Hydration of Na+, Ni2+, and Sm3+ in the Interlayer of Hectorite: A Quasielastic Neutron Scattering Study

International audienceQuasielastic neutron scattering experiments were performed with Na−hectorite, Ni−hectorite, and Sm−hectorite samples in order to find out whether Sm3+ is present in the clay interlayer as a fully hydrated cation (outer-sphere complex), or, as it follows from neutron diffraction data analysis, it is dehydrated and bound to the clay surface (inner-sphere complex). The results obtained for the Sm−hectorite were compared with other interlayer cations: strongly hydrated Ni2+ and relatively weakly hydrated Na+. It was found that water mobility in the Sm−hectorite sample is very close to the water mobility in Ni−hectorite. This is only possible if the Sm3+ ion is fully hydrated. It was shown that water molecules hydrating Ni2+ and Sm3+ exhibit diffusion mobility measurable with backscattering spectrometers. The diffusion coefficients of the exchangeable cations were found using the slow exchange approximations DNi = (0.05 − 0.14) × 10−9 m2/s and DSm = (0.04 − 0.18) × 10−9 m2/s

Radiation hydrodynamics of SN 1987A: I. Global analysis of the light curve for the first 4 months

The optical/UV light curves of SN 1987A are analyzed with the multi-energy group radiation hydrodynamics code STELLA. The calculated monochromatic and bolometric light curves are compared with observations shortly after shock breakout, during the early plateau, through the broad second maximum, and during the earliest phase of the radioactive tail. We have concentrated on a progenitor model calculated by Nomoto & Hashimoto and Saio, Nomoto, & Kato, which assumes that 14 solar masses of the stellar mass is ejected. Using this model, we have updated constraints on the explosion energy and the extent of mixing in the ejecta. In particular, we determine the most likely range of E/M (explosion energy over ejecta mass) and R_0 (radius of the progenitor). In general, our best models have energies in the range E = (1.1 +/- 0.3) x 10^{51} ergs, and the agreement is better than in earlier, flux-limited diffusion calculations for the same explosion energy. Our modeled B and V fluxes compare well with observations, while the flux in U undershoots after about 10 days by a factor of a few, presumably due to NLTE and line transfer effects. We also compare our results with IUE observations, and a very good quantitative agreement is found for the first days, and for one IUE band (2500-3000 A) as long as for 3 months. We point out that the V flux estimated by McNaught & Zoltowski should probably be revised to a lower value.Comment: 27 pages AASTeX v.4.0 + 35 postscript figures. ApJ, accepte

Macromolecular structure determination using X-rays, neutrons and electrons: recent developments in Phenix.

Diffraction (X-ray, neutron and electron) and electron cryo-microscopy are powerful methods to determine three-dimensional macromolecular structures, which are required to understand biological processes and to develop new therapeutics against diseases. The overall structure-solution workflow is similar for these techniques, but nuances exist because the properties of the reduced experimental data are different. Software tools for structure determination should therefore be tailored for each method. Phenix is a comprehensive software package for macromolecular structure determination that handles data from any of these techniques. Tasks performed with Phenix include data-quality assessment, map improvement, model building, the validation/rebuilding/refinement cycle and deposition. Each tool caters to the type of experimental data. The design of Phenix emphasizes the automation of procedures, where possible, to minimize repetitive and time-consuming manual tasks, while default parameters are chosen to encourage best practice. A graphical user interface provides access to many command-line features of Phenix and streamlines the transition between programs, project tracking and re-running of previous tasks

The CCP4 suite : integrative software for macromolecular crystallography

The Collaborative Computational Project No. 4 (CCP4) is a UK-led international collective with a mission to develop, test, distribute and promote software for macromolecular crystallography. The CCP4 suite is a multiplatform collection of programs brought together by familiar execution routines, a set of common libraries and graphical interfaces. The CCP4 suite has experienced several considerable changes since its last reference article, involving new infrastructure, original programs and graphical interfaces. This article, which is intended as a general literature citation for the use of the CCP4 software suite in structure determination, will guide the reader through such transformations, offering a general overview of the new features and outlining future developments. As such, it aims to highlight the individual programs that comprise the suite and to provide the latest references to them for perusal by crystallographers around the world

