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

PubMed

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 extremely unusual bridging mode. This is in contrast to the chelating monomer, cis-[TeCl(4){o-C(6)H(4)(SeMe)(2)}], formed with the analogous selenoether and may be attributed to small differences in the ligand chelate bite angles. The wider bite angle xylyl-linked bidentates, o-C(6)H(4)(CH(2)EMe(2))(2) behave differently; the thioether forms cis-chelated [TeX(4){o-C(6)H(4)(CH(2)SMe)(2)}] confirmed crystallographically, whereas the selenoether undergoes C-Se cleavage and rearrangement on treatment with TeX(4), forming the cyclic selenonium salts, [C(9)H(11)Se](2)[TeX(6)]. The tetrathiamacrocycle, [14]aneS(4) (1,4,8,11-tetrathiacyclotetradecane), does not react cleanly with TeCl(4), but forms the very poorly soluble [TeCl(4)([14]aneS(4))](n), shown by crystallography to be a zig-zag polymer with exo-coordinated [14]aneS(4) units linked via alternate S atoms to a cis-TeCl(4) unit. Trends in the (125)Te{(1)H} NMR shifts for this series of Te(IV) halides chalcogenoether complexes are discussed.

Structure and properties of the anions MF4-, MCl4- and MBr4- (M = C, Si, Ge)

NASA Astrophysics Data System (ADS)

Grein, Friedrich

2015-04-01

Density functional theory (DFT), Møller-Plesset (MP2) and coupled cluster with single and double substitutions including non-iterative triple excitations (CCSD(T)) calculations on the anions MX4-, with M = C, Si, Ge and X = F, Cl, Br, show that GeF4-, SiCl4-, GeCl4- and SiBr4- prefer a C2v conformation, but CCl4- is an elongated C3v structure. CBr4- has Td symmetry in MP2, but is slightly more stable in elongated C3v form with DFT and CCSD(T). GeBr4- has Td symmetry. CF4- and SiF4- are unstable with respect to loss of an electron. Vertical electron affinities (EAs) are negative also for CCl4 and SiCl4, and close to zero for GeF4 and SiBr4. Adiabatic EAs range from 0.47 eV for SiCl4 to 1.78 eV for GeBr4. The lowest excited states at Td symmetry are 2T2 resonances with energies of 2.1-3.5 eV, resulting from excitation of the a1 singly occupied molecular orbital to vacant t2 orbitals. Vertical excitation energies (VEEs) and vibrational frequencies are given for the most stable anionic geometries. Comparison with experimental VEEs for CCl4- is made. From dissociation energies of MX4, MX4-, MX3 and MX3-, appearance energies of X-, MX3-, X2- and MX2- were calculated. Most were found to be in reasonable agreement with experimental values. Theoretical spin densities and g-factors have been compared with experimental results available for CCl4-, SiCl4- and GeCl4-.

40 CFR Appendix A to Subpart A of... - Class I Controlled Substances

Code of Federal Regulations, 2010 CFR

2010-07-01

...) 1.0 C2 F3 Cl3-Trichlorotrifluoroethane (CFC-113) 0.8 C2 F4 Cl2-Dichlorotetrafluoroethane (CFC-114) 1... F4 Br2-Dibromotetrafluoroethane (Halon-2402) 6.0 All isomers of the above chemicals C. Group III: CF3...) 1.0 C3 F2 Cl6-(CFC-212) 1.0 C3 F3 Cl5-(CFC-213) 1.0 C3 F4 Cl4-(CFC-214) 1.0 C3 F5 Cl3-(CFC-215) 1.0...

Double-inversion mechanisms of the X⁻ + CH₃Y [X,Y = F, Cl, Br, I] SN2 reactions.

PubMed

Szabó, István; Czakó, Gábor

2015-03-26

The double-inversion and front-side attack transition states as well as the proton-abstraction channels of the X(-) + CH3Y [X,Y = F, Cl, Br, I] reactions are characterized by the explicitly correlated CCSD(T)-F12b/aug-cc-pVTZ(-PP) level of theory using small-core relativistic effective core potentials and the corresponding aug-cc-pVTZ-PP bases for Br and I. In the X = F case the double-inversion classical(adiabatic) barrier heights are 28.7(25.6), 15.8(13.4), 13.2(11.0), and 8.6(6.6) kcal mol(-1) for Y = F, Cl, Br, and I, respectively, whereas the barrier heights are in the 40-90 kcal mol(-1) range for the other 12 reactions. The abstraction channels are always above the double-inversion saddle points. For X = F, the front-side attack classical(adiabatic) barrier heights, 45.8(44.8), 31.0(30.3), 24.7(24.2), and 19.5(19.3) kcal mol(-1) for Y = F, Cl, Br, and I, respectively, are higher than the corresponding double-inversion ones, whereas for the other systems the front-side attack saddle points are in the 35-70 kcal mol(-1) range. The double-inversion transition states have XH···CH2Y(-) structures with Cs point-group symmetry, and the front-side attack saddle points have either Cs (X = F or X = Y) or C1 symmetry with XCY angles in the 78-88° range. On the basis of the previous reaction dynamics simulations and the minimum energy path computations along the inversion coordinate of selected XH···CH2Y(-) systems, we suggest that the double inversion may be a general mechanism for SN2 reactions.

Halide addition/abstraction in phosphido derivatives: isolation of the thallium and silver intermediates.

PubMed

Forniés, Juan; Fortuño, Consuelo; Ibáñez, Susana; Martín, Antonio

2008-07-07

Reaction of unsaturated (44e (-) skeleton) [PdPt 2(mu-PPh 2) 2(mu-P 2Ph 4)(R F) 4] 4 with Br (-) produces the saturated (48e (-) skeleton) complex [NBu 4][(R F) 2Pt(mu-PPh 2)(mu-Br)Pd(mu-PPh 2)(mu-P 2Ph 4)Pt(R F) 2] 5 without any M-M' bond. Attempts to eliminate Br (-) of 5 with Ag (+) in CH 2Cl 2 as a solvent gives a mixture of [(R F) 2Pt (III)(mu-PPh 2) 2Pt (III)(R F) 2] and some other unidentified products as a consequence of oxidation and partial fragmentation. However, when the reaction of 5 with Ag (+) is carried out in CH 3CN, no oxidation is observed but the elimination of Br (-) and the formation of [(R F) 2(CH 3CN)Pt(mu-PPh 2)Pd(mu-PPh 2)(mu-P 2Ph 4)Pt(R F) 2] 6 (46e (-) skeleton), a complex with a Pt-Pd bond, takes place. It is noteworthy that the reaction of 5 with TlPF 6 in CH 2Cl 2 does not precipitate TlBr but forms the adduct [(R F) 2PtTl(mu-PPh 2)(mu-Br)Pd(mu-PPh 2)(mu-P 2Ph 4)Pt(R F) 2] 7 with a Pt-Tl bond. Likewise, 5 reacts with [AgOClO 3(PPh 3)] in CH 2Cl 2 forming the adduct [AgPdPt 2(mu-Br)(mu-PPh 2) 2(mu-Ph 2P-PPh 2)(R F) 4(PPh 3)] 8, which contains a Pt-Ag bond. Both adducts are unstable in a CH 3CN solution, precipitating TlBr or AgBr and yielding the unsaturated 6. The treatment of [NBu 4] 2[(R F) 2Pt(mu-PPh 2) 2Pd(mu-PPh 2) 2Pt(R F) 2] in CH 3CN with I 2 (1:1 molar ratio) at 233 K yields a mixture of 4 and 6, which after recrystallization from CH 2Cl 2 is totally converted in 4. If the reaction with I 2 is carried out at room temperature, a mixture of the isomers [NBu 4][(R F) 2Pt(mu-PPh 2)(mu-I)Pd(mu-PPh 2)(mu-P 2Ph 4)Pt(R F) 2] 9 and [NBu 4][(R F)(PPh 2R F)Pt(mu-PPh 2)(mu-I)Pd(mu-PPh 2) 2Pt(R F) 2] 10 are obtained. The structures of the complexes have been established on the bases of NMR data, and the X-ray structures of 5- 8 have been studied. The relationship between the different complexes has been studied.

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

ERIC Educational Resources Information Center

Beauchamp, Guy

2005-01-01

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

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.

PubMed

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.

Comprehensive theoretical studies on the low-lying electronic states of NiF, NiCl, NiBr, and NiI.

PubMed

Zou, Wenli; Liu, Wenjian

2006-04-21

The low-lying electronic states of the nickel monohalides, i.e., NiF, NiCl, NiBr, and NiI, are investigated by using multireference second-order perturbation theory with relativistic effects taken into account. For the energetically lowest 11 lambda-S states and 26 omega states there into, the potential energy curves and corresponding spectroscopic constants (vertical and adiabatic excitation energies, equilibrium bond lengths, vibrational frequencies, and rotational constants) are reported. The calculated results are grossly in very good agreement with those solid experimental data. In particular, the ground state of NiI is shown to be different from those of NiF, NiCl, and NiBr, being in line with the recent experimental observation. Detailed analyses are provided on those states that either have not been assigned or have been incorrectly assigned by previous experiments.

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

NASA Astrophysics Data System (ADS)

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.

Molecular structures and thermodynamic properties of 12 gaseous cesium-containing species of nuclear safety interest: Cs 2, CsH, CsO, Cs 2O, CsX, and Cs 2X 2 (X = OH, Cl, Br, and I)

NASA Astrophysics Data System (ADS)

Badawi, Michael; Xerri, Bertrand; Canneaux, Sébastien; Cantrel, Laurent; Louis, Florent

2012-01-01

Ab initio electronic structure calculations at the coupled cluster level with a correction for the triples extrapolated to the complete basis set limit have been made for the estimation of the thermochemical properties of Cs 2, CsH, CsO, Cs 2O, CsX, and Cs 2X 2 (X = OH, Cl, Br, and I). The standard enthalpies of formation and standard molar entropies at 298 K, and the temperature dependence of the heat capacities at constant pressure were evaluated. The calculated thermochemical properties are in good agreement with their literature counterparts. For Cs 2, CsH, CsOH, Cs 2(OH) 2, CsCl, Cs 2Cl 2, CsBr, CsI, and Cs 2I 2, the calculated ΔfH298K∘ values are within chemical accuracy of the most recent experimental values. Based on the excellent agreement observed between our calculated ΔfH298K∘ values and their literature counterparts, the standard enthalpies of formation at 298 K are estimated to be the following: ΔfH298K∘ (CsO) = 17.0 kJ mol -1 and ΔfH298K∘ (Cs 2Br 2) = -575.4 kJ mol -1.

Electron affinity of perhalogenated benzenes: A theoretical DFT study

NASA Astrophysics Data System (ADS)

Volatron, François; Roche, Cécile

2007-10-01

The potential energy surfaces (PES) of unsubstituted and perhalogenated benzene anions ( CX6-, X = F, Cl, Br, and I) were explored by means of DFT-B3LYP calculations. In the F and Cl cases seven extrema were located and characterized. In the Br and I cases only one minimum and two extrema were found. In each case the minimum was recomputed at the CCSD(T) level. The electron affinities of C 6X 6 were calculated (ZPE included). The results obtained agree well with the experimental determinations when available. The values obtained in the X = Br and the X = I cases are expected to be valuable predictions.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Prestwich, G.D.; Streinz, L.

A series of mono, di-, and trihalogenated acetate analogs of Z11-16:Ac were prepared and examined for electrophysiological activity in antennae of males of the diamondback moth, Plutella xylostella. In addition, two potential affinity labels, a diazoacetate (Dza) and a trifluoromethyl ketone (Tfp), were evaluated for EAG activity. The Z11-16:Ac showed the highest activity in EAG assays, followed by the fluorinated acetates, but other haloacetates were essentially inactive. The effects of these analogs on the hydrolysis of (/sup 3/H)Z11-16:Ac to (/sup 3/H)Z11-16:OH by antennal esterases was also examined. The three fluorinated acetates showed the greatest activity as inhibitors in competition assays,more » with rank order F/sub 2/Ac > F/sub 3/Ac > FAc > AC > Cl/sub 2/Ac > ClAc > Dza > Br/sub 2/Ac > BrAc > Tfp > I > Cl/sub 3/Ac > Br/sub 3/Ac > OH. The relative polarities of the haloacetates, as determined by TLC mobility, are in the order mono- > di- > trihalo, but F, Cl, Br, and I all confer similar polarities within a substitution group. Thus, the steric size appears to be the predominant parameter affecting the interactions of the haloacetate analogs with both receptor and catabolic proteins in P. xylostella males.« less

Physical Chemistry of Energetic Nitrogen Compounds

DTIC Science & Technology

1993-10-01

2177 (1981). 8. R.F. Heiner, III, H . Helvajian , G.ý. Holloway,-and J.B. Koffend, J. Phys. Chem . 93, 7813 (1989). 9. D.D. Bell and R.D. Coombe, J. Chem...Deuterium Atom Reactions with NFC12 . . . . . . . . . . . . . . . . . . . . . . . . . 15 3. The Reaction of H Atomps with NF2Cl .............. 22 V...or Br,) was admitted downstream such that a portion of the F atoms were converted to H , Cl or Br atoms prior to the admission of HN3 to the flow. When

The selective activation of a C-F bond with an auxiliary strong Lewis acid: a method to change the activation preference of C-F and C-H bonds.

PubMed

Wang, Lin; Sun, Hongjian; Li, Xiaoyan; Fuhr, Olaf; Fenske, Dieter

2016-11-15

The selective activation of the C-F bonds in substituted (2,6-difluorophenyl)phenylimines (2,6-F 2 H 3 C 6 -(C[double bond, length as m-dash]NH)-n'-R-C 6 H 4 (n' = 2, R = H (1); n' = 2, R = Me (2); n' = 4, R = tBu (3))) by Fe(PMe 3 ) 4 with an auxiliary strong Lewis acid (LiBr, LiI, or ZnCl 2 ) was explored. As a result, iron(ii) halides ((H 5 C 6 -(C[double bond, length as m-dash]NH)-2-FH 3 C 6 )FeX(PMe 3 ) 3 (X = Br (8); Cl (9)) and (n-RH 4 C 6 -(C[double bond, length as m-dash]NH)-2'-FH 3 C 6 )FeX(PMe 3 ) 3 (n = 2, R = Me, X = Br (11); n = 4, R = tBu, X = I (12))) were obtained. Under similar reaction conditions, using LiBF 4 instead of LiBr or ZnCl 2 , the reaction of (2,6-difluorophenyl)phenylimine with Fe(PMe 3 ) 4 afforded an ionic complex [(2,6-F 2 H 3 C 6 -(C[double bond, length as m-dash]NH)-H 4 C 6 )Fe(PMe 3 ) 4 ](BF 4 ) (10) via the activation of a C-H bond. The method of C-F bond activation with an auxiliary strong Lewis acid is appropriate for monofluoroarylmethanimines. Without the Lewis acid, iron(ii) hydrides ((2-RH 4 C 6 -(C[double bond, length as m-dash]NH)-2'-FH 3 C 6 )FeH(PMe 3 ) 3 (R = H (13); Me (14))) were generated from the reactions of Fe(PMe 3 ) 4 with the monofluoroarylmethanimines (2-FH 4 C 6 -(C[double bond, length as m-dash]NH)-2'-RC 6 H 4 (R = H (4); Me (5))); however, in the presence of ZnCl 2 or LiBr, iron(ii) halides ((2-RH 4 C 6 -(C[double bond, length as m-dash]NH)-H 4 C 6 )FeX(PMe 3 ) 3 (R = H, X = Cl (15); R = Me, X = Br (16))) could be obtained through the activation of a C-F bond. Furthermore, a C-F bond activation with good regioselectivity in (pentafluorophenyl)arylmethanimines (F 5 C 6 -(C[double bond, length as m-dash]NH)-2,6-Y 2 C 6 H 3 (Y = F (6); H (7))) could be realized in the presence of ZnCl 2 to produce iron(ii) chlorides ((2,6-Y 2 H 3 C 6 -(C[double bond, length as m-dash]NH)-F 4 C 6 )FeCl(PMe 3 ) 3 (Y = F (17); H (18))). This series of iron(ii) halides could be used to catalyze the hydrosilylation reaction of aldehydes. Due to the stability of iron(ii) halides to high temperature, the reaction mixture was allowed to be heated to 100 °C and the reaction could finish within 0.5 h.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sergentu, Dumitru-Claudiu; CEISAM, UMR CNRS 6230, Université de Nantes, 2 Rue de la Houssinière, BP 92208, 44322 Nantes Cedex 3; Amaouch, Mohamed

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

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

NASA Astrophysics Data System (ADS)

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.

High energy chemical laser system

DOEpatents

Gregg, D.W.; Pearson, R.K.

1975-12-23

A high energy chemical laser system is described wherein explosive gaseous mixtures of a reducing agent providing hydrogen isotopes and interhalogen compounds are uniformly ignited by means of an electrical discharge, flash- photolysis or an electron beam. The resulting chemical explosion pumps a lasing chemical species, hydrogen fluoride or deuterium fluoride which is formed in the chemical reaction. The generated lasing pulse has light frequencies in the 3- micron range. Suitable interhalogen compounds include bromine trifluoride (BrF$sub 3$), bromine pentafluoride (BrF$sub 5$), chlorine monofluoride (ClF), chlorine trifluoride (ClF$sub 3$), chlorine pentafluoride (ClF$sub 5$), iodine pentafluoride (IF$sub 5$), and iodine heptafluoride (IF$sub 7$); and suitable reducing agents include hydrogen (H$sub 2$), hydrocarbons such as methane (CH$sub 4$), deuterium (D$sub 2$), and diborane (B$sub 2$H$sub 6$), as well as combinations of the gaseous compound and/or molecular mixtures of the reducing agent.

Crystal growth and near infrared optical properties of Pr 3+ doped lead halide materials for resonantly pumped eye safe laser applications

NASA Astrophysics Data System (ADS)

Jones, Ivy Krystal

In this dissertation the material development and optical spectroscopy of Pr3+ activated low phonon energy halide crystals is presented for possible applications in resonantly pumped eye-safe solid-state laser gain media. In the last twenty years, the developments in fiber and diode lasers have enabled highly efficient resonant pumping of Pr3+ doped crystals for possible lasing in the 1.6--1.7 microm region. In this work, the results of the purification, crystal growth, and near-infrared (NIR) spectroscopic characterization of Pr3+ doped lead (II) chloride, PbCl2 and lead (II) bromide, PbBr2 are presented. The investigated PbCl2 and PbBr2 crystals are non-hygroscopic with maximum phonon energies between ~180--200 cm-1, which enable efficient emission in the NIR spectral region (~ 1.6 microm) from the 3F3/3F4 → 3H4 transition of Pr3+ ions. The commercial available starting materials were purchased as ultra dry, high purity (~ 99.999 %) beads and purified through a combination of zone-refinement and halogenation. The crystal growth of Pr3+ doped PbCl 2 and PbBr2 was performed via vertical Bridgman technique using a two-zone furnace. The resulting Pr3+ doped PbCl 2 and PbBr2 crystals exhibited characteristic IR absorption bands in the 1.5--1.7 microm region (3H4 → 3F3/3F4), which allow for resonant pumping using commercial diode lasers. A broad IR emission band centered at ~1.6 microm was observed under ~1445 nm diode laser excitation from both Pr3+ doped halides. This dissertation presents comparative spectroscopic results for Pr 3+:PbCl2 and Pr3+:PbBr2 including NIR absorption and emission studies, lifetime measurements, modelling of radiative and non-radiative decay rates, determination of transition cross-section, and the net effective gain cross sections.

Haloacetate analogs of pheromones: Effects on catabolism and electrophysiology inPlutella xylostella.

PubMed

Prestwich, G D; Streinz, L

1988-03-01

A series of mono-, di-, and trihalogenated acetate analogs of Zl 1-16: Ac were prepared and examined for electrophysiological activity in antennae of males of the diamondback moth,Plutella xylostella. In addition, two potential affinity labels, a diazoacetate (Dza) and a trifluoromethyl ketone (Tfp), were evaluated for EAG activity. The Z11-16∶Ac showed the highest activity in EAG assays, followed by the fluorinated acetates, but other halo-acetates were essentially inactive. The polar diazoacetate and the trifluoromethyl ketone were also very weak EAG stimulants. The effects of these analogs on the hydrolysis of [(3)H]Z11-16∶Ac to [(3)H]Z11-16∶OH by antennal esterases was also examined. The three fluorinated acetates showed the greatest activity as inhibitors in competition assays, with rank order F2Ac > F(3)Ac > FAc > Ac > Cl2Ac > ClAc > Dza > Br2Ac > BrAc > Tfp > I > Cl3Ac > Br3Ac > OH. The relative polarities of the haloacetates, as determined by TLC mobility, are in the order mono- > di- > trihalo, but F, Cl, Br, and I all confer similar polarities within a substitution group. Thus, the steric size appears to be the predominant parameter affecting the interactions of the haloacetate analogs with both receptor and catabolic proteins inP. xylostella males.

A Highly Reactive Dicationic Iridium(III) Catalyst for Polarized Nazarov Cyclization

PubMed Central

Vaidya, Tulaza; Atesin, Abdurrahman C.; Herrick, Ildiko R.; Frontier, Alison J.; Eisenberg, Richard

2010-01-01

Pushing the Nazarov Envelope A new electrophilic complex [IrBr(CO)(diethylisopropylidene malonate)((R)-(+)-BINAP)](SbF6)2 (2) exhibits unusual activity in the catalysis of polarized Nazarov cyclization. Aryl vinyl ketones that show poor reactivity with well-known catalysts such as [Ir(CH3)(CO)(1,2-diiodobenzene)(dppe)](B(Arf)4−)2 (1), Sc(OTf)3 + LiClO4 and Cu(ClO4)2, can be cyclized with 2 + AgSbF6 (1:1) under mild conditions with concurrent AgBr precipitation. PMID:20358570

Evidence for Interfacial Halogen Bonding.

PubMed

Swords, Wesley B; Simon, Sarah J C; Parlane, Fraser G L; Dean, Rebecca K; Kellett, Cameron W; Hu, Ke; Meyer, Gerald J; Berlinguette, Curtis P

2016-05-10

A homologous series of donor-π-acceptor dyes was synthesized, differing only in the identity of the halogen substituents about the triphenylamine (TPA; donor) portion of each molecule. Each Dye-X (X=F, Cl, Br, and I) was immobilized on a TiO2 surface to investigate how the halogen substituents affect the reaction between the light-induced charge-separated state, TiO2 (e(-) )/Dye-X(+) , with iodide in solution. Transient absorption spectroscopy showed progressively faster reactivity towards nucleophilic iodide with more polarizable halogen substituents: Dye-F < Dye-Cl < Dye-Br < Dye-I. Given that all other structural and electronic properties for the series are held at parity, with the exception of an increasingly larger electropositive σ-hole on the heavier halogens, the differences in dye regeneration kinetics for Dye-Cl, Dye-Br, and Dye-I are ascribed to the extent of halogen bonding with the nucleophilic solution species. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Fabrication Techniques for III-V Micro-Opto-Electro-Mechanical Systems

DTIC Science & Technology

2002-03-26

Trifluoride . . . . . . . . . . . . . . . . . . . . . 2-33 ClF3 Chlorine Trifluoride . . . . . . . . . . . . . . . . . . . . . 2-33 xix Symbol Page O2 Oxygen...dimensionless) . . . . . . . . . . . . 2-36 HCl Hydrochloric Acid . . . . . . . . . . . . . . . . . . . . . . 3-16 M Molarity (moles/liter...interhalogen etch gases have been synthesized and used to etch silicon. These gases include bromine triflouride (BrF3) and chlorine trifluoride (ClF3) [27

Catalog of infrared and cryo-optical properties for selected materials

NASA Technical Reports Server (NTRS)

Heaney, James B.; Alley, Phillip W.; Bradley, Scott E.

1991-01-01

This report will describe the status of an effort to catalog the refractive index, absorption, reflectance and transmittance of selected IR transmitting materials over the wavelength range from 1 to 1000 microns, and at temperatures from 300 to about 2 K. Data are presented for LiF, CaF2, BaF2, KBr, and TlBr, as well as for KRS-5 (TlBr-I) and KRS-6 (TlBr-Cl). A cryooptical measurements facility at NASA-Goddard, which has been used to generate some of the cataloged data, is also described.

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

NASA Technical Reports Server (NTRS)

Hsu, H-J.; DeMore, W.

1994-01-01

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

New iodide-based molten salt systems for high temperature molten salt batteries

NASA Astrophysics Data System (ADS)

Fujiwara, Syozo; Kato, Fumio; Watanabe, Syouichiro; Inaba, Minoru; Tasaka, Akimasa

Novel multi-component molten salt systems containing iodides, LiF-LiBr-LiI, LiF-NaBr-LiI, and LiF-LiCl-LiBr-LiI, were investigated for use as electrolytes in high temperature molten salt batteries to improve the discharge rate-capability. The iodide-based molten salts showed higher ionic conductivity (∼3 S cm -1 at 500 °C) than conventional LiCl-KCl, and had low enough melting points (below 400 °C) that can be used in practical high temperature molten salt batteries. The iodide-based salts showed instability at temperatures higher than 280 °C in dried air. The decomposition mechanism of iodide-based molten salts was discussed, and it was found that elimination of oxygen from the environment is effective to stabilize the iodide-based molten salts at high temperatures.

Syntheses of amide based anion receptors and investigation of their associations with anions and their molecular structures using proton NMR titration and DFT methods

NASA Astrophysics Data System (ADS)

Navakhun, Korakot; Sawangsri, Ranu; Ruangpornvisuti, Vithaya

2014-03-01

The synthesized disubstituted isophthalamide and pyridine-2,6dicarboxamide derivatives of nine compounds were prepared. Their association constants with tetrabutylammonium fluoride (TBA·F), tetrabutylammonium chloride (TBA·Cl), tetrabutylammonium bromide (TBA·Br), tetrabutylammonium dihydrogenphosphate (TBA·H2PO4), tetrabutylammonium hydrogensulphate (TBA·HSO4) and tetrabutylammonium nitrate (TBA·NO3) were obtained by 1H NMR titration technique. The optimized structures of compounds 1-9 and their association with F-, Cl-, Br-, HPO4-, HSO4- and NO3- were obtained using the B3LYP/6-31+G(d) method. The most favorable complex of compound 3 with Br- was found. The high association constants of complexes 1-6 with F- are expected. Associations of all receptors with anions are exothermic and spontaneous reactions. Thermodynamic properties of all associations obtained using B3LYP/6-31+G(d) method are reported.

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

PubMed

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.

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

PubMed

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

2016-08-23

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

Tracing halogen and B cycling in subduction zones based on obducted, subducted and forearc serpentinites of the Dominican Republic.

PubMed

Pagé, Lilianne; Hattori, Keiko

2017-12-19

Serpentinites are important reservoirs of fluid-mobile elements in subduction zones, contributing to volatiles in arc magmas and their transport into the Earth's mantle. This paper reports halogen (F, Cl, Br, I) and B abundances of serpentinites from the Dominican Republic, including obducted and subducted abyssal serpentinites and forearc mantle serpentinites. Abyssal serpentinite compositions indicate the incorporation of these elements from seawater and sediments during serpentinization on the seafloor and at slab bending. During their subduction and subsequent lizardite-antigorite transition, F and B are retained in serpentinites, whilst Cl, Br and I are expelled. Forearc mantle serpentinite compositions suggest their hydration by fluids released from subducting altered oceanic crust and abyssal serpentinites, with only minor sediment contribution. This finding is consistent with the minimal subduction of sediments in the Dominican Republic. Forearc mantle serpentinites have F/Cl and B/Cl ratios similar to arc magmas, suggesting the importance of serpentinite dehydration in the generation of arc magmatism in the mantle wedge.

Graphene-like monolayer InSe–X: several promising half-metallic nanosheets in spintronics

NASA Astrophysics Data System (ADS)

Liu, Jun; Kang, Wei; Zhou, Ting-Yan; Ma, Chong-Geng

2018-04-01

Several half-metallic graphene-like nanosheets, namely halogen atom adsorbed InSe–X (X  =  F, Cl, Br and I) nanosheets, are predicted by first-principles calculations. Then, their structural, electric and magnetic properties are studied in detail. The calculated negative adsorption energies of these InSe–X nanosheets ensure that they attain stable adsorption structures, which suggests that they may be prepared experimentally. The pristine InSe monolayer is a typical semi-conductor, whereas it is interesting that the X ion (X  =  F, Cl, Br and I) adsorbed InSe–X nanosheets are electronically conductive. They can be promising and good candidates for applications of half-metallic 2D materials. The calculated magnetic moments of these nanosheets are close to 1.0 µ B. In the InSe–F nanosheet, there are sp2 hybridized orbitals due to the crystal field effect, and its electroconductibility, half-metallicity and magnetic moments originate from the In and Se ions, not the F ion. However, in InSe–X (X  =  Cl, Br and I) nanosheets, there are sp3 hybridized orbitals, and their electroconductibility, half-metallicity and magnetic moments originate mainly from X ions, together partially with the In and Se ions.

Experimental Investigations of Boron, Lithium, and Halogens During High-Temperature Water-Rock Interaction: Insights into the Yellowstone Hydrothermal System

NASA Astrophysics Data System (ADS)

Cullen, J. T.; Hurwitz, S.; Thordsen, J. J.; Barnes, J.

2017-12-01

B, Li, and halogens (Cl, F, Br) are used extensively in studies of thermal waters to infer fluid equilibrium conditions with the host reservoir lithology, and quantify the possible fraction of a magmatic component in thermal waters. Apart from fluorine, the limited number of minerals that incorporate these elements support the notion that they preferentially partition into an aqueous fluid during high temperature water-rock interaction. Although limited experimental work is largely consistent with these observations, a rigorous experimental investigation is required to quantify the mobility of these elements under conditions emulating a silicic hydrothermal system. Here we present the results from water-rhyolite interaction batch experiments conducted over a range of temperatures between 150 °C and 350 °C and 250 bar. Powdered obsidian from Yellowstone was reacted with MiliQ water and sampled intermittently throughout the duration of the 90 day experiment. The experimental data show that at temperatures ≤ 200 °C, B, Cl, Br, and Li are not readily leached from the rhyolite, whereas aqueous F- concentration increases by a factor of 3.5 when the temperature was increased from 150 °C to 200 °C. Between 200 °C and 250 °C, B concentration increased by more than an order of magnitude and Cl- concentration increased by a factor of 5. F- concentration increased by a factor of 3. Between 250 °C and 300 °C the opposite trend was observed, in which F- concentration decreased by 60%, Br- concentration increased by a factor of 5, and Cl- and B concentrations increased by more than an order of magnitude. The progressive decrease of aqueous F- at T ≥ 300 °C is likely controlled by precipitation into a fluorine bearing secondary mineral(s). Our experimental results demonstrate that leaching of B, Li, Cl, F, and Br from rhyolite is highly temperature-dependent between 150 °C and 350 °C. These results can provide context to infer the sources of solutes discharged at thermal springs and the subsurface water-rhyolite equilibrium temperatures in the Yellowstone hydrothermal system. Work to characterize the alteration mineralogy and the temperature-dependent stable Cl, Li, and B isotope fractionation is currently ongoing. Keywords: Yellowstone, hydrothermal, halogens, experiments, water-rock interaction

Experimental Investigations of Boron, Lithium, and Halogens During High-Temperature Water-Rock Interaction: Insights into the Yellowstone Hydrothermal System

NASA Astrophysics Data System (ADS)

Cullen, J. T.; Hurwitz, S.; Thordsen, J. J.; Barnes, J.

2016-12-01

B, Li, and halogens (Cl, F, Br) are used extensively in studies of thermal waters to infer fluid equilibrium conditions with the host reservoir lithology, and quantify the possible fraction of a magmatic component in thermal waters. Apart from fluorine, the limited number of minerals that incorporate these elements support the notion that they preferentially partition into an aqueous fluid during high temperature water-rock interaction. Although limited experimental work is largely consistent with these observations, a rigorous experimental investigation is required to quantify the mobility of these elements under conditions emulating a silicic hydrothermal system. Here we present the results from water-rhyolite interaction batch experiments conducted over a range of temperatures between 150 °C and 350 °C and 250 bar. Powdered obsidian from Yellowstone was reacted with MiliQ water and sampled intermittently throughout the duration of the 90 day experiment. The experimental data show that at temperatures ≤ 200 °C, B, Cl, Br, and Li are not readily leached from the rhyolite, whereas aqueous F- concentration increases by a factor of 3.5 when the temperature was increased from 150 °C to 200 °C. Between 200 °C and 250 °C, B concentration increased by more than an order of magnitude and Cl- concentration increased by a factor of 5. F- concentration increased by a factor of 3. Between 250 °C and 300 °C the opposite trend was observed, in which F- concentration decreased by 60%, Br- concentration increased by a factor of 5, and Cl- and B concentrations increased by more than an order of magnitude. The progressive decrease of aqueous F- at T ≥ 300 °C is likely controlled by precipitation into a fluorine bearing secondary mineral(s). Our experimental results demonstrate that leaching of B, Li, Cl, F, and Br from rhyolite is highly temperature-dependent between 150 °C and 350 °C. These results can provide context to infer the sources of solutes discharged at thermal springs and the subsurface water-rhyolite equilibrium temperatures in the Yellowstone hydrothermal system. Work to characterize the alteration mineralogy and the temperature-dependent stable Cl, Li, and B isotope fractionation is currently ongoing. Keywords: Yellowstone, hydrothermal, halogens, experiments, water-rock interaction

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Demissie, Taye B.

2015-12-31

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

Volatile element chemistry in the solar nebula - Na, K, F, Cl, Br, and P

NASA Technical Reports Server (NTRS)

Fegley, B., Jr.; Lewis, J. S.

1980-01-01

The results of the most extensive set to date of thermodynamic calculations on the equilibrium chemistry of several hundred compounds of the elements Na, K, F, Cl, Br, and P in a solar composition system are reported. Two extreme models of accretion are investigated. In one extreme complete chemical equilibrium between condensates and gases is maintained because the time scale for accretion is long compared to the time scale for cooling or dissipation of the nebula. Condensates formed in this homogeneous accretion model include several phases such as whitlockite, alkali feldspars, and apatite minerals which are found in chondrites. In the other extreme complete isolation of newly formed condensates from prior condensates and gases occurs due to a time scale for accretion that is short relative to the time required for nebular cooling or dissipation. The condensates produced in this heterogeneous accretion model include alkali sulfides, ammonium halides, and ammonium phosphates. None of these phases are found in chondrites. Available observations of the Na, K, F, Cl, Br, and P elemental abundances in the terrestrial planets are found to be compatible with the predictions of the homogeneous accretion model.

Tetrahalide complexes of the [U(NR)2]2+ ion: synthesis, theory, and chlorine K-edge X-ray absorption spectroscopy.

PubMed

Spencer, Liam P; Yang, Ping; Minasian, Stefan G; Jilek, Robert E; Batista, Enrique R; Boland, Kevin S; Boncella, James M; Conradson, Steven D; Clark, David L; Hayton, Trevor W; Kozimor, Stosh A; Martin, Richard L; MacInnes, Molly M; Olson, Angela C; Scott, Brian L; Shuh, David K; Wilkerson, Marianne P

2013-02-13

Synthetic routes to salts containing uranium bis-imido tetrahalide anions [U(NR)(2)X(4)](2-) (X = Cl(-), Br(-)) and non-coordinating NEt(4)(+) and PPh(4)(+) countercations are reported. In general, these compounds can be prepared from U(NR)(2)I(2)(THF)(x) (x = 2 and R = (t)Bu, Ph; x = 3 and R = Me) upon addition of excess halide. In addition to providing stable coordination complexes with Cl(-), the [U(NMe)(2)](2+) cation also reacts with Br(-) to form stable [NEt(4)](2)[U(NMe)(2)Br(4)] complexes. These materials were used as a platform to compare electronic structure and bonding in [U(NR)(2)](2+) with [UO(2)](2+). Specifically, Cl K-edge X-ray absorption spectroscopy (XAS) and both ground-state and time-dependent hybrid density functional theory (DFT and TDDFT) were used to probe U-Cl bonding interactions in [PPh(4)](2)[U(N(t)Bu)(2)Cl(4)] and [PPh(4)](2)[UO(2)Cl(4)]. The DFT and XAS results show the total amount of Cl 3p character mixed with the U 5f orbitals was roughly 7-10% per U-Cl bond for both compounds, which shows that moving from oxo to imido has little effect on orbital mixing between the U 5f and equatorial Cl 3p orbitals. The results are presented in the context of recent Cl K-edge XAS and DFT studies on other hexavalent uranium chloride systems with fewer oxo or imido ligands.

X2Y2 isomers: tuning structure and relative stability through electronegativity differences (X = H, Li, Na, F, Cl, Br, I; Y = O, S, Se, Te).

PubMed

El-Hamdi, Majid; Poater, Jordi; Bickelhaupt, F Matthias; Solà, Miquel

2013-03-04

We have studied the XYYX and X2YY isomers of the X2Y2 species (X = H, Li, Na, F, Cl, Br, I; Y = O, S, Se, Te) using density functional theory at the ZORA-BP86/QZ4P level. Our computations show that, over the entire range of our model systems, the XYYX isomers are more stable than the X2YY forms except for X = F and Y = S and Te, for which the F2SS and F2TeTe isomers are slightly more stable. Our results also point out that the Y-Y bond length can be tuned quite generally through the X-Y electronegativity difference. The mechanism behind this electronic tuning is the population or depopulation of the π* in the YY fragment.

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

NASA Astrophysics Data System (ADS)

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.

Halogen content in Lesser Antilles arc volcanic rocks : exploring subduction recycling

NASA Astrophysics Data System (ADS)

Thierry, Pauline; Villemant, Benoit; Caron, Benoit

2016-04-01

Halogens (F, Cl, Br and I) are strongly reactive volatile elements which can be used as tracers of igneous processes, through mantle melting, magma differentiation and degassing or crustal material recycling into mantle at subduction zones. Cl, Br and I are higly incompatible during partial melting or fractional cristallization and strongly depleted in melts by H2O degassing, which means that no Cl-Br-I fractionation is expected through magmatic differenciation [current thesis]. Thus, Cl/Br/I ratios in lavas reflect the halogen content of their mantle sources. Whereas these ratios seemed quite constant (e.g. Cl/Br =300 as seawater), recent works suggest significant variations in arc volcanism [1,2]. In this work we provide high-precision halogen measurements in volcanic rocks from the recent activity of the Lesser Antilles arc (Montserrat, Martinique, Guadeloupe, Dominique). Halogen contents of powdered samples were determined through extraction in solution by pyrohydrolysis and analysed by Ion Chromatography for F and Cl and high performance ICP-MS (Agilent 8800 Tripe Quad) for Cl, Br and I [3,4]. We show that lavas - and mantle sources - display significant vraiations in Cl/Br/I ratios along the Lesser Antilles arc. These variations are compared with Pb, Nd and Sr isotopes and fluid-mobile elements (Ba, U, Sr, Pb etc.) compositions which vary along the arc from a nothern ordinary arc compositions to a southern 'crustal-like' composition [5,6]. These characteristics are attributed to subducted sediments recycling into the mantle wedge, whose contribution vary along the arc from north to south [7,8]. The proportion of added sediments is also related to the distance to the trench as sediment melting and slab dehydration may occur depending on the slab depth [9]. Further Cl-Br-I in situ measurements by LA-ICP-MS in Lesser Antilles arc lavas melt inclusions will be performed, in order to provide better constraints on the deep halogen recycling cycle from crust to mantle. 1. Villemant, B., Mouatt, J. & Michel, A., 2008. Earth Planet. Sci. Lett. 269(1), 212-229. 2. Kutterolf, S. et al., 2015. Earth Planet. Sci. Lett. 429, 234-246. 3. Michel, A. & Villemant, B., 2003. Geostand. Geoanalytical Res. 27(2), 163-171. 4. Balcone-Boissard, H., Michel, A. & Villemant, B., 2009. Geostand. Geoanalytical Res. 33(4), 477-485. 5. White, W. M. & Dupré, B., 1986. J. Geophys. Res. 91(B6), 5927. 6. Labanieh, S. et al., 2010. Earth Planet. Sci. Lett. 298(1-2), 35-46. 7. Turner, S. et al., 1996. Earth Planet. Sci. Lett. 142(1-2), 191-207. 8. Carpentier, M., Chauvel, C. & Mattielli, N., 2008. Earth Planet. Sci. Lett. 272(1-2), 199-211. 9. Labanieh, S. et al., 2012. J. Petrol. 53(12), 2441-2464.

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

PubMed

Groen, C P; Oskam, A; Kovács, A

2000-12-25

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

Experimental and Estimated Rate Constants for the Reactions of Hydroxyl Radicals with Several Halocarbons

NASA Technical Reports Server (NTRS)

DeMore, W.B.

1996-01-01

Relative rate experiments are used to measure rate constants and temperature dependencies of the reactions of OH with CH3F (41), CH2FCl (31), CH2BrCl (30B1), CH2Br2 (3OB2), CHBr3 (2OB3), CF2BrCHFCl (123aBl(alpha)), and CF2ClCHCl2 (122). Rate constants for additional compounds of these types are estimated using an empirical rate constant estimation method which is based on measured rate constants for a wide range of halocarbons. The experimental data are combined with the estimated and previously reported rate constants to illustrate the effects of F, Cl, and Br substitution on OH rate constants for a series of 19 halomethanes and 25 haloethanes. Application of the estimation technique is further illustrated for some higher hydrofluorocarbons (HFCs), including CHF2CF2CF2CF2H (338pcc), CF3CHFCHFCF2CF3 (43-10mee), CF3CH2CH2CF3 (356ffa), CF3CH2CF2CH2CF3 (458mfcf), CF3CH2CHF2 (245fa), and CF3CH2CF2CH3 (365mfc). The predictions are compared with literature data for these compounds.

Activation barriers for series of exothermic homologous reactions. V. Boron group diatomic species reactions

NASA Astrophysics Data System (ADS)

Blue, Alan S.; Belyung, David P.; Fontijn, Arthur

1997-09-01

Semiempirical configuration interaction (SECI) theory is used to predict activation barriers E, as defined by k(T)=ATn exp(-E/RT). Previously SECI has been applied to homologous series of oxidation reactions of s1, s2, and s2p1 metal atoms. Here it is extended to oxidation reactions of diatomic molecules containing one s2p1 atom. E values are calculated for the reactions of BH, BF, BCl, AlF, AlCl, AlBr, GaF, GaI, InCl, InBr, InI, TlF, TlCl, TlBr, and TlI with O2, CO2, SO2, or N2O. These values correlate with the sums of the ionization potentials and Σ-Π promotion energies of the former minus the electron affinities of the latter. In the earlier work n was chosen somewhat arbitrarily, which affected the absolute values of E. Here it is shown that examination of available experimental and theoretical results allows determination of the best values of n. Using this approach yields n=1.9 for the present series. For the seven reactions which have been studied experimentally, the average deviation of the SECI activation barrier prediction from experiment is 4.0 kJ mol-1. Energy barriers are calculated for another 52 reactions.

Behavior of Halogen Bonds of the Y-X⋅⋅⋅π Type (X, Y=F, Cl, Br, I) in the Benzene π System, Elucidated by Using a Quantum Theory of Atoms in Molecules Dual-Functional Analysis.

PubMed

Sugibayashi, Yuji; Hayashi, Satoko; Nakanishi, Waro

2016-08-18

The nature of halogen bonds of the Y-X-✶-π(C6 H6 ) type (X, Y=F, Cl, Br, and I) have been elucidated by using the quantum theory of atoms in molecules (QTAIM) dual-functional analysis (QTAIM-DFA), which we proposed recently. Asterisks (✶) emphasize the presence of bond-critical points (BCPs) in the interactions in question. Total electron energy densities, Hb (rc ), are plotted versus Hb (rc )-Vb (rc )/2 [=(ħ(2) /8m)∇(2) ρb (rc )] for the interactions in QTAIM-DFA, in which Vb (rc ) are potential energy densities at the BCPs. Data for perturbed structures around fully optimized structures were used for the plots, in addition to those of the fully optimized ones. The plots were analyzed by using the polar (R, θ) coordinate for the data of fully optimized structures with (θp , κp ) for those that contained the perturbed structures; θp corresponds to the tangent line of the plot and κp is the curvature. Whereas (R, θ) corresponds to the static nature, (θp , κp ) represents the dynamic nature of the interactions. All interactions in Y-X-✶-π(C6 H6 ) are classified by pure closed-shell interactions and characterized to have vdW nature, except for Y-I-✶-π(C6 H6 ) (Y=F, Cl, Br) and F-Br-✶-π(C6 H6 ), which have typical hydrogen-bond nature without covalency. I-I-✶-π(C6 H6 ) has a borderline nature between the two. Y-F-✶-π(C6 H6 ) (Y=Br, I) were optimized as bent forms, in which Y-✶-π interactions were detected. The Y-✶-π interactions in the bent forms are predicted to be substantially weaker than those in the linear F-Y-✶-π(C6 H6 ) forms. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Synthesis, structure and reactivity of a terminal magnesium fluoride compound, [TpBut,Me]MgF: hydrogen bonding, halogen bonding and C-F bond formation.

PubMed

Rauch, Michael; Ruccolo, Serge; Mester, John Paul; Rong, Yi; Parkin, Gerard

2016-01-01

The bulky tris(3- tert -butyl-5-pyrazolyl)hydroborato ligand, [Tp Bu t ,Me ], has been employed to obtain the first structurally characterized example of a molecular magnesium compound that features a terminal fluoride ligand, namely [Tp Bu t ,Me ]MgF, via the reaction of [Tp Bu t ,Me ]MgMe with Me 3 SnF. The chloride, bromide and iodide complexes, [Tp Bu t ,Me ]MgX (X = Cl, Br, I), can also be obtained by an analogous method using Me 3 SnX. The molecular structures of the complete series of halide derivatives, [Tp Bu t ,Me ]MgX (X = F, Cl, Br, I) have been determined by X-ray diffraction. In each case, the Mg-X bond lengths are shorter than the sum of the covalent radii, thereby indicating that there is a significant ionic component to the bonding, in agreement with density functional theory calculations. The fluoride ligand of [Tp Bu t ,Me ]MgF undergoes halide exchange with Me 3 SiX (X = Cl, Br, I) to afford [Tp Bu t ,Me ]MgX and Me 3 SiF. The other halide derivatives [Tp Bu t ,Me ]MgX undergo similar exchange reactions, but the thermodynamic driving forces are much smaller than those involving fluoride transfer, a manifestation of the often discussed silaphilicity of fluorine. In accord with the highly polarized Mg-F bond, the fluoride ligand of [Tp Bu t ,Me ]MgF is capable of serving as a hydrogen bond and halogen bond acceptor, such that it forms adducts with indole and C 6 F 5 I. [Tp Bu t ,Me ]MgF also reacts with Ph 3 CCl to afford Ph 3 CF, thereby demonstrating that [Tp Bu t ,Me ]MgF may be used to form C-F bonds.

A two force-constant model for complexes B⋯M-X (B is a Lewis base and MX is any diatomic molecule): Intermolecular stretching force constants from centrifugal distortion constants D(J) or Δ(J).

PubMed

Bittner, Dror M; Walker, Nicholas R; Legon, Anthony C

2016-02-21

A two force-constant model is proposed for complexes of the type B⋯MX, in which B is a simple Lewis base of at least C2v symmetry and MX is any diatomic molecule lying along a Cn axis (n ≥ 2) of B. The model assumes a rigid subunit B and that force constants beyond quadratic are negligible. It leads to expressions that allow, in principle, the determination of three quadratic force constants F11, F12, and F22 associated with the r(B⋯M) = r2 and r(M-X) = r1 internal coordinates from the equilibrium centrifugal distortion constants DJ (e) or ΔJ (e), the equilibrium principal axis coordinates a1 and a2, and equilibrium principal moments of inertia. The model can be applied generally to complexes containing different types of intermolecular bond. For example, the intermolecular bond of B⋯MX can be a hydrogen bond if MX is a hydrogen halide, a halogen-bond if MX is a dihalogen molecule, or a stronger, coinage-metal bond if MX is a coinage metal halide. The equations were tested for BrCN, for which accurate equilibrium spectroscopic constants and a complete force field are available. In practice, equilibrium values of DJ (e) or ΔJ (e) for B⋯MX are not available and zero-point quantities must be used instead. The effect of doing so has been tested for BrCN. The zero-point centrifugal distortion constants DJ (0) or ΔJ (0) for all B⋯MX investigated so far are of insufficient accuracy to allow F11 and F22 to be determined simultaneously, even under the assumption F12 = 0 which is shown to be reasonable for BrCN. The calculation of F22 at a series of fixed values of F11 reveals, however, that in cases for which F11 is sufficiently larger than F22, a good approximation to F22 is obtained. Plots of F22 versus F11 have been provided for Kr⋯CuCl, Xe⋯CuCl, OC⋯CuCl, and C2H2⋯AgCl as examples. Even in cases where F22 ∼ F11 (e.g., OC⋯CuCl), such plots will yield either F22 or F11 if the other becomes available.

A two force-constant model for complexes B⋯M-X (B is a Lewis base and MX is any diatomic molecule): Intermolecular stretching force constants from centrifugal distortion constants DJ or ΔJ

NASA Astrophysics Data System (ADS)

Bittner, Dror M.; Walker, Nicholas R.; Legon, Anthony C.

2016-02-01

A two force-constant model is proposed for complexes of the type B⋯MX, in which B is a simple Lewis base of at least C2v symmetry and MX is any diatomic molecule lying along a Cn axis (n ≥ 2) of B. The model assumes a rigid subunit B and that force constants beyond quadratic are negligible. It leads to expressions that allow, in principle, the determination of three quadratic force constants F11, F12, and F22 associated with the r(B⋯M) = r2 and r(M-X) = r1 internal coordinates from the equilibrium centrifugal distortion constants DJ e or ΔJ e , the equilibrium principal axis coordinates a1 and a2, and equilibrium principal moments of inertia. The model can be applied generally to complexes containing different types of intermolecular bond. For example, the intermolecular bond of B⋯MX can be a hydrogen bond if MX is a hydrogen halide, a halogen-bond if MX is a dihalogen molecule, or a stronger, coinage-metal bond if MX is a coinage metal halide. The equations were tested for BrCN, for which accurate equilibrium spectroscopic constants and a complete force field are available. In practice, equilibrium values of DJ e or ΔJ e for B⋯MX are not available and zero-point quantities must be used instead. The effect of doing so has been tested for BrCN. The zero-point centrifugal distortion constants DJ 0 or ΔJ 0 for all B⋯MX investigated so far are of insufficient accuracy to allow F11 and F22 to be determined simultaneously, even under the assumption F12 = 0 which is shown to be reasonable for BrCN. The calculation of F22 at a series of fixed values of F11 reveals, however, that in cases for which F11 is sufficiently larger than F22, a good approximation to F22 is obtained. Plots of F22 versus F11 have been provided for Kr⋯CuCl, Xe⋯CuCl, OC⋯CuCl, and C2H2⋯AgCl as examples. Even in cases where F22 ˜ F11 (e.g., OC⋯CuCl), such plots will yield either F22 or F11 if the other becomes available.

A 3D-analysis of cluster formation and dynamics of the X(-)-benzene (X = F, Cl, Br, I) ionic dimer solvated by Ar atoms.

PubMed

Albertí, Margarita; Huarte-Larrañaga, Fermín; Aguilar, Antonio; Lucas, José M; Pirani, Fernando

2011-05-14

The specific influence of X(-) ions (X = F,Cl, Br, I) in the solvation process of halide-benzene (X(-)-Bz) ionic heterodimers by Ar atoms is investigated by means of molecular dynamic (MD) simulations. The gradual evolution from cluster rearrangement to solvation dynamics is discussed by considering ensembles of n (n = 1-15 and n = 30) Ar atoms around the X(-)-Bz stable ionic dimers. The potential energy surfaces employed are based on an atom/ion-atom and atom/ion-bond decomposition, which has been developed previously by some of the authors. The outcome of the dynamics is analyzed by employing radial distribution functions (RDF) and tridimensional (3D) probability densities.

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

NASA Astrophysics Data System (ADS)

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.

Laser cooling of MgCl and MgBr in theoretical approach

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wan, Mingjie; Shao, Juxiang; Huang, Duohui

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Nelson, A. J.; Voss, L. F.; Beck, P. R.

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.

Origin of selenium–gold interaction in F{sub 2}CSe⋯AuY (Y = CN, F, Cl, Br, OH, and CH{sub 3}): Synergistic effects

DOE Office of Scientific and Technical Information (OSTI.GOV)

Guo, Xin; Yang, Yu-Ping; Li, Qing-Zhong, E-mail: liqingzhong1990@sina.com, E-mail: lihaibei@sdu.edu.cn

Selenium–gold interaction plays an important role in crystal materials, molecular self-assembly, and pharmacochemistry involving gold. In this paper, we unveiled the mechanism and nature of selenium–gold interaction by studying complexes F{sub 2}CSe⋯AuY (Y = CN, F, Cl, Br, OH, and CH{sub 3}). The results showed that the formation of selenium–gold interaction is mainly attributed to the charge transfer from the lone pair of Se atom to the Au—Y anti-bonding orbital. Energy decomposition analysis indicated that the polarization energy is nearly equivalent to or exceeds the electrostatic term in the selenium–gold interaction. Interestingly, the chalcogen–gold interaction becomes stronger with the increasemore » of chalcogen atomic mass in F{sub 2}CX⋯AuCN (X = O, S, Se, and Te). The cyclic ternary complexes are formed with the introduction of NH{sub 3} into F{sub 2}CSe⋯AuY, in which selenium–gold interaction is weakened and selenium–nitrogen interaction is strengthened due to the synergistic effects.« less

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Li, Wan-Lu; Li, Yong; Xu, Congqiao

2015-12-07

Systematic theoretical and experimental investigations have been performed to understand the periodicity and electronic structures of trivalent-gold halides using gold tetrahalides [AuX4]⁻ anions (X = F, Cl, Br, I, At, Uus). The [AuX4]⁻ (X = Cl, Br, I) anions were produced in gas phase and their negative-ion photoelectron spectra were obtained, which exhibited rich and well-resolved spectral peaks. We calculated the adiabatic as well as vertical electron detachment energies using density functional methods with scalar and spin-orbit coupling relativistic effects. The simulated photoelectron spectra based on these calculations are in good agreement with the experimental spectra. Our results show thatmore » the trivalent Au(III) oxidation state becomes progressively less stable while Au(I) is preferred when the halides become heavier along the Period Table. This trend reveals that the oxidation state of metals in complexes can be manipulated through ligand design« less

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

NASA Technical Reports Server (NTRS)

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

1994-01-01

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

Local unitary transformation method for large-scale two-component relativistic calculations: case for a one-electron Dirac Hamiltonian.

PubMed

Seino, Junji; Nakai, Hiromi

2012-06-28

An accurate and efficient scheme for two-component relativistic calculations at the spin-free infinite-order Douglas-Kroll-Hess (IODKH) level is presented. The present scheme, termed local unitary transformation (LUT), is based on the locality of the relativistic effect. Numerical assessments of the LUT scheme were performed in diatomic molecules such as HX and X(2) (X = F, Cl, Br, I, and At) and hydrogen halide clusters, (HX)(n) (X = F, Cl, Br, and I). Total energies obtained by the LUT method agree well with conventional IODKH results. The computational costs of the LUT method are drastically lower than those of conventional methods since in the former there is linear-scaling with respect to the system size and a small prefactor.

Crystal structure, electronic structure, temperature-dependent optical and scintillation properties of CsCe 2Br 7

DOE PAGES

Wu, Yuntao; Shi, Hongliang; Chakoumakos, Bryan C.; ...

2015-10-05

CsCe 2Br 7 is a self-activated inorganic scintillator that shows promising performance, but the understanding of the important structure-property relationships is lacking. In this work, we conduct a comprehensive study on CCsCe 2Br 7. The crystal structure of CsCe 2Br 7 is refined using single crystal X-ray study for the first time. It crystallizes into the orthorhombic crystal system with Pmnb space group. Its electronic structure is revealed by Density Functional Theory (DFT) calculations. Two cerium emission centers are identified and the energy barriers related to the thermal quenching to 4f ground states of Ce 3+ for these two Cemore » centers are evaluated. CsCe 2Br 7 single crystal has better light yield and energy resolution than CsCe 2Cl 7, but with an additional slow decay component of 1.7 s. The existence of a deep trap with a depth of 0.9 eV in CsCe 2Cl 7 contributes to its higher afterglow level in comparison to that of CsCe 2Br 7. The most possible point defects in CsCe 2Cl 7 and CsCe 2Br 7 are proposed by considering the vapour pressure in the growth atmosphere upon melting point.« less

Investigating the Weak to Evaluate the Strong: An Experimental Determination of the Electron Binding Energy of Carborane Anions and the Gas phase Acidity of Carborane Acids

DOE Office of Scientific and Technical Information (OSTI.GOV)

Meyer, Matthew M; Wang, Xue B; Reed, Christopher A

2009-12-23

Five CHB 11X 6Y 5 - carborane anions from the series X = Br, Cl, I and Y = H, Cl, CH 3 were generated by electrospray ionization, and their reactivity with a series of Brønsted acids and electron transfer reagents were examined in the gas phase. The undecachlorocarborane acid, H(CHB 11Cl 11), was found to be far more acidic than the former record holder, (1-C 4F 9SO 2) 2NH (i.e., ΔH° acid = 241 ± 29 vs 291.1 ± 2.2 kcal mol -1) and bridges the gas-phase acidity and basicity scales for the first time. Its conjugate base, CHBmore » 11Cl 11 -, was found by photoelectron spectroscopy to have a remarkably large electron binding energy (6.35 ± 0.02 eV) but the value for the (1-C 4F 9SO 2) 2N - anion is even larger (6.5 ± 0.1 eV). Consequently, it is the weak H-(CHB 11Cl 11) BDE (70.0 kcal mol -1, G3(MP2)) compared to the strong BDE of (1-C 4F 9SO 2) 2N-H (127.4 ± 3.2 kcal mol -1) that accounts for the greater acidity of carborane acids.« less

Structural analysis of pyridine-imino boronic esters involving secondary interactions on solid state

NASA Astrophysics Data System (ADS)

Sánchez-Portillo, Paola; Arenaza-Corona, Antonino; Hernández-Ahuactzi, Irán F.; Barba, Victor

2017-04-01

Twelve boronic esters (1a-1l) synthesized from 4-halo- substituted arylboronic acids (halo = F, Cl, Br, I and CF3) with 2-amino-2- alkyl (H, Me) -1,3-propanediol in presence of (3- or 4)-pyridine carboxaldehyde are described. A solvent mixture toluene/methanol 1:4 ratio was used. All compounds include both donor/acceptor functional groups, which are the necessary elements to self-assembly of the molecular species. Several secondary interactions as I⋯N, Br⋯Br, Br⋯B, F⋯B, Csbnd H⋯N, Csbnd H⋯O, Br⋯π and Csbnd H⋯π support the 1D and 2D polymeric frameworks in solid state. The coordination of the nitrogen atom from the pyridine moiety with the boron atom was not observed in either solution or solid state.

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

DOE PAGES

Nelson, A. J.; Voss, L. F.; Beck, P. R.; ...

2013-01-12

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.

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

NASA Astrophysics Data System (ADS)

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.

2013-04-01

Device-grade TlBr was subjected 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, SOCl2, 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.

Theoretical study of the kinetics of reactions of the monohalogenated methanes with atomic chlorine.

PubMed

Brudnik, Katarzyna; Twarda, Maria; Sarzyński, Dariusz; Jodkowski, Jerzy T

2013-04-01

Ab initio calculations at the G2 level were used in a theoretical description of the kinetics and mechanism of the hydrogen abstraction reactions from fluoro-, chloro- and bromomethane by chlorine atoms. The profiles of the potential energy surfaces show that mechanism of the reactions under investigation is complex and consists of two - in the case of CH3F+Cl - and of three elementary steps for CH3Cl+Cl and CH3Br+Cl. The heights of the energy barrier related to the H-abstraction are of 8-10 kJ mol(-1), the lowest value corresponds to CH3Cl+Cl and the highest one to CH3F+Cl. The rate constants were calculated using the theoretical method based on the RRKM theory and the simplified version of the statistical adiabatic channel model. The kinetic equations derived in this study[Formula: see text]and[Formula: see text]allow a description of the kinetics of the reactions under investigation in the temperature range of 200-3000 K. The kinetics of reactions of the entirely deuterated reactants were also included in the kinetic analysis. Results of ab initio calculations show that D-abstraction process is related with the energy barrier of 5 kJ mol(-1) higher than the H-abstraction from the corresponding non-deuterated reactant molecule. The derived analytical equations for the reactions, CD3X+Cl, CH2X+HCl and CD2X+DCl (X = F, Cl and Br) are a substantial supplement of the kinetic data necessary for the description and modeling of the processes of importance in the atmospheric chemistry.

Gold(I) and Gold(III) Complexes of Cyclic (Alkyl)(amino)carbenes

PubMed Central

2016-01-01

The chemistry of Au(I) complexes with two types of cyclic (alkyl)(amino)carbene (CAAC) ligands has been explored, using the sterically less demanding dimethyl derivative Me2CAAC and the 2-adamantyl ligand AdCAAC. The conversion of (AdCAAC)AuCl into (AdCAAC)AuOH by treatment with KOH is significantly accelerated by the addition of tBuOH. (AdCAAC)AuOH is a convenient starting material for the high-yield syntheses of (AdCAAC)AuX complexes by acid/base and C–H activation reactions (X = OAryl, CF3CO2, N(Tf)2, C2Ph, C6F5, C6HF4, C6H2F3, CH2C(O)C6H4OMe, CH(Ph)C(O)Ph, CH2SO2Ph), while the cationic complexes [(AdCAAC)AuL]+ (L = CO, CNtBu) and (AdCAAC)AuCN were obtained by chloride substitution from (AdCAAC)AuCl. The reactivity toward variously substituted fluoroarenes suggests that (AdCAAC)AuOH is able to react with C–H bonds with pKa values lower than about 31.5. This, together with the spectroscopic data, confirm the somewhat stronger electron-donor properties of CAAC ligands in comparison to imidazolylidene-type N-heterocyclic carbenes (NHCs). In spite of this, the oxidation of Me2CAAC and AdCAAC gold compounds is much less facile. Oxidations proceed with C–Au cleavage by halogens unless light is strictly excluded. The oxidation of (AdCAAC)AuCl with PhICl2 in the dark gives near-quantitative yields of (AdCAAC)AuCl3, while [Au(Me2CAAC)2]Cl leads to trans-[AuCl2(Me2CAAC)2]Cl. In contrast to the chemistry of imidazolylidene-type gold NHC complexes, oxidation products containing Au–Br or Au–I bonds could not be obtained; whereas the reaction with CsBr3 cleaves the Au–C bond to give mixtures of [AdCAAC-Br]+[AuBr2]− and [(AdCAAC-Br)]+ [AuBr4]−, the oxidation of (AdCAAC)AuI with I2 leads to the adduct (AdCAAC)AuI·I2. Irrespective of the steric demands of the CAAC ligands, their gold complexes proved more resistant to oxidation and more prone to halogen cleavage of the Au–C bonds than gold(I) complexes of imidazole-based NHC ligands. PMID:26146436

The effect and influence of cis-ligands on the electronic and oxidizing properties of nonheme oxoiron biomimetics. A density functional study.

PubMed

de Visser, Sam P; Nam, Wonwoo

2008-12-18

Density functional theory studies on the nature of the cis effect and cis influence of ligands on oxoiron nonheme complexes have been performed. A detailed analysis of the electronic and oxidizing properties of [Fe(IV)O(TPA)L](+) with L = F(-), Cl(-), and Br(-) and TPA = tris-(2-pyridylmethyl)amine are presented and compared with [Fe(IV)O(TPA)NCCH(3)](2+). The calculations show that the electronic cis effect is determined by favorable orbital overlap between first-row elements with the metal, which are missing between the metal and second- and third-row elements. As a consequence, the metal 3d block is split into a one-below-two set of orbitals with L = Cl(-) and Br(-), and the HOMO/LUMO energy gap is widened with respect to the system with L = F(-). However, this larger HOMO/LUMO gap does not lead to large differences in electron affinities of the complexes. Moreover, a quantum mechanical analysis of the binding of the ligand shows that it is built up from a large electric field effect of the ligand on the oxoiron species and a much smaller quantum mechanical effect due to orbital overlap. These contributions are of similar strength for the three tested halogen cis ligands and result in similar reactivity patterns with substrates. The calculations show that [Fe(IV)O(TPA)L](+) with L = F(-), Cl(-), and Br(-) have closely lying triplet and quintet spin states, but only the quintet spin state is reactive with substrates. Therefore, the efficiency of the oxidant will be determined by the triplet-quintet spin state crossing of the reaction. The reaction of styrene with a doubly charged reactant, that is, [Fe(V)O(TPA)L](2+) with L = F(-), Cl(-), and Br(-) or [Fe(V)O(TPA)NCCH(3)](3+), leads to an initial electron transfer from the substrate to the metal followed by a highly exothermic epoxidation mechanism. These reactivity differences are mainly determined by the overall charge of the system rather than the nature of the cis ligand.

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

NASA Astrophysics Data System (ADS)

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.

Dissociative Photoionization of 1-Halogenated Silacyclohexanes: Silicon Traps the Halogen.

PubMed

Bodi, Andras; Sigurdardottir, Katrin Lilja; Kvaran, Ágúst; Bjornsson, Ragnar; Arnason, Ingvar

2016-11-23

The threshold photoelectron spectra and threshold photoionization mass spectra of 1-halogenated-1-silacyclohexanes, for the halogens X = F, Cl, Br, and I, have been obtained using synchrotron vacuum ultraviolet radiation and photoelectron photoion coincidence spectroscopy. As confirmed by a similar ionization onset and density functional theory molecular orbitals, the ionization to the ground state is dominated by electron removal from the silacyclohexane ring for X = F, Cl, and Br, and from the halogen lone pair for X = I. The breakdown diagrams show that the dissociative photoionization mechanism is also different for X = I. Whereas the parent ions decay by ethylene loss for X = F to Br in the low-energy regime, the iodine atom is lost for X = I. The first step is followed by a sequential ethylene loss at higher internal energies in each of the compounds. It is argued that the tendency of silicon to lower bond angles stabilizes the complex cation in which C 2 H 4 is η 2 -coordinated to it, and which precedes ethylene loss. Together with the relatively strong silicon-halogen bonds and the increased inductive effect of the silacyclohexane ring in stabilizing the cation, this explains the main differences observed in the fragmentation of the halogenated silacyclohexane and halogenated cyclohexane ions. The breakdown diagrams have been modeled taking into account slow dissociations at threshold and the resulting kinetic shift. The 0 K appearance energies have been obtained to within 0.08 eV for the ethylene loss for X = F to Br (10.56, 10.51, and 10.51 eV, respectively), the iodine atom loss for X = I (10.11 eV), the sequential ethylene loss for X = F to I (12.29, 12.01, 11.94, and 11.86 eV, respectively), and the minor channels of H loss for X = F (10.56 eV) and propylene loss in X = Cl (also at 10.56 eV). The appearance energies for the major channels likely correspond to the dissociative photoionization reaction energy.

Electroactive materials for rechargeable batteries

DOEpatents

Wu, Huiming; Amine, Khalil; Abouimrane, Ali

2016-10-25

A secondary battery including a cathode having a primary cathode active material and an alkaline source material selected from the group consisting of Li.sub.2O, Li.sub.2O.sub.2, Li.sub.2S, LiF, LiCl, Li.sub.2Br, Na.sub.2O, Na.sub.2O.sub.2, Na.sub.2S, NaF, NaCl, and a mixture of any two or more thereof; an anode having an anode active material; an electrolyte; and a separator.

40 CFR Appendix F to Subpart A of... - Listing of Ozone-Depleting Chemicals

Code of Federal Regulations, 2011 CFR

2011-07-01

... 40 Protection of Environment 17 2011-07-01 2011-07-01 false Listing of Ozone-Depleting Chemicals F..., Subpt. A, App. F Appendix F to Subpart A of Part 82—Listing of Ozone-Depleting Chemicals Controlled...-Monochloropentafluoroethane (CFC-115) 0.6 400.0 2.0 0.00 All isomers of the above chemicals [Reserved] 2. Group II: CF2 ClBr...

40 CFR Appendix F to Subpart A of... - Listing of Ozone-Depleting Chemicals

Code of Federal Regulations, 2010 CFR

2010-07-01

... 40 Protection of Environment 17 2010-07-01 2010-07-01 false Listing of Ozone-Depleting Chemicals F..., Subpt. A, App. F Appendix F to Subpart A of Part 82—Listing of Ozone-Depleting Chemicals Controlled...-Monochloropentafluoroethane (CFC-115) 0.6 400.0 2.0 0.00 All isomers of the above chemicals [Reserved] 2. Group II: CF2 ClBr...

Oxidation/reduction reactions at the metal contact-TlBr interface: an x-ray photoelectron spectroscopy study

NASA Astrophysics Data System (ADS)

Nelson, A. J.; Swanberg, E. L.; Voss, L. F.; Graff, R. T.; Conway, A. M.; Nikolic, R. J.; Payne, S. A.; Kim, H.; Cirignano, L.; Shah, K.

2014-09-01

TlBr radiation detector operation degrades with time at room temperature and is thought to be due to electromigration of Tl and Br vacancies within the crystal as well as the metal contacts migrating into the TlBr crystal itself due to electrochemical reactions at the metal/TlBr interface. X-ray photoemission spectroscopy (XPS) was used to investigate the metal contact surface/interfacial structure on TlBr devices. Device-grade TlBr was polished and subjected to a 32% HCl etch to remove surface damage prior to Mo or Pt contact deposition. High-resolution photoemission measurements on the Tl 4f, Br 3d, Cl 2p, Mo 3d and Pt 4f core lines were used to evaluate surface chemistry and non-equilibrium interfacial diffusion. Results indicate that anion substitution at the TlBr surface due to the HCl etch forms TlBr1-xClx with consequent formation of a shallow heterojunction. In addition, a reduction of Tl1+ to Tl0 is observed at the metal contacts after device operation in both air and N2 at ambient temperature. Understanding contact/device degradation versus operating environment is useful for improving radiation detector performance.

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

PubMed

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

2016-04-01

The fast method of the simultaneous determination of F(-), Cl(-), Br(-) and SO4(2-) anions in the deionized water on the trace level by ion chromatography using thorough cleaning of respective water containers, 10 μM NaHCO3 water solution as eluent, short Metrohm (50 × 4 mm) separation column and a large water volume injection is proposed. Calculated detection limits are 10(-9)-10(-8)% depending on the element. The method for the fast screening of plant oil samples for the total fluorine-, chlorine-, bromine- and sulfur-organic compounds content (calculated for the respective elements) on the trace level is developed. It is based on the high temperature combustion of oil sample in oxygen flow, absorption of the conversion products in deionized water and whole absorbate volume analysis for F(-), Cl(-), Br(-) and SO4(2-) anions, corresponding to the respective elements, using the developed method of these anions analysis by ion chromatography. The samples of soya, olive, sunflower and cotton seed oil were analyzed. The method detection limits (for 1mg sample) were 2 × 10(-6)%, 2 × 10(-6)%, 5 × 10(-6)% and 5 × 10(-6)% for fluorine, chlorine, bromine and sulfur, respectively. The relative standard deviation was ≤ 15%. The method gives the compressed information about the total content of all target and nontarget fluorine-, chlorine-, bromine- and sulfur-organic compounds in plant oils. Copyright © 2015. Published by Elsevier B.V.

Spectroscopy and heats of formation of CXI (X = Br, Cl, F) iodocarbenes: quantum chemical characterisation of the ?, ? and ? states

NASA Astrophysics Data System (ADS)

Bacskay, George B.

