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.     

Estimating the largest singular values of large sparse matrices via modified moments

We describe a procedure for determining a few of the largest singular values of a large sparse matrix. The method by Golub and Kent which uses the method of modified moments for estimating the eigenvalues of operators used in iterative methods for the solution of linear systems of equations is appropriately modified in order to generate a sequence of bidiagonal matrices whose singular values approximate those of the original sparse matrix. A simple Lanczos recursion is proposed for determining the corresponding left and right singular vectors. The potential asynchronous computation of the bidiagonal matrices using modified moments with the iterations of an adapted Chebyshev semi-iterative (CSI) method is an attractive feature for parallel computers. Comparisons in efficiency and accuracy with an appropriate Lanczos algorithm (with selective re-orthogonalization) are presented on large sparse (rectangular) matrices arising from applications such as information retrieval and seismic reflection tomography. This procedure is essentially motivated by the theory of moments and Gauss quadrature.This author's work was supported by the National Science Foundation under grants NSF CCR-8717492 and CCR-910000N (NCSA), the U.S. Department of Energy under grant DOE DE-FG02-85ER25001, and the Air Force Office of Scientific Research under grant AFOSR-90-0044 while at the University of Illinois at Urbana-Champaign Center for Supercomputing Research and Development.This author's work was supported by the U.S. Army Research Office under grant DAAL03-90-G-0105, and the National Science Foundation under grant NSF DCR-8412314.     

Zero-temperature properties of randomly self-interacting polymers

We study the zero-temperature behavior of several simple models for randomly self-interacting polymers in one and 1+1 dimensions. Results are based on exact enumeration and closed-form expressions.     

Europium-151 Mössbauer spectroscopic and XANES investigation of europium-exchanged Y-zeolite

Eu³⁺ in ca. 10 wt% europium-exchanged Y-zeolite is partially reduced by treatment in hydrogen at 600°C to Eu²⁺. The reduction of Eu³⁺ is more readily achieved in Y-zeolite than in europium(III) oxide. The discrepancy in the extent of reduction as revealed by¹⁵¹Eu Mössbauer spectroscopy and near edge X-ray absorption fine structure (XANES) is associated with any difference in the recoil free fractions of Eu²⁺ and Eu³⁺ which may exist at 298 K and the enhanced sensitivity of the XANES to changes in the europium oxidation state.     

Interpretive approach to collective effects of electrons in multicenter problems

Interpretive theoretical tools prove valuable in guiding the analysis of experiments in the realm of atomic clusters. Here, we review basic elements of an analytic approach that makes it possible to find and visualize the effective electrostatic potential and Coulomb correlations in multicenter problems. To illustrate the utility of these concepts we apply them to exploring molecular-doped metallic clusters. This study is aiming at a systematic, visual assessment of changes induced in screening, Coulomb correlation and effective potential by varying the charge of the electronegative impurity and its position in the cluster cage.     

57Fe Mössbauer Spectroscopy Study of LaFe1−x Co x O3 (x=0 and 0.5) Formed by Mechanical Milling

Hyperfine Interactions - Perovskite-related phases of the type LaFe1?x Co x O3 (x=0 and 0.5) have been synthesised by milling techniques. The materials are of smaller particle size and more...