Atmospheric reaction of Cl + methacrolein: a theoretical study on the mechanism, and pressure- and temperature-dependent rate constants.

Science.gov (United States)

Sun, Cuihong; Xu, Baoen; Zhang, Shaowen

2014-05-22

Methacrolein is a major degradation product of isoprene, the reaction of methacrolein with Cl atoms may play some roles in the degradation of isoprene where these species are relatively abundant. However, the energetics and kinetics of this reaction, which govern the reaction branching, are still not well understood so far. In the present study, two-dimensional potential energy surfaces were constructed to analyze the minimum energy path of the barrierless addition process between Cl and the C═C double bond of methacrolein, which reveals that the terminal addition intermediate is directly formed from the addition reaction. The terminal addition intermediate can further yield different products among which the reaction paths abstracting the aldehyde hydrogen atom and the methyl hydrogen atom are dominant reaction exits. The minimum reaction path for the direct aldehydic hydrogen atom abstraction is also obtained. The reaction kinetics was calculated by the variational transition state theory in conjunction with the master equation method. From the theoretical model we predicted that the overall rate constant of the Cl + methacrolein reaction at 297 K and atmospheric pressure is koverall = 2.3× 10(-10) cm(3) molecule(-1) s(-1), and the branching ratio of the aldehydic hydrogen abstraction is about 12%. The reaction is pressure dependent at P pressure limit at about 100 Torr. The calculated results could well account for the experimental observations.

Experimental Charge Density Study of Trichromium Linear Metal String Complex – Cr3(dpa)4Cl2

DEFF Research Database (Denmark)

Wu, Lai-Chin; Cheng, Ming-Chuan; Thomsen, Maja Krüger

An experimental and theoretical charge density study, based on Bader’s Quantum Theory: Atoms in Molecule (QTAIM), on a trichromium metal string complex, Cr3(dpa)4Cl2(C2H5OC2H5)x(CH2Cl2)1-x (1, dpa- = bis(2-pyridyl)amido)) is performed. The structure and multipole model of 1 are performed by using...... experimental X-ray diffraction data which are collected at both 100 K using conventional X-ray source (DS1) and 15 K using synchrotron source (DS2). The three chromium metal string is bridged by four dpa- ligands. These tri-chromium metal ions are bonded to each other and terminated by two Cl- ions on the both...... ends, forming a [Cl(1)Cr(1)Cr(2)Cr(3)Cl(2)] linear string. Each Cr atoms are coordinated by four N atoms of each dpa- ligand. This metal string is slightly unsymmetrical at both data sets. The bond distance, from DS1 (DS2), of Cr(1)Cr(2), 2.3480(2) (2.3669(1)) Å, is 0.03 (0.003) Å shorter than Cr...

Recombination of chlorine atoms on plasma-conditioned stainless steel surfaces in the presence of adsorbed Cl{sub 2}

Energy Technology Data Exchange (ETDEWEB)

Stafford, Luc; Poirier, Jean-Sebastien; Margot, Joelle [Departement de Physique, Universite de Montreal, Montreal, Quebec, H3C 3J7 (Canada); Khare, Rohit; Guha, Joydeep; Donnelly, Vincent M, E-mail: luc.stafford@umontreal.c, E-mail: vmdonnelly@uh.ed [Department of Chemical and Biomolecular Engineering, University of Houston, Houston, TX 77204 (United States)

2009-03-07

We investigated the interactions of atomic and molecular chlorine with plasma-conditioned stainless steel surfaces through both experiments and modelling. The recombination of Cl during adsorption and desorption of Cl{sub 2} was characterized using a rotating-substrate technique in which portions of the cylindrical substrate surface are periodically exposed to an inductively coupled chlorine plasma and then to an Auger electron spectrometer in separate, differentially pumped chambers. After several hours of exposure to the Cl{sub 2} plasma, the stainless steel substrate became coated with a Si-oxychloride-based layer (Fe : Si : O : Cl {approx} 1 : 13 : 13 : 3) due to chlorine adsorption and the erosion of the silica discharge tube. Desorption of Cl{sub 2} from this surface was monitored through measurements of pressure rises in the Auger chamber as a function of substrate rotation frequency. Significant adsorption and desorption of Cl{sub 2} was observed with the plasma off, similar to that observed previously on plasma-conditioned anodized aluminium surfaces, but with much faster desorption rates that are most likely attributable to the smoother and non-porous stainless steel surface morphology. When the plasma was turned on, a much larger pressure rise was observed due to Langmuir-Hinshelwood recombination of Cl atoms. Recombination coefficients, {gamma}{sub Cl}, ranged from 0.004 to 0.03 and increased with Cl-to-Cl{sub 2} number density ratio. This behaviour was observed previously for anodized aluminium surfaces, and was explained by the blocking of Cl recombination sites by adsorbed Cl{sub 2}. Application of this variable recombination coefficient to the modelling of high-density chlorine plasmas gives a much better agreement with measured Cl{sub 2} percent dissociations compared with predictions obtained with a recombination coefficient that is independent of plasma conditions.

Atomistics of Ge deposition on Si(100) by atomic layer epitaxy.

Science.gov (United States)

Lin, D S; Wu, J L; Pan, S Y; Chiang, T C

2003-01-31

Chlorine termination of mixed Ge/Si(100) surfaces substantially enhances the contrast between Ge and Si sites in scanning tunneling microscopy observations. This finding enables a detailed investigation of the spatial distribution of Ge atoms deposited on Si(100) by atomic layer epitaxy. The results are corroborated by photoemission measurements aided by an unusually large chemical shift between Cl adsorbed on Si and Ge. Adsorbate-substrate atomic exchange during growth is shown to be important. The resulting interface is thus graded, but characterized by a very short length scale of about one monolayer.

Moderation and absorption effects on hot replacement reactions of 38Cl atoms in mixtures of ortho-dichlorobenzene and hexafluorobenzene

International Nuclear Information System (INIS)

Berei, K.; Gado, J.; Kereszturi, A.; Szatmary, Z.; Vass, Sz.

1989-10-01

Conditions are given for the equivalence of the Estrup-Wolfgang description of the hot atom reaction kinetics with the first-order Hurwitz approximation in the neutron slowing down theory. Conclusions are drawn for the applicability of this approach for describing hot atom replacement processes in reactive mixtures. Analytical and numerical calculations were carried out to explain an unusual concentration dependence of 38 Cl-for-Cl substitution, found experimentally in liquid binary mixtures of ortho-dichlorobenzene and hexafluorobenzene. (author) 39 refs.; 4 figs.; 2 tabs

Transformation mechanism of n-butyl terminated Si nanoparticles embedded into Si1-xCx nanocomposites mixed with Si nanoparticles and C atoms

International Nuclear Information System (INIS)

Shin, J.W.; Oh, D.H.; Kim, T.W.; Cho, W.J.

2009-01-01

Bright-field transmission electron microscopy (TEM) images, high-resolution TEM (HRTEM) images, and fast-Fourier transformed electron-diffraction patterns showed that n-butyl terminated Si nanoparticles were aggregated. The formation of Si 1-x C x nanocomposites was mixed with Si nanoparticles and C atoms embedded in a SiO 2 layer due to the diffusion of C atoms from n-butyl termination shells into aggregated Si nanoparticles. Atomic force microscopy (AFM) images showed that the Si 1-x C x nanocomposites mixed with Si nanoparticles and C atoms existed in almost all regions of the SiO 2 layer. The formation mechanism of Si nanoparticles and the transformation mechanism of n-butyl terminated Si nanoparticles embedded into Si 1-x C x nanocomposites mixed with Si nanoparticles and C atoms are described on the basis of the TEM, HRTEM, and AFM results. These results can help to improve the understanding of the formation mechanism of Si nanoparticles.

Selective coupling reaction between 2,6-diiodoanisoles and terminal alkynes catalyzed by Pd(PPh32Cl2 and CuI

Directory of Open Access Journals (Sweden)

Allan F. C. Rossini

2012-06-01

Full Text Available The cross-coupling reaction between aryl halides and terminal alkynes, catalyzed by palladium complexes and copper (I salts, consists in an efficient synthetic tool for the formation of C-C bonds, resulting in disubstituted acetylenic compounds. Accordingly, in this work we present our preliminary results involving the selective cross-coupling reaction between 2,6-diiodoanisoles and terminal alkynes, catalyzed by Pd(PPh32Cl2 and CuI, in the formation of 2-iodo-alkynylanisoles (scheme 1.

Investigations of the stability of the neutral silver atom in Nasub(x)Agsub(1-x)Cl-mixed crystals by EPR-spectroscopy

International Nuclear Information System (INIS)

Muessig, T.; Granzer, F.

1983-01-01

In most of the theories of the photographic process in the classical silver halide systems, the neutral silver atom, Ag 0 , still plays an important role. Up till now, however, all attempts failed to detect the Ag 0 in pure AgCl and AgBr, while its detection in NaCl, weakly doped with Ag does not impose any problems applying EPR-spectroscopy. Benefiting from some peculiarities of the NaCl-AgCl-phase diagram, Nasub(x)Agsub(1-x)Cl-mixed crystals were grown and the stability of the Ag 0 -centre was followed by EPR-measurements. From the results obtained by gradually augmenting the Ag-content up to 30 mol.% and cooling down the crystals to 20 K, there seems to be only little chance, to detect the neutral silver atom in pure AgCl, even at very low temperatures by EPR-spectroscopy. Simultaneously the-EPR signal of the Ag 2 + -centre was studied and the occurrence of a very strong EPR-line at g = 1.88 in decomposed mixed crystals was interpreted. (author)

Interplay of intra-atomic and interatomic effects: An investigation of the 2p core level spectra of atomic Fe and molecular FeCl2

International Nuclear Information System (INIS)

Richter, T.; Wolff, T.; Zimmermann, P.; Godehusen, K.; Martins, M.

2004-01-01

The 2p photoabsorption and photoelectron spectra of atomic Fe and molecular FeCl 2 were studied by photoion and photoelectron spectroscopy using monochromatized synchrotron radiation and atomic or molecular beam technique. The atomic spectra were analyzed with configuration interaction calculations yielding excellent agreement between experiment and theory. For the analysis of the molecular photoelectron spectrum which shows pronounced interatomic effects, a charge transfer model was used, introducing an additional 3d 7 configuration. The resulting good agreement between the experimental and theoretical spectrum and the remarkable similarity of the molecular with the corresponding spectrum in the solid phase opens a way to a better understanding of the interplay of the interatomic and intra-atomic interactions in the 2p core level spectra of the 3d metal compounds

Kinetics and Mechanism of the Gas-Phase Reaction of Selected Carbonyls with Cl Atoms between 250 and 340 K

Science.gov (United States)

Hasson, A. S.; Algrim, L.; Abdelhamid, A.; Tyndall, G. S.; Orlando, J. J.

2013-12-01

Carbonyls are important products from the gas phase degradation of most volatile organic compounds. Their atmospheric reactions therefore have a significant impact on atmospheric composition, particularly in aged air masses. While the reactions of short-chain linear carbonyls are well understood, the chemistry of larger (> C6) and branched carbonyl is more uncertain. To provide insight into these reactions, the reactions of three carbonyls (methyl isopropyl ketone, MIK; di-isopropyl ketone, DIK; and diethyl ketone, DEK) with chlorine atoms were investigated between 250 and 340 K and 1 atm in the presence and absence of NOx and an HO2 source (methanol). Experiments were performed in a photochemical reactor using a combination of long-path Fourier transform infra-red spectroscopy, proton transfer reaction mass spectrometry and gas chromatography with flame ionization detection. The kinetics were studied using the relative rate technique with butanone and isopropanol as the reference compounds. The Arrhenius expression for the three rate coefficients was determined to be k(DEK+Cl) = 3.87 x 10-11e(2 × 7 kJ/mol)/RT cm3 molecules-1 s-1 , k(MIPK+Cl) = 7.20 x 10-11e(0.2× 8 kJ/mol)/RT cm3 molecules-1 s-1 , and k(DIPK+Cl) = 3.33 x 10-10e(-3× 8 kJ/mol)/RT cm3 molecules-1 s-1 . Measured reaction products accounted for 38-72 % of the reacted carbon and were consistent with strong deactivation of the carbon atom adjacent to the carbonyl group with respect to H-atom abstraction by Cl atoms. The product distributions also provide insight into radical recycling from the organic peroxy + HO2 reaction, and the relative rates of isomerization, fragmentation and reaction with O2 for carbonyl-containing alkoxy radicals. Implications of these results will be discussed.

Polarizabilities and hyperpolarizabilities for the atoms Al, Si, P, S, Cl, and Ar: Coupled cluster calculations.

Science.gov (United States)

Lupinetti, Concetta; Thakkar, Ajit J

2005-01-22

Accurate static dipole polarizabilities and hyperpolarizabilities are calculated for the ground states of the Al, Si, P, S, Cl, and Ar atoms. The finite-field computations use energies obtained with various ab initio methods including Moller-Plesset perturbation theory and the coupled cluster approach. Excellent agreement with experiment is found for argon. The experimental alpha for Al is likely to be in error. Only limited comparisons are possible for the other atoms because hyperpolarizabilities have not been reported previously for most of these atoms. Our recommended values of the mean dipole polarizability (in the order Al-Ar) are alpha/e(2)a(0) (2)E(h) (-1)=57.74, 37.17, 24.93, 19.37, 14.57, and 11.085 with an error estimate of +/-0.5%. The recommended values of the mean second dipole hyperpolarizability (in the order Al-Ar) are gamma/e(4)a(0) (4)E(h) (-3)=2.02 x 10(5), 4.31 x 10(4), 1.14 x 10(4), 6.51 x 10(3), 2.73 x 10(3), and 1.18 x 10(3) with an error estimate of +/-2%. Our recommended polarizability anisotropy values are Deltaalpha/e(2)a(0) (2)E(h) (-1)=-25.60, 8.41, -3.63, and 1.71 for Al, Si, S, and Cl respectively, with an error estimate of +/-1%. The recommended hyperpolarizability anisotropies are Deltagamma/e(4)a(0) (4)E(h) (-3)=-3.88 x 10(5), 4.16 x 10(4), -7.00 x 10(3), and 1.65 x 10(3) for Al, Si, S, and Cl, respectively, with an error estimate of +/-4%. (c) 2005 American Institute of Physics.

Atomic-layer deposition of silicon nitride

CERN Document Server

Yokoyama, S; Ooba, K

1999-01-01

Atomic-layer deposition (ALD) of silicon nitride has been investigated by means of plasma ALD in which a NH sub 3 plasma is used, catalytic ALD in which NH sub 3 is dissociated by thermal catalytic reaction on a W filament, and temperature-controlled ALD in which only a thermal reaction on the substrate is employed. The NH sub 3 and the silicon source gases (SiH sub 2 Cl sub 2 or SiCl sub 4) were alternately supplied. For all these methods, the film thickness per cycle was saturated at a certain value for a wide range of deposition conditions. In the catalytic ALD, the selective deposition of silicon nitride on hydrogen-terminated Si was achieved, but, it was limited to only a thin (2SiO (evaporative).

Carboxyl-terminal Truncations of ClC-Kb Abolish Channel Activation by Barttin Via Modified Common Gating and Trafficking.

Science.gov (United States)

Stölting, Gabriel; Bungert-Plümke, Stefanie; Franzen, Arne; Fahlke, Christoph

2015-12-18

ClC-K chloride channels are crucial for auditory transduction and urine concentration. Mutations in CLCNKB, the gene encoding the renal chloride channel hClC-Kb, cause Bartter syndrome type III, a human genetic condition characterized by polyuria, hypokalemia, and alkalosis. In recent years, several Bartter syndrome-associated mutations have been described that result in truncations of the intracellular carboxyl terminus of hClC-Kb. We here used a combination of whole-cell patch clamp, confocal imaging, co-immunoprecipitation, and surface biotinylation to study the functional consequences of a frequent CLCNKB mutation that creates a premature stop codon at Trp-610. We found that W610X leaves the association of hClC-Kb and the accessory subunit barttin unaffected, but impairs its regulation by barttin. W610X attenuates hClC-Kb surface membrane insertion. Moreover, W610X results in hClC-Kb channel opening in the absence of barttin and prevents further barttin-mediated activation. To describe how the carboxyl terminus modifies the regulation by barttin we used V166E rClC-K1. V166E rClC-K1 is active without barttin and exhibits prominent, barttin-regulated voltage-dependent gating. Electrophysiological characterization of truncated V166E rClC-K1 demonstrated that the distal carboxyl terminus is necessary for slow cooperative gating. Since barttin modifies this particular gating process, channels lacking the distal carboxyl-terminal domain are no longer regulated by the accessory subunit. Our results demonstrate that the carboxyl terminus of hClC-Kb is not part of the binding site for barttin, but functionally modifies the interplay with barttin. The loss-of-activation of truncated hClC-Kb channels in heterologous expression systems fully explains the reduced basolateral chloride conductance in affected kidneys and the clinical symptoms of Bartter syndrome patients. © 2015 by The American Society for Biochemistry and Molecular Biology, Inc.

Carboxyl-terminal Truncations of ClC-Kb Abolish Channel Activation by Barttin Via Modified Common Gating and Trafficking*

Science.gov (United States)

Stölting, Gabriel; Bungert-Plümke, Stefanie; Franzen, Arne; Fahlke, Christoph

2015-01-01

ClC-K chloride channels are crucial for auditory transduction and urine concentration. Mutations in CLCNKB, the gene encoding the renal chloride channel hClC-Kb, cause Bartter syndrome type III, a human genetic condition characterized by polyuria, hypokalemia, and alkalosis. In recent years, several Bartter syndrome-associated mutations have been described that result in truncations of the intracellular carboxyl terminus of hClC-Kb. We here used a combination of whole-cell patch clamp, confocal imaging, co-immunoprecipitation, and surface biotinylation to study the functional consequences of a frequent CLCNKB mutation that creates a premature stop codon at Trp-610. We found that W610X leaves the association of hClC-Kb and the accessory subunit barttin unaffected, but impairs its regulation by barttin. W610X attenuates hClC-Kb surface membrane insertion. Moreover, W610X results in hClC-Kb channel opening in the absence of barttin and prevents further barttin-mediated activation. To describe how the carboxyl terminus modifies the regulation by barttin we used V166E rClC-K1. V166E rClC-K1 is active without barttin and exhibits prominent, barttin-regulated voltage-dependent gating. Electrophysiological characterization of truncated V166E rClC-K1 demonstrated that the distal carboxyl terminus is necessary for slow cooperative gating. Since barttin modifies this particular gating process, channels lacking the distal carboxyl-terminal domain are no longer regulated by the accessory subunit. Our results demonstrate that the carboxyl terminus of hClC-Kb is not part of the binding site for barttin, but functionally modifies the interplay with barttin. The loss-of-activation of truncated hClC-Kb channels in heterologous expression systems fully explains the reduced basolateral chloride conductance in affected kidneys and the clinical symptoms of Bartter syndrome patients. PMID:26453302

{sup 36}Cl exposure dating with a 3-MV tandem

Energy Technology Data Exchange (ETDEWEB)

Steier, Peter, E-mail: peter.steier@univie.ac.a [VERA Laboratory, Fakultaet fuer Physik - Isotopenforschung, Universitaet Wien, Waehringer Strasse 17, A-1090 Wien (Austria); HPK H 31, Institut fuer Teilchenphysik, ETH Zuerich, Schafmattstr. 20 CH-8093 Zuerich (Switzerland); Forstner, Oliver; Golser, Robin; Kutschera, Walter; Martschini, Martin [VERA Laboratory, Fakultaet fuer Physik - Isotopenforschung, Universitaet Wien, Waehringer Strasse 17, A-1090 Wien (Austria); HPK H 31, Institut fuer Teilchenphysik, ETH Zuerich, Schafmattstr. 20 CH-8093 Zuerich (Switzerland); Merchel, Silke [CEREGE, CNRS-IRD-Universite Aix-Marseille, Europole Mediterraneen de L' Arbois, 13545 Aix-en-Provence (France); Forschungszentrum Dresden-Rossendorf, D-01314 Dresden (Germany); HPK H 31, Institut fuer Teilchenphysik, ETH Zuerich, Schafmattstr. 20 CH-8093 Zuerich (Switzerland); Orlowski, Tobias; Priller, Alfred [VERA Laboratory, Fakultaet fuer Physik - Isotopenforschung, Universitaet Wien, Waehringer Strasse 17, A-1090 Wien (Austria); HPK H 31, Institut fuer Teilchenphysik, ETH Zuerich, Schafmattstr. 20 CH-8093 Zuerich (Switzerland); Vockenhuber, Christof [Forschungszentrum Dresden-Rossendorf, D-01314 Dresden (Germany); HPK H 31, Institut fuer Teilchenphysik, ETH Zuerich, Schafmattstr. 20 CH-8093 Zuerich (Switzerland); Wallner, Anton [VERA Laboratory, Fakultaet fuer Physik - Isotopenforschung, Universitaet Wien, Waehringer Strasse 17, A-1090 Wien (Austria); HPK H 31, Institut fuer Teilchenphysik, ETH Zuerich, Schafmattstr. 20 CH-8093 Zuerich (Switzerland)

2010-04-15

{sup 36}Cl AMS measurements at natural isotopic concentrations have yet been performed only at tandem accelerators with 5 MV terminal voltage or beyond. We have developed a method to detect {sup 36}Cl at natural terrestrial isotopic concentrations with a 3-MV system, operated above specifications at 3.5 MV. An effective separation was obtained with an optimized split-anode ionization chamber design (adopted from the ETH/PSI Zurich AMS group), providing a suppression factor of up to 30,000 for the interfering isobar {sup 36}S. Despite the good separation, a relatively high sulfur output from the ion source ({sup 36}S{sup -}/{sup 35}Cl{sup -} approx 4 x 10{sup -10} for samples prepared from chemically pure reagents), and a possibly cross contamination resulted in a background corresponding to {sup 36}Cl/Cl approx 3 x 10{sup -14}. The method was applied to samples containing between 10{sup 5} and 10{sup 6} atoms {sup 36}Cl/g rock from sites in Italy and Iran, which were already investigated by other laboratories for surface exposure dating. The {sup 36}Cl/Cl ratios in the range from 2 x 10{sup -13} to 5 x 10{sup -12} show a generally good agreement with the previous results. These first measurements demonstrate that also 3-MV tandems, constituting the majority of dedicated AMS facilities, are capable of {sup 36}Cl exposure dating, which is presently the domain of larger facilities.

Density functional study of manganese atom adsorption on hydrogen-terminated armchair boron nitride nanoribbons

Energy Technology Data Exchange (ETDEWEB)

Abdullahi, Yusuf Zuntu [Department of Physics, Faculty of Science, Universiti Putra Malaysia, 43400 UPM Serdang, Selangor (Malaysia); Department of Physics, Faculty of Science, Kaduna State University, P.M.B. 2339, Kaduna State (Nigeria); Rahman, Md. Mahmudur, E-mail: mahmudur@upm.edu.my [Department of Physics, Faculty of Science, Universiti Putra Malaysia, 43400 UPM Serdang, Selangor (Malaysia); Shuaibu, Alhassan [Department of Physics, Faculty of Science, Universiti Putra Malaysia, 43400 UPM Serdang, Selangor (Malaysia); Department of Physics, Faculty of Science, Nigerian Defence Academy, P.M.B 2109 Kaduna (Nigeria); Abubakar, Shamsu [Department of Physics, Faculty of Science, Universiti Putra Malaysia, 43400 UPM Serdang, Selangor (Malaysia); Department of Physics, Faculty of Science, Yobe State University, P.M.B. 1144, Yobe State (Nigeria); Zainuddin, Hishamuddin [Department of Physics, Faculty of Science, Universiti Putra Malaysia, 43400 UPM Serdang, Selangor (Malaysia); Institute for Mathematical Research, Universiti Putra Malaysia, 43400 UPM Serdang, Selangor (Malaysia); Muhida, Rifki [Department of Physics-Energy Engineering, Surya University, Gedung 01 Scientia Business Park, Jl. Boulevard Gading Serpong Blok O/1, Summarecon Serpong, Tangerang 15810, Banten (Indonesia); Setiyanto, Henry [Analytical Chemistry Research Group, Faculty of Mathematics and Natural Sciences, Institut Teknologi Bandung, Jl. Ganesha no. 10, Bandung 40132 (Indonesia)

2014-08-15

In this paper, we have investigated stable structural, electric and magnetic properties of manganese (Mn) atom adsorption on armchair hydrogen edge-terminated boron nitride nanoribbon (A-BNNRs) using first principles method based on density-functional theory with the generalized gradient approximation. Calculation shows that Mn atom situated on the ribbons of A-BNNRs is the most stable configuration, where the bonding is more pronounced. The projected density of states (PDOS) of the favored configuration has also been computed. It has been found that the covalent bonding of boron (B), nitrogen (N) and Mn is mainly contributed by s, d like-orbitals of Mn and partially occupied by the 2p like-orbital of N. The difference in energy between the inner and the edge adsorption sites of A-BNNRs shows that Mn atoms prefer to concentrate at the edge sites. The electronic structures of the various configurations are wide, narrow-gap semiconducting and half-metallic, and the magnetic moment of Mn atoms are well preserved in all considered configurations. This has shown that the boron nitride (BN) sheet covered with Mn atoms demonstrates additional information on its usefulness in future spintronics, molecular magnet and nanoelectronics devices.

Density functional study of manganese atom adsorption on hydrogen-terminated armchair boron nitride nanoribbons

International Nuclear Information System (INIS)

Abdullahi, Yusuf Zuntu; Rahman, Md. Mahmudur; Shuaibu, Alhassan; Abubakar, Shamsu; Zainuddin, Hishamuddin; Muhida, Rifki; Setiyanto, Henry

2014-01-01

In this paper, we have investigated stable structural, electric and magnetic properties of manganese (Mn) atom adsorption on armchair hydrogen edge-terminated boron nitride nanoribbon (A-BNNRs) using first principles method based on density-functional theory with the generalized gradient approximation. Calculation shows that Mn atom situated on the ribbons of A-BNNRs is the most stable configuration, where the bonding is more pronounced. The projected density of states (PDOS) of the favored configuration has also been computed. It has been found that the covalent bonding of boron (B), nitrogen (N) and Mn is mainly contributed by s, d like-orbitals of Mn and partially occupied by the 2p like-orbital of N. The difference in energy between the inner and the edge adsorption sites of A-BNNRs shows that Mn atoms prefer to concentrate at the edge sites. The electronic structures of the various configurations are wide, narrow-gap semiconducting and half-metallic, and the magnetic moment of Mn atoms are well preserved in all considered configurations. This has shown that the boron nitride (BN) sheet covered with Mn atoms demonstrates additional information on its usefulness in future spintronics, molecular magnet and nanoelectronics devices.

N-Chlorosuccinimide (NCS): A Novel Initiator for Atom Transfer Radical Polymerization of Methyl Methacrylate

Institute of Scientific and Technical Information of China (English)

WANG,Xia-Yan; CHANG,Li-Qun; ZHOU,Hong; ZHANG,Ke-Da

2006-01-01

Atom transfer radical polymerization (ATRP) of methyl methacrylate (MMA) was achieved, using N-chlorosuccinimide (NCS) as an initiator together with catalytic system CuCl/PMDETA (N,N,N',N',N"-pentamethyldiethyl-enetriamine), CuCl/MA5-DETA (N,N,N',N',N"-penta(methylacrylate)diethylenetriamine), and CuCl/bipy (bipy=2,2'-bipyridyl) respectively. The results indicated that the polymerization possessed typical controlled/living radical polymerization characteristics. The analysis for terminal group of obtained polymer by 1H NMR proved that NCS is an initiator for ATRP. In comparison with NBS, the polymerization rate was slower and the resulted polymer had narrower molecular weight distribution (MWD) when NCS was employed as the initiator.

Surface structure and reaction property of CuCl2-PdCl2 bimetallic catalyst in methanol oxycarbonylation: A DFT approach

International Nuclear Information System (INIS)

Meng, Qingsen; Wang, Shengping; Shen, Yongli; Yan, Bing; Wu, Yuanxin; Ma, Xinbin

2014-01-01

Surface structure of CuCl 2 -PdCl 2 bimetallic catalyst (Wacker-type catalyst) was built employing density functional theory (DFT) calculations, and the reaction mechanism of methanol oxycarbonylation over the CuCl 2 -PdCl 2 surfaces was also investigated. On the CuCl 2 -PdCl 2 surface, the active site for methanol oxidation was confirmed as Cu-Cl-Cu (Pd). Comparing with pure CuCl 2 surface, the introduction of Pd atom causes the electron repopulation on the surface and lowers the energy barrier for methanol oxidation, but the number of the active site decreases with the increasing of Pd doping volume. Agreed with previous experimental results, the Pd site is most favorable for the CO insertion, indicated by the lowest activation barrier for the formation of COOCH 3 on Pd atom. The lowest energy barrier for the formation of DMC appears when COOCH 3 species adsorbed on Pd atom and methoxyl adsorbed on Cu atoms, which is 0.42 eV. Finally, the reconstruction of the unsaturated surface is a spontaneous and exothermic process. Comparing with other surfaces, the rate-limiting step, methanol oxidation, on CuCl 2 -PdCl 2 surface with Pd/Cu = 1:17 has the lowest energy barrier, which is agreed with the experimental observation that PdCl 2 -CuCl 2 catalyst with Pd/Cu = 1:20 has the favorable activity. The adsorbed methoxyl will further lower the activation barrier of methanol oxidation, which is agreed with experimental observation that the Wacker-type catalysts have an induction period in the methanol oxidative carbonylation system.

Atomic-scale observation of structural and electronic orders in the layered compound ?-RuCl3

OpenAIRE

Ziatdinov, M.; Banerjee, A.; Maksov, A.; Berlijn, T.; Zhou, W.; Cao, H. B.; Yan, J.-Q.; Bridges, C. A.; Mandrus, D. G.; Nagler, S. E.; Baddorf, A. P.; Kalinin, S. V.

2016-01-01

A pseudospin-1/2 Mott phase on a honeycomb lattice is proposed to host the celebrated two-dimensional Kitaev model which has an elusive quantum spin liquid ground state, and fascinating physics relevant to the development of future templates towards topological quantum bits. Here we report a comprehensive, atomically resolved real-space study by scanning transmission electron and scanning tunnelling microscopies on a novel layered material displaying Kitaev physics, ?-RuCl3. Our local crystal...

Osteogenic cell differentiation on H-terminated and O-terminated nanocrystalline diamond films

Directory of Open Access Journals (Sweden)

Liskova J

2015-01-01

Full Text Available Jana Liskova,1 Oleg Babchenko,2 Marian Varga,2 Alexander Kromka,2 Daniel Hadraba,1 Zdenek Svindrych,1 Zuzana Burdikova,1 Lucie Bacakova1 1Institute of Physiology, Academy of Sciences of the Czech Republic, Prague, Czech Republic; 2Institute of Physics, Academy of Sciences of the Czech Republic, Prague, Czech Republic Abstract: Nanocrystalline diamond (NCD films are promising materials for bone implant coatings because of their biocompatibility, chemical resistance, and mechanical hardness. Moreover, NCD wettability can be tailored by grafting specific atoms. The NCD films used in this study were grown on silicon substrates by microwave plasma-enhanced chemical vapor deposition and grafted by hydrogen atoms (H-termination or oxygen atoms (O-termination. Human osteoblast-like Saos-2 cells were used for biological studies on H-terminated and O-terminated NCD films. The adhesion, growth, and subsequent differentiation of the osteoblasts on NCD films were examined, and the extracellular matrix production and composition were quantified. The osteoblasts that had been cultivated on the O-terminated NCD films exhibited a higher growth rate than those grown on the H-terminated NCD films. The mature collagen fibers were detected in Saos-2 cells on both the H-terminated and O-terminated NCD films; however, the quantity of total collagen in the extracellular matrix was higher on the O-terminated NCD films, as were the amounts of calcium deposition and alkaline phosphatase activity. Nevertheless, the expression of genes for osteogenic markers – type I collagen, alkaline phosphatase, and osteocalcin – was either comparable on the H-terminated and O-terminated films or even lower on the O-terminated films. In conclusion, the higher wettability of the O-terminated NCD films is promising for adhesion and growth of osteoblasts. In addition, the O-terminated surface also seems to support the deposition of extracellular matrix proteins and extracellular matrix

Atmospheric chemistry of trans-CF3CH=CHCl: Kinetics of the gas-phase reactions with Cl atoms, OH radicals, and O3

DEFF Research Database (Denmark)

Andersen, Mads Peter Sulbaek; Nilsson, Elna Johanna Kristina; Nielsen, Ole John

2008-01-01

Long path length Fourier transform infrared (FTIR)–smog chamber techniques were used to study the kinetics of the gas-phase reactions of Cl atoms, OH radicals and O3 with trans-3,3,3-trifluoro-1-chloropropene, t-CF3CH CHCl, in 700 Torr total pressure at 295±2K. Values of k(Cl + t-CF3CH CHCl) = (5...

Ab initio study of F- and Cl-functionalized single wall carbon nanotubes

International Nuclear Information System (INIS)

Pan, H; Feng, Y P; Lin, J Y

2006-01-01

First-principles calculations were carried out to study the functionalization of single wall carbon nanotubes by the chemical absorption of F and Cl atoms. Our results confirmed that the band gap of semiconductor zigzag carbon nanotubes is reduced on addition of F or Cl atoms on the walls of the nanotubes. For metallic armchair nanotubes, the doubly degenerate states crossing the Fermi level were separated by the introduction of F or Cl atoms. An additional energy level emerged near the Fermi level, due to coupling between the carbon nanotube and the F or Cl atom. For zigzag nanotubes, charge transfers of 0.27e from the tube to the Cl atom and of 0.41e to the F atom took place, while for armchair nanotubes, the charge transfers from the nanotube to Cl and F are 0.25 and 0.42e, respectively. The Cl-C and F-C bond lengths were found to be 2.09 and 1.49 A, respectively. The systems show semiconducting behaviour when charged with one electron per halogen atom, but remain metallic under hole injection, regardless of the chirality of the carbon nanotubes

A Three-Step Atomic Layer Deposition Process for SiN x Using Si2Cl6, CH3NH2, and N2 Plasma.

Science.gov (United States)

Ovanesyan, Rafaiel A; Hausmann, Dennis M; Agarwal, Sumit

2018-06-06

We report a novel three-step SiN x atomic layer deposition (ALD) process using Si 2 Cl 6 , CH 3 NH 2 , and N 2 plasma. In a two-step process, nonhydrogenated chlorosilanes such as Si 2 Cl 6 with N 2 plasmas lead to poor-quality SiN x films that oxidize rapidly. The intermediate CH 3 NH 2 step was therefore introduced in the ALD cycle to replace the NH 3 plasma step with a N 2 plasma, while using Si 2 Cl 6 as the Si precursor. This three-step process lowers the atomic H content and improves the film conformality on high-aspect-ratio nanostructures as Si-N-Si bonds are formed during a thermal CH 3 NH 2 step in addition to the N 2 plasma step. During ALD, the reactive surface sites were monitored using in situ surface infrared spectroscopy. Our infrared spectra show that, on the post-N 2 plasma-treated SiN x surface, Si 2 Cl 6 reacts primarily with the surface -NH 2 species to form surface -SiCl x ( x = 1, 2, or 3) bonds, which are the reactive sites during the CH 3 NH 2 cycle. In the N 2 plasma step, reactive -NH 2 surface species are created because of the surface H available from the -CH 3 groups. At 400 °C, the SiN x films have a growth per cycle of ∼0.9 Å with ∼12 atomic percent H. The films grown on high-aspect-ratio nanostructures have a conformality of ∼90%.

HOCl and Cl2 observations in marine air

Directory of Open Access Journals (Sweden)

R. Sommariva

2011-08-01

Full Text Available Cl atoms in the marine atmosphere may significantly impact the lifetimes of methane and other hydrocarbons. However, the existing estimates of Cl atom levels in marine air are based on indirect evidence. Here we present measurements of the Cl precursors HOCl and Cl2 in the marine boundary layer during June of 2009 at the Cape Verde Atmospheric Observatory in the eastern tropical Atlantic. These are the first measurements of tropospheric HOCl. HOCl and Cl2 levels were low in air with open ocean back trajectories, with maximum levels always below 60 and 10 ppt (pmol/mol, respectively. In air with trajectories originating over Europe, HOCl and Cl2 levels were higher, with HOCl maxima exceeding 100 ppt each day and Cl2 reaching up to 35 ppt. The increased Cl cycling associated with long distance pollutant transport over the oceans likely impacts a wide geographic area and represents a mechanism by which human activities have increased the reactivity of the marine atmosphere. Data-constrained model simulations indicate that Cl atoms account for approximately 15 % of methane destruction on days when aged polluted air arrives at the site. A photochemical model does not adequately simulate the observed abundances of HOCl and Cl2, raising the possibility of an unknown HOCl source.

Surface structure and reaction property of CuCl{sub 2}-PdCl{sub 2} bimetallic catalyst in methanol oxycarbonylation: A DFT approach

Energy Technology Data Exchange (ETDEWEB)

Meng, Qingsen [Key Laboratory for Green Chemical Technology of Ministry of Education, Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), School of Chemical Engineering and Technology, Tianjin University, Tianjin 300072 (China); Wang, Shengping, E-mail: spwang@tju.edu.cn [Key Laboratory for Green Chemical Technology of Ministry of Education, Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), School of Chemical Engineering and Technology, Tianjin University, Tianjin 300072 (China); Shen, Yongli; Yan, Bing [Key Laboratory for Green Chemical Technology of Ministry of Education, Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), School of Chemical Engineering and Technology, Tianjin University, Tianjin 300072 (China); Wu, Yuanxin [School of Chemical Engineering and Pharmacy, Wuhan Institute of Technology, Wuhan 430073 (China); Ma, Xinbin [Key Laboratory for Green Chemical Technology of Ministry of Education, Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), School of Chemical Engineering and Technology, Tianjin University, Tianjin 300072 (China)

2014-02-15

Surface structure of CuCl{sub 2}-PdCl{sub 2} bimetallic catalyst (Wacker-type catalyst) was built employing density functional theory (DFT) calculations, and the reaction mechanism of methanol oxycarbonylation over the CuCl{sub 2}-PdCl{sub 2} surfaces was also investigated. On the CuCl{sub 2}-PdCl{sub 2} surface, the active site for methanol oxidation was confirmed as Cu-Cl-Cu (Pd). Comparing with pure CuCl{sub 2} surface, the introduction of Pd atom causes the electron repopulation on the surface and lowers the energy barrier for methanol oxidation, but the number of the active site decreases with the increasing of Pd doping volume. Agreed with previous experimental results, the Pd site is most favorable for the CO insertion, indicated by the lowest activation barrier for the formation of COOCH{sub 3} on Pd atom. The lowest energy barrier for the formation of DMC appears when COOCH{sub 3} species adsorbed on Pd atom and methoxyl adsorbed on Cu atoms, which is 0.42 eV. Finally, the reconstruction of the unsaturated surface is a spontaneous and exothermic process. Comparing with other surfaces, the rate-limiting step, methanol oxidation, on CuCl{sub 2}-PdCl{sub 2} surface with Pd/Cu = 1:17 has the lowest energy barrier, which is agreed with the experimental observation that PdCl{sub 2}-CuCl{sub 2} catalyst with Pd/Cu = 1:20 has the favorable activity. The adsorbed methoxyl will further lower the activation barrier of methanol oxidation, which is agreed with experimental observation that the Wacker-type catalysts have an induction period in the methanol oxidative carbonylation system.

Kinetic isotope effects in the gas phase reactions of OH and Cl with CH3Cl, CD3Cl, and 13CH3Cl

Directory of Open Access Journals (Sweden)

A. A. Gola

2005-01-01

Full Text Available The kinetic isotope effects in the reactions of CH3Cl, 13CH3Cl and CD3Cl with OH radicals and Cl atoms were studied in relative rate experiments at 298±2 K and 1013±10 mbar. The reactions were carried out in a smog chamber using long path FTIR detection and the spectroscopic data analyzed employing a non-linear least squares spectral fitting method using measured high-resolution infrared spectra as well as absorption cross sections from the HITRAN database. The reaction rates of 13CH3Cl and CD3Cl with OH and Cl were determined relative to CH3Cl as: kOH+CH3ClkOH+CH3Cl/kOH+13CH3Cl}kOH+13CH3Cl=1.059±0.008, kOH+CH3ClkOH+CH3Cl/kOH+CD3ClkOH+CD3Cl=3.9±0.4, kCl+CH3ClkCl+CH3Cl/kCl+13CH3ClkCl+13CH3Cl =1.070±0.010 and kCl+CH3ClkCl+CH3Cl/kCl+CD3ClkCl+CD3Cl=4.91±0.07. The uncertainties given are 2σ from the statistical analyses and do not include possible systematic errors. The unexpectedly large 13C kinetic isotope effect in the OH reaction of CH3Cl has important implications for the global emission inventory of CH3Cl.

Well-defined 4-arm stars with hydroxy-terminated polyethylene, polyethylene-b-polycaprolactone and polyethylene-b-(polymethyl methacrylate) 2 arms

KAUST Repository

Zhang, Zhen

2016-07-20

Bis-boron-thexyl-silaboracycle was prepared by hydroboration of 1,4-bis(methyldivinylsilyl)butane with thexylborane and used to initiate the polyhomologation of dimethylsulfoxonium methylide to afford well-defined hydroxy-terminated 4-arm polyethylene (PE) stars. The synthesized PE stars were transformed to (PE-b-PCL)4 starblock copolymers via the ring-opening polymerization of ϵ-caprolactone (CL) initiated by the hydroxyl end groups of (PE-OH)4 in the presence of P2-tBu phosphazene base. Esterification of the hydroxyl groups of the OH-terminated PE star with 2,2-dichloroacetyl chloride led to (PE-Cl2)4 which was used as initiator (eight initiating atom transfer radical polymerization, ATRP, sites) for the synthesis of (PE-b-PMMA2)4 dendrimer-like stars by the ATRP of methyl methacrylate (MMA). All intermediates and final products were characterized by high temperature gel permeation chromatography and proton nuclear magnetic resonance spectroscopy. © 2016 The Royal Society of Chemistry.

AN INTELLIGENT NEURO-FUZZY TERMINAL SLIDING MODE CONTROL METHOD WITH APPLICATION TO ATOMIC FORCE MICROSCOPE

Directory of Open Access Journals (Sweden)

Seied Yasser Nikoo

2016-11-01

Full Text Available In this paper, a neuro-fuzzy fast terminal sliding mode control method is proposed for controlling a class of nonlinear systems with bounded uncertainties and disturbances. In this method, a nonlinear terminal sliding surface is firstly designed. Then, this sliding surface is considered as input for an adaptive neuro-fuzzy inference system which is the main controller. A proportinal-integral-derivative controller is also used to asist the neuro-fuzzy controller in order to improve the performance of the system at the begining stage of control operation. In addition, bee algorithm is used in this paper to update the weights of neuro-fuzzy system as well as the parameters of the proportinal-integral-derivative controller. The proposed control scheme is simulated for vibration control in a model of atomic force microscope system and the results are compared with conventional sliding mode controllers. The simulation results show that the chattering effect in the proposed controller is decreased in comparison with the sliding mode and the terminal sliding mode controllers. Also, the method provides the advantages of fast convergence and low model dependency compared to the conventional methods.

STM imaging of buried P atoms in hydrogen-terminated Si for the fabrication of a Si:P quantum computer

Energy Technology Data Exchange (ETDEWEB)

Oberbeck, L.; Curson, N.J.; Hallam, T.; Simmons, M.Y.; Clark, R.G

2004-10-01

The fabrication of atomic-scale devices in silicon requires the encapsulation of dopant atoms which have been incorporated into the silicon surface at atomically precise positions using scanning tunnelling microscopy (STM) lithography. During silicon encapsulation, it is important to minimise segregation and diffusion of dopant atoms in order to retain the lithography defined device structure. Buried dopant imaging using STM is capable of imaging dopant atoms such as phosphorus after encapsulation in silicon several monolayers below the silicon surface, thus making it possible to check the integrity of the device structure. To fabricate buried phosphorus-doped samples, we use phosphine gas as a source of phosphorus atoms and incorporate the phosphorus atoms into a Si(001) surface during an annealing step. Molecular beam epitaxy is used to encapsulate the dopant atoms with several monolayers of silicon. After encapsulation, we hydrogen terminate the silicon surface in order to image the buried phosphorus dopants using STM. We show that a buried phosphorus atom appears as a bright glow superimposed on the silicon dimer structure in empty state STM images, whereas filled state images only show a very faint protrusion in the vicinity of the phosphorus atom. We highlight the importance of our results for the fabrication of atomic-scale devices.

STM imaging of buried P atoms in hydrogen-terminated Si for the fabrication of a Si:P quantum computer

International Nuclear Information System (INIS)

Oberbeck, L.; Curson, N.J.; Hallam, T.; Simmons, M.Y.; Clark, R.G.

2004-01-01

The fabrication of atomic-scale devices in silicon requires the encapsulation of dopant atoms which have been incorporated into the silicon surface at atomically precise positions using scanning tunnelling microscopy (STM) lithography. During silicon encapsulation, it is important to minimise segregation and diffusion of dopant atoms in order to retain the lithography defined device structure. Buried dopant imaging using STM is capable of imaging dopant atoms such as phosphorus after encapsulation in silicon several monolayers below the silicon surface, thus making it possible to check the integrity of the device structure. To fabricate buried phosphorus-doped samples, we use phosphine gas as a source of phosphorus atoms and incorporate the phosphorus atoms into a Si(001) surface during an annealing step. Molecular beam epitaxy is used to encapsulate the dopant atoms with several monolayers of silicon. After encapsulation, we hydrogen terminate the silicon surface in order to image the buried phosphorus dopants using STM. We show that a buried phosphorus atom appears as a bright glow superimposed on the silicon dimer structure in empty state STM images, whereas filled state images only show a very faint protrusion in the vicinity of the phosphorus atom. We highlight the importance of our results for the fabrication of atomic-scale devices

Chemical reactions of recoil atoms and thermal atoms of tritium with haloid benzenes

International Nuclear Information System (INIS)

Simirskij, Yu.N.; Firsova, L.P.

1978-01-01

Radiochemical yields have been determined for the products of substitution of hydrogen atoms and halides in Cl-, Br-, and I-benzenes with tritium atoms obtained during thermal dissociation of T 2 and with recoil atoms T arising in nuclear reaction 6 Li(n, P)T. It is shown that in the series of Cl-, Br-, and I-benzenes yields of the products of substitution of halides atoms with tritium grow, whereas those of hydrogen atom substitution change only little. The correlation nature of the yields of substitution products of halide atoms with tritium remains constant in a wide range of the initial kinetic energies of T atoms for the recoil atoms with E 0 =2.7 MeV and for the completely thermolized atoms during thermal dissociation of T 2

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

Science.gov (United States)

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

2016-09-06

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

Interaction of different poisons with MgCl{sub 2}/TiCl{sub 4} based Ziegler-Natta catalysts

Energy Technology Data Exchange (ETDEWEB)

Bahri-Laleh, Naeimeh, E-mail: n.bahri@ippi.ac.ir

2016-08-30

Highlights: • The interactions between different classes of poison molecules and TiCl{sub 4}/MgCl{sub 2} type Ziegler-Natta catalyst is considered. • Poisons strongly stabilize MgCl{sub 2} crystal surfaces, mostly Ti active center relative to the unpoisoned solid. • Poison molecules decrease catalyst activity by increasing E{sub TS} in olefin polymerization. • Poison molecules do not have significant effect in stereospecifity of ZN catalysts in propylene polymerization. - Abstract: Adsorption of different poison molecules on activated MgCl{sub 2} is investigated within DFT using a cluster model of the MgCl{sub 2} surface with (MgCl{sub 2}){sub 16} formula containing four 4-coordinated and eight 5-coordinated Mg atoms as (110) and (104) surfaces, respectively. Studied poison molecules are chosen as possible impurities in hydrocarbon solvents and monomer feeds and contain water, hydrogensulfide, carbondioxide, molecular oxygen and methanol. First, adsorption of 1–4 molecules of different poisons to the (104) and (110) lateral cuts of MgCl{sub 2}, as well as their adsorption on [MgCl{sub 2}]/TiCl{sub 2}Et active center and AlEt{sub 3} cocatalyst is considered. Results reveal that poisons strongly stabilize both crystal surfaces, mostly Ti active center relative to the unpoisoned solid. Second, energy barrier (E{sub TS}) for ethylene insertion in the presence of different poisons located on the first and second Mg atom relative to the active Ti is calculated. While poison molecule located on the second Mg does not change E{sub TS}, coordination of it into the first Mg atom increases E{sub TS} by 0.9–1.2 kcal mol{sup −1}. In the last part of this manuscript, the stereoselective behavior of active Ti species, with and without poison molecules and external electron donor, is fully explored.

SYNTHESIS OF BLOCK COPOLYMER BY INTEGRATED LIVING ANIONIC POLYMERIZATION-ATOM TRANSFER RADICAL POLYMERIZATION (ATRP)

Institute of Scientific and Technical Information of China (English)

Bing Liu; Feng Liu; Ning Luo; Sheng-kang Ying; Qing Liu

2000-01-01

Alpha-trichloroacetoxy terminated polystyrene oligomer (PS-CH2CH2OCOCCl3) and poly-(styrene-b-butadiene)oligomer [P(S-b-B)-CH2CH2OCOCCl3)] were synthesized by living anionic polymeri-zation using n-butyllithium as initiator.Then the PS-CH2CH2OCOCCl3 (PS-Cl3) or P(S-b-B)-CH2CH2O-COCCl3 (PSB-Cl3) was used as the macroinitiator in the polymerization of (meth)acrylates in the presence of CuX/bpy. AB diblock and ABC triblock copolymers were prepared by the integrated living anionic polymerization (LAP)-atom transfer radical polymerization (ATRP). The structures of the PSB-Cl3 and the P(S-b-MMA) were identified by FTIR and 1H-NMR spectrum, respectively. A new way to design block copolymers (the combination of LAP and ATRP) was developed.

Atmospheric degradation of industrial fluorinated acrylates and methacrylates with Cl atoms at atmospheric pressure and 298 K

Science.gov (United States)

Rivela, Cynthia B.; Blanco, María B.; Teruel, Mariano A.

2018-04-01

The gas-phase reaction of Cl atom with 2,2,2-trifluoroethylacrylate (k1), 1,1,1,3,3,3-hexafluoroisopropylacrylate (k2), 2,2,2-trifluoroethylmethacrylate (k3) and 1,1,1,3,3,3-hexafluoroisopropylmethacrylate (k4), have been investigated at 298 K and 1 atm using the relative method by gas chromatography coupled with flame ionization detection (GC-FID). The values obtained are (in cm3 molecule-1 s-1): k1(Cl+CH2=CHC(O)OCH2CF3) = (2.41 ± 0.57) × 10-10, k2(Cl+CH2=CHC(O)OCH(CF3)2) = (1.39 ± 0.34) × 10-10, k3(Cl+CH2=C(CH3)C(O)OCH2CF3) = (2.22 ± 0.45) × 10-10, and k4(Cl +CH2=C(CH3)C(O)OCH(CF3)2 = (2.44 ± 0.52) × 10-10. Products identification studies were performed by solid-phase microextraction (SPME) method, with on-fiber products derivatization using o-(2,3,4,5,6-pentafluorobenzyl) hydroxylamine hydrochloride, coupled with gas chromatography with mass spectrometry detection (GC-MS). Chloroacetone, trifluoroacetaldehyde and formaldehyde were observed as degradation products and a general mechanism is proposed. Additionally, reactivity trends and atmospheric implications are discussed. Significant ozone photochemical potentials (POCP) and acidification potentials lead to local and or regional impact of the esters under study although is expected to a have a minor impact on global warming and climate change.

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

Science.gov (United States)

Derbel, Amira; Mhiri, Tahar; Graia, Mohsen

2015-10-01

In the title complex, chlorido-tetra-kis-(1H-imidazole-κN (3))cobalt(II) chloride, [CoCl(C3H4N2)4]Cl, the Co(II) cation has a distorted square-pyramidal coordination environment. It is coordinated by four N atoms of four imidazole (Im) groups in the basal plane, and by a Cl atom in the apical position. It is isostructural with [Cu(Im)4Cl]Cl [Morzyk-Ociepa et al. (2012 ▸). J. Mol. Struct. 1028, 49-56] and [Cu(Im)4Br]Br [Hossaini Sadr et al. (2004 ▸). Acta Cryst. E60, m1324-m1326]. In the crystal, the [CoCl(C3H4N2)4](+) cations and Cl(-) anions are linked via N-H⋯Cl hydrogen bonds, forming layers parallel to (010). These layers are linked via C-H⋯Cl hydrogen bonds and C-H⋯π and π-π [inter-centroid distance = 3.794 (2) Å] inter-actions, forming a three-dimensional framework. The IR spectrum shows vibrational bands typical for imidazol groups. The monoclinic unit cell of the title compound emulates an ortho-rhom-bic cell as its β angle is close to 90°. The crystal is twinned, with the refined ratio of twin components being 0.569 (1):0.431 (1).

Atomic-resolution characterization of the effects of CdCl2 treatment on poly-crystalline CdTe thin films

Science.gov (United States)

Paulauskas, T.; Buurma, C.; Colegrove, E.; Guo, Z.; Sivananthan, S.; Chan, M. K. Y.; Klie, R. F.

2014-08-01

Poly-crystalline CdTe thin films on glass are used in commercial solar-cell superstrate devices. It is well known that post-deposition annealing of the CdTe thin films in a CdCl2 environment significantly increases the device performance, but a fundamental understanding of the effects of such annealing has not been achieved. In this Letter, we report a change in the stoichiometry across twin boundaries in CdTe and propose that native point defects alone cannot account for this variation. Upon annealing in CdCl2, we find that the stoichiometry is restored. Our experimental measurements using atomic-resolution high-angle annular dark field imaging, electron energy-loss spectroscopy, and energy dispersive X-ray spectroscopy in a scanning transmission electron microscope are supported by first-principles density functional theory calculations.

Atmospheric production rate of 36Cl

International Nuclear Information System (INIS)

Parrat, Y.; Hajdas, W.; Baltensperger, U.; Synal, H.A.; Kubik, P.W.; Gaeggeler, H.W.; Suter, M.

1997-01-01

Using experimental cross sections, a new calculation of the atmospheric production rate of 36 Cl was carried out. A mean production rate of 20 atoms m -2 s -1 was obtained, which is lower than mean 36 Cl deposition rates. (author) 2 figs., 7 refs

The centrifugal sudden distorted wave method for chemical reactions: Application to Cl+HCl → ClH+Cl

International Nuclear Information System (INIS)

Amaee, B.; Connor, J.N.L.; Schatz, G.C.

1987-01-01

The authors describe a method for calculating cross sections for atom plus diatom reactive collisions based on the centrifugal sudden distorted wave (CSDW) approximation. This method is nearly exact at low energies where reactive cross sections are small. Representative CPU times are given for applications of CSDW method to the Cl + HCl → ClH + Cl reaction using CDC 7600, Cyber 176, Cyber 205, Cray XMP and Cray 2 computers. Calculations show that the product HCl molecule is highly rotationally excited, (receiving 40-50% of the available energy) and that the shape of the product rotational distribution is nearly independent of reagent rotational state. The authors also calculated product differential cross sections and find them to be backward peaked at low energies

Functionalization of hydroxyl terminated polybutadiene with ...

Indian Academy of Sciences (India)

CBDT), has been covalently attached at the terminal carbon atoms of the hydroxyl terminated polybutadiene (HTPB) backbone. The modification of HTPB backbone by CBDT molecule does not affect the unique physico-chemical properties such ...

Atomic switch: atom/ion movement controlled devices for beyond von-neumann computers.

Science.gov (United States)

Hasegawa, Tsuyoshi; Terabe, Kazuya; Tsuruoka, Tohru; Aono, Masakazu

2012-01-10

An atomic switch is a nanoionic device that controls the diffusion of metal ions/atoms and their reduction/oxidation processes in the switching operation to form/annihilate a conductive path. Since metal atoms can provide a highly conductive channel even if their cluster size is in the nanometer scale, atomic switches may enable downscaling to smaller than the 11 nm technology node, which is a great challenge for semiconductor devices. Atomic switches also possess novel characteristics, such as high on/off ratios, very low power consumption and non-volatility. The unique operating mechanisms of these devices have enabled the development of various types of atomic switch, such as gap-type and gapless-type two-terminal atomic switches and three-terminal atomic switches. Novel functions, such as selective volatile/nonvolatile, synaptic, memristive, and photo-assisted operations have been demonstrated. Such atomic switch characteristics can not only improve the performance of present-day electronic systems, but also enable development of new types of electronic systems, such as beyond von- Neumann computers. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Origin of the p-type character of AuCl3 functionalized carbon nanotubes

KAUST Repository

Murat, Altynbek

2014-02-13

The microscopic origin of the p-type character of AuCl3 functionalized carbon nanotubes (CNTs) is investigated using first-principles self-interaction corrected density functional theory (DFT). Recent DFT calculations suggest that the p-type character of AuCl3 functionalized CNTs is due to the Cl atoms adsorbed on the CNTs. We test this hypothesis and show that adsorbed Cl atoms only lead to a p-type character for very specific concentrations and arrangements of the Cl atoms, which furthermore are not the lowest energy configurations. We therefore investigate alternative mechanisms and conclude that the p-type character is due to the adsorption of AuCl4 molecules. The unraveling of the exact nature of the p-doping adsorbates is a key step for further development of AuCl3 functionalized CNTs in water sensor applications. © 2014 American Chemical Society.

26Al and 36Cl AMS system at University of Tsukuba: A progress report

International Nuclear Information System (INIS)

Sasa, Kimikazu; Nagashima, Yasuo; Takahashi, Tsutomu; Seki, Riki; Tosaki, Yuki; Sueki, Keisuke; Bessho, Kotaro; Matsumura, Hiroshi; Miura, Taichi; He, Ming

2007-01-01

With the current AMS system on the 12UD Pelletron tandem accelerator at University of Tsukuba, we are able to measure the long-lived radioisotopes of 14 C, 26 Al, 36 Cl and 129 I by employing a molecular pilot beam method that stabilizes the terminal voltage with 0.1% accuracy. Several major improvements have been made to increase the sensitivity of the AMS system to 26 Al and 36 Cl radioisotopes. For 26 Al-AMS, the ions extracted from the ion source have been changed from Al - to AlO - by using an Al 2 O 3 target sample. In addition, 26 MgO - molecular ions are used as a pilot beam to control the terminal voltage through slit current feedback. Also, a fully-stripping AMS technique is used to achieve an effective detection limit of better than 5 x 10 -15 for the 26 Al/ 27 Al ratio. For 36 Cl-AMS, the terminal voltage has been increased from 9 MV to 10 MV, thereby increasing the energy of the 36 Cl 9+ beam to 100 MeV. This energy increment helps us to get a clearer separation between 36 Cl and 36 S in a new ΔE-E detector. In addition, the yield of 36 Cl 9+ is increased by 1.5 times as a result of the higher ion energy at the terminal stripper foil. The standard deviation of the fluctuations of the 36 Cl/ 35 Cl ratio is within ±2%, and the effective detection limit is better than 2.0 x 10 -14

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

International Nuclear Information System (INIS)

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

2000-01-01

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

Atomic switches: atomic-movement-controlled nanodevices for new types of computing

International Nuclear Information System (INIS)

Hino, Takami; Hasegawa, Tsuyoshi; Terabe, Kazuya; Tsuruoka, Tohru; Nayak, Alpana; Ohno, Takeo; Aono, Masakazu

2011-01-01

Atomic switches are nanoionic devices that control the diffusion of metal cations and their reduction/oxidation processes in the switching operation to form/annihilate a metal atomic bridge, which is a conductive path between two electrodes in the on-state. In contrast to conventional semiconductor devices, atomic switches can provide a highly conductive channel even if their size is of nanometer order. In addition to their small size and low on-resistance, their nonvolatility has enabled the development of new types of programmable devices, which may achieve all the required functions on a single chip. Three-terminal atomic switches have also been developed, in which the formation and annihilation of a metal atomic bridge between a source electrode and a drain electrode are controlled by a third (gate) electrode. Three-terminal atomic switches are expected to enhance the development of new types of logic circuits, such as nonvolatile logic. The recent development of atomic switches that use a metal oxide as the ionic conductive material has enabled the integration of atomic switches with complementary metal-oxide-semiconductor (CMOS) devices, which will facilitate the commercialization of atomic switches. The novel characteristics of atomic switches, such as their learning and photosensing abilities, are also introduced in the latter part of this review. (topical review)

Atomic control of substrate termination and heteroepitaxial growth of SrTiO sub 3 /LaAlO sub 3 films

CERN Document Server

Kim, D W; Choi, C; Lim, K D; Noh, T W; Lee, D R; Park, J H; Lee, K B

2000-01-01

The roles of substrate termination in the growth behaviors of SrTiO sub 3 (STO) films were investigated. With heat treatment and an atomic layer deposition technique, LaAlO sub 3 (LAO) substrates with two kinds of terminations, i.e., LaO- and AlO sub 2 -terminated ones, could be prepared. On top of them STO films were grown by using laser molecular beam epitaxy. In the case of the STO/LaO-LAO film, a transition from layer-by-layer growth to island growth was observed after growth of about 10 monolayers (ML). On the other hand, the STO/AlO sub 2 -LAO film could be grown in a layer-by-layer mode with a flat surface up to 40 ML. We suggest that defects induced by charge compensation influence the strain states and the physical properties of oxide heterostructures significantly.