2015-07-01

The equilibrium energies of the iodocarbenes CXI (X = Br, Cl, F) in their ?, ? and ? states and their atomisation and dissociation energies in the complete basis limit were determined by extrapolating valence correlated (R/U)CCSD(T) and Davidson corrected multi-reference configuration interaction (MRCI) energies calculated with the aug-cc-pVxZ (x = T,Q,5) basis sets and the ECP28MDF pseudopotential of iodine plus corrections for core and core-valence correlation, scalar relativity, spin-orbit coupling and zero-point energies. Spin-orbit energies were computed in a large basis of configurations chosen so as to accurately describe dissociation to the 3P and 2P states of C and of the halogens X and I, respectively. The computed singlet-triplet splittings are 13.6, 14.4 and 27.3 kcal mol-1 for X = Br, Cl and F, respectively. The enthalpies of formation at 0 K are predicted to be 97.4, 82.6 and 38.1 kcal mol-1 with estimated errors of ±1.0 kcal mol-1. The ? excitation energies (T00) in CBrI and CClI are calculated to be 41.1 and 41.7 kcal mol-1, respectively. The Renner-Teller intersections in both molecules are predicted to be substantially higher than the dissociation barriers on the ? surfaces. By contrast, in CFI the ? state is found to be unbound with respect to dissociation.

Effects of strong hydrogen bonds and weak intermolecular interactions on supramolecular assemblies of 4-fluorobenzylamine

NASA Astrophysics Data System (ADS)

Wang, Shi; Ding, Xue-Hua; Li, Yong-Hua; Huang, Wei

2015-07-01

A series of supramolecular salts have been obtained by the self-assembly of 4-fluorobenzylamine and halide ions or metal chloride with 18-crown-6 as the host in the hydrochloric acid medium, i.e. (C7H9FN)+ṡX- (X = Cl-, 1; Br-, 2), [(C7H9FN)2ṡ(18-crown-6)2]2+ṡ(MCl4)2- (M = Mn, 3; Co, 5; Zn, 7; Cd, 8), [(C7H9FN)ṡ(18-crown-6)]+ṡ(FeCl4)- (4) and [(C7H9FN)ṡ(18-crown-6)]+ṡ1/2(CuCl4)2- (6). Structural analyses indicate that 1-2 crystallize in the triclinic space group P-1, 4 in orthorhombic space group Pnma and 3, 5, 6-8 in the monoclinic space group P21/c or C2/c. In these compounds, extensive intermolecular interactions have been utilized for the self-assembly of diverse supramolecular architectures, ranging from strong N-H⋯X (X = O, Cl, Br) hydrogen bonds to weak C-H⋯Y (Y = F, Cl, π) interactions. N-H⋯Cl/Br hydrogen bonds offer the major driving force in the crystal packing of salts 1-2 while N-H⋯O hydrogen bonds are found in salts 3-8.

Halogens as tracers of protosolar nebula material in comet 67P/Churyumov-Gerasimenko

NASA Astrophysics Data System (ADS)

Dhooghe, Frederik; De Keyser, Johan; Altwegg, Kathrin; Briois, Christelle; Balsiger, Hans; Berthelier, Jean-Jacques; Calmonte, Ursina; Cessateur, Gaël; Combi, Michael R.; Equeter, Eddy; Fiethe, Björn; Fray, Nicolas; Fuselier, Stephen; Gasc, Sébastien; Gibbons, Andrew; Gombosi, Tamas; Gunell, Herbert; Hässig, Myrtha; Hilchenbach, Martin; Le Roy, Léna; Maggiolo, Romain; Mall, Urs; Marty, Bernard; Neefs, Eddy; Rème, Henri; Rubin, Martin; Sémon, Thierry; Tzou, Chia-Yu; Wurz, Peter

2017-12-01

We report the first in situ detection of halogens in a cometary coma, that of 67P/Churyumov-Gerasimenko. Neutral gas mass spectra collected by the European Space Agency's Rosetta spacecraft during four periods of interest from the first comet encounter up to perihelion indicate that the main halogen-bearing compounds are HF, HCl and HBr. The bulk elemental abundances relative to oxygen are ∼8.9 × 10-5 for F/O, ∼1.2 × 10-4 for Cl/O and ∼2.5 × 10-6 for Br/O, for the volatile fraction of the comet. The cometary isotopic ratios for 37Cl/35Cl and 81Br/79Br match the Solar system values within the error margins. The observations point to an origin of the hydrogen halides in molecular cloud chemistry, with frozen hydrogen halides on dust grains, and a subsequent incorporation into comets as the cloud condensed and the Solar system formed.

Synthesis and analysis of 2-[211At]-L-phenylalanine and 4-[211At]-L-phenylalanine and their uptake in human glioma cell cultures in-vitro.

PubMed

Meyer, Geerd J; Walte, Almut; Sriyapureddy, Siva R; Grote, Michaela; Krull, Doris; Korkmaz, Zekiye; Knapp, Wolfram H

2010-06-01

2-[211At]-L-phenylalanine and 4-[211At]-L-phenylalanine were prepared from the corresponding iodo and bromo derivatives using the Cu(+)-assisted nucleophilic exchange. 4-[211At]-L-phenylalanine was additionally prepared by destannylation of the BOC-derivatized 4-tributylstannyl-L-phenylalanine. Radiochemical yields of 2-[211At]-L-phenylalanine and 4-[211At]-L-phenylalanine by nucleophilic exchange were 52-74% and 65-85%. Radiochemical yield of 4-[211At]-L-phenylalanine by electrophilic destannylation was 35-50%. HPLC sequence analysis showed that 2-[211At]-L-phenylalanine followed the halogen sequence (F

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

NASA Technical Reports Server (NTRS)

Friedl, Randall R.; Sander, Stanley P.

1988-01-01

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

Photoemission analysis of chemically modified TlBr surfaces for improved radiation detectors

NASA Astrophysics Data System (ADS)

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

2013-09-01

Device-grade TlBr was subjected to various chemical treatments used in room temperature radiation detector fabrication to determine the resulting surface composition and electronic structure. Samples of as polished TlBr were treated separately with 2%Br:MeOH, 10%HF, 10%HCl and 96%SOCl2 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. Results suggest anion substitution at the surface with subsequent shallow heterojunction formation. Surface chemistry and valence band electronic structure were further correlated with the goal of optimizing the long-term stability and radiation response.

Electron affinities, molecular structures, and thermochemistry of the fluorine, chlorine and bromine substituted methyl radicals

NASA Astrophysics Data System (ADS)

Li, Qian-Shu; Zhao, Jun-Fang; Xie, Yaoming; Schaefer, Henry F., III

Four independent density functional theory (DFT) methods have been employed to study the structures and electron affinities of the methyl and F-, Cl- and Br-substituted methyl radicals and their anions. The methods used have been carefully calibrated against a comprehensive tabulation of experimental electron affinities (Chemical Reviews, 2002, 102, 231). The first dissociation energies together with the vibrational frequencies of these species are also reported. The basis sets used in this work are of double- ζ plus polarization quality with additional s- and p-type diffuse functions, labelled as DZP++. Previously observed trends in the prediction of bond lengths by the DFT methods are also demonstrated for the F-, Cl- and Br-substituted methyl radicals and their anions. Generally, the Hartree-Fock/DFT hybrid methods predict shorter and more reliable bond lengths than the pure DFT methods. Neutral-anion energy differences reported in this work are the adiabatic electron affinity (EAad), the vertical electron affinity (EAvert), and the vertical detachment energy (VDE). Compared with the available experimental electron affinities, the BHLYP method predicts much lower values, while the other methods predict values (EAad, EAvert, VDE) close to each other and almost within the experimental range. For those systems without reliable experimental measurements, our best adiabatic EAs predicted by BLYP are 0.78 (CHF2), 1.23 (CHFCl), 1.44 (CHFBr), 1.61 (CHClBr), 2.24 (CF2Cl), 2.42 (CF2Br), 2.56 (CFBr2), 2.36 (CCl2Br), 2.46 (CClBr2), and 2.44 eV (CFClBr). The most striking feature of these predictions is that they display an inverse relationship between halogen electronegativity and EA. The DZP++ B3LYP method determines the vibrational frequencies in best agreement with available experimental results for this series, with an average relative error of ~2%. The value of using a variety of DFT methods is observed in that BHLYP does best for geometries, BLYP for electron affinities, and B3LYP for vibrational frequencies. These theoretical results serve to resolve several disagreements between competing experiments. Several other experiments appear to have drawn incorrect conclusions. For example, CHCl2 is significantly pyramidal, unlike the experimental inferences, and clearly the experimental CCl2 - Cl dissociation energy is too large.

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

NASA Astrophysics Data System (ADS)

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.

Variation of sigma-hole magnitude with M valence electron population in MX(n)Y(4-n) molecules (n = 1-4; M = C, Si, Ge; X, Y = F, Cl, Br).

PubMed

McDowell, Sean A C; Joseph, Jerelle A

2014-01-14

Sigma holes are described as electron-deficient regions on atoms, particularly along the extension of covalent bonds, due to non-uniform electron density distribution on the surface of these atoms. A computational study of MX(n)Y(4-n) molecules (n = 1-4; M = C, Si, Ge; X, Y = F, Cl, Br) was undertaken and it is shown that the relative sigma hole potentials on M due to X-M and Y-M can be adequately explained in terms of the variation in the valence electron population of the central M atom. A model is proposed for the depletion of the M valence electron population which explains the trends in sigma hole strengths, especially those that cannot be accounted for solely on the basis of relative electronegativities.

Ab initio study of the barrier to internal rotation in simple amides. 1. N, N-dimethylformamide and N, N-dimethylcarbamic halogenides

NASA Astrophysics Data System (ADS)

Vassilev, Nikolay G.; Dimitrov, Valentin S.

1999-06-01

Free energies of activation for rotation about the amide C-N bond in X-C(O)N(CH 3) 2 (X=H, F, Cl and Br) were calculated at the MP2(fc)/6-31+G*//6-31G* and MP2(fc)/6-311++G**//6-311++G** levels and compared with NMR gas-phase data. The results of calculations indicate that the repulsion between X and methyl group in ground state and the repulsion between X or oxygen and nitrogen lone pair in transition states (TS) are largely responsible for the difference in the free energies of the studied amides. For X=H (DMF), the anti TS is more stable; for the cases X=Cl, Br, the syn TS is more stable, while for the case X=F the two transition states are energetically almost equivalent.

Transmittance of optical materials from 0.17 micro to 3.0 micro.

PubMed

McCarthy, D E

1967-11-01

The transmittance of thirty-one optical materials is given from 0.17, micro to 3.0 micro. Included are NaCl, KBr, CsBr, CsI, CaF(2), BaF(2), NaF, TlBr, TICL, KRS-5, KRS-6, T-12, KC, CuC, T O(2), ADP, KDP, SrTiO(3), GaP, CaCO(3), CdSe, As(2)S(3), ruby, Al(2)O(3), Irtran 1-6, and quartz. All are synthetic with the exception of CaCO(3). In many cases, the short wavelength cutoff of the synthetic materials is less than that which has been reported for naturally occurring materials.

On chemical inhibition of shock wave ignition of hydrogen-oxygen mixtures

NASA Astrophysics Data System (ADS)

Drakon, A. V.; Eremin, A. V.; Mikheyeva, E. Yu

2018-01-01

In this work an influence of the wide range of various inhibitors, namely CCl4, CF3H, C2F4Br2, (CH3O)3P, CF3I and C3F7I on shock-induced ignition of hydrogen was experimentally investigated. Observed temperature dependencies of induction times indicates that CF3H and (CH3O)3P do not show noticeable inhibiting activity at given conditions, while the effectiveness of halogen-containing specie dramatically increases in a row Cl → Br → I. It is shown that the most effective inhibitors of ignition of hydrogen-oxygen mixtures are iodinated hydrocarbons CF3I and C3F7I.

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

NASA Astrophysics Data System (ADS)

Behnke, Wolfgang; Zetzsch, Cornelius

2010-05-01

We observed bromine explosions (a fast production of atomic Br and Cl under tropospheric conditions) in various smog chamber experiments in Teflon bags at room temperature at a relative humidity of about 80% in the presence of NaCl/NaBr-aerosol, simulated sunlight and ozone (200 - 400 ppb). Time profiles of ozone and hydrocarbons (HCs: n-butane, 2,2-dimethylbutane, tetramethylbutane and toluene, initially about 2 ppb each) were monitored to determine concentrations and source strengths of OH radicals, atomic Cl and Br and the corresponding time profiles of BrCl and Br2 as their photolytic precursors. The number and size of aerosols are measured as well as their chemical composition (Br-, Cl- and oxalic acid). Full records of raw data from the smog chamber runs are available at www.eurochamp.org for potential users. Chemical box model calculations deliver concentrations of various intermediates, such as aldehydes, HO2 and RO2 radicals and the inorganic halogen compounds ClO, BrO, HOCl and HOBr, where HOBr from O3 + Br- => BrO- + O2 in the aqueous/adsorbed phase induces the following gas-phase/ heterogeneous chain reaction Br + O3 => BrO + O2(1) BrO + HO2 => HOBr + O2(2a) HOBr + (Aerosol) => HOBrad(3) Surface-adsorbed HOBr reacts with Br- or Cl- to produce Br2 or BrCl, both of which are released and photolysed. Formation of Br2 should prevail up to Cl-/Br- -ratios of about 104 (Fickert, S., J.W. Adams, J.N. Crowley, J. Geophys. Res., D104, 23719-23727, 1999). A maximum of this ratio is reached about 30 minutes after the beginning and decreases during the next hours - probably by reaction of Br2 with oxalate and absorption of HBr, formed from the reaction of Br with aldehydes. Parallel to chain reaction (1)-(3) a chain reaction replacing Br by Cl seems possible but can not be realized, since the main sink of atomic Cl is its reaction with hydrocarbons - leading to chain termination - in contrast to atomic Br (ratio of rates: kCl[O3]/kCl[HC] ~ 0.1; kBr[O3]/kBr[toluene] ~ 100). Formation of aldehydes (R-CHO) interferes with the chain reaction (1) - (3) markedly, since kBr[O3] ≈kBr[R-CHO]. The chain reaction is limited by availability of ozone (degradation of HCs by atomic Cl stops completely with vanishing ozone), of HO2 (HCs are required to form HO2) and of aerosol. The central question is: will sufficient HO2 be formed from degradation of HCs to explain the magnitude of the formed Br2 and BrCl in our experiments? We found that the formation of HO2 should be by a factor of 2-4 larger to explain the formation of Br2 and BrCl. Which other sources for the formation of HOBr besides reaction (2a) are then available? The rate of CH3O2with BrO is 25% of that with HO2 (Enami, S.; Yamanaka, T.; Nakayama, T.; Hashimoto, S.; Kawasaki, M.; Shallcross, D.E.; Nakano, Y.; Ishiwata, T., J. Phys. Chem. A, 11, 3342 - 3348, 2007), suggesting that other RO2 radicals must contribute. In our model calculations we use this rate constant for all RO2 radicals to obtain reasonable agreement between the produced HOBr and the formed BrCl and Br2 necessary for our experimental degradation results. So reaction scheme (1) - (3) should be completed by: BrO + RO2 => HOBr + products (2b) The German Science Foundation (DFG) supported this research in unit 783 (HALOPROC).

Weak hydrogen bonding and fluorous interactions in the chloride and bromide salts of 4-[(2,2,3,3-tetrafluoropropoxy)methyl]pyridinium.

PubMed

Lu, Norman; Wei, Rong Jyun; Lin, Kwan Yu; Alagesan, Mani; Wen, Yuh Sheng; Liu, Ling Kang

2017-04-01

Neutralization of 4-[(2,2,3,3-tetrafluoropropoxy)methyl]pyridine with hydrohalo acids HX (X = Cl and Br) yielded the pyridinium salts 4-[(2,2,3,3-tetrafluoropropoxy)methyl]pyridinium chloride, C 9 H 10 F 4 NO + ·Cl - , (1), and 4-[(2,2,3,3-tetrafluoropropoxy)methyl]pyridinium bromide, C 9 H 10 F 4 NO + ·Br - , (2), both carrying a fluorous side chain at the para position of the pyridinium ring. Single-crystal X-ray diffraction techniques revealed that (1) and (2) are isomorphous. The halide anions accept four hydrogen bonds from N-H, ortho-C-H and CF 2 -H groups. Two cations and two anions form a centrosymmetric dimeric building block, utilizing complimentary N-H...X...H-Csp 3 connections. These dimers are further crosslinked, utilizing another complimentary Csp 2 -H...X...H-Csp 2 connection. The pyridinium rings are π-stacked, forming columns running parallel to the a axis that make angles of ca 44-45° with the normal to the pyridinium plane. There are also supramolecular C-H...F-C interactions, namely bifurcated C-H...F and bifurcated C-F...H interactions; additionally, one type II C-F...F-C halogen bond has been observed.

Microsolvation effects on the reactivity of oxy-nucleophiles: the case of gas-phase SN2 reactions of YO-(CH3OH) n=1,2 towards CH3Cl.

PubMed

Yun-Yun, Liu; Fang-Zhou, Qiu; Jun, Zhu; Yi, Ren; Kai-Chung, Lau

2017-06-01

The modified G4(MP2) method was applied to explore microsolvation effects on the reactivity of four solvated normal oxy-nucleophiles YO - (CH 3 OH) n=1,2 (Y = CH 3 , C 2 H 5 , FC 2 H 4 , ClC 2 H 4 ), and five α-oxy-nucleophiles YO - (CH 3 OH) n=1,2 (Y = HO, CH 3 O, F, Cl, Br), in gas-phase S N 2 reactions towards the substrate CH 3 Cl. Based on a Brønsted-type plot, our calculations reveal that the overall activation barriers of five microsolvated α-oxy-nucleophiles are obviously smaller than the prediction from the correlation line constructed by four normal microsolvated ones to different degrees, and clearly demonstrate the existence of an α-effect in the presence of one or two methanol molecule(s). Moreover, it was found that the α-effect of the mono-methanol microsolvated α-nucleophile is stronger than that of the monohydrated α-nucleophile. However, the α-effect of YO - (CH 3 OH) 2 becomes weaker for Y = HO and CH 3 O, whereas it becomes stronger for Y = F, Cl, Br than that of YO - (H 2 O) 2 , which can be explained by analyses of the activation strain model in the two cases. It was also found that the rationale about the low ionization energy of α-nucleophile inducing the α-effect was not widely significant. Graphical abstract Variation of alpha-effect in the gas-phase S N 2 reaction with the microsolvation.

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

NASA Astrophysics Data System (ADS)

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

2014-06-01

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

Exploring the Reactivity Trends in the E2 and SN2 Reactions of X(-) + CH3CH2Cl (X = F, Cl, Br, HO, HS, HSe, NH2 PH2, AsH2, CH3, SiH3, and GeH3).

PubMed

Wu, Xiao-Peng; Sun, Xiao-Ming; Wei, Xi-Guang; Ren, Yi; Wong, Ning-Bew; Li, Wai-Kee

2009-06-09

The reactivity order of 12 anions toward ethyl chloride has been investigated by using the G2(+) method, and the competitive E2 and SN2 reactions are discussed and compared. The reactions studied are X(-) + CH3CH2Cl → HX + CH2═CH2 + Cl(-) and X(-) + CH3CH2Cl → CH3CH2X + Cl(-), with X = F, Cl, Br, HO, HS, HSe, NH2 PH2, AsH2, CH3, SiH3, and GeH3. Our results indicate that there is no general and straightforward relationship between the overall barriers and the proton affinity (PA) of X(-); instead, discernible linear correlations only exist for the X's within the same group of the periodic table. Similar correlations are also found with the electronegativity of central atoms in X, deformation energy of the E2 transition state (TS), and the overall enthalpy of reaction. It is revealed that the electronegativity will significantly affect the barrier height, and a more electronegative X will stabilize the E2 and SN2 transition states. Multiple linear regression analysis shows that there is a reasonable linear correlation between E2 (or SN2) overall barriers and the linear combination of PA of X(-) and electronegativity of the central atom.

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

PubMed

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.

Remarkably Enhancing Green-Excitation Efficiency for Solar Energy Utilization: Red Phosphors Ba2ZnS3:Eu2+, X- Co-Doped Halide Ions (X = Cl, Br, I).

PubMed

Luo, Tingting; Du, Yun; Qiu, Zhongxian; Li, Yanmei; Wang, Xiaofang; Zhou, Wenli; Zhang, Jilin; Yu, Liping; Lian, Shixun

2017-05-15

Eu 2+ -activated Ba 2 ZnS 3 has been reported as a red phosphor with a broad emission band peaking at 650 nm under blue excitation for white-LED. In this study, Ba 2 ZnS 3 :Eu 2+ , X - (X = F, Cl, Br, I) phosphors doped with halide ions were prepared by traditional high-temperature solid-state reaction. Phase identification of powders was performed by X-ray powder diffraction analysis, confirming the existence of single-phase Ba 2 ZnS 3 crystals without dopant. The corresponding excitation spectra showed an additional broad band in the green region peaking at 550 nm when the phosphor was halogenated except by the smallest F - . It was proved that the green-excitation efficiency successively strengthened from Cl - , to Br - , to I - , which suggested larger halide ions made a greater contribution to the further splitting of the t 2g energy level of the doped Eu 2+ ions in the host Ba 2 ZnS 3 , and the optimized formula Ba 1.995 ZnS 2.82 :Eu 2+ 0.005 , I - 0.18 showed a potential application in solar spectral conversion for agricultural greenhouse and solar cell. Defect chemistry theory and crystal field theory provided insights into the key role of halide ions in enhancing green-excitation efficiency.

Experimental studies of transplutonium metals and compounds under pressure

DOE Office of Scientific and Technical Information (OSTI.GOV)

Peterson, J.R.; Haire, R.G.; Benedict, U.

1986-01-01

The structural behavior of the first four transplutonium metals and two Bk-Cf alloys as a function of pressure has been studied in diamond anvil cells via x-ray diffraction. The sequence of structures exhibited as pressure is increased is dhcp ..-->.. ccp ..-->.. orthorhombic. In addition a distorted ccp phase is observed in Am, Bk/sub 0.40/Cf/sub 0.60/, and Cf between the ccp and orthorhombic phases. Diamond anvil cells have also been used to contain AmI/sub 3/, CfBr/sub 3/, and CfCl/sub 3/ under pressure for investigation by absorption spectrophotometry. Both AmI/sub 3/ and CfBr/sub 3/ exhibit pressure-induced, irreversible phase transformations to themore » PuBr/sub 3/-type orthorhombic structure, a more dense form of these compounds. Thus the driving force for these transformations is more efficient crystal packing. Both hexagonal (to 22 GPa) and orthorhombic (to 35 GPa) CfCl/sub 3/ exhibit only reversible spectral changes with pressure. This probably reflects their nearly identical RTP unit cell volumes. In both cases the spectra obtained are consistent with a continuous alteration of the RTP structure with pressure; physical compression seems to make a given f-f transition easier. Additional data are being sought to elucidate more completely the behavior of CfCl/sub 3/ under pressure. 23 refs., 4 figs.« less

GC X GCTOFMS OF SYNTHETIC PYRETHROIDS IN FOODS SAMPLES

EPA Science Inventory

Pyrethrins are natural insecticides in the extract of chrysanthemum flowers1. Pyrethroids are synthetic forms of pyrethrins, and many are halogenated (F, Cl, Br). Synthetic pyrethroids have become popular replacements for organophosphorus pesticides, which have become increasin...

GTE_TRACEP_P3B Parameters 1

Atmospheric Science Data Center

2013-02-19

... Methyl bromide (CH3Br) Bromopropane (C3H7 Br) Methyl Chloride (CH3Cl) Ethyl Chloride (C2H5Cl) Vinyl chloride (C2H3Cl) ... Trichloroethylene (C2HCl3) Tetrachloroethylene (C2Cl4) Methylene bromide (CH2Br2) Chlorodibromomethane (CHClBr2) Bromoform ...

GTE_TRACEP_DC8 Parameters 4

Atmospheric Science Data Center

2013-02-18

... Methyl bromide (CH3Br) Bromopropane (C3H7Br) Methyl Chloride(CH3Cl) Ethyl Chloride (C2H5Cl) Vinyl chloride (C2H3Cl) ... Trichloroethylene (C2HCl3) Tetrachloroethylene (C2Cl4) Methylene bromide (CH2Br2) Chlorodibromomethane(CHClBr2) Bromoform ...

Spectrum of excess partial molar absorptivity. Part II: a near infrared spectroscopic study of aqueous Na-halides.

PubMed

Sebe, Fumie; Nishikawa, Keiko; Koga, Yoshikata

2012-04-07

Our earlier thermodynamic studies suggested that F(-) and Cl(-) form hydration shells with the hydration number 14 ± 2 and 2.3 ± 0.6, respectively, and leave the bulk H(2)O away from hydration shells unperturbed. Br(-) and I(-), on the other hand, form hydrogen bonds directly with the momentarily existing hydrogen bond network of H(2)O, and retard the degree of entropy-volume cross fluctuation inherent in liquid H(2)O. The effect of the latter is stronger for I(-) than Br(-). Here we seek additional information about this qualitative difference between Cl(-) and (Br(-) and I(-)) pair by near infrared (NIR) spectroscopy. We analyze the ν(2) + ν(3) band of H(2)O in the range 4600-5500 cm(-1) of aqueous solutions of NaCl, NaBr and NaI, by a new approach. From observed absorbance, we calculate excess molar absorptivity, ε(E), excess over the additive contributions of solute and solvent. ε(E) thus contains information about the effect of inter-molecular interactions in the ν(2) + ν(3) spectrum. The spectrum of ε(E) shows three bands; two negative ones at 5263 and 4873 cm(-1), and the positive band at 5123 cm(-1). We then define and calculate the excess partial molar absorptivity of each salt, ε(E)(salt). From the behaviour of ε(E)(salt) we suggest that the negative band at 5263 cm(-1) represents free H(2)O without much hydrogen bonding under the influence of local electric field of ions. Furthermore, from a sudden change in the x(salt) (mole fraction of salt) dependence of ε(E)(salt), we suggest that there is an ion-pairing in x(salt) > 0.032, 0.036, and 0.04 for NaCl, NaBr and NaI respectively. The positive band of ε(E) at 5123 cm(-1) is attributed to a modestly organized hydrogen bond network of H(2)O (or liquid-likeness), and the x(salt) dependence of ε indicated a qualitative difference in the effect of Cl(-) from those of Br(-) and I(-). Namely, the values of ε(E)(salt) stay constant for Cl(-) but those for Br(-) and I(-) decrease smoothly on increasing the salt mole fraction. The mole fraction dependence of ε(E)(salt) at the 4873 cm(-1) band, due to ice-likeness in H(2)O, shows a subtle difference between Cl(-) and (Br(-), I(-)) pair.

THE RECIPROCAL SYSTEM FORMED BY THE CHLORIDES AND THE BROMIDES OF LITHIUM AND THALLIUM (in Russian)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bergman, A.G.; Arabadzhan, A.S.

1963-06-01

The phase diagrams of 2 series of continuous solid solutions, the Li, K:: Cl,Br and the Li,Tl:: Cl,Br were investigated, as part of a study of the relation between thermal effect of equilibrium reactions and the structure of the melts. In the second system, the heat of the exchange reaction LiCl + TlBr in equilibrium LiBr + TlCl amounts to 8.19 kcal/mole, being larger than that of the corresponding reaction in the Li,K:: Cl,Br system; this affects the crystallization surface in the system. A Pt crucible and Pt, Au, Pd/Pt-Rh thermocouple were used in the thermal studies. It was foundmore » that the liquidus surface consists of 2 fields of continuous series of solid solutions. The joint crystallization curve has a maximum at 392 deg C at the stable portion of the LiCl-TlBr system. There is crest in the liquidus surface corresponding to the stable diagonal LiCl--TlBr; this is visible more markedly in the Li(Cl,Br) field. (TTT)« less

Effect of ionic liquids with different cations and anions on photosystem and cell structure of Scenedesmus obliquus.

PubMed

Xia, Yilu; Liu, Dingdong; Dong, Ying; Chen, Jiazheng; Liu, Huijun

2018-03-01

The rapid increase in the production and practical application of ionic liquids (ILs) could pose potential threats to aquatic systems. In this study, we investigated the effects of four ILs with different cations and anions, including 1-hexyl-3-methylimidazolium nitrate ([HMIM]NO 3 ), 1-hexyl-3-methylimidazolium chloride ([HMIM]Cl), N-hexyl-3-metylpyridinium chloride ([HMPy]Cl), and N-hexyl-3-metylpyridinium bromide ([HMPy]Br), on photosystem and cellular structure of Scenedesmus obliquus. The results indicated that ILs are phytotoxic to S. obliquus. The contents of chlorophyll a, chlorophyll b and total chlorophyll decreased with increasing ILs concentrations. The chlorophyll fluorescence parameters of photosynthetic system II (PSII), including minimal fluorescence yield (F 0 ), potential efficiency of PSII (F v /F o ), maximum quantum efficiency of PSII photochemistry (F v /F m ), yield of photochemical quantum [Y(II)], and non-photochemical quenching coefficient without measuring F 0 ' (NPQ), were all affected. This indicates that ILs could damage PSII, inhibit the primary reaction of photosynthesis, interdict the process of electron-transfer and lead to loss of heat-dissipating ability. ILs also increased cell membrane permeability of S. obliquus, influenced the cellular ultrastructure, changed the morphology of algae cells and destroyed the cell wall, cell membrane and organelles. The results indicated that imidazolium ILs had greater effect than pyridinium ILs, NO 3 - -IL and Br - -IL had greater effect than Cl - -IL. To minimize threats to the environment, the structure of ILs should be taken into consideration. Copyright © 2017 Elsevier Ltd. All rights reserved.

Halogen Containing Gases as Lubricants for Crystallized Glass Ceramic Metal Combinations at Temperatures to 1500 F

NASA Technical Reports Server (NTRS)

Buckley, Donald H.; Johnson, Robert L.

1960-01-01

Pyroceram 9608 (a crystallized glass ceramic) has been considered for use in high-temperature bearing and seal applications. One of the problems encountered with Pyroceram is the lack of availability of lubricants for the temperature range in which this material becomes practical. Experiments were conducted with Pyroceram sliding on various nickel- and cobalt-base alloys using reactive halogen-containing gases as lubricants. Friction and wear data were obtained as a function of sliding velocity and temperature. Studies were made with a hemispherical rider (3/16-in. rad., Pyroceram 9608) sliding in a circumferential path on the flat surface of a rotating disk (2(1/2) in. diam., nickel- or cobalt-base alloys). The specimens were run in an atmosphere of the various gases with a load of 1200 grams, a sliding velocity of 3200 feet per minute, and temperatures from 75 to 1500 F. The gas CF2Br-CF2Br was found to be an effective lubricant for Pyroceram 9608 sliding on Hastelloy R-235 and Inconel X up to 1400 F. The gas CF2Cl-CF2Cl provided effective lubrication for Pyroceram sliding on various cobalt-base alloys at 1000 F.

Likelihood of atom-atom contacts in crystal structures of halogenated organic compounds.

PubMed

Jelsch, Christian; Soudani, Sarra; Ben Nasr, Cherif

2015-05-01

The likelihood of occurrence of intermolecular contacts in crystals of halogenated organic compounds has been analysed statistically using tools based on the Hirshfeld surface. Several families of small halogenated molecules (containing organic F, Cl, Br or I atoms) were analysed, based on chemical composition and aromatic or aliphatic character. The behaviour of crystal contacts was also probed for molecules containing O or N. So-called halogen bonding (a halogen making short interactions with O or N, or a π interaction with C) is generally disfavoured, except when H is scarce on the molecular surface. Similarly, halogen⋯halogen contacts are more rare than expected, except for molecules that are poor in H. In general, the H atom is found to be the preferred partner of organic halogen atoms in crystal structures. On the other hand, C⋯C interactions in parallel π-stacking have a high propensity to occur in halogenated aromatic molecules. The behaviour of the four different halogen species (F, Cl, Br, I) is compared in several chemical composition contexts. The analysis tool can be refined by distinguishing several types for a given chemical species, such as H atoms bound to O or C. Such distinction shows, for instance, that C-H⋯Cl and O-H⋯O are the preferred interactions in compounds containing both O and Cl.

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

PubMed

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

2013-04-04

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.

Trinitromethyl Ethers and Other Derivatives as Superior Oxidizers

DTIC Science & Technology

2011-08-26

well as comparable or superior energy content, so that its performance will be at least equivalent to that of AP. Oxygen balance (relative to CO2) for...21]: 6 C(NO2)4 + M+Cl – → ClC(NO2)3 + M+NO2 – ClC(NO2)3 + LiBr → BrC(NO2)3 + ClC(NO2)2Br BrC(NO2)3 + LiCl → ClC(NO2)3 + LiBr ...hindrance parameter α > 8.87 would not be stable; where Ustrain is the strain energy or the potential energy of the molecule in the minimum position

The protonated 2-halogenated imidazolium cation as the noncovalent interaction donor: the σ-hole and π-hole interactions.

PubMed

Wang, Jingjing; Mo, Lixin; Li, Xiaoyan; Geng, Zongke; Zeng, Yanli

2016-12-01

The σ-hole and π-hole of the protonated 2-halogenated imidazolium cation (XC 3 H 4 N 2 + ; X = F, Cl, Br, I) were investigated and analyzed. The monomers of (CH 3 ) 3 SiY(Y=F, Cl, Br, I), considered as the Lewis base, were combined with the σ-hole and π-hole of XC 3 H 4 N 2 + to form the σ-hole and π-hole interactions in the bimolecular complexes (CH 3 ) 3 SiY · · · XC 3 H 4 N 2 + and (CH 3 ) 3 SiY · · · C 3 (X)H 4 N 2 + (X/Y=F, Cl, Br, I), respectively. For both the σ-hole and π-hole interactions, the equilibrium geometries of complexes show regular changes according to the sequence of heavy sequence of the noncovalent interaction acceptors and donors. The electrostatic energy is the main contribution in the formation of both kinds of interactions, it has linear relations with the V S,max values of σ-hole and the V' S,max values of π-hole. Both the σ-hole and π-hole interactions belong to the closed-shell and noncovalent interactions. The π-hole interactions are stronger than the σ-hole interactions. For the π-hole interactions, the contribution percents of the dispersion energies are somewhat greater than those of the σ-hole interactions, while it is contrary for the polarization energy. Graphical Abstract The protonated 2-halogenated imidazolium cation as the noncovalent interaction donor: the σ-hole and π-hole interactionsᅟ.

Gas-Phase Brønsted Superacidity of Some Derivatives of Monocarba-closo-Borates: a Computational Study

NASA Astrophysics Data System (ADS)

Lipping, Lauri; Leito, Ivo; Koppel, Ivar; Koppel, Ilmar A.

2009-10-01

The structures and gas-phase acidities (GA) of several CB11H12H-based carborane acid derivatives (HA) have been calculated with DFT B3LYP method using 6-311+G**, 6-311++G** basis sets. In order to verify the obtained GA values, several systems were also studied at G3(MP2) level of theory. Inserted substituents (CF3, F, Cl, Br, I, CN, CH3, etc.) followed the "belts" of the monocarborane cage starting from the boron antipodal to the carbon. In general, the predicted intrinsic gas-phase acidities of the systems varied according to the substituents in the following order of decreasing strength: CF3 > F > Cl > Br > I > CN > CH3. Nevertheless, some inconsistencies occurred. F and CN derivatives with lower degree of substitution had weaker intrinsic acidities than the respective Cl derivatives, but the situation was reversed in the case of a larger number of substituents. To obtain better understanding how the substituents influence the basicity of the carborane anion, three hypothetical reaction series were investigated, in which the protonation center was fixed on the boron atom (B12), antipodal to the carbon (C1), and a single substituent replaced the hydrogens at the vertexes of the three remaining positions (C1, B2, and B7). The intrinsic gas-phase acidities in these series of neutral carborane-based acids CB11X1H11H are found to clearly depend on the field-inductive and resonance effects of the substituent X. Some influence of the polarizability of X on the reaction center (B12) could be detected only in the alpha position (B7).

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

PubMed

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.

Nighttime OClO in the Winter Arctic Vortex

NASA Technical Reports Server (NTRS)

Canty, T.; Riviere, E. D.; Salawitch, R. J.; Berthet, G.; Renard, J. -B.; Pfeilsticker, K.; Dorf, M.; Butz, A.; Bosch, H.; Stimpfle, R. M.;

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

NASA Astrophysics Data System (ADS)

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.

UV photolysis of 4-iodo-, 4-bromo-, and 4-chlorophenol: Competition between C-Y (Y = halogen) and O-H bond fission

NASA Astrophysics Data System (ADS)

Sage, Alan G.; Oliver, Thomas A. A.; King, Graeme A.; Murdock, Daniel; Harvey, Jeremy N.; Ashfold, Michael N. R.

2013-04-01

The wavelength dependences of C-Y and O-H bond fission following ultraviolet photoexcitation of 4-halophenols (4-YPhOH) have been investigated using a combination of velocity map imaging, H Rydberg atom photofragment translational spectroscopy, and high level spin-orbit resolved electronic structure calculations, revealing a systematic evolution in fragmentation behaviour across the series Y = I, Br, Cl (and F). All undergo O-H bond fission following excitation at wavelengths λ ≲ 240 nm, on repulsive ((n/π)σ*) potential energy surfaces (PESs), yielding fast H atoms with mean kinetic energies ˜11 000 cm-1. For Y = I and Br, this process occurs in competition with prompt C-I and C-Br bond cleavage on another (n/π)σ* PES, but no Cl/Cl* products unambiguously attributable to one photon induced C-Cl bond fission are observed from 4-ClPhOH. Differences in fragmentation behaviour at longer excitation wavelengths are more marked. Prompt C-I bond fission is observed following excitation of 4-IPhOH at all λ ≤ 330 nm; the wavelength dependent trends in I/I* product branching ratio, kinetic energy release, and recoil anisotropy suggest that (with regard to C-I bond fission) 4-IPhOH behaves like a mildly perturbed iodobenzene. Br atoms are observed when exciting 4-BrPhOH at long wavelengths also, but their velocity distributions suggest that dissociation occurs after internal conversion to the ground state. O-H bond fission, by tunnelling (as in phenol), is observed only in the cases of 4-FPhOH and, more weakly, 4-ClPhOH. These observed differences in behaviour can be understood given due recognition of (i) the differences in the vertical excitation energies of the C-Y centred (n/π)σ* potentials across the series Y = I < Br < Cl and the concomitant reduction in C-Y bond strength, cf. that of the rival O-H bond, and (ii) the much increased spin-orbit coupling in, particularly, 4-IPhOH. The present results provide (another) reminder of the risks inherent in extrapolating photochemical behaviour measured for one molecule at one wavelength to other (related) molecules and to other excitation energies.

5-(Halomethyl)uridine derivatives as potential antitumor radiosensitizers: A DFT study

NASA Astrophysics Data System (ADS)

Wang, Shoushan; Zhang, Min; Liu, Peng; Xie, Shilei; Cheng, Faliang; Wang, Lishi

2018-01-01

Considering the fact that the efficiency of the uridine-5-methyl radical in producing cytotoxic DNA intrastrand cross-link lesions is greatly higher than that of the uridine-5-yl radical, the radiosensitizing action of 5-(halomethyl)uridines (5-XCH2U, X = F, Cl, or Br) is studied in the present work. It is found that 5-XCH2U has sufficient electron affinity to capture a pre-hydrated or a hydrated electron, and electron attachment leads to significantly facile X- elimination forming the uridine-5-methyl radical. All these three halogenated uridine derivatives are shown to be potential radiosensitizers, with their radiosensitizing abilities increased in an order 5-FCH2U < 5-ClCH2U ≈ 5-BrCH2U.

Picosecond pulse radiolysis of direct and indirect radiolytic effects in highly concentrated halide aqueous solutions.

PubMed

Balcerzyk, Anna; Schmidhammer, Uli; El Omar, Abdel Karim; Jeunesse, Pierre; Larbre, Jean-Philippe; Mostafavi, Mehran

2011-08-25

Recently we measured the amount of the single product, Br(3)(-), of steady-state radiolysis of highly concentrated Br(-) aqueous solutions, and we showed the effect of the direct ionization of Br(-) on the yield of Br(3)(-). Here, we report the first picosecond pulse-probe radiolysis measurements of ionization of highly concentrated Br(-) and Cl(-) aqueous solutions to describe the oxidation mechanism of the halide anions. The transient absorption spectra are reported from 350 to 750 nm on the picosecond range for halide solutions at different concentrations. In the highly concentrated halide solutions, we observed that, due to the presence of Na(+), the absorption band of the solvated electron is shifted to shorter wavelengths, but its decay, taking place during the spur reactions, is not affected within the first 4 ns. The kinetic measurements in the UV reveal the direct ionization of halide ions. The analysis of pulse-probe measurements show that after the electron pulse, the main reactions in solutions containing 1 M of Cl(-) and 2 M of Br(-) are the formation of ClOH(-•) and BrOH(-•), respectively. In contrast, in highly concentrated halide solutions, containing 5 M of Cl(-) and 6 M of Br(-), mainly Cl(2)(-•) and Br(2)(-•) are formed within the electron pulse without formation of ClOH(-•) and BrOH(-•). The results suggest that, not only Br(-) and Cl(-) are directly ionized into Br(•) and Cl(•) by the electron pulse, the halide atoms can also be rapidly generated through the reactions initiated by excitation and ionization of water, such as the prompt oxidation by the hole, H(2)O(+•), generated in the coordination sphere of the anion. © 2011 American Chemical Society

Star-like superalkali cations featuring planar pentacoordinate carbon

DOE Office of Scientific and Technical Information (OSTI.GOV)

Guo, Jin-Chang; Tian, Wen-Juan; Zhao, Xue-Feng

Superalkali cations, known to possess low vertical electron affinities (VEAs), high vertical detachment energies, and large highest occupied molecular orbital (HOMO)-lowest unoccupied molecular orbital (LUMO) energy gaps, are intriguing chemical species. Thermodynamically, such species need to be the global minima in order to serve as the promising targets for experimental realization. In this work, we propose the strategies of polyhalogenation and polyalkalination for designing the superalkali cations. By applying these strategies, the local-minimum planar pentacoordinate carbon (ppC) cluster CBe{sub 5} can be modified to form a series of star-like superalkali ppC or quasi-ppC CBe{sub 5}X{sub 5}{sup +} (X = F,more » Cl, Br, Li, Na, K) cations containing a CBe{sub 5} moiety. Polyhalogenation and polyalkalination on the CBe{sub 5} unit may help eliminate the high reactivity of bare CBe{sub 5} molecule by covering the reactive Be atoms with noble halogen anions and alkali cations. Computational exploration of the potential energy surfaces reveals that the star-like ppC or quasi-ppC CBe{sub 5}X{sub 5}{sup +} (X = F, Cl, Br, Li, Na, K) clusters are the true global minima of the systems. The predicted VEAs for CBe{sub 5}X{sub 5}{sup +} range from 3.01 to 3.71 eV for X = F, Cl, Br and 2.12–2.51 eV for X = Li, Na, K, being below the lower bound of the atomic ionization potential of 3.89 eV in the periodic table. Large HOMO-LUMO energy gaps are also revealed for the species: 10.76–11.07 eV for X = F, Cl, Br and 4.99–6.91 eV for X = Li, Na, K. These designer clusters represent the first series of superalkali cations with a ppC center. Bonding analyses show five Be–X–Be three-center two-electron (3c-2e) σ bonds for the peripheral bonding, whereas the central C atom is associated with one 6c-2e π bond and three 6c-2e σ bonds, rendering (π and σ) double aromaticity. Born-Oppenheimer molecular dynamics simulations indicate that the CBe{sub 5} motif is robust in the clusters. As planar hypercoordination carbon species are often thermodynamically unstable and highly reactive, the superalkali cation characters of these ppC species should be highlighted, which may be suitable for experimental realization.« less

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

PubMed

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 < BrOCl ≈ Br(2) < BrCl. Our results indicate that species other than HOBr can influence bromination rates under conditions typical of drinking water and wastewater chlorination.

An ab initio study of the electronic structure and relative stability of the halogenated thiophosphorus compounds SPX (X = Cl, F, Br) and their isomers

NASA Astrophysics Data System (ADS)

Nowek, Andrzej; Richardson, Rhonda; Babinec, Peter; Leszczyński, Jerzy

1997-12-01

The electronic structure and relative stability of the halogenated thiophosphorus compounds SPCl, SPF, and SPBr and their isomers ClSP, FSP, and BrSP were investigated using ab initio post-Hartree-Fock methods. Molecular geometries of all these structures together with the transition states between isomers, have been optimized at the SCF, MP2, and CCSD levels. Single-point CCSD(T) and MP4 calculations have been performed at the optimal CCSD and MP2 geometries. All calculations have been done using the standard 6-311G(2d) basis set. Harmonic vibrational frequencies and IR intensities for all species were calculated at the correlated levels, and they are in good agreement with the available data from matrix-isolated IR spectroscopy. Because the isomers ClSP, FSP, and BrSP have not yet been experimentally observed, we extended our study by calculating of equilibrium constants of isomerization using Eyring transition state theory, and we have found that at sufficiently high temperatures (≈ 1000 K) the equilibrium constants are large enough for the possible detection of these isomers.

Magnetic Transitions in Iron Porphyrin Halides by Inelastic Neutron Scattering and Ab-initio Studies of Zero-Field Splittings

DOE PAGES

Stavretis, Shelby E.; Atanasov, Mihail; Podlesnyak, Andrey A.; ...

2015-10-02

Zero-field splitting (ZFS) parameters of nondeuterated metalloporphyrins [Fe(TPP)X] (X = F, Br, I; H 2TPP = tetraphenylporphyrin) are determined by inelastic neutron scattering (INS). The ZFS values are D = 4.49(9) cm –1 for tetragonal polycrystalline [Fe(TPP)F], and D = 8.8(2) cm –1, E = 0.1(2) cm –1 and D = 13.4(6) cm –1, E = 0.3(6) cm –1 for monoclinic polycrystalline [Fe(TPP)Br] and [Fe(TPP)I], respectively. Along with our recent report of the ZFS value of D = 6.33(8) cm –1 for tetragonal polycrystalline [Fe(TPP)Cl], these data provide a rare, complete determination of ZFS parameters in a metalloporphyrin halide series.more » The electronic structure of [Fe(TPP)X] (X = F, Cl, Br, I) has been studied by multireference ab initio methods: the complete active space self-consistent field (CASSCF) and the N-electron valence perturbation theory (NEVPT2) with the aim of exploring the origin of the large and positive zero-field splitting D of the 6A 1 ground state. D was calculated from wave functions of the electronic multiplets spanned by the d 5 configuration of Fe(III) along with spin–orbit coupling accounted for by quasi degenerate perturbation theory. Results reproduce trends of D from inelastic neutron scattering data increasing in the order from F, Cl, Br, to I. A mapping of energy eigenvalues and eigenfunctions of the S = 3/2 excited states on ligand field theory was used to characterize the σ- and π-antibonding effects decreasing from F to I. This is in agreement with similar results deduced from ab initio calculations on CrX 6 3- complexes and also with the spectrochemical series showing a decrease of the ligand field in the same directions. A correlation is found between the increase of D and decrease of the π- and σ-antibonding energies e λ X (λ = σ, π) in the series from X = F to I. Analysis of this correlation using second-order perturbation theory expressions in terms of angular overlap parameters rationalizes the experimentally deduced trend. Furthermore, D parameters from CASSCF and NEVPT2 results have been calibrated against those from the INS data, yielding a predictive power of these approaches. Methods to improve the quantitative agreement between ab initio calculated and experimental D and spectroscopic transitions for high-spin Fe(III) complexes are proposed.« less

Magnetic Transitions in Iron Porphyrin Halides by Inelastic Neutron Scattering and Ab Initio Studies of Zero-Field Splittings.

PubMed

Stavretis, Shelby E; Atanasov, Mihail; Podlesnyak, Andrey A; Hunter, Seth C; Neese, Frank; Xue, Zi-Ling

2015-10-19

Zero-field splitting (ZFS) parameters of nondeuterated metalloporphyrins [Fe(TPP)X] (X = F, Br, I; H₂TPP = tetraphenylporphyrin) have been directly determined by inelastic neutron scattering (INS). The ZFS values are D = 4.49(9) cm⁻¹ for tetragonal polycrystalline [Fe(TPP)F], and D = 8.8(2) cm⁻¹, E = 0.1(2) cm⁻¹ and D = 13.4(6) cm⁻¹, E = 0.3(6) cm⁻¹ for monoclinic polycrystalline [Fe(TPP)Br] and [Fe(TPP)I], respectively. Along with our recent report of the ZFS value of D = 6.33(8) cm⁻¹ for tetragonal polycrystalline [Fe(TPP)Cl], these data provide a rare, complete determination of ZFS parameters in a metalloporphyrin halide series. The electronic structure of [Fe(TPP)X] (X = F, Cl, Br, I) has been studied by multireference ab initio methods: the complete active space self-consistent field (CASSCF) and the N-electron valence perturbation theory (NEVPT2) with the aim of exploring the origin of the large and positive zero-field splitting D of the ⁶A₁ ground state. D was calculated from wave functions of the electronic multiplets spanned by the d⁵ configuration of Fe(III) along with spin–orbit coupling accounted for by quasi degenerate perturbation theory. Results reproduce trends of D from inelastic neutron scattering data increasing in the order from F, Cl, Br, to I. A mapping of energy eigenvalues and eigenfunctions of the S = 3/2 excited states on ligand field theory was used to characterize the σ- and π-antibonding effects decreasing from F to I. This is in agreement with similar results deduced from ab initio calculations on CrX₆³⁻ complexes and also with the spectrochemical series showing a decrease of the ligand field in the same directions. A correlation is found between the increase of D and decrease of the π- and σ-antibonding energies e(λ)(X) (λ = σ, π) in the series from X = F to I. Analysis of this correlation using second-order perturbation theory expressions in terms of angular overlap parameters rationalizes the experimentally deduced trend. D parameters from CASSCF and NEVPT2 results have been calibrated against those from the INS data, yielding a predictive power of these approaches. Methods to improve the quantitative agreement between ab initio calculated and experimental D and spectroscopic transitions for high-spin Fe(III) complexes are proposed.

Fabrication of Low-Loss Halide Glass Fibers.

DTIC Science & Technology

1985-09-01

chalcogenides, have some merit. Well known, also are the polycrystalline halide materials such as KRS-5, TlBr , *TlI and AgCl and their single...tension of the melt zone is high enough to *" eliminate sagging in the fibers. Using this technique, ( TlBr )I (KRS-5), TlBr , CuCl, AgCl, and AgBr have

Photo-assisted etching of silicon in chlorine- and bromine-containing plasmas

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhu, Weiye; Sridhar, Shyam; Liu, Lei

2014-05-28

Cl{sub 2}, Br{sub 2}, HBr, Br{sub 2}/Cl{sub 2}, and HBr/Cl{sub 2} feed gases diluted in Ar (50%–50% by volume) were used to study etching of p-type Si(100) in a rf inductively coupled, Faraday-shielded plasma, with a focus on the photo-assisted etching component. Etching rates were measured as a function of ion energy. Etching at ion energies below the threshold for ion-assisted etching was observed in all cases, with Br{sub 2}/Ar and HBr/Cl{sub 2}/Ar plasmas having the lowest and highest sub-threshold etching rates, respectively. Sub-threshold etching rates scaled with the product of surface halogen coverage (measured by X-ray photoelectron spectroscopy) andmore » Ar emission intensity (7504 Å). Etching rates measured under MgF{sub 2}, quartz, and opaque windows showed that sub-threshold etching is due to photon-stimulated processes on the surface, with vacuum ultraviolet photons being much more effective than longer wavelengths. Scanning electron and atomic force microscopy revealed that photo-etched surfaces were very rough, quite likely due to the inability of the photo-assisted process to remove contaminants from the surface. Photo-assisted etching in Cl{sub 2}/Ar plasmas resulted in the formation of 4-sided pyramidal features with bases that formed an angle of 45° with respect to 〈110〉 cleavage planes, suggesting that photo-assisted etching can be sensitive to crystal orientation.« less

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

NASA Astrophysics Data System (ADS)

Seo, Jung Hun; Zajacz, Zoltán

2016-06-01

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

Toxic Hazards Research Unit annual technical report, 1972

NASA Technical Reports Server (NTRS)

Macewen, J. D.; Vernot, E. H.

1972-01-01

The activities of the Toxic Hazards Research Unit (THRU) for the period of June 1971 through May 1972 are reviewed in this report. Acute inhalation toxicity experiments were conducted on hydrogen chloride (HCl) gas and aerosol, ethyl bromide (C2H5Br), hydrogen bromide (HBr), hydrogen sulfide (H2S), ammonia (NH3), chlorine (CL2), and silane (SiH4). Subacute toxicity studies were conducted on chlorine pentafluoride (ClF5), dichloromethane (CH2Cl2) and coal tar volatiles. Further toxicity studies of subacute and chronic responses to inhaled monomethylhydrazine (MMH) are also described.

Electronegativity, charge transfer, crystal field strength, and the point charge model revisited.

PubMed

Tanner, Peter A; Ning, Lixin

2013-02-21

Although the optical spectra of LnCl(6)(3-) systems are complex, only two crystal field parameters, B(40) and B(60), are required to model the J-multiplet crystal field splittings in octahedral symmetry. It is found that these parameters exhibit R(-5) and R(-7) dependence, respectively, upon the ionic radius Ln(3+)(VI), but not upon the Ln-Cl distance. More generally, the crystal field strengths of LnX(6) systems (X = Br, Cl, F, O) exhibit linear relationships with ligand electronegativity, charge transfer energy, and fractional ionic character of the Ln-X bond.

GTE_TRACEP_DC8 Parameters 6

Atmospheric Science Data Center

2013-02-18

... Trichloroethylene (C2HCl3) Carbon tetrachloride (CCl4) Methylene bromide (CH2Br2) Chlorobromomethane (CH2BrCl) Dichloromethane ... Methylbromide (CH3Br) Chloroform (CH3CCl3) Methyl Chloride (CH3Cl) Methyl Iodide (CH3I) Chlorodibromomethane (CHBr2Cl) ...

GTE_TRACEP_P3B Parameters 4

Atmospheric Science Data Center

2013-02-19

... Trichloroethylene (C2HCl3) Carbon tetrachloride (CCl4) Methylene bromide (CH2Br2) Chlorobromomethane (CH2BrCl) Dichloromethane ... Methylbromide (CH3Br) Chloroform (CH3CCl3) Methyl Chloride (CH3Cl) Methyl Iodide (CH3I) Chlorodibromomethane (CHBr2Cl) ...

An easy prepared dual-channel chemosensor for selective and instant detection of fluoride based on double Schiff-base

NASA Astrophysics Data System (ADS)

Leng, Yan-Li; Zhang, Jian-Hui; Li, Qiao; Zhang, You-Ming; Lin, Qi; Yao, Hong; Wei, Tai-Bao

2016-10-01

A colorimetric and fluorescent dual-channel fluoride chemosensor N,N‧-bis (4-diethylaminosalicylidene) hydrazine (sensor S) bearing two imine groups has been designed and synthesized. This structurally simple probe displays rapid response and high selectivity for fluoride over other common anions (Cl-, Br-, I-, AcO-, H2PO4-, HSO4-, ClO4-, CN- and SCN-) in a highly polar aqueous DMSO solution. Mechanism studies suggested that the sensor firstly combined with F- through hydrogen bonds and then experienced the deprotonation process at higher concentrations of F- anion to the two Ar-OH groups. The detection limit was 5.78 × 10- 7 M of F-, which points to the high detection sensitivity. Test strips based on sensor S were fabricated, which could act as a convenient and efficient F- test kit to detect F- for ;in-the-field; measurement.

Theoretical study of X⁻ · 1 · YF (1 = triazine, X = Cl, Br and I, Y = H, Cl, Br, I, PH₂ and AsH₂): noncovalently electron-withdrawing effects on anion-arene interactions.

PubMed

Chen, Yishan; Yao, Lifeng

2014-01-01

The ternary complexes X(-) · 1 · YF (1 = triazine, X = Cl, Br and I, Y = H, Cl, Br, I, PH2 and AsH2) have been investigated by MP2 calculations to understand the noncovalently electron-withdrawing effects on anion-arene interactions. The results indicate that in binary complexes (1 · X(-)), both weak σ-type and anion-π complexes can be formed for Cl(-) and Br(-), but only anion-π complex can be formed for I(-). Moreover, the hydrogen-bonding complex is the global minimum for all three halides in binary complexes. However, in ternary complexes, anion-π complex become unstable and only σ complex can retain in many cases for Cl(-) and Br(-). Anion-π complex keeps stable only when YF = HF. In contrast with binary complexes, σ complex become the global minimum for Cl(-) and Br(-) in ternary complexes. These changes in binding mode and strength are consistent with the results of covalently electron-withdrawing effects. However, in contrast with the covalently electron-withdrawing substituents, Cl(-) and Br(-) can attack the aromatic carbon atom to form a strong σ complex when the noncovalently electron-withdrawing effect is induced by halogen bonding. The binding behavior for I(-) is different from that for Cl(-) and Br(-) in two aspects. First, the anion-π complex for I(-) can also keep stable when the noncovalent interaction is halogen bonding. Second, the anion-π complex for I(-) is the global minimum when it can retain as a stable structure.

THERMODYNAMIC PROPERTIES OF Zr AND Hf HALIDES (in Rumanian)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lungu, S.N.

1962-01-01

The following standard heats of formation were found: ZrCl/sub 3/, 178.6 plus or minus 3.2; ZrCl/sub 2/, 124.3 plus or minus 3; ZrBr/sub 3/, 151 plus or minus 7; Zr Br/sbu 2/, 100 plus or minus 6; ZrI/sub 3/, 103 plus or minus 6; ZrI/sub 2/, 68 plus or minus 4; and HfCl/sub 4/, 239.4 plus or minus 5.5; HfCl/sub 3/, 186.6; HfCl/sub 2/, 130; HfBr/sub 4/, 200; HfBr/sub 3/, 157; HfBr / sub 2/, 108; HfI/sub 4/, 140; HfI/sub 3/, 113; and HfI/sub 2/, 72 kcal/mole. (R.V.J.)

Crystal structures, vibrational spectra and DFT calculations of five halogeno-derivatives of 7-azaindole (3Br7AI, 4Br7AI, 4Cl7AI, 3Br4Cl7AI and 5Br3Cl7AI): a comparative study

NASA Astrophysics Data System (ADS)

Morzyk-Ociepa, Barbara; Dysz, Karolina; Turowska-Tyrk, Ilona; Michalska, Danuta

2018-01-01

Structures and vibrational spectra of 3-bromo-7-azaindole (3Br7AI), 4-bromo-7-azaindole (4Br7AI), 4-chloro-7-azaindole (4Cl7AI), 5-bromo-3-chloro-7-azaindole (5Br3Cl7AI) and 3-bromo-4-chloro-7-azaindole (3Br4Cl7AI) have been investigated. For the first time a single crystal analysis is reported for the three compounds: 3Br7AI (P21/n space group; a = 12.6586(3), b = 3.98664(12), c = 14.1189(4)Å, β = 100.901(2)o, Z = 4); 4Br7AI (P21/n space group; a = 5.38136 (13), b = 9.2262 (2), c = 13.9806 (4)Å, β = 90.052 (2)o, Z = 4); and 5Br3Cl7AI (C2/c space group; a = 22.9444(10), b = 3.91953(12), c = 17.8500(6)Å, β = 102.621(4)o, Z = 8). In the crystal structure, a pair of molecules forms a centrosymmetric dimer connected by dual nearly linear Nsbnd H⋯N hydrogen bonds between the pyrrole and pyridine rings. In addition, the structures of 4Br7AI and 5Br3Cl7AI are stabilized by C2sbnd H2⋯Br hydrogen bonds. The IR and Raman spectra of all compounds and their N-deuterated derivatives were recorded in the solid state. The theoretical molecular structures and vibrational spectra of the centrosymmetric dimers of five investigated compounds were calculated using the B3LYP method with the 6-311G++(d,p) basis set. The optimized structural parameters and the calculated vibrational spectra reproduce well the experiment. Detailed vibrational assignments for all these compounds have been made on the basis of the calculated potential energy distributions (PEDs). The characteristic marker bands for the chloro- and bromo-derivativeds of 7-azaindoles are reported.

Proposed method of hydrogeochemical exploration for salt deposits using ClBr ratios, Eastern Province, Kingdom of Saudi Arabia

USGS Publications Warehouse

Smith, C.L.

1991-01-01

Despite the value of the salt (NaCl) and brine used by the chemical industry, geochemical prospecting techniques are not customarily employed in the search for these raw materials. In this study, Br geochemistry is used as the basis for a proposed hydrogeochemical prospecting technique that was designed to search for shallow halite beds in the Eastern Province of the Kingdom of Saudi Arabia. Near-surface brine samples were collected at Sabkhah Jayb Uwayyid, both directly above and distant from a buried salt bed. Brine samples collected both directly above and offset to the north-west of the salt bed had ClBr ratios > 8000. The regional background ClBr ratio of fresh nonmarime ground water is ???300. The large range in ClBr ratios and the association of high ClBr ratios with the buried salt body suggest that the ratio can be useful in hydrogeochemical prospecting for sibakh-associated, shallow salt bodies. ?? 1991.

Gas-particle phase partitioning and particle size distribution of chlorinated and brominated polycyclic aromatic hydrocarbons in haze.

PubMed

Jin, Rong; Zheng, Minghui; Yang, Hongbo; Yang, Lili; Wu, Xiaolin; Xu, Yang; Liu, Guorui

2017-12-01

Chlorinated and brominated polycyclic aromatic hydrocarbons (Cl/Br-PAHs) are emerging semi-volatile organic pollutants in haze-associated particulate matter (PM). Their gas-particle phase partitioning and distribution among PM fractions have not been clarified. Clarification would increase understanding of atmospheric behavior and health risks of Cl/Br-PAHs. In this study, samples of the gas phase and 4 PM phases (aerodynamic diameters (d ae ) > 10 μm, 2.5-10 μm, 1.0-2.5 μm, and <1.0 μm) were collected simultaneously during haze events in Beijing and analyzed. Normalized histogram distribution indicated that the Cl/Br-PAHs tended to adhere to fine particles. Over 80% of the Cl-PAHs and 70% of the Br-PAHs were associated with fine PM (d ae  < 2.5 μm). The gas-particle phase partitioning and PM distribution of Cl/Br-PAHs when heating of buildings was required, which was associated with haze events, were obviously different from those when heating was not required. The relationship between the logarithmic geometric mean diameters of the Cl/Br-PAH congeners and reciprocal of the temperature (1/T) suggested that low air temperatures during the heating period could lead to high proportions of Cl/Br-PAHs in the fine particles. Increased coal burning during the heating period also contributed to high Cl/Br-PAH loads in the fine particles. Copyright © 2017 Elsevier Ltd. All rights reserved.

A complex Ar⋯Agsbnd I produced by laser ablation and characterised by rotational spectroscopy and ab initio calculations: Variation of properties along the series Ar⋯Agsbnd X (X = F, Cl, Br and I)

NASA Astrophysics Data System (ADS)

Medcraft, Chris; Mullaney, John C.; Walker, Nicholas R.; Legon, Anthony C.

2017-05-01

A complex of argon with silver iodide (Ar⋯Agsbnd I) has been formed in the gas phase by laser ablation of a silver iodide rod in the presence of a pulse of argon gas and its ground-state rotational spectrum has been detected by means of a chirped-pulse, F-T microwave instrument. Ar⋯Agsbnd I was characterised both by experimental properties determined from its rotational spectrum and by ab initio calculations carried out at the CCSD(T)(F12c)/cc-pVTZ-F12 explicitly correlated level of theory. The molecule was shown to be linear in the ground state, with atoms in the order shown. The Ar⋯Ag and Agsbnd I bond lengths r0(Ar⋯Ag) = 2.6759 Å and r0(Agsbnd I) = 2.5356 Å, the dissociation energy De = 16.7 kJ mol-1 for the process Ar⋯Agsbnd I = Ar + Agsbnd I, the intermolecular quadratic stretching force constant FAr⋯Ag = F22 = 20.2(8) N m-1 and the increase 0.033 in the ionicity ic of Agsbnd I when it enters the complex are reported. The opportunity has been taken to compare the way in which these properties vary along the series Ar⋯Agsbnd X (X = F, Cl, Br and I).

Occurrence, profiles, and toxic equivalents of chlorinated and brominated polycyclic aromatic hydrocarbons in E-waste open burning soils.

PubMed

Nishimura, Chiya; Horii, Yuichi; Tanaka, Shuhei; Asante, Kwadwo Ansong; Ballesteros, Florencio; Viet, Pham Hung; Itai, Takaaki; Takigami, Hidetaka; Tanabe, Shinsuke; Fujimori, Takashi

2017-06-01

We conducted this study to assess the occurrence, profiles, and toxicity of chlorinated polycyclic aromatic hydrocarbons (Cl-PAHs) and brominated polycyclic aromatic hydrocarbons (Br-PAHs) in e-waste open burning soils (EOBS). In this study, concentrations of 15 PAHs, 26 Cl-PAHs and 14 Br-PAHs were analyzed in EOBS samples. We found that e-waste open burning is an important emission source of Cl-PAHs and Br-PAHs as well as PAHs. Concentrations of total Cl-PAHs and Br-PAHs in e-waste open burning soil samples ranged from 21 to 2800 ng/g and from 5.8 to 520 ng/g, respectively. Compared with previous studies, the mean of total Cl-PAH concentrations of the EOBS samples in this study was higher than that of electronic shredder waste, that of bottom ash, and comparable to fly ash from waste incinerators in Korea and Japan. The mean of total Br-PAH concentrations of the EOBS samples was generally three to four orders of magnitude higher than those in incinerator bottom ash and comparable to incinerator fly ash, although the number of Br-PAH congeners measured differed among studies. We also found that the Cl-PAH and Br-PAH profiles were similar among all e-waste open burning soil samples but differed from those in waste incinerator fly ash. The profiles and principal component analysis results suggested a unique mechanism of Cl-PAH and Br-PAH formation in EOBS. In addition, the Cl-PAHs and Br-PAHs showed high toxicities equivalent to PCDD/Fs measured in same EOBS samples when calculated based on their relative potencies to benzo[a]pyrene. Along with chlorinated and brominated dioxins and PAHs, Cl-PAHs and Br-PAHs are important environmental pollutants to investigate in EOBS. Copyright © 2016 Elsevier Ltd. All rights reserved.

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

PubMed

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.

Genetic Modifiers of Ovarian Cancer

DTIC Science & Technology

2013-06-01

Barile M, Genuardi M, Arnold N, Meindl A, Sutter C, Wappenschmidt B, Domchek SM, Pfeiler G, Friedman E, Jensen UB, Robson M, Shah S, Lazaro C, Mai PL...Peissel B, Sellers TA, Ficarazzi F, Barile M, Ziogas A, Ashworth A, Gentry-Maharaj A, Jones M, Ramus SJ, Orr N, Menon U, Pearce CL, Brüning T, Pike

Chaos in the classical mechanics of bound and quasi-bound HX-4He complexes with X = F, Cl, Br, CN.

PubMed

Gamboa, Antonio; Hernández, Henar; Ramilowski, Jordan A; Losada, J C; Benito, R M; Borondo, F; Farrelly, David

2009-10-01

The classical dynamics of weakly bound floppy van der Waals complexes have been extensively studied in the past except for the weakest of all, i.e., those involving He atoms. These complexes are of considerable current interest in light of recent experimental work focussed on the study of molecules trapped in small droplets of the quantum solvent (4)He. Despite a number of quantum investigations, details on the dynamics of how quantum solvation occurs remain unclear. In this paper, the classical rotational dynamics of a series of van der Waals complexes, HX-(4)He with X = F, Cl, Br, CN, are studied. In all cases, the ground state dynamics are found to be almost entirely chaotic, in sharp contrast to other floppy complexes, such as HCl-Ar, for which chaos sets in only at relatively high energies. The consequences of this result for quantum solvation are discussed. We also investigate rotationally excited states with J = 1 which, except for HCN-(4)He, are actually resonances that decay by rotational pre-dissociation.

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.

PubMed

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.

Construction of halide-bridged tungsten-copper-sulfide double cubanelike clusters from a new precursor [(Tp*WS2)2(μ-S2)].

PubMed

Wei, Li-Pei; Ren, Zhi-Gang; Zhu, Lian-Wen; Yan, Wen-Yan; Sun, Sha; Wang, Hui-Fang; Lang, Jian-Ping; Sun, Zhen-Rong

2011-05-16

Treatment of [Et(4)N][Tp*WS(3)] (1) (Tp* = hydridotris(3,5-dimethylpyrazol-1-yl)borate) with 2 equiv of AgSCN in MeCN afforded a novel neutral compound [(Tp*WS(2))(2)(μ-S(2))] (2). Reactions of 2 with excess CuX (X = Cl, Br, I) in MeCN and CH(2)Cl(2) or CHCl(3) formed three neutral W/Cu/S clusters [{Tp*W(μ(3)-S)(3)Cu(3)(μ-Cl)}(2)Cu(μ-Cl)(2)(μ(7)-Cl)(MeCN)](2) (3), [{Tp*W(μ(3)-S)(3)Cu(3)}(2)Br(μ-Br)(2)(μ(4)-Br)(MeCN)] (4), and [{Tp*W(μ(3)-S)(3)Cu(3)}(2){Cu(2)(μ-I)(4)(μ(3)-I)(2)}] (5), respectively. On the other hand, treatment of 2 with CuX (X = Cl, Br) in the presence of Et(4)NX (X = Cl, Br) produced two anionic W/Cu/S clusters [Et(4)N][{Tp*W(μ(3)-S)(3)Cu(3)X}(2)(μ-X)(2)(μ(4)-X)] (6: X = Cl; 7 X = Br). Compounds 2-7 were characterized by elemental analysis, IR, UV-vis, (1)H NMR, electrospray ionization (ESI) mass spectra, and single-crystal X-ray crystallography. The dimeric structure of 2 can be viewed as two [Tp*WS(2)] fragments in which two W atoms are connected by one S(2)(2-) dianion. Compounds 3-7 all possess unique halide-bridged double cubanelike frameworks. For 3, two [Tp*W(μ(3)-S)(3)Cu(3)](2+) dications are linked via a μ(7)-Cl(-) bridge, two μ-Cl(-) bridges, and a [Cu(MeCN)(μ-Cl)(2)](+) bridge. For 4, one [Tp*W(μ(3)-S)(3)Cu(3)(MeCN)](2+) dication and one [Tp*W(μ(3)-S)(3)Cu(3)Br](+) cation are linked via a μ(4)-Br(-) and two μ-Br(-) bridges. For 5, the two [Tp*W(μ(3)-S)(3)Cu(3)](2+) dications are bridged by a linear [(μ-I)(2)Cu(μ(3)-I)(2)Cu(μ-I)(2)](4+) species. For 6 and 7, two [Tp*W(μ(3)-S)(3)Cu(3)X](+) cations are linked by a μ(4)-X(-) and two μ-X(-) bridges (X = Cl, Br). In addition, the third-order nonlinear optical (NLO) properties of 2-7 in MeCN/CH(2)Cl(2) were investigated by using femtosecond degenerate four-wave mixing (DFWM) technique.

Effect of water on the fluorine and chlorine partitioning behavior between olivine and silicate melt.

