlorine boracite, Ni 3 B 7 O 13 Cl (Ni-Cl) at 298 K [M r = 495.25, orthorhombic, Pca2 1 , a = 8.5105 (4), b = 8.4984 (4), c = 12.0324 (5) A, V = 870.25 (7) A 3 , Z = 4, D x = 3.78 Mg m -3 , λ(Mo Kα) = 0.7107 A, μ = 6.8 mm -1 , F(000) = 960, R = 3.5, wR = 3.1%, 2082 reflections] are reported. The metal surroundings of Co-Br and Ni-Cl were analyzed in detail and show two metal sites (Co2, Co3; Ni2, Ni3) with chemically similar environments and one metal site (Co1; Ni1) with a different environment. Six B atoms have a tetrahedral or slightly distorted tetrahedral coordination, whereas one B atom (B4) has triangular surroundings in both compounds. (orig.)

Determination of Au, Sb, As, Br, Na, K, Cd, Mn and Cl in rice from Vietnam by neutron activation analysis

International Nuclear Information System (INIS)

Tran Van, L.; Teherani, D.K.

1988-01-01

Gold, antimony, arsenic, bromine, sodium, potassium, cadmium, manganese and chlorine were determined by neutron activation analysis in various rice seed, brand layer and husk samples from Vietnam. The following concentration values were found: Au 0.05-0.28 ppm, Sb 0.05-1.08 ppm, As 0.08-0.94 ppm, Br 0.82-6.72 ppm, Na 16.71-25.71 ppm, K 2582-5163 ppm, Mn 19.26-33.43 ppm, Cd 0.51-2.42 ppm and Cl 205.20-828.61 ppm in rice seed. Statistically significant differences in Au, Sb, Cd contents were detected in rice seed and husk, as well as brand layer and husk. (author) 8 refs.; 3 figs

Effects of CsBr addition on the performance of CH3NH3PbI3-xClx-based solar cells

Science.gov (United States)

Ueoka, Naoki; Oku, Takeo; Ohishi, Yuya; Tanaka, Hiroki; Suzuki, Atsushi; Sakamoto, Hiroki; Yamada, Masahiro; Minami, Satoshi; Tsukada, Shinichiro

2018-01-01

Perovskite-type photovoltaic devices were prepared by a spin-coating method using a precursor solution of CH3NH3I and lead(II) chloride in N,N-dimethylformamide. Effects of cesium bromide (CsBr) addition on the photovoltaic properties and microstructures of the perovskite phase were investigated. The fill factor was increased by adding the CsBr to the CH3NH3PbI3-xClx precursor solution, which resulted in increase of the conversion efficiency. The crystallinity of the CH3NH3PbI3-xClx perovskite phase was also improved by adding the CsBr to the H3NH3PbI3-xClx precursor solution.

Theoretical investigation of the Te4Br2 molecule in ionic liquids

International Nuclear Information System (INIS)

Elfgen, Roman; Holloczki, Oldamur; Ray, Promit; Kirchner, Barbara; Groh, Matthias F.; Ruck, Michael

2017-01-01

Material synthesis in ionic liquids, at or near room temperature, is currently a subject of immense academic interest. In order to illuminate molecular-level details and the underlying chemistry, we carried out molecular simulations of a single Te 4 Br 2 molecule dissolved in the ionic liquid 1-ethyl-3-methylimidazolium chloride, as well as in the ionic liquid mixed with aluminum chloride. Although the ethyl side chain is much too short to show detailed microheterogeneity, significant structuring with the small chloride anions is seen in case of the pure ionic liquid. In the case of the mixture, formation of larger anionic clusters is distinctly observed and analyzed. Due to the tendency of ionic liquids to dissociate, there is a pronounced shift to elongated Te-Br distances in both investigated solvents. However, only in the AlCl 3 -containing liquid, we observe the reaction of the open chain-like Te 4 Br 2 molecule to a closed square-like Te 4 Br + and AlCl 3 Br - ion. The molecular arrangement of the [Te 4 ] 2+ unit shows negligible deviation from that in the experimental crystal structure. (copyright 2017 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

Br2 production from the heterogeneous reaction of gas-phase OH with aqueous salt solutions: Impacts of acidity, halide concentration, and organic surfactants.

Science.gov (United States)

Frinak, Elizabeth K; Abbatt, Jonathan P D

2006-09-07

This study reports the first laboratory measurement of gas-phase Br2 production from the reaction between gas-phase hydroxyl radicals and aqueous salt solutions. Experiments were conducted at 269 K in a rotating wetted-wall flow tube coupled to a chemical-ionization mass spectrometer for analysis of gas-phase components. From both pure NaBr solutions and mixed NaCl/NaBr solutions, the amount of Br2 released was found to increase with increasing acidity, whereas it was found to vary little with increasing concentration of bromide ions in the sample. For mixed NaCl/NaBr solutions, Br2 was formed preferentially over Cl2 unless the Br- levels in the solution were significantly depleted by OH oxidation, at which point Cl2 formation was observed. Presence of a surfactant in solution, sodium dodecyl sulfate, significantly suppressed the formation of Br2; this is the first indication that an organic surfactant can affect the rate of interfacial mass transfer of OH to an aqueous surface. The OH-mediated oxidation of bromide may serve as a source of active bromine in the troposphere and contribute to the subsequent destruction of ozone that proceeds in marine-influenced regions of the troposphere.

Synthesis and Biological Evaluation of (S)-Amino-2-methyl-4-[(76)Br]bromo-3-(E)-butenoic Acid (BrVAIB) for Brain Tumor Imaging.

Science.gov (United States)

Burkemper, Jennifer L; Huang, Chaofeng; Li, Aixiao; Yuan, Liya; Rich, Keith; McConathy, Jonathan; Lapi, Suzanne E

2015-11-12

The novel compound, (S)-amino-2-methyl-4-[(76)Br]bromo-3-(E)-butenoic acid (BrVAIB, [(76)Br]5), was characterized against the known system A tracer, IVAIB ([(123)I]8). [(76)Br]5 was prepared in a 51% ± 19% radiochemical yield with high radiochemical purity (≥98%). The biological properties of [(76)Br]5 were compared with those of [(123)I]8. Results showed that [(76)Br]5 undergoes mixed amino acid transport by system A and system L transport, while [(123)I]8 had less uptake by system L. [(76)Br]5 demonstrated higher uptake than [(123)I]8 in DBT tumors 1 h after injection (3.7 ± 0.4% ID/g vs 1.5 ± 0.3% ID/g) and also showed higher uptake vs [(123)I]8 in normal brain. Small animal PET studies with [(76)Br]5 demonstrated good tumor visualization of intracranial DBTs up to 24 h with clearance from normal tissues. These results indicate that [(76)Br]5 is a promising PET tracer for brain tumor imaging and lead compound for a mixed system A and system L transport substrate.

Experimental and theoretical studies of solvent effects on the hydrogen bonds in homoconjugated cations of substituted 4-halo (Cl, Br) pyridine N-oxide derivatives

Energy Technology Data Exchange (ETDEWEB)

Gurzynski, Lukasz [Department of General and Inorganic Chemistry, University of Gdansk, Sobieskiego 18, 80-952 Gdansk (Poland); Puszko, Aniela [Department of Organic Chemistry, School of Economics, Wroclaw (Poland); Makowski, Mariusz [Department of General and Inorganic Chemistry, University of Gdansk, Sobieskiego 18, 80-952 Gdansk (Poland); Chmurzynski, Lech [Department of General and Inorganic Chemistry, University of Gdansk, Sobieskiego 18, 80-952 Gdansk (Poland)], E-mail: lech@chem.univ.gda.pl

2007-09-15

Hydrogen bond OHO-type bridges formed between six substituted 4-halo (Cl, Br) pyridine N-oxide systems and their simple cations have been investigated by using the potentiometric titration method. The formation constants of these complexes (expressed as lgK{sub BHB{sup +}}) have been determined in two non-aqueous aprotic solvents with different polarity, i.e., acetone (AC) and acetonitrile (AN). It has been observed that tri- and tetra-substituted pyridine N-oxides [B] and their cationic acids [BH{sup +}] form stable homocomplexed cations [BHB{sup +}] stabilized by O...H...O bridges in both solvents used. It has been found that the most stable homocomplexed system is formed by 3,5-dimethyl-4-chloropyridine N-oxide (3,5Me{sub 2}4ClPyO). The lgK{sub BHB{sup +}} values for this compound in acetone and acetonitrile are 3.15 and 2.82, respectively. Furthermore, by using ab initio methods at the RHF and MP2 levels utilizing the Gaussian 6-31++G{sup **} basis set, the energies of formation of the homocomplexed cations and Gibbs free energies have been determined in vacuo. The calculated energy parameters in vacuo have been compared with the cationic homoconjugation constants determined potentiometrically in acetone and acetonitrile to establish a correlation between these magnitudes. Additionally, the results of potentiometric measurements have been used to determine the acidity constants of the conjugate acids of N-oxides.

CsPbBr{sub 3} nanocrystal saturable absorber for mode-locking ytterbium fiber laser

Energy Technology Data Exchange (ETDEWEB)

Zhou, Yan; Li, Yue; Xu, Jianqiu; Tang, Yulong, E-mail: yulong@sjtu.edu.cn [Key Laboratory for Laser Plasmas (MOE), Department of Physics and Astronomy, Collaborative Innovation Center of IFSA, Shanghai Jiao Tong University, Shanghai 200240 (China); Hu, Zhiping; Tang, Xiaosheng [Key Laboratory of Optoelectronic Technology and Systems of the Education Ministry of China, College of Optoelectronic Engineering, Chongqing University, Chongqing 400044 (China)

2016-06-27

Cesium lead halide perovskite nanocrystals (CsPbX{sub 3}, X = Cl, Br, I) have been reported as efficient light-harvesting and light-emitting semiconductor materials, but their nonlinear optical properties have been seldom touched upon. In this paper, we prepare layered CsPbBr{sub 3} nanocrystal films and characterize their physical properties. Broadband linear absorption from ∼0.8 to over 2.2 μm and nonlinear optical absorption at the 1-μm wavelength region are measured. The CsPbBr{sub 3} saturable absorber (SA), manufactured by drop-casting of colloidal CsPbBr{sub 3} liquid solution on a gold mirror, shows modulation depth and saturation intensity of 13.1% and 10.7 MW/cm{sup 2}, respectively. With this SA, mode-locking operation of a polarization-maintained ytterbium fiber laser produces single pulses with duration of ∼216 ps, maximum average output power of 10.5 mW, and the laser spectrum is centered at ∼1076 nm. This work shows that CsPbBr{sub 3} films can be efficient SA candidates for fiber lasers and also have great potential to become broadband linear and nonlinear optical materials for photonics and optoelectronics.

Brændeovnes bidrag til luftforurening

DEFF Research Database (Denmark)

Pedersen, Jens Christian

2010-01-01

Brændeovnenes bidrag til luftforurening er blevet kortlagt med en hidtil uset detaljeringsgrad. Det er forskere fra Danmarks Miljøundersøgelser (DMU) på Aarhus Universitet som står bag kortlægningen. En omfattende målekampagne i Slagslunde viser at brændeovnene bidrager væsentligt til partikelfor......Brændeovnenes bidrag til luftforurening er blevet kortlagt med en hidtil uset detaljeringsgrad. Det er forskere fra Danmarks Miljøundersøgelser (DMU) på Aarhus Universitet som står bag kortlægningen. En omfattende målekampagne i Slagslunde viser at brændeovnene bidrager væsentligt til...

Annealing Effect on (FAPbI31−x(MAPbBr3x Perovskite Films in Inverted-Type Perovskite Solar Cells

Directory of Open Access Journals (Sweden)

Lung-Chien Chen

2016-09-01

Full Text Available This study determines the effects of annealing treatment on the structure and the optical and electronic behaviors of the mixed (FAPbI31−x(MAPbBr3x perovskite system. The experimental results reveal that (FAPbI31−x(MAPbBr3x (x ~ 0.2 is an effective light-absorbing material for use in inverted planar perovskite solar cells owing to its large absorbance and tunable band gap. Therefore, good band-matching between the (FAPbI31−x(MAPbBr3x and C60 in photovoltaic devices can be controlled by annealing at various temperatures. Accordingly, an inverted mixed perovskite solar cell with a record efficiency of 12.0% under AM1.5G irradiation is realized.

Inhibition of Ps Formation in Benzene and Cyclohexane by CH3CI and CH3Br

DEFF Research Database (Denmark)

Wikander, G.; Mogensen, O. E.; Pedersen, Niels Jørgen

1983-01-01

Positron-annihilation lifetime spectra have been measured for mixtures of CH3Cl and CH3Br in cyclohexane and of CH3Cl in benzene. The ortho-positronium (Ps) yield decreased monotonically from 38% and 43% in cyclohexane and benzene respectively to 11% in pure CH3Cl and 6% in pure CH3Br. The strength......− anions to form Ps. while it forms a bound state with the halides. X−. CH3Cl was a roughly three times weaker Ps inhibitor in benzene than in cyclohexane, which shows that CH3Cl− does not dechlorinate in times comparable to or shorter than 400–500 ps in benzene. An improved model for the explanation of Ps...

[11C]copper(I) cyanide: a new radioactive precursor or 11C-cyanation and functionalization of haloarenes

International Nuclear Information System (INIS)

Ponchant, M.; Hinnen, F.; Demphel, S.; Crouzel, C.

1997-01-01

Radiosyntheses of [cyano- 11 C]benzonitriles, [carboyxyl- 11 C]benzoic acids, [carbonyl- 11 C]benzamides and [tetrazoyl- 11 C]5-biphenyl-1H-tetrazoles are described. [Cyano- 11 C]benzonitriles were prepared using the Rosenmund-von Braun reaction in one step from [ 11 C]hydrogen cyanide via [ 11 C]copper(1) cyanide in 2 min. [Carboxyl- 11 C]benzoic acids and [carbonyl- 11 C]benzamides were prepared from [cyano- 11 C]benzonitrile-complexes using basic hydrogen peroxide for 3 min in N,N-dimethylformamide at 180 and 80 o C, respectively. [Tetrazoyl- 11 C]5-biphenyl-1H-tetrazoles were obtained from [cyano- 11 C]benzonitrile-complexes in 7 min by cyclization with trimethyltin azide followed by acid hydrolysis at 180 o C. These labelled compounds were obtained in a one-pot procedure with good average specific radioactivities [500 mCi/μmol) at the end of synthesis] and in satisfactory average radiochemical yields (24-69%) at 40 min from the end of radionuclide production. This new radioactive precursor, [ 11 C]copper(I) cyanide, should give access to new 11 C-labelled ligands for positron emission tomography. (author)

BENZYLIDENESALICYLOYLHYDRAZINATO- N,OTIN(IV] (R = OCH3, Br, N(CH32 AND THEIR ANTI-INFLAMMATORY ACTIVITY

Directory of Open Access Journals (Sweden)

N. V. Shmatkova

2014-11-01

Full Text Available The complexes [SnCl4(2-OH-HB-4R-b] ·CH3CN (R = 4-OCH3 (І, 4-Br(II were obtained by interaction of SnCl4 with salicyloylhydrazones 4–R- benzaldehydes (2-OH-HB-4R-b in acetonitrile. The composition and structure (O(C=O-N(CH=N – the coordination of ligand’s amide form were established by element analysis methods, conductometry, thermogravimetry and IR spectroscopy. It was studied the anti-inflammatory activity of (I, II and previously synthesized, structurally characterized [SnCl4(2-OH-HB-4R-b∙H] (R=N (CH32 (III in model of aseptic carrageenan induced swelling, and it is shown that compound (II demonstrates the highest activity.