Application of PXAMS technique for 36Cl analysis in soil collected at Semipalatinsk Nuclear Test Site

International Nuclear Information System (INIS)

Tolmachyov, S.; Maeda, Y.; Mitarai, S.; Nakashima, T.; Momoshima, N.; Yamamoto, M.

2001-01-01

36 Cl in soil samples from the Semipalatinsk Nuclear Test Site (former USSR) was measured at Kyushu University Tandem Laboratory (KUTL) by accelerator mass spectrometry (AMS) coupled with projectile X-ray detection (PXD) technique. The separation of competing 36 S and 3 6Cl atomic isobars, was satisfactory by PXD technique. Measured 36 Cl/Cl atom ratio was (5.0 ± 0.6) x 10 -10 and an average activity of 36 Cl was calculated as (2.0 ± 0.2) mBq/g, which is in a good agreement with that obtained by liquid scintillation counting (LSC) method previously. Currently developed AMS system at the Kyushu University can be applied for routine 36 Cl analysis at 36 Cl/Cl = 10 -11 atom ratio level. (author)

Activation measurements for thermal neutrons. Part F. 36Cl measurements in Japan

International Nuclear Information System (INIS)

Nagashima, Yasuo; Seki, Riki; Matsuhiro, Takeshi; Takahashi, Tsutomu; Sasa, Kimikazu; Usui, Toshihide; Sueki, Keisuke

2005-01-01

The development of the accelerator mass spectrometry (AMS) system at the Tandem Accelerator Center of the University of Tsukuba was started in 1995, using the university's own molecular pilot beam technique. Presently, it is the only facility in Japan used to measure 36 Cl (Nagashima et al. 2000). The sensitivity of the 36 Cl AMS system is around 10 -14 36 Cl/Cl atom ratio, which is enough to measure the natural level of the 36 Cl/Cl ratio. The system is characterized by long-term stability, enabling high-quality, continuous measurements over many hours. Our AMS system was used to measure 36 Cl produced in soil by neutrons released into the environment at the time of the JCO criticality accident in Tokai-mura in 1999 (Seki et al. 2003). At the beginning of 2001, our group joined the collaborative efforts to investigate and clarify the discrepancy observed between measurements and calculations of neutron activities induced by the atomic bombings in Hiroshima and Nagasaki. Using our AMS system, 36 Cl was measured in granite samples from Hiroshima exposed to atomic-bomb neutrons and in distant, unexposed samples. (author)

Adsorption of small NaCl clusters on surfaces of silicon nanostructures

International Nuclear Information System (INIS)

Amsler, Maximilian; Alireza Ghasemi, S; Goedecker, Stefan; Neelov, Alexey; Genovese, Luigi

2009-01-01

We have studied possible adsorption geometries of neutral NaCl clusters on the disordered surface of a large silicon model tip used in non-contact atomic force microscopy. The minima hopping method was used to determine low energy model tip configurations as well as ground state geometries of isolated NaCl clusters. The combined system was treated with density functional theory. Alkali halides have proven to be strong structure seekers and tend to form highly stable ground state configurations whenever possible. The favored adsorption geometry for four Na and four Cl atoms was found to be an adsorption of four NaCl dimers due to the formation of Cl-Si bonds. However, for larger NaCl clusters, the increasing energy required to dissociate the cluster into NaCl dimers suggests that adsorption of whole clusters in their isolated ground state configuration is preferred.

35Cl NQR spectra of group 1 and silver dichloromethanesulfonates

International Nuclear Information System (INIS)

Gillette, Gabriel; Wulfsberg, Gary

2008-01-01

The dichloromethanesulfonates of silver and other +1-charged cations, M + (Cl 2 CHSO 3 - ) (M = Ag, Tl, Li, Na, K, Rb, Cs) were synthesized and studied by 35 Cl NQR. Dichloromethanesulfonic acid was prepared by the methanolysis of dichloromethanesulfonyl chloride, and was then neutralized with the carbonates of the +1-charged cations to produce the corresponding dichloromethanesulfonate salt. This NQR study completed the investigation of the chloroacetates and chloromethanesulfonates of silver, Ag + (Cl x CH 3-x SO 3 - ) and Ag + (Cl x CH 3-x CO 2 - ), and suggests (1) that the ability of organochlorine atoms to coordinate to silver decreases as the number of electron-withdrawing groups (Cl, SO 3 - , CO 2 - ) attached to the carbon atom increases; (2) that the unusually large NQR spectral width found among M + (Cl 2 CHCO 2 + ) salts is not present among M + (Cl 2 CHSO 3 + ) salts, and therefore is not generally characteristic of the dichloromethyl group in salts.

Atmospheric production rate of {sup 36}Cl

Energy Technology Data Exchange (ETDEWEB)

Parrat, Y.; Hajdas, W.; Baltensperger, U.; Synal, H.A.; Kubik, P.W.; Gaeggeler, H.W. [Paul Scherrer Inst. (PSI), Villigen (Switzerland); Suter, M. [Eidgenoessische Technische Hochschule, Zurich (Switzerland)

1997-09-01

Using experimental cross sections, a new calculation of the atmospheric production rate of {sup 36}Cl was carried out. A mean production rate of 20 atoms m{sup -2}s{sup -1} was obtained, which is lower than mean {sup 36}Cl deposition rates. (author) 2 figs., 7 refs.

Products and mechanism of the reaction of Cl atoms with unsaturated alcohols

Science.gov (United States)

Rodríguez, Ana; Rodríguez, Diana; Soto, Amparo; Bravo, Iván; Diaz-de-Mera, Yolanda; Notario, Alberto; Aranda, Alfonso

2012-04-01

The products of the chlorine atom initiated oxidation of different unsaturated alcohols were determined at atmospheric pressure and ambient temperature, in a 400 L teflon reaction chamber using GC-FID and GC-MS for the analysis. The major products detected (with molar yields in brackets) are: chloroacetaldehyde (50 ± 8%) and acrolein (27 ± 2%) from allyl alcohol; acetaldehyde (77 ± 11%), chloroacetaldehyde (75 ± 18%), and methyl vinyl ketone (17 ± 2%) from 3-buten-2-ol; acetone (55 ± 4%) and chloroacetaldehyde (59 ± 8%) from 2-methyl-3-buten-2-ol; chloroacetone (18 ± 1%) and methacrolein (8 ± 1%) from 2-methyl-2-propen-1-ol; acetaldehyde (20 ± 1%), crotonaldehyde (6 ± 3%), 3-choloro-4-hydroxy-2-butanone (2 ± 2%) and 2-chloro-propanal (4 ± 5%) from crotyl alcohol; and acetone (24 ± 3%) from 3-methyl-2-buten-1-ol. The experimental data suggests that addition of Cl to the double bond of the unsaturated alcohol is the dominant reaction pathway compared to the H-abstraction channel.

Synthesis and IR spectral study of MoO2Cl2 molecular complex with acetoacetanilides. Crystal structure of MoO2Cl2 complex with acetoacet-2-toluidine

International Nuclear Information System (INIS)

Abramenko, V.L.; Sergienko, V.S.; Churakov, A.V.

2000-01-01

Certain MoO 2 Cl 2 complexes with acetoacetanilide derivatives were synthesized, two IR spectral study being performed. Crystal and molecular structure of MoO 2 Cl 2 complex with acetoacet-2-toluidine (HL) was determined using X-ray diffraction analysis. The crystals are monoclinic, a = 7.621 (7), b = 9.498 (3), c = 19.980 (9) A, β = 95.16 (7), Z = 4, sp.gr. P2 1 /n. Coordination polyhedron of Mo atom is a distorted octahedron with two O oxoatoms in cis-position, two Cl atom in mutual trans-position and two O(HL) atoms in trans-positions in reference to O(oxo) [ru

A new 36Cl hydrological model and 36Cl systematics in the Jordan River/Dead Sea system

International Nuclear Information System (INIS)

Paul, M.; Fink, D.; Meirav, O.; Kaim, R.

1986-01-01

Accelerator mass spectrometry results of 36 Cl for the Jordan River/Dead Sea system show that the amount of chloride leached from rocks ranges from approx. 70% in source springs to >90% in water bodies downstream. Furthermore, the amount of water left after evaporation decreases from approx. 50% in the source springs to 20% in the intermediate Lake Kinneret. In the terminal Dead Sea, 99% of the stable chloride originates from ancient rocks and evaporite formations while approx. 80% of its 36 Cl content is of meteoric origin. Using 36 Cl measurements, the accumulation time of the Dead Sea salt is estimated to be 19,000-25,000 yr. (author)

Ligand sphere conversions in terminal carbide complexes

DEFF Research Database (Denmark)

Morsing, Thorbjørn Juul; Reinholdt, Anders; Sauer, Stephan P. A.

2016-01-01

Metathesis is introduced as a preparative route to terminal carbide complexes. The chloride ligands of the terminal carbide complex [RuC(Cl)2(PCy3)2] (RuC) can be exchanged, paving the way for a systematic variation of the ligand sphere. A series of substituted complexes, including the first...... example of a cationic terminal carbide complex, [RuC(Cl)(CH3CN)(PCy3)2]+, is described and characterized by NMR, MS, X-ray crystallography, and computational studies. The experimentally observed irregular variation of the carbide 13C chemical shift is shown to be accurately reproduced by DFT, which also...... demonstrates that details of the coordination geometry affect the carbide chemical shift equally as much as variations in the nature of the auxiliary ligands. Furthermore, the kinetics of formation of the sqaure pyramidal dicyano complex, trans-[RuC(CN)2(PCy3)2], from RuC has been examined and the reaction...

Activation measurements for thermal neutrons. Part D. 36Cl measurements in the United States

International Nuclear Information System (INIS)

Straume, Tore; Men, Ping; Marchetti, Alfredo A.; Egbert, Stephen D.; Roberts, James A.; Fujita, Shoichiro; Shizuma, Kiyoshi; Hoshi, Masaharu

2005-01-01

A large number of measurements were performed in the United States of 36 Cl in both granite and concrete samples obtained from various locations and distances in Hiroshima and Nagasaki. These measurements employed accelerator mass spectrometry (AMS) to quantify the number of atoms of 36 Cl per atom of total Cl in the sample. Results of these measurements are presented in this section and discussed in the context of the DS02 dosimetry reevaluation effort for Hiroshima and Nagasaki atomic-bomb survivors. (J.P.N.)

Growth models of coexisting p(2 × 1) and c(6 × 2) phases on an oxygen-terminated Cu(110) surface studied by noncontact atomic force microscopy at 78 K

International Nuclear Information System (INIS)

Li, Yan Jun; Lee, Seung Hwan; Kinoshita, Yukinori; Wen, Huanfei; Naitoh, Yoshitaka; Sugawara, Yasuhiro; Ma, Zong Min; Nomura, Hikaru

2016-01-01

We present an experimental study of coexisting p(2 × 1) and c(6 × 2) phases on an oxygen-terminated Cu(110) surface by noncontact atomic force microscopy (NC-AFM) at 78 K. Ball models of the growth processes of coexisting p(2 × 1)/c(6 × 2) phases on a terrace and near a step are proposed. We found that the p(2 × 1) and c(6 × 2) phases are grown from the super Cu atoms on both sides of O–Cu–O rows of an atomic spacing. In this paper, we summarize our investigations of an oxygen-terminated Cu(110) surface by NC-AFM employing O- and Cu-terminated tips. Also, we state several problems and issues for future investigation. (paper)

Anomalous H/D isotope effect on 35Cl NQR frequencies in piperidinium p-chlorobenzoate

International Nuclear Information System (INIS)

Nakano, Ryo; Honda, Hisashi; Kimura, Taiki; Nakata, Eiichi; Takamizawa, Satoshi; Noro, Sumiko; Ishimaru, Shin'ichi

2008-01-01

Anomalous isotope effects were detected in the 35 Cl nuclear quadrupole resonance (NQR) frequency of piperidinium p-chlrobenzoate (C 5 H 10 NH. ClC 6 H 4 COOH) by deuteration of hydrogen atoms. The atoms were determined to form two kinds of N-H...O type H-bonds in the crystal structure. Large frequency shifts of the 35 Cl resonance lines reaching 288 kHz at 77 K and 278 kHz at room temperature were caused upon deuteration, in spite of the fact that the Cl atoms in the molecule do not form hydrogen bonds in the crystal. Results of single crystal X-ray diffraction measurements and density-functional-theorem calculations suggest that a dihedral-angle change of 1.8 o between benzene and the piperidine ring contributes to 35 Cl NQR anomalous frequency shifts.

Study of atomic excitations in sputtering with the use of N, O, F, Ne, Na, Cl, and Ar projectiles

International Nuclear Information System (INIS)

Jensen, H.K.; Veje, E.

1985-01-01

Solid magnesium has been bombarded with 80 keV ions of N, O, F, Ne, Na, Cl, and Ar, and excitation of sputtered magnesium atoms and ions has been studied. Relative level excitation probabilities depend strongly on the projectile, the dependences for Mg I levels being different from those for Mg II levels. With all projectiles, the resonance level in Mg II is excited stronger than the resonance level in Mg I. Very little radiation is observed from the projectiles except for sodium. The results are discussed. (orig.)

The oxidation of ReCl_5 with oleum: synthesis and crystal structure of Re_2O_4Cl_4(SO_4)

International Nuclear Information System (INIS)

Betke, Ulf; Wickleder, Mathias S.

2012-01-01

The reaction of ReCl_5 and fuming sulfuric acid (25 % SO_3) in a sealed glass tube at 200 C led to red, needle shaped single crystals of Re_2O_4Cl_4(SO_4) (monoclinic, C2/c, a = 1501.8(2) pm, b = 1545.9(2) pm, c = 945.18(8) pm, β = 98.761(9) , Z = 8). In the crystal structure the [ReO_2] moieties are linked by [SO_4]"2"- tetrahedra to chains along the [101] direction. Each sulfate ion connects four rhenium atoms, additional two chloride ions complete the octahedral coordination sphere of each rhenium atom according to "1_∞[ReO_2_/_1Cl_2_/_1(SO_4)_2_/_4]. (Copyright copyright 2012 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

InCl3/NaClO: a reagent for allylic chlorination of terminal olefins

International Nuclear Information System (INIS)

Pisoni, Diego S.; Gamba, Douglas; Fonseca, Carlos V.; Costa, Jesse S. da; Petzhold, Cesar L.; Oliveira, Eduardo R. de; Ceschi, Marco A.

2006-01-01

Indium trichloride promotes the chlorination of terminal olefins in the presence of sodium hypochlorite with good results. Carvone was chosen as a model compound to examine some of the general features of this reaction, such as stoichiometry, temperature, reaction time and product conversion. Treatment of β-pinene with sodium hypochlorite in the presence of indium trichloride resulted in a facile rearrangement to selectively yield perillyl chloride, which is an important precursor for C-7 oxygenated limonenes. (author)

Microscopic Structure of DX Centers in Cd0.8Zn0.2Te:Cl

International Nuclear Information System (INIS)

Shan, Y.Y.; Lynn, K.G.; Szeles, C.; Asoka-Kumar, P.; Thio, T.; Bennett, J.W.; Beling, C.B.; Fung, S.; Becla, P.

1997-01-01

Photoexcitation of chlorine DX centers induces a transition of the Cl atoms to the shallow-donor state and persistent photoconductivity at low temperature in Cd 0.8 Zn 0.2 Te:Cl. The relaxation of the substitutional Cl atoms to the DX state at 140K is coincident with a decrease of the positron line-shape parameter and an increase of annihilation with high-momentum core electrons. The results indicate positron trapping and annihilation at DX centers and at chlorine A centers. The data support the bond breaking model of the DX centers and the outward relaxation of the Cl and Cd(Zn) atoms along the [111] direction. The thermal barrier for the shallow-deep transition was found to be 0.44eV. copyright 1997 The American Physical Society

Converting hcp Mg-Al-Zn alloy into bcc Mg-Li-Al-Zn alloy by electrolytic deposition and diffusion of reduced lithium atoms in a molten salt electrolyte LiCl-KCl

International Nuclear Information System (INIS)

Lin, M.C.; Tsai, C.Y.; Uan, J.Y.

2007-01-01

A body-centered cubic (bcc) Mg-12Li-9Al-1Zn (wt.%) alloy was fabricated in air by electrolysis from LiCl-KCl molten salt at 500 deg. C. Electrolytic deposition of Li atoms on cathode (Mg-Al-Zn alloy) and diffusion of the Li atoms formed the bcc Mg-Li-Al-Zn alloy with 12 wt.% Li and only 0.264 wt.% K. Low K concentration in the bcc Mg alloy strip after the electrolysis process resulted from 47% atomic size misfit between K and Mg atoms and low solubility of K in Mg matrix

Structure and properties of Mn4Cl9: An antiferromagnetic binary hyperhalogen

Science.gov (United States)

Li, Yawei; Zhang, Shunhong; Wang, Qian; Jena, Puru

2013-02-01

Calculations based on density functional theory show that the structure of Mn4Cl9 anion is that of a Mn atom at the core surrounded by three MnCl3 moieties. Since Mn is predominantly divalent and MnCl3 is known to be a superhalogen with a vertical detachment energy (VDE) of 5.27 eV, Mn4Cl9 can be viewed as a hyperhalogen with the formula unit Mn(MnCl3)3. Indeed, the calculated VDE of Mn4Cl9 anion, namely 6.76 eV, is larger than that of MnCl3 anion. More importantly, unlike previously discovered hyperhalogens, Mn4Cl9 is the first such hyperhalogen species composed of only two constituent atoms. We further show that Mn4Cl9 can be used as a ligand to design molecules with even higher VDEs. For example, Li[Mn(MnCl3)3]2 anion has a VDE of 7.26 eV. These negatively charged clusters are antiferromagnetic with most of the magnetic moments localized at the Mn sites. Our studies show new pathways for creating binary hyperhalogens.

Atomic composition of WC/ and Zr/O-terminated diamond Schottky interfaces close to ideality

Energy Technology Data Exchange (ETDEWEB)

Piñero, J.C., E-mail: josecarlos.pinero@uca.es [Dpto. Ciencias de los Materiales, Universidad de Cádiz, Puerto Real, Cádiz,11510 (Spain); Araújo, D. [Dpto. Ciencias de los Materiales, Universidad de Cádiz, Puerto Real, Cádiz,11510 (Spain); Fiori, A. [National Institute for Materials Science, Tsukuba, Ibaraki (Japan); Traoré, A. [Institut Néel, CNRS-UJF, av. des Martyrs, Grenoble,38042 France (France); Villar, M.P. [Dpto. Ciencias de los Materiales, Universidad de Cádiz, Puerto Real, Cádiz,11510 (Spain); Eon, D.; Muret, P.; Pernot, J. [Institut Néel, CNRS-UJF, av. des Martyrs, Grenoble,38042 France (France); Teraji, T. [National Institute for Materials Science, Tsukuba, Ibaraki (Japan)

2017-02-15

Highlights: • Metal/O-terminated diamond interfaces are analyzed by a variety of TEM techniques. • Thermal treatment is shown to modify structural and chemical interface properties. • Electrical behavior vs annealing is shown to be related with interface modification. • Interfaces are characterized with atomic resolution to probe inhomogeneities. • Oxide formation and modification is demonstrated in both Schottky diodes. - Abstract: Electrical and nano-structural properties of Zr and WC-based Schottky power diodes are compared and used for investigating oxide-related effects at the diamond/metal interface. Differences in Schottky barrier heights and ideality factors of both structures are shown to be related with the modification of the oxygen-terminated diamond/metal interface configuration. Oxide formation, oxide thickness variations and interfacial oxygen redistribution, associated with thermal treatment are demonstrated. Ideality factors close to ideality (n{sub WC} = 1.02 and n{sub Zr} = 1.16) are obtained after thermal treatment and are shown to be related with the relative oxygen content at the surface (OCR{sub WC} = 3.03 and OCR{sub Zr} = 1.5). Indeed, thermal treatment at higher temperatures is shown to promote an escape of oxygen for the case of the WC diode, while it generates a sharper accumulation of oxygen at the metal/diamond interface for the case of Zr diode. Therefore, the metal-oxygen affinity is shown to be a key parameter to improve diamond-based Schottky diodes.

Anomalous H/D isotope effect on {sup 35}Cl NQR frequencies in piperidinium p-chlorobenzoate

Energy Technology Data Exchange (ETDEWEB)

Nakano, Ryo; Honda, Hisashi, E-mail: hhonda@yokohama-cu.ac.jp [Yokohama City University, Graduate School of Integrated Science (Japan); Kimura, Taiki [Yokohama City University, Faculty of Science (Japan); Nakata, Eiichi; Takamizawa, Satoshi; Noro, Sumiko [Yokohama City University, Graduate School of Integrated Science (Japan); Ishimaru, Shin' ichi [Tokyo Denki University, Department of Green and Sustainable Chemistry (Japan)

2008-01-15

Anomalous isotope effects were detected in the {sup 35}Cl nuclear quadrupole resonance (NQR) frequency of piperidinium p-chlrobenzoate (C{sub 5}H{sub 10}NH. ClC{sub 6}H{sub 4}COOH) by deuteration of hydrogen atoms. The atoms were determined to form two kinds of N-H...O type H-bonds in the crystal structure. Large frequency shifts of the {sup 35}Cl resonance lines reaching 288 kHz at 77 K and 278 kHz at room temperature were caused upon deuteration, in spite of the fact that the Cl atoms in the molecule do not form hydrogen bonds in the crystal. Results of single crystal X-ray diffraction measurements and density-functional-theorem calculations suggest that a dihedral-angle change of 1.8{sup o} between benzene and the piperidine ring contributes to {sup 35}Cl NQR anomalous frequency shifts.

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

Science.gov (United States)

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

1986-01-01

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

Atoms, molecules & elements

CERN Document Server

Graybill, George

2007-01-01

Young scientists will be thrilled to explore the invisible world of atoms, molecules and elements. Our resource provides ready-to-use information and activities for remedial students using simplified language and vocabulary. Students will label each part of the atom, learn what compounds are, and explore the patterns in the periodic table of elements to find calcium (Ca), chlorine (Cl), and helium (He) through hands-on activities.

{sup 35}Cl NQR spectra of group 1 and silver dichloromethanesulfonates

Energy Technology Data Exchange (ETDEWEB)

Gillette, Gabriel; Wulfsberg, Gary, E-mail: gwulfsbe@mtsu.edu [Middle Tennessee State University, Department of Chemistry (United States)

2008-01-15

The dichloromethanesulfonates of silver and other +1-charged cations, M{sup +} (Cl{sub 2}CHSO{sub 3}{sup -}) (M = Ag, Tl, Li, Na, K, Rb, Cs) were synthesized and studied by {sup 35}Cl NQR. Dichloromethanesulfonic acid was prepared by the methanolysis of dichloromethanesulfonyl chloride, and was then neutralized with the carbonates of the +1-charged cations to produce the corresponding dichloromethanesulfonate salt. This NQR study completed the investigation of the chloroacetates and chloromethanesulfonates of silver, Ag{sup +} (Cl{sub x}CH{sub 3-x}SO{sub 3}{sup -}) and Ag{sup +}(Cl{sub x}CH{sub 3-x}CO{sub 2}{sup -}), and suggests (1) that the ability of organochlorine atoms to coordinate to silver decreases as the number of electron-withdrawing groups (Cl, SO{sub 3}{sup -}, CO{sub 2}{sup -}) attached to the carbon atom increases; (2) that the unusually large NQR spectral width found among M{sup +} (Cl{sub 2}CHCO{sub 2}{sup +}) salts is not present among M{sup +} (Cl{sub 2}CHSO{sub 3}{sup +}) salts, and therefore is not generally characteristic of the dichloromethyl group in salts.

Analytical formulae for total cross sections for electron scattering by atoms (N, O, F, Ne, P, S, Cl, Ar, As, Se, Br, Kr) between 0.5-10 keV

International Nuclear Information System (INIS)

Williart, A.

2001-01-01

Analytical formulae for total cross sections for electron scattering by atoms which are close to the noble gases (Ne, Ar and Kr), for electron energies ranging from 0.5 to 10 keV, have been obtained in this study. We have shown, previously, that molecular total cross sections, at these energies, depend on target polarizability and the number of target electrons. A similar behaviour has been supposed for total cross sections of some atoms (N, O, F, P, S, Cl, As, Se and Br). The obtained expression depends on atomic parameters and it is based in some correlation derived from noble gases. The applicability of the formula has been checked by comparison with available data for atomic oxygen. (orig.)

Analytical formulae for total cross sections for electron scattering by atoms (N, O, F, Ne, P, S, Cl, Ar, As, Se, Br, Kr) between 0.5-10 keV

Energy Technology Data Exchange (ETDEWEB)

Williart, A. [Univ. Nacional de Educacion a Distancia, Madrid (Spain). Dept. de Fisica de los Materiales; Garcia, G. [Centro de Investigaciones Energeticas, Medioambientales y Tecnologicas, Madrid (Spain)

2001-10-01

Analytical formulae for total cross sections for electron scattering by atoms which are close to the noble gases (Ne, Ar and Kr), for electron energies ranging from 0.5 to 10 keV, have been obtained in this study. We have shown, previously, that molecular total cross sections, at these energies, depend on target polarizability and the number of target electrons. A similar behaviour has been supposed for total cross sections of some atoms (N, O, F, P, S, Cl, As, Se and Br). The obtained expression depends on atomic parameters and it is based in some correlation derived from noble gases. The applicability of the formula has been checked by comparison with available data for atomic oxygen. (orig.)

Magnetism of triangular nanoflakes with different compositions and edge terminations

International Nuclear Information System (INIS)

Zhang Shunhong; Zhou Jian; Li Xiaowei; Wang Qian

2012-01-01

Since the discovery of the giant magnetoresistance effect, extensive research has been devoted to finding new materials for spintronic devices. The hotly pursued nanostructure-based magnetic materials are potential candidates for such applications. Among them, graphene triangular nanoflakes (G-TNFs), due to their special magnetic configurations, can serve as building blocks for design of new C-based magnetic materials. This motivates the present study to systematically investigate how magnetism of the TNFs changes with their edge termination, composition, and atomic distribution. Using density functional theory, we show that the F-terminated G-TNFs have similar magnetic behavior to the H-terminated G-TNFs. Besides the edge terminations, partially hydrogenation of interior C atoms in the G-TNFs breaks the conjugate π orbitals and thus leads to extra net magnetic moment. The IV-group binary SiC-TNFs resemble the G-TNFs in magnetic properties, while the III–V group binary BN- and AlN-TNFs are different although they also have honeycomb structures. The different magnetic behaviors originate from the different occupations of p z atomic orbitals and the resulting change of conjugate π molecular orbitals. This study provides physical insight on tuning the magnetic behavior of TNFs through controlling their composition, size, and edge termination.

Photochemistry of CS2/Cl complexes-combined pulse radiolysis-laser flash photolysis studies

International Nuclear Information System (INIS)

Sumiyoshi, Takashi; Nakayama, Masayoshi; Fujiyoshi, Ryoko; Sawamura, Sadashi

2006-01-01

Complexes of chlorine atoms and carbon disulfide (CS 2 ) were produced by pulse radiolysis of CS 2 in halocarbons and photochemical reactions were studied by laser flash photolysis. Excitation of CS 2 /Cl complexes resulted in rapid and permanent photobleaching. The photobleaching of CS 2 /Cl complexes is due to intermolecular chlorine atom abstraction in CCl 4 with a quantum yield of 0.04, while that ascribed to hydrogen atom abstraction in 1,2-dichloroethane has a quantum yield of 0.21. The effects of additives are discussed based on the bond dissociation energy

RATE CONSTANTS FOR THE REACTIONS OF OH RADICALS AND CL ATOMS WITH DI-N-PROPYL ETHER AND DI-N-BUTYL ETHER AND THEIR DEUTERATED ANALOGS. (R825252)

Science.gov (United States)

Using relative rate methods, rate constants for the gas-phase reactions of OH radicals and Cl atoms with di-n-propyl ether, di-n-propyl ether-d14, di-n-butyl ether and di-n-butyl ether-d18 have been measured at 296 ? 2 K and atmos...

[(PhCH2O2P(CH32CHNCH(CH32]2PdCl2/CuI as Cocatalyst for Coupling-Cyclization of 2-Iodophenol with Terminal Alkynes in Water

Directory of Open Access Journals (Sweden)

Panli Jiang

2018-03-01

Full Text Available A new and efficient [(PhCH2O2P(CH32CHNCH(CH32]2PdCl2/CuI-co-catalyzed coupling-cyclization reactions of 2-iodophenol with terminal alkynes is described. Different 2-substitued benzo[b]furan derivatives are obtained in good to excellent yields. This protocol employs a relatively low palladium(II catalyst loading in water under air conditions.

Compact Termination for Structural Soft-goods

Data.gov (United States)

National Aeronautics and Space Administration — Glass fiber is unique in its ability to withstand atomic oxygen and ultraviolet radiation in-space environments. However, glass fiber is also difficult to terminate...

LASER RADIATION CHARACTERISTICS (BRIEF COMMUNICATIONS): Conversion of KrCl and XeCl laser radiation to the visible spectral range by stimulated Raman scattering in lead vapor

Science.gov (United States)

Evtushenko, Gennadii S.; Mel'chenko, S. V.; Panchenko, Aleksei N.; Tarasenko, Viktor F.

1990-04-01

Conversion of KrCl and XeCl laser radiation by stimulated Raman scattering was achieved in lead vapor. The KrCl laser radiation was converted into three lines in the visible region at λ = 406, 590, and 723 nm by transitions from both the ground and first excited levels of the lead atom. The conversion efficiency of XeCl laser radiation of low spatial coherence was found to be limited by the activation of a competing nonlinear process.

36Cl measurements of Hiroshima concrete samples

International Nuclear Information System (INIS)

Matsuhiro, T.; Nagashima, Y.; Seki, R.; Takahashi, T.

2002-01-01

The 36 Cl AMS studies are reported. A new steps of procedure of a sample preparation is developed and a tremendous reduction of sulphur background has been achieved. The 36 Cl contents of two atomic bombed concrete samples, old Hiroshima Bank one and Gokoku Shrine one, have been measured as a function of 36 Cl to Cl ratio by the Tsukuba AMS system. The 36 Cl to Cl ratio of the old Hiroshima Bank sample shows very nice agreement with the result of γ measurement of 152 Eu. Otherwise, the ratio is about 20% smaller than an estimation by the DS86 dosimetry system. A result of the Gokoku Shrine sample is also smaller than a depth profile estimation by the same DS86. It might be clear that the DS86 has a tendency of overestimation. It seems that a calculation method and/or the parameters used in the calculation are requested to be improved. (author)

Infiltration at Yucca Mountain, Nevada, traced by 36Cl

International Nuclear Information System (INIS)

Norris, A.E.; Wolfsberg, K.; Gifford, S.K.; Bentley, H.W.; Elmore, D.

1987-04-01

Measurements of chloride and 36 Cl in soils from two locations near Yucca Mountain, Nevada, have been used to trace the infiltration of precipitation in this arid region. The results show that the 36 Cl fallout from nuclear weapons testing formed a well-defined peak at one location, with a maximum 0.5m below the surface. The structure of the 36 Cl bomb pulse at the other location was much more complex, and quantity of 36 Cl in the bomb pulse was 12 atoms 36 Cl/m 2 in the bomb pulse at the first location. The data indicate hydrologic activity subsequent to the 36 Cl bomb pulse fallout at one location, but none at the other location. 11 refs

Molecular beam electric deflection of the tetrahalides CF4, CCl4, SiF4, SiCl4, GeCl4, TiF4, TiCl4, VF4, and VCl4

International Nuclear Information System (INIS)

Muenter, A.A.; Dyke, T.R.; Falconer, W.E.; Klemperer, W.

1975-01-01

Using molecular beam electric deflection, the temperature dependence of polar behavior has been studied for the molecules CF 4 , CCl 4 , SiF 4 , SiCl 4 , GeCl 4 , TiF 4 TiCl 4 , VF 4 , VF 4 , and VCl 4 . A number of these molecules show polar behavior consistent with a vibrationally induced dipole moment for states with one or both of the triply degenerate vibrations excited. In four of the tetrachloride species, the presence of a vibrationally induced dipole moment was confirmed by the change in polar behavior with isotopic substituion of the Cl atoms. The deflection behavior of the transition metal tetrahalides varied from nonpolar in VCl 4 to very polar in TiF 4

Interplay between structure and transport properties of molten salt mixtures of ZnCl2-NaCl-KCl: A molecular dynamics study.

Science.gov (United States)

Manga, Venkateswara Rao; Swinteck, Nichlas; Bringuier, Stefan; Lucas, Pierre; Deymier, Pierre; Muralidharan, Krishna

2016-03-07

Molten mixtures of network-forming covalently bonded ZnCl2 and network-modifying ionically bonded NaCl and KCl salts are investigated as high-temperature heat transfer fluids for concentrating solar power plants. Specifically, using molecular dynamics simulations, the interplay between the extent of the network structure, composition, and the transport properties (viscosity, thermal conductivity, and diffusion) of ZnCl2-NaCl-KCl molten salts is characterized. The Stokes-Einstein/Eyring relationship is found to break down in these network-forming liquids at high concentrations of ZnCl2 (>63 mol. %), while the Eyring relationship is seen with increasing KCl concentration. Further, the network modification due to the addition of K ions leads to formation of non-bridging terminal Cl ions, which in turn lead to a positive temperature dependence of thermal conductivity in these melts. This new understanding of transport in these ternary liquids enables the identification of appropriate concentrations of the network formers and network modifiers to design heat transfer fluids with desired transport properties for concentrating solar power plants.

Cl-intercalated graphene on SiC: Influence of van der Waals forces

KAUST Repository

Cheng, Yingchun; Zhu, Zhiyong; Schwingenschlö gl, Udo

2013-01-01

The atomic and electronic structures of Cl-intercalated epitaxial graphene on SiC are studied by first-principles calculations. By increasing the Cl concentration, doping levels from n-type to slightly p-type are achieved on the SiC(0001) surface, while a wider range of doping levels is possible on the SiC(0001̄) surface. We find that the Cl atoms prefer bonding to the substrate rather than to the graphene. By varying the Cl concentration the doping level can be tailored. Consideration of van der Waals forces improves the distance between the graphene and the substrate as well as the binding energy, but it is not essential for the formation energy. For understanding the doping mechanism the introduction of non-local van der Waals contributions to the exchange correlation functional is shown to be essential. Copyright © EPLA, 2013.

Influencia de las emociones en el juicio clínico de los profesionales de la salud a propósito del diagnóstico de enfermedad terminal

Directory of Open Access Journals (Sweden)

María Paz García-Caro

2010-01-01

Full Text Available En España, el proceso de morir se describe con frecuencia como «malo» o incluso como «muy malo». Entre los motivos, destacan las dificultades de los profesionales de la salud para afrontar la muerte y para asistir y acompañar en el proceso de morir a sus enfermos. A la influencia del contexto cultural actual en cuanto al sentido de la muerte y al modo de morir, se unen situaciones de carácter clínico y profesional como el momento del diagnóstico de una enfermedad terminal, con importantes implicaciones emocionales para el profesional, el enfermo y la familia, y un efecto directo en la respuesta asistencial a la situación. Planteamos un estudio cualitativo de tipo fenomenológico, fundamentado en la Grounded Theory, sobre una muestra final de 42 entrevistas en profundidad a médicos y enfermeros de diferentes ámbitos asistenciales de la provincia de Granada (España, para conocer, en su propio contexto, el punto de vista de los profesionales implicados en la atención al enfermo terminal. Los datos se analizaron con el software ATLAS.tí siguiendo una codificación temática. Los resultados muestran el efecto que el factor emocional tiene en el juicio clínico del profesional y justifican la necesidad de ampliar y profundizar en su estudio.

The structure of PbCl2 on the {100} surface of NaCl and its consequences for crystal growth

Science.gov (United States)

Townsend, Eleanor R.; Brugman, Sander J. T.; Blijlevens, Melian A. R.; Smets, Mireille M. H.; de Poel, Wester; van Enckevort, Willem J. P.; Meijer, Jan A. M.; Vlieg, Elias

2018-04-01

The role that additives play in the growth of sodium chloride is a topic which has been widely researched but not always fully understood at an atomic level. Lead chloride (PbCl2) is one such additive which has been reported to have growth inhibition effects on NaCl {100} and {111}; however, no definitive evidence has been reported which details the mechanism of this interaction. In this investigation, we used the technique of surface x-ray diffraction to determine the interaction between PbCl2 and NaCl {100} and the structure at the surface. We find that Pb2+ replaces a surface Na+ ion, while a Cl- ion is located on top of the Pb2+. This leads to a charge mismatch in the bulk crystal, which, as energetically unfavourable, leads to a growth blocking effect. While this is a similar mechanism as in the anticaking agent ferrocyanide, the effect of PbCl2 is much weaker, most likely due to the fact that the Pb2+ ion can more easily desorb. Moreover, PbCl2 has an even stronger effect on NaCl {111}.

Multiple-scattering and DV-Xα analyses of a Cl-passivated Ge(111) surface

International Nuclear Information System (INIS)

Cao, S; Tang, J-C; Shen, S-L

2003-01-01

The multiple-scattering cluster and DV-Xα methods have been employed to analyse the chlorine 1s near edge x-ray absorption fine structure (NEXAFS) of a Cl-passivated Ge(111) surface. Our detailed analysis demonstrates how the chlorine atoms form a perfect monochloride structure with Cl bonding to the topmost Ge atom. Our calculation reveals the interaction in the chlorine layer is multipolar electrostatic forces. Furthermore, the DV-Xα cluster calculation shows that the orbital contour of the sharp Cl-Ge resonance exhibits a global symmetry, which confirms it to be σ * -like. The above studies are found to enrich previous experimental NEXAFS investigations

Effect of atomic vibrations in XANES: polarization-dependent damping of the fine structure at the Cu K-edge of (creat)2CuCl4.

Science.gov (United States)

Šipr, Ondřej; Vackář, Jiří; Kuzmin, Alexei

2016-11-01

Polarization-dependent damping of the fine structure in the Cu K-edge spectrum of creatinium tetrachlorocuprate [(creat) 2 CuCl 4 ] in the X-ray absorption near-edge structure (XANES) region is shown to be due to atomic vibrations. These vibrations can be separated into two groups, depending on whether the respective atoms belong to the same molecular block; individual molecular blocks can be treated as semi-rigid entities while the mutual positions of these blocks are subject to large mean relative displacements. The effect of vibrations can be efficiently included in XANES calculations by using the same formula as for static systems but with a modified free-electron propagator which accounts for fluctuations in interatomic distances.

36Cl-AMS measurements with 3-MV tandem accelerator

International Nuclear Information System (INIS)

Wang Huijuan; Guan Yongjing; Zhang Wei; Jiang Shan; Ming He

2013-01-01

36 C- is one of the most interesting nuclides in accelerator mass spectrometry (AMS) measurements. The application of 36 Cl has been widely applied in various fields. All most all of 36 Cl AMS measurements at natural isotopic concentrations have yet been performed at tandem accelerator with 5 MV or higher terminal voltage. The measure improvement of 36 Cl and other medium heavy isotopes performed at 3 MV in AMS facilities is one of the hottest topics in AMS measurements. In order to increase the suppression factor of 36 S, the energy loss straggling and angular straggling of 36 Cl and 36 S ions in various counter gases (P10, isobutane and propane) were investigated. Some groundwater samples were measured with energy of 32 MeV, and the results were in good agreement with the result obtained with ion energy of 72 MeV. The results indicate that the approximate detection limit of 36 Cl in 3 MV AMS facility is 36 Cl/Cl=1 × 10 -14 , and the uncertainty is 30% when the sample with isotopic ration 36 Cl/Cl≈10 -13 . (authors)

Rhodium-catalyzed Chemo- and Regioselective Cross-dimerization of Two Terminal Alkynes

Science.gov (United States)

Xu, Hua-Dong; Zhang, Ren-Wei; Li, Xiaoxun; Huang, Suyu; Tang, Weiping; Hu, Wen-Hao

2013-01-01

Cross-dimerization of terminal arylacetylenes and terminal propargylic alcohols/amides has been achieved in the effect of a rhodium catalyst. This method features high chemo- and regioselectivities rendering convenient and atom economical access to functionalized enynes. PMID:23356993

The coordination and atom transfer chemistry of titanium porphyrin complexes

Energy Technology Data Exchange (ETDEWEB)

Hays, James Allen [Iowa State Univ., Ames, IA (United States)

1993-11-05

Preparation, characterization, and reactivity of (η²- alkyne)(meso-tetratolylpoprphrinato)titanium(II) complexes are described, along with inetermetal oxygen atom transfer reactions involving Ti(IV) and Ti(III) porphyrin complexes. The η²- alkyne complexes are prepared by reaction of (TTP)TiCl₂ with LiAlH₄ in presence of alkyne. Structure of (OEP)Ti(η²-Ph-C≡C-Ph) (OEP=octaethylporphryin) was determined by XRD. The compounds undergo simple substitution to displace the alkyne and produce doubly substituted complexes. Structure of (TTP)Ti(4-picoline)₂ was also determined by XRD. Reaction of (TTP)Ti=O with (OEP)Ti-Cl yields intermetal O/Cl exchange, which is a one-electron redox process mediated by O atom transfer. Also a zero-electron redox process mediated by atom transfer is observed when (TTP)TiCl₂ is reacted with (OEP)Ti=O.

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

Directory of Open Access Journals (Sweden)

Mohammad Navid Soltani Rad

2018-03-01

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

Measurement of the 36Cl deposition flux in central Japan: natural background levels and seasonal variability

International Nuclear Information System (INIS)

Tosaki, Yuki; Tase, Norio; Sasa, Kimikazu; Takahashi, Tsutomu; Nagashima, Yasuo

2012-01-01

Essential parameters for the applications of 36 Cl as a tracer in groundwater studies include the initial 36 Cl/Cl ratio, at the time of recharge, and/or the natural background deposition flux of 36 Cl in the recharge area. To facilitate the hydrological use of 36 Cl in central Japan, this study aimed to obtain a precise estimate of the long-term average local 36 Cl flux and to characterize its seasonal variability. The 36 Cl in precipitation was continuously monitored in Tsukuba, central Japan over a period of >5 years. The 36 Cl flux showed a clear seasonal variation with an annual peak during the spring, which was attributed to the seasonal variability of tropopause height. The long-term average 36 Cl flux (32 ± 2 atoms m −2 s −1 ), estimated from the measured data, was consistent with the prediction from the 36 Cl latitudinal fallout model scaled using the global mean production rate of 20 atoms m −2 s −1 . The initial 36 Cl/Cl ratio was estimated to be (41 ± 6) × 10 −15 , which is similar to that of pre-bomb groundwater in the Tsukuba Upland. An observation period covering an 11-year solar cycle would yield more accurate estimates of the values, given the increased 36 Cl flux during the solar minimum. - Highlights: ► We monitored 36 Cl in precipitation in central Japan over a period of >5 years. ► The 36 Cl flux varied seasonally, with a peak in spring. ► The long-term average 36 Cl flux and the initial 36 Cl/Cl ratio were 32 ± 2 atoms m −2 s −1 and (41 ± 6) × 10 −15 , respectively. ► An observation period covering an 11-year solar cycle would yield more accurate estimates of the values, given the increased 36 Cl flux during the solar minimum.

Governing parameters and dynamics of turbulent spray atomization from modern GDI injectors

International Nuclear Information System (INIS)

Moon, Seoksu; Li, Tianyun; Sato, Kiyotaka; Yokohata, Hideaki

2017-01-01

Understanding the governing parameters and dynamics of turbulent spray atomization is essential for the advancement of fuel injection technologies, but no concrete understandings have been derived previously. The current study investigates the governing parameters and dynamics of turbulent spray atomization by experimental observations of near-nozzle spray phenomena using an X-ray imaging technique. The effects of critical injection parameters such as fuel property, injection pressure and ambient density on near-nozzle liquid feature size and velocity distributions were extensively studied using three injection nozzles having different levels of initial flow turbulence and dispersion. Based on the results, the governing parameters and dynamics of turbulent spray atomization and the issues on the advanced fuel injection control of modern engines were thoroughly discussed. The results showed that fuel and injection pressure effects on spray atomization became insignificant from a critical Weber number which decreased upon the increase in initial flow turbulence and dispersion. The increase in ambient density increased the resultant droplet size at downstream due to the faster deceleration of spray which brought the atomization termination location closer to the nozzle exit. The spray atomization was terminated at the location of ca. 72% exit velocity regardless of the injection condition. - Highlights: • Governing parameters and dynamics of turbulent spray atomization are investigated. • Fuel and injection pressure effects on atomization are saturated from critical We. • High ambient density increases drop sizes due to faster termination of atomization. • Atomization terminates when the spray velocity decays to ca. 72% of exit velocity. • Strategies for improvement of current injection technologies are discussed.

35Cl NQR spectra of complexes of tetrachlorostannane with substituted benzoyl chlorides

International Nuclear Information System (INIS)

Feshin, V.P.; Dogushin, G.V.; Lazarev, I.M.; Voronkov, M.G.; Feshina, E.V.

1987-01-01

35 Cl NQR spectra of mixtures of SnCl 4 with 2-, 3- and 4-XC 6 H 4 COCl were obtained. The electronic and steric structure of the complexes obtained was established. Their formation and structure depend on the nature of substituents X. Complexes with a trigonal-bipyramidal structure are formed with the participation of the carbonyl oxygen atom of the ligand as an electron-donor-center, and complexes with trans-octahedral structure, with the participation of the sulfur atom of the X = CH 3 S substituent

Two-center three-electron bonding in ClNH{sub 3} revealed via helium droplet infrared laser Stark spectroscopy: Entrance channel complex along the Cl + NH{sub 3} → ClNH{sub 2} + H reaction

Energy Technology Data Exchange (ETDEWEB)

Moradi, Christopher P.; Douberly, Gary E., E-mail: douberly@uga.edu [Department of Chemistry, University of Georgia, Athens, Georgia 30602-2556 (United States); Xie, Changjian; Guo, Hua [Department of Chemistry and Chemical Biology, University of New Mexico, Albuquerque, New Mexico 87131 (United States); Kaufmann, Matin [Department of Physical Chemistry II, Ruhr-University Bochum, D-44801 Bochum (Germany)

2016-04-28

Pyrolytic dissociation of Cl{sub 2} is employed to dope helium droplets with single Cl atoms. Sequential addition of NH{sub 3} to Cl-doped droplets leads to the formation of a complex residing in the entry valley to the substitution reaction Cl + NH{sub 3} → ClNH{sub 2} + H. Infrared Stark spectroscopy in the NH stretching region reveals symmetric and antisymmetric vibrations of a C{sub 3v} symmetric top. Frequency shifts from NH{sub 3} and dipole moment measurements are consistent with a ClNH{sub 3} complex containing a relatively strong two-center three-electron (2c–3e) bond. The nature of the 2c–3e bonding in ClNH{sub 3} is explored computationally and found to be consistent with the complexation-induced blue shifts observed experimentally. Computations of interconversion pathways reveal nearly barrierless routes to the formation of this complex, consistent with the absence in experimental spectra of two other complexes, NH{sub 3}Cl and Cl–HNH{sub 2}, which are predicted in the entry valley to the hydrogen abstraction reaction Cl + NH{sub 3} → HCl + NH{sub 2}.

Atomic structure of diamond {111} surfaces etched in oxygen water vapor

International Nuclear Information System (INIS)

Theije, F.K. de; Reedijk, M.F.; Arsic, J.; Enckevort, W.J.P. van; Vlieg, E.

2001-01-01

The atomic structure of the {111} diamond face after oxygen-water-vapor etching is determined using x-ray scattering. We find that a single dangling bond diamond {111} surface model, terminated by a full monolayer of -OH fits our data best. To explain the measurements it is necessary to add an ordered water layer on top of the -OH terminated surface. The vertical contraction of the surface cell and the distance between the oxygen atoms are generally in agreement with model calculations and results on similar systems. The OH termination is likely to be present during etching as well. This model experimentally confirms the atomic-scale mechanism we proposed previously for this etching system

Halogen atom reactions activated by nuclear transformations. Progress report, February 15, 1975--February 14, 1976

International Nuclear Information System (INIS)

Rack, E.P.

1976-02-01

High energy reactions of halogen atoms or ions, activated by nuclear transformations, are being studied in gaseous, high pressure, and condensed phase saturated and unsaturated hydrocarbons, halomethanes, and other organic systems. Experimental and theoretical data are presented in the following areas: systematics of iodine hot atom reactions in halomethanes, reactions and systematics of iodine reactions with pentene and butene isomers, radiative neutron capture activated reactions of iodine with acetylene, gas to liquid to solid transition in hot atom chemistry, kinetic theory applications of hot atom reactions and the mathematical development of caging reactions, solvent dependence of the stereochemistry of the 38 Cl for Cl substitution following 37 Cl(n,γ) 38 Cl in liquid meso and dl-(CHFCl) 2 . A technique was also developed for the radioassay of Al in urine specimens

Chloride Ion Transport by the E. coli CLC Cl-/H+ Antiporter: A Combined Quantum-Mechanical and Molecular-Mechanical Study.

Science.gov (United States)

Wang, Chun-Hung; Duster, Adam W; Aydintug, Baris O; Zarecki, MacKenzie G; Lin, Hai

2018-01-01

We performed steered molecular dynamics (SMD) and umbrella sampling simulations of Cl - ion migration through the transmembrane domain of a prototypical E. coli CLC Cl - /H + antiporter by employing combined quantum-mechanical (QM) and molecular-mechanical (MM) calculations. The SMD simulations revealed interesting conformational changes of the protein. While no large-amplitude motions of the protein were observed during pore opening, the side chain rotation of the protonated external gating residue Glu148 was found to be critical for full access of the channel entrance by Cl - . Moving the anion into the external binding site (S ext ) induced small-amplitude shifting of the protein backbone at the N-terminal end of helix F. As Cl - traveled through the pore, rigid-body swinging motions of helix R separated it from helix D. Helix R returned to its original position once Cl - exited the channel. Population analysis based on polarized wavefunction from QM/MM calculations discovered significant (up to 20%) charge loss for Cl - along the ion translocation pathway inside the pore. The delocalized charge was redistributed onto the pore residues, especially the functional groups containing π bonds (e.g., the Tyr445 side chain), while the charges of the H atoms coordinating Cl - changed almost negligibly. Potentials of mean force computed from umbrella sampling at the QM/MM and MM levels both displayed barriers at the same locations near the pore entrance and exit. However, the QM/MM PMF showed higher barriers (~10 kcal/mol) than the MM PMF (~2 kcal/mol). Binding energy calculations indicated that the interactions between Cl - and certain pore residues were overestimated by the semi-empirical PM3 Hamiltonian and underestimated by the CHARMM36 force fields, both of which were employed in the umbrella sampling simulations. In particular, CHARMM36 underestimated binding interactions for the functional groups containing π bonds, missing the stabilizations of the Cl - ion due

The oxidation of ReCl{sub 5} with oleum: synthesis and crystal structure of Re{sub 2}O{sub 4}Cl{sub 4}(SO{sub 4})

Energy Technology Data Exchange (ETDEWEB)

Betke, Ulf; Wickleder, Mathias S. [Carl von Ossietzky University of Oldenburg, Institute of Pure and Applied Chemistry (Germany)

2012-01-15

The reaction of ReCl{sub 5} and fuming sulfuric acid (25 % SO{sub 3}) in a sealed glass tube at 200 C led to red, needle shaped single crystals of Re{sub 2}O{sub 4}Cl{sub 4}(SO{sub 4}) (monoclinic, C2/c, a = 1501.8(2) pm, b = 1545.9(2) pm, c = 945.18(8) pm, β = 98.761(9) , Z = 8). In the crystal structure the [ReO{sub 2}] moieties are linked by [SO{sub 4}]{sup 2-} tetrahedra to chains along the [101] direction. Each sulfate ion connects four rhenium atoms, additional two chloride ions complete the octahedral coordination sphere of each rhenium atom according to {sup 1}{sub ∞}[ReO{sub 2/1}Cl{sub 2/1}(SO{sub 4}){sub 2/4}]. (Copyright copyright 2012 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

Effects of edge reconstruction on the common groups terminated zigzag phosphorene nanoribbon

International Nuclear Information System (INIS)

Xiao, Huaping; Guo, Sumei; Zhang, Chunxiao; He, Chaoyu; Zhong, Jianxin

2017-01-01

Edge configuration plays an important role in the electronic properties of nano-structures. In this work, we perform first-principles calculations to study the effects of the cooperation between neighbor groups on the edge configuration and the electronic properties of zigzag-PNRs (ZPNRs) terminated by common groups H, F, O, S and OH. We find that the cooperation has little effect on the H(F)-terminated ZPNRs, but gives rise to an edge reconstruction for the O(S)-terminated ZPNRs. The edge reconstruction derives from the repulsion between neighbor O atoms and the distortion of the P skeleton induced by the p state coupling among the edge, second edge and third edge P atoms. In comparison to the H-terminated ZPNRs, O-terminated ZPNRs are also a semiconductor and enlarge the band gap, but bring about an extra transport channel for the charge transport at the edge and decreases the effective mass of the electron and hole. OH-terminated ZPNRs also undergo a doubling of the unit cell (UC) along the periodic direction because of the different directions of the neighbor O–H bonds. In comparison with the H-terminated ZPNRs, OH-terminated ZPNRs show a similar band gap and electronic effective mass, but increase the effective mass of the hole. (paper)

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

Science.gov (United States)

Khiri, D; Hochlaf, M; Chambaud, G

2016-08-04

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

Cl-36 in polar ice, rainwater and seawater

Science.gov (United States)

Finkel, R. C.; Nishiizumi, K.; Elmore, D.; Ferraro, R. D.; Gove, H. E.

1980-01-01

Concentrations of the cosmogenic radioisotope Cl-36 in Antarctic ice, rain, and an upper limit of the seawater value are determined using van de Graaff accelerator high energy mass spectrometry. Cl-36 concentrations in Antarctic ice range between 2.5 to 8.7 x 10 to the 6th atoms Cl-36/kg, while those concentrations in samples collected at the Alan Hills ice field locations where meteorites have been brought to the surface by glacial flow and ablation are found to vary by more than a factor of three. This variation is attributed either to the effects of atmospheric mixing and scavenging or to radioactive decay in old ice. The Cl-36 concentration found in a present sample of rainwater is much lower than that reported in samples collected in the early 1960's, suggesting the occurrence of a decrease in the concentration of atmospheric Cl-36 derived from nuclear weapons tests over this time period.

Spectral interferences in atomic absorption spectrometry, (5)

International Nuclear Information System (INIS)

Daidoji, Hidehiro

1979-01-01

Spectral interferences were observed in trace element analysis of concentrated solutions by atomic absorption spectrometry. Molecular absorption and emission spectra for strontium chloride and nitrate, barium chloride and nitrate containing 12 mg/ml of metal ion in airacetylene flame were measured in the wavelength range from 200 to 700 nm. The absorption and emission spectra of SrO were centered near 364.6 nm. The absorption spectra of SrOH around 606.0, 671.0 and 682.0 nm were very strong. And, emission spectrum of BaOH in the wavelength range from 480 to 550 nm was stronger. But, the absorption of this band spectrum was very weak. In the wavelength range from 200 to 400 nm, some unknown bands of absorption were observed for strontium and barium. Absorption spectra of SrCl and BaCl were observed in the argon-hydrogen flame. Also, in the carbon tube atomizer, the absorption spectra of SrCl and BaCl were detected clearly in the wavelength range from 185 to 400 nm. (author)

The inhibition effect and mechanism of L-cysteine on the corrosion of bronze covered with a CuCl patina

International Nuclear Information System (INIS)

Wang, Tianran; Wang, Julin; Wu, Yuqing

2015-01-01

Highlights: • CuCl patina was synthesized on bronze electrodes with electrochemical method. • L-cysteine was used as a green inhibitor for bronze covered with CuCl patina. • The inhibition efficiency reached above 90%. • The inhibition mechanism of L-cysteine on CuCl patina was investigated. - Abstract: CuCl patina was synthesized on bronze electrodes with electrochemical method. The inhibition effect and mechanism of L-cysteine (Cys) on bronze covered with CuCl patina have been studied with electrochemical impedance spectroscopy (EIS) and X-ray photoelectron spectroscopy (XPS) techniques. The EIS results show that Cys stabilized the CuCl patina to a great extent. The hydrolysis reaction of CuCl was inhibited effectively and an inhibition efficiency of over 90% was achieved. The XPS analyses indicate that the chemisorption of Cys molecules on CuCl surface occurred through sulfur atom in thiol and nitrogen atom in amino group

Compact Termination for Structural Soft-goods

Science.gov (United States)

Wilkes, Robert, Jr.

2013-01-01

Glass fiber is unique in its ability to withstand atomic oxygen and ultraviolet radiation in-space environments. However, glass fiber is also difficult to terminate by traditional methods without decreasing its strength significantly. Glass fiber products are especially sensitive to bend radius, and do not work very well with traditional 'sewn loop on pin' type connections. As with most composites, getting applied loads from a metallic structure into the webbing without stress concentrations is the key to a successful design. A potted end termination has been shown in some preliminary work to out-perform traditional termination methods. It was proposed to conduct a series of tensile tests on structural webbing or cord to determine the optimum potting geometry, and to then be able to estimate a weight and volume savings over traditional sewn-overa- pin connections. During the course of the investigation into potted end terminations for glass fiber webbing, a new and innovative connection was developed that has lower weight, reduced fabrication time, and superior thermal tolerance over the metallic end terminations that were to be optimized in the original proposal. This end termination essentially transitions the flexible glass fiber webbing into a rigid fiberglass termination, which can be bolted/fastened with traditional methods

Prediction of drug terminal half-life and terminal volume of distribution after intravenous dosing based on drug clearance, steady-state volume of distribution, and physiological parameters of the body.

Science.gov (United States)

Berezhkovskiy, Leonid M

2013-02-01

The steady state, V(ss), terminal volume of distribution, V(β), and the terminal half-life, t(1/2), are commonly obtained from the drug plasma concentration-time profile, C(p)(t), following intravenous dosing. Unlike V(ss) that can be calculated based on the physicochemical properties of drugs considering the equilibrium partitioning between plasma and organ tissues, t(1/2) and V(β) cannot be calculated that way because they depend on the rates of drug transfer between blood and tissues. Considering the physiological pharmacokinetic model pertinent to the terminal phase of drug elimination, a novel equation that calculates t(1/2) (and consequently V(β)) was derived. It turns out that V(ss), the total body clearance, Cl, equilibrium blood-plasma concentration ratio, r; and the physiological parameters of the body such as cardiac output, and blood and tissue volumes are sufficient for determination of terminal kinetics. Calculation of t(1/2) by the obtained equation appears to be in good agreement with the experimentally observed vales of this parameter in pharmacokinetic studies in rat, monkey, dog, and human. The equation for the determination of the pre-exponent of the terminal phase of C(p)(t) is also found. The obtained equation allows to predict t(1/2) in human assuming that V(ss) and Cl were either obtained by allometric scaling or, respectively, calculated in silico or based on in vitro drug stability measurements. For compounds that have high clearance, the derived equation may be applied to calculate r just using the routine data on Cl, V(ss), and t(1/2), rather than doing the in vitro assay to measure this parameter. Copyright © 2012 Wiley Periodicals, Inc.

MICROSTRUCTURE OF THE HELIOSPHERIC TERMINATION SHOCK: IMPLICATIONS FOR ENERGETIC NEUTRAL ATOM OBSERVATIONS

International Nuclear Information System (INIS)

Zank, G. P.; Heerikhuisen, J.; Pogorelov, N. V.; Burrows, R.; McComas, D.

