octahedral tav hydrazido-substituted: Topics by WorldWideScience.org

Corrective measures evaluation work plan : Technical Area V Groundwater : revision 0.

This document, which is prepared as directed by the Compliance Order on Consent (COOC) issued by the New Mexico Environment Department, identifies and outlines a process to evaluate remedial alternatives to identify a corrective measure for the Sandia National Laboratories New Mexico Technical Area (TA)-V Groundwater. The COOC provides guidance for implementation of a Corrective Measures Evaluation (CME) for the TA-V Groundwater. This Work Plan documents an initial screening of remedial technologies and presents a list of possible remedial alternatives for those technologies that passed the screening. This Work Plan outlines the methods for evaluating these remedial alternatives and describes possible site-specific evaluation activities necessary to estimate remedy effectiveness and cost. These methods will be reported in the CME Report. This Work Plan outlines the CME Report, including key components and a description of the corrective ...

2004-04-01

Spin transition in octahedral metal complexes containing tetraazamacrocyclic ligands

This document, which is prepared as directed by the Compliance Order on Consent (COOC) issued by the New Mexico Environment Department, identifies and outlines a process to evaluate remedial alternatives to identify a corrective measure for the Sandia National Laboratories/New Mexico Technical Area (TA)-V Groundwater. The COOC provides guidance for implementation of a Corrective Measures Evaluation (CME) for the TA-V Groundwater. This Work Plan documents an initial screening of remedial technologies and presents a list of possible remedial alternatives for those technologies that passed the screening. This Work Plan outlines the methods for evaluating these remedial alternatives and describes possible site-specific evaluation activities necessary to estimate remedy effectiveness and cost. These methods will be reported in the CME Report. This Work Plan outlines the CME Report, including key components and a description of the corrective ...

2004-12-01

British Library Electronic Table of Contents (United Kingdom)

This review focusses on spin crossover complexes with octahedral metal ions which are bound to a tetraazamacrocyclic ligand and additionally either to two monodentate ligands or to one bidentate ligand. Macrocyclic ligands with a sufficiently large ring size prefer to coordinate to metal ions in an equatorial fashion yielding trans-octahedral coordination environments. In contrast, twelve-membered tetraazamacrocycles with high steric rigidity, such as 2,11-diaza[3.3](2,6)pyridinophanes or 2,11-dithia[3.3](2,6)pyridinophane, are prone to form cis-octahedral complexes. While the electronic and the steric properties of the coordinated tetraazamacrocycle in trans-octahedral complexes are very likely responsible for the paucity of observed spin transitions, the cis-octahedral coordination mode ...

2009-01-01

Application of ?- and ?-Isomerism of Octahedral Metal Complexes for Inducing Chiral Nematic Phases

UK PubMed Central (United Kingdom)

The Δ- and Λ-isomerism of octahedral metal complexes is employed as a source of chirality for inducing chiral nematic phases. By applying a wide range of chiral metal complexes as a...Full Text Available

Quantifying octahedral rotations in strained perovskite oxide films.

Universal spectrochemical series of six-coordinate octahedral metal complexes for modifying the ligand field splitting.

We have measured the oxygen positions in LaNiO{sub 3} films to elucidate the coupling between epitaxial strain and oxygen octahedral rotations. The oxygen positions are determined by comparing the measured and calculated intensities of half-order Bragg peaks, arising from the octahedral rotations. Combining ab initio density-functional calculations with these experimental results, we show how strain systematically modifies both bond angles and lengths in this functional perovskite oxide.

2010-07-20

Targeting a Ruthenium Complex to the Nucleus with Short Peptides

We studied a novel universal spectrochemical series of six-coordinated octahedral 3d transition metal complexes, which can be used for any combination of central metal atom and ligand molecules. A two dimensional spectrochemical series could be used to estimate the ligand field splitting energy of not only known compounds but also the unknown compounds. Therefore, it should be possible to control the physical properties, such as the electronic and magnetic properties and the optical phenomena of octahedral transition metal complexes by modifying the ligand field splitting. PMID:19378561

2009-01-28

UK PubMed Central (United Kingdom)

In an effort to develop octahedral metal complexes as chemotherapeutic and diagnostic agents targeted to DNA, it is critical to optimize the properties of their cellular uptake. Appending d-octaarginine...Full Text Available

2010-05-15

Insertion of a Bulky Rhodium Complex into a DNA Cytosine-Cytosine Mismatch: An NMR Solution Study

UK PubMed Central (United Kingdom)

The bulky octahedral complex, Rh(bpy)₂chrysi³⁺ (chrysi = 5, 6- chrysenequinone diimine), binds single base mismatches in a DNA duplex with micromolar binding affinities...Full Text Available

2007-10-10

Natural gels: crystal-chemistry of short range ordered components in Al, Fe, and Si systems

Manganese oxide nanowires, films, and membranes and methods of making

In this review, the most important inorganic natural gels are presented: opal, aluminosilicate (allophanes) and hydrous iron oxides and silicates. It is demonstrated that natural gels are ordered at the atomic scale. In allophanes, Al is distributed between octahedral and tetrahedral sites. The amount of Al increases as Al/Si ratio decreases. Si-rich allophane have a local structure around Al and Si very different of that is known in kaolinite or halloysite. Transformation of Si-rich allophanes to crystallized minerals implies dissolution-recrystallization processes. On the contrary, in iron silicate with Fe/Si = 0.72, Si and Fe environments are close to those found in nontronite. The gel transformation to Fe-smectite may occur by long range ordering during ageing. In ferric silicate gels, the similarity of local structure around Fe in poorly ordered precursors and what is known in crystallized minerals suggests a solid transformation during ageing. This difference ...

1997-07-01

Coordination polymers assembled through pi-pi interactions

Nanowires, films, and membranes comprising ordered porous manganese oxide-based octahedral molecular sieves, and methods of making, are disclosed. A single crystal ultra-long nanowire includes an ordered porous manganese oxide-based octahedral molecular sieve, and has an average length greater than about 10 micrometers and an average diameter of about 5 nanometers to about 100 nanometers. A film comprises a microporous network comprising a plurality of single crystal nanowires in the form of a layer, wherein a plurality of layers is stacked on a surface of a substrate, wherein the nanowires of each layer are substantially axially aligned. A free standing membrane comprises a microporous network comprising a plurality of single crystal nanowires in the form of a layer, wherein a plurality of layers is aggregately stacked, and wherein the nanowires of each layer are substantially axially aligned.

