International Nuclear Information System (INIS)

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 ...

British Library Electronic Table of Contents (United Kingdom)

We propose and demonstrate a facile room-temperature synthetic method for obtaining water-soluble magnetic Fe3O4 nanoparticles (NPs) by combining the in situ synthesis and decomposition of a magnetic polymer hydrogel. The Fe3O4 NPs with average diameters of 6.3-8.3nm were synthesized in a cross-linked polyacrylamide (PAAm) hydrogel by coprecipitating iron ions. The decomposition of the magnetic polymer hydrogel by an aqueous solution of sodium hydroxide led to the transfer of Fe3O4 NPs into the aqueous medium. The NPs can be dispersed stably in water for more than three months. The Fe3O4 NPs were characterized by X-ray photoelectron spectra (XPS), X-ray ...

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A magnetic core/shell Fe3O4/FeMnOx catalyst was prepared by a simple oxidation-precipitation method. The catalyst was characterized by X-ray diffraction, transmission electron microscope, X-ray photoelectron spectroscopy, Fourier transform infrared spectroscopy, thermogravimetric analysis and cyclic voltammetry. The characterization studies verified that Fe3O4 core was coated with a layer of Fe-Mn oxide. The Fe3O4/FeMnOx was found to be an effective and stable heterogeneous catalyst for the discoloration of methylene blue (MB) in aqueous solution by H2O2. The high catalytic activity is due to the FeMnOx shell, which not only increased the surface hydroxyl groups, but also enhanced the interfacial electron transfer. The discoloration of MB ...

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We describe a simple one-pot thermal decomposition method for the production of a stable colloidal suspension of narrowly dispersed superparamagnetic Fe3O4-Ag core-shell nanostructures. These biocompatible nanostructures are highly toxic to microorganisms. Antimicrobial activity studies were carried out on both Gram negative (Escherichia coli and Proteus vulgaris) and Gram positive (Bacillus megaterium and Staphylococcus aureus) bacterial strains. Efforts have been made to understand the underlying molecular mechanism of such antibacterial actions. The effect of the core-shell nanostructures on Gram negative strains was found to be better than that observed for silver nanoparticles. The minimum inhibitory concentration (MIC) values of these nanostructures were found to be considerably lowe...

Science.gov (United States)

BackgroundIn recent years, near-infrared fluorescence (NIRF)-labeled iron nanoparticles have been synthesized and applied in a number of applications, including the labeling of human cells for monitoring the engraftment process, imaging tumors, sensoring the in vivo molecular environment surrounding nanoparticles and tracing their in vivo biodistribution. These studies demonstrate that NIRF-labeled iron nanoparticles provide an efficient probe for cell labeling. Furthermore, the in vivo imaging studies show excellent performance of the NIR fluorophores. However, there is a limited selection of NIRF-labeled iron nanoparticles with an optimal wavelength for imaging around 800 nm, where tissue autofluorescence is minimal. Therefore, it is necessary to develop additional alternative NIRF-labeled iron nanoparticles for application in this area.ResultsThis study manufactured 12-nm DMSA-coated Fe3O4 ...

International Nuclear Information System (INIS)

Structure and magnetic properties of the thermal decomposition products of Fe(III(Co(II) acrylate complex were analysed. The crystalline phases, which were found in the fully processed material, at 643 K, were Fe_3O_4, CoFe_2O_4 and CoO and had a mean particle size of about 30 nm. In the intermediate stages of the thermolysis iron was present in a form of Fe"I"I"I (trivalent low-spin iron), Fe"2"+ (divalent high-spin iron), and Fe_3O_4. The coercivity and remanence were measured versus temperature in the range of 5-300 K, in 1.1 T applied field. Both _MH_c and M_r, decreased showing room temperature values of 0.038 T and 7.49 mT, for coercivity and remanence, respectively. At temperatures below 200 K the hysteresis loops were asymmetrical, opened and shifted towards negative field values. (author)

International Nuclear Information System (INIS)

Superparamagnetic MFe23+O4 (M=Mn2+, Fe2+ and Co2+) inverse spinel ferrite (ISF) nanoparticles with narrow size distribution having average diameters of 6-8 nm were synthesized by a diol reduction of organic metals and the surface was modified to be hydrophilic by coating with succimer. Magnetic resonance imaging (MRI) contrast enhancement by dipolar coupling defined interactions between the synthesized ISFs and protons in the bulk water was investigated with initial susceptibility, magnetization and anisotropy of the succimer-coated ISFs. The relaxivity ratios, r2/r1, for MnFe2O4, Fe3O4 and CoFe2O4 were measured to be 12.2, 23.1 and 62.3, respectively, which demonstrate the potential usefulness of these magnetic nanoparticles as T2 contrast agents for MRI.