The short-range order of ions in clay minerals: Sm3+ coordination

International audienceExperimental techniques as neutron diffraction (ND) with isotopic substitution (NDIS), extended X-ray absorption fine structure spectroscopy (EXAFS), and quasielastic neutron scattering (QENS), in combination with molecular dynamics (MD) simulations, are usually applied to the study of noncrystalline solids, but they are also very useful for the study of complex systems, where the short range order provides an insight of its structure and dynamics. Here, they are used in the study of the coordination of the Sm3þ in the interlayer of hydrated synthetic montmorillonite and hectorite. The ND results indicate that not all oxygen atoms in the first coordination shell of the Sm3þ belong to water molecules, supporting the formation of theSm3þ inner-sphere complex.On the other hand, the other techniques suggest that the adsorbed Sm3þ cations form outer-sphere complexes with the clay surface. The hypothesis making compatible all results is that there are different Sm species adsorbed in the clay interlayer: a part of Sm is in the Sm3þ cationic form, forming outer-sphere adsorption complexes, another part is hydrolyzed and present in the interlayer space as Sm(OH)2þ, SmðOHÞþ 2 , or SmðOHÞ0 3 species. The latter are more hydrophobic than Sm3þ cations and can be dehydrated and are able to stick to the clay surface

Superconducting integrated submillimeter receiver for TELIS

In this report an overview of the results on the development of a single-chip superconducting integrated receiver for the Terahertz Limb Sounder (TELIS) balloon project intended to measure a variety of stratosphere trace gases is presented. The Superconducting Integrated Receiver (SIR) comprises in one chip a planar antenna integrated with a superconductor-insulator-superconductor (SIS) mixer, a superconducting Flux Flow Oscillator (FFO) acting as Local Oscillator (LO) and a second SIS harmonic mixer (HM) for FFO phase locking. As a result of the FFO design optimization a free-running linewidth between 9 and 1.5 MHz has been measured in the frequency range 500-710 GHz resulting in phase-locking of 35 to 95% of the FFO power correspondingly. A new generation of the SIR devices with improved FFO performance and optimized interface between FFO and SIS/HM has been developed and comprehensively tested. As a result all required TELIS parameters were demonstrated., Phase-locked FFO operation over entire SIR channel frequency range has been realized, spectral resolution below 1 MHz has been confirmed by gas cell and CW signal measurements. An uncorrected double side band (DSB) noise temperature below 250 K has been measured with the phase-locked FFO. The intermediate frequency bandwidth 4-8 GHz; has been realized. To ensure remote operation of the phase-locked SIR several procedures for its automatic computer control have been developed and tested

“Hydrotriphylites” Li1-xFe1+x(PO4)1-y(OH)4y as Cathode Materials for Li-ion Batteries

Lithium iron phosphate LiFePO4 triphylite is now one of the core positive electrode (cathode) materials enabling the Li-ion battery technology for stationary energy storage applications, which are important for broad implementation of the renewable energy sources. Despite the apparent simplicity of its crystal structure and chemical composition, LiFePO4 is prone to off-stoichiometry and demonstrates rich defect chemistry owing to variations in the cation content and iron oxidation state, and to the redistribution of the cations and vacancies over two crystallographically distinct octahedral sites. The importance of the defects stems from their impact on the electrochemical performance, particularly on limiting the capacity and rate capability through blocking the Li ion diffusion along the channels of the olivine-type LiFePO4 structure. Up to now the polyanionic (i.e. phosphate) sublattice has been considered idle on this playground. Here, we demonstrate that under hydrothermal conditions up to 16% of the phosphate groups can be replaced with hydroxyl groups yielding the Li1-xFe1+x(PO4)1-y(OH)4y solid solutions, which we term “hydrotriphylites”. This substitution has tremendous effect on the chemical composition and crystal structure of the lithium iron phosphate causing abundant population of the Li-ion diffusion channels with the iron cations and off-center Li displacements due to their tighter bonding to oxygens. These perturbations trigger the formation of an acentric structure and increase the activation barriers for the Li-ion diffusion. The “hydrotriphylite”-type substitution also affects the magnetic properties by progressively lowering the Néel temperature. The off-stoichiometry caused by this substitution critically depends on the overall concentration of the precursors and reducing agent in the hydrothermal solutions, placing it among the most important parameters to control the chemical composition and defect concentration of the LiFePO4-based cathodes