Composition-dependent hot carrier relaxation dynamics in cesium lead halide (CsPbX{sub 3}, X=Br and I) perovskite nanocrystals

Energy Technology Data Exchange (ETDEWEB)

Chung, Heejae; Jung, Seok Il; Kim, Hyo Jin; Cha, Wonhee; Sim, Eunji; Kim, Dongho [Department of Chemistry, Yonsei University, Seoul (Korea, Republic of); Koh, Weon-Kyu [Device Laboratory, Samsung Advanced Institute of Technology, Suwon (Korea, Republic of); Kim, Jiwon [School of Integrated Technology and Underwood International College, Yonsei University, Incheon (Korea, Republic of)

2017-04-03

Cesium-based perovskite nanocrystals (NCs) have outstanding photophysical properties improving the performances of lighting devices. Fundamental studies on excitonic properties and hot-carrier dynamics in perovskite NCs further suggest that these materials show higher efficiencies compared to the bulk form of perovskites. However, the relaxation rates and pathways of hot-carriers are still being elucidated. By using ultrafast transient spectroscopy and calculating electronic band structures, we investigated the dependence of halide in Cs-based perovskite (CsPbX{sub 3} with X=Br, I, or their mixtures) NCs on the hot-carrier relaxation processes. All samples exhibit ultrafast (<0.6 ps) hot-carrier relaxation dynamics with following order: CsPbBr{sub 3} (310 fs)>CsPbBr{sub 1.5}I{sub 1.5} (380 fs)>CsPbI{sub 3} NC (580 fs). These result accounts for a reduced light emission efficiency of CsPbI{sub 3} NC compared to CsPbBr{sub 3} NC. (copyright 2017 Wiley-VCH Verlag GmbH and Co. KGaA, Weinheim)

Improving the first hyperpolarizability of anthracene through interaction with HX molecules (Xdbnd F, Cl, Br): A theoretical study

Science.gov (United States)

Abdolmaleki, Ahmad; Dadsetani, Mehrdad; Zabardasti, Abedin

2018-05-01

The variations in nonlinear optical activity (NLO) of anthracene (C14H10) was investigated via intermolecular interactions between C14H10 and HX molecules (Xdbnd F, Cl and Br) using B3LYP-D3 method at 6-311++G(d,p) basis set. The stabilization of those complexes was investigated via vibrational analysis, quantum theory of atoms in molecules, molecular electrostatic potential, natural bond orbitals and symmetry-adapted perturbation theory (SAPT) analysis. Furthermore, the optical spectra and the first hyperpolarizabilities of C14H10⋯HX complexes were computed. The adsorption of hydrogen halide through C14H10⋯HX complex formation, didn't change much the linear optical activities of C14H10 molecule, but the magnitude of the first hyperpolarizability of the C14H10⋯HX complexes to be as much as that of urea.

Conclusive evidence on the mechanism of the rhodium-mediated decyanative borylation.

Science.gov (United States)

Esteruelas, Miguel A; Oliván, Montserrat; Vélez, Andrea

2015-09-30

The stoichiometric reactions proposed in the mechanism of the rhodium-mediated decyanative borylation have been performed and all relevant intermediates isolated and characterized including their X-ray structures. Complex RhCl{xant(P(i)Pr2)2} (1, xant(P(i)Pr2)2 = 9,9-dimethyl-4,5-bis(diisopropylphosphino)xanthene) reacts with bis(pinacolato)diboron (B2pin2), in benzene, to give the rhodium(III) derivative RhHCl(Bpin){xant(P(i)Pr2)2} (4) and PhBpin. The reaction involves the oxidative addition of B2pin2 to 1 to give RhCl(Bpin)2{xant(P(i)Pr2)2}, which eliminates ClBpin generating Rh(Bpin){xant(P(i)Pr2)2} (2). The reaction of the latter with the solvent yields PhBpin and the monohydride RhH{xant(P(i)Pr2)2} (6), which adds the eliminated ClBpin. Complex 4 and its catecholboryl counterpart RhHCl(Bcat){xant(P(i)Pr2)2} (7) have also been obtained by oxidative addition of HBR2 to 1. Complex 2 is the promoter of the decyanative borylation. Thus, benzonitrile and 4-(trifluoromethyl)benzonitrile insert into the Rh-B bond of 2 to form Rh{C(R-C6H4)═NBpin}{xant(P(i)Pr2)2} (R = H (8), p-CF3 (9)), which evolve into the aryl derivatives RhPh{xant(P(i)Pr2)2} (3) and Rh(p-CF3-C6H4){xant(P(i)Pr2)2} (10), as a result of the extrusion of CNBpin. The reactions of 3 and 10 with B2pin2 yield the arylBpin products and regenerate 2.

Brüsseli I (uuesti sõnastatud) määrus: kas põhjalik muutus Eesti rahvusvahelises tsiviilkohtumenetluses? / Maarja Torga

Index Scriptorium Estoniae

Torga, Maarja, 1984-

2014-01-01

Alates 10. jaan. 2015 peavad Eesti kohtud ja kohtutäiturid hakkama nn Brüsseli I määruse (EÜ/44/2001) asemel kohaldama Brüsseli I määruses (EL/1215/2012) sisalduvaid sätteid (kohtualluvuse määramise, kohtulahendite ja ametlike dokumentide tunnustamise või täitmise kohta). Ülevaade määruse kohaldamisalast ja peamistest muudatustest ning vahekorrast teiste õigusaktidega

Crystal structure of transition metal halides TiCl4, α-TiCl3, WCl4 and TiI2

International Nuclear Information System (INIS)

Troyanov, S.I.; Snigireva, E.M.

2000-01-01

Crystal structures of TiCl 4 , α-TiCl 3 , WCl 4 and TiI 2 are determined by x-ray diffraction method. For crystalline WCl 4 general for phases of this type space group C2/m is confirmed. Linear chains of WCl 6 octahedrons joined through the opposite edges exist in structure. Short W-W distances (2.69 A) in linear chains differentiate the structure of WCl 6 . Laminar structure of TiI 2 is belongs to CdI 2 structural type. Iodine atoms form slightly distorted hexagonal face-centered packing, titanium atoms fill up octahedral hollows in two-layer packing of iodine atoms with Ti-I distances equal 2.903 A [ru

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)

Energy Technology Data Exchange (ETDEWEB)

Demissie, Taye B., E-mail: taye.b.demissie@uit.no; Komorovsky, Stanislav; Repisky, Michal; Ruud, Kenneth [Centre for Theoretical and Computational Chemistry, Department of Chemistry, UiT The Arctic University of Norway, N-9037 Tromsø (Norway); Jaszuński, Michał [Institute of Organic Chemistry, Polish Academy of Sciences, Kasprzaka 44, 01 224 Warszawa (Poland)

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.

Positron emission intensities in the decay of 64Cu, 76Br and 124I

International Nuclear Information System (INIS)

Qaim, S.M.; Bisinger, T.; Hilgers, K.; Nayak, D.; Coenen, H.H.

2007-01-01

The relatively long-lived positron emitters 64 Cu (t 1/2 = 12.7 h), 76 Br (t 1/2 = 16.2 h) and 124 I (t 1/2 = 4.18 d) are finding increasing applications in positron emission tomography (PET). For precise determination of their positron emission intensities, each radionuclide was prepared via a charged particle induced reaction in a ''no-carrier-added'' form and with high radionuclidic purity. It was then subjected to γ-ray and X-ray spectroscopy as well as to anticoincidence beta and γγ-coincidence counting. The positron emission intensities measured were: 64 Cu (17.8 ± 0.4)%, 76 Br (58.2 ± 1.9)% and 124 I (22.0 ± 0.5)%. The intensity of the weak 1346 keV γ-ray emitted in the decay of 64 Cu was determined as (0.54 ± 0.03)%. Some implications of the precisely determined nuclear data are discussed. (orig.)

Thermodynamic assessment of EuBr2 unary and LiBr-EuBr2 and NaBr-EuBr2 binary systems

International Nuclear Information System (INIS)

Gong, Weiping; Gaune-Escard, Marcelle

2009-01-01

As a basis for the design and development of molten salt mixtures, thermodynamic calculations of the phase diagrams and thermodynamic properties were carried out on the EuBr 2 unary and LiBr-EuBr 2 and NaBr-EuBr 2 binary systems over a wide temperature and composition range, respectively. The Gibbs energy of EuBr 2 was evaluated using an independent polynomial to fit the experimental heat capacity, the thermodynamic parameters for each phase in the LiBr-EuBr 2 and NaBr-EuBr 2 systems were optimized by using available experimental information on phase diagrams. A regular substitutional solution model for the liquid phase and Neumann-Kopp rule for the stoichiometric compound LiEu 2 Br 5 were adopted to reproduce the experimental data with reasonable excess Gibbs energy. Comparisons between the calculated phase diagrams and thermodynamic quantities show that all reliable experimental information is satisfactorily accounted for by the present thermodynamic description. Some thermodynamic properties were predicted to check the suitability of the present calculation.

The fundamental flaw of the HSAB principle is revealed by a complete speciation analysis of the [PtCl(6-n)Br(n)](2-) (n = 0-6) system.

Science.gov (United States)

Gerber, W J; van Wyk, P-H; van Niekerk, D M E; Koch, K R

2015-02-28

Bjerrum's model of step-wise ligand exchange is extended to compute a complete speciation diagram for the [PtCl6-nBrn](2-) (n = 0-6) system including all 17 equilibrium constants concerning the Pt(IV) chlorido-bromido exchange reaction network (HERN). In contrast to what the hard soft acid base (HSAB) principle "predicts", the thermodynamic driving force for the replacement of chloride by bromide in an aqueous matrix, for each individual ligand exchange reaction present in the Pt(IV) HERN, is due to the difference in halide hydration energy and not bonding interactions present in the acid-base complex. A generalized thermodynamic test calculation was developed to illustrate that the HSAB classified class (b) metal cations Ag(+), Au(+), Au(3+), Rh(3+), Cd(2+), Pt(2+), Pt(4+), Fe(3+), Cd(2+), Sn(2+) and Zn(2+) all form thermodynamically stable halido complexes in the order F(-) ≫ Cl(-) > Br(-) > I(-) irrespective of the sample matrix. The bonding interactions in the acid-base complex, e.g. ionic-covalent σ-bonding, Π-bonding and electron correlation effects, play no actual role in the classification of these metal cations using the HSAB principle. Instead, it turns out that the hydration/solvation energy of halides is the reason why metal cations are categorized into two classes using the HSAB principle which highlights the fundamental flaw of the HSAB principle.

Compton profiles and electronic structure of HgBr{sub 2} and HgI{sub 2}

Energy Technology Data Exchange (ETDEWEB)

Ahmed, G.; Dashora, Alpa [Department of Physics, University College of Science, M.L. Sukhadia University, Udaipur, 313001 Rajasthan (India); Sharma, M. [Physics Division, State Forensic Science Laboratory, Jaipur, 302016 Rajasthan (India); Ahuja, B.L. [Department of Physics, University College of Science, M.L. Sukhadia University, Udaipur, 313001 Rajasthan (India)], E-mail: blahuja@yahoo.com

2010-02-15

In this paper, we present the first-ever experimental Compton line shapes of HgBr{sub 2} and HgI{sub 2} using {sup 137}Cs Compton spectrometer. To compare our experimental momentum densities, we have computed the Compton profiles using Hartree-Fock and density functional theory within linear combination of atomic orbitals. We have also computed the energy bands and density of states using the linear combination of atomic orbitals and full potential linearized augmented plane wave method. On the basis of equal-valence-electron-density profiles, it is seen that HgI{sub 2} is more covalent than HgBr{sub 2} which is in agreement with the valence charge densities. The experimental isotropic profiles are found to be relatively in better agreement with the Hartree-Fock data. We have also discussed the photoluminescence and detection properties of both the halides.

Elastic properties of distorted triangular lattice KNiCl3-family compounds

International Nuclear Information System (INIS)

Nishiwaki, Yoichi; Hasegawa, Takumi; Machida, Kenichi; Takeuchi, Yoshio

2006-01-01

In order to discuss the condensation of the K 4 -mode in KNiCl 3 -family compounds, the temperature dependences of the elastic compliances of KNiCl 3 , RbMnBr 3 , RbFeBr 3 , and RbCoBr 3 were measured. In each compound, the temperature dependence of the elastic compliances s 33 showed a sharp discontinuity at the point of structural phase transition from a prototype P6 3 /mmc structure. The structural phase transitions of the KNiCl 3 -family compounds are induced by the condensation of the K 4 -mode at the Brilluoin zone boundary in the P6 3 /mmc structure. When the K 4 -mode is regarded as an order parameter η, the Landau free energy includes coupling term η 2 T 3 , where T 3 is an external stress. The experimental results were interpreted satisfactorily on the basis of a phenomenological Landau theory. (author)

Fernández de Oviedo (<i>Historia General y Natural de las Indiasi>, Libro VI, cap. LI y la etología clásica

Directory of Open Access Journals (Sweden)

Lens-Tuero, Jesús

1997-06-01

Full Text Available Not available.<br>>El presente trabajo se propone llamar la atención sobre un notable texto de Fernández de Oviedo (Historia General y Natural de las Indias, Libro VI, cap. LI que, en la medida que conocemos, no ha sido objeto de un comentario adecuado. En dicho texto se refiere el establecimiento de un pacto entre el hombre y el animal para asegurarse la supervivencia y mutuo beneficio, y la transformación de tal pacto en una relación de amistad y afecto. Tales relaciones pueden ser iluminadas desde la antropología clásica, en la que dichas categorías desempeñaron un papel no carente de relevancia.

State-to-state dynamics of H+HX collisions. II. The H+HX→HX/sup dagger/+H (X = Cl,Br,I) reactive exchange and inelastic collisions at 1.6 eV collision energy

International Nuclear Information System (INIS)

Aker, P.M.; Germann, G.J.; Tabor, K.D.; Valentini, J.J.