2008-10-21

CERN Document Server

Chapter one is a review of the relevant literature. In chapter two the coordination chemistry of biphenyl-tailed terpyridines with octahedral metal dications is investigated. The effect of different metal ions on their aggregation modes in the solid state is also investigated. In chapter three the coordination chemistry of polyaryl-tailed terpyridines with octahedral metal dications is investigated. The effect of different aryl tails on their aggregation modes in the solid state is investigated. In chapter four the pi-pi aggregation of molecular boxes through biphenyl tails is studied. In chapter five the immobilisation of aryl tailed complexes into polyelectrolyte films has been investigated, and the arrangement of these complexes in the films has been compared with same complexes in the crystal, thus moving from three dimensional aggregation to two dimensions.

2001-01-01

Comparison of EH with SW-Xsub(alpha) calculations

A precise structure redetermination of nickel ammonium sulfate hexahydrate, Ni(H_2O)_6.2NH_4.2SO_4

The electronic structure of octahedral metal atom clusters Me_6 of 3d, 4d, and 5d transition metal atoms (V, Cr; Nb, Mo; Ta, W) has been calculated applying two different quantum-chemical approximation methods (Extended Hueckel (EH) method; SW-Xsub(alpha) method). Equilibrium structures, energy level schemes, Fermi energies and band widths as well as densities of states of clusters are discussed in detail.

1981-01-01

Inverse spinel materials. A new class of high voltage cathode materials for Li-ion batteries

The Ni(H_2O)_6 ion is located at an inversion center. Six octahedral water molecules surround the Ni"I"I ion and form hydrogen bonds with the sulfate groups. Each ammonium group binds to the sulfate groups through hydrogen bonds. (orig.).

1994-05-01

EPR and FT-IR spectroscopic studies of Bi2O3-B2O3-CuO glasses

The influence of Cr on the structure and electrochemical properties of LiCoVO{sub 4} was studied using X-Ray diffraction, scanning electron microscopy, Raman Spectroscopy and cycle tests. Doping levels up to 10 mol% were achieved, which improved the electrochemical stability of the structure of LiCoVO{sub 4}, resulting in a significant increase in the initial charge and discharge capacity. The Raman spectroscopy data for the Cr-doped LiCoVO{sub 4} is similar as for LiCoVO{sub 4}. The replacement of a dopant for the Co-ion in the inverse spinel structure causes several Raman shifts. The X-ray diffraction patterns show no new phases and combined with the Raman spectroscopy data it is concluded that the Cr dopant will be located at the octahedral site (16d) where they create an electronic pathway that enhances the electronic conductivity. However, the capacity dropped significantly after prolonged cycling, which is due to the diffusion of V{sup 5+} ions from the ...

2003-07-01

Synthesis and characterization of nickel(II), chromium(III), cobalt(II), copper(II), zinc(II), and cadmium(II) complexes with isatin- isonicotinoylhydrazone

EPR and FT-IR absorption measurements have been performed for xCuO.(100-x)[2Bi2O3.B2O3] glass system, with 0?x?50 mol%. The mode in which the addition of the copper ions influences the structure of 2Bi2O3.B2O3 glass matrix was analyzed. The EPR absorption spectra revealed the presence in the glass structure of Cu2+ ions in axially distorted octahedral environments. EPR data pointed out the simultaneous presence of Cu2+ and Cu+ ionic species in the glasses with x?5 mol%. For x>10 mol%, the Cu2+ ions participate in the superexchange magnetic interactions, which increase with CuO content. The FT-IR spectra showed the presence of some bands that are assigned to vibrations of Bi-O bonds from BiO3 pyramidal and BiO6 octahedral units and B-O bonds from BO3 and BO4 units. The data obtained by these measurements reveal the structural changes in the 2Bi2O3.B2O3 glass matrix by controlled doping of CuO.

2008-10-01

Comparison of EH with SW-Xsub(alpha) calculations. Electronic structure of 3d, 4d, and 5d metal atom clusters

A few metal complexes of isatin-isonicotinoylhydrazone with Ni(II), Cr(III), Co(II), Cu(II), Zn(II) and Cd(II) have been prepared and characterized on the basis of elemental analyses, infrared and electronic spectra as well as "1H NMR spectra, conductivity and magnetic measurements. In view of the results obtained, it has been found that two molecules of isatin-isonicotinoylhydrazone are chelated to the central metal ion as bis-uninegative ONO tridentate ligand forming non-electrolytic octahedral metal complexes. (author)

1997-03-01

Synthesis and Crystal Structures of Octahedral Metal Complexes containing the New Dianion [PhP(Se,O)Se-Se(O,Se)PPh]2-

The electronic structure of octahedral metal atom clusters Me/sub 6/ of 3d, 4d, and 5d transition metal atoms (V, Cr; Nb, Mo; Ta, W) has been calculated applying two different quantum-chemical approximation methods (Extended Hueckel (EH) method; SW-Xsub(alpha) method). Equilibrium structures, energy level schemes, Fermi energies and band widths as well as densities of states of clusters are discussed in detail.

1981-01-01

British Library Electronic Table of Contents (United Kingdom)

The synthesis and structures of three new compounds are reported. [Mg2{PhP(Se,O)Se-Se(O,Se)PPh}2(thf)7(H2O)3] (1), [Mg{PhP(Se,O)Se-Se(O,Se)PPh}(thf)3(H2O)] (2), and [Mn{PhP(Se,O)Se-Se(O,Se)PPh}(thf)3(H2O)] (3) were prepared by treatment of Woollins reagent [PhP(Se)(m-Se)]2 with the corresponding hydrated metal acetates.