2010-01-01

The Voyager 2 plasma observations of the proton distribution function downstream of the quasi-perpendicular heliospheric termination shock (TS) showed that upstream thermal solar wind ions played little role in the shock dissipation mechanism, being essentially transmitted directly through the shock. Instead, the hot supra-thermal pickup ion (PUI) component is most likely responsible for the dissipation at the TS. Consequently, the downstream proton distribution function will be a complicated superposition of relatively cool thermal solar wind protons and hot PUIs that have experienced either direct transmission or reflection at the TS cross-shock potential. We develop a simple model for the TS microstructure that allows us to construct approximate proton distribution functions for the inner heliosheath. The distribution function models are compared to κ-distributions, showing the correspondence between the two. Since the interpretation of energetic neutral atom (ENA) fluxes measured at 1 AU by IBEX will depend sensitively on the form of the underlying proton distribution function, we use a three-dimensional MHD-kinetic global model to model ENA spectra at 1 AU and ENA skymaps across the IBEX energy range. We consider both solar minimum and solar maximum-like global models, showing how ENA skymap structure can be related to global heliospheric structure. We suggest that the ENA spectra may allow us to probe the directly the microphysics of the TS, while the ENA skymaps reveal heliospheric structure and, at certain energies, are distinctly different during solar minimum and maximum.

Quantum mechanical study on hydrogen bonds between 3-aminophenol and CH{sub x}Cl{sub 4-}x (x=1, 2, 3): Effect of the number of halogen atoms

Energy Technology Data Exchange (ETDEWEB)

Lee, So Young; Kang, Hyuk [Dept. of Chemistry, Ajou University, Suwon (Korea, Republic of)

2015-03-15

Hydrogen bonds between 3-aminophenol and three chlorine-substituted methanes (CHCl{sub 3}, CH{sub 2}Cl{sub 2}, and CH{sub 3}Cl) were quantum mechanically studied at MP2/aug-cc-pVDZ level. Several low-energy structures with a hydrogen bond were identified for all chlorinated methanes, and the properties of their C[BOND]H stretching vibrations were investigated. When it is hydrogen-bonded to 3-aminophenol (3AP), the C[BOND]H stretching frequency of CHCl{sub 3} is blue-shifted by 18–54 cm−1, and its IR absorption intensity is 48–74 times increased, depending on the isomer. The symmetric and antisymmetric C[BOND]H stretches of CH{sub 2}Cl{sub 2} and CH{sub 3}Cl are shifted in either direction by a few cm−1 upon hydrogen-bonding to 3AP, and their IR intensity was increased by a few times. It is concluded that all chlorinated methanes can make a π-hydrogen bond to 3AP but only CHCl{sub 3}, the one with the most chlorine atoms, makes a blue-shifting hydrogen bond, or an “antihydrogen bond”.

Morphology, composition and electrical properties of SnO{sub 2}:Cl thin films grown by atomic layer deposition

Energy Technology Data Exchange (ETDEWEB)

Cheng, Hsyi-En, E-mail: sean@mail.stust.edu.tw; Wen, Chia-Hui; Hsu, Ching-Ming [Department of Electro-Optical Engineering, Southern Taiwan University of Science and Technology, Tainan 71005, Taiwan (China)

2016-01-15

Chlorine doped SnO{sub 2} thin films were prepared using atomic layer deposition at temperatures between 300 and 450 °C using SnCl{sub 4} and H{sub 2}O as the reactants. Composition, structure, surface morphology, and electrical properties of the as-deposited films were examined. Results showed that the as-deposited SnO{sub 2} films all exhibited rutile structure with [O]/[Sn] ratios between 1.35 and 1.40. The electrical conductivity was found independent on [O]/[Sn] ratio but dependent on chlorine doping concentration, grain size, and surface morphology. The 300 °C-deposited film performed a higher electrical conductivity of 315 S/cm due to its higher chlorine doping level, larger grain size, and smoother film surface. The existence of Sn{sup 2+} oxidation state was demonstrated to minimize the effects of chlorine on raising the electrical conductivity of films.

Dissociation dynamics of anionic and excited neutral fragments of gaseous SiCl4 following Cl 2p and Si 2p core-level excitations

International Nuclear Information System (INIS)

Chen, J M; Lu, K T; Lee, J M; Chou, T L; Chen, H C; Chen, S A; Haw, S C; Chen, T H

2008-01-01

The state-selective dissociation dynamics for anionic and excited neutral fragments of gaseous SiCl 4 following Cl 2p and Si 2p core-level excitations were characterized by combining measurements of the photon-induced anionic dissociation, x-ray absorption and UV/visible dispersed fluorescence. The transitions of core electrons to high Rydberg states/doubly excited states in the vicinity of both Si 2p and Cl 2p ionization thresholds of gaseous SiCl 4 lead to a remarkably enhanced production of anionic, Si - and Cl - , fragments and excited neutral atomic, Si*, fragments. This enhancement via core-level excitation near the ionization threshold of gaseous SiCl 4 is explained in terms of the contributions from the Auger decay of doubly excited states, shake-modified resonant Auger decay, or/and post-collision interaction. These complementary results provide insight into the state-selective anionic and excited neutral fragmentation of gaseous molecules via core-level excitation.

Bis[2-phenyl-1-(phenyliminioisoindoline] di-μ-chlorido-bis[dichloridopalladate(II] benzene disolvate

Directory of Open Access Journals (Sweden)

Stephen R. Foley

2008-07-01

Full Text Available In the title compound, (C20H17N22[Pd2Cl6]·2C6H6, the dichloride-bridged [Pd2Cl6]2− anion lies across an inversion center with each PdII ion in a slightly distorted square-planar environment. In the crystal structure, two cations and an anion are connected via N—H...Cl hydrogen bonds between the NH groups of the iminioisoindoline cations and terminal Cl atoms of a hexachloridodipalladate(II anion. The Pd—Cl distance of the terminal chloride engaged in hydrogen bonding is slightly longer than the Pd—Cl distance of the adjacent terminal chloride which is not involved in hydrogen bonding.

An unusually stable chlorophosphite: What makes BIFOP–Cl so robust against hydrolysis?

Directory of Open Access Journals (Sweden)

Roberto Blanco Trillo

2015-03-01

Full Text Available Two chlorophosphites, the biphenyl-based BIFOP–Cl and the diphenyl ether-based O–BIFOP–Cl, exhibit striking differences regarding their reaction with water. While BIFOP–Cl is nearly completely unreactive, its oxo-derivative O–BIFOP–Cl reacts instantly with water, yielding a tricyclic hydrocarbon unit after rearrangement. The analysis of the crystal structure of O–BIFOP–Cl and BIFOP–Cl revealed that the large steric demand of encapsulating fenchane units renders the phosphorus atom nearly inaccessible by nucleophilic reagents, but only for BIFOP–Cl. In addition to the steric effect, a hypervalent P(III–O interaction as well as an electronic conjugation effect causes the high reactivity of O–BIFOP–Cl. A DFT study of the hydrolysis in BIFOP–Cl verifies a higher repulsive interaction to water and a decreased leaving tendency of the chloride nucleofuge, which is caused by the fenchane units. This high stability of BIFOP–Cl against nucleophiles supports its application as a chiral ligand, for example, in Pd catalysts.

Hydrolysis of CuCl{sub 2} in the Cu-Cl thermochemical cycle for hydrogen production: Experimental studies using a spray reactor with an ultrasonic atomizer

Energy Technology Data Exchange (ETDEWEB)

Ferrandon, Magali S.; Lewis, Michele A. [Argonne National Laboratory, Chemical Sciences and Engineering Division, 9700 S. Cass Ave., Argonne, IL 60439 (United States); Alvarez, Francisco; Shafirovich, Evgeny [The University of Texas at El Paso, Mechanical Engineering Department, 500 W. University Ave., El Paso, TX 79968 (United States)

2010-03-15

The Cu-Cl thermochemical cycle is being developed as a hydrogen production method. Prior proof-of-concept experimental work has shown that the chemistry is viable while preliminary modeling has shown that the efficiency and cost of hydrogen production have the potential to meet DOE's targets. However, the mechanisms of CuCl{sub 2} hydrolysis, an important step in the Cu-Cl cycle, are not fully understood. Although the stoichiometry of the hydrolysis reaction, 2CuCl{sub 2} + H{sub 2}O <-> Cu{sub 2}OCl{sub 2} + 2HCl, indicates a necessary steam-to-CuCl{sub 2} molar ratio of 0.5, a ratio as high as 23 has been typically required to obtain near 100% conversion of the CuCl{sub 2} to the desired products at atmospheric pressure. It is highly desirable to conduct this reaction with less excess steam to improve the process efficiency. Per Le Chatelier's Principle and according to the available equilibrium-based model, the needed amount of steam can be decreased by conducting the hydrolysis reaction at a reduced pressure. In the present work, the experimental setup was modified to allow CuCl{sub 2} hydrolysis in the pressure range of 0.4-1 atm. Chemical and XRD analyses of the product compositions revealed the optimal steam-to-CuCl{sub 2} molar ratio to be 20-23 at 1 atm pressure. The experiments at 0.4 atm and 0.7 atm showed that it is possible to lower the steam-to-CuCl{sub 2} molar ratio to 15, while still obtaining good yields of the desired products. An important effect of running the reaction at reduced pressure is the significant decrease of CuCl concentration in the solid products, which was not predicted by prior modeling. Possible explanations based on kinetics and residence times are suggested. (author)

The lanthanoid(III) chloride oxoselenates(IV) MCl[SeO3] (M = Sm - Lu) with HoCl[TeO3]- or B-type structure

International Nuclear Information System (INIS)

Lipp, C.; Schleid, T.

2008-01-01

The B-type lanthanoid(III) chloride oxoselenates(IV) MCl[SeO 3 ] (M = Sm - Lu) crystallize in the orthorhombic space group Pnma (no. 62) with Z = 4 in the structure type of HoCl[TeO 3 ]. Their lattice constants are decreasing following the lanthanoid contraction from a = 730.01(7), b = 707.90(7), c 895.64(9) pm for SmCl[SeO 3 ] to a = 714.63(7), b = 681.76(7), c = 864.05(9) pm for LuCl[SeO 3 ]. In contrast to NdCl[SeO 3 ], the only representative of the A-type structure, where the coordination numbers of the Nd 3+ cations are 7+2 and 8, the B-type structure is dominated by pentagonal bipyramids [MO 5 Cl 2 ] 9- (CN(M 3+ ) = 7), which are connected via trans-oriented O..O edges to ∞ 1 {[MO 4/2 e O 1/1 t Cl 2/1 t ] 5- } chains (e = edge-sharing, t = terminal) running parallel to the [010] direction. Their inclination relative to each other allows for an alternating interconnection of these chains via Cl - and ψ 1 -tetrahedral [SeO 3 ] 2- anions to form a three-dimensional structure. The distances within the [SeO 3 ] 2- groups are in the normal range (d(Se-O) = 165 - 172 pm), while those of the O 2- and Cl - anions to the central M 3+ cation diminish in dependence of the increasing atomic number (d(M-O) = 226 - 244 pm / 216 - 232 pm, d(M-Cl) 277 - 278 pm / 266 - 270 pm, M = Sm / Lu). For the synthesis of the chloride oxoselenates(IV) MCl[SeO 3 ] the respective lanthanoid sesquioxide (M 2 O 3 ) and selenium dioxide (SeO 2 ) were reacted with either an eutectic mixture of RbCl and LiCl or with the corresponding lanthanoid trichloride (MCl 3 ) in evacuated silica ampoules for either five weeks at 500 C or one week at 850 C. (orig.)

He atom-surface scattering: Surface dynamics of insulators, overlayers and crystal growth

International Nuclear Information System (INIS)

Safron, S.A.; Skofronick, J.G.

1994-01-01

This progress report describes work carried out in the study of surface structure and dynamics of ionic insulators, the microscopic interactions controlling epitaxial growth and the formation of overlayers, and energy exchange in multiphonon surface scattering. The approach used is to employ high resolution helium atom scattering to study the geometry and structural features of the surfaces. Experiments have been carried out on the surface dynamics of RbCl and preliminary studies done on CoO and NiO. Epitaxial growth and overlayer dynamics experiments on the systems NaCl/NaCl(001), KBr/NaCl(001), NaCl/KBr(001) and KBr/RbCl(001) have been performed. They have collaborated with two theoretical groups to explore models of overlayer dynamics with which to compare and to interpret their experimental results. They have carried out extensive experiments on the multiphonon scattering of helium atoms from NaCl and, particularly, LiF. Work has begun on self-assembling organic films on gold and silver surfaces (alkyl thiols/Au(111) and Ag(111))

Chemically induced magnetism in atomically precise gold clusters.

Science.gov (United States)

Krishna, Katla Sai; Tarakeshwar, Pilarisetty; Mujica, Vladimiro; Kumar, Challa S S R

2014-03-12

Comparative theoretical and experimental investigations are reported into chemically induced magnetism in atomically-precise, ligand-stabilized gold clusters Au25 , Au38 and Au55 . The results indicate that [Au25 (PPh3 )10 (SC12 H25 )5 Cl2 ](2+) and Au38 (SC12 H25 )24 are diamagnetic, Au25 (SC2 H4 Ph)18 is paramagnetic, and Au55 (PPh3 )12 Cl6 , is ferromagnetic at room temperature. Understanding the magnetic properties resulting from quantum size effects in such atomically precise gold clusters could lead to new fundamental discoveries and applications. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Ion Binding Energies Determining Functional Transport of ClC Proteins

Science.gov (United States)

Yu, Tao; Guo, Xu; Zou, Xian-Wu; Sang, Jian-Ping

2014-06-01

The ClC-type proteins, a large family of chloride transport proteins ubiquitously expressed in biological organisms, have been extensively studied for decades. Biological function of ClC proteins can be reflected by analyzing the binding situation of Cl- ions. We investigate ion binding properties of ClC-ec1 protein with the atomic molecular dynamics simulation approach. The calculated electrostatic binding energy results indicate that Cl- at the central binding site Scen has more binding stability than the internal binding site Sint. Quantitative comparison between the latest experimental heat release data isothermal titration calorimetry (ITC) and our calculated results demonstrates that chloride ions prefer to bind at Scen than Sint in the wild-type ClC-ec1 structure and prefer to bind at Sext and Scen than Sint in mutant E148A/E148Q structures. Even though the chloride ions make less contribution to heat release when binding to Sint and are relatively unstable in the Cl- pathway, they are still part contributors for the Cl- functional transport. This work provides a guide rule to estimate the importance of Cl- at the binding sites and how chloride ions have influences on the function of ClC proteins.

Scandium Terminal Imido Chemistry.

Science.gov (United States)

Lu, Erli; Chu, Jiaxiang; Chen, Yaofeng

2018-02-20

Research into transition metal complexes bearing multiply bonded main-group ligands has developed into a thriving and fruitful field over the past half century. These complexes, featuring terminal M═E/M≡E (M = transition metal; E = main-group element) multiple bonds, exhibit unique structural properties as well as rich reactivity, which render them attractive targets for inorganic/organometallic chemists as well as indispensable tools for organic/catalytic chemists. This fact has been highlighted by their widespread applications in organic synthesis, for example, as olefin metathesis catalysts. In the ongoing renaissance of transition metal-ligand multiple-bonding chemistry, there have been reports of M═E/M≡E interactions for the majority of the metallic elements of the periodic table, even some actinide metals. In stark contrast, the largest subgroup of the periodic table, rare-earth metals (Ln = Sc, Y, and lanthanides), have been excluded from this upsurge. Indeed, the synthesis of terminal Ln═E/Ln≡E multiple-bonding species lagged behind that of the transition metal and actinide congeners for decades. Although these species had been pursued since the discovery of a rare-earth metal bridging imide in 1991, such a terminal (nonpincer/bridging hapticities) Ln═E/Ln≡E bond species was not obtained until 2010. The scarcity is mainly attributed to the energy mismatch between the frontier orbitals of the metal and the ligand atoms. This renders the putative terminal Ln═E/Ln≡E bonds extremely reactive, thus resulting in the formation of aggregates and/or reaction with the ligand/environment, quenching the multiple-bond character. In 2010, the stalemate was broken by the isolation and structural characterization of the first rare-earth metal terminal imide-a scandium terminal imide-by our group. The double-bond character of the Sc═N bond was unequivocally confirmed by single-crystal X-ray diffraction. Theoretical investigations revealed the presence

Germylenes: structures, electron affinities, and singlet-triplet gaps of the conventional XGeCY(3) (X = H, F, Cl, Br, and I; Y = F and Cl) species and the unexpected cyclic XGeCY(3) (Y = Br and I) systems.

Science.gov (United States)

Bundhun, Ashwini; Abdallah, Hassan H; Ramasami, Ponnadurai; Schaefer, Henry F

2010-12-23

A systematic investigation of the X-Ge-CY(3) (X = H, F, Cl, Br, and I; Y = F, Cl, Br, and I) species is carried out using density functional theory. The basis sets used for all atoms (except iodine) in this work are of double-ζ plus polarization quality with additional s- and p-type diffuse functions, and denoted DZP++. Vibrational frequency analyses are performed to evaluate zero-point energy corrections and to determine the nature of the stationary points located. Predicted are four different forms of neutral-anion separations: adiabatic electron affinity (EA(ad)), zero-point vibrational energy corrected EA(ad(ZPVE)), vertical electron affinity (EA(vert)), and vertical detachment energy (VDE). The electronegativity (χ) reactivity descriptor for the halogens (X = F, Cl, Br, and I) is used as a tool to assess the interrelated properties of these germylenes. The topological position of the halogen atom bound to the divalent germanium center is well correlated with the trend in the electron affinities and singlet-triplet gaps. For the expected XGeCY(3) structures (X = H, F, Cl, Br, and I; Y = F and Cl), the predicted trend in the electron affinities is well correlated with simpler germylene derivatives (J. Phys. Chem. A 2009, 113, 8080). The predicted EA(ad(ZPVE)) values with the BHLYP functional range from 1.66 eV (FGeCCl(3)) to 2.20 eV (IGeCF(3)), while the singlet-triplet splittings range from 1.28 eV (HGeCF(3)) to 2.22 eV (FGeCCl(3)). The XGeCY(3) (Y = Br and I) species are most often characterized by three-membered cyclic systems involving the divalent germanium atom, the carbon atom, and a halogen atom.

Determination of 36Cl in environmental samples collected in the JCO by AMS

International Nuclear Information System (INIS)

Seki, R.; Tsukuba Univ., Ibaraki; Arai, D.; Nagashima, Y.; Takahashi, T.; Matsuhiro, T.; Imanaka, T.

2003-01-01

Long-lived chlorine, 36 Cl (T 1/2 = 301,000 y) in environmental samples has been measured by the AMS system installed in Tandem Accelerator Center, University of Tsukuba. A tri-carbon-molecular 12 C 3 - pilot beam method is used to stabilize the terminal voltage of the tandem. A small amount of pure carbon graphite is well mixed into a AgCl target material for creating Cl - and 12 C 3 - in the ion source. A 36 S isobaric interference in the system is eliminated to determine 36 Cl in environmental samples by chemical procedure. Some samples containing chlorine such as soil, chemical reagents and table salt have been collected in the JCO criticality accident site and analyzed to detect neutron-induced 36 Cl. The experimental result has been compared with a theoretical calculation. (author)

Energy dissipation unveils atomic displacement in the noncontact atomic force microscopy imaging of Si(111 )-(7 ×7 )

Science.gov (United States)

Arai, Toyoko; Inamura, Ryo; Kura, Daiki; Tomitori, Masahiko

2018-03-01

The kinetic energy of the oscillating cantilever of noncontact atomic force microscopy (nc-AFM) at room temperature was considerably dissipated over regions between a Si adatom and its neighboring rest atom for Si(111 )-(7 ×7 ) in close proximity to a Si tip on the cantilever. However, nc-AFM topographic images showed no atomic features over those regions, which were the hollow sites of the (7 ×7 ). This energy dissipation likely originated from displacement of Si adatoms with respect to the tip over the hollow sites, leading to a lateral shift of the adatoms toward the rest atom. This interaction led to hysteresis over each cantilever oscillation cycle; when the tip was retracted, the Si adatom likely returned to its original position. To confirm the atomic processes involved in the force interactions through Si dangling bonds, the Si(111 )-(7 ×7 ) surface was partly terminated with atomic hydrogen (H) and examined by nc-AFM. When the Si adatoms and/or the rest atoms were terminated with H, the hollow sites were not bright (less dissipation) in images of the energy dissipation channels by nc-AFM. The hollow sites acted as metastable sites for Si adatoms in surface diffusion and atom manipulation; thus, the dissipation energy which is saturated on the tip likely corresponds to the difference in the potential energy between the hollow site and the Si adatom site. In this study, we demonstrated the ability of dissipation channels of nc-AFM to enable visualization of the dynamics of atoms and molecules on surfaces, which cannot be revealed by nc-AFM topographic images alone.

Atom transfer radical polymerization of styrene under pulsed microwave irradiation

International Nuclear Information System (INIS)

Cheng Zhenping; Zhu Xiulin; Zhou Nianchen; Zhu Jian; Zhang Zhengbiao

2005-01-01

A homogeneous solution atom transfer radical polymerization (ATRP) and reverse atom transfer radical polymerization (RATRP) of styrene (St) in N,N-dimethylformamide (DMF) were successfully carried out under pulsed microwave irradiation (PMI), using 1-bromo-1-phenylethane (1-PEBr)/CuCl/N,N,N',N'',N''-pentamethyldiethylenetriamine (PMDETA) as an initiating system at 85 deg. C and 2,2'-azo-bis-isobutyrontrile (AIBN)/CuCl 2 /PMDETA as an initiating system at 95 deg. C, respectively. The polymerization rates under PMI were greatly increased in comparison with those under identical conventional heating (CH)

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

Energy Technology Data Exchange (ETDEWEB)

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

2007-08-22

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

Atomic structures of a monolayer of AlAs, GaAs, and InAs on Si(111)

International Nuclear Information System (INIS)

Lee, Geunjung; Yoon, Younggui

2010-01-01

We study atomic structures of a monolayer of AlAs, GaAs, and InAs on a Si(111) substrate from first-principles. The surface with the stacking sequence of ...SiSiMAsSiAs is energetically more stable than the surface with the stacking sequence of ...SiSiSiAsMAs, where M is Al, Ga, or In. The atomic structure of the three top layers of the low-energy surfaces are quite robust, irrespective of M, and the atomic structure of the AlAsSiAs terminated surface and that of the GaAsSiAs terminated surface are very similar. For the high-energy AsMAs terminated surfaces, the broken local tetrahedral symmetry plays an important role in the atomic structures. The calculated atomic structures of InAs on the Si(111) substrate depart most from the structure of crystalline Si.

SO2 absorption in EmimCl-TEG deep eutectic solvents.

Science.gov (United States)

Yang, Dezhong; Zhang, Shaoze; Jiang, De-En; Dai, Sheng

2018-05-23

Deep eutectic solvents (DESs) based on 1-ethyl-3-methylimidazolium chloride (EmimCl) and triethylene glycol (TEG) with different molar ratios (from 6 : 1 to 1 : 1) were prepared. FTIR and theoretical calculation indicated that the C2-H on the imidazolium ring form hydrogen bonds with the hydroxyl group rather than the ether O atom of the TEG. The EmimCl-TEG DESs can efficiently capture SO2; in particular, EmimCl-TEG (6 : 1) can capture 0.54 g SO2 per gram of solvent at 0.10 atm and 20 °C, the highest absorption amount for DESs under the same conditions. Theoretical calculation showed that the high SO2 absorption capacity was mainly due to the strong charge-transfer interaction between SO2 and the anion Cl-. Moreover, SO2 desorption in the DESs can be controlled by tuning the interaction between EmimCl and TEG, and the DESs can be cycled many times.

Insights into the Electronic Structure of Ozone and Sulfur Dioxide from Generalized Valence Bond Theory: Addition of Hydrogen Atoms.

Science.gov (United States)

Lindquist, Beth A; Takeshita, Tyler Y; Dunning, Thom H

2016-05-05

Ozone (O3) and sulfur dioxide (SO2) are valence isoelectronic species, yet their properties and reactivities differ dramatically. In particular, O3 is highly reactive, whereas SO2 is chemically relatively stable. In this paper, we investigate serial addition of hydrogen atoms to both the terminal atoms of O3 and SO2 and to the central atom of these species. It is well-known that the terminal atoms of O3 are much more amenable to bond formation than those of SO2. We show that the differences in the electronic structure of the π systems in the parent triatomic species account for the differences in the addition of hydrogen atoms to the terminal atoms of O3 and SO2. Further, we find that the π system in SO2, which is a recoupled pair bond dyad, facilitates the addition of hydrogen atoms to the sulfur atom, resulting in stable HSO2 and H2SO2 species.

A kilobyte rewritable atomic memory

Science.gov (United States)

Kalff, Floris; Rebergen, Marnix; Fahrenfort, Nora; Girovsky, Jan; Toskovic, Ranko; Lado, Jose; FernáNdez-Rossier, JoaquíN.; Otte, Sander

The ability to manipulate individual atoms by means of scanning tunneling microscopy (STM) opens op opportunities for storage of digital data on the atomic scale. Recent achievements in this direction include data storage based on bits encoded in the charge state, the magnetic state, or the local presence of single atoms or atomic assemblies. However, a key challenge at this stage is the extension of such technologies into large-scale rewritable bit arrays. We demonstrate a digital atomic-scale memory of up to 1 kilobyte (8000 bits) using an array of individual surface vacancies in a chlorine terminated Cu(100) surface. The chlorine vacancies are found to be stable at temperatures up to 77 K. The memory, crafted using scanning tunneling microscopy at low temperature, can be read and re-written automatically by means of atomic-scale markers, and offers an areal density of 502 Terabits per square inch, outperforming state-of-the-art hard disk drives by three orders of magnitude.

Study of NaCl:Mn2+ nanostructures in the Suzuki phase by optical spectroscopy and atomic force microscopy

International Nuclear Information System (INIS)

Mejía-Uriarte, E.V.; Kolokoltsev, O.; Navarrete Montesinos, M.; Camarillo, E.; Hernández A, J.; Murrieta S, H.

2015-01-01

NaCl:Mn 2+ nanostructures in the Suzuki phase have been studied by fluorescence (emission and excitation) spectroscopy and atomic force microscopy (AFM) as a function of temperature. The “as-grown” samples give rise to two broad emission bands that peak at 508 (green emission) and 610 nm (red emission). The excitation spectrum shows peaks at 227 nm and 232 nm for emission wavelengths at 508 nm and 610 nm, respectively. When the samples are heated continuously from room temperature up to 220 °C, the green emission (associated to the excitation peak at 227 nm) disappears at a temperature close to 120 °C, whilst only the red emission remains, which is characteristic of manganese ions. AFM images on the (0 0 1) surface (freshly cleaved) show several conformations of nanostructures, such as disks of 20–50 nm in diameter. Particularly, the images also reveal nanostructures with rectangular shape of ~280×160 nm 2 and ~6 nm height; these are present only in samples with green emission associated to the Suzuki phase. Then, the evidence suggests that this topographic configuration might be related to the interaction with the first neighbors and the next neighbors, according to the configuration that has been suggested for the Suzuki phase. - Highlights: • NaCl:Mn 2+ single crystals in the Suzuki phase contain rectangular nanostructures. • Double emission of manganese ions: green (508 nm) and red (610 nm) bands. • The excitation peak at 227 nm is attributed to rectangular nanostructures. • The green emission band associated to Suzuki phase is extinguished at 120 °C

Doping-Induced Anisotropic Self-Assembly of Silver Icosahedra in [Pt2Ag23Cl7(PPh3)10] Nanoclusters

KAUST Repository

Bootharaju, Megalamane Siddaramappa; Kozlov, Sergey M.; Cao, Zhen; Harb, Moussab; Maity, Niladri; Shkurenko, Aleksander; Parida, Manas R.; Hedhili, Mohamed N.; Eddaoudi, Mohamed; Mohammed, Omar F.; Bakr, Osman; Cavallo, Luigi; Basset, Jean-Marie

2017-01-01

Atomically precise self-assembled architectures of noble metals with unique surface structures are necessary for prospective applications. However, the synthesis of such structures based on silver is challenging because of their instability. In this work, by developing a selective and controlled doping strategy, we synthesized and characterized a rod-shaped, charge-neutral, diplatinum-doped Ag nanocluster (NC) of [Pt2Ag23Cl7(PPh3)10]. Its crystal structure revealed the self-assembly of two Pt-centered Ag icosahedra through vertex sharing. Five bridging and two terminal chlorides and 10 PPh3 ligands were found to stabilize the cluster. Electronic structure simulations corroborated structural and optical characterization of the cluster and provided insights into the effect of the Pt dopants on the optical properties and stability of the cluster. Our study will open new avenues for designing novel self-assembled NCs using different elemental dopants.

Doping-Induced Anisotropic Self-Assembly of Silver Icosahedra in [Pt2Ag23Cl7(PPh3)10] Nanoclusters

KAUST Repository

Bootharaju, Megalamane Siddaramappa

2017-01-09

Atomically precise self-assembled architectures of noble metals with unique surface structures are necessary for prospective applications. However, the synthesis of such structures based on silver is challenging because of their instability. In this work, by developing a selective and controlled doping strategy, we synthesized and characterized a rod-shaped, charge-neutral, diplatinum-doped Ag nanocluster (NC) of [Pt2Ag23Cl7(PPh3)10]. Its crystal structure revealed the self-assembly of two Pt-centered Ag icosahedra through vertex sharing. Five bridging and two terminal chlorides and 10 PPh3 ligands were found to stabilize the cluster. Electronic structure simulations corroborated structural and optical characterization of the cluster and provided insights into the effect of the Pt dopants on the optical properties and stability of the cluster. Our study will open new avenues for designing novel self-assembled NCs using different elemental dopants.

Di-μ-chlorido-bis(chlorido{2,2′-[3-(1H-imidazol-4-ylmethyl-3-azapentane-1,5-diyl]diphthalimide}copper(II

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Xi-Xi Wang

2009-12-01

Full Text Available The centrosymmetric dinuclear CuII complex, [Cu2Cl4(C24H21N5O42], was synthesized by the reaction of CuCl2·2H2O with the tripodal ligand 2,2′-[3-(1H-imidazol-4-ylmethyl-3-azapentane-1,5-diyl]diphthalimide (L. Each of the CuII ions is coordinated by two N atoms from the ligand, two bridging Cl atoms and one terminal Cl atom. The CuII coordination can be best be described as a transition state between four- and five-coordination, since one of the bridging Cl atoms has a much longer Cu—Cl bond distance [2.7069 (13 Å] than the other [2.2630 (12 Å]. In addition, the Cu...Cu distance is 3.622 (1 Å. The three-dimensional structrure is generated by N—H...O, C—H...O and C—H...Cl hydrogen bonds and π–π interactions [centroid–centroid distances = 3.658 (4 and 4.020 (4 Å].

75 FR 37994 - Airworthiness Directives; Bombardier, Inc. Model CL-600-1A11 (CL-600), CL-600-2A12 (CL-601), CL...

Science.gov (United States)

2010-07-01

... provides data for replacement of the accumulators. The commenter requests that stronger language be... numbers 1004 through 1085 inclusive; (2) Bombardier, Inc. CL-600-2A12 (CL-601) airplanes, serial numbers 3001 through 3066 inclusive; and (3) Bombardier, Inc. CL-600-2B16 (CL-601-3A, CL-601-3R, and CL- 604...

Synthesis and characterization of technetium(III) complexes containing 2,2'-bipyridine and 1,10-phenanthroline. X-ray crystal structures of cis (Cl),trans(P)-[TcCl2(P(CH3)2C6H5)2(bpy)]B(C6H5)4, cis (Cl),trans(P)-[TcCl2(P(CH3)2C6H5)2(phen)]B(C6H5)4, and cis (Cl),trans(P)-[TcCl2(P(CH3CH2)(C6H5)2)2(bpy)]SO3CF3

International Nuclear Information System (INIS)

Wilcox, B.E.; Ho, D.M.; Deutsch, E.

1989-01-01

Technetium(III) complexes of the general formula cis(Cl),trans(P)-[TcCl 2 (P) 2 L] + , where (P) is dimethylphenylphosphine (PMe 2 Ph) or ethyldiphenylphosphine (PEtPh 2 ) and L is 2,2'-bipyridine (bpy), 4,4'-dimethyl-2,2'-bipyridine (Me 2 bpy), or 1,10-phenanthroline (phen), have been synthesized and characterized. They are prepared by L substitution onto, with concomitant displacement of one chloride and one phosphine ligand from, the mer-TcCl 3 (P) 3 starting material in refluxing ethanol. Analysis of these complexes by fast atom bombardment mass spectrometry (in the positive ion mode) provides fingerprint mass spectra that exhibit peaks assigned to the molecular ion M + as well as peaks assigned to M + minus one or more monodentate ligands. Results of single-crystal x-ray structure determinations of cis(Cl),trans(P)-[TcCl 2 (PMe 2 Ph) 2 (bpy)]BPh 4 (A), cis(Cl),trans(P)-[TcCl 2- (PMe 2 Ph) 2 (phen)]BPh 4 (B), and cis(Cl),trans(P)-[TcCl 2 (PEtPh 2 ) 2 (bpy)]SO 3 CF 3 (C), with formula weights of 921.62, 945.64, and 903.65, respectively are reported. 26 refs., 5 figs., 5 tabs

Crystal structure of catena-poly[N,N,N′,N′-tetramethylguanidinium [(chloridocadmate-di-μ-chlorido

Directory of Open Access Journals (Sweden)

Mamadou Ndiaye

2016-01-01

Full Text Available In the structure of the title salt, {(C5H14N3[CdCl3]}n, the CdII atom of the complex anion is five-coordinated by one terminal and four bridging Cl atoms. The corresponding coordination polyhedron is a distorted trigonal bipyramid, with Cd—Cl distances in the range 2.4829 (4–2.6402 (4 Å. The bipyramids are condensed into a polyanionic zigzag chain extending parallel to [101]. The tetramethylguanidinium cations are situated between the polyanionic chains and are linked to them through N—H...Cl hydrogen bonds, forming a layered network parallel to (010.

AMS Measurement of 36Cl with a Q3D Magnetic Spectrometer at CIAE

International Nuclear Information System (INIS)

Li Chaoli; He Ming; Wu Shaoyong; Li Zhenyu; Liu Jiancheng; Dong Kejun; Jiang Shan; Zhang Wei; He Xianwen

2012-01-01

The ratio of 36 Cl/Cl can determine the exposure age of surface rocks and monitor the secular equilibrium of 36 Cl of sedimentary and igneous rock in groundwater. Due to the uncertainty effects of different chemical separation processes for removing 36 S, there is a high degree of uncertainty in 36 Cl accelerator mass spectrometry (AMS) measurements if the ratio of 36 Cl/Cl is lower than 10 -14 . A 36 Cl AMS higher sensitivity measurement has been set up by using a ΔE-Q3D method at the China Institute of Atomic Energy (CIAE). The performances of ΔE-Q3D method for 36 Cl-AMS measurement had been systemically studied. The experimental results show that the ΔE-Q3D method has a higher isobar suppression factor. Taking advantage of direct removing 36 S, the sample preparation can be simplified and the uncertainty effects of different chemical separation processes can be reduced in 36 Cl AMS measurements.

The Text of a Protocol between the Agency and the Governments of Thailand and the United States of America Terminating the Agreement between the International Atomic Energy Agency, the Government of the Kingdom of Thailand and the Government of the United States of America for the Application of Safeguards and Terminating the Protocol Suspending that Agreement

International Nuclear Information System (INIS)

1976-01-01

The text of a protocol between the Agency and the Governments of Thailand and the United States of America terminating the Agreement between the International Atomic Energy Agency, the Government of the Kingdom of Thailand and the Government of the United States of America for the Application of Safeguards and terminating the Protocol suspending that Agreement is reproduced in this document for the information of all Members. The Protocol entered into force on 27 June 1974, pursuant to Section 6 thereof.

Effect of Cl substituent in the aromatic tetracycline ring on its reactivity with solvated electrons

Energy Technology Data Exchange (ETDEWEB)

Dziegielewski, J O; Glowacki, P [Universytet Slaski, Katowice (Poland). Inst. Chemii; Goracy, J; Orlowska-Dudek, D; Sloma, E [Wroclaw Univ. (Poland) Inst. Chemii

1984-09-18

Decomposition yields of tetracycline hydrochloride (TC.HCl) and chlorotetracycline hydrochloride (ClTC.HCl) in methanol solution saturated with Ar or N/sub 2/O were determined. Rate constants of the reaction esub(s)/sup -/ with some antibiotics were obtained. It was demonstrated by /sup 1/H NMR that the radical formed by degradation of 7-C-Cl group is recombined with the H atoms leading to ClTC.HCl being converted into tetracycline hydrochloride (TC.HCl).

Liquid-vapor equilibrium in LaCl3-LuCl3 and PrCl3-NdCl3 systems

International Nuclear Information System (INIS)

Nisel'son, L.A.; Lyzlov, Yu.N.; Solov'ev, S.I.

1978-01-01

The liquid-vapour equilibrium in the systems LaCl 3 -LuCl 3 and PrCl 3 -NdCl 3 was studied by the boiling-point method. It was established that the system LaCl 3 -LuCl 3 is near-ideal. In the PrCl 3 -NdCl 3 system, a considerable positive deviation from the ideal with the formation of an azeotrope was detected. The azeotrope has a ''smeared-out'' minimum, which falls on a mixture containing approximately 65 mol.% neodymium trichloride. The boiling point of this mixture at a pressure of 1 mm Hg is approximately 975 deg C. The relative volatility coefficients in both systems were studied by the Raleigh distillation method. The presence of the azeotrope in the system PrCl 3 -NdCl 3 is confirmed by the nature of the dependence of the relative volatility coefficient on the composition of the mixture

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

Science.gov (United States)

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

2017-03-01

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

Theoretical investigation of the oxidation pathways of the Cl-initiated reaction of 2-methyl-3-buten-2-ol

Science.gov (United States)

Zhang, Weichao; Zhang, Dongju

2012-12-01

The mechanism and products of the reaction of 2-methyl-3-buten-2-ol (MBO232) with Cl atoms in the presence of O2 have been elucidated by performing high-level quantum chemistry calculations. The geometries of the reactants, intermediates, transition states, and products are optimized at the MP2(full)/6-311G(d, p) level, and their single-point energies are refined at the CCSD(T)/6-311 + G(d, p) level. The potential energy surface profiles have been constructed at the CCSD(T)/6-311 + G(d, p)//MP2(full)/6-311G(d, p) + 0.95 × ZPE level of theory, and the possible channels involved in the reaction are also discussed. The calculations indicate that the reaction predominantly proceeds via the addition of Cl atoms to the double bond rather than the direct abstraction of the H atoms in MBO232. The nascent adducts (CH3)2C(OH)CHCH2Cl (IM1) and (CH3)2C(OH)CHClCH2 (IM2) do not undergo subsequent isomerization and dissociation reactions, but rather react with O2. The theoretical results show that the major products are CH2ClCHO and CH3C(O)CH3 for the reaction of MBO232 + Cl in the presence of O2, which is in good agreement with the experimental finding.

The charge state distribution of Be, C, Cl and Al ions at the Lund Pelletron accelerator with the recently modified terminal pumping in use

International Nuclear Information System (INIS)

Kiisk, Madis; Hellborg, Ragnar; Persson, Per; Faarinen, Mikko; Skog, Goeran; Stenstroem, Kristina

2004-01-01

Some years ago terminal pumping for the gas stripper system at the 3 MV Lund Tandem Pelletron accelerator was installed and charge state distribution measurements using the new installation were reported. Since then, new modifications of the mechanical design of the stripper system have been made. The results of pressure profile measurements as well as the results of charge state distribution measurements in a N 2 and Ar gas stripper at different, new geometrical modifications of the stripper system using C, Be, Al and Cl ion beams are reported. A comparison between pressure profiles obtained for different geometries shows a clear improvement of the vacuum conditions outside the stripper housing for the smallest conductance pipes between the stripper system and the accelerator tubes. These improvements are also well reflected in the charge state distribution measurements, as a higher mean charge state is obtained under the same vacuum conditions in the accelerator tubes for the improved stripper system in comparison with the former mechanical design

Electron scattering in graphene with adsorbed NaCl nanoparticles

Energy Technology Data Exchange (ETDEWEB)

Drabińska, Aneta, E-mail: Aneta.Drabinska@fuw.edu.pl; Kaźmierczak, Piotr; Bożek, Rafał; Karpierz, Ewelina; Wysmołek, Andrzej; Kamińska, Maria [Faculty of Physics, University of Warsaw, Pasteura 5, 02-093 Warsaw (Poland); Wołoś, Agnieszka [Faculty of Physics, University of Warsaw, Pasteura 5, 02-093 Warsaw (Poland); Institute of Physics, Polish Academy of Sciences, Al. Lotników 32/46, 02-668 Warsaw (Poland); Pasternak, Iwona; Strupiński, Włodek [Institute of Electronic Materials Technology, Wólczyńska 133, 01-919 Warsaw (Poland); Krajewska, Aleksandra [Institute of Electronic Materials Technology, Wólczyńska 133, 01-919 Warsaw (Poland); Institute of Optoelectronics, Military University of Technology, Kaliskiego 2, 00-908 Warsaw (Poland)

2015-01-07

In this work, the results of contactless magnetoconductance and Raman spectroscopy measurements performed for a graphene sample after its immersion in NaCl solution were presented. The properties of the immersed sample were compared with those of a non-immersed reference sample. Atomic force microscopy and electron spin resonance experiments confirmed the deposition of NaCl nanoparticles on the graphene surface. A weak localization signal observed using contactless magnetoconductance showed the reduction of the coherence length after NaCl treatment of graphene. Temperature dependence of the coherence length indicated a change from ballistic to diffusive regime in electron transport after NaCl treatment. The main inelastic scattering process was of the electron-electron type but the major reason for the reduction of the coherence length at low temperatures was additional, temperature independent, inelastic scattering. We associate it with spin flip scattering, caused by NaCl nanoparticles present on the graphene surface. Raman spectroscopy showed an increase in the D and D′ bands intensities for graphene after its immersion in NaCl solution. An analysis of the D, D′, and G bands intensities proved that this additional scattering is related to the decoration of vacancies and grain boundaries with NaCl nanoparticles, as well as generation of new on-site defects as a result of the decoration of the graphene surface with NaCl nanoparticles. The observed energy shifts of 2D and G bands indicated that NaCl deposition on the graphene surface did not change carrier concentration, but reduced compressive biaxial strain in the graphene layer.

Electron scattering in graphene with adsorbed NaCl nanoparticles

International Nuclear Information System (INIS)

Drabińska, Aneta; Kaźmierczak, Piotr; Bożek, Rafał; Karpierz, Ewelina; Wysmołek, Andrzej; Kamińska, Maria; Wołoś, Agnieszka; Pasternak, Iwona; Strupiński, Włodek; Krajewska, Aleksandra

2015-01-01

In this work, the results of contactless magnetoconductance and Raman spectroscopy measurements performed for a graphene sample after its immersion in NaCl solution were presented. The properties of the immersed sample were compared with those of a non-immersed reference sample. Atomic force microscopy and electron spin resonance experiments confirmed the deposition of NaCl nanoparticles on the graphene surface. A weak localization signal observed using contactless magnetoconductance showed the reduction of the coherence length after NaCl treatment of graphene. Temperature dependence of the coherence length indicated a change from ballistic to diffusive regime in electron transport after NaCl treatment. The main inelastic scattering process was of the electron-electron type but the major reason for the reduction of the coherence length at low temperatures was additional, temperature independent, inelastic scattering. We associate it with spin flip scattering, caused by NaCl nanoparticles present on the graphene surface. Raman spectroscopy showed an increase in the D and D′ bands intensities for graphene after its immersion in NaCl solution. An analysis of the D, D′, and G bands intensities proved that this additional scattering is related to the decoration of vacancies and grain boundaries with NaCl nanoparticles, as well as generation of new on-site defects as a result of the decoration of the graphene surface with NaCl nanoparticles. The observed energy shifts of 2D and G bands indicated that NaCl deposition on the graphene surface did not change carrier concentration, but reduced compressive biaxial strain in the graphene layer

Theoretical introduction to the 37Cl solar neutrino experiment

International Nuclear Information System (INIS)

Bahcall, J.N.

1978-01-01

A theoretical introduction is given to the chlorine 37 solar neutrino experiment. From the definition of an SNU as 10 -36 captures per target atom per second the discussion proceeds to stellar evolution, the neutrino absorption cross sections, nuclear reactions, and lastly the implications for astronomy and for physics of the 37 Cl experiment

Thermal 18F atom addition to olefins

International Nuclear Information System (INIS)

Rogers, P.J.M.

1986-01-01

The addition of thermal 18 F atoms to olefins was investigated using various substrate molecules. The 18 F atoms were produced by the 19 F(n,2n) 18 F nuclear reaction with >10 5 eV of energy which is removed by multiple collisions with SF 6 molecules before reaction occurs with an olefin. By varying the SF 6 /substrate mole ratio it was demonstrated that the fraction of non-thermal reactions is dependent upon the frequency of non-reactive energy reducing collisions with SF 6 . The rate constants for addition and abstraction reactions with propene, cis-1-chloropropene and trans-1-chloropropene were determined. The substitution of a C1 atom for the olefinic H atom in the C 1 position does not affect the rate of 18 F bond formation but it changes the orientation of attack. The 18 F atom prefers the terminal carbon-in propene and propene-d 6 by a factor of 1.35 while the preference is less than 0.5 for the terminal carbon in cis-1-chloropropene and trans-1-chloropropene. The addition of 18 F atoms to olefins creates vibrationally excited fluoroalkyl radicals which can either decompose or stabilize by collision with another molecule. The rate constants for decomposition of excited CH 3 CHCHC1F radicals formed by 18 F addition to cis-1-chloropropene and trans-1-chloropropene are competitive with C 1 -C 2 bond rotation. The 18 F atoms add to the parent molecule with retention of geometry and a memory of the geometry persists as demonstrated by the cis-1-fluoropropene/trans-1-fluoropropene decomposition product ratio

Terminal ileum of patients who underwent colonoscopy: endoscopic, histologic and clinical aspects Íleo terminal de pacientes submetidos a colonoscopia: aspectos endoscópicos, histológicos e clínicos

Directory of Open Access Journals (Sweden)

Marcelo Maia Caixeta de Melo

2009-06-01

ção endoscópica e histológica desse segmento são escassos e ainda persistem dúvidas quanto à necessidade de biopsias em pacientes com ileoscopia normal. OBJETIVO: Estudar o íleo terminal de pacientes submetidos a colonoscopia, considerando correlação endoscópica e histológica; concordância entre resultados da avaliação histológica inicial e revisão de lâminas e chance de indivíduos com ileoscopia normal, com dor abdominal e ou diarreia crônica apresentarem alterações histológicas. MÉTODOS: Estudo prospectivo, no qual foram selecionados 111 pacientes, que apresentaram ao exame endoscópico do íleo terminal mucosa lisa e sem enantema. Foram realizadas biopsias da mucosa ileal nesses indivíduos, sendo as lâminas examinadas rotineiramente e revisadas posteriormente. RESULTADOS: A correlação entre pacientes com ileoscopia normal e íleo com arquitetura histológica preservada foi de 99,1%. A concordância entre avaliação histológica inicial e revisão de lâminas calculada pelo teste de Kappa, foi 0,21. Nos pacientes com ileoscopia normal, com dor abdominal e ou diarreia crônica, a chance de apresentarem alterações histológicas foi 2,5 vezes maior em relação aos demais. CONCLUSÃO: A correlação entre achados endoscópicos e histológicos foi elevada. A concordância entre avaliação histológica inicial e revisão de lâminas não foi satisfatória. A chance de indivíduos com ileoscopia normal, com dor abdominal e ou diarreia crônica, apresentarem alterações histológicas foi maior, porém a importância clínica desse dado não foi avaliada.

Changes in the geometries of C₂H₂ and C₂H₄ on coordination to CuCl revealed by broadband rotational spectroscopy and ab-initio calculations.

Science.gov (United States)

Stephens, Susanna L; Bittner, Dror M; Mikhailov, Victor A; Mizukami, Wataru; Tew, David P; Walker, Nicholas R; Legon, Anthony C

2014-10-06

The molecular geometries of isolated complexes in which a single molecule of C2H4 or C2H2 is bound to CuCl have been determined through pure rotational spectroscopy and ab-initio calculations. The C2H2···CuCl and C2H4···CuCl complexes are generated through laser vaporization of a copper rod in the presence of a gas sample undergoing supersonic expansion and containing C2H2 (or C2H4), CCl4, and Ar. Results are presented for five isotopologues of C2H2···CuCl and six isotopologues of C2H4···CuCl. Both of these complexes adopt C(2v), T-shaped geometries in which the hydrocarbon binds to the copper atom through its π electrons such that the metal is equidistant from all H atoms. The linear and planar geometries of free C2H2 and C2H4, respectively, are observed to distort significantly on attachment to the CuCl unit, and the various changes are quantified. The ∠(*-C-H) parameter in C2H2 (where * indicates the midpoint of the C≡C bond) is measured to be 192.4(7)° in the r0 geometry of the complex representing a significant change from the linear geometry of the free molecule. This distortion of the linear geometry of C2H2 involves the hydrogen atoms moving away from the copper atom within the complex. Ab-initio calculations at the CCSD(T)(F12*)/AVTZ level predict a dihedral ∠(HCCCu) angle of 96.05° in C2H4···CuCl, and the experimental results are consistent with such a distortion from planarity. The bonds connecting the carbon atoms within each of C2H2 and C2H4, respectively, extend by 0.027 and 0.029 Å relative to the bond lengths in the isolated molecules. Force constants, k(σ), and nuclear quadrupole coupling constants, χ(aa)(Cu), [χ(bb)(Cu) - χ(cc)(Cu)], χ(aa)(Cl), and [χ(bb)(Cl) - χ(cc)(Cl)], are independently determined for all isotopologues of C2H2···CuCl studied and for four isotopologues of C2H4···CuCl.

Catalysis of the reduction of Tl+ and of CH2Cl2 by colloidal silver in aqueous solution

International Nuclear Information System (INIS)

Henglein, A.

1979-01-01

(CH 3 ) 2 COH radicals (1-hydroxy-1-methylethyl) do not reduce Tl + or CH 2 Cl 2 in homogeneous aqueous solution. In the presence of 2.5 x 10 -4 g atom/L of colloidal silver, Tl + is reduced to yield colloidal thallium, and CH 2 Cl 2 to yield Cl - plus CH 3 Cl. These reactions occur in competition with the silver-catalyzed reduction of water. Tl + is reduced in a one-electron transfer reaction and CH 2 Cl 2 in a two-electron transfer process. The effects are understood in terms of the colloidal particles acting as a pool for electrons that is continuously charged by the organic radicals and discharged by water or dissolved substrates. The specific rate for the CH 2 Cl 2 reduction at the silver pool is 4.3 x 10 3 times greater than that of the water reduction. Electrochemical considerations are carried out to estimate a stationary potential of -0.62 V (vs the standard hydrogen electrode) for the electron pool and to discuss the energetics of the observed reactions and the possible role of adsorbed hydrogen atoms. Colloidal silver and organic radicals were radiolytically produced. 7 figures

Anisotropic Interactions between Cold Rydberg Atoms

Science.gov (United States)

2015-09-28

AFRL-AFOSR-CL-TR-2015-0002 Anisotropic interactions between cold Rydberg atoms Luis Marcassa INSTITUTO DE FISICA DE SAO CARLOS Final Report 09/28...problem with the report +551633739806 Organization / Institution name Instituto de Fisica de Sao Carlos Grant/Contract Title The full title of the

Electron detachment in ion-atom collisions

International Nuclear Information System (INIS)

Vreugd, C. de.

1980-01-01

The electron detachment process that occurs in negative ion-atom collisions is investigated. Differential cross sections were measured for the collisions of F - , Cl - , Br - , I - on He, Ne, Ar, Kr, Xe, Na and K. Electron energy distributions were obtained for some of the systems. (Auth.)

Study of sample preparation in the measurement of 36Ar(n, p)36Cl reaction cross section

International Nuclear Information System (INIS)

Jiang Songsheng; Hemick, T.K.

1992-01-01

The preparation of enriched 36 Ar gas samples and 36 Cl samples for the use in the AMS measurement of 36 Ar(n, p) 36 Cl reaction cross section was described. The 36 Ar samples prepared had the volumes of about 0.4 ml and the weights of about 0.5 mg. The uncertainty in atomic numbers of 36 Ar was (0.3∼0.4)%. The reaction product, 36 Cl, in the 36 Ar was collected and the AgCl samples were prepared

Reduction behaviors of Zr for LiCl-KCl-ZrCl4 and LiCl-KCl-ZrCl4-CdCl2

International Nuclear Information System (INIS)

Kim, Si Hyung; Yoon, Jongho; Kim, Gha Young; Kim, Tack Jin; Shim, Joon Bo; Kim, Kwang Rag; Jung, Jae Hoo; Ahn, Do Hee; Paek, Seungwoo

2013-01-01

The reduction potentials of most of the zirconium ions on the solid cathode are smaller (about 0.4V) than that of uranium, and thus zirconium can be recovered prior to uranium during the reduction stage. In the case of a liquid cadmium cathode, which is one of the major cathodes, the reduction potential can be changed because zirconium reacts with the liquid cadmium. Up to now, it has not been well known what the reduction potential of Zr was on the liquid Cd cathode. According to the Cd-Zr phase diagram, there are four intermetallic compounds between cadmium and zirconium. It is easier to use the solid cathode than the liquid cadmium cathode in LiCl-KCl-ZrCl 4 containing CdCl 2 to identify the formation of the Cd-Zr phase. In this study, the reduction behaviors of zirconium were compared in the LiCl-KCl-ZrCl 4 and LiCl-KCl-ZrCl 4 -CdCl 2 solutions when using a solid cathode. The reduction behavior of Zr at a solid W cathode and a Cd-coated W cathode was compared in a LiCl-KCl-ZrCl 4 solution at 500 .deg. C. It was observed from the results using a solid W cathode that Zr 4+ ions were gradually oxidized to Zr 2+ , Zr, and ZrCl during the reduction sweep, but the final oxidation peak of Zr 2+ to Zr 4+ seemed to be unclear during the oxidation sweep. In the case of the Cd-coated W electrode, only a Cd 2 Zr phase was formed at 500 .deg. C, which seemed to be related to the melting point of Cd-Zr intermetallics. Through additional studies at different temperatures, the formation behavior will be studied

He atom-surface scattering: Surface dynamics of insulators, overlayers and crystal growth

International Nuclear Information System (INIS)

1992-01-01

Investigations in this laboratory have focused on the surface structure and dynamics of ionic insulators and on epitaxial growth onto alkali halide crystals. In the later the homoepitaxial growth of NaCl/NaCl(001) and the heteroepitaxial growth of KBr/NaCl(001), NaCl/KBr(001) and KBr/RbCl(001) have been studied by monitoring the specular He scattering as a function of the coverage and by measuring the angular and energy distributions of the scattered He atoms. These data provide information on the surface structure, defect densities, island sizes and surface strain during the layer-by-layer growth. The temperature dependence of these measurements also provides information on the mobilities of the admolecules. He atom scattering is unique among surface probes because the low-energy, inert atoms are sensitive only to the electronic structure of the topmost surface layer and are equally applicable to all crystalline materials. It is proposed for the next year to exploit further the variety of combinations possible with the alkali halides in order to carry out a definitive study of epitaxial growth in the ionic insulators. The work completed so far, including measurements of the Bragg diffraction and surface dispersion at various stages of growth, appears to be exceptionally rich in detail, which is particularly promising for theoretical modeling. In addition, because epitaxial growth conditions over a wide range of lattice mismatches is possible with these materials, size effects in growth processes can be explored in great depth. Further, as some of the alkali halides have the CsCl structure instead of the NaCl structure, we can investigate the effects of the heteroepitaxy with materials having different lattice preferences. Finally, by using co-deposition of different alkali halides, one can investigate the formation and stability of alloys and even alkali halide superlattices

Synthesis of trans-disubstituted alkenes by cobalt-catalyzed reductive coupling of terminal alkynes with activated alkenes.

Science.gov (United States)

Mannathan, Subramaniyan; Cheng, Chien-Hong

2012-09-10

A cobalt-catalyzed reductive coupling of terminal alkynes, RC≡CH, with activated alkenes, R'CH=CH(2), in the presence of zinc and water to give functionalized trans-disubstituted alkenes, RCH=CHCH(2)CH(2)R', is described. A variety of aromatic terminal alkynes underwent reductive coupling with activated alkenes including enones, acrylates, acrylonitrile, and vinyl sulfones in the presence of a CoCl(2)/P(OMe)(3)/Zn catalyst system to afford 1,2-trans-disubstituted alkenes with high regio- and stereoselectivity. Similarly, aliphatic terminal alkynes also efficiently participated in the coupling reaction with acrylates, enones, and vinyl sulfone, in the presence of the CoCl(2)/P(OPh)(3)/Zn system providing a mixture of 1,2-trans- and 1,1-disubstituted functionalized terminal alkene products in high yields. The scope of the reaction was also extended by the coupling of 1,3-enynes and acetylene gas with alkenes. Furthermore, a phosphine-free cobalt-catalyzed reductive coupling of terminal alkynes with enones, affording 1,2-trans-disubstituted alkenes as the major products in a high regioisomeric ratio, is demonstrated. In the reactions, less expensive and air-stable cobalt complexes, a mild reducing agent (Zn) and a simple hydrogen source (water) were used. A possible reaction mechanism involving a cobaltacyclopentene as the key intermediate is proposed. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Scanning tunneling microscopy study of the possible topological surface states in BiTeCl

International Nuclear Information System (INIS)

Yan, Y J; Ren, M Q; Liu, X; Huang, Z C; Jiang, J; Fan, Q; Miao, J; Xie, B P; Zhang, T; Feng, D L; Xiang, F; Wang, X

2015-01-01

Recently, the non-centrosymmetric bismuth tellurohalides such as BiTeCl are being studied as possible candidates for topological insulators. While some photoemission studies showed that BiTeCl is an inversion asymmetric topological insulator, others showed that it is a normal semiconductor with Rashba splitting. Meanwhile, first-principle calculations have failed to confirm the existence of topological surface states in BiTeCl so far. Therefore, the topological nature of BiTeCl requires further investigation. Here we report a low-temperature scanning tunneling microscopy study on the surface states of BiTeCl single crystals. On the tellurium (Te) -terminated surfaces with relatively low defect density, evidence for topological surface states is observed in the quasi-particle interference patterns, both in the anisotropy of the scattering vectors and the fast decay of the interference near the step edges. Meanwhile, on the samples with much higher defect densities, we observed surface states that behave differently. Our results may help to resolve the current controversy on the topological nature of BiTeCl. (paper)

?????????? ?????, ?????????? ??????????? ?? ?????????? ?????????? ????? ? ?????? ???????? ZnCl2 +NH4Cl

OpenAIRE

Kuntyi, Orest; Zozulya, Galyna

2010-01-01

Zinc cementation by magnesium from ZnCl2 + NH4Cl aqueous solutions has been investigated. The amount of magnesium has been established as 0.8?2.0 g per 1 g of conditioned zinc to obtain recovery degree ? 99 %. At low concentrations of Zn2+ ions (0.025?0.1 M ZnCl2) dispersed deposit is formed with nanoparticles of reduced metal; at high concentrations (0.25?0.5 M) coarse-crystalline and fern-shaped deposit is formed. ?????????? ?????????? ????? ??????? ? ?????? ???????? ZnCl2 + NH4Cl. ????????...

Spontaneous nano-gap formation in Ag film using NaCl sacrificial layer for Raman enhancement

Science.gov (United States)

Min, Kyungchan; Jeon, Wook Jin; Kim, Youngho; Choi, Jae-Young; Yu, Hak Ki

2018-03-01

We report the method of fabrication of nano-gaps (known as hot spots) in Ag thin film using a sodium chloride (NaCl) sacrificial layer for Raman enhancement. The Ag thin film (20-50 nm) on the NaCl sacrificial layer undergoes an interfacial reaction due to the AgCl formed at the interface during water molecule intercalation. The intercalated water molecules can dissolve the NaCl molecules at interfaces and form the ionic state of Na+ and Cl-, promoting the AgCl formation. The Ag atoms can migrate by the driving force of this interfacial reaction, resulting in the formation of nano-size gaps in the film. The surface-enhanced Raman scattering activity of Ag films with nano-size gaps has been investigated using Raman reporter molecules, Rhodamine 6G (R6G).

