Lithium Insertion Mechanism in Iron-Based Oxyfluorides with Anionic Vacancies Probed by PDF Analysis

The mechanism of lithium insertion that occurs in an iron oxyfluoride sample with a hexagonal–tungsten–bronze (HTB)-type structure was investigated by the pair distribution function. This study reveals that upon lithiation, the HTB framework collapses to yield disordered rutile and rock salt phases followed by a conversion reaction of the fluoride phase toward lithium fluoride and nanometer-sized metallic iron. The occurrence of anionic vacancies in the pristine framework was shown to strongly impact the electrochemical activity, that is, the reversible capacity scales with the content of anionic vacancies. Similar to FeOF-type electrodes, upon de-lithiation, a disordered rutile phase forms, showing that the anionic chemistry dictates the atomic arrangement of the re-oxidized phase. Finally, it was shown that the nanoscaling and structural rearrangement induced by the conversion reaction allow the in situ formation of new electrode materials with enhanced electrochemical properties.     

The mapping properties of the radiosity operator along an edge

In this article we study the radiosity operator along an edge between two adjacent half‐planes. First we show that the radiosity operator is invertible in a whole scale of anisotropic Sobolev spaces. In the absence of any shadows we are able to derive regularity properties of the solution, which depend only on the angle between the half‐planes, the reflectivity coefficients and the right‐hand side. This work can be considered as a supplement to the article of Rathsfeld (Mathematical Methods in the Applied Sciences 1999; 22 : 217–241). Copyright © 2002 John Wiley & Sons, Ltd.     

A posteriori error estimates for a time discrete scheme for a phase-field system of Penrose-Fife type

A time discrete scheme is used to approximate the solution toa phase field system of Penrose–Fife type with a non-conservedorder parameter. An a posteriori error estimate is presentedthat allows the estimation of the difference between continuousand semidiscrete solutions by quantities that can be calculatedfrom the approximation and given data.     

Trovacenchemie. 13 [1] Weg und Irrweg zu Di([5]trovacenyl)keton

Trovacene Chemistry. 13 [1] On Being Lead and Mislead in the Synthesis of Di([5]trovacenyl)ketone Di([5]trovacenyl)ketone ( 3¨ ) has been prepared from lithio‐[5]trovacene and dimethylcarbamoyl chloride and studied by X‐ray diffraction, cyclic voltammetry, magnetic susceptometry and EPR spectroscopy. Slight variation of the synthetic protocol affords an unusual trinuclear complex 5 ? that is also fully characterized. Spin‐spin exchange interaction is smaller in 3¨ than in 1,1‐di([5]trovacenylethene ( 2¨ ), which differs from 3¨ by a replacement of O for CH₂. The novel trinuclear complex 5 ? , however, displays exchange coupling very similar to that observed in 1‐methoxy‐2,5,6‐tri([5]trovacenyl)benzene ( 7 ? ). In both cases, an unsymmetrical triangular arrangement of S = 1/2 centers is encountered. These findings are discussed in terms of the nature of the respective spacers.     

On a generalized $L_2$ projection and some related stability estimates in Sobolev spaces

Summary. In this paper we investigate a stability estimate needed in hybrid finite and boundary element methods, especially in hybrid coupled domain decomposition methods including mortar finite elements. This stability estimate is equivalent to the stability of a generalized projection in certain Sobolev spaces. Using piecewise linear trial spaces and appropriate piecewise constant test spaces, the stability of the generalized projection is proved assuming some mesh conditions locally. Received April 11, 2000 / Revised version received February 15, 2001 / Published online July 25, 2001     

On the Spectra of Carbon Nano-Structures

An explicit derivation of dispersion relations and spectra for periodic Schrödinger operators on carbon nano-structures (including graphene and all types of single-wall nano-tubes) is provided.     

Capabilities of double focussing magnetic sector-ICP-MS for the determination of trace elements in body fluids (blood, blood serum, urine) at the example of control materials

The capability of double focussing magnetic sector inductively coupled plasma mass spectrometry (HR-ICP-MS) for the determination of trace elements in different body fluids was investigated in commercially available control materials. The elements included in this study were: Al, As, Cd, Cr, Co, Cu, Hg, Mn, Ni, Pb, Sb, Se, Tl and Zn. Sample preparation, instrument stability and the results, which are in very good agreement to the given values, are presented and discussed. Received: 27 August 1997 / Revised: 19 November 1997 / Accepted: 23 November 1997     

Zur Elektronenstruktur metallorganischer Komplexe der f‐Elemente. 64 Äußert sich die zwitterionische Natur des Triphenylphosphanoxid‐Liganden auch in seinen spektrochemischen Eigenschaften?

Electronic Structures of Organometallic Compounds of f Elements. 64 Does the Zwitterionic Nature of the Triphenylphosphine Oxide Ligand Manifest itself in its Spectrochemical Properties? The triphenylphosphine oxide mono adducts of the moiety tris(η⁵‐cyclopentadienyl)lanthanide(III) (Ln(Cp)₃; Ln = Pr ( 1 ), La ( 2 )) were synthesized and structurally characterized. The Ln–O distances of these compounds are noticeably shorter than those of the corresponding THF adducts. A crystal field (CF) analysis of the optical spectra of 1 leads to a low absolute value of the quadratic CF parameter which is comparable with those of [Pr(Cp)₃(L)]^? adducts with anionic bases but not with [Pr(Cp)₃(MeTHF)]. Reasons for the latter finding are presented.     

Field dependent critical fluctuations aboveT g in the ESR line width of the spin glassAgMn

The ESR of the spin glassAgMn (2.7 and 9.6 at %) has been investigated below and aboveT _g(0.1T _g<T<5T _g) at various microwave frequencies. The analysis yields:1) No explicit frequency dependence but strong magnetic field effects, inherent with ESR-experiments.2) Part of the excess line width is identified as critical spin fluctuations, following a power law. However, because of the presence of the applied field, the reduced temperaturet is not a good scaling variable. We choose the non-linear susceptibility X _s divided byH ², which scales as the order parameter susceptibility. The experiment yieldsW _ex(X _s /H ²) ^p ,p=0.42. From this we deduce z3.     

Oriented immobilization of Desulfovibrio gigas hydrogenase onto carbon electrodes by covalent bonds for nonmediated oxidation of H2

The orientation of hydrogenase bound covalently to a pyrolytic graphite edge electrode modified with a 4-aminophenyl monolayer can be modulated via electrostatic interactions during the immobilization step. At low ionic strength and when the amino groups of the electrode surface are mostly protonated, the hydrogenase is immobilized with the negatively charged region that surrounds its 4Fe4S cluster nearer to the protein surface facing the electrode. This allows direct electron transfer between the immobilized hydrogenase and the electrode, which is observed by the strong catalytic currents measured in the presence of the H2 substrate. Therefore, a very stable enzymatic electrode is produced that catalyzes nonmediated H2 oxidation.