2007-01-01

Relationship between the electronic structure of passive films and the susceptibility to pitting corrosion of stainless steels; Relations entre la structure electronique des films de passivation formes sur les aciers inoxydables et la susceptibilite de ces derniers a la corrosion par piqures

Metallointercalators and Metalloinsertors

The passive films formed on 316L stainless steel in various NaCl solutions have been investigated by capacitance measurements (Mott-Schottky). Pitting parameters have been determined using the galvano-kinetic polarisation method. The obtained results reveal the existence of a shallow and a deep donor level localised in the band gap of the semiconducting oxide film. These energy levels are due to iron ions in the tetrahedral and octahedral positions. It also appears that the participation of the deep donor level effects the electric field. The study developed allows us to compare characteristic parameters of the electronic structure of the passive film to those related to pitting susceptibility. (authors) 25 refs.

1998-04-01

Metallo-intercalators and metallo-insertors.

Since the elucidation of the structure of double helical DNA, the construction of small molecules that recognize and react at specific DNA sites has been an area of considerable interest. In particular, the study of transition metal complexes that bind DNA with specificity has been a burgeoning field. This growth has been due in large part to the useful properties of metal complexes, which possess a wide array of photophysical properties and allow for the modular assembly of an ensemble of recognition elements. Here we review recent experiments in our laboratory aimed at the design and study of octahedral metal complexes that bind DNA non-covalently and target reactions to specific sites. Emphasis is placed both on the variety of methods employed to confer site-specificity and upon the many applications for these complexes. Particular attention is given to the family of complexes recently designed that target single base mismatches in duplex DNA through ...

2007-09-20

1 2 3

Crystal Field Studies on MgGa2O4:Ni2+

Since the elucidation of the structure of double helical DNA, the construction of small molecules that recognize and react at specific DNA sites has been an area of considerable interest. In particular, the study of transition metal complexes that bind DNA with specificity has been a burgeoning field. This growth has been due in large part to the useful properties of metal complexes, which possess a wide array of photophysical attributes and allow for the modular assembly of an ensemble of recognition elements. Here we review recent experiments in our laboratory aimed at the design and study of octahedral metal complexes that bind DNA non-covalently and target reactions to specific sites. Emphasis is placed both on the variety of methods employed to confer site-specificity and upon the many applications for these complexes. Particular attention is given to the family of complexes recently designed that target single base mismatches in duplex DNA through ...

2007-09-20

Complexation of nitrogen and sulphur donor Schiff's base ligand to Cr(III) and Ni(II) metal ions: Synthesis, spectroscopic and antipathogenic studies

The energy levels scheme of octahedrally coordinated Ni2+ ion in single crystal, powder nano-single crystal, ceramics and glass-ceramics of MgGa2O4 host matrix, has been calculated in the exchange charge model of crystal field. The parameters of the crystal field acting on the Ni2+ ion are calculated from the crystal structure data, after optimization of the geometry of the system. The energy level schemes have been calculated by diagonalization of the crystal field Hamiltonian of this system. The obtained results were compared with experimental data; a good agreement were demonstrated, which confirm the validity of the model and used method.

2010-08-04

British Library Electronic Table of Contents (United Kingdom)

2,6-Diacetyl pyridine based ligand was synthesized by the reaction of 2,6-diacetyl pyridine with thiocarbohydrazide in presence of acetic acid. The coordination compounds with Cr(III) and Ni(II) metal ions having [Cr(L)X]X2 and [Ni(L)X]X compositions (where L=ligand and X=NO3^-, Cl^- and CH3COO^-) were synthesized and characterized by physicochemical and spectral studies. The studies like elemental analyses, molar conductance measurements, magnetic susceptibility measurements, IR, UV-Vis, NMR, mass and EPR reveal that the complexes are octahedral. The compounds were examined against the pathogenic fungal and bacterial strains like Alternaria brassicae, Aspergillus niger, Fusarium oxysporum, Xanthomonas compestris and Pseudomonas aeruginosa. A. niger causes the diseases Apergillosis and Oto...

2011-01-01

Effects of inorganic cation templates on octahedral molecular sieves of manganese oxide

EPR and FT-IR spectroscopic studies of Bi{sub 2}O{sub 3}-B{sub 2}O{sub 3}-CuO glasses

Five hydrated inorganic divalent cations, Mg[sup 2+], Co[sup 2+], Ni[sup 2+], Cu[sup 2+], and Zn[sup 2+], have successfully been used as templates for the synthesis of manganese oxide octahedral molecular sieves (OMS-1) having the todorokite structure. The OMS-1 samples have been well characterized by X-ray diffraction, differential scanning calorimetry, thermogravimetric analysis, scanning electron microscopy/energy dispersive X-ray studies, inductively coupled plasma analysis, electron paramagnetic resonance, Fourier transform infrared spectroscopy, thiosulfate titration, and cyclohexane sorption. Catalytic CO oxidation and 2-propanol decomposition were carried out. Results show that these OMS-1 samples with a tunnel size of about 6.9 angstroms are crystalline and chemically pure. They have the following formulas: Mg[sub 3.17]Mn[sub 5.05]O[sub 12] [center dot] 4.52H[sub 2]O, Co[sub 1.84]Mn[sub 5.59]O[sub 12] [center dot] 3.45H[sub 2]O, Ni[sub 1.64]Mn[sub ...

1994-11-30

X-ray and IR analysis of Cu-Si ferrite

EPR and FT-IR absorption measurements have been performed for xCuO.(100-x)[2Bi{sub 2}O{sub 3}.B{sub 2}O{sub 3}] glass system, with 0{<=}x{<=}50 mol%. The mode in which the addition of the copper ions influences the structure of 2Bi{sub 2}O{sub 3}.B{sub 2}O{sub 3} glass matrix was analyzed. The EPR absorption spectra revealed the presence in the glass structure of Cu{sup 2+} ions in axially distorted octahedral environments. EPR data pointed out the simultaneous presence of Cu{sup 2+} and Cu{sup +} ionic species in the glasses with x{>=}5 mol%. For x>10 mol%, the Cu{sup 2+} ions participate in the superexchange magnetic interactions, which increase with CuO content. The FT-IR spectra showed the presence of some bands that are assigned to vibrations of Bi-O bonds from BiO{sub 3} pyramidal and BiO{sub 6} octahedral units and B-O bonds from BO{sub 3} and BO{sub 4} units. The data obtained by these measurements reveal the ...