1989-01-01

We report measurement of product state distributions for the rotationally and/or vibrationally excited HX formed in collisions of translationally hot H atoms with HX (X = Cl, Br, and I) at 1.6 eV collision energy. The product state distributions are probed after only one collision of the fast H atom, using coherent anti-Stokes Raman scattering spectroscopy. Whether proceeding by inelastic collisions or reactive exchange, the transfer of translational energy to vibrational and rotational energy is quite inefficient in H+HX collisions at 1.6 eV. For all three hydrogen halides only 2--3% of the initial translational energy appears as HX vibration. For H+HCl only 6% of the initial energy is converted to HCl rotational energy, while for H+HBr and H+HI, this percentage is twice as large, 11--12%, but still small. The indistinguishability of the two H atoms involved makes it impossible to distinguish reactive exchange from inelastic energy transfer in these H+HX collisions. However, the difference in rotational energy partitioning for H+HBr and H+HI as compared with H+HCl, suggests that reactive exchange is dominant in the former and inelastic energy transfer dominates in the latter. The total cross sections for the combined energy transfer/reactive exchange do not change much with the identity of X, being 13 +- 3, 11 +- 2, and 11 +- 2 A 2 , for H+HCl, H+HBr, and H+HI, respectively

3+ and [Sb13Se16Br2] 5+ - Double and quadruple spiro cubanes from ionic liquids

KAUST Repository

Ahmed, Ejaz; Breternitz, Joachim; Groh, Matthias Friedrich; Isaeva, Anna A.; Ruck, Michael J.

2014-01-01

The reaction of antimony and selenium in the bromine-rich Lewis acidic ionic liquid [BMIm]Br·4.7AlBr3 (BMIm: 1-butyl-3- methylimidazolium) in the presence of a small amount of NbCl5 at 160 °C yielded dark-red crystals of [Sb7Se8Br 2][AlX4]3. For X

Preparation of radioactive labelled compounds. Pt. 2. 82Br labelled organic bromine compounds by isotopic exchange

International Nuclear Information System (INIS)

Otto, R.

1988-05-01

Studies on isotopic exchange between organic bromine compounds and 82 Br labelled dioxane dibromide in the presence of AlCl 3 are described. The results obtained enable to develop a simple and quick preparation method for the labelling with 82 Br [fr

Extraction behaviour and mechanism of Pt(iv) and Pd(ii) by liquid-liquid extraction with an ionic liquid [HBBIm]Br.

Science.gov (United States)

Liu, Wenhui; Wang, Qi; Zheng, Yan; Wang, Shubin; Yan, Yan; Yang, Yanzhao

2017-06-06

In this study, a method of one-step separation and recycling of high purity Pd(ii) and Pt(iv) using an ionic liquid, 1-butyl-3-benzimidazolium bromate ([HBBIm]Br), was investigated. The effects of [HBBIm]Br concentration, initial metal concentration, and loading capacity of [HBBIm]Br were examined in detail. It was observed that [HBBIm]Br was a very effective extractant for selectively extracting Pd(ii) and precipitating Pt(iv). Through selectively extracting Pd(ii) and precipitating Pt(iv), each metal with high purity was separately obtained from mixed Pd(ii) and Pt(iv) multi-metal solution. The method of one-step separation of Pd(ii) and Pt(iv) is simple and convenient. The anion exchange mechanism between [HBBIm]Br and Pt(iv) was proven through Job's method and FTIR and 1 H NMR spectroscopies. The coordination mechanism between [HBBIm]Br and Pd(ii) was demonstrated via single X-ray diffraction and was found to be robust and distinct, as supported by the ab initio quantum-chemical studies. The crystals of the [PdBr 2 ·2BBIm] complex were formed first. Moreover, the influence of the concentrations of hydrochloric acid, sodium chloride, and sodium nitrate on the precipitation of Pt(iv) and extraction of Pd(ii) was studied herein. It was found that only the concentration of H + could inhibit the separation of Pt(iv) because H + could attract the anion PtCl 6 2- ; thus, the exchange (anion exchange mechanism) between the anions PtCl 6 2- and Br - was prevented. However, both the concentration of H + and Cl - can obviously inhibit the extraction of Pd(ii) because H + and Cl - are the reaction products and increasing their concentration can inhibit the progress of the reaction (coordination mechanism).

An i.r. investigation on some calcium aluminate hydrates, Ca2Al(OH)6+X-.yH2O (= 3CaO.Al2O3.CaX2.nH2O, X- = univalent anion)

NARCIS (Netherlands)

Houtepen, C.J.M.; Stein, H.N.

1976-01-01

The i.r. spectra of some hydrated and dehydrated calcium aluminate hydrates of the type Ca2Al(OH)6+X-·yH2O with X- = Cl-, Br-, J-, ClO3-, NO3-, ClO4- (y = 2) and X- = BrO3-, JO3- (2

Pathways for the OH + Br2 → HOBr + Br and HOBr + Br → HBr + BrO Reactions.

Science.gov (United States)

Wang, Hongyan; Qiu, Yudong; Schaefer, Henry F

2016-02-11

The OH radical reaction with Br2 and the subsequent reaction HOBr + Br are of exceptional importance to atmospheric chemistry and environmental chemistry. The entrance complex, transition state, and exit complex for both reactions have been determined using the coupled-cluster method with single, double, and perturbative triple excitations CCSD(T) with correlation consistent basis sets up to size cc-pV5Z and cc-pV5Z-PP. Coupled cluster effects with full triples (CCSDT) and full quadruples (CCSDTQ) are explicitly investigated. Scalar relativistic effects, spin-orbit coupling, and zero-point vibrational energy corrections are evaluated. The results from the all-electron basis sets are compared with those from the effective core potential (ECP) pseudopotential (PP) basis sets. The results are consistent. The OH + Br2 reaction is predicted to be exothermic 4.1 ± 0.5 kcal/mol, compared to experiment, 3.9 ± 0.2 kcal/mol. The entrance complex HO···BrBr is bound by 2.2 ± 0.2 kcal/mol. The transition state lies similarly well below the reactants OH + Br2. The exit complex HOBr···Br is bound by 2.7 ± 0.6 kcal/mol relative to separated HOBr + Br. The endothermicity of the reaction HOBr + Br → HBr + BrO is 9.6 ± 0.7 kcal/mol, compared with experiment 8.7 ± 0.3 kcal/mol. For the more important reverse (exothermic) HBr + BrO reaction, the entrance complex BrO···HBr is bound by 1.8 ± 0.6 kcal/mol. The barrier for the HBr + BrO reaction is 6.8 ± 0.9 kcal/mol. The exit complex (Br···HOBr) for the HBr + BrO reaction is bound by 1.9 ± 0.2 kcal/mol with respect to the products HOBr + Br.

Exploring Polaronic, Excitonic Structures and Luminescence in Cs4PbBr6/CsPbBr3.

Science.gov (United States)

Kang, Byungkyun; Biswas, Koushik

2018-02-15

Among the important family of halide perovskites, one particular case of all-inorganic, 0-D Cs 4 PbBr 6 and 3-D CsPbBr 3 -based nanostructures and thin films is witnessing intense activity due to ultrafast luminescence with high quantum yield. To understand their emissive behavior, we use hybrid density functional calculations to first compare the ground-state electronic structure of the two prospective compounds. The dispersive band edges of CsPbBr 3 do not support self-trapped carriers, which agrees with reports of weak exciton binding energy and high photocurrent. The larger gap 0-D material Cs 4 PbBr 6 , however, reveals polaronic and excitonic features. We show that those lattice-coupled carriers are likely responsible for observed ultraviolet emission around ∼375 nm, reported in bulk Cs 4 PbBr 6 and Cs 4 PbBr 6 /CsPbBr 3 composites. Ionization potential calculations and estimates of type-I band alignment support the notion of quantum confinement leading to fast, green emission from CsPbBr 3 nanostructures embedded in Cs 4 PbBr 6 .

Toxic and radiosensitizina effect of reduced nitroimidazoles on E.COLI B/r cells

International Nuclear Information System (INIS)

Ryabchenko, N.I.; Semin, Yu.A.; Petrova, K.M.; Kutmin, A.I.

1983-01-01

The spectrophotometric method was used to study the rate of chemical reduction of misonidazole and metronidazole by NH 4 Cl and Zn in the atmosphere of argon and oxygen. Reduction of drugs increased their toxicity for hypoxic and oxygenated E. coli B/r. The reduced metronidazole is a more effective radiosensitizer of hypoxic E. coli B/r than the original compound

Hurtigste versus mest brændstoføkonomiske ruter

DEFF Research Database (Denmark)

Andersen, Ove; Krogh, Benjamin Bjerre; Lahrmann, Harry

2013-01-01

Der er stort fokus på at forbedre brændstoføkonomien i transportbranchen generelt. I denne artikel anvendes brændstoftallene fra Controller Area Network Bus (CANBus) kombineret med GPS data til at skabe et digitalt vejkort, hvor det er muligt at sammenligne de hurtigste ruter med de mest brændsto...

Ultrasonic irradiation-promoted one-pot synthesis of CH3NH3PbBr3 quantum dots without using flammable CH3NH2 precursor

Science.gov (United States)

Jiang, Han; Wang, Chunlei; Lv, Changgui; Xu, Shuhong; Zhu, Li; Zhang, Ruohu; Cui, Yiping

2017-02-01

At present, the CH3NH3PbBr3 quantum dots (QDs) reported in the literature usually contain two synthesis steps: the initial preparation of CH3NH3Br via the reaction of flammable CH3NH2 and HBr, together with the subsequent formation of CH3NH3PbBr3 QDs. To avoid the use of dangerous CH3NH2, this work develops a novel one-pot method for synthesizing CH3NH3PbBr3 QDs using safe and commercially available reactants (CH3NH3Cl, KBr and PbCl2). It is found that ultrasonic treatment plays a key role during the synthesis of CH3NH3PbBr3 QDs. Without ultrasonic irradiation, it is not possible to synthesize CH3NH3PbBr3 QDs under heating or vigorous stirring. Aliquots of samples taken at different ultrasonic irradiation time intervals show a time-dependent redshift in the emission wavelength. This suggests the formation of CH3NH3PbCl3 QDs first, followed by the formation of CH3NH3PbBr3 QDs through ultrasonically promoted halide exchange. Moreover, mixed CH3NH3PbCl x Br3-x QDs with a tunable emission wavelength can also be prepared through this one-pot method by controlling the ultrasonic irradiation time. In comparison to the previous two-step method, the current one-pot method is simpler, less time-consuming and does not use flammable CH3NH2. The as-prepared CH3NH3PbBr3 QDs show a comparable photoluminescence (PL) quantum yield (QY) to that of the literature. What is more, the ultrasonic time-controlled emission wavelength of CH3NH3PbCl x Br3-x QDs also provides an alternative way of tuning QD emission to the traditional way of controlling the halide ratios.

X-ray photoemission analysis of chemically modified TlBr surfaces for improved radiation detectors

International Nuclear Information System (INIS)

Nelson, A. J.; Voss, L. F.; Beck, P. R.; Graff, R. T.; Conway, A. M.; Nikolic, R. J.; Payne, S. A.; Lee, J.-S.; Kim, H.; Cirignano, L.; Shah, K.

2013-01-01

We subjected device-grade TlBr to various chemical treatments used in room temperature radiation detector fabrication to determine the resulting surface composition and electronic structure. As-polished TlBr was treated separately with HCl, SOCl 2 , Br:MeOH and HF solutions. High-resolution photoemission measurements on the valence band electronic structure and Tl 4f, Br 3d, Cl 2p and S 2p core lines were used to evaluate surface chemistry and shallow heterojunction formation. Surface chemistry and valence band electronic structure were correlated with the goal of optimizing the long-term stability and radiation response

Angular correlation for gamma-gamma transitions in 81Br and 83Br nuclei

International Nuclear Information System (INIS)

Matheus, R.

1984-01-01

The directional angular correlation of coincident gamma transitions in 81 Br and 83 Br have been measured following the β - decay of 81 Se(T sub(1/2) = 18.6 min) and 83 Se(T sub(1/2) = 22.6 min) respectively, using Ge(Li) - high purity Ge and Ge(Li)-NaI(Tl) spectrometers. The radioactive sources were prepared by irradiating with neutrons in the IEA-R1 reactor, metallic selenium (natural) to produce 81 Se and samples of metallic selenium enriched (to approx. 90% in 82 Se) to produce 83 Se. Measurements have been carried out for the gamma cascades 260-276 KeV, 290-276 KeV and 552-276 KeV in 81 Br and the gamma cascades 225(510)-356 KeV, 510-356 KeV, 572-(510)-356 KeV, 718-(225)-(510)-356 KeV, 1064-356 KeV, 718-225 KeV, 718-(225)-510 KeV, 836-718 KeV, 718-(225)-866 KeV, 883-718 KeV and 1895-799 KeV in 83 Br. The multipole mixing ratios, σ(E2/M1), were determined for 3 gamma transitions in 81 Br and 11 gamma transitions in 83 Br. In the case of 81 Br present results confirmed some of the earlier results. The spin and parity assignment were made to the majority of levels in 81 Br and 83 Br involved in the present study, some of them confirming the earlier results. A comparison of some of the nuclear properties of the 79 Br, 81 Br and 83 Br is made based on the available experimental data. The experimental results are also discussed qualitatively in terms of some nuclear models applicable for the description of the properties of odd-A bromine isotopes. (Author) [pt

A Study of Inverted-Type Perovskite Solar Cells with Various Composition Ratios of (FAPbI31−x(MAPbBr3x

Directory of Open Access Journals (Sweden)

Lung-Chien Chen

2016-10-01

Full Text Available This work presents mixed (FAPbI31−x(MAPbBr3x perovskite films with various composition ratios, x (x = 0–1, which are formed using the spin coating method. The structural, optical, and electronic behaviors of the mixed (FAPbI31−x(MAPbBr3x perovskite films are discussed. A device with structure glass/indium tin oxide (ITO/poly(3,4-ethylenedioxythiophene polystyrene sulfonate (PEDOT:PSS/mixed perovskite/C60/BCP/Ag was fabricated. The mixed perovskite film was an active light-harvesting layer. PEDOT:PSS was a hole transporting layer between the ITO and perovskite. Both C60 and bathocuproine (BCP were electron transporting layers. MAPbBr3 was added to FAPbI3 with a composition ratio of x = 0.2, stabilizing the perovskite phase, which exhibited a uniform and dense morphology. The optimal device exhibited band matching with C60, resulting in a low series resistance (Rsh and a high fill factor (FF. Therefore, the device with composition (FAPbI31−x(MAPbBr3x and x = 0.2 exhibited outstanding performance.

Investigation of LaBr3:Ce probe for gamma-ray spectroscopy and dosimetry

Science.gov (United States)

Maghraby, Ahmed M.; Alzimami, K. S.; Alkhorayef, M. A.; Alsafi, K. G.; Ma, A.; Alfuraih, A. A.; Alghamdi, A. A.; Spyrou, N. M.

2014-02-01

The main thrust of this work is the investigation of performance of relatively new commercial LaBr3:Ce probe (Inspector 1000™ with LaBr3:Ce crystal) for gamma-ray spectroscopy and dosimetry measurements in comparison to LaCl3:Ce and NaI:Tl scintillators. The crystals were irradiated by a wide range of energies (57Co, 22Na, 18F, 137Cs and 60Co). The study involved recording of detected spectra and measurement of energy resolution, photopeak efficiency, internal radioactivity measurements as well as dose rate. The Monte Carlo package, Geant4 Application for Tomographic Emission (GATE) was used to validate the experiments. Overall results showed very good agreement between the measurements and the simulations. The LaBr3:Ce crystal has excellent energy resolution, energy resolutions of (3.37±0.05)% and (2.98±0.07)% for a 137Cs 662 keV and a 60Co 1332 keV gamma-ray point sources respectively, were recorded. The disadvantage of the lanthanum halide scintillators is their internal radioactivity. Inspector 1000™ with LaBr3:Ce scintillator has shown an accurate and quick dose measurements at Positron Emission Tomography (PET) Units which allows accurate assessment of the radiation dose received by staff members compared to the use of electronic personal dosimeters (EPD).

