Heteroleptic samarium(III) halide complexes probed by fluorescence-detected L3-edge X-ray absorption spectroscopy

Addition of various oxidants to the near-linear Sm(II) complex [Sm(N††)2] (1), where N†† is the bulky bis(triisopropylsilyl)amide ligand {N(SiiPr3)2}, afforded a family of heteroleptic three-coordinate Sm(III) halide complexes, [Sm(N††)2(X)] (X = F, 2-F; Cl, 2-Cl; Br, 2-Br; I, 2-I). In addition, the trinuclear cluster [{Sm(N††)}3(μ2-I)3(μ3-I)2] (3), which formally contains one Sm(II) and two Sm(III) centres, was isolated during the synthesis of 2-I. Complexes 2-X are remarkably stable towards ligand redistribution, which is often a facile process for heteroleptic complexes of smaller monodentate ligands in lanthanide chemistry, including the related bis(trimethylsilyl)amide {N(SiMe3)2} (N′′). Complexes 2-X and 3 have been characterised by single crystal X-ray diffraction, elemental analysis, multinuclear NMR, FTIR and electronic spectroscopy. The Lα1 fluorescence-detected X-ray absorption spectrum recorded at the Sm L3-edge for 2-X exhibited a resolved pre-edge peak defined as an envelope quadrupole-allowed 2p → 4f transition. The X-ray absorption spectral features were successfully reproduced using time-dependent density functional theoretical (TD-DFT) calculations that synergistically supports the experimental observations as well as the theoretical model upon which the electronic structure and bonding in lanthanide complexes is derived

Performance analysis of the generalised projection identification for time-varying systems

© The Institution of Engineering and Technology 2016. The least mean square methods include two typical parameter estimation algorithms, which are the projection algorithm and the stochastic gradient algorithm, the former is sensitive to noise and the latter is not capable of tracking the timevarying parameters. On the basis of these two typical algorithms, this study presents a generalised projection identification algorithm (or a finite data window stochastic gradient identification algorithm) for time-varying systems and studies its convergence by using the stochastic process theory. The analysis indicates that the generalised projection algorithm can track the time-varying parameters and requires less computational effort compared with the forgetting factor recursive least squares algorithm. The way of choosing the data window length is stated so that the minimum parameter estimation error upper bound can be obtained. The numerical examples are provided

Robust H-infinity filtering for 2-D systems with intermittent measurements

This paper is concerned with the problem of robust H∞ filtering for uncertain two-dimensional (2-D) systems with intermittent measurements. The parameter uncertainty is assumed to be of polytopic type, and the measurements transmission is assumed to be imperfect, which is modeled by a stochastic variable satisfying the Bernoulli random binary distribution. Our attention is focused on the design of an H∞ filter such that the filtering error system is stochastically stable and preserves a guaranteed H∞ performance. This problem is solved in the parameter-dependent framework, which is much less conservative than the quadratic approach. By introducing some slack matrix variables, the coupling between the positive definite matrices and the system matrices is eliminated, which greatly facilitates the filter design procedure. The corresponding results are established in terms of linear matrix inequalities, which can be easily tested by using standard numerical software. An example is provided to show the effectiveness of the proposed approac

Design Opportunities for AAC and Children with Severe Speech and Physical Impairments

Augmentative and alternative communication (AAC) technologies can support children with severe speech and physical impairments (SSPI) to express themselves. Yet, these seemingly 'enabling' technologies are often abandoned by this target group, suggesting a need to understand how they are used in communication. Little research has considered the interaction between people, interaction design and the material dimension of AAC. To address this, we report on a qualitative video study that examines the situated communication of five children using AAC in a special school. Our findings offer a new perspective on reconceptualising AAC design and use revealing four areas for future design: (1) incorporating an embodied view of communication, (2) designing to emphasise children's competence and agency, (3) regulating the presence, prominence and value of AAC, and (4) supporting a wider range of communicative functions that help address children's needs

The reconstruction software for the MICE scintillating fibre trackers

The Muon Ionization Cooling Experiment (MICE) will demonstrate the principle of muon beam phase-space reduction via ionization cooling. Muon beam cooling will be required for the proposed Neutrino Factory or Muon Collider. The phase-space before and after the cooling cell must be measured precisely. This is achieved using two scintillating-fibre trackers, each placed in a solenoidal magnetic field. This paper describes the software reconstruction for the fibre trackers: the GEANT4 based simulation; the implementation of the geometry; digitisation; space-point reconstruction; pattern recognition; and the final track fit based on a Kalman filter. The performance of the software is evaluated by means of Monte Carlo studies and the precision of the final track reconstruction is evaluated