PubMed

Joachim, Bastian; Stechern, André; Ludwig, Thomas; Konzett, Jürgen; Pawley, Alison; Ruzié-Hamilton, Lorraine; Clay, Patricia L; Burgess, Ray; Ballentine, Christopher J

2017-01-01

Halogens show a range from moderate (F) to highly (Cl, Br, I) volatile and incompatible behavior, which makes them excellent tracers for volatile transport processes in the Earth's mantle. Experimentally determined fluorine and chlorine partitioning data between mantle minerals and silicate melt enable us to estimate Mid Ocean Ridge Basalt (MORB) and Ocean Island Basalt (OIB) source region concentrations for these elements. This study investigates the effect of varying small amounts of water on the fluorine and chlorine partitioning behavior at 1280 °C and 0.3 GPa between olivine and silicate melt in the Fe-free CMAS+F-Cl-Br-I-H 2 O model system. Results show that, within the uncertainty of the analyses, water has no effect on the chlorine partitioning behavior for bulk water contents ranging from 0.03 (2) wt% H 2 O (D Cl ol/melt = 1.6 ± 0.9 × 10 -4 ) to 0.33 (6) wt% H 2 O (D Cl ol/melt = 2.2 ± 1.1 × 10 -4 ). Consequently, with the effect of pressure being negligible in the uppermost mantle (Joachim et al. Chem Geol 416:65-78, 2015), temperature is the only parameter that needs to be considered for the determination of chlorine partition coefficients between olivine and melt at least in the simplified iron-free CMAS+F-Cl-Br-I-H 2 O system. In contrast, the fluorine partition coefficient increases linearly in this range and may be described at 1280 °C and 0.3 GPa with ( R 2  = 0.99): [Formula: see text]. The observed fluorine partitioning behavior supports the theory suggested by Crépisson et al. (Earth Planet Sci Lett 390:287-295, 2014) that fluorine and water are incorporated as clumped OH/F defects in the olivine structure. Results of this study further suggest that fluorine concentration estimates in OIB source regions are at least 10% lower than previously expected (Joachim et al. Chem Geol 416:65-78, 2015), implying that consideration of the effect of water on the fluorine partitioning behavior between Earth's mantle minerals and silicate melt is vital for a correct estimation of fluorine abundances in OIB source regions. Estimates for MORB source fluorine concentrations as well as chlorine abundances in both mantle source regions are within uncertainty not affected by the presence of water.

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.

PubMed

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.

Dynamical Bifurcation in Gas-Phase XH- + CH3 Y SN 2 Reactions: The Role of Energy Flow and Redistribution in Avoiding the Minimum Energy Path.

PubMed

Proenza, Yaicel G; de Souza, Miguel A F; Longo, Ricardo L

2016-11-02

The gas-phase reactions of XH - (X=O, S) + CH 3 Y (Y=F, Cl, Br) span nearly the whole range of S N 2 pathways, and show an intrinsic reaction coordinate (IRC) (minimum energy path) with a deep well owing to the CH 3 XH⋅⋅⋅Y - (or CH 3 S - ⋅⋅⋅HF) hydrogen-bonded postreaction complex. MP2 quasiclassical-type direct dynamics starting at the [HX⋅⋅⋅CH 3 ⋅⋅⋅Y] - transition-state (TS) structure reveal distinct mechanistic behaviors. Trajectories that yield the separated CH 3 XH+Y - (or CH 3 S - +HF) products directly are non-IRC, whereas those that sample the CH 3 XH⋅⋅⋅Y - (or CH 3 S - ⋅⋅⋅HF) complex are IRC. The IRCIRC/non-IRC ratios of 90:10, 40:60, 25:75, 2:98, 0:100, and 0:100 are obtained for (X, Y)=(S, F), (O, F), (S, Cl), (S, Br), (O, Cl), and (O, Br), respectively. The properties of the energy profiles after the TS cannot provide a rationalization of these results. Analysis of the energy flow in dynamics shows that the trajectories cross a dynamical bifurcation, and that the inability to follow the minimum energy path arises from long vibration periods of the X-C⋅⋅⋅Y bending mode. The partition of the available energy to the products into vibrational, rotational, and translational energies reveals that if the vibrational contribution is more than 80 %, non-IRC behavior dominates, unless the relative fraction of the rotational and translational components is similar, in which case a richer dynamical mechanism is shown, with an IRC/non-IRC ratio that correlates to this relative fraction. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Atomic contributions from spin-orbit coupling to 29Si NMR chemical shifts in metallasilatrane complexes.

PubMed

Autschbach, Jochen; Sutter, Kiplangat; Truflandier, Lionel A; Brendler, Erica; Wagler, Jörg

2012-10-01

New members of a novel class of metallasilatrane complexes [X-Si-(μ-mt)(4)-M-Y], with M=Ni, Pd, Pt, X=F, Cl, Y=Cl, Br, I, and mt=2-mercapto-1-methylimidazolide, have been synthesized and characterized structurally by X-ray diffraction and by (29)Si solid-state NMR. Spin-orbit (SO) effects on the (29)Si chemical shifts induced by the metal, by the sulfur atoms in the ligand, and by heavy halide ligands Y=Cl, Br, I were investigated with the help of relativistic density functional calculations. Operators used in the calculations were constructed such that SO coupling can selectively be switched off for certain atoms. The unexpectedly large SO effects on the (29)Si shielding in the Ni complex with X=Y=Cl reported recently originate directly from the Ni atom, not from other moderately heavy atoms in the complex. With respect to Pd, SO effects are amplified for Ni owing to its smaller ligand-field splitting, despite the smaller nuclear charge. In the X=Cl, Y=Cl, Br, I series of complexes the Y ligand strongly modulates the (29)Si shift by amplifying or suppressing the metal SO effects. The pronounced delocalization of the partially covalent M←Y bond plays an important role in modulating the (29)Si shielding. We also demonstrate an influence from the X ligand on the (29)Si SO shielding contributions originating at Y. The NMR spectra for [X-Si-(μ-mt)(4)-M-Y] must be interpreted mainly based on electronic and relativistic effects, rather than structural differences between the complexes. The results highlight the sometimes unintuitive role of SO coupling in NMR spectra of complexes containing heavy atoms. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Halocarbon emissions by selected tropical seaweeds: species-specific and compound-specific responses under changing pH.

PubMed

Mithoo-Singh, Paramjeet Kaur; Keng, Fiona S-L; Phang, Siew-Moi; Leedham Elvidge, Emma C; Sturges, William T; Malin, Gill; Abd Rahman, Noorsaadah

2017-01-01

Five tropical seaweeds, Kappaphycus alvarezii (Doty) Doty ex P.C. Silva, Padina australis Hauck, Sargassum binderi Sonder ex J. Agardh (syn. S. aquifolium (Turner) C. Agardh), Sargassum siliquosum J. Agardh and Turbinaria conoides (J. Agardh) Kützing, were incubated in seawater of pH 8.0, 7.8 (ambient), 7.6, 7.4 and 7.2, to study the effects of changing seawater pH on halocarbon emissions. Eight halocarbon species known to be emitted by seaweeds were investigated: bromoform (CHBr 3 ), dibro-momethane (CH 2 Br 2 ), iodomethane (CH 3 I), diiodomethane (CH 2 I 2 ), bromoiodomethane (CH 2 BrI), bromochlorometh-ane (CH 2 BrCl), bromodichloromethane (CHBrCl 2 ), and dibro-mochloromethane (CHBr 2 Cl). These very short-lived halocarbon gases are believed to contribute to stratospheric halogen concentrations if released in the tropics. It was observed that the seaweeds emit all eight halocarbons assayed, with the exception of K. alvarezii and S. binderi for CH 2 I 2 and CH 3 I respectively, which were not measurable at the achievable limit of detection. The effect of pH on halocarbon emission by the seaweeds was shown to be species-specific and compound specific. The highest percentage changes in emissions for the halocarbons of interest were observed at the lower pH levels of 7.2 and 7.4 especially in Padina australis and Sargassum spp., showing that lower seawater pH causes elevated emissions of some halocarbon compounds. In general the seaweed least affected by pH change in terms of types of halocarbon emission, was P. australis . The commercially farmed seaweed K. alvarezii was very sensitive to pH change as shown by the high increases in most of the compounds in all pH levels relative to ambient. In terms of percentage decrease in maximum quantum yield of photosynthesis ( F v ∕ F m ) prior to and after incubation, there were no significant correlations with the various pH levels tested for all seaweeds. The correlation between percentage decrease in the maximum quantum yield of photosynthesis ( F v ∕ F m ) and halocarbon emission rates, was significant only for CH 2 BrCl emission by P. australis ( r  = 0.47; p  ≤ 0.04), implying that photosynthesis may not be closely linked to halocarbon emissions by the seaweeds studied. Bromine was the largest contributor to the total mass of halogen emitted for all the seaweeds at all pH. The highest total amount of bromine emitted by K. alvarezii (an average of 98% of total mass of halogens) and the increase in the total amount of chlorine with decreasing seawater pH fuels concern for the expanding seaweed farming activities in the ASEAN region.

Cooperative and diminutive unusual weak bonding in F3CX···HMgH···Y and F3CX···Y···HMgH trimers (X = Cl, Br; Y = HCN, and HNC).

PubMed

Solimannejad, Mohammad; Malekani, Masumeh; Alkorta, Ibon

2010-11-18

MP2 calculations with cc-pVTZ basis set were used to analyze intermolecular interactions in F(3)CX···HMgH···Y and F(3)CX···Y···HMgH triads (X = Cl, Br; Y = HCN, and HNC) which are connecting with three kinds of unusual weak interactions, namely halogen-hydride, dihydrogen, and σ-hole. To understand the properties of the systems better, the corresponding dyads are also studied. Molecular geometries, binding energies, and infrared spectra of monomers, dyads, and triads were investigated at the MP2/cc-pVTZ computational level. Particular attention is given to parameters such as cooperative energies, cooperative dipole moments, and many-body interaction energies. Those complexes with simultaneous presence of a σ-hole bond and a dihydrogen bond show cooperativity energy ranging between -1.02 and -2.31 kJ mol(-1), whereas those with a halogen-hydride bond and a dihydrogen bond are diminutive, with this energetic effect between 0.1 and 0.63 kJ mol(-1). The electronic properties of the complexes have been analyzed using the molecular electrostatic potential (MEP), the electron density shift maps, and the parameters derived from the atoms in molecules (AIM) methodology.

Benchmark ab Initio Characterization of the Complex Potential Energy Surfaces of the X- + NH2Y [X, Y = F, Cl, Br, I] Reactions.

PubMed

Hajdu, Bálint; Czakó, Gábor

2018-02-22

We report a comprehensive high-level explicitly correlated ab initio study on the X - + NH 2 Y [X,Y = F, Cl, Br, I] reactions characterizing the stationary points of the S N 2 (Y - + NH 2 X) and proton-transfer (HX + NHY - ) pathways as well as the reaction enthalpies of various endothermic additional product channels such as H - + NHXY, XY - + NH 2 , XY + NH 2 - , and XHY - + NH. Benchmark structures and harmonic vibrational frequencies are obtained at the CCSD(T)-F12b/aug-cc-pVTZ(-PP) level of theory, followed by CCSD(T)-F12b/aug-cc-pVnZ(-PP) [n = Q and 5] and core correlation energy computations. In the entrance and exit channels we find two equivalent hydrogen-bonded C 1 minima, X - ···HH'NY and X - ···H'HNY connected by a C s first-order saddle point, X - ···H 2 NY, as well as a halogen-bonded front-side complex, X - ···YNH 2 . S N 2 reactions can proceed via back-side attack Walden inversion and front-side attack retention pathways characterized by first-order saddle points, submerged [X-NH 2 -Y] - and high-energy [H 2 NXY] - , respectively. Product-like stationary points below the HX + NHY - asymptotes are involved in the proton-transfer processes.

UV photolysis of 4-iodo-, 4-bromo-, and 4-chlorophenol: competition between C-Y (Y = halogen) and O-H bond fission.

PubMed

Sage, Alan G; Oliver, Thomas A A; King, Graeme A; Murdock, Daniel; Harvey, Jeremy N; Ashfold, Michael N R

2013-04-28

The wavelength dependences of C-Y and O-H bond fission following ultraviolet photoexcitation of 4-halophenols (4-YPhOH) have been investigated using a combination of velocity map imaging, H Rydberg atom photofragment translational spectroscopy, and high level spin-orbit resolved electronic structure calculations, revealing a systematic evolution in fragmentation behaviour across the series Y = I, Br, Cl (and F). All undergo O-H bond fission following excitation at wavelengths λ ≲ 240 nm, on repulsive ((n∕π)σ∗) potential energy surfaces (PESs), yielding fast H atoms with mean kinetic energies ∼11,000 cm(-1). For Y = I and Br, this process occurs in competition with prompt C-I and C-Br bond cleavage on another (n∕π)σ∗ PES, but no Cl∕Cl∗ products unambiguously attributable to one photon induced C-Cl bond fission are observed from 4-ClPhOH. Differences in fragmentation behaviour at longer excitation wavelengths are more marked. Prompt C-I bond fission is observed following excitation of 4-IPhOH at all λ ≤ 330 nm; the wavelength dependent trends in I∕I∗ product branching ratio, kinetic energy release, and recoil anisotropy suggest that (with regard to C-I bond fission) 4-IPhOH behaves like a mildly perturbed iodobenzene. Br atoms are observed when exciting 4-BrPhOH at long wavelengths also, but their velocity distributions suggest that dissociation occurs after internal conversion to the ground state. O-H bond fission, by tunnelling (as in phenol), is observed only in the cases of 4-FPhOH and, more weakly, 4-ClPhOH. These observed differences in behaviour can be understood given due recognition of (i) the differences in the vertical excitation energies of the C-Y centred (n∕π)σ∗ potentials across the series Y = I < Br < Cl and the concomitant reduction in C-Y bond strength, cf. that of the rival O-H bond, and (ii) the much increased spin-orbit coupling in, particularly, 4-IPhOH. The present results provide (another) reminder of the risks inherent in extrapolating photochemical behaviour measured for one molecule at one wavelength to other (related) molecules and to other excitation energies.

The subtle balance of weak supramolecular interactions: The hierarchy of halogen and hydrogen bonds in haloanilinium and halopyridinium salts.

PubMed

Raatikainen, Kari; Cametti, Massimo; Rissanen, Kari

2010-01-15

THE SERIES OF HALOANILINIUM AND HALOPYRIDINIUM SALTS: 4-IPhNH₃Cl (1), 4-IPhNH₃Br (5), 4-IPhNH₃H₂PO₄ (6), 4-ClPhNH₃H₂PO₄ (8), 3-IPyBnCl (9), 3-IPyHCl (10) and 3-IPyH-5NIPA (3-iodopyridinium 5-nitroisophthalate, 13), where hydrogen or/and halogen bonding represents the most relevant non-covalent interactions, has been prepared and characterized by single crystal X-ray diffraction. This series was further complemented by extracting some relevant crystal structures: 4-BrPhNH₃Cl (2, CCDC ref. code TAWRAL), 4-ClPhNH₃Cl (3, CURGOL), 4-FPhNH₃Cl (4, ANLCLA), 4-BrPhNH₃H₂PO₄, (7, UGISEI), 3-BrPyHCl, (11, CIHBAX) and 3-ClPyHCl, (12, VOQMUJ) from Cambridge Structural Database for sake of comparison. Based on the X-ray data it was possible to highlight the balance between non-covalent forces acting in these systems, where the relative strength of the halogen bonding C-X...A⁻ (X = I, Br or Cl) and the ratio between the halogen and hydrogen bonds [C-X...A⁻ : D-H...A⁻] varied across the series.

Relaxation-phenomena in LiAl/FeS-cells

NASA Astrophysics Data System (ADS)

Borger, W.; Kappus, W.; Panesar, H. S.

A theoretical model of the capacity of strongly relaxing electrochemical systems is applied to the LiAl/FeS system. Relaxation phenomena in LiAl and FeS electrodes can be described by this model. Experimental relaxation data indicate that lithium transport through the alpha-LiAl layer to the particle surface is the capacity limiting process at high discharge current density in the LiAl electrode in LiCl-KCl and LiF-LiCl-LiBr mixtures. Strong relaxation is observed in the FeS electrode with LiCl-KCl electrolyte caused by lithium concentration gradients and precipitation of KCl in the pores.

Magneto-structural correlations in dirhenium(iv) complexes possessing magnetic pathways with even or odd numbers of atoms.

PubMed

Pedersen, Anders H; Julve, Miguel; Martínez-Lillo, José; Cano, Joan; Brechin, Euan K

2017-09-12

The employment of pyrazine (pyz), pyrimidine (pym) and s-triazine (triz) ligands in Re IV chemistry leads to the isolation of a family of complexes of general formula (NBu 4 ) 2 [(ReX 5 ) 2 (μ-L)] (L = pyz, X = Cl (1) or Br (2); L = pym, X = Br (3); L = triz, X = Br (4)). 1-4 are dinuclear compounds where two pentahalorhenium(iv) fragments are connected by bidentate pyz, pym and triz ligands. Variable-temperature magnetic measurements, in combination with detailed theoretical studies, uncover the underlying magneto-structural correlation whereby the nature of the exchange between the metal ions is dictated by the number of intervening atoms. That is, the spin-polarization mechanism present dictates that odd and even numbers of atoms favour ferromagnetic (F) and antiferromagnetic (AF) exchange interactions, respectively. Hence, while the pyz ligand in 1 and 2 mediates AF coupling, the pym and triz ligands in 3 and 4 promote F interactions.

Molecular orbital analysis of the inverse halogen dependence of nuclear magnetic shielding in LaX₃, X = F, Cl, Br, I.

PubMed

Moncho, Salvador; Autschbach, Jochen

2010-12-01

The NMR nuclear shielding tensors for the series LaX(3), with X = F, Cl, Br and I, have been computed using two-component relativistic density functional theory based on the zeroth-order regular approximation (ZORA). A detailed analysis of the inverse halogen dependence (IHD) of the La shielding was performed via decomposition of the shielding tensor elements into contributions from localized and delocalized molecular orbitals. Both spin-orbit and paramagnetic shielding terms are important, with the paramagnetic terms being dominant. Major contributions to the IHD can be attributed to the La-X bonding orbitals, as well as to trends associated with the La core and halogen lone pair orbitals, the latter being related to X-La π donation. An 'orbital rotation' model for the in-plane π acceptor f orbital of La helps to rationalize the significant magnitude of deshielding associated with the in-plane π donation. The IHD goes along with a large increase in the shielding tensor anisotropy as X becomes heavier, which can be associated with trends for the covalency of the La-X bonds, with a particularly effective transfer of spin-orbit coupling induced spin density from iodine to La in LaI(3). Copyright © 2010 John Wiley & Sons, Ltd.

Ab Initio Characterization of Triatomic Bromine Molecules of Potential Interest in Stratospheric Chemistry

NASA Technical Reports Server (NTRS)

Lee, Timothy J.

1995-01-01

The equilibrium structures, harmonic vibrational frequencies, quadratic force fields, dipole moments, and IR intensities of several triatomic bromine compounds of known or potential importance in stratospheric ozone depletion chemistry have been determined using the CCSD(T) electron correlation method in conjunction with a basis set of triple zeta double polarized (TZ2P) quality. Specifically, the molecules included in the present study are HOBr, HBrO, FOBr, FBrO, BrNO, BrON, Br2O, BrBrO, BrCN, BrNC, ClOBr, ClBrO, and BrClO. Very accurate isomeric energy differences have also been determined at the CCSD(T) level with atomic natural orbital basis sets that include through g-type functions. In most cases, the isomer with a normal neutral Lewis dot structure is the lowest energy form, with the single exception that FBrO is predicted to be 11.1 kcal/mol (0 K) lower in energy than FOBr. In all cases, however, the hypervalent isomer is more stable relative to the isomer with a normal Lewis dot structure as compared to the chlorine analogs. Consistent with this observation, the energy of the last three molecules given above increases in the order ClOBr less than ClBrO less than BrClO. The CCSD(T)/TZ2P geometries and vibrational frequencies are in good agreement with the available experimental data. Heats of formation are determined for all species using a combination of theoretical isomeric, homodesmic, and isodesmic reaction energies. The accuracy of these quantities is ultimately dependent on the reliability of the experimental heat of formation of HOBr.

Ab Initio Characterization of Triatomic Bromine Molecules of Potential Interest in Stratospheric Chemistry

NASA Technical Reports Server (NTRS)

Lee. Timothy J.

1995-01-01

The equilibrium structures, harmonic vibrational frequencies, quadratic force fields, dipole moments, and IR intensities of several triatomic bromine compounds of known or potential importance in stratospheric ozone depletion chemistry have been determined using the CCSD(T) electron correlation method in conjunction with a basis set of triple zeta double polarized (TZ2P) quality. Specifically, the molecules included in the present study are HOBr, HBrO, FOBr, FBrO, BrNO, BrON, Br2O, BrBrO, BrCN, BrNC, ClOBr, ClBrO, and BrClO. Very accurate isomeric energy differences have also been determined at the CCSD(T) level with atomic natural orbital basis sets that include through g-type functions. In most cases, the isomer with a normal neutral Lewis dot structure is the lowest energy form, with the single exception that FBRO is predicted to be 11.1 kcal/mol (0 K) lower in energy than FOBr. In all cases, however, the hypervalent isomer is more stable relative to the isomer with a normal Lewis dot structure as compared to the chlorine analogs. Consistent with this observation, the energy of the last three molecules given above increases in the order ClOBr less than ClBrO less than BrClO. The CCSD(T)/TZ2P geometries and vibrational frequencies are in good agreement with the available experimental data. Heats of formation are determined for all species using a combination of theoretical isomeric, homodesmic, and isodesmic reaction energies. The accuracy of these quantities is ultimately dependent on the reliability of the experimental heat of formation of HOBr.

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

NASA Technical Reports Server (NTRS)

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

1997-01-01

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

Larger spontaneous polarization ferroelectric inorganic-organic hybrids: [PbI3](infinity) chains directed organic cations aggregation to Kagomé-shaped tubular architecture.

PubMed

Zhao, Hai-Rong; Li, Dong-Ping; Ren, Xiao-Ming; Song, You; Jin, Wan-Qin

2010-01-13

Four isostructural inorganic-organic hybrid ferroelectric compounds, assembled from achiral 3-R-benzylidene-1-aminopyridiniums (R = NO(2), Br, Cl, or F for 1-4, respectively) and [PbI(3)](-) anions with the chiral Kagomé-shaped tubular aggregating architecture, show larger spontaneous polarizations.

Specific anion binding to sulfobetaine micelles and kinetics of nucleophilic reactions.

PubMed

Marte, Luisa; Beber, Rosane C; Farrukh, M Akhyar; Micke, Gustavo A; Costa, Ana C O; Gillitt, Nicholas D; Bunton, Clifford A; Di Profio, Pietro; Savelli, Gianfranco; Nome, Faruk

2007-08-23

With fully micellar bound substrates reactions of OH- with benzoic anhydride, Bz(2)O, and of Br- with methyl naphthalene-2-sulfonate, MeONs, in micellized sulfobetaines are strongly inhibited by NaClO4 which displaces the nucleophilic anions from the micellar pseudophases. Micellar incorporations of ClO4- and Br- are estimated with an ion-selective electrode and by electrophoresis, and partitioning of Br- between water and micelles is related to changes in NMR spectral (79)Br- line widths. Extents of inhibition by ClO4- of these nucleophilic reactions in the micellar pseudophase are related to quantitative displacement of the reactive anions from the micelles by ClO4-. The kinetic data are correlated with physical evidence on the strong interactions between sulfobetaines and ClO4-, which turn sulfobetaine micelles anionic and effectively provoke displacement of OH- and Br-.

The use of functionalized zirconocenes as precursors to silica-supported zirconocene olefin polymerization catalysts

NASA Astrophysics Data System (ADS)

Cheng, Xu

2001-07-01

Me3Si substituents adjacent to Cp2MCl2 (M = Ti, Zr, Hf) are converted to BrMe2Si groups using BBr 3. The high reactivity of the Si-Br bonds toward nucleophiles such as water suggested that these substituents could react with hydroxylated silica surfaces, immobilizing the metallocenes. This dissertation concerns the syntheses of electrophile-functionalized zirconocene dihalide complexes and their use as precursors to silica-supported metallocene olefin polymerization catalysts. First we extended the metallocene "functionalization" chemistry to obtain substituents bearing more than one electrophilic bond. (Me3Sn) 2C5H4 combined with CpZrCl3 in toluene to afford (eta5-Me3Sn-C5H4)CpZrCl 2 (A). Reactions of A with electrophiles (E-X = Cl2B-Cl, I-Cl, and I-I) afforded (eta5-XMe 2Sn-C5H4)CpZrCl2 (and E-Me) cleanly. The reaction of A with BBr3 afforded either (eta5-BrMe2Sn-C5H4)CpZrBr2 (25 °C, 10 min) or (eta5-Br2MeSn-C5H 4)CpZrBr2 (25 °C, 15 h). Ph2MeSi-C5H 4Li combined with ZrCl4•2THF to afford (eta 5-Ph2MeSi-C5H4)2ZrCl 2 (B). The reaction of B with BCl3 led to incomplete cleavage of the Ph-Si bonds, however treatment of B with BBr3 afforded (eta5-Br2MeSi-C 5H4)2ZrBr2 (C) efficiently. X-ray crystal structures of (eta5-ClMe2Sn-C 5H4)CpZrCl2•1/2toluene, (eta 5-Br2MeSn-C5H4)CpZrBr2•THF, B, and C were obtained. Metallocene C reacts with water to afford an oligosiloxane-supported zirconocene dibromide. Spectroscopic characterization suggested a stereoregular structure in which the metallocene units have meso symmetry. The oligomeric substance showed high activity for homogeneous ethylene polymerization. Supported metallocene olefin polymerization catalysts were prepared by combining a functionalized metallocene precursor (Cp2ZrBr 2 bearing either BrMe2Si or Br2MeSi groups) and partially dehydroxylated silica. The activities of the immobilized zirconocene catalysts decreased and the stabilities increased with increasing number of tethers. The immobilized catalyst prepared from (eta5-Br 2MeSi-C5H4)2ZrBr2, which is assumed to form two "double-tethers" to silica, was significantly more active than the catalyst prepared from [eta5-1,3-(BrMe 2Si)2C5H3]2ZrBr2, which is assumed to form four "single-tethers" to silica. Catalyst leaching was observed in all the immobilized zirconocene catalysts. Finally we report model studies on the stability of the Si-O-Si bonds toward methylaluminoxane (MAO). The reaction of (eta5-BrMe 2Si-C5H4)CpZrBr2 with tBuMe 2SiOH results in the formation of Si-O-Si bonds; addition of NEt 3 results in further reaction to afford Si-O-Zr bonds. The reaction of Me3Si-O-SiMe3 with MAO showed that Si-O-Si bonds can be cleaved under the conditions of our polymerization reactions.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Nakazaki, Nobuya, E-mail: nakazaki.nobuya.58x@st.kyoto-u.ac.jp; Takao, Yoshinori; Eriguchi, Koji

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

Unveiling the Shape Evolution and Halide-Ion-Segregation in Blue-Emitting Formamidinium Lead Halide Perovskite Nanocrystals Using an Automated Microfluidic Platform.

PubMed

Lignos, Ioannis; Protesescu, Loredana; Emiroglu, Dilara Börte; Maceiczyk, Richard; Schneider, Simon; Kovalenko, Maksym V; deMello, Andrew J

2018-02-14

Hybrid organic-inorganic perovskites and in particular formamidinium lead halide (FAPbX 3 , X = Cl, Br, I) perovskite nanocrystals (NCs) have shown great promise for their implementation in optoelectronic devices. Specifically, the Br and I counterparts have shown unprecedented photoluminescence properties, including precise wavelength tuning (530-790 nm), narrow emission linewidths (<100 meV) and high photoluminescence quantum yields (70-90%). However, the controlled formation of blue emitting FAPb(Cl 1-x Br x ) 3 NCs lags behind their green and red counterparts and the mechanism of their formation remains unclear. Herein, we report the formation of FAPb(Cl 1-x Br x ) 3 NCs with stable emission between 440 and 520 nm in a fully automated droplet-based microfluidic reactor and subsequent reaction upscaling in conventional laboratory glassware. The thorough parametric screening allows for the elucidation of parametric zones (FA-to-Pb and Br-to-Cl molar ratios, temperature, and excess oleic acid) for the formation of nanoplatelets and/or NCs. In contrast to CsPb(Cl 1-x Br x ) 3 NCs, based on online parametric screening and offline structural characterization, we demonstrate that the controlled synthesis of Cl-rich perovskites (above 60 at% Cl) with stable emission remains a challenge due to fast segregation of halide ions.

A theoretical investigation on Cu/Ag/Au bonding in XH2P⋯MY(X = H, CH3, F, CN, NO2; M = Cu, Ag, Au; Y = F, Cl, Br, I) complexes

NASA Astrophysics Data System (ADS)

Wang, Zhaoxu; Liu, Yi; Zheng, Baishu; Zhou, Fengxiang; Jiao, Yinchun; Liu, Yuan; Ding, XunLei; Lu, Tian

2018-05-01

Intermolecular interaction of XH2P...MY (X = H, CH3, F, CN, NO2; M = Cu, Ag, Au; Y = F, Cl, Br, I) complexes was investigated by means of an ab initio method. The molecular interaction energies are in the order Ag < Cu < Au and increased with the decrease of RP...M. Interaction energies are strengthened when electron-donating substituents X connected to XH2P, while electron-withdrawing substituents produce the opposite effect. The strongest P...M bond was found in CH3H2P...AuF with -70.95 kcal/mol, while the weakest one was found in NO2H2P...AgI with -20.45 kcal/mol. The three-center/four-electron (3c/4e) resonance-type of P:-M-:Y hyperbond was recognized by the natural resonance theory and the natural bond orbital analysis. The competition of P:M-Y ↔ P-M:Y resonance structures mainly arises from hyperconjugation interactions; the bond order of bP-M and bM-Y is in line with the conservation of the idealized relationship bP-M + bM-Y ≈ 1. In all MF-containing complexes, P-M:F resonance accounted for a larger proportion which leads to the covalent characters for partial ionicity of MF. The interaction energies of these Cu/Ag/Au complexes are basically above the characteristic values of the halogen-bond complexes and close to the observed strong hydrogen bonds in ionic hydrogen-bonded species.

In-situ Cl/Br measurements in scapolite and fluid inclusions by LA-ICP-MS: A powerful tool to constrain fluid sources

NASA Astrophysics Data System (ADS)

Hammerli, J.; Rusk, B.; Spandler, C.; Oliver, N. H. S.; Emsbo, P.

2012-04-01

Chlorine and bromine are highly conservative elements, and are therefore widely used to trace the origin of fluids in sedimentary and hydrothermal/magmatic systems (e.g. Hanor & McIntosh, 2007; Nahnybida et al., 2009). Halogens are important ligands for metal transport in hydrothermal solutions and thus their behavior in hydrothermal environments is crucial for comprehending ore-forming processes. Besides fluid inclusions, scapolite-group minerals hold great potential as a tracer of igneous, metamorphic, and hydrothermal processes, as no Cl/Br fractionation in scapolite has been observed and therefore halogen ratios in scapolite are thought to mirror the halogen ratios in coexisting melts and fluids (Pan & Dong, 2003). Hence, Cl/Br ratios in fluid inclusions and minerals can be utilized to trace the origin of fluids and fluid-rock interaction pathways. Due to their high ionization energies, bromine and chlorine are not routinely measured by LA-ICP-MS and suitable standards are rare. Little is known about the potential interferences and analytical limitations of in-situ chlorine and bromine analysis by LA-ICP-MS. Nevertheless, Seo et al. (2011) showed that quantification of Br and Cl in single synthetic and natural fluid inclusions is possible. In this study, we have analyzed several scapolite grains of known bromine and chlorine concentrations by LA-ICP-MS and assess the capabilities and limitations of this method. The results show that Cl/Br ratios measured by LA-ICP-MS closely reproduce known values determined by microprobe (Cl), the Noble Gas Method (Br) and INAA (Br) (Kendrick, 2011; Lieftink et al., 1993) using laser ablation spot sizes from 24-120 μm. The well-characterized scapolite grains cover bromine concentrations from 50-883 ppm and chlorine concentrations from 3 to 4 wt.%. In order to further assess the method, we analyzed Cl/Br ratios in natural fluid inclusions hosted in sphalerite that were previously characterized by crush and leach ion chromatography. This is the first time that bulk crush and leach Cl/Br analyses can be compared with Cl/Br ratios within individual fluid inclusions. Our LA-ICP-MS measurements are in good agreement with bulk crush and leach analyses. For instance, molar Cl/Br ratios of single fluid inclusions (183±33) in sphalerite form East Tennessee match those obtained by crush and leach (206±8) Additionally, scapolite in samples from dykes of the Burstall granite, associated banded skarns and metasediments from the Mary Kathleen Fold Belt, Queensland, Australia are being studied. Scapolite is highly luminescent and therefore, cathodoluminescence images resolve chemical zoning in scapolite group minerals that, in combination with in-situ Cl/Br analyses, is a powerful tool to better understand fluid sources and fluid-rock interaction within various geological environments.

A novel coumarin-pyrazole-triazine based fluorescence chemosensor for fluoride detection via deprotonation process: Experimental and theoretical studies

NASA Astrophysics Data System (ADS)

Yalçın, Ergin; Alkış, Meltem; Seferoğlu, Nurgül; Seferoğlu, Zeynel

2018-03-01

A novel fluorescence coumarin-pyrazole-triazine based chemosensor (CPT) bearing 5-hydroxypyrazole as a receptoric part was synthesized and characterized by using IR, 1H/13C NMR and HRMS for the purpose of recognition of anions in DMSO. The most stable tautomeric form of CPT was determined by experimental techniques and theoretical calculations. The selectivity and sensitivity of CPT towards anions (CN-, F-, Cl-, Br-, I-, AcO-, HSO4-, H2PO4- and ClO4-) were determined using spectrophotometric and 1H NMR titration techniques as the experimental approach, and the results were explained by employing theoretical calculations. It was found to be suitable for the selective detection of F- in the presence of CN- and AcO- as competing anions. In addition, CPT exhibits significant "light-up" effect after interaction with TFA in CH2Cl2.

Silver Complexes of Dihalogen Molecules.

PubMed

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

2016-08-01

The perfluorohexane-soluble and donor-free silver compound Ag(A) (A=Al(OR(F) )4 ; R(F) =C(CF3 )3 ) prepared using a facile novel route has unprecedented capabilities to form unusual and weakly bound complexes. Here, we report on the three dihalogen-silver complexes Ag(Cl2 )A, Ag(Br2 )A, and Ag(I2 )A derived from the soluble silver compound Ag(A) (characterized by single-crystal/powder XRD, Raman spectra, and quantum-mechanical calculations). © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Tuning of chain chirality by interchain stacking forces and the structure-property relationship in coordination systems constructed by meridional FeIII cyanide and MnIII Schiff bases.

PubMed

Sohn, Ah Ram; Lim, Kwang Soo; Kang, Dong Won; Song, Jeong Hwa; Koh, Eui Kwan; Moon, Dohyun; Hong, Chang Seop

2016-12-06

We synthesized six Fe(iii)-Mn(iii) bimetallic compounds by self-assembling the newly developed mer-Fe cyanide PPh 4 [Fe(Clqpa)(CN) 3 ]·H 2 O (1) and PPh 4 [Fe(Brqpa)(CN) 3 ]·H 2 O (2) with Mn Schiff base Mn(5-Xsalen) + cations. These compounds include [Fe(Xqpa)(CN) 3 ][Mn(5-Ysalen)]·pMeOH·qH 2 O [qpaH 2 = N-(quinolin-8-yl)picolinamide; salen = N,N'-ethylenebis(salicylideneiminato) dianion; X = Cl, Y = H (3); X = Cl, Y = Br (4); X = Br, Y = H (5); X = Br, Y = F (6); X = Br, Y = Cl (7); X = Br, Y = Br (8)]. When precursor 1 was used, compounds 3 and 4 were isolated to give a dinuclear entity and a linear chain structure, respectively. The reaction of precursor 2 with the Schiff bases afforded four linear Fe(iii)-Mn(iii) chain complexes. Chain chirality with P- and M-helicity emerges in 4, 7, and 8, while 5 exhibits chain helicity opposite to the previous chain complexes and 6 presents no chain helicity. Such a structural feature is heavily dependent on the interchain π-π contacts and the Fe precursor bridging unit. Chiral induction from a local ethylenediamine link of Y-salen is propagated over the chain via noncovalent π-π interactions. All the bimetallic compounds show antiferromagnetic interactions transmitted by the cyanide linkage. A field-induced metamagnetic transition is involved in 4, 7, and 8, while a field-induced two-step transition is evident in 6. From a magnetostructural viewpoint, the coupling constant is primarily governed by the Mn-N ax -C ax angle (ax = axial) in the bimetallic chain complexes composed of mer-Fe(iii) tricyanides, although the torsion angle plays a role.

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

USGS Publications Warehouse

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

2013-01-01

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

Two-Dimensional Large Gap Topological Insulators with Tunable Rashba Spin-Orbit Coupling in Group-IV films

PubMed Central

Zhang, Shou-juan; Ji, Wei-xiao; Zhang, Chang-wen; Li, Ping; Wang, Pei-ji

2017-01-01

The coexistence of nontrivial topology and giant Rashba splitting, however, has rare been observed in two-dimensional (2D) films, limiting severely its potential applications at room temperature. Here, we through first-principles calculations to propose a series of inversion-asymmetric group-IV films, ABZ2 (A ≠ B = Si, Ge, Sn, Pb; Z = F, Cl, Br), whose stability are confirmed by phonon spectrum calculations. The analyses of electronic structures reveal that they are intrinsic 2D TIs with a bulk gap as large as 0.74 eV, except for GeSiF2, SnSiCl2, GeSiCl2 and GeSiBr2 monolayers which can transform from normal to topological phases under appropriate tensile strain of 4, 4, 5, and 4%, respectively. The nontrivial topology is identified by Z2 topological invariant together with helical edge states, as well as the berry curvature of these systems. Another prominent intriguing feature is the giant Rashba spin splitting with a magnitude reaching 0.15 eV, the largest value reported in 2D films so far. The tunability of Rashba SOC and band topology can be realized through achievable compressive/tensile strains (−4 ~ 6%). Also, the BaTe semiconductor is an ideal substrate for growing ABZ2 films without destroying their nontrivial topology. PMID:28368035

Laboratory determination of the carbon kinetic isotope effects (KIEs) for reactions of methyl halides with various nucleophiles in solution

USGS Publications Warehouse

Baesman, S.M.; Miller, L.G.

2005-01-01

Large carbon kinetic isotope effects (KIEs) were measured for reactions of methyl bromide (MeBr), methyl chloride (MeCl), and methyl iodide (MeI) with various nucleophiles at 287 and 306 K in aqueous solutions. Rates of reaction of MeBr and MeI with H2O (neutral hydrolysis) or Cl- (halide substitution) were consistent with previous measurements. Hydrolysis rates increased with increasing temperature or pH (base hydrolysis). KIEs for hydrolysis were 51 ?? 6??? for MeBr and 38 ?? 8??? for MeI. Rates of halide substitution increased with increasing temperature and greater reactivity of the attacking nucleophile, with the fastest reaction being that of MeI with Br-. KIEs for halide substitution were independent of temperature but varied with the reactant methyl halide and the attacking nucleophile. KIEs were similar for MeBr substitution with Cl- and MeCl substitution with Br- (57 ?? 5 and 60 ?? 9??? respectively). The KIE for halide exchange of MeI was lower overall (33 ?? 8??? and was greater for substitution with Br- (46 ?? 6???) than with Cl- (29 ?? 6???). ?? Springer Science + Business Media, Inc. 2005.

Investigations of the Rg-BrCl (Rg = He, Ne, Ar, Kr, Xe) binary van der Waals complexes: ab initio intermolecular potential energy surfaces, vibrational states and predicted pure rotational transition frequencies

NASA Astrophysics Data System (ADS)

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

2017-03-01

The intermolecular potential energy surfaces (PESs) of the ground electronic state for the Rg-BrCl (Rg = He, Ne, Ar, Kr, Xe) van der Waals complexes have been constructed by using the coupled-cluster method in combination with the augmented quadruple-zeta correlation-consistent basis sets supplemented with an additional set of bond functions. The features of the anisotropic PESs for these complexes are remarkably similar, which are characterized by three minima and two saddle points between them. The global minimum corresponds to a collinear Rg-Br-Cl configuration. Two local minima, correlate with an anti-linear Rg-Cl-Br geometry and a nearly T-shaped structure, can also be located on each PES. The quantum bound state calculations enable us to investigate intermolecular vibrational states and rotational energy levels of the complexes. The transition frequencies are predicted and are fitted to obtain their corresponding spectroscopic constants. In general, the periodic trends are observed for this complex family. Comparisons with available experimental data for the collinear isomer of Ar-BrCl demonstrate reliability of our theoretical predictions, and our results for the other two isomers of Ar-BrCl as well as for other members of the complex family are also anticipated to be trustable. Except for the collinear isomer of Ar-BrCl, the data presented in this paper would be beneficial to improve our knowledge for these experimentally unknown species.

Diarylhalotelluronium(IV) cations [(8-Me2NC10H6)2TeX]+ (X = Cl, Br, I) stabilized by intramolecularly coordinating N-donor substituents.

PubMed

Beckmann, Jens; Bolsinger, Jens; Duthie, Andrew; Finke, Pamela

2013-09-14

The stoichiometrically controlled halogenation of the intramolecularly coordinated diaryltelluride (8-Me2NC10H6)2Te using SO2Cl2, Br2 and I2 was studied. At an equimolar ratio, the diarylhalotelluronium cations [(8-Me2NC10H6)2TeX](+) (1, X = Cl; 2, X = Br; 3, X = I) formed and were isolated as 1·Cl(-)·H2O·1/2THF, 2·Br(-), and 3·I(-), respectively. When the same reactions were carried out in the presence of KPF6, 1·PF6(-) and 22·Br(-)·PF6(-) were obtained. The chlorination of (8-Me2NC10H6)2Te with an excess of SO2Cl2 occurred with a double electrophilic substitution at the 8-dimethylaminonaphthyl residues (in the ortho- and para-positions) and afforded the diaryltellurium dichloride (5,7-Cl2-8-Me2NC10H4)2TeCl2 (4). The bromination of (8-Me2NC10H6)2Te with three equivalents of Br2 took place with a single electrophilic substitution at the 8-dimethylaminonaphthyl residues (in the para-positions) and provided the diaryltellurium dibromide (5-Br-8-Me2NC10H5)2TeBr2 (5), while an excess of Br2 produced the diarylbromotelluronium cation [(5-Br-8-Me2NC10H5)2TeBr](+) (6) that was isolated as 6·Br3(-). The reaction of (8-Me2NC10H6)2Te with two or three equivalents of iodine provided 3·I3(-) and 3·I3(-)·I2, respectively. In the presence of water, 1·Cl(-)·H2O·1/2THF, 2·Br(-), 3·I(-) and 3·I3(-) hydrolyzed to give the previously known diarylhydroxytelluronium cation [(8-Me2NC10H6)2TeOH](+) (7) that was isolated as 7·Cl(-), 7·Br(-)·H2O·THF, 7·I(-) and 7·I3(-)·H2O, respectively. The molecular structures of 1-7 were investigated in the solid-state by (125)Te MAS NMR spectroscopy and X-ray crystallography and in solution by multinuclear NMR spectroscopy ((1)H, (13)C, (125)Te), electrospray mass spectrometry and conductivity measurements. The stabilization of cations 1-3 by the intramolecular coordination was estimated by DFT calculations at the B3PW91/TZ level of theory.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Li, Chao; Feng, Kai; Tu, Heng

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

Degradation of methyl bromide and methyl chloride in soil microcosms: Use of stable C isotope fractionation and stable isotope probing to identify reactions and the responsible microorganisms

USGS Publications Warehouse

Miller, L.G.; Warner, K.L.; Baesman, S.M.; Oremland, R.S.; McDonald, I.R.; Radajewski, S.; Murrell, J.C.

2004-01-01

Bacteria in soil microcosm experiments oxidized elevated levels of methyl chloride (MeCl) and methyl bromide (MeBr), the former compound more rapidly than the latter. MeBr was also removed by chemical reactions while MeCl was not. Chemical degradation dominated the early removal of MeBr and accounted for more than half of its total loss. Fractionation of stable carbon isotopes during chemical degradation of MeBr resulted in a kinetic isotope effect (KIE) of 59 ?? 7???. Soil bacterial oxidation dominated the later removal of MeBr and MeCl and was characterized by different KIEs for each compound. The KIE for MeBr oxidation was 69 ?? 9??? and the KIE for MeCl oxidation was 49 ?? 3???. Stable isotope probing revealed that different populations of soil bacteria assimilated added 13C-labeled MeBr and MeCl. The identity of the active MeBr and MeCl degrading bacteria in soil was determined by analysis of 16S rRNA gene sequences amplified from 13C-DNA fractions, which identified a number of sequences from organisms not previously thought to be involved in methyl halide degradation. These included Burkholderia , the major clone type in the 13C-MeBr fraction, and Rhodobacter, Lysobacter and Nocardioides the major clone types in the 13C-MeCl fraction. None of the 16S rRNA gene sequences for methyl halide oxidizing bacteria currently in culture (including Aminobacter strain IMB-1 isolated from fumigated soil) were identified. Functional gene clone types closely related to Aminobacter spp. were identified in libraries containing the sequences for the cmuA gene, which codes for the enzyme known to catalyze the initial step in the oxidation of MeBr and MeCl. The cmuA gene was limited to members of the alpha-Proteobacteria whereas the greater diversity demonstrated by the 16S rRNA gene may indicate that other enzymes catalyze methyl halide oxidation in different groups of bacteria. Copyright ?? 2004 Elsevier Ltd.

Degradation of methyl bromide and methyl chloride in soil microcosms: Use of stable C isotope fractionation and stable isotope probing to identify reactions and the responsible microorganisms

NASA Astrophysics Data System (ADS)

Miller, Laurence G.; Warner, Karen L.; Baesman, Shaun M.; Oremland, Ronald S.; McDonald, Ian R.; Radajewski, Stefan; Murrell, J. Colin

2004-08-01

Bacteria in soil microcosm experiments oxidized elevated levels of methyl chloride (MeCl) and methyl bromide (MeBr), the former compound more rapidly than the latter. MeBr was also removed by chemical reactions while MeCl was not. Chemical degradation dominated the early removal of MeBr and accounted for more than half of its total loss. Fractionation of stable carbon isotopes during chemical degradation of MeBr resulted in a kinetic isotope effect (KIE) of 59 ± 7‰. Soil bacterial oxidation dominated the later removal of MeBr and MeCl and was characterized by different KIEs for each compound. The KIE for MeBr oxidation was 69 ± 9‰ and the KIE for MeCl oxidation was 49 ± 3‰. Stable isotope probing revealed that different populations of soil bacteria assimilated added 13C-labeled MeBr and MeCl. The identity of the active MeBr and MeCl degrading bacteria in soil was determined by analysis of 16S rRNA gene sequences amplified from 13C-DNA fractions, which identified a number of sequences from organisms not previously thought to be involved in methyl halide degradation. These included Burkholderia, the major clone type in the 13C-MeBr fraction, and Rhodobacter, Lysobacter and Nocardioides the major clone types in the 13C-MeCl fraction. None of the 16S rRNA gene sequences for methyl halide oxidizing bacteria currently in culture (including Aminobacter strain IMB-1 isolated from fumigated soil) were identified. Functional gene clone types closely related to Aminobacter spp. were identified in libraries containing the sequences for the cmuA gene, which codes for the enzyme known to catalyze the initial step in the oxidation of MeBr and MeCl. The cmuA gene was limited to members of the alpha-Proteobacteria whereas the greater diversity demonstrated by the 16S rRNA gene may indicate that other enzymes catalyze methyl halide oxidation in different groups of bacteria.

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

PubMed

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

2016-06-28

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

Halo-substituted thiosemicarbazones and their copper(II), nickel(II) complexes: Detailed spectroscopic characterization and study of antitumour activity against HepG2 human hepatoblastoma cells

NASA Astrophysics Data System (ADS)

Jagadeesh, M.; Kalangi, Suresh K.; Sivarama Krishna, L.; Reddy, A. Varada

2014-01-01

Copper(II) and nickel(II) complexes of two different halogen substituted thiosemicarbazone ligands were synthesized. The ligands 3,4-difluoroacetophenone thiosemicarbazone (1) and 2-bromo-4'-chloroacetophenone thiosemicarbazone (2) were characterized and confirmed spectroscopically by FT-IR, FT-Raman, UV-vis and fluorescence spectral analysis, while the respective copper(II) complexes [Cu(C9H9N3F2S)2Cl2] (1a), [Cu(C9H9N3ClBrS)2Cl2] (2a) and nickel(II) complexes [Ni(C9H9N3F2S)2] (1b), [Ni(C9H9N3ClBrS)2] (2b) were characterized by FT-IR, UV-vis and electron paramagnetic spectroscopy (EPR). The EPR spectra of the Cu(II) complexes provided the rhombic octahedral and axial symmetry of the complexes 1a and 2a respectively. For the complex 1a, the g values calculated as g1 = 2.1228, g2 = 2.0706 and g3 = 2.001 between 2900 and 3300 G. While for the complex 2a, a set of two resonance absorptions were observed. The synthesized compounds were tested for antitumor activity and showed that the ability to kill liver cancer cells significantly. Out of all the synthesized compounds, copper(II) complexes 1a and 2a showed high cytotoxic effect on liver cancer cells with 67.51% and 42.77% of cytotoxicity respectively at 100 μM.

Pentavalent uranium trans-dihalides and -pseudohalides.

PubMed

Lewis, Andrew J; Nakamaru-Ogiso, Eiko; Kikkawa, James M; Carroll, Patrick J; Schelter, Eric J

2012-05-21

Pentavalent uranium complexes of the formula U(V)X(2)[N(SiMe(3))(2)](3) (X = F(-), Cl(-), Br(-), N(3)(-), NCS(-)) are accessible from the oxidation of U(III)[N(SiMe(3))(2)](3) through two sequential, one-electron oxidation reactions (halides) and substitution through salt metathesis (pseudohalides). Uranium(v) mixed-halides are also synthesized by successive one-electron oxidation reactions.

Extended Fenske-Hall LCAO MO Calculations for Mixed Methylene Dihalides

NASA Astrophysics Data System (ADS)

Ziemann, Hartmut; Paulun, Manfred

1988-10-01

The electronic structure of mixed methylene dihalides CH2XY (X, Y = F, Cl, Br. I) has been studied using extended Fenske-Hall LCAO MO method. The comparison with available photoelec­tron spectra confirmes previous assignments of all bands with binding energies <100 eV. The electronic structure changes occurring upon varying the halogen substituents are discussed.

Method of selective reduction of halodisilanes with alkyltin hydrides

DOEpatents

D'Errico, John J.; Sharp, Kenneth G.

1989-01-01

The invention relates to the selective and sequential reduction of halodisilanes by reacting these compounds at room temperature or below with trialkyltin hydrides or dialkyltin dihydrides without the use of free radical intermediates. The alkyltin hydrides selectively and sequentially reduce the Si-Cl, Si-Br or Si-I bonds while leaving intact the Si-Si and Si-F bonds present.

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).

PubMed

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 interacting fragments. The π-bonding contribution is 14-22% of the total orbital contribution.

ANALYSIS OF ENERGY LOSSES OF A 30-kev ELECTRON BEAM IN THE FLUORIDE, CHLORIDE, AND BROMIDE OF LITHIUM (in French)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pradal, F.; Gout, C.

1963-02-01

The energy loss of a 30-kev electron beam in films of LiF, LiCl, and LiBr were analyzed with a magnetic spectrograph. For LiF, the results are compared to the absorption curve in the ultraviolet. The rays observed seem due to the excitation of valence band electrons of the 2s band of F/sup -/ and the 1s band of Li/sup +/. In some cases, energy losses less than 10 ev were observed, which seems connected to the presence of color centers. (tr-auth)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhukov, A. A., E-mail: azhukov@issp.ac.ru; Chernysheva, M. V.; Eliseev, A. A.

We report the results on the measurements of the work function of single-walled carbon nanotubes encapsulated by Agl (AgI@SWCNT), AgCl (AgCl@SWCNT), and CuBr (CuBr@SWCNT) by the local Kelvin probe technique. We found the values of the work function of tubes encapsulated with AgI and AgCl (Φ(AgI@SWCNT) = 5.08 ± 0.02, Φ(AgCl@SWCNT) = 5.10 ± 0.02 eV) to exceed substantially that of pristine carbon nanotubes, and the value of the work function of carbon nanotubes encapsulated with CuBr is Φ(CuBr@SWCNT) = 4.89 ± 0.03 (eV). The measurements are carried out using different kinds of microscope probes including multi-walled carbon nanotube tips.

Halide anion effects on coordination polymerization of cadmium(II) halide with 1: 1 mixed ligands

NASA Astrophysics Data System (ADS)

Ryu, Minjoo; Lee, Young-A.; Jung, Ok-Sang

2018-05-01

Insight into self-assembly of CdX2 (X = Cl and Br) with a mixture of L1 and L2 (L1 = diallylbis(3-pyridyl)silane; L2 = diallylbis(4-pyridyl)silane) was carried out. The self-assembly of CdCl2 with the 1: 1 mixture of L1 and L2 produces only 2D [CdCl2(L1)(L2)] with heteroleptic ligands, whereas that of CdBr2 with the 1: 1 mixture of L1 and L2 gives rise to the statistical mixture of 2D sheet [CdBr2(L1)2]·2H2O, 1D loop-chain [CdBr2(L2)2]·2CH2Cl2, and the 2D [CdBr2(L1)(L2)] with heteroleptic ligands.

A simple distillation method to extract bromine from natural water and salt samples for isotope analysis by multi-collector inductively coupled plasma mass spectrometry.

PubMed

Eggenkamp, H G M; Louvat, P

2018-04-30

In natural samples bromine is present in trace amounts, and measurement of stable Br isotopes necessitates its separation from the matrix. Most methods described previously need large samples or samples with high Br/Cl ratios. The use of metals as reagents, proposed in previous Br distillation methods, must be avoided for multi-collector inductively coupled plasma mass spectrometry (MC-ICP-MS) analyses, because of risk of cross-contamination, since the instrument is also used to measure stable isotopes of metals. Dedicated to water and evaporite samples with low Br/Cl ratios, the proposed method is a simple distillation that separates bromide from chloride for isotopic analyses by MC-ICP-MS. It is based on the difference in oxidation potential between chloride and bromide in the presence of nitric acid. The sample is mixed with dilute (1:5) nitric acid in a distillation flask and heated over a candle flame for 10 min. The distillate (bromine) is trapped in an ammonia solution and reduced to bromide. Chloride is only distilled to a very small extent. The obtained solution can be measured directly by MC-ICP-MS for stable Br isotopes. The method was tested for a variety of volumes, ammonia concentrations, pH values and distillation times and compared with the classic ion-exchange chromatography method. The method more efficiently separates Br from Cl, so that samples with lower Br/Cl ratios can be analysed, with Br isotope data in agreement with those obtained by previous methods. Unlike other Br extraction methods based on oxidation, the distillation method presented here does not use any metallic ion for redox reactions that could contaminate the mass spectrometer. It is efficient in separating Br from samples with low Br/Cl ratios. The method ensures reproducible recovery yields and a long-term reproducibility of ±0.11‰ (1 standard deviation). The distillation method was successfully applied to samples with low Br/Cl ratios and low Br amounts (down to 20 μg). Copyright © 2018 John Wiley & Sons, Ltd.

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

PubMed

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

2015-04-28

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

Investigations of the Rg-BrCl (Rg=He, Ne, Ar, Kr, Xe) binary van der Waals complexes: ab initio intermolecular potential energy surfaces, vibrational states and predicted pure rotational transition frequencies.

PubMed

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

2017-03-05

The intermolecular potential energy surfaces (PESs) of the ground electronic state for the Rg-BrCl (Rg=He, Ne, Ar, Kr, Xe) van der Waals complexes have been constructed by using the coupled-cluster method in combination with the augmented quadruple-zeta correlation-consistent basis sets supplemented with an additional set of bond functions. The features of the anisotropic PESs for these complexes are remarkably similar, which are characterized by three minima and two saddle points between them. The global minimum corresponds to a collinear Rg-Br-Cl configuration. Two local minima, correlate with an anti-linear Rg-Cl-Br geometry and a nearly T-shaped structure, can also be located on each PES. The quantum bound state calculations enable us to investigate intermolecular vibrational states and rotational energy levels of the complexes. The transition frequencies are predicted and are fitted to obtain their corresponding spectroscopic constants. In general, the periodic trends are observed for this complex family. Comparisons with available experimental data for the collinear isomer of Ar-BrCl demonstrate reliability of our theoretical predictions, and our results for the other two isomers of Ar-BrCl as well as for other members of the complex family are also anticipated to be trustable. Except for the collinear isomer of Ar-BrCl, the data presented in this paper would be beneficial to improve our knowledge for these experimentally unknown species. Copyright © 2016 Elsevier B.V. All rights reserved.

Tuneable reactivity with PPh3 and SnX2 of four- and five-coordinate Pd(II) and Pt(II) complexes containing polyphosphines.

PubMed

Fernández-Anca, Damián; García-Seijo, M Inés; García-Fernández, M Esther

2013-07-28

The reactivity of the unusual d(8) trigonal-bipyramidal systems [MX(PP3)]X (X = Cl: M = Pd(1a), Pt(2a); X = Br: M = Pd(3a), Pt(4a); X = I: M = Pd(5a), Pt(6a); PP3 = tris[2-(diphenylphosphino)ethyl]phosphine) in CHCl3-CH3OH, the square-pyramidal compounds [MCl(NP3)]Cl (M = Pd(7a); Pt(8a); NP3 = tris[2-(diphenylphosphino)ethyl]amine) in CD3OD-DMF and the distorted square-planar mononuclear [MX(PNP)]X (M = Pd: X = Cl(10a); M = Pt: X = I(10b); PNP = bis[2-(diphenylphosphino)ethyl]amine) and the heteronuclear [PdAu2X4(PP3)] [X = I(9a), Cl(14a), Br(15a)] and [MAuX2(PP3)]X [M = Pd: X = Cl(16a); M = Pt: X = Cl(17a), Br(18a)] species in CDCl3 with PPh3 + SnX2 has been explored to establish the factors that influence the nature of the products. With the mononuclear precursors the course of the reaction is strongly dependent on the tripodal or linear arrangement of the polydentate ligand and in the former case on the halogen. Thus, while for chlorides (1a-2a, 7a-8a) and bromides (3a-4a) the reaction led to the trigonal-bipyramidal compounds [M(SnCl3)(AP3)][SnCl3] [A = P: M = Pd(1), Pt(2); A = N: M = Pd(7), Pt(8)], [MBr(PP3)][SnBr3] [M = Pd(4), Pt(6)] containing M-Sn and M-Br bonds, respectively, for iodides (5a-6a) resulted in the unknown neutral square-planar compounds [MI2(PP(PO)2)(SnI2)2] [M = Pd(9) and Pt(10)] bearing two dangling P=O-SnI2 units and P2MI2 environments. However, complexes of the type [PtCl(PP2PO)X]X' [X = SnCl2, X' = [SnCl3](-)(11)] and [M(PP(PO)2)2X4]X'2 [X = SnCl2, X' = [SnCl3](-): M = Pd(12), Pt(13)] showing P=O-SnCl2 arms were obtained by direct reaction of [PtCl(PP2PO)]Cl (11a) and [M(PP(PO)2)2]Cl2 [M = Pd(12a), Pt(13a)] with SnCl2 in CH3OH. Although complex 9 was also prepared by interaction of the heteronuclear iodide 9a with PPh3 + SnI2 in CDCl3, the use of the neutral and ionic heteronuclear chlorides and bromides (14a-18a) as starting materials afforded the distorted square-planar ionic systems [MAuX'(PP3)(PPh3)][SnX3]2 [M = Pd: X = Cl, X' = SnCl3(-)(14); X = Br, X' = SnBr3(-)(15); M = Pt: X = Cl, X' = SnCl3(-)(17); X = Br, X' = SnBr3(-)(18)] containing M-SnX3 and P-Au-PPh3 functionalities. It was found that these reactions where the heteronuclear species are the precursors proceed via the trigonal-bipyramidal halides not only with X = Cl and Br(1a-4a) but also I(5a). When the precursors were 10a and 10b the reaction occurred with formation of [Pd(PNP)(PPh3)][SnCl3]2 (23) and [Pt(PNP)(PPh3)][SnCl2I]2 (24) showing M-PPh3 units and trihalostannato counter anions.

In situ observations of midlatitude stratospheric ClO and BrO

NASA Technical Reports Server (NTRS)

Brune, William H.; Anderson, James C.

1986-01-01

A balloon-borne experiment to measure midlatitude stratospheric BrO and ClO concentrations by NO chemical conversion/atomic resonance fluorescence was flown from Palestine, Texas, on May 20 1986. In this first study of BrO, no signal attributable to BrO was detected, and upper limits (2 sigma uncertainty) between 35 and 24 km altitude give BrO mixing ratios less than 15 pptv. Current models predict mixing ratios that are 1.7 times larger. Measurements of ClO were obtained at less than 0.2-km altitude resolution from 41 to 22 km. The smoothly varying altitude profile lies within the range of two-dimensional model calculations.

Deviation from the trans -Effect in Ligand-Exchange Reactions of Zeise’s Ions PtCl 3(C 2H 4) - with Heavier Halides (Br –, I - )

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hou, Gao-Lei; Govind, Niranjan; Xantheas, Sotiris S.

Four new Zeise’s family ions with mixed-halide ligands, i.e., PtCl nX 3-n(C 2H 4) - (X = Br, I; n = 1, 2), were synthesized via ligand-exchange reactions of KX salts with KPtCl 3(C 2H 4) 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 (–Cl 3) > 4.56 (–Cl 2Br) > 4.53 (–ClBr 2) > 4.34 (–Cl 2I) > 4.30 eV (–ClI 2).more » 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 –Cl 2X, and the trans-isomer for –ClX 2 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.« less

Ni(II)-tetrahedral complexes: Characterization, antimicrobial properties, theoretical studies and a new family of charge-transfer transitions

NASA Astrophysics Data System (ADS)

Sarı, Nurşen; Şahin, Songül Çiğdem; Öğütcü, Hatice; Dede, Yavuz; Yalcin, Soydan; Altundaş, Aliye; Doğanay, Kadir

2013-04-01

A new amine containing selenium and their five imine, (SeSchX)(X: -H, F, Cl, Br, CH3), and Ni (II) complexes, [Ni(SeSchX)(H2O)2]Cl/[Ni(SeSchCl)(H2O)Cl], were synthesized. The compounds were characterized by means of elemental analyses, 13C and 1H NMR (for imine), FT-IR, UV-Visible spectroscopy, TGA/DTA and elemental analyses. [Ni(SeSchCl)(H2O)Cl] complex from Ni(II) complexes changes color from yellow to orange in the range pH 5-7. [Ni(SeSchCl)(H2O)Cl] complex has ligand-to-metal charge-transfer (LMCT) transitions in the basic medium. Excitation characteristics and energetic of [Ni(SeSchCl)(H2O)Cl] complex, examined via TD-DFT calculations, reveals transitions of LMCT and π → π* character that matches the experimental values. [Ni(SeSchCl)(H2O)Cl] complex showed the highest antibacterial activity when compared to other complexes reported in this work.

Rejection of Bromide and Bromate Ions by a Ceramic Membrane.

PubMed

Moslemi, Mohammadreza; Davies, Simon H; Masten, Susan J

2012-12-01

Effects of pH and the addition of calcium chloride (CaCl(2)) on bromate (BrO(3) (-)) and bromide (Br(-)) rejection by a ceramic membrane were investigated. Rejection of both ions increased with pH. At pH 8, the rejection of BrO(3) (-) and Br(-) was 68% and 63%, respectively. Donnan exclusion appears to play an important role in determining rejection of BrO(3) (-) and Br(-). In the presence of CaCl(2), rejection of BrO(3) (-) and Br(-) ions was greatly reduced, confirming the importance of electrostatic interactions in determining rejection of BrO(3) (-) and Br(-). The effect of Ca(2+) is so pronounced that in most natural waters, rejection of both BrO(3) (-) and Br(-) by the membrane would be extremely small.

Direct evidence of a multicentre halogen bond: unexpected contraction of the P-XXX-P fragment in triphenylphosphine dihalides.

PubMed

Nikitin, Kirill; Müller-Bunz, Helge; Gilheany, Declan

2013-02-18

Triphenylhalophosphonium halides, Ph(3)PX(2), form crystals comprising bridged linear cations [Ph(3)P-X-X-X-PPh(3)](+) where the X(3) bridge is shortened from 6.56 Å in Cl-Cl-Cl to 6.37 Å in the Br-Br-Br system. It is proposed that this structure is stabilised by five-centre/six-electron (5c-6e) hypervalent interactions.

Selective detection of pyrophosphate anion by a simple Cd(II) based terpyridine complex

NASA Astrophysics Data System (ADS)

Purohit, Aditya Kumar; Ghosh, Biswa Nath; Kar, Pravin Kumar

2018-01-01

A simple ratiometric terpyridine-Cd(ll) complex was synthesized by the treatment of CdCl2 with terpyridine ligand 4‧-(4-N,N‧-dimethylaminophenyl)-2,2‧:6‧,2″-terpyridine. The synthesized complex was found to act as a selective fluorescent chemosensor for pyrophosphate P2O74 - (PPi) over other anions like F-, Cl-, Br-, CO32 -, SO32 -, AcO-, NO2-, and H2PO4-. Furthermore, the receptor probe was also successfully employed in HeLa cell for PPi detection, which indicates this can be used as a chemosensor for cells.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Buragohain, Amlan; Couck, Sarah; Van Der Voort, Pascal

Four existing and three new functionalized chromium terephthalates having MIL-101 topology and denoted as Cr-MIL-101-X (existing ones with X=–F, 1-F; –Cl, 2-Cl; –Br, 3-Br; –CH{sub 3}, 4-CH{sub 3}; new ones with X=–C{sub 6}H{sub 4}, 5-C{sub 6}H{sub 4}; –F{sub 2}, 6-F{sub 2}, –(CH{sub 3}){sub 2}, 7-(CH{sub 3}){sub 2}) were synthesized under hydrothermal conditions. All the materials except 5-C{sub 6}H{sub 4} could be prepared by a general synthetic route, in which the mixtures of CrO{sub 3}, H{sub 2}BDC-X (BDC=1,4-benzenedicarboxylate) linkers, conc. HCl and water with a molar ratio of 1:1:3.9:222.2 were reacted at 180 °C for 144 h. Compared to the 144more » h of synthesis time, three of the compounds, namely 1-Cl, 2-Br and 5-C{sub 6}H{sub 4}, could be prepared in much shorter reaction times (12–18 h at 180–210 °C). The materials possess high thermal stability up to 270–300 °C in an air atmosphere. The activated compounds exhibit significant porosity (S{sub BET} range: 1273–2135 m{sup 2} g{sup −1}). At 0 °C and 1 bar, the CO{sub 2} adsorption capacities of the compounds fall in the 1.7–2.9 mmol g{sup −1} range. Compounds 1-F and 6-F{sub 2} showed enhanced CO{sub 2} uptake values compared to parent Cr-MIL-101. The benzene adsorption capacities of the compounds lie in the range of 66.2–139.5 molecules per unit cell at 50 °C and p/p{sub 0}=0.35. The increased benzene uptake value of 1-F compared to un-functionalized Cr-MIL-101 and 4-CH{sub 3} suggests that the fluorination has induced more hydrophobicity in Cr-MIL-101 as compared to the methylation. - Graphical abstract: Benzene adsorption by seven functionalized Cr-MIL-101-X metal-organic framework (MOF) materials Display Omitted - Highlights: • Seven functionalized Cr-MIL-101-X materials were synthesized solvothermally. • All Cr-MIL-101-X materials exhibited high thermal stability up to 270–300 °C in air. • All Cr-MIL-101-X compounds displayed considerable porosity towards N{sub 2}, CO{sub 2} and benzene. • Mono- and di-fluorinated Cr-MIL-101 materials showed enhanced CO{sub 2} adsorption capacities. • Cr-MIL-101-F adsorbed more benzene than non- and methyl-functionalized Cr-MIL-101.« less

Formation of unprecedented actinidecarbon triple bonds in uranium methylidyne molecules

PubMed Central

Lyon, Jonathan T.; Hu, Han-Shi; Andrews, Lester; Li, Jun

2007-01-01

Chemistry of the actinide elements represents a challenging yet vital scientific frontier. Development of actinide chemistry requires fundamental understanding of the relative roles of actinide valence-region orbitals and the nature of their chemical bonding. We report here an experimental and theoretical investigation of the uranium methylidyne molecules X3UCH (X = F, Cl, Br), F2ClUCH, and F3UCF formed through reactions of laser-ablated uranium atoms and trihalomethanes or carbon tetrafluoride in excess argon. By using matrix infrared spectroscopy and relativistic quantum chemistry calculations, we have shown that these actinide complexes possess relatively strong UC triple bonds between the U 6d-5f hybrid orbitals and carbon 2s-2p orbitals. Electron-withdrawing ligands are critical in stabilizing the U(VI) oxidation state and sustaining the formation of uranium multiple bonds. These unique UC-bearing molecules are examples of the long-sought actinide-alkylidynes. This discovery opens the door to the rational synthesis of triple-bonded actinidecarbon compounds. PMID:18024591

Using Kalman Filter Chemical Data Assimilation to Study Ozone Catalytic Loss Cycles in January 1992

NASA Technical Reports Server (NTRS)

Lary, David J.

2002-01-01

This paper presents for the first time a global study of the ozone catalytic destruction cycles operating in the stratosphere using a stratospheric analyses for January 1992. The chemical analyses were produced using a Kalman filter data assimilation system. Because a major component of the variability of trace gases is due to the atmospheric motions the analyses have been cast in a flow-tracking coordinate system that moves with the large scale flow pattern. Particular attention is paid to the kinetic aspects of these cycles such as the rate limiting step and chain length. Although it is an important kinetic parameter, the chain length of the various cycles is seldom considered when the various catalytic cycles are discussed. This survey highlights that in the low stratosphere the cycles involving HO2 and halogens (notably bromine) are particularly important. In approximate order of effectiveness the most important ozone loss cycles in the polar lower stratosphere are the BrO/ClO, HO2/BrO, and OH/HO2 cycles. The ClO/ClO cycle clearly delineates the regions of chlorine activation. The chain length of the HO2/ClO, OH/HO2, Br/BrO, and ClO/NO2, clearly delineate the vortex edge region. The chain length of the BrO/NO2 and Cl/NO2 cycles highlight the regions of chemical processing outside the vortex where streamers of chemically processed air are stripped-off and transported away from the vortex. This is also true in the very low stratosphere for the Cl/ClO and BrO/ClO cycles.

Tunable White-Light Emission in Single-Cation-Templated Three-Layered 2D Perovskites (CH 3 CH 2 NH 3 ) 4 Pb 3 Br 10–x Cl x

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mao, Lingling; Wu, Yilei; Stoumpos, Constantinos C.

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 EA 4Pbmore » 3Br 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 EA 4Pb 3Br 10, which results in broadband white-light emission of EA 4Pb 3Cl 10 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 EA 4Pb 3Br 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 EA 4Pb 3Cl 10 and EA 4Pb 3Br 10 are direct band gap semiconductors. The color rendering index (CRI) of the series improves from 66 (EA 4Pb 3Cl 10) to 83 (EA 4Pb 3Br 0.5Cl 9.5), displaying high tunability and versatility of the title compounds.« less

Electronic and optical properties of MAPbX3 perovskites (X = I, Br, Cl): a unified DFT and GW theoretical analysis.

PubMed

Mosconi, Edoardo; Umari, Paolo; De Angelis, Filippo

2016-10-05

Materials engineering is a key for the enhancement of photovoltaics technology. This is particularly true for the novel class of perovskite solar cells. Accurate theoretical modelling can help establish general trends of behavior when addressing structural changes. Here, we consider the effects due to halide substitution in organohalide CH 3 NH 3 PbX 3 perovskites exploring the halide series with X = Cl, Br, I. For this task, we use accurate DFT and GW methods including spin-orbit coupling. We find the expected band gap increase when moving from X = I to Cl, in line with the experimental data. Most notably, the calculated absorption coefficients for I, Br and Cl are nicely reproducing the behavior reported experimentally. A common feature of all the simulated band structures is a significant Rashba effect. This is similar for MAPbI 3 and MAPbBr 3 while MAPbCl 3 shows in general a reduced Rashba interaction coefficient. Finally, a monotonic increase of the exciton reduced masses is calculated when moving from I to Br to Cl, in line with the stronger excitonic character of the lighter perovskite halides.