(μ-3-Acetyl-5-carboxylato-4-methylpyrazolido-1:2κ4N2,O3:N1,O5-μ-chlorido-tetrapyridine-1κ2N,2κ2N-chlorido-1κCl-dicopper(II propan-2-ol solvate

Directory of Open Access Journals (Sweden)

Sergey Malinkin

2009-10-01

Full Text Available The title compound, [Cu2(C7H6N2O3Cl2(C5H5N4]·C3H8O, is a binuclear pyrazolate complex, in which the two CuII atoms have different coordination numbers and are connected by a bridging Cl atom. One CuII atom has a distorted square-pyramidal coordination environment formed by two pyridine N atoms, one bridging Cl atom and an N,O-chelating pyrazolate ligand. The other CuII atom adopts an octahedral geometry defined by two pyridine N atoms at the axial positions, two Cl atoms and the coordinated pyrazolate ligand in the equatorial plane. An O—H...O hydrogen bond connects the complex molecules and propan-2-ol solvent molecules into pairs. These pairs form columns along the a axis.

Electronic and magnetic properties of nonmetal atoms doped blue phosphorene: First-principles study

Energy Technology Data Exchange (ETDEWEB)

Zheng, Huiling; Yang, Hui [Key Laboratory of Physics and Technology for Advanced Batteries (Ministry of Education), Department of Physics, Jilin University, Changchun 130012 (China); Wang, Hongxia [College of Mathematics, Physics and Information Science, Zhejiang Ocean University, Zhoushan 316000 (China); Du, Xiaobo [Key Laboratory of Physics and Technology for Advanced Batteries (Ministry of Education), Department of Physics, Jilin University, Changchun 130012 (China); Yan, Yu, E-mail: yanyu@jlu.edu.cn [Key Laboratory of Physics and Technology for Advanced Batteries (Ministry of Education), Department of Physics, Jilin University, Changchun 130012 (China)

2016-06-15

Using first-principles calculations, we study the geometrical structure, electronic structure and magnetic properties of substitutionally doped blue phosphorene with a series of nonmetallic atoms, including F, Cl, B, N, C, Si and O. The calculated formation energies and molecular dynamics simulations indicate that F, Cl, B, N, C, Si and O doped blue phosphorene are stable. Moreover, the substitutional doping of F, Cl, B and N cannot induce the magnetism in blue phosphorene due to the saturation or pairing of the valence electron of dopant and its neighboring P atoms. In contrast, ground states of C, Si and O doped blue phosphorene are spin-polarized and the magnetic moments induced by a doping atom are all 1.0 μ{sub B}, which is attributed to the appearance of an unpaired valence electron of C and Si and the formation of a nonbonding 3p electron of a neighboring P atom around O. Furthermore, the magnetic coupling between the moments induced by two C, Si and O are found to be long-range anti-ferromagnetic and the origin of the coupling can be attributed to the p–p hybridization interaction involving polarized electrons. - Highlights: • F, Cl, B, N, C, Si and O doped blue phosphorene are stable. • Substitutional doping of C, Si and O can produce the magnetism in blue phosphorene. • Magnetic coupling between two C, Si and O is long-range anti-ferromagnetic.

Soluble Collectin-12 (CL-12) Is a Pattern Recognition Molecule Initiating Complement Activation via the Alternative Pathway

DEFF Research Database (Denmark)

Ma, Ying Jie; Hein, Estrid; Munthe-Fog, Lea

2015-01-01

and may recognize certain bacteria and fungi, leading to opsonophagocytosis. However, based on its structural and functional similarities with soluble collectins, we hypothesized the existence of a fluid-phase analog of CL-12 released from cells, which may function as a soluble pattern-recognition...... of the terminal complement complex. These results demonstrate the existence of CL-12 in a soluble form and indicate a novel mechanism by which the alternative pathway of complement may be triggered directly by a soluble pattern-recognition molecule....... nonreducing conditions it presented multimeric assembly forms. Immunoprecipitation and Western blot analysis of human umbilical cord plasma enabled identification of a natural soluble form of CL-12 having an electrophoretic mobility pattern close to that of shed soluble recombinant CL-12. Soluble CL-12 could...

Probing the atomic structure of metallic nanoclusters with the tip of a scanning tunneling microscope.

Science.gov (United States)

Schouteden, Koen; Lauwaet, Koen; Janssens, Ewald; Barcaro, Giovanni; Fortunelli, Alessandro; Van Haesendonck, Chris; Lievens, Peter

2014-02-21

Preformed Co clusters with an average diameter of 2.5 nm are produced in the gas phase and are deposited under controlled ultra-high vacuum conditions onto a thin insulating NaCl film on Au(111). Relying on a combined experimental and theoretical investigation, we demonstrate visualization of the three-dimensional atomic structure of the Co clusters by high-resolution scanning tunneling microscopy (STM) using a Cl functionalized STM tip that can be obtained on the NaCl surface. More generally, use of a functionalized STM tip may allow for systematic atomic structure determination with STM of nanoparticles that are deposited on metal surfaces.

Growth kinetics and initial stage growth during plasma-enhanced Ti atomic layer deposition

CERN Document Server

Kim, H

2002-01-01

We have investigated the growth kinetics of plasma-enhanced Ti atomic layer deposition (ALD) using a quartz crystal microbalance. Ti ALD films were grown at temperatures from 20 to 200 deg. C using TiCl sub 4 as a source gas and rf plasma-produced atomic H as the reducing agent. Postdeposition ex situ chemical analyses of thin films showed that the main impurity is oxygen, mostly incorporated during the air exposure prior to analysis. The thickness per cycle, corresponding to the growth rate, was measured by quartz crystal microbalance as a function of various key growth parameters, including TiCl sub 4 and H exposure time, rf plasma power, and sample temperature. The growth rates were independent of TiCl sub 4 exposure above 1x10 sup 3 L, indicating typical ALD mode growth. The key kinetic parameters for Cl extraction reaction and TiCl sub 4 adsorption kinetics were obtained and the growth kinetics were modeled to predict the growth rates based upon these results. Also, the dependency of growth kinetics on d...

Atomic emission spectroscopy

Science.gov (United States)

Andrew, K. H.

1975-01-01

The relationship between the Slater-Condon theory and the conditions within the atom as revealed by experimental data was investigated. The first spectrum of Si, Rb, Cl, Br, I, Ne, Ar, and Xe-136 and the second spectrum of As, Cu, and P were determined. Methods for assessing the phase stability of fringe counting interferometers and the design of an autoranging scanning system for digitizing the output of an infrared spectrometer and recording it on magnetic tape are described.

Nano-scale patterning on sulfur terminated GaAs (0 0 1) surface by scanning tunneling microscope

International Nuclear Information System (INIS)

Yagishita, Yuki; Toda, Yusuke; Hirai, Masakazu; Fujishiro, Hiroki Inomata

2004-01-01

We perform nano-scale patterning on a sulfur (S) terminated GaAs (0 0 1) surface by a scanning tunneling microscope (STM) in ultra-high vacuum (UHV). A multi-layer of S deposited by using (NH 4 ) 2 S x solution is changed to a mono-layer after annealing at 560 deg. C for 15 h, which terminates the GaAs (0 0 1) surface. Groove structures with about 0.23 nm in depth and about 5 nm in width are patterned successfully on the S-terminated surface. We investigate dependences of both depth and width of the patterned groove on the tunneling current and the scanning speed of tip. It is observed that topmost S atoms are extracted together with first-layer Ga atoms, because of the larger binding energy of S-Ga bond

Liquid crystals with novel terminal chains as ferroelectric liquid crystal hosts

International Nuclear Information System (INIS)

Cosquer, G.Y.

2000-02-01

Changes to the molecular structure of liquid crystals can have a significant effect upon their mesomorphism and ferroelectric properties. Most of the research in liquid crystal for display applications concentrates on the design and synthesis of novel mesogenic cores to which straight terminal alkyl or alkoxy chains are attached. However, little is known about the effects upon the mesomorphism and ferroelectric properties of varying the terminal chains. The compounds prepared in this work have a common core - a 2,3-difluoroterphenyl unit with a nine-atom alkyl (nonyl) or alkoxy (octyloxy) chain at the 4-position, but with an unusual chain at the 4''-position. In some cases the terminal chain contains hetero atoms such as silicon, oxygen, chlorine and bromine or has a bulky end group. In total 46 final materials were synthesised in an attempt to understand the effect of an unusual terminal chains on mesomorphism and for some of these compounds the effect upon the switching times when added to a standard ferroelectric mixture were investigated. It was found that most compounds containing a bulky end group only displayed a smectic C phase, compounds with a halogen substituent as an end unit displayed a smectic A phase and that increasing the chain flexibility by introducing an oxygen atom in the chain reduces the melting and clearing points. The electro-optical measurements carried out on ferroelectric mixtures containing a bulky end group compound showed that shorter switching times were produced than for the ferroelectric mixture containing a straight chain compound. It is suggested that a bulky end group diminishes te extent of interlayer mixing in the chiral smectic C phase and therefore the molecules move more easily with ferroelectric switching. (author)

36Cl production and mobility in the Cigar Lake uranium deposit

International Nuclear Information System (INIS)

Cornett, R.J.; Fabryka-Martin, J.; Cramer, J.J.; Andrew, H.R.; Koslowsky, V.T.

2010-01-01

Can accelerator mass spectrometry (AMS) studies validate risk assessments of the long-term behaviour of contaminants such as radionuclides? AMS measurements on samples from the 1.3 billion-year-old Cigar Lake uranium ore deposit provide one approach to address this question. In Cigar Lake, elevated concentrations of uranium enhance the in situ neutron flux that produces 36 Cl and other radionuclides. We calculated the production of 36 Cl using a Monte Carlo neutron transport code. We then tested for the loss of 36 Cl from ore samples collected from an 8 m stratigraphic section through the deposit by comparing the predicted values (assuming equilibrium between production and decay) with the concentrations measured by AMS. The 36 Cl:Cl atom ratios within the ore were more than two orders of magnitude higher than in the surrounding host rock and ranged from 4 to 64 x 10 -12 . The 36 Cl concentrations in the ore, rock, clay and fracture infilling minerals all agree with the values predicted by the Monte Carlo simulations. We conclude that 36 Cl has very limited mobility. Even in matrix adjacent to more permeable fractures, there is no evidence that the measured isotopic ratios deviate significantly from the predicted values.

Ab initio R1 mechanism of photostimulated oxygen isotope exchange reaction on a defect TiO{sub 2} surface: The case of terminal oxygen atom exchange

Energy Technology Data Exchange (ETDEWEB)

Kevorkyants, Ruslan, E-mail: ruslan.kevorkyants@gmail.com; Sboev, Mikhail N.; Chizhov, Yuri V.

2017-05-01

Highlights: • DFT R1 mechanism of photostimulated oxygen isotope exchange between {sup 16}O{sup 18}O and terminal oxygen atom of a defect surface of nanocrystalline TiO{sub 2} is proposed. • The mechanism involves four adsorption intermediates and five transition states. • Activation energy of the reaction is 0.24 eV. • G-tensors of O{sub 3}{sup −} intermediates match EPR data on O{sub 2} adsorbed on UV-irradiated TiO{sub 2} surface. - Abstract: Based on density functional theory we propose R1 mechanism of photostimulated oxygen isotope exchange (POIEx) reaction between {sup 16}O{sup 18}O and terminal oxygen atom of a defect TiO{sub 2} surface, which is modeled by amorphous Ti{sub 8}O{sub 16} nanocluster in excited S{sup 1} electronic state. The proposed mechanism involves four adsorption intermediates and five transition states. The computed activation energy of the POIEx equals 0.24 eV. The computed g-tensors of the predicted ozonide O{sub 3}{sup −} chemisorption species match well EPR data on O{sub 2} adsorption on UV-irradiated nanocrystalline TiO{sub 2}. This match serves a mean of justification of the proposed R1 mechanism of the POIEx reaction. In addition, it is found that the proposed R1 POIEx reaction’s mechanism differs from R1 mechanism of thermo-assisted OIEx reaction on a surface of supported vanadium oxide catalyst VO{sub x}/TiO{sub 2} reported earlier.

Anisotropic etching of polycrystalline silicon with a hot Cl2 molecular beam

International Nuclear Information System (INIS)

Suzuki, K.; Hiraoka, S.; Nishimatsu, S.

1988-01-01

A hot Cl 2 molecular (Cl/sup */ 2 ) beam was successfully applied to achieve highly anisotropic, highly selective, and almost damage-free etching of polycrystalline Si. The anisotropy, the ratio of etch rates in vertical and horizontal directions, was larger than 25. The selectivity, the ratio of polycrystalline Si and SiO 2 etch rates, was larger than 1000. The Cl/sup */ 2 beam was produced by free jet expansion of a Cl 2 gas heated in a graphite furnace. The furnace temperature was 830 0 C. The substrate temperature was 180 0 C. The average total energy (0.38 eV) of a Cl/sup */ 2 molecule impinging on a substrate surface is much lower than the critical energy (approximately 10 eV) to displace the atoms of the etched material and to cause surface damage. This is the essential reason why this highly selective and almost damage-free etching has been achieved. The highly anisotropic etching mechanism is explained by a model taking into account the directional incidence of Cl/sup */ 2 molecules to the surface, and the deactivation process of the Cl/sup */ 2 molecules on a cold surface

Heterogeneous compute in computer vision: OpenCL in OpenCV

Science.gov (United States)

Gasparakis, Harris

2014-02-01

We explore the relevance of Heterogeneous System Architecture (HSA) in Computer Vision, both as a long term vision, and as a near term emerging reality via the recently ratified OpenCL 2.0 Khronos standard. After a brief review of OpenCL 1.2 and 2.0, including HSA features such as Shared Virtual Memory (SVM) and platform atomics, we identify what genres of Computer Vision workloads stand to benefit by leveraging those features, and we suggest a new mental framework that replaces GPU compute with hybrid HSA APU compute. As a case in point, we discuss, in some detail, popular object recognition algorithms (part-based models), emphasizing the interplay and concurrent collaboration between the GPU and CPU. We conclude by describing how OpenCL has been incorporated in OpenCV, a popular open source computer vision library, emphasizing recent work on the Transparent API, to appear in OpenCV 3.0, which unifies the native CPU and OpenCL execution paths under a single API, allowing the same code to execute either on CPU or on a OpenCL enabled device, without even recompiling.

Local work-function changes of Pt(111) studied by STM and IRAS: coadsorption of Cl - with H 3O +, NO, and CO molecules

Science.gov (United States)

Fukushima, Takashi; Song, Moon-Bong; Ito, Masatoki

2000-10-01

The coadsorption of chloride anion (Cl -) with hydronium cation (H 3O +), nitrogen monoxide (NO), and carbon monoxide (CO) on Pt(111) was studied in an ultra-high-vacuum system using scanning tunneling microscopy (STM), infrared reflection absorption spectroscopy (IRAS), and low-energy electron diffraction (LEED). HCl molecules adsorbed on Pt(111) at 100 K form a (3×3) structure ( θCl -=0.44). Water adsorption on the 3×3 structure produces c(4×2)-(Cl -+H 3O +) coadsorption structures. The hydronium cation adsorbs through oxygen lone pair, and hydrogen bonding (OH…Cl) extends on the surface with these structures. Stretching absorption bands of NO (or CO) adsorbed on the 3×3-Cl - and c(4×2)-(Cl -+H 3O +) adlayers on Pt(111) show remarkably higher and lower frequency shifts, respectively. The frequency shifts can be explained by the local charge density states of platinum atoms derived from electron withdrawal or supply from the coadsorbates (Cl - or H 3O +) to platinum atoms.

Etude de la fixation d'atomes de brome dans les traces latentes d'ions

Science.gov (United States)

Vareille, J. C.; Moliton, J. P.; Decossas, J. L.; Teyssier, J. L.; Delaunay, B.

1981-09-01

We show that the branching of bromide atoms is possible on chemically active sites produced by Kr 8+, Cl 6+ and He 2+ ion irradiation on cellulose triacetate. The number of fixed atoms increases with ion fluence and atomic number. These results are in good agreement with those concerning radical yield around the ions' path.

Determination of Chlorine in Milk via Molecular Absorption of SrCl Using High-Resolution Continuum Source Graphite Furnace Atomic Absorption Spectrometry.

Science.gov (United States)

Ozbek, Nil; Akman, Suleyman

2016-07-20

Total chlorine in milk was determined via the molecular absorption of diatomic strontium monochloride at 635.862 nm using high-resolution continuum source graphite furnace atomic absorption spectrometry. The effects of coating the graphite furnace, using different modifiers, amount of molecule-forming element, and different calibrants were investigated and optimized. Chlorine concentrations in milk samples were determined in a Zr-coated graphite furnace using 25 μg of Sr as the molecule-forming reagent and applying a pyrolysis temperature of 600 °C and a molecule-forming temperature of 2300 °C. Linearity was maintained up to 500 μg mL(-1) of Cl. The method was tested by analyzing a certified reference wastewater. The results were in the uncertainty limits of the certified value. The limit of detection of the method was 1.76 μg mL(-1). The chlorine concentrations in various cow milk samples taken from the market were found in the range of 588-1472 mg L(-1).

The Heliospheric Termination Shock

Science.gov (United States)

Jokipii, J. R.

2013-06-01

The heliospheric termination shock is a vast, spheroidal shock wave marking the transition from the supersonic solar wind to the slower flow in the heliosheath, in response to the pressure of the interstellar medium. It is one of the most-important boundaries in the outer heliosphere. It affects energetic particles strongly and for this reason is a significant factor in the effects of the Sun on Galactic cosmic rays. This paper summarizes the general properties and overall large-scale structure and motions of the termination shock. Observations over the past several years, both in situ and remote, have dramatically revised our understanding of the shock. The consensus now is that the shock is quite blunt, is with the front, blunt side canted at an angle to the flow direction of the local interstellar plasma relative to the Sun, and is dynamical and turbulent. Much of this new understanding has come from remote observations of energetic charged particles interacting with the shock, radio waves and radiation backscattered from interstellar neutral atoms. The observations and the implications are discussed.

Atomic substitutions in synthetic apatite; Insights from solid-state NMR spectroscopy

Science.gov (United States)

Vaughn, John S.

Apatite, Ca5(PO4)3X (where X = F, Cl, or OH), is a unique mineral group capable of atomic substitutions for cations and anions of varied size and charge. Accommodation of differing substituents requires some kind of structural adaptation, e.g. new atomic positions, vacancies, or coupled substitutions. These structural adaptations often give rise to important physicochemical properties relevant to a range of scientific disciplines. Examples include volatile trapping during apatite crystallization, substitution for large radionuclides for long-term storage of nuclear fission waste, substitution for fluoride to improve acid resistivity in dental enamel composed dominantly of hydroxylapatite, and the development of novel biomaterials with enhanced biocompatibility. Despite the importance and ubiquity of atomic substitutions in apatite materials, many of the mechanisms by which these reactions occur are poorly understood. Presence of substituents at dilute concentration and occupancy of disordered atomic positions hinder detection by bulk characterization methods such as X-ray diffraction (XRD) and infrared (IR) spectroscopy. Solid-state nuclear magnetic resonance (NMR) spectroscopy is an isotope-specific structural characterization technique that does not require ordered atomic arrangements, and is therefore well suited to investigate atomic substitutions and structural adaptations in apatite. In the present work, solid-state NMR is utilized to investigate structural adaptations in three different types of apatite materials; a series of near-binary F, Cl apatite, carbonate-hydroxylapatite compositions prepared under various synthesis conditions, and a heat-treated hydroxylapatite enriched in 17O. The results indicate that hydroxyl groups in low-H, near binary F,Cl apatite facilitate solid-solution between F and Cl via column reversals, which result in average hexagonal symmetry despite very dilute OH concentration ( 2 mol percent). In addition, 19F NMR spectra indicate

Reactions of the dirhenium(II) complexes Re2X4(dppm)2 (X = Cl, Br; dppm = Ph2PCH2PPh2) with isocyanides. 5. Mixed carbonyl-isocyanide and carbonyl-isocyanide-nitrile complexes of stoichiometry (Re2Cl3(dppm)2(CO)(CNR)(L))PF6 (R = t-Bu, xyl (Xylyl); L = t-BuNC, xylNC, MeCN, EtCN). Structural characterization of the cation (Cl2(CO)Re(μ-dppm)2ReCl (CN-t-Bu)2)+

International Nuclear Information System (INIS)

Fanwick, P.E.; Price, A.C.; Walton, R.A.

1988-01-01

Several dirhenium (II) species that contain mixed sets of carbonyl, isocyanide, and/or nitrile ligands have been prepared from the reactions between Re 2 Cl 4 (dppm) 2 (CO)(CNR) (dppm = Ph 2 PCHPPh 2 ; R = t-Bu, xyl (xylyl)), and the appropriate ligands in the presence of TlPF 6 . The crystal structures of these compounds are reported. The terminally-bound ligand noted in the complexes (Re 2 Cl 3 (dppm) 2 (CO)(CN-t-Bu) 2 )PF 6 and (Re 2 CL 3 (dppm) 2 (CO)(CN-t-Bu)(CNxyl))PF 6 indicates structures that have not been previously reported. Complexes in which there are mixed sets of carbonyl, isocyanide, and nitrile ligands, viz. (Re 2 Cl 3 (dppm) 2 (CO)(CNR)(CNR'))PF 6 are also reported. 20 refs., 1 fig., 5 tabs

A Simplified Numerical Study of the Kr/Cl2 Plasma Chemistry in Dielectric Barrier Discharge

International Nuclear Information System (INIS)

Bachir, N. Larbi Daho; Belasri, A.

2013-01-01

In this paper, the generation of excimers and exciplexe radiation in mixtures of rare gas with halogen by homogeneous dielectric barrier discharge (DBD) is investigated. The typical characteristics of an excilamp based on KrCl* exciplexe molecules and the kinetic processes for the formation and the decay of this molecules in the Kr/Cl 2 mixture are studied. The computer model developed is based on the Kr/Cl 2 mixture chemistry, the equivalent electric circuit and the Boltzmann equations. The importance in the kinetic processes of some species such as the metastable state of Krypton (Kr*( 3 P 0,2 )) and the negative ion of chloride (Cl − ) is considered. The results illustrate the time variations of charged species (n e , Kr + , Cl − , Cl + , Cl + 2 , Kr + 2 ), excited atoms and molecules (Kr*( 3 P 0,2 ), Kr*( 3 P 1 ), Cl*, Cl* 2 ), the excimers (Kr* 2 , KrCl*(B), KrCl*(C), Kr 2 Cl*) and the UV photon concentrations (in 222 nm, 235 nm, 258 nm and 325 nm range). The effects of chlorine concentration and the total gas pressure in the Kr-Cl 2 discharge on the electric parameters and radiation emissions are investigated. (low temperature plasma)

Highly Dense Isolated Metal Atom Catalytic Sites

DEFF Research Database (Denmark)

Chen, Yaxin; Kasama, Takeshi; Huang, Zhiwei

2015-01-01

-ray diffraction. A combination of electron microscopy images with X-ray absorption spectra demonstrated that the silver atoms were anchored on five-fold oxygen-terminated cavities on the surface of the support to form highly dense isolated metal active sites, leading to excellent reactivity in catalytic oxidation......Atomically dispersed noble-metal catalysts with highly dense active sites are promising materials with which to maximise metal efficiency and to enhance catalytic performance; however, their fabrication remains challenging because metal atoms are prone to sintering, especially at a high metal...... loading. A dynamic process of formation of isolated metal atom catalytic sites on the surface of the support, which was achieved starting from silver nanoparticles by using a thermal surface-mediated diffusion method, was observed directly by using in situ electron microscopy and in situ synchrotron X...

Transformación en el tiempo: definiendo el sitio de Xuenkal, Yucatán, durante el periodo Clásico Terminal Transformation in time: Defining the nature of Xuenkal, Yucatan, during the Terminal Classic

Directory of Open Access Journals (Sweden)

T. Kam Manahan

2010-01-01

Full Text Available El antiguo centro maya de Xuenkal, ubicado en la región Cupul, aproximadamente a 45 km hacia el noreste de Chichén Itzá fue uno de los sitios tierra adentro que contaban con una ocupación Sotuta sustancial. La investigación del Proyecto Arqueológico Xuenkal (PAX se enfoca en el estudio de la cultura material Sotuta y su relación con la ocupación Cehpech del Clásico Tardío-Terminal con el propósito de entender la naturaleza de tal transición. Utilizando una metodología de excavación de pozos de sondeo en contextos domésticos sugerimos que la ocupación pre-Sotuta fue mucho más robusta de lo que originalmente pensábamos. Los resultados del estudio del patrón de asentamiento demuestran que existía un asentamiento Cehpech extensivo que se extendía hacia la periferia, y las excavaciones de las unidades domésticas revelan que durante el Clásico Tardío Xuenkal era un asentamiento mucho más próspero de lo que imaginábamos y que sus pobladores probablemente tenían un contacto estrecho y recíproco con sus vecinos de Ek' Balam, Kulubá y Cobá. En contraste, el asentamiento Sotuta se limita a grupos residenciales localizados dentro del núcleo del sitio. Estos datos en conjunto sugieren que el control que ejerció Sotuta sobre Xuenkal está probablemente ligado al resultado de un conflicto político regional, más que una transformación autóctona.The ancient Maya center of Xuenkal, located in the Cupul region about 45 km northeast of Chichén Itzá, is one of the few known interior sites that witnessed a substantial Sotuta occupation. Proyecto Arqueológico Xuenkal (PAX research is investigating the Sotuta material and its relationship to preceding Late-Terminal Classic Cehpech settlement in order to understand the nature of this transition. Drawing upon extensive test excavations and broad excavations of household groups, we suggest that the pre-Sotuta Xuenkal occupation was much more robust than previously hypothesized

QMX: A versatile environment for hybrid calculations applied to the grafting of Al 2 Cl 3 Me 3 on a silica surface

KAUST Repository

Kerber, Torsten

2013-01-23

We present a new software to easily perform QM:MM and QM:QM\\' calculations called QMX. It follows the subtraction scheme and it is implemented in the Atomic Simulation Environment (ASE). Special attention is paid to couple molecular calculations with periodic boundaries approaches. QMX inherits the flexibility and versatility of the ASE package: any combination of methods namely force field, semiempirical, first principle, and ab initio, can be used as hybrid potential energy surface (PES). Its ease of use is demonstrated by considering the adsorption of Al2Cl3Me3 on silica surface and by combining different levels of theory (from standard DFT to MP2 calculations) for the so-called High Level cluster with standard PW91 density functional theory calculations for the Low Level environment. It is shown that the High Level cluster must contain the silanol group close to the aluminum atoms. The bridging adsorption is favored by 58 kJ mol-1 at the MP2:PW91 level with respect to the terminal position. Using large clusters at the MP2:PW91 level, it is shown that PW91 calculations are sufficient for structure optimization but that embedded methods are required for accurate energy profiles. © 2013 Wiley Periodicals, Inc.

Electrochemical deposition of La-Mg alloys in LaCl3-MgCl2-KCl system with molten salt electrolysis process

Directory of Open Access Journals (Sweden)

Sahoo Kumar D.

2014-01-01

Full Text Available La-Mg alloys of different compositions were prepared by electrolysis of LaCl3-MgCl2-KCl melts. Different phases of La-Mg alloys were characterized by X-ray diffraction (XRD and Scanning Electron Microscopy (SEM. Energy dispersive spectrometry (EDS and Inductively Coupled Plasma-Atomic Emission Spectroscopy (ICP-AES analyses showed that chemical compositions of La-Mg alloys were consistent with phase structures of XRD pattern, and magnesium content in the alloy could be controlled by electrolysis parameters. The effects of various process parameters such as concentration of magnesium chloride in the bath, temperature of electrolysis and cathode current density on the current efficiency have been investigated. A maximum current efficiency of 85% and yield of 80% was obtained from the bath at 12.5A/cm2 current density at an operating temp 850°C.

The electrolysis of an acidic NaCl solution with a graphite anode-II. atomic chlorine present in a graphite electrode

NARCIS (Netherlands)

Janssen, L.J.J.; Hoogland, J.G.

1970-01-01

A graphite electrode at which Cl is evolved takes up Cl, this being the cause of a gradually decreasing Cl evolution after the current has been s witched off. From the fact that by immersion in alkali, O is evolved, it must be concluded that this Cl is present in at. form. Detn. of the amt. taken up

The initial stages of NaCl dissolution: Ion or ion pair solvation?

Science.gov (United States)

Klimes, Jiri; Michaelides, Angelos

2009-03-01

The interaction of water with rock salt (NaCl) is important in a wide variety of natural processes and human activities. A lot is known about NaCl dissolution at the macroscopic level but we do not yet have a detailed atomic scale picture of how salt crystals dissolve. Here we report an extensive series of density functional theory, forcefield and molecular dynamics studies of water clusters at flat and defective NaCl surfaces and NaCl clusters. The focus is on answering seemingly elementary questions such as how many water molecules are needed before it becomes favorable to extract an ion or a pair of ions from the crystal or the cluster. It turns out, however, that the answers to these questions are not so straightforward: below a certain number of water molecules (˜ 12) solvation of individual ions is less costly and above this number solvation of ion pairs is favored. These results reveal a hitherto unknown complexity in the NaCl dissolution process born out of a subtle interplay between water-water and water-ion interactions.

Study of atomic and molecular emission spectra of Sr by laser induced breakdown spectroscopy (LIBS).

Science.gov (United States)

Bhatt, Chet R; Alfarraj, Bader; Ayyalasomayajula, Krishna K; Ghany, Charles; Yueh, Fang Y; Singh, Jagdish P

2015-12-01

Laser Induced Breakdown Spectroscopy (LIBS) is an ideal analytical technique for in situ analysis of elemental composition. We have performed a comparative study of the quantitative and qualitative analysis of atomic and molecular emission from LIBS spectra. In our experiments, a mixture of SrCl2 and Al2O3 in powder form was used as a sample. The atomic emission from Sr and molecular emission from SrCl and SrO observed in LIBS spectra were analyzed. The optimum laser energies, gate delays, and gate widths for selected atomic lines and molecular bands were determined from spectra recorded at various experimental parameters. These optimum experimental conditions were used to collect calibration data, and the calibration curves were used to predict the Sr concentration. Limits of detection (LODs) for selected atomic and molecular emission spectra were determined.

High 36Cl/Cl ratios in Chernobyl groundwater

International Nuclear Information System (INIS)

Roux, Céline; Le Gal La Salle, Corinne; Simonucci, Caroline; Van Meir, Nathalie; Fifield, L. Keith; Diez, Olivier; Bassot, Sylvain

2014-01-01

After the explosion of the Chernobyl Nuclear Power Plant in April 1986, contaminated material was buried in shallow trenches within the exclusion zone. A 90 Sr plume was evidenced downgradient of one of these trenches, trench T22. Due to its conservative properties, 36 Cl is investigated here as a potential tracer to determine the maximal extent of the contamination plume from the trench in groundwater. 36 Cl/Cl ratios measured in groundwater, trench soil water and leaf leachates are 1–5 orders of magnitude higher than the theoretical natural 36 Cl/Cl ratio. This contamination occurred after the Chernobyl explosion and currently persists. Trench T22 acts as an obvious modern point source of 36 Cl, however other sources have to be involved to explain such contamination. 36 Cl contamination of groundwater can be explained by dilution of trench soil water by uncontaminated water (rainwater or deep groundwater). With a plume extending further than that of 90 Sr, radionuclide which is impacted by retention and decay processes, 36 Cl can be considered as a suitable tracer of contamination from the trench in groundwater provided that modern release processes of 36 Cl from trench soil are better characterized. - Highlights: • High 36 Cl/Cl ratios measured in the Chernobyl Pilot Site groundwater. • Trench T22 acts as a modern source of groundwater contamination by 36 Cl but other sources are involved. • Contamination results from dilution of a contaminated “T22” soil water with rainwater. • Processes involved in the modern release need to be investigated

Atmospheric chemistry of 4 : 2 fluorotelomer alcohol (CF3(CF2)(3)CH2CH2OH): Products and mechanism of Cl atom initiated oxidation

DEFF Research Database (Denmark)

Hurley, MD; Ball, JC; Wallington, TJ

2004-01-01

Smog chamber/FTIR techniques were used to study the products and mechanism of the Cl atom initiated oxidation of 4:2 fluorotelomer alcohol (CF3(CF2)(3)CH2CH2OH) in 700 Torr of N-2/O-2 diluent at 296 K. CF3(CF2)(3)CH2CHO is the sole primary oxidation product. CF3(CF2)(3)CHO, CF3(CF2)(3)CH2COOH...... respectively. Using relative rate techniques, a value of k(Cl + CF3(CF2)(3)CH2CHO) = (1.84 +/- 0.30) x 10(-11) cm(3) molecule(-1) s(-1) was determined. The yield of the perfluorinated acid, CF3(CF2)(3)COOH, from the 4:2 fluorotelomer alcohol increased with the diluent gas oxygen concentration......, and CF3(CF2)(3)CH2C(O)OOH are secondary oxidation products. Further irradiation results in the formation of CF3(CF2)(3)COOH, COF2, and CF3OH. CF3(CF2)(3)CHO, CF3(CF2)(3)CH2COOH, and CF3(CF2)(3)CH2C(O)OOH are formed from CF3(CF2)(3)CH2CHO oxidation in yields of 46 27 and less than or equal to 27...

CCl 4 chemistry on the reduced selvedge of a α-Fe 2O 3(0 0 0 1) surface: a scanning tunneling microscopy study

Science.gov (United States)

Rim, Kwang Taeg; Fitts, Jeffrey P.; Müller, Thomas; Adib, Kaveh; Camillone, Nicholas; Osgood, Richard M.; Joyce, S. A.; Flynn, George W.

2003-09-01

Scanning tunneling microscopy (STM) and low energy electron diffraction (LEED) were used to study the degradation of CCl 4 on the reduced selvedge of a natural single crystal α-Fe 2O 3(0 0 0 1) surface in ultrahigh vacuum. Before exposure to CCl 4, STM images indicate that approximately 85% of the reduced surface exhibits a Fe 3O 4(1 1 1) 2 × 2 termination, while the remaining 15% is terminated by 1 × 1 and superstructure phases. Images obtained after room temperature dosing with CCl 4 and subsequent flashing to 600 K reveal that chlorine atoms are adsorbed only on surface regions with the Fe 3O 4(1 1 1) 2 × 2 termination, not on 1 × 1 and superstructure regions. Chlorine atoms from dissociative adsorption of CCl 4 are observed to occupy two distinct positions located atop lattice protrusions and in threefold oxygen vacancy sites. However, in companion chemical labeling experiments, chlorine atoms provided by room temperature, dissociative Cl 2 adsorption on this surface are found to occupy sites atop lattice protrusions exclusively. The clear dissimilarity in STM feature shape and brightness at the two distinct chlorine adsorption sites arising from CCl 4 dissociation as well as the results of the Cl 2 chemical labeling experiments are best explained via reactions on a Fe 3O 4(1 1 1) 2 × 2 selvedge terminated by a 1/4 monolayer of tetrahedrally coordinated iron atoms. On this surface, adsorption atop an iron atom occurs for both the CCl 4 and Cl 2 dissociative reactions. A second adsorption site, assigned as binding to second layer iron atoms left exposed following surface oxygen atom abstraction resulting in the formation of phosgene (COCl 2), only appears in the case of reaction with CCl 4. The reaction mechanism and active site requirements for CCl 4 degradation on iron oxide surfaces are discussed in light of this evidence and in the context of our previously reported results from Auger electron spectroscopy (AES), LEED, temperature-programmed desorption

Raman spectra of the system TeCl4-SbCl5

International Nuclear Information System (INIS)

Brockner, W.; Demiray, A.F.

1980-01-01

Raman spectra of the solid and molten TeCl 4 . SbCl 5 addition compound and of some TeCl 4 -SbCl 5 mixtures have been recorded. Two modifications of the crystalline TeCl 4 -SbCl 5 compound have been found. The structure of the melt can be described by the equilibrium TeCl 3 + + SbCl 6 - reversible TeCl 4 + SbCl 5 lying on the left side. Mixtures with other stoichiometry contain the 1:1 adduct only and excess TeCl 4 or SbCl 5 , respectively. Such melts are built up by the ionic species TeCl 3 + and SbCl 6 - also and TeCl 4 or SbCl 5 according to stoichiometry. (author)

A hydrochemical investigation using 36Cl/Cl in groundwaters

International Nuclear Information System (INIS)

Metcalfe, Richard

2003-03-01

This report describes 36 Cl studies which were undertaken during the H14 financial year. The results of this study suggest that, if 36 Cl data can be obtained for groundwaters at spatial scales comparable with, or smaller than, the spatial scales of the variability in in-situ 36 Cl production in the host rock, the data could potentially be useful for interpreting groundwater origins and flow paths. Four groundwater samples and one onsen water sample from the Tono area were collected for 36 Cl analysis. The groundwater samples came from boreholes MSB-2 and MSB-4 in the MIU Construction Site, whereas the onsen water was taken from Oniiwa Onsen (Komatsuya). In addition, a single sample from borehole HDB-1 at Horonobe was also sent for analysis. Supporting rock chemical data and wireline geophysical data have also been evaluated, to provide a basis for interpreting the 36 Cl data. Rock analyses and spectral gamma wireline data were used to estimate theoretical limiting equilibrium 36 Cl/Cl ratios in the rock. These have been compared with the compositions measured for groundwater samples, enabling a judgement to be made as to: whether the waters have resided for long enough in the rock to approach equilibrium (> c. 1.5 Ma); the spatial scales of mixing of the dissolved Cl in the groundwater. The estimates of in-situ 36 Cl/Cl production made with the newly available rock chemical data and wireline geophysical data have enabled 36 Cl data obtained previously from MIU-4, KNA-6 and DH-12 during H12 and H13 to be interpreted more confidently. In particular it seems that 36 Cl/Cl ratios measured previously in groundwater samples from MIU-4 are not in equilibrium with in-situ production in the granite. Furthermore, they imply that the Cl is homogenised, at least on the scale of the upper half of borehole. In contrast, the data from DH-12 imply that the Cl could be in equilibrium with in-situ 36 Cl production in the granite, which would be consistent with a relatively long

Rational synthesis of high nuclearity Mo/Fe/S clusters: the reductive coupling approach in the convenient synthesis of (Cl(4)-cat)(2)Mo(2)Fe(6)S(8)(PR(3))(6) [R = Et, (n)Pr, (n)Bu] and the new [(Cl(4)-cat)(2)Mo(2)Fe(2)S(3)O(PEt(3))(3)Cl]-1/2(Fe(PEt(3))(2)(MeCN)(4)) and (Cl(4)-cat)(2)Mo(2)Fe(3)S(5)(PEt(3))(5) clusters.

Science.gov (United States)

Han, J; Koutmos, M; Ahmad, S A; Coucouvanis, D

2001-11-05

A general method for the synthesis of high nuclearity Mo/Fe/S clusters is presented and involves the reductive coupling of the (Et(4)N)(2)[(Cl(4)-cat)MoOFeS(2)Cl(2)] (I) and (Et(4)N)(2)[Fe(2)S(2)Cl(4)] (II) clusters. The reaction of I and II with Fe(PR(3))(2)Cl(2) or sodium salts of noncoordinating anions such as NaPF(6) or NaBPh(4) in the presence of PR(3) (R = Et, (n)Pr, or (n)Bu) affords (Cl(4)-cat)(2)Mo(2)Fe(6)S(8)(PR(3))(6) [R = Et (IIIa), (n)Pr (IIIb), (n)Bu (IIIc)], Fe(6)S(6)(PEt(3))(4)Cl(2) (IV) and (PF(6))[Fe(6)S(8)(P(n)Pr(3))(6)] (V) as byproducts. The isolation of (Et(4)N)[Fe(PEt(3))Cl(3)] (VI), NaCl, and SPEt(3) supports a reductive coupling mechanism. Cluster IV and V also have been synthesized by the reductive self-coupling of compound II. The reductive coupling reaction between I and II by PEt(3) and NaPF(6) in a 1:1 ratio produces the (Et(4)N)(2)[(Cl(4)-cat)Mo(L)Fe(3)S(4)Cl(3)] clusters [L = MeCN (VIIa), THF (VIIb)]. The hitherto unknown [(Cl(4)-cat)(2)Mo(2)Fe(2)S(3)O(PEt(3))(3)Cl](+) cluster (VIII) has been isolated as the 2:1 salt of the (Fe(PEt(3))(2)(MeCN)(4))(2+) cation after the reductive self-coupling reaction of I in the presence of Fe(PEt(3))(2)Cl(2). Cluster VIII crystallizes in the monoclinic space group P2(1)/c with a = 11.098(3) A, b = 22.827(6) A, c = 25.855(6) A, beta = 91.680(4) degrees, and Z = 4. The formal oxidation states of metal atoms in VIII have been assigned as Mo(III), Mo(IV), Fe(II), and Fe(III) on the basis of zero-field Mössbauer spectra. The Fe(PEt(3))(2)(MeCN)(4) cation of VIII is also synthesized independently, isolated as the BPh(4)(-) salt (IX), and has been structurally characterized. The reductive coupling of compound I also affords in low yield the new (Cl(4)-cat)(2)Mo(2)Fe(3)S(5)(PEt(3))(5) cluster (X) as a byproduct. Cluster X crystallizes in the monoclinic space group P2(1)/n with a = 14.811(3) A, b = 22.188(4) A, c = 21.864(4) A, beta = 100.124(3) degrees, and Z = 4 and the structure shows very short Mo

(μ-3-Acetyl-5-carboxyl­ato-4-methyl­pyrazolido-1:2κ4 N 2,O 3:N 1,O 5)-μ-chlorido-tetra­pyridine-1κ2 N,2κ2 N-chlorido-1κCl-dicopper(II) propan-2-ol solvate

Science.gov (United States)

Malinkin, Sergey; Penkova, Larisa; Pavlenko, Vadim A.; Haukka, Matti; Fritsky, Igor O.

2009-01-01

The title compound, [Cu2(C7H6N2O3)Cl2(C5H5N)4]·C3H8O, is a binuclear pyrazolate complex, in which the two CuII atoms have different coordination numbers and are connected by a bridging Cl atom. One CuII atom has a distorted square-pyramidal coordination environment formed by two pyridine N atoms, one bridging Cl atom and an N,O-chelating pyrazolate ligand. The other CuII atom adopts an octa­hedral geometry defined by two pyridine N atoms at the axial positions, two Cl atoms and the coordinated pyrazolate ligand in the equatorial plane. An O—H⋯O hydrogen bond connects the complex mol­ecules and propan-2-ol solvent mol­ecules into pairs. These pairs form columns along the a axis. PMID:21577764

Further studies on hydration of alkynes by the PtCl4-CO catalyst

Energy Technology Data Exchange (ETDEWEB)

Israelsohn, Osnat; Vollhardt, K. Peter C.; Blum, Jochanan

2002-01-18

Under CO atmosphere, between 80 and 120 C, a glyme solution of PtCl{sub 4} forms a carbonyl compound that promotes hydration of internal as well as terminal alkynes to give aldehyde-free ketones. The catalytic process depends strongly on the electronic and steric nature of the substrates. Part of the carbonyl functions of the catalyst can be replaced by phosphine ligands. Chiral DIOP reacts with the PtCl{sub 4}-CO compound to give a catalyst that promotes partial kinetic resolution of a racemic alkyne. Replacement of part of the CO by polystyrene-bound diphenylphosphine enables to attach the catalyst to the polymeric support. Upon entrapment of the platinum compound in a silica sol-gel matrix, it reacts as a partially recyclable catalyst. A reformulated mechanism for the PdCl{sub 4}-CO catalyzed hydration is suggested on the basis of the present study.

Successive phase transitions in perovskites. II. Cell distortion and atomic displacements

Energy Technology Data Exchange (ETDEWEB)

Aleksandrov, K S; Pozdnyakova, L A; Orlova, T A [AN SSSR, Novosibirsk. Inst. Fiziki; Krasnoyarskij Gosudarstvennyj Univ. (USSR))

1977-01-01

A method is suggested for evaluating the structural and thermodynamic parameters from cell distortions at phase transformation. The method was applied for investigation of successive phase transformations in CsPbCl/sub 3/ and CsSrCl/sub 3/ crystals. By studying the temperature dependencies of the lattice parameters, the phase stereo groups for these crystals were established; the respective rotation angles and atom displacements were also evaluated.

High (36)Cl/Cl ratios in Chernobyl groundwater.

Science.gov (United States)

Roux, Céline; Le Gal La Salle, Corinne; Simonucci, Caroline; Van Meir, Nathalie; Fifield, L Keith; Diez, Olivier; Bassot, Sylvain; Simler, Roland; Bugai, Dmitri; Kashparov, Valery; Lancelot, Joël

2014-12-01

After the explosion of the Chernobyl Nuclear Power Plant in April 1986, contaminated material was buried in shallow trenches within the exclusion zone. A (90)Sr plume was evidenced downgradient of one of these trenches, trench T22. Due to its conservative properties, (36)Cl is investigated here as a potential tracer to determine the maximal extent of the contamination plume from the trench in groundwater. (36)Cl/Cl ratios measured in groundwater, trench soil water and leaf leachates are 1-5 orders of magnitude higher than the theoretical natural (36)Cl/Cl ratio. This contamination occurred after the Chernobyl explosion and currently persists. Trench T22 acts as an obvious modern point source of (36)Cl, however other sources have to be involved to explain such contamination. (36)Cl contamination of groundwater can be explained by dilution of trench soil water by uncontaminated water (rainwater or deep groundwater). With a plume extending further than that of (90)Sr, radionuclide which is impacted by retention and decay processes, (36)Cl can be considered as a suitable tracer of contamination from the trench in groundwater provided that modern release processes of (36)Cl from trench soil are better characterized. Copyright © 2014 Elsevier Ltd. All rights reserved.

Mechanism underlying bioinertness of self-assembled monolayers of oligo(ethyleneglycol)-terminated alkanethiols on gold: protein adsorption, platelet adhesion, and surface forces.

Science.gov (United States)

Hayashi, Tomohiro; Tanaka, Yusaku; Koide, Yuki; Tanaka, Masaru; Hara, Masahiko

2012-08-07

The mechanism underlying the bioinertness of the self-assembled monolayers of oligo(ethylene glycol)-terminated alkanethiol (OEG-SAM) was investigated with protein adsorption experiments, platelet adhesion tests, and surface force measurements with an atomic force microscope (AFM). In this work, we performed systematic analysis with SAMs having various terminal groups (-OEG, -OH, -COOH, -NH(2), and -CH(3)). The results of the protein adsorption experiment by the quartz crystal microbalance (QCM) method suggested that having one EG unit and the neutrality of total charges of the terminal groups are essential for protein-resistance. In particular, QCM with energy dissipation analyses indicated that proteins absorb onto the OEG-SAM via a very weak interaction compared with other SAMs. Contrary to the protein resistance, at least three EG units as well as the charge neutrality of the SAM are found to be required for anti-platelet adhesion. When the identical SAMs were formed on both AFM probe and substrate, our force measurements revealed that only the OEG-SAMs possessing more than two EG units showed strong repulsion in the range of 4 to 6 nm. In addition, we found that the SAMs with other terminal groups did not exhibit such repulsion. The repulsion between OEG-SAMs was always observed independent of solution conditions [NaCl concentration (between 0 and 1 M) and pH (between 3 and 11)] and was not observed in solution mixed with ethanol, which disrupts the three-dimensional network of the water molecules. We therefore concluded that the repulsion originated from structured interfacial water molecules. Considering the correlation between the above results, we propose that the layer of the structured interfacial water with a thickness of 2 to 3 nm (half of the range of the repulsion observed in the surface force measurements) plays an important role in deterring proteins and platelets from adsorption or adhesion.

Reactions UF{sub 4} - ClF, UF{sub 4} - ClF{sub 3}, UF{sub 5} - ClF, UF{sub 5} - ClF{sub 3}; Reactions UF{sub 4} - ClF, UF{sub 4} - ClF{sub 3}, UF{sub 5} - ClF, UF{sub 5} - ClF{sub 3}

Energy Technology Data Exchange (ETDEWEB)

Luce, M; Benoit, R; Hartmanshenn, O [Commissariat a l' Energie Atomique, Saclay (France). Centre d' Etudes Nucleaires

1968-07-01

The reaction between ClF{sub 3} and UF{sub 4} is partially explained by the study of the reactions of the three systems: UF{sub 4}-ClF, UF{sub 5}-ClF and UF{sub 5}-ClF{sub 3}. The analytical techniques used are: the micro-sublimation, the infra-red spectroscopy and the thermogravimetry. The origin of the by-products is indicated. (authors) [French] La reaction entre ClF{sub 3} et UF{sub 4} est partiellement expliquee grace a l'etude des reactions des trois systemes UF{sub 4}-ClF, UF{sub 5}-ClF et UF{sub 5}-ClF{sub 3}. Les techniques analytiques utilisees sont: la micro-sublimation, la spectroscopie infrarouge et la thermogravimetrie. L'origine des sous-produits est indiquee. (auteurs)

Synthesis and Crystal Structure of Di-μ-chlorido-bis{chlorido[4-ethyl- N-(pyridin-2-ylmethylidene-κ N)aniline-κ N]mercury(II)}

Science.gov (United States)

Khalaj, M.; Seftejani, F. B.; Ghazanfarpour-Darjani, M.; Lalegani, A.

2017-12-01

The centrosymmetric dinuclear title complex [Hg2Cl4(dip)2] was synthesized using the Schiff base bidentate ligand (E)-4-ethyl- N-(pyridine-2-ylmethylene)benzeneamine ( dip) and mercury(II) chloride salts. It has been characterized by elemental analysis, X-ray diffraction, and UV-Visible and infrared spectroscopic techniques. The X-ray analysis shows that the title compound crystallizes in the monoclinic sp. gr. P21/n, Z = 2 with a = 7.8233(17) Å, b = 15.178(3) Å, c = 12.559(3) Å, β = 97.021(3)°. The Hg(II) ion has a distorted trigonal-bipyramidal coordination environment formed by the bischelating N-heterocyclic ligands, two bridging Cl atoms and one terminal Cl atom.

Different coordination modes for disulfoxides towards diorganotin(IV) dichlorides. X-ray crystal structures of 1,2-cis-bis-(phenylsulfinyl)ethene (rac-,cis-cbpse) and adducts [{l_brace}Ph{sub 2}SnCl{sub 2}(meso-bpse){r_brace}{sub n}] and [{l_brace}n-Bu{sub 2}SnCl{sub 2}(pdtd){r_brace}{sub 2}

Energy Technology Data Exchange (ETDEWEB)

Sousa, Gerimario F. de [Universidade de Brasilia (UnB), DF (Brazil). Inst. de Quimica], e-mail: gfreitas@unb.br; Ellena, Javier [Universidade de Sao Paulo (USP), Sao Carlos, SP (Brazil). Inst. de Fisica; Malta, Valeria R.S. [Universidade Federal de Alagoas (UFAL), Maceio, AL (Brazil). Dept. de Quimica e Biotecnologia; Ardisson, Jose D. [Centro de Desenvolvimento da Tecnologia Nuclear (CDTN/CNEN-MG), Belo Horizonte, MG (Brazil). Lab. de Fisica Aplicada

2009-07-01

The reactions of meso-1,2-bis(phenylsulfinyl)ethane (meso-bpse) with Ph{sub 2}SnCl{sub 2}, 2-phenyl-1,3-dithiane trans-1-trans-3-dioxide (pdtd) with n-Bu{sub 2}SnCl{sub 2} and 1,2-cis-bis-(phenylsulfinyl) ethene (rac-,cis-cbpse) with Ph{sub 2}SnCl{sub 2}, in 1:1 molar ratio, yielded [{l_brace}Ph{sub 2}SnCl{sub 2}(meso-bpse){r_brace}{sub n}], [{l_brace}n-Bu{sub 2}SnCl{sub 2}(pdtd){r_brace}{sub 2}] and [{l_brace}Ph{sub 2}SnCl{sub 2}(rac,cis-cbpse){r_brace}x] (x = 2 or n), respectively. All adducts were studied by IR, Moessbauer and {sup 119}Sn NMR spectroscopic methods, elemental analysis and single crystal X-ray diffractometry. The X-ray crystal structure of [{l_brace}Ph{sub 2}SnCl{sub 2}(meso-bpse){r_brace}{sub n}] revealed the occurrence of infinite chains in which the tin(IV) atoms appear in a distorted octahedral geometry with Cl atoms in cis and Ph groups in trans positions. The X-ray crystal structure of [{l_brace}n-Bu{sub 2}SnCl{sub 2}(pdtd){r_brace}{sub 2}] revealed discrete centrosymmetric dimeric species in which the tin(IV) atoms possess a distorted octahedral geometry with bridging disulfoxides in cis and n-butyl moieties in trans positions. The spectroscopic data indicated that the adduct containing the rac,cis-cbpse ligand can be dimeric or polymeric. The X-ray structural analysis of the free rac-,cis-cbpse sulfoxide revealed that the crystals belong to the C2/c space group. (author)

Ion irradiation of {sup 37}Cl implanted nuclear graphite: Effect of the energy deposition on the chlorine behavior and consequences for the mobility of {sup 36}Cl in irradiated graphite

Energy Technology Data Exchange (ETDEWEB)

Toulhoat, N., E-mail: nelly.toulhoat@univ-lyon1.fr [Université de Lyon, Université Lyon 1, CNRS/IN2P3, UMR5822, Institut de Physique Nucléaire de Lyon (IPNL) (France); CEA/DEN, Centre de Saclay (France); Moncoffre, N. [Université de Lyon, Université Lyon 1, CNRS/IN2P3, UMR5822, Institut de Physique Nucléaire de Lyon (IPNL) (France); Bérerd, N.; Pipon, Y. [Université de Lyon, Université Lyon 1, CNRS/IN2P3, UMR5822, Institut de Physique Nucléaire de Lyon (IPNL) (France); Université de Lyon, Université Lyon, IUT Lyon-1 département chimie (France); Blondel, A. [Université de Lyon, Université Lyon 1, CNRS/IN2P3, UMR5822, Institut de Physique Nucléaire de Lyon (IPNL) (France); Andra, Châtenay-Malabry (France); Galy, N. [Université de Lyon, Université Lyon 1, CNRS/IN2P3, UMR5822, Institut de Physique Nucléaire de Lyon (IPNL) (France); Sainsot, P. [Université de Lyon, Université Lyon 1, LaMCoS, INSA-Lyon, CNRS UMR5259 (France); Rouzaud, J.-N.; Deldicque, D. [Laboratoire de Géologie de l’Ecole Normale Supérieure (ENS), Paris, UMR CNRS-ENS 8538 (France)

2015-09-15

Graphite is used in many types of nuclear reactors due to its ability to slow down fast neutrons without capturing them. Whatever the reactor design, the irradiated graphite waste management has to be faced sooner or later regarding the production of long lived or dose determining radioactive species such as {sup 14}C, {sup 3}H or {sup 36}Cl. The first carbon dioxide cooled, graphite moderated nuclear reactors resulted in a huge quantity of irradiated graphite waste for which the management needs a previous assessment of the radioactive inventory and the radionuclide’s location and speciation. As the detection limits of usual spectroscopic methods are generally not adequate to detect the low concentration levels (<1 ppm) of the radionuclides, we used an indirect approach based on the implantation of {sup 37}Cl, to simulate the presence of {sup 36}Cl. Our previous studies show that temperature is one of the main factors to be considered regarding the structural evolution of nuclear graphite and chlorine mobility during reactor operation. However, thermal release of chlorine cannot be solely responsible for the depletion of the {sup 36}Cl inventory. We propose in this paper to study the impact of irradiation and its synergetic effects with temperature on chlorine release. Indeed, the collision of the impinging neutrons with the graphite matrix carbon atoms induces mainly ballistic collisions. However, a small part of the recoil carbon atom energy is also transferred to the lattice through electronic excitation. This paper aims at elucidating the effects of the different irradiation regimes (ballistic and electronic) using ion irradiation, on the mobility of implanted {sup 37}Cl, taking into account the initial disorder level of the nuclear graphite.

Correlation between atomic negative muon capture and electron distribution in organic sp2-hybridization compounds CxHyClz

International Nuclear Information System (INIS)

Sakai, Yoichi; Tominaga, Takeshi; Ikuta, Shigeru

1986-01-01

The atomic negative muon capture ratios determined experimentally in organic sp 2 -hybridization compound, C x H y Cl z , were compared with the electron populations of carbon atomic orbitals obtained by an ab initio molecular orbital calculation in such systems. A clear positive correlation was found between the C 2s and C 2pz populations and the negative muon capture ratio A (C/Cl), suggesting the mesomolecular process in the initial stage of muon capture. (orig.)

Systematic UHV-AFM experiments on Na nano-particles and nano-structures in NaCl

NARCIS (Netherlands)

Sugonyako, A.V.; Turkin, A.A.; Gaynutdinov, R.; Vainshtein, D.I.; Hartog, H.W. den; Bukharaev, A.A.

2005-01-01

Results of systematic AFM (atomic force microscopy) experiments on heavily and moderatly irradiated NaCl samples are presented. The sodium nanoparticles and structures of nanoparticles are poduced in sodium chloride during irradiation. The AFM images of the nanoparticles have been obtained in ultra

Structure of Chloro bis(1,10-phenanthroline)Cobalt(II) Complex, [Co(phen)2(Cl)(H2O)]Cl · 2H2O

International Nuclear Information System (INIS)

Zhao, Pu Su; Lu, Lu De; Jian, Fang Fang

2003-01-01

The crystal structure of [Co(phen) 2 (Cl)(H 2 O)] Cl · 2H 2 O(phen=1,10-phenanthroline) has been determined by X-ray crystallography. It crystallizes in the triclinic system, space group P 1 , with lattice parameters a=9.662(2), b=11.445(1), c=13.037(2)A, α=64.02(1), β=86.364(9), γ=78.58(2) .deg., and Z=2. The coordinated cations contain a six-coordinated cobalt atom chelated by two phen ligands and one chloride anion and one water ligand in cis arrangement. In addition to the chloride coordinated to the cobalt, there are one chloride ion and four water molecules which complete the crystal structure. In the solid state, the title compound forms three dimensional network structure through hydrogen bonds, within which exists the strongest hydrogen bond (O(3)-O(4)=2.33A). The intermolecular hydrogen bonds connect the [Co(phen) 2 (Cl)(H 2 O)] 1+ , H 2 O moieties and chloride ion

Atmospheric chemistry of CF3CF═CH2 and (Z)-CF3CF═CHF: Cl and NO3 rate coefficients, Cl reaction product yields, and thermochemical calculations.

Science.gov (United States)

Papadimitriou, Vassileios C; Lazarou, Yannis G; Talukdar, Ranajit K; Burkholder, James B

2011-01-20

Rate coefficients, k, for the gas-phase reactions of Cl atoms and NO(3) radicals with 2,3,3,3-tetrafluoropropene, CF(3)CF═CH(2) (HFO-1234yf), and 1,2,3,3,3-pentafluoropropene, (Z)-CF(3)CF═CHF (HFO-1225ye), are reported. Cl-atom rate coefficients were measured in the fall-off region as a function of temperature (220-380 K) and pressure (50-630 Torr; N(2), O(2), and synthetic air) using a relative rate method. The measured rate coefficients are well represented by the fall-off parameters k(0)(T) = 6.5 × 10(-28) (T/300)(-6.9) cm(6) molecule(-2) s(-1) and k(∞)(T) = 7.7 × 10(-11) (T/300)(-0.65) cm(3) molecule(-1) s(-1) for CF(3)CF═CH(2) and k(0)(T) = 3 × 10(-27) (T/300)(-6.5) cm(6) molecule(-2) s(-1) and k(∞)(T) = 4.15 × 10(-11) (T/300)(-0.5) cm(3) molecule(-1) s(-1) for (Z)-CF(3)C═CHF with F(c) = 0.6. Reaction product yields were measured in the presence of O(2) to be (98 ± 7)% for CF(3)C(O)F and (61 ± 4)% for HC(O)Cl in the CF(3)CF═CH(2) reaction and (108 ± 8)% for CF(3)C(O)F and (112 ± 8)% for HC(O)F in the (Z)-CF(3)CF═CHF reaction, where the quoted uncertainties are 2σ (95% confidence level) and include estimated systematic errors. NO(3) reaction rate coefficients were determined using absolute and relative rate methods. Absolute measurements yielded upper limits for both reactions between 233 and 353 K, while the relative rate measurements yielded k(3)(295 K) = (2.6 ± 0.25) × 10(-17) cm(3) molecule(-1) s(-1) and k(4)(295 K) = (4.2 ± 0.5) × 10(-18) cm(3) molecule(-1) s(-1) for CF(3)CF═CH(2) and (Z)-CF(3)CF═CHF, respectively. The Cl-atom reaction with CF(3)CF═CH(2) and (Z)-CF(3)CF═CHF leads to decreases in their atmospheric lifetimes and global warming potentials and formation of a chlorine-containing product, HC(O)Cl, for CF(3)CF═CH(2). The NO(3) reaction has been shown to have a negligible impact on the atmospheric lifetimes of CF(3)CF═CH(2) and (Z)-CF(3)CF═CHF. The energetics for the reaction of Cl, NO(3), and OH with CF

Influences of H on the Adsorption of a Single Ag Atom on Si(111-7 × 7 Surface

Directory of Open Access Journals (Sweden)

Lin Xiu-Zhu

2009-01-01

Full Text Available Abstract The adsorption of a single Ag atom on both clear Si(111-7 × 7 and 19 hydrogen terminated Si(111-7 × 7 (hereafter referred as 19H-Si(111-7 × 7 surfaces has been investigated using first-principles calculations. The results indicated that the pre-adsorbed H on Si surface altered the surface electronic properties of Si and influenced the adsorption properties of Ag atom on the H terminated Si surface (e.g., adsorption site and bonding properties. Difference charge density data indicated that covalent bond is formed between adsorbed Ag and H atoms on 19H-Si(111-7 × 7 surface, which increases the adsorption energy of Ag atom on Si surface.