2008-10-01

Synthesis, characterization and biological evaluation of mononuclear Co(II), Ni(II), Cu(II) and Pd(II) complexes with new N2O2 Schiff base ligands.

Polycrystalline soft ferrite, Cu1+xSixFe2?2xO4 (x=0.0, 0.05, 0.1, 0.15, 0.2 and 0.3) were prepared by standard ceramic technique. The X-ray analysis confirmed the single phase formation of the samples up to x=0.1 beside a second phase for x?0.15. The lattice parameter was found to decrease with composition(x), which is attributed to ionic size difference of cations involved. The bulk density measurements shows two different behavior for x0.15. The IR spectra of Cu Si ferrite system have been analyzed in the frequency range 200 1200 cm?1. It revealed two prominent bands ?1 and ?2 which are assigned to tetrahedral and octahedral metal complexes, respectively. The position of the highest frequency band is around 575 cm?1 while the lower frequency band is around 400 cm?1.

2006-08-01

Magnetic and Moessbauer study of some transition metal based nitroprussides

New tetradentate N(2)O(2) donor Schiff bases and their mononuclear Co(II), Ni(II), Cu(II), and Pd(II) complexes were synthesized and characterized extensively by IR, (1)H-, (13)C-NMR, mass, ESR, conductivity measurements, elemental and thermal analysis. Specifically the magnetic and electronic spectral measurements demonstrate the octahedral structures of cobalt(II), nickel(II) complexes and square planar geometries of copper(II), palladium(II) complexes. All the ligands and complexes were screened for their in vitro antibacterial activity against two gram-positive bacteria (Bacillus subtilis, Staphylococcus aureus) and two gram-negative bacteria (Escherichia coli, Klebsiella pneumonia). In this study, Pd(II) complexes exhibited potent antibacterial activity against B. subtilis, S. aureus whereas other metal complexes also exerted good activity towards all tested strains even than standard drugs streptomycin and ampicillin. PMID:21297294

2011-02-01

Luminescent property and catalytic activity of Ru(II) carbonyl complexes containing N, O donor of 2-hydroxy-1-naphthylideneimines

Susceptibility data of freshly precipitated nitroprussides TM[Fe(CN){sub 5}NO] n H{sub 2}O (TM=Mn, Fe, Co, Ni, Cu) follow very well modified Curie-Weiss law down to T=5 K indicating paramagnetic state; nitroprusside (NP) containing Zn is diamagnetic with a sign of paramagnetic contribution. Deviation from Curie-Weiss law and magnetization measurements on MnNP, FeNP and CoNP below T=5 K can indicate ferrimagnetic ordering at low temperatures. A hysteresis behaviour in ZFC and FC magnetisation with the temperature of bifurcation T{sub b}=6 K was found for CoNP and FeNP. Moessbauer spectra taken at room temperature (besides FeNP) consist of a single symmetric quadrupole-split doublet with parameters {delta} and {delta} typical for Fe{sup II} ions in octahedral sites. A more complicated spectrum of FeNP is a consequence of different Fe environments.

2004-05-01

British Library Electronic Table of Contents (United Kingdom)

The reaction of the chelating ligands (obtained by the condensation of 2-hydroxy-1-naphthaldehyde with various primary amines) with [RuHCl(CO)(EPh3)2(B)] (where E=P; B=PPh3, py or pip: E=As; B=AsPh3) in benzene afforded new stable ruthenium(II) carbonyl complexes of the general formula [Ru(Cl)(CO)(EPh3)(B)(L)] (L=anion of bidentate Schiff bases). The structure of the new complexes was investigated using elemental analyses, spectral (FT-IR, UV-vis and 1H NMR) and electrochemical studies and is found to be octahedral. All the metal complexes exhibit characteristic MLCT absorption and luminescence bands in the visible region. The luminescence efficiency of the ruthenium(II) complexes was explained based on the ligand environment around the metal ion. These complexes catalyze oxidation of prim...

2007-01-01

Influence of composite LiCl-KCl molten salt on microstructure and electrochemical performance of spinel Li4Ti5O12

Influence of composite LiCl-KCl molten salt on microstructure and electrochemical performance of spinel Li4Ti5O12

A series of spinel Li4Ti5O12 samples were synthesized via a composite molten-salt method (CMSM) using the mixtures of LiCl and KCl with different L values (L is defined as the molar ratio of LiCl:KCl) as the reaction media. It is found that the melting point of the composite molten salt can effectively influence the formation of particles, and leads to different electrochemical performances of the as-prepare Li4Ti5O12. The investigations of X-ray diffraction (XRD), particle size distribution (PSD), Brunauer-Emmet-Teller (BET) surface area, and scanning electron microscopy (SEM) indicate that the as-prepared Li4Ti5O12 with L = 1.5 is a pure phase, and has uniform homogeneous octahedral shape particles, rather narrow PSD, and high BET surface area. Electrochemical tests show that the optimized Li4Ti5O12 with L = 1.5 has an initial discharge capacity of 169 mAh g-1 and an initial charge-discharge efficiency of 94% at 0.2 C rate, and achieves good rate performances ...

2008-12-30

British Library Electronic Table of Contents (United Kingdom)

A series of spinel Li4Ti5O12 samples were synthesized via a composite molten-salt method (CMSM) using the mixtures of LiCl and KCl with different L values (L is defined as the molar ratio of LiCl:KCl) as the reaction media. It is found that the melting point of the composite molten salt can effectively influence the formation of particles, and leads to different electrochemical performances of the as-prepare Li4Ti5O12. The investigations of X-ray diffraction (XRD), particle size distribution (PSD), Brunauer-Emmet-Teller (BET) surface area, and scanning electron microscopy (SEM) indicate that the as-prepared Li4Ti5O12 with L=1.5 is a pure phase, and has uniform homogeneous octahedral shape particles, rather narrow PSD, and high BET surface area. Electrochemical tests show that the optimized...