International Nuclear Information System (INIS)

Rapid corrosion of PWR steam generator carbon steel support structures and consequential denting of steam generator tubes led to considerable investigation of the mechanism of corrosion and for palliatives. The basic mechanism is now fairly well understood. Chloride present in the boiler feedwater from condenser leakage is concentrated in the support plate crevice as a result of the superheat present. This leads to the formation of a low pH acid ferrous chloride environment either through the hydrolysis of a weak base chloride such as MgCl_2 or the combined action of a neutral chloride with an oxidizing agent. Rapid attack of the carbon steel ensues with the Fe_3O_4 corrosion product forming at the metal/oxide interface. This oxide has a volume approximately twice that of the steel consumed and thus eventually fills the crevice between the tube and the support plate. Oxide growth continues leading to ...

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 ...

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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.

Science.gov (United States)

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

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

Energy Technology Data Exchange (ETDEWEB)

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.

International Nuclear Information System (INIS)

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.

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ZnO thin films were electrodeposited in aqueous solution on gilded p-type Si wafer substrates. Thermal treatments were carried out on different films in Ar atmosphere at different temperatures, between 200 and 600 {sup 0}C. Surface morphology studies using scanning electron microscopy and atomic force microscopy show a smooth surface for an annealing temperature of 400 {sup 0}C with a roughness mean square value of about 15 nm and a precipitation of ZnO microcrystals on the deposit surface at 600 {sup 0}C. X-ray diffraction experiments reveal a decrease in the c-parameter value from 5.223 to 5.206 A after treatment at 600 {sup 0}C, due to the removal of hydrogen from the film. Raman spectroscopy analyses show an improvement in the crystal quality of the film and a decrease in the compressive stress inside the deposit. Photoluminescence observations reveal an important change in the UV emission band after annealing at 200 {sup 0}C. A visible region emission band at ...

International Nuclear Information System (INIS)

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.

Energy Technology Data Exchange (ETDEWEB)

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.

Energy Technology Data Exchange (ETDEWEB)

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.

Science.gov (United States)

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 ...

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...

Energy Technology Data Exchange (ETDEWEB)

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 ...

Science.gov (United States)

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

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...

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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...

Energy Technology Data Exchange (ETDEWEB)

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 ...

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.

Energy Technology Data Exchange (ETDEWEB)

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}.

Science.gov (United States)

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 ...

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...

International Nuclear Information System (INIS)

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 ...

Energy Technology Data Exchange (ETDEWEB)

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 ...

Energy Technology Data Exchange (ETDEWEB)

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 ...

Energy Technology Data Exchange (ETDEWEB)

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 ...

Energy Technology Data Exchange (ETDEWEB)

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 ...

Energy Technology Data Exchange (ETDEWEB)

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 ...

Energy Technology Data Exchange (ETDEWEB)

Pr{sub 2}[Mo{sub 2}C{sub 3}] was obtained by arc melting of the elements followed by annealing at 1500 C in arc welded and sealed Mo-ampoules. The compound was characterised by chemical analyses, X-ray diffraction and metallography. The crystal structure (monoclinic, P2{sub 1}/c, Z = 4, a = 597.99(10) pm, b = 665.15(11) pm, c = 1185.60(19) pm and {beta} = 111.631(5) ) represents a new structure type containing a three dimensional polyanion {sub {infinity}}{sup 3}[(Mo{sub 2}C{sub 3}){sup 6-}] with Molybdenum(III) in a distorted tetrahedral coordination by carbo-ligands. Tetrameric building-blocks, Mo{sub 4}C{sub 10}, of edge sharing MoC{sub 4}-tetrahedra are arranged to form layers running parallel to (100). The layers are interconnected along [100] by sharing common apices of the MoC{sub 4} tetrahedra. The coordination polyhedra around praseodymium represent distorted (PrC{sub 5})-arrangements (mono capped tetrahedra and square pyramids). The metal atoms together form a distorted motif ...