Crystal structure of dichloridobis(dimethyl N-cyanodithioiminocarbonatecobalt(II

Directory of Open Access Journals (Sweden)

Mouhamadou Birame Diop

2016-01-01

Full Text Available The structure of the mononuclear title complex, [{(H3CS2C=NC[triple-bond] N}2CoCl2], consists of a CoII atom coordinated in a distorted tetrahedral manner by two Cl− ligands and the terminal N atoms of two dimethyl N-cyanodithioiminocarbonate ligands. The two organic ligands are almost coplanar, with a dihedral angle of 5.99 (6° between their least-squares planes. The crystal packing features pairs of inversion-related complexes that are held together through C—H...Cl and C—H...S interactions and π–π stacking [centroid-to-centroid distance = 3.515 (su? Å]. Additional C—H...Cl and C—H...S interactions, as well as Cl...S contacts < 3.6 Å, consolidate the crystal packing.

Optimizing atomic force microscopy for characterization of diamond-protein interfaces

Czech Academy of Sciences Publication Activity Database

Rezek, Bohuslav; Ukraintsev, Egor; Kromka, Alexander

2011-01-01

Roč. 6, Apr. (2011), 337/1-337/10 ISSN 1931-7573 R&D Projects: GA MŠk(CZ) LC06040; GA ČR(CZ) GAP108/11/0794; GA AV ČR KAN400100701; GA MŠk LC510 Institutional research plan: CEZ:AV0Z10100521 Keywords : atomic force microscopy (AFM) * nanocrystalline diamond * oxygen-terminated diamond * hydrogen-terminated diamond * proteins * fetal bovine serum (FBS) Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 2.726, year: 2011

Atomic energy indemnification system in Japan

International Nuclear Information System (INIS)

Hoshino, Eiichi

1980-01-01

The Japanese legislation on the indemnification by atomic energy enterprisers for atomic energy damages, published in 1961 and enforced in 1962, includes the law concerning indemnification for atomic energy damages and the law concerning atomic energy damage indemnification contracts (hereafter referred to as ''the law concerning indemnification contracts''). While the Japanese laws are same as the foreign legislation in the provisions of the responsibility of atomic energy damages without the error of atomic energy enterprisers, exemption reasons are more important in this respect. When damages are due to exceptionally grave natural disasters or social disturbances, atomic energy enterprisers are exempted from the responsibility. Indemnification amounts are determined, but the Japanese laws do not limit then, different from the foreign regulations. The periods for demanding indemnification are not defined particularly in the law concerning indemnification contracts, and the general basic rules of the civil law are applied. As a result, the demand right terminates in 3 years after the injured persons find damage and offenders, and in 20 years since the unlawful act (Article 724, Civil law). The indemnification liability for atomic energy damages is focused on atomic energy enterprisers concerned in the same way as the foreign laws. The measures for assuring the execution of indemnification responsibility consist in principle of the firm conbination of the liability insurance contracts with private insurance companies and the indemnification contracts for atomic energy damages with the state. The damages of employes suffered in works are excluded from indemnification, which has been the main issue of discussion since the enactment of atomic energy laws. (Okada, K.)

Modelling atomic scale manipulation with the non-contact atomic force microscope

International Nuclear Information System (INIS)

Trevethan, T; Watkins, M; Kantorovich, L N; Shluger, A L; Polesel-Maris, J; Gauthier, S

2006-01-01

We present the results of calculations performed to model the process of lateral manipulation of an oxygen vacancy in the MgO(001) surface using the non-contact atomic force microscope (NC-AFM). The potential energy surfaces for the manipulation as a function of tip position are determined from atomistic modelling of the MgO(001) surface interacting with a Mg terminated MgO tip. These energies are then used to model the dynamical evolution of the system as the tip oscillates and at a finite temperature using a kinetic Monte Carlo method. The manipulation process is strongly dependent on the lateral position of the tip and the system temperature. It is also found that the expectation value of the point at which the vacancy jumps depends on the trajectory of the oscillating cantilever as the surface is approached. The effect of the manipulation on the operation of the NC-AFM is modelled with a virtual dynamic AFM, which explicitly simulates the entire experimental instrumentation and control loops. We show how measurable experimental signals can result from a single controlled atomic scale event and suggest the most favourable conditions for achieving successful atomic scale manipulation experimentally

Selective synthesis of clinoatacamite Cu2(OH)3Cl and tenorite CuO nanoparticles by pH control

DEFF Research Database (Denmark)

Engelbrekt, Christian; Malcho, Phillip; Andersen, Jonas

2014-01-01

, it directed the growth of Cu2(OH)3Cl to provide pure clinoatacamite without the presence of related poly- morphs. The products were characterized by transmission electron microscopy, infrared spectroscopy, ultraviolet–visible light spectroscopy, X-ray powder diffraction (XRD), scanning transmission X......-ray microscopy and atomic force microscopy. Infrared spectroscopy was essential for characterization of closely related polymorphs of Cu2(OH)3Cl indistinguishable by XRD. A plausible mechanism has been proposed and discussed for the formation of the CuO and Cu2(OH)3Cl nanostructures....

Bumetanide is not capable of terminating status epilepticus but enhances phenobarbital efficacy in different rat models.

Science.gov (United States)

Töllner, Kathrin; Brandt, Claudia; Erker, Thomas; Löscher, Wolfgang

2015-01-05

In about 20-40% of patients, status epilepticus (SE) is refractory to standard treatment with benzodiazepines, necessitating second- and third-line treatments that are not always successful, resulting in increased mortality. Rat models of refractory SE are instrumental in studying the changes underlying refractoriness and to develop more effective treatments for this severe medical emergency. Failure of GABAergic inhibition is a likely cause of the development of benzodiazepine resistance during SE. In addition to changes in GABAA receptor expression, trafficking, and function, alterations in Cl(-) homeostasis with increased intraneuronal Cl(-) levels may be involved. Bumetanide, which reduces intraneuronal Cl(-) by inhibiting the Cl(-) intruding Na(+), K(+), Cl(-) cotransporter NKCC1, has been reported to interrupt SE induced by kainate in urethane-anesthetized rats, indicating that this diuretic drug may be an interesting candidate for treatment of refractory SE. In this study, we evaluated the effects of bumetanide in the kainate and lithium-pilocarpine models of SE as well as a model in which SE is induced by sustained electrical stimulation of the basolateral amygdala. Unexpectedly, bumetanide alone was ineffective to terminate SE in both conscious and anesthetized adult rats. However, it potentiated the anticonvulsant effect of low doses of phenobarbital, although this was only seen in part of the animals; higher doses of phenobarbital, particularly in combination with diazepam, were more effective to terminate SE than bumetanide/phenobarbital combinations. These data do not suggest that bumetanide, alone or in combination with phenobarbital, is a valuable option in the treatment of refractory SE in adult patients. Copyright © 2014 Elsevier B.V. All rights reserved.

The crystal structure of TeCl3+AuCl4-

International Nuclear Information System (INIS)

Jones, P.G.; Jentsch, D.; Schwarzmann, E.

1986-01-01

TeCl 3 + AuCl 4 - crystallizes in the triclinic space group Panti 1 with a=7.564(2), b=7.720(3), c=8.964(3) A, α=78.26(3), β=88.84(3), γ=89.35(3) 0 , Z=2. The structure was refined to R 0.041 for 1380 reflections. The cation polyhedron, including secondary Te...Cl interactions, is a square pyramid with mean Te-Cl 2.294, Te...Cl 3.028 A. The secondary interactions link the ions to form centrosymmetric (TeCl 3 .AuCl 4 ) 2 dimers. (orig.)

Raman and electronic transport characterization of few- and single-layer-thick α-RuCl3

Science.gov (United States)

Zhou, Boyi; Henriksen, Erik

The layered magnetic semiconductor α-RuCl3, having a honeycomb lattice of spin-1/2 moments, has been identified as a potential candidate material to realize the Kitaev quantum spin liquid. In particular, bulk RuCl3 crystals have been studied and found to be on the cusp of manifesting QSL behavior. As the QSL is primarily a two-dimensional phenomenon, and since the layers of RuCl3 are weakly coupled, we propose to create and study a 2D spin-1/2 honeycomb system by isolating single sheets. Here we report the exfoliation of RuCl3 down to few- and single-layer-thick samples, which we characterize by Raman spectroscopy and atomic force microscopy at room temperature. We will also report our progress on measurements of basic electronic transport properties in the 2D RuCl3 system by controlling the chemical potential via gating in a field-effect configuration.

Pulse radiolysis studies of the reactions of bromine atoms and dimethyl sulfoxide bromine atom complexes with alcohols

Science.gov (United States)

Sumiyoshi, Takashi; Fujiyoshi, Ryoko; Katagiri, Miho; Sawamura, Sadashi

2007-05-01

Dimethylsulfoxide (DMSO)-Br complexes were generated by pulse radiolysis of DMSO/bromomethane mixtures and the formation mechanism and spectral characteristics of the formed complexes were investigated in detail. The rate constant for the reaction of bromine atoms with DMSO and the extinction coefficient of the complex were obtained to be 4.6×10 9 M -1 s -1 and 6300 M -1 cm -1 at the absorption maximum of 430 nm. Rate constants for the reaction of bromine atoms with a series of alcohols were determined in CBrCl 3 solutions applying a competitive kinetic method using the DMSO-Br complex as the reference system. The obtained rate constants were ˜10 8 M -1 s -1, one or two orders larger than those reported for highly polar solvents. Rate constants of DMSO-Br complexes with alcohols were determined to be ˜ 10 7 M -1 s -1. A comparison of the reactivities of Br atoms and DMSO-Br complexes with those of chlorine atoms and chlorine atom complexes which are ascribed to hydrogen abstracting reactants strongly indicates that hydrogen abstraction from alcohols is not the rate determining step in the case of Br atoms and DMSO-Br complexes.

Activation Measurements for Thermal Neutrons, Part D. U.S. Measurements of 36Cl in Mineral Samples from Hiroshima and Nagasaki

International Nuclear Information System (INIS)

Tore Straume; Alfredo A, Marchetti; Stephen D, Egbert; James A, Roberts; Ping Men; Shoichiro Fujita; Kiyoshi Shizuma; Masaharu Hoshi; G, Rugel; W, Ruhm; G, Korschinek; J. E. McAninch; K. L. Carroll; T. Faestermann; K. Knie; R. E. Martinelli; A. Wallner; C. Wallner

2005-01-01

The present paper presents the 36 Cl measurement effort in the US. A large number of 36 Cl measurements have been made in both granite and concrete samples obtained from various locations and distances in Hiroshima and Nagasaki. These measurements employed accelerator mass spectrometry (AMS) to quantify the number of atoms of 36 Cl per atom of total Cl in the sample. Results from these measurements are presented here and discussed in the context of the DS02 dosimetry reevaluation effort for Hiroshima and Nagasaki atomic-bomb survivors. The production of 36 Cl by bomb neutrons in mineral samples from Hiroshima and Nagasaki was primarily via the reaction 35 Cl(n,γ) 36 Cl. This reaction has a substantial thermal neutron cross-section (43.6 b at 0.025 eV) and the product has a long half-life (301,000 y). hence, it is well suited for neutron-activation detection in Hiroshima and Nagasaki using AMS more than 50 years after the bombings. A less important reaction for bomb neutrons, 39 K(n,α) 36 Cl, typically produces less than 10% of the 36 Cl in mineral samples such as granite and concrete, which contain ∼ 2% potassium. In 1988, only a year after the publication of the DS86 final report (Roesch 1987), it was demonstrated experimentally that 36 Cl measured using AMS should be able to detect the thermal neutron fluences at the large distances most relevant to the A-bomb survivor dosimetry. Subsequent measurements in mineral samples from both Hiroshima and Nagasaki validated the experimental findings. The potential utility of 36 Cl as a thermal neutron detector in Hiroshima was first presented by Haberstock et al. who employed the Munich AMS facility to measure 36 Cl/Cl ratios in a gravestone from near the hypocenter. That work subsequently resulted in an expanded 36 Cl effort in Germany that paralleled the US work. More recently, there have also been 36 Cl measurements made by a Japanese group. The impetus for the extensive 36 Cl and other neutron activation

Atomic absorption analysis of serial titanium alloys

International Nuclear Information System (INIS)

Gorlova, M.N.; Feofanova, N.M.; Kornyushkova, Yu.D.

1977-01-01

Atom-absorption technique is described, which makes it possible to rapidly and precisely determine the following alloying elements and admixtures in titanium alloys: Al (2.0 - 8.5%); Mo (0.5 - 8%); Cr (0.5 - 12%); Si (0.2 - 0.5%); Mn(0.2 - 2.5%); V(0.5 - 6%); Sn(2.0 - 3.0%); Fe(0.1 - 1.0%); Zr(2.0 - 12.0%). The atom absorption method with flame atomization of the sample provides for best results if the alloy is dissolved in a mixture HCl + HBF 4 in the ratio 2:1. In order to obtain correct results the standard solutions must contain titanium in concentrations corresponding to the weight of the sample being analyzed. Sensitivity of zirconium determination may be increased approximately twofold by adding 10 mg/ml of FeCl 3 into the solution. Being as precise, as the classic analytical methods, the atom absorption technique is about 5 times more efficient

Crystal structure, vibrational spectra, optical and DFT studies of bis (3-azaniumylpropyl) azanium pentachloroantimonate (III) chloride monohydrate (C6H20N3)SbCl5·Cl·H2O

Science.gov (United States)

Ahmed, Houssem Eddine; Kamoun, Slaheddine

2017-09-01

The crystal structure of (C6H20N3)SbCl5·Cl·H2O is built up of [NH3(CH2)3NH2(CH2)3NH3]3 + cations, [SbCl5]2 - anions, free Cl- anions and neutral water molecules connected together by Nsbnd H ⋯ Cl, Nsbnd H ⋯ O and Osbnd H ⋯ Cl hydrogen bonds. The optical band gap determined by diffuse reflection spectroscopy (DRS) is 3.78 eV for a direct allowed transition. Optimized molecular geometry, atomic Mulliken charges, harmonic vibrational frequencies, HOMO-LUMO and related molecular properties of the (C6H20N3)SbCl5·Cl·H2O compound were calculated by Density functional theory (DFT) using B3LYP method with GenECP sets. The calculated structural parameters (bond lengths and angles) are in good agreement with the experimental XRD data. The vibrational unscaled wavenumbers were calculated and scaled by a proper scaling factor of 0.984. Acceptable consistency was observed between calculated and experimental results. The assignments of wavenumbers were made on the basis of potential energy distribution (PED) using Vibrational Energy Distribution Analysis (VEDA) software. The HOMO-LUMO study was extended to calculate various molecular parameters like ionization potential, electron affinity, global hardness, electro-chemical potential, electronegativity and global electrophilicity of the given molecule.

Diamond surface: atomic and electronic structure

International Nuclear Information System (INIS)

Pate, B.B.

1984-01-01

Experimental studies of the diamond surface (with primary emphasis on the (111) surface) are presented. Aspects of the diamond surface which are addressed include (1) the electronic structure, (2) the atomic structure, and (3) the effect of termination of the lattice by foreign atoms. Limited studies of graphite are discussed for comparison with the diamond results. Experimental results from valence band and core level photoemission spectroscopy (PES), Auger electron spectroscopy (AES), low energy electron diffraction (LEED), and carbon 1s near edge x-ray absorption fine structure (NEXAFS) spectroscopy (both the total electron yield (TEY) and Auger electron yield (AEY) techniques) are used to study and characterize both the clean and hydrogenated surface. In addition, the interaction of hydrogen with the diamond surface is examined using results from vibrational high resolution low energy electron loss spectroscopy (in collaboration with Waclawski, Pierce, Swanson, and Celotta at the National Bureau of Standards) and photon stimulated ion desorption (PSID) yield at photon energies near the carbon k-edge (hv greater than or equal to 280 eV). Both EELS and PSID verify that the mechanically polished 1 x 1 surface is hydrogen terminated and also that the reconstructed surface is hydrogen free. The (111) 2 x 2/2 x 1 reconstructed surface is obtained from the hydrogenated (111) 1 x 1:H surface by annealing to approx. = 1000 0 C. We observe occupied intrinsic surface states and a surface chemical shift (0.95 +- 0.1 eV) to lower binding energy of the carbon 1s level on the hydrogen-free reconstructed surface. Atomic hydrogen is found to be reactive with the reconstructed surface, while molecular hydrogen is relatively inert. Exposure of the reconstructed surface to atomic hydrogen results in chemisorption of hydrogen and removal of the intrinsic surface state emission in and near the band gap region

Preparation of Substituted Enol Derivatives From Terminal Alkynes and Their Synthetic Utility

Science.gov (United States)

DeBergh, John R.; Spivey, Kathleen M.; Ready, Joseph M.

2009-01-01

Stereodefined enol derivatives of aldehydes are prepared from terminal alkynes. Specifically, terminal alkynes are known to undergo Cp2ZrCl2-catalyzed methylalumination. Here, we show that the resultant vinylalanes can be oxygenated with peroxyzinc species to generate trisubstituted enolates. Electrophilic trapping with carboxylic anydrides or silyl triflates yields trisubstituted enol esters or silanes, respectively. The tandem carbometalation/oxygenation tolerates free and protected alcohols, heterocycles, olefins and nitriles. Likewise, amination can be accomplished using azodicarboxylates. Stereodefined enol esters can undergo asymmetric dihydroxylation to yield optically-active α-hydroxy aldehydes. Reduction with NaBH4 provides the diols of 1,1-disubstituted olefins in excellent ee. An application of this methodology to the enantioselective synthesis of the insect pheromone frontalin is presented. Finally, α-hydroxy aldehydes are shown to undergo homologation to a terminal alkyne, reductive amination, oxidation and olefination. Preliminary results indicate that tandem carbometalation/amination can be accomplished with azodicarboxylates. In this way, ene-hydrazines are formed in excellent yield. PMID:18517202

The microstructure of irradiated hydroxy-terminated polybutadiene

International Nuclear Information System (INIS)

Wu Yiming; Zhou Dezhen; Zhang Zhiping; Jing Yudong; Ying Shengkang

1989-01-01

Hydroxy-terminated polybutadiene (HTPB) is one kind of plybutadiene chief chain structure polymer terminated with hydroxyl groups. Because there are double-bonds in the chief chain, the α-hydrogen atom is very active, and crosslink reaction is easy to take place under γ-ray irradiation. The property of HTPB is affected by γ-ray directly. So it is significant practically and theoreticaly to study the change in structure and property under radiation. The microstructure of HTPB solute molecules and the change of molecular weight with radiation dose were studied by infrared spectra, NMR and GPC in the work. The effects of radiation on HTPB were discussed from the viewpoint of the change of solute molecular structure and gel kinetics. The measured gel dose of HPTB is 0.605 MGY, G = 1.802, thus the authors came to the conclusion that reaction is the chief process in the irradiation of HPTB

Improvement of pre-treatment method for 36Cl/Cl measurement of Cl in natural groundwater by AMS

International Nuclear Information System (INIS)

Nakata, Kotaro; Hasegawa, Takuma

2011-01-01

Estimation of 36 Cl/Cl by accelerator mass spectrometry (AMS) is a useful method to trace hydrological processes in groundwater. For accurate estimation, separation of SO 4 2- from Cl - in groundwater is required because 36 S affects AMS measurement of 36 Cl. Previous studies utilized the difference in solubility between BaSO 4 and BaCl 2 (BaSO 4 method) to chemically separate SO 4 2- from Cl - . However, the accuracy of the BaSO 4 method largely depends on operator skill, and consequently Cl - recovery is typically incomplete (70-80%). In addition, the method is time consuming (>1 week), and cannot be applied directly to dilute solutions. In this study, a method based on ion-exchange column chromatography (column method) was developed for separation of Cl - and SO 4 2- . Optimum conditions were determined for the diameter and height of column, type and amount of resin, type and concentration of eluent, and flow rate. The recovery of Cl - was almost 100%, which allowed complete separation from SO 4 2- . The separation procedure was short ( 4 methods, and then analyzed by AMS to estimate 36 S counts and 36 Cl/Cl values. 36 S counts in samples processed by the column method were stable and lower than those from the BaSO 4 method. The column method has the following advantages over the BaSO 4 method: (1) complete and stable separation of Cl - and SO 4 2- , (2) less operator influence on results, (3) short processing time ( - , and (5) concentration of Cl - and separation from SO 4 2- in the one system for dilute solutions.

Visible-light induced photocatalysis of AgCl@Ag/titanate nanotubes/nitrogen-doped reduced graphite oxide composites

Science.gov (United States)

Pan, Hongfei; Zhao, Xiaona; Fu, Zhanming; Tu, Wenmao; Fang, Pengfei; Zhang, Haining

2018-06-01

High recombination rate of photogenerated electron-hole pairs and relatively narrow photoresponsive range of TiO2-based photocatalysts are the remaining challenges for their practical applications. To address such challenges, photocatalysts consisting of AgCl covered Ag nanoparticles (AgCl@Ag), titanate nanotubes (TiNT), and nitrogen-doped reduced graphite oxide (rGON) are fabricated through alkaline hydrothermal process, followed by deposition and in situ surface-oxidation of silver nanoparticles. In the synthesized photocatalysts, the titanate nanotubes have average length of about 100 nm with inner diameters of about 5 nm and the size of the formed silver nanoparticles is in the range of 50-100 nm. The synthesized photocatalyst degrades almost all the model organic pollutant Rhodamine B in 35 min and remains 90% of photocatalytic efficiency after 5 degradation cycles under visible light irradiation. Since the oxidant FeCl3 applied for oxidation of surface Ag to AgCl is difficult to be completely removed due to the high adsorption capacity of TiNT and rGON, the effect of reside Fe atoms on photocatalytic activity is evaluated and the results reveal that the residue Fe atom only affect the initial photodegradation performance. Nevertheless, the results demonstrate that the formed composite catalyst is a promising candidate for antibiosis and remediation in aquatic environmental contamination.

Dimeric structure of the N-terminal domain of PriB protein from Thermoanaerobacter tengcongensis solved ab initio

Energy Technology Data Exchange (ETDEWEB)

Liebschner, Dorothee [National Cancer Institute, Argonne National Laboratory, Argonne, IL 60439 (United States); Brzezinski, Krzysztof [National Cancer Institute, Argonne National Laboratory, Argonne, IL 60439 (United States); University of Bialystok, 15-399 Bialystok (Poland); Dauter, Miroslawa [Argonne National Laboratory, Argonne, IL 60439 (United States); Dauter, Zbigniew, E-mail: dauter@anl.gov [National Cancer Institute, Argonne National Laboratory, Argonne, IL 60439 (United States); Nowak, Marta; Kur, Józef; Olszewski, Marcin, E-mail: dauter@anl.gov [Gdansk University of Technology, 80-952 Gdansk (Poland); National Cancer Institute, Argonne National Laboratory, Argonne, IL 60439 (United States)

2012-12-01

The N-terminal domain of the PriB protein from the thermophilic bacterium T. tengcongensis (TtePriB) was expressed and its crystal structure has been solved at the atomic resolution of 1.09 Å by direct methods. PriB is one of the components of the bacterial primosome, which catalyzes the reactivation of stalled replication forks at sites of DNA damage. The N-terminal domain of the PriB protein from the thermophilic bacterium Thermoanaerobacter tengcongensis (TtePriB) was expressed and its crystal structure was solved at the atomic resolution of 1.09 Å by direct methods. The protein chain, which encompasses the first 104 residues of the full 220-residue protein, adopts the characteristic oligonucleotide/oligosaccharide-binding (OB) structure consisting of a five-stranded β-barrel filled with hydrophobic residues and equipped with four loops extending from the barrel. In the crystal two protomers dimerize, forming a six-stranded antiparallel β-sheet. The structure of the N-terminal OB domain of T. tengcongensis shows significant differences compared with mesophile PriBs. While in all other known structures of PriB a dimer is formed by two identical OB domains in separate chains, TtePriB contains two consecutive OB domains in one chain. However, sequence comparison of both the N-terminal and the C-terminal domains of TtePriB suggests that they have analogous structures and that the natural protein possesses a structure similar to a dimer of two N-terminal domains.

In-terminal ECR Ion Source of the Tandem Accelerator at JAERI

CERN Document Server

Matsuda, M; Takeuchi, S

1999-01-01

Electron Cyclotron Resonance Ion Source(ECRIS)s are able to produce intense beams of highly charged positive ions and used injection system for cyclotron, linac as well as experiments of atomic physics. The tandem accelerator system has been benefiting from use of an electron stripper at the high voltage terminal. The most probable charged state after a foil stripper is, however, much lower than the highest charge state of ions with an intensity of more than several emA from a high performance ECRIS. With respect to beam current, the life time of stripper foils decrease with increasing beam current. Especially for very heavy ions, it is difficult to obtain a stable and intense beam for a long time without foil exchange. Use of an ECRIS in a tandem accelerator is expected to increase beam intensity, beam energy and beam species. A small permanent magnet ECRIS has been installed in the high voltage terminal of the vertical and folded type 20UR Pelletron tandem accelerator at Japan Atomic Energy Research Institu...

Synthesis and characterization of technetium(III) complexes with nitrogen heterocycles by O atom transfer from oxotechnetium(V) cores. Crystal structures of mer-[Cl3(pic)3Tc] and mer-[Cl3(pic)(PMe2Ph)2Tc] (pic = 4-picoline). Electrochemical parameters fore the reduction of TcII, TcIII, and TcIV

International Nuclear Information System (INIS)

Lu, Jun; Yamano, Akahito; Clarke, M.J.

1990-01-01

The combination of pyridine ligands, (OCl 4 Tc) - , and O atom acceptors of different cone angles, such as PMe 2 Ph or PPh 3 , results in Tc III complexes that vary in the coordination of the phosphine ligand. The compounds mer[Cl 3 (4-picoline) 3 Tc] and mer-(Cl 3 (4-picoline)(PMe 2 Ph) 2 Tc) have been obtained in good yield and have been characterized spectroscopically and by single-crystal x-ray diffraction. The crystal structure data are reported. Linear correlations of technetium reduction potentials in DMF with electrochemical ligand additivity parameters (E L 's) have been obtained for the Tc II,I , Tc III,II , and Tc IV,III couples. The slope and intercept (S M , I M ) pairs for each technetium oxidation-reduction couple, respectively, are (1.39, -2.07), (1.29, -0.91), and (1.00, 0.65). 32 refs., 3 figs., 6 tabs

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

International Nuclear Information System (INIS)

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

1984-01-01

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

Evaluation report on CCTF core-I reflood tests Cl-17(Run 36) and Cl-20(Run 39)

International Nuclear Information System (INIS)

Murao, Yoshio; Iguchi, Tadashi

1983-02-01

In the safety analysis of the reflood phase of a PWR LOCA, the core thermo-hydrodynamic behavior is analyzed as a phenomena in a single channel core. In other words, the core thermo-hydrodynamic behavior is treated one-dimensionally. In order to confirm the validity of the one-dimensional treatment, tests named Asymmetric power test Cl-17(Run 36) and Asymmetric temperature test Cl-20(Run 39) were performed, whose test conditions were similar to the base case test Cl-5(Run 14) (the reference test for the parametric effect tests) except for the power distribution and the initial temperature distribution in core, respectively. First the results of the base case test were investigated. And the results of Asymmetric power test and Asymmetric temperature test were compared with the results of the base case test. The main conclusions are as follows: (1) The water accumulation was observed along the whole core even above quench front almost simultaneously just after reflood initiation and almost terminated within 20 to 30 seconds. The flow pattern was recognized as a slug flow. (2) In the lower two-thirds of the core, bottom quench was observed and the core water accumulation was one-dimensional even under the thermally asymmetric conditions. (3) In the upper portion of the core, the multi-dimensional effect was observed, i.e. the top quench occurred locally. (4) The water accumulation behavior or void fraction in the lower two-thirds of the core, i.e. our concerning region for the peak clad temperature analysis, and the core behavior for system analysis can be one-dimensionally analyzed with a representing single channel core. (author)

Effects of dilute aqueous NaCl solution on caffeine aggregation

Energy Technology Data Exchange (ETDEWEB)

Sharma, Bhanita; Paul, Sandip, E-mail: sandipp@iitg.ernet.in [Department of Chemistry, Indian Institute of Technology, Guwahati 781039, Assam (India)

2013-11-21

The effect of salt concentration on association properties of caffeine molecule was investigated by employing molecular dynamics simulations in isothermal-isobaric ensemble of eight caffeine molecules in pure water and three different salt (NaCl) concentrations, at 300 K temperature and 1 atm pressure. The concentration of caffeine was taken almost at the solubility limit. With increasing salt concentration, we observe enhancement of first peak height and appearance of a second peak in the caffeine-caffeine distribution function. Furthermore, our calculated solvent accessible area values and cluster structure analyses suggest formation of higher order caffeine cluster on addition of salt. The calculated hydrogen bond properties reveal that there is a modest decrease in the average number of water-caffeine hydrogen bonds on addition of NaCl salt. Also observed are: (i) decrease in probability of salt contact ion pair as well as decrease in the solvent separated ion pair formation with increasing salt concentration, (ii) a modest second shell collapse in the water structure, and (iii) dehydration of hydrophobic atomic sites of caffeine on addition of NaCl.

Effects of dilute aqueous NaCl solution on caffeine aggregation

International Nuclear Information System (INIS)

Sharma, Bhanita; Paul, Sandip

2013-01-01

The effect of salt concentration on association properties of caffeine molecule was investigated by employing molecular dynamics simulations in isothermal-isobaric ensemble of eight caffeine molecules in pure water and three different salt (NaCl) concentrations, at 300 K temperature and 1 atm pressure. The concentration of caffeine was taken almost at the solubility limit. With increasing salt concentration, we observe enhancement of first peak height and appearance of a second peak in the caffeine-caffeine distribution function. Furthermore, our calculated solvent accessible area values and cluster structure analyses suggest formation of higher order caffeine cluster on addition of salt. The calculated hydrogen bond properties reveal that there is a modest decrease in the average number of water-caffeine hydrogen bonds on addition of NaCl salt. Also observed are: (i) decrease in probability of salt contact ion pair as well as decrease in the solvent separated ion pair formation with increasing salt concentration, (ii) a modest second shell collapse in the water structure, and (iii) dehydration of hydrophobic atomic sites of caffeine on addition of NaCl

Tl{sub 10}Hg{sub 3}Cl{sub 16}: Single crystal growth, electronic structure and piezoelectric properties

Energy Technology Data Exchange (ETDEWEB)

Khyzhun, O.Y., E-mail: khyzhun@ipms.kiev.ua [Frantsevych Institute for Problems of Materials Science, National Academy of Sciences of Ukraine, 3 Krzhyzhanivsky Street, 03142 Kyiv (Ukraine); Piasecki, M. [Institute of Physics, J.Dlugosz University Częstochowa, Armii Krajowej 13/15, Częstochowa PL-42-217 (Poland); Kityk, I.V. [Electrical Engineering Department, Częstochowa University Technology, Armii Krajowej 17, PL-42-200 Częstochowa (Poland); Luzhnyi, I. [Frantsevych Institute for Problems of Materials Science, National Academy of Sciences of Ukraine, 3 Krzhyzhanivsky Street, 03142 Kyiv (Ukraine); Fedorchuk, A.O. [Department of Inorganic and Organic Chemistry, Lviv National University of Veterinary Medicine and Biotechnologies, 50 Pekarska Street, 79010 Lviv (Ukraine); Fochuk, P.M. [Yuriy Fed’kovych Chernivtsi National University, 2 Kotziubynskoho Street, 58012 Chernivtsi (Ukraine); Levkovets, S.I. [Department of Inorganic and Physical Chemistry, Lesya Ukrainka Eastern European National University, 13 Voli Avenue, 43025 Lutsk (Ukraine); Karpets, M.V. [Frantsevych Institute for Problems of Materials Science, National Academy of Sciences of Ukraine, 3 Krzhyzhanivsky Street, 03142 Kyiv (Ukraine); Parasyuk, O.V. [Department of Inorganic and Physical Chemistry, Lesya Ukrainka Eastern European National University, 13 Voli Avenue, 43025 Lutsk (Ukraine)

2016-10-15

Single crystal of the ternary halide Tl{sub 10}Hg{sub 3}Cl{sub 16} was grown using Bridgman-Stockbarger method. For the Tl{sub 10}Hg{sub 3}Cl{sub 16} crystal, we have measured X-ray photoelectron spectra for both pristine and Ar{sup +} ion-bombarded surfaces and additionally investigated photoinduced piezoelectricity. Our data indicate that the Tl{sub 10}Hg{sub 3}Cl{sub 16} single crystal surface is very sensitive with respect to Ar{sup +} ion-bombardment. In particular, Ar{sup +} ion-bombardment with energy of 3.0 keV over 5 min at an ion current density of 14 μA/cm{sup 2} causes significant changes of the elemental stoichiometry of the Tl{sub 10}Hg{sub 3}Cl{sub 16} surface resulting in an abrupt decrease of the mercury content in the top surface layers of the studied single crystal. As a result of the treatment, the mercury content becomes nil in the top surface layers. In addition, the present XPS measurements allow for concluding about very low hygroscopicity of the Tl{sub 10}Hg{sub 3}Cl{sub 16} single crystal surface. The property is extremely important for the crystal handling in optoelectronic or nano-electronic devices working at ambient conditions. The photoinduced piezoelectricity has been explored for Tl{sub 10}Hg{sub 3}Cl{sub 16} depending on nitrogen (λ=371 nm) laser power density and temperature. - Graphical abstract: As-grown single crystal boule of Tl{sub 10}Hg{sub 3}Cl{sub 16}; dependence of the effective piezoelecric coefficient d{sub 33} versus the photoinducing nitrogen laser power density, I, at different temperatures, T; and packing of the polyhedra of halide atoms around Hg atoms in the Tl{sub 10}Hg{sub 3}Cl{sub 16} structure. - Highlights: • High-quality Tl{sub 10}Hg{sub 3}Cl{sub 16} single crystal has been grown by Bridgman-Stockbarger method. • Electronic structure of Tl{sub 10}Hg{sub 3}Cl{sub 16} is studied by the XPS method. • Tl{sub 10}Hg{sub 3}Cl{sub 16} single crystal surface is sensitive with respect to Ar{sup +} ion

Low-temperature anharmonicity in cesium chloride (CsCl)

Energy Technology Data Exchange (ETDEWEB)

Sist, Mattia; Faerch Fischer, Karl Frederik; Brummerstedt Iversen, Bo [Center for Materials Crystallography, Department of Chemistry and iNANO, Aarhus University (Denmark); Kasai, Hidetaka [Center for Materials Crystallography, Department of Chemistry and iNANO, Aarhus University (Denmark); Faculty of Pure and Applied Sciences, TIMS and CiRfSE, University of Tsukuba (Japan)

2017-03-20

Anharmonic lattice vibrations govern heat transfer in materials, and anharmonicity is commonly assumed to be dominant at high temperature. The textbook cubic ionic defect-free crystal CsCl is shown to have an unexplained low thermal conductivity at room temperature (ca. 1 W/(m K)), which increases to around 13 W/(m K) at 25 K. Through high-resolution X-ray diffraction it is unexpectedly shown that the Cs atomic displacement parameter becomes anharmonic at 20 K. (copyright 2017 Wiley-VCH Verlag GmbH and Co. KGaA, Weinheim)

Exotic atoms: Hadronic and muonic atoms 1969--1997. Technical progress report, February 1, 1996--August 31, 1997

International Nuclear Information System (INIS)

Kunselman, R.

1997-01-01

Since this is a terminal progress-report it is a synopsis over the total time of the grant. The author has utilized exotic hadronic and muonic atoms as tools to access information concerning questions to do with particle, nuclear, and atomic physics. The information has answered fundamental questions about lepton conservations, quark models, tests of the CPT theorem, QED energies, and nuclear structure. The present experiments involve reactions with a variety of hydrogen isotopic mixtures to form solid targets to produce muonic hydrogen isotope atoms. The method relies on muon capture by a proton and transfer of the muon from the proton to a deuteron or a triton. The resulting muonic deuterium or muonic tritium will not immediately thermalize because of the very low elastic cross sections of the Ramsauer-Townsend effect, and are emitted from the surface of the layer and escape into a vacuum region. A second solid hydrogen isotopic target is produced downstream on which the muonic hydrogen atom can react and the time of flight measured

Determination of the equilibrium constant of FeZrCl6 formation from FeCl3 and ZrCl4

International Nuclear Information System (INIS)

Berdonosov, S.S.; Kharisov, B.I.; Nikitin, M.I.

1992-01-01

Equilibrium pressures of chlorine formed in the course of reaction FeCl 3 +ZrCl 4 ↔ FeZrCl 6 +0.5 Cl 2 were determined at the temperatures of 250-325 deg C. The values of equilibrium constant K p of the reaction mentioned at the temperatures of 250, 275, 300 and 325 deg were calculated, taking into consideration the determined values of p Cl2 and literature data on equilibrium pressures of ZrCl 4 and FeCl 3 vapours

Atomic-scale friction on stepped surfaces of ionic crystals.

Science.gov (United States)

Steiner, Pascal; Gnecco, Enrico; Krok, Franciszek; Budzioch, Janusz; Walczak, Lukasz; Konior, Jerzy; Szymonski, Marek; Meyer, Ernst

2011-05-06

We report on high-resolution friction force microscopy on a stepped NaCl(001) surface in ultrahigh vacuum. The measurements were performed on single cleavage step edges. When blunt tips are used, friction is found to increase while scanning both up and down a step edge. With atomically sharp tips, friction still increases upwards, but it decreases and even changes sign downwards. Our observations extend previous results obtained without resolving atomic features and are associated with the competition between the Schwöbel barrier and the asymmetric potential well accompanying the step edges.

Interplay Between Structure and Conductivity in 1-Ethyl-3-methylimidazolium tetrafluoroborate/(δ-MgCl2)f Electrolytes for Magnesium Batteries

International Nuclear Information System (INIS)

Bertasi, Federico; Vezzù, Keti; Nawn, Graeme; Pagot, Gioele; Di Noto, Vito

2016-01-01

The synthesis, physicochemical properties and conductivity mechanism of a family of ionic liquid-based electrolytes for use in secondary Mg batteries are reported. The electrolytes are obtained by dissolving controlled amounts of δ-MgCl 2 salt into the ionic liquid (IL) 1-ethyl-3-methylimidazolium tetrafluoroborate (EMImBF 4 ) which acts as a solvent. δ-MgCl 2 consists of an inorganic ribbon of Mg atoms covalently bonded together through bridging chlorine atoms. Due to this peculiar structural motif, with respect to the electrolytes based on conventional Mg salts, it is possible to achieve electrolytes of higher Mg concentration. Thus, concatenated anionic complexes bridged via halogen atoms are formed, improving the electrochemical performance of these materials. Electrolytes with a general formula EMImBF 4 /(δ-MgCl 2 ) f with f ranging from 0 to 0.117 are obtained. The composition of the obtained materials is determined by Inductively Coupled Plasma Atomic Emission Spectroscopy (ICP-AES). The properties of these systems are investigated by means of Thermogravimetric Analysis (TGA), Differential Scanning Calorimetry (DSC), and vibrational spectroscopy in both medium (MIR) and far infrared (FIR). Finally, Broadband Electrical Spectroscopy (BES) is carried out with the aim to elucidate the electrical response of the electrolytes in terms of their polarization and relaxation phenomena and to propose a conductivity mechanism. At 20 °C the highest conductivity (0.007 S/cm) is observed for the electrolyte with c Mg = 0.00454 mol Mg /kg IL .

A first-principles study on the magnetic properties of nonmetal atom doped phosphorene monolayers.

Science.gov (United States)

Zheng, Huiling; Zhang, Jianmin; Yang, Baishun; Du, Xiaobo; Yan, Yu

2015-07-07

In order to induce magnetism in two-dimensional semiconductors for their applications in spintronic devices and novel chemical and electronic properties of semiconducting phosphorene, the geometrical structure, electronic and magnetic properties of doped phosphorene monolayers with a series of nonmetal atoms, including H, F, Cl, Br, I, B, C, Si, N, As, O, S and Se, were systematically investigated using first-principles calculations. The results show that although the substitutional doping of H, F, Cl, Br, I, B, N, O, S or Se results in large structural deformation at the doping sites of phosphorene monolayers, all neutral nonmetal atom doped systems are stable. The calculated formation energies reveal that the substitutional doping of numerous nonmetal atoms in phosphorene monolayer are possible under appropriate experimental conditions, and the charged dopants C(-), Si(-), S(+) and Se(+) are stable. Moreover, the substitutional doping of H, F, Cl, Br, I, B, N, As, C(-), Si(-), S(+) or Se(+) cannot induce magnetism in phosphorene monolayer due to the saturation or pairing of valence electrons of dopant and its neighboring P atoms, whereas ground states of neutral C, Si, O, S or Se doped systems are magnetic due to the appearance of an unpaired valence electron of C and Si or the formation of a nonbonding 3p electron of a neighboring P atom around O, S and Se. Furthermore, the magnetic coupling between the moments induced by two Si, O, S or Se are long-range anti-ferromagnetic and the coupling can be attributed to the hybridization interaction involving polarized electrons, whereas the coupling between the moments induced by two C is weak.

Separation of CsCl and SrCl_2 from a ternary CsCl-SrCl_2-LiCl via a zone refining process for waste salt minimization of pyroprocessing

International Nuclear Information System (INIS)

Shim, Moonsoo; Choi, Ho Gil; Yi, Kyung Woo; Hwang, Il Soon; Lee, Jong Hyeon

2016-01-01

The purification of LiCl salt mixture has traditionally been carried out by a melt crystallization process. To improve the throughput of zone refining, three heaters were installed in the zone refiner. The zone refining method was used to grow pure LiCl salt ingots from LiCl-CsCl-SrCl_2 salt mixture. The main investigated parameters were the heater speed and the number of passes. A change in the LiCl crystal grain size was observed according to the horizontal direction. From each zone refined salt ingot, samples were collected horizontally. To analyze the concentrations of Sr and Cs, an inductively coupled plasma optical emission spectrometer and inductively coupled plasma mass spectrometer were used, respectively. The experimental results show that Sr and Cs concentrations at the initial region of the ingot were low and reached their peak at the final freezing region of the salt ingot. Concentration results of zone refined salt were compared with theoretical results yielded by the proposed model to validate its predictions. The k_e_f_f of Sr and Cs were 0.13 and 0.11, respectively. The decontamination factors of Sr and Cs were 450 and 1650, respectively. - Highlights: • The LiCl-CsCl-SrCl_2 salt ingot was purified by zone refining technique to minimize waste salt. • The concentration distribution of Cs and Sr were analyzed by mass transfer equation. • The decontamination factors of Cs and Sr were 1600 and 450 respectively in case of 60% of recovery yield.

Ethylene homo- and copolymerization chain-transfers: A perspective from supported (n BuCp) 2 ZrCl 2 catalyst active centre distribution

KAUST Repository

Atiqullah, Muhammad; Al-Harthi, Mamdouh A.; Anantawaraskul, Siripon; Emwas, Abdul-Hamid M.

2015-01-01

/MAO/(nBuCp)2ZrCl2 - were applied to evaluate the active-centre-dependent ethylene homo- and copolymerization rates, as well as the corresponding chain termination rates. This approach, from a microkinetic mechanistic viewpoint, elucidates better the 1-hexene

Grazing incidence collisions of ions and atoms with surfaces: from charge exchange to atomic diffraction; Collisions rasantes d'ions ou d'atomes sur les surfaces: de l'echange de charge a la diffraction atomique

Energy Technology Data Exchange (ETDEWEB)

Rousseau, P

2006-09-15

This thesis reports two studies about the interaction with insulating surfaces of keV ions or atoms under grazing incidence. The first part presents a study of charge exchange processes occurring during the interaction of singly charged ions with the surface of NaCl. In particular, by measuring the scattered charge fraction and the energy loss in coincidence with electron emission, the neutralization mechanism is determined for S{sup +}, C{sup +}, Xe{sup +}, H{sup +}, O{sup +}, Kr{sup +}, N{sup +}, Ar{sup +}, F{sup +}, Ne{sup +} and He{sup +}. These results show the importance of the double electron capture as neutralization process for ions having too much potential energy for resonant capture and not enough for Auger neutralization. We have also studied the ionisation of the projectile and of the surface, and the different Auger-like neutralization processes resulting in electron emission, population of conduction band or excited state. For oxygen scattering, we have measured an higher electron yield in coincidence with scattered negative ion than with scattered atom suggesting the transient formation above the surface of the oxygen doubly negative ion. The second study deals with the fast atom diffraction, a new phenomenon observed for the first time during this work. Due to the large parallel velocity, the surface appears as a corrugated wall where rows interfere. Similarly to the Thermal Atom Scattering the diffraction pattern corresponds to the surface potential and is sensitive to vibrations. We have study the H-NaCl and He-LiF atom-surface potentials in the 20 meV - 1 eV range. This new method offers interesting perspectives for surface characterisation. (author)

Free radical hydrogen atom abstraction from saturated hydrocarbons: A crossed-molecular-beams study of the reaction Cl + C{sub 3}H{sub 8} {yields} HCl + C{sub 3}H{sub 7}

Energy Technology Data Exchange (ETDEWEB)

Blank, D.A.; Hemmi, N.; Suits, A.G.; Lee, Y.T. [Lawrence Berkeley National Lab., CA (United States)

1997-04-01

The abstraction of hydrogen atoms from saturated hydrocarbons are reactions of fundamental importance in combustion as well as often being the rate limiting step in free radical substitution reactions. The authors have begun studying these reactions under single collision conditions using the crossed molecular beam technique on beamline 9.0.2.1, utilizing VUV undulator radiation to selectively ionize the scattered hydrocarbon free radical products (C{sub x}H{sub 2x+1}). The crossed molecular beam technique involves two reactant molecular beams fixed at 90{degrees}. The molecular beam sources are rotatable in the plane defined by the two beams. The scattered neutral products travel 12.0 cm where they are photoionized using the VUV undulator radiation, mass selected, and counted as a function of time. In the authors initial investigations they are using halogen atoms as protypical free radicals to abstract hydrogen atoms from small alkanes. Their first study has been looking at the reaction of Cl + propane {r_arrow} HCl + propyl radical. In their preliminary efforts the authors have measured the laboratory scattering angular distribution and time of flight spectra for the propyl radical products at collision energies of 9.6 kcal/mol and 14.9 kcal/mol.

Di-μ-chlorido-bis{chlorido[(R/(S-1,5-diphenyl-3-(2-pyridyl-κN-2-pyrazoline-κN2]zinc(II}

Directory of Open Access Journals (Sweden)

Miquel Barceló-Oliver

2010-08-01

Full Text Available In the centrosymmetric binuclear title compound, [Zn2Cl4(C20H17N32], the coordination geometry of the ZnII ion can be described as a distorted ZnN2Cl3 trigonal bipyramid (τ = 0.89, arising from the N,N′-bidentate ligand, a terminal chloride ion and two bridging chloride ions. The N atoms occupy one axial and one equatorial site and the terminal chloride ion occupies an equatorial site. The dihedral angle between the pyridine and pyrazole rings is 12.8 (2°. In the crystal, aromatic π–π stacking [centroid–centroid separations = 3.812 (3 and 3.848 (3 Å] and C—H...Cl and C—H...π interactions help to establish the packing.

Investigation of the surface terminations of icosahedral AlPdMn quasicrystal based on a modified non-spherical model

International Nuclear Information System (INIS)

Yu Fengmei; Zou Huamin; Wang Jianbo; Wang Renhui

2004-01-01

The atomic positions are obtained from a modified non-spherical model of icosahedral AlPdMn quasicrystal (Fang et al 2003 J. Phys.: Condens. Matter 15 4947) by the cut method. The four-shell pseudo-Mackay clusters (PMCs) were searched for in a box of 400 A x 400 A x 400 A. The results show that the number of atoms in the fourth shell, an icosidodecahedron, of the pseudo-Mackay cluster can vary from 15 to 30 because of the cluster overlap, and about 99.96% of the total atoms are included in such incomplete pseudo-Mackay clusters. The characteristics of the atom distribution in the planes perpendicular to a fivefold axis indicate that the planes, which are 1.56 A apart from their neighbouring planes, are expected to be the terminal surfaces. If one such a plane and its closest neighbouring plane, between which the spacing is 0.48 A, are considered as a thin layer or a corrugated surface, these layers are also the layers with the maximum density. The pair of corrugated surfaces that are 1.56 A apart have almost identical chemical composition. These planes form terraces that follow the rule of the Fibonacci sequence with two step heights, 6.60 and 4.08 A. On the corrugated surfaces perpendicular to a fivefold axis the pentagonal holes arise from the interspaces of adjacent incomplete PMCs. For the atomic planes normal to a twofold axis, the planes with spacing of 1.48 A from their adjacent planes might be expected to be the terminal surfaces, which form terraces with step heights of 6.28 and 3.88 A following the rule of the Fibonacci sequence. For the atomic planes normal to a threefold axis, the planes with spacing of 0.86 A from their adjacent planes might be expected to be the terminal surfaces. No similar results were found for the atomic layers perpendicular to a pseudo-twofold axis

Atomic absorption spectrophotometry of europium using an enhancing effect of ammonium perchlorate

International Nuclear Information System (INIS)

Oguro, Hiroshi

1976-01-01

In the atomic absorption spectrophotometry of europium in air-acetylene flame, ammonium perchlorate (NH 4 ClO 4 ) increases the absorption of europium. In the case of 0.5 M NH 4 ClO 4 , the increase is by about 1.5 times. In this paper, a method for eliminating the interferences of many coexisting compounds using an enhancing effect and a method for determining Eu 2 O 3 in La 2 O 3 were investigated. The working conditions using Nippon Jarrell-Ash model AA-1 atomic absorption/flame emission spectrophotometer were as follows; wavelength 4594 A, lamp current 15 mA, burner height 10 mm, air flow-rate 6.51/min, acetylene flow-rate 1.81/min. Though the enhancing or depressing effects of HCl, HNO 3 , HBr and HClO 4 in concentrations below 0.1 M were eliminated by 0.5 M NH 4 ClO 4 , the remarkable depressing effects of H 2 SO 4 and H 3 PO 4 on europium could not be eliminated. The interferences of Na + , K + , Cs + and Al 3+ in the concentration of 200 ppm were not eliminated, but those of other cations including rare earth elements were completely eliminated. Lanthanum in the range of (2000--10000) ppm increased the absorption of europium by about 1.4 times. But the effect of lanthanum in the range of (0--9000) ppm was also eliminated by NH 4 ClO 4 . The calibration curve for europium in the presence of NH 4 ClO 4 was linear in the range of (0--400) ppm with a sensitivity larger by about 1.5 times than that for europium alone. The analytical procedure is as follows. A sample is dissolved in HCl and NH 4 ClO 4 is added. Europium in the sample solution is determined by atomic absorption method using air-acetylene flame. For practical samples, the values obtained were in fair agreement with those by the flame emission method using a nitrous oxide-acetylene flame. The coefficients of variation by the present method were (3.7--2.4)% (Eu 2 O 3 content (1--3)%). (auth.)

On pulse duration of self-terminating lasers

International Nuclear Information System (INIS)

Bokhan, P A

2011-01-01

The problem of the maximum pulse duration τ max of self-terminating lasers is considered. It is shown that the duration depends on the transition probability in the laser channel, on the decay rate of the resonant state in all other channels, and on the excitation rate of the metastable state. As a result, τ max is found to be significantly shorter than previously estimated. The criteria for converting the 'self-terminating' lasing to quasi-cw lasing are determined. It is shown that in the case of nonselective depopulation of the metastable state, for example in capillary lasers or in a fast flow of the active medium gas, it is impossible to obtain continuous lasing. Some concrete examples are considered. It is established that in several studies of barium vapour lasers (λ = 1.5 μm) and nitrogen lasers (λ = 337 nm), collisional lasing is obtained by increasing the relaxation rate of the metastable state in collisions with working particles (barium atoms and nitrogen molecules). (lasers)

Synthesis of cationic diphosphine ruthenium complexes with nido-dicarbaundecaborate anions. Molecular structure of [RuCl(dppe)2]+[7,8-nido-C2B9H12]-

International Nuclear Information System (INIS)

Cheredilin, D.N.; Dolgushin, F.M.; Balagurova, E.V.; Godovikov, I.A.; Chizhevskij, I.T.

2004-01-01

Five new diphosphine ruthenium(II) complexes with nido-dicarbaundecaborate anions were synthesized. The composition and structure of the complexes were confirmed by data of 1 H, 31 P{ 1 H} NMR and elementary analysis. The crystal and molecular structure of solvated complex [RuCl(dppe) 2 + [7,8-nido-C 2 B 9 H 12 ] - ·CH 2 Cl 2 was ascertained by the method of X-ray diffraction analysis. It is shown that coordination sphere of ruthenium atom in the complex cation is a distorted trigonal bipyramid. The distances from ruthenium atom to phosphorus atoms are 2.398(1) and 2.391(1) A, while the angle P-Ru-P equals 175.85(5) Deg [ru

Hot atom chemistry of mixed crystals. 35 years of research

International Nuclear Information System (INIS)

Mueller, H.

1993-01-01

When this contribution was prepared, the author decided to present the more personal aspects of his work and the concepts that directed him. Since the time when the author interested in solid state hot atom chemistry more than 30 years ago, still now the generally accepted theory has not been existed. The irradiation test by using the BEPO pile in Harwell is reported. The use of glass fiber paper instead of cellulose paper was investigated. The real problem of the different models of primary retention should be solved. The idea of mixed crystal systems was the result of an experimental accident. The attempt of preparing mixed crystals, the papers that the author has written, the procedures of the experiment such as electrophoresis, the results of the electrophoretic separation are discussed. The next step was obviously the investigation of the ligand recoil. The production of the transient ligand vacancy complexes and their final fate resulted in mixed hexachlorobromometallate species is shown for the system K 2 O s Cl 6 -K 2 O s Br 6 (n,γ) 38 Cl. The reaction of the 38 Cl, the information about recoil atom reactions which increased with the complexity of target substances, and the resulted informations are reported. (K.I.)71 refs

Atom transfer radical copolymerization of styrene and butyl acrylate

NARCIS (Netherlands)

Chambard, G.; Klumperman, B.; Matyjaszewski, K.

2000-01-01

Atom transfer radical polymerization of styrene and butyl acrylate has been investigated from a kinetic point of view. Attention is focused on the activation of the dormant species as well as on the termination that plays a role in these reactions. It has been shown that the activation of a styrene

Improved 36Cl performance at the ASTER HVE 5 MV accelerator mass spectrometer national facility

International Nuclear Information System (INIS)

Finkel, R.; Arnold, M.; Aumaître, G.; Benedetti, L.; Bourlès, D.; Keddadouche, K.; Merchel, S.

2013-01-01

The HVE 5 MV ASTER AMS national facility at CEREGE was accepted in 2007. Since then we have continued to optimize performance for 36 Cl. Cl-36 analyses use AgCl, a Cs negative ion sputter source, Ar stripping to +5 in the terminal of the Tandetron™ accelerator at 5 MV and a silicon nitride post-acceleration stripper foil to enhance suppression of 36 S relative to 36 Cl. The major challenges to obtaining the desired performance for Earth science applications are ion source memory, mass fractionation effects, 36 S isobar suppression and sensitivity. Redesign of the SO110 ion source by HVE to change the size of the aperture and the shape of cathode significantly reduced ion source memory to less than ∼0.1%, a level that can be compensated for by matching standards to samples. We observe small systematic drifts in 35 Cl/ 37 Cl ratios over time, the source of which is not yet determined. Measurement of standards indicates that this effect limits the precision of 35 Cl/ 37 Cl ratio determination to about 2%. 36 S is suppressed in several ways. First, the sample chemistry has been designed to reduce S to low levels. Second, cathodes are constructed of low-S nickel, enabling direct target loading without the use of AgBr pre-packing. Third, a post-acceleration Si 3 N 4 stripper foil differentially absorbs energy from 36 Cl and 36 S. A subsequent electrostatic deflector is then able to suppress 36 S by a factor of ∼240 relative to 36 Cl. Differential energy loss in the detector further suppresses 36 S by about 10 −4 , for an overall suppression factor of 4 × 10 −7 . 36 S count rates are typically equivalent to a background 36 Cl/Cl of ∼10 −15 . At typical 35 Cl currents of ∼20 μA Cl 5+ samples with 36 Cl/ 35 Cl of 6 × 10 −14 can be measured to ±5% statistical uncertainty with 1 h of analysis time. Typical machine blanks have 36 Cl/Cl ∼2 × 10 −15 .

F/Cl + C2H2 reactions: Are the addition and hydrogen abstraction direct processes?

International Nuclear Information System (INIS)

Li Jilai; Geng Caiyun; Huang Xuri; Zhan Jinhui; Sun Chiachung

2006-01-01

The reactions of atomic radical F and Cl with acetylene have been studied theoretically using ab initio quantum chemistry methods and transition state theory. The doublet potential energy surfaces were calculated at the CCSD(T)/aug-cc-pVDZ//CCSD/6-31G(d,p), CCSD(T)/aug-cc-pVDZ//UMP2/6-311++G(d,p) and compound method Gaussian-3 levels. Two reaction mechanisms including the addition-elimination and the hydrogen abstraction reaction mechanisms are considered. In the addition-elimination reactions, the halogen atoms approach C 2 H 2 , perpendicular to the C≡C triple bond, forming the pre-reactive complex C1 at the reaction entrance. C1 transforms to intermediate isomer I1 via transition state TSC1/1 with a negative/small barrier for C 2 H 2 F/C 2 H 2 Cl system, which can proceed by further eliminating H atom endothermally. While the hydrogen abstraction reactions also involve C1 for the fluorine atom abstraction of hydrogen, yet the hydrogen abstraction by chlorine atom first forms a collinear hydrogen-bonded complex C2. The other reaction pathways on the doublet PES are less competitive due to thermodynamical or kinetic factors. According to our results, the presence of pre-reactive complexes indicates that the simple hydrogen abstraction and addition in the halogen atoms reaction with unsaturated hydrocarbon should be more complex. Furthermore, based on the analysis of the kinetics of all channels through which the addition and abstraction reactions proceed, we expect that the actual feasibility of the reaction channels may depend on the reaction conditions in the experiment. The present study may be helpful for probing the mechanisms of the title reactions and understanding the halogen chemistry

Use of thermodynamic calculation for investigating phase diagram of the ternary system NaCl-PbCl2-NdCl3

International Nuclear Information System (INIS)

Kostygov, V.I.; Potemin, S.S.

1984-01-01

Thermodynamic calculation of meltability diagram of ternary system NaCl-PbCl 2 -NdCl 3 with the use of literature and experimental data on meltability diagrams of binary systems forming it, as well as data on crystallization heats of the components, has been carried out. Equations are derived under condition of pseudoperfection of the ternary system. 64 mol.% PbCl 2 , 26 mol.% NaCl, 10 mol.% NdCl 3 and average temperature of crystallization 391 deg C correspond to the calculated composition of the ternary eutectics, 49 mol.% PbCl 2 , 35 mol.% NaCl, 16 mol.% NdCl 3 and average temperature of peritectic transformation 416 deg C - to the composition of the ternary peritectic. The results obtained agree well with the experimental data

Interaction between exo-nido-ruthenacarborane [Cl(Ph3P)2Ru]-5,6,10-(μ-H)3-10-H-7,8-C2B9H8 and bromine

International Nuclear Information System (INIS)

Timofeev, S.V.; Lobanova, I.A.; Petrovskij, P.V.; Starikova, Z.A.; Bregadze, V.I.