2008-01-01

Fully relativistic analysis of the absorption spectra of Ca_3Sc_2Ge_3O_1_2:Ni"2"+

Electrochemical properties of Cu{sub 2}O/Cu composite particles prepared by a novel and facile method

Systematic analysis of the energy level schemes, ground state absorption (GSA) and covalency effects for the Ni"2"+ ion in Ca_3Sc_2Ge_3O_1_2 was performed. The recently developed first-principles approach to the analysis of the absorption spectra of impurity ions in crystals based on the discrete variational multi-electron method (DV-ME) [K. Ogasawara et al., Phys. Rev. B 64, 115413 (2001)] was used in the calculations. As a result, complete energy level schemes of Ni"2"+ and its absorption spectra at both possible crystallographic positions (distorted octahedral Sc"3"+ and tetrahedral Ge"4"+ positions) were calculated, assigned and compared with experimental data. Energies of the charge transfer (CT) transitions for both positions are estimated. Numerical contributions of all possible electron configurations into the calculated energy states were determined. By performing analysis of the molecular orbitals (MO) population, it was shown that the covalency of the ...

2006-10-01

EPR, optical, infrared and Raman studies of VO"2"+ ions in polyvinylalcohol films

In this study, Cu{sub 2}O/Cu composite particles were synthesized using an innovative chemical reduction method without any template and surfactant. X-ray diffraction (XRD) analysis revealed that the product mainly consisted of Cu{sub 2}O phase coexisting with a Cu phase. FE-SEM images showed that the octahedral shaped particles were Cu{sub 2}O. The electrochemical performance of the Cu{sub 2}O/Cu particles was investigated with regards to the working electrode material in alkaline solution. The particles had a maximum discharge capacity of 222.9 mAh/g at a discharge current density of 60 mA/g and a high value of 109.1 mAh/g after 50 charge-discharge cycles. Cyclic voltammetry revealed that the reaction between Cu{sub 2}O and Cu is the major electrochemical reaction during the charging and discharging process. Electrochemical impedance spectroscopy revealed that the formation of Cu{sub 2}O on the surface of Cu particles increased the contact resistance and the ...

2010-07-01

Diaqua[N,Nprime-(o-phenylene)bis(pyridine-2-carboxamidato)-k4N]manganes e(III) perchlorate

Electron paramagnetic resonance (EPR), optical, infrared and Raman spectral studies have been carried out on vanadyl ions doped in polyvinylalcohol (PVA) films. The spin-Hamiltonian parameters (g and A) and the molecular orbital coefficients (#beta#_2"*"2 and k) have been evaluated. The values of spin-Hamiltonian parameters confirm that the vanadyl ions are present in PVA films as VO"2"+ molecular ions in an octahedral site with a tetragonal compression (C_4_v). The temperature variation EPR studies reveal that the variation of number of spins with temperature is in accordance with Boltzmann law. It is interesting to observe that the variation of susceptibility with temperature obeys Curie-Weiss law. The FT-IR and FT-Raman spectrum exhibits few bands, which are attributed to O-H, C-H, C-C and C-O groups of stretching and bending vibrations. The optical absorption spectrum exhibits two bands, which are assigned to "2B_2_g->"2B_1_g and "2B_2_g->"2E_g ...

2007-01-15

British Library Electronic Table of Contents (United Kingdom)

In the MnIII complex of the title compound, [MnIII(C18H12N4O2)(H2O)2]ClO4, the MnIII atom is coordinated by four N atoms from the bpb2- [1,2-bis(pyridine-2-carboxamido)benzene] ligand located in the equatorial plane and two O atoms of water molecules at axial positions, yielding a distorted MnN4O2 octahedral coordination geometry. The bpb2- ligand is nearly planar, with a maximum deviation of 0.2311 (3) A from the mean plane. The MnIII complex cation and the perchlorate anion, both of which are located on twofold rotation axes, are connected by O-H...O and C-H...O hydrogen bonds into a three-dimensional supramolecular network structure.

2007-01-01

Crystalline and Liquid Crystalline Organic-Inorganic Hybrid Salts with Cation-Sensitized Hexanuclear Molybdenum Cluster Complex Anion Luminescence

British Library Electronic Table of Contents (United Kingdom)

Abstract The salts [Cnmim]2[Mo6Cl14] (mim = methylimidazolium; n = 4, 6, 12, 16, 18) have been obtained by reaction of CnmimCl with MoCl2. Thermal analysis shows the melting point decreases with increasing alkyl chain length of the cation. The imidazolium chloromolybdates(II) with n = 6-18 decompose above 340 C; [C18mim]2[Mo6Cl14] is thermally stable up to 390 C. All compounds are insensititve to the constituents of the atmosphere. Of the higher melting salts [Cnmim]2[Mo6Cl14] (n = 4, 6), high-quality single crystals could be obtained. Single-crystal X-ray structural analyses clearly show that the cluster complex anion [Mo6Cl14]2- has an electron-precise octahedral {Mo6} cluster. For [C4mim]2[Mo6Cl14], two polymorphs differing in the cation alkyl-side-chain conformation were obtained. The ...

2011-01-01

Comparative crystal field study of Ni{sup 2+} energy levels in NiCl{sub 2}, NiBr{sub 2}, and NiI{sub 2} crystals

Comparative crystal field study of Ni"2"+ energy levels in NiCl_2, NiBr_2, and NiI_2 crystals

The exchange charge model of crystal field theory has been used to analyze systematically the ground state absorption spectra of octahedrally coordinated Ni{sup 2+} ion in isostructural nickel halide crystals NiCl{sub 2}, NiBr{sub 2}, and NiI{sub 2}. The parameters of the crystal field acting on the Ni{sup 2+} ion are calculated from the available crystal structure data. The obtained energy level schemes are compared with experimental absorption spectra; a good agreement with experimental data is demonstrated. Dependencies of the crystal field invariants and covalence effects on the type of ligands are considered. It is shown numerically that the overlap effects between Ni{sup 2+} ion and ligands increase with an increase of the ligands' atomic number resulting in the following order of the degree of covalence: NiI{sub 2}>NiBr{sub 2}>NiCl{sub 2}.

2006-01-15

Chiral salicyloxazolines as auxiliaries for the asymmetric synthesis of ruthenium polypyridyl complexes.