A spectrophotometric study of aqueous Au(III) halide-hydroxide complexes at 25-80 °C

NASA Astrophysics Data System (ADS)

Usher, Al; McPhail, D. C.; Brugger, Joël

2009-06-01

The mobility and transport of gold in low-temperature waters and brines is affected by the aqueous speciation of gold, which is sensitive in particular to pH, oxidation and halide concentrations. In this study, we use UV-Vis spectrophotometry to identify and measure the thermodynamic properties of Au(III) aqueous complexes with chloride, bromide and hydroxide. Au(III) forms stable square planar complexes with hydroxide and halide ligands. Based on systematic changes in the absorption spectra of solutions in three binary systems NaCl-NaBr, NaCl-NaOH and NaBr-NaOH at 25 °C, we derived log dissociation constants for the following mixed and end-member halide and hydroxide complexes: [AuCl 3Br] -, [AuCl 2Br 2] -, [AuBr 3Cl] - and [AuBr 4] -; [AuCl 3(OH)] -, [AuCl 2(OH) 2] -, [AuCl(OH) 3] - and [Au(OH) 4] -; and [AuBr 3(OH)] -, [AuBr 2(OH) 2] - and [AuBr(OH) 3] -. These are the first reported results for the mixed chloride-bromide complexes. Increasing temperature to 80 °C resulted in an increase in the stability of the mixed chloride-bromide complexes, relative to the end-member chloride and bromide complexes. For the [AuCl (4-n)(OH) n] - series of complexes ( n = 0-4), there is an excellent agreement between our spectrophotometric results and previous electrochemical results of Chateau et al. [Chateau et al. (1966)]. In other experiments, the iodide ion (I -) was found to be unstable in the presence of Au(III), oxidizing rapidly to I 2(g) and causing Au to precipitate. Predicted Au(III) speciation indicates that Au(III) chloride-bromide complexes can be important in transporting gold in brines with high bromide-chloride ratios (e.g., >0.05), under oxidizing (atmospheric), acidic (pH < 5) conditions. Native gold solubility under atmospheric oxygen conditions is predicted to increase with decreasing pH in acidic conditions, increasing pH in alkaline conditions, increasing chloride, especially at acid pH, and increasing bromide for bromide/chloride ratios greater than 0.05. The results of our study increase the understanding of gold aqueous geochemistry, with the potential to lead to new methods for mineral exploration, hydrometallurgy and medicine.

Proceedings of the International Pyrotechnics Seminar (6th) Held at Estes Park, Colorado, 17-21 July 1978

DTIC Science & Technology

1978-06-01

in metal form, and not as an oxide , as with conventional HC compositions. "That verified the fact that the aluminum did not take part in the chemical...the melting of the protective oxide layer on the aluminum particle with an attendant increase in surface reaction rate leading to ignition. Oxide ...detonation 5 aluminum BrF5 partial detonation 6 propylene oxide ClF3 partial detonation 621 041 IR! Each teat used about 5 kg of fuel, about 400 g

Impacts of inorganic anions and natural organic matter on thermally activated persulfate oxidation of BTEX in water.

PubMed

Ma, Jie; Yang, Yongqi; Jiang, Xianchenghao; Xie, Zhuoting; Li, Xiaoxuan; Chen, Changzhao; Chen, Hongkun

2018-01-01

The present study investigated the impacts of water matrix constituents (CO 3 2- , HCO 3 - , Cl - , Br - , PO 4 3- , HPO 4 2- , H 2 PO 4 - , NO 3 - , SO 4 2- and natural organic matters (NOM) on the oxidation of a mixture of benzene, toluene, ethylbenzene, and xylenes (BTEX) by thermally activated persulfate (PS). In the absence of matrix constituents, the BTEX oxidation rates decreased in the following order: xylenes > toluene ≈ ethylbenzene > benzene. HCO 3 - /CO 3 2- and NOM inhibited the BTEX oxidation and the inhibiting effects became more pronounced as the HCO 3 - /CO 3 2- /NOM concentration increased. SO 4 2- , NO 3 - , PO 4 3- and H 2 PO 4 - did not affect the BTEX oxidation while HPO 4 2- slightly inhibited the reaction. The impacts of Cl - and Br - were complex. Cl - inhibited the benzene oxidation while 100 mM and 500 mM of Cl - promoted the oxidation of m-xylene and p-xylene. Br - completely suppressed the benzene oxidation while 500 mM of Br - strongly promoted the oxidation of xylenes. Detailed explanations on the influence of each matrix constituent were discussed. In addition, various halogenated degradation byproducts were detected in the treatments containing Cl - and Br - . Overall, this study indicates that some matrix constituents such as NOM, HCO 3 - , CO 3 2- , H 2 PO 4 - , Cl - and Br - may reduce the BTEX removal efficiency of sulfate radical-based advanced oxidation process (SR-AOP) and the presence of Cl - and Br - may even lead to the formation of toxic halogenated byproducts. Copyright © 2017 Elsevier Ltd. All rights reserved.

Influence of halogenides on luminescence from silver molecular clusters in photothermorefractive glasses

NASA Astrophysics Data System (ADS)

Dubrovin, V. D.; Ignat'ev, A. I.; Nikonorov, N. V.; Sidorov, A. I.

2014-05-01

It is shown experimentally that a rise in the sodium halogenide (NaCl, NaBr) concentration in photothermorefractive glasses increases the intensity of luminescence from silver neutral molecular clusters. Substitution of NaBr for NaCl with their concentration being the same shifts the luminescence band toward longer waves and raises its intensity. These findings can be explained by the formation of molecular clusters of type Ag n -Hal (Hal = Cl, Br) in photothermorefractive glass.

Sticky ions in biological systems.

PubMed Central

Collins, K D

1995-01-01

Aqueous gel sieving chromatography on Sephadex G-10 of the Group IA cations (Li+, Na+, K+, Rb+, Cs+) plus NH4+ as the Cl- salts, in combination with previous results for the halide anions (F-, Cl-, Br-, I-) as the Na+ salts [Washabaugh, M.W. & Collins, K.D. (1986) J. Biol. Chem. 261, 12477-12485], leads to the following conclusions. (i) The small monovalent ions (Li+, Na+, F-) flow through the gel with water molecules attached, whereas the large monovalent ions (K+, Rb+, Cs+, Cl-, Br-, I-) adsorb to the nonpolar surface of the gel, a process requiring partial dehydration of the ion and implying that these ions bind the immediately adjacent water molecules weakly. (ii) The transition from strong to weak hydration occurs at a radius of about 1.78 A for the monovalent anions, compared with a radius of about 1.06 A for the monovalent cations (using ionic radii), indicating that the anions are more strongly hydrated than the cations for a given charge density. (iii) The anions show larger deviations from ideal behavior (an elution position corresponding to the anhydrous molecular weight) than do the cations and dominate the chromatographic behavior of the neutral salts. These results are interpreted to mean that weakly hydrated ions (chaotropes) are "pushed" onto weakly hydrated surfaces by strong water-water interactions and that the transition from strong ionic hydration to weak ionic hydration occurs where the strength of ion-water interactions approximately equals the strength of water-water interactions in bulk solution. PMID:7539920

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

PubMed

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

2016-08-01

The synergistic Ag(+) /X2 system (X=Cl, Br, I) is a very strong, but ill-defined oxidant-more powerful than X2 or Ag(+) alone. Intermediates for its action may include [Agm (X2 )n ](m+) complexes. Here, we report on an unexpectedly variable coordination chemistry of diiodine towards this direction: (A)Ag-I2 -Ag(A), [Ag2 (I2 )4 ](2+) (A(-) )2 and [Ag2 (I2 )6 ](2+) (A(-) )2 ⋅(I2 )x≈0.65 form by reaction of Ag(A) (A=Al(OR(F) )4 ; R(F) =C(CF3 )3 ) with diiodine (single crystal/powder XRD, Raman spectra and quantum-mechanical calculations). The molecular (A)Ag-I2 -Ag(A) is ideally set up to act as a 2 e(-) oxidant with stoichiometric formation of 2 AgI and 2 A(-) . Preliminary reactivity tests proved this (A)Ag-I2 -Ag(A) starting material to oxidize n-C5 H12 , C3 H8 , CH2 Cl2 , P4 or S8 at room temperature. A rough estimate of its electron affinity places it amongst very strong oxidizers like MF6 (M=4d metals). This suggests that (A)Ag-I2 -Ag(A) will serve as an easily in bulk accessible, well-defined, and very potent oxidant with multiple applications. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Exceptional enhancement of Raman scattering on silver chlorobromide nanocube photonic crystals: chemical and photonic contributions

DOE PAGES

Li, Zheng; Gosztola, David J.; Sun, Cheng-Jun; ...

2015-02-02

Photonic crystals made from self-assembly of mono-dispersed AgCl xBr 1-x nanocubes, which are not plasmonically active, have been discovered to exceptionally enhance Raman scattering of molecules chemically adsorbed on their surfaces. Comprehensive control measurements and X-ray absorption near-edge structure spectroscopy indicate that the Raman enhancement on the AgCl xBr 1-x nanocube photonic crystals is primarily ascribed to the chemical enhancement mechanism associated with the chemical interactions between adsorbing molecules and the AgCl xBr 1-x surfaces. In addition, the ordering of the AgCl xBr 1-x nanocubes in the photonic crystals can selectively reflect Raman scattering back to the detector at themore » bandgap position of the photonic crystals to provide additional enhancement, i.e., photonic mode enhancement. The thiophenol molecules adsorbed on the AgCl 0.44Br 0.56 nanocube photonic crystals exhibit astonishingly strong Raman signals that are on the same order of magnitude as those recorded from the thiophenol molecules adsorbed on the assembled Ag nanocubes.« less

The Substituent Effects on π-type Pnicogen Bond Interaction

NASA Astrophysics Data System (ADS)

Zhu, Jian-Qing; Cao, Sheng-Wei; Wang, Wei; Xu, Xiao-Lu; Xu, Hui-Ying

2017-05-01

Intermolecular interactions between PH2Cl and Ar-R (R=H, OH, NH2, CH3, Br, Cl, F, CN, NO2) were calculated by using MP2/aug-cc-pVDZ quantum chemical method. It has been shown from our calculations that the aromatic rings with electron-withdrawing groups represent much weaker binding affinities than those with electron-donating groups. The charge-transfer interaction between PH2Cl and Ar-R plays an important role in the formation of pnicogen bond complexes, as revealed by NBO analysis. The π-type halogen bond was also calculated and comparison of these two π-type interactions was made. It has been revealed that the π-type pnicogen bond systems are more stable than the halogen bond ones.

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

NASA Astrophysics Data System (ADS)

Bachir-Bey, Nassim; Matray, Jean-Michel

2014-05-01

This work is part of research conducted by the Institute of Radiological and Nuclear Safety (IRSN) on the geological disposal of High-Level and Intermediate-Level Long-Lived (HL-ILLL) radioactive waste in deep clayrocks. In France, the choice of the potential host rock for the geological storage is focused on the Callovian-Oxfordian (COx) of Meuse/Haute-Marne from its low permeability, capacity for self- sealing, high sorption and ability to radionuclide (RN) transport by diffusion. IRSN, which plays an expert role for ASN has its own underground research laboratory in a clayrock which has strong analogies to the COx. This is the Toarcian/Domerian clayrock located at Tournemire in southern Aveyron in France. The purpose of this study was to assess the transfer of RN in the Tournemire clayrock through the study of halides contents and of their stable isotopes (Cl-, Br-, Cl-/Br-, d37Cl, d81Br). The approach used was multiple and consisted for halides to: 1) Assess their stock in different fractions of the rock by applying several techniques including i) alkaline fusion for their total stock, ii) leaching to access their stock in porewater and to mineral phases sensitive to dissolution iii) cubic diffusion for their stock in porewater, 2) Get their diffusive transport parameters of a selection of samples from the upper Toarcian by cubic diffusion experiments modelled using the Hytec transport code developed by Mines ParisTech and 3) Model their transport after palaeohydrogeological known changes of the Tournemire massif. The experimental approach, conducted at the LAME lab, did not lead to an operational protocol for the alkaline fusion due to an incomplete rock dissolution. Leaching was used to characterize the concentrations of halides in the fractions of pore water and of minerals sensitive to dissolution. The results show levels of halides much higher than those of pore water with very low Cl/Br ratios likely resulting from the dissolution of mineral species. The cubic diffusion produced the pore diffusion coefficients for Cl and Br as well as their concentration in the porewater. Cubic diffusion also allowed to estimate a Cl to Br pore diffusion coefficient ratio, necessary to calculate the profiles of Cl/Br. These estimates have required the use of the transport code Hytec i) for dimensioning and implementing the experiment in a time frame compatible with the work period, ii) for analysing the sensitiveness of the model to the accessible porosity and to the diffusion coefficient which act respectively to the steady phase and transient phase of the experiments, and finally, iii ) for adjusting the pore diffusion coefficients of Cl and Br to an accessible porosity of 3-4%. The Hytec code was then used to check the consistency of the current profiles of chlorides, bromides, 35Cl , 37Cl , d37Cl, Cl/Br in 1D, a fake drilling assumed crossing the entire clayrock. The assumption is that halides have undergone a diffusive transport between seawater trapped during sedimentation and meteoric waters infiltrated at different times to domain boundaries. Four scenarios were tested according to the paleohydrogeological history of the massif. All tracers and scenarios are consistent with a unique marine source of halides more or less diluted by meteoric waters. The duration of the diffusive exchange initially suggested 85 ± 10 Ma (Bensenouci, 2010) is never contradicted despite uncertainties related to changes in boundary conditions. This body of evidence would suggest that molecular diffusion is the transport process which has affected and still affect the Tournemire clayrock, outside fault zones. The d37Cl results expected on the surrounding carbonated aquifers, leachates and fracture waters (including d81Br values) should help to refine the models and the results.

Does the 4f-shell contribute to bonding in tetravalent lanthanide halides?

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ji, Wen-Xin; School of Chemistry and Chemical Engineering, Ningxia University, 750015 Yinchuan; Xu, Wei

2014-12-28

Lanthanide tetrahalide molecules LnX{sub 4} (Ln = Ce, Pr, Tb; X = F, Cl, Br, I) have been investigated by density functional theory at the levels of the relativistic Zero Order Regular Approximation and the relativistic energy-consistent pseudopotentials, using frozen small- and medium-cores. The calculated bond lengths and vibrational frequencies are close to the experimental data. Our calculations indicate 4f shell contributions to bonding in LnX{sub 4}, in particular for the early lanthanides, which show significant overlap between the Ln 4f-shell and the halogen np-shells. The 4f shells contribute to Ln-X bonding in LnX{sub 4} about one third more thanmore » in LnX{sub 3}.« less

Determination of the total drug-related chlorine and bromine contents in human blood plasma using high performance liquid chromatography-tandem ICP-mass spectrometry (HPLC-ICP-MS/MS).

PubMed

Klencsár, Balázs; Bolea-Fernandez, Eduardo; Flórez, María R; Balcaen, Lieve; Cuyckens, Filip; Lynen, Frederic; Vanhaecke, Frank

2016-05-30

A fast, accurate and precise method for the separation and determination of the total contents of drug-related Cl and Br in human blood plasma, based on high performance liquid chromatography - inductively coupled plasma - tandem mass spectrometry (HPLC-ICP-MS/MS), has been developed. The novel approach was proved to be a suitable alternative to the presently used standard methodology (i.e. based on a radiolabelled version of the drug molecule and radiodetection), while eliminating the disadvantages of the latter. Interference-free determination of (35)Cl has been accomplished via ICP-MS/MS using H2 as reaction gas and monitoring the (35)ClH2(+) reaction product at mass-to-charge ratio of 37. Br could be measured "on mass" at a mass-to-charge of 79. HPLC was relied on for the separation of the drug-related entities from the substantial amount of inorganic Cl. The method developed was found to be sufficiently precise (repeatability <10% RSD) and accurate (recovery between 95 and 105%) and shows a linear dynamic range (R(2)>0.990) from the limit of quantification (0.05 and 0.01 mg/L for Cl and Br in blood plasma, respectively) to at least 5 and 1mg/L for Cl and Br, respectively. Quantification via either external or internal standard calibration provides reliable results for both elements. As a proof-of-concept, human blood plasma samples from a clinical study involving a newly developed Cl- and Br-containing active pharmaceutical ingredient were analysed and the total drug exposure was successfully described. Cross-validation was achieved by comparing the results obtained on Cl- and on Br-basis. Copyright © 2016 Elsevier B.V. All rights reserved.

First-principles thermodynamics study of phase stability in inorganic halide perovskite solid solutions

NASA Astrophysics Data System (ADS)

Bechtel, Jonathon S.; Van der Ven, Anton

2018-04-01

Halide substitution gives rise to a tunable band gap as a function of composition in halide perovskite materials. However, photoinduced phase segregation, observed at room temperature in mixed halide A Pb (IxBr1-x) 3 systems, limits open circuit voltages and decreases photovoltaic device efficiencies. We investigate equilibrium phase stability of orthorhombic P n m a γ -phase CsM (XxY1-x) 3 perovskites where M is Pb or Sn, and X and Y are Br, Cl, or I. Finite-temperature phase diagrams are constructed using a cluster expansion effective Hamiltonian parameterized from first-principles density-functional-theory calculations. Solid solution phases for CsM (IxBr1-x) 3 and CsM (BrxCl1-x) 3 are predicted to be stable well below room temperature while CsM (IxCl1-x) 3 systems have miscibility gaps that extend above 400 K. The height of the miscibility gap correlates with the difference in volume between end members. Also layered ground states are found on the convex hull at x =2 /3 for CsSnBr2Cl ,CsPbI2Br , and CsPbBrCl2. The impact of these ground states on the finite temperature phase diagram is discussed in the context of the experimentally observed photoinduced phase segregation.

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

NASA Technical Reports Server (NTRS)

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

1986-01-01

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

Simulation calculations of efficiencies and silicon consumption for CH3NH3PbI3-x-y Br x Cl y /crystalline silicon tandem solar cells

NASA Astrophysics Data System (ADS)

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

2017-04-01

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 MAPbI3 (MA  =  CH3NH3), MAPbI3-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 MAPbI3-x-y Br x Cl y are performed using first-principles calculations including the spin-orbit coupling (SOC) effect. MAPbI3-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 MAPbI3-x-y Br x Cl y /c-Si TSCs with the five sets of x and y are calculated. Among them, the MAPbI2.375Br0.5Cl0.125/c-Si TSC achieves the highest efficiency of 35.1% with a 440 nm thick top cell and 50 µm thick c-Si when applying the LBM. When applying the TMM, the highest efficiency of 32.5% is predicted with a 580 nm thick MAPbI2.375Br0.5Cl0.125 top cell and 50 µm thick c-Si. Compared with the limiting efficiency of 27.1% for a 190 µm thick c-Si single junction solar cell (SC), the MAPbI2.375Br0.5Cl0.125/c-Si TSC shows a superior performance of high efficiency and low c-Si consumption.

Tunable White-Light Emission in Single-Cation-Templated Three-Layered 2D Perovskites (CH3CH2NH3)4Pb3Br10-xClx.

PubMed

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

2017-08-30

Two-dimensional (2D) hybrid halide perovskites come as a family (B) 2 (A) n-1 Pb n X 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 EA 4 Pb 3 Br 10-x Cl 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 EA 4 Pb 3 Cl 10 having a much larger distortion than that of EA 4 Pb 3 Br 10 , which results in broadband white-light emission of EA 4 Pb 3 Cl 10 in contrast to narrow blue emission of EA 4 Pb 3 Br 10 . 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 EA 4 Pb 3 Br 10-x Cl 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 EA 4 Pb 3 Cl 10 and EA 4 Pb 3 Br 10 are direct band gap semiconductors. The color rendering index (CRI) of the series improves from 66 (EA 4 Pb 3 Cl 10 ) to 83 (EA 4 Pb 3 Br 0.5 Cl 9.5 ), displaying high tunability and versatility of the title compounds.

Passive Q-switching of a Tm:YLF laser with a Co2+ doped silver halide saturable absorber

NASA Astrophysics Data System (ADS)

Hecht, Harel; Burshtein, Zeev; Katzir, Abraham; Noach, Salman; Sokol, Maxim; Frumker, Eugene; Galun, Ehud; Ishaaya, Amiel A.

2017-02-01

We report a successful passive Q-switching of a Tm:YLF laser operating at λ = 1.9 μm, using a Co2+:AgCl0.5Br0.5 saturable absorber. Approximately 200-ns long, 150 μJ pulses were obtained. Increase in pump energy resulted in repetitive pulsing, with a repetition rate approximately proportional to the pump pulse energy. Room-temperature optical transmission saturation curves measured in ∼1-mm thick Co2+:AgCl0.5Br0.5 plates yielded a ground state absorption cross section σgs =(7.8 ± 0.5) ×10-18 cm2 , and an excited state absorption cross section σes =(3.3 ± 0.3) ×10-18 cm2 , at λ = 1.9 μm. The lifetime of the A2(4F) second excited-state of the octahedral O symmetry was τ∗ =(0.6 ± 0.06) ns .

Tailoring Oxygen Sensitivity with Halide Substitution in Difluoroboron Dibenzoylmethane Polylactide Materials

PubMed Central

DeRosa, Christopher A.; Kerr, Caroline; Fan, Ziyi; Kolpaczynska, Milena; Mathew, Alexander S.; Evans, Ruffin E.; Zhang, Guoqing; Fraser, Cassandra L.

2015-01-01

The dual-emissive properties of solid-state difluoroboron β-diketonate-poly(lactic acid) (BF2bdkPLA) materials have been utilized for biological oxygen sensing. In this work, BF2dbm(X)PLA materials were synthesized, where X = H, F, Cl, Br, and I. The effects of changing the halide substituent and PLA polymer chain length on the optical properties in dilute CH2Cl2 solutions and solid-state polymer films were studied. These luminescent materials show fluorescence, phosphorescence, and lifetime tunability on the basis of molecular weight, as well as lifetime modulation via the halide substituent. Short BF2dbm(Br)PLA (6.0 kDa) and both short and long BF2dbm(I)PLA polymers (6.0 or 20.3 kDa) have fluorescence and intense phosphorescence ideal for ratiometric oxygen sensing. The lighter halide-dye polymers with hydrogen, fluorine, and chlorine substitution have longer phosphorescence lifetimes and can be utilized as ultrasensitive oxygen sensors. Photostability was also analyzed for the polymer films. PMID:26480236

Long-term room temperature stability of TlBr gamma detectors

NASA Astrophysics Data System (ADS)

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

2011-09-01

TlBr is a material of interest for use in room temperature gamma ray detector applications due to is wide bandgap 2.7 eV and high average atomic number (Tl 81, Br 35). Researchers have achieved energy resolutions of 1.3 % at 662 keV, demonstrating the potential of this material system. However, these detectors are known to polarize using conventional configurations, limiting their use. Continued improvement of room temperature, high-resolution gamma ray detectors based on TlBr requires further understanding of the degradation mechanisms. While high quality material is a critical starting point for excellent detector performance, we show that the room temperature stability of planar TlBr gamma spectrometers can be significantly enhanced by treatment with both hydrofluoric and hydrochloric acid. By incorporating F or Cl into the surface of TlBr, current instabilities are eliminated and the longer term current of the detectors remains unchanged. 241Am spectra are also shown to be more stable for extended periods; detectors have been held at 2000 V/cm for 52 days with less than 10% degradation in peak centroid position. In addition, evidence for the long term degradation mechanism being related to the contact metal is presented.

Hydrocarbon oxidation by beta-halogenated dioxoruthenium(VI) porphyrin complexes: effect of reduction potential (RuVI/V) and C-H bond-dissociation energy on rate constants.

PubMed

Che, Chi-Ming; Zhang, Jun-Long; Zhang, Rui; Huang, Jie-Sheng; Lai, Tat-Shing; Tsui, Wai-Man; Zhou, Xiang-Ge; Zhou, Zhong-Yuan; Zhu, Nianyong; Chang, Chi Kwong

2005-11-18

beta-Halogenated dioxoruthenium(VI) porphyrin complexes [Ru(VI)(F(28)-tpp)O(2)] [F(28)-tpp=2,3,7,8,12,13, 17,18-octafluoro-5,10,15,20-tetrakis(pentafluorophenyl)porphyrinato(2-)] and [Ru(VI)(beta-Br(8)-tmp)O(2)] [beta-Br(8)-tmp=2,3,7,8,12,13,17,18-octabromo-5,10,15,20- tetrakis(2,4,6-trimethylphenyl)porphyrinato(2-)] were prepared from reactions of [Ru(II)(por)(CO)] [por=porphyrinato(2-)] with m-chloroperoxybenzoic acid in CH(2)Cl(2). Reactions of [Ru(VI)(por)O(2)] with excess PPh(3) in CH(2)Cl(2) gave [Ru(II)(F(20)-tpp)(PPh(3))(2)] [F(20)-tpp=5,10,15,20-tetrakis(pentafluorophenyl)porphyrinato(2-)] and [Ru(II)(F(28)-tpp)(PPh(3))(2)]. The structures of [Ru(II)(por)(CO)(H(2)O)] and [Ru(II)(por)(PPh(3))(2)] (por=F(20)-tpp, F(28)-tpp) were determined by X-ray crystallography, revealing the effect of beta-fluorination of the porphyrin ligand on the coordination of axial ligands to ruthenium atom. The X-ray crystal structure of [Ru(VI)(F(20)-tpp)O(2)] shows a Ru=O bond length of 1.718(3) A. Electrochemical reduction of [Ru(VI)(por)O(2)] (Ru(VI) to Ru(V)) is irreversible or quasi-reversible, with the E(p,c)(Ru(VI/V)) spanning -0.31 to -1.15 V versus Cp(2)Fe(+/0). Kinetic studies were performed for the reactions of various [Ru(VI)(por)O(2)], including [Ru(VI)(F(28)-tpp)O(2)] and [Ru(VI)(beta-Br(8)-tmp)O(2)], with para-substituted styrenes p-X-C(6)H(4)CH=CH(2) (X=H, F, Cl, Me, MeO), cis- and trans-beta-methylstyrene, cyclohexene, norbornene, ethylbenzene, cumene, 9,10-dihydroanthracene, xanthene, and fluorene. The second-order rate constants (k(2)) obtained for the hydrocarbon oxidations by [Ru(VI)(F(28)-tpp)O(2)] are up to 28-fold larger than by [Ru(VI)(F(20)-tpp)O(2)]. Dual-parameter Hammett correlation implies that the styrene oxidation by [Ru(VI)(F(28)-tpp)O(2)] should involve rate-limiting generation of a benzylic radical intermediate, and the spin delocalization effect is more important than the polar effect. The k(2) values for the oxidation of styrene and ethylbenzene by [Ru(VI)(por)O(2)] increase with E(p,c)(Ru(VI/V)), and there is a linear correlation between log k(2) and E(p,c)(Ru(VI/V)). The small slope (approximately 2 V(-1)) of the log k(2) versus E(p,c)(Ru(VI/V)) plot suggests that the extent of charge transfer is small in the rate-determining step of the hydrocarbon oxidations. The rate constants correlate well with the C-H bond dissociation energies, in favor of a hydrogen-atom abstraction mechanism.

L-Cysteine halogenides: A new family of salts with an L-cysteine⋯L-cysteinium dimeric cation

NASA Astrophysics Data System (ADS)

Ghazaryan, V. V.; Minkov, V. S.; Boldyreva, E. V.; Petrosyan, A. M.

2016-10-01

Two L-cysteinium-halogenides with (L-cysteine···L-cysteinium) dimeric cations have been obtained, (L-Cys⋯L-Cys+)·Cl-, and (L-Cys⋯L-Cys+)·Br-. Both salts crystallize in monoclinic space group P21. Although these salts have the same dimeric cations and isotypical halogen anions, crystal packing is different. The main difference between the two salts rests in the conformation of (L-Cys⋯L-Cys+) dimeric cation, which also differs from that of the dimeric cation in the previously reported compound L-Cys+(L-Cys⋯L-Cys+)·F-·(F-⋯HF). The dimeric cation is formed by a very short O-H⋯O hydrogen bond with d(O···O) of 2.449(2) Å and 2.435(11) Å in the chloride and bromide, respectively. In addition to crystal structure analysis, Infrared and Raman spectra have been registered and discussed with a particular focus on intermolecular interactions. The L-Cys+·Br-·H2O salt with a simple L-cysteinium cation was also obtained and the crystal structure solved. It resembles its chloride analogue, L-Cys+·Cl-·H2O.

Widely Applicable n-Type Molecular Doping for Enhanced Photovoltaic Performance of All-Polymer Solar Cells.

PubMed

Xu, Yalong; Yuan, Jianyu; Sun, Jianxia; Zhang, Yannan; Ling, Xufeng; Wu, Haihua; Zhang, Guobing; Chen, Junmei; Wang, Yongjie; Ma, Wanli

2018-01-24

A widely applicable doping design for emerging nonfullerene solar cells would be an efficient strategy in order to further improve device photovoltaic performance. Herein, a family of compound TBAX (TBA= tetrabutylammonium, X = F, Cl, Br, or I, containing Lewis base anions are considered as efficient n-dopants for improving polymer-polymer solar cells (all-PSCs) performance. In all cases, significantly increased fill factor (FF) and slightly increased short-circuit current density (J sc ) are observed, leading to a best PCE of 7.0% for all-PSCs compared to that of 5.8% in undoped devices. The improvement may be attributed to interaction between different anions X - (X = F, Cl, Br, and I) in TBAX with the polymer acceptor. We reveal that adding TBAX at relatively low content does not have a significantly impact on blend morphology, while it can reduce the work function (WF) of the electron acceptor. We find this simple and solution processable n-type doping can efficiently restrain charge recombination in all-polymer solar cell devices, resulting in improved FF and J sc. More importantly, our findings may provide new protocles and insights using n-type molecular dopants in improving the performance of current polymer-polymer solar cells.

Room Temperature Quantum Spin Hall Insulator in Ethynyl-Derivative Functionalized Stanene Films

PubMed Central

Zhang, Run-wu; Zhang, Chang-wen; Ji, Wei-xiao; Li, Sheng-shi; Yan, Shi-shen; Hu, Shu-jun; Li, Ping; Wang, Pei-ji; Li, Feng

2016-01-01

Quantum spin Hall (QSH) insulators feature edge states that topologically protected from backscattering. However, the major obstacles to application for QSH effect are the lack of suitable QSH insulators with a large bulk gap. Based on first-principles calculations, we predict a class of large-gap QSH insulators in ethynyl-derivative functionalized stanene (SnC2X; X = H, F, Cl, Br, I), allowing for viable applications at room temperature. Noticeably, the SnC2Cl, SnC2Br, and SnC2I are QSH insulators with a bulk gap of ~0.2 eV, while the SnC2H and SnC2F can be transformed into QSH insulator under the tensile strains. A single pair of topologically protected helical edge states is established for the edge of these systems with the Dirac point locating at the bulk gap, and their QSH states are confirmed with topological invariant Z2 = 1. The films on BN substrate also maintain a nontrivial large-gap QSH effect, which harbors a Dirac cone lying within the band gap. These findings may shed new light in future design and fabrication of large-gap QSH insulators based on two-dimensional honeycomb lattices in spintronics. PMID:26728874

Spin-orbit coupling calculations with the two-component normalized elimination of the small component method

NASA Astrophysics Data System (ADS)

Filatov, Michael; Zou, Wenli; Cremer, Dieter

2013-07-01

A new algorithm for the two-component Normalized Elimination of the Small Component (2cNESC) method is presented and tested in the calculation of spin-orbit (SO) splittings for a series of heavy atoms and their molecules. The 2cNESC is a Dirac-exact method that employs the exact two-component one-electron Hamiltonian and thus leads to exact Dirac SO splittings for one-electron atoms. For many-electron atoms and molecules, the effect of the two-electron SO interaction is modeled by a screened nucleus potential using effective nuclear charges as proposed by Boettger [Phys. Rev. B 62, 7809 (2000), 10.1103/PhysRevB.62.7809]. The use of the screened nucleus potential for the two-electron SO interaction leads to accurate spinor energy splittings, for which the deviations from the accurate Dirac Fock-Coulomb values are on the average far below the deviations observed for other effective one-electron SO operators. For hydrogen halides HX (X = F, Cl, Br, I, At, and Uus) and mercury dihalides HgX2 (X = F, Cl, Br, I) trends in spinor energies and SO splittings as obtained with the 2cNESC method are analyzed and discussed on the basis of coupling schemes and the electronegativity of X.

Transformation of methylparaben during water chlorination: Effects of bromide and dissolved organic matter on reaction kinetics and transformation pathways.

PubMed

Yoom, Hoonsik; Shin, Jaedon; Ra, Jiwoon; Son, Heejong; Ryu, Dongchoon; Kim, Changwon; Lee, Yunho

2018-09-01

The reaction kinetics, products, and pathways of methylparaben (MeP) during water chlorination with and without bromide (Br - ) were investigated to better understand the fate of parabens in chlorinated waters. During the chlorination of MeP-spiked waters without Br - , MeP was transformed into mono-Cl-MeP and di-Cl-MeP with apparent second-order rate constants (k app ) of 64M -1 s -1 and 243M -1 s -1 at pH7, respectively, while further chlorination of di-Cl-MeP was relatively slower (k app =1.3M -1 s -1 at pH7). With increasing Br - concentration, brominated MePs, such as mono-Br-MeP, Br-Cl-MeP, and di-Br-MeP, became major transformation products. The di-halogenated MePs (di-Cl-MeP, Br,Cl-MeP, and di-Br-MeP) showed relatively low reactivity to chlorine at pH7 (k app =1.3-4.6M -1 s -1 ) and bromine (k app =32-71M -1 s -1 ), which explains the observed high stability of di-halogenated MePs in chlorinated waters. With increasing pH from 7 to 8.5, the transformation of di-halogenated MePs was further slowed due to the decreasing reactivity of di-MePs to chlorine. The formation of the di-halogenated MePs and their further transformation become considerably faster at Br - concentrations higher than 0.5μM (40μg/L). Nonetheless, the accelerating effect of Br - diminishes in the presence of dissolved organic matter (DOM) extract (Suwannee River humic acid (SRHA)) due to a more rapid consumption of bromine by DOM than chlorine. The effect of Br - on the fate of MeP was less in the tested real water matrices, possibly due to a more rapid bromine consumption by the real water DOM compared to SRHA. A kinetic model was developed based on the determined species-specific second-order rate constants for chlorination/bromination of MeP and its chlorinated and brominated MePs and the transformation pathway information, which could reasonably simulate the transformation of MePs during the chlorination of water in the presence of Br - and selected DOM. Copyright © 2017 Elsevier B.V. All rights reserved.

Spectrophotometric estimation of bromide ion in excess chloride media.

PubMed

Adimurthy, S; Susarla, V R K S; Reddy, M P; Ramachandraiah, G

2005-10-31

The redox reaction between bromate and chloride ions in the presence and the absence of two or less equivalents of bromide ion ascertaining the formation of bromine chloride species of type BrCl and BrCl(2)(-) in subsequent reactions in 4% H(2)SO(4), has been studied by spectrophotometry. Calibration graphs for the bromide ion estimation in 0.1% KBrO(3)-4% H(2)SO(4) medium are determined separately in the presence of known amounts of NaCl. The effect of Cl(-) ion percentage on the determination of Br(-) ion is studied and reported herewith a suitable equation for a precise, reliable and quick spectrophotometric estimation.

Simultaneously promoting charge separation and photoabsorption of BiOX (X = Cl, Br) for efficient visible-light photocatalysis and photosensitization by compositing low-cost biochar

NASA Astrophysics Data System (ADS)

Li, Min; Huang, Hongwei; Yu, Shixin; Tian, Na; Dong, Fan; Du, Xin; Zhang, Yihe

2016-11-01

Exploration of novel and efficient composite photocatalysts is of great significance for advancing the practical application of photocatalysis. BiOX (X = Cl, Br) is a kind of promising photocatalysts, but the charge separation efficiency and photoabsorption need to be ameliorated. In this work, we first employ a low-cost and easily accessable carbon material biochar to modify BiOX (X = Cl, Br) and develop biochar/BiOX (X = Cl, Br) composite photocatalysts via a facile in-situ deposition method. The as-prepared composites are detailedly characterized by SEM, SEM-mapping, TEM, XRD and XPS, and DRS result demonstrates that the visible-light absorption of BiOX (X = Cl, Br) catalysts can be exceedingly enhanced by biochar. The biochar/BiOX (X = Cl, Br) composites are found to unfold remarkably enhanced visible-light-driven photocatalytic activity toward degradation of MO and photocurrent generation. The strengthened photocatalytic performance mainly stems from the profoundly improved charge separation and delivery efficiency, as evidenced by the electrochemical impedance spectra (EIS), photoluminescence (PL), and time-resolved PL decay spectra. Additionally, the biochar exerts importance in enhancing the two different types of photochemical reactions of BiOBr and BiOCl, in which the photocatalytic mechanisms are found to be photocatalysis and photosensitization process, respectively. The present work may open up a new avenue for framing economic and efficient photocatalytic materials and new composite materials for photoelectric application.

Cationic aza-macrocyclic complexes of germanium(II) and silicon(IV).

PubMed

Everett, Matthew; Jolleys, Andrew; Levason, William; Light, Mark E; Pugh, David; Reid, Gillian

2015-12-28

[GeCl2(dioxane)] reacts with the neutral aza-macrocyclic ligands L, L = Me3tacn (1,4,7-trimethyl-1,4,7-triazacyclononane), Me4cyclen (1,4,7,10-tetramethyl-1,4,7,10-tetraazacyclododecane) or Me4cyclam (1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane) and two mol. equiv. of Me3SiO3SCF3 in thf solution to yield the unusual and hydrolytically very sensitive [Ge(L)][O3SCF3]2 as white solids in moderate yield. Using shorter reaction times [Ge(Me3tacn)]Cl2 and [Ge(Me3tacn)]Cl[O3SCF3] were also isolated; the preparation of [Ge(Me4cyclen)][GeCl3]2 is also described. The structures of the Me3tacn complexes show κ(3)-coordination of the macrocycle, with the anions interacting only weakly to produce very distorted five- or six-coordination at germanium. In contrast, the structure of [Ge(Me4cyclen)][O3SCF3]2 shows no anion interactions, and a distorted square planar geometry at germanium from coordination to the tetra-aza macrocycle. Crystal structures of the Si(iv) complexes, [SiCl3(Me3tacn)]Y (Y = O3SCF3, BAr(F); [B{3,5-(CF3)2C6H3}4]) and [SiHCl2(Me3tacn)][BAr(F)], obtained from reaction of SiCl4 or SiHCl3 with Me3tacn, followed by addition of either Me3SiO3SCF3 or Na[BAr(F)], contain distorted octahedral cations, with facialκ(3)-coordinated Me3tacn. The open-chain triamine, Me2NCH2CH2N(Me)CH2CH2NMe2 (pmdta), forms [SiCl3(pmdta)][BAr(F)] and [SiBr3(pmdta)][BAr(F)] under similar conditions, containing mer-octahedral cations.

Tests of halogen photochemistry using in situ measurements of ClO and BrO in the lower polar stratosphere

NASA Astrophysics Data System (ADS)

Avallone, Linnea M.; Toohey, Darin W.

2001-05-01

In situ observations of the halogen oxides ClO and BrO made from the NASA ER-2 during the Airborne Arctic Stratospheric Expedition (AASE) I and II missions are used to test current understanding of photochemical parameters. Measurements of ClO obtained during AASE I in the dark perturbed polar vortex are analyzed with respect to temperature to derive the equilibrium expression for the ClO/Cl2O2 system. Assuming photochemical steady state and complete activation of chlorine (ClO + 2Cl2O2 = Cly), observations of ClO made during AASE II are used to derive the photolysis rate of Cl2O2. The photolysis rate derived from atmospheric observations is compared to J values calculated with a photochemical model and various values for the absorption cross section of Cl2O2. The photolysis rate calculated with the cross section of Huder and DeMore [1995] is shown to be systematically too small, while those of Burkholder et al. [1990] and Cox and Hayman [1988] are too large to be consistent with atmospheric observations. Observations of BrO made during AASE II indicate that our understanding of the inorganic bromine budget in the polar regions is incomplete. A possible role for the adduct BrOOCl is investigated.

Characterization and identification of Na-Cl sources in ground water

USGS Publications Warehouse

Panno, S.V.; Hackley, Keith C.; Hwang, H.-H.; Greenberg, S.E.; Krapac, I.G.; Landsberger, S.; O'Kelly, D. J.

2006-01-01

Elevated concentrations of sodium (Na+) and chloride (Cl -) in surface and ground water are common in the United States and other countries, and can serve as indicators of, or may constitute, a water quality problem. We have characterized the most prevalent natural and anthropogenic sources of Na+ and Cl- in ground water, primarily in Illinois, and explored techniques that could be used to identify their source. We considered seven potential sources that included agricultural chemicals, septic effluent, animal waste, municipal landfill leachate, sea water, basin brines, and road deicers. The halides Cl-, bromide (Br-), and iodide (I-) were useful indicators of the sources of Na+-Cl- contamination. Iodide enrichment (relative to Cl-) was greatest in precipitation, followed by uncontaminated soil water and ground water, and landfill leachate. The mass ratios of the halides among themselves, with total nitrogen (N), and with Na+ provided diagnostic methods for graphically distinguishing among sources of Na+ and Cl- in contaminated water. Cl/Br ratios relative to Cl- revealed a clear, although overlapping, separation of sample groups. Samples of landfill leachate and ground water known to be contaminated by leachate were enriched in I- and Br-; this provided an excellent fingerprint for identifying leachate contamination. In addition, total N, when plotted against Cl/Br ratios, successfully separated water contaminated by road salt from water contaminated by other sources. Copyright ?? 2005 National Ground Water Association.

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

PubMed

Li, Junxia; Wang, Yanxin; Xie, Xianjun

2016-02-15

In order to identify the salinization processes and its impact on arsenic, fluoride and iodine enrichment in groundwater, hydrogeochemical and environmental isotope studies have been conducted on groundwater from the Datong basin, China. The total dissolved solid (TDS) concentrations in groundwater ranged from 451 to 8250 mg/L, and 41% of all samples were identified as moderately saline groundwater with TDS of 3000-10,000 mg/L. The results of groundwater Cl concentrations, Cl/Br molar ratio and Cl isotope composition suggest that three processes including water-rock interaction, surface saline soil flushing, and evapotranspiration result in the groundwater salinization in the study area. The relatively higher Cl/Br molar ratio in groundwater from multiple screening wells indicates the contribution of halite dissolution from saline soil flushed by vertical infiltration to the groundwater salinization. However, the results of groundwater Cl/Br molar ratio model indicate that the effect of saline soil flushing practice is limited to account for the observed salinity variation in groundwater. The plots of groundwater Cl vs. Cl/Br molar ratio, and Cl vs δ(37)Cl perform the dominant effects of evapotranspiration on groundwater salinization. Inverse geochemical modeling results show that evapotranspiration may cause approximately 66% loss of shallow groundwater to account for the observed hydrochemical pattern. Due to the redox condition fluctuation induced by irrigation activities and evapotranspiration, groundwater salinization processes have negative effects on groundwater arsenic enrichment. For groundwater iodine and fluoride enrichment, evapotranspiration partly accounts for their elevation in slightly saline water. However, too strong evapotranspiration would restrict groundwater fluoride concentration due to the limitation of fluorite solubility. Copyright © 2015. Published by Elsevier B.V.

Die Interhalogenkationen [Br2F5]+ und [Br3F8].

PubMed

Ivlev, Sergei; Karttunen, Antti; Buchner, Magnus; Conrad, Matthias; Kraus, Florian

2018-05-02

Wir berichten über die Synthese und Charakterisierung der bislang einzigen Polyhalogenkationen, in denen verbrückende Fluoratome vorliegen. Das [Br2F5]+-Kation enthält eine symmetrische [F2Br-µ-F-BrF2]-Brücke, das [Br3F8]+-Kation enthält unsymmetrische µ-F-Brücken. Die Fluoronium-Ionen wurden in Form ihrer [SbF6]--Salze erhalten und Raman-, und 19F-NMR-spektroskopisch, sowie durch Röntgenbeugung am Einkristall untersucht. Quantenchemische Rechnungen, sowohl für die isolierten Kationen in der Gasphase, als auch für die Festkörper selbst, wurden durchgeführt. Populationsanalysen zeigen, dass die µ-F-Atome die am stärksten negativ partialgeladenen Atome der Kationen sind. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Naked-eye determination of oxalate anion in aqueous solution with copper ion and pyrocatechol violet.

PubMed

Su, Jing; Sun, Yuan-Qiang; Huo, Fang-Jun; Yang, Yu-Tao; Yin, Cai-Xia

2010-11-01

A novel strategy for the determination of oxalate anions was successfully established using a copper ion and pyrocatechol violet (PV) ensemble. The sensor ensemble can discriminate oxalate over other common anions including F(-), Cl(-), I(-), Br(-), HPO(4)(2-), PO(4)(3-), AcO(-), CO(3)(2-), SO(4)(2-), ClO(4)(-), P(2)O(7)(4-), S(2-) (deposited by Ag(+)), CN(-) (shielded by Fe(3+)) and can detect oxalate at low microgram levels in quasi-physiological aqueous solutions. The detection of the oxalate anion gives rise to a rapid observable visual color change from blue to yellow.

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

NASA Astrophysics Data System (ADS)

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.

Exposure of flight attendants to pyrethroid insecticides on commercial flights: urinary metabolite levels and implications

PubMed Central

Wei, Binnian; Mohan, Krishnan R.; Weisel, Clifford P.

2011-01-01

Pyrethroid insecticides have been used for disinsection of commercial aircrafts. However, little is known about the pyrethroids exposure of flight attendants. The objective of the study was to assess pyrethroids exposure of flight attendants working on commercial aircrafts through monitoring the urinary pyrethroids metabolite levels. Eighty four urine samples were collected from 28 flight attendants, 18 – 65 years of age, with seventeen working on planes that were non-disinsected, and eleven working on planes that had been disinsected. Five urinary metabolites of pyrethroids were measured using gas chromatographic–mass spectrometric method: 3-phenoxybenzoic acid (3-PBA), cis-/trans-3-(2,2-Dichlorovinyl)-2,2-dimethylcyclo-propane carboxylic acid (cis-/trans-Cl2CA), cis-3-(2,2-dibromovinyl)-2,2-dimethylcyclo-propane-1-carboxylic acid (cis-Br2CA) and 4-fluoro-3-phenoxybenzoic acid (4F-3-PBA). Flight attendants working on disinsected planes had significantly higher urinary levels of 3-PBA, cis- and trans-Cl2CA in pre, post- and 24hr-post flight samples than those on planes which did not report having been disinsected. Urinary levels of cis-Br2CA and 4F-3-PBA did not show significant differences between the two groups. Flight attendants working on international flights connected to Australia had higher urinary levels of 3-PBA, cis- and trans-Cl2CA than those on either domestic and other international flights flying among Asia, Europe and North America. Post-disinsection duration (number of days from disinsection date to flight date) was the most significant factor affecting the urinary pyrethroid metabolites levels of 3-PBA, cis- and trans-Cl2CA of the group flying on disinsected aircraft. It was concluded that working on commercial aircrafts disinsected by pyrethroids resulted in elevated body burden of 3-PBA, cis- and trans-Cl2CA. PMID:21937269

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)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Demissie, Taye B., E-mail: taye.b.demissie@uit.no; Komorovsky, Stanislav; Repisky, Michal

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 formore » 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.« less

Enhanced ozone loss by active inorganic bromine chemistry in the tropical troposphere

NASA Astrophysics Data System (ADS)

Le Breton, Michael; Bannan, Thomas J.; Shallcross, Dudley E.; Khan, M. Anwar; Evans, Mathew J.; Lee, James; Lidster, Richard; Andrews, Stephen; Carpenter, Lucy J.; Schmidt, Johan; Jacob, Daniel; Harris, Neil R. P.; Bauguitte, Stephane; Gallagher, Martin; Bacak, Asan; Leather, Kimberley E.; Percival, Carl J.

2017-04-01

Bromine chemistry, particularly in the tropics, has been suggested to play an important role in tropospheric ozone loss although a lack of measurements of active bromine species impedes a quantitative understanding of its impacts. Recent modelling and measurements of bromine monoxide (BrO) by Wang et al. (2015) have shown current models under predict BrO concentrations over the Pacific Ocean and allude to a missing source of BrO. Here, we present the first simultaneous aircraft measurements of atmospheric bromine monoxide, BrO (a radical that along with atomic Br catalytically destroys ozone) and the inorganic Br precursor compounds HOBr, BrCl and Br2 over the Western Pacific Ocean from 0.5 to 7 km. The presence of 0.17-1.64 pptv BrO and 3.6-8 pptv total inorganic Br from these four species throughout the troposphere causes 10-20% of total ozone loss, and confirms the importance of bromine chemistry in the tropical troposphere; contributing to a 6 ppb decrease in ozone levels due to halogen chemistry. Observations are compared with a global chemical transport model and find that the observed high levels of BrO, BrCl and HOBr can be reconciled by active multiphase oxidation of halide (Br- and Cl-) by HOBr and ozone in cloud droplets and aerosols. Measurements indicate that 99% of the instantaneous free Br in the troposphere up to 8 km originates from inorganic halogen photolysis rather than from photolysis of organobromine species.

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

PubMed

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 CuX(2)(pyzO)(H(2)O)(2) complexes are compared to the related CuX(2)(pyrazine) materials.

Chloride and bromide sources in water: Quantitative model use and uncertainty

NASA Astrophysics Data System (ADS)

Horner, Kyle N.; Short, Michael A.; McPhail, D. C.

2017-06-01

Dissolved chloride is a commonly used geochemical tracer in hydrological studies. Assumptions underlying many chloride-based tracer methods do not hold where processes such as halide-bearing mineral dissolution, fluid mixing, or diffusion modify dissolved Cl- concentrations. Failure to identify, quantify, or correct such processes can introduce significant uncertainty to chloride-based tracer calculations. Mass balance or isotopic techniques offer a means to address this uncertainty, however, concurrent evaporation or transpiration can complicate corrections. In this study Cl/Br ratios are used to derive equations that can be used to correct a solution's total dissolved Cl- and Br- concentration for inputs from mineral dissolution and/or binary mixing. We demonstrate the equations' applicability to waters modified by evapotranspiration. The equations can be used to quickly determine the maximum proportion of dissolved Cl- and Br- from each end-member, providing no halide-bearing minerals have precipitated and the Cl/Br ratio of each end member is known. This allows rapid evaluation of halite dissolution or binary mixing contributions to total dissolved Cl- and Br-. Equation sensitivity to heterogeneity and analytical uncertainty is demonstrated through bench-top experiments simulating halite dissolution and variable degrees of evapotranspiration, as commonly occur in arid environments. The predictions agree with the experimental results to within 6% and typically much less, with the sensitivity of the predicted results varying as a function of end-member compositions and analytical uncertainty. Finally, we present a case-study illustrating how the equations presented here can be used to quantify Cl- and Br- sources and sinks in surface water and groundwater and how the equations can be applied to constrain uncertainty in chloride-based tracer calculations.

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)

NASA Astrophysics Data System (ADS)

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.

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

NASA Technical Reports Server (NTRS)

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

1982-01-01

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

Introducing various ligands into superhalogen anions reduces their electronic stabilities

NASA Astrophysics Data System (ADS)

Smuczyńska, Sylwia; Skurski, Piotr

2008-02-01

The vertical electron detachment energies (VDE) of six NaX2- anions (where X = F, Cl, Br) were calculated at the OVGF level with the 6-311++G(3df) basis sets. In all the cases studied the VDE exceeds the electron affinity of chlorine atom and thus those species were classified as superhalogen anions. The largest vertical binding energy was found for the NaF2- system (6.644 eV). The strong VDE dependence on the ligand type, ligand-central atom distance, and the character of the highest occupied molecular orbital (HOMO) was observed and discussed.

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

NASA Astrophysics Data System (ADS)

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.

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

PubMed

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

2014-01-28

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

Strength order and nature of the π-hole bond of cyanuric chloride and 1,3,5-triazine with halide.

PubMed

Wang, Hui; Li, Chen; Wang, Weizhou; Jin, Wei Jun

2015-08-28

The (13)C NMR chemical shift moving upfield indicates the main model of π-holeX(-) bond between cyanuric chloride/1,3,5-triazine (3ClN/3N), which possess both the π-hole and σ-hole, and X(-). (13)C NMR and UV absorption titration in acetonitrile confirmed that the bonding abilities of 3ClN/3N with X(-) follow the order I(-) > Br(-) > Cl(-), which is apparently the order of the charge transfer ability of halide to 3ClN/3N. Chemical calculations showed that the bonding abilities in solution were essentially consistent with those obtained by titration experiments. However, the results in the gas phase were the reverse, i.e., π-holeCl(-) > π-holeBr(-) > π-holeI(-) in bonding energy, which obeys the order of electrostatic interaction. In fact, the π-hole bond and σ-hole bond compete with solvation and possible anion-hydrogen bond between a solvent molecule and a halide in solution. An explanation is that the apparent charge transfer order of π-/σ-holeI(-) > π-/σ-holeBr(-) > π-/σ-holeCl(-) occurs for weak π-hole bonds and σ-hole bonds, whereas the order of electrostatic attraction of π-/σ-holeCl(-) > π-/σ-holeBr(-) > π-/σ-holeI(-) is valid for strong bonds. It can be concluded by combining energy decomposition analysis and natural bond orbital analysis that the π-holeX(-) bond and σ-holeX(-) bond are electrostatically attractive in nature regardless of whether the order is I(-) > Br(-) > Cl(-) or the reverse.

'Pincer' dicarbene complexes of some early transition metals and uranium.

PubMed

Pugh, David; Wright, Joseph A; Freeman, Sandra; Danopoulos, Andreas A

2006-02-14

The complexes [(C-N-C)MX(n)(thf)(m)] with the 'pincer' 2,6-bis(imidazolylidene)pyridine, (C-N-C) = 2,6-bis(arylimidazol-2-ylidene)pyridine, aryl = 2,6-Pr(i)2C6H3, M = V, X = Cl, n = 2, m = 1 1a; M = Cr, X = Cl, n = 2, m = 0, 2a, X = Br, 2b; M = Mn, X = Br, n = 2, m = 0, 3; M = Nb, X = Cl, n = 3, m = 0, 4; and M = U, X = Cl, n = 4, m = 0, 5, were synthesised by (a) substitution of labile tmed (1a), thf (2a, 3, 5) or dme (4) by free (C-N-C) or by (b) reaction of the bisimidazolium salt (CH-N-CH)Br2 with {Cr[N(SiMe3)2]2(thf)2} followed by amine elimination (2b). Attempted alkylation of 1a, 2, 3a and 4 with Grignard or alkyl lithiums gave intractable mixtures, and in one case [reaction of 1a with (mesityl)MgBr] resulted in exchange of Cl by Br (1b). Oxidation of 1a or [(C-N-C)VCl3] with 4-methylmorpholine N-oxide afforded the trans-V(C-N-C)(=O)Cl2, 6, which by reaction with AgBF4 in MeCN gave trans-[V(C-N-C)(=O)(MeCN)2][BF4]2, 7. Reaction of 1a with p-tolyl azide gave trans-V(C-N-C)(=N-p-tolyl)Cl2 8. The complex trans-Ti(C-N-C)(=NBu(t))Cl2, 9, was prepared by substitution of the pyridine ligands in Ti(NBu(t))Cl2(py)3 by C-N-C.

Stability of bromine, iodine monochloride, copper (II) chloride, and nickel (II) chloride intercalated pitch-based graphite fibers

NASA Technical Reports Server (NTRS)

Gaier, James R.; Slabe, Melissa E.; Shaffer, Nanette

1987-01-01

Four different grades of pitch-based graphite fibers (Amoco P-55, P-75, P-100. and P-120) were intercalated with each of four different intercalates: bromine (Br2), iodine monochloride (ICl), copper (II) chloride (CuCl2), and nickel (II) chloride (NiCl2). The P-55 fibers did not react with Br2 or NiCl2, and the P-75 did not react with NiCl2. The stability of the electrical resistance of the intercalated fibers was monitored over long periods of time in ambient, high humidity (100 percent at 60 C), vacuum (10 to the -6 torr), and high temperature (up to 400 C) conditions. Fibers with lower graphitization form graphite intercalation compounds (GIC's) which are more stable than those with higher graphitization (i.e., P-55 (most stable) greater than P-75 greater than P-100 greater than P-120 (least stable). Br2 formed the most stable GIC's followed in order of decreasing stability by ICl, CuCl2, and NiCl2. While Br2 GIC's had the most stability, ICl had the advantages of forming GIC's with slightly greater reduction in resistance (by about 10%) than Br2, and the ability to intercalate P-55 fiber. Transition metal chlorides are susceptible to water vapor and high temperature. The stability of fibers in composites differs.

Coordination trends in alkali metal crown ether uranyl halide complexes: the series [A(crown)]2[UO(2)X(4)] where A=Li, Na, K and X=Cl, Br.

PubMed

Danis, J A; Lin, M R; Scott, B L; Eichhorn, B W; Runde, W H

2001-07-02

UO(2)(C(2)H(3)O(2))(2).2H(2)O reacts with AX or A(C(2)H(3)O(2) or ClO(4)) (where A = Li, Na, K; X = Cl, Br) and crown ethers in HCl or HBr aqueous solutions to give the sandwich-type compounds [K(18-crown-6)](2)[UO(2)Cl(4)] (1), [K(18-crown-6)](2)[UO(2)Br(4)] (2), [Na(15-crown-5)](2)[UO(2)Cl(4)] (3), [Na(15-crown-5)](2)[UO(2)Br(4)] (4), [Li(12-crown-4)](2)[UO(2)Cl(4)] (5), and [Li(12-crown-4)](2)[UO(2)Br(4)] (6). The compounds have been characterized by single-crystal X-ray diffraction, powder diffraction, elemental analysis, IR, and Raman spectroscopy. The [UO(2)X(4)](2-) ions coordinate to two [A(crown)](+) cations through the four halides only (2), through two halides only (3), through the two uranyl oxygens and two halides (3, 4), or through the two uranyl oxygen atoms only (5, 6). Raman spectra reveal nu(U-O) values that correlate with expected trends. The structural trends are discussed within the context of classical principles of hard-soft acid-base theory.

Method of selective reduction of polyhalosilanes with alkyltin hydrides

DOEpatents

Sharp, Kenneth G.; D'Errico, John J.

1989-01-01

The invention relates to the selective and stepwise reduction of polyhalosilanes by reacting at room temperature or below with alkyltin hydrides without the use of free radical intermediates. Alkyltin hydrides selectively and stepwise reduce the Si--Br, Si--Cl, or Si--I bonds while leaving intact any Si--F bonds. When two or more different halogens are present on the polyhalosilane, the halogen with the highest atomic weight is preferentially reduced.

C–H bond halogenation catalyzed or mediated by copper: an overview

PubMed Central

Hao, Wenyan

2015-01-01

Summary Carbon–halogen (C–X) bonds are amongst the most fundamental groups in organic synthesis, they are frequently and widely employed in the synthesis of numerous organic products. The generation of a C–X bond, therefore, constitutes an issue of universal interest. Herein, the research advances on the copper-catalyzed and mediated C–X (X = F, Cl, Br, I) bond formation via direct C–H bond transformation is reviewed. PMID:26664634

Squarylium-based chromogenic anion sensors

NASA Astrophysics Data System (ADS)

Lee, Eun-Mi; Gwon, Seon-Yeong; Son, Young-A.; Kim, Sung-Hoon

2012-09-01

A squarylium (SQ) dye was synthesized by the reaction between squaric acid and 2,3,3-trimethylindolenine and its anion sensing properties were investigated using absorption and emission spectroscopy. This chemosensor exhibited high selectivity for CN- as compared with F-, CHCO2-, Br-, HPO4-, Cl-, and NO3- in acetonitrile, which was attributed to the formation of a 1:1 squarylium:CN- coordination complex, the formation of which was supported by the calculated geometry of the complex.

Quasicharacteristic radiation of relativistic electrons at orientation motion in lithium halides crystals along charged planes and axes

NASA Astrophysics Data System (ADS)

Maksyuta, N. V.; Vysotskii, V. I.; Efimenko, S. V.

2016-07-01

The paper deals with the investigation of the orientation motion of relativistic electrons in charged (111) planes and charged [110] axes of lithium halides ionic crystals of LiF, LiCl, LiBr and LiI. On the basis of these investigations the spectra of quasicharacteristic radiation for the electron beams with various Lorentz-factors both in planar and axial cases have been calculated numerically.

Fundamental studies of gas phase ionic reactions by ion mobility spectrometry

NASA Technical Reports Server (NTRS)

Giles, K.; Knighton, W. B.; Sahlstrom, K. E.; Grimsrud, E. P.

1995-01-01

Ion mobility spectrometry (IMS) provides a promising approach to the study of gas phase ionic reactions in buffer gases at unusually high pressures. This point is illustrated here by studies of the Sn2 nucleophilic displacement reaction, Cl(-) + CH3Br yields Br + CH3Br, using IMS at atmospheric pressure. The equilibrium clustering reaction, Cl(-)(CHCI3)(n - 1) + CHCI3 yields Cl(-)(CHCI3)(n), where n = 1 and 2, and the effect of clustering on the Sn2 reaction with CH3Br have also been characterized by this IMS-based kinetic method. Present problems and anticipated improvements in the application of ion mobility spectrometry to studies of other gas phase ionic processes are discussed.

P3N-PIPO, a Frameshift Product from the P3 Gene, Pleiotropically Determines the Virulence of Clover Yellow Vein Virus in both Resistant and Susceptible Peas

PubMed Central

Suzuki, Haruka; Miyashita, Yuri; Choi, Sun Hee; Hisa, Yusuke; Rihei, Shunsuke; Shimada, Ryoko; Jeon, Eun Jin; Abe, Junya; Uyeda, Ichiro

2016-01-01

ABSTRACT Peas carrying the cyv1 recessive resistance gene are resistant to clover yellow vein virus (ClYVV) isolates No.30 (Cl-No.30) and 90-1 (Cl-90-1) but can be infected by a derivative of Cl-90-1 (Cl-90-1 Br2). The main determinant for the breaking of cyv1 resistance by Cl-90-1 Br2 is P3N-PIPO produced from the P3 gene via transcriptional slippage, and the higher level of P3N-PIPO produced by Cl-90-1 Br2 than by Cl-No.30 contributes to the breaking of resistance. Here we show that P3N-PIPO is also a major virulence determinant in susceptible peas that possess another resistance gene, Cyn1, which does not inhibit systemic infection with ClYVV but causes hypersensitive reaction-like lethal systemic cell death. We previously assumed that the susceptible pea cultivar PI 226564 has a weak allele of Cyn1. Cl-No.30 did not induce cell death, but Cl-90-1 Br2 killed the plants. Our results suggest that P3N-PIPO is recognized by Cyn1 and induces cell death. Unexpectedly, heterologously strongly expressed P3N-PIPO of Cl-No.30 appears to be recognized by Cyn1 in PI 226564. The level of P3N-PIPO accumulation from the P3 gene of Cl-No.30 was significantly lower than that of Cl-90-1 Br2 in a Nicotiana benthamiana transient assay. Therefore, Cyn1-mediated cell death also appears to be determined by the level of P3N-PIPO. The more efficiently a ClYVV isolate broke cyv1 resistance, the more it induced cell death systemically (resulting in a loss of the environment for virus accumulation) in susceptible peas carrying Cyn1, suggesting that antagonistic pleiotropy of P3N-PIPO controls the resistance breaking of ClYVV. IMPORTANCE Control of plant viral disease has relied on the use of resistant cultivars; however, emerging mutant viruses have broken many types of resistance. Recently, we revealed that Cl-90-1 Br2 breaks the recessive resistance conferred by cyv1, mainly by accumulating a higher level of P3N-PIPO than that of the nonbreaking isolate Cl-No.30. Here we show that a susceptible pea line recognized the increased amount of P3N-PIPO produced by Cl-90-1 Br2 and activated the salicylic acid-mediated defense pathway, inducing lethal systemic cell death. We found a gradation of virulence among ClYVV isolates in a cyv1-carrying pea line and two susceptible pea lines. This study suggests a trade-off between breaking of recessive resistance (cyv1) and host viability; the latter is presumably regulated by the dominant Cyn1 gene, which may impose evolutionary constraints upon P3N-PIPO for overcoming resistance. We propose a working model of the host strategy to sustain the durability of resistance and control fast-evolving viruses. PMID:27279605

Ionic liquids and solids with paramagnetic anions.

PubMed

Krieger, Brenna M; Lee, Heather Y; Emge, Thomas J; Wishart, James F; Castner, Edward W

2010-08-21

Four paramagnetic ionic compounds have been prepared and their magnetic, structural and thermal properties have been investigated. The four compounds are methylbutylpyrrolidinium tetrachloroferrate(III) ([Pyrr(14)](+)/[FeCl(4)](-)), methyltributylammonium tetrachloroferrate(III) ([N(1444)](+)/[FeCl(4)](-)), butylmethylimidazolium tetrachloroferrate(III) ([bmim](+)/[FeCl(4)](-)) and tetrabutylammonium bromotrichloroferrate(III) ([N(4444)](+)/[FeBrCl(3)](-)). Temperature-dependent studies of their magnetic behaviors show that all four compounds are paramagnetic at ambient temperatures. Glass transitions are observed for only two of the four compounds, [Pyrr(14)](+)/[FeCl(4)](-) and [bmim](+)/[FeCl(4)](-). Crystal structures for [Pyrr(14)](+)/[FeCl(4)](-) and [N(1444)](+)/[FeCl(4)](-) are compared with the previously reported [N(4444)](+)/[FeBrCl(3)](-).

Analysis of I-Br-Cl in single fluid inclusions by LA-ICP-MS

NASA Astrophysics Data System (ADS)

Giehl, C.; Fusswinkel, T.; Beermann, O.; Garbe-Schönberg, D.; Scholten, L.; Wagner, T.

2017-12-01

Halogens are excellent tracers of hydrothermal fluid sources and in-situ LA-ICP-MS analysis of Cl and Br in single fluid inclusions has provided fundamentally new insight into hydrothermal fluid flow and ore formation. There is mounting evidence that enrichment and depletion of Br relative to Cl may be caused by a number of processes beyond seawater evaporation and halite dissolution which cannot be discriminated on the basis of Br/Cl ratios alone. Expanding the analytical capabilities of fluid inclusion LA-ICP-MS analysis to include iodine would allow to discern between selective and coupled enrichment processes of Cl, Br and I, even in geologically complex samples that are inaccessible to bulk extraction techniques. We present iodine concentration data determined by LA-ICP-MS analysis of synthetic fluid inclusions, using the Sca17 scapolite reference material for external standardization (Seo et al., 2011). Iodine concentrations in Sca17 were determined using the Durango apatite standard. Four starting solutions containing I (0.3, 1.5, 27, 78 µg/g), Br (941, 1403, 2868, 4275 µg/g), Na (30.7, 94.7 mg/g), and Cl (50, 137 mg/g) (analyzed by ICP-OES and ICP-MS at CAU Kiel) were prepared by dissolving reagent grade chemical powders in ultra-pure water. Spherical inclusions (up to 40 µm) were synthesized from the starting solutions in pre-cracked, HF-treated synthetic quartz crystals which were placed in gold capsules and equilibrated at 600°C, 100/200 MPa in cold seal pressure vessels. Fluid inclusion LA-ICP-MS analysis (University of Helsinki) yielded average I concentrations in excellent agreement with the starting solutions (27.3 µg/g ± 14 %RSD for the 27 µg/g solution and 77.6 µg/g ± 8.3 %RSD for the 78 µg/g solution). Average Br and I concentrations deviate less than 10 % from solution concentration values. For the low I concentration solutions, the synthetic inclusions were too small to detect I. Thus, given suitable standard materials and sufficient inclusion sizes, LA-ICP-MS fluid inclusion microanalysis can be used to determine accurate I-Br-Cl concentration data and track the sources of crustal fluids in a wide range of geological settings. Seo, J.H., Guillong, M., Aerts, M., Zajacz, Z., Heinrich, C.A., 2011. Microanalysis of S, Cl, and Br in fluid inclusions by LA-ICP-MS. Chemical Geology 284, 35-44.

Syntheses and structure characterization of ten acid-base hybrid crystals based on imidazole derivatives and mineral acids

NASA Astrophysics Data System (ADS)

Hu, Kaikai; Deng, Bowen; Jin, Shouwen; Ding, Aihua; Jin, Shide; Zhu, Jin; Zhang, Huan; Wang, Daqi

2018-04-01

Cocrystallization of the imidazole derivatives with a series of mineral acids gave a total of ten hybrid salts with the compositions: [(H2bzm)(Cl)2·3H2O] (1), [(H2bzm)(ClO4)2] (2), [(H2bze)(Cl)2·2H2O] (3), [(H2bze)(Br)2·2H2O] (4), [(H2bzp)(Cl)2·4H2O] (5), [(H2bzp)(Br)2·4H2O] (6), (2-(imidazol-1-yl)-1-phenylethanone): (phosphoric acid) [(Himpeta)+(H2PO4)-] (7), [(H2impd)(Br)2] (8), [(H2impd)(ClO4)2] (9), and [(Hbzml)(Cl)] (10). The ten salts have been characterised by X-ray diffraction analysis, IR, and elemental analysis, and the melting points of all the salts were also reported. And their structural and supramolecular aspects are fully analyzed. The result reveals that among the ten investigated crystals the ring N atoms of the imidazole are protonated when the acids are deprotonated, and the crystal packing is interpreted in terms of the strong charge-assisted classical H-bonds between the NH+ and deprotonated acidic groups. Further analysis of the crystal packing of the salts indicated that a different set of additional CHsbnd O, CH2sbnd O, CHsbnd Cl, CH2sbnd Cl, CHsbnd N, CHsbnd Br, CH2sbnd Br, Osbnd O, O-π, Br-π, CH-π, and π-π associations contribute to the stabilization and expansion of the total high-dimensional frameworks. For the coexistence of the various weak nonbonding interactions these structures adopted homo or hetero supramolecular synthons or both. Some classical supramolecular synthons, such as R21(7), R22(7), R22(8), and R42(8), usually observed in the organic solids, were again shown to be involved in constructing some of these H-bonding networks.

Antiulcerogenic effect of a hydroalcoholic extract and its organic fractions of Neurolaena lobata (L.) R.BR.

PubMed

Gracioso, J S; Hiruma-Lima, C A; Souza Brito, A R

2000-07-01

Neurolaena lobata is a species used widely in Caribbean folk medicine to treat gastric pain and ulcers. The hexane (HxF), chloroform (ClF) and aqueous (H2OF) fractions of a hydroalcoholic extract (HE) of N. lobata aerial parts were investigated for their ability to prevent ulceration of the gastric mucosa. In the stress-induced gastric model the HE, HxF and ClF fractions produced a significant reduction of gastric lesion formation by 48, 70 and 52%, respectively. HE, HxF and ClF fractions (41, 57 and 51%, respectively) also reduced significantly the gastric lesions induced by the combination of indomethacin and bethanechol, and the ulcers induced by HCl/ethanol solution by 77, 86 and 83%, respectively (P < 0.05). The pylorus-ligature experiment demonstrated that the HE, HxF and ClF fractions changed significantly the gastric juice parameters, such as pH values (increases to 5.4, 4.9 and 4.8, respectively) and acid output (decreased by 4.6, 5.8 and 6.2 mEq mL(-1) 4h respectively) and gastric content (increased by 400, 410 and 390 mg, respectively) in animals. In the animals pre-treated orally with the HxF fraction, prostaglandin synthesis was increased significantly, by 104%, and free mucus production was increased by 54 % in the gastric mucosa (P < 0.001). The H2OF did not exhibit activity in any of the experimental models assayed. The data suggest that the HE and mainly the HxF of fractions from N. lobata present a significant anti-ulcer effect when assessed in these ulcer-induced models. Although the mechanism underlying this antiulcerogenic effect remains unknown, it seems to be related to an increased activity of the defensive mechanisms of the stomach, such as prostaglandin synthesis and mucus production.

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

NASA Astrophysics Data System (ADS)

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).