2001-01-01

Interaction between exo-nido-ruthenacarborane [Cl(Ph 3 P) 2 Ru]-5,6,10-(μ-H) 3 -10-H-7,8-C 2 B 9 H 8 with bromine in CH 2 Cl 2 solutions at 0 deg C studied using the methods of elementary analysis, NMR, IR spectroscopy and X-ray diffraction analysis. It was ascertained that the reaction gives rise to bromine atom substitution for chlorine atom in octahedral surrounding of ruthenium atom with formation of complex [Br(Ph 3 P) 2 Ru]-5,6,10-(μ-H) 3 -10-H-7,8-C 2 B 9 H 8 . The complex is crystallized in monoclinic crystal system with the following unit cell parameters a = 12.592 (1), b = 20.687 (2), c = 16.628 (2) A, β = 94.372 (3) deg, sp. gr. P2 1 /n, Z = 4. Coordination octahedron of ruthenium atom is formed by three hydrogen atoms bound with boron atoms in one triangular face of carborane, two phosphorus atoms and one bromine atom [ru

SEPARATION OF CsCl FROM LiCl-CsCl MOLTEN SALT BY COLD FINGER MELT CRYSTALLIZATION

Directory of Open Access Journals (Sweden)

JOSHUA R. VERSEY

2014-06-01

Full Text Available This study provides a fundamental understanding of a cold finger melt crystallization technique by exploring the heat and mass transfer processes of cold finger separation. A series of experiments were performed using a simplified LiCl-CsCl system by varying initial CsCl concentrations (1, 3, 5, and 7.5 wt%, cold finger cooling rates (7.4, 9.8, 12.3, and 14.9 L/min, and separation times (5, 10, 15, and 30 min. Results showed a potential recycling rate of 0.36 g/min with a purity of 0.33 wt% CsCl in LiCl. A CsCl concentrated drip formation was found to decrease crystal purity especially for smaller crystal formations. Dimensionless heat and mass transfer correlations showed that separation production is primarily influenced by convective transfer controlled by cooling gas flow rate, where correlations are more accurate for slower cooling gas flow rates.

Nuclear spin-spin coupling constants of linear carbon chains terminated by coronene molecules: a first principles study

International Nuclear Information System (INIS)

Oliveira, Joao Paulo Cavalcante; Mota, F. de Brito; Rivelino, Roberto

2011-01-01

Full text. Carbon nano wires made of long linear atomic chains have attracted considerable interest due to their potential applications in nano electronics. We report a density-functional-theory study of the nuclear spin-spin coupling constants for nano assemblies made of two coronene molecules bridged by carbon linear chains, considering distinct sizes and spin multiplicities. Also, we examine the effects of two terminal conformations (syn and anti) of the terminal anchor pieces on the magnetic properties of the carbon chains via 13 C NMR calculations. Our results reveal that simplified chemical models such as those based on cumulenes or polyynes are not appropriate to describe the linear chains with sp 2 terminations. For these types of atomic chains, the electronic ground state of the even-numbered chains can be singlet or triplet, whereas the ground state of the odd-numbered chains can be doublet or quartet. We discuss how the 13 C NMR chemical shift absorption is affected by increasing the size and changing the parity of the linear carbon chains. We have found that the J coupling constants between the carbon atoms in the linear chains present a well-defined pattern, in good accordance with our electronic structure calculations. For example, in the -C 4 - units we obtain couplings of 43.8, 114.5, 84.6, 114.5, and 43.8 Hz from one end to the other

Experimental comparison of the critical ionization velocity in atomic and molecular gases

International Nuclear Information System (INIS)

Axnaes, I.

1978-08-01

The critical ionization velocity usub(c) of Ne, Kr, Xe, Cl 2 , O 2 , CO, CO 2 , NH 3 and H 2 O is investigated experimentally in a coaxial plasma gun. Together with experimental data obtained in earlier experiments the present results make it possible to make a systematic comparison between the critical ionization velocity for atomic and molecular gases. It is found that atomic and molecular gases tend to have values of critical ionization velocity which are respectively smaller and larger than the theoretical values. The current dependence of usub(c) is found to be different for atomic and molecular gases. A number of atomic and molecular processes relevant to the experiment are discussed

Comparison of detector systems for the separation of 36Cl and 36S with a 3-MV tandem

International Nuclear Information System (INIS)

Orlowski, Tobias; Forstner, Oliver; Golser, Robin; Kutschera, Walter; Merchel, Silke; Martschini, Martin; Priller, Alfred; Steier, Peter; Vockenhuber, Christof; Wallner, Anton

2010-01-01

The possibility of detecting 36 Cl for geological exposure dating has been explored for several years at VERA (the Vienna Environmental Research Accelerator). First results on real samples were obtained with an ionization chamber (developed at the ETH/PSI, Zuerich, Switzerland) with two anodes. To improve the suppression of 36 S, we equipped the ionization chamber with an exit window and added a Time-of-Flight (TOF) system with a double-sided silicon strip detector (50 x 50 mm 2 ) as stop detector. We optimized the TOF setup by using silicon nitride foils to reduce scattering tails in the energy spectra. At 3 MV terminal voltage, corresponding to a particle energy of 24 MeV of 36 Cl 7+ , we achieved a 36 S 7+ -suppression of 21,500 (50% 36 Cl-detector-efficiency).

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

International Nuclear Information System (INIS)

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

2010-01-01

The complex compounds (H 3 L . Cl)[CoCl 4 ] (I) and H 2 L[CuBr 4 ] (II), where L is 2,4,6-tri(N,N-dimethylamino)methylphenol, were isolated in the crystalline state and studied by X-ray diffraction. The organic cations were found to be outer-sphere ligands. All three nitrogen atoms of the tertiary amino groups are protonated. In compound I, the H 3 L 3+ cation exists as the cis tautomer. In compound II, the H 2 L 2+ dication exists as the trans isomer. In the crystal structure, the dications are arranged in layers via hydrogen bonds.

Residual salt separation from simulated spent nuclear fuel reduced in a LiCl-Li2O salt

International Nuclear Information System (INIS)

Hur, Jin-Mok; Hong, Sun-Seok; Seo, Chung-Seok

2006-01-01

The electrochemical reduction of spent nuclear fuel in LiCl-Li 2 O molten salt for the conditioning of spent nuclear fuel requires the separation of the residual salts from a reduced metal product after the reduction process. Considering the behavior of spent nuclear fuel during the electrochemical reduction process, a surrogate material matrix was constructed and inactive tests on a salt separation were carried out to produce the data required for active tests. Fresh uranium metal prepared from the electrochemical reduction of U 3 O 8 powder was used as the surrogates of the spent nuclear fuel Atomic Energy Society of Japan, Tokyo, Japan, All rights reservedopyriprocess. LiCl, Li 2 O, Y 2 O 3 and SrCl 2 were selected as the components of the residual salts. Interactions between the salts and their influence on the separation of the residual salts were analyzed by differential scanning calorimetry (DSC) and thermogravimetry (TG). Eutectic melting of LiCl-Li 2 O and LiCl-SrCl 2 led to a melting point which was lower than that of the LiCl molten salt was observed. Residual salts were separated by a vaporization method. Co-vaporization of LiCl-Li 2 O and LiCl-SrCl 2 was achieved below the temperatures which could make the uranium metal oxidation by Li 2 O possible. The salt vaporization rates at 950degC were measured as follows: LiCl-8 wt% Li 2 O>LiCl>LiCl-8 wt% SrCl 2 >SrCl 2 . (author)

AMS of 36Cl with the VERA 3 MV tandem accelerator

International Nuclear Information System (INIS)

Martschini, Martin; Andersson, Pontus; Forstner, Oliver; Golser, Robin; Hanstorp, Dag; Lindahl, Anton O.; Kutschera, Walter; Pavetich, Stefan; Priller, Alfred; Rohlén, Johan; Steier, Peter; Suter, Martin; Wallner, Anton

2013-01-01

Recent progress with compact ionization chambers has opened new possibilities for isobar suppression in accelerator mass spectrometry (AMS). Separation of 36 Cl (t 1/2 = 0.30 Ma) at natural isotopic levels from its stable isobar 36 S became feasible at particle energies of 24 MeV, which are also accessible for medium-sized tandem accelerators with 3 MV terminal voltage like VERA (Vienna Environmental Research Accelerator). Investigations with an ionization chamber revealed how physics favors isobar separation even at energies below the maximum of the Bragg curve. The strong energy focusing effect at high energy losses reduces energy straggling significantly and isobar separation steadily increases up to almost full energy loss. With an optimized detection setup, sulfur suppression factors of 2 × 10 4 have been achieved. Refraining from the additional use of degrader foils has the benefit of high transmission to the detector (∼16%), but requires a low sulfur output from the ion source. Therefore several backing materials have been screened for sulfur content. The dependence of the sulfur output on the AgCl sample size has been investigated as well. Precision and accuracy have been thoroughly assessed over the last two years. Since drifts in the spectra are efficiently corrected by monitoring the position of the 36 S peak, the reproducibility for high ratio samples ( 36 Cl/Cl > 10 −12 ) is better than 2%. Our blank value of 36 Cl/Cl ≈ (5 ± 5) × 10 −16 is competitive to other labs. 36 Cl has become a routine AMS-isotope at VERA. Recently we also explored novel techniques for additional sulfur suppression already in the ion source. While results with a small gas reaction cell in front of the sputter target were discouraging, a decrease in the sulfur/chlorine ratio by one order of magnitude was achieved by directing 300 mW continuous wave laser beam at 445 nm towards the cathode in the ion source.

Roughness generation during Si etching in Cl{sub 2} pulsed plasma

Energy Technology Data Exchange (ETDEWEB)

Mourey, Odile; Petit-Etienne, Camille; Cunge, Gilles, E-mail: gilles.cunge@cea.fr; Darnon, Maxime; Despiau-Pujo, Emilie; Brichon, Paulin; Lattu-Romain, Eddy; Pons, Michel; Joubert, Olivier [Univ. Grenoble Alpes, CNRS, CEA-Leti Minatec, LTM, F-38054 Grenoble Cedex (France)

2016-07-15

Pulsed plasmas are promising candidates to go beyond limitations of continuous waves' plasma. However, their interaction with surfaces remains poorly understood. The authors investigated the silicon etching mechanism in inductively coupled plasma (ICP) Cl{sub 2} operated either in an ICP-pulsed mode or in a bias-pulsed mode (in which only the bias power is pulsed). The authors observed systematically the development of an important surface roughness at a low duty cycle. By using plasma diagnostics, they show that the roughness is correlated to an anomalously large (Cl atoms flux)/(energetic ion flux) ratio in the pulsed mode. The rational is that the Cl atom flux is not modulated on the timescale of the plasma pulses although the ion fluxes and energy are modulated. As a result, a very strong surface chlorination occurs during the OFF period when the surface is not exposed to energetic ions. Therefore, each energetic ion in the ON period will bombard a heavily chlorinated silicon surface, leading to anomalously high etching yield. In the ICP pulsed mode (in which the ion energy is high), the authors report yields as high as 40, which mean that each individual ion impacts will generate a “crater” of about 2 nm depth at the surface. Since the ion flux is very small in the pulsed ICP mode, this process is stochastic and is responsible for the roughness initiation. The roughness expansion can then be attributed partly to the ion channeling effect and is probably enhanced by the formation of a SiClx reactive layer with nonhomogeneous thickness over the topography of the surface. This phenomenon could be a serious limitation of pulsed plasma processes.

Photodetachment and UV-Vis spectral properties of Cl2rad -·nHO clusters: Extrapolation to bulk

Science.gov (United States)

Pathak, A. K.; Mukherjee, T.; Maity, D. K.

2008-03-01

Vertical detachment energy (VDE) and UV-Vis spectra of Cl2rad -·nHO clusters ( n = 1-11) are reported based on first principle electronic structure calculations. VDE of the hydrated clusters are calculated following second order Moller-Plesset perturbation (MP2) as well as coupled cluster theory with 6-311++G(d,p) set of basis function. The excess electron in these hydrated clusters is mainly localized over the solute Cl atoms. A linear relationship is obtained for VDE vs. ( n + 2.6) -1/3 and bulk VDE of Cl2rad - aqueous solution is calculated as 10.61 eV at CCSD(T) level of theory. UV-Vis spectra of these hydrated clusters are calculated applying CI with single electron (CIS) excitation procedure. Simulated UV-Vis spectra of Cl2rad -·10HO cluster is noted to be in excellent agreement with the reported spectra of Cl2rad - (aq) system, λmax for Cl2rad -·11HO system is calculated to be red shifted though.

True atomic-scale imaging of a spinel Li{sub 4}Ti{sub 5}O{sub 12}(111) surface in aqueous solution by frequency-modulation atomic force microscopy

Energy Technology Data Exchange (ETDEWEB)

Kitta, Mitsunori, E-mail: m-kitta@aist.go.jp; Kohyama, Masanori [Research Institute for Ubiquitous Energy Devices, National Institute of Advanced Industrial Science and Technology, 1-8-31 Midorigaoka, Ikeda, Osaka 563-8577 (Japan); Onishi, Hiroshi [Department of Chemistry, Graduate School of Science, Kobe University 1-1 Rokkodai, Nada, Kobe 657-8501 (Japan)

2014-09-15

Spinel-type lithium titanium oxide (LTO; Li{sub 4}Ti{sub 5}O{sub 12}) is a negative electrode material for lithium-ion batteries. Revealing the atomic-scale surface structure of LTO in liquid is highly necessary to investigate its surface properties in practical environments. Here, we reveal an atomic-scale image of the LTO(111) surface in LiCl aqueous solution using frequency-modulation atomic force microscopy. Atomically flat terraces and single steps having heights of multiples of 0.5 nm were observed in the aqueous solution. Hexagonal bright spots separated by 0.6 nm were also observed on the flat terrace part, corresponding to the atomistic contrast observed in the ultrahigh vacuum condition, which suggests that the basic atomic structure of the LTO(111) surface is retained without dramatic reconstruction even in the aqueous solution.

Influence of the chlorine concentration on the radiation efficiency of a XeCl exciplex lamp

Energy Technology Data Exchange (ETDEWEB)

Avtaeva, S. V., E-mail: s_avtaeva@mail.ru [Kyrgyz-Russian Slavic University (Kyrgyzstan); Sosnin, E. A. [Russian Academy of Sciences, Institute of High-Current Electronics, Siberian Branch (Russian Federation); Saghi, B. [Mohamed Boudiaf University of Sciences and Technology, Department of Electronics (Algeria); Panarin, V. A. [Russian Academy of Sciences, Institute of High-Current Electronics, Siberian Branch (Russian Federation); Rahmani, B. [Mohamed Boudiaf University of Sciences and Technology, Department of Electronics (Algeria)

2013-09-15

The influence of the chlorine concentration on the radiation efficiency of coaxial exciplex lamps (excilamps) excited by a dielectric barrier discharge (DBD) in binary Xe-Cl{sub 2} mixtures at pressures of 240–250 Torr is investigated experimentally and theoretically. The experiments were carried out at Cl{sub 2} concentrations in the range of 0.01–1%. The DBD characteristics were calculated in the framework of a one-dimensional hydrodynamic model at Cl{sub 2} concentrations in the range of 0.1–5%. It is found that the radiation intensities of the emission bands of Xe*{sub 2}(172 nm) and XeCl* (308 nm) are comparable when the chlorine concentration in the mixture is in the range of 0.01–0.1%. In this case, in the mixture, the radiation intensity of the Xe*{sub 2} molecule rapidly decreases with increasing Cl{sub 2} concentration and, at a chlorine concentration of ≥0.2%, the radiation of the B → X band of XeCl* molecules with a peak at 308 nm dominates in the discharge radiation. The radiation efficiency of this band reaches its maximum value at chlorine concentrations in the range of 0.4–0.5%. The calculated efficiencies of DBD radiation exceed those obtained experimentally. This is due to limitations of the one-dimensional model, which assumes the discharge to be uniform in the transverse direction, whereas the actual excilamp discharge is highly inhomogeneous. The influence of the chlorine concentration on the properties of the DBD plasma in binary Xe-Cl{sub 2} mixtures is studied numerically. It is shown that an increase in the Cl{sub 2} concentration in the mixture leads to the attachment of electrons to chlorine atoms and a decrease in the electron density and discharge conductivity. As a result, the electric field and the voltage drop across the discharge gap increase, which, in turn, leads to an increase in the average electron energy and the probability of dissociation of Cl{sub 2} molecules and ionization of Xe atoms and Cl{sub 2} molecules

Influence of the chlorine concentration on the radiation efficiency of a XeCl exciplex lamp

International Nuclear Information System (INIS)

Avtaeva, S. V.; Sosnin, E. A.; Saghi, B.; Panarin, V. A.; Rahmani, B.

2013-01-01

The influence of the chlorine concentration on the radiation efficiency of coaxial exciplex lamps (excilamps) excited by a dielectric barrier discharge (DBD) in binary Xe-Cl 2 mixtures at pressures of 240–250 Torr is investigated experimentally and theoretically. The experiments were carried out at Cl 2 concentrations in the range of 0.01–1%. The DBD characteristics were calculated in the framework of a one-dimensional hydrodynamic model at Cl 2 concentrations in the range of 0.1–5%. It is found that the radiation intensities of the emission bands of Xe* 2 (172 nm) and XeCl* (308 nm) are comparable when the chlorine concentration in the mixture is in the range of 0.01–0.1%. In this case, in the mixture, the radiation intensity of the Xe* 2 molecule rapidly decreases with increasing Cl 2 concentration and, at a chlorine concentration of ≥0.2%, the radiation of the B → X band of XeCl* molecules with a peak at 308 nm dominates in the discharge radiation. The radiation efficiency of this band reaches its maximum value at chlorine concentrations in the range of 0.4–0.5%. The calculated efficiencies of DBD radiation exceed those obtained experimentally. This is due to limitations of the one-dimensional model, which assumes the discharge to be uniform in the transverse direction, whereas the actual excilamp discharge is highly inhomogeneous. The influence of the chlorine concentration on the properties of the DBD plasma in binary Xe-Cl 2 mixtures is studied numerically. It is shown that an increase in the Cl 2 concentration in the mixture leads to the attachment of electrons to chlorine atoms and a decrease in the electron density and discharge conductivity. As a result, the electric field and the voltage drop across the discharge gap increase, which, in turn, leads to an increase in the average electron energy and the probability of dissociation of Cl 2 molecules and ionization of Xe atoms and Cl 2 molecules. The total energy deposited in the discharge

Influence of the chlorine concentration on the radiation efficiency of a XeCl exciplex lamp

Science.gov (United States)

Avtaeva, S. V.; Sosnin, E. A.; Saghi, B.; Panarin, V. A.; Rahmani, B.

2013-09-01

The influence of the chlorine concentration on the radiation efficiency of coaxial exciplex lamps (excilamps) excited by a dielectric barrier discharge (DBD) in binary Xe-Cl2 mixtures at pressures of 240-250 Torr is investigated experimentally and theoretically. The experiments were carried out at Cl2 concentrations in the range of 0.01-1%. The DBD characteristics were calculated in the framework of a one-dimensional hydrodynamic model at Cl2 concentrations in the range of 0.1-5%. It is found that the radiation intensities of the emission bands of Xe*2(172 nm) and XeCl* (308 nm) are comparable when the chlorine concentration in the mixture is in the range of 0.01-0.1%. In this case, in the mixture, the radiation intensity of the Xe*2 molecule rapidly decreases with increasing Cl2 concentration and, at a chlorine concentration of ≥0.2%, the radiation of the B → X band of XeCl* molecules with a peak at 308 nm dominates in the discharge radiation. The radiation efficiency of this band reaches its maximum value at chlorine concentrations in the range of 0.4-0.5%. The calculated efficiencies of DBD radiation exceed those obtained experimentally. This is due to limitations of the one-dimensional model, which assumes the discharge to be uniform in the transverse direction, whereas the actual excilamp discharge is highly inhomogeneous. The influence of the chlorine concentration on the properties of the DBD plasma in binary Xe-Cl2 mixtures is studied numerically. It is shown that an increase in the Cl2 concentration in the mixture leads to the attachment of electrons to chlorine atoms and a decrease in the electron density and discharge conductivity. As a result, the electric field and the voltage drop across the discharge gap increase, which, in turn, leads to an increase in the average electron energy and the probability of dissociation of Cl2 molecules and ionization of Xe atoms and Cl2 molecules. The total energy deposited in the discharge rises with increasing

Self-assembled monolayers of semi-fluorinated thiols and disulfides with a potentially antibacterial terminal fragment on gold surfaces

International Nuclear Information System (INIS)

Thebault, P.; Taffin de Givenchy, E.; Guittard, F.; Guimon, C.; Geribaldi, S.

2008-01-01

Attempts to elaborate the best organized cationic self-assembled monolayers (SAMs) with sulfur derivatives containing potentially bactericidal quaternary ammonium salt moieties have been performed on gold with the final aim to obtain contact-active antibacterial surfaces. Four molecules bearing two hydrocarbon spacers with different lengths between the sulfur atom and the quaternized nitrogen atom, and two different terminal semi-fluorinated alkyl chains have been synthesised and used in view to evaluate their capacity for leading to the highest densities and the highest organization of potentially active molecules on the metal surface. The formation and quality of SAMs characterized by X-ray photoelectron spectroscopy, Internal Reflexion Infra Red Imaging, contact angle and blocking factor measurements depend on the lengths of both the hydrocarbon spacer and terminal perfluorinated chain

Separation of CsCl and SrCl{sub 2} from a ternary CsCl-SrCl{sub 2}-LiCl via a zone refining process for waste salt minimization of pyroprocessing

Energy Technology Data Exchange (ETDEWEB)

Shim, Moonsoo [Graduate School of Energy Science and Technology, Chungnam National University, 99 Daehak-ro, Yuseong-gu, Daejeon, 34134 (Korea, Republic of); Choi, Ho Gil; Yi, Kyung Woo; Hwang, Il Soon [Graduate School of Seoul National University, 1 Gwanak-ro, Gwanak-gu, Seoul 08826 (Korea, Republic of); Lee, Jong Hyeon, E-mail: jonglee@cnu.ac.kr [Graduate School of Energy Science and Technology, Chungnam National University, 99 Daehak-ro, Yuseong-gu, Daejeon, 34134 (Korea, Republic of); Graduate School of Department of Advanced Materials Engineering, Chungnam National University, 99 Daehak-ro, Yuseong-gu, Daejeon, 34134 (Korea, Republic of); Rapid Solidified Materials Research Center, Chungnam National University, 99 Daehak-ro, Yuseong-gu, Daejeon, 34134 (Korea, Republic of)

2016-11-15

The purification of LiCl salt mixture has traditionally been carried out by a melt crystallization process. To improve the throughput of zone refining, three heaters were installed in the zone refiner. The zone refining method was used to grow pure LiCl salt ingots from LiCl-CsCl-SrCl{sub 2} salt mixture. The main investigated parameters were the heater speed and the number of passes. A change in the LiCl crystal grain size was observed according to the horizontal direction. From each zone refined salt ingot, samples were collected horizontally. To analyze the concentrations of Sr and Cs, an inductively coupled plasma optical emission spectrometer and inductively coupled plasma mass spectrometer were used, respectively. The experimental results show that Sr and Cs concentrations at the initial region of the ingot were low and reached their peak at the final freezing region of the salt ingot. Concentration results of zone refined salt were compared with theoretical results yielded by the proposed model to validate its predictions. The k{sub eff} of Sr and Cs were 0.13 and 0.11, respectively. The decontamination factors of Sr and Cs were 450 and 1650, respectively. - Highlights: • The LiCl-CsCl-SrCl{sub 2} salt ingot was purified by zone refining technique to minimize waste salt. • The concentration distribution of Cs and Sr were analyzed by mass transfer equation. • The decontamination factors of Cs and Sr were 1600 and 450 respectively in case of 60% of recovery yield.

Content of Pb, Cd and Cl in forest trees caused by the traffic of motor vehicles

Energy Technology Data Exchange (ETDEWEB)

Mankovska, B

1977-01-01

The contents of Pb, Cd in spruce trees and soil polluted by the traffic of motor vehicles was determined by the method of atomic absorption, that of Cl by the mercurometric method. In general the raised level of Pb, Cd and Cl was found in the soils and assimilation organs close to the roadway. The most important factors influencing this raise are mentioned: the age of needles, season of year, character of surface of plant organs, tree species, both horizontal and vertical distance from the road. There is a statistically very high significant relation (at 95% level of significance) between the amount of Pb and Cd in mg in mg.kg/sup -1/ and horizontal distance from the road; that of Cl is lower.

Electric conductivity of PCl5-ZrCl4, PCl5-TaCl5, and PCl5-MoCl5 molten mixtures

International Nuclear Information System (INIS)

Salyulev, A.B.; Red'kin, A.A.; Moskalenko, N.I.

1997-01-01

When mixing individual molecular melts of PCl 5 with ZrCl 4 , TaCl 5 or with MoCl 5 , an essential (by several orders) increase in electric conductivity (up to 0.02-0.1 Ohm -1 ·cm -1 ), which stems, in all probability, from the appearance of complex ions PCl 4 + , ZrCl 5 - , ZrCl 6 2- , TaCl 5 - and MoCl 6 - in the molten mixtures as a result of chemical interaction

Atmospheric chemistry of CH3O(CF2CF2O)(n)CH3 (n=1-3): Kinetics and mechanism of oxidation initiated by Cl atoms and OH radicals, IR spectra, and global warmin potentials

DEFF Research Database (Denmark)

Andersen, Mads Peter Sulbæk; Hurley, MD; Wallington, TJ

2004-01-01

Smog chambers equipped with FTIR spectrometers were used to study the Cl atom and OH radical initiated oxidation of CH3O(CF2CF2O)(n)CH3 (n = 1-3) in 720 +/- 20 Torr of air at 296 +/- 3 K. Relative rate techniques were used to measure k(Cl + CH3O(CF2CF2O)(n)CH3) (3.7 +/- 10.7) x 10(-13) and k......(OH + CH3O(CF2CF2O)(n)CH3) = (2.9 +/- 0.5) x 10(-11) cm(3) molecule(-1) s(-1) leading to an estimated atmospheric lifetime of 2 years for CH3O(CF2CF2O),CH3. The Cl initiated oxidation of CH3O(CF2CF2O),CH3 in air diluent gives CH3O(CF2CF2O)(n)C(O)H in a yield which is indistinguishable from 100 Further...... oxidation leads to the diformate, H(O)CO(CF2CF2O)(n)C(O)H. A rate constant of k(Cl + CH3O(CF2CF2O)(n)CHO) = (1.81 +/- 0.36) x 10(-13) cm(3) molecule(-1) s-1 was determined. Quantitative infrared spectra for CH3O(CF2CF2O)(n)CH3 (n = 1-3) were recorded and used to estimate halocarbon global warming potentials...

Probing the Surface Charge on the Basal Planes of Kaolinite Particles with High-Resolution Atomic Force Microscopy.

Science.gov (United States)

Kumar, N; Andersson, M P; van den Ende, D; Mugele, F; Siretanu, I

2017-12-19

High-resolution atomic force microscopy is used to map the surface charge on the basal planes of kaolinite nanoparticles in an ambient solution of variable pH and NaCl or CaCl 2 concentration. Using DLVO theory with charge regulation, we determine from the measured force-distance curves the surface charge distribution on both the silica-like and the gibbsite-like basal plane of the kaolinite particles. We observe that both basal planes do carry charge that varies with pH and salt concentration. The silica facet was found to be negatively charged at pH 4 and above, whereas the gibbsite facet is positively charged at pH below 7 and negatively charged at pH above 7. Investigations in CaCl 2 at pH 6 show that the surface charge on the gibbsite facet increases for concentration up to 10 mM CaCl 2 and starts to decrease upon further increasing the salt concentration to 50 mM. The increase of surface charge at low concentration is explained by Ca 2+ ion adsorption, while Cl - adsorption at higher CaCl 2 concentrations partially neutralizes the surface charge. Atomic resolution imaging and density functional theory calculations corroborate these observations. They show that hydrated Ca 2+ ions can spontaneously adsorb on the gibbsite facet of the kaolinite particle and form ordered surface structures, while at higher concentrations Cl - ions will co-adsorb, thereby changing the observed ordered surface structure.

Seperation of CsCl from LiCl-CsCl molten salt by cold finger melt cryst allization

Energy Technology Data Exchange (ETDEWEB)

Versey, Joshua R. [Dept. of Chemical and Materials Engineering and Nuclear Engineering Program University of Idaho, Idaho (United States); Phongikaroon, Supathorn [Dept. of Mechanical and Nuclear Engineering Virginia Commonwealth University, Richmond (Korea, Republic of); Simpson, Michael F. [Dept. of Metallurgical Engineering University of Utah, Utah (Korea, Republic of)

2014-06-15

This study provides a fundamental understanding of a cold finger melt crystallization technique by exploring the heat and mass transfer processes of cold finger separation. A series of experiments were performed using a simplified LiCl-CsCl system by varying initial CsCl concentrations (1, 3, 5, and 7.5 wt%), cold finger cooling rates (7.4, 9.8, 12.3, and 14.9 L/min), and separation times (5, 10, 15, and 30 min). Results showed a potential recycling rate of 0.36 g/min with a purity of 0.33 wt% CsCl in LiCl. A CsCl concentrated drip formation was found to decrease crystal purity especially for smaller crystal formations. Dimensionless heat and mass transfer correlations showed that separation production is primarily influenced by convective transfer controlled by cooling gas flow rate, where correlations are more accurate for slower cooling gas flow rates.

[μ-Bis(diphenylphosphanyl-κPmethane]decacarbonyltri-μ-hydrido-trirhenium(I(3 Re—Re dichloromethane solvate

Directory of Open Access Journals (Sweden)

Ahmed F. Abdel-Magied

2011-12-01

Full Text Available In the title compound, [Re3(μ-H3(C25H22P2(CO10]·CH2Cl2, the three Re atoms form a triangle bearing ten terminal carbonyl groups and three edge-bridging hydrides. The bis(diphenylphosphanylmethane ligand bridges two Re atoms. Neglecting the Re—Re interactions, each Re atom is in a slightly distorted octahedral coordination environment. The dichloromethane solvent molecule is disordered over two sets of sites with fixed occupancies of 0.6 and 0.4.

Distribution of {sup 36}Cl/Cl in a river-recharged aquifer: Implications for the fallout rate of bomb-produced {sup 36}Cl

Energy Technology Data Exchange (ETDEWEB)

Tosaki, Yuki, E-mail: tosaki@tac.tsukuba.ac.j [Sustainable Environmental Studies, Graduate School of Life and Environmental Sciences, University of Tsukuba, 1-1-1 Tennodai, Tsukuba, Ibaraki 305-8572 (Japan); Massmann, Gudrun [Institute of Geological Sciences, Department of Earth Sciences, Freie Universitaet Berlin, Malteserstrasse 74-100, 12249 Berlin (Germany); Tase, Norio [Sustainable Environmental Studies, Graduate School of Life and Environmental Sciences, University of Tsukuba, 1-1-1 Tennodai, Tsukuba, Ibaraki 305-8572 (Japan); Sasa, Kimikazu; Takahashi, Tsutomu [Tandem Accelerator Complex, Research Facility Center for Science and Technology, University of Tsukuba, 1-1-1 Tennodai, Tsukuba, Ibaraki 305-8577 (Japan); Matsushi, Yuki [Department of Nuclear Engineering and Management, School of Engineering, University of Tokyo, 2-11-16 Yayoi, Bunkyo-ku, Tokyo 113-0032 (Japan); Tamari, Michiko [Department of Chemistry, Graduate School of Pure and Applied Sciences, University of Tsukuba, 1-1-1 Tennodai, Tsukuba, Ibaraki 305-8571 (Japan); Nagashima, Yasuo [Tandem Accelerator Complex, Research Facility Center for Science and Technology, University of Tsukuba, 1-1-1 Tennodai, Tsukuba, Ibaraki 305-8577 (Japan); Bessho, Kotaro; Matsumura, Hiroshi [Radiation Science Center, High Energy Accelerator Research Organization (KEK), 1-1 Oho, Tsukuba, Ibaraki 305-0801 (Japan)

2010-04-15

Distribution of {sup 36}Cl/Cl ratios in a river-recharged aquifer was investigated in the Oderbruch area, northeastern Germany. The aquifer is confined up to 3.5-4 km inland, where it changes to an unconfined condition. The {sup 36}Cl/Cl ratios in the confined area were in the range between 4.6 x 10{sup -14} and 23.1 x 10{sup -14}, showing a peak at 2-3 km away from the river. A plot of {sup 36}Cl/Cl vs. reciprocal Cl{sup -} concentrations indicated possible effect of the Cl{sup -} concentration variation on the observed {sup 36}Cl/Cl ratios. After accounting for this effect, the estimated {sup 36}Cl fallout rates for the last 30 yrs show reasonable agreement with the Dye-3 data and the mid-latitude background value. The results suggest that a local {sup 36}Cl fallout curve can be constructed from groundwater when dispersive mixing is of minor importance.

The neutron diffraction of molten TlCl, TlBr, and TlI

International Nuclear Information System (INIS)

Satow, T.; Uemura, O.; Hoshino, K.; Watanabe, T.

1984-01-01

Structure factors S(K) for liquid TlCl, TlBr, and TlI are determined by neutron diffraction measurements. Atomic radial distribution functions (RDF) derived from S(K) are presented. All RDF values are slightly smaller than those of their solid state counter parts. Results show that TlX has a tendency not to retain cesium-chloride type local order, but to take sodium-chloride type order when melting

Modulation of electronic and optical properties in mixed halide perovskites CsPbCl3xBr3(1-x) and CsPbBr3xI3(1-x)

Science.gov (United States)

Zhou, Ziqi; Cui, Yu; Deng, Hui-Xiong; Huang, Le; Wei, Zhongming; Li, Jingbo

2017-03-01

The recent discovery of lead halide perovskites with band gaps in the visible presents important potential in the design of high efficient solar cells. CsPbCl3, CsPbBr3 and CsPbI3 are stable compounds within this new family of semiconductors. By performing the first-principles calculation, we explore the structural, electronic and optical properties of CsPbCl3xBr3(1-x) and CsPbBr3xI3(1-x) with various compositions of halide atoms. Structural stability is demonstrated with halide atoms distributing randomly at the halide atomic sites. CsPbCl3xBr3(1-x) and CsPbBr3xI3(1-x) exhibit the modulation of their band gaps by varying the halide composition. Our results also indicate that CsPbCl3xBr3(1-x) and CsPbBr3xI3(1-x) with different halide compositions are suitable to application to solar cells for the general features are well preserved. Good absorption to lights of different wavelengths has been obtained in these mixed halide perovskites.

An MCM modeling study of nitryl chloride (ClNO2) impacts on oxidation, ozone production and nitrogen oxide partitioning in polluted continental outflow

Science.gov (United States)

Riedel, T. P.; Wolfe, G. M.; Danas, K. T.; Gilman, J. B.; Kuster, W. C.; Bon, D. M.; Vlasenko, A.; Li, S.-M.; Williams, E. J.; Lerner, B. M.; Veres, P. R.; Roberts, J. M.; Holloway, J. S.; Lefer, B.; Brown, S. S.; Thornton, J. A.

2014-04-01

Nitryl chloride (ClNO2) is produced at night by reactions of dinitrogen pentoxide (N2O5) on chloride containing surfaces. ClNO2 is photolyzed during the morning hours after sunrise to liberate highly reactive chlorine atoms (Cl·). This chemistry takes place primarily in polluted environments where the concentrations of N2O5 precursors (nitrogen oxide radicals and ozone) are high, though it likely occurs in remote regions at lower intensities. Recent field measurements have illustrated the potential importance of ClNO2 as a daytime Cl· source and a nighttime NOx reservoir. However, the fate of the Cl· and the overall impact of ClNO2 on regional photochemistry remain poorly constrained by measurements and models. To this end, we have incorporated ClNO2 production, photolysis, and subsequent Cl· reactions into an existing master chemical mechanism (MCM version 3.2) box model framework using observational constraints from the CalNex 2010 field study. Cl· reactions with a set of alkenes and alcohols, and the simplified multiphase chemistry of N2O5, ClNO2, HOCl, ClONO2, and Cl2, none of which are currently part of the MCM, have been added to the mechanism. The presence of ClNO2 produces significant changes to oxidants, ozone, and nitrogen oxide partitioning, relative to model runs excluding ClNO2 formation. From a nighttime maximum of 1.5 ppbv ClNO2, the daytime maximum Cl· concentration reaches 1 × 105 atoms cm-3 at 07:00 model time, reacting mostly with a large suite of volatile organic compounds (VOC) to produce 2.2 times more organic peroxy radicals in the morning than in the absence of ClNO2. In the presence of several ppbv of nitrogen oxide radicals (NOx = NO + NO2), these perturbations lead to similar enhancements in hydrogen oxide radicals (HOx = OH + HO2). Neglecting contributions from HONO, the total integrated daytime radical source is 17% larger when including ClNO2, which leads to a similar enhancement in integrated ozone production of 15%. Detectable

Oxygen termination of homoepitaxial diamond surface by ozone and chemical methods: An experimental and theoretical perspective

Science.gov (United States)

Navas, Javier; Araujo, Daniel; Piñero, José Carlos; Sánchez-Coronilla, Antonio; Blanco, Eduardo; Villar, Pilar; Alcántara, Rodrigo; Montserrat, Josep; Florentin, Matthieu; Eon, David; Pernot, Julien

2018-03-01

Phenomena related with the diamond surface of both power electronic and biosensor devices govern their global behaviour. In particular H- or O-terminations lead to wide variations in their characteristics. To study the origins of such aspects in greater depth, different methods to achieve oxygen terminated diamond were investigated following a multi-technique approach. DFT calculations were then performed to understand the different configurations between the C and O atoms. Three methods for O-terminating the diamond surface were performed: two physical methods with ozone at different pressures, and an acid chemical treatment. X-ray photoelectron spectroscopy, spectroscopic ellipsometry, HRTEM, and EELS were used to characterize the oxygenated surface. Periodic-DFT calculations were undertaken to understand the effect of the different ways in which the oxygen atoms are bonded to carbon atoms on the diamond surface. XPS results showed the presence of hydroxyl or ether groups, composed of simple Csbnd O bonds, and the acid treatment resulted in the highest amount of O on the diamond surface. In turn, ellipsometry showed that the different treatments led to the surface having different optical properties, such as a greater refraction index and extinction coefficient in the case of the sample subjected to acid treatment. TEM analysis showed that applying temperature treatment improved the distribution of the oxygen atoms at the interface and that this generates a thinner amount of oxygen at each position and higher interfacial coverage. Finally, DFT calculations showed both an increase in the number of preferential electron transport pathways when π bonds and ether groups appear in the system, and also the presence of states in the middle of the band gap when there are π bonds, Cdbnd C or Cdbnd O.

trans-(Cl)-[Ru(5,5'-diamide-2,2'-bipyridine)(CO)2 Cl2 ]: Synthesis, Structure, and Photocatalytic CO2 Reduction Activity.

Science.gov (United States)

Kuramochi, Yusuke; Fukaya, Kyohei; Yoshida, Makoto; Ishida, Hitoshi

2015-07-06

A series of trans-(Cl)-[Ru(L)(CO)2 Cl2 ]-type complexes, in which the ligands L are 2,2'-bipyridyl derivatives with amide groups at the 5,5'-positions, are synthesized. The C-connected amide group bound to the bipyridyl ligand through the carbonyl carbon atom is twisted with respect to the bipyridyl plane, whereas the N-connected amide group is in the plane. DFT calculations reveal that the twisted structure of the C-connected amide group raises the level of the LUMO, which results in a negative shift of the first reduction potential (Ep ) of the ruthenium complex. The catalytic abilities for CO2 reduction are evaluated in photoreactions (λ>400 nm) with the ruthenium complexes (the catalyst), [Ru(bpy)3 ](2+) (bpy=2,2'-bipyridine; the photosensitizer), and 1-benzyl-1,4-dihydronicotinamide (the electron donor) in CO2 -saturated N,N-dimethylacetamide/water. The logarithm of the turnover frequency increases by shifting Ep a negative value until it reaches the reduction potential of the photosensitizer. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Simple preparations of Pd6Cl12, Pt6Cl12, and Qn[Pt2Cl8+n], n=1, 2 (Q=TBA+, PPN+) and structural characterization of [TBA][Pt2Cl9] and [PPN]2[Pt2Cl10].C7H8.

Science.gov (United States)

Dell'Amico, Daniela Belli; Calderazzo, Fausto; Marchetti, Fabio; Ramello, Stefano; Samaritani, Simona

2008-02-04

The hexanuclear Pd6Cl12, i.e., the crystal phase classified as beta-PdCl2, was obtained by reacting [TBA]2[Pd2Cl6] with AlCl3 (or FeCl3) in CH2Cl2. The action of AlCl3 on PtCl42-, followed by digestion of the resulting solid in 1,2-C2H4Cl2 (DCE), CHCl3, or benzene, produced Pt6Cl12.DCE, Pt6Cl12.CHCl3, or Pt6Cl12.C6H6, respectively. Treating [TBA]2[PtCl6] with a slight excess of AlCl3 afforded [TBA][Pt2Cl9], whose anion was established crystallographically to be constituted by two "PtCl6" octahedra sharing a face. Dehydration of H2PtCl6.nH2O with SOCl2 gave an amorphous compound closely analyzing as PtCl4, reactive with [Q]Cl in SOCl2 to yield [Q][Pt2Cl9] or [Q]2[Pt2Cl10], depending on the [Q]Cl/Pt molar ratio (Q=TBA+, PPN+). A single-crystal X-ray diffraction study has shown [PPN]2[Pt2Cl10].C7H8 to contain dinuclear anions formed by two edge-sharing PtCl6 octahedra.

Platinum-Catalyzed, Terminal-Selective C(sp(3))-H Oxidation of Aliphatic Amines.

Science.gov (United States)

Lee, Melissa; Sanford, Melanie S

2015-10-14

This Communication describes the terminal-selective, Pt-catalyzed C(sp(3))-H oxidation of aliphatic amines without the requirement for directing groups. CuCl2 is employed as a stoichiometric oxidant, and the reactions proceed in high yield at Pt loadings as low as 1 mol%. These transformations are conducted in the presence of sulfuric acid, which reacts with the amine substrates in situ to form ammonium salts. We propose that protonation of the amine serves at least three important roles: (i) it renders the substrates soluble in the aqueous reaction medium; (ii) it limits binding of the amine nitrogen to Pt or Cu; and (iii) it electronically deactivates the C-H bonds proximal to the nitrogen center. We demonstrate that this strategy is effective for the terminal-selective C(sp(3))-H oxidation of a variety of primary, secondary, and tertiary amines.

Synthesis of substituted mono- and diindole C-nucleoside analogues from sugar terminal alkynes by sequential sonogashira/heteroannulation reaction.

Science.gov (United States)

Zhang, Fuyi; Mu, Delong; Wang, Liming; Du, Pengfei; Han, Fen; Zhao, Yufen

2014-10-17

The synthesis of substituted mono- and diindole C-nucleoside analogues has been achieved in good to excellent yields by sequential Sonogashira coupling/NaAuCl4-catalyzed heteroannulation reactions of substituted 2-iodoanilines with various sugar terminal alkynes in one pot. The method is general, mild, and efficient and suitable for a wide range of sugar substrates, and 42 examples are given. The amino group of the substituted 2-iodoanilines is unprotected. The sugar terminal alkynes include furanosides, pyranosides, and acyclic glycosides with free hydroxyl groups, sensitive functional subtituents, and various protecting groups having different steric hindrance.

Orientation correlation and intermolecular structure of GeCl4, VCl4 and other tetrachloride liquids

International Nuclear Information System (INIS)

Nath, P.P.; Sarkar, S.; Joarder, R.N.

2007-01-01

The intermolecular structure and correlation of GeCl 4 , VCl 4 and other tetrachloride liquids can be well described by Misawa's orientation correlation model originally applied to liquid CCl 4 . The model supports on average a specific 'corner' to 'face' correlation, but evidently very different from 'Apollo' type model. The Misawa model appears to work, in some respect, even better than reference interaction site model (RISM) used for long to describe intermolecular structure of such molecular systems. The test and comparison are made through the calculation of small asymmetric part of the intermolecular structure and evaluation of partial atom-atom distribution functions

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

Directory of Open Access Journals (Sweden)

Varsha Rani

2017-03-01

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

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.

Science.gov (United States)

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.

Adsorbed layers on (111)InAs faces in contact with In-As-Cl-H gas phase, and the possibility of phase transitions in the adsorbed layers

Science.gov (United States)

Chernov, A. A.; Ruzaikin, M. P.

1981-04-01

Adsorption of various species existing in the In-As-Cl-H CVD gaseous system on both InAs (111) faces is considered. Arsenic is supposed to be adsorbed in the form of triangles As 3 and tetrahedrons As 4, each of them occupying 3 atomic sites above In or As atoms on (111)In or (111)As, respectively. The system of polyatomic adsorption equations was used to find the coverages of the faces by various species. Admolecule-surface bond strengths are taken to be equal to the ones for the single bonds in molecules. Pauling electronegativities were used to find the effective charges of the atoms in the adsorption layer. Thus, the dipole moments of adsorbed molecules which arise are directed along the In-As bonds in the InAs lattice. With this geometry, the calculated electrostatic dipole-dipole attraction between InCl molecules forming a dense layer on (111)As exceeds 12 kcal/mol. Thus, condensation of the two-dimensional gas of adsorbed InCl molecules should be expected. Corresponding S-shape isotherms θ( P) are calculated for different As 3 vapor pressures, θ and P being the surface coverage and bulk vapor pressure of InCl. Intervals of {InCl 3}/{H 2} ratios at different temperatures where the two-dimensional condensation may occur, are presented for realistic CVD conditions. Two-dimensional condensation may result in sharp changes in kinetic coefficient and thus in autho-oscillations in growth rate and doping level creating periodic superstructures. Nucleation and CVD growth processes are discussed.

Electrochemical deposition of Prussian blue on hydrogen terminated silicon(111)

International Nuclear Information System (INIS)

Zhao Jianwei; Zhang Yan; Shi Chuanguo; Chen, Hongyuan; Tong Lianming; Zhu Tao; Liu Zhongfan

2006-01-01

Electrochemical deposition of Prussian blue (PB) was performed by cyclic voltammetry on hydrogen terminated n-type Si(111) surface. The characterization of the samples based on atomic force microscopy and X-ray diffraction spectroscopy showed a nanocrystal form of the PB films on the silicon surface. The thickness of PB films as a function of the potential cycling number was monitored simultaneously by Raman spectroscopy, proving that the growth of the films is in a good controllable manner

Purification, crystallization and X-ray diffraction analysis of the C-terminal protease domain of Venezuelan equine encephalitis virus nsP2

International Nuclear Information System (INIS)

Russo, Andrew T.; Watowich, Stanley J.

2006-01-01

The C-terminal protease domain of Venezuelan equine encephalitis virus (VEEV) nsP2 has been overexpressed in E. coli, purified and successfully crystallized. Native crystals diffract to beyond 2.5 Å resolution and isomorphous heavy-atom derivatives suitable for phase analysis have been identified. The C-terminal region of Venezuelan equine encephalitis virus (VEEV) nsP2 is responsible for proteolytic processing of the VEEV polyprotein replication complex. This action regulates the activity of the replication complex and is essential for viral replication, thus making nsP2 a very attractive target for development of VEEV therapeutics. The 338-amino-acid C-terminal region of VEEV nsP2 has been overexpressed in Escherichia coli, purified and crystallized. Crystals diffract to beyond 2.5 Å resolution and belong to the orthorhombic space group P2 1 2 1 2 1 . Isomorphous heavy-atom derivatives suitable for phase analysis have been obtained and work on building a complete structural model is under way

Purification, crystallization and X-ray diffraction analysis of the C-terminal protease domain of Venezuelan equine encephalitis virus nsP2

Energy Technology Data Exchange (ETDEWEB)

Russo, Andrew T.; Watowich, Stanley J., E-mail: watowich@xray.utmb.edu [Department of Biochemistry and Molecular Biology, University of Texas Medical Branch, Galveston, TX (United States)

2006-06-01

The C-terminal protease domain of Venezuelan equine encephalitis virus (VEEV) nsP2 has been overexpressed in E. coli, purified and successfully crystallized. Native crystals diffract to beyond 2.5 Å resolution and isomorphous heavy-atom derivatives suitable for phase analysis have been identified. The C-terminal region of Venezuelan equine encephalitis virus (VEEV) nsP2 is responsible for proteolytic processing of the VEEV polyprotein replication complex. This action regulates the activity of the replication complex and is essential for viral replication, thus making nsP2 a very attractive target for development of VEEV therapeutics. The 338-amino-acid C-terminal region of VEEV nsP2 has been overexpressed in Escherichia coli, purified and crystallized. Crystals diffract to beyond 2.5 Å resolution and belong to the orthorhombic space group P2{sub 1}2{sub 1}2{sub 1}. Isomorphous heavy-atom derivatives suitable for phase analysis have been obtained and work on building a complete structural model is under way.

Using isotope 36Cl to study utilization of Cl by crops and distribution and movement of Cl in soil

International Nuclear Information System (INIS)

Pan Jiarong; Wen Xianfang; Tang Nianxin

1991-06-01

Results from using isotope 36 Cl show that a large quantity of Cl is absorbed and utilized by spring wheat, cotton and tobacco from the chloride fertilizers. The utilization coefficient of Cl increases with the growing time of plants and reaches peak at mature stage. The utilization coefficient of above plants are 26.72%, 3317% and 26.19% respectively. The absorption and utilization of residual Cl in soil is much smaller than that in fertilizers, and the utilization coefficient is decreasing with the increasing of growth season. For spring wheat, utilization coefficient is 12.7% in second season and 9.3% in third season. The ability of absorbing and utilizing Cl from organic materials by crops is very low and the utilization coefficient is 10% or less, that depends on circumstances. For rice the utilization coefficient is 3.1% in dry land and 24.3% in flooded land. The distribution of absorbed Cl is mainly in stalk, a little in husk and a few in seeds and roots. After irrigating water it is equivalent to 9.1 mm of rainfall in soil, the Cl moves rapidly to depth 10∼12 cm. Cl moves faster in porous soil than in clay soil, and faster in horizontal direction than in vertical direction

Thermodynamic properties of thulium and ytterbium in fused NaCl-KCl-CsCl eutectic

Energy Technology Data Exchange (ETDEWEB)

Novoselova, A., E-mail: A.Novoselova@ihte.uran.ru [Institute of High-Temperature Electrochemistry, Ural Division, Russian Academy of Science, S. Kovalevskaya Str., 22, Ekaterinburg 620990 (Russian Federation); Smolenski, V. [Institute of High-Temperature Electrochemistry, Ural Division, Russian Academy of Science, S. Kovalevskaya Str., 22, Ekaterinburg 620990 (Russian Federation)

2011-07-15

Research highlights: > Tm and Yb chloride compounds as fission products. > The investigation of electrochemical properties of lanthanides. > Determination of the apparent standard redox potentials of the couple Ln(III)/Ln(II) in fused NaCl-KCl-CsCl eutectic at (823 to 973) K. > The calculation of the basic thermodynamic properties of redox reaction in molten salt. - Abstract: This work presents the results of a study of the Tm{sup 3+}/Tm{sup 2+} and Yb{sup 3+}/Yb{sup 2+} couple redox potentials vs. Cl{sup -}/Cl{sub 2} reference electrode at the temperature range (823 to 973) K in fused NaCl-KCl-CsCl eutectic by direct potentiometric method. Initial concentrations of TmCl{sub 3} and YbCl{sub 3} in solvents did not exceed 5.0 mol%. Basic thermodynamic properties of the reactions TmCl{sub 2(l)} + 1/2 Cl{sub 2(g)} {r_reversible} TmCl{sub 3(l)} and YbCl{sub 2(l)} + 1/2 Cl{sub 2(g)} {r_reversible} YbCl{sub 3(l)} were calculated using the temperature dependencies of apparent standard potentials of the couples E{sub Tm{sup 3+}/Tm{sup 2+*}} and E{sub Yb{sup 3+}/Yb{sup 2+*}}.

cl-Supercontinuous Functions

Directory of Open Access Journals (Sweden)

D. Singh

2007-10-01

Full Text Available Basic properties of cl-supercontinuity, a strong variant of continuity, due to Reilly and Vamanamurthy [Indian J. Pure Appl. Math., 14 (1983, 767–772], who call such maps clopen continuous, are studied. Sufficient conditions on domain or range for a continuous function to be cl-supercontinuous are observed. Direct and inverse transfer of certain topological properties under cl-supercontinuous functions are studied and existence or nonexistence of certain cl-supercontinuous function with specified domain or range is outlined.

Atom-Dependent Edge-Enhanced Second-Harmonic Generation on MoS2 Monolayers.

Science.gov (United States)

Lin, Kuang-I; Ho, Yen-Hung; Liu, Shu-Bai; Ciou, Jian-Jhih; Huang, Bo-Ting; Chen, Christopher; Chang, Han-Ching; Tu, Chien-Liang; Chen, Chang-Hsiao

2018-02-14

Edge morphology and lattice orientation of single-crystal molybdenum disulfide (MoS 2 ) monolayers, a transition metal dichalcogenide (TMD), possessing a triangular shape with different edges grown by chemical vapor deposition are characterized by atomic force microscopy and transmission electron microscopy. Multiphoton laser scanning microscopy is utilized to study one-dimensional atomic edges of MoS 2 monolayers with localized midgap electronic states, which result in greatly enhanced optical second-harmonic generation (SHG). Microscopic S-zigzag edge and S-Mo Klein edge (bare Mo atoms protruding from a S-zigzag edge) terminations and the edge-atom dependent resonance energies can therefore be deduced based on SHG images. Theoretical calculations based on density functional theory clearly explain the lower energy of the S-zigzag edge states compared to the corresponding S-Mo Klein edge states. Characterization of the atomic-scale variation of edge-enhanced SHG is a step forward in this full-optical and high-yield technique of atomic-layer TMDs.

Well logging, atom and geology

International Nuclear Information System (INIS)

Serra, O.

1994-01-01

Well logging techniques exploit interactions of gamma photons and neutrons with atoms. Interactions of neutrons of different energies with atoms allow the detection and evaluation of the weight percentage of several elements composing the rocks (C, O, Si, Ca, Fe, S); spectrometry of gamma rays produced by thermal neutron absorption allows for the weight percentage determination of Si, Ca, Fe, S, Cl, H, Ti and Gd, etc. High resolution detectors (germanium doped by Li, at liquid nitrogen temperature) allow the recognition of more elements. Other techniques involving neutrons consist in determining the population in epithermal neutrons at a certain distance of the neutron source (measurement of the hydrogen index). By analyzing the intensity of the gamma flux produced by Compton scattering, the electronic and bulk densities of the rocks are measured. All these data lead to the detection and evaluation of ore deposits (uranium and potassium) and coal, and determination of the lithology, the main minerals composing the rocks, petrophysical properties... 1 fig

First remote sensing measurements of ClOOCl along with ClO and ClONO2 in activated and deactivated Arctic vortex conditions using new ClOOCl IR absorption cross sections

Directory of Open Access Journals (Sweden)

M. Birk

2010-02-01

Full Text Available Active chlorine species play a dominant role in the catalytic destruction of stratospheric ozone in the polar vortices during the late winter and early spring seasons. Recently, the correct understanding of the ClO dimer cycle was challenged by the release of new laboratory absorption cross sections (Pope et al., 2007 yielding significant model underestimates of observed ClO and ozone loss (von Hobe et al., 2007. Under this aspect, nocturnal Arctic stratospheric limb emission measurements carried out by the balloon version of the Michelson Interferometer for Passive Atmospheric Sounding (MIPAS-B from Kiruna (Sweden on 11 January 2001 and 20/21 March 2003 have been reanalyzed with regard to the chlorine reservoir species ClONO2 and the active species, ClO and ClOOCl (Cl2O2. New laboratory measurements of IR absorption cross sections of ClOOCl for various temperatures and pressures allowed for the first time the retrieval of ClOOCl mixing ratios from remote sensing measurements. High values of active chlorine (ClOx of roughly 2.3 ppbv at 20 km were observed by MIPAS-B in the cold mid-winter Arctic vortex on 11 January 2001. While nighttime ClOOCl shows enhanced values of nearly 1.1 ppbv at 20 km, ClONO2 mixing ratios are less than 0.1 ppbv at this altitude. In contrast, high ClONO2 mixing ratios of nearly 2.4 ppbv at 20 km have been observed in the late winter Arctic vortex on 20 March 2003. No significant ClOx amounts are detectable on this date since most of the active chlorine has already recovered to its main reservoir species ClONO2. The observed values of ClOx and ClONO2 are in line with the established polar chlorine chemistry. The thermal equilibrium constants between the dimer formation and its dissociation, as derived from the balloon measurements, are on the lower side of reported data and in good agreement with values recommended by von Hobe et al. (2007. Calculations with the ECHAM/MESSy Atmospheric Chemistry model (EMAC using

Mass spectrometric measurement of hydrogen isotope fractionation for the reactions of chloromethane with OH and Cl

Directory of Open Access Journals (Sweden)

F. Keppler

2018-05-01

Full Text Available Chloromethane (CH3Cl is an important provider of chlorine to the stratosphere but detailed knowledge of its budget is missing. Stable isotope analysis is a potentially powerful tool to constrain CH3Cl flux estimates. The largest degree of isotope fractionation is expected to occur for deuterium in CH3Cl in the hydrogen abstraction reactions with its main sink reactant tropospheric OH and its minor sink reactant Cl atoms. We determined the isotope fractionation by stable hydrogen isotope analysis of the fraction of CH3Cl remaining after reaction with hydroxyl and chlorine radicals in a 3.5 m3 Teflon smog chamber at 293 ± 1 K. We measured the stable hydrogen isotope values of the unreacted CH3Cl using compound-specific thermal conversion isotope ratio mass spectrometry. The isotope fractionations of CH3Cl for the reactions with hydroxyl and chlorine radicals were found to be −264±45 and −280±11 ‰, respectively. For comparison, we performed similar experiments using methane (CH4 as the target compound with OH and obtained a fractionation constant of −205±6 ‰ which is in good agreement with values previously reported. The observed large kinetic isotope effects are helpful when employing isotopic analyses of CH3Cl in the atmosphere to improve our knowledge of its atmospheric budget.

Optical properties and surface topography of CdCl2 activated CdTe thin films

Science.gov (United States)

Patel, S. L.; Purohit, A.; Chander, S.; Dhaka, M. S.

2018-05-01

The effect of post-CdCl2 heat treatment on optical properties and surface topography of evaporated CdTe thin films is investigated. The pristine and thermally annealed films were subjected to UV-Vis spectrophotometer and atomic force microscopy (AFM) to investigate the optical properties and surface topography, respectively. The absorbance is found to be maximum (˜90%) at 320°C temperature and transmittance found to be minimum and almost constant in ultraviolet and visible regions. The direct band gap is increased from 1.42 eV to 2.12 eV with post-CdCl2 annealing temperature. The surface topography revealed that the uniformity is improved with annealing temperature and average surface roughness is found in the range of 83.3-144.3 nm as well as grains have cylindrical hill-like shapes. The investigated results indicate that the post-CdCl2 treated films annealed at 320°C may be well-suitable for thin film solar cells as an absorber layer.

Reaction mechanism of oxygen atoms with unsaturated hydrocarbons by the crossed molecular beams method

Energy Technology Data Exchange (ETDEWEB)

Buss, R.J.; Baseman, R.J.; Guozhong, H.; Lee, Y.T.

1982-04-01

From a series of studies of the reaction of oxygen atoms with unsaturated hydrocarbons using the crossed molecular beam method, the dominant reaction mechanisms were found to be the simple substitution reactions with oxygen atoms replacing H, Cl, Br atom or alkyl groups. Complication due to secondary reaction was avoided by carrying out experiments under single collisions and observing primary products directly. Primary products were identified by measuring the angular and velocity distributions of products at all the mass numbers which could be detected by the mass spectrometer, and from comparison of these distributions, applying the requirement of energy and momentum conservation.

Reaction Mechanism of Oxygen Atoms with Unsaturated Hydrocarbons by the Crossed-Molecular-Beams Method

Science.gov (United States)

Buss, R. J.; Baseman, R. J.; Guozhong, H.; Lee, Y. T.