The exchange charge model of crystal field theory has been used to analyze systematically the ground state absorption spectra of octahedrally coordinated Ni"2"+ ion in isostructural nickel halide crystals NiCl_2, NiBr_2, and NiI_2. The parameters of the crystal field acting on the Ni"2"+ ion are calculated from the available crystal structure data. The obtained energy level schemes are compared with experimental absorption spectra; a good agreement with experimental data is demonstrated. Dependencies of the crystal field invariants and covalence effects on the type of ligands are considered. It is shown numerically that the overlap effects between Ni"2"+ ion and ligands increase with an increase of the ligands' atomic number resulting in the following order of the degree of covalence: NiI_2>NiBr_2>NiCl_2.

2006-01-15

A new solid-state process for synthesis of LiMn{sub 1.5}Ni{sub 0.5}O{sub 4-{delta}} spinel

Chiral auxiliaries are promising emerging tools for the asymmetric synthesis of octahedral metal complexes. We recently introduced chiral salicyloxazolines as coordinating bidentate chiral ligands which provide excellent control over the metal-centered configuration in the course of ligand substitution reactions and can be removed afterward in an acid-induced fashion under complete retention of configuration (J. Am. Chem. Soc. 2009, 131, 9602-9603). Here reported is our detailed investigation of this sequence of reactions, affording virtually enantiopure ruthenium polypyridyl complexes. The control of the metal-centered chirality by the coordinated chiral salicyloxazolinate ligand was evaluated as a function of reaction conditions, the employed bidentate 2,2'-bipyridine and 1,10-phenanthroline ligands, and the substituent at the asymmetric 5-position of the oxazoline heterocycle. Most striking was the strong influence of the reaction solvent, with aprotic solvents ...

2010-09-01

A joint computational and experimental study of a novel dioxomolybdenum(VI) complex bearing chiral N,N-dimethyllactamide ligand

A new two-step solid-state process was developed for synthesis of a pure phase 4.7 V LiMn{sub 1.5}Ni{sub 0.5}O{sub 4-{delta}} (LMNO) spinel of good electrochemical properties. This process which was based on formation of stable Ni{sub 1-x}Mn{sub 2}O{sub 4-{delta}} (x {<=} 0.33) spinel followed by subsequent lithiation, demonstrated the emerging of LiMn{sub 1.5}Ni{sub 0.5}O{sub 4-{delta}} frame work at temperatures of as low as 350 C. During this lithiation process, migration of metal ions (Ni/Mn) from partially occupied tetrahedral 8a sites (in Ni{sub 0.67}Mn{sub 2}O{sub 4-{delta}}) toward octahedral 16d site occurred. The resultant spinel material displayed low irreversible loss, a 97% columbic efficiency and 6% loss in discharge capacity after 100 cycles at 60 C. (author)

2010-08-01

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British Library Electronic Table of Contents (United Kingdom)

A new cis-dioxomolybdenum complex MoO2(DMLA)2 (DMLA=N,N-dimethyllactamide) has been synthesized and characterized by X-ray crystallography, H NMR and IR spectroscopies and electronic structure calculations at DFT/B3LYP level. This compound (chemical formula C10H20MoO6N2) crystallizes in the orthorhombic space group P212121 with Z=4, a=6.9357(2)?, b=11.8761(4)?, c=17.7251(5), V=1460.00(8)?3 and renders a slightly distorted octahedral structure with two long Mo-O bonds (2.253(3)? and 2.257(3)?) trans to each of the MoO groups and with two short Mo-O bonds of 1.942(3)4? cis to them. The MoO bond length are 1.715(3) and 1.704(3)?). Each lactamide ligand is bidentate; they are coordinated in their deprotonated form with the carbonyl oxygen occupy...

2011-01-01

Vacancy ordering and oxygen dynamics in oxide ion conducting La1-xSrxGa1-xMgxO3-x ceramics: 71Ga, 25Mg and 17O NMR

Synthesis, structure and characterisation of the n=4 Aurivillius phase Bi5Ti3CrO15

The oxygen vacancies distribution in the rigid lattice and the thermally activated motion of oxygen atoms are studied in La1-xSrxGa1-xMgxO3-x (x=0.00; 0.05; 0.10; 0.15 and 0.20) compounds. For that 71Ga, 25Mg and 17O NMR was performed from 100 K up to 670 K, and ion conductivity measurements were carried out up to 1273 K. The comparison of the electric field gradients at the Ga- and Mg-sites evidences that oxygen vacancies appear exclusively near gallium cations as a species trapped below room temperature in local clusters, GaO5/2-#square#-GaO5/2. These clusters decay at higher temperature into mobile constituents of the structural octahedra Ga(O5/6#square#1/6)6/2. At the same time, the nearest octahedral oxygen environment of magnesium cations persists at different doping levels. The case of two adjacent vacant anion sites is found highly unlikely within the studied doping range. The thermally activated oxygen motion starts to develop above room temperature as is ...

2011-01-01

Synthesis and crystal structure of a new open-framework iron phosphate (NH4)4Fe3(OH)2F2[H3(PO4)4]: Novel linear trimer of corner-sharing Fe(III) octahedra

The n=4 Aurivillius phase, Bi5Ti3CrO15, was synthesised by solid state reaction. Rietveld analysis of high resolution neutron diffraction data demonstrated this material to adopt the polar space group A21am at room temperature, transforming to the aristotype I4/mmm structure above 650 oC. This phase transition is coincident with an anomaly in DSC signal and relative permittivity, which are characteristic of a ferroelectric-paraelectric phase transition. Bi5Ti3CrO15 exhibits paramagnetic behaviour at low temperature, with short range antiferromagnetic interactions, but no evidence for long range magnetic ordering. This is considered a consequence of significant disorder of Ti and Cr over the available octahedral sites, as demonstrated by analysis of neutron diffraction data. -- Graphical abstract: We report here the synthesis, structure and characterisation of the n=4 Aurivillius phase Bi5Ti3CrO15. Analysis of neutron powder diffraction and XANES data, supported by ...