Anion dependent ion pairing in concentrated ytterbium halide solutions

NASA Astrophysics Data System (ADS)

Klinkhammer, Christina; Böhm, Fabian; Sharma, Vinay; Schwaab, Gerhard; Seitz, Michael; Havenith, Martina

2018-06-01

We have studied ion pairing of ytterbium halide solutions. THz spectra (30-400 cm-1) of aqueous YbCl3 and YbBr3 solutions reveal fundamental differences in the hydration structures of YbCl3 and YbBr3 at high salt concentrations: While for YbBr3 no indications for a changing local hydration environment of the ions were experimentally observed within the measured concentration range, the spectra of YbCl3 pointed towards formation of weak contact ion pairs. The proposed anion specificity for ion pairing was confirmed by supplementary Raman measurements.

Electronic Structure Approach to Tunable Electronic Properties of Hybrid Organic-Inorganic Perovskites

NASA Astrophysics Data System (ADS)

Liu, Garnett; Huhn, William; Mitzi, David B.; Kanai, Yosuke; Blum, Volker

We present a study of the electronic structure of layered hybrid organic-inorganic perovskite (HOIP) materials using all-electron density-functional theory. Varying the nature of the organic and inorganic layers should enable systematically fine-tuning the carrier properties of each component. Using the HSE06 hybrid density functional including spin-orbit coupling (SOC), we validate the principle of tuning subsystem-specific parts of the electron band structures and densities of states in CH3NH3PbX3 (X=Cl, Br, I) compared to a modified organic component in layered (C6H5C2H4NH3) 2PbX4 (X=Cl, Br, I) and C20H22S4N2PbX4 (X=Cl, Br, I). We show that tunable shifts of electronic levels indeed arise by varying Cl, Br, I as the inorganic components, and CH3NH3+ , C6H5C2H4NH3+ , C20H22S4N22 + as the organic components. SOC is found to play an important role in splitting the conduction bands of the HOIP compounds investigated here. The frontier orbitals of the halide shift, increasing the gap, when Cl is substituted for Br and I.

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).

PubMed

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 < I and Y = I < Br < Cl for given Y and X, respectively. The emission lifetimes (τ em ) of the clusters also increase in the sequence Y = I < 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.

Intermediate Temperature Fluids Life Tests - Experiments

DTIC Science & Technology

2007-06-01

TiCl4, TiBr4, and eutectic diphenyl/diphenyl oxide (Therminol VP-1/Dowtherm A). All of the life tests except for the GaCl3 are ongoing; the GaCl3...763 85.5 Eutectic Diphenyl/Diphenyl Oxide 285 530 770 31 Antimony Tribromide SbBr3 370 553 1178 55 Antimony Trichloride SbCl3 346 556 794 Cesium...From a Compatibility Standpoint) Have High Decomposition Potentials, While Halides/ Salts of Good Envelope Materials Have Low Decomposition Potentials

Mercury monohalides: suitability for electron electric dipole moment searches.

PubMed

Prasannaa, V S; Vutha, A C; Abe, M; Das, B P

2015-05-08

Heavy polar diatomic molecules are the primary tools for searching for the T-violating permanent electric dipole moment of the electron (eEDM). Valence electrons in some molecules experience extremely large effective electric fields due to relativistic interactions. These large effective electric fields are crucial to the success of polar-molecule-based eEDM search experiments. Here we report on the results of relativistic ab initio calculations of the effective electric fields in a series of molecules that are highly sensitive to an eEDM, the mercury monohalides (HgF, HgCl, HgBr, and HgI). We study the influence of the halide anions on E_{eff}, and identify HgBr and HgI as attractive candidates for future electric dipole moment search experiments.

Crystal structure of {2,6-bis-[(di-methyl-amino)-meth-yl]phenyl-κ3N,C1,N'}(bromido/chlorido)-mercury(II).

PubMed

Gupta, Anand; Singh, Harkesh B; Butcher, Ray J

2017-11-01

In the mol-ecular structure of the title compound, {2,6-bis-[(di-methyl-amino)-meth-yl]phenyl-κ 3 N , C 1 , N '}[bromido/chlorido-(0.30/0.70)]mercury(II)-{2,6-bis-[(di-methyl-amino)-meth-yl]phenyl-κ 3 N , C 1 , N '}[bromido/chlorido-(0.24/0.76)]mer-cury(II) (1/1), [HgBr 0.30 Cl 0.70 (C 12 H 19 N 2 )]·[HgBr 0.24 Cl 0.76 (C 12 H 19 N 2 )], there are two mol-ecules in the asymmetric unit of formula L Hg X { L = 2,6-bis-[(di-methyl-amino)-meth-yl]phenyl and X = Cl/Br}. In each mol-ecule, the halide site is mixed Cl/Br, with occupancies of 0.699 (7):0.301 (7) and 0.763 (7):0.237 (7), respectively. The two mol-ecules are linked into dimers by a combination of Hg⋯Hg [Hg⋯Hg = 3.6153 (3) Å] and C-H⋯Cl and C-H⋯π inter-actions.

Electronic effects of Se and Pb dopants in TlBr

NASA Astrophysics Data System (ADS)

Smith, Holland M.; Phillips, David J.; Sharp, Ian D.; Beeman, Jeffrey W.; Chrzan, Daryl C.; Haegel, Nancy M.; Haller, Eugene E.; Ciampi, Guido; Kim, Hadong; Shah, Kanai S.

2012-05-01

Deep levels in Se- and Pb-doped bulk TlBr detectors were characterized with photo-induced conductivity transient spectroscopy (PICTS) and cathodoluminescence (CL). Se-doped TlBr revealed two traps with energies of 0.35 and 0.45 eV in PICTS spectra. The Pb-doped material revealed three levels with energies of 0.11, 0.45, and 0.75 eV. CL measurements in both materials correlate with optical transitions involving some of the identified levels. The ambipolar carrier lifetimes of Se-doped and Pb-doped TlBr were measured with microwave reflectivity transients and found to be significantly lower than the lifetime of undoped TlBr.

Orientational glasses. II. Calculation of critical thresholds in ACNxMn{1-x} mixtures

NASA Astrophysics Data System (ADS)

Galam, Serge; Depondt, Philippe

1992-10-01

Using a simple steric hindrance based idea, critical thresholds which occur in the phase diagram of ACNxMn{1-x} mixtures, where A stands for K, Na or Rb while Mn represents Br, Cl or I, are calculated. The cyanide density x is divided into a free-to-reorient part x_r, and a frozen-in part x_f. The latter term x_f is calculated from microscopic characteristics of the molecules involved. Two critical thresholds x_c and x_d for the disappearance of respectively, ferroelastic transitions and ferroelastic domains are obtained. The calculated values are in excellent agreement with available experimental results. Predictions are made for additionnal mixtures. Une idée simple d'encombrement stérique permet de calculer des seuils critiques qui apparaissent dans le diagramme de phase de mélanges ACNxMn{1-x}, où A représente K, Na ou Rb, et Mn, des atoms du type Br, Cl ou I. La concentration x du cyanure est divisée en une partie x_r de molécules libres de se réorienter, et une partie de molécules gelées x_f. Ce dernier terme x_f est calculé à partir des caractéristiques microscopiques des molécules concernées. Deux seuils critiques x_c et x_d pour la disparition respectivement des transitions et des domaines ferroelastiques sont obtenus. Les valeurs calculées sont en excellent accord avec les résultats expérimentaux disponibles. Des prédictions sont faites pour d'autres mélanges.

DOE Office of Scientific and Technical Information (OSTI.GOV)

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

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, themore » 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.« less

Fast and accurate predictions of covalent bonds in chemical space.

PubMed

Chang, K Y Samuel; Fias, Stijn; Ramakrishnan, Raghunathan; von Lilienfeld, O Anatole

2016-05-07

We assess the predictive accuracy of perturbation theory based estimates of changes in covalent bonding due to linear alchemical interpolations among molecules. We have investigated σ bonding to hydrogen, as well as σ and π bonding between main-group elements, occurring in small sets of iso-valence-electronic molecules with elements drawn from second to fourth rows in the p-block of the periodic table. Numerical evidence suggests that first order Taylor expansions of covalent bonding potentials can achieve high accuracy if (i) the alchemical interpolation is vertical (fixed geometry), (ii) it involves elements from the third and fourth rows of the periodic table, and (iii) an optimal reference geometry is used. This leads to near linear changes in the bonding potential, resulting in analytical predictions with chemical accuracy (∼1 kcal/mol). Second order estimates deteriorate the prediction. If initial and final molecules differ not only in composition but also in geometry, all estimates become substantially worse, with second order being slightly more accurate than first order. The independent particle approximation based second order perturbation theory performs poorly when compared to the coupled perturbed or finite difference approach. Taylor series expansions up to fourth order of the potential energy curve of highly symmetric systems indicate a finite radius of convergence, as illustrated for the alchemical stretching of H2 (+). Results are presented for (i) covalent bonds to hydrogen in 12 molecules with 8 valence electrons (CH4, NH3, H2O, HF, SiH4, PH3, H2S, HCl, GeH4, AsH3, H2Se, HBr); (ii) main-group single bonds in 9 molecules with 14 valence electrons (CH3F, CH3Cl, CH3Br, SiH3F, SiH3Cl, SiH3Br, GeH3F, GeH3Cl, GeH3Br); (iii) main-group double bonds in 9 molecules with 12 valence electrons (CH2O, CH2S, CH2Se, SiH2O, SiH2S, SiH2Se, GeH2O, GeH2S, GeH2Se); (iv) main-group triple bonds in 9 molecules with 10 valence electrons (HCN, HCP, HCAs, HSiN, HSiP, HSiAs, HGeN, HGeP, HGeAs); and (v) H2 (+) single bond with 1 electron.

Investigation of a mercurous chloride acousto-optic cell based on longitudinal acoustic mode.

PubMed

Gupta, Neelam

2009-03-01

A number of spectral imagers using acousto-optic tunable filters (AOTFs) operating from the UV to the longwave infrared (LWIR) using KDP, MgF(2), TeO(2), and Tl(3)AsSe(3) crystals to cover different spectral regions have been developed. In the LWIR there is a lack of high quality acousto-optic (AO) materials. Mercurous halide (Hg(2)Cl(2) and Hg(2)Br(2)) crystals are highly anisotropic with a high AO figure of merit due to slow acoustic velocities and high photoelastic constants and are transparent over a wide spectral region from 0.35 to 20 mum for Hg(2)Cl(2) and from 0.4 to 30 mum for Hg(2)Br(2). AO modulators, deflectors, and AOTFs based on these crystals can operate over a wide spectral range. Single crystals of these materials are being grown and some prototype devices have been fabricated. Results are presented from device characterization for an AO cell fabricated in Hg(2)Cl(2) based on longitudinal acoustic mode propagation. This device was very useful in demonstrating the AO interaction as well as soundness of the transducer bonding technique. Acoustic phase velocity is calculated and measured, diffraction efficiency is obtained from experiments, and the AO figure of merit of the sample is evaluated.

Spectral studies related to dissociation of HBr, HCl and BrO

NASA Technical Reports Server (NTRS)

Ginter, M. L.

1986-01-01

Concern over halogen catalyzed decomposition of O3 in the upper atmosphere has generated need for data on the atomic and molecular species X, HX and XO (where X is Cl and Br). Of special importance are Cl produced from freon decomposition and Cl and Br produced from natural processes and from other industrial and agricultural chemicals. Basic spectral data is provided on HCl, HBr, and BrO necessary to detect specific states and energy levels, to enable detailed modeling of the processes involving molecular dissociation, ionization, etc., and to help evaluate field experiments to check the validity of model calculations for these species in the upper atmosphere. Results contained in four published papers and two major spectral compilations are summarized together with other results obtained.

Rate constants and temperature dependences for the reactions of hydroxyl radical with several halogenated methanes, ethanes, and propanes by relative rate measurements

NASA Technical Reports Server (NTRS)

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

1995-01-01

Rate constants of 15 OH reactions with halogen-substituted alkanes, C1 to C3, were studied using a relative rate technique in the temperature range 283-403 K. Compounds studied were CHF2Cl (22), CHF2Br (22B), CH3F (41), CH2F2 (32), CHF3 (23), CHClFCCl2F (122a), CHCl2CF3 (123), CHClFCF3 (124), CH3CF3 (143a), CH3CH2F (161), CF3CHFCF3 (227ea), CF3CH2CF3 (236fa), CF3CHFCHF2 (236ea), and CHF2CF2CH2F (245ca). Using CH4, CH3CCl3, CF3CF2H, and C2H6 as primary reference standards (JPL 92-20 rate constants), absolute rate constants are derived. Results are in good agreement with previous experimental results for six of the compounds studied, including CHF2Cl, CHF2Br, CH2F2, CH3CF3, CHFClCFCl2, and CF3CHFCF3. For the remainder the relative rate constants are lower than those derived from experiments in which OH loss was used to measure the reaction rate. Comparisons of the derived Arrhenius A factors with previous literature transition-state calculations show order of magnitude agreement in most cases. However, the experimental A factors show a much closer proportionality to the number of H atoms in the molecule than is evident from the transition state calculations. For most of the compounds studied, an A factor of (8 +/- 3)E-13 cm(exp 3)/(molecule s) per C-H bond is observed. A new measurement of the ratio k(CH3CCl3)/k(CH4) is reported that is in good agreement with previous data.

Congener-specific determination of ultratrace levels of chlorinated and brominated polycyclic aromatic hydrocarbons in atmosphere and industrial stack gas by isotopic dilution gas chromatography/high resolution mass spectrometry method.

PubMed

Jin, Rong; Liu, Guorui; Zheng, Minghui; Fiedler, Heidelore; Jiang, Xiaoxu; Yang, Lili; Wu, Xiaolin; Xu, Yang

2017-08-04

Isotopic dilution gas chromatography combined with high resolution mass spectrometry (GC/HRMS) has overwhelming advantages with respect to the accuracy of congener-specific ultratrace analysis of complex persistent organic pollutants (POPs) in environmental matrices. However, an isotopic dilution GC/HRMS method for analysis of chlorinated and brominated polycyclic aromatic hydrocarbons (Cl-PAHs and Br-PAHs) using 13 C-labelled congeners as internal standards has not been established. In this study, a method for identification and quantification of 38 congeners of Cl-PAHs and Br-PAHs in atmosphere and stack gas samples from waste incinerators was developed using the isotopic dilution GC/HRMS technique. The instrumental detection limits of the GC/HRMS method ranged from 0.2pg to 1.8pg for Cl-PAH congeners, and 0.7pg to 2.7pg for Br-PAH congeners, which were about three orders of magnitude lower than those of the GC/quadrupole MS method. This new method developed was also the first to enable determination of Cl-PAH and Br-PAH homologs comprising congeners with the same molecular skeleton and chlorine or bromine substitution numbers. Among the detected congeners, seven Cl-PAH congeners and thirteen Br-PAH congeners that were abundant in the atmosphere and stack gases released from waste incinerators were firstly detected in real samples and reported using the established isotopic dilution GC/HRMS method. The developed isotopic dilution GC/HRMS is significant and needed for better studying the environmental behavior and health risk of Cl-PAHs and Br-PAHs. Copyright © 2017 Elsevier B.V. All rights reserved.

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

PubMed

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

2016-09-06

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.

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

PubMed

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).

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

PubMed

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.

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.

PubMed

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.

Redox shuttles for lithium ion batteries

DOEpatents

Weng, Wei; Zhang, Zhengcheng; Amine, Khalil

2014-11-04

Compounds may have general Formula IVA or IVB. ##STR00001## where, R.sup.8, R.sup.9, R.sup.10, and R.sup.11 are each independently selected from H, F, Cl, Br, CN, NO.sub.2, alkyl, haloalkyl, and alkoxy groups; X and Y are each independently O, S, N, or P; and Z' is a linkage between X and Y. Such compounds may be used as redox shuttles in electrolytes for use in electrochemical cells, batteries and electronic devices.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zeng, Yijie; Xing, Huaizhong, E-mail: xinghz@dhu.edu.cn; Lu, Aijiang

2015-08-07

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

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

PubMed

Chen, Zhenhua; Corminboeuf, Clémence; Mo, Yirong

2014-08-07

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

A comment on "The interaction of X2 (X = F, Cl, and Br) with active sites of graphite" [Xu et al., Chem. Phys. Lett., 418, 413 (2006)

NASA Astrophysics Data System (ADS)

Lechner, Christoph; Baranek, Philippe; Vach, Holger

2018-04-01

In their article, Xu et al. (2006) present the adsorption energies for the chemisorption of the three halogens F2 , Cl2 , and Br2 on the active sites of graphite. The three investigated systems are the three most stable surfaces, (0 0 1), (1 0 0), and (1 1 0); the latter two are also called zigzag and armchair surface, respectively. Due to some inconsistencies in their article, we re-evaluated the results of Xu et al. in order to investigate the impact on the adsorption energies of the halogens. For the (0 0 1) surface, our results agree with Xu et al. However, for the other two surfaces we find major differences. Contrary to Xu et al., we find that the halogens adsorb the strongest on the zigzag surface. The second strongest adsorption is found on the armchair surface for the symmetric configurations, the third strongest for the asymmetric configurations. Several reasons are given which explain this discrepancy. The most striking source of error in the work of Xu et al. is due to the fact that they did not choose the correct spin multiplicities for the model systems which means that they performed the calculations in excited states. This leads to errors between 50 and 600% for the zigzag surface and 3-42% for the armchair surface.

P3N-PIPO, a Frameshift Product from the P3 Gene, Pleiotropically Determines the Virulence of Clover Yellow Vein Virus in both Resistant and Susceptible Peas.

PubMed

Atsumi, Go; Suzuki, Haruka; Miyashita, Yuri; Choi, Sun Hee; Hisa, Yusuke; Rihei, Shunsuke; Shimada, Ryoko; Jeon, Eun Jin; Abe, Junya; Nakahara, Kenji S; Uyeda, Ichiro

2016-08-15

Peas carrying the cyv1 recessive resistance gene are resistant to clover yellow vein virus (ClYVV) isolates No.30 (Cl-No.30) and 90-1 (Cl-90-1) but can be infected by a derivative of Cl-90-1 (Cl-90-1 Br2). The main determinant for the breaking of cyv1 resistance by Cl-90-1 Br2 is P3N-PIPO produced from the P3 gene via transcriptional slippage, and the higher level of P3N-PIPO produced by Cl-90-1 Br2 than by Cl-No.30 contributes to the breaking of resistance. Here we show that P3N-PIPO is also a major virulence determinant in susceptible peas that possess another resistance gene, Cyn1, which does not inhibit systemic infection with ClYVV but causes hypersensitive reaction-like lethal systemic cell death. We previously assumed that the susceptible pea cultivar PI 226564 has a weak allele of Cyn1 Cl-No.30 did not induce cell death, but Cl-90-1 Br2 killed the plants. Our results suggest that P3N-PIPO is recognized by Cyn1 and induces cell death. Unexpectedly, heterologously strongly expressed P3N-PIPO of Cl-No.30 appears to be recognized by Cyn1 in PI 226564. The level of P3N-PIPO accumulation from the P3 gene of Cl-No.30 was significantly lower than that of Cl-90-1 Br2 in a Nicotiana benthamiana transient assay. Therefore, Cyn1-mediated cell death also appears to be determined by the level of P3N-PIPO. The more efficiently a ClYVV isolate broke cyv1 resistance, the more it induced cell death systemically (resulting in a loss of the environment for virus accumulation) in susceptible peas carrying Cyn1, suggesting that antagonistic pleiotropy of P3N-PIPO controls the resistance breaking of ClYVV. Control of plant viral disease has relied on the use of resistant cultivars; however, emerging mutant viruses have broken many types of resistance. Recently, we revealed that Cl-90-1 Br2 breaks the recessive resistance conferred by cyv1, mainly by accumulating a higher level of P3N-PIPO than that of the nonbreaking isolate Cl-No.30. Here we show that a susceptible pea line recognized the increased amount of P3N-PIPO produced by Cl-90-1 Br2 and activated the salicylic acid-mediated defense pathway, inducing lethal systemic cell death. We found a gradation of virulence among ClYVV isolates in a cyv1-carrying pea line and two susceptible pea lines. This study suggests a trade-off between breaking of recessive resistance (cyv1) and host viability; the latter is presumably regulated by the dominant Cyn1 gene, which may impose evolutionary constraints upon P3N-PIPO for overcoming resistance. We propose a working model of the host strategy to sustain the durability of resistance and control fast-evolving viruses. Copyright © 2016, American Society for Microbiology. All Rights Reserved.

Self-assembly of five 8-hydroxyquinolinate-based complexes: tunable core, supramolecular structure, and photoluminescence properties.

PubMed

Yuan, Guozan; Shan, Weilong; Qiao, Xuelong; Ma, Li; Huo, Yanping

2014-07-01

Five new Zn(II) complexes, namely [Zn(3)(L)(6)] (1), [Zn(2)(Cl)(2)(L)(2) (py)(2)] (2), [Zn(2)(Br)(2) (L)(2)(py)(2)] (3), [Zn(L)(2)(py)] (4), and [Zn(2)(OAc)(2)(L)(2)(py)(2)] (5), were prepared by the solvothermal reaction of ZnX(2) (X(-) =Cl(-), Br(-), F(-), and OAc(-)) salts with a 8-hydroxyquinolinate ligand (HL) that contained a trifluorophenyl group. All of the complexes were characterized by elemental analysis, IR spectroscopy, and powder and single-crystal X-ray crystallography. The building blocks exhibited unprecedented structural diversification and their self-assembly afforded one mononuclear, three binuclear, and one trinuclear Zn(II) structures in response to different anions and solvent systems. Complexes 1-5 featured four types of supramolecular network controlled by non-covalent interactions, such as π⋅⋅⋅π-stacking, C-H⋅⋅⋅π, hydrogen-bonding, and halogen-related interactions. Investigation of their photoluminescence properties exhibited disparate emission wavelengths, lifetimes, and quantum yields in the solid state. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Oxidation of methyl halides by the facultative methylotroph strain IMB-1

USGS Publications Warehouse

Schaefer, J.K.; Oremland, R.S.

1999-01-01

Washed cell suspensions of the facultative methylotroph strain IMB-1 grown on methyl bromide (MeBr) were able to consume methyl chloride (MeCl) and methyl iodide (MeI) as well as MeBr. Consumption of >100 ??M MeBr by cells grown on glucose, acetate, or monomethylamine required induction. Induction was inhibited by chloramphenicol. However, cells had a constitutive ability to consume low concentrations (<20 nM) of MeBr. Glucose-grown cells were able to readily oxidize [14C]formaldehyde to 14CO2 but had only a small capacity for oxidation of [14C]methanol. Preincubation of cells with MeBr did not affect either activity, but MeBr-induced cells had a greater capacity for [14C]MeBr oxidation than did cells without preincubation. Consumption of MeBr was inhibited by MeI, and MeCl consumption was inhibited by MeBr. No inhibition of MeBr consumption occurred with methyl fluoride, propyl iodide, dibromomethane, dichloromethane, or difluoromethane, and in addition cells did not oxidize any of these compounds. Cells displayed Michaelis-Menten kinetics for the various methyl halides, with apparent K(s) values of 190, 280, and 6,100 nM for MeBr, MeI, and MeCl, respectively. These results suggest the presence of a single oxidation enzyme system specific for methyl halides (other than methyl fluoride) which runs through formaldehyde to CO2. The ease of induction of methyl halide oxidation in strain IMB-1 should facilitate its mass culture for the purpose of reducing MeBr emissions to the atmosphere from fumigated soils.

Heterometallic aggregates of copper(I) with metalloligand Sn(edt)2 (edt = ethane-1,2-dithiolate): syntheses and structures of [Sn(edt)2Cl(mu-I)(mu3-I)(CuPPh3)3], [Sn(edt)2(mu-Br)2(mu3-Br)2(CuPPh3)4], and [{Sn(edt)2}3(mu-OH)3Cu5(PPh3)8][PF6]2.

PubMed

Han, Yan-Gong; Xu, Chao; Duan, Taike; Wu, Fang-Hui; Zhang, Qian-Feng; Leung, Wa-Hung

2009-09-21

The treatment of a slurry of an equimolar mixture of [Sn(edt)(2)] (edt = ethane-1,2- dithiolate) and [Et(4)N]Cl.xH(2)O with CuI in the presence of PPh(3) gave a tetranuclear compound, [Sn(edt)(2)Cl(mu-I)(mu(3)-I)(CuPPh(3))(3)] (1), which consists of a rectangular-pyramidal [Sn(edt)(2)Cl](-) moiety ligated by three [Cu(PPh(3))](+) fragments via the sulfur atoms of the edt(2-) ligands. The treatment of a slurry of [Sn(edt)(2)] and excess [Et(4)N]Br with [Cu(MeCN)(4)][PF(6)] in the presence of PPh(3) afforded a pentanuclear compound, [Sn(edt)(2)(mu-Br)(2)(mu(3)-Br)(2)(CuPPh(3))(4)] (2), which comprises two [(CuPPh(3))(2)(mu-Br)](+) fragments symmetrically ligating an octahedral trans-[Sn(edt)(2)Br(2)](2-) moiety via the sulfur and bromide atoms. Reaction of [Sn(edt)(2)] with [Cu(MeCN)(4)][PF(6)] and PPh(3) in a mixed MeCN/CH(2)Cl(2) solution yielded a novel octanuclear compound, [{Sn(edt)(2)}(3)(mu-OH)(3)Cu(5)(PPh(3))(8)][PF(6)](2) (3), which may be described as a triangular [{Sn(edt)(2)}(3)(mu-OH)(3)](3-) core chelated by three [Cu(PPh(3))(2)](+) species and capped by two [Cu(PPh(3))](+) species. The luminescent properties of compounds 1, 2, and 3 were investigated in a CH(2)Cl(2) solution at room temperature. Upon excitation at lambda > 360 nm, these compounds are luminescent in CH(2)Cl(2) solution with emissions having maxima at 422, 515, and 494 nm, respectively.

Liquid-liquid distribution of ion associates of tetrabromoindate(III) with quaternary ammonium counter ions.

PubMed

Yamamoto, K; Matsumoto, A

1997-11-01

The solvent extraction of an ion associate of tetrabromoindate(III) ion, InBr(-)(4), with quaternary ammonium cations (Q(+)) has been studied. The extraction constant (K(ex)) were determined for the ion associates of InBr(-)(4) with Q(+) between an aqueous phase and several organic phases (chloroform, chlorobenzene, benzene and toluene). A linear relationship was found between log K(ex) and the total number of carbon atoms in Q(+); from the slope of the lines, the contribution of a methylene group to log K(ex) was calculated to be 0.91 for the chloroform extraction system and 0.52 for the other extraction systems. The extractability with alkyltrimethylammonium cations was larger than that with symmetrical tetraalkylammonium cations and the mean difference in log K(ex) for two cations (one of each type) with the same number of carbon atoms was about 1.3. From the extraction constant obtained, the extractability of InBr(-)(4) among metal-halogeno complex anions was in the order TlBr(-)(4) > BiI(-)(4) > AuBr(-)(4) > AuCl(-)(4) > TlCl(-)(4) > InBr(-)(4) > CuCl(-)(2).

Concentration Effects and Ion Properties Controlling the Fractionation of Halides during Aerosol Formation

NASA Technical Reports Server (NTRS)

Guzman, Marcelo I.; Athalye, Richa R.; Rodriguez, Jose M.

2012-01-01

During the aerosolization process at the sea surface, halides are incorporated into aerosol droplets, where they may play an important role in tropospheric ozone chemistry. Although this process may significantly contribute to the formation of reactive gas phase molecular halogens, little is known about the environmental factors that control how halides selectively accumulate at the air-water interface. In this study, the production of sea spray aerosol is simulated using electrospray ionization (ESI) of 100 nM equimolar solutions of NaCl, NaBr, NaI, NaNO2, NaNO3, NaClO4, and NaIO4. The microdroplets generated are analyzed by mass spectrometry to study the comparative enrichment of anions (f (Isub x-)) and their correlation with ion properties. Although no correlation exists between f (sub x-) and the limiting equivalent ionic conductivity, the correlation coefficient of the linear fit with the size of the anions R(sub x-), dehydration free-energy ?Gdehyd, and polarizability alpha, follows the order: (R(sub x-)(exp -2)) > (R(sub x-)(exp -1)) >(R(sub x-) > delta G(sub dehyd) > alpha. The same pure physical process is observed in H2O and D2O. The factor f (sub x-) does not change with pH (6.8-8.6), counterion (Li+, Na+, K+, and Cs+) substitution effects, or solvent polarity changes in methanol - and ethanol-water mixtures (0 <= xH2O <= 1). Sodium polysorbate 20 surfactant is used to modify the structure of the interface. Despite the observed enrichment of I- on the air-water interface of equimolar solutions, our results of seawater mimic samples agree with a model in which the interfacial composition is increasingly enriched in I- < Br- < Cl- over the oceanic boundary layer due to concentration effects in sea spray aerosol formation.

Diversity of band gap and photoluminescence properties of lead halide perovskite: A halogen-dependent spectroscopic study

NASA Astrophysics Data System (ADS)

Yu, Wenlei; Jiang, Yunfeng; Zhu, Xiuwei; Luo, Chunhua; Jiang, Kai; Chen, Liangliang; Zhang, Juan

2018-05-01

The effects of halogen substitution on microstructure, optical absorption, and phonon modes for perovskite CH3NH3PbX3 (MAPbX3, X = I/Br/Cl) films grown on FTO substrates have been investigated. The X-ray diffraction analysis exhibited good crystallization, and the strong diffraction peak assigned to (1 0 0) c for X = Br/Cl shifted toward a higher angle compared to (1 1 0) t of MAPbI3. Band-gap tuning from 1.63 to 2.37 to 3.11 eV in the I-Br-Cl series can be found due to the halogen effects. These energy values closely match the positions of peak determined from photoluminescence experiments. The remarkable absorption dip and emission peak appear for the MAPbBr3, suggesting higher crystallinity under the same preparation conditions. The wavenumbers of main IR-vibrations slightly decrease with ionic radius of the halogen increasing (in the order of Cl-Br-I), which related to the increasing polarizability. These results provide important progress towards the understanding of the halide role in the realization of high performance MAPbX3-based solar cells.

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

NASA Astrophysics Data System (ADS)

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

2009-10-01

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

The origin of the conductivity maximum in molten salts. II. SnCl{sub 2} and HgBr{sub 2}

DOE Office of Scientific and Technical Information (OSTI.GOV)

Aravindakshan, Nikhil P.; Kuntz, Colin M.; Gemmell, Kyle E.

2016-09-07

The phenomenon of electrical conductivity maxima of molten salts versus temperature during orthobaric (closed-vessel) conditions is further examined via ab initio simulations. Previously, in a study of molten BiCl{sub 3}, a new theory was offered in which the conductivity falloff at high temperatures is due not to traditional ion association, but to a rise in the activation energy for atomic ions hopping from counterion to counterion. Here this theory is further tested on two more inorganic melts which exhibit conductivity maxima: another high-conducting melt (SnCl{sub 2}, σ{sub max} = 2.81 Ω{sup −1} cm{sup −1}) and a low-conducting one (HgBr{sub 2},more » σ{sub max} = 4.06 × 10{sup −4} Ω{sup −1} cm{sup −1}). First, ab initio molecular dynamics simulations were performed and again appear successful in reproducing the maxima for both these liquids. Second, analysis of the simulated liquid structure (radial distributions, species concentrations) was performed. In the HgBr{sub 2} case, a very molecular liquid like water, a clear Grotthuss chain of bromide transfers was observed in simulation when seeding the system with a HgBr{sup +} cation and HgBr{sub 3}{sup −} anion. The first conclusion is that the hopping mechanism offered for molten BiCl{sub 3} is simply the Grotthuss mechanism for conduction, applicable not just to H{sup +} ions, but also to halide ions in post-transition-metal halide melts. Second, it is conjectured that the conductivity maximum is due to rising activation energy in network-covalent (halide-bridging) melts (BiCl{sub 3}, SnCl{sub 2}, PbCl{sub 2}), but possibly a falling Arrhenius prefactor (collision frequency) for molecular melts (HgBr{sub 2}).« less

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

NASA Astrophysics Data System (ADS)

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).

Spectroscopic Studies of Lasing Transitions in the Diatomic Mercury Halides.

DTIC Science & Technology

1982-06-01

ground states. In addition the-.. DO I JA 7 1470~ CDITION oF I Nov 46 is OSSOLETE S/ N 0 102- LF- 0 14- 6601 SECURITY CLASSIFICATION Of’ TIS PAGE t11hm...and/or- S/ N 0O102- LF 014- 6601 SECURITY CLASSIFICATION OF THInS PAG4fMkR Deftue 3 Progress Summary Our work in the first year of this contract has...concentrated on the recording and analysis of B-*X spectra for the single isotopic HgX species, 200Hg 35Cl , 200Hg 79Br, 200Hg 1271, and 200Hg 1291. In

Multifrequency electron paramagnetic resonance and electron-nuclear double-resonance studies of photo-hole processes in AgBr and AgCl emulsion grains

NASA Astrophysics Data System (ADS)

Eachus, R. S.; Pawlik, Th D.; Baetzold, R. C.

2000-10-01

By using a combination of multifrequency EPR spectroscopy, ENDOR spectroscopy and calculations of structure and energy, the reactivities of photo-generated holes in microcrystalline AgBr and AgCl dispersions (photographic emulsions) have been followed in detail. Progress has been facilitated by the use of both gelatin and polyvinyl alcohol (PVA) as peptizers. The initial trapped hole centres produced by band-gap excitation have been identified. In AgBr, this species is [(Br4)3-.V], a neutral complex formed from hole trapping by the four nearest neighbours of a surface Ag+ vacancy (=V). [(Br4)3-.V] reacts with gelatin to produce a transient organic radical at the grain's surface. It does not, however, react with PVA. The formation of the oxidized gelatin radical might involve atomic bromine as an intermediate. In AgCl, the well-known self-trapped hole centre (AgCl6)4- is the initial hole species. The hole diffuses by an electron exchange process until it is trapped by a silver ion on the grain's surface or within its penultimate layer of lattice ions. It is subsequently released from this Ag2+ site to be retrapped at a centre containing four equivalent Cl- ions. The precise identity of this defect has yet to be determined, but its decay also results in the oxidation of gelatin.

Synthesis, structure, and magnetic properties of new layered phosphate halides Sr2Cu5(PO4)4X2·8H2O (X = Cl, Br) with a crown-like building unit.

PubMed

Qiu, Chaoqun; He, Zhangzhen; Cui, Meiyan; Tang, Yingying; Chen, Sihuai

2017-03-27

Two new compounds Sr 2 Cu 5 (PO 4 ) 4 X 2 ·8H 2 O (X = Cl and Br) are synthesized by a conventional hydrothermal method. Sr 2 Cu 5 (PO 4 ) 4 Cl 2 ·8H 2 O crystallizes in the tetragonal system with a space group of P42 1 2, while Sr 2 Cu 5 (PO 4 ) 4 Br 2 ·8H 2 O crystallizes in the space group P4/nmm, which are found to have a similar framework of layered structure, in which the crown-like {Cu 5 (PO 4 ) 4 X 2 } building units connect to each other forming a 2D corrugated sheet with vacancies, while the Sr 2+ cations are located along the vacancies. The spin lattice of two compounds built by Cu 2+ ions shows a new type of corrugated square. Magnetic measurements confirmed that both Sr 2 Cu 5 (PO 4 ) 4 X 2 ·8H 2 O (X = Cl and Br) exhibit antiferromagnetic ordering at low temperatures. A fit of theoretical model shows exchange interaction J = -25.62 K for the Cl-analogue and J/k B = -26.47 K for the Br-analogue.

A novel fluoride ion colorimetric chemosensor based on coumarin.

PubMed

Zhuang, Xiaoqing; Liu, Weimin; Wu, Jiasheng; Zhang, Hongyan; Wang, Pengfei

2011-09-01

A novel visible colorimetric sensor (L1) with high selectivity for fluoride ion based on coumarin has been synthesized by a simple modification of our earlier report. The chemosensor L1 shows an obvious color change from yellow to blue upon addition of fluoride ion with a large red shift of 145 nm in acetonitrile, and without interference of other anions such as Cl-, Br-, I-, NO3-, H2PO4-, HSO4-, and AcO-. The investigation of 1H NMR spectrum titration indicates the proposed mechanism is that F- first establishes a hydrogen bonding interaction with L1, and then the formation of [F-H-F]- induces deprotonation. Copyright © 2011 Elsevier B.V. All rights reserved.

Revisiting the Dielectric Constant Effect on the Nucleophile and Leaving Group of Prototypical Backside Sn2 Reactions: a Reaction Force and Atomic Contribution Analysis.

PubMed

Pedraza-González, Laura Milena; Galindo, Johan Fabian; Gonzalez, Ronald; Reyes, Andrés

2016-10-09

The solvent effect on the nucleophile and leaving group atoms of the prototypical F - + CH 3 Cl → CH 3 F + Cl - backside bimolecular nucleophilic substitution reaction (S N 2) is analyzed employing the reaction force and the atomic contributions methods on the intrinsic reaction coordinate (IRC). Solvent effects were accounted for using the polarizable continuum solvent model. Calculations were performed employing eleven dielectric constants, ε, ranging from 1.0 to 78.5, to cover a wide spectrum of solvents. The reaction force data reveals that the solvent mainly influences the region of the IRC preceding the energy barrier, where the structural rearrangement to reach the transition state occurs. A detailed analysis of the atomic role in the reaction as a function of ε reveals that the nucleophile and the carbon atom are the ones that contribute the most to the energy barrier. In addition, we investigated the effect of the choice of nucleophile and leaving group on the ΔE 0 and ΔE ↕ of Y - + CH 3 X → YCH 3 + X - (X,Y= F, Cl, Br, I) in aqueous solution. Our analysis allowed us to find relationships between the atomic contributions to the activation energy and leaving group ability and nucleophilicity.

[The tasks and aims of hospital psychiatry today and in the future].

PubMed

Honig, A; Sierink, D; Verwey, B

Care provided by consultation-liaison (CL) psychiatry and general hospital (GH) psychiatry varies widely. This means that certain services are almost unrecognisable and therefore less readily available to patients.
AIM: To describe the core tasks of current CL- and GH-psychiatry care and to suggest how these tasks can best be performed and developed in the future.
METHOD: We conducted a selective review of relevant CL- and GH-related literature and combined the information we obtained with the results of a consultation with CL-psychiatrists about how CL- and GL psychiatry should function in the future.
RESULTS: Core tasks of CL- and GH-psychiatry are: 1. inpatient and outpatient care for complex patients with combined somatic and psychiatric problems (including addiction) and 2. acute care, diagnosis and treatment of patients referred to the Emergency Department. We gave an outline of how the quality of training can be maintained and/or improved and we suggest ways in which the funding of CL- and GH-psychiatry can be safeguarded and, if possible, increased in the future.
CONCLUSION: We strongly recommend that large teaching hospitals and all university hospitals should have at their disposal a psychiatric consultation service that includes psychiatric Emergency Department facilities and specialised CL and GH inpatient and outpatient facility such as a medical-psychiatric unit. The CL- and GH-service should have a psychiatrist as gatekeeper and should be integrated into the hospital's chain of care. Partners in this chain of care are interns who have other medical specialisms, mental health specialists employed at other (mainly psychiatric) hospitals and general practitioners (GPs).

Metal complexes of 3-(4-bromophenyl)-1-pyridin-2-ylprop-2-en-1-one thiosemicarbazone: cytotoxic activity and investigation on the mode of action of the gold(III) complex.

PubMed

Sâmia, Luciana B P; Parrilha, Gabrieli L; Da Silva, Jeferson G; Ramos, Jonas P; Souza-Fagundes, Elaine M; Castelli, Silvia; Vutey, Venn; Desideri, Alessandro; Beraldo, Heloisa

2016-06-01

Complexes [Au(PyCT4BrPh)Cl]Cl (1), [Pt(PyCT4BrPh)Cl]0.5KCl (2), and [Pd(PyCT4BrPh)Cl]KCl (3) were obtained with 3-(4-bromophenyl)-1-pyridin-2-ylprop-2-en-1-one thiosemicarbazone (HPyCT4BrPh). Although complexes (2) and (3) did not exhibit potent cytotoxic activity, HPyCT4BrPh and its gold(III) complex (1) proved to be highly cytotoxic against HL-60 (human promyelocytic leukemia) and THP-1 (human monocytic leukemia) cells, and against MDA-MB 231 and MCF-7 (human breast adenocarcinoma) solid tumor cells. Except for HL-60 cells, upon coordination to gold(III) a 2- to 3-fold increase in the cytotoxic effect was observed. An investigation on the possible biological targets of the gold(III) complex was carried out. Complex (1) but not the free thiosemicarbazone inhibits the enzymatic activity of thioredoxin reductase (TrxR). The affinity of 1 for TrxR suggests metal binding to a selenol residue in the active site of the enzyme. While HPyCT4BrPh was inactive, 1 was able to inhibit topoisomerase IB (Topo IB) activity. Hence, inhibition of TrxR and Topo IB could contribute to the mechanism of cytotoxic action of complex (1).

Size-resolved chemical composition of aerosol emitted by Erebus volcano, Antarctica

NASA Astrophysics Data System (ADS)

Ilyinskaya, E.; Oppenheimer, C.; Mather, T. A.; Martin, R. S.; Kyle, P. R.

2010-03-01

Persistent, open-vent degassing of Erebus volcano, Antarctica, is a significant point source of gases and aerosol to the austral polar troposphere. We report here on the chemical composition and size distribution of the Erebus aerosol, focusing on the water-soluble fraction. The aerosol was sampled at the rim of the active crater using a cascade impactor, which collected and sized particles in 14 size bins from >10 to 0.01 μm. The soluble fraction of the Erebus aerosol is distinct from other volcanic sources in several respects. It is dominated by chloride-bearing particles (over 30% of total mass) and has an unusually high Cl-/SO42- molar ratio of 3.5. Coarse particles contribute little to the total mass of the soluble fraction. Elevated concentrations of F-, Cl-, Br-, and SO42- are found in a narrow particle size fraction of 0.1-0.25 μm. The detection of particulate Br- reinforces our understanding of the potential for quiescent volcanic emissions to deplete tropospheric ozone. The small aerosol size reflects the low atmospheric temperature and humidity, which inhibit particle growth. Halide-alkali metal salts (Na, K)(Cl, F) appear to be the most abundant species in the aerosol. The concentration of Pb is high compared to other volcanoes; its exsolution may be promoted by the high abundance of halogens in Erebus magma. Despite the previously reported high NOx content in the plume, we did not detect significant quantities of nitrate in the near-vent aerosol. Our findings emphasize the potential regional significance of emissions from Erebus for understanding the Antarctic atmospheric composition and glaciochemical records.

Linking precious metal enrichment and halogen cycling in mafic magmatic systems: insights from the Rum layered intrusion, NW Scotland

NASA Astrophysics Data System (ADS)

Kelly, A. P.; O'Driscoll, B.; Clay, P. L.; Burgess, R.

2017-12-01

Layered intrusions host the world's largest known concentrations of the platinum-group elements (PGE). Emphasis has been attached to the role of halogen-bearing fluids in concentrating the precious metals, but whether this occurs at the magmatic stage, or via subsequent metasomatism, is actively debated. One obstacle to progress has been the analytical difficulty of measuring low abundances of the halogens in the cumulate products of layered intrusions. To elucidate the importance of the halogens in facilitating PGE-mineralisation, as well as fingerprint halogen provenance and assess the importance of halogen cycling in mafic magma systems more generally, a suite of samples encompassing different stages of activity of the Palaeogene Rum layered intrusion was investigated. Halogen abundances were measured by neutron irradiation noble gas mass spectrometric analysis, permitting the detection of relatively low (ppm-ppb) abundances of Cl, Br and I in mg-sized samples. The samples include PGE-enriched chromite seams, various cumulates (e.g., peridotites), picrites (approximating the Rum parental magma), and pegmatites representing volatile-rich melts that circulated the intrusion at a late-stage in its solidification history. The new data reveal that PGE-bearing chromite seams contain relatively low Cl concentrations (2-3 ppm), with high molar ratios of Br/Cl and I/Cl (0.005 and 0.009, respectively). The picrites and cumulates have Br/Cl and I/Cl ratios close to sub-continental lithospheric mantle values of approximately 0.0013 and 0.00002, respectively, and thus likely reflect the Rum magma source region. A positive correlation between Cl and Br signifies comparable partitioning behaviour in all samples. However, I is more variable, displaying a positive correlation with Cl for more primitive samples (e.g. picrite and peridotite), and seemingly decoupling from Br and Cl in chromite seams and pegmatites. The relative enrichment of I over Cl in the chromite seams points to the local involvement of an organic-rich sedimentary assimilant and potentially represents an important trigger for PGE-mineralisation. Similarly high I/Cl signatures in some of the late-stage pegmatites suggest that fluids with this distinctive composition circulated the cooling Rum intrusion for a protracted period of time.

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

PubMed

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.

Density Functional Study of Structures and Electron Affinities of BrO4F/BrO4F−

PubMed Central

Gong, Liangfa; Xiong, Jieming; Wu, Xinmin; Qi, Chuansong; Li, Wei; Guo, Wenli

2009-01-01

The structures, electron affinities and bond dissociation energies of BrO4F/BrO4F− species have been investigated with five density functional theory (DFT) methods with DZP++ basis sets. The planar F-Br…O2…O2 complexes possess 3A′ electronic state for neutral molecule and 4A′ state for the corresponding anion. Three types of the neutral-anion energy separations are the adiabatic electron affinity (EAad), the vertical electron affinity (EAvert), and the vertical detachment energy (VDE). The EAad value predicted by B3LYP method is 4.52 eV. The bond dissociation energies De (BrO4F → BrO4-mF + Om) (m = 1–4) and De− (BrO4F− → BrO4-mF− + Om and BrO4F− → BrO4-mF + Om−) are predicted. The adiabatic electron affinities (EAad) were predicted to be 4.52 eV for F-Br…O2…O2 (3A′←4A′) (B3LYP method). PMID:19742128

THE INTERSECTION OF STABLE AND NON-EQUILIBRIUM TETRAHEDRA IN A MUTUAL 7- COMPONENT SYSTEM OF Li, Na, Rb, T1/Br, C1, NO$sub 3$, SO$sub 4$ (in Russian)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dombrovskaya, N.S.; Khakhlova, N.V.; Alekseeva, E.A.

1961-04-21

The most stable configuration of the mixture of the 16 salts formed from Li, Na, Rb, Tl/Br, Cl, NO/sub 3/, and S0/sub 4/ con ture which however interact, resulting in a stable mixture. On the basis of exchange reactions the following equation has been derived: LiBr + NaNO/sub 3/ + RbCl + 1/2Tl/sub 2/SO/sub 4/ = 1/ 2LiSO/sub 4/ + NaCl + RbNO/sub 3/ + TlBr. In addition, several binary complexes are also formed, such as Li/sub 2/SO/sub 4/ - Rb/sub 2/SO/sub 4/, 4Li/sub 2/SO/ sub 4/ - RbSO /sub 4/, RbCl - 2Li/sub 2/SO/sub 4/ and possible others. Inmore » view of the great interest, the intersection of stable and non-equilibrium tetrahedra consisting of components of both, was experimentally studied by thermai analysis. On the basis of cooling curves the following deflection points have been observed: 453 deg C, precipitation of the first Li/sub 2/SO/sub 4/ crystals; 409 deg , coprecipitation of Li/sub 2/SO/sub 4/ and NaCl; 391 deg , coprecipitation of Li/sub 2/SO/sub 4/, NaCl snd TlBr; and finally at 107 deg , formation of the quaternary eutectic with the previously mentioned salts + RbNO/sub 3/. The microstructures of the stable and non-equilibrium phases are quite similar. (TTT)« less

Brominated VSLSs in and over the East Pacific During the Halocarbon Air-Sea Transect - Pacific Cruise (HalocAST-P)

NASA Astrophysics Data System (ADS)

Liu, Y.; Yvon-Lewis, S. A.; Hu, L.; Smith, R. W.; Shen, L.; Bianchi, T. S.; Campbell, L.

2010-12-01

Brominated very short lived substances (VSLSs), such as bromoform (CHBr3), dibromomethane (CH2Br2), dibromochloromethane (CHClBr2), and dichlorobromomethane (CHBrCl2) can potentially supply a significant amount of inorganic bromine (Bry) to the troposphere and lower stratosphere. Bromine radicals are 50 - 100 times more efficient in depleting ozone (O3) than chlorine radicals; therefore, these compounds are important to the ozone chemistry in the atmosphere. CHBr3, CH2Br2, CHClBr2 and CHBrCl2 are thought to be produced mainly by phytoplankton in the open ocean. During the Halocarbon Air-Sea Transect - Pacific (HalocAST - P) cruise we examined the distributions of halocarbons in the East Pacific Ocean and in the overlying atmosphere. The cruise started from Punta Arenas, Chile on March 29, and finished at Seattle, WA, United States on April 29 2010. Continuous underway measurements of the atmospheric and surface seawater concentrations along with depth profiles of CHBr3, CH2Br2, CHClBr2, CHBrCl2, and a suite of other halogenated compounds were measured over a large cross latitudinal transect. The brominated VSLS measured during this cruise generally exhibit a correlation with chlorophyll a, supporting biogenic production as the predominate source for these compounds in the open ocean. Here, we will be discussing air and seawater concentrations, saturation anomalies, fluxes, and depth profiles for CHBr3, CH2Br2, CHClBr2, and CHBrCl2. Cyanobacteria counts, pigment compositions, nutrient and dissolved organic carbon (DOC) concentrations in the water column were also measured and serve as useful tools for understanding the biological production of these brominated VSLSs.

Fluoride-selective colorimetric sensor based on thiourea binding site and anthraquinone reporter.

PubMed

Wu, Fang-ying; Hu, Mei-hua; Wu, Yu-mei; Tan, Xiao-fang; Zhao, Yong-qiang; Ji, Zhao-jun

2006-11-01

A structurally simple colorimetric sensor, N-4-nitrobenzene-N'-1'-anthraquinone-thiourea (1), for anions was synthesized and characterized by (1)H NMR, ESI mass and IR methods. In acetonitrile, the addition of F(-) changed 1 solution from colorless to yellow. In the presence of other anions such as CH(3)CO(2)(-), H(2)PO(4)(-), HSO(4)(-) and Cl(-), however, the absorption spectrum of 1 was slightly red shifted with no obvious color changes observed. The association constants of anionic complexes followed the order of F(-)>CH(3)CO(2)(-)>H(2)PO(4)(-)>HSO(4)(-)>Cl(-)>Br(-), which was different from the order of anion basicity. AM1 calculation results indicated that the most stable configuration of 1 existed in the Z-E-conformation with a six-membered ring via intramolecular hydrogen bond. This made thiourea moiety of 1 in an unfavorable conformation to bond with oxygen-anionic substrates such as CH(3)CO(2)(-) and H(2)PO(4)(-), thus leading to a high selectivity and sensitivity for the detection of F(-).

Fluoride-selective optical sensor based on the dipyrrolyl-tetrathiafulvalene chromophore.

PubMed

Rivadehi, Shadi; Reid, Ellen F; Hogan, Conor F; Bhosale, Sheshanath V; Langford, Steven J

2012-01-28

A chemosensor bearing dipyrrolyl motifs as recognition sites and a tetrathiafulvalene redox tag has been evaluated as an optical and redox sensor for a series of anions (F(-), Cl(-), Br(-), HSO(4)(-), CH(3)COO(-), and H(2)PO(4)(-)) in DCM solution. The receptor shows specific optical signaling for fluoride but little electrochemical effect in solution. The solid-state performance of the sensor leads to measurable changes in water. Design implications towards better systems based on these results and other examples are discussed.

Genetic Modifiers of Ovarian Cancer

DTIC Science & Technology

2014-08-01

Barile M, Pensotti V, Pasini B, Dolcetti R, Giannini G, Laura Putignano A, Varesco L, Radice P, Mai PL, Greene MH, Andrulis IL, Glendon G, Ozcelik H... Barile 17 M, Bernard L, Viel A, Giannini G, Varesco L, Radice P, Greene MH, Mai PL, Easton DF, Chenevix-Trench G; for kConFab investigators, Offit K...Peissel B, Sellers TA, Ficarazzi F, Barile M, Ziogas A, Ashworth A, Gentry-Maharaj A, Jones M, Ramus SJ, Orr N, Menon U, Pearce CL, Brüning T, Pike MC

Redox shuttles for lithium ion batteries

DOEpatents

Weng, Wei; Zhang, Zhengcheng; Amine, Khalil

2016-03-22

An electrolyte may include compounds of general Formula IVA or IVB. ##STR00001## where, R.sup.8, R.sup.9, R.sup.10, and R.sup.11 are each independently selected from H, F, Cl, Br, CN, NO.sub.2, alkyl, haloalkyl, and alkoxy groups; X and Y are each independently O, S, N, or P; and Z' is a linkage between X and Y, and at least one of R.sup.8, R.sup.9, R.sup.10, and R.sup.11 is other than H.

Bromide supplementation exacerbated the renal dysfunction, injury and fibrosis in a mouse model of Alport syndrome.

PubMed

Yokota, Tsubasa; Omachi, Kohei; Suico, Mary Ann; Kojima, Haruka; Kamura, Misato; Teramoto, Keisuke; Kaseda, Shota; Kuwazuru, Jun; Shuto, Tsuyoshi; Kai, Hirofumi

2017-01-01

A seminal study recently demonstrated that bromide (Br-) has a critical function in the assembly of type IV collagen in basement membrane (BM), and suggested that Br- supplementation has therapeutic potential for BM diseases. Because salts of bromide (KBr and NaBr) have been used as antiepileptic drugs for several decades, repositioning of Br- for BM diseases is probable. However, the effects of Br- on glomerular basement membrane (GBM) disease such as Alport syndrome (AS) and its impact on the kidney are still unknown. In this study, we administered daily for 16 weeks 75 mg/kg or 250 mg/kg (within clinical dosage) NaBr or NaCl (control) via drinking water to 6-week-old AS mice (mouse model of X-linked AS). Treatment with 75 mg/kg NaBr had no effect on AS progression. Surprisingly, compared with 250 mg/kg NaCl, 250 mg/kg NaBr exacerbated the progressive proteinuria and increased the serum creatinine and blood urea nitrogen in AS mice. Histological analysis revealed that glomerular injury, renal inflammation and fibrosis were exacerbated in mice treated with 250 mg/kg NaBr compared with NaCl. The expressions of renal injury markers (Lcn2, Lysozyme), matrix metalloproteinase (Mmp-12), pro-inflammatory cytokines (Il-6, Il-8, Tnf-α, Il-1β) and pro-fibrotic genes (Tgf-β, Col1a1, α-Sma) were also exacerbated by 250 mg/kg NaBr treatment. Notably, the exacerbating effects of Br- were not observed in wild-type mice. These findings suggest that Br- supplementation needs to be carefully evaluated for real positive health benefits and for the absence of adverse side effects especially in GBM diseases such as AS.

Competing E2 and SN2 Mechanisms for the F- + CH3CH2I Reaction.

PubMed

Yang, Li; Zhang, Jiaxu; Xie, Jing; Ma, Xinyou; Zhang, Linyao; Zhao, Chenyang; Hase, William L

2017-02-09

Anti-E2, syn-E2, inv-, and ret-S N 2 reaction channels for the gas-phase reaction of F - + CH 3 CH 2 I were characterized with a variety of electronic structure calculations. Geometrical analysis confirmed synchronous E2-type transition states for the elimination of the current reaction, instead of nonconcerted processes through E1cb-like and E1-like mechanisms. Importantly, the controversy concerning the reactant complex for anti-E2 and inv-S N 2 paths has been clarified in the present work. A positive barrier of +19.2 kcal/mol for ret-S N 2 shows the least feasibility to occur at room temperature. Negative activation energies (-16.9, -16.0, and -4.9 kcal/mol, respectively) for inv-S N 2, anti-E2, and syn-E2 indicate that inv-S N 2 and anti-E2 mechanisms significantly prevail over the eclipsed elimination. Varying the leaving group for a series of reactions F - + CH 3 CH 2 Y (Y = F, Cl, Br, and I) leads to monotonically decreasing barriers, which relates to the gradually looser TS structures following the order F > Cl > Br > I. The reactivity of each channel nearly holds unchanged except for the perturbation between anti-E2 and inv-S N 2. RRKM calculation reveals that the reaction of the fluorine ion with ethyl iodide occurs predominately via anti-E2 elimination, and the inv-S N 2 pathway is suppressed, although it is energetically favored. This phenomenon indicates that, in evaluating the competition between E2 and S N 2 processes, the kinetic or dynamical factors may play a significant role. By comparison with benchmark CCSD(T) energies, MP2, CAM-B3LYP, and M06 methods are recommended to perform dynamics simulations of the title reaction.

Method for production of hydrocarbons from hydrates

DOEpatents

McGuire, Patrick L.

1984-01-01

A method of recovering natural gas entrapped in frozen subsurface gas hydrate formations in arctic regions. A hot supersaturated solution of CaCl.sub.2 or CaBr.sub.2, or a mixture thereof, is pumped under pressure down a wellbore and into a subsurface hydrate formation so as to hydrostatically fracture the formation. The CaCl.sub.2 /CaBr.sub.2 solution dissolves the solid hydrates and thereby releases the gas entrapped therein. Additionally, the solution contains a polymeric viscosifier, which operates to maintain in suspension finely divided crystalline CaCl.sub.2 /CaBr.sub.2 that precipitates from the supersaturated solution as it is cooled during injection into the formation.

Rejection of Bromide and Bromate Ions by a Ceramic Membrane

PubMed Central

Moslemi, Mohammadreza; Davies, Simon H.; Masten, Susan J.

2012-01-01

Abstract Effects of pH and the addition of calcium chloride (CaCl2) on bromate (BrO3−) and bromide (Br−) rejection by a ceramic membrane were investigated. Rejection of both ions increased with pH. At pH 8, the rejection of BrO3− and Br− was 68% and 63%, respectively. Donnan exclusion appears to play an important role in determining rejection of BrO3− and Br−. In the presence of CaCl2, rejection of BrO3− and Br− ions was greatly reduced, confirming the importance of electrostatic interactions in determining rejection of BrO3− and Br−. The effect of Ca2+ is so pronounced that in most natural waters, rejection of both BrO3− and Br− by the membrane would be extremely small. PMID:23236251

Synthetic, Infrared, 1H and 13C NMR Spectral Studies on N-(2-/3-Substituted Phenyl)-4-Substituted Benzenesulphonamides, 4-X'C6H4SO2NH(2-/3-XC6H4), where X' = H, CH3, C2H5, F, Cl or Br, and X = CH3 or Cl

NASA Astrophysics Data System (ADS)

Gowda, B. Thimme; Shetty, Mahesha; Jayalakshmi, K. L.

2005-02-01

Twenty three N-(2-/3-substituted phenyl)-4-substituted benzenesulphonamides of the general formula, 4-X'C6H4SO2NH(2-/3-XC6H4), where X' = H, CH3, C2H5, F, Cl or Br and X = CH3 or Cl have been prepared and characterized, and their infrared spectra in the solid state, 1H and 13C NMR spectra in solution were studied. The N-H stretching vibrations, νN-H, absorb in the range 3285 - 3199 cm-1, while the asymmetric and symmetric SO2 vibrations vary in the ranges 1376 - 1309 cm-1 and 1177 - 1148 cm-1, respectively. The S-N and C-N stretching vibrations absorb in the ranges 945 - 893 cm-1 and 1304 - 1168 cm-1, respectively. The compounds do not exhibit particular trends in the variation of these frequencies on substitution either at ortho or meta positions with either a methyl group or Cl. The observed 1H and 13C chemical shifts of are assigned to protons and carbons of the two benzene rings. Incremental shifts of the ring protons and carbons due to -SO2NH(2-/3-XC6H4) groups in C6H5SO2NH(2-/3-XC6H4), and 4- X'C6H4SO2- and 4-X'C6H4SO2NH- groups in 4-X'C6H4SO2NH(C6H5) are computed and employed to calculate the chemical shifts of the ring protons and carbons in the substituted compounds, 4-X'C6H4SO2NH(2-/3-XC6H4). The computed values agree well with the observed chemical shifts.

Thioether coordination to divalent selenium halide acceptors--synthesis, properties and structures.

PubMed

Jolleys, Andrew; Levason, William; Reid, Gillian

2013-02-28

The tetravalent SeCl(4) and SeBr(4) are reduced in the presence of thioether ligands L (SMe(2), tht) or L-L (MeS(CH(2))(n)SMe (n = 2 or 3), o-C(6)H(4)(SMe)(2)) in MeCN solution at 0 °C, forming Se(II) thioether complexes, including the crystallographically characterised halo-bridged chain polymers [SeX(2)(SMe(2))] (X = Cl or Br), molecular trans-[SeX(2)(tht)(2)], cis-[SeBr(2){MeS(CH(2))(2)SMe}] and the thioether-bridged polymer [SeBr(2){MeS(CH(2))(3)SMe}], as the main products, together with halogenated ligand. The [SeX(2)(L)(2)] and [SeX(2)(L-L)] complexes are all based upon distorted square planar coordination, with two Se-based lone pairs assumed to occupy the (vacant) axial sites, and Se-S bond distances of ca. 2.4-2.6 Å. The 1:1 species [SeX(2)(SMe(2))] are T-shaped with trans X groups and weak intermolecular SeX contacts. The SeCl(2)-thioether complexes are less stable than the bromides, both in solution in CH(2)Cl(2) and as solids at ambient temperature. Reaction of SeBr(4) with o-C(6)H(4)(SMe(2))(2) leads to the red complex cis-[SeBr(2){κ(1)-o-C(6)H(4)(SMe)(2)}(2)] as the major product; together with a minor (yellow) product formed via bromination of the aromatic ring, [SeBr(2){4-Br-1,2-(SMe)(2)-C(6)H(3)}(2)]. The crystal structure confirms a V-shaped SeBr(2) unit with long (weak) κ(1)-interactions to one S donor (meta to the Br) from two brominated ligands--an extremely rare coordination mode for an o-phenylene dithioether. Similar reaction of o-C(6)H(4)(SMe(2))(2) with SeCl(4) leads to several species, including monosulfonium cation, [1](+) formed by coupling of one thioether group to the C4-position of the phenylene backbone in an adjacent molecule, confirmed crystallographically. Carbon-sulfur coupling is also evident in the reaction of SeX(4) with o-C(6)H(4)(CH(2)SMe)(2), leading to two related cyclic sulfonium species, [2](+) and [3](+), which were structurally characterised as [SeBr(4)](2-) and [Se(2)Cl(6)](2-) salts respectively. Reaction of SeX(4) with SeMe(2) leads to halogenation of the ligand to form Me(2)SeX(2) and reduction of the SeX(4) to elemental selenium.

Performance of an alkalophilic and halotolerant laccase from gamma-proteobacterium JB in the presence of industrial pollutants.

PubMed

Singh, Gursharan; Sharma, Prince; Capalash, Neena

2009-08-01

An alkalophilic and halotolerant laccase from gamma-proteobacterium JB catalyzed in high concentrations of organic solvents and various salts. The enzyme retained 80-100% activity in 10% concentration of dimethylsulfoxide (DMSO), ethanol, acetone or methanol; 100, 85 and 50% activity in 20 mM MgCl(2), 5.0 mM MnCl(2) and 0.1 mM CuCl(2); 140, 120 and 110% activity in 5.0 mM MnSO(4), 10 mM MgSO(4) and 1mM CaSO(4), respectively. Sodium halides inhibited the enzyme in the order: F(-)> Br(-)> I(-)> Cl(-). In 0.5 M NaCl, pH 6.0, laccase was approximately 60% active. Decolorization of indigo carmine by laccase at pH 9.0 was not inhibited even in the presence of 0.5 M NaCl. Release of chromophoric, reducing and hydrophobic compounds during biobleaching of straw rich-soda pulp by laccase was not inhibited when the enzyme was applied in the presence of 1 M NaCl at pH 8.0. Laccase retained 50% residual activity even when incubated with 5% calcium hypochlorite for 30 min.

Lone pair effect, structural distortions, and potential for superconductivity in Tl perovskites.

PubMed

Schoop, Leslie M; Müchler, Lukas; Felser, Claudia; Cava, R J

2013-05-06

Drawing the analogy to BaBiO3, we investigate via ab initio electronic structure calculations potential new superconductors of the type ATlX3 with A = Rb and Cs and X = F, Cl, and Br, with a particular emphasis on RbTlCl3. On the basis of chemical reasoning, supported by the calculations, we show that Tl-based perovskites have structural and charge instabilities driven by the lone pair effect, similar to the case of BaBiO3, effectively becoming A2Tl(+)Tl(3+)X6. We find that upon hole doping of RbTlCl3, structures without Tl(+) and Tl(3+) charge disproportionation become more stable, although the ideal cubic perovskite, often viewed as the best host for superconductivity, should not be the most stable phase in the system. The known superconductor (Sr,K)BiO3 and hole doped RbTlCl3, predicted to be most stable in the same tetragonal structure, display highly analogous calculated electronic band structures.

Deriving an atmospheric budget of total organic bromine using airborne in situ measurements from the western Pacific area during SHIVA

NASA Astrophysics Data System (ADS)

Sala, S.; Bönisch, H.; Keber, T.; Oram, D. E.; Mills, G.; Engel, A.

2014-07-01

During the recent SHIVA (Stratospheric Ozone: Halogen Impacts in a Varying Atmosphere) project an extensive data set of all halogen species relevant for the atmospheric budget of total organic bromine was collected in the western Pacific region using the Falcon aircraft operated by the German Aerospace agency DLR (Deutsches Zentrum für Luft- und Raumfahrt) covering a vertical range from the planetary boundary layer up to the ceiling altitude of the aircraft of 13 km. In total, more than 700 measurements were performed with the newly developed fully automated in situ instrument GHOST-MS (Gas chromatograph for the Observation of Tracers - coupled with a Mass Spectrometer) by the Goethe University of Frankfurt (GUF) and with the onboard whole-air sampler WASP with subsequent ground-based state-of-the-art GC / MS analysis by the University of East Anglia (UEA). Both instruments yield good agreement for all major (CHBr3 and CH2Br2) and minor (CH2BrCl, CHBrCl2 and CHBr2Cl) VSLS (very short-lived substances), at least at the level of their 2σ measurement uncertainties. In contrast to the suggestion that the western Pacific could be a region of strongly increased atmospheric VSLS abundance (Pyle et al., 2011), we found only in the upper troposphere a slightly enhanced amount of total organic bromine from VSLS relative to the levels reported in Montzka and Reimann et al. (2011) for other tropical regions. From the SHIVA observations in the upper troposphere, a budget for total organic bromine, including four halons (H-1301, H-1211, H-1202, H-2402), CH3Br and the VSLS, is derived for the level of zero radiative heating (LZRH), the input region for the tropical tropopause layer (TTL) and thus also for the stratosphere. With the exception of the two minor VSLS CHBrCl2 and CHBr2Cl, excellent agreement with the values reported in Montzka and Reimann et al. (2011) is found, while being slightly higher than previous studies from our group based on balloon-borne measurements.

MERCURY REMOVAL FROM STACK GAS BY AQUEOUS SCRUBBING

EPA Science Inventory

Fundamental results will be obtained on the reaction kinetics in mass transfer boundary layers for the following systems:

Hg(g)/Cl2(g)/SO2(g)/sulfite
Hg(g)/ClO2(g)/SO2...

• Post-synthetic halide conversion and selective halogen capture in hybrid perovskites† †Electronic supplementary information (ESI) available. CCDC 1048945–1048947. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c5sc01135c

  PubMed Central

  Solis-Ibarra, D.; Smith, I. C.

  2015-01-01

  Reaction with halogen vapor allows us to post-synthetically exchange halides in both three- (3D) and two-dimensional (2D) organic–inorganic metal-halide perovskites. Films of 3D Pb–I perovskites cleanly convert to films of Pb–Br or Pb–Cl perovskites upon exposure to Br2 or Cl2 gas, respectively. This gas–solid reaction provides a simple method to produce the high-quality Pb–Br or Pb–Cl perovskite films required for optoelectronic applications. Reactivity with halogens can be extended to the organic layers in 2D metal-halide perovskites. Here, terminal alkene groups placed between the inorganic layers can capture Br2 gas through chemisorption to form dibromoalkanes. This reaction's selectivity for Br2 over I2 allows us to scrub Br2 to obtain high-purity I2 gas streams. We also observe unusual halogen transfer between the inorganic and organic layers within a single perovskite structure. Remarkably, the perovskite's crystallinity is retained during these massive structural rearrangements. PMID:29218171

• Temperature dependence of dissociative electron attachment to bromo-chlorotoluene isomers: Competition between detachment of Cl- and Br-

  NASA Astrophysics Data System (ADS)

  Mahmoodi-Darian, Masoomeh; Huber, Stefan E.; Mauracher, Andreas; Probst, Michael; Denifl, Stephan; Scheier, Paul; Märk, Tilmann D.

  2018-02-01

  Dissociative electron attachment to three isomers of bromo-chlorotoluene was investigated in the electron energy range from 0 to 2 eV for gas temperatures in the range of 392-520 K using a crossed electron-molecular beam apparatus with a temperature regulated effusive molecular beam source. For all three molecules, both Cl- and Br- are formed. The ion yields of both halogenides show a pronounced temperature effect. In the case of Cl- and Br-, the influence of the gas temperature can be observed at the threshold peak close to 0 eV. The population of molecules that have some of their out-of-plane modes excited varies strongly in the temperature range investigated, indicating that such vibrations might play a role in the energy transfer towards bond breaking. Potential energy curves for the abstraction of Cl- and Br- were calculated and extrapolated into the metastable domain. The barriers in the diabatic curves approximated in this way agree well with the ones derived from the temperature dependence observed in the experiments.

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

  PubMed

  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.

• Formation and Characterization of Silver Nanoparticle Composite with Poly(p-Br/F-phenylsilane).

  PubMed

  Roh, Sung-Hee; Noh, Ji Eun; Woo, Hee-Gweon; Cho, Myong-Shik; Sohn, Honglae

  2015-02-01

  The one-pot production and structural characterization of composites of silver nanoparticles with poly(p-Br/F-phenylsilane), Br/F-PPS, have been performed. The conversion of Ag+ ions to stable Ag0 nanoparticles is mediated by the copolymer Br/F-PPS having both possibly reactive Si-H bonds in the polymer backbone and C-Br bonds in the substituents along with relatively inert C-F bonds. Transmission electron microscopy and field emission scanning electron microscopy analyses show the formation of the composites where silver nanoparticles (less than 30 nm of size) are well dispersed over the Br/F-PPS matrix. X-ray diffraction patterns are consistent with that for face-centered-cubic typed silver. The polymer solubility in toluene implys that the cleavage of C-Br bond and the Si-F dative bonding may not be occurred appreciably at ambient temperature. Nonetheless, thermogravimetric analysis data suggest that some sort of cross-linking could take place at high temperature. Most of the silver particles undergo macroscopic aggregation without Br/F-PPS, which indicates that the polysilane is necessary for stabilizing the silver nanoparticles.

• Electrophoresis-chemiluminescence detection of phenols catalyzed by hemin.

  PubMed

  Shu, Lu; Zhu, Jinkun; Wang, Qingjiang; He, Pingang; Fang, Yuzhi

  2014-09-01

  Based on the catalytic activity of hemin, an efficient biocatalyst, an indirect capillary electrophoresis-chemiluminescence (CE-CL) detection method for phenols using a hemin-luminol-hydrogen peroxide system was developed. Through a series of static injection experiments, hemin was found to perform best in a neutral solution rather than an acidic or alkaline medium. Although halide ions such as Br(-) and F(-) could further enhance the CL signal catalyzed by hemin, it is difficult to apply these conditions to this CE-CL detection system because of the self-polymerization of hemin, as it hinders the CE process. The addition of concentrated ammonium hydroxide to an aqueous/dimethyl sulfoxide solution of hemin-luminol afforded a stable CE-CL baseline. The indirect CE-CL detection of five phenols using this method gave the following limits of detections: 4.8 × 10(-8) mol/L (o-sec-butylphenol), 4.9 × 10(-8) mol/L (o-cresol), 5.4 × 10(-8) mol/L (m-cresol), 5.3 × 10(-8) mol/L (2,4-dichlorophenol) and 7.1 × 10(-8) mol/L (phenol). Copyright © 2013 John Wiley & Sons, Ltd.