Understanding the Effects of NaCl, NaBr and Their Mixtures on Silver Nanowire Nucleation and Growth in Terms of the Distribution of Electron Traps in Silver Halide Crystals

Directory of Open Access Journals (Sweden)

Yunjun Rui

2018-03-01

Full Text Available In recent years, many research groups have synthesized ultra-thin silver nanowires (AgNWs with diameters below 30 nm by employing Cl− and Br− simultaneously in the polyol process. However, the yield of AgNWs in this method was low, due to the production of Ag nanoparticles (AgNPs as an unwanted byproduct, especially in the case of high Br− concentration. Here, we investigated the roles of Cl− and Br− in the preparation of AgNWs and then synthesized high aspect ratio (up to 2100 AgNWs in high yield (>85% AgNWs using a Cl− and Br− co-mediated method. We found that multiply-twinned particles (MTPs with different critical sizes were formed and grew into AgNWs, accompanied by a small and large amount of AgNPs for the NaCl and NaBr additives, respectively. For the first time, we propose that the growth of AgNWs of different diameters and yields can be understood based on the electron trap distribution (ETD of the silver halide crystals. For the case of Cl− and Br− co-additives, a mixed silver halide crystal of AgBr1−xClx was formed, rather than the AgBr/AgCl mixture reported previously. In this type of crystal, the ETD is uniform, which is beneficial for the synthesis of AgNWs with small diameter (30~40 nm and high aspect ratio. AgNW transparent electrodes were prepared in air by rod coating. A sheet resistance of 48 Ω/sq and transmittance of 95% at 550 nm were obtained without any post-treatment.

The structure of molten CuCl, CuI and their mixtures as investigated by using neutron diffraction

International Nuclear Information System (INIS)

Drewitt, James W E; Salmon, Philip S; Takeda, Shin'ichi; Kawakita, Yukinobu

2009-01-01

The structure of molten CuCl, CuI and their mixtures (CuCl) x (CuI) 1-x with x = 0.294, 0.576, 0.801 was studied by using neutron diffraction. The results are discussed by reference to the information that is available on the structure of CuCl and CuI from experiment, theory and computer simulation. The comparison points to a need for more realistic models for the CuCl-CuI system which should take into account the presence of chemical bonds that have been found in CuI by the application of ab initio molecular dynamics methods.

Atmospheric Lifetime of CHF2Br, a Proposed Substitute for Halons.

Science.gov (United States)

Talukdar, R; Mellouki, A; Gierczak, T; Burkholder, J B; McKeen, S A; Ravishankara, A R

1991-05-03

The rate coefficients, k(1), for the reaction of OH with CHF(2)Br have been measured using pulsed photolysis and discharge flow techniques at temperatures (T) between 233 and 432 K to be k(1), = (7.4 +/- 1.6) x 10(-13) exp[-(1300 +/- 100)/T] cubic centimeters per molecule per second. The ultraviolet absorption cross sections, sigma, of this molecule between 190 and 280 nanometers were measured at 296 K. The k(1), and sigma values were used in a one-dimensional model to obtain an atmospheric lifetime of approximately 7 years for CHF(2)Br. This lifetime is shorter by approximately factors of 10 and 2 than those for CF(3)Br and CF(2)ClBr, respectively. The ozone depletion potentials of the three compounds will reflect these lifetimes.

Temporalizar la historia. Sobre la <i>Historik> de Reinhart Koselleck

Directory of Open Access Journals (Sweden)

Chignola, Sandro

2007-12-01

Full Text Available Reinhart Koselleck’s <i>Historik>, following german classic hermeneutics, represents an important philosophical attempt in formalizing the trascendental categories for historical experience of time. The article focuses on Koselleck’s attemp and try to demonstrate that, referring to Kant’s philosophy of history and as Michel Foucault did, Koselleck assumes, in a circular way, the formal criteria for his <i>Historik> from the experience of temporalization and acceleration of history which mark modernity as an epoch.<br>>La <i>Historik> de Reinhart Koselleck representa un importante intento filosófico —llevado a cabo siguiendo la estela de la hermenéutica clásica alemana— de formalizar las categorías trascendentales de la experiencia histórica del tiempo. El ensayo pone a prueba la hipótesis de Koselleck y pretende demostrar cómo éste, refiriéndose a Kant y de manera análoga a Foucault, extrae circularmente los criterios formales para su <i>Historik> a partir de la experiencia de aceleración y temporalización de la historia que caracteriza a la modernidad como época.

Fabrication and Characterization of CH3NH3PbI3−x−yBrxCly Perovskite Solar Cells

Directory of Open Access Journals (Sweden)

Atsushi Suzuki

2016-05-01

Full Text Available Fabrication and characterization of CH3NH3PbI3−x−yBrxCly perovskite solar cells using mesoporous TiO2 as electron transporting layer and 2,2′,7,7′-tetrakis-(N,N-di-4-methoxyphenylamino-9,9′-spirobifluorene as a hole-transporting layer (HTL were performed. The purpose of the present study is to investigate role of halogen doping using iodine (I, bromine (Br and chlorine (Cl compounds as dopant on the photovoltaic performance and microstructures of CH3NH3PbI3−x−yBrxCly perovskite solar cells. The X-ray diffraction identified a slight decrease of crystal spacing in the perovskite crystal structure doped with a small amount of I, Br, and Cl in the perovskite compounds. Scanning electron microscopy (SEM and energy dispersive X-ray spectroscopy (EDX showed the perovskite crystal behavior depended on molar ratio of halogen of Pb, I, Br and Cl. Incorporation of the halogen doping into the perovskite crystal structure improved photo generation, carrier diffusion without carrier recombination in the perovskite layer and optimization of electronic structure related with the photovoltaic parameters of open-circuit voltage, short-circuit current density and conversion efficiency. The energy diagram and photovoltaic mechanisms of the perovskite solar cells were discussed in the context of the experimental results.

Theoretical investigation of the Te{sub 4}Br{sub 2} molecule in ionic liquids

Energy Technology Data Exchange (ETDEWEB)

Elfgen, Roman [Mulliken Center for Theoretical Chemistry, University of Bonn, Beringstr. 4+6, 53115, Bonn (Germany); Max Planck Institute for Chemical Energy Conversion, Stiftstr. 34-36, 45413, Muehlheim an der Ruhr (Germany); Holloczki, Oldamur; Ray, Promit; Kirchner, Barbara [Mulliken Center for Theoretical Chemistry, University of Bonn, Beringstr. 4+6, 53115, Bonn (Germany); Groh, Matthias F. [Department of Chemistry and Food Chemistry, Dresden University of Technology, 01062, Dresden (Germany); Ruck, Michael [Department of Chemistry and Food Chemistry, Dresden University of Technology, 01062, Dresden (Germany); Max Planck Institute for Chemical Physics of Solids, Noethnitzer Str. 40, 01187, Dresden (Germany)

2017-01-15

Material synthesis in ionic liquids, at or near room temperature, is currently a subject of immense academic interest. In order to illuminate molecular-level details and the underlying chemistry, we carried out molecular simulations of a single Te{sub 4}Br{sub 2} molecule dissolved in the ionic liquid 1-ethyl-3-methylimidazolium chloride, as well as in the ionic liquid mixed with aluminum chloride. Although the ethyl side chain is much too short to show detailed microheterogeneity, significant structuring with the small chloride anions is seen in case of the pure ionic liquid. In the case of the mixture, formation of larger anionic clusters is distinctly observed and analyzed. Due to the tendency of ionic liquids to dissociate, there is a pronounced shift to elongated Te-Br distances in both investigated solvents. However, only in the AlCl{sub 3}-containing liquid, we observe the reaction of the open chain-like Te{sub 4}Br{sub 2} molecule to a closed square-like Te{sub 4}Br{sup +} and AlCl{sub 3}Br{sup -} ion. The molecular arrangement of the [Te{sub 4}]{sup 2+} unit shows negligible deviation from that in the experimental crystal structure. (copyright 2017 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

Ammonium dynamics in the disordered α-phase of K1-x(NH4)xY (Y = Cl, Br, I). A neutron scattering study

International Nuclear Information System (INIS)

Natkaniec, I.; Smirnov, L.S.; Shuvalov, L.A.

2002-01-01

The effect of temperature and concentration on the lattice parameters and amplitude-weighted phonon density of states in mixed salts of ammonium-potassium halides is investigated by neutron powder diffraction and incoherent inelastic neutron scattering. In the disordered α-phase (NaCl type) ammonium ions exhibit a fast stochastic reorientation at phonon frequency rates down to ca. 80 K. At 10 K, the incoherent inelastic neutron scattering spectra display four distinct ammonium excitations: two (resonant) modes below and two (localized) above the Debye cut-off energy of potassium halides. High-frequency localized modes correspond to translational and librational vibrations of NH 4 ions. These modes are typical for the ordered phases of ammonium halides. The effect of ammonium concentration on localized and resonant modes is studied for the K 1-x (NH 4 ) x I mixed salts. The harmonic excitations of ammonium in a hypothetical low-temperature α-phase of NH 4 I are approximated to ca. 30, 95, 155 and 250 cm -1 . In a real low-temperature ordered γ-phase of NH 4 I, translational ammonium vibrations are observed at ca. 140-160 cm -1 and librational vibrations at ca.300 cm -1

Intramolecular charge transfer of 4-(dimethylamino)benzonitrile probed by time-resolved fluorescence and transient absorption: No evidence for two ICT states and a πσ* reaction intermediate

International Nuclear Information System (INIS)

Zachariasse, Klaas A.; Druzhinin, Sergey I.; Senyushkina, Tamara; Kovalenko, Sergey A.

2009-01-01

For the double exponential fluorescence decays of the locally excited (LE) and intramolecular charge transfer (ICT) states of 4-(dimethylamino)benzonitrile (DMABN) in acetonitrile (MeCN) the same times τ 1 and τ 2 are observed. This means that the reversible LE ICT reaction, starting from the initially excited LE state, can be adequately described by a two state mechanism. The most important factor responsible for the sometimes experimentally observed differences in the nanosecond decay time, with τ 1 (LE) 1 (ICT), is photoproduct formation. By employing a global analysis of the LE and ICT fluorescence response functions with a time resolution of 0.5 ps/channel in 1200 channels reliable kinetic and thermodynamic data can be obtained. The arguments presented in the literature in favor of a πσ* state with a bent CN group as an intermediate in the ICT reaction of DMABN are discussed. From the appearance of an excited state absorption (ESA) band in the spectral region between 700 and 800 nm in MeCN for N,N-dimethylanilines with CN, Br, F, CF 3 , and C(=O)OC 2 H 2 p-substituents, it is concluded that this ESA band cannot be attributed to a πσ * state, as only the C-C≡N group can undergo the required 120 deg. bending.

Electronic structure, photoemission spectra, and vacuum-ultraviolet optical spectra of CsPbCl3 and CsPbBr3

Science.gov (United States)

Heidrich, K.; Schäfer, W.; Schreiber, M.; Söchtig, J.; Trendel, G.; Treusch, J.; Grandke, T.; Stolz, H. J.

1981-11-01

Optical spectra of CsPbCl3 and CsPbBr3 have been measured in the range from 2 to 10 eV and have been combined with ultraviolet-photoemission-spectroscopy (UPS)-measurements at 21.1 and 40.8 eV. A quantitative band calculation is presented, which takes into account anion-anion interaction as well as electronic states of the Cs+ ion. The prominent features of earlier band models and measurements are reestablished through our measurements and calculations, namely that the valence band consists of anionic p functions and Pb 6s functions, the lowest conduction band being Pb 6p type, and the lowest gap occuring at the R point of the Brillouin zone. Inclusion of a further (Cs 6s-type) conduction band, however, is necessary to bring the calculated joint density of states into agreement with vacuum-ultraviolet optical spectra. The calculated densities of states of the valence bands are in quantitative agreement with those deduced from our UPS measurements.

A calculation of the physical parameters responsible for the enhancement of radiation damage due to the incorporation of Br/I atoms into the DNA

International Nuclear Information System (INIS)

Charlton, D.E.

1992-01-01

It is well known that when analogs of thymidine containing iodine or bromine are incorporated into the DNA of irradiated cells there is a decrease of the D 0 . Three mechanisms for this effect have been discussed: (a) photoactivation of the Br/I atom and the production of Auger electrons, (b) creation of highly reactive uracil radicals by the interaction of hydrated electrons with BrUdR/IUdR, leading to SSB, and (c) interference with repair or the fixation of the damage by the presence of the Br/I atoms. Experiments to investigate photoactivation of the Br/I atoms will include all three, so that knowledge of the relative size of each contribution is useful. The first process is reasonably well understood and here the second process is examined. It is assumed that the incorporated analogs only produce radicals if they are present in a region of DNA containing energy depositions. An SSB produced by this radical can combine with a nearby SSB produced by electron damage to give a DSB, thus increasing the yield of DSB compared to the yield without the analog present. The increased yields at various levels of Br/I incorporation are compared to experiment for different models of radical action

Postsynthesis Transformation of Insulating Cs4PbBr6 Nanocrystals into Bright Perovskite CsPbBr3 through Physical and Chemical Extraction of CsBr.

Science.gov (United States)

Palazon, Francisco; Urso, Carmine; De Trizio, Luca; Akkerman, Quinten; Marras, Sergio; Locardi, Federico; Nelli, Ilaria; Ferretti, Maurizio; Prato, Mirko; Manna, Liberato

2017-10-13

Perovskite-related Cs 4 PbBr 6 nanocrystals present a "zero-dimensional" crystalline structure where adjacent [PbBr 6 ] 4- octahedra do not share any corners. We show in this work that these nanocrystals can be converted into "three-dimensional" CsPbBr 3 perovskites by extraction of CsBr. This conversion drastically changes the optoelectronic properties of the nanocrystals that become highly photoluminescent. The extraction of CsBr can be achieved either by thermal annealing (physical approach) or by chemical reaction with Prussian Blue (chemical approach). The former approach can be simply carried out on a dried film without addition of any chemicals but does not yield a full transformation. Instead, reaction with Prussian Blue in solution achieves a full transformation into the perovskite phase. This transformation was also verified on the iodide counterpart (Cs 4 PbI 6 ).

OClO and BrO observations in the volcanic plume of Mt. Etna - implications on the chemistry of chlorine and bromine species in volcanic plumes

Science.gov (United States)

Gliß, J.; Bobrowski, N.; Vogel, L.; Platt, U.