2011-02-01

Synthesis and characterization of LiCo{sub y}Ni{sub (1-y)}VO{sub 4} lithium insertion materials

A new iron phosphate (NH4)4Fe3(OH)2F2[H3(PO4)4] has been synthesized hydrothermally at HF concentrations from 0.5 to 1.2 mL. Single-crystal X-ray diffraction analysis reveals its three-dimensional open-framework structure (monoclinic, space group P21/n (No. 14), a=6.2614(13) A, b=9.844(2) A, c=14.271(3) A, ?=92.11(1)o, V=879.0(3) A3). This structure is built from isolated linear trimers of corner-sharing Fe(III) octahedra, which are linked by (PO4) groups to form ten-membered-ring channels along [1 0 0]. This isolated, linear trimer of corner-sharing Fe(III) octahedra, [(FeO4)3(OH)2F2], is new and adds to the diverse linkages of Fe polyhedra as secondary building units in iron phosphates. The trivalent iron at octahedral sites for the title compound has been confirmed by synchrotron Fe K-edge XANES spectra and magnetic measurements. Magnetic measurements also show that this compound exhibit a strong antiferromagnetic exchange below TN=17 K, consistent with ...

2010-12-01

Swelling behavior of a simple ferritic alloy

A family of mixed LiCo{sub y}Ni{sub (1-y)}VO{sub 4} (y=0.2, 0.5 and 0.8) compounds of potential use as high voltage cathode materials in lithium batteries, has been synthesized and characterized. The X-ray diffraction analysis showed that these compounds adopt an inverse spinel structure where in average 85% of the Ni{sup 2+} and Co{sup 2+} ions occupy octahedral sites and the other 15% occupy tetrahedral sites with the V{sup 5+} ions, although this occupation share is somewhat influenced by the preparation temperature. The annealing temperature plays also a key role in determining the particle size, as demonstrated by scanning electron microscope analysis. Cycling voltammetry tests showed that the lithium insertion-deinsertion process in the LiCo{sub y}Ni{sub (1-y)}VO{sub 4} electrode materials occurs reversibly around 4.3-4.4 V vs. Li, as also confirmed by cycling tests. The cycling capacity is somewhat modest; however, the trend of the cycling curves leads to ...

2000-02-01

Influence of composite LiCl-KCl molten salt on microstructure and electrochemical performance of spinel Li{sub 4}Ti{sub 5}O{sub 12}

The swelling behavior which results from simulated fusion environment irradiation of Fe-10% Cr has been characterized with transmission electron microscopy. Specimens were bombarded at 850 K with: a ''triple-beam'' of He"+, D_2"+, and 4 MeV Fe"+"+ ions to 0.3, 1, 3, 10, 30, and 100 dpa (displacement per atom); a ''dual-beam'' of He"+ and 4 MeV Fe"+"+ ions to 30 and 100 dpa; and a ''single-beam'' of 4 MeV Fe"+"+ ions to 30 dpa. The helium and hydrogen injection rates were approx. =10 appm He/dpa and approx. =40 appm D/dpa. Cavities were observed for damage levels of 3 dpa and greater. The swelling was <0.1% for damage levels <30 dpa, but at 100 dpa, there was an increase in the swelling to 2.5% for the ''triple-beam'' irradiation and 1.2% for the ''dual-beam'' irradiation. The swelling rates between 30 and 100 dpa correlate well with calculated values assuming a steady-state swelling-rate regime has been reached. Calculations show the rapid cavity growth associated with this ...

Ground and excited state absorption of Ni{sup 2+} ions in MgAl{sub 2}O{sub 4}: Crystal field analysis

A series of spinel Li{sub 4}Ti{sub 5}O{sub 12} samples were synthesized via a composite molten-salt method (CMSM) using the mixtures of LiCl and KCl with different L values (L is defined as the molar ratio of LiCl:KCl) as the reaction media. It is found that the melting point of the composite molten salt can effectively influence the formation of particles, and leads to different electrochemical performances of the as-prepare Li{sub 4}Ti{sub 5}O{sub 12}. The investigations of X-ray diffraction (XRD), particle size distribution (PSD), Brunauer-Emmet-Teller (BET) surface area, and scanning electron microscopy (SEM) indicate that the as-prepared Li{sub 4}Ti{sub 5}O{sub 12} with L = 1.5 is a pure phase, and has uniform homogeneous octahedral shape particles, rather narrow PSD, and high BET surface area. Electrochemical tests show that the optimized Li{sub 4}Ti{sub 5}O{sub 12} with L = 1.5 has an initial discharge capacity of 169 mAh g{sup -1} and an initial ...

2008-12-30

Fully relativistic analysis of the absorption spectra of Ca{sub 3}Sc{sub 2}Ge{sub 3}O{sub 12}:Ni{sup 2+}

The exchange charge model (ECM) of crystal field is utilized to provide the theoretical explanation of the ground state absorption and the excited state absorption observed for the octahedrally coordinated Ni{sup 2+} ions in the spinel MgAl{sub 2}O{sub 4}. The ECM enables modeling of the crystal field parameters (CFPs) for the impurity ions based on the crystal structure data of the host lattice. To ensure the reliability of the CFPs, the convergence of the CFP values with the increasing number of the coordination spheres taken into account in the ECM calculations is considered. The trigonal CFPs B{sub 2}{sup 0},B{sub 4}{sup 0}andB{sub 4}{sup -3} determined by the ECM, together with the appropriate Racah parameters B and C, serve as input to two crystal field analysis computer packages, which compute the energy level schemes within the whole 3d{sup 8} configuration. The cubic approximation utilizing only one CFP Dq is also discussed. Basic features of the ground ...

2007-04-25

Facile synthesis and the sensitized luminescence of europium ions-doped titanate nanowires

Systematic analysis of the energy level schemes, ground state absorption (GSA) and covalency effects for the Ni{sup 2+} ion in Ca{sub 3}Sc{sub 2}Ge{sub 3}O{sub 12} was performed. The recently developed first-principles approach to the analysis of the absorption spectra of impurity ions in crystals based on the discrete variational multi-electron method (DV-ME) [K. Ogasawara et al., Phys. Rev. B 64, 115413 (2001)] was used in the calculations. As a result, complete energy level schemes of Ni{sup 2+} and its absorption spectra at both possible crystallographic positions (distorted octahedral Sc{sup 3+} and tetrahedral Ge{sup 4+} positions) were calculated, assigned and compared with experimental data. Energies of the charge transfer (CT) transitions for both positions are estimated. Numerical contributions of all possible electron configurations into the calculated energy states were determined. By performing analysis of the molecular orbitals (MO) population, it was ...