• A Rich Morphological Diversity of Biosaline Drying Patterns Is Generated by Different Bacterial Species, Different Salts and Concentrations: Astrobiological Implications

  NASA Astrophysics Data System (ADS)

  Gómez Gómez, José María; Medina, Jesús; Rull, Fernando

  2016-07-01

  Biosaline formations (BSFs) are complex self-organized biomineral patterns formed by "hibernating" bacteria as the biofilm that contains them dries out. They were initially described in drying biofilms of Escherichia coli cells + NaCl. Due to their intricate 3-D morphology and anhydrobiosis, these biomineralogical structures are of great interest in astrobiology. Here we report experimental data obtained with various alkali halide salts (NaF, NaCl, NaBr, LiCl, KCl, CsCl) on BSF formation with E. coli and Bacillus subtilis bacteria at two saline concentrations: 9 and 18 mg/mL. Our results indicate that, except for LiCl, which is inactive, all the salts assayed are active during BSF formation and capable of promoting the generation of distinctive drying patterns at each salt concentration. Remarkably, the BSFs produced by these two bacterial species produce characteristic architectural hallmarks as the BSF dries. The potential biogenicity of these biosaline drying patterns is studied, and the astrobiological implications of these findings are discussed.

• Synergistic Interactions of Sugars/Polyols and Monovalent Salts with Phospholipids Depend upon Sugar/Polyol Complexity and Anion Identity.

  PubMed

  Clark, Ginevra A; Henderson, J Michael; Heffern, Charles; Akgün, Bülent; Majewski, Jaroslaw; Lee, Ka Yee C

  2015-11-24

  We found that interactions of dipalmitoylphosphatidylcholine (DPPC) lipid monolayers with sugars are influenced by addition of NaCl. This work is of general importance in understanding how sugar-lipid-salt interactions impact biological systems. Using Langmuir isothermal compressions, fluorescence microscopy, atomic force microscopy, and neutron reflectometry, we examined DPPC monolayers upon addition of sugars/polyols and/or monovalent salts. Sugar-lipid interactions in the presence of NaCl increased with increasing complexity of the sugar/polyol in the order glycerol ≪ glucose < trehalose. When the anion was altered in the series NaF, NaCl, and NaBr, only minor differences were observed. When comparing LiCl, NaCl, and KCl, sodium chloride had the greatest influence on glucose and trehalose interactions with DPPC. We propose that heterogeneity created by cation binding allows for sugars to bind the lipid headgroups. While cation binding increases in the order K(+) < Na(+) < Li(+), lithium ions may also compete with glucose for binding sites. Thus, both cooperative and competitive factors contribute to the overall influence of salts on sugar-lipid interactions.

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

  PubMed

  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.

• Studies on the in vivo sensitivity of spindle microtubules to calcium ions and evidence for a vesicular calcium-sequestering system

  PubMed Central

  1981-01-01

  I microinjected calcium ions into echinoderm eggs during mitosis to determine the calcium sensitivity of microtubules (Mts) in vivo. Spindle birefringence (BR), a measure of the number of aligned Mts in the spindle, is locally, rapidly, and reversibly abolished by small volumes of microinjected CaCl2 (1 mM). Rapid return of BR is followed by anaphase, and subsequent divisions are normal. Similar doses of MgCl2, BaCl2, KCl, NaCl, pH buffers, distilled water, or vegetable oil have no effect on spindle BR, whereas large doses of such agents sometimes cause slow, uniform loss in BR over the course of a minute or more. Of the ions tested, only Sr++ causes effects comparable to Ca++. Ca-EGTA buffers, containing greater than micromolar free Ca++, abolishes BR in a manner similar to millimolar concentrations of injected CaCl2. Caffeine, a potent uncoupler of the Ca++-pump/ATPase of sarcoplasmic reticulum, causes a local, transient depression in spindle BR in the injected region. Finally, injection of potassium oxalate results in the formation of small, highly BR crystals, presumably CA- oxalate, in Triton-sensitive compartments in the cytoplasm. Taken together, these findings demonstrate that spindle Mts are sensitive to levels of free Ca++ in the physiological range, provide evidence for the existence of a strong cytoplasmic Ca++-sequestering system, and support the notion that Mt assembly and disassembly in local regions of the spindle may be orchestrated by local changes in the cytoplasmic free Ca++ concentration during mitosis. An appendix offers the design of a new chamber for immobilizing echinoderm eggs for injection, a new method for determining the volume of the injected solution, and a description of the microinjection technique, which was designed, but never fully described, by Hiramoto (Y. Hiramoto, Exp. Cell. Res., 1962, 27:416-426.). PMID:7194345

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

  PubMed

  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.

• PREPUBERTAL EXPOSURES TO COMPOUNDS THAT INCREASE PROLACTIN SECRETION IN THE MALE RAT: EFFECTS ON ADULT PROSTATE

  EPA Science Inventory

  Prepubertal exposure to compounds that increase prolactin secretion in the male rat: effects on the adult prostate.
  
  Stoker TE, Robinette CL, Britt BH, Laws SC, Cooper RL.
  
  Endocrinology Branch, Reproductive Toxicology Division, National Health and Environmental Effec...

• Photoproduction of I2, Br2, and Cl2 on n-semiconducting powder

  NASA Technical Reports Server (NTRS)

  Reichman, B.; Byvik, C. E.

  1981-01-01

  The photosynthetic production of Br2 and Cl2 and the photocatalytic production of I2 from aqueous solutions of the respective halide ions in the presence of platinized semiconducting n-TiO2 powder are reported. Reactions were produced in 2-3 M oxygen-saturated aqueous solutions of KI, KBr or NaCl containing Pt-TiO2 powder which were irradiated by a high-pressure mercury lamp at a power of 400 mW/sq cm. Halogens are found to be produced in greater quantities when platinized TiO2 powders are used rather than pure TiO2, and rates of halogen production are observed to increase from Cl2 to Br2 to I2. The presence of the synthetic reactions producing Br2 and Cl2 with a net influx of energy indicates that an effective separation of the photoproduced electron-hole pair occurs in the semiconductor. Quantum efficiencies of the reaction, which increase with decreasing solution pH, are found to be as high as 30%, implying a solar-to-chemical energy conversion efficiency between 0.03% and 3% for the case of chlorine production. It is concluded that the photoproduction of halogens may be of practical value if product halogens are efficiently removed from the reaction cell.

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

  NASA Technical Reports Server (NTRS)

  Anderson, James G.

  1996-01-01

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

• Redox properties of biscyclopentadienyl uranium(V) imido-halide complexes: a relativistic DFT study.

  PubMed

  Elkechai, Aziz; Kias, Farida; Talbi, Fazia; Boucekkine, Abdou

  2014-06-01

  Calculations of ionization energies (IE) and electron affinities (EA) of a series of biscyclopentadienyl imido-halide uranium(V) complexes Cp*2U(=N-2,6-(i)Pr2-C6H3)(X) with X =  F, Cl, Br, and I, related to the U(IV)/U(V) and U(V)/U(VI) redox systems, were carried out, for the first time, using density functional theory (DFT) in the framework of the relativistic zeroth order regular approximation (ZORA) coupled with the conductor-like screening model (COSMO) solvation approach. A very good linear correlation (R(2) =  0.993) was obtained, between calculated ionization energies at the ZORA/BP86/TZP level, and the experimental half-wave oxidation potentials E1/2. A similar linear correlation between the computed electron affinities and the electrochemical reduction U(IV)/U(III) potentials (R(2) =  0.996) is obtained. The importance of solvent effects and of spin-orbit coupling is definitively confirmed. The molecular orbital analysis underlines the crucial role played by the 5f orbitals of the central metal whereas the Nalewajski-Mrozek (N-M) bond indices explain well the bond distances variations following the redox processes. The IE variation of the complexes, i.e., IE(F) < IE(Cl) < IE(Br) < IE(I) is also well rationalized considering the frontier MO diagrams of these species. Finally, this work confirms the relevance of the Hirshfeld charges analysis which bring to light an excellent linear correlation (R(2) =  0.999) between the variations of the uranium charges and E1/2 in the reduction process of the U(V) species.

• Theoretical study of mixed MLaX(4) (M = Na, K, Cs; X = F, Cl, Br, I) rare earth/alkali metal halide complexes.

  PubMed

  Groen, Cornelis Petrus; Oskam, Ad; Kovács, Attila

  2003-02-10

  The structure, bonding, and vibrational properties of the mixed MLaX(4) (M = Na, K, Cs; X = F, Cl, Br, I) rare earth/alkali metal halide complexes have been studied using the MP2 method in conjunction with polarized triple-zeta valence basis sets and quasi-relativistic effective core potentials for the heavy atoms. From the three characteristic structures, possessing 1- (C(3)(v)), 2- (C(2)(v)), or 3-fold coordination (C(3)(v)) between the alkali metal and the bridging halide atoms, the bi- and tridentate forms are stable isomers with close dissociation energies. In general, for the complexes existing of lighter alkali metals and halogens, the bidentate structure corresponds to the global minimum of the potential energy surface, while the heavier analogues favor the tridentate structure. At experimentally relevant temperatures (T > 800 K), however, the isomerization entropy leads to a domination of the bidentate structures over the tridentate forms for all complexes. An important effect of the size of the alkali metal is manifested in the larger stabilities of the K and Cs complexes. The natural atomic charges are in agreement with strong electrostatic interactions in the title complexes. The marginal covalent contributions show a slight increasing trend in the heavier analogues. The calculated vibrational data indicate that infrared spectroscopy may be an effective tool for experimental investigation and characterization of MLaX(4) molecules.

Thermodynamic analysis of the interaction of partially hydrophobic cationic polyelectrolytes with sodium halide salts in water

NASA Astrophysics Data System (ADS)

Bončina, Matjaž; Lukšič, Miha; Seručnik, Mojca; Vlachy, Vojko

2014-05-01

Isothermal titration calorimetry was used to determine the temperature and concentration dependence of the enthalpy of mixing of 3,3- and 6,6-ionene fluorides, bromides, and iodides with low molecular weight salts (NaF, NaCl, NaBr, and NaI) in water. The magnitudes of the enthalpies, measured in the temperature range from 273 to 318 K, depended on the number of methylene groups on the ionene polyion (hydrophobicity), and on the anion of the added salt (ion-specificity). All enthalpies of mixing of 3,3- and 6,6-ionene fluorides with low molecular weight salts (NaCl, NaBr, and NaI) were negative, which is in contrast to the predictions of standard theories of polyelectrolyte solutions. This fact was interpreted in the light of the ion-water short-range interactions that are not accounted for in those theories. In contrast, the enthalpies of mixing of 3,3- and 6,6-ionene bromides and iodides with NaF were positive, being in accord with theory. Using the calorimetric data, we performed a model thermodynamic analysis of the polyelectrolyte-salt mixing process to obtain changes in the apparent standard Gibbs free energy, enthalpy, entropy, and heat capacity relative to the pure ionene fluorides in water. The results prove that halide ions replace fluoride counterions with a strength increasing in the order chloride < bromide < iodide. The process is enthalpy governed, accompanied by a positive change in the heat capacity.

Investigations on the direct introduction of cigarette smoke for trace elements analysis by inductively coupled plasma mass spectrometry

NASA Astrophysics Data System (ADS)

Chang, Michael J.; Naworal, John D.; Walker, Kathleen; Connell, Chris T.

2003-11-01

Direct introduction of mainstream cigarette smoke into an inductively coupled plasma mass spectrometry (ICP-MS) has been investigated with respect to its feasibility for on-line analysis of trace elements. An automated apparatus was designed and built interfacing a smoking machine with an ICP-MS for smoke generation, collection, injection and analysis. Major and minor elements present in the particulate phase and the gas phase of mainstream cigarette smoke of 2R4F reference cigarettes have been qualitatively identified by examination of their full mass spectra. This method provides a rapid-screening analysis of the transfer of trace elements into mainstream smoke during cigarette combustion. A full suite of elements present in the whole cigarette smoke has been identified, including As, B, Ba, Br, Cd, Cl, Cs, Cu, Hg, I, K, Li, Mn, Na, Pb, Rb, Sb, Sn, Tl and Zn. Of these elements, the major portions of B, Ba, Cs, Cu, K, Li, Mn, Na, Pb, Rb, Sn, Tl and Zn are present in the particulate phase, whereas the major portion of Hg is present in the gas phase. As, Br, Cd, Cl, I and Sb exist in a distribution between the gas phase and the particulate phase. Depending on the element, the precision of measurement ranges from 5 to 25% in terms of relative standard deviation of peak height and peak area, based on the fourth puff of 2R4F mainstream cigarette smoke analyzed in five smoking replicates.

Unraveling halide hydration: A high dilution approach.

PubMed

Migliorati, Valentina; Sessa, Francesco; Aquilanti, Giuliana; D'Angelo, Paola

2014-07-28

The hydration properties of halide aqua ions have been investigated combining classical Molecular Dynamics (MD) with Extended X-ray Absorption Fine Structure (EXAFS) spectroscopy. Three halide-water interaction potentials recently developed [M. M. Reif and P. H. Hünenberger, J. Chem. Phys. 134, 144104 (2011)], along with three plausible choices for the value of the absolute hydration free energy of the proton (ΔG [minus sign in circle symbol]hyd[H+]), have been checked for their capability to properly describe the structural properties of halide aqueous solutions, by comparing the MD structural results with EXAFS experimental data. A very good agreement between theory and experiment has been obtained with one parameter set, namely LE, thus strengthening preliminary evidences for a ΔG [minus sign in circle symbol]hyd[H] value of -1100 kJ mol(-1) [M. M. Reif and P. H. Hünenberger, J. Chem. Phys. 134, 144104 (2011)]. The Cl(-), Br(-), and I(-) ions have been found to form an unstructured and disordered first hydration shell in aqueous solution, with a broad distribution of instantaneous coordination numbers. Conversely, the F(-) ion shows more ordered and defined first solvation shell, with only two statistically relevant coordination geometries (six and sevenfold complexes). Our thorough investigation on the effect of halide ions on the microscopic structure of water highlights that the perturbation induced by the Cl(-), Br(-), and I(-) ions does not extend beyond the ion first hydration shell, and the structure of water in the F(-) second shell is also substantially unaffected by the ion.

Enhanced sensitivity to the time variation of the fine-structure constant and m{p}/m{e} in diatomic molecules.

PubMed

Flambaum, V V; Kozlov, M G

2007-10-12

Sensitivity to temporal variation of the fundamental constants may be strongly enhanced in transitions between narrow close levels of different nature. This enhancement may be realized in a large number of molecules due to cancellation between the ground state fine-structure omega{f} and vibrational interval omega{v} [omega=omega{f}-nomega{v} approximately 0, delta omega/omega=K(2delta alpha/alpha+0.5 delta mu/mu), K>1, mu=m{p}/m{e}]. The intervals between the levels are conveniently located in microwave frequency range and the level widths are very small. Required accuracy of the shift measurements is about 0.01-1 Hz. As examples, we consider molecules Cl(+)(2), CuS, IrC, SiBr, and HfF(+).

ANALYSES OF THE INTERACTIONS WITHIN BINARY MIXTURES OF CARCINOGENIC PAHS USING MORPHOLOGICAL CELL TRANSFORMATION OF C3H10T1/2CL8 CELLS

EPA Science Inventory

ANALYSES OF THE INTERACTIONS WITHIN BINARY MIXTURES OF CARCINOGENIC PAHS USING MORPHOLOGICAL CELL TRANSFORMATION OF C3HIOT1/2 CL8 CELLS.

Studies of defined mixtures of carcinogenic polycyclic aromatic hydrocarbons (PAH) have identified three major categories of interacti...

Temperature Dependence of Thermodynamic Properties of Thallium Chloride and Thallium Bromide

NASA Astrophysics Data System (ADS)

Kavanoz, H. B.

2015-02-01

Thermodynamic properties as lattice parameters, thermal expansion, heat capacities Cp and Cv, bulk modulus, and Gruneisen parameter of ionic halides TlCl and TlBr in solid and liquid phases were studied using classical molecular dynamics simulation (MD) with interionic Vashistha-Rahman (VR) model potential. In addition to the static and transport properties which have been previously reported by the author [13], this study further confirms that temperature dependence of the calculated thermophysical properties of TlCl and TlBr are in agreement with the available experimental data at both solid and liquid phases in terms of providing an alternative rigid ion potential. The results give a fairly good description of TlCl and TlBr in the temperature range 10-1000 K.

Observations of Bromine Chloride (BrCl) at an Arctic Coastal Site

NASA Astrophysics Data System (ADS)

McNamara, S. M.; Garner, N.; Wang, S.; Raso, A. R. W.; Thanekar, S.; Fuentes, J. D.; Shepson, P. B.; Pratt, K.

2017-12-01

Chlorine and bromine chemistry in the Arctic boundary layer have significant impacts on tropospheric ozone depletion and the fates of atmospheric pollutants such as methane, a greenhouse gas, and mercury. However, there is sparse understanding of halogen production and removal pathways due to a lack of observations. Here, we report chemical ionization mass spectrometry measurements of bromine chloride (BrCl) observed at Utqiaġvik (Barrow), AK during March-May 2016. Over the course of the three-month study, two distinct BrCl diurnal trends were identified, and production mechanisms were explored using 0-dimensional modeling, constrained by a suite of reactive halogen measurements. The findings in this work highlight coupled chlorine and bromine chemistry, as well as halogen activation pathways in the Arctic.

Ionic Liquids and Solids with Paramagnetic Anions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Castner, Jr., E.W.; Wishart, J.; Krieger, B.M.

2010-06-18

Four paramagnetic ionic compounds have been prepared and their magnetic, structural and thermal properties have been investigated. The four compounds are methylbutylpyrrolidinium tetrachloroferrate(III) ([Pyrr{sub 14}]{sup +}/[FeCl{sub 4}]{sup -}), methyltributylammonium tetrachloroferrate(III) ([N{sub 1444}]{sup +}/[FeCl{sub 4}]{sup -}), butylmethylimidazolium tetrachloroferrate(III) ([bmim]{sup +}/[FeCl{sub 4}]{sup -}) and tetrabutylammonium bromotrichloroferrate(III) ([N{sub 4444}]{sup +}/[FeBrCl{sub 3}]{sup -}). Temperature-dependent studies of their magnetic behaviors show that all four compounds are paramagnetic at ambient temperatures. Glass transitions are observed for only two of the four compounds, [Pyrr{sub 14}]{sup +}/[FeCl{sub 4}]{sup -} and [bmim]{sup +}/[FeCl{sub 4}]{sup -}. Crystal structures for [Pyrr{sub 14}]{sup +}/[FeCl{sub 4}]{sup -} and [N{sub 1444}]{sup +}/[FeCl{sub 4}]{sup -}more » are compared with the previously reported [N{sub 4444}]{sup +}/[FeBrCl{sub 3}]{sup -}.« less

IDENTIFICATION OF STEREOCHEMICAL CONFIGURATIONS OF CYCLOPENTA[CD]PYRENE-DNA ADDUCTS IN STRAIN A/J MOUSE LUNG AND C3H10T1/2CL8 CELLS

EPA Science Inventory

Identification of Sterochemical Configurations of Cyclopent A[cd]Pyrene DNA Adducts in Strain A/J Mouse Lung and C3H10T1/2CL8 Cells.

Four major and several minor DNA adducts were resolved by 32P-postlabeling analysis of DNA from strain A/J mouse lung and C3H10T1/2CL8 (C3H...

Continued development of thallium bromide and related compounds for gamma-ray spectrometers

NASA Astrophysics Data System (ADS)

Kim, H.; Churilov, A.; Ciampi, G.; Cirignano, L.; Higgins, W.; Kim, S.; O'Dougherty, P.; Olschner, F.; Shah, Kanai

2011-02-01

Thallium bromide (TlBr) and related ternary compounds, TlBrI and TlBrCl, have been under development for room temperature gamma-ray spectroscopy due to high density, high Z and wide bandgap of the material. Low melting point and cubic crystal structure of selected compositions of these compounds facilitate crystal growth by melt techniques. Recent advances in material purification, crystal growth, and device processing have led to mobility-lifetime products of electrons in the mid 10 -3 cm 2/V range enabling working detectors of greater than 15 mm thickness to be fabricated. In this paper we report on our recent progress on TlBr detector development and first results from TlBr xCl 1- x devices. Pulse height spectra will be presented from TlBr arrays as thick as 18 mm. Depth corrected spectra will also be presented. For a 5 mm thick TlBr array, energy resolution of less than 1% (FWHM at 662 keV) was obtained after depth correction.

Silver chlorobromide nanocubes with significantly improved uniformity: synthesis and assembly into photonic crystals

DOE Office of Scientific and Technical Information (OSTI.GOV)

Li, Zheng; Okasinski, John S.; Gosztola, David J.

2015-01-01

Silver chlorobromide (AgClxBr1-x, 0 < x < 1) nanocubes with a highly uniform size, morphology, and crystallinity have been successfully synthesized through a co-precipitation of Ag+ ions with both Cl- and Br- ions in ethylene glycol containing polyvinyl pyrrolidone at mild temperatures. Compositions of the synthesized nanocubes can be easily tuned by controlling the molar ratio of Cl- to Br- ions in the reaction solutions. The size of the nanocubes is determined by varying a number of parameters including the molar ratio of Cl- to Br- ions, injection rate of Ag+ ions, and reaction temperature. The real-time formation of colloidalmore » AgClxBr1-x nanocubes has been monitored, for the first time, by in situ highenergy synchrotron X-ray diffraction. The time-resolved results reveal that a fast injection rate of Ag+ ions is critical for the formation of AgClxBr1-x nanocubes with a highly pure face-centered cubic crystalline phase. The improved uniformity of the AgClxBr1-x nanocubes is beneficial for assembling them into order superlattices (e.g., photonic crystals) even by simply applying centrifugation forces. The stop band of the resulting photonic crystals can be easily tuned from the ultraviolet to the infrared region by using AgClxBr1-x nanocubes with different sizes. The variation of the dielectric constant of AgClxBr1-x associated with the change of the relative concentration of halide ions provides an additional knob to tune the optical properties of photonic crystals.« less

Temperature-Dependent Kinetics Studies of the Reactions Br((sup 2)P3/2) + H2S yields SH + HBr and Br((sup 2)P3/2) + CH3SH yields CH3S + HBr. Heats of Formation of SH and CH3S Radicals

NASA Technical Reports Server (NTRS)

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

1997-01-01

Time resolved resonance fluorescence detection of Br(sup 2)P3/2) atom disappearance or appearance following 266-nm laser flash photolysis of CF2Br2/H2S/H2/N2, CF2Br2/CH3SH/H2/N2, Cl2CO/H2S/HBr/N2, and CH3SSCH3/HBr/H2/N2 mixtures has been employed to study the kinetics of the reactions Br((sup 2)P3/2) + H2S = SH + HBr (1,-1) and Br((sup2)P3/2) + CH3SH = CH3S + HBr (2, -2) as a function of temperature over the range 273-431K. Arrhenius expressions in units of 10(exp -12) cu cm/molecule/s which describe the results are k1 = (14.2 +/- 3.4) exp[(-2752 +/- 90)/T],(k-1) = (4.40 +/- 0.92) exp[(-971 +/- 73)/T],k(2) = (9.24 +/- 1.15) exp[(-386 +/- 41)/T], and k(-2) = (1.46 +/-0.21) exp[(-399 +/-41)/T; errors are 2 sigma and represent precision only. By examining Br((sup 2)P3/2) equilibrium kinetics following 355nm laser flash photolysis of Br2/CH3SH/H2/N2 mixtures, a 298 K rate coefficient of (1.7 +/- 0.5) x 10(exp -10) cu cm/molecule/s has been obtained for the reaction CH3S + Br2 yields CH3SBr + Br. To our knowledge, these are the first kinetic data reported for each of the reactions studied. Measured rate coefficients, along with known rate coefficients for similar radical + H2S, CH3SH, HBr,Br2 reactions are considered in terms of possible correlations of reactivity with reaction thermochemistry and with IP - EA, the difference between the ionization potential of the electron donor and the electron affinity of the electron acceptor. Both thermochemical and charge-transfer effects appear to be important in controlling observed reactivities. Second and third law analyses of the equilibrium data for reactions 1 and 2 have been employed to obtain the following enthalpies of reaction in units of kcal/mol: for reaction 1, Delta-H(298) = 3.64 +/- 0.43 and Delta-H(0) = 3.26 +/-0.45; for reaction 2, Delta-H(298) = -0.14 +/- 0.28 and Delta-H(0) = -0.65 +/- 0.36. Combining the above enthalpies of reaction with the well-known heats of formation of Br, HBr, H2S, and CH3SH gives the following heats of formation for the RS radicals in units of kcal/mol: Delta-H(sub f)(sub 0)(SH) = 34.07 +/- 0.72, Delta-H(sub f)(sub 298)(SH) = 34.18 +/- 0.68, Delta-H(sub f)(sub 0)(CH3S) = 31.44 +/- 0.54, Delta-H(sub f)(sub 298)(CH3S) = 29.78 +/- 0.44; errors are 2 sigma and represent estimates of absolute accuracy. The SH heat of formation determined from our data agrees well with literature values but has reduced error limits compared to other available values. The CH3S heat of formation determined from our date is near the low end of the range of previous estimates and is 3-4 kcal/mol lower than values derived from recent molecular beam photofragmentation studies.

The geochemistry of groundwater resources in the Jordan Valley: The impact of the Rift Valley brines

USGS Publications Warehouse

Farber, E.; Vengosh, A.; Gavrieli, I.; Marie, Amarisa; Bullen, T.D.; Mayer, B.; Polak, A.; Shavit, U.

2007-01-01

The chemical composition of groundwater in the Jordan Valley, along the section between the Sea of Galilee and the Dead Sea, is investigated in order to evaluate the origin of the groundwater resources and, in particular, to elucidate the role of deep brines on the chemical composition of the regional groundwater resources in the Jordan Valley. Samples were collected from shallow groundwater in research boreholes on two sites in the northern and southern parts of the Jordan Valley, adjacent to the Jordan River. Data is also compiled from previous published studies. Geochemical data (e.g., Br/Cl, Na/Cl and SO4/Cl ratios) and B, O, Sr and S isotopic compositions are used to define groundwater groups, to map their distribution in the Jordan valley, and to evaluate their origin. The combined geochemical tools enabled the delineation of three major sources of solutes that differentially affect the quality of groundwater in the Jordan Valley: (1) flow and mixing with hypersaline brines with high Br/Cl (>2 ?? 10-3) and low Na/Cl (<0.8) ratios; (2) dissolution of highly soluble salts (e.g., halite, gypsum) in the host sediments resulting in typically lower Br/Cl signal (<2 ?? 10-3); and (3) recharge of anthropogenic effluents, primarily derived from evaporated agricultural return flow that has interacted (e.g., base-exchange reactions) with the overlying soil. It is shown that shallow saline groundwaters influenced by brine mixing exhibit a north-south variation in their Br/Cl and Na/Cl ratios. This chemical trend was observed also in hypersaline brines in the Jordan valley, which suggests a local mixing process between the water bodies. ?? 2007 Elsevier Ltd. All rights reserved.

Heterogeneity of Equilibrium Molten Globule State of Cytochrome c Induced by Weak Salt Denaturants under Physiological Condition

PubMed Central

Rahaman, Hamidur; Alam Khan, Md. Khurshid; Hassan, Md. Imtaiyaz; Islam, Asimul; Moosavi-Movahedi, Ali Akbar; Ahmad, Faizan

2015-01-01

While many proteins are recognized to undergo folding via intermediate(s), the heterogeneity of equilibrium folding intermediate(s) along the folding pathway is less understood. In our present study, FTIR spectroscopy, far- and near-UV circular dichroism (CD), ANS and tryptophan fluorescence, near IR absorbance spectroscopy and dynamic light scattering (DLS) were used to study the structural and thermodynamic characteristics of the native (N), denatured (D) and intermediate state (X) of goat cytochorme c (cyt-c) induced by weak salt denaturants (LiBr, LiCl and LiClO4) at pH 6.0 and 25°C. The LiBr-induced denaturation of cyt-c measured by Soret absorption (Δε 400) and CD ([θ]409), is a three-step process, N ↔ X ↔ D. It is observed that the X state obtained along the denaturation pathway of cyt-c possesses common structural and thermodynamic characteristics of the molten globule (MG) state. The MG state of cyt-c induced by LiBr is compared for its structural and thermodynamic parameters with those found in other solvent conditions such as LiCl, LiClO4 and acidic pH. Our observations suggest: (1) that the LiBr-induced MG state of cyt-c retains the native Met80-Fe(III) axial bond and Trp59-propionate interactions; (2) that LiBr-induced MG state of cyt-c is more compact retaining the hydrophobic interactions in comparison to the MG states induced by LiCl, LiClO4 and 0.5 M NaCl at pH 2.0; and (3) that there exists heterogeneity of equilibrium intermediates along the unfolding pathway of cyt-c as highly ordered (X1), classical (X2) and disordered (X3), i.e., D ↔ X3 ↔ X2 ↔ X1 ↔ N. PMID:25849212

Heterogeneity of equilibrium molten globule state of cytochrome c induced by weak salt denaturants under physiological condition.

PubMed

Rahaman, Hamidur; Alam Khan, Md Khurshid; Hassan, Md Imtaiyaz; Islam, Asimul; Moosavi-Movahedi, Ali Akbar; Ahmad, Faizan

2015-01-01

While many proteins are recognized to undergo folding via intermediate(s), the heterogeneity of equilibrium folding intermediate(s) along the folding pathway is less understood. In our present study, FTIR spectroscopy, far- and near-UV circular dichroism (CD), ANS and tryptophan fluorescence, near IR absorbance spectroscopy and dynamic light scattering (DLS) were used to study the structural and thermodynamic characteristics of the native (N), denatured (D) and intermediate state (X) of goat cytochorme c (cyt-c) induced by weak salt denaturants (LiBr, LiCl and LiClO4) at pH 6.0 and 25°C. The LiBr-induced denaturation of cyt-c measured by Soret absorption (Δε400) and CD ([θ]409), is a three-step process, N ↔ X ↔ D. It is observed that the X state obtained along the denaturation pathway of cyt-c possesses common structural and thermodynamic characteristics of the molten globule (MG) state. The MG state of cyt-c induced by LiBr is compared for its structural and thermodynamic parameters with those found in other solvent conditions such as LiCl, LiClO4 and acidic pH. Our observations suggest: (1) that the LiBr-induced MG state of cyt-c retains the native Met80-Fe(III) axial bond and Trp59-propionate interactions; (2) that LiBr-induced MG state of cyt-c is more compact retaining the hydrophobic interactions in comparison to the MG states induced by LiCl, LiClO4 and 0.5 M NaCl at pH 2.0; and (3) that there exists heterogeneity of equilibrium intermediates along the unfolding pathway of cyt-c as highly ordered (X1), classical (X2) and disordered (X3), i.e., D ↔ X3 ↔ X2 ↔ X1 ↔ N.

Radiocarbon evidence for a naturally produced, bioaccumulating halogenated organic compound.

PubMed

Reddy, Christopher M; Xu, Li; O'Neil, Gregory W; Nelson, Robert K; Eglinton, Timothy I; Faulkner, D John; Norstrom, Ross; Ross, Peter S; Tittlemier, Sheryl A

2004-04-01

Halogenated organic compounds (HOCs) such as 1,1'-dimethyl-3,3',4,4'-tetrabromo-5,5'-dichloro-2,2'-bipyrrole (DBP-Br4Cl2) and heptachloro-1'-methyl-1,2'-bipyrrole (Q1) have been detected worldwide, sometimes at high levels in Antarctic air, seabird eggs, the blubber of marine mammals, and, most notably, even human milk. To date, it has been difficult to determine whether these compounds are natural products or derived from industrial synthesis. Molecular-level 14C analysis of these compounds is particularly appealing because most industrial compounds are manufactured from petrochemicals (14C-free) and natural compounds should have "modern" or "contemporary" 14C levels. To investigate the source of DBP-Br4Cl2, we isolated 600 microg of this compound (150 microg of carbon) from marine animal extracts by employing gel permeation chromatography, Florisil column chromatography, and two-dimensional preparative capillary gas chromatography. The purified DBP-Br4Cl2 was split into two samples (75 microg of carbon each) and analyzed by accelerator mass spectrometry for 14C content. The delta14C values were -449 percent per thousand and -467 percent per thousand, corresponding to conventional 14C ages of 4740 and 5000 years before present (BP), respectively. The presence of detectable 14C in the DBP-Br4Cl2 strongly points to at least a natural or biogenic source. However, these delta14C values for DBP-Br4Cl2 are more depleted than expected for a recently synthesized natural product. Several explanations are discussed, but additional samples

Effect of halo-substituted aromatic salts on counterion binding constants obtained from cationic nanoparticle catalyzed reactions of piperidine and phenyl salicylate

NASA Astrophysics Data System (ADS)

Fagge, Ibrahim I.; Yusof, Nor Saadah M.; Zain, Sharifuddin Md; Khan, M. Niyaz

2017-12-01

Halo-substitutions at 3-position of benzene ring of the salts of aromatic carboxylate, MX, revealed the effect of two different halide ions (Br- and Cl-) on the counterion binding constants obtained from cationic nanoparticle catalyzed piperidinolysis of ionized phenyl salicylate (PhS-). The values of observed rate constant, kobs, determined at a constant total concentration of cetyltrimethylammonium bromide, [CTABr]T, piperidine, ([P]T), [PhS-]T, NaOH, and various concentration of MX (MX = 3-BrC6H4CO2Na and 3-ClC6H4CO2Na), were determined using UV-visible X spectrophotometric technique at 35 °C and 370 nm. The average value of nanoparticle binding constant, KXBr, for X- = 3-BrC6H4CO2- (RXBr = 57) was found to be about 2-fold larger than that for X- = 3-ClC6H4CO2- (RXBr = 30). These XX values were dependent of substituents 3-Br and 3-Cl, and independent of [CTABr]T. Both are related to the presence of different extent of viscoelastic worm-like nanoparticles formation in the [CTABr]T of 6 and 10 mM.

Voltage Dependence of Proton Pumping by Bacteriorhodopsin Mutants with Altered Lifetime of the M Intermediate

PubMed Central

Geibel, Sven; Lörinczi, Èva; Bamberg, Ernst; Friedrich, Thomas

2013-01-01

The light-driven proton pump bacteriorhodopsin (BR) from Halobacterium salinarum is tightly regulated by the [H+] gradient and transmembrane potential. BR exhibits optoelectric properties, since spectral changes during the photocycle are kinetically controlled by voltage, which predestines BR for optical storage or processing devices. BR mutants with prolonged lifetime of the blue-shifted M intermediate would be advantageous, but the optoelectric properties of such mutants are still elusive. Using expression in Xenopus oocytes and two-electrode voltage-clamping, we analyzed photocurrents of BR mutants with kinetically destabilized (F171C, F219L) or stabilized (D96N, D96G) M intermediate in response to green light (to probe H+ pumping) and blue laser flashes (to probe accumulation/decay of M). These mutants have divergent M lifetimes. As for BR-WT, this strictly correlates with the voltage dependence of H+ pumping. BR-F171C and BR-F219L showed photocurrents similar to BR-WT. Yet, BR-F171C showed a weaker voltage dependence of proton pumping. For both mutants, blue laser flashes applied during and after green-light illumination showed reduced M accumulation and shorter M lifetime. In contrast, BR-D96G and BR-D96N exhibited small photocurrents, with nonlinear current-voltage curves, which increased strongly in the presence of azide. Blue laser flashes showed heavy M accumulation and prolonged M lifetime, which accounts for the strongly reduced H+ pumping rate. Hyperpolarizing potentials augmented these effects. The combination of M-stabilizing and -destabilizing mutations in BR-D96G/F171C/F219L (BR-tri) shows that disruption of the primary proton donor Asp-96 is fatal for BR as a proton pump. Mechanistically, M destabilizing mutations cannot compensate for the disruption of Asp-96. Accordingly, BR-tri and BR-D96G photocurrents were similar. However, BR-tri showed negative blue laser flash-induced currents even without actinic green light, indicating that Schiff base deprotonation in BR-tri exists in the dark, in line with previous spectroscopic investigations. Thus, M-stabilizing mutations, including the triple mutation, drastically interfere with electrochemical H+ gradient generation. PMID:24019918

Selective Complexation of Cyanide and Fluoride Ions with Ammonium Boranes: A Theoretical Study on Sensing Mechanism Involving Intramolecular Charge Transfer and Configurational Changes.

PubMed

Bhat, Haamid R; Jha, Prakash C

2017-05-18

The anion binding selectivity and the recognition mechanism of two isomeric boranes, namely, 4-[bis(2,4,6-trimethylphenyl)boranyl]-N,N,N-trimethylaniline ([p-(Mes 2 B)C 6 H 4 (NMe 3 )] + , 1, where "Mes" represents mesitylene and "Me" represents methyl) and 2-[bis(2,4,6-trimethylphenyl)boranyl]-N,N,N-trimethylaniline ([o-(Mes 2 B)C 6 H 4 (NMe 3 )] + , 2) has been investigated using density functional theory (DFT) and time dependent-density functional theory (TD-DFT) methods. Natural population analysis indicates that the central boron atoms in 1 and 2 are the most active centers for nucleophilic addition of anions. The negative magnitude of free energy changes (ΔG) reveals that out of CN - , F - , Cl - , Br - , NO 3 - , and HSO 4 - only the binding of CN - and F - with 1 and 2 is thermodynamically feasible and spontaneous. In addition, the calculated binding energies reveal that the CN - is showing lesser binding affinity than F - both with 1 and 2, while other ions, viz. NO 3 - , HSO 4 - , Br - , and Cl - , either do not bind at all or show very insignificant binding energy. The first excited states (S 1 ) of 1 and 2 are shown to be the local excited states with π → σ* transition by frontier molecular orbital analysis, whereas fourth excited states (S 4 ) of 4-[bis(2,4,6-trimethylphenyl)boranyl]-N,N,N-trimethylaniline cyanide ([p-(Mes 2 B)C 6 H 4 (NMe 3 )] CN, 1CN, the cyano form of 1) and 4-[bis(2,4,6-trimethylphenyl)boranyl]-N,N,N-trimethylaniline fluoride ([p-(Mes 2 B)C 6 H 4 (NMe 3 )] F, 1F, the fluoro form of 1) and fifth excited state (S 5 ) of 2-[bis(2,4,6-trimethylphenyl)boranyl]-N,N,N-trimethylaniline fluoride ([o-(Mes 2 B)C 6 H 4 (NMe 3 )] F, 2F, the fluoro form of 2) are charge separation states that are found to be responsible for the intramolecular charge transfer (ICT) process. The synergistic effect of ICT and partial configuration changes induce fluorescence quenching in 1CN, 1F, and 2F after a significant internal conversion (IC) from S 4 and S 5 to S 1.

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

NASA Technical Reports Server (NTRS)

Anderson, James G.

2001-01-01

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

MRS Symposium on Advanced Tomographic Imaging Methods for the Analysis of Materials

DTIC Science & Technology

1991-08-01

Manufactured in the United States of America ,’ - - - - ... . , . . : . . . . •-a Contents PREFACE ix MATERIALS RESEARCH SOCIETY SYMPOSIUM PROCEEDINGS x PART...prototype used for many NQR studies, NaClO,, which has four chlorine atoms per unit cell. The electric field gradient for each has q - 0 and are oriented...110 Reeeces 1. G. N. Hounsfield , Br. J. Radiol. 4(6 1016 (1973). Z L Shep and B. F. Logan, IE Trans. Nud. Sd. 2L,21 (1974). 3. R. M. Merseraeu and A. V

Excimer Laser Research.

DTIC Science & Technology

1975-08-01

and sample cylinder were repeatedly allowed to outgas at room temperature (under vacuum but valved off) and then cooled with liquid N_ snd pumped...i i I i | I I I I i I i i i | I I i i i i i l i | I l I I I 320 330 340 350 360 E7470 WAVELENGTH (nm) 2 2 Fig. 9 Densitometer Trace of XeF...2, Xs are within 10%. eFor Arl, Nel, NeBr, NeCl, and the helium halides the inert-gas ionization potential is so large that the Coulomb curve does

Squarylium-based chromogenic anion sensors.

PubMed

Lee, Eun-Mi; Gwon, Seon-Yeong; Son, Young-A; Kim, Sung-Hoon

2012-09-01

A squarylium (SQ) dye was synthesized by the reaction between squaric acid and 2,3,3-trimethylindolenine and its anion sensing properties were investigated using absorption and emission spectroscopy. This chemosensor exhibited high selectivity for CN(-) as compared with F(-), CH(3)CO(2)(-), Br(-), H(2)PO(4)(-), Cl(-), and NO(3)(-) in acetonitrile, which was attributed to the formation of a 1:1 squarylium:CN(-) coordination complex, the formation of which was supported by the calculated geometry of the complex. Copyright © 2012 Elsevier B.V. All rights reserved.

A newly synthesized thiazole derivative as a fluoride ion chemosensor: naked-eye, spectroscopic, electrochemical and NMR studies.

PubMed

Sarıgüney, Ahmet Burak; Saf, Ahmet Özgür; Coşkun, Ahmet

2014-07-15

2,3-Indoledione 3-thiosemicarbazone (TSCI) and a novel compound 3-(2-(4-(4-phenoxyphenyl)thiazol-2-yl)hydrazono)indolin-2-one (FTHI) were synthesized with high yield and characterized by spectroscopic techniques. The complexation behaviors of TSCI and FTHI for various anionic species (F(-), Cl(-), Br(-), I(-), NO2(-), NO3(-), BzO(-), HSO4(-), ClO4(-)) in CH3CN were investigated and compared by UV-vis spectroscopy, cyclic voltammetry and (1)H NMR titration techniques. FTHI showed high degree of selectivity for fluoride over other anions. This selectivity could be easily observed by the naked eye, indicating that FTHI is potential colorimetric sensor for fluoride anion. Copyright © 2014 Elsevier B.V. All rights reserved.

Volatilization, transport and sublimation of metallic and non-metallic elements in high temperature gases at Merapi Volcano, Indonesia

USGS Publications Warehouse

Symonds, R.B.; Rose, William I.; Reed, M.H.; Lichte, F.E.; Finnegan, David L.

1987-01-01

Condensates, silica tube sublimates and incrustations were sampled from 500-800??C fumaroles and lava samples were collected at Merapi Volcano, Indonesia in Jan.-Feb., 1984. With respect to the magma, Merapi gases are enriched by factors greater than 105 in Se, Re, Bi and Cd; 104-105 in Au, Br, In, Pb and W; 103-104 in Mo, Cl, Cs, S, Sn and Ag; 102-103 in As, Zn, F and Rb; and 1-102 in Cu, K, Na, Sb, Ni, Ga, V, Fe, Mn and Li. The fumaroles are transporting more than 106 grams/day ( g d) of S, Cl and F; 104-106 g/d of Al, Br, Zn, Fe, K and Mg; 103-104 g d of Pb, As, Mo, Mn, V, W and Sr; and less than 103 g d of Ni, Cu, Cr, Ga, Sb, Bi, Cd, Li, Co and U. With decreasing temperature (800-500??C) there were five sublimate zones found in silica tubes: 1) cristobalite and magnetite (first deposition of Si, Fe and Al); 2) K-Ca sulfate, acmite, halite, sylvite and pyrite (maximum deposition of Cl, Na, K, Si, S, Fe, Mo, Br, Al, Rb, Cs, Mn, W, P, Ca, Re, Ag, Au and Co); 3) aphthitalite (K-Na sulfate), sphalerite, galena and Cs-K. sulfate (maximum deposition of Zn, Bi, Cd, Se and In; higher deposition of Pb and Sn); 4) Pb-K chloride and Na-K-Fe sulfate (maximum deposition of Pb, Sn and Cu); and 5) Zn, Cu and K-Pb sulfates (maximum deposition of Pb, Sn, Ti, As and Sb). The incrustations surrounding the fumaroles are also chemically zoned. Bi, Cd, Pb, W, Mo, Zn, Cu, K, Na, V, Fe and Mn are concentrated most in or very close to the vent as expected with cooling, atmospheric contamination and dispersion. The highly volatile elements Br, Cl, As and Sb are transported primarily away from high temperature vents. Ba, Si, P, Al, Ca and Cr are derived from wall rock reactions. Incomplete degassing of shallow magma at 915??C is the origin of most of the elements in the Merapi volcanic gas, although it is partly contaminated by particles or wall rock reactions. The metals are transported predominantly as chloride species. As the gas cools in the fumarolic environment, it becomes saturated with sublimate phases that fractionate from the gas in the order of their equilibrium saturation temperatures. Devolatilization of a cooling batholith could transport enough acids and metals to a hydrothermal system to play a significant role in forming an ore deposit. However, sublimation from a high temperature, high velocity carrier gas is not efficient enough to form a large ore deposit. Re, Se, Cd and Bi could be used as supporting evidence for magmatic fluid transport in an ore deposit. ?? 1987.

Factors affecting the roles of reactive species in the degradation of micropollutants by the UV/chlorine process.

PubMed

Wu, Zihao; Guo, Kaiheng; Fang, Jingyun; Yang, Xueqin; Xiao, Hong; Hou, Shaodong; Kong, Xiujuan; Shang, Chii; Yang, Xin; Meng, Fangang; Chen, Liwei

2017-12-01

The UV/chlorine process is an emerging advanced oxidation process (AOP) that produces various reactive species, such as hydroxyl radicals (HO) and reactive chlorine species (RCS). The effects of the treatment conditions, such as chlorine dosage and pH, and the water matrix components of natural organic matter (NOM), alkalinity, ammonia and halides, on the kinetics and reactive species in the degradation of four micropollutants, metronidazole (MDZ), nalidixic acid (NDA), diethyltoluamide (DEET) and caffeine (CAF), by the UV/chlorine process were investigated. The degradation of MDZ and CAF was primarily attributable to HO and ClO, respectively, while that of NDA was primarily attributable to both ClO and CO 3 - . HO, Cl and CO 3 - are important for the degradation of DEET. The second-order rate constants for ClO with CAF and CO 3 - with NDA were determined to be 5.1 (±0.2) × 10 7  M -1 s -1 and 1.4 (±0.1) × 10 7  M -1 s -1 , respectively. Increasing chlorine dosage slightly changed the contribution of HO but linearly increased that of ClO to micropollutant degradation. Increasing pH decreased the contribution of either HO or Cl but not that of ClO. Both NOM and bicarbonate decreased the contributions of HO and Cl, whereas NOM but not bicarbonate significantly decreased that of ClO. The contribution of either HO or Cl first rose and then fell as the molar ratio of ammonia to chlorine increased from 0 to 1:1, while that of ClO decreased. The co-presence of high concentrations of Cl - and Br - enhanced the contribution of ClBr - and BrCl. Copyright © 2017 Elsevier Ltd. All rights reserved.

PERINATAL EXPOSURE TO ESTROGENIC COMPOUNDS AND THE SUBSEQUENT EFFECTS ON THE PROSTRATE OF THE ADULT RAT: EVALUATION OF INFLAMMATION IN THE VENTRAL AND LATERAL LOBES

EPA Science Inventory

Perinatal exposure to estrogenic compounds and the subsequent effects on the prostate of the adult rat: evaluation of inflammation in the ventral and lateral lobes.

Stoker TE, Robinette CL, Cooper RL.

Endocrinology Branch, Reproductive Toxicology Division, National ...

First principles and experimental study of the electronic structure and phase stability of bulk thallium bromide

NASA Astrophysics Data System (ADS)

Smith, Holland M.; Zhou, Yuzhi; Ciampi, Guido; Kim, Hadong; Cirignano, Leonard J.; Shah, Kanai S.; Haller, E. E.; Chrzan, D. C.

2013-08-01

We apply state-of-art first principle calculations to study the polymorphism and electronic structure of three previously reported phases of TlBr. The calculated band structures of NaCl-structure phase and orthorhombic-structure phase have different features than that of commonly observed CsCl-structure phase. We further interpret photoluminescence spectra based on our calculations. Several peaks close to calculated band gap values of the NaCl-structure phase and the orthorhombic-structure phase are found in unpolished TlBr samples.

Pitting corrosion of titanium. The relationship between pitting potential and competitive anion adsorption at the oxide film/electrolyte interface

DOE Office of Scientific and Technical Information (OSTI.GOV)

Basame, S.B.; White, H.S.

2000-04-01

The potential-dependent breakdown of the native oxide film ({approximately}20 {angstrom} thick) on titanium has been investigated in aqueous Br{sup {minus}} solutions and in solutions that contain a mixture of Br{sup {minus}} and anions that inhibit oxide breakdown (i.e., Cl{sup {minus}}, I{sup {minus}}, SO{sub 4}{sup 2{minus}}, Fe(CN){sub 6}{sup 4{minus}}, and Fe(CN){sub 6}{sup 3{minus}}). The oxide film is unstable in neutral pH solutions containing only Br{sup {minus}}, resulting in the formation of stable corrosion pits at relatively low potentials ({approximately}1.4 V vs. Ag/AgCl). The pitting potential, E{sub p}, is strongly dependent upon the concentration of Br{sup {minus}}, and can be modeled usingmore » a Langmuir isotherm to describe the adsorption of Br{sup {minus}} at the oxide film/electrolyte interface. Addition of a second anion inhibits oxide film breakdown, as indicated by a large positive shift in E{sub p} and a decrease in the number of stable corrosion pits. The dependence of E{sub p} on the relative concentrations of Br{sup {minus}} and the inhibitor anion is consistent with competitive adsorption of the anions. Equilibrium adsorption coefficients for I{sup {minus}}, Br{sup {minus}}, and Cl{sup {minus}} are estimated from the dependence of E{sub p} on anion concentration. The results are used to establish a physical basis for the anomalously low pitting potential for titanium in aqueous Br{sup {minus}} solutions.« less

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

NASA Astrophysics Data System (ADS)

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 three systems, together with the results obtained through a full diagonalization within crystal field and charge transfer states.

Cl sup minus -HCO sub 3 sup minus exchange is present with Na sup + -K sup + -Cl sup minus cotransport in rabbit parotid acinar basolateral membranes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Turner, R.J.; George, J.N.

1988-03-01

The presence of a sodium-independent electroneutral Cl{sup {minus}}-anion exchanger in a basolateral membrane vesicle preparation from the rabbit parotid is demonstrated. This exchanger is shared by HCO{sub 3}{sup {minus}}, NO{sub 3}{sup {minus}}, Br{sup {minus}}, F{sup {minus}}, and formate, but not by thiocyanate, acetate, methylsulfate, gluconate, or hydroxyl ions. In order of relative potency, the exchanger is inhibited by SITS {ge} phloretin > furosemide > bumetanide {ge} phlorizin. A Na{sup +}-K{sup +}-dependent component of chloride flux, presumably due to the Na{sup +}-K{sup +}-Cl{sup {minus}} cotransporter already characterized in this preparation, was also observed. {sup 36}Cl uptake into vesicles loaded with KClmore » exhibited an overshoot of intravesicular ({sup 36}Cl) due to {sup 36}Cl-Cl exchange. However, when vesicles were loaded with both KCl and NaCl the height of the overshoot was considerably decreased indicating a Na{sup +}-K{sup +}-dependent dissipation of the intravesicular to extravesicular chloride gradient. This experiment provides strong evidence that the Na{sup +}-K{sup +}Cl{sup {minus}} cotransporter and the Cl{sup {minus}} HCO{sub 3}{sup {minus}} exchange are present in the same membrane vesicles. These results indicate that Cl{sup {minus}}-HCO{sub 3}{sup {minus}} exchange is present in the basolateral membrane of parotid acinar cells and thus that this transporter may play a significant role in salivary secretion.« less

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

PubMed

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.

Mononuclear ruthenium(III) complexes containing chelating thiosemicarbazones: Synthesis, characterization and catalytic property

NASA Astrophysics Data System (ADS)

Raja, N.; Ramesh, R.

2010-02-01

Mononuclear ruthenium(III) complexes of the type [RuX(EPh 3) 2(L)] (E = P or As; X = Cl or Br; L = dibasic terdentate dehydroacetic acid thiosemicarbazones) have been synthesized from the reaction of thiosemicarbazone ligands with ruthenium(III) precursors, [RuX 3(EPh 3) 3] (where E = P, X = Cl; E = As, X = Cl or Br) and [RuBr 3(PPh 3) 2(CH 3OH)] in benzene. The compositions of the complexes have been established by elemental analysis, magnetic susceptibility measurement, FT-IR, UV-vis and EPR spectral data. These complexes are paramagnetic and show intense d-d and charge transfer transitions in dichloromethane. The complexes show rhombic EPR spectra at LNT which are typical of low-spin distorted octahedral ruthenium(III) species. All the complexes are redox active and display an irreversible metal centered redox processes. Complex [RuCl(PPh 3) 2(DHA-PTSC)] ( 5) was used as catalyst for transfer hydrogenation of ketones in the presence of isopropanol/KOH and was found to be the active species.

SERUM HORMONE CHARACTERIZATION AND EXOGENEOUS HORMONE RESCUE OF BROMODICHLOROMETHANE-INDUCED PREGNANCY LOSS IN THE F344 RAT

EPA Science Inventory

SERUM HORMONE CHARACTERIZATION AND EXOGENEOUS HORMONE RESCUE OF BROMODICHLOROMETHANE-INDUCED
PREGNANCY LOSS IN THE F344 RAT
Susan R. Bielmeier*, Deborah S. Best^, and Michael G. Narotsky^

ABSTRACT
Previously, we demonstrated that bromodichloromethane (BDCM), a d...

Hydration of the Atlantis Massif: Halogen, Noble Gas and In-Situ δ18O Constraints

NASA Astrophysics Data System (ADS)

Williams, M. J.; Kendrick, M. A.; Rubatto, D.

2017-12-01

A combination of halogen (Cl, Br, I), noble gases (He, Ne, Ar, Kr and Xe) and in situ oxygen isotope analysis have been utilized to investigate the fluid-mobile element record of hydration and alteration processes at the Atlantis Massif (30°N on the Mid-Atlantic Ridge). The sample suite investigated includes serpentinite, talc-amphibole ± chlorite schist and hydrated gabbro recovered by seafloor drilling undertaken at sites on a transect across the Atlantis Massif during IODP Expedition 357. Serpentine mesh and veins analysed in-situ by SHRIMP SI exhibit δ18O from 6‰ down to ≈0‰, suggesting serpentinization temperatures of 150 to >280°C and water/rock ratios >5. Differences of 1.5-2.5‰ are observed between adjacent generations of serpentine, but the δ18O range is similar at each investigated drilling site. Halogen and noble gas abundances in serpentinites, talc-amphibole schist and hydrated gabbro have been measured by noble gas mass spectrometry of both irradiated and non-irradiated samples. Serpentinites contain low abundances of halogens and noble gases (e.g. 70-430 ppm Cl, 4.7-12.2 x 10-14 mol/g 36Ar) relative to other seafloor serpentinites. The samples have systematically different Br/Cl and I/Cl ratios related to their mineralogy. Serpentinites retain mantle-like Br/Cl with a wide variation in I/Cl that stretches toward seawater values. Talc-amphibole schists exhibit depletion of Br and I relative to Cl with increasing Cl abundances, suggesting tremolite exerts strong control on halogen abundance ratios. Serpentinites show no evidence of interaction with halogen-rich sedimentary pore fluids. Iodine abundances are variable across serpentinites, and are decoupled from Br and Cl; iodine enrichment (up to 530 ppb) is observed within relatively oxidised and clay-bearing samples. Serpentinized harzburgites exhibit distinct depletion of Kr and Xe relative to atmospheric 36Ar in seawater. Oxygen isotope compositions and low abundances of both halogens and noble gases are consistent with high water/rock ratios. Successive generations of serpentine have δ18O trends suggesting exposure to higher W/R ratios during exhumation and deformation of the massif. Low noble gas abundances of may also be influenced by thermal loss related to impregnation and intrusion of the Massif by gabbros and dolerites.

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.

PubMed

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.

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

NASA Technical Reports Server (NTRS)

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

1997-01-01

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

Two-Dimensional Lead(II) Halide-Based Hybrid Perovskites Templated by Acene Alkylamines: Crystal Structures, Optical Properties, and Piezoelectricity.

PubMed

Du, Ke-Zhao; Tu, Qing; Zhang, Xu; Han, Qiwei; Liu, Jie; Zauscher, Stefan; Mitzi, David B

2017-08-07

A series of two-dimensional (2D) hybrid organic-inorganic perovskite (HOIP) crystals, based on acene alkylamine cations (i.e., phenylmethylammonium (PMA), 2-phenylethylammonium (PEA), 1-(2-naphthyl)methanammonium (NMA), and 2-(2-naphthyl)ethanammonium (NEA)) and lead(II) halide (i.e., PbX 4 2- , X = Cl, Br, and I) frameworks, and their corresponding thin films were fabricated and examined for structure-property relationship. Several new or redetermined crystal structures are reported, including those for (NEA) 2 PbI 4 , (NEA) 2 PbBr 4 , (NMA) 2 PbBr 4 , (PMA) 2 PbBr 4 , and (PEA) 2 PbI 4 . Non-centrosymmetric structures from among these 2D HOIPs were confirmed by piezoresponse force microscopy-especially noteworthy is the structure of (PMA) 2 PbBr 4 , which was previously reported as centrosymmetric. Examination of the impact of organic cation and inorganic layer choice on the exciton absorption/emission properties, among the set of compounds considered, reveals that perovskite layer distortion (i.e., Pb-I-Pb bond angle between adjacent PbI 6 octahedra) has a more global effect on the exciton properties than octahedral distortion (i.e., variation of I-Pb-I bond angles and discrepancy among Pb-I bond lengths within each PbI 6 octahedron). In addition to the characteristic sharp exciton emission for each perovskite, (PMA) 2 PbCl 4 , (PEA) 2 PbCl 4 , (NMA) 2 PbCl 4 , and (PMA) 2 PbBr 4 exhibit separate, broad "white" emission in the long wavelength range. Piezoelectric compounds identified from these 2D HOIPs may be considered for future piezoresponse-type energy or electronic applications.

A vanadium-dependent bromoperoxidase in the marine red alga Kappaphycus alvarezii (Doty) Doty displays clear substrate specificity.

PubMed

Kamenarska, Zornitsa; Taniguchi, Tomokazu; Ohsawa, Noboru; Hiraoka, Masanori; Itoh, Nobuya

2007-05-01

Bromoperoxidase activity was initially detected in marine macroalgae belonging to the Solieriaceae family (Gigartinales, Rhodophyta), including Solieria robusta (Greville) Kylin, Eucheuma serra J. Agardh and Kappaphycus alvarezii (Doty) Doty, which are important industrial sources of the polysaccharide carrageenan. Notably, the purification of bromoperoxidase was difficult because due to the coexistence of viscoid polysaccharides. The activity of the partially purified enzyme was dependent on the vanadate ion, and displayed a distinct substrate spectrum from that of previously reported vanadium-dependent bromoperoxidases of marine macroalgae. The enzyme was specific for Br- and I- ions and inactive toward F- and Cl-. The K(m) values for Br- and H2O2 were 2.5x10(-3) M and 8.5x10(-5) M, respectively. The halogenated product, dibromoacetaldehyde, that accumulated in K. alvarezii was additionally determined.

New molecular assemblies of redox isomers, [CrIII(X4SQ)3-n(X4Cat)n]-n (X = Cl and Br; n = 0, 1, and 2), with metallocenium cations, [MIIICp2]+ (M = Co and Fe): X-ray crystal structures and physical properties.

PubMed

Chang, H C; Miyasaka, H; Kitagawa, S

2001-01-01

A series of redox isomers of [CrIII(X4SQ)(X4Cat)2]2-, [CrIII(X4SQ)2(X4Cat)]-, and [CrIII(X4SQ)3]0 (X = Cl and Br, SQ = semiquinonate, and Cat = catecholate) have been synthesized and characterized as charge-transfer (CT) compounds with metallocenium cations: (CoIIICp2)2[CrIII(Cl4SQ)(Cl4Cat)2] (1), (CoIIICp2)2[CrIII(Br4SQ)(Br4Cat)2] (2), (FeIIICp2)[CrIII(Cl4SQ)2(Cl4Cat)].C6H6 (4), (FeIIICp2)[CrIII(Br4SQ)2(Br4Cat)].CS2 (5), and (FeIIICp2)[CrIII(Cl4SQ)2(Cl4Cat)][CrIII(Cl4SQ)3] (6). First, the oxidation states of the chromium complexes are strongly dependent on the redox potentials of the metallocenes used. The CoIICp2, exhibiting stronger reduction power than FeIICp2, is useful for two-electron reduction of the [CrIII(X4SQ)3]0, affording [CrIII(X4SQ)(X4Cat)2]2- (1 and 2), which are first isolated and crystallographically characterized in the solid state. In contrast the reaction with FeIICp2 affords only [CrIII(X4SQ)2(X4Cat)]- (4 and 5). Second, solvents influence crystal structures of these compounds. The solvent set of C6H6/CS2 gives 1:1:C6H6 compound 4 with unique charged anions, [CrIII(Cl4SQ)2(Cl4Cat)]-, while the other set, n-C6H12/CS2, affords 1:2 compound 6 including the two redox isomers, [CrIII(Cl4SQ)2(Cl4Cat)]- and [CrIII(Cl4SQ)3]0. The [CrIII(X4SQ)(X4Cat)2]2- anions in 1 and 2 show no significant interconnection between them (discrete type), while the [CrIII(X4SQ)2(X4Cat)]- anions in 4-6 show one-dimensional column-type structures with the aid of intermolecular stacking interactions of the ligand moieties. The anions in 4 show additional stacking interaction with the [FeIIICp2]+ to form one-dimensional ...[D][A][S][D][A]... (D = [FeIIICp2]+, A = [CrIII(Cl4SQ)2(Cl4Cat)]-, and S = C6H6) type mixed-stack arrangements similar to that of previously reported (CoIIICp2)[CrIII(Cl4SQ)2(Cl4Cat)].C6H6 (3). Compound 6 forms a two-dimensional sheet structure where the two redox isomers, [CrIII(Cl4SQ)2(Cl4Cat)]- and [CrIII(Cl4SQ)3]0, are included. The sheet is regarded as a mixed-valence molecular assembly. Two types of the anions, [CrIII(X4SQ)(X4Cat)2]2- (1 and 2) and [CrIII(X4SQ)2(X4Cat)]- (4-6), exhibiting an intramolecular mixed-valence state, show intramolecular intervalence CT transition (IVCT) from the Cat to the SQ at near 5800 and 4300 cm-1, respectively, both in the solution and in the solid states. The intermolecular mixed-valence state of 6 was characterized by absorption spectroscopy, electric conductivity, and SQUID magnetometry. Interestingly, this mixed-valence state of the chromium module is dependent on the redox active nature of the coordinated ligands.

Substitution and addition reactions of •OH with p-substituted-phenols

NASA Astrophysics Data System (ADS)

Albarrán, Guadalupe; Galicia-Jiménez, Eduardo; Mendoza, Edith; Schuler, Robert H.

2017-04-01

The directing effect of a hydroxyl group on the substitution and addition reactions of •OH to the substituted and free positions in aromatic rings of p-substituted-phenols were studied in aqueous solutions containing either K3Fe(CN)6 as an oxidant of the substituted hydroxycyclohexadienyl radical initially formed or using ascorbic acid. The results showed that the attack of the •OH to the substituted position (ipso position) was followed by elimination of the substituent producing hydroquinone. The addition reaction of the •OH to the free position on the ring produced 4-substituent-catechol and 4-substituent-resorcinol derivatives. Identification and quantification of the radiolytic products were carried out using high performance liquid chromatography. The results of the yields are given for the p-halogen-phenols (p-X-Ph) p-F-Ph, p-Cl-Ph, p-Br-Ph and p-I-Ph. Other compounds, p-nitro-Ph, p-OH-benzoic acid, p-OH-benzonitrile, p-OH-benzaldehyde, p-OH-anisole and p-OH-benzyl alcohol (represented as p-Z-Ph), were only studied using K3Fe(CN)6 as the oxidant. The results show that the p-X-Ph are attacked by the •OH at the ipso position to the halogen in the proportion 1:0.53:0.46:0.11 for F>Cl>Br>I. The •OH attacked at the ipso position to the p-Z-Phs through a substitution reaction, which depended on the substituent group. Thus, the strongly deactivating groups produced less hydroquinone, indicating less substitution reaction than the strongly activating groups.

The Hydrogen Bonded Structures of Two 5-Bromobarbituric Acids and Analysis of Unequal C5–X and C5–X′ Bond Lengths (X = X′ = F, Cl, Br or Me) in 5,5-Disubstituted Barbituric Acids

PubMed Central

Gelbrich, Thomas; Braun, Doris E.; Oberparleiter, Stefan; Schottenberger, Herwig; Griesser, Ulrich J.

2017-01-01

The crystal structure of the methanol hemisolvate of 5,5-dibromobarbituric acid (1MH) displays an H-bonded layer structure which is based on N–H⋯O=C, N–H⋯O(MeOH) and (MeOH)O–H⋯O interactions. The barbiturate molecules form an H-bonded substructure which has the fes topology. 5,5′-Methanediylbis(5-bromobarbituric acid) 2, obtained from a solution of 5,5-dibromobarbituric acid in nitromethane, displays a N–H⋯O=C bonded framework of the sxd type. The conformation of the pyridmidine ring and the lengths of the ring substituent bonds C5–X and C5–X′ in crystal forms of 5,5-dibromobarbituric acid and three closely related analogues (X = X′ = Br, Cl, F, Me) have been investigated. In each case, a conformation close to a C5-endo envelope is correlated with a significant lengthening of the axial C5–X′ in comparison to the equatorial C5–X bond. Isolated molecule geometry optimizations at different levels of theory confirm that the C5-endo envelope is the global conformational energy minimum of 5,5-dihalogenbarbituric acids. The relative lengthening of the axial bond is therefore interpreted as an inherent feature of the preferred envelope conformation of the pyrimidine ring, which minimizes repulsive interactions between the axial substituent and pyrimidine ring atoms. PMID:28670485

TETRAHALOINDATE(III)-BASED IONIC LIQUIDS IN THE COUPLING REACTION OF CARBON DIOXIDE AND EPOXIDES TO GENERATE CYCLIC CARBONATES: H-BONDING AND MECHANISTIC STUDIES

EPA Science Inventory

The microwave reactions of InX₃ with [Q]Y produce a series of tetrahaloindate(III)-based ionic liquids (ILs) with a general formula of [Q][InX₃Y] (Q = imidazolium, phosphonium, ammonium, and pyridinium; X = Cl, Br, I; Y = Cl, Br). The reaction of CO₂

EVALUATION OF BENZO[C]CHRYSENE DIHYDRODIOLS IN THE MORPHOLOGICAL CELL TRANSFORMATION OF MOUSE EMBRYO FIBROBLAST C3H10T1/2CL8 CELLS

EPA Science Inventory

EVALUATION OF BENZO[c]CHRYSENE DIHYDRODIOLS IN THE MORPHOLOGICAL CELL TRANSFORMATION OF MOUSE EMBRYO FIBROBLAST C3H10T?CL8 CELLS

Abstract The morphological cell transforming activities of three dihydrodiols of benzo[c]chrysene (B[c]C), trans-B[c]C-7,8-diol, trans-B[c]C-9...

All-Solid-State Mechanochemical Synthesis and Post-Synthetic Transformation of Inorganic Perovskite-type Halides.

PubMed

Pal, Provas; Saha, Sujoy; Banik, Ananya; Sarkar, Arka; Biswas, Kanishka

2018-02-06

All-inorganic and hybrid perovskite type halides are generally synthesized by solution-based methods, with the help of long chain organic capping ligands, complex organometallic precursors, and high boiling organic solvents. Herein, a room temperature, solvent-free, general, and scalable all-solid-state mechanochemical synthesis is demonstrated for different inorganic perovskite type halides, with versatile structural connectivity in three (3D), two (2D), and zero (0D) dimensions. 3D CsPbBr 3 , 2D CsPb 2 Br 5 , 0D Cs 4 PbBr 6 , 3D CsPbCl 3 , 2D CsPb 2 Cl 5 , 0D Cs 4 PbCl 6 , 3D CsPbI 3 , and 3D RbPbI 3 have all been synthesized by this method. The all-solid-state synthesis is materialized through an inorganic retrosynthetic approach, which directs the decision on the solid-state precursors (e.g., CsX and PbX 2 (X=Cl/Br/I) with desired stoichiometric ratios. Moreover, post-synthetic structural transformations from 3D to 2D and 0D perovskite halides were performed by the same mechanochemical synthetic approach at room temperature. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Determination of Halide Concentrations at the Interface of Zwitterionic Micelles by Chemical Trapping: Influence of the Orientation of the Dipole and the Nature of the Cation.

PubMed

Cuccovia; Romsted; Chaimovich

1999-12-01

The interfacial concentrations of Cl(-) and Br(-) in aqueous zwitterionic micelles were determined by chemical trapping by analyzing product yields from spontaneous dediazoniation of micelle-bound 2,6-dimethyl-4-hexadecylbenzenediazonium ion. Interfacial concentrations of Cl(-) and Br(-) in 3-(N-hexadecyl-N, N-dimethylammonio) propane sulfonate, HPS, micelles were higher than in bulk solutions prepared with Li(+), Na(+), Rb(+), Cs(+), tetramethylammonium (TMA(+)), Mg(+2), and Ca(+2) salts. In contrast, the interfacial concentrations of Cl(-) and Br(-) were generally lower than in bulk solution in hexadecylphosphoryl choline, HDPC, micelles for all salts except Mg(+2) and Ca(+2). In both HPS and HDPC micelles the interfacial concentration of Br(-) was higher than that of Cl(-), showing that binding is anion selective. The cation had a large effect on the interfacial concentration of halide ions with HDPC micelles decreasing in the order Ca(2+) > Mg(2+) > Li(+) > Na(+) > K(+) > Cs(+) > Rb(+) > TMA(+). These results are the first direct and extensive determination of local halide ion concentration at the surface of zwitterionic micelles, and they demonstrate that chemical trapping methodology will work in membranes at physiologically relevant salt concentrations. Copyright 1999 Academic Press.

Anion dependent self-assembly of 56-metal Cd-Ln nanoclusters with enhanced near-infrared luminescence properties

NASA Astrophysics Data System (ADS)

Yang, Xiaoping; Schipper, Desmond; Zhang, Lijie; Yang, Keqin; Huang, Shaoming; Jiang, Jijun; Su, Chengyong; Jones, Richard A.

2014-08-01

Two series of Cd-Ln clusters: nano-drum [Ln8Cd24L12(OAc)48] and nano-double-drum [Ln12Cd44L20Cl30(OAc)54] (Ln = Nd and Yb) were prepared using a flexible Schiff base ligand bearing two aryl-Br groups. Chloride (Cl-) ions, together with the interactions of Br with other electronegative atoms, play a key role in the formation of the nano-double-drums. The structures were studied by TEM and photophysical properties were determined.Two series of Cd-Ln clusters: nano-drum [Ln8Cd24L12(OAc)48] and nano-double-drum [Ln12Cd44L20Cl30(OAc)54] (Ln = Nd and Yb) were prepared using a flexible Schiff base ligand bearing two aryl-Br groups. Chloride (Cl-) ions, together with the interactions of Br with other electronegative atoms, play a key role in the formation of the nano-double-drums. The structures were studied by TEM and photophysical properties were determined. Electronic supplementary information (ESI) available: Full experimental and characterization details for 1-4. CCDC 972369-972372. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c4nr03075c

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

PubMed

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.

Solubility of lysozyme in polyethylene glycol-electrolyte mixtures: the depletion interaction and ion-specific effects.