2014-10-01

mechanism in literature often referred to as "bromine explosion" and that OClO is formed in the "BrO + ClO"-reaction. BrO and OClO concentrations were estimated from the measured SCDs assuming a circular plume shape. In addition, mixing ratios of ClO were determined from the retrieved OClO and BrO-SCDs assuming chemical equilibrium between formation of OClO (BrO + ClO) and its destruction (photolysis). Mean abundances in the young plume (τBrO = 1.35 ppb, OClO = 300 ppt and ClO = 139 ppt with peak values of 600 ppt (OClO), 2.7 ppb (BrO) and 235 ppt (ClO) respectively. The prevailing Cl-atom concentrations in the plume could be estimated from the rate of increase of OClO and BrO in the young plume and the determined ClO and OClO concentrations. Values between 5.1 × 106 cm-3 (at 40 ppb O3) and 2.1 × 108 cm-3 (at 1 ppb O3) were found. Based on that, a potential - chlorine induced - depletion of tropospheric methane (CH4) in the plume was investigated. CH4-lifetimes between 13 h (at 1 ppb O3) and 23 days (at 40 ppb O3) were found. These are considerably small compared to the atmospheric lifetime of CH4. However, the impact of gaseous chlorine on the CH4-budget in the plume environment was assessed to be relatively small, mainly due to plume dispersion (decrease of Cl number densities) and permanent mixing of the plume with the surrounding atmosphere (net supply of O3 and CH4).

Wet chemical synthesis and luminescence in Ca5(PO4)3M:Eu2+ (M = Br, I) phosphors for solid state lighting

Science.gov (United States)

Mungmode, C. D.; Gahane, D. H.; Moharil, S. V.

2018-05-01

A simple wet chemical synthesis of Eu2+ activated Ca5(PO4)3Br and Ca5(PO4)3I phosphors and their photoluminescence is reported. Formation of Ca5(PO4)3Br is confirmed by X-ray diffraction (XRD). Synthesized phosphors are analyzed for photoluminescence (PL) spectrum. A bright blue emission is observed when phosphors are excited by near Ultra Violet (nUV) radiations. Photoluminescence emission spectrum for (Ca0.985Eu0.015)5(PO4)3Br is centered at 457 nm and for (Ca0.985Eu0.015)5(PO4)3 I it peaks at 455 nm when excited by 365 nm near UV radiation. Eu2+ luminescence in Ca5(PO4)3Br is reported for the first time. The phosphors can be efficiently excited by nUV radiations. This shows that phosphors may be used as blue phosphor in pcLED for Solid State Lighting.

Cu ion disordering in high ionic conductor Rb4Cu16I7Cl13

International Nuclear Information System (INIS)

Kawaji, Hitoshi; Atake, Tooru; Kanno, Ryoji; Izumi, Fujio; Yamamoto, Osamu.

1993-01-01

The properties of a high ionic conductor Rb 4 Cu 16 I 7+x Cl 13-x were studied by neutron and X-ray diffraction, and heat capacity measurements. The structure parameters of Rb 4 Cu 16 I 7.2 Cl 12.8 were obtained by the Rietveld analysis of TOF neutron diffraction data between 50 and 300 K, which showed gradual excitation of migration of Cu ions from Cu(3) site into Cu(2) site with increasing temperature from about 100 K to room temperature. The heat capacity was measured between 10 and 300 K using a high precision adiabatic calorimeter. An abnormal increase was observed in the heat capacity curve above about 100 K. The excess heat capacity showed a broad anomaly with a maximum at about 190 K. The measurements were also made of Rb 4 Cu 16 I 7 Cl 13 which showed slight different properties from Rb 4 Cu 16 I 7.2 Cl 12.8 . (author)

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).

Science.gov (United States)

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.

Highly efficient transition metal-free coupling of acid chlorides with terminal alkynes in [bmim]Br: A rapid route to access ynones using MgCl2

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Mohammad Navid Soltani Rad

2018-03-01

Full Text Available A simple, mild, highly efficient and transition metal-free protocol for synthesis of ynones in an ionic liquid is described. In this approach, the coupling reaction of different acid chlorides with terminal alkynes was efficiently carried out using 0.05 mol% MgCl2 in the presence of triethylamine in [bmim]Br at room temperature to afford the corresponding ynones in good to excellent yields. This method is highly efficient for various acid chlorides and alkynes including aliphatic, aromatic, and heteroaromatic substrates bearing different functional groups. The influence of some parameters in this reaction including type of ionic liquid, base and catalyst has been discussed.

Relaxed electric dipole moments of polar molecules interacting with a slow positron: H{sub 2}O and CH{sub 3}X (X=F, Cl, Br)

Energy Technology Data Exchange (ETDEWEB)

Assafrao, Denise; Mohallem, Jose R, E-mail: rachid@fisica.ufmg.b [Laboratorio de Atomos e Moleculas Especiais, Departamento de FIsica, ICEx, Universidade Federal de Minas Gerais, PO Box 702, 30123-970, Belo Horizonte, MG (Brazil)

2010-08-14

The variation in the electric dipole moments of H{sub 2}O, CH{sub 3}F, CH{sub 3}Cl and CH{sub 3}Br as their geometries relax due to interaction with a positron is evaluated. The results are in good agreement with a recently observed empirical dependence of the positron binding energy on molecular properties (Danielson et al 2009 J. Phys. B: At. Mol. Opt. Phys. 42 235203). For binding energies larger than 100 meV relaxation could alter significantly the analysis of the binding, but it is in the prospect of generating effective potentials for positron scattering by molecules that the effect can be more important.

Thermodynamic assessment of NdBr3 unary and LiBr-NdBr3 binary system

International Nuclear Information System (INIS)

Gong Weiping; Gaune-Escard, Marcelle

2006-01-01

Phase diagram and thermodynamic properties calculations were carried out on the NdBr 3 unary and the LiBr-NdBr 3 binary systems over the entire temperature and composition range, respectively. The Gibbs energy of NdBr 3 was evaluated using an independent polynomial to fit the experimental thermodynamic properties. The liquid phase in the LiBr-NdBr 3 system was described by the two sub-lattice ionic solution model (Li + ) P : (Br - , NdBr 6 -3 , NdBr 3 ) Q . Comparisons between the calculated phase diagram and thermodynamic quantities show that all reliable experimental information was satisfactorily accounted for by the present thermodynamic description

Two ternary mixed-anion chlorides with divalent europium: Eu{sub 2}H{sub 3}Cl and Eu{sub 7}F{sub 12}Cl{sub 2}

Energy Technology Data Exchange (ETDEWEB)

Reckeweg, Olaf [Baker Laboratory, Department of Chemistry and Chemical Biology, Cornell University, Ithaca, NY 14853-1301 (United States); Institut fuer Anorganische Chemie, Universitaet Stuttgart, Pfaffenwaldring 55, 70569 Stuttgart (Germany); DiSalvo, Francis J. [Baker Laboratory, Department of Chemistry and Chemical Biology, Cornell University, Ithaca, NY 14853-1301 (United States); Wolf, Sarah; Schleid, Thomas [Institut fuer Anorganische Chemie, Universitaet Stuttgart, Pfaffenwaldring 55, 70569 Stuttgart (Germany)

2014-06-15

Dark ruby-red, transparent, triangular plate-shaped single crystals of Eu{sub 2}H{sub 3}Cl and colorless, transparent, needle-shaped single crystals of Eu{sub 7}F{sub 12}Cl{sub 2} were obtained by solid-state reactions of Eu, NaH, NaCl, and Na (2:4:1:2 molar ratio) or Eu, EuCl{sub 3}, and LiF (1:1:4 molar ratio), respectively, in silica-jacketed tantalum ampoules at 900 C for 13 h. Eu{sub 2}H{sub 3}Cl crystallizes isotypically to Ba{sub 2}H{sub 3}X (X = Cl, Br, I) in the trigonal space group P anti 3m1 (no. 164) with lattice parameters a = 409.67(4) and c = 696.18(7) pm, whereas Eu{sub 7}F{sub 12}Cl{sub 2} crystallizes isotypically to Ba{sub 7}F{sub 12}Cl{sub 2} or Sr{sub 7}H{sub 12}Cl{sub 2} in the hexagonal space group P anti 6 (no. 174) with lattice parameters a = 1002.31(5) and c = 392.54(2) pm. Both compounds contain Eu{sup 2+} cations with coordination numbers as high as nine (Eu{sub 7}F{sub 12}Cl{sub 2}) and ten (Eu{sub 2}H{sub 3}Cl) with respect to the halide anions (F{sup -} or H{sup -} and Cl{sup -}). The structural results are corroborated by EUTAX and MAPLE calculations on both ternary mixed-anion europium(II) chlorides in comparison to these for related binary and ternary compounds with divalent europium. (Copyright copyright 2014 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

Synthesis, vibrational and optical properties of a new three-layered organic-inorganic perovskite (C4H9NH3)4Pb3I4Br6

International Nuclear Information System (INIS)

Dammak, T.; Elleuch, S.; Bougzhala, H.; Mlayah, A.; Chtourou, R.; Abid, Y.

2009-01-01

An organic-inorganic hybrid perovskite (C 4 H 9 NH 3 ) 4 Pb 3 I 4 Br 6 was synthesized and studied by X-ray diffraction, Raman and infrared spectroscopies, optical transmission and photoluminescence. The title compound, abbreviated (C 4 ) 4 Pb 3 I 4 Br 6 , crystallises in a periodic two-dimensional multilayer structure with P2 1 /a space group. The structure is built up from alternating inorganic and organic layers. Each inorganic layer consists of three sheets of PbX 6 (X=I, Br) octahedra. Raman and infrared spectra of the title compound were recorded in the 100-3500 and 400-4000 cm -1 frequency ranges, respectively. An assignment of the observed vibration modes is reported. Optical transmission measurements, performed on thin films of (C 4 ) 4 Pb 3 I 4 Br 6 , revealed two absorption bands at 474 and 508 nm. Photoluminescence measurements have shown a green emission peak at 519 nm.

The feasibility of boron containing phosphors in thermal neutron image plates, in particular the systems M sub 2 B sub 5 O sub 9 X : Eu sup 2 sup + (M=Ca, Sr, Ba; X=Cl, Br) Part II: experimental results

CERN Document Server

Knitel, M J; Dorenbos, P; Eijk, C W E; Berezovskaya, I V; Dotsenko, V

2000-01-01

The storage phosphor properties of the compounds M sub 2 B sub 5 O sub 9 X : Eu sup 2 sup + (M=Ca, Sr, Ba; X=Cl, Br) have been studied. The best compounds, Sr sub 2 B sub 5 O sub 9 Br : Eu sup 2 sup + and Ca sub 2 B sub 5 O sub 9 Br : Eu sup 2 sup + , show a photostimulated luminescence yield of, respectively, 21 and 14 photons per incident thermal neutron. They contain natural boron. With these yields, image plates with detective quantum efficiency values of more than 40% are envisaged when using enriched sup 1 sup 0 B, but the stimulation energy at 633 nm is too high.

Electrochemistry in near-critical and supercritical fluids. 3. Studies of Br/sup -/, I/sup -/, and hydroquinone in aqueous solutions

Energy Technology Data Exchange (ETDEWEB)

Flarsheim, W.J.; Tsou, Y.M.; Trachtenberg, I.; Johnston, K.P.; Bard, A.J.

1986-07-31

A new type of apparatus has been constructed for carrying out electrochemistry in near-critical and supercritical aqueous solutions. The following systems have been studied at a platinum electrode: H/sub 2/O/O/sub 2/, I/sup -//I/sub 2/, Br/sup -//Br/sub 2/, and hydroquinone/benzoquinone. The compact alumina flow cell can be heated or cooled quickly and can be recharged with fresh electrolyte solution while at high temperature and pressure. A large reduction in the potential required for the electrolysis of water was observed. Diffusivities have been measured for iodide ions and hydroquinone. General agreement with the Stokes-Einstein model was observed in the temperature range 25-375/sup 0/C.

Approaching the limit of Cu(II)/Cu(I) mixed valency in a Cu(I)Br2-N-methylquinoxalinium hybrid compound.

Science.gov (United States)

Leblanc, Nicolas; Sproules, Stephen; Pasquier, Claude; Auban-Senzier, Pascale; Raffy, Helene; Powell, Annie K

2015-08-18

A novel 1D hybrid salt (MQ)[CuBr2]∞ (MQ = N-methylquinoxalinium) is reported. Structural, spectroscopic and magnetic investigations reveal a minimal Cu(II) doping of less than 0.1%. However it is not possible to distinguish Cu(I) and Cu(II). The unusually close packing of the organic moieties and the dark brown colour of the crystals suggest a defect electronic structure.

Process of radiation damage in BaFX:Eu2+ (X=Br, I) photo-stimulable phosphor for imaging plate (IP)

International Nuclear Information System (INIS)

Kato, Munetaka; Takahashi, Kenji

2005-01-01

Imaging Plate (IP) is a 2-dimensional radiation detector utilizing photo-stimulable phosphors. Photo-stimulated luminescence (PSL) is a kind of process in radiation-induced reactions and IP can be repeatedly performed. The mechanism of PSL is reviewed and the radiation damage, which is a phenomenon that the luminescence goes down under X-ray irradiation, is also referred to. The relation between the composition of BaFX: Eu 2+ (X=Br, I), which is widely used in IPs, and the degree of radiation damage is investigated. The degree of radiation damage is smaller in the mixed crystal system of Br and I such as BaFBr 0.85 I 0.15 :Eu 2+ than in BaFBr: Eu 2+ and BaFI: Eu 2+ . This is explained by the characteristics of luminescence centers and F centers under X-ray irradiation. (author)

Energy- and temperature dependences of secondary electron emission of CsI- and CsBr layers doped with Cd

International Nuclear Information System (INIS)

Galij, P.V.; Tsal', N.A.

1983-01-01

The energy and temperature dependences of the secondary electron emission coefficient (SEEC) of CsI-Cd-, CsBr-Cd-, CsI-CsBr layers have been studied. The effect of bivalent cadmium impurity on the SEEC value is investigated. It is shown that implantation of small amounts of Cd 2+ impurity into the lattice of the initial monocrystals might increase the SEEC values of the layers. Temperature dependences (TD) of SEEC are measured and the possibility of comparing experimental results with the Dekker formula is analyzed. A conclusion is drawn that the Dekker model well describes the TD of SEEC of doped layers at temperatures T < or approximately 100 deg C. At elevated temperatures., along with secondary electron scattering on phonons, one should take into account their scattering on vacancies

Structure of the fully ferroelectric/fully ferroelastic orthohombic room-temperature phase of cobalt bromine boracite, Co[sub 3]B[sub 7]O[sub 13]Br and nickel chlorine boracite, Ni[sub 3]B[sub 7]O[sub 13]Cl

Energy Technology Data Exchange (ETDEWEB)

Kubel, F; Mao, S Y; Schmid, H [Dept. de Chemie Minerale, Analytique et Applique, Geneva Univ. (Switzerland)

1992-07-15

The X-ray crystal structures of optically controlled single-domain crystals of fully ferroelectric/fully ferroelastic cobalt bromine boracite, Co[sub 3]B[sub 7]O[sub 13]Br (Co-Br) at 298 K [M[sub r] = 540.38, orthorhombic, Pca2[sub 1], a = 8.5614 (2), b = 8.5657 (2), c = 12.1196 (3) A, V = 888.78 (4) A[sup 3], Z = 4, D[sub x] = 4.04 Mg m[sup -3], [lambda](Mo K[alpha]) = 0.7107 A, [mu] = 10.61 mm[sup -1], F(000) = 1020, R = 7.0, wR = 5.4%, 2824 reflections] and of nickel chlorine boracite, Ni[sub 3]B[sub 7]O[sub 13]Cl (Ni-Cl) at 298 K [M[sub r] = 495.25, orthorhombic, Pca2[sub 1], a = 8.5105 (4), b = 8.4984 (4), c = 12.0324 (5) A, V = 870.25 (7) A[sup 3], Z = 4, D[sub x] = 3.78 Mg m[sup -3], [lambda](Mo K[alpha]) = 0.7107 A, [mu] = 6.8 mm[sup -1], F(000) = 960, R = 3.5, wR = 3.1%, 2082 reflections] are reported. The metal surroundings of Co-Br and Ni-Cl were analyzed in detail and show two metal sites (Co2, Co3; Ni2, Ni3) with chemically similar environments and one metal site (Co1; Ni1) with a different environment. Six B atoms have a tetrahedral or slightly distorted tetrahedral coordination, whereas one B atom (B4) has triangular surroundings in both compounds. (orig.).