2006-10-15

Electronic and geometric structure of transition-metal nanoclusters

Europium (Eu) ions-doped titanate nanowires were synthesized via a sol-gel-hydrothermal chemistry and they were found to be roll multilayered trititanate-type nanowires intercalated with Eu3+ and alkali ions. The average diameter was about 20 nm for nanowires synthesized in NaOH solution and about 10 nm for nanowires synthesized in KOH solution. Under ultraviolet excitation the nanowires showed bright red emission corresponding to 5D0-7Fj of Eu3+ ions at room temperature, which was attributed to the non-radiative energy transfer from the surrounding Ti-O octahedral nanosheets to the central Eu3+ ions in interlayer. The luminescent properties of nanowires were influenced by the type of co-intercalated alkali ions, doping degree, hydrothermal and annealing temperatures. The intensity ratio of 5D0-7F2 to 5D0-7F1 of titanate nanowires intercalated with Eu3+ and Na+ ions was higher than that of titanate nanowires intercalated with Eu3+ and K+ ions. The emission ...

2009-04-15

Atomic interactions between plutonium and helium.

A massively-parallel ab initio computer code, which uses Gaussian bases, pseudopotentials, and the local density approximation, permits the study of transition-metal systems with literally hundreds of atoms. We present total energies and relaxed geometries for Ru, Pd, and Ag clusters with N = 55, 135, and 140 atoms; we also used the DMOL code to study 13-atom Pd and Cu clusters, with and without hydrogen. The N = 55 and 135 clusters were chosen because of simultaneous cubo-octahedral (fcc) and icosahedral (icos) sub-shell closings, and we find icos geometries are preferred. Remarkably large compressions of the central atoms are observed for the icos structures (up to 6% compared with bulk interatomic spacings), while small core compressions ({approx} 1 %) are found for the fcc geometry. In contrast, large surface compressive relaxations are found for the fcc clusters ({approx} 2-3% in average nearest neighbor spacing), while the icos surface displays small ...

1996-08-01

Biogenic iron oxyhydroxide formation at mid-ocean ridge hydrothermal vents: Juan de Fuca Ridge

An essential issue in gallium (Ga)-stabilized fcc-phase plutonium ({delta}-Pu) is the formation of helium (He) voids and bubbles emanating from the radiolytic decay of the Pu. The rate of formation of He voids and bubbles is related to the He-defect formation energies and their associated migration barriers. The size and shape distributions of the bubbles are coupled to these critical migration processes. The values of the defect formation energies, internal pressure, and migration barriers can be estimated from atomistic calculations. Complicating this picture is the destruction of He-filled voids and bubbles by subsequent radiolytic decay events. The present study concerns the construction of the necessary potential energy surfaces for the Pu-He and He-He interactions within the modified embedded atom method (MEAM). Once fully tested, the potentials will be used to estimate the He-defect formation energies and barriers to the migration of these defects for both interstitial and ...

2002-01-01

Comparison on the growth of oxide films formed in alloy 800 and alloy 600 in an aqueous medium at high temperature

Here we examine Fe speciation within Fe-encrusted biofilms formed during 2-month seafloor incubations of sulfide mineral assemblages at the Main Endeavor Segment of the Juan de Fuca Ridge. The biofilms were distributed heterogeneously across the surface of the incubated sulfide and composed primarily of particles with a twisted stalk morphology resembling those produced by some aerobic Fe-oxidizing microorganisms. Our objectives were to determine the form of biofilm-associated Fe, and identify the sulfide minerals associated with microbial growth. We used micro-focused synchrotron-radiation X-ray fluorescence mapping (mu XRF), X-ray absorption spectroscopy (mu EXAFS), and X-ray diffraction (mu XRD) in conjunction with focused ion beam (FIB) sectioning, and highresolution transmission electron microscopy (HRTEM). The chemical and mineralogical composition of an Fe-encrusted biofilm was queried at different spatial scales, and the spatial relationship between primary sulfide and ...

2008-05-22

Hydration of swelling clay and bacteria interaction. An experimental in situ reaction study; Hydratation des argiles gonflantes et influence des bacteries. Etude experimentale de reaction in situ

Alloy 800 and Alloy 600 are well known for their resistance to corrosion in an aqueous medium at high pressure and temperature, for which they have been widely used for more than 3 decades in different structural components of water refrigerated nuclear reactors, especially as material for the steam generator tubes (SG) in these nuclear plants. The SG tubes in the Atucha I and Embalse Nuclear Plants are made with Alloy 800. The speed of corrosion of these materials in a reactor's refrigerant medium, while very small is perfectly measurable and can be described by parabolic or logarithmic type kinetics. In other words this speed is high in the first states of growth during the formation of a protective oxide film but then drops to almost stationary values. One characteristic of these films is the formation of a double layer (or duplex): i) an internal adhering layer, of approximately constant thickness, formed by small microcrystals (#<=#0.05 mm), ii) a less adhering external one, ...

2006-12-01

Carbomolybdates(III): On Pr{sub 2}[Mo{sub 2}C{sub 3}] and structural relations to Er{sub 2}Mo{sub 2}C{sub 3}; Carbomolybdate(III): Zur Kenntnis von Pr{sub 2}[Mo{sub 2}C{sub 3}] sowie Strukturbeziehungen zu Er{sub 2}Mo{sub 2}C{sub 3}

This study reports on the physical-chemical behaviour of swelling di-octahedral clays (smectites) and their interaction with aqueous solutions and bacteria (Shewanella putrefaciens). Experimental results are presented for compacted clays, hydrated under confined volume conditions, using a new type of reaction-cell (the 'wet-cell' of Warr and Hoffman, 2004) that was designed for in situ X-ray diffraction (XRD) measurement. For comparison, dispersed clay systems were studied using standard batch solutions subjected to varying degrees of agitation. The combination of time-dependent in situ XRD measurements with gravimetric measurements and calculated diffraction patterns using the CALCMIX software (Plancon and Drits, 1999) allowed to successful quantification of the dynamics of water uptake and storage. This analytical procedure combined with published water vapour adsorption data enabled determination of the abundance of structured water layers, ...

2008-01-15