PubMed

Boncina, Matjaz; Rescic, Jurij; Vlachy, Vojko

2008-08-01

The solubility of aqueous solutions of lysozyme in the presence of polyethylene glycol and various alkaline salts was studied experimentally. The protein-electrolyte mixture was titrated with polyethylene glycol, and when precipitation of the protein occurred, a strong increase of the absorbance at 340 nm was observed. The solubility data were obtained as a function of experimental variables such as protein and electrolyte concentrations, electrolyte type, degree of polymerization of polyethylene glycol, and pH of the solution; the last defines the net charge of the lysozyme. The results indicate that the solubility of lysozyme decreases with the addition of polyethylene glycol; the solubility is lower for a polyethylene glycol with a higher degree of polymerization. Further, the logarithm of the protein solubility is a linear function of the polyethylene glycol concentration. The process is reversible and the protein remains in its native form. An increase of the electrolyte (NaCl) concentration decreases the solubility of lysozyme in the presence and absence of polyethylene glycol. The effect can be explained by the screening of the charged amino residues of the protein. The solubility experiments were performed at two different pH values (pH = 4.0 and 6.0), where the lysozyme net charge was +11 and +8, respectively. Ion-specific effects were systematically investigated. Anions such as Br(-), Cl(-), F(-), and H(2)PO(4)(-) (all in combination with Na(+)), when acting as counterions to a protein with positive net charge, exhibit a strong effect on the lysozyme solubility. The differences in protein solubility for chloride solutions with different cations Cs(+), K(+), and Na(+) (coions) were much smaller. The results at pH = 4.0 show that anions decrease the lysozyme solubility in the order F(-) < H(2)PO(4)(-) < Cl(-) < Br(-) (the inverse Hofmeister series), whereas cations follow the direct Hofmeister series (Cs(+) < K(+) < Na(+)) in this situation.

Expanding the Chemistry of Actinide Metallocene Bromides. Synthesis, Properties and Molecular Structures of the Tetravalent and Trivalent Uranium Bromide Complexes: (C 5Me 4R) 2UBr 2, (C 5Me 4R) 2U(O-2,6- iPr 2C 6H 3)(Br), and [K(THF)][(C 5Me 4R) 2UBr 2] (R = Me, Et)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lichtscheidl, Alejandro Gaston; Pagano, Justin K.; Scott, Brian Lindley

The organometallic uranium species (C 5Me 4R) 2UBr 2 (R = Me, Et) were obtained by treating their chloride analogues (C 5Me 4R) 2UCl 2 (R = Me, Et) with Me 3SiBr. Treatment of (C 5Me 4R) 2UCl 2 and (C 5Me 4R) 2UBr 2 (R = Me, Et) with K(O-2,6- iPr 2C 6H 3) afforded the halide aryloxide mixed-ligand complexes (C 5Me 4R) 2U(O-2,6- iPr 2C 6H 3)(X) (R = Me, Et; X = Cl, Br). Complexes (C 5Me 4R) 2U(O-2,6- iPr 2C 6H 3)(Br) (R = Me, Et) can also be synthesized by treating (C 5Me 4R) 2U(O-2,6-more » iPr 2C 6H 3)(Cl) (R = Me, Et) with Me 3SiBr, respectively. Reduction of (C 5Me 4R) 2UCl 2 and (C 5Me 4R) 2UBr 2 (R = Me, Et) with KC 8 led to isolation of uranium(III) “ate” species [K(THF)][(C 5Me 5) 2UX 2] (X = Cl, Br) and [K(THF) 0.5][(C 5Me 4Et) 2UX 2] (X = Cl, Br), which can be converted to the neutral complexes (C 5Me 4R) 2U[N(SiMe 3) 2] (R = Me, Et). Analyses by nuclear magnetic resonance spectroscopy, X-ray crystallography, and elemental analysis are also presented.« less

Expanding the Chemistry of Actinide Metallocene Bromides. Synthesis, Properties and Molecular Structures of the Tetravalent and Trivalent Uranium Bromide Complexes: (C 5Me 4R) 2UBr 2, (C 5Me 4R) 2U(O-2,6- iPr 2C 6H 3)(Br), and [K(THF)][(C 5Me 4R) 2UBr 2] (R = Me, Et)

DOE PAGES

Lichtscheidl, Alejandro Gaston; Pagano, Justin K.; Scott, Brian Lindley; ...

2016-01-06

The organometallic uranium species (C 5Me 4R) 2UBr 2 (R = Me, Et) were obtained by treating their chloride analogues (C 5Me 4R) 2UCl 2 (R = Me, Et) with Me 3SiBr. Treatment of (C 5Me 4R) 2UCl 2 and (C 5Me 4R) 2UBr 2 (R = Me, Et) with K(O-2,6- iPr 2C 6H 3) afforded the halide aryloxide mixed-ligand complexes (C 5Me 4R) 2U(O-2,6- iPr 2C 6H 3)(X) (R = Me, Et; X = Cl, Br). Complexes (C 5Me 4R) 2U(O-2,6- iPr 2C 6H 3)(Br) (R = Me, Et) can also be synthesized by treating (C 5Me 4R) 2U(O-2,6-more » iPr 2C 6H 3)(Cl) (R = Me, Et) with Me 3SiBr, respectively. Reduction of (C 5Me 4R) 2UCl 2 and (C 5Me 4R) 2UBr 2 (R = Me, Et) with KC 8 led to isolation of uranium(III) “ate” species [K(THF)][(C 5Me 5) 2UX 2] (X = Cl, Br) and [K(THF) 0.5][(C 5Me 4Et) 2UX 2] (X = Cl, Br), which can be converted to the neutral complexes (C 5Me 4R) 2U[N(SiMe 3) 2] (R = Me, Et). Analyses by nuclear magnetic resonance spectroscopy, X-ray crystallography, and elemental analysis are also presented.« less

RESIDENTIAL PESTICIDE USE AND URINARY ORGANOPHOSPHATE METABOLITES IN PRE-SCHOOL CHILDREN

EPA Science Inventory

Residential Pesticide Use and Urinary Organophosphate Metabolites in Pre-School Children
CL Carty1, P Mendola1, D Barr2, L Needham2, D Walsh1

1Epidemiology and Biomarkers Branch, Human Studies Division, National Health and Environmental Effects Research Laboratory, U.S....

Effects of cations and anions as aggregating agents on SERS detection of cotinine (COT) and trans-3'-hydroxycotinine (3HC).

PubMed

Han, Sungyub; Hong, Seongmin; Li, Xiao

2013-11-15

The sensitivity of surface-enhanced Raman spectroscopy (SERS) highly depends on experimental factors including aggregating agents and pH. Using silver nanoparticles as the substrate, the effect of five cationic (K(+), Na(+), Mg(2+), Li(+), Ca(2+)) and three anionic (Cl(-), Br(-), I(-)) aggregating agents was examined on the SERS detection of tobacco-related biomarkers, namely cotinine (COT) and trans-3'-hydroxycotinine (3HC). The optimal concentrations of the aggregating agents with respect to highest SERS intensity varied widely (from 1.5 mM for MgCl2 to 150 mM for LiCl). Both cations and anions strongly influenced the SERS enhancement. When Cl(-) was used as the anion, Mg(2+) and Na(+) exhibited the highest SERS intensities for COT and 3HC, respectively. When Mg(2+) was used as the cation, Cl(-) and Br(-) generated the highest SERS enhancement for COT and 3HC, respectively. Clearly, SERS enhancement also depended on the target molecule. Among the 11 aggregating agent combinations tested, the highest SERS enhancement is obtained using 1.5 mM MgCl2 for COT at pH 7.0 and 50 mM NaBr for 3HC at pH 3.0. Copyright © 2013 Elsevier Inc. All rights reserved.

Multifunctional silicon surfaces: reaction of dichlorocarbene generated from Seyferth reagent with hydrogen-terminated silicon (111) surfaces.

PubMed

Liu, Wenjun; Sharp, Ian D; Tilley, T Don

2014-01-14

Insertion of dichlorocarbene (:CCl2), generated by decomposition of the Seyferth reagent PhHgCCl2Br, into the Si-H bond of a tertiary silane to form a Si-CCl2H group is an efficient homogeneous, molecular transformation. A heterogeneous version of this reaction, between PhHgCCl2Br and a silicon (111) surface terminated by tertiary Si-H bonds, was studied using a combination of surface-sensitive infrared and X-ray photoelectron spectroscopies. The insertion of dichlorocarbene into surface Si-H bonds parallels the corresponding reaction of silanes in solution, to produce surface-bound dichloromethyl groups (Si-CCl2H) covering ∼25% of the silicon surface sites. A significant fraction of the remaining Si-H bonds on the surface was converted to Si-Cl/Br groups during the same reaction, with PhHgCCl2Br serving as a halogen atom source. The presence of two distinct environments for the chlorine atoms (Si-CCl2H and Si-Cl) and one type of bromine atom (Si-Br) was confirmed by Cl 2p, Br 3d, and C 1s X-ray photoelectron spectroscopy. The formation of reactive, halogen-terminated atop silicon sites was also verified by reaction with sodium azide or the Grignard reagent (CH3MgBr), to produce Si-N3 or Si-Me functionalities, respectively. Thus, reaction of a hydrogen-terminated silicon (111) surface with PhHgCCl2Br provides a facile route to multifunctional surfaces possessing both stable silicon-carbon and labile silicon-halogen sites, in a single pot synthesis. The reactive silicon-halogen groups can be utilized for subsequent transformations and, potentially, the construction of more complex organic-silicon hybrid systems.

A novel strategy to construct Janus metallamacrocycles with both a Ru-arene face and an imidazolium face.

PubMed

Li, Ji; Zhang, Peipei; Xu, Yan; Su, Zhi; Qian, Yong; Li, Shunli; Yu, Tao; Sadler, Peter J; Liu, Hong-Ke

2017-11-28

The bottom-up construction of highly functional metallamacrocycles from simple building blocks is a challenge of much current interest. We have used solvothermal reactions of a bifunctional p-bitmb ligand with [Ru(arene)X 2 ] 2 in CH 2 Cl 2 or CH 2 Br 2 to generate the novel mononuclear metallamacrocyclic [RuX(arene)L 2 CH 2 ]X 3 complexes 1-3 (1, arene = p-cym, X = Cl; 2, arene = bip, X = Cl; 3, arene = p-cym, X = Br), which were characterized by various techniques. These complexes are "bowl-like" and have two faces: one coordinative Ru centre (arene)Ru(N,N)X bridged by L (L = 1,4-bis(imidazol-1-ylmethyl)-2,3,5,6-tetramethylbenzene, p-bitmb) to a dipositive bis-imidazolinium centre. Cl - or Br - anions can be trapped inside the cavity of the "bowl-like" structure, forming H-bonds with the backbone. Experimental (NMR and ESI-MS) and computational (DFT calculations) studies show that the source of the bridging -CH 2 - group is the dihalogenated solvent (CH 2 Cl 2 or CH 2 Br 2 ) that links the two arms of an initially formed non-cyclic complex (arene)RuX 2 L 2 by a mechanism of nucleophilic substitution. Optimization of the reaction conditions afforded the macrocyclic complexes in almost quantitative yields. The applications of these complexes as anti-proliferative agents towards cancer cells and for selective anion sensing have been explored.

Laser flash photolysis studies of atmospheric free radical chemistry using optical diagnostic techniques

NASA Technical Reports Server (NTRS)

Wine, Paul H.; Nicovich, J. M.; Hynes, Anthony J.; Stickel, Robert E.; Thorn, R. P.; Chin, Mian; Cronkhite, Jeffrey A.; Shackelford, Christie J.; Zhao, Zhizhong; Daykin, Edward P.

1993-01-01

Some recent studies carried out in our laboratory are described where laser flash photolytic production of reactant free radicals has been combined with reactant and/or product detection using time-resolved optical techniques to investigate the kinetics and mechanisms of important atmospheric chemical reactions. Discussed are (1) a study of the radical-radical reaction O + BrO yields Br + O2 where two photolysis lasers are employed to prepare the reaction mixture and where the reactants O and BrO are monitored simultaneously using atomic resonance fluorescence to detect O and multipass UV absorption to detect BrO; (2) a study of the reaction of atomic chlorine with dimethylsulfide (CH3SCH3) where atomic resonance fluorescence detection of Cl is employed to elucidate the kinetics and tunable diode laser absorption spectroscopy is employed to investigate the HCl product yield; and (3) a study of the aqueous phase chemistry of Cl2(-) radicals where longpath UV absorption spectroscopy is employed to investigate the kinetics of the Cl2(-) + H2O reaction.

Major element compositions of fluid inclusions from hydrothermal vein-type deposits record eroded sedimentary units in the Schwarzwald district, SW Germany

NASA Astrophysics Data System (ADS)

Walter, Benjamin F.; Burisch, Mathias; Marks, Michael A. W.; Markl, Gregor

2017-12-01

Mixing of sedimentary formation fluids with basement-derived brines is an important mechanism for the formation of hydrothermal veins. We focus on the sources of the sediment-derived fluid component in ore-forming processes and present a comprehensive fluid inclusion study on 84 Jurassic hydrothermal veins from the Schwarzwald mining district (SW Germany). Our data derive from about 2300 fluid inclusions and reveal differences in the average fluid composition between the northern, central, and southern Schwarzwald. Fluids from the northern and southern Schwarzwald are characterised by high salinities (18-26 wt% NaCl+CaCl2), low Ca/(Ca+Na) mole ratios (0.1-0.4), and variable Cl/Br mass ratios (30-1140). In contrast, fluids from the central Schwarzwald show even higher salinities (23-27 wt% NaCl+CaCl2), higher Ca/(Ca+Na) mole ratios (0.2-0.9), and less variable Cl/Br mass ratios (40-130). These fluid compositions correlate with the nature and thickness of the now eroded sedimentary cover rocks. Compared to the northern and the southern Schwarzwald, where halite precipitation occurred during the Middle Triassic, the sedimentary basin in the central Schwarzwald was relatively shallow at this time and no halite was precipitated. Accordingly, Cl/Br ratios of fluids from the central Schwarzwald provide no evidence for the reaction of a sedimentary brine with halite, whereas those from the northern and southern Schwarzwald do. Instead, elevated Ca/(Ca+Na), high SO4 contents, and relatively low Cl/Br imply the presence of a gypsum dissolution brine during vein formation in the central Schwarzwald which agrees with the reconstructed regional Triassic geology. Hence, the information archived in fluid inclusions from hydrothermal veins in the crystalline basement has the potential for reconstructing sedimentary rocks in the former overburden.

RESCUE OF BROMODICHLOROMETHANE-INDUCED PREGNANCY LOSS IN THE F344 RAT BY EXOGENOUS PROGESTERONE AND HCG

EPA Science Inventory

Rescue of bromodichloromethane-induced pregnancy loss in the F344 rat by exogenous progesterone and hCG.

Susan R. Bielmeier1, Deborah S. Best2 and Michael G. Narotsky2

1 Curriculum in Toxicology, Univ. of North Carolina, Chapel Hill, NC, USA
2 Reproductive Toxico...

Optical sensing of hydrogen sulphate using rhodamine 6G hydrazide from aqueous medium

NASA Astrophysics Data System (ADS)

Upadhyay, Yachana; Bothra, Shilpa; Kumar, Rajender; Choi, Heung-Jin; Sahoo, Suban K.

2017-06-01

This communication reports the application of rhodamine 6G hydrazide (L) for the selective colorimetric and turn-on fluorescent sensing of hydrogen sulphate ions from aqueous medium. The ring opening of the colourless spirocyclic form of L was selectively triggered in the presence of HSO4- among the other tested anions (F-, Cl-, Br-, I-, AcO-, H2PO4-, NO3-, ClO4-, CN-, HO-, AsO33 - and SO42 -), which gives rise to a pink colour and strong fluorescence in the visible region. Sensor L showed a detection limit down to micromolar range without any interference from the other tested competitive anions. Sensor L was applied for the construction of two inputs (HO- and HSO4-) INHIBIT type molecular logic gate and naked-eye detection of HSO4- using test paper strips.

Modification of the Selectivity Properties of Tubular Ceramic Membranes after Alkaline Treatment

PubMed Central

Dutournié, Patrick; Limousy, Lionel; Anquetil, Jérôme

2017-01-01

This work focuses on the selectivity modification of ceramic membranes after a mild alkaline treatment. Filtration of pure salt-water solutions was carried out with commercial titania membranes before and after the treatment. After treatment, the rejection of NaF significantly decreased, while the rejection of NaCl and NaBr increased. Additionally, NaI and Na2SO4 remained close to zero. Pore size and electrical charge being almost unchanged, only significant modifications in the dielectric effects can explain this modification of selectivity. Therefore, the surface chemistry and the interaction (nature and magnitude) with the solvent and with the species present in the solution appear to be modified by the alkaline treatment. This trend is also illustrated by discussing the electric and the dielectric properties that were numerically identified before and after treatment. The alkaline treatment significantly decreased the apparent dielectric constant of NaCl-water solution in the pore, highlighting the rejection of sodium chloride. Contrariwise, the modification of the surface chemistry increased the apparent dielectric constant of NaF-water solution by promoting fluoride transmission. PMID:29160802

Modification of the Selectivity Properties of Tubular Ceramic Membranes after Alkaline Treatment.

PubMed

Dutournié, Patrick; Limousy, Lionel; Anquetil, Jérôme; Déon, Sébastien

2017-11-21

This work focuses on the selectivity modification of ceramic membranes after a mild alkaline treatment. Filtration of pure salt-water solutions was carried out with commercial titania membranes before and after the treatment. After treatment, the rejection of NaF significantly decreased, while the rejection of NaCl and NaBr increased. Additionally, NaI and Na₂SO₄ remained close to zero. Pore size and electrical charge being almost unchanged, only significant modifications in the dielectric effects can explain this modification of selectivity. Therefore, the surface chemistry and the interaction (nature and magnitude) with the solvent and with the species present in the solution appear to be modified by the alkaline treatment. This trend is also illustrated by discussing the electric and the dielectric properties that were numerically identified before and after treatment. The alkaline treatment significantly decreased the apparent dielectric constant of NaCl-water solution in the pore, highlighting the rejection of sodium chloride. Contrariwise, the modification of the surface chemistry increased the apparent dielectric constant of NaF-water solution by promoting fluoride transmission.

Sensitivity of Tropospheric Chemical Composition to Halogen-Radical Chemistry Using a Fully Coupled Size-Resolved Multiphase Chemistry-Global Climate System: Halogen Distributions, Aerosol Composition, and Sensitivity of Climate-Relevant Gases

DOE Office of Scientific and Technical Information (OSTI.GOV)

Long, M.; Keene, W. C.; Easter, Richard C.

Observations and model studies suggest a significant but highly non-linear role for halogens, primarily Cl and Br, in multiphase atmospheric processes relevant to tropospheric chemistry and composition, aerosol evolution, radiative transfer, weather, and climate. The sensitivity of global atmospheric chemistry to the production of marine aerosol and the associated activation and cycling of inorganic Cl and Br was tested using a size-resolved multiphase coupled chemistry/global climate model (National Center for Atmospheric Research’s Community Atmosphere Model (CAM); v3.6.33). Simulation results showed strong meridional and vertical gradients in Cl and Br species. The simulation reproduced most available observations with reasonable confidence permittingmore » the formulation of potential mechanisms for several previously unexplained halogen phenomena including the enrichment of Br- in submicron aerosol, and the presence of a BrO maximum in the polar free troposphere. However, simulated total volatile Br mixing ratios were generally high in the troposphere. Br in the stratosphere was lower than observed due to the lack of long-lived organobromine species in the simulation. Comparing simulations using chemical mechanisms with and without reactive Cl and Br species demonstrated a significant temporal and spatial sensitivity of primary atmospheric oxidants (O3, HOx, NOx), CH4, and non-methane hydrocarbons (NMHC’s) to halogen cycling. Simulated O3 and NOx were globally lower (65% and 35%, respectively, less in the planetary boundary layer based on median values) in simulations that included halogens. Globally, little impact was seen in SO2 and non-sea-salt SO42- processing due to halogens. Significant regional differences were evident: The lifetime of nss-SO42- was extended downwind of large sources of SO2. The burden and lifetime of DMS (and its oxidation products) were lower by a factor of 5 in simulations that included halogens, versus those without, leading to a 20% reduction in nss-SO42- in the southern hemisphere planetary boundary layer based on median values.« less

FORMALDEHYDE-INDUCED GENE EXPRESSION IN F344 RAT NASAL RESPIRATORY EPITHELIUM.

EPA Science Inventory

Formaldehyde-induced gene expression in F344 rat nasal respiratory epithelium

ABSTRACT

Formaldehyde, an occupational and environmental toxicant used extensively in the manufacturing of many household and personal use products, is known to induce squamous cell carci...

Photoelectron spectroscopy of aqueous solutions: Streaming potentials of NaX (X = Cl, Br, and I) solutions and electron binding energies of liquid water and X{sup −}

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kurahashi, Naoya; Horio, Takuya; Suzuki, Toshinori, E-mail: suzuki@kuchem.kyoto-u.ac.jp

2014-05-07

The streaming potentials of liquid beams of aqueous NaCl, NaBr, and NaI solutions are measured using soft X-ray, He(I), and laser multiphoton ionization photoelectron spectroscopy. Gaseous molecules are ionized in the vicinity of liquid beams and the photoelectron energy shifts are measured as a function of the distance between the ionization point and the liquid beam. The streaming potentials change their polarity with concentration of electrolytes, from which the singular points of concentration eliminating the streaming potentials are determined. The streaming currents measured in air also vanish at these concentrations. The electron binding energies of liquid water and I{sup −},more » Br{sup −}, and Cl{sup −} anions are revisited and determined more accurately than in previous studies.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zimmermann, Iwan; Kremer, Reinhard K.; Johnsson, Mats, E-mail: mats.johnsson@mmk.su.se

The new compounds Mn{sub 4}(TeO{sub 3})(SiO{sub 4})X{sub 2} (X=Br, Cl) were synthesized by solid state reactions in sealed evacuated silica tubes. The compounds crystallize in the monoclinic space group P2{sub 1}/m with the unit cell parameters a=5.5463(3) Å (5.49434(7) Å), b=6.4893(4) Å (6.44184(9) Å), c=12.8709(7) Å (12.60451(18) Å), β=93.559(5)° (94.1590(12)°) and Z=2 for the respective Br and Cl analogues. Manganese adopts various distorted coordination polyhedra; [MnO{sub 6}] octahedra, [MnO{sub 5}] tetragonal pyramids and [MnO{sub 2}X{sub 2}] tetrahedra. Other building blocks are [SiO{sub 4}] tetrahedra and [TeO{sub 3}] trigonal pyramids. The structure is made up from layers having no net chargemore » that are connected via weak Van der Waal interactions. The layers that are parallel to (1 1 0) consist of two manganese oxide sheets which are separated by [SiO{sub 4}] tetrahedra. On the outer sides of the sheets are the [MnO{sub 2}X{sub 2}] tetrahedra and the [TeO{sub 3}] trigonal pyramids connected so that the halide ions and the stereochemically active lone pairs on the tellurium atoms protrude from the layers. Magnetic susceptibility measurements reveal a Curie law with a Weiss temperature of θ=−153(3) K for temperatures ≥100 K and indicate antiferromagnetic ordering at T{sub N} ∼4 K. Possible structural origins of the large frustration parameter of f=38 are discussed. - Graphical abstract: Table of contents caption. The new compounds Mn{sub 4}(TeO{sub 3})(SiO{sub 4})X{sub 2} (X=Br, Cl) are layered with weak Van der Waal interactions in between the layers. Manganese adopts various distorted coordination polyhedral, other building blocks are [SiO{sub 4}] tetrahedra and [TeO{sub 3}] trigonal pyramids. Magnetic susceptibility measurements indicate antiferromagnetic ordering at low temperatures and a large frustration parameter. - Highlights: • Two new isostructural oxohalide compounds are described. • The compounds are the first examples of oxohalides containing both Te{sup 4+} and Si{sup 4+}. • Both compounds display the unusual coordination polyhedron MnO{sub 2}X{sub 2} (X=Cl, Br). • The compounds are made up of charge neutral layers connected via weak interactions. • The compounds are antiferromagnetic and display a large frustration parameter.« less

Structures and properties of spherical 90-vertex fullerene-like nanoballs.

PubMed

Scheer, Manfred; Schindler, Andrea; Bai, Junfeng; Johnson, Brian P; Merkle, Roger; Winter, Rainer; Virovets, Alexander V; Peresypkina, Eugenia V; Blatov, Vladislav A; Sierka, Marek; Eckert, Hellmut

2010-02-15

By applying the proper stoichiometry of 1:2 to [Cp(R)Fe(eta(5)-P(5))] and CuX (X=Cl, Br) and dilution conditions in mixtures of CH(3)CN and solvents like CH(2)Cl(2), 1,2-Cl(2)C(6)H(4), toluene, and THF, nine spherical giant molecules having the simplified general formula [Cp(R)Fe(eta(5)-P(5))]@[{Cp(R)Fe(eta(5)-P(5))}(12){CuX}(25)(CH(3)CN)(10)] (Cp(R)=eta(5)-C(5)Me(5) (Cp*); eta(5)-C(5)Me(4)Et (Cp(Et)); X=Cl, Br) have been synthesized and structurally characterized. The products consist of 90-vertex frameworks consisting of non-carbon atoms and forming fullerene-like structural motifs. Besides the mostly neutral products, some charged derivatives have been isolated. These spherical giant molecules show an outer diameter of 2.24 (X=Cl) to 2.26 nm (X=Br) and have inner cavities of 1.28 (X=Cl) and 1.20 nm (X=Br) in size. In most instances the inner voids of these nanoballs encapsulate one molecule of [Cp*Fe(eta(5)-P(5))], which reveals preferred orientations of pi-pi stacking between the cyclo-P(5) rings of the guest and those of the host molecules. Moreover, pi-pi and sigma-pi interactions are also found in the packing motifs of the balls in the crystal lattice. Electrochemical investigations of these soluble molecules reveal one irreversible multi-electron oxidation at E(p)=0.615 V and two reduction steps (-1.10 and -2.0 V), the first of which corresponds to about 12 electrons. Density functional calculations reveal that during oxidation and reduction the electrons are withdrawn or added to the surface of the spherical nanomolecules, and no Cu(2+) species are involved.

Synthesis, Structure, and Antiproliferative Activity of Three Gallium(III) Azole Complexes

PubMed Central

Zanias, Stergios; Papaefstathiou, Giannis S.; Raptopoulou, Catherine P.; Papazisis, Konstantinos T.; Vala, Vasiliki; Zambouli, Dimitra; Kortsaris, Alexandros H.; Kyriakidis, Dimitrios A.; Zafiropoulos, Theodoros F.

2010-01-01

As part of our interest into the bioinorganic chemistry of gallium, gallium(III) complexes of the azole ligands 2,1,3-benzothiadiazole (btd), 1,2,3-benzotriazole (btaH), and 1-methyl-4,5-diphenylimidazole (L) have been isolated. Reaction of btaH or btd with GaBr3 or GaCl3 resulted in the mononuclear complexes [GaBr3(btaH)2] (1) and [GaCl3(btd)2] (2), respectively, while treatment of GaCl3 with L resulted in the anionic complex (LH)2[GaCl4] (3). All three complexes were characterized by single-crystal X-ray crystallography and IR spectroscopy, while their antiproliferative activities were investigated against a series of human and mouse cancer cell lines. PMID:20721278

BIOTRANSFORMATION AND GENOTOXICITY OF THE DRINKING WATER DISINFECTION BYPRODUCT BROMODICHLOROMETHANE: DNA BINDING MEDIATED BY GLUTATHIONE TRANSFERASE THETA 1-1

EPA Science Inventory

The drinking water disinfection byproduct bromodichloromethane (CHBrCl2) was
previously shown to be mutagenic in Salmonella typhimurium that overexpress rat glutathione
transferase theta 1-1 (GSTT1-1). Several experimental approaches were undertaken in this study
to inve...

EFFECTS OF BROMODICHLOROMETHANE (BDCM) ON EX VIVO LUTEAL FUNCTION IN THE PREGNANT F344 RAT

EPA Science Inventory

EFFECTS OF BROMODICHLOROMETHANE (BDCM) ON EX VIVO LUTEAL FUNCTION IN THE PREGNANT F344 RAT.

S. R. Bielmeier1, A. S. Murr2, D. S. Best2, J. M. Goldman2, and M. G. Narotsky2

1 Curriculum in Toxicology, Univ. of North Carolina, Chapel Hill, NC, USA
2 Reproductive T...

EFFECTS OF BROMODICHLOROMETHANE (BDCM) ON EX VIVO LUTEAL FUNCTION IN THE F344 RAT

EPA Science Inventory

EFFECTS OF BROMODICHLOROMETHANE (BDCM) ON EX VIVO LUTEAL FUNCTION IN THE PREGNANT F344 RAT.

S. R. Bielmeier1, A. S. Murr2, D. S. Best2, J. M. Goldman2, and M. G. Narotsky2

1 Curriculum in Toxicology, Univ. of North Carolina, Chapel Hill, NC, USA
2 Reproductive T...

DOE Office of Scientific and Technical Information (OSTI.GOV)

Varley, J. B.; Conway, A. M.; Voss, L. F.

Thallium bromide (TlBr) crystals subjected to hydrochloric acid (HCl) chemical treatments have been shown to advantageously affect device performance and longevity in TlBr-based room temperature radiation detectors, yet the exact mechanisms of the improvements remain poorly understood. Here in this paper, we investigate the influence of several HCl chemical treatments on device-grade TlBr and describe the changes in the composition and electronic structure of the surface. Composition analysis and depth profiles obtained from secondary ion mass spectrometry (SIMS) identify the extent to which each HCl etch condition affects the detector surface region and forms of a graded TlBr/TlBr 1-xCL xmore » surface heterojunction. Using a combination of X-ray photoemission spectroscopy (XPS) and hybrid density functional calculations, we are able to determine the valence band offsets, band gaps, and conduction band offsets as a function of Cl content over the entire composition range of TIBr 1-xC1 X. This study establishes a strong correlation between device process conditions, surface chemistry, and electronic structure with the goal of further optimizing the long-term stability and radiation response of TlBr-based detectors.« less

Acute Toxicity of Smoke Screen Materials to Aquatic Organisms, White Phosphorus-Felt, Red Phosphorus-Butyl Rubber and SGF (Smoke Generator Fuel) No. 2 Fog Oil

DTIC Science & Technology

1986-04-01

anions (F’, Cl’, Br , N83%, S042-) in the water matrices. Detection limits were 0.02 mg/L for phosphate -P and 0.01 mg/L for phosphite -P...resulted in a lower ratio of phosphate to total P and also a lower ratio of phosphite to phosphate . Static and bubbling procedures and the resulting...testing, respectively. Changes with dilution in percentage of P as phosphate or phosphite were minor when ana- lyzed fresh and precipitation had not

State-of-the art of selective detection and identification of I-, Br-, Cl-, and F-containing compounds in gas chromatography and liquid chromatography.

PubMed

Brede, Cato; Pedersen-Bjergaard, Stig

2004-09-24

This review article presents an overview of halogen-specific detection in gas chromatography (GC) and liquid chromatography (LC). Attention is primarily focused on the use of plasma emission spectroscopy and plasma mass spectrometry as detectors, but other halogen-selective detection principles are also mentioned. Different instrumental configurations are discussed both with respect to technical set-up and performance, the principal reasons for halogen-selective detection are highlighted, and recent applications are reviewed from areas such as environmental chemistry, petroleum characterization, and drug analysis.

Nitromethane with IBX/TBAF as a nitrosating agent: synthesis of nitrosamines from secondary or tertiary amines under mild conditions.

PubMed

Potturi, Hima K; Gurung, Ras K; Hou, Yuqing

2012-01-06

Aliphatic or aromatic N,N-disubstituted nitrosamine was generated in fair to excellent yield from the reaction of a secondary or tertiary amine with o-iodoxybenzoic acid (IBX) or o-iodosylbenzoic acid (IBA)/R(4)NX (X = halide) and nitromethane. The product yield was strongly influenced by both the halide of R(4)NX and iodanes. IBX gave a higher yield than IBA, while the halides follow F(-) > Cl(-) > Br(-) ∼ I(-). Nitrous acid formed in situ from nitromethane and IBX (or IBA)/halides is likely responsible for the observed reaction.

Synthesis and anion recognition studies of novel bis (4-hydroxycoumarin) methane azo dyes

NASA Astrophysics Data System (ADS)

Panitsiri, Amorn; Tongkhan, Sukanya; Radchatawedchakoon, Widchaya; Sakee, Uthai

2016-03-01

Four new bis (4-hydroxycoumarin) methane azo dyes were synthesized by the condensation of 4-hydroxycoumarin with four different azo salicylaldehydes and their structures were characterized by FT-IR, 1H NMR, 13C NMR, HRMS. Anion binding ability in dimethyl sulfoxide (DMSO) solutions with tetrabutylammonium (TBA) salts (F-, Cl-, Br-, I-, AcO- and H2PO4-) was investigated by the naked eye, as well as UV-visible spectroscopy. The sensor shows selective recognition towards fluoride and acetate. The binding affinity of the sensors with fluoride and acetate was calculated using UV-visible spectroscopic technique.

Volatile Element Geochemistry in the Lower Atmosphere of Venus

NASA Technical Reports Server (NTRS)

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

2004-01-01

We computed equilibrium abundances of volatile element compounds as a function of altitude in Venus lower atmosphere. The elements included are generally found in volcanic gases and sublimates on Earth and may be emitted in volcanic gases on Venus or volatilized from its hot surface. We predict: 1) PbS, Bi2S3, or possibly a Pb-Bi sulfosalt are the radar bright heavy metal frost in the Venusian highlands; 2) It should be possible to determine Venus' age by Pb-Pb dating of PbS condensed in the Venusian highlands, which should be a representative sample of Venusian lead; 3) The gases HBr, PbCl2, PbBr2, As4O6, As4S4, Sb4O6, BiSe, InBr, InCl, Hg, TlCl, TlBr, SeS, Se2-7, HI, I, I2, ZnCl2, and S2O have abundances greater than 0.1 ppbv in our nominal model and may be spectroscopically observable; 4) Cu, Ag, Au, Zn, Cd, Ge, and Sn are approx. 100 % condensed at the 740 K (0 km) level on Venus.

Methyl chloride and methyl bromide emissions from baking: an unrecognized anthropogenic source.

PubMed

Thornton, Brett F; Horst, Axel; Carrizo, Daniel; Holmstrand, Henry

2016-05-01

Methyl chloride and methyl bromide (CH3Cl and CH3Br) are the largest natural sources of chlorine and bromine, respectively, to the stratosphere, where they contribute to ozone depletion. We report the anthropogenic production of CH3Cl and CH3Br during breadbaking, and suggest this production is an abiotic process involving the methyl ester functional groups in pectin and lignin structural polymers of plant cells. Wide variations in baking styles allow only rough estimates of this flux of methyl halides on a global basis. A simple model suggests that CH3Br emissions from breadbaking likely peaked circa 1990 at approximately 200tonnes per year (about 0.3% of industrial production), prior to restrictions on the dough conditioner potassium bromate. In contrast, CH3Cl emissions from breadbaking may be of similar magnitude as acknowledged present-day CH3Cl industrial emissions. Because the mechanisms involve functional groups and compounds widely found in plant materials, this type of methyl halide production may occur in other cooking techniques as well. Copyright © 2016 Elsevier B.V. All rights reserved.

Deriving an atmospheric budget of total organic bromine using airborne in-situ measurements from the Western Pacific during SHIVA

NASA Astrophysics Data System (ADS)

Sala, S.; Bönisch, H.; Keber, T.; Oram, D. E.; Mills, G.; Engel, A.

2014-02-01

During the SHIVA (Stratospheric Ozone: Halogen Impacts in a Varying Atmosphere) project an extensive dataset of all halogen species relevant for the atmospheric budget of total organic bromine has been collected in the West Pacific region using the FALCON aircraft operated by the German Aerospace agency DLR (Deutsches Zentrum für Luft- und Raumfahrt) covering a vertical range from the planetary boundary layer up to the ceiling altitude of the aircraft of 13 km. In total, more than 700 measurements were performed with the newly developed fully-automated in-situ instrument GHOST-MS (Gas cHromatograph for the Observation of Tracers - coupled with a Mass Spectrometer) by the Goethe University of Frankfurt (GUF) and with the onboard whole-air sampler WASP with subsequent ground based state-of-the-art GC/MS analysis by the University of East Anglia (UEA). Both instruments yield good agreement for all major (CHBr3 and CH2Br2) and minor (CHBrCl, CHBrCl2 and CHBr2Cl) VSLS (very short-lived substances), at least at the level of their 2 σ measurement uncertainties. In contrast to the suggestion that the Western Pacific could be a major source region for VSLS (Pyle et al., 2011), we found only slightly enhanced mixing ratios of brominated halogen source gases relative to the levels reported in Montzka et al. (2011) for other tropical regions. A budget for total organic bromine, including all four halons,CH3Br and the VSLS, is derived for the upper troposphere, the input region for the TTL and thus also for the stratosphere, compiled from the SHIVA dataset. With exception of the two minor VSLS CHBrCl2 and CHBr2Cl, excellent agreement with the values reported in Montzka et al. (2011) is found, while being slightly higher than previous studies from our group based on balloon-borne measurements.

Effect of chlorination on the TlBr band edges for improved room temperature radiation detectors: Effect of chlorination on the TlBr band edges for radiation detectors

DOE PAGES

Varley, J. B.; Conway, A. M.; Voss, L. F.; ...

2015-02-09

Thallium bromide (TlBr) crystals subjected to hydrochloric acid (HCl) chemical treatments have been shown to advantageously affect device performance and longevity in TlBr-based room temperature radiation detectors, yet the exact mechanisms of the improvements remain poorly understood. Here in this paper, we investigate the influence of several HCl chemical treatments on device-grade TlBr and describe the changes in the composition and electronic structure of the surface. Composition analysis and depth profiles obtained from secondary ion mass spectrometry (SIMS) identify the extent to which each HCl etch condition affects the detector surface region and forms of a graded TlBr/TlBr 1-xCL xmore » surface heterojunction. Using a combination of X-ray photoemission spectroscopy (XPS) and hybrid density functional calculations, we are able to determine the valence band offsets, band gaps, and conduction band offsets as a function of Cl content over the entire composition range of TIBr 1-xC1 X. This study establishes a strong correlation between device process conditions, surface chemistry, and electronic structure with the goal of further optimizing the long-term stability and radiation response of TlBr-based detectors.« less

Synthesis, Crystal and Electronic Structures, and Optical Properties of (CH 3NH 3) 2CdX 4 (X = Cl, Br, I)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Roccanova, Rachel; Ming, Wenmei; Whiteside, Vincent R.

Here, we report the synthesis, crystal and electronic structures, as well as optical properties of the hybrid organic–inorganic compounds MA 2CdX 4 (MA = CH 3NH 3; X = Cl, Br, I). MA 2CdI 4 is a new compound, whereas, for MA 2CdCl 4 and MA 2CdBr 4, structural investigations have already been conducted but electronic structures and optical properties are reported here for the first time. Single crystals were grown through slow evaporation of MA 2CdX 4 solutions with optimized conditions yielding mm-sized colorless (X = Cl, Br) and pale yellow (X = I) crystals. Single crystal and variablemore » temperature powder X-ray diffraction measurements suggest that MA 2CdCl 4 forms a 2D layered perovskite structure and has two structural transitions at 283 and 173 K. In contrast, MA 2CdBr 4 and MA 2CdI 4 adopt 0D K 2SO 4-derived crystal structures based on isolated CdX 4 tetrahedra and show no phase transitions down to 20 K. The contrasting crystal structures and chemical compositions in the MA 2CdX 4 family impact their air stabilities, investigated for the first time in this work; MA 2CdCl 4 is air-stable, whereas MA 2CdBr 4 and MA 2CdI 4 partially decompose when left in air. Optical absorption measurements suggest that MA 2CdX 4 have large optical band gaps above 3.9 eV. Room temperature photoluminescence spectra of MA 2CdX 4 yield broad peaks in the 375–955 nm range with full width at half-maximum values up to 208 nm. These PL peaks are tentatively assigned to self-trapped excitons in MA 2CdX 4 following the crystal and electronic structure considerations. The bands around the Fermi level have small dispersions, which is indicative of high charge localization with significant exciton binding energies in MA 2CdX 4. On the basis of our combined experimental and computational results, MA 2CdX 4 and related compounds may be of interest for white-light-emitting phosphors and scintillator applications.« less

Synthesis, Crystal and Electronic Structures, and Optical Properties of (CH 3NH 3) 2CdX 4 (X = Cl, Br, I)

DOE PAGES

Roccanova, Rachel; Ming, Wenmei; Whiteside, Vincent R.; ...

2017-11-02

Here, we report the synthesis, crystal and electronic structures, as well as optical properties of the hybrid organic–inorganic compounds MA 2CdX 4 (MA = CH 3NH 3; X = Cl, Br, I). MA 2CdI 4 is a new compound, whereas, for MA 2CdCl 4 and MA 2CdBr 4, structural investigations have already been conducted but electronic structures and optical properties are reported here for the first time. Single crystals were grown through slow evaporation of MA 2CdX 4 solutions with optimized conditions yielding mm-sized colorless (X = Cl, Br) and pale yellow (X = I) crystals. Single crystal and variablemore » temperature powder X-ray diffraction measurements suggest that MA 2CdCl 4 forms a 2D layered perovskite structure and has two structural transitions at 283 and 173 K. In contrast, MA 2CdBr 4 and MA 2CdI 4 adopt 0D K 2SO 4-derived crystal structures based on isolated CdX 4 tetrahedra and show no phase transitions down to 20 K. The contrasting crystal structures and chemical compositions in the MA 2CdX 4 family impact their air stabilities, investigated for the first time in this work; MA 2CdCl 4 is air-stable, whereas MA 2CdBr 4 and MA 2CdI 4 partially decompose when left in air. Optical absorption measurements suggest that MA 2CdX 4 have large optical band gaps above 3.9 eV. Room temperature photoluminescence spectra of MA 2CdX 4 yield broad peaks in the 375–955 nm range with full width at half-maximum values up to 208 nm. These PL peaks are tentatively assigned to self-trapped excitons in MA 2CdX 4 following the crystal and electronic structure considerations. The bands around the Fermi level have small dispersions, which is indicative of high charge localization with significant exciton binding energies in MA 2CdX 4. On the basis of our combined experimental and computational results, MA 2CdX 4 and related compounds may be of interest for white-light-emitting phosphors and scintillator applications.« less

Quantitative and Qualitative Involvement of P3N-PIPO in Overcoming Recessive Resistance against Clover Yellow Vein Virus in Pea Carrying the cyv1 Gene

PubMed Central

Choi, Sun Hee; Hagiwara-Komoda, Yuka; Atsumi, Go; Shimada, Ryoko; Hisa, Yusuke; Naito, Satoshi

2013-01-01

In pea carrying cyv1, a recessive gene for resistance to Clover yellow vein virus (ClYVV), ClYVV isolate Cl-no30 was restricted to the initially infected cells, whereas isolate 90-1 Br2 overcame this resistance. We mapped the region responsible for breaking of cyv1-mediated resistance by examining infection of cyv1 pea with chimeric viruses constructed from parts of Cl-no30 and 90-1 Br2. The breaking of resistance was attributed to the P3 cistron, which is known to produce two proteins: P3, from the main open reading frame (ORF), and P3N-PIPO, which has the N-terminal part of P3 fused to amino acids encoded by a small open reading frame (ORF) called PIPO in the +2 reading frame. We introduced point mutations that were synonymous with respect to the P3 protein but nonsynonymous with respect to the P3N-PIPO protein, and vice versa, into the chimeric viruses. Infection of plants with these mutant viruses revealed that both P3 and P3N-PIPO were involved in overcoming cyv1-mediated resistance. Moreover, P3N-PIPO quantitatively affected the virulence of Cl-no30 in cyv1 pea. Additional expression in trans of the P3N-PIPO derived from Cl-no30, using White clover mosaic virus as a vector, enabled Cl-no30 to move to systemic leaves in cyv1 pea. Susceptible pea plants infected with chimeric ClYVV possessing the P3 cistron of 90-1 Br2, and which were therefore virulent toward cyv1 pea, accumulated more P3N-PIPO than did those infected with Cl-no30, suggesting that the higher level of P3N-PIPO in infected cells contributed to the breaking of resistance by 90-1 Br2. This is the first report showing that P3N-PIPO is a virulence determinant in plants resistant to a potyvirus. PMID:23616656

Electromodulation spectroscopy of excitons in simple cubic TlCl and TlBr

DOE Office of Scientific and Technical Information (OSTI.GOV)

McClelland, J.F.; Lynch, D.W.

1979-03-15

Transmission and electromodulated transmission spectra have been measured in the direct Wannier exciton region for TlCl and TlBr. The spectra were obtained at a sample temperature between 5 and 6 K for a range of applied electric fields. The data have been reduced to obtain the electric-field-induced changes in the dielectric function and compared in detail to the calculations of Blossey. The experimental results support the trends predicted by the calculations.

THE K-REGION DIHYDRODIOL OF BENZO[A]PYRENE INDUCES DNA DAMAGE AND MORPHOLOGICAL CELL TRANSFORMATION IN C3H10T1/2CL8 MOUSE EMBRYO CELLS WITHOUT THE FORMATION OF DETECTABLE STABLE COVALENT DNA ADDUCTS

EPA Science Inventory

The K -region dihydrodiol ofbenzo[ a ]pyrene induces DNA damage and morphological cell transformation in C3HlOTY2CL8 mouse embryo cells without the formation of detectable stable covalent DNA adducts

Benzo[ a ]pyrene (B[ a ]P) is the most thoroughly studied polycyclic aro...

Guest-tuned spin crossover in flexible supramolecular assemblies templated by a halide (Cl -, Br - or I - )

DOE Office of Scientific and Technical Information (OSTI.GOV)

Darawsheh, M. D.; Barrios, L. A.; Roubeau, O.

Ligand 1,3-bis(3-(pyridin-2-yl)-1H-pyrazol-5-yl)benzene, L, forms mononuclear spin crossover complexes [FeL 3] 2+ with pendant arms that cause them to dimerize through numerous intermolecular interactions forming supramolecular (X@[FeL 3] 2) 3+ cations. Finally, hey have the flexibility to encapsulate Cl -, Br - or I -, which allow tuning the magnetic properties, in the solid state and in solution.

Guest-tuned spin crossover in flexible supramolecular assemblies templated by a halide (Cl -, Br - or I - )

DOE PAGES

Darawsheh, M. D.; Barrios, L. A.; Roubeau, O.; ...

2016-12-05

Ligand 1,3-bis(3-(pyridin-2-yl)-1H-pyrazol-5-yl)benzene, L, forms mononuclear spin crossover complexes [FeL 3] 2+ with pendant arms that cause them to dimerize through numerous intermolecular interactions forming supramolecular (X@[FeL 3] 2) 3+ cations. Finally, hey have the flexibility to encapsulate Cl -, Br - or I -, which allow tuning the magnetic properties, in the solid state and in solution.

Bipyrimidine ruthenium(II) arene complexes: structure, reactivity and cytotoxicity.

PubMed

Betanzos-Lara, Soledad; Novakova, Olga; Deeth, Robert J; Pizarro, Ana M; Clarkson, Guy J; Liskova, Barbora; Brabec, Viktor; Sadler, Peter J; Habtemariam, Abraha

2012-10-01

The synthesis and characterization of complexes [(η(6)-arene)Ru(N,N')X][PF(6)], where arene is para-cymene (p-cym), biphenyl (bip), ethyl benzoate (etb), hexamethylbenzene (hmb), indane (ind) or 1,2,3,4-tetrahydronaphthalene (thn), N,N' is 2,2'-bipyrimidine (bpm) and X is Cl, Br or I, are reported, including the X-ray crystal structures of [(η(6)-p-cym)Ru(bpm)I][PF(6)], [(η(6)-bip)Ru(bpm)Cl][PF(6)], [(η(6)-bip)Ru(bpm)I][PF(6)] and [(η(6)-etb)Ru(bpm)Cl][PF(6)]. Complexes in which N,N' is 1,10-phenanthroline (phen), 1,10-phenanthroline-5,6-dione or 4,7-diphenyl-1,10-phenanthroline (bathophen) were studied for comparison. The Ru(II) arene complexes undergo ligand-exchange reactions in aqueous solution at 310 K; their half-lives for hydrolysis range from 14 to 715 min. Density functional theory calculations on [(η(6)-p-cym)Ru(bpm)Cl][PF(6)], [(η(6)-p-cym)Ru(bpm)Br][PF(6)], [(η(6)-p-cym)Ru(bpm)I][PF(6)], [(η(6)-bip)Ru(bpm)Cl][PF(6)], [(η(6)-bip)Ru(bpm)Br][PF(6)] and [(η(6)-bip)Ru(bpm)I][PF(6)] suggest that aquation occurs via an associative pathway and that the reaction is thermodynamically favourable when the leaving ligand is I > Br ≈ Cl. pK (a)* values for the aqua adducts of the complexes range from 6.9 to 7.32. A binding preference for 9-ethylguanine (9-EtG) compared with 9-ethyladenine (9-EtA) was observed for [(η(6)-p-cym)Ru(bpm)Cl][PF(6)], [(η(6)-hmb)Ru(bpm)Cl](+), [(η(6)-ind)Ru(bpm)Cl](+), [(η(6)-thn)Ru(bpm)Cl](+), [(η(6)-p-cym)Ru(phen)Cl](+) and [(η(6)-p-cym)Ru(bathophen)Cl](+) in aqueous solution at 310 K. The X-ray crystal structure of the guanine complex [(η(6)-p-cym)Ru(bpm)(9-EtG-N7)][PF(6)](2) shows multiple hydrogen bonding. Density functional theory calculations show that the 9-EtG adducts of all complexes are thermodynamically preferred compared with those of 9-EtA. However, the bmp complexes are inactive towards A2780 human ovarian cancer cells. Calf thymus DNA interactions for [(η(6)-p-cym)Ru(bpm)Cl][PF(6)] and [(η(6)-p-cym)Ru(phen)Cl][PF(6)] consist of weak coordinative, intercalative and monofunctional coordination. Binding to biomolecules such as glutathione may play a role in deactivating the bpm complexes.

Premelting phenomena in pseudo-binary ionic crystals

NASA Astrophysics Data System (ADS)

Matsunaga, Shigeki

2010-04-01

The theory of the premelting phenomena in ionic crystals on the basis of the concept of the heterophase fluctuation has been applied to the pseudo-binary ionic crystals, KCl-NaCl, AgBr-AgCl and AgBr-CuBr systems. Molecular dynamics simulations (MD) have been performed to examine the ionic configurations in their premelting region in the vicinity of their melting points. Liquid-like clusters have been observed in the results of MD utilizing the Lindemann instability condition. The sizes of liquid-like clusters have been estimated by theory and MD. The characteristics of the dynamical behavior of ions in the premelting region have been examined by the mean square displacement and the velocity correlation functions.

Selective cyclopalladation of R3P=NCH2Aryl iminophosphoranes. Experimental and computational study.

PubMed

Bielsa, Raquel; Navarro, Rafael; Urriolabeitia, Esteban P; Lledós, Agustí

2007-11-26

The orientation of the orthopalladation of iminophosphoranes R3P=NCH2Aryl (R=Ph, Aryl=Ph (1a), C6H(4)-2-Br (1b), C6H4-Me-2 (1e), C6H3-(Me)(2)-2,5 (1f); R=p-tolyl, Aryl=Ph (1c); R=m-tolyl, Aryl=Ph (1d); R3P=MePh2P, and Aryl=Ph (1g)) has been studied. 1a reacts with Pd(OAc)2 (OAc=acetate) giving endo-[Pd(micro-Cl){C,N-C6H4(PPh2=NCH2Ph)-2}]2 (3a), while exo-[Pd(micro-Br){C,N-C6H4(CH2N=PPh3)-2}]2 (3b) could only be obtained by the oxidative addition of 1b to Pd2(dba)3. The endo form of the metalated ligand is favored kinetically and thermodynamically, as shown by the conversion of exo-[Pd(micro-OAc){C,N-C6H4(CH2N=PPh3)-2}]2 (2b) into endo-[Pd(micro-OAc){C,N-C6H4(PPh2=NCH2Ph)-2}]2 (2a) in refluxing toluene. The orientation of the reaction is not affected by the introduction of electron-releasing substituents at the Ph rings of the PR3 (1c and 1d) or the benzyl units (1e and 1f), and endo complexes (3c-3f) were obtained in all cases. The palladation of MePh2P=NCH2Ph (1g) can be regioselectively oriented as a function of the solvent. The exo isomer [Pd(micro-Cl){C6H4(CH2N=PPh2Me)-2}]2 (exo-3g) is obtained in refluxing CH2Cl2, while endo-[Pd(micro-Cl){C,N-C6H4(PPh(Me)=NCH2Ph)-2}]2 (endo-3g) can be isolated as a single isomer in refluxing toluene. In this case, the exo metalation is kinetically favored while an endo process occurs under thermodynamic control, as shown through the rearrangement of [Pd(micro-OAc){C6H4(CH2N=PPh2Me)-2}]2 (exo-2g) into [Pd(micro-OAc){C,N-C6H4(P(Ph)Me=NCH2Ph)-2}]2 (endo-2g) in refluxing toluene. The preference for the endo palladation of 1a and the kinetic versus thermodynamic control in 1g has been explained through DFT studies of the reaction mechanism.

Trace element geochemistry of volcanic gases and particles from 1983-1984 eruptive episodes of Kilauea Volcano

NASA Astrophysics Data System (ADS)

Crowe, Bruce M.; Finnegan, David L.; Zoller, William H.; Boynton, William V.

1987-12-01

Compositional data have been obtained for volcanic gases and particles collected from fume emitted at the Pu'u O'o vent on the east rift zone of Kilauea volcano. The samples were collected by pumping fume through a filter pack system consisting of a front stage particulate filter followed by four base-treated filters (7LiOH). Particles and condensed phases are trapped on the particulate filter, and acidic gases are collected on the treated filters. The filters are analyzed for 30 elements by instrumental neutron activation analysis. Fume samples were collected from the Pu'u O'o vent for two eruptive episodes: (1) 7 days after episode 11 (cooling vent samples) and (2) the waning stage of episode 13 (active vent samples). Additional samples were collected by aircraft from the gas plume released during the lava fountaining phase of episode 17 (aircraft samples). Element concentrations in the vent gases were > 104 μg m-3 for S, Cl, and F. Enrichment factors (EFs) for the volcanic fume versus the source magma were calculated using the volatile element Br as the reference element for normalization and the U.S. Geological Survey standard BHVO-1 as the magma standard. This removes the ash dilution effect obtained by using an ash constituent (Al, Sc, or Mg) as the reference element. Bromine-normalized EFs (× 105) range from 101 to 102 for Na, K, and Cu; 102 to 105 for Zn, W, Sb, In, Ir, Ag, F, and As; and > 105 for Au, Cd, Re, Cl, Se, and S. The highest enrichment factors are for aircraft samples collected during the most gas-rich phase of an eruption cycle. Metal and volatile-element data form two groups: (1) elements showing little or no variation in abundance ratios with sample type (group 1: Cl, Br, and Re) and (2) elements that show significant variation in abundance ratios by sample type (group 2: Zn, W, Sb, In, Ir, Au, and Cd). Bivariate plots of elements of the first group versus elements of the second group separate by sample type. The separation corresponds to samples collected during eruptive activity versus samples collected during repose periods. Monitoring trace metal ratios in volcanic fume could provide an additional tool for predicting volcanic eruptions. The F/Cl ratio of cooling vent samples is higher than those of active vent or aircraft samples, and the ratio is inversely correlated with EFs for most volatile metals.

Cyclic nucleotides induce long-term augmentation of glutamate-activated chloride current in molluscan neurons.

PubMed

Bukanova, Julia V; Solntseva, Elena I; Skrebitsky, Vladimir G

2005-12-01

1. Literature data indicate that serotonin induces the long-term potentiation of glutamate (Glu) response in molluscan neurons. The aim of present work was to elucidate whether cyclic nucleotides can cause the same effect. 2. Experiments were carried out on isolated neurons of the edible snail (Helix pomatia) using a two-microelectrode voltage-clamp method. 3. In the majority of the cells examined, the application of Glu elicited a Cl- -current. The reversal potential (Er) of this current lied between -35 and -55 mV in different cells. 4. Picrotoxin, a blocker of Cl- -channels, suppressed this current equally on both sides of Er. Furosemide, an antagonist of both Cl- -channels and the Na+/K+/Cl- -cotransporter, had a dual effect on Glu-response: decrease in conductance, and shift of Er to negative potentials. 5. A short-term (2 min) cell treatment with 8-Br-cAMP or 8-Br-cGMP caused long-term (up to 30 min) change in Glu-response. At a holding potential of -60 mV, which was close to the resting level, an increase in Glu-activated inward current was observed. This potentiation seems to be related to the right shift of Er of Glu-activated Cl- -current rather than to the increase in conductance of Cl- -channels. The blocking effect of picrotoxin rested after 8-Br-cAMP treatment. 6. The change in the Cl- -homeostasis as a possible mechanism for the observed effect of cyclic nucleotides is discussed.

Novel ternary molten salt electrolytes for intermediate-temperature sodium/nickel chloride batteries

NASA Astrophysics Data System (ADS)

Li, Guosheng; Lu, Xiaochuan; Coyle, Christopher A.; Kim, Jin Y.; Lemmon, John P.; Sprenkle, Vincent L.; Yang, Zhenguo

2012-12-01

The sodium-nickel chloride (ZEBRA) battery is operated at relatively high temperature (250-350 °C) to achieve adequate electrochemical performance. Reducing the operating temperature in the range of 150200 °C can not only lead to enhanced cycle life by suppressing temperature-related degradations, but also allow the use of lower cost materials for construction. To achieve adequate electrochemical performance at lower operating temperatures, reduction in ohmic losses is required, including the reduced ohmic resistance of β″-alumina solid electrolyte (BASE) and the incorporation of low melting point secondary electrolytes. In present work, planar-type Na/NiCl2 cells with a thin BASE (600 μm) and low melting point secondary electrolyte were evaluated at reduced temperatures. Molten salts used as secondary electrolytes were fabricated by the partial replacement of NaCl in the standard secondary electrolyte (NaAlCl4) with other lower melting point alkali metal salts such as NaBr, LiCl, and LiBr. Electrochemical characterization of these ternary molten salts demonstrated improved ionic conductivity and sufficient electrochemical window at reduced temperatures. Furthermore, Na/NiCl2 cells with 50 mol% NaBr-containing secondary electrolyte exhibited reduced polarizations at 175 °C compared to the cell with the standard NaAlCl4 catholyte. The cells also exhibited stable cycling performance even at 150 °C.

Human and livestock waste as a reduced carbon source contributing to the release of arsenic to shallow Bangladesh groundwater.

PubMed

Whaley-Martin, K J; Mailloux, B J; van Geen, A; Bostick, B C; Ahmed, K M; Choudhury, I; Slater, G F

2017-10-01

Recent studies have demonstrated that the supply of relatively young organic carbon stimulates the release of arsenic to groundwater in Bangladesh. This study explores the potential role of human and livestock waste as a significant source of this carbon in a densely populated rural area with limited sanitation. Profiles of aquifer sediment samples were analyzed for phytosterols and coprostanol to assess the relative contributions of plant-derived and human/livestock waste-derived organic carbon at two well-characterized sites in Araihazar. Coprostanol concentrations increased with depth from non-detection (<10m at Site B and <23m at Site F) to maxima of 1.3 and 0.5ng/g in aquifer sands recovered from 17m (Site B) and 26m (Site F), respectively. The commonly used sewage contamination index ([5β-coprostanol]/([5α-cholestanol]+[5β-coprostanol])) exceeds 0.7 between 12 and 19m at Site B and between 24 and 26m at Site F, indicating input of human/livestock waste to these depths. Urine/fecal input within the same depth range is supported by groundwater Cl/Br mass ratios >1000 compared to Cl/Br <500 at depths >50m. Installed tube wells in the area's study sites may act as a conduit for DOC and specifically human/livestock waste into the aquifer during flood events. The depth range of maximum input of human/livestock waste indicated by these independent markers coincides with the highest dissolved Fe (10-20mg/L) and As (200-400μg/L) concentrations in groundwater at both sites. The new findings suggest that the oxidation of human/livestock waste coupled to the reductive dissolution of iron-(oxy)-hydroxides and/or arsenate may enhance groundwater contamination with As. Copyright © 2017. Published by Elsevier B.V.

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

PubMed

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.

CALCULATED MOLECULAR STRUCTURES AND POTENTIAL ENERGY FUNCTIONS OF PAHS WITH METHYL CROWDING IN THE BAY REGION AND THEIR METABOLITES: COMPARISON TO EXPERIMENTAL STRUCTURES

EPA Science Inventory

Abstract Title: Calculated molecular structures and potential energy functions of P AHs with methyl crowding in the bay region and their metabolites: Comparison to experimental structures.

Abstract:
PAHs with methyl group substitution near a bay region represent a cl...

Molecular simulations and density functional theory calculations of bromine in clathrate hydrate phases

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dureckova, Hana, E-mail: houci059@uottawa.ca; Woo, Tom K., E-mail: tom.woo@uottawa.ca; Alavi, Saman, E-mail: saman.alavi@nrc-cnrc.gc.ca

Bromine forms a tetragonal clathrate hydrate structure (TS-I) very rarely observed in clathrate hydrates of other guest substances. The detailed structure, energetics, and dynamics of Br{sub 2} and Cl{sub 2} in TS-I and cubic structure I (CS-I) clathrate hydrates are studied in this work using molecular dynamics and quantum chemical calculations. X-ray diffraction studies show that the halogen-water–oxygen distances in the cages of these structures are shorter than the sum of the van der Waals radii of halogen and oxygen atoms. This suggests that the stabilizing effects of halogen bonding or other non-covalent interactions (NCIs) may contribute to the formationmore » of the unique tetragonal bromine hydrate structure. We performed molecular dynamics simulations of Br{sub 2} and Cl{sub 2} clathrate hydrates using our previously developed five-site charge models for the dihalogen molecules [Dureckova et al. Can. J. Chem. 93, 864 (2015)] which reproduce the computed electrostatic potentials of the dihalogens and account for the electropositive σ-hole of the halogen bond donor (the dihalogen). Analysis of the radial distribution functions, enthalpies of encapsulation, velocity and orientation autocorrelation functions, and polar angle distributions are carried out for Br{sub 2} and Cl{sub 2} guests in various cages to contrast the properties of these guests in the TS-I and CS-I phases. Quantum chemical partial geometry optimizations of Br{sub 2} and Cl{sub 2} guests in the hydrate cages using the M06-2X functional give short halogen-water distances compatible with values observed in X-ray diffraction experiments. NCI plots of guest-cage structures are generated to qualitatively show the relative strength of the non-bonding interactions between dihalogens and water molecules. The differences between behaviors of Br{sub 2} and Cl{sub 2} guests in the hydrate cages may explain why bromine forms the unique TS-I phase.« less

Determination of bromine, chlorine and iodine in environmental aqueous samples by epithermal neutron activation analysis and Compton suppression

USGS Publications Warehouse

Landsberger, S.; O'Kelly, D. J.; Braisted, J.; Panno, S.

2006-01-01

Halides, particularly Br- and Cl-, have been used as indicators of potential sources of Na+ and Cl- in surface water and groundwater with limited success. Contamination of groundwater and surface water by Na+ and Cl- is a common occurrence in growing urban areas and adversely affects municipal and private water supplies in Illinois and other states, as well as vegetation in environmentally sensitive areas. Neutron activation analysis (NAA) can be effectively used to determine these halogens, but often the elevated concentrations of sodium and chlorine in water samples can give rise to very high detection limits for bromine and iodine due to elevated backgrounds from the activation process. We present a detailed analytical scheme to determine Cl, Br and I in aqueous samples with widely varying Na and Cl concentrations using epithermal NAA in conjunction with Compton suppression. ?? 2006 Akade??miai Kiado??.

Using Cl/Br ratios and other indicators to assess potential impacts on groundwater quality from septic systems: A review and examples from principal aquifers in the United States

USGS Publications Warehouse

Katz, B.G.; Eberts, S.M.; Kauffman, L.J.

2011-01-01

A detailed review was made of chemical indicators used to identify impacts from septic tanks on groundwater quality. Potential impacts from septic tank leachate on groundwater quality were assessed using the mass ratio of chloride-bromide (Cl/Br), concentrations of selected chemical constituents, and ancillary information (land use, census data, well depth, soil characteristics) for wells in principal aquifers of the United States. Chemical data were evaluated from 1848 domestic wells in 19 aquifers, 121 public-supply wells in 6 aquifers, and associated monitoring wells in four aquifers and their overlying hydrogeologic units. Based on previously reported Cl/Br ratios, statistical comparisons between targeted wells (where Cl/Br ratios range from 400 to 1100 and Cl concentrations range from 20 to 100 mg/L) and non-targeted wells indicated that shallow targeted monitoring and domestic wells (0.5. mg/L) shallow groundwater from target domestic wells, relative to non-target wells (1.5. mg/L), corresponded to significantly higher potassium, boron, chloride, dissolved organic carbon, and sulfate concentrations, which may also indicate the influence of septic-tank effluent. Impacts on groundwater quality from septic systems were most evident for the Eastern Glacial Deposits aquifer and the Northern High Plains aquifer that were associated with the number of housing units using septic tanks, high permeability of overlying sediments, mostly oxic conditions, and shallow wells. Overall, little or no influence from septic systems were found for water samples from the deeper public-supply wells.The Cl/Br ratio is a useful first-level screening tool for assessing possible septic tank influence in water from shallow wells (<20 m) with the range of 400-1100. The use of this ratio would be enhanced with information on other chloride sources, temporal variability of chloride and bromide concentrations in shallow groundwater, knowledge of septic-system age and maintenance, and the use of multiple tracers (combination of additional chemical and microbiological indicators). ?? 2010.

Aspects of the history of 66095 based on trace elements in clasts and whole rock

NASA Technical Reports Server (NTRS)

Jovanovic, S.; Reed, G. W., Jr.

1982-01-01

Halogens, P, U and Na are reported in anorthositic and basaltic clasts and matrix from rusty rock 66095. Large fractions of Cl and Br associated with the separated phases from 66095 are soluble in H2O. Up to two orders of magnitude variation in concentrations of these elements in the breccia components and varying H2O-soluble Cl/Br ratios indicate different sources of volatiles. An approximately constant ratio of the H2O- to 0.1 M HNO3-soluble Br in the various components suggests no appreciable alteration in the original distributions of this element in the breccia forming processes. Up to 50% or more of the phosphorus and of the non-H2O-soluble Cl was dissolved from most of the breccia components by 0.1 M HNO3. Clast and matrix residues from the leaching steps contain, in most cases, the Cl/P2O5 ratio found in 66095 whole rock and in a number of other Apollo 16 samples. Evidence that phosphates are the major P-phases in the breccia is based on the 0.1 M acid solubility of Cl and P in the matrix sample and on elemental concentrations which are consistent with those of KREEP.

Elastic collisions of low-energy electrons with SiY4 (Y = Cl, Br, I) molecules

NASA Astrophysics Data System (ADS)

Bettega, M. H. F.

2011-11-01

We employed the Schwinger multichannel method to compute elastic integral, differential, and momentum transfer cross sections for low-energy electron collisions with SiY4 (Y = Cl, Br, I) molecules. The calculations were carried out in the static-exchange and static-exchange plus polarization approximations for energies up to 10 eV. The elastic integral cross section for SiCl4 and SiBr4, computed in the static-exchange plus polarization approximation, shows two shape resonances belonging to the T2 and E symmetries of the Td group, and for SiI4 shows one shape resonance belonging to the E symmetry of the Td group. The present results agree well in shape with experimental total cross sections. The positions of the resonances observed in the calculated integral cross sections are also in agreement with the experimental positions. We have found the presence of a virtual state for SiCl4 and a Ramsauer-Townsend minimum for SiI4 at 0.5 eV. The present results show that the proper inclusion of polarization effects is crucial in order to correctly describe the resonance spectra of these molecules and also to identify a Ramsauer-Townsend minimum for SiI4 and a virtual state for SiCl4.

Chemical and isotopic constrains on the origin of brine and saline groundwater in Hetao plain, Inner Mongolia.

PubMed

Liu, Jun; Chen, Zongyu; Wang, Lijuan; Zhang, Yilong; Li, Zhenghong; Xu, Jiaming; Peng, Yurong

2016-08-01

The origin and evolution of brine and saline groundwater have always been a challenged work for geochemists and hydrogeologists. Chemical and isotopic data of brine and saline waters were used to trace the sources of salinity and therefore to understand the transport mechanisms of groundwater in Xishanzui, Inner Mongolia. Both Cl/Br (molar) versus Na/Br (molar) and Cl (meq/L) versus Na (meq/L) indicated that salinity was from halite dissolution or at least a significant impact by halite dissolution. The logarithmic plot of the concentration trends of Cl (mg/L) versus Br (mg/L) for the evaporation of seawater and the Qinghai Salt Lake showed that the terrestrial halite dissolution was the dominated contribution for the salinity of this brine. The stable isotope ratios of hydrogen and oxygen suggested that the origin of brine was from paleorecharge water which experienced mixing of modern water in shallow aquifer. δ(37)Cl values ranged from -0.02 to 3.43 ‰ (SMOC), and reflecting mixing of different sources. The Cl isotopic compositions suggest that the dissolution of halite by paleometeoric water had a great contribution to the salinity of brine, and the contributions of the residual seawater and the dissolution of halite by the Yellow River water could be excluded.

Continued development of room temperature semiconductor nuclear detectors

NASA Astrophysics Data System (ADS)

Kim, Hadong; Cirignano, Leonard; Churilov, Alexei; Ciampi, Guido; Kargar, Alireza; Higgins, William; O'Dougherty, Patrick; Kim, Suyoung; Squillante, Michael R.; Shah, Kanai

2010-08-01

Thallium bromide (TlBr) and related ternary compounds, TlBrI and TlBrCl, have been under development for room temperature gamma ray spectroscopy due to several promising properties. Due to recent advances in material processing, electron mobility-lifetime product of TlBr is close to Cd(Zn)Te's value which allowed us to fabricate large working detectors. We were also able to fabricate and obtain spectroscopic results from TlBr Capacitive Frisch Grid detector and orthogonal strip detectors. In this paper we report on our recent TlBr and related ternary detector results and preliminary results from Cinnabar (HgS) detectors.

Detection methods for atoms and radicals in the gas phase

NASA Astrophysics Data System (ADS)

Hack, W.

This report lists atoms and free radicals in the gas phase which are of interest for environmental and flame chemistry and have been detected directly. The detection methods which have been used are discussed with respect to their range of application, specificity and sensitivity. In table 1, detection methods for the five atoms of group IV (C, Si, Ge, Sn, Pb) and about 60 radicals containing at least one atom of group IV are summarized (CH, Cd, Cf, CC1, CBr, Cn, Cs, CSe, CH2, CD2, Chf, Cdf, CHC1, CHBr, CF2, CC12, CBr2, CFC1, CFBr, CH3, CD3, CF3, CH2F, CH2C1, CH2Br, CHF2, CHC12, CHBr2, Hco, Fco, CH30, CD30, CH2OH, CH3S, Nco, CH4N, CH302, CF302; C2, C2N, C2H, C20, C2HO, C2H3, C2F3, C2H5, C2HsO, C2H4OH, CH3CO, CD3CO, C2H3O, C2H502, CH3COO2, C2H4N, C2H6N, C3; Si, SiF, SiF2, SiO, SiC, Si2; Ge, GeC, GeO, GeF, GeF2, GeCl2, Sn, SnF, SnO, SnF2, Pb, PbF, PbF2, PbO, PbS). In table 2 detection methods for about 25 other atoms and 60 radicals are listed: (H, D, O, O2, Oh, Od, HO2, DO2, F, Ci, Br, I, Fo, Cio, BrO, Io, FO2, C1O2, Li, Na, K, Rb, Cs, N, N3, Nh, Nd, Nf, Nci, NBr, NH2, ND2, Nhd, Nhf, NF2, NC12, N2H3, No, NO2, NO3, Hno, Dno, P, Ph, Pd, Pf, Pci, PH2, PD2, PF2, Po, As, AsO, AsS, Sb, Bi, S, S2, Sh, Sd, Sf, SF2, So, Hso, Dso, Sn, Se, Te, Se2, SeH, SeD, SeF, SeO, SeS, SeN, TeH, TeO, Bh, BH2, Bo, Bn, B02, Cd, Hg, UF5). The tables also cite some recent kinetic applications of the various methods.