1982-04-01

From a series of studies of the reaction of oxygen atoms with unsaturated hydrocarbons using the crossed molecular beam method, the dominant reaction mechanisms were found to be the simple substitution reactions with oxygen atoms replacing H, Cl, Br atom or alkyl groups. Complication due to secondary reaction was avoided by carrying out experiments under single collisions and observing primary products directly. Primary products were identified by measuring the angular and velocity distributions of products at all the mass numbers which could be detected by the mass spectrometer, and from comparison of these distributions, applying the requirement of energy and momentum conservation.

Bibliography of electron and photon cross sections with atoms and molecules published in the 20th century. Halogen molecules

International Nuclear Information System (INIS)

Hayashi, Makoto

2003-12-01

A bibliographies of original and review reports of experiments or theories of electron and photon cross sections and also electron swarm data are presented for atomic or molecular species with specified targets. These works covered 17 atoms and 51 molecules. The present bibliography is only for halogen molecules (F 2 , Cl 2 , Br 2 , I 2 ). About 190(F 2 ), 360(Cl 2 ), 140(Br 2 ) and 240(I 2 ) papers were compiled respectively. A comprehensive author indexes for each molecule are included. The bibliography covers the period 1901 through 2000 for F 2 -I 2 . Finally, author's comments for F 2 -I 2 electron collision cross sections are given. (author)

First-principle calculations of the structural, elastic and bonding properties of Cs{sub 2}NaLnCl{sub 6} (Ln=La–Lu) cubic elpasolites

Energy Technology Data Exchange (ETDEWEB)

Ma, C.G.; Liu, D.X.; Feng, B.; Tian, Y.; Li, L. [College of Sciences, Chongqing University of Posts and Telecommunications, Chongqing 400065 (China); Brik, M.G., E-mail: mikhail.brik@ut.ee [College of Sciences, Chongqing University of Posts and Telecommunications, Chongqing 400065 (China); Institute of Physics, University of Tartu, Ravila 14C, Tartu 50411 (Estonia); Institute of Physics, Jan Dlugosz University, Armii Krajowej 13/15, PL-42200 Czestochowa (Poland)

2016-01-15

For the first time the structural, elastic and bonding properties of 15 elpasolite crystals Cs{sub 2}NaLnCl{sub 6} (Ln denotes all lanthanides from La to Lu) were calculated systematically using the CRYSTAL09 program. Several trends in the variation of these properties in relation to the atomic number Z of the Ln ions were found; in particular, the lattice parameter of these compounds decreases with Z (which can lead to the increased crystal field splittings of the 5d states for the heavier Ln ions), whereas the elastic constants and Debye temperature increase. The degree of covalency of the Ln–Cl chemical bonds is increased toward the end of the lanthanide series. - Highlights: • Structural, elastic and bonding properties of 15 cubic elpasolites Cs{sub 2}NaLnCl{sub 6} (Ln=La,…,Lu) are calculated. • Relations between these quantities and Ln atomic number were found. • Possible correlation between the elastic properties and Stokes shift is proposed.

Consequences of atomic layer etching on wafer scale uniformity in inductively coupled plasmas

Science.gov (United States)

Huard, Chad M.; Lanham, Steven J.; Kushner, Mark J.

2018-04-01

Atomic layer etching (ALE) typically divides the etching process into two self-limited reactions. One reaction passivates a single layer of material while the second preferentially removes the passivated layer. As such, under ideal conditions the wafer scale uniformity of ALE should be independent of the uniformity of the reactant fluxes onto the wafers, provided all surface reactions are saturated. The passivation and etch steps should individually asymptotically saturate after a characteristic fluence of reactants has been delivered to each site. In this paper, results from a computational investigation are discussed regarding the uniformity of ALE of Si in Cl2 containing inductively coupled plasmas when the reactant fluxes are both non-uniform and non-ideal. In the parameter space investigated for inductively coupled plasmas, the local etch rate for continuous processing was proportional to the ion flux. When operated with saturated conditions (that is, both ALE steps are allowed to self-terminate), the ALE process is less sensitive to non-uniformities in the incoming ion flux than continuous etching. Operating ALE in a sub-saturation regime resulted in less uniform etching. It was also found that ALE processing with saturated steps requires a larger total ion fluence than continuous etching to achieve the same etch depth. This condition may result in increased resist erosion and/or damage to stopping layers using ALE. While these results demonstrate that ALE provides increased etch depth uniformity, they do not show an improved critical dimension uniformity in all cases. These possible limitations to ALE processing, as well as increased processing time, will be part of the process optimization that includes the benefits of atomic resolution and improved uniformity.

Crystal structure, NMR study, dc-conductivity and dielectric relaxation studies of a new compound [C2H10N2]Cd(SCN2Cl2

Directory of Open Access Journals (Sweden)

Gargouri M.

2012-06-01

Full Text Available The crystal structure, the solid NMR spectroscopy and the complex impedance study have been carried out on [C2H10N2]CdCl2(SCN2. Characterization by single crystal X-ray crystallography shows that the cadmium atoms have à 2N2S2Cl hexa-coordination sphere, exhibiting pseudo-octahedral geometry. The cadmium atoms are bridged by two thiocyanate ions generating 1-D polymeric-chains. These chains are themselves interconnected by means of N-H…Cl(NCS hydrogen bonds originating from the organic cation [(NH32(CH22]2+. 111Cd isotropic chemical shifts span a range of 268ppm. The cadmium atom exhibits multiplets that result from 111Cd-14N spin-spin coupling. Examination of 111Cd and 13C MAS line shapes shows direct measurement of the indirect spin-spin coupling constant 2J(111Cd, 14N = 105Hz and the dipolar coupling constant of 1381Hz . Impedance spectroscopy measurements of [C2H10N2]CdCl2(SCN2 have been studied from 209Hz to 5 MHz over the temperature range 300-370 K. The Cole-Cole (Z” versus Z’ plots are fitted to two equivalent circuits models. The formalism of complex permittivity and impedance were employed to analyze the experimental data. The dc conductivity follows the Arrhenius relation with an activation energy Ea = 0.54 (3 eV.

Synthesis and molecular structures of niobocene derivatives containing Nb-Sn-Nb metallochain

International Nuclear Information System (INIS)

Skripkin, Yu.V.; Volkov, O.G.; Pasynskij, A.A.

1985-01-01

The [Cp 2 Nb(CO)] 2 SnCl 2 (1) complex is synthesized in the form of crystals with 63% yield by the Cp 2 Nb(CO)H reaction wih SnCl 4 in THF in the presence of Et 3 N. The complex 1 is also prepared by interaction of Cp 2 Nb(CO)H with Cp 2 Nb(CO)SnCl 3 with 16% yield. The crystalline more sluble analog [(CH 3 C 5 H 4 ) 2 Nb(CO)] 2 ShCl 2 (2) is extracted, which contains the chain of Nb-Sn-Nb with short Nb-Sn(2.840)2)A bonds and 140.69(5) deg angle between them. The (Cp 2 NbH) 2 Sn(Cl)Et (3) complex is prepared wih 12% yield, possessing the structure analogous to type 2. In 3 each fragment CpNb is connected with the terminal hydride (Nb-H, 1.66(1) and 1.69(1)A) atom forms shortened bond with tin atom Nb-Sn 2.868(1) and 2.856(1) A, NbSnNb angle is 129.44(5)

Electrochemical behavior of Th(IV) and its electrodeposition from ThF_4-LiCl-KCl melt

International Nuclear Information System (INIS)

Wang, Xianbin; Huang, Wei; Gong, Yu; Jiang, Feng; Zheng, Haiyang; Zhu, Tiejian; Long, Dewu; Li, Qingnuan

2016-01-01

The electrochemical behavior of Th(IV) ion on molybdenum (Mo) electrode was studied by cyclic voltammetry (CV) and square wave voltammetry (SWV) technologies at 773 K in ThF_4-LiCl-KCl melt. The reduction of Th(IV) to metal Th at −1.67 V (vs. Ag/AgCl) is a four-electron exchange process, which is quasi-reversible and diffusion-controlled. The diffusion coefficient (D) and activation energy of diffusion process for Th(IV) were determined to be 3.77 × 10"−"5 cm"2 s"−"1 and 59.2 kJ mol"−"1. The pulse potential electrolysis of ThF_4-LiCl-KCl melt revealed that 86.8% of Th(IV) can be separated from the melt based on the inductively coupled plasma atomic emission spectrometer (ICP-AES) results.

Quantitative assessment of intermolecular interactions by atomic force microscopy imaging using copper oxide tips

Science.gov (United States)

Mönig, Harry; Amirjalayer, Saeed; Timmer, Alexander; Hu, Zhixin; Liu, Lacheng; Díaz Arado, Oscar; Cnudde, Marvin; Strassert, Cristian Alejandro; Ji, Wei; Rohlfing, Michael; Fuchs, Harald

2018-05-01

Atomic force microscopy is an impressive tool with which to directly resolve the bonding structure of organic compounds1-5. The methodology usually involves chemical passivation of the probe-tip termination by attaching single molecules or atoms such as CO or Xe (refs 1,6-9). However, these probe particles are only weakly connected to the metallic apex, which results in considerable dynamic deflection. This probe particle deflection leads to pronounced image distortions, systematic overestimation of bond lengths, and in some cases even spurious bond-like contrast features, thus inhibiting reliable data interpretation8-12. Recently, an alternative approach to tip passivation has been used in which slightly indenting a tip into oxidized copper substrates and subsequent contrast analysis allows for the verification of an oxygen-terminated Cu tip13-15. Here we show that, due to the covalently bound configuration of the terminal oxygen atom, this copper oxide tip (CuOx tip) has a high structural stability, allowing not only a quantitative determination of individual bond lengths and access to bond order effects, but also reliable intermolecular bond characterization. In particular, by removing the previous limitations of flexible probe particles, we are able to provide conclusive experimental evidence for an unusual intermolecular N-Au-N three-centre bond. Furthermore, we demonstrate that CuOx tips allow the characterization of the strength and configuration of individual hydrogen bonds within a molecular assembly.

Influence of 8-aminoquinoline on the corrosion behaviour of copper in 0.1 M NaCl

International Nuclear Information System (INIS)

Cubillos, M.; Sancy, M.; Pavez, J.; Vargas, E.; Urzua, R.; Henriquez-Roman, J.; Tribollet, B.; Zagal, J.H.; Paez, M.A.

2010-01-01

The corrosion behaviour of copper in aerated 0.1 M NaCl solution in presence of 8-aminoquinoline (8-AQ), using open circuit potential (OCP) measurements, potentiodynamic polarization, electrochemical impedance spectroscopy (EIS) measurements and atomic force microscopy (AFM), was studied. The measurements revealed that the effect of 8-AQ is dependent on its concentration. For concentrations up to 10 -3 M, the organic compound displaces the corrosion potential following no trend and also reduces the anodic current. In contrast, for concentrations higher than 10 -3 , 8-AQ reduces markedly both, the anodic and cathodic currents and consequently, the corrosion current density of copper. After 9 days of exposure in chloride solution, containing the organic compound, potentiodynamic polarization analyses showed a significant reduction in the anodic response and a less significant reduction in the cathodic response, which is associated with a film formed at the copper surface of about 10 μm in thickness and visually observed by a colour change of the copper surface. In order to elucidate the most likely interaction between the 8-AQ molecule and the different molecular structures probably present on copper surfaces in chloride solutions, some results obtained from theoretical calculations are presented. The following molecular structures were considered: CuCl molecule, CuCl 2 - complex, and little copper clusters defect representation built as five atoms on C 4v symmetry. Thus, based on the geometric, energetic, frontier orbital, and Total Electronic Density analysis done for the optimized states found for the systems investigated, we suggest that the most probable interaction of 8-AQ proceeds above CuCl units and free copper sites.

Visible Light Emission from Atomic Scale Patterns Fabricated by the Scanning Tunneling Microscope

DEFF Research Database (Denmark)

Thirstrup, C.; Sakurai, M.; Stokbro, Kurt

1999-01-01

Scanning tunneling microscope (STM) induced light emission from artificial atomic scale structures comprising silicon dangling bonds on hydrogen-terminated Si(001) surfaces has been mapped spatially and analyzed spectroscopically in the visible spectral range. The light emission is based on a novel...

Deposition of O atomic layers on Si(100) substrates for epitaxial Si-O superlattices: investigation of the surface chemistry

Energy Technology Data Exchange (ETDEWEB)

Jayachandran, Suseendran, E-mail: suseendran.jayachandran@imec.be [KU Leuven, Department of Metallurgy and Materials, Castle Arenberg 44, B-3001 Leuven (Belgium); IMEC, Kapeldreef 75, 3001 Leuven (Belgium); Delabie, Annelies; Billen, Arne [KU Leuven, Department of Chemistry, Celestijnenlaan 200F, B-3001 Leuven (Belgium); IMEC, Kapeldreef 75, 3001 Leuven (Belgium); Dekkers, Harold; Douhard, Bastien; Conard, Thierry; Meersschaut, Johan; Caymax, Matty [IMEC, Kapeldreef 75, 3001 Leuven (Belgium); Vandervorst, Wilfried [KU Leuven, Department of Physics and Astronomy, Celestijnenlaan 200D, B-3001 Leuven (Belgium); IMEC, Kapeldreef 75, 3001 Leuven (Belgium); Heyns, Marc [KU Leuven, Department of Metallurgy and Materials, Castle Arenberg 44, B-3001 Leuven (Belgium); IMEC, Kapeldreef 75, 3001 Leuven (Belgium)

2015-01-01

Highlights: • Atomic layer is deposited by O{sub 3} chemisorption reaction on H-terminated Si(100). • O-content has critical impact on the epitaxial thickness of the above-deposited Si. • Oxygen atoms at dimer/back bond configurations enable epitaxial Si on O atomic layer. • Oxygen atoms at hydroxyl and more back bonds, disable epitaxial Si on O atomic layer. - Abstract: Epitaxial Si-O superlattices consist of alternating periods of crystalline Si layers and atomic layers of oxygen (O) with interesting electronic and optical properties. To understand the fundamentals of Si epitaxy on O atomic layers, we investigate the O surface species that can allow epitaxial Si chemical vapor deposition using silane. The surface reaction of ozone on H-terminated Si(100) is used for the O deposition. The oxygen content is controlled precisely at and near the atomic layer level and has a critical impact on the subsequent Si deposition. There exists only a small window of O-contents, i.e. 0.7–0.9 atomic layers, for which the epitaxial deposition of Si can be realized. At these low O-contents, the O atoms are incorporated in the Si-Si dimers or back bonds (-OSiH), with the surface Si atoms mainly in the 1+ oxidation state, as indicated by infrared spectroscopy. This surface enables epitaxial seeding of Si. For O-contents higher than one atomic layer, the additional O atoms are incorporated in the Si-Si back bonds as well as in the Si-H bonds, where hydroxyl groups (-Si-OH) are created. In this case, the Si deposition thereon becomes completely amorphous.

A temperature dependence kinetics study of the reactions of Cl/2-P-3/2/ with O3, CH4, and H2O2

Science.gov (United States)

Watson, R.; Machado, G.; Fischer, S.; Davis, D. D.

1976-01-01

The temperature dependence of two chlorine atom reactions of considerable fundamental importance to stratospheric chemistry was studied using the technique of flash photolysis-resonance fluorescence. The reactions of interest were: (1) Cl + O3 yields ClO + O2 studied at 220-350 K, and (2) Cl + CH4 yields CH3 + HCl studied at 218-401 K. In addition, the reaction Cl + H2O2 yields HCl + HO2 was studied at 300 K. The corresponding rate constants are provided for the three reactions. The new rate data implies the need to revise downward by a factor of 2.4-3 the magnitude of the ozone perturbation due to the presence of ClO/x/ species in the stratosphere, predicted by earlier model calculations.

Reduction behavior of UO22+ in molten LiCl-RbCl and LiCl-KCl eutectics by using tungsten

Science.gov (United States)

Nagai, Takayuki; Uehara, Akihiro; Fujii, Toshiyuki; Yamana, Hajimu

2013-08-01

The reduction of uranium from UO22+ to UO2+ or U4+ in molten LiCl-RbCl and LiCl-KCl eutectics was examined by using tungsten and chlorine gas. Spectrophotometric technique was adopted to determine the concentration of uranium species. When tungsten was immersed into the LiCl-RbCl eutectic melt at 400 °C without supplying chlorine gas, 36% of the total weight of the hexavalent of UO22+ was reduced to the pentavalent of UO2+. Under purging chlorine gas into the melt, 96% of UO22+ was reduced to the tetravalent of U4+. Tungsten oxy-chloride of WOCl4 was produced via the reductions of UO22+, which was volatized from the melt and adsorbed on the upper part of experimental cell. On the other hand, 84% of UO22+ in the LiCl-KCl eutectic melt at 500 °C was reduced to U4+ by using tungsten and chlorine gas.

Reactions UF4 - ClO2F and UF5 - ClO2F

International Nuclear Information System (INIS)

Benoit, Raymond; Besnard, Ginette; Hartmanshenn, Olivier; Luce, Michel; Mougin, Jacques; Pelissie, Jean

1970-02-01

The study of the reaction UF 4 - ClO 2 F between 0 deg. and 100 deg. C, by various techniques (micro-sublimation, isopiestic method, IR and UV spectrography, thermogravimetry and X-ray diffraction) shows that intermediate steps are possible before the production of UF 5 . The whole reaction may be schematised by two equations: (1) n UF 4 + ClO 2 F → n UF x + ClO 2 (4 4 + ClO 2 F → UF x + 1/2 Cl 2 + O 2 . The more the temperature rises, the more the second equation becomes experimentally verified. The reaction at 0 deg. C between UF 5 and ClO 2 F may be represented by: UF 5 + ClO 2 F → UF 6 ClO 2 . The reactions: UF 5 + ClO 2 F → UF 6 + ClO 2 , UF 5 + ClO 2 F → UF 6 + 1/2 Cl 2 + O 2 are verified, the first and the second at 25 deg. C., the second from 50 deg. to 150 deg. C. From the results of AGRON it is possible to predict the residual solids before complete volatilization as UF 6 . The IR spectra of ClO 2 F adsorbed on UF 4 and UF x at 60 deg. C have been compared with those of gaseous ClO 2 F and UF 6 adsorbed on UF 4 . (authors) [fr

Catalysis of the reduction of Tl+ and of CH2Cl2 by colloidal silver in aqueous solution

International Nuclear Information System (INIS)

Henglein, A.

1979-01-01

(CH 3 ) 2 COH radicals (1-hydroxy-1-methylethyl) do not reduce Tl + or CH 2 CL 2 in homogeneous aqueous solution. In the presence of 2.5 x 10 -4 g atom/L of colloidal silver, Tl + is reduced to yield colloidal thallium, and CH 2 Cl 2 to yield Cl - plus CH 3 Cl. These reactions occur in competition with the silver-catalyzed reduction of water. Tl + is reduced in a one-electron transfer reaction and CH 2 Cl 2 in a two-electron transfer process. The effects are understood in terms of the colloidal particles acting as a pool for electrons that is continuously charged by the organic radicals and discharged by water or dissolved substrates. The specific rate for the CH 2 Cl 2 reduction at the silver pool is 4.3 x 10 3 times greater than that of the water reduction. Electrochemical considerations are carried out to estimate a stationary potential of -0.62 V (vs the standard hydrogen electrode) for the electron pool and to discuss the energetics of the observed reactions and tha materials handling point of view, are being determined

CL316,243, a β3-adrenergic receptor agonist, induces muscle hypertrophy and increased strength.

Science.gov (United States)

Puzzo, Daniela; Raiteri, Roberto; Castaldo, Clotilde; Capasso, Raffaele; Pagano, Ester; Tedesco, Mariateresa; Gulisano, Walter; Drozd, Lisaveta; Lippiello, Pellegrino; Palmeri, Agostino; Scotto, Pietro; Miniaci, Maria Concetta

2016-11-22

Studies in vitro have demonstrated that β3-adrenergic receptors (β3-ARs) regulate protein metabolism in skeletal muscle by promoting protein synthesis and inhibiting protein degradation. In this study, we evaluated whether activation of β3-ARs by the selective agonist CL316,243 modifies the functional and structural properties of skeletal muscles of healthy mice. Daily injections of CL316,243 for 15 days resulted in a significant improvement in muscle force production, assessed by grip strength and weight tests, and an increased myofiber cross-sectional area, indicative of muscle hypertrophy. In addition, atomic force microscopy revealed a significant effect of CL316,243 on the transversal stiffness of isolated muscle fibers. Interestingly, the expression level of mammalian target of rapamycin (mTOR) downstream targets and neuronal nitric oxide synthase (NOS) was also found to be enhanced in tibialis anterior and soleus muscles of CL316,243 treated mice, in accordance with previous data linking β3-ARs to mTOR and NOS signaling pathways. In conclusion, our data suggest that CL316,243 systemic administration might be a novel therapeutic strategy worthy of further investigations in conditions of muscle wasting and weakness associated with aging and muscular diseases.

Cyclic voltammetric study of the reduction of U(III) to uranium metal in molten LiCl-NaCl-CaCl2-BaCl2-UCl3

International Nuclear Information System (INIS)

Poa, D.S.; Tomczuk, Z.; Steunenberg, R.K.

1986-01-01

Cyclic voltammetry was used to investigate the electrochemistry of the reduction of UCl 3 to uranium metal in molten LiCl-NaCl-CaCl 2 -BaCl 2 (49.7-8.0-26.5-15.8 mol %) containing dissolved UCl 3 . The purpose of the study was to obtain information on the kinetics of the reaction, which will be used in the design of electrorefining equipment for the reprocessing of core and blanket fuel discharged from the Integral Fast Reactor (IFR). The electrorefining operation employs the above salt as the electrolyte and a liquid cadmium pool as the anode

Variation in yield ratios of fragment ions and of ion-pairs from CF2Cl2 following monochromatic soft X-ray absorption

International Nuclear Information System (INIS)

Suzuki, I.H.; Saito, N.; Bozek, J.D.

1995-01-01

Fragment ions produced from CF 2 Cl 2 have been measured from 44 to 1200eV using a time-of-flight mass spectrometer and monochromatized synchrotron radiation. Positively charged ion pairs from this molecule were observed in the inner-shell excitation regions using a Selected photoion-photoion coincidence technique. Obtained yield ratios of fragment ions indicate that the atomic chlorine ion, Cl + , has the greatest intensity at all photon energies above 60eV and exhibits a steep increase at the Cl L 2,3 -edges. Some fragment ions, in particular CF 2 + , have a clear intensity increase at the transitions of inner-shell electrons to unoccupied molecular orbitals. The ion pair F + - Cl + exhibits the highest yield at most photon energies, and some of the branching ratios for ion-pair production changed significantly near the Cl L 2,3 -edges. (author)

Molecular dynamics simulations of the effect of NaCl-doping on the calcination characteristics in desulfurization processes

Energy Technology Data Exchange (ETDEWEB)

Murakami, T.; Kurita, N.; Naruse, I. [Toyohashi University of Technology, Toyohashi (Japan)

2003-03-01

Desulfurization performance of wasted seashells was found to be over twice as high as that of limestone, which was currently used as a desulfurizer in fluidized bed coal combustors. NaCl-doping into limestone was also found to be effective in improving the desulfurization efficiency. From X-ray diffraction (XRD) analyses of calcined seashell, limestone and NaCl-doped limestone, on the other hand, not only the calcined seashell but also the NaCl-doped limestone had strong peaks of CaO crystal, and those two materials also had high desulfurization activity. This improvement was hypothesized to be due to NaCl causing a change in the crystal structure of CaO. In order to elucidate the effect of NaCl addition on the CaO crystal structure in the incineration of CaCO{sub 3} the change of structures was simulated by means of molecular dynamics simulations of CaO. In the simulation one molecule of NaCl was exchanged into one molecule of CaO. A pair correlation functions and the distances between Ca and O atoms, which were obtained by the simulations, were compared with those from the crystal CaO. NaCl-doping affected the crystalization temperature of CaO. The crystallization temperature increased due to adding a little bit of NaCl. From the result of the pair correlation functions obtained in NaCl-doped CaO, the difference of the potential energy of NaCl from that of CaO seemed to contribute to the crystallization of the bulk of CaO. The simulation and experimental results obtained suggested that NaCl-doping contributed to crystallizing the CaO molecules.

Electrodeposition of Isolated Platinum Atoms and Clusters on Bismuth-Characterization and Electrocatalysis.

Science.gov (United States)

Zhou, Min; Dick, Jeffrey E; Bard, Allen J

2017-12-06

We describe a method for the electrodeposition of an isolated single Pt atom or small cluster, up to 9 atoms, on a bismuth ultramicroelectrode (UME). This deposition was immediately followed by electrochemical characterization via the hydrogen evolution reaction (HER) that occurs readily on the electrodeposited Pt but not on Bi. The observed voltammetric current plateau, even for a single atom, which behaves as an electrode, allows the estimation of deposit size. Pt was plated from solutions of femtomolar PtCl 6 2- , which allowed precise control of the arrival of ions and thus the plating rate on the Bi UME, to one ion every few seconds. This allowed the atom-by-atom fabrication of isolated platinum deposits, ranging from single atoms to 9-atom clusters. The limiting currents in voltammetry gave the size and number of atoms of the clusters. Given the stochasticity of the plating process, we show that the number of atoms plated over a given time (10 and 20 s) follows a Poisson distribution. Taking the potential at a certain current density as a measure of the relative rate of the HER, we found that the potential shifted positively as the size increased, with single atoms showing the largest overpotentials compared to bulk Pt.

Comparison of detector systems for the separation of {sup 36}Cl and {sup 36}S with a 3-MV tandem

Energy Technology Data Exchange (ETDEWEB)

Orlowski, Tobias, E-mail: a0447924@unet.univie.ac.a [VERA Laboratory, Fakultaet fuer Physik, Universitaet Wien, Waehringer Str. 17, Wien 1090 (Austria); Forstner, Oliver; Golser, Robin; Kutschera, Walter [VERA Laboratory, Fakultaet fuer Physik, Universitaet Wien, Waehringer Str. 17, Wien 1090 (Austria); Merchel, Silke [CEREGE, CNRS-IRD-Universite Aix-Marseille, Europole Mediterraneen de L' Arbois, BP 80, Aix-en-Provence 13545 (France); Forschungszentrum Dresden-Rossendorf, D-01314 Dresden (Germany); Martschini, Martin; Priller, Alfred; Steier, Peter [VERA Laboratory, Fakultaet fuer Physik, Universitaet Wien, Waehringer Str. 17, Wien 1090 (Austria); Vockenhuber, Christof [HPK H 31, Institut fuer Teilchenphysik, ETH Zuerich, Schafmattstr. 20 CH-8093 Zuerich (Switzerland); Wallner, Anton [VERA Laboratory, Fakultaet fuer Physik, Universitaet Wien, Waehringer Str. 17, Wien 1090 (Austria)

2010-04-15

The possibility of detecting {sup 36}Cl for geological exposure dating has been explored for several years at VERA (the Vienna Environmental Research Accelerator). First results on real samples were obtained with an ionization chamber (developed at the ETH/PSI, Zuerich, Switzerland) with two anodes. To improve the suppression of {sup 36}S, we equipped the ionization chamber with an exit window and added a Time-of-Flight (TOF) system with a double-sided silicon strip detector (50 x 50 mm{sup 2}) as stop detector. We optimized the TOF setup by using silicon nitride foils to reduce scattering tails in the energy spectra. At 3 MV terminal voltage, corresponding to a particle energy of 24 MeV of {sup 36}Cl{sup 7+}, we achieved a {sup 36}S{sup 7+}-suppression of 21,500 (50% {sup 36}Cl-detector-efficiency).

Oxidative addition of the chloromethane C-Cl bond to Pd, an ab initio benchmark and DFT validation study

NARCIS (Netherlands)

de Jong, G.T.; Bickelhaupt, F.M.

2006-01-01

We have computed a state-of-the-art benchmark potential energy surface (PES) for the archetypal oxidative addition of the chloromethane C-Cl bond to the palladium atom and have used this to evaluate the performance of 26 popular density functionals, covering LDA, GGA, meta-GGA, and hybrid density

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

Science.gov (United States)

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

2012-06-21

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

Controlling the surface termination of NdGaO3 (110): the role of the gas atmosphere.

Science.gov (United States)

Cavallaro, Andrea; Harrington, George F; Skinner, Stephen J; Kilner, John A

2014-07-07

In this work the effect of gas atmosphere on the surface termination reconstruction of single crystal NdGaO3 (110) (NGO) during thermal annealing was analyzed. Using Low Energy Ion Scattering (LEIS) it has been possible to study the chemical composition of the first atomic layer of treated NGO single crystal samples. NGO has been analyzed both as-received and after a specific thermal treatment at 1000 °C under different gas fluxes (argon, nitrogen, static air, synthetic air, nitrogen plus 5% hydrogen and wet synthetic air respectively). Thermal annealing of perovskite single crystals, as already reported in the literature, is used to obtain a fully A-cation surface termination. Nevertheless the effect of the gas-atmosphere on this process has not been previously reported. By the use of sequential low energy Ar(+) sputtering combined with the primary ion LEIS analysis, the reconstruction of the outermost atomic layers has allowed the clarification of the mechanism of NGO neodymium surface enrichment. It is proposed that the gallium at the surface is submitted to a reduction/evaporation mechanism caused by low oxygen partial pressure and/or high water pressure in the vector gas. Below the first surface atomic layers of an as-received NGO single-crystal a gallium-rich phase has also been observed.

Intermediate-range chemical ordering of cations in molten RbCl-AgCl

Energy Technology Data Exchange (ETDEWEB)

Tahara, S. [Department of Physics and Earth Sciences, Faculty of Science, University of the Ryukyus, Okinawa 903-0213 (Japan); Research and Utilization Division, Japan Synchrotron Radiation Research Institute (JASRI, SPring-8), Hyogo 679-5198 (Japan); Kawakita, Y. [J-PARC Center, Japan Atomic Energy Agency (JAEA), Ibaraki 319-1195 (Japan); Shimakura, H. [Faculty of Pharmacy, Niigata University of Pharmacy and Applied Life Sciences, Niigata 956-8603 (Japan); Ohara, K. [Research and Utilization Division, Japan Synchrotron Radiation Research Institute (JASRI, SPring-8), Hyogo 679-5198 (Japan); Fukami, T. [Department of Physics and Earth Sciences, Faculty of Science, University of the Ryukyus, Okinawa 903-0213 (Japan); Takeda, S. [Department of Physics, Faculty of Sciences, Kyushu University, Fukuoka 812-8581 (Japan)

2015-07-28

A first sharp diffraction peak (FSDP) is observed in the X-ray total structure factor of a molten mixture of RbCl-AgCl, while both pure melts of RbCl and AgCl do not exhibit FSDP individually. Molecular dynamics simulations were performed to investigate the origin of the FSDP with the polarizable ion model (PIM). Coexistence of covalent Ag–Cl and ionic Rb–Cl bonds leads the system to evolve intermediate range ordering, which is simulated by introducing the induced polarization in different ways between Ag–Cl with fully polarizable treatment based on Vashishta-Raman potential and Rb–Cl with suppression over-polarization in the nearest neighbor contribution based on Born-Meyer potential. The partial structure factors for both the Ag–Ag and Rb–Rb correlations, S{sub AgAg}(Q) and S{sub RbRb}(Q), show a positive contribution to the FSDP, while S{sub AgRb}(Q) for the Ag–Rb correlation exhibits a negative contribution, indicating that Ag and Rb ions are distributed in an alternating manner within the intermediate-range length scale. The origin of the intermediate-range chemical ordering of cations can be ascribed to the preferred direction of the dipole moments of anions in the PIM.

Intermediate-range chemical ordering of cations in molten RbCl-AgCl

International Nuclear Information System (INIS)

Tahara, S.; Kawakita, Y.; Shimakura, H.; Ohara, K.; Fukami, T.; Takeda, S.

2015-01-01

A first sharp diffraction peak (FSDP) is observed in the X-ray total structure factor of a molten mixture of RbCl-AgCl, while both pure melts of RbCl and AgCl do not exhibit FSDP individually. Molecular dynamics simulations were performed to investigate the origin of the FSDP with the polarizable ion model (PIM). Coexistence of covalent Ag–Cl and ionic Rb–Cl bonds leads the system to evolve intermediate range ordering, which is simulated by introducing the induced polarization in different ways between Ag–Cl with fully polarizable treatment based on Vashishta-Raman potential and Rb–Cl with suppression over-polarization in the nearest neighbor contribution based on Born-Meyer potential. The partial structure factors for both the Ag–Ag and Rb–Rb correlations, S AgAg (Q) and S RbRb (Q), show a positive contribution to the FSDP, while S AgRb (Q) for the Ag–Rb correlation exhibits a negative contribution, indicating that Ag and Rb ions are distributed in an alternating manner within the intermediate-range length scale. The origin of the intermediate-range chemical ordering of cations can be ascribed to the preferred direction of the dipole moments of anions in the PIM

ZnCl 2- and NH 4Cl-hydroponics gel electrolytes for zinc-carbon batteries

Science.gov (United States)

Khalid, N. H.; Ismail, Y. M. Baba; Mohamad, A. A.

Absorbency testing is used to determine the percentage of ZnCl 2 or NH 4Cl solution absorbed by a hydroponics gel (HPG). It is found that the absorbency of ZnCl 2 or NH 4Cl solution decreases with increasing solution concentration. The conductivity of ZnCl 2- and NH 4Cl-HPG electrolytes is dependent on the solution concentration. A mixture of salt solution with HPG yields excellent gel polymer electrolytes with conductivities of 0.026 and 0.104 S cm -1 at 3 M ZnCl 2 and 7 M NH 4Cl, respectively. These gel electrolytes are then used to produce zinc-carbon cells. The fabricated cells give capacities of 8.8 and 10.0 mAh, have an internal resistance of 25.4 and 19.8 Ω, a maximum power density of 12.7 and 12.2 mW cm -2, and a short-circuit current density of 29.1 and 33.9 mA cm -2 for ZnCl 2- and NH 4Cl-HPG electrolytes, respectively.

Anomalous H/D isotope effect on 35Cl NQR frequencies and H/D isotope effect on 1H MAS NMR spectra in pyrrolidinium p-chlorobenzoate

International Nuclear Information System (INIS)

Nakano, Ryo; Honda, Hisashi; Nakata, Eiichi; Takamizawa, Satoshi; Noro, Sumiko; Kimura, Taiki; Kyo, Shin-shin; Ishimaru, Shin'ichi; Miyake, Ryosuke

2010-01-01

An anomalous isotope effect was observed in the 35 Cl NQR frequency of pyrrolidinium p-chlorobenzoate (C 4 H 8 NH 2 + ·ClC 6 H 4 COO - ) by deuterium substitution of hydrogen atoms which form two kinds of N-H...O type hydrogen bonds. Large negative frequency shifts of the 35 Cl resonance lines, reaching 309 kHz at 77 K and 267 kHz at 293 K, were obtained upon deuteration, although the Cl atom in the molecule formed no hydrogen bonds in the crystal. 1 H MAS NMR lines showed significant changes by the deuterium substitution, while in contrast, small shifts of 13 C CP/MAS NMR signals were obtained. Our measurements of 1 H NMR spin-lattice relaxation times (T 1 ) suggested that the H/D isotope shifts detected from the 35 Cl NQR frequencies and 1 H NMR spectra are due to structural changes rather than molecular dynamics. Single-crystal X-ray diffraction measurements showed two remarkable H/D isotope differences in the molecular arrangements, (1) the N-H length along the crystallographic a axis became 1 pm shorter, and (2) the dihedral angle between benzene and the pyrrolidine ring changed by 1.1(2)deg upon deuteration. Using density functional theory estimations, the anomalous 35 Cl NQR frequency shifts and 1 H MAS NMR line-shape changes could be explained by the dihedral angle change rather than the N-H length difference. (author)

Electric conductivity of PCl{sub 5}-ZrCl{sub 4}, PCl{sub 5}-TaCl{sub 5}, and PCl{sub 5}-MoCl{sub 5} molten mixtures; Ehlektroprovodnost` rasplavlennykh sistem PCl{sub 5}-ZrCl{sub 4}, PCl{sub 5}-TaCl{sub 5}, i PCl{sub 5}-MoCl{sub 5}

Energy Technology Data Exchange (ETDEWEB)

Salyulev, A B; Red` kin, A A; Moskalenko, N I [Inst. Vysokotemperaturnoj Ehlektrokhimii UrO RAN, Ekaterinburg (Russian Federation)

1997-05-01

When mixing individual molecular melts of PCl{sub 5} with ZrCl{sub 4}, TaCl{sub 5} or with MoCl{sub 5}, an essential (by several orders) increase in electric conductivity (up to 0.02-0.1 Ohm{sup -1}{center_dot}cm{sup -1}), which stems, in all probability, from the appearance of complex ions PCl{sub 4}{sup +}, ZrCl{sub 5}{sup -}, ZrCl{sub 6}{sup 2-}, TaCl{sub 5}{sup -} and MoCl{sub 6}{sup -} in the molten mixtures as a result of chemical interaction. 12 refs., 3 figs., 1 tab.

Hydrothermal crystallization of amorphous titania films deposited using low temperature atomic layer deposition

Energy Technology Data Exchange (ETDEWEB)

Mitchell, D.R.G. [Institute of Materials Engineering, ANSTO, PMB 1, Menai, NSW 2234 (Australia)], E-mail: drm@ansto.gov.au; Triani, G.; Zhang, Z. [Institute of Materials Engineering, ANSTO, PMB 1, Menai, NSW 2234 (Australia)

2008-10-01

A two stage process (atomic layer deposition, followed by hydrothermal treatment) for producing crystalline titania thin films at temperatures compatible with polymeric substrates (< 130 deg. C) has been assessed. Titania thin films were deposited at 80 deg. C using atomic layer deposition. They were extremely flat, uniform and almost entirely amorphous. They also contained relatively high levels of residual Cl from the precursor. After hydrothermal treatment at 120 deg. C for 1 day, > 50% of the film had crystallized. Crystallization was complete after 10 days of hydrothermal treatment. Crystallization of the film resulted in the formation of coarse grained anatase. Residual Cl was completely expelled from the film upon crystallization. As a result of the amorphous to crystalline transformation voids formed at the crystallization front. Inward and lateral crystal growth resulted in voids being localized to the film/substrate interface and crystallite perimeters resulting in pinholing. Both these phenomena resulted in films with poor adhesion and film integrity was severely compromised.

Energy-related atomic and molecular structure and scattering studies. Annual progress report, July 1, 1980-June 30, 1981

International Nuclear Information System (INIS)

Bederson, B.

1981-02-01

The basic goals of this program concern the experimental determination of properties of atoms and molecules and molecular clusters that are important in a wide range of energy-related processes, in particular, measurements of polarizabilities of highly polar molecules and their polymers, and of a number of important atomic elements distributed through the periodic table, as well as of the scattering of low-energy electrons by these same systems. The most significant scientific accomplishment of the program during the past year has been the completion of measurements of the dc electric dipole polarizabilities of a number of alkali halide dimers [(KCl) 2 , (RbCl) 2 , (CsCl) 2 , (KF) 2 , and (CsF) 2 ]. An experiment was completed to measure the total cross sections for the scattering of low-energy electrons by atomic lithium, a very significant experimental test of a relatively simple, many-body system, which is amenable to elaborate computational determination

Estimation of the basicity of the donor strength of terminal groups in cationic polymethine dyes

Science.gov (United States)

Kachkovsky, Alexey; Obernikhina, Nataliya; Prostota, Yaroslav; Naumenko, Antonina; Melnyk, Dmitriy; Yashchuk, Valeriy

2018-02-01

The well-known conception of the basicity of the terminal groups in the cationic polymethine dyes showing their donor properties is examined (considered) in detail. The various approachs are proposed to quantitative quantum-chemical estimation of a donor strength of the terminal groups in cationic polymethine dyes: shift of the frontier levels upon introducing terminal residues in comparison with unsybstituted polymethine cation; transferring of the electron density from the terminal groups to the polymethine chain and hence manifested itself as a redistribution of total positive charge between molecular fragments; changes of the charge alternation at carbon atoms along the chain. All approach correlate between them and agree with the concept of the basicity as a capability of terminal heterocycles to show its donor properties in the polymethine dyes. The results of the fulfilled calculations of numerous examples are presented; the proposed parameters point correctly the tendency in the change donor strength upon varying of the chemical constitution: the dimension of cycle, introducing of various heteroatoms, linear or angular annelating by benzene ring; as well as direct to take into consideration the existence of local levels.

Electronic properties of graphene nano-flakes: energy gap, permanent dipole, termination effect, and Raman spectroscopy.

Science.gov (United States)

Singh, Sandeep Kumar; Neek-Amal, M; Peeters, F M

2014-02-21

The electronic properties of graphene nano-flakes (GNFs) with different edge passivation are investigated by using density functional theory. Passivation with F and H atoms is considered: C(N(c)) X(N(x)) (X = F or H). We studied GNFs with 10 GNFs and enhance the electric polarization, (iii) the mutual interaction of bilayer GNFs can be understood by dipole-dipole interaction which were found sensitive to the relative orientation of the GNFs, (iv) the permanent dipoles depend on the edge terminated atom, while the energy gap is independent of it, and (v) the presence of heptagon and pentagon defects in the GNFs results in the largest difference between the energy of the spin-up and spin-down electrons which is larger for the H-passivated GNFs as compared to F-passivated GNFs. Our study shows clearly the effect of geometry, size, termination, and bilayer on the electronic properties of small GNFs. This study reveals important features of graphene nano-flakes which can be detected using Raman spectroscopy.

OpenCL programming guide

CERN Document Server

Munshi, Aaftab; Mattson, Timothy G; Fung, James; Ginsburg, Dan

2011-01-01

Using the new OpenCL (Open Computing Language) standard, you can write applications that access all available programming resources: CPUs, GPUs, and other processors such as DSPs and the Cell/B.E. processor. Already implemented by Apple, AMD, Intel, IBM, NVIDIA, and other leaders, OpenCL has outstanding potential for PCs, servers, handheld/embedded devices, high performance computing, and even cloud systems. This is the first comprehensive, authoritative, and practical guide to OpenCL 1.1 specifically for working developers and software architects. Written by five leading OpenCL authorities, OpenCL Programming Guide covers the entire specification. It reviews key use cases, shows how OpenCL can express a wide range of parallel algorithms, and offers complete reference material on both the API and OpenCL C programming language. Through complete case studies and downloadable code examples, the authors show how to write complex parallel programs that decompose workloads across many different devices. They...

The importance of dye chemistry and TiCl4 surface treatment in the behavior of Al2O3 recombination barrier layers deposited by atomic layer deposition in solid-state dye-sensitized solar cells

KAUST Repository

Brennan, Thomas P.

2012-01-01

Atomic layer deposition (ALD) was used to fabricate Al 2O 3 recombination barriers in solid-state dye-sensitized solar cells (ss-DSSCs) employing an organic hole transport material (HTM) for the first time. Al 2O 3 recombination barriers of varying thickness were incorporated into efficient ss-DSSCs utilizing the Z907 dye adsorbed onto a 2 μm-thick nanoporous TiO 2 active layer and the HTM spiro-OMeTAD. The impact of Al 2O 3 barriers was also studied in devices employing different dyes, with increased active layer thicknesses, and with substrates that did not undergo the TiCl 4 surface treatment. In all instances, electron lifetimes (as determined by transient photovoltage measurements) increased and dark current was suppressed after Al 2O 3 deposition. However, only when the TiCl 4 treatment was eliminated did device efficiency increase; in all other instances efficiency decreased due to a drop in short-circuit current. These results are attributed in the former case to the similar effects of Al 2O 3 ALD and the TiCl 4 surface treatment whereas the insulating properties of Al 2O 3 hinder charge injection and lead to current loss in TiCl 4-treated devices. The impact of Al 2O 3 barrier layers was unaffected by doubling the active layer thickness or using an alternative ruthenium dye, but a metal-free donor-π-acceptor dye exhibited a much smaller decrease in current due to its higher excited state energy. We develop a model employing prior research on Al 2O 3 growth and dye kinetics that successfully predicts the reduction in device current as a function of ALD cycles and is extendable to different dye-barrier systems. © This journal is the Owner Societies 2012.

Single OR molecule and OR atomic circuit logic gates interconnected on a Si(100)H surface

International Nuclear Information System (INIS)

Ample, F; Joachim, C; Duchemin, I; Hliwa, M

2011-01-01

Electron transport calculations were carried out for three terminal OR logic gates constructed either with a single molecule or with a surface dangling bond circuit interconnected on a Si(100)H surface. The corresponding multi-electrode multi-channel scattering matrix (where the central three terminal junction OR gate is the scattering center) was calculated, taking into account the electronic structure of the supporting Si(100)H surface, the metallic interconnection nano-pads, the surface atomic wires and the molecule. Well interconnected, an optimized OR molecule can only run at a maximum of 10 nA output current intensity for a 0.5 V bias voltage. For the same voltage and with no molecule in the circuit, the output current of an OR surface atomic scale circuit can reach 4 μA.

Study of electron impact inelastic scattering of chlorine molecule (Cl2)

Science.gov (United States)

Yadav, Hitesh; Vinodkumar, Minaxi; Limbachiya, Chetan; Vinodkumar, P. C.

2018-02-01

A theoretical study is carried out for electron interactions with the chlorine molecule (Cl2) for incident energies ranging from 0.01 to 5000 eV. This wide range of energy has allowed us to investigate a variety of processes and report data on symmetric excitation energies, dissociative electron attachment (DEA), total excitation cross sections, and ionization cross section (Q ion) along with total inelastic cross sections (Q inel). The present study is important since Cl2 is a prominent gas for plasma etching and its anionic atoms are important in the etching of semiconductor wafers. In order to compute the total inelastic cross sections, we have employed the ab initio R-matrix method (0.01 to 15 eV) together with the spherical complex optical potential method (∼15 to 5000 eV). The R-matrix calculations are performed using a close coupling method, and we have used DEA estimator via Quantemol-N to calculate the DEA fragmentation and cross sections. The present study finds overall good agreement with the available experimental data. Total excitation and inelastic cross sections of e-{{{Cl}}}2 scattering for a wide energy range (0.01 to 5 keV) are reported for the first time, to the best of our knowledge.

UV laser-induced histone-DNA crosslinking proceeds via the N-terminal tails

International Nuclear Information System (INIS)

Stefanovski, V.; Dimitrov, S.; Angelov, D.; Keskinova, E.; Pashev, I.

1990-01-01

The covalent crosslinking of histones to DNA by UV laser irradiation is accomplished solely via the N-terminal part of the molecule. Irradiated isolated calfthymus nuclei are treated with clostripain. The crosslinked protein-DNA complexes are isolated and the presence of each core histone analyzed by dot-immunoassay using antibodies, specific to the central globular domain of the respective histone. The reaction is negative for all core histones i.e. the globular domain is absent. It means that this domain has not been crosslinked to DNA and, once cleaved by clostripain, it has been stripped from DNA during the centrigugation in CsCl. This peculiar property of the crosslinked procedure makes it particularly useful in addressing some yet unanswered questions concerning histone-DNA interactions, such as the interaction of the N-terminal tails with linker DNA, the effect of the transient postsynthetic histone acetylation on its interaction with DNA, etc. These questions are now under study. 1 fig., 6 refs

On formation mechanism of Pd-Ir bimetallic nanoparticles through thermal decomposition of [Pd(NH3)4][IrCl6

Science.gov (United States)

Asanova, Tatyana I.; Asanov, Igor P.; Kim, Min-Gyu; Gerasimov, Evgeny Yu.; Zadesenets, Andrey V.; Plyusnin, Pavel E.; Korenev, Sergey V.

2013-10-01

The formation mechanism of Pd-Ir nanoparticles during thermal decomposition of double complex salt [Pd(NH3)4][IrCl6] has been studied by in situ X-ray absorption (XAFS) and photoelectron (XPS) spectroscopies. The changes in the structure of the Pd and Ir closest to the surroundings and chemical states of Pd, Ir, Cl, and N atoms were traced in the range from room temperature to 420 °C in inert atmosphere. It was established that the thermal decomposition process is carried out in 5 steps. The Pd-Ir nanoparticles are formed in pyramidal/rounded Pd-rich (10-200 nm) and dendrite Ir-rich (10-50 nm) solid solutions. A d charge depletion at Ir site and a gain at Pd, as well as the intra-atomic charge redistribution between the outer d and s and p electrons of both Ir and Pd in Pd-Ir nanoparticles, were found to occur.

On formation mechanism of Pd–Ir bimetallic nanoparticles through thermal decomposition of [Pd(NH3)4][IrCl6

International Nuclear Information System (INIS)

Asanova, Tatyana I.; Asanov, Igor P.; Kim, Min-Gyu; Gerasimov, Evgeny Yu.; Zadesenets, Andrey V.; Plyusnin, Pavel E.; Korenev, Sergey V.

2013-01-01

The formation mechanism of Pd–Ir nanoparticles during thermal decomposition of double complex salt [Pd(NH 3 ) 4 ][IrCl 6 ] has been studied by in situ X-ray absorption (XAFS) and photoelectron (XPS) spectroscopies. The changes in the structure of the Pd and Ir closest to the surroundings and chemical states of Pd, Ir, Cl, and N atoms were traced in the range from room temperature to 420 °C in inert atmosphere. It was established that the thermal decomposition process is carried out in 5 steps. The Pd–Ir nanoparticles are formed in pyramidal/rounded Pd-rich (10–200 nm) and dendrite Ir-rich (10–50 nm) solid solutions. A d charge depletion at Ir site and a gain at Pd, as well as the intra-atomic charge redistribution between the outer d and s and p electrons of both Ir and Pd in Pd–Ir nanoparticles, were found to occur.Graphical Abstract

Rate constant and mechanism of the reaction Cl + CFCl₂H → CFCl₂ + HCl over the temperature range 298-670 K in N₂ or N₂/O₂ diluent.

Science.gov (United States)

Kaiser, E W; Jawad, Khadija M

2014-05-08

The rate constant of the reaction Cl + CFCl2H (k1) has been measured relative to the established rate constant for the reaction Cl + CH4 (k2) at 760 Torr. The measurements were carried out in Pyrex reactors using a mixture of CFCl2H, CH4, and Cl2 in either N2 or N2/O2 diluent. Reactants and products were quantified by GC/FID analysis. Cl atoms were generated by irradiation of the mixture with 360 nm light to dissociate the Cl2 for temperatures up to ~550 K. At higher temperature, the Cl2 dissociated thermally, and no irradiation was used. Over the temperature range 298-670 K, k1 is consistently a factor of ~5 smaller than that of k2 with a nearly identical temperature dependence. The optimum non-Arrhenius rate constant is represented by the expression k1 = 1.14 × 10(-22) T(3.49) e(-241/T) cm(3) molecule(-1) s(-1) with an estimated uncertainty of ±15% including uncertainty in the reference reaction. CFCl3 formed from the reaction CFCl2 + Cl2 (k3) is the sole product in N2 diluent. In ~20% O2 at 298 K, the CFCl3 product is suppressed. The rate constant of reaction 3 was measured relative to that of reaction 4 [CFCl2 + O2 (k4)] giving the result k3/k4 = 0.0031 ± 0.0005 at 298 K. An earlier experiment by others observed C(O)FCl to be the major product of reaction channel 4 [formed via the sequence, CFCl2(O2) → CFCl2O → C(O)FCl + Cl]. Our current experiments verified that there is a Cl atom chain reaction in the presence of O2 as required by this mechanism.

Platinum-Catalyzed Terminal-Selective C(sp3)–H Oxidation of Aliphatic Amines

Science.gov (United States)

Lee, Melissa; Sanford, Melanie S.

2016-01-01

This paper describes the terminal-selective Pt-catalyzed C(sp3)–H oxidation of aliphatic amines without the requirement for directing groups. CuCl2 is employed as a stoichiometric oxidant, and the reactions proceed in high yield at Pt loadings as low as 1 mol %. These transformations are conducted in the presence of sulfuric acid, which reacts with the amine substrates in situ to form ammonium salts. We propose that protonation of the amine serves at least three important roles: (i) it renders the substrates soluble in the aqueous reaction medium; (ii) it limits binding of the amine nitrogen to Pt or Cu; and (ii) it electronically deactivates the C–H bonds proximal to the nitrogen center. We demonstrate that this strategy is effective for the terminal-selective C(sp3)–H oxidation of a variety of primary, secondary and tertiary amines. PMID:26439251

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

KAUST Repository

Ahmed, Ejaz

2014-01-08

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

Localization of cesium on montmorillonite surface investigated by frequency modulation atomic force microscopy

Science.gov (United States)

Araki, Yuki; Satoh, Hisao; Okumura, Masahiko; Onishi, Hiroshi

2017-11-01

Cation exchange of clay mineral is typically analyzed without microscopic study of the clay surfaces. In order to reveal the distribution of exchangeable cations at the clay surface, we performed in situ atomic-scale observations of the surface changes in Na-rich montmorillonite due to exchange with Cs cations using frequency modulation atomic force microscopy (FM-AFM). Lines of protrusion were observed on the surface in aqueous CsCl solution. The amount of Cs of the montmorillonite particles analyzed by energy dispersive X-ray spectrometry was consistent with the ratio of the number of linear protrusions to all protrusions in the FM-AFM images. The results showed that the protrusions represent adsorbed Cs cations. The images indicated that Cs cations at the surface were immobile, and their occupancy remained constant at 10% of the cation sites at the surface with different immersion times in the CsCl solution. This suggests that the mobility and the number of Cs cations at the surface are controlled by the permanent charge of montmorillonite; however, the Cs distribution at the surface is independent of the charge distribution of the inner silicate layer. Our atomic-scale observations demonstrate that surface cations are distributed in different ways in montmorillonite and mica.

Determination of trace elements in Egyptian cane sugar (Deshna Factories) by neutron activation, atomic absorption spectrophotometric and inductively coupled plasma-atomic emission spectrometric analysis

International Nuclear Information System (INIS)

Awadallah, R.M.; Sherif, M.K.; Mohamed, A.E.; Grass, F.

1986-01-01

Multielement instrumental neutron activation (INAA), inductively coupled plasma-atomic emission spectrometric (ICP-AES) and atomic absorption spectrophotometric (AAS) analyses were utilized for the determination of Ag, Al, As, Au, Ba, Be, Br, Ca, Cd, Ce, Cl, Co, Cr, Cu, Eu, Fe, Ga, Hf, K, La, Li, Lu, Mg, Mn, Na, Nb, Ni, P, Pb, Sb, Sc, Se, Sm, Sn, Sr, Ta, Th, Ti, U, V, W and Zn in sugar cane plant, raw juice, juice in different stages, syrup, deposits, molasses, A, B and C sugar, refinery 1 and 2 sugar, and in soil samples picked up from the immediate vicinity of the cane plant roots at surface, 30 and 60 cm depth, respectively. (author)

Density of molten salt Mixtures of eutectic LiCl-KCl containing UCl{sub 3}, CeCl{sub 3}, or LaCl{sub 3}

Energy Technology Data Exchange (ETDEWEB)

Zhang, C.; Simpson, M. F. [Dept. of Metallurgical Engineering, University of Utah, Salt Lake City (United States)

2017-06-15

Densities of molten salt mixtures of eutectic LiCl-KCl with UCl{sub 3}, CeCl{sub 3}, or LaCl{sub 3} at various concentrations (up to 13 wt%) were measured using a liquid surface displacement probe. Linear relationships between the mixture density and the concentration of the added salt were observed. For LaCl{sub 3} and CeCl{sub 3}, the measured densities were signifcantly higher than those previously reported from Archimedes’ method. In the case of LiCl-KCl-UCl{sub 3}, the data ft the ideal mixture density model very well. For the other salts, the measured densities exceeded the ideal model prediction by about 2%.

Reactions of POxCly- ions with O2(a 1[Delta]g), H2O, and Cl2 at 298 K

Science.gov (United States)

Midey, Anthony J.; Dotan, Itzhak; Viggiano, A. A.

2008-06-01

The rate constants and product branching ratios for the reactions of phosphorus oxychloride anions, POxCly- for x = 1-2 and y = 1-3, with O2(a 1[Delta]g), Cl2, and H2O have been measured in a selected ion flow tube (SIFT) at 298 K. A mixture of O2(a 1[Delta]g) in O2 has been produced using a recently designed chemical singlet oxygen generator (sparger) with an emission detection scheme adopted previously in our laboratory. The experiments continue a series of investigations into the oxidation reactions of POxCly- ions, searching for pathways to the terminal PO2- and PO3- ions observed in combustion chemistry with POCl3 present. None of the POxCly- ions react with H2O or O2(a 1[Delta]g). The O2(a 1[Delta]g) rate constants have a limit of <1 × 10-11 cm3 s-1, except for PO2Cl- where a limit of <5 × 10-11 cm3 s-1 has been determined. The H2O rate constants have limits of <1 × 10-11 cm3 s-1. All of the POxCly- ions react with Cl2, excluding PO3- and PO2Cl2-. Depending on the reactant ion, Cl-, Cl2- or PO2Cl2- product ions form.

Pressure-frozen 1,2,3-trichloropropane.

Science.gov (United States)

Podsiadło, Marcin; Katrusiak, Andrzej

2006-12-01

The structure of 1,2,3-trichloropropane, ClCH2CHClCH2Cl, in-situ crystallized in a diamond-anvil cell, has been determined by single-crystal X-ray diffraction at 0.28 and 0.35 GPa. A melting point at 295 K and 0.22 GPa has been determined. The molecular conformation of aliphatic chain and terminal Cl atoms is approximately C2 symmetric. Of the intermolecular contacts, the tightest are the Cl...Cl and then the Cl...H contacts, whereas the H...H distances are considerably longer than the sum of the van der Waals radii and leave narrow voids in the structure. The elevated pressure reduces the H...H separations but hardly affects the Cl...Cl distances. The crystal growth rates, compression and types of intermolecular interactions in the structures can be correlated with the directions of the Cl...Cl contacts, which can be considered the main motif responsible for the molecular arrangement in the structure.

Electrodeposition of Al-Ta alloys in NaCl-KCl-AlCl{sub 3} molten salt containing TaCl{sub 5}

Energy Technology Data Exchange (ETDEWEB)

Sato, Kazuki; Matsushima, Hisayoshi; Ueda, Mikito, E-mail: mikito@eng.hokudai.ac.jp

2016-12-01

Highlights: • Electrodeposition of Al-Ta alloys in an AlCl{sub 3}-NaCl-KCl-TaCl{sub 5} melt was carried out. • We were obtained 72 at% Ta-Al alloy at 0.3 V. • Amorphous Ta-Al was formed in high Ta concentration. - Abstract: To form Al-Ta alloys for high temperature oxidation resistance components, molten salt electrolysis was carried out in an AlCl{sub 3}-NaCl-KCl melt containing TaCl{sub 5} at 423 K. The voltammogram showed two cathodic waves at 0.45 V and 0.7 V vs. Al/Al(III), which may correspond to reduction from Ta(V) to Ta(III) and from Ta(III) to tantalum metal, respectively. Electrodeposits of Al and Ta were obtained in the range from −0.05 to 0.3 V and the highest concentration of Ta in the electrodeposit was 72 at% at 0.3 V. With increasing Ta content in the alloy, the morphology of the electrodeposits became powdery and the particle size smaller.

The method of local increments for the calculation of adsorption energies of atoms and small molecules on solid surfaces. Part I. A single Cu atom on the polar surfaces of ZnO.

Science.gov (United States)

Schmitt, Ilka; Fink, Karin; Staemmler, Volker

2009-12-21

The method of local increments is used in connection with the supermolecule approach and an embedded cluster model to calculate the adsorption energy of single Cu atoms at different adsorption sites at the polar surfaces of ZnO. Hartree-Fock calculations for the full system, adsorbed atom and solid surface, and for the fragments are the first step in this approach. In the present study, restricted open-shell Hartree-Fock (ROHF) calculations are performed since the Cu atom possesses a singly-occupied 4s orbital. The occupied Hartree-Fock orbitals are then localized by means of the Foster-Boys localization procedure. The correlation energies are expanded into a series of many-body increments which are evaluated separately and independently. In this way, the very time-consuming treatment of large systems is replaced with a series of much faster calculations for small subunits. In the present application, these subunits consist of the orbitals localized at the different atoms. Three adsorption situations with rather different bonding characteristics have been studied: a Cu atom atop a threefold-coordinated O atom of an embedded Zn(4)O(4) cluster, a Cu atom in an O vacancy site at the O-terminated ZnO(000-1) surface, and a Cu atom in a Zn vacancy site at the Zn-terminated ZnO(0001) surface. The following properties are analyzed in detail: convergence of the many-body expansion, contributions of the different n-body increments to the adsorption energy, treatment of the singly-occupied orbital as "localized" or "delocalized". Big savings in computer time can be achieved by this approach, particularly if only the localized orbitals in the individual increment under consideration are described by a large correlation adapted basis set, while all other orbitals are treated by a medium-size Hartree-Fock-type basis set. In this way, the method of local increments is a powerful alternative to the widely used methods like DFT or RI-MP2.