Characterization of glial cell K-Cl cotransport.

Science.gov (United States)

Gagnon, Kenneth B E; Adragna, Norma C; Fyffe, Robert E W; Lauf, Peter K

2007-01-01

The molecular mechanism of K-Cl cotransport (KCC) consists of at least 4 isoforms, KCC 1, 2, 3, and 4 which, in multiple combinations, exist in most cells, including erythrocytes and neuronal cells. We utilized reverse-transcriptase-polymerase chain reaction (RT-PCR) and ion flux studies to characterize KCC activity in an immortalized in vitro cell model for fibrous astrocytes, the rat C6 glioblastoma cell. Isoform-specific sets of oligonucleotide primers were synthesized for NKCC1, KCC1, KCC2, KCC3, KCC4, and also for NKCC1 and actin. K-Cl cotransport activity was determined by measuring either the furosemide-sensitive, or the Cl(-)-dependent bumetanide-insensitive Rb(+) (a K(+) congener) influx in the presence of the Na/K pump inhibitor ouabain. Rb(+) influx was measured at a fixed external Cl concentrations, [Cl(-)](e), as a function of varying external Rb concentrations, [Rb(+)](e), and at a fixed [Rb(+)](e) as a function of varying [Cl(-)](e), and with equimolar Cl replacement by anions of the chaotropic series. RT-PCR of C6 glioblastoma (C6) cells identified mRNA for three KCC isoforms (1, 3, and 4). NKCC1 mRNA was also detected. The apparent K(m) for KCC-mediated Rb(+) influx was 15 mM [Rb(+)](e), and V(max) 12.5 nmol Rb(+) * mg protein(-1) * minute(-1). The calculated apparent K(m) for external Cl(-) was 13 mM and V(max) 14.4 nmol Rb(+) * mg protein(-1) * minute(-1). The anion selectivity sequence of the furosemide-sensitive Rb(+) influx was Cl(-)>Br-=NO(3)(-)>I(-)=SCN(-)>Sfm(-) (sulfamate). Established activators of K-Cl cotransport, hyposmotic shock and N-ethylmaleimide (NEM) pretreatment, stimulated furosemide-sensitive Rb(+) influx. A ñ50% NEM-induced loss of intracellular K(+) was prevented by furosemide. We have identified by RT-PCR the presence of three distinct KCC isoforms (1, 3, and 4) in rat C6 glioblastoma cells, and functionally characterized the anion selectivity and kinetics of their collective sodium-independent cation-chloride cotransport

23Na and 35/37Cl as NMR probes of growth and shape of sodium taurodeoxycholate micellar aggregates in the presence of NaCl.

Science.gov (United States)

Asaro, Fioretta; Feruglio, Luigi; Galantini, Luciano; Nardelli, Alessia

2013-02-15

The growth of the aggregates of the dihydroxylated bile salt sodium taurodeoxycholate (NaTDC) upon NaCl addition and the involvement of the counterion were investigated by NMR spectroscopy of monoatomic ionic species. (23)Na T(1) values from 0.015, 0.100, and 0.200 mol kg(-1) NaTDC solutions in D(2)O, at variable NaCl content, proved to be sensitive to the transition from primary to secondary aggregates, which occurs in the former sample, and to intermicellar interaction. Some (79)Br NMR measurements were performed on a 0.100 mol kg(-1) NaTDC sample added by NaBr in place of NaCl for comparison purposes. The (23)Na, (35)Cl, and (37)Cl double quantum filtered (DQF) patterns, from the 0.100 mol kg(-1) NaTDC sample, and (23)Na ones also from the 0.200 mol kg(-1) NaTDC one, in the presence of 0.750 mol kg(-1) NaCl, are a clear manifestation of motional anisotropy. Moreover, the DQF spectra of (23)Na and (37)Cl, which possess close quadrupole moments, display a striking similarity. The DQF lineshapes were simulated exploiting the Scilab environment to obtain an estimate of the residual quadrupole splitting magnitude. These results support the description of NaTDC micelles as cylindrical aggregates, strongly interacting at high ionic strengths, and capable of association with added electrolytes. Copyright © 2012 Elsevier Inc. All rights reserved.

Historia del Laboratorio Clínico en Bogotá

Directory of Open Access Journals (Sweden)

Alberto Gómez Gutiérrez

2008-12-01

Full Text Available

Pioneros del Laboratorio Clínico Bogotano en el Siglo XX.

Federico Lleras Acosta<br />César Uribe Piedrahita<br />Pedro J. Almánzar<br />Roberto Franco Franco<br />Andrés Soriano Lleras<br />Hernando Forero Rubio<br />Luis Patiño Camargo<br />Alfonso Rueda Herrera<br />Venancio Rueda Angarita<br />Guillermo Aparicio Jaramillo<br />Hernando Groot Liévano<br />Eduardo Caballero Ferreira<br />Daniel Gamboa Galvis<br />César Mendoza Posada<br />Luis Callejas Arboleda<br />César Gómez Vil legas<br />Hernando Gómez Vesga<br />Carlos Gómez Vesga<br />Francisco de Castro<br />Alfredo Escallón Anjel<br />Irenarco Venegas<br />Jaime Saravia<br />Fernando Cortés Boshell<br />Victor Ortiz Manrique<br />Miguel Guzmán Urrego<br />Carlos García Cortés<br />Beatriz Cavelier Gaviria<br />Blanca Osario de Patiño<br />Pala Grutzlender<br />r\\lelly de Cediel<br />Hermana Rosa<br />Cecilia de Caro<br />Inés Gómez Delgado

El primer Laboratorio Clinico de la historia fue un espacio reducido con una mesa y un asiento, y

contaba con un único instrumento que era el propio médico que observaba, probaba e interpretaba un<br />fluido obtenido involuntariamente por su paciente: su orina. Un pequeño frasco de vidrio bastaba<br />para preparar la prueba. El valor diagnóstico de la orina fue sustentándose con la experiencia médica<br />esencialmente árabe y judía, y ya en el siglo IX de nuestra era el médico Jacob Isaac Ben Salomón Al<br />Israelí (c860-953 había escrito el libro que sería traducido en la Escuela Salernitana del siglo XI por<br />Constantino el Africano (c1 01 0-1 087 bajo el título de Liber de urinis.

Ion yields of laser aligned CH3I and CH3Br from multiple orbitals

NARCIS (Netherlands)

He, Lanhai; Pan, Yun; Yang, Yujun; Luo, Sizuo; Lu, Chunjing; Zhao, Huifang; Li, Dongxu; Song, Lele; Stolte, Steven; Ding, Dajun; Roeterdink, Wim G.

2016-01-01

We have measured the alignment influence on ion yields of CH3I and CH3Br molecules in the laser intensity regime from 1013 W/cm2 to 1015 W/cm2. The hexapole state-selection technique combined with laser induced alignment has been employed to obtain aligned (〈P2(cosθ)〉=0.7) and anti-aligned

El conflicto interior y sus secuelas. Rastreo a través del <i>“Glossarium Mediae Latinitatis Cataloniae”i>

Directory of Open Access Journals (Sweden)

Gómez Rabal, Ana

2008-12-01

Full Text Available Comparison between Classical Latin and Romance languages allows us to see the development of the idea of “conflict”. Having that progression in mind, this paper focuses on the study of the lexicographical problem which arises from the use of the Latin noun <i>conflictus> and its changing semantic field, through the analysis of Latin documents generated in Catalonia in the High Middle Ages, which form the basis of the research for the <i>Glossarium Mediae Latinitatis Cataloniaei>.
>La comparación entre el latín clásico y las lenguas románicas lleva a constatar la evolución del concepto de conflicto. Teniendo presente esa evolución, el estudio de la documentación latina producida en la Cataluña altomedieval y la consulta del material que sirve de base para la elaboración del <i>Glossarium Mediae Latinitatis Cataloniaei> permiten plantear un problema lexicográfico en torno al sustantivo latino <i>conflictus> y comprobar cómo queda cubierto su campo semántico.

Retração de caninos superiores com bráquetes autoligados e convencionais

OpenAIRE

Mezomo, Maurício Barbieri

2008-01-01

O objetivo deste ensaio clínico randomizado tipo boca dividida foi avaliar e comparar o fechamento dos espaços durante a retração dos caninos permanentes superiores com os bráquetes autoligado “SmartClip” e convencional “Gemini”. A amostra foi constituída de 13 pacientes portadores de maloclusão de Classe I com biprotrusão ou Classe II 1ª divisão de Angle, com média de idade de 18 anos e 4 meses, sendo 3 do gênero masculino e 10 do feminino. Todos os indivíduos foram submetidos à extração ter...

Cross sections for (p,n) and (d,2n) reactions on /sup 79/Br and /sup 127/I: An evaluation of literature and model calculated results

Energy Technology Data Exchange (ETDEWEB)

Lanier, R.G.; Mustafa, M.G.; West, H.I. Jr.

1989-02-01

We have evaluated (p,n) and (d,2n) cross sections on /sup 79/Br and /sup 127/I, and made these cross sections available for test diagnostics. We believe that these interim cross sections are of reasonable accuracy and should be used for diagnostic interpretations until more precise measurements can be made. Our evaluation consisted of a literature search and an examination of the available experimental data. These data were supplemented by statistical model calculations using both the STAPRE and ALICE codes. We found reasonably good measured data (from threshold to the peak of the excitation function) for the (p,n) reaction on both /sup 79/Br and /sup 127/I. The literature data for the (d,2n) reaction on /sup 127/I are questionable and no data were found for the (d,2n) reaction on /sup 79/Br. We have, therefore, relied completely on calculations for the (d,2n) cross sections for both /sup 79/Br and /sup 127/I. 4 figs., 5 tabs.

Brain regional distributions of the minor and trace elements, Na, Mg, Cl, K, Mn, Zn, Rb and Br, in young and aged mice

International Nuclear Information System (INIS)

Amano, R.; Oishi, S.; Ishie, M.; Kimura, M.

2001-01-01

Brain regional cerebral concentrations of minor and trace elements, Na, Mg, Cl, K, Mn, Zn, Rb and Br were determined in young and aged mice, by instrumental neutron activation analysis for small amounts of regional (corpus striatum, cerebellum, cerebral cortex, hippocampus, midbrain, pons and medulla olfactory bulb) samples. Significant age-related differences were found for Mn concentration in all brain regions: The Mn concentration of the young brain was higher than those of aged brain, in addition, Zn was distributed heterogeneously, and highly concentrated in cerebral cortex and hippocampus regions in both young and aged mice. These results suggest that, in the aged brain, Mn is required less than in the young brain, on the other hand, Zn is required equally in both young and aged brains. (author)

Enhanced ionic conductivity with Li{sub 7}O{sub 2}Br{sub 3} phase in Li{sub 3}OBr anti-perovskite solid electrolyte

Energy Technology Data Exchange (ETDEWEB)

Zhu, Jinlong, E-mail: jlzhu04@physics.unlv.edu, E-mail: yusheng.zhao@unlv.edu, E-mail: zhaoys@sustc.edu.cn; Li, Shuai; Zhang, Yi; Howard, John W.; Wang, Yonggang; Kumar, Ravhi S.; Wang, Liping [High Pressure Science and Engineering Center, University of Nevada, Las Vegas, Nevada 89154 (United States); Lü, Xujie [Center for Integrated Nanotechnologies and Earth and Environmental Sciences Division, Los Alamos National Laboratory, Los Alamos, New Mexico 87545 (United States); Li, Yutao [Materials Research Program and The Texas Materials Institute, University of Texas at Austin, Texas 78712 (United States); Zhao, Yusheng, E-mail: jlzhu04@physics.unlv.edu, E-mail: yusheng.zhao@unlv.edu, E-mail: zhaoys@sustc.edu.cn [High Pressure Science and Engineering Center, University of Nevada, Las Vegas, Nevada 89154 (United States); Department of Physics, South University of Science and Technology of China, Guangdong 518055 (China)

2016-09-05

Cubic anti-perovskites with general formula Li{sub 3}OX (X = Cl, Br, I) were recently reported as superionic conductors with the potential for use as solid electrolytes in all-solid-state lithium ion batteries. These electrolytes are nonflammable, low-cost, and suitable for thermoplastic processing. However, the primary obstacle of its practical implementation is the relatively low ionic conductivity at room temperature. In this work, we synthesized a composite material consisting of two anti-perovskite phases, namely, cubic Li{sub 3}OBr and layered Li{sub 7}O{sub 2}Br{sub 3,} by solid state reaction routes. The results indicate that with the phase fraction of Li{sub 7}O{sub 2}Br{sub 3} increasing to 44 wt. %, the ionic conductivity increased by more than one order of magnitude compared with pure phase Li{sub 3}OBr. Formation energy calculations revealed the meta-stable nature of Li{sub 7}O{sub 2}Br{sub 3}, which supports the great difficulty in producing phase-pure Li{sub 7}O{sub 2}Br{sub 3} at ambient pressure. Methods of obtaining phase-pure Li{sub 7}O{sub 2}Br{sub 3} will continue to be explored, including both high pressure and metathesis techniques.

Synthesis and characterization of the 1.1 adducts of copper(1) halides with bidentatate N,N-bis(benzophenone)-1,2-diiminoethane Schiff bases: Crystal structures of [Cu(bz2en)2][CuX2](X=Br,l) complexes

NARCIS (Netherlands)

Kia, Reza; Mirkhani, Valiollah; Harkema, Sybolt; van Hummel, G.J.

2007-01-01

1:1 adducts of N,N′-bis(benzophenone)-1,2-diiminoethane (bz2en) with copper(I) chloride, bromide and iodide, [Cu(bz2en)2][CuX2] (X = Cl, Br, and I), have been synthesized and the structures of the solid bromide and iodide adducts were determined by X-ray crystallography from single-crystal data. The

Bromine-rich Zinc Bromides: Zn6Br12(18-crown-6)2×(Br2)5, Zn4Br8(18-crown-6)2×(Br2)3, and Zn6Br12(18-crown-6)2×(Br2)2.