Time-dependent disturbances of chloride salts on overall redox reaction and luminescence in Vibrio fischeri.

PubMed

Yu, Zhenyang; Zhang, Jing; Hou, Meifang

2018-05-01

The redox state of NADH/NADPH balance (nicotinamide adenine dinucleotide/nicotinamide adenine dinucleotide phosphate) is crucial in cellular homeostasis. Recent studies reported that sodium halide ions (NaX, X = F - , Cl - , Br - and I - ) stimulated NAD(P)H in Vibrio fischeri (VF). However, it remained unanswered whether this pattern applied in salts with other cations, e.g., K + , Mg 2+ and Ca 2+ , whose aquatic concentrations were increased by anthropogenic activities and climate change. Currently, VF were incubated with chloride salts, including KCl, MgCl 2 and CaCl 2 , and effects were measured in a time-dependent fashion. Both NADH and NADPH showed stimulation that increased over time, and the greatest maximum stimulation at 24 h was CaCl 2  > MgCl 2  > KCl. The changes of NADH/NADPH ratios over time in CaCl 2 , MgCl 2 and KCl were descendent, ascendant and stable, respectively. Simultaneously, FMN:NAD(P)H reaction catalyst (luciferase, in the form of expression levels of lux A and lux B), adenosine triphosphate and the expression levels of its regulating gene adk were also stimulated. The luminescence showed even more significant stimulations than the overall redox reaction. Together with earlier reported effects of NaCl, the chloride salts commonly disturbed the redox state and influenced the adaption of organisms to challenging environments. Copyright © 2018 Elsevier Ltd. All rights reserved.

Nitrosyl Iodide, Ino: Millimeter-Wave Spectroscopy Guided by AB Initio Quantum Chemical Computation

NASA Astrophysics Data System (ADS)

Bailleux, Stephane; Duflot, Denis; Aiba, Shohei; Ozeki, Hiroyuki

2015-06-01

In the series of the nitrosyl halides, XNO (where X = {F, Cl, Br, I}), the millimeter-wave spectrum of INO remains so far unknown. We report our investigation on the first high-resolution rotational spectroscopy of nitrosyl iodide, INO. One of the motivation for this work comes from the growing need in developing a more complete understanding of atmospheric chemistry, especially halogen and nitrogen oxides chemistry that adversely impacts ozone levels. In the family of the nitrogen oxyhalides such as nitrosyl (XNO), nitryl (XNO), nitrite (XONO), and nitrate (XON0_2) halides, those with X = {F, Cl, Br} have been well studied, both theoretically and experimentally. However, relatively little is known about the iodine-containing analogues, although they also are of potential importance in tropospheric chemistry. In 1991, the Fourier-transform IR spectroscopic detection of INO, INO_2 and IONO_2 in the gas phase has been reported The INO molecule was generated by in situ mixing continuously I_2 and NO in a 50-cm long reaction glass tube whose outlet was connected to the absorption cell using a teflon tube. At the time of writing this abstract, 68 μ_a-type transitions (K_a = 0-10), all weak, have been successfully assigned. The hyperfine structures due to both I and N nuclei will also be presented. S.B. and D.D. acknowledge support from the Laboratoire d'Excellence CaPPA (Chemical and Physical Properties of the Atmosphere) through contract ANR-10-LABX-005 of the Programme d'Investissement d'Avenir. I. Barnes, K. H. Becker and J. Starcke, J. Phys. Chem. 1991, 95, 9736-9740.

Electronegativity equalization method: parameterization and validation for organic molecules using the Merz-Kollman-Singh charge distribution scheme.

PubMed

Jirousková, Zuzana; Vareková, Radka Svobodová; Vanek, Jakub; Koca, Jaroslav

2009-05-01

The electronegativity equalization method (EEM) was developed by Mortier et al. as a semiempirical method based on the density-functional theory. After parameterization, in which EEM parameters A(i), B(i), and adjusting factor kappa are obtained, this approach can be used for calculation of average electronegativity and charge distribution in a molecule. The aim of this work is to perform the EEM parameterization using the Merz-Kollman-Singh (MK) charge distribution scheme obtained from B3LYP/6-31G* and HF/6-31G* calculations. To achieve this goal, we selected a set of 380 organic molecules from the Cambridge Structural Database (CSD) and used the methodology, which was recently successfully applied to EEM parameterization to calculate the HF/STO-3G Mulliken charges on large sets of molecules. In the case of B3LYP/6-31G* MK charges, we have improved the EEM parameters for already parameterized elements, specifically C, H, N, O, and F. Moreover, EEM parameters for S, Br, Cl, and Zn, which have not as yet been parameterized for this level of theory and basis set, we also developed. In the case of HF/6-31G* MK charges, we have developed the EEM parameters for C, H, N, O, S, Br, Cl, F, and Zn that have not been parameterized for this level of theory and basis set so far. The obtained EEM parameters were verified by a previously developed validation procedure and used for the charge calculation on a different set of 116 organic molecules from the CSD. The calculated EEM charges are in a very good agreement with the quantum mechanically obtained ab initio charges. 2008 Wiley Periodicals, Inc.

Silver(i) complexes with 1'-(diphenylphosphino)-1-cyanoferrocene: the art of improvisation in coordination.

PubMed

Škoch, Karel; Uhlík, Filip; Císařová, Ivana; Štěpnička, Petr

2016-06-28

1'-(Diphenylphosphino)-1-cyanoferrocene () reacts with silver(i) halides at a 1 : 1 metal-to-ligand ratio to afford the heterocubane complexes [Ag(μ3-X)(-κP)]4, where X = Cl (), Br (), and I (). In addition, the reaction with AgCl with 2 equiv. of leads to chloride-bridged dimer [(μ-Cl)2{Ag(-κP)2}2] () and, presumably, also to [(μ(P,N)-){AgCl(-κP)}]2 (). While similar reactions with AgCN furnished only the insoluble coordination polymer [(-κP)2Ag(NC)Ag(CN)]n (), those with AgSCN afforded the heterocubane [Ag(-κP)(μ-SCN-S,S,N)]4 () and the thiocyanato-bridged disilver(i) complex [Ag(-κP)2(μ-SCN-S,N)]2 (), thereby resembling reactions in the AgCl- system. Attempted reactions with AgF led to ill-defined products, among which [Ag(-κP)2(μ-HF2)]2 () and [(μ-SiF6){Ag(-κP)2}2] () could be identified. The latter compound was prepared also from Ag2[SiF6] and . Reactions between and AgClO4 or Ag[BF4] afforded disilver complexes [(μ(P,N)-)Ag(ClO4-κO)]2 () and [(μ(P,N)-)Ag(BF4-κF)]2 () featuring pseudolinear Ag(i) centers that are weakly coordinated by the counter anions. A similar reaction with Ag[SbF6] followed by crystallization from ethyl acetate produced an analogous complex, albeit with coordinated solvent, [(μ(P,N)-)Ag(AcOEt-κO)]2[SbF6]2 (). Ultimately, a compound devoid of any additional ligands at the Ag(i) centers, [(μ(P,N)-)Ag]2[B(C6H3(CF3)2-3,5)4]2 (), was obtained from the reaction of with silver(i) tetrakis[3,5-bis(trifluoromethyl)phenyl]borate. The reaction of Ag[BF4] with two equivalents of produced unique coordination polymer [Ag(-κP)(μ(P,N)-)]n[BF4]n (), the structure of which contained one of the phosphinoferrocene ligands coordinated as a P,N-chelate and the other forming a bridge to an adjacent Ag(i) center. All of these compounds were structurally characterized by single-crystal X-ray crystallography, revealing that the lengths of the bonds between silver and its anionic ligand(s) typically exceed the sum of the respective covalent radii, which is in line with the results of theoretical calculations at the density-functional theory (DFT) level, suggesting that standard covalent dative bonds are formed between silver and phosphorus (soft acid/soft base interactions) while the interactions between silver and the ligand's nitrile group (if coordinated) or the supporting anion are of predominantly electrostatic nature.

Subthreshold parallel pumping experiments on the quasi one-dimensional S = {1}/{2} ferromagnets [C 6H 11NH 3]CuBr 3 and [C 6H 11NH 3]CuCl 3

NASA Astrophysics Data System (ADS)

Hoogerbeets, R.; Wiegers, S. A. J.; Van Duyneveldt, A. J.

1985-04-01

Subthreshold parallel pumping experiments on [C 6H 11NH 3]CuBr 3 (abbreviated as CHAB) and [C 6H 11NH 3]CuCl 3 (CHAC) at 9.6 and 18.3 GHz are reported. It is shown that the experimental results can be explained using the values of the parameters as have been obtained from previously reported FMR measurements.

(H, Li)Br and LiOH Solvation Bonding Dynamics: Molecular Nonbond Interactions and Solute Extraordinary Capabilities.

PubMed

Sun, Chang Q; Chen, Jiasheng; Gong, Yinyan; Zhang, Xi; Huang, Yongli

2018-01-25

We resolved the O:H-O bond transition from the mode of ordinary water to its hydration in terms of its phonon stiffness (vibration frequency shift Δω), order of fluctuation (line width), and number fraction (phonon abundance), f x (C) = N hyd /N total . The f x (C) follows f H (C) = 0, f Li (C) ∝ f OH (C) ∝ C, and f Br (C) ∝ 1 - exp(-C/C 0 ) toward saturation with C being the solute concentration. The invariant df x (C)/dC suggests that the solute forms a constantly sized hydration droplet without responding to interference of other ions because its hydrating H 2 O dipoles fully screen its electric field. However, the number inadequacy of the highly ordered hydration H 2 O dipoles partially screens the large Br - . The Br - then interacts repulsively with other Br - anions, which weakens its electric field and the f Br (C) approaches saturation at higher solute concentration. The consistency in the concentration trend of the f LiBr (C), the Jones-Dole viscosity η(C), and the surface stress of LiBr solution clarifies their common origin of ionic polarization. The resultant energy of the solvent H-O exothermic elongation by O: ⇔ :O repulsion and the solute H-O endothermic contraction by bond-order deficiency heats up the LiOH solution. An estimation of at least 0.15 eV (160% of the O:H cohesive energy of 0.1 eV) suggests that the H-O elongation is the main source heating up the solution, while the molecular motion, structure fluctuation, or even evaporation dissipates energy caped at 0.1 eV.

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

PubMed

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

2016-08-23

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

MORPHOLOGICAL CELL TRANSFORMATION OF C3H10T1/2CL8 MOUSE EMBRYO CELLS BY THE K-REGION DIHYDRODIOL OF BENZO[A]PYRENE OCCURS IN COINCIDENCE WITH DNA DAMAGE, BUT WITHOUT THE FORMATION OF DETECTABLE STABLE COVALENT DNA ADDUCTS

EPA Science Inventory

Abstract:

Benzo[a]pyrene (B[a]P) has been the most thoroughly studied polycyclic aromatic hydrocarbon (PAH). Many mechanisms have been suggested to explain its carcinogenic activity, yet many questions still remain. K-region diols of PAHs are common metabolic inter...

The interaction of mercury with halogenated graphene

NASA Astrophysics Data System (ADS)

Kirchofer, Abigail; Sasmaz, Erdem; Wilcox, Jennifer

2011-03-01

The interaction of mercury with halogenated graphene was studied using plane-wave density functional theory. Various configurations of H, Hg, O and Br or Cl on the zigzag edge sites of graphene were investigated. Although Hg-Br (or -Cl) complexes were found to be stable on the surface, the most stable configurations found were those with Hg adjacent to O. The surface atoms Hg, O, and Br tend to repel each other during geometric optimization, moving towards an H atom nearest-neighbor where possible. The strength of the Hg-graphene interaction is very sensitive to the local environment. The Hg-graphene binding energy is strongest when the Hg is located next to a surface O but not immediately next to a bound Br. DOS analysis revealed that Hg adsorption involves a gain in Hg 6 p-states and a loss in Hg 5 s electron density, resulting in an oxidized surface-bound Hg complex. DOS analysis suggests that Br strengthens the Hg-graphene interaction by modifying the surface carbon electron density; however, when Br is adjacent to Hg, a direct Hg-Br interaction weakens the Hg-C bond. These investigations provide insight into the mechanism associated with enhanced Hg adsorption on Br-functionalized carbon materials for Hg emissions reductions from coal-fired power plant applications. The authors acknowledge the financial support by Electric Power Research Institute (EPRI).

Effects of a Reservoir Water on the GW Quality in a Coastal Aquifer of Semi-arid Region, North-east of Tunisia

NASA Astrophysics Data System (ADS)

Uchida, C.; Kawachi, A.; Tsujimura, M.; Tarhouni, J.

2015-12-01

This study investigated effects of a reservoir water in a salinized shallow aquifer based on spatial distribution of geochemical properties in groundwater (GW). In many coastal shallow aquifers of arid and semi-arid regions, groundwater table (GWT) depression and salinization have occurred due to GW overexploitation. In Korba aquifer, north-east of Tunisia, after a dam reservoir has been constructed in order to assure a water resource for irrigation, improvement of GW level and quality have been observed in the downstream area of the dam (area-A), while the GW in the other area (area-B) still has high salinity. This study, therefore, aimed to investigate the effects of the reservoir water on the GW quality. In June 2013, water quality survey and sampling were carried out at 60 wells (GW), a dam reservoir, river and the sea. Major ions, boron, bromide, and oxygen-18 and deuterium in collected samples were analyzed. From the results, in the area-B, the GWT was lower than the sea level and the high salinity were observed. The Br- concentration of the GW was correlated with the Cl- concentration, and the values of B/Cl- and Br-/Cl- of the GW were similar to the seawater. Since the GWT depression allowed the seawater to intrude into the aquifer, the GW salinization occurred in this area. On the other hand, in the area-A, GWT was higher than the seawater level, and the Na+ and Cl- concentrations were lower than the area-B. Especially, in the irrigated areas by using the reservoir water, the isotopic values, B/Cl- and Br-/Cl- of the GW were relatively higher than the others. The reservoir water has high isotopic values due to evaporation effect, and the B/Cl- and Br-/Cl- values become higher due to organic matters in sediment of the reservoir or soil in the filtration process. Thus, in addition to the direct infiltration from the reservoir into the aquifer, irrigation using a reservoir water probably has a positive impact on the GW quality in this area.

Chlorate Formation Mechanism in the Presence of Sulfate Radical, Chloride, Bromide and Natural Organic Matter.

PubMed

Hou, Shaodong; Ling, Li; Dionysiou, Dionysios D; Wang, Yuru; Huang, Jiajia; Guo, Kaiheng; Li, Xuchun; Fang, Jingyun

2018-06-05

Halides and natural organic matter (NOM) are inevitable in aquatic environment and influence the degradation of contaminants in sulfate radical (SO 4 •- )-based advanced oxidation processes. This study investigated the formation of chlorate in the coexposure of SO 4 •- , chloride (Cl - ), bromide (Br - ) and/or NOM in UV/persulfate (UV/PDS) and cobalt(II)/peroxymonosulfate (Co/PMS) systems. The formation of chlorate increased with increasing Cl - concentration in the UV/PDS system, however, in the Co/PMS system, it initially increased and then decreased. The chlorate formation involved the formation of hypochlorous acid/hypochlorite (HOCl/OCl - ) as an intermediate in both systems. The formation was primarily attributable to SO 4 •- in the UV/PDS system, whereas Co(III) played a significant role in the oxidation of Cl - to HOCl/OCl - and SO 4 •- was important for the oxidation of HOCl/OCl - to chlorate in the Co/PMS system. The pseudo-first-order rate constants ( k') of the transformation from Cl - to HOCl/OCl - were 3.32 × 10 -6 s -1 and 9.23 × 10 -3 s -1 in UV/PDS and Co/PMS, respectively. Meanwhile, k' of HOCl/OCl - to chlorate in UV/PDS and Co/PMS were 2.43 × 10 -3 s -1 and 2.70 × 10 -4 s -1 , respectively. Br - completely inhibited the chlorate formation in UV/PDS, but inhibited it by 45.2% in Co/PMS. The k' of SO 4 •- reacting with Br - to form hypobromous acid/hypobromite (HOBr/OBr - ) was calculated to be 378 times higher than that of Cl - to HOCl/OCl - , but the k' of Co(III) reacting with Br - to form HOBr/OBr - was comparable to that of Cl - to HOCl/OCl - . NOM also significantly inhibited the chlorate formation, due to the consumption of SO 4 •- and reactive chlorine species (RCS, such as Cl·, ClO· and HOCl/OCl - ). This study demonstrated the formation of chlorate in SO 4 •- -based AOPs, which should to be considered in their application in water treatment.

AN APPROACH TO THE DEVELOPMENT OF MODELS TO QUANTITATIVELY ASSESS THE EFFECTS OF EXPOSURE TO ENVIRONMENTALLY RELEVANT LEVELS OF ENDOCRINE DISRUPTORS

EPA Science Inventory

An approach to the development of quantitative models to assess the effects of exposure to environmentally relevant levels of endocrine disruptors on homeostasis in adults.

Ben-Jonathan N, Cooper RL, Foster P, Hughes CL, Hoyer PB, Klotz D, Kohn M, Lamb DJ, Stancel GM.
<...

Effect of ionic liquid treatment on the ultrastructural and topochemical features of compression wood in Japanese cedar (Cryptomeria japonica).

PubMed

Kanbayashi, Toru; Miyafuji, Hisashi

2016-07-18

The morphological and topochemical changes in wood tissues in compression wood of Japanese cedar (Cryptomeria japonica) upon treated with two types of ionic liquids, 1-ethyl-3-methylimidazolium chloride ([C2mim][Cl]) and 1-ethylpyridinium bromide ([EtPy][Br]) were investigated. Compression wood tracheids were swollen by both ionic liquids but their swelling behaviors were different in the types of ionic liquids used. Under the polarized light, we confirmed that crystalline cellulose in compression wood is amorphized by [C2mim][Cl] treatment whereas it changes slightly by [EtPy][Br] treatment. Raman microscopic analyses revealed that [C2mim][Cl] can preferentially liquefy polysaccharides in compression wood whereas [EtPy][Br] liquefy lignin. In addition, the interaction of compression wood with ionic liquids is different for the morphological regions. These results will assist in the use of ionic liquid treatment of woody biomass to produce valuable chemicals, bio-fuels, bio-based composites and other products.

Effect of ionic liquid treatment on the ultrastructural and topochemical features of compression wood in Japanese cedar (Cryptomeria japonica)

PubMed Central

Kanbayashi, Toru; Miyafuji, Hisashi

2016-01-01

The morphological and topochemical changes in wood tissues in compression wood of Japanese cedar (Cryptomeria japonica) upon treated with two types of ionic liquids, 1-ethyl-3-methylimidazolium chloride ([C2mim][Cl]) and 1-ethylpyridinium bromide ([EtPy][Br]) were investigated. Compression wood tracheids were swollen by both ionic liquids but their swelling behaviors were different in the types of ionic liquids used. Under the polarized light, we confirmed that crystalline cellulose in compression wood is amorphized by [C2mim][Cl] treatment whereas it changes slightly by [EtPy][Br] treatment. Raman microscopic analyses revealed that [C2mim][Cl] can preferentially liquefy polysaccharides in compression wood whereas [EtPy][Br] liquefy lignin. In addition, the interaction of compression wood with ionic liquids is different for the morphological regions. These results will assist in the use of ionic liquid treatment of woody biomass to produce valuable chemicals, bio-fuels, bio-based composites and other products. PMID:27426470

Synthesis and characterization of monomeric Mn (IV) and pseudo-tetrameric Mn (III) complexes: magnetic properties of Mn (III) complex.

PubMed

Yahsi, Yasemin; Kara, Hulya

2014-06-05

Two novel monomer Mn (IV) [Mn(3,5-ClL1)2]⋅(CH3OH), (1), [3,5-ClL1H2=N-(2-hydroxyethyl)-3,5-dichlorosalicylaldimine] (1) and hydrogen-bonded pseudo-tetramer Mn (III) [Mn(5-BrL2)(H2O)2]2⋅[Mn(5-BrL2)(H2O)]2⋅2⋅(ClO4), (2), [5-BrL2H2=N,N'-bis(5-bromosalicylidenato)-1,2-diamino-2-methylpropane)] (2) Schiff base complexes have been synthesized and their crystal structures have been determined by single crystal X-ray diffraction analysis. A variable temperature magnetic susceptibility measurement study has been performed for complex (2) and the result indicates there is a very weak antiferromagnetic interaction (J=-0.40±0.016cm(-1)) between the two manganese (III) centers. Copyright © 2014 Elsevier B.V. All rights reserved.

Salts in the dry valleys of Antartica

NASA Technical Reports Server (NTRS)

Gibson, E. K., Jr.; Presley, B. J.; Hatfield, J.

1984-01-01

The Dry Valleys of Antarctica are examples of polar deserts which are rare geological features on the Earth. Such deserts typically have high salinities associated with their closed-basin waters and on many surficial materials throughout them. In order to examine the possible sources for the salts observed in association with the soils in the Dry Valleys. The chloride and bromide concentrations of the water leachates from 58 soils and core samples were measured. The Cl/Br ratio for seawater is 289 and ratios measured for most of the 58 soils studied (greater than 85% of the soils studied) was larger than the seawater ratio (ratios typically were greater than 1000 and ranged up to 50,000). The enrichment in Cl relative to Br is strong evidence that the alts present within the soils were derived from seawater during ordinary evaporation processes, and not from the deposition of Cl and Br from aerosols or from rock weathering as has often been suggested.

Density functional theory study of homologous organometallic molecules of the [RhXL2]2 (X=Cl, Br, or I; L=CO, PH3, or PF3) type

NASA Astrophysics Data System (ADS)

Seuret, P.; Weber, J.; Wesolowski, T. A.

Density functional theory generalized gradient approximation calculations, which were tested in our previous detailed study of [RhCl(PF3)2]2 (Seuret et al., 2003, Phys. Chem. chem. Phys., 5, 268-274), were applied for a series of homologous organometallic compounds of the [RhXL2]2 (X = Cl, Br, or I; L = CO, PH3, or PF3) type. Various properties of the studied compounds were obtained. Optimized geometries of [RhCl(PH3)2]2 and [RhCl(CO)2]2 are in very good agreement with available experimental data. Geometries of other compounds as well as other properties (thermochemistry of selected fragmentation channels, barriers to structural changes, frontier orbitals) which are not available experimentally were predicted. All the considered compounds are not planar. Enforcing planarity of the central [RhX]2 moiety requires only a small energetic cost ranging from 2.2 to 3.9 kcal mol-1. The analysis of frontier orbitals indicates that the metals provide the most favourable site for the electrophilic attack in all considered compounds. The analysis of the shape of the lowest unoccupied molecular orbitals indicates that the halogens and ligands provide the most favourable site for the nucleophilic attack for [RhCl(CO)2]2 or [RhCl(PF3)2]. For [RhBr(PF3)2]2, [RhI(PF3)2]2 and [RhCl(PH3)2]2, the nucleophilic attack on the halogen is less probable. Except for [RhCl(CO)2]2, the least energetically expensive decomposition channel involves initial separation of ligands. For [RhCl(CO)2]2, its decomposition into the RhCl(CO)2 fragments was found to be the least energetically expensive fragmentation reaction which is probably one of the reasons for the known catalytic activity of this compound.

Polymer-Nanoparticle Hybrid Photovoltaic Research for U.S. Air Force Applications

DTIC Science & Technology

2010-01-06

6 S S O S S O II xi xiviii xii (69%) (93%) (64%) (92%) 4S SBr Br S S OO OO II S S OO aReagents and Conditions: i.THF, n- BuLi , C6H13Br, -78oC, ii...CHCl3, FeCl3 (cat.), Br2, iii. THF, n- BuLi , B(OBu)3, -78oC, 2 M HCl, iv. Toluene, 1,3-propandiol, Reflux, v. (a) Ether, n- BuLi -78oC, (b) 3...thiophenecarboxaldehyde, vi. (a) n- BuLi (2eqiv.), -23oC, I2 (3eqiv.), (b) Na2SO3 and HI solun, vii. CH2Cl2, P.C.C, r.t, viii. Cu, DMF, Reflux, ix

Singlet Excited States of Cl and Br Molecules: New Theories Applied to the -XO and -XO2 (X=C1 and Br) Chromophores

NASA Technical Reports Server (NTRS)

Lee, Timothy J.; Srinivasan, Parthiban; Head-Gordon, Martin; Huo, Winifred (Technical Monitor)

1998-01-01

Electronic excitation energies are determined using single-reference based theories derived from response equations involving perturbation theory and coupled-cluster theory. These methods are applied to the singlet manifold of excited electronic states of the HClO, HBrO, HOClO, HOBrO, HClO2, and HBrO2 molecules. The reliability of the various perturbation theory approaches is assessed by comparison to the linear-response singles and doubles coupled-cluster (LRCCSD) method. The excitation energies for the Y-XO compounds are compared and contrasted for Y=H and HO, and X=Cl and Br. A similar comparison is performed for the H-XO2 compounds.

Reactions of rhenium(V) and molybdenum(V) oxypentahalides with 5,7,7,12,14,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ashurova, N.Kh.; Yakubov, K.G.

1993-11-01

The author studied complexation reactions of rhenium(V) and molybdenum(V) with a macrocyclic ligand 5,7,7,12,14,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane (Tet a). The authors found that in hydrohalic acid medium, the onium complexes [H{sub 2}(Tet a)][EOX{sub 5}] are formed, with E = Re, Mo; X = Cl, Br. Reactions of [EOX{sub 5}]{sup 2{minus}} with (Tet a) in nitrometane yield complexes of molecular and cation types [EO(Tet a)Cl{sub 3}] and [EO(Tet a)Br]Br{sub 2}. Composition and structure of the obtained compounds are established by elemental analysis, conductometry, and mid- and far-IR spectroscopy.

Photoinduced Br Desorption from CsBr Thin Films Grown on Cu(100)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Halliday, Matthew T.; Joly, Alan G.; Hess, Wayne P.

2015-10-22

Thin films of CsBr deposited onto metals such as copper are potential photocathode materials for light sources and other applications. We investigate desorption dynamics of Br atoms from CsBr films grown on insulator (KBr, LiF) and metal (Cu) substrates induced by sub-bandgap 6.4 eV laser pulses. The experimental results demonstrate that the peak kinetic energy of Br atoms desorbed from CsBr/Cu films is much lower than that for the hyperthermal desorption from CsBr/LiF films. Kelvin probe measurements indicate negative charge at the surface following Br desorption from CsBr/Cu films. Our ab initio calculations of excitons at CsBr surfaces demonstrate thatmore » this behavior can be explained by an exciton model of desorption including electron trapping at the CsBr surface. Trapped negative charges reduce the energy of surface excitons available for Br desorption. We examine the electron-trapping characteristics of low-coordinated sites at the surface, in particular, divacancies and kink sites. We also provide a model of cation desorption caused by Franck-Hertz excitation of F centers at the surface in the course of irradiation of CsBr/Cu films. These results provide new insights into the mechanisms of photoinduced structural evolution of alkali halide films on metal substrates and activation of metal photocathodes coated with CsBr.« less

AB Initio Study of the Structure and Spectroscopic Properties of Halogenated Thioperoxy Radicals

NASA Technical Reports Server (NTRS)

Munoz, Luis A.; Binning, R. C., Jr.; Weiner, Brad R.; Ishikawa, Yasuyuki

1997-01-01

Thioperoxy (XSO or XOS) radicals exist in a variety of chemical environments, and they have as a consequence drawn some interest. HSO, an important species in the chemistry of the troposphere, has been examined both experimentally. The halogenated (X = F, Cl or Br) peroxy species and isovalent thioperoxy species have been studied less, but they too are potentially interesting because oxidized sulfur species and halogen sources are present in the atmosphere. Learning the fate of XSO and XOS radicals is important to understanding the atmospheric oxidation chemistry of sulfur compounds. Of these, FSO and ClSO are particularly interesting because they have been directly detected spectroscopically. Recent studies in our laboratory on the photochemistry of thionyl halides (X2SO; where X = F or Cl) have suggested new ways to generate XSO species. The laser-induced photodissociation of thionyl fluoride, F2SO, at 193 nm and thionyl chloride, ClSO, at 248 nm is characterized by a radical mechanism, X2SO -> XSO + X. The structure of FSO has been characterized experimentally by Endo et cd. employing microwave spectroscopy. Using the unrestricted Hartree-Fock (UHF) self-consistent field (SCF) method, Sakai and Morokuma computed the electronic structure of the ground (sup 2)A" and the first excited (sup 2)A' states of FSO. Electron correlation was not taken into account in their study. In a laser photodissociation experiment, Huber et al. identified ClSO mass spectromctrically. ClSO has also been detected in low temperature matrices by EPR and in the gas phase by far IR laser magnetic resonance. Although the structure of FSO is known in detail, the only study, experimental or theoretical, of CISO has been an ab initio HFSCF study by Hinchliffe. Electron correlation corrections were also excluded from this study. In order to better understand the isomerization and dissociation dynamics of the radical species, we have performed ab initio correlated studies of the potential energy surfaces (PES) of ClSO and its isomer ClOS at the QCISD(T)/6-31 G* level of theory. For FSO and FOS, more extensive QCISD/6-31 1G(2df) calculations have been possible, and the results are summarized here.

THE INDUCTION OF ABERRANT CRYPT FOCI IN THE COLONS OF MALE F344/N RATS EXPOSED TO THIHALOMETHANE MIXTURES IN THE DRINKING WATER

EPA Science Inventory

THE INDUCTION OF ABERRANT CRYPT FOCI IN THE COLONS OF MALE F344/N
RATS EXPOSED TO TRIHALOMETHANE MIXTURES IN THE DRINKING WATER

The trihalomethanes (THM), bromoform (TBM) and bromodichloromethane (BDCM), administered by corn oil gavage were found to increase large...

EFFECTS OF BROMODICHLOROMETHANE (BDCM) ON EX VIVO LUTEAL FUNCTION IN THE F344 RAT DURING PREGNANCY

EPA Science Inventory

Effects of Bromodichloromethane (BDCM) on Ex Vivo Luteal Function In the Pregnant F344 Rat

Susan R. Bielmeier1, Ashley S. Murr2, Deborah S. Best2, Jerome M. Goldman2, and Michael G. Narotsky2

1Curriculum in Toxicology, Univ. of North Carolina, Chapel Hill, NC 27599,...

Comparison of advanced thermal and electrical storage for parabolic dish solar thermal power systems

NASA Astrophysics Data System (ADS)

Fujita, T.; Birur, G. C.; Schredder, J. M.; Bowyer, J. M.; Awaya, H. I.

Parabolic dish solar concentrator cluster concepts are explored, with attention given to thermal storage systems coupled to Stirling and Brayton cycle power conversion devices. Sensible heat storage involving molten salt (NaOH), liquid sodium, and solid cordierite bricks are considered for 1500 F thermal storage systems. Latent heat storage with NaF-MgF2 phase change materials are explored in terms of passive, active, and direct contact designs. Comparisons are made of the effectiveness of thermal storage relative to redox, Na-S, Zn-Cl, and Zn-Br battery storage systems. Molten lead trickling down through a phase change eutectic, the NaF-MgF2, formed the direct contact system. Heat transport in all systems is effected through Inconel pipes. Using a cost goal of 120-150 mills/kWh as the controlling parameter, sensible heat systems with molten salts transport with either Stirling or Brayton engines, or latent heat systems with Stirling engines, and latent heat-Brayton engine with direct contact were favored in the analyses. Battery storage systems, however, offered the most flexibility of applications.

Comparison of advanced thermal and electrical storage for parabolic dish solar thermal power systems

NASA Technical Reports Server (NTRS)

Fujita, T.; Birur, G. C.; Schredder, J. M.; Bowyer, J. M.; Awaya, H. I.

1982-01-01

Parabolic dish solar concentrator cluster concepts are explored, with attention given to thermal storage systems coupled to Stirling and Brayton cycle power conversion devices. Sensible heat storage involving molten salt (NaOH), liquid sodium, and solid cordierite bricks are considered for 1500 F thermal storage systems. Latent heat storage with NaF-MgF2 phase change materials are explored in terms of passive, active, and direct contact designs. Comparisons are made of the effectiveness of thermal storage relative to redox, Na-S, Zn-Cl, and Zn-Br battery storage systems. Molten lead trickling down through a phase change eutectic, the NaF-MgF2, formed the direct contact system. Heat transport in all systems is effected through Inconel pipes. Using a cost goal of 120-150 mills/kWh as the controlling parameter, sensible heat systems with molten salts transport with either Stirling or Brayton engines, or latent heat systems with Stirling engines, and latent heat-Brayton engine with direct contact were favored in the analyses. Battery storage systems, however, offered the most flexibility of applications.

Computational Discovery of Two Lead Free Halide Double Perovskites with Band Gaps in the Visible Range: Cs2BiAgCl6 and Cs2BiAgBr6

NASA Astrophysics Data System (ADS)

Filip, Marina; Volonakis, George; Haghighirad, Amir Abbas; Hillman, Samuel; Sakai, Nobuya; Wenger, Bernard; Snaith, Henry; Giustino, Feliciano

The perovskite solar cell is emerging as one of the most promising solution processable photovoltaic technologies, with an efficiency that now exceeds the performance of thin-film silicon devices. This performance is exclusively due to the optimum optoelectronic properties of the prototypical methylammonium lead-iodide perovskite (MAPI). However, the presence of lead in MAPI, and its problematic stability in ambient conditions poses concerns for its potential environmental impact. These concerns are motivating the search for novel non-toxic halide perovskites with similar optoelectronic properties to MAPI. In this work we will present the computational search for the homovalent and the heterovalent replacement of Pb in lead-halide perovskites. This search has lead to the computational discovery and experimental synthesis of two stable lead-free halide double perovskites based on Bi and Ag: Cs2BiAgCl6 and Cs2BiAgBr6. These new compounds are highly stable, they are semiconducting and absorb light in the visible range. In this talk we will present the electronic and optical properties of Cs2BiAgCl6 and Cs2BiAgBr6 calculated within DFT and GW and discuss the stability and formability of the entire Cs2BB'X6 family of semiconductors (B = Bi, Sb, B = Cu, Ag, Au, X = Cl, Br, I). This work was supported by the and the Leverhulme Trust (RL-2012-001).

Mutual neutralization of He{sup +} with the anions Cl{sup −}, Br{sup −}, I{sup −}, and SF{sub 6}{sup −}

DOE Office of Scientific and Technical Information (OSTI.GOV)

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

2016-05-28

Mutual neutralization (MN) rate coefficients k{sub MN} for He{sup +} with the anions Cl{sup −}, Br{sup −}, I{sup −}, and SF{sub 6}{sup −} are reported from 300 to 500 K. The measured rate coefficients may contain a contribution from transfer ionization, i.e., double ionization of the anion. The large rate coefficient for He{sup +} + SF{sub 6}{sup −} (2.4 × 10{sup −7} cm{sup 3} s{sup −1} at 300 K) is consistent with earlier polyatomic MN results found to have a reduced mass dependence of μ{sup −1/2}. Neutralization of He{sup +} by the atomic halides follows the trend observed earlier for Ne{sup +},more » Ar{sup +}, Kr{sup +}, and Xe{sup +} neutralized by atomic halides, k{sub MN} (Cl{sup −}) < k{sub MN} (Br{sup −}) < k{sub MN} (I{sup −}). Only an upper limit could be measured for the neutralization of He{sup +} by Cl{sup −}. Predictions of the rate coefficients from a previously proposed simple model of atomic–atomic MN results are consistent with the present He{sup +}–halide rate coefficients. The temperature dependences are modestly negative for Br{sup −} and I{sup −}, while that for SF{sub 6}{sup −} is small or negligible.« less

Pressure and temperature dependences of the ionic conductivities of the thallous halidesTlCl, TlBr, and TlI

DOE Office of Scientific and Technical Information (OSTI.GOV)

Samara, G.A.

1981-01-15

Detailed studies of the pressure and temperature dependences of the ionic conductivities of TlCl and TlBr have allowed determination of the lattice volume relaxations and energies associated with the formation and motion of Schottky defects in these crystals. The volume relaxations deduced from the conductivity are found to be comparable in magnitude with values calculated from the strain energy model and a dynamical model. The association energy of Tl/sup +/ vacancies and divalent impurities was also determined for TlBr. A particularly important result is the finding that for these CsCl-type crystals the relaxation of the lattice associated with vacancy formationmore » is outward. Earlier studies on ionic crystals having the NaCl structure have yielded a similar result. This outward relaxation thus appears to be a general result for ionic crystals of both the NaCl and CsCl types (and possibly other ionic lattice types), in disagreement with earlier theoretical calculations which show that the relaxation should be inward for all models of ionic vacancies investigated. The conductivity of TlI was studied in both the (low temperature and pressure) orthorhombic phase as well as in the cubic CsCl-type phase. There is a large electronic contribution to the conductivity in the orthorhombic phase. An interesting result for all three materials is the observation in the cubic phase of a pressure-induced transition from ionic to electronic conduction. This is in qualitative agreement with what is known about the pressure dependences of the electronic structure of these materials.« less

Synthesis, characterization and optical non-linearity of two heterobimetallic copper clusters containing tetraselenometalates

NASA Astrophysics Data System (ADS)

Zhang, Qian-Feng; Zhang, Chi; Song, Ying-Lin; Xin, Xin-Quan

2000-07-01

Cluster [{MoCu 3Se 3Br}(PPh 3) 3Se]·3THF·H 2O ( 1·3THF·H 2O) was prepared from reaction of [Et 4N] 2[MoSe] 4, Cu(PPh 3) 2NO 3 and Et 4N·Br in CH 2Cl 2 solution; also, 1 can be also obtained from the reaction of [MoSe 4Cu 4Py 6Br 2] and excess PPh 3 in a DMF-CH 2Cl 2 mixture solvent. The 95Mo NMR technique was used to monitor the above two reaction processes. X-ray crystallographic structure determination shows that it contains a strongly distorted cubane-like {MoCu 3Se 3Br} core. The coordination of the central Mo atom and each Cu atom are distorted from tetrahedral. Cluster [{WCu 3Se 3Cl}(PPh 3) 3Se] ( 2) was synthesized by the reaction of [Et 4N] 2[WSe] 4 and Cu(PPh 3) 2Cl in the solid state for nonlinear optical (NLO) studies. Its structure was reported by Ibers (Inorg. Chem. 31 (1992) 4365). The NLO properties of clusters 1 and 2 were studied. Both NLO absorption and refraction were obtained, and their effective third-order non-linearities were detected with α2=3.4×10 -10 and 5.9×10 -10 m/W and n2=-1.5×10 -17 and -1.3×10 -17 m 2/W , respectively, for the same concentration CH 2Cl 2 solution of 1 and 2. Influence of skeletal atoms to nonlinear absorption is also discussed in the paper.

Ultrasonically-enhanced preparation, characterization of CaFe-layered double hydroxides with various interlayer halide, azide and oxo anions (CO32-, NO3-, ClO4-).

PubMed

Szabados, Márton; Varga, Gábor; Kónya, Zoltán; Kukovecz, Ákos; Carlson, Stefan; Sipos, Pál; Pálinkó, István

2018-01-01

An ultrasonically-enhanced mechanochemical method was developed to synthesize CaFe-layered double hydroxides (LDHs) with various interlayer anions (CO 3 2- , NO 3 - , ClO 4 - , N 3 - , F - , Cl - , Br - and I - ). The duration of pre-milling and ultrasonic irradiation and the variation of synthesis temperature in the wet chemical step were investigated to obtain the optimal parameters of preparation. The main method to characterize the products was X-ray diffractometry, but infrared and synchrotron-based X-ray absorption spectroscopies as well as thermogravimetric measurements were also used to learn about fine structural details. The synthesis method afforded successful intercalation of the anions, among others the azide anion, a rarely used counter ion providing a system, which enables safe handling the otherwise highly reactive anion. The X-ray absorption spectroscopic measurements revealed that the quality of the interlayered anions could modulate the spatial arrangement of the calcium ions around the iron(III) ions, but only in the second coordination sphere. Copyright © 2017 Elsevier B.V. All rights reserved.

Application of ESI-HRMS for molybdenum speciation in natural waters: An investigation of molybdate-halide reactions.

PubMed

Dang, Duc Huy; Evans, R Douglas

2018-03-01

High resolution electrospray ionization mass spectrometry (ESI-HRMS) was used to study the speciation of molybdate in interaction with halides (Cl, F, Br). Desolvation during electrospray ionization induced alteration of aqueous species but method optimization successfully suppressed artefact compounds. At low Mo concentrations, chloro(oxo)molybdate and fluoro(oxo)molybdate species were found and in natural samples, MoO 3 Cl was detected for the first time, to the best of our knowledge. Apparent equilibrium constants for Cl substitution on molybdate were calculated for a range of pH values from 4.5 to 8.5. A minor alteration in speciation during the gas phase (conversion of doubly charged MoO 4 2- to HMoO 4 - ) did not allow investigation of the molybdate acid-base properties; however this could be determined by speciation modeling. This study provides further evidence that ESI-HRMS is a fast and suitable tool to Deceasedassess the speciation of inorganic compounds such as Mo. Copyright © 2017 Elsevier B.V. All rights reserved.

Constraining the global bromomethane budget from carbon stable isotopes

NASA Astrophysics Data System (ADS)

Bahlmann, Enno; Wittmer, Julian; Greule, Markus; Zetzsch, Cornelius; Seifert, Richard; Keppler, Frank

2016-04-01

Despite intense research in the last two decades, the global bromomethane (CH3Br) budget remains unbalanced with the known sinks exceeding the known sources by about 25%. The reaction with OH is the largest sink for CH3Br. We have determined the kinetic isotope effects for the reactions of CH3Br with the OH and Cl radical in order to better constrain the global CH3Br budget from an isotopic perspective. The isotope fractionation experiments were performed at 20±1°C in a 3500 L Teflon smog-chamber with initial CH3Br mixing ratios of about 2 and 10 ppm and perflourohexane (25 ppb) as internal standard. Atomic chlorine (Cl) was generated via photolysis of molecular chlorine (Cl2) using a solar simulator with an actinic flux comparable to that of the sun in mid-summer in Germany. OH radicals were generated via the photolysis of ozone (O3) at 253.7 nm in the presence of water vapor (RH = 70%).The mixing ratios of CH3Br, and perflourohexane were monitored by GC-MS with a time resolution of 15 minutes throughout the experiments. From each experiment 10 to 15 sub samples were taken in regular time intervals for subsequent carbon isotope ratio determinations by GC-IRMS performed at two independent laboratories in parallel. We found a kinetic isotope effect (KIE) of 17.6±3.3‰ for the reaction of CH3Br with OH and a KIE of 9.8±1.4 ‰ for the reaction with Cl*. We used these fractionation factors along with new data on the isotopic composition of CH3Br in the troposphere (-34±7‰) and the surface ocean (-26±7‰) along with reported source signatures, to constrain the unknown source from an isotopic perspective. The largest uncertainty in estimating the isotopic composition of the unknown source arises from the soil sink. Microbial degradation in soils is the second largest sink and assigned with a large fractionation factors of about 50‰. However, field experiments revealed substantially smaller apparent fractionation factors ranging from 11 to 22‰. In addition, simple model studies suggest that the soil uptake of CH3Br and hence its isotopic effect is largely controlled by diffusion resulting in an even smaller apparent isotopic fractionation. As a consequence, the estimated source signature for the unknown source is discussed with respect to the assumptions made for the soil sink.

Synthesis and the crystal and molecular structures of (H{sub 3}L . Cl)[CoCl{sub 4}] and H{sub 2}L[CuBr{sub 4}] (L is 2,4,6-Tri(N,N-dimethylamino)methylphenol)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kovalchukova, O. V., E-mail: okovalchukova@mail.ru; Stash, A. I.; Strashnova, S. B.

2010-05-15

The complex compounds (H{sub 3}L . Cl)[CoCl{sub 4}] (I) and H{sub 2}L[CuBr{sub 4}] (II), where L is 2,4,6-tri(N,N-dimethylamino)methylphenol, were isolated in the crystalline state and studied by X-ray diffraction. The organic cations were found to be outer-sphere ligands. All three nitrogen atoms of the tertiary amino groups are protonated. In compound I, the H{sub 3}L{sup 3+} cation exists as the cis tautomer. In compound II, the H{sub 2}L{sup 2+} dication exists as the trans isomer. In the crystal structure, the dications are arranged in layers via hydrogen bonds.

Rigid 2D networks of copper(II) complexes containing diallylbis(pyridin-3-yl)silane: Insight into anion and media effects on catechol oxidation catalysis

NASA Astrophysics Data System (ADS)

Ryu, Minjoo; Lee, Young-A.; Jung, Ok-Sang

2018-01-01

The self-assembly of CuX2 (X- = Cl-, Br-, NO3-, ClO4-, and BF4-) with a new diallylbis(pyridin-3-yl)silane ligand (L) gives rise to the similar 2D coordination networks with composition of Cu(II) and L of 1: 2 irrespective of anions and solvents. The 2D networks of [CuCl2L2]·2H2O, [CuBr2L2]·2H2O, and [Cu(H2O)2L2]·(NO3)2 are packed in a staggered mode while the similar networks of [Cu(BF4)2L2] and [Cu(ClO4)2L2] are arrayed in a eclipsed fashion. These crystals of all 2D networks have been employed as catalysts for 3,5-di-tert-butylcatechol (3,5-DBCat) oxidation, showing the catalytic effects in the order of [CuCl2L2]·2H2O > [CuBr2L2]·2H2O > [Cu(H2O)2L2]·(NO3)2 > [Cu(ClO4)2L2] > [Cu(BF4)2L2] in chloroform and exhibiting the catalytic effects of only [Cu(H2O)2L2]·(NO3)2 in acetone. Thus, the catalytic effect on catechol oxidation is strongly dependent on anions and media.

Composition and source of salinity of ore-bearing fluids in Cu-Au systems of the Carajás Mineral Province, Brazil

USGS Publications Warehouse

Xavier, Roberto; Rusk, Brian; Emsbo, Poul; Monteiro, Lena

2009-01-01

The composition and Cl/Br – NaCl ratios of highly saline aqueous inclusions from large tonnage (> 100 t) IOCG deposits (Sossego, Alvo 118, and Igarapé Bahia) and a Paleoproterozoic intrusion-related Cu-Au-(Mo-W-Bi-Sn) deposit (Breves; < 50 Mt)) in the Carajás Mineral Province have been analysed by LA-ICP-MS and ion chromatography. In both Cu-Au systems, brine inclusions are Ca-dominated (5 to 10 times more than in porphyry Cu-Au fluids), and contain percent level concentrations of Na and K. IOCG inclusion fluids, however, contain higher Sr, Ba, Pb, and Zn concentrations, but significantly less Bi, than the intrusion-related Breves inclusion fluids. Cu is consistently below detection limits in brine inclusions from the IOCG and intrusion-related systems and Fe was not detected in the latter. Cl/Br and Na/Cl ratios of the IOCG inclusion fluids range from entirely evaporative brines (bittern fluids; e.g. Igarapé Bahia and Alvo 118) to values that indicate mixing with magma-derived brines. Cl/Br and Na/Cl ratios of the Breves inclusion fluids strongly suggest the involvement of magmatic brines, but that possibly also incorporated bittern fluids. Collectively, these data demonstrate that residual evaporative and magmatic brines were important components of the fluid regime involved in the formation of Cu-Au systems in the Carajás Mineral Province.

Salt-induced inhibition of the precipitin reaction of concanavalin A with polysaccharides and glycoprotein.

PubMed

Salahuddin, A; Begum, R; Averill, B K

1984-06-15

The time course of the precipitin reactions of concanavalin A with glycogen, dextran and ovalbumin was investigated by a light-scattering method near 30 degrees C in 10 mM-Tris/HCl buffer, pH 7.4, containing neutral salts, i.e. NaCl, KCl, NaBr, KI and NaClO4. With 0.8 microM-lectin and 0.36 mg of glycogen/ml, the half-life, t 1/2, of the precipitin reaction was independent of salt concentration between 0.1 M and 1.5 M, and was the same (175s) in the presence of NaCl, KCl, NaBr and KI but was significantly (27%) higher in NaClO4. In contrast, the five salts caused significant to marked enhancement in t 1/2 for the reactions of concanavalin A with dextran and ovalbumin. Likewise, whereas the turbidity produced in 1 h as a result of lectin-glycogen precipitation remained unchanged, those measured for the binding of dextran and ovalbumin were decreased in the presence of three salts. The increase in t 1/2 and decrease in turbidity were found to be higher with NaClO4, followed by KI; NaBr produced moderate and NaCl (or KCl) small but generally significant inhibition of the precipitin reactions with dextran and ovalbumin. The results showed that the lectin-ligand precipitin reactions involve salt-sensitive polar interactions that are less pronounced with compactly folded ligands such as glycogen.

Synthetic and Spectroscopic Studies on N-(i,j-Disubstituted Phenyl)-4- Substituted Benzenesulphonamides, 4-X'C6H4SO2NH(i,j-X2C6H3), where X' = H, CH3, C2H5, F, Cl or Br; i, j = 2, 3; 2, 4; 2, 5; 2, 6 or 3, 4; and X = CH3 or Cl

NASA Astrophysics Data System (ADS)

Shetty, Mahesha; Gowda, B. Thimme

2005-02-01

Fifty four N-(i,j-disubstituted phenyl)-4-substituted benzenesulphonamides of the general formula 4-X'C6H4SO2NH(i,j-X2C6H3), where X' = H, CH3, C2H5, F, Cl or Br; i,j = 2,3; 2,4; 2,5; 2,6 or 3, 4; and X = CH3 or Cl, are prepared and characterized and their infrared, 1H and 13C NMR spectra in solution are studied. The N-H stretching vibrations νN-H absorb in the range 3305 - 3205 cm-1, while the asymmetric and symmetric SO2 vibrations vary in the ranges 1377 - 1307 cm-1 and 1184 - 1128 cm-1, respectively. The N-(i,j-disubstituted phenyl)-4-substituted benzenesulphonamides show C-S, S-N and C-N stretching vibrations in the ranges 844 - 800 cm-1, 945 - 891 cm-1 and 1309 - 1170 cm-1, respectively. The compounds do not exhibit particular trends in the variation of these frequencies on substitution either at ortho or meta positions with either a methyl group or Cl. The observed 1H and 13C chemical shifts of are assigned to protons and carbon atoms of the two benzene rings. Incremental shifts of the ring protons and carbon atoms due to -SO2NH(i,j-X2C6H3) groups in C6H5SO2NH(i,j-X2C6H3) and 4-X'C6H4SO2NH- groups in 4-X'C6H4SO2NH(C6H*) are computed and employed to calculate the chemical shifts of the ring protons and carbon atoms in the substituted compounds 4-X'C6H4SO2NH(i,j-X2C6H3). The different methods of calculation lead to almost the same values in most cases and agree well with the observed chemical shifts, indicating the validity of the principle of additivity of the substituent effects with chemical shifts in these compounds.

Infrared Fiber Optics.

DTIC Science & Technology

1980-09-01

attention for IR fiber fabrication to date and gives their transmission ranges. At HRL, we have studied KCI, KBr, 8 TlBr , and KRS-5 (TlBrI); Honeywell...past three years to suc- cessfully fabricate KRS-5 and TlBr fibers. Polycrystalline fibers of these Tl-containing salts were prepared with losses as...crystalline materials such as KRS-5 (TIBrI), TlBr , AgCl, and KCI have been used for a variety of 10.6-pm, CO2 laser applications.1 - 4 The losses in the

Electronic structure and vibrational analysis of AHA⋯HX complexes

NASA Astrophysics Data System (ADS)

Joshi, Kaustubh A.; Gejji, Shridhar P.

2005-10-01

Electronic structures of the binary complexes of acetohydroxamic acid (AHA) and hydrogen halides, HX (X = F, Cl, Br) have been investigated using the second order perturbation theory. In the lowest energy structure of AHA⋯HF complex, hydrogen fluoride acts as a proton-donor with carbonyl oxygen and simultaneously as a proton-acceptor with the hydroxyl group. For chloro- and bromo-substituted derivatives, however, the lowest minimum possesses hydrogen-bonded interactions with the carbonyl oxygen in addition to those from the methyl proton of AHA. Frequency shifts of NH and CN stretching vibrations enable one to distinguish different conformers of AHA⋯HX complexes.

Alkali metal and alkali earth metal gadolinium halide scintillators

DOEpatents

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

2016-08-02

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

Quantum spin Hall insulator in halogenated arsenene films with sizable energy gaps

PubMed Central

Wang, Dongchao; Chen, Li; Shi, Changmin; Wang, Xiaoli; Cui, Guangliang; Zhang, Pinhua; Chen, Yeqing

2016-01-01

Based on first-principles calculations, the electronic and topological properties of halogenated (F-, Cl-, Br- and I-) arsenene are investigated in detail. It is found that the halogenated arsenene sheets show Dirac type characteristic in the absence of spin-orbital coupling (SOC), whereas energy gap will be induced by SOC with the values ranging from 0.194 eV for F-arsenene to 0.255 eV for I-arsenene. Noticeably, these four newly proposed two-dimensional (2D) systems are verified to be quantum spin Hall (QSH) insulators by calculating the edge states with obvious linear cross inside bulk energy gap. It should be pointed out that the large energy gap in these 2D materials consisted of commonly used element is quite promising for practical applications of QSH insulators at room temperature. PMID:27340091

The effects of local bond relaxations on the electronic and photocatalysis performances of nonmetal doped 3R-MoS2 based photocatalyst: density functional theory

NASA Astrophysics Data System (ADS)

Chen, Dajin; Lu, Song; Li, Huanhuan; Li, Can; Li, Lei; Gong, Yinyan; Niu, Lengyuan; Liu, Xinjuan; Wang, Tao

2017-03-01

To investigate the effects of local bond relaxations on the electronic and photocatalysis performances of MoS2 photocatalyst, the thermodynamic, electronic and optical performances of nonmetal doped 3R-MoS2 have been calculated using density functional theory. Results shown that the positive or negative charges of impurity ions are decided by the Pauling electronegativity differences between Mo (or S) and nonmetal atoms, the H, B, Si, Cl, Br and I ions priority to occupy the interstitial site and the other ones tend to occupy the substitutional site. The localized electrons around NM ions are caused by the relaxed Mo-NM and S1-NM bonds, which can effectively affect the electronic and photocatalytic performances of specimens. The optical performances have been altered by the slightest changes of band gap and the newly formed impurity levels; the active sites have been also changed based on the different distributions of the highest occupied molecular orbital and the lowest unoccupied molecular orbital. In brief, the B, N, F, Si, P, Cl, As, Se, Te and Br ions contribute to the separation of photogenerated e-/h+ pairs and enhance the photocatalysis efficiency, but the H, C, O, and I ions will become the recombination centers of photogenerated e-/h+ pairs and should be avoided adding into 3R-MoS2.

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

PubMed

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

2012-10-15

Across West Bengal and Bangladesh, concentrations of Cl in much groundwater exceed the natural, upper limit of 10 mg/L. The Cl/Br mass ratios in groundwaters range up to 2500 and scatter along mixing lines between waste-water and dilute groundwater, with many falling near the mean end-member value for waste-water of 1561 at 126 mg/L Cl. Values of Cl/Br exceed the seawater ratio of 288 in uncommon NO(3)-bearing groundwaters, and in those containing measurable amounts of salt-corrected SO(4) (SO(4) corrected for marine salt). The data show that shallow groundwater tapped by tube-wells in the Bengal Basin has been widely contaminated by waste-water derived from pit latrines, septic tanks, and other methods of sanitary disposal, although reducing conditions in the aquifers have removed most evidence of NO(3) additions from these sources, and much evidence of their additions of SO(4). In groundwaters from wells in palaeo-channel settings, end-member modelling shows that >25% of wells yield water that comprises ≥10% of waste-water. In palaeo-interfluvial settings, only wells at the margins of the palaeo-interfluvial sequence contain detectable waste water. Settings are identifiable by well-colour survey, owner information, water composition, and drilling. Values of Cl/Br and faecal coliform counts are both inversely related to concentrations of pollutant As in groundwater, suggesting that waste-water contributions to groundwater in the near-field of septic-tanks and pit-latrines (within 30 m) suppress the mechanism of As-pollution and lessen the prevalence and severity of As pollution. In the far-field of such sources, organic matter in waste-water may increase groundwater pollution by As. Copyright © 2012. Published by Elsevier B.V.

THE INDUCTION OF COLORECTAL NEOPLASIA BY A MIXTURE HIGH IN BROMINATED TRIHALOMETHANES (THMS) ADMINISTERED IN THE DRINKING WATER TO MALE F344/N RATS

EPA Science Inventory

THE INDUCTION OF COLORECTAL NEOPLASIA BY A MIXTURE HIGH IN BROMINA TED TRIHALOMETHANES (THMS) ADMINISTERED IN THE DRINKING W A TER TO MALE F344/N RA TS.

Abstract:

The THMs are the most widely distributed and concentrated of the chlorine disinfection by-products (D...

Expanding Water/Base Tolerant Frustrated Lewis Pair Chemistry to Alkylamines Enables Broad Scope Reductive Aminations

PubMed Central

Fasano, Valerio

2017-01-01

Abstract Lower Lewis acidity boranes demonstrate greater tolerance to combinations of water/strong Brønsted bases than B(C6F5)3, this enables Si−H bond activation by a frustrated Lewis pair (FLP) mechanism to proceed in the presence of H2O/alkylamines. Specifically, BPh3 has improved water tolerance in the presence of alkylamines as the Brønsted acidic adduct H2O–BPh3 does not undergo irreversible deprotonation with aliphatic amines in contrast to H2O–B(C6F5)3. Therefore BPh3 is a catalyst for the reductive amination of aldehydes and ketones with alkylamines using silanes as reductants. A range of amines inaccessible using B(C6F5)3 as catalyst, were accessible by reductive amination catalysed by BPh3 via an operationally simple methodology requiring no purification of BPh3 or reagents/solvent. BPh3 has a complementary reductive amination scope to B(C6F5)3 with the former not an effective catalyst for the reductive amination of arylamines, while the latter is not an effective catalyst for the reductive amination of alkylamines. This disparity is due to the different pK a values of the water–borane adducts and the greater susceptibility of BPh3 species towards protodeboronation. An understanding of the deactivation processes occurring using B(C6F5)3 and BPh3 as reductive amination catalysts led to the identification of a third triarylborane, B(3,5‐Cl2C6H3)3, that has a broader substrate scope being able to catalyse the reductive amination of both aryl and alkyl amines with carbonyls. PMID:27977048

Crystal growth and crystal structures of six novel phases in the Mn/As/O/Cl(Br) system, as well as magnetic properties of α-Mn3(AsO4)2

NASA Astrophysics Data System (ADS)

Weil, Matthias; Kremer, Reinhard K.

2017-01-01

Chemical vapour transport reactions (900 °C → 820 °C, Cl2 or Br2 as transport agent) of in situ formed Mn3(AsO4)2 yielded the orthoarsenates(V) α-Mn3(AsO4)2 and β-Mn3(AsO4)2 as well as the oxoarsenate(V) halide compounds Mn7(AsO4)4Cl2, Mn11(AsO4)7Cl, Mn11(AsO4)7Br and Mn5(AsO4)3Cl. The crystal structures of all six phases were determined from single crystal X-ray diffraction data. The crystal structures of α-and β-Mn3(AsO4)2 are isotypic with the corresponding phosphate phases γ- and α-Mn3(PO4)2, respectively, and are reported here for the first time. A comparative discussion with other structures of general composition M3(AsO4)2 (M = Mg; divalent first-row transition metal) is given. The unique crystal structures of Mn7(AsO4)4Cl2 and that of the two isotypic Mn11(AsO4)7X (X = Cl, Br) structures are composed of two [MnO5] polyhedra, two [MnO4Cl2] polyhedra (one with site symmetry 1 bar), two AsO4 tetrahedra, and one [MnO5] polyhedron, three [MnO6] octahedra (one with site symmetry.m.), one [MnO4X], one [MnO5X] polyhedron and four AsO4 tetrahedra, respectively. The various polyhedra of the three arsenate(V) halides are condensed into three-dimensional framework structures by corner- and edge-sharing. Mn5(AsO4)3Cl adopts the chloroapatite structure. The magnetic and thermal properties of pure polycrystalline samples of a-Mn3(AsO4)2 were investigated in more detail. The magnetic susceptibility proves all Mn atoms to be in the oxidation state +2 yielding an effective magnetic moment per Mn atom of 5.9 μB. Long-range antiferromagnetic ordering is observed below 8.2 K consistent with the negative Curie-Weiss temperature of -50 K derived from the high temperature susceptibility data.

Tandem Lewis/Brønsted homogeneous acid catalysis: conversion of glucose to 5-hydoxymethylfurfural in an aqueous chromium(iii) chloride and hydrochloric acid solution

DOE PAGES

Swift, T. Dallas; Nguyen, Hannah; Anderko, Andrzej; ...

2015-07-25

Here, a kinetic model for the tandem conversion of glucose to 5-hydroxymethylfurfural (HMF) through fructose in aqueous CrCl 3–HCl solution was developed by analyzing experimental data. We show that the coupling of Lewis and Brønsted acids in a single pot overcomes equilibrium limitations of the glucose–fructose isomerization leading to high glucose conversions and identify conditions that maximize HMF yield. Adjusting the HCl/CrCl 3 concentration has a more pronounced effect on HMF yield at constant glucose conversion than that of temperature or CrCl 3 concentration. This is attributed to the interactions between HCl and CrCl 3 speciation in solution that leadsmore » to HMF yield being maximized at moderate HCl concentrations for each CrCl 3 concentration. This volcano-like behavior is accompanied with a change in the rate-limiting step from fructose dehydration to glucose isomerization as the concentration of the Brønsted acid increases. The maximum HMF yield in a single aqueous phase is only modest and appears independent of catalysts’ concentrations as long as they are appropriately balanced. However, it can be further maximized in a biphasic system. Our findings are consistent with recent studies in other tandem reactions catalyzed by different catalysts.« less

Tandem Lewis/Brønsted homogeneous acid catalysis: conversion of glucose to 5-hydoxymethylfurfural in an aqueous chromium(iii) chloride and hydrochloric acid solution

DOE Office of Scientific and Technical Information (OSTI.GOV)

Swift, T. Dallas; Nguyen, Hannah; Anderko, Andrzej

Here, a kinetic model for the tandem conversion of glucose to 5-hydroxymethylfurfural (HMF) through fructose in aqueous CrCl 3–HCl solution was developed by analyzing experimental data. We show that the coupling of Lewis and Brønsted acids in a single pot overcomes equilibrium limitations of the glucose–fructose isomerization leading to high glucose conversions and identify conditions that maximize HMF yield. Adjusting the HCl/CrCl 3 concentration has a more pronounced effect on HMF yield at constant glucose conversion than that of temperature or CrCl 3 concentration. This is attributed to the interactions between HCl and CrCl 3 speciation in solution that leadsmore » to HMF yield being maximized at moderate HCl concentrations for each CrCl 3 concentration. This volcano-like behavior is accompanied with a change in the rate-limiting step from fructose dehydration to glucose isomerization as the concentration of the Brønsted acid increases. The maximum HMF yield in a single aqueous phase is only modest and appears independent of catalysts’ concentrations as long as they are appropriately balanced. However, it can be further maximized in a biphasic system. Our findings are consistent with recent studies in other tandem reactions catalyzed by different catalysts.« less

Assessment of the use of selected chemical and microbiological constituents as indicators of wastewater in curtain drains from home sewage-treatment systems in Medina County, Ohio

USGS Publications Warehouse

Dumouchelle, Denise H.

2006-01-01

Many home sewage-treatment systems (HSTS) in Ohio use curtain or perimeter drains to depress the level of the subsurface water in and around the systems. These drains could possibly intercept partially untreated wastewater and release potential pathogens to ground-water and surface-water bodies. The quality of water in curtain drains from two different HSTS designs in Medina County, Ohio, was investigated using several methods. Six evaporation-transpiration-absorption (ETA) and five leach-line (LL) systems were investigated by determining nutrient concentrations, chloride/bromide ratios (Cl/Br), Escherichia coli (E. coli ) concentrations, coliphage genotyping, and genetic fingerprinting of E. coli. Water samples were collected at 11 sites and included samples from curtain drains, septic tanks, and residential water wells. Nitrate concentrations in the curtain drains ranged from 0.03 to 3.53 mg/L (milligrams per liter), as N. Concentrations of chloride in 10 of the 11 curtain drains ranged from 5.5 to 21 mg/L; the chloride concentration in the eleventh curtain drain was 340 mg/L. Bromide concentrations in 11 curtain drains ranged from 0.01 to 0.22 mg/L. Cl/Br ratios ranged from 86 to 2,000. F-specific coliphage were not found in any curtain-drain samples. Concentrations of E. coli in the curtain drains ranged from 1 to 760 colonies per 100 milliliters. The curtain-drain water-quality data were evaluated to determine whether HSTS-derived water was present in the curtain drains. Nutrient concentrations were too low to be of use in the determination. The Cl/Br ratios appear promising. Coliphage was not detected in the curtain drains, so genotyping could not be attempted. E. coli concentrations in the curtain drains were all less than those from the corresponding HSTS; only one sample exceeded the Ohio secondary-contact water-quality standard. The genetic fingerprinting data were inconclusive because multiple links between unrelated sites were found. Although the curtain-drain samples from the ETA systems showed somewhat more evidence of the presence of HSTS water than did the LL systems, most of the approaches were inconclusive by themselves. The best evidence of HSTS water, from the Cl/Br ratios, indicates that the water in 10 of the 11 curtain drains, at both HSTS types, was a mixture of dilute ground water and HSTS-derived water; the 11th drain also show some effects of the HSTS, although road salt-affected water may be present. Therefore, it appears that there is no difference between the ETA and LL systems with respect to the water quality in curtain drains.

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

NASA Astrophysics Data System (ADS)

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.

Synthesis, Structure, and Optical Properties of Antiperovskite-Derived Ba2MQ3X (M = As, Sb; Q = S, Se; X = Cl, Br, I) Chalcohalides.

PubMed

Wang, Ruiqi; Zhang, Xian; He, Jianqiao; Bu, Kejun; Zheng, Chong; Lin, Jianhua; Huang, Fuqiang

2018-02-05

Six isostructural antiperovskite-derived chalcohalides, Ba 2 MQ 3 X (M = As, Sb; Q = S, Se; X = Cl, Br, I), crystallizing in the space group Pnma, have been synthesized by solid-state reactions. The crystal structure features a 3D framework with the [XBa 5 ] 9+ disordered square pyramids as building blocks and [MQ 3 ] 3- units filling the interspace. [XBa 5 ] 9+ disordered square pyramids are edge-sharing along [010], derived from the fusing of the two pyramids in octahedral [XBa 6 ] 11+ . Surprisingly, Ba 2 AsS 3 X (X = Cl, Br, I) show almost the same optical band gap of 2.80 eV, and Ba 2 AsSe 3 X (X = Br, I) also have a similar band gap of 2.28 eV. The optical band gap of Ba 2 SbS 3 I is 2.64 eV. First-principles calculations reveal that the optical absorption is attributed to the transitions between Q np at the valence band maximum (VBM) and M np-Q np at the conduction band minimum (CBM). These compounds also possess interesting photoluminescence properties with splitting emission peaks on excitation at 200 nm.

X-ray absorption spectroscopy and EPR studies of oriented spinach thylakoid preparations

DOE Office of Scientific and Technical Information (OSTI.GOV)

Andrews, J.C.

In this study, oriented Photosystem II (PS II) particles from spinach chloroplasts are studied with electron paramagnetic resonance (EPR) and x-ray absorption spectroscopy (XAS) to determine more details of the structure of the oxygen evolving complex (OEC). The nature of halide binding to Mn is also studied with Cl K-edge and Mn EXAFS (extended x-ray absorption fine structure) of Mn-Cl model compounds, and with Mn EXAFS of oriented PS II in which Br has replaced Cl. Attention is focused on the following: photosynthesis and the oxygen evolving complex; determination of mosaic spread in oriented photosystem II particles from signal IImore » EPR measurement; oriented EXAFS--studies of PS II in the S{sub 2} state; structural changes in PS II as a result of treatment with ammonia: EPR and XAS studies; studies of halide binding to Mn: Cl K-edge and Mn EXAFS of Mn-Cl model compounds and Mn EXAFS of oriented Br-treated photosystem II.« less

AN ADDITIVE EFFECT OF A MIXTURE OF AMMONIUM PERCHLORATE AND SODIUM CHLORATE ON PITUTARY-THYROID AXIS IN MALE F-344 RATS

EPA Science Inventory

An Additive Effect of a Mixture of Ammonium Perchlorate
and Sodium Chlorate on Pitutary-Thyroid Axis in Male F-344 Rats

Moazzam A. Khan 1,2,, 3Suzanne E. Fenton. 2Adam E. Swank, ZGeremy W. Knapp, 2Susan D.
Hester, and 2Douglas C. Wolf. 1NRC, 2Environmental Carcinog...

DICHLOROACETIC ACID (DCA) INHIBITS PROLIFERATION AND APOPTOSIS IN NORMAL HEPATOCYTES OF MALE F344 RATS

EPA Science Inventory

Dichloroacetic acid (DCA} inhibits proliferation and apoptosis in nonnal hepatocytes of
male F344 rats.

Large segments of the population are chronically exposed to dichloroacetic acid (DCA}: DCA is a by product of the chlorine disinfection of drinking water, a metab...

APOPTOSIS AND PROLIFERATION DURING DICHLOROACETIC ACID (DCA) INDUCED HEPTACELLULAR CARCINOGENESIS IN THE F344 MALE RAT

EPA Science Inventory

Apoptosis and Proliferation During DicWoroacetic Acid (DCA) Induced Hepatocellular
Carcinogenesis in the F344 Male Rat

Chlorine, introduced into public drinking \\\\'ater supplies for disinfection, can react with organic compounds in surface waters to form toxic by-prod...

Changes in charge density vs changes in formal oxidation states: The case of Sn halide perovskites and their ordered vacancy analogues

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dalpian, Gustavo M.; Liu, Qihang; Stoumpos, Constantinos C.

Shifting the Fermi energy in solids by doping, defect formation, or gating generally results in changes in the charge density distribution, which reflect the ability of the bonding pattern in solids to adjust to such external perturbations. In the traditional chemistry textbook, such changes are often described by the formal oxidation states (FOS) whereby a single atom type is presumed to absorb the full burden of the perturbation (change in charge) of the whole compound. In the present paper, we analyze the changes in the position-dependence charge density due to shifts of the Fermi energy on a general physical basis,more » comparing with the view of the FOS picture. We use the halide perovskites CsSnX3 (X = F, Cl, Br, I) as examples for studying the general principle. When the solar absorber CsSnI3 (termed 113) loses 50% of its Sn atoms, thereby forming the ordered vacancy compound Cs2SnI6 (termed 216), the Sn is said in the FOS picture to change from Sn(II) to Sn(IV). To understand the electronic properties of these two groups we studied the 113 and 216 compound pairs CsSnCl3 and Cs2SnCl6, CsSnBr3 and Cs2SnBr6, and CsSnI3 and Cs2SnI6, complementing them by CsSnF3 and Cs2SnF6 in the hypothetical cubic structure for completing the chemical trends. These materials were also synthesized by chemical routes and characterized by x-ray diffraction, 119Sn-Mössbauer spectroscopy, and K-edge x-ray absorption spectroscopy. We find that indeed in going from 113 to 216 (equivalent to the introduction of two holes per unit) there is a decrease in the s charge on Sn, in agreement with the FOS picture. However, at the same time, we observe an increase of the p charge via downshift of the otherwise unoccupied p level, an effect that tends to replenish much of the lost s charge. At the end, the change in the charge on the Sn site as a result of adding two holes to the unit cell is rather small. This effect is theoretically explained as a “self-regulating response” [Raebiger, Lany, and Zunger, Nature (London) 453, 763 (2008)] whereby the system rehybridizes to minimize the effect of the charge perturbation created by vacancy formation. Rather than having a single preselected atom (here Sn) absorb the full brunt of the perturbation producing two holes, we find that the holes are distributed in a complex pattern throughout the octahedral systems of X6 ligands, forming hole orbitals with some specific symmetries. This clarifies the relation between FOS and charge transfer that can be applied to a wide variety of materials.« less