'Seeing' Atoms: The Crystallographic Revolution.

Science.gov (United States)

Schwarzenbach, Dieter

2014-02-26

Laue's experiment in 1912 of the diffraction of X-rays by crystals led to one of the most influential discoveries in the history of science: the first determinations of crystal structures, NaCl and diamond in particular, by W. L. Bragg in 1913. For the first time, the visualisation of the structure of matter at the atomic level became possible. X-ray diffraction provided a sort of microscope with atomic resolution, atoms became observable physical objects and their relative positions in space could be seen. All branches of science concerned with matter, solid-state physics, chemistry, materials science, mineralogy and biology, could now be firmly anchored on the spatial arrangement of atoms. During the ensuing 100 years, structure determination by diffraction methods has matured into an indispensable method of chemical analysis. We trace the history of the development of 'small-structure' crystallography (excepting macromolecular structures) in Switzerland. Among the pioneers figure Peter Debye and Paul Scherrer with powder diffraction, and Paul Niggli and his Zurich School with space group symmetry and geometrical crystallography. Diffraction methods were applied early on by chemists at the Universities of Bern and Geneva. By the 1970s, X-ray crystallography was firmly established at most Swiss Universities, directed by full professors. Today, chemical analysis by structure determination is the task of service laboratories. However, the demand of diffraction methods to solve problems in all disciplines of science is still increasing and powerful radiation sources and detectors are being developed in Switzerland and worldwide.

Molecular dynamics simulations of single siloxane dendrimers: Molecular structure and intramolecular mobility of terminal groups

Science.gov (United States)

Kurbatov, A. O.; Balabaev, N. K.; Mazo, M. A.; Kramarenko, E. Yu.

2018-01-01

Molecular dynamics simulations of two types of isolated siloxane dendrimers of various generations (from the 2nd to the 8th) have been performed for temperatures ranging from 150 K to 600 K. The first type of dendrimer molecules has short spacers consisting of a single oxygen atom. In the dendrimers of the second type, spacers are longer and comprised of two oxygen atoms separated by a single silicon atom. A comparative analysis of molecular macroscopic parameters such as the gyration radius and the shape factor as well as atom distributions within dendrimer interior has been performed for varying generation number, temperature, and spacer length. It has been found that the short-spacer dendrimers of the 7th and 8th generations have a stressed central part with elongated bonds and deformed valence angles. Investigation of the time evolution of radial displacements of the terminal Si atoms has shown that a fraction of the Si groups have a reduced mobility. Therefore, rather long time trajectories (of the order of tens of nanoseconds) are required to study dendrimer intramolecular dynamics.

The collectins CL-L1, CL-K1 and CL-P1, and their roles in complement and innate immunity

DEFF Research Database (Denmark)

Hansen, Soren W K; Ohtani, Katsuki; Roy, Nitai

2016-01-01

as CL-LK) and its activation of the lectin pathway via MASPs, drew new attention in the complement biology, which was further strengthened by the observed interactions between CL-P1 and CRP-C1q-factor H or properdin. Deficiency of either CL-K1 or MASP-3 has been demonstrated in 3MC syndrome patients...

NbCl 5 and CrCl 3 catalysts effect on synthesis and hydrogen ...

Indian Academy of Sciences (India)

Two kinds of novel materials, Mg–1.6 mol% Ni–0.4 mol% NiO–2 mol% MCl (MCl = NbCl5, CrCl3), along with Mg–1.6 mol% Ni–0.4 mol% NiO for comparison, were examined for their potential use in hydrogen storage applications, having been fabricated via cryomilling. The effects of NbCl5 and CrCl3 on hydrogen storage ...

Zinc and palladium traces separation from uranium by tri-n-octylamine extraction. Direct determination in organic phase by atomic absorption

Energy Technology Data Exchange (ETDEWEB)

de Moraes, S; Cipriani, M; Abrao, A

1974-12-01

A procedure for the extraction and determination of Zn and Pd as traces from nuclear grade uranium ADU, UO/sub 2/, UO/sub 3/, U/sub 3/O/sub 8/ is introduced. The elements are extracted from UO/sub 2/Cl/sub 2/-HCl-KI solution with tri-n-octylamine in benzene and determined by atomic absorption spectrophotometry. The adition of potassium iodide to the UO/sub 2/Cl/sub 2/-HCl solutions improved the extraction of both elements. Direct burn of the organic phase in the atomic absorption spectrophotometer using hydrogen-air flame provided enhancement of the absorbance for both elements. The relative standard deviations were Zn, 3% and Pd, 2.9%.

An unexpected oxidation: NaK5Cl2(S2O62 revisited

Directory of Open Access Journals (Sweden)

William T. A. Harrison

2017-02-01

Full Text Available The title compound, NaK5Cl2(S2O62 [systematic name: sodium pentapotassium dichloride bis(dithionate], arose as an unexpected product from an organic synthesis that used dithionite (S2O42− ions as a reducing agent to destroy excess permanganate ions. Compared to the previous study [Stanley (1953. Acta Cryst. 6, 187–196], the present tetragonal structure exhibits a root 2a × root 2a × c super-cell due to subtle changes in the orientations of the dithionate anions. The structure can be visualized as a three-dimensional framework of [001] columns of alternating trans-NaO4Cl2 and KO4Cl2 octahedra cross-linked by the dithionate ions with the interstices occupied by KO6Cl2 polyhedra to generate a densely packed three-dimensional framework. The asymmetric unit comprises two sodium ions (site symmetries 4 and -4, four potassium ions (site symmetries = -4, 4, 1 and 1, three chloride ions (site symmetries = 4, 4 and 2 and two half-dithionate ions (all atoms on general positions. Both dithionate ions are completed by crystallographic inversion symmetry. The crystal chosen for data collection was found to be rotationally twinned by 180° about the [100] axis in reciprocal space with a 0.6298 (13:0.3702 (13 domain ratio.

Legal questions concerning the termination of spent fuel element reprocessing

International Nuclear Information System (INIS)

John, Michele

2005-01-01

The thesis on legal aspects of the terminated spent fuel reprocessing in Germany is based on the legislation, jurisdiction and literature until January 2004. The five chapters cover the following topics: description of the problem; reprocessing of spent fuel elements in foreign countries - practical and legal aspects; operators' responsibilities according to the atomic law with respect to the reprocessing of Geman spent fuel elements in foreign countries; compatibility of the prohibition of Geman spent fuel element reprocessing in foreign countries with international law, European law and German constitutional law; results of the evaluation

Termination layer compensated tunnelling magnetoresistance in ferrimagnetic Heusler compounds with high perpendicular magnetic anisotropy.

Science.gov (United States)

Jeong, Jaewoo; Ferrante, Yari; Faleev, Sergey V; Samant, Mahesh G; Felser, Claudia; Parkin, Stuart S P

2016-01-18

Although high-tunnelling spin polarization has been observed in soft, ferromagnetic, and predicted for hard, ferrimagnetic Heusler materials, there has been no experimental observation to date of high-tunnelling magnetoresistance in the latter. Here we report the preparation of highly textured, polycrystalline Mn3Ge films on amorphous substrates, with very high magnetic anisotropy fields exceeding 7 T, making them technologically relevant. However, the small and negative tunnelling magnetoresistance that we find is attributed to predominant tunnelling from the lower moment Mn-Ge termination layers that are oppositely magnetized to the higher moment Mn-Mn layers. The net spin polarization of the current reflects the different proportions of the two distinct termination layers and their associated tunnelling matrix elements that result from inevitable atomic scale roughness. We show that by engineering the spin polarization of the two termination layers to be of the same sign, even though these layers are oppositely magnetized, high-tunnelling magnetoresistance is possible.

Bis(μ-2-hydroxymethyl-2-methylpropane-1,3-diolatobis[dichloridotitanium(IV] diethyl ether disolvate

Directory of Open Access Journals (Sweden)

Joyce M. Waters

2013-12-01

Full Text Available The title complex, [Ti2Cl4{CH3C(CH2O2(CH2OH}2], lies across a centre of symmetry with a diethyl ether solvent molecule hydrogen bonded to the –CH2OH groups on either side of it. The TiIV atom is coordinated in a distorted octahedral geometry by a tripodal ligand and two terminal chloride atoms. There are three coordination modes for the tripodal ligand distinguishable on the basis of their very different Ti—O bond lengths. For the terminal alkoxo ligand, the Ti—O distance is 1.760 (1 Å, the asymmetric bridge system has Ti—O bond lengths of 1.911 (1 and 2.048 (1 Å. The Ti—O bond length for the alcohol O atom is the longest at 2.148 (1 Å.

Human ClC-6 is a late endosomal glycoprotein that associates with detergent-resistant lipid domains.

Directory of Open Access Journals (Sweden)

Sofie Ignoul

Full Text Available BACKGROUND: The mammalian CLC protein family comprises nine members (ClC-1 to -7 and ClC-Ka, -Kb that function either as plasma membrane chloride channels or as intracellular chloride/proton antiporters, and that sustain a broad spectrum of cellular processes, such as membrane excitability, transepithelial transport, endocytosis and lysosomal degradation. In this study we focus on human ClC-6, which is structurally most related to the late endosomal/lysomal ClC-7. PRINCIPAL FINDINGS: Using a polyclonal affinity-purified antibody directed against a unique epitope in the ClC-6 COOH-terminal tail, we show that human ClC-6, when transfected in COS-1 cells, is N-glycosylated in a region that is evolutionary poorly conserved between mammalian CLC proteins and that is located between the predicted helices K and M. Three asparagine residues (N410, N422 and N432 have been defined by mutagenesis as acceptor sites for N-glycosylation, but only two of the three sites seem to be simultaneously N-glycosylated. In a differentiated human neuroblastoma cell line (SH-SY5Y, endogenous ClC-6 colocalizes with LAMP-1, a late endosomal/lysosomal marker, but not with early/recycling endosomal markers such as EEA-1 and transferrin receptor. In contrast, when transiently expressed in COS-1 or HeLa cells, human ClC-6 mainly overlaps with markers for early/recycling endosomes (transferrin receptor, EEA-1, Rab5, Rab4 and not with late endosomal/lysosomal markers (LAMP-1, Rab7. Analogously, overexpression of human ClC-6 in SH-SY5Y cells also leads to an early/recycling endosomal localization of the exogenously expressed ClC-6 protein. Finally, in transiently transfected COS-1 cells, ClC-6 copurifies with detergent-resistant membrane fractions, suggesting its partitioning in lipid rafts. Mutating a juxtamembrane string of basic amino acids (amino acids 71-75: KKGRR disturbs the association with detergent-resistant membrane fractions and also affects the segregation of ClC-6

Salt precipitation and dissolution in the late Quaternary Dead Sea: Evidence from chemical and δ37Cl composition of pore fluids and halites

Science.gov (United States)

Levy, Elan J.; Yechieli, Yoseph; Gavrieli, Ittai; Lazar, Boaz; Kiro, Yael; Stein, Mordechai; Sivan, Orit

2018-04-01

The chemical composition and δ37Cl of pore fluids from the ICDP core drilled in the deepest floor of the terminal and hypersaline Dead Sea, and halites from the adjacent Mount Sedom salt diapir, are used to establish the dynamics of halite precipitation and dissolution during the last interglacial and glacial periods. Between ∼132 and 116 thousand years ago (ka) halites precipitated in the lake resulting in the expulsion of Na+ and Cl- from the residual solution. Over 50% of the Cl- reservoir was removed, resulting in a decrease in the Na/Cl ratio from 0.57 to 0.19. This process was accompanied by a decrease in δ37Cl values in the precipitating halites and the associated residual Cl- in the lake. The observed decrease fits a Rayleigh distillation curve with a fractionation factor of Δ(NaCl-Dead Sea solution) = +0.32‰ (±0.12) determined in the present study. This behavior implies negligible contribution of external sources of Cl- to the lake during the main peak of the last interglacial, MIS5e. Subsequently, during the last glacial (ca. 117 to 17 ka) dissolution of halite took place, the Na+ and Cl- inventory were replenished, accompanied by an increase in Na/Cl from 0.21 to 0.55 and in the δ37Cl values from -0.46‰ to -0.12‰. While the lake underwent significant dilution during that time, the decrease in salinity was somewhat suppressed by the dissolution of the halite which was mostly derived from Mount Sedom salt diapir.

Organizational Relationship Termination Competence

DEFF Research Database (Denmark)

Ritter, Thomas; Geersbro, Jens

2011-01-01

termination are found to significantly affect a firm's relationship termination competence. The findings suggest that managers should regard termination as a legitimate option in customer relationship management. In order to decrease the number of unwanted customers, managers must accept termination......Most firms are involved in a number of customer relationships that drain the firm's resources. However, many firms are hesitant to address this problem. This paper investigates customer relationship termination at the organizational level. We develop and analyze the organizational dimensions...... of organizational termination in order to improve our understanding of the management of termination. The impact of these termination dimensions on the percentage of unwanted customers is developed and tested using PLS on data gathered from a cross-sectional survey of more than 800 sales representatives. We find...

Kinetics and Mechanism of the Polymerization of Methyl Methacrylate in a Y(acac)3/n-BuMgCl System

Institute of Scientific and Technical Information of China (English)

无

2000-01-01

Based on the kinetics equation proposed by T. Kagiya, the kinetic study on the polymerization of methyl methacrylate(MMA) by Y(acac)3/n-BuMgCl was carried out with a dilatometer. It was found that the rate of propagation is the first order with respect to the concentration of both active center and monomer. Thus, the equation of propagation rate can be described as Rp=Kp[c*][M]. In addition, the instantaneous chain initiation and single molecular termination were concluded for the present system. The activation energy is close to 32 kJ/mol. In the polymerization, n-BuMgCl acts not only as the cocatalyst, but also as chain transfer agent with cI=3.6×10-4.

Kitimat LNG terminal

International Nuclear Information System (INIS)

Schmaltz, I.; Boulton, R.

2007-01-01

Kitimat Liquefied Natural Gas (LNG) terminal is a terminal development company owned by Galveston LNG, a privately owned Canadian energy development company. This presentation provided information on Kitimat LNG with particular reference to its terminal located in Bish Cove on the Douglas Channel in British Columbia. This LNG terminal is reported to be the only fully permitted regasification terminal on the west coast of Canada and the United States. The presentation addressed market fundamentals including several graphs, such as world natural gas proved reserves in 2006; LNG supplements to Canadian gas supplies; global LNG demand for 2005-2020; average annual United States LNG imports; and global LNG liquefaction projects. Other market fundamentals were described, including that Kitimat is the only other approved terminal aside from the Costa Azul terminal in Mexico; Kitimat is the only west coast LNG import terminal that connects to midwest and eastern North American markets through existing gas pipelines; LNG producers are looking for destination diversification; and markets and marketers are looking for supply diversification. The authors noted that by 2010, western Canadian gas demand will exceed Californian demand. Other topics that were discussed in the presentation included Canadian natural gas field receipts; unadjusted bitumen production outlook; oil sands gas demand; forward basis fundamentals; and the commercial drivers of the Kitimat LNG terminal. The presentation also discussed the pacific trail pipelines, a partnership between Galveston LNG and Pacific Northern Gas to develop the natural gas transmission line from Kitimat to Summit. The presentation concluded with a discussion of the benefits of Kitimat LNG terminal such as providing access to the largest natural gas markets in the world via major gas transmission lines with spare capacity. figs

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

International Nuclear Information System (INIS)

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

2008-01-01

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

Radiation processes in organic halides (Cl, Br, I) studied by ESR spectroscopy

International Nuclear Information System (INIS)

Symons, M.C.R.

1980-01-01

Electron-loss from alkyl halides (Cl, Br, I) gives Rhal. + which may dimerise to give (Rhal-halR) + σ* radicals with characteristic ESR spectra, or may lose H + to give α-halo radicals (R 2 Chal) also with well characterised ESR spectra. Electron-capture gives dissociation, but there may be weak residual charge-transfer interaction between R. and hal - which gives rise to well defined hyperfine coupling from the halide nuclei. Loss of β-hydrogen gives β-halo radicals, R 2 C-CH 2 hal (Cl,Br) whose conformation, established by ESR spectroscopy, is such that the halogen atom lies out of the radical plane so that overlap between the half-filled 2p(π) orbital and the C-hal (σ) orbital is maximised. Electron addition to α-halocarboxylates and related compounds probably gives β-halo radical anions, (R 2 C[hal]CO 2 H) - with a similar preferred conformation. Alternative structures are considered for these species. (author)

Evaluation report on CCTF CORE-I REFLOOD TEST Cl-1, (Run 010)

International Nuclear Information System (INIS)

Sudoh, Takashi; Murao, Yoshio.

1983-09-01

This report describes the effects of the loop flow resistance on the thermohydraulic behavior in the primary system during the reflood phase. The investigation is based on the results of the test Cl-1 which was performed with increased loop flow resistance in the Cylindrical Core Test Facility (CCTF) at Japan Atomic Energy Research Institute. The loop flow resistance was about 40% higher in the present test than in the reference test Cl-5. The results of two tests were compared and the following conclusions were obtained: 1) The total loop flow rate and the core flooding rate were reduced by about 20% with the increased loop flow resistance 2) The core heat transfer was also lowered, then, the turnaround and the quench times extended at the locations above the core midplane. 3) The measured maximum temperature in the core was 50 K higher for the present test than for the reference test. (author)

Al2O3 dielectric layers on H-terminated diamond: Controlling surface conductivity

Science.gov (United States)

Yang, Yu; Koeck, Franz A.; Dutta, Maitreya; Wang, Xingye; Chowdhury, Srabanti; Nemanich, Robert J.

2017-10-01

This study investigates how the surface conductivity of H-terminated diamond can be preserved and stabilized by using a dielectric layer with an in situ post-deposition treatment. Thin layers of Al2O3 were grown by plasma enhanced atomic layer deposition (PEALD) on H-terminated undoped diamond (100) surfaces. The changes of the hole accumulation layer were monitored by correlating the binding energy of the diamond C 1s core level with electrical measurements. The initial PEALD of 1 nm Al2O3 resulted in an increase of the C 1s core level binding energy consistent with a reduction of the surface hole accumulation and a reduction of the surface conductivity. A hydrogen plasma step restored the C 1s binding energy to the value of the conductive surface, and the resistance of the diamond surface was found to be within the range for surface transfer doping. Further, the PEALD growth did not appear to degrade the surface conductive layer according to the position of the C 1s core level and electrical measurements. This work provides insight into the approaches to establish and control the two-dimensional hole-accumulation layer of the H-terminated diamond and improve the stability and performance of H-terminated diamond electronic devices.

Crystal structure, quantum mechanical investigation, IR and NMR spectroscopy of two new organic perchlorates: (C6H18N3)·(ClO4)3H2O (I) and (C9H11N2)·ClO4(II)

Science.gov (United States)

Bayar, I.; Khedhiri, L.; Soudani, S.; Lefebvre, F.; Ferretti, V.; Ben Nasr, C.

2018-06-01

The reaction of perchloric acid with 1-(2-aminoethyl)piperazine or 5,6-dimethyl-benzimidazole results in the formation of 1-(2-amonioethyl)piperazine-1,4-dium triperchlorate hydrate (C6H18N3)·(ClO4)3·H2O (I) or 5,6-dimethyl-benzylimidazolium perchlorate (C9H11N2)·ClO4(II). Both compounds were fully structurally characterized including single crystal X-ray diffraction analysis. Compound (I) crystallizes in the centrosymmetric triclinic space group P 1 bar with the lattice parameters a = 7.455 (2), b = 10.462 (2), c = 10.824 (2) Å, α = 80.832 (2), β = 88.243 (2), γ = 88.160 (2) °, Z = 2 and V = 832.77 (3) Å3. Compound (II) has been found to belong to the P21/c space group of the monoclinic system, with a = 7.590 (3), b = 9.266 (3), c = 16.503 (6) Å, β = 107.38 (2) °, V = 1107.69 (7) Å3 and Z = 4. The structures of (I) and (II) consist of slightly distorted [ClO4]- tetrahedra anions and 1-(2-amonioethyl)piperazine-1,4-dium trication (I) or 5,6-dimethyl-benzylimidazolium cations (II) and additionally a lattice water in (I). The crystal structures of (I) and (II) exhibit complex three-dimensional networks of H-bonds connecting all their components. In the atomic arrangement of (I), the ClO4- anions form corrugated chains, while in (II) the atomic arrangement exhibits wide pseudo-hexagonal channels of ClO4 tetrahedra including the organic entities. The lattice water serves as a link between pairs of cations and pairs of anions via several Osbnd H⋯O and N-H⋯O interactions in compound (I). The vibrational absorption bands were identified by infrared spectroscopy. These compounds were also investigated by solid-state 13C, 35Cl and 15N NMR spectroscopy. DFT calculations allowed the attribution of the IR and NMR bands. Intermolecular interactions were investigated by Hirshfeld surfaces. Electronic properties such as HOMO and LUMO energies were derived.

Electron and Oxygen Atom Transfer Chemistry of Co(II) in a Proton Responsive, Redox Active Ligand Environment.

Science.gov (United States)

Cook, Brian J; Pink, Maren; Pal, Kuntal; Caulton, Kenneth G

2018-05-21

The bis-pyrazolato pyridine complex LCo(PEt 3 ) 2 serves as a masked form of three-coordinate Co II and shows diverse reactivity in its reaction with several potential outer sphere oxidants and oxygen atom transfer reagents. N-Methylmorpholine N-oxide (NMO) oxidizes coordinated PEt 3 from LCo(PEt 3 ) 2 , but the final cobalt product is still divalent cobalt, in LCo(NMO) 2 . The thermodynamics of a variety of oxygen atom transfer reagents, including NMO, are calculated by density functional theory, to rank their oxidizing power. Oxidation of LCo(PEt 3 ) 2 with AgOTf in the presence of LiCl as a trapping nucleophile forms the unusual aggregate [LCo(PEt 3 ) 2 Cl(LiOTf) 2 ] 2 held together by Li + binding to very nucleophilic chloride on Co(III) and triflate binding to those Li + . In contrast, Cp 2 Fe + effects oxidation to trivalent cobalt, to form (HL)Co(PEt 3 ) 2 Cl + ; proton and the chloride originate from solvent in a rare example of CH 2 Cl 2 dehydrochlorination. An unexpected noncomplementary redox reaction is reported involving attack by 2e reductant PEt 3 nucleophile on carbon of the 1e oxidant radical Cp 2 Fe + , forming a P-C bond and H + ; this reaction competes in the reaction of LCo(PEt 3 ) 2 with Cp 2 Fe + .

76 FR 41653 - Airworthiness Directives; Bombardier, Inc. Model CL-600-2A12 (CL-601) and CL-600-2B16 (CL-601-3A...

Science.gov (United States)

2011-07-15

... p.m., Monday through Friday, except Federal holidays. The AD docket contains the NPRM, the.... Model CL-600-2A12 (CL-601) airplanes, serial numbers 3001 through 3066 inclusive on which Bombardier... Variants) airplanes, serial numbers 5001 through 5194 inclusive on which Bombardier Service Bulletin 601...

Systematic UHV-AFM experiments on Na nano-particles and nano-structures in NaCl

OpenAIRE

Sugonyako, A.V.; Turkin, A.A.; Gaynutdinov, R.; Vainshtein, D.I.; Hartog, H.W. den; Bukharaev, A.A.

2005-01-01

Results of systematic AFM (atomic force microscopy) experiments on heavily and moderatly irradiated NaCl samples are presented. The sodium nanoparticles and structures of nanoparticles are poduced in sodium chloride during irradiation. The AFM images of the nanoparticles have been obtained in ultra high vacuum (UHV) in the non-contact mode with an Omicron UHV AFM/STM system. The sizes and arrangements of the observed particles depend on the irradiation conditions. The melting behaviour of the...

Atom-by-atom assembly

International Nuclear Information System (INIS)

Hla, Saw Wai

2014-01-01

Atomic manipulation using a scanning tunneling microscope (STM) tip enables the construction of quantum structures on an atom-by-atom basis, as well as the investigation of the electronic and dynamical properties of individual atoms on a one-atom-at-a-time basis. An STM is not only an instrument that is used to ‘see’ individual atoms by means of imaging, but is also a tool that is used to ‘touch’ and ‘take’ the atoms, or to ‘hear’ their movements. Therefore, the STM can be considered as the ‘eyes’, ‘hands’ and ‘ears’ of the scientists, connecting our macroscopic world to the exciting atomic world. In this article, various STM atom manipulation schemes and their example applications are described. The future directions of atomic level assembly on surfaces using scanning probe tips are also discussed. (review article)

Microtribological study of perfluoropolyether with different functional groups coated on hydrogen terminated Si

Energy Technology Data Exchange (ETDEWEB)

Minn, Myo; Satyanarayana, Nalam [Department of Mechanical Engineering, National University of Singapore, 9 Engineering Drive 1, Singapore 117576 (Singapore); Sinha, Sujeet K., E-mail: mpesks@nus.edu.sg [Department of Mechanical Engineering, National University of Singapore, 9 Engineering Drive 1, Singapore 117576 (Singapore); Kondo, Hirofumi [Sony Chemical and Information Device Corporation, R and D Division, 1078 Kamiishikawa, Kanuma 322-8503 (Japan)

2012-01-15

Friction and wear properties of different perfluoropolyether (PFPE) films with and without hydrogen termination on Si (Si-H) were studied using a ball-on-disk tribometer. The physical and chemical properties of the films were evaluated using contact angle measurement, atomic force microscopy and X-ray photoelectron spectroscopy. Coating of PFPEs onto bare Si has lowered the coefficient of friction (from 0.6 for Si to {approx}0.05 with PFPE) and enhanced the wear durability (20,000 times) in comparison with those for bare Si which failed immediately. The introduction of hydrogen termination onto Si prior to PFPE coating has further increased the wear durability of PFPE with different functional groups several times (>5 times) under a normal load of 30 mN and a sliding speed of 0.052 m/s.

Preparation of PtRu/Carbon hybrid materials by hydrothermal carbonization: A study of the Pt:Ru atomic ratio

International Nuclear Information System (INIS)

Tusi, Marcelo Marques; Brandalise, Michele; Correa, Olandir Vercino; Oliveira Neto, Almir; Linardi, Marcelo; Spinace, Estevam Vitorio; Villalba, Juan Carlo

2009-01-01

PtRu/Carbon materials with different Pt:Ru atomic ratios (30:70, 50:50, 60:40, 80:20 and 90:10) and 5 wt% of nominal metal load were prepared by hydrothermal carbonization using H 2 PtCl 6.6 H 2 O and RuCl 3. xH 2 O as metals sources and catalysts of the carbonization process and starch as carbon source and reducing agent. The obtained materials were treated at 900 deg C under argon and characterized by EDX, XRD and cyclic voltammetry. The electro-oxidation of methanol was studied by cyclic voltammetry and chronoamperometry using thin porous coating technique. The PtRu/Carbon materials showed Pt:Ru atomic ratios obtained by EDX similar to the nominal ones. XRD analysis showed that Pt face-cubic centered (FCC) and Ru hexagonal close-packed (HCP) phases coexist in the obtained materials. The average crystallite sizes of the Pt (FCC) phase were in the range of 8-12 nm. The material prepared with Pt:Ru atomic ratio of 50:50 showed the best performance for methanol electro-oxidation. (author)

Effect of oxide ion concentration on the electrochemical oxidation of carbon in molten LiCl

International Nuclear Information System (INIS)

Yun, J. W.; Choi, I. K.; Park, Y. S.; Kim, W. H.

2001-01-01

The continuous measurement of lithium oxide concentration was required in DOR (Direct Oxide Reduction) process, which converts spent nuclear fuel to metal form, for the reactivity monitor and effective control of the process. The concentration of lithium oxide was measured by the electrochemical method, which was based on the phenomenon that carbon atoms of glassy carbon electrode electrochemically react with oxygen ions of lithium oxide in molten LiCl medium. From the results of electrode polarization experiments, the trend of oxidation rate of carbon atoms was classified into two different regions, which were proportional and non-proportional ones, dependent on the amount of lithium oxide. Below about 2.5 wt % Li 2 O, as the carbon atom ionization rate was fast enough for reacting with diffusing lithium oxide to the surface of carbon electrode. In this concentration range, the oxidation rate of carbon atoms was controlled by the diffusion of lithium oxide, and the concentration of lithium oxide could be measured by electrochemical method. But, above 2.5 wt % Li 2 O, the oxidation rate of carbon atoms was controlled by the applied electrochemical potential, because the carbon atom ionization rate was suppressed by the huge amounts of diffusing Li 2 O. Above this concentration, the electrochemical method was not applicable to determine the concentration of lithium oxide

Thermal gravimetric analysis of the CsCuCl3, Cs2CuCl4 and Cs2CuCl4x2H2O crystals

International Nuclear Information System (INIS)

Soboleva, L.V.; Vasil'eva, M.G.

1977-01-01

The thermal characteristics of crystals of Cs 2 CuCl 4 , Cs 2 CuCl 4 x2H 2 O, and CsCuCl 3 were investigated thermogravimetrically. The derivatogram of the Cs 2 CuCl 4 crystal is characterized by the presence of a single endothermal effect at 505 deg C. The derivatogram of the Cs 2 CuCl 4 x2H 2 O crystal contains three endothermal effects: at 40, 135, and 480 deg C. The derivatogram of the CsCuCl 3 crystal shows the presence of two endothermal effects at 142 and 455 deg C. The thermogravimetric data on Cs 2 CuCl 4 and CsCuCl 3 crystals reveal crystal decomposition on melting; hence, these crystals cannot be grown from melts

Atomic site occupancies and magnetic properties of Ni-doped FeAl intermetallic compounds

CERN Document Server

Ko, K Y; Yoon, S

1999-01-01

Neutron and X-ray powder diffraction revealed FeAl sub 1 sub - sub x Ni sub x alloys to have the B2(CsCl) structure with a virtually constant lattice parameter of 2.91 A and with the Ni atoms preferring the Fe sites. The annealed specimens showed paramagnetism for x 0.25 whereas the rapidly solidified specimens showed superparamagnetism for x = 0.25. The magnetization increased as the Ni concentration (x) increased. The rapidly solidified specimens, in general, showed stronger magnetic properties than the annealed ones. The magnetic properties were explained in terms of the local environmental model for magnetic atoms.

Terminal parent phosphanide and phosphinidene complexes of zirconium(IV)

Energy Technology Data Exchange (ETDEWEB)

Stafford, Hannah; Rookes, Thomas M.; Wildman, Elizabeth P.; Wooles, Ashley J.; Liddle, Stephen T. [School of Chemistry, The University of Manchester (United Kingdom); Balazs, Gabor; Scheer, Manfred [Institute of Inorganic Chemistry, University of Regensburg (Germany)

2017-06-19

The reaction of [Zr(Tren{sup DMBS})(Cl)] [Zr1; Tren{sup DMBS}=N(CH{sub 2}CH{sub 2}NSiMe{sub 2}Bu{sup t}){sub 3}] with NaPH{sub 2} gave the terminal parent phosphanide complex [Zr(Tren{sup DMBS})(PH{sub 2})] [Zr2; Zr-P=2.690(2) Aa]. Treatment of Zr2 with one equivalent of KCH{sub 2}C{sub 6}H{sub 5} and two equivalents of benzo-15-crown-5 ether (B15C5) afforded an unprecedented example (outside of matrix isolation) of a structurally authenticated transition-metal terminal parent phosphinidene complex [Zr(Tren{sup DMBS})(PH)][K(B15C5){sub 2}] [Zr3; Zr=P=2.472(2) Aa]. DFT calculations reveal a polarized-covalent Zr=P double bond, with a Mayer bond order of 1.48, and together with IR spectroscopic data also suggest an agostic-type Zr..HP interaction [ angle {sub ZrPH}=66.7 ] which is unexpectedly similar to that found in cryogenic, spectroscopically observed phosphinidene species. Surprisingly, computational data suggest that the Zr=P linkage is similarly polarized, and thus as covalent, as essentially isostructural U=P and Th=P analogues. (copyright 2017 Wiley-VCH Verlag GmbH and Co. KGaA, Weinheim)

Cationic polyhydrido cluster complexes. Crystal and molecular structures of (Ir3(Ph2P(CH2)3PPh2)3(H)7(CO))2+ and (Ir3(Ph2P(CH2)2(2-py))3(H)7)2+

International Nuclear Information System (INIS)

Hsienhau Wang; Casalnuovo, A.L.; Johnson, B.J.; Mueting, A.M.; Pignolet, L.H.

1988-01-01

Two new cationic polyhydrido cluster complexes of iridium have been synthesized and characterized by single-crystal x-ray diffraction and by ir and 1 H and 31 P NMR spectroscopy (Ir 3 (dppp) 3 (H) 7 (CO)) 2+ (2) and (Ir3 (PN) 3 (H) 7)2+ (5), where dppp = 1,3-bis(diphenylphosphino)propane and PN = 1-(2-pyridyl)-2-(diphenylphosphino)ethane, were synthesized by the reaction of CO with (Ir 3 (dppp) 3 (H) 7 ) 2+ (1) in CH 2 Cl 2 solution and H 2 with (Ir(PN)(COD)) + (4) in CH 3 OH solution, respectively. Crystal structures for both compounds is reported. The hydride positions were not located in the crystal structure analyses but were deduced from structural and 1 H NMR data. The molecular structure of 2 consists of a bilateral triangle of three iridium atoms with a carbonyl at the vertex and a chelating dppp ligand on each iridium atom. 1 H NMR data with use of acetone-d 6 as solvent showed that 2 possesses four doubly bridging hydrides and three terminal hydrides, yielding C 1 symmetry. The molecular structure of 5 consists of an approximately equilateral triangle of three iridium atoms (average Ir-Ir distance 2.746 (1) angstrom) with one PN ligand chelated to each iridium atom. 1 H NMR analysis, with use of CD 2 Cl 2 as solvent, showed that 5 has one triply bridging hydride and six terminal hydrides, giving C 3 symmetry. (Ir 3 (dppp) 3 (H) 7 (CH 3 C 6 H 4 NC)) 2+ (3) a complex structurally analogous to 2, was synthesized from 1 and p-tolyl isocyanide in CH 2 Cl 2 solution and characterized by ir and 1 H and 31 P NMR spectroscopy. 44 refs., 3 figs., 3 tabs

Theoretical atomic and molecular physics: Progress report, July 1, 1988 through June 30, 1989

International Nuclear Information System (INIS)

Lane, N.F.

1989-01-01

The theoretical atomic and molecular physics program at Rice University emphasizes fundamental questions regarding the structure and collision dynamics of various atomic and molecular systems with some attention given to atomic processes at surfaces. Our activities have been centered on continuing the projects initiated last year as well as beginning some new studies. These include: differential elastic and charge-transfer scattering and alignment and orientation of the excited electron cloud in ion-atom, atom-atom and ion-molecule collisions, using a molecular-orbital representation and both semiclassical and quantal methods; quenching of low-lying Rydberg states of a sodium atom in a collision with a rare-gas atom, using a semiclassical representation; so far, target atoms He, Ne and Ar have been studied; chemiionization and ion-pair formation in a collision of a Li atom with a metastable He atom at intermediate collision energies, using a combination of quantal and semi-classical methods; Penning ionization of alkali atoms Na and K, using advanced Cl and Stieltjes imaging methods; radiative and nonradiative charge-transfer in He + + H collisions at ultra-low collision energies, using quantal methods; elastic and inelastic processes in electron-molecule collisions, using the continuum-multiple-scattering method; and inelastic collision processes in dense, high-temperature plasmas. Selected highlights of our research progress are briefly summarized in this paper

Poly(vinyl acetate-Based Block Copolymer/Clay Nanocomposites Prepared by In Situ Atom Transfer Radical Polymerization

Directory of Open Access Journals (Sweden)

M.A. Semsarzadeh

2009-12-01

Full Text Available Atom transfer radical polymerization of styrene (St and methyl methacrylate (MMA was performed at 90oC in the absence and presence of nanoclay (Cloisite 30B. Trichloromethyl-terminated poly(vinyl acetate telomerand CuCl/ PMDETA were used as a macroinitiator and catalyst system, respectively. The experimental results showed that the atom transfer radical polymerization of St and MMA in the absence or presence of nanoclay proceeds via a controlled/living mode. It was observed that nanoclay significantly enhances the homopolymerization rate of MMA, which was attributed to the activated conjugated C=C bond of MMA monomer via interaction between the carbonyl group of MMA monomer and the hydroxyl moiety (Al-O-H of nanoclay as well as the effect of nanoclay on the dynamic equilibrium between the active (macro radicals and dormant species.Homopolymerization rate of St (a non-coordinative monomer with nanoclay decreased slightly in the presence of nanoclay. This could be explained by insertion of a portion of macroinitiator into the clay galleries, where no sufficient St monomer exists due to the low compatibility or interaction of St monomer with nanoclay to react with the macroinitiator. The results obtained from XRD, TEM and TGA analyses were fully in agreement with the kinetic data. Structure of the poly(vinyl acetate-bpolystyrene nanocomposite was found to be a combination of stacking layers and exfoliated structures while poly(vinyl acetate-b-poly(methyl methacryale nanocomposite had an exfoliated structure. This difference in the structure of nanocomposites was attributed to the different capability of the monomers (styrene and methyl methacrylate to react with the hydroxyl moiety (Al-O-H of nanoclay.

Infrared (1-12 μm) atomic and molecular emission signatures from energetic materials using laser-induced breakdown spectroscopy

Science.gov (United States)

Kumi Barimah, E.; Hömmerich, U.; Brown, E.; Yang, C. S.-C.; Trivedi, S. B.; Jin, F.; Wijewarnasuriya, P. S.; Samuels, A. C.; Snyder, A. P.

2013-05-01

Laser-induced breakdown spectroscopy (LIBS) is a powerful analytical technique to detect the elemental composition of solids, liquids, and gases in real time. For example, recent advances in UV-VIS LIBS have shown great promise for applications in chemical, biological, and explosive sensing. The extension of conventional UVVIS LIBS to the near-IR (NIR), mid-IR (MIR) and long wave infrared (LWIR) regions (~1-12 μm) offers the potential to provide additional information due to IR atomic and molecular signatures. In this work, a Q-switched Nd: YAG laser operating at 1064 nm was employed as the excitation source and focused onto several chlorate and nitrate compounds including KClO3, NaClO3, KNO3, and NaNO3 to produce intense plasma at the target surface. IR LIBS studies on background air, KCl , and NaCl were also included for comparison. All potassium and sodium containing samples revealed narrow-band, atomic-like emissions assigned to transitions of neutral alkali-metal atoms in accordance with the NIST atomic spectra database. In addition, first evidence of broad-band molecular LIBS signatures from chlorate and nitrate compounds were observed at ~10 μm and ~7.3 μm, respectively. The observed molecular emissions showed strong correlation with FTIR absorption spectra of the investigated materials.

Coercivity enhancement of sintered Nd-Fe-B magnets by chemical bath deposition of TbCl{sub 3}

Energy Technology Data Exchange (ETDEWEB)

Guo, Shuai, E-mail: gshuai@nimte.ac.cn; Zhang, Xiaofeng; Ding, Guangfei; Chen, Renjie; Yan, Aru [Key Laboratory of Magnetic Materials and Devices, Ningbo Institute of Material Technology and Engineering, Chinese Academy of Sciences, Ningbo 315201 (China); Zhejiang Province Key Laboratory of Magnetic Materials and Application Technology, Ningbo Institute of Material Technology and Engineering, Chinese Academy of Sciences, Ningbo 315201 (China); Lee, Don [Key Laboratory of Magnetic Materials and Devices, Ningbo Institute of Material Technology and Engineering, Chinese Academy of Sciences, Ningbo 315201 (China); University of Dayton, Dayton, Ohio 45469 (United States)

2014-05-07

The chemical bath deposition (CBD) and the grain boundary diffusion method were combined to diffuse the heavy rare earth for obtain the thick magnets with high coercivity and low heavy rare earth. The jet mill powders were soaked into the alcohol solution of 0.2 wt. % TbCl{sub 3}. A thin layer of TbCl{sub 3} was wrapped to the surface of (PrNd){sub 2}Fe{sub 14}B powder particles. The coercivity of magnet is increased from 11.89 kOe to 14.72 kOe without significant reduction of remanence after grain boundary diffusion in the sintering and the annealing processes. The temperature coefficients of the remanence and the coercivity are improved by the substitution of PrNd by Tb in the surface of grains. The highly accelerated temperature/humidity stress test (HAST) results indicate that the CBD magnet has poor corrosion resistance, attributing to the present of Cl atoms in the grain boundaries.

Determination of 36Cl/Cl ratio in ground water using the accelerator mass spectrometry technique

International Nuclear Information System (INIS)

Sharma, Suman; Deodhar, A.S.; Saravana Kumar, U.; Surendran, P.; Shrivastava, A.; Gupta, A.K.; Nair, J.P.; Yadav, M.L.; Hemalatha, M.; Sparrow, H.; Mahata, K.; Thomas, R.G.; Bhagwat, P.V.; Kailas, S.; Kale, R.M.

2009-01-01

The Accelerator Mass Spectrometry (AMS) programme using the 14 MV Pelletron Accelerator at Mumbai has been initiated with major emphasis on the determination of 36 Cl in water samples, of interest to hydrology and environment. In order to carry out the AMS measurement, a beam chopper to cut down beam intensity by a factor of 20 has been developed and commissioned. A multi-anode gas -si detector has been built to separate 36 Cl from the interfering 36 S. A new TPS system has been procured to operate the machine in the GVM mode. Standard and blank samples from Prime lab, Purdue have been employed in these measurements to standardise the technique for 36 Cl/Cl ratio determination. The detector was calibrated using the stable 35,37 Cl ions. The background 36 Cl in the system has been measured using the blank sample from Purdue and it was estimated that the ratio of 36 Cl/Cl was of the order of 10 -13 in the present setup. Ground water samples collected from South India were converted to AgCl and put in the SNICS ion source for the AMS measurements. These ground water samples, with 14 C content estimated to be in the range of 1 to 4 pMC indicate that the samples may be more than 35,000 years old. Using the AMS technique we have determined the 36 Cl/Cl ratio values for these ground water samples. They are found to range between 2 to 5 x 10 -12 . Additional measurements are planned to determine the age of the water samples and to understand the reasons for the observed high values of 36 Cl in these samples. (author)

Observations of ClNO2 and PANs in a mid-continental urban environment

Science.gov (United States)

Furgeson, A.; Mielke, L.; Osthoff, H. D.

2010-12-01

Nitrogen oxides play many important roles in regional air quality, for example, through the catalytic photochemical production of O3 involving NOx (=NO+NO2), which in urban environments is primarily of anthropogenic origin. NOx can be converted to reservoir species, such as peroxyacyl nitrates (PANs), or removed from the atmosphere, mainly by conversion to HNO3, which is removed predominantly through heterogeneous uptake and dry deposition. The main HNO3 production pathways are reaction of NO2 with OH during the day and heterogeneous reactions involving N2O5 at night. It has been known for some time that heterogeneous N2O5 hydrolysis (i.e., N2O5 + H2O → 2HNO3) competes with ClNO2 formation (i.e., N2O5 + Cl- → ClNO2 + NO3-) on chloride containing aerosol, but the latter reaction is believed to be only of significance in marine and coastal environments. Formation of ClNO2 is significant as it reduces the rate of nocturnal NOx removal and activates chlorine by releasing highly reactive Cl atoms following ClNO2 photolysis after sunrise. Recent field measurements by Thornton and coworkers have shown the efficient formation of ClNO2 in mid-continental air at a distance greater than 1,000 km from the nearest coastline. In this presentation, measurements of peroxyacyl nitrates and ClNO2 by chemical ionization mass spectrometry (CIMS) on the rooftop of a 6-story building in Calgary, Alberta, Canada, are described. The CIMS was operated in negative ion mode and equipped with a heated inlet to dissociate PANs to NO2 and the corresponding PA radicals, which are converted to the respective carboxylate anions using iodide reagent ion. ClNO2 was monitored as the cluster ion (ClNO2)I- at m/z 208 and 210. The CIMS was calibrated for peroxyacyl nitrates using a newly developed photolysis source, which was also used to deliver an internal standard during the measurement intensive. Measurements took place during spring and fall of 2010. During spring, we observed in excess of 200

Molecular recognition of chromophore molecules to amine terminated surfaces

International Nuclear Information System (INIS)

Flores-Perez, Rosangelly; Ivanisevic, Albena

2007-01-01

We report the design and characterization of quartz surfaces that can bind to three retinal based chromophores. The amine terminated surfaces were engineered in order to mimic the environment of the opsin protein that accommodates binding of chromophore molecules in the human eye. Each surface coupling step was characterized by water contact angle measurements, ellipsometry, atomic force microscopy, X-ray photoelectron spectroscopy, and transmission infrared spectroscopy. The spectroscopic techniques confirmed that the three chromophore molecules can bind to the surface using a Schiff base mode. Our data suggests that the availability of the amine groups on the surface is critical in the accommodation of the binding of different chromophores

Electronic transport properties of copper and gold at atomic scale

Energy Technology Data Exchange (ETDEWEB)

Mohammadzadeh, Saeideh

2010-11-23

The factors governing electronic transport properties of copper and gold atomic-size contacts are theoretically examined in the present work. A two-terminal conductor using crystalline electrodes is adopted. The non-equilibrium Green's function combined with the density functional tight-binding method is employed via gDFTB simulation tool to calculate the transport at both equilibrium and non-equilibrium conditions. The crystalline orientation, length, and arrangement of electrodes have very weak influence on the electronic characteristics of the considered atomic wires. The wire width is found to be the most effective geometric aspect determining the number of conduction channels. The obtained conductance oscillation and linear current-voltage curves are interpreted. To analyze the conduction mechanism in detail, the transmission channels and their decomposition to the atomic orbitals are calculated in copper and gold single point contacts. The presented results offer a possible explanation for the relation between conduction and geometric structure. Furthermore, the results are in good agreement with available experimental and theoretical studies. (orig.)

(nBuCp)2ZrCl2-catalyzed Ethylene-4M1P Copolymerization: Copolymer Backbone Structure, Melt Behavior, and Crystallization

KAUST Repository

Atiqullah, Muhammad

2016-01-08

The judicious design of methylaluminoxane (MAO) anions expands the scope for developing industrial metallocene catalysts. Therefore, the effects of MAO anion design on the backbone structure, melt behavior, and crystallization of ethylene−4-methyl-1-pentene (E−4M1P) copolymer were investigated. Ethylene was homopolymerized, as well as copolymerized with 4M1P, using (i) MAO anion A (unsupported [MAOCl2]−) premixed with dehydroxylated silica, (nBuCp)2ZrCl2, and Me2SiCl2; and (ii) MAO anion B (Si−O−Me2Si−[MAOCl2]−) supported with (nBuCp)2ZrCl2 on Me2SiCl2-functionalized silica. Unsupported Me2SiCl2, opposite to the supported analogue, acted as a co-chain transfer agent with 4M1P. The modeling of polyethylene melting and crystallization kinetics, including critical crystallite stability, produced insightful results. This study especially illustrates how branched polyethylene can be prepared from ethylene alone using particularly one metallocene-MAO ion pair, and how a compound, that functionalizes silica as well as terminates the chain, can synthesize ethylene−α-olefin copolymers with novel structures. Hence, it unfolds prospective future research niches in polyethyne systhesis. This article is protected by copyright. All rights reserved.

ZnCl{sub 2}- and NH{sub 4}Cl-hydroponics gel electrolytes for zinc-carbon batteries

Energy Technology Data Exchange (ETDEWEB)

Khalid, N.H.; Ismail, Y.M. Baba; Mohamad, A.A. [School of Materials and Mineral Resources Engineering, Universiti Sains Malaysia, 14300 Nibong Tebal, Penang (Malaysia)

2008-01-21

Absorbency testing is used to determine the percentage of ZnCl{sub 2} or NH{sub 4}Cl solution absorbed by a hydroponics gel (HPG). It is found that the absorbency of ZnCl{sub 2} or NH{sub 4}Cl solution decreases with increasing solution concentration. The conductivity of ZnCl{sub 2}- and NH{sub 4}Cl-HPG electrolytes is dependent on the solution concentration. A mixture of salt solution with HPG yields excellent gel polymer electrolytes with conductivities of 0.026 and 0.104 S cm{sup -1} at 3 M ZnCl{sub 2} and 7 M NH{sub 4}Cl, respectively. These gel electrolytes are then used to produce zinc-carbon cells. The fabricated cells give capacities of 8.8 and 10.0 mAh, have an internal resistance of 25.4 and 19.8 {omega}, a maximum power density of 12.7 and 12.2 mW cm{sup -2}, and a short-circuit current density of 29.1 and 33.9 mA cm{sup -2} for ZnCl{sub 2}- and NH{sub 4}Cl-HPG electrolytes, respectively. (author)

PrP N-terminal domain triggers PrPSc-like aggregation of Dpl

International Nuclear Information System (INIS)

Erlich, Paul; Cesbron, Jean-Yves; Lemaire-Vieille, Catherine; Curt, Aurelie; Andrieu, Jean-Pierre; Schoehn, Guy; Jamin, Marc; Gagnon, Jean

2008-01-01

Transmissible spongiform encephalopathies are fatal neurodegenerative disorders thought to be transmitted by self-perpetuating conformational conversion of a neuronal membrane glycoprotein (PrP C , for 'cellular prion protein') into an abnormal state (PrP Sc , for 'scrapie prion protein'). Doppel (Dpl) is a protein that shares significant biochemical and structural homology with PrP C . In contrast to its homologue PrP C , Dpl is unable to participate in prion disease progression or to achieve an abnormal PrP Sc -like state. We have constructed a chimeric mouse protein, composed of the N-terminal domain of PrP C (residues 23-125) and the C-terminal part of Dpl (residues 58-157). This chimeric protein displays PrP-like biochemical and structural features; when incubated in presence of NaCl, the α-helical monomer forms soluble β-sheet-rich oligomers which acquire partial resistance to pepsin proteolysis in vitro, as do PrP oligomers. Moreover, the presence of aggregates akin to protofibrils is observed in soluble oligomeric species by electron microscopy

In-situ atomic layer deposition growth of Hf-oxide

International Nuclear Information System (INIS)

Karavaev, Konstantin

2010-01-01

We have grown HfO 2 on Si(001) by atomic layer deposition (ALD) using HfCl 4 , TEMAHf, TDMAHf and H 2 O as precursors. The early stages of the ALD were investigated with high-resolution photoelectron spectroscopy and X-ray absorption spectroscopy. We observed the changes occurring in the Si 2p, O 1s, Hf 4f, Hf 4d, and Cl 2p (for HfCl 4 experiment) core level lines after each ALD cycle up to the complete formation of two layers of HfO 2 . The investigation was carried out in situ giving the possibility to determine the properties of the grown film after every ALD cycle or even after a half cycle. This work focused on the advantages in-situ approach in comparison with ex-situ experiments. The study provides to follow the evolution of the important properties of HfO 2 : contamination level, density and stoichiometry, and influence of the experimental parameters to the interface layer formation during ALD. Our investigation shows that in-situ XPS approach for ALD gives much more information than ex-situ experiments. (orig.)

In-situ atomic layer deposition growth of Hf-oxide

Energy Technology Data Exchange (ETDEWEB)

Karavaev, Konstantin

2010-06-17

We have grown HfO{sub 2} on Si(001) by atomic layer deposition (ALD) using HfCl{sub 4}, TEMAHf, TDMAHf and H{sub 2}O as precursors. The early stages of the ALD were investigated with high-resolution photoelectron spectroscopy and X-ray absorption spectroscopy. We observed the changes occurring in the Si 2p, O 1s, Hf 4f, Hf 4d, and Cl 2p (for HfCl{sub 4} experiment) core level lines after each ALD cycle up to the complete formation of two layers of HfO{sub 2}. The investigation was carried out in situ giving the possibility to determine the properties of the grown film after every ALD cycle or even after a half cycle. This work focused on the advantages in-situ approach in comparison with ex-situ experiments. The study provides to follow the evolution of the important properties of HfO{sub 2}: contamination level, density and stoichiometry, and influence of the experimental parameters to the interface layer formation during ALD. Our investigation shows that in-situ XPS approach for ALD gives much more information than ex-situ experiments. (orig.)

Investigations on the production of labelled organic compounds by recoil labelling with gamma,n-produced 11-C-atoms

International Nuclear Information System (INIS)

Wagenbach, U.

1981-01-01

''Hot'' 11 C atoms are produced from 12 C(γ,n) 11 C nuclear reactions by bremsstrahlung at the 65 MeV electron linear accelerator in Giessen. The relative retention in various C-atoms of the amino acid, methionine, is determined by splitting of the terminal C-atoms of the molecule and by independent determination of the content of 11 C in the isolated and derived fragments. The terminal groups (thiomethyl or carboxyl groups) each carry approx. 25% of the total retained radioactivity, the remaining 50% being spread over the three inner carbon atoms. The activation of alkylamines, crystallised as hydrochlorides, hydrofluorides, oxalates and sulphates, leads to similar yields of direct labelling from 5 to 15%. Amines activated in the liquid state show a retention of less than 5%. The yields for labelled synthetic products are between 10 and 15% for amino acids and are often higher for crystallised amines. Amines activated in the liquid state produced greater yields of synthesis products but at the same time an increase in the product range. The labelled synthesis products can be separated faster by suitable methods such as preparative HPLC and are then available for carrier-free studies in the life sciences. (orig./EF) [de

Kinetic of the gas-phase reactions of OH radicals and Cl atoms with Diethyl Ethylphosphonate and Triethyl Phosphate

KAUST Repository

Laversin, H.; El Masri, A.; Rachidi, Mariam El; Roth, E.; Chakir, A.

2015-01-01

pressure and at different temperatures. The calculated rate constants were fitted to the Arrhenius expression over the temperature range 298 – 352 K. The following expressions (in cm3molecule-1s-1) were obtained for the reactions of OH and CL with DEEP

The unique N-terminal zinc finger of synaptotagmin-like protein 4 reveals FYVE structure.

Science.gov (United States)

Miyamoto, Kazuhide; Nakatani, Arisa; Saito, Kazuki

2017-12-01

Synaptotagmin-like protein 4 (Slp4), expressed in human platelets, is associated with dense granule release. Slp4 is comprised of the N-terminal zinc finger, Slp homology domain, and C2 domains. We synthesized a compact construct (the Slp4N peptide) corresponding to the Slp4 N-terminal zinc finger. Herein, we have determined the solution structure of the Slp4N peptide by nuclear magnetic resonance (NMR). Furthermore, experimental, chemical modification of Cys residues revealed that the Slp4N peptide binds two zinc atoms to mediate proper folding. NMR data showed that eight Cys residues coordinate zinc atoms in a cross-brace fashion. The Simple Modular Architecture Research Tool database predicted the structure of Slp4N as a RING finger. However, the actual structure of the Slp4N peptide adopts a unique C 4 C 4 -type FYVE fold and is distinct from a RING fold. To create an artificial RING finger (ARF) with specific ubiquitin-conjugating enzyme (E2)-binding capability, cross-brace structures with eight zinc-ligating residues are needed as the scaffold. The cross-brace structure of the Slp4N peptide could be utilized as the scaffold for the design of ARFs. © 2017 The Protein Society.

Terahertz reflection spectroscopy of aqueous NaCl and LiCl solutions

DEFF Research Database (Denmark)

Jepsen, Peter Uhd; Merbold, Hannes

2010-01-01

frequencies. Whereas both the real and imaginary part of the permittivity of NaCl increases with concentration,we see that the imaginary part of the permittivity of LiCl (related to the absorption)decreases with increasing salt concentration. We relate these changes to the behavior...

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

International Nuclear Information System (INIS)

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

1997-01-01

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

Heterogeneous computing with OpenCL

CERN Document Server

2013-01-01

Heterogeneous Computing with OpenCL teaches OpenCL and parallel programming for complex systems that may include a variety of device architectures: multi-core CPUs, GPUs, and fully-integrated Accelerated Processing Units (APUs) such as AMD Fusion technology. Designed to work on multiple platforms and with wide industry support, OpenCL will help you more effectively program for a heterogeneous future. Written by leaders in the parallel computing and OpenCL communities, this book will give you hands-on OpenCL experience to address a range of fundamental parallel algorithms. The authors explore memory spaces, optimization techniques, graphics interoperability, extensions, and debugging and profiling. Intended to support a parallel programming course, Heterogeneous Computing with OpenCL includes detailed examples throughout, plus additional online exercises and other supporting materials.

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

Science.gov (United States)

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

2013-04-04

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

The Cathodic Behavior of Ti(III) Ion in a NaCl-2CsCl Melt

Science.gov (United States)

Song, Yang; Jiao, Shuqiang; Hu, Liwen; Guo, Zhancheng

2016-02-01

The cathodic behavior of Ti(III) ions in a NaCl-2CsCl melt was investigated by cyclic voltammetry, chronopotentiometry, and square wave voltammetry with a tungsten electrode being the working electrode at different temperatures. The results show that the cathodic behavior of Ti(III) ion consists of two irreversible steps: Ti3+ + e = Ti2+ and Ti2+ + 2 e = Ti. The diffusion coefficient for the Ti(III) ion in the NaCl-2CsCl eutectic is 1.26 × 10-5 cm2 s-1 at 873 K (600 °C), increases to be 5.57 × 10-5 cm2 s-1 at 948K (675°C), and further rises to 10.8 × 10-5 cm2 s-1 at 1023 (750 °C). Moreover, galvanostatic electrolysis performed on a titanium electrode further presents the feasibility of electrodepositing metallic titanium in the molten NaCl-2CsCl-TiCl3 system.

On formation mechanism of Pd-Ir bimetallic nanoparticles through thermal decomposition of [Pd(NH{sub 3}){sub 4}][IrCl{sub 6}

Energy Technology Data Exchange (ETDEWEB)

Asanova, Tatyana I., E-mail: nti@niic.nsc.ru; Asanov, Igor P. [Nikolaev Institute of Inorganic Chemistry SB RAS (Russian Federation); Kim, Min-Gyu [Pohang University of Science and Technology, Beamline Research Division (Korea, Republic of); Gerasimov, Evgeny Yu. [Boreskov Institute of Catalysis SB RAS (Russian Federation); Zadesenets, Andrey V.; Plyusnin, Pavel E.; Korenev, Sergey V. [Nikolaev Institute of Inorganic Chemistry SB RAS (Russian Federation)

2013-10-15

The formation mechanism of Pd-Ir nanoparticles during thermal decomposition of double complex salt [Pd(NH{sub 3}){sub 4}][IrCl{sub 6}] has been studied by in situ X-ray absorption (XAFS) and photoelectron (XPS) spectroscopies. The changes in the structure of the Pd and Ir closest to the surroundings and chemical states of Pd, Ir, Cl, and N atoms were traced in the range from room temperature to 420 Degree-Sign C in inert atmosphere. It was established that the thermal decomposition process is carried out in 5 steps. The Pd-Ir nanoparticles are formed in pyramidal/rounded Pd-rich (10-200 nm) and dendrite Ir-rich (10-50 nm) solid solutions. A d charge depletion at Ir site and a gain at Pd, as well as the intra-atomic charge redistribution between the outer d and s and p electrons of both Ir and Pd in Pd-Ir nanoparticles, were found to occur.Graphical Abstract.

The mechanisms underlying the enhanced resolution of atomic force microscopy with functionalized tips

International Nuclear Information System (INIS)

Moll, Nikolaj; Gross, Leo; Mohn, Fabian; Curioni, Alessandro; Meyer, Gerhard

2010-01-01

By functionalizing the tip of an atomic force microscope (AFM) with a molecule or an atom that significantly contributes to the tip-sample interaction, the resolution can be dramatically enhanced. The interaction and therefore the resolution crucially depend on the chemical nature of the tip termination. Employing a tip functionalized with a CO molecule, atomic resolution of a pentacene molecule was recently demonstrated. In this work, the interaction between the CO tip and the pentacene imaged are studied with first principles calculations. The calculated frequency shifts compare very well with the experiment. The different energy contributions are analyzed and the Pauli energy is computed. We demonstrate that the source of the high resolution is Pauli repulsion, whereas van der Waals and electrostatic interactions only add a diffuse attractive background.

Chemical effects of (n, γ) nuclear reaction on (Mo6Cl8)Cl4