Science.gov (United States)

Hausmann, David; Feldmann, Claus

2016-06-20

The bromine-rich zinc bromides Zn6Br12(18-crown-6)2×(Br2)5 (1), Zn4Br8(18-crown-6)2×(Br2)3 (2), and Zn6Br12(18-crown-6)2×(Br2)2 (3) are prepared by reaction of ZnBr2, 18-crown-6, and elemental bromine in the ionic liquid [MeBu3N][N(Tf)2] (N(Tf)2 = bis(trifluoromethylsulfonyl)amide). Zn6Br12(18-crown-6)2×(Br2)5 (1) is formed instantaneously by the reaction. Even at room temperature, compound 1 releases bromine, which was confirmed by thermogravimetry (TG) and mass spectrometry (MS). The release of Br2 can also be directly followed by the color and density of the title compounds. With controlled conditions (2 weeks, 25 °C, absence of excess Br2) Zn6Br12(18-crown-6)2×(Br2)5 (1) slowly releases bromine with conconcurrent generation of Zn4Br8(18-crown-6)2×(Br2)3 (2) (in ionic liquid) and Zn6Br12(18-crown-6)2×(Br2)2 (3) (in inert oil). All bromine-rich zinc bromides contain voluminous uncharged (e.g., Zn3Br6(18-crown-6), Zn2Br4(18-crown-6)) or ionic (e.g., [Zn2Br3(18-crown-6)](+), [(Zn2Br6)×(Br2)2](2-)) building units with dibromine molecules between the Zn oligomers and partially interconnecting the Zn-containing building units. Due to the structural similarity, the bromine release is possible via crystal-to-crystal transformation with retention of the crystal shape.

New results on two synthetic conductors (TMTSF)2BrO4 and (BEDT-TTF)2I3

DEFF Research Database (Denmark)

Mortensen, Kell; Jacobsen, C. S.; Bechgaard, K.

1985-01-01

The authors present experimental studies of transport properties of (TMTSF)2BrO4 and (BEDT-TTF)2I3 . The behaviour of the TMTSF salt suggests transport via variable-range hopping among localized states. The BEDT-TTF-salt exhibits thermopower which indicates almost isotropic metallic behaviour in ...

Preparation and characterization of (R,S)-[76Br]BrQNB: an analogue of QNB for PET

International Nuclear Information System (INIS)

Strijckmans, V.; Loc'h, C.; Ottaviani, M.; Maziere, B.; Lee, K.S.; Zeeberg, B.R.

1997-01-01

(R,S)-[ 76 Br]BrQNB was prepared for imaging mAChR by PET . (R,S)QNB was labelled with bromine-76 by electrophilic substitution of the tributylstannyl precursor using peracetic acid as oxidizing agent. The exchange between bromine-76 and the leaving group occurred in 20 min at room temperature. A chemically and radiochemically pure product was obtained with a final radiolabelling yield of 30%. Preliminary evaluation of pharmacological properties was performed in rats. In brain, biodistribution and autoradiography studies showed that the preferential localization of (R,S)-[ 76 Br]BrQNB was m-AChR rich structures. 6 h p.i. the radioactivity uptake in the posterior cortex was 1% ID/g and the striatum to cerebellum radioactivity ratio was 13.5. Metabolite study revealed that the radiotracer remains unchanged in brain for at least 3 h. (Author)

Z-(-,-)-[76Br]BrQNP: a high affinity PET radiotracer for central and cardiac muscarinic receptors

International Nuclear Information System (INIS)

Strijckmans, V.; Coulon, C.; Loc'h, C.; Maziere, B.; Luo, H.; McPherson, D.W.; Knapp, F.F.

1996-01-01

Racemic E-1-azabicyclo[2.2.2]oct-3-yl α-(1-bromo-1-1-propen-3-yl)-α -hydroxy-α-phenylacetate (BrQNP) was prepared and evaluated in vivo as a potential candidate for imaging muscarinic acetylcholinergic receptors by Positron Emission Tomography. Initial in vivo blocking studies utilizing Z-(-,-)-[ 125 I]IQNP as a radiolabelled muscarinic probe demonstrated that a preinjection of cold E-BrQNP effectively blocks the uptake of the radiolabelled probe in the brain and heart, by 71% and 86% respectively. Z-(-,-)-[ 76 Br]BrQNP was prepared by electrophilic substitution from a tributylstannyl precursor. Peracetic acid and chloramine T was evaluated as oxidizing agents. After purification by SPE and RP-HPLC, radiolabelling yields of 85% and 95% were obtained with peracetic acid and chloramine T, respectively. The final radiochemical yield was 70% for both oxidizing agents. (author)

Evaluation of the levels of Br, Cl, K, Mg, Mn and V in Perna perna Mussels (Linnaeus, 1758: Mollusca, Bivalvia) collected in coast of Sao Paulo, Brazil

International Nuclear Information System (INIS)

Seo, Daniele; Vasconcellos, Marina B.A.; Saiki, Mitiki; Catharino, Marilia G.M.; Moreira, Edson G.; Sousa, Eduinetty C.P.M. de

2013-01-01

In this study the content of Br, Cl, K, Mg, Mn and V was evaluated in samples of Perna perna mussels collected in coastal regions of Sao Paulo (Ponta de Itaipu and Palmas Island, in Santos) subjected to anthropogenic contamination, to compare these values with those of mussels from reference site of Cocanha Beach (in Caraguatatuba). The mussels were collected seasonally from September 2008 to July 2009. They were cleaned, ground, homogenized, lyophilized and then analyzed by Instrumental Neutron Activation Analysis (INAA). The INAA procedure consisted in the irradiation of the samples and synthetic elemental standards for 8 and 10 s, under a thermal neutron flux of 6.6 x 10 12 n cm -2 s -1 in the IEA-R1 nuclear research reactor. For quality control of analytical results, certified reference materials NIST 1566b Oyster Tissue and NIST 2876 Mussel Tissue were analyzed and their results indicated good accuracy. The ranges of concentrations (dry basis) of the elements obtained in mussels collected for the four seasons of the year were: 173.80 to 358.99 mg kg -1 for Br; 45658 ± 1811 to 109166 ± 824 mg kg -1 for Cl; 7043 ± 856 to 12506 ± 675 mg kg -1 for K; 2774 ± 211 to 5691 ± 717 mg kg -1 for Mg; 7.01 ± 0.30 to 29.74 ± 3.32 mg kg -1 for Mn and 0.77 ± 0.02 to 3.43 ± 0.28 mg kg -1 for V. The seasonal and spatial variations of these element concentrations were in this study. (author)

Evaluation of the levels of Br, Cl, K, Mg, Mn and V in Perna perna Mussels (Linnaeus, 1758: Mollusca, Bivalvia) collected in coast of Sao Paulo, Brazil

Energy Technology Data Exchange (ETDEWEB)

Seo, Daniele; Vasconcellos, Marina B.A.; Saiki, Mitiki; Catharino, Marilia G.M.; Moreira, Edson G., E-mail: danyseo@uol.com.br, E-mail: mbvascon@ipen.br, E-mail: mitiko@ipen.br, E-mail: mgcatharino@uol.com.br, E-mail: emoreira@ipen.br [Instituto de Pesquisas Energeticas e Nucleares (IPEN/CNEN-SP), Sao Paulo, SP (Brazil); Sousa, Eduinetty C.P.M. de, E-mail: edvinett@usp.br [Universidade de Sao Paulo (IO/USP), Sao Paulo, SP (Brazil). Instituto Oceanografico. Laboratorio de Ecotoxicologia Marinha e Microfitobentos

2013-07-01

In this study the content of Br, Cl, K, Mg, Mn and V was evaluated in samples of Perna perna mussels collected in coastal regions of Sao Paulo (Ponta de Itaipu and Palmas Island, in Santos) subjected to anthropogenic contamination, to compare these values with those of mussels from reference site of Cocanha Beach (in Caraguatatuba). The mussels were collected seasonally from September 2008 to July 2009. They were cleaned, ground, homogenized, lyophilized and then analyzed by Instrumental Neutron Activation Analysis (INAA). The INAA procedure consisted in the irradiation of the samples and synthetic elemental standards for 8 and 10 s, under a thermal neutron flux of 6.6 x 10{sup 12} n cm{sup -2} s{sup -1} in the IEA-R1 nuclear research reactor. For quality control of analytical results, certified reference materials NIST 1566b Oyster Tissue and NIST 2876 Mussel Tissue were analyzed and their results indicated good accuracy. The ranges of concentrations (dry basis) of the elements obtained in mussels collected for the four seasons of the year were: 173.80 to 358.99 mg kg{sup -1} for Br; 45658 ± 1811 to 109166 ± 824 mg kg{sup -1} for Cl; 7043 ± 856 to 12506 ± 675 mg kg{sup -1} for K; 2774 ± 211 to 5691 ± 717 mg kg{sup -1} for Mg; 7.01 ± 0.30 to 29.74 ± 3.32 mg kg{sup -1} for Mn and 0.77 ± 0.02 to 3.43 ± 0.28 mg kg{sup -1} for V. The seasonal and spatial variations of these element concentrations were in this study. (author)

Transformation of Sintered CsPbBr3 Nanocrystals to Cubic CsPbI3 and Gradient CsPbBrxI3-x through Halide Exchange.

Science.gov (United States)

Hoffman, Jacob B; Schleper, A Lennart; Kamat, Prashant V

2016-07-13

All-inorganic cesium lead halide (CsPbX3, X = Br(-), I(-)) perovskites could potentially provide comparable photovoltaic performance with enhanced stability compared to organic-inorganic lead halide species. However, small-bandgap cubic CsPbI3 has been difficult to study due to challenges forming CsPbI3 in the cubic phase. Here, a low-temperature procedure to form cubic CsPbI3 has been developed through a halide exchange reaction using films of sintered CsPbBr3 nanocrystals. The reaction was found to be strongly dependent upon temperature, featuring an Arrhenius relationship. Additionally, film thickness played a significant role in determining internal film structure at intermediate reaction times. Thin films (50 nm) showed only a small distribution of CsPbBrxI3-x species, while thicker films (350 nm) exhibited much broader distributions. Furthermore, internal film structure was ordered, featuring a compositional gradient within film. Transient absorption spectroscopy showed the influence of halide exchange on the excited state of the material. In thicker films, charge carriers were rapidly transferred to iodide-rich regions near the film surface within the first several picoseconds after excitation. This ultrafast vectorial charge-transfer process illustrates the potential of utilizing compositional gradients to direct charge flow in perovskite-based photovoltaics.

Operating Experience with the BR-5 Reactor; Experience acquise aupres du reacteur BR-5; Opyt ehkspluatatsii reaktora BR-5; Experiencia practica con el reactor BR-5

Energy Technology Data Exchange (ETDEWEB)

Lejpunskij, A. I.; Kazachkovskij, O. D.; Pinkhasik, M. S.; Aristarkhov, N. N.; Karpov, A. V.; Larin, E. P.; Efimov, I. A.

1963-10-15

remontnykh rabot na radioaktivnom zhidkometallicheskom konture reaktora na bystrykh nejtronakh BR-5. Osveshchayutsya voprosy ehkspluatatsii reaktora posle dostizheniya proektnogo 2%-nogo vygoraniya topliva pri nalichii nekotorogo narusheniya plotnosti otdel'nykh teplovydelyaptsikh ehlementov. Provoditsya opyt po razgruzke aktivnoj zony, issledovaniyu sostoyaniya i germetichnosti teplovydelyaptsikh ehlementov, dezaktivatsii oborudovaniya i truboprovodov I radioaktivnogo kontura posle dostizheniya 5% vygoraniya topliva. (author)

General Strategy for Rapid Production of Low-Dimensional All-Inorganic CsPbBr3 Perovskite Nanocrystals with Controlled Dimensionalities and Sizes.

Science.gov (United States)

Liu, Wenna; Zheng, Jinju; Cao, Sheng; Wang, Lin; Gao, Fengmei; Chou, Kuo-Chih; Hou, Xinmei; Yang, Weiyou

2018-02-05

Currently, all-inorganic CsPbX 3 (X = Br, I, Cl) perovskite nanocrystals (NCs) are shining stars with exciting potential applications in optoelectronic devices such as solar cells, light-emitting diodes, lasers, and photodetectors, due to their superior performance in comparison to their organic-inorganic hybrid counterparts. In the present work, we report a general strategy based on a microwave technique for the rapid production of low-dimensional all-inorganic CsPbBr 3 perovskite NCs with tunable morphologies within minutes. The effect of the key parameters such as the introduced ligands, solvents, and PbBr 2 precursors and microwave powers as well as the irradiation times on the production of perovskite NCs was systematically investigated, which allowed their growth with tunable dimensionalities and sizes. As a proof of concept, the ratio of OA to OAm as well as the concentration of PbBr 2 precursor played important roles in triggering the anisotropic growth of the perovskite NCs, favoring their growth into 1D/2D single-crystalline nanostructures. Meanwhile, their sizes could be tailored by controlling the microwave powers and irradiation times. The mechanism for the tunable growth of perovskite NCs is discussed.

Excess Enthalpies of Mixing of Binary Mixtures of NaCl, KCl, NaBr ...

African Journals Online (AJOL)

NJD

2004-07-01

Jul 1, 2004 ... NaBr and KBr in Mixed Ternary Solvent Systems at 298.15 K. Bal Raj Deshwala* ... industrial waters and their thermodynamic properties are of practical interest for .... The enthalpy of mixing (∆Hm) is the difference between the excess enthalpy of the ..... tural (categorized by softness, open- ness, and ...

Multicenter (FXn/NH3 Halogen Bonds (X = Cl, Br and n = 1–5. QTAIM Descriptors of the Strength of the X∙∙∙N Interaction

Directory of Open Access Journals (Sweden)

Gabriel J. Buralli

2017-11-01

Full Text Available In the present work an in depth deep electronic study of multicenter XBs (FXn/NH3 (X = Cl, Br and n = 1–5 is conducted. The ways in which X∙∙∙X lateral contacts affect the electrostatic or covalent nature of the X∙∙∙N interactions are explored at the CCSD(T/aug-cc-pVTZ level and in the framework of the quantum theory of atoms in molecules (QTAIM. Calculations show that relatively strong XBs have been found with interaction energies lying between −41 and −90 kJ mol−1 for chlorine complexes, and between −56 and −113 kJ mol−1 for bromine complexes. QTAIM parameters reveal that in these complexes: (i local (kinetics and potential energy densities measure the ability that the system has to concentrate electron charge density at the intermolecular X∙∙∙N region; (ii the delocalization indices [δ(A,B] and the exchange contribution [VEX(X,N] of the interacting quantum atoms (IQA scheme, could constitute a quantitative measure of the covalence of these molecular interactions; (iii both classical electrostatic and quantum exchange show high values, indicating that strong ionic and covalent contributions are not mutually exclusive.

LiCl-LiI molten salt electrolyte with bismuth-lead positive electrode for liquid metal battery

Science.gov (United States)

Kim, Junsoo; Shin, Donghyeok; Jung, Youngjae; Hwang, Soo Min; Song, Taeseup; Kim, Youngsik; Paik, Ungyu

2018-02-01

Liquid metal batteries (LMBs) are attractive energy storage device for large-scale energy storage system (ESS) due to the simple cell configuration and their high rate capability. The high operation temperature caused by high melting temperature of both the molten salt electrolyte and metal electrodes can induce the critical issues related to the maintenance cost and degradation of electrochemical properties resulting from the thermal corrosion of materials. Here, we report a new chemistry of LiCl-LiI electrolyte and Bi-Pb positive electrode to lower the operation temperature of Li-based LMBs and achieve the long-term stability. The cell (Li|LiCl-LiI|Bi-Pb) is operated at 410 °C by employing the LiCl-LiI (LiCl:LiI = 36:64 mol %) electrolyte and Bi-Pb alloy (Bi:Pb = 55.5:44.5 mol %) positive electrode. The cell shows excellent capacity retention (86.5%) and high Coulombic efficiencies over 99.3% at a high current density of 52 mA cm-2 during 1000th cycles.

Determination of molecular stopping cross section of {sup 12}C, {sup 16}O, {sup 28}Si, {sup 35}Cl, {sup 58}Ni, {sup 79}Br, and {sup 127}I in silicon nitride

Energy Technology Data Exchange (ETDEWEB)

Barradas, N.P., E-mail: nunoni@ctn.ist.utl.pt [Centro de Ciências e Tecnologias Nucleares, Instituto Superior Técnico, Unversidade de Lisboa, Estrada Nacional 10 ao km 139.7, 2695-066 Bobadela LRS (Portugal); Bergmaier, A. [Institut für Angewandte Physik und Messtechnik, Fakultät für Luft und Raumfahrttechnik, Werner-Heisenberg-Weg 39, D-85577 Neubiberg (Germany); Mizohata, K. [Department of Physics, University of Helsinki, P.O. Box 43, FI-00014 University of Helsinki (Finland); Msimanga, M. [iThemba LABS Gauteng, National Research Foundation, Private Bag 11, WITS 2050, Johannesburg (South Africa); Department of Physics, Tshwane University of Technology, Private Bag X680, Pretoria 0001 (South Africa); Räisänen, J. [Department of Physics, University of Helsinki, P.O. Box 43, FI-00014 University of Helsinki (Finland); Sajavaara, T. [Department of Physics, University of Jyväskylä, Survontie 9, 40014 Jyväskylä (Finland); Simon, A. [International Atomic Energy Agency, Division of Physical and Chemical Sciences, Vienna International Centre, P.O. Box 100, A-1400 Vienna (Austria); Institute of Nuclear Research of the Hungarian Academy of Sciences, (ATOMKI), P.O. Box 51, H-4001 Debrecen (Hungary)

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 Si{sub 3}N{sub 4}, 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 {sup 12}C, {sup 16}O, {sup 28}Si, {sup 35}Cl, {sup 58}Ni, {sup 79}Br, and {sup 127}I 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.

Cl- channels of the gastric parietal cell that are active at low pH.

Science.gov (United States)

Cuppoletti, J; Baker, A M; Malinowska, D H

1993-06-01

HCl secretion across mammalian gastric parietal cell apical membrane may involve Cl- channels. H(+)-K(+)-ATPase-containing membranes isolated from gastric mucosa of histamine-stimulated rabbits were fused to planar lipid bilayers. Channels were recorded with symmetric 800 mM CsCl solutions, pH 7.4. A linear current-voltage (I-V) relationship was obtained, and conductance was 28 +/- 1 pS at 800 mM CsCl. Conductance was 6.9 +/- 2 pS at 150 mM CsCl. Reversal potential was +22 mV with a fivefold cis-trans CsCl concentration gradient, indicating that the channel was anion selective with a discrimination ratio of 6:1 for Cl- over Cs+. Anion selectivity of the channel was I- > Cl- > or = Br- > NO3-, and gluconate was impermeant. Channels obtained at pH 7.4 persisted when pH of medium bathing the trans side of the bilayer (pHtrans) was reduced to pH 3, without a change in conductance, linearity of I-V relationship, or ion selectivity. In contrast, asymmetric reduction of pH of medium bathing the cis side of the bilayer from 7.4 to 3 always resulted in loss of channel activity. At pH 7.4, open probability (Po) of the channel was voltage dependent, i.e., predominantly open at +80 mV but mainly closed at -80 mV. In contrast, with low pHtrans, channel Po at -80 mV was increased 3.5-fold. The Cl- channel was Ca2+ indifferent. In absence of ionophores, ion selectivity for support of H(+)-K(+)-ATPase activity and H+ transport was consistent with that exhibited by the channel and could be limited by substitution with NO3-, whereas maximal H(+)-K(+)-ATPase activity was indifferent to anion present, demonstrating that anion transport can be rate limiting. Cl- channels with similar characteristics (conductance, linear I-V relationship, and ion selectivity) were also present in H(+)-K(+)-ATPase-containing vesicles isolated from resting (cimetidine-treated) gastric mucosa, exhibiting at -80 mV a pH-independent approximately 3.5-fold lower Po than stimulated vesicle channels. At -80 m

Highly Emissive Divalent-Ion-Doped Colloidal CsPb1–xMxBr3 Perovskite Nanocrystals through Cation Exchange

Science.gov (United States)

2017-01-01

Colloidal CsPbX3 (X = Br, Cl, and I) perovskite nanocrystals (NCs) have emerged as promising phosphors and solar cell materials due to their remarkable optoelectronic properties. These properties can be tailored by not only controlling the size and shape of the NCs but also postsynthetic composition tuning through topotactic anion exchange. In contrast, property control by cation exchange is still underdeveloped for colloidal CsPbX3 NCs. Here, we present a method that allows partial cation exchange in colloidal CsPbBr3 NCs, whereby Pb2+ is exchanged for several isovalent cations, resulting in doped CsPb1–xMxBr3 NCs (M= Sn2+, Cd2+, and Zn2+; 0 50%), sharp absorption features, and narrow emission of the parent CsPbBr3 NCs. The blue-shift in the optical spectra is attributed to the lattice contraction that accompanies the Pb2+ for M2+ cation exchange and is observed to scale linearly with the lattice contraction. This work opens up new possibilities to engineer the properties of halide perovskite NCs, which to date are demonstrated to be the only known system where cation and anion exchange reactions can be sequentially combined while preserving the original NC shape, resulting in compositionally diverse perovskite NCs. PMID:28260380

Dissociative photoionization of IBr following I(4d) and Br(3d) inner-shell excitations in the range of 60 ∼ 133 eV: remarkable biased charge spread relevant to the core-hole states

International Nuclear Information System (INIS)

Boo, Bong Hyun; Koyano, Inosuke

2002-01-01

Dissociative photoionization of an interhalogen molecule, iodine monobromide (IBr), spanning the I(4d) and the Br(3d) inner-shell excitation/ionization regions has been studied by using time-of-flight (TOF) mass spectrometry coupled to synchrotron radiation in the range of 60 ∼ 133 eV. The total and the individual photoion yields have been recorded as functions of the photon energy. Here, a giant shape resonance has been observed owing to the I(4d 10 ) →I(4d 9 εf) transition, the transition probability for which outweighs that for the Br(3d 10 ) →Br(3d 9 εf) excitation. In addition to the huge resonance, discrete resonances owing to the Br(3d) -1 IBr(4pσ + ) and the Br(3d -1 )Br(5p) transitions, with very weak intensities, are observed at 70.5 and 73.6 eV and have spin-orbit splittings of = 1.0 and = 0.9 eV, respectively. The dissociation processes of singly and doubly charged parent ions have also been evaluated from the variations of the individual ion and photoion-photoion coincidence (PIPICO) yields with the photon energy. Below the Br(3d) threshold, including the Br(3d) discrete excitation region, 60 + and I 2+ ions are exclusively formed with a trace number of Br + ions. Slightly above the Br(3d) threshold, more specifically at 77.5 eV, however, photoionization events leading to the formations of Br + and Br 2- prevail. At higher energies beyond the Br(3d) threshold, 78 + and I 2+ turn out to exceed again those for Br + and Br 2+ , respectively. Over the entire energy range examined, a remarkable biased charge spread in dissociative photoionization events is observed, presumably reflecting the fact that charge localized mostly in the excited atoms relevant to the specific inner-shell excitation, which can be accounted for mainly by a two-step decay process via a fast dissociation followed by autoionization upon vuv absorption

Metathesis Polymerization Reactions Induced by the Bimetallic Complex (Ph4P2[W2(μ-Br3Br6

Directory of Open Access Journals (Sweden)

Despoina Chriti

2015-12-01

Full Text Available The reactivity of the bimetallic complex (Ph4P2[W2(μ-Br3Br6] ({W 2.5 W}7+, a′2e3 towards ring opening metathesis polymerization (ROMP of norbornene (NBE and some of its derivatives, as well as the mechanistically related metathesis polymerization of phenylacetylene (PA, is presented. Our results show that addition of a silver salt (AgBF4 is necessary for the activation of the ditungsten complex. Polymerization of PA proceeds smoothly in tetrahydrofuran (THF producing polyphenylacetylene (PPA in high yields. On the other hand, the ROMP of NBE and its derivatives is more efficient in CH2Cl2, providing high yields of polymers. 13C Cross Polarization Magic Angle Spinning (CPMAS spectra of insoluble polynorbornadiene (PNBD and polydicyclopentadiene (PDCPD revealed the operation of two mechanisms (metathetic and radical for cross-linking, with the metathesis pathway prevailing.

35,37Cl, and 79,81Br, and 69,71Ga nuclear quadrupole resonance of complexes of gallium trichloride and aluminum bromide with nitriles and amines

International Nuclear Information System (INIS)

Popkova, L.A.; Gur'yanova, E.N.; Muromtsev, V.I.; Zhukov, A.P.

1989-01-01

The formation of an intermolecular bond in complexes of the electron donor-acceptor (DA) type is accompanied by a redistribution of electron density in both components of the complex. Valuable information on the character of the changes undergone by the donor and acceptor molecules in complexation can be obtained from NQR spectrometry. The present work is aimed at correlating NQR frequencies and multiplicity of spectra with the redistribution of electron density among orbitals of the central atom and the transfer of electron density to the halogen atoms upon complexation. The authors have investigated the 35,37 Cl, 69,71 Ga, and 79,81 Br NQR spectra of complexes of gallium trichloride and aluminum bromide with nitriles and amines

Neutral complexes of the indium dihalides

Energy Technology Data Exchange (ETDEWEB)

Sinclair, I.; Worrall, I.J. (Lancaster Univ. (UK))

1982-03-15

The neutral complexes In/sub 2/X/sub 4/.2L (X=Cl, Br, I; L 1,4-dioxan, tetrahydropyran, tetrahydrofuran, tetrahydrothiophene), In/sub 2/X/sub 4/.2L (X=Br, I; Ldimethylsulphide), In/sub 2/X/sub 4/.4L (X=Cl, Br, I; Lpiperidine, piperazine, morpholine), and In/sub 2/X/sub 4/.4L (X=Br, I; L=pyridine, dimethylsulphoxide) have been prepared. Solid state Raman spectra indicate that the compounds contain indium-indium bonds.

Electron impact scattering study of hypohalous acids HOX (X = F, Cl, Br, I)

Science.gov (United States)

Yadav, Hitesh; Bhutadia, Harshad; Prajapati, Dinesh; Desai, Hardik; Vinodkumar, Minaxi; Vinodkumar, P. C.

2018-05-01

In this article we aim to report total cross sections (TCS) QT, total elastic cross sections (Qel), total inelastic cross sections (Qinel) i.e. (total ionizations cross sections (Qion)+total electronic excitation cross sections (Qexc)) from threshold of the target to 5000 eV energy range. We have used a well-defined theoretical methodology Spherical Complex Optical Potential (SCOP) to compute QT, Qel and Qinel and Complex Scattering Potential - ionization contribution (CSP - ic) method to report the (Qion). The cross-sectional data reported here for the Hypohalous Acids is for the first time and the present data can become a guideline for the experimentalist to study these targets.

Light-emitting diodes based on two-dimensional PA2(CsPbBr3)n-1PbBr4 layered perovskites%基于PA2(CsPbBr3)n-1PbBr4二维层状钙钛矿的电致发光二极管

Institute of Scientific and Technical Information of China (English)

孟妍; 牛连斌; 许龙; 林春燕; 熊自阳; 熊祖洪; 陈平

2018-01-01

进一步提高全无机卤铅钙钛矿材料CsPbBr3的发光效率,对制备高效率、高稳定性的电致发光二极管(PeLED)具有重要意义.制备纳米级的钙钛矿量子点,一方面有助于提高激子的束缚能和钙钛矿晶体的荧光效率,另一方面也有利于形成连续、致密的二维层状钙钛矿薄膜.本文采用“原位生长”的策略,将一种具有长链结构的丙基溴化胺(CH3CH2CH2NH3Br,PABr)作为添加剂,与CsPbBr3的前驱体溶液进行共混,得到PA2(CsPbBr3)n-1PbBr4钙钛矿量子点.形成的二维层状钙钛矿薄膜均匀致密,在光致发光条件下,呈现出明亮的蓝绿光发射(发光峰位于506 nm).在电致发光方面,基于PA2(CsPbBr3)n-1PbBr4的PeLED启亮电压为～4.2 V,最大亮度为～2370 cd/m2,最高电流效率为～1.06 cd/A,最高EQE为～0.57％.相较于传统方法,本工作在制作工艺、成膜质量以及PeLED的发光效率有了显著的提升,为将来进一步探索低成本、高效率的蓝光PeLEDs提供了一种可行的思路.%Solution-processed organometal halide perovskites (formulated as ABX3,where A is the methylammonium (CH3NH3+)(MA) or metal cesium cation (Cs+),B is the lead cation (Pb2+) and X is the halide anion (Br-,I-,Cl-)) are promising candidates for next generation light-emitting materials owing to their unique optoelectronic properties.These properties mainly include extremely high photoluminescence quantum yield (PLQY),easily tunable band gap and narrow emission characteristics.During the past two years,impressive progresses have been made in perovskite light-emitting diodes (PeLED) with hybrid organic-inorganic perovskite materials (i.e.,CH3NH3PbBr3).So far,the best external quantum efficiency (EQE) of CH3NH3PbBr3-based PeLED was reaching up to ～8.53％ which was close to the results of organic light-emitting diodes (OLED).Despite the remarkable performance of the devices demonstrated,the stability of organic-inorganic hybrid perovskites

Why is AgBr not a superionic conductor

International Nuclear Information System (INIS)

Andreoni, W.; Tosi, M.P.

1982-03-01

The behaviour of AgCl and AgBr is contrasted with that of fluorite-type crystals, which also are Frenkel conductors at low temperatures but undergo a diffuse transition to a superionic phase before melting. Concentrating on AgBr for which the relevant defect parameters are better known, a Debye-Hueckel model for the interactions between defects, modified for saturation of screening at high defect concentrations, is used to show that both Frenkel and Schottky disorder are present and rapidly increasing with temperature in the hot solid, with the Schottky component rapidly overtaking the Frenkel component. It is suggested that this defect behaviour frustrates a superionic transition and leads to melting accompanied by an anomalous ionic conductivity in the premelting region. The model is tested by a comparison with data on the Frenkel defect concentration in superionic PbF 2 . (author)