Comparative study of X-ray charge-density data on CoSb3

CoSb3is an example of a highly challenging case for experimental charge-density analysis due to the heavy elements (suitability factor of ∼0.01), the perfect crystallinity and the high symmetry of the compound. It is part of a family of host–guest structures that are potential candidates for use as high-performance thermoelectric materials. Obtaining and analysing accurate charge densities of the undoped host structure potentially can improve the understanding of the thermoelectric properties of this family of materials. In a previous study, analysis of the electron density gave a picture of covalent Co–Sb and Sb–Sb interactions together with relatively low atomic charges based on state-of-the-art experimental and theoretical data. In the current study, several experimental X-ray diffraction data sets collected on the empty CoSb3framework are compared in order to probe the experimental requirements for obtaining data of high enough quality for charge-density analysis even in the case of very unsuitable crystals. Furthermore, the quality of the experimental structure factors is tested by comparison with theoretical structure factors obtained from periodic DFT calculations. The results clearly show that, in the current study, the data collected on high-intensity, high-energy synchrotron sources and very small crystals are superior to data collected at conventional sources, and in fact necessary for a meaningful charge-density study, primarily due to greatly diminished effects of extinction and absorption which are difficult to correct for with sufficient accuracy.

Spin line groups

Spin line groups describe the symmetries of spin arrangements in quasi-one-dimensional systems. These groups are derived for the first family of line groups. Among them, magnetic groups are singled out as a special case. Spin arrangements generated by the derived groups are first discussed for single-orbit systems and then the conclusions are extended to multi-orbit cases. The results are illustrated by the examples of a CuO2zigzag chain, a13C nanotube and the hexaferrite Ba2Mg2Fe12O22. Applications to neutron diffraction and classical ground-state determination are indicated.

Direct phasing of nanocrystal diffraction

Recent experiments at free-electron laser X-ray sources have been able to resolve the intensity distributions about Bragg peaks in nanocrystals of large biomolecules. Information derived from small shifts in the peak positions augment the Bragg samples of the particle intensity with samples of its gradients. Working on the assumption that the nanocrystal is entirely generated by lattice translations of a particle, an algorithm is developed that reconstructs the particle from intensities and intensity gradients. Unlike traditional direct phasing methods that require very high resolution data in order to exploit sparsity of the electron density, this method imposes no constraints on the contrast other than positivity and works well at low resolution. Successful reconstructions are demonstrated with simulatedP1 lysozyme nanocrystal data down to a signal-to-noise ratio of 2 in the intensity gradients.

More about residual values

The usual residual values are complemented by expectation values based solely on the experimental data and the number of model parameters. These theoreticalRvalues serve as benchmark values when all of the basic assumptions for a least-squares refinement,i.e.no systematic errors and a fully adequate model capable of describing the data, are fulfilled. The prediction ofRvalues as presented here is applicable to any field where model parameters are fitted to data with known precision. For crystallographic applications,F2-based residual benchmark values are given. They depend on the first and second moments of variance, intensity and significance distributions, 〈σ2〉, 〈Io2〉, 〈Io2/σ2〉. Possible applications of the theoreticalRvalues are, for example, as a data-quality measure or the detection of systematic deviations between experimental data and model predicted data, although the theoreticalRvalues cannot identify the origin of these systematic deviations. The change inRvalues due to application of a weighting scheme is quantified with the theoreticalRvalues.

Distribution rules of systematic absences on the Conway topograph and their application to powder auto-indexing

This paper presents several general properties of systematic absences that are available before unit-cell parameters and the space group have been determined. The properties are given in the form of distribution rules of Miller indices corresponding to systematic absences on atopograph. A topograph is a graph whose edges are associated with a set of four lattice vectors satisfying Ito's equation 2(|l1*|2+ |l2*|2) = |l1*+l2*|2+ |l1*−l2*|2. It is possible to integrate global information about extinct reflections by using topographs. As an example of the application of these rules, a new powder auto-indexing algorithm is introduced, focusing on its theoretical aspects.

Homometry in the light of coherent beams

Two systems are homometric if they are indistinguishable by diffraction. A distinction is first made between Bragg and diffuse scattering homometry, and it is shown that in the last case coherent diffraction can allow the diffraction diagrams to be differentiated. The study of the Rudin–Shapiro sequence, homometric to random sequences, allows one to manipulate independently two-point and four-point correlation functions, and to show their effect on the statistics of speckle patterns. This study provides evidence that long-range order in high-order correlation functions has a measurable effect on the speckle statistics.

Platonic solids generate their four-dimensional analogues

This paper shows how regular convex 4-polytopes – the analogues of the Platonic solids in four dimensions – can be constructed from three-dimensional considerations concerning the Platonic solids alone.Viathe Cartan–Dieudonné theorem, the reflective symmetries of the Platonic solids generate rotations. In a Clifford algebra framework, the space of spinors generating such three-dimensional rotations has a natural four-dimensional Euclidean structure. The spinors arising from the Platonic solids can thus in turn be interpreted as vertices in four-dimensional space, giving a simple construction of the four-dimensional polytopes 16-cell, 24-cell, theF4root system and the 600-cell. In particular, these polytopes have `mysterious' symmetries, that are almost trivial when seen from the three-dimensional spinorial point of view. In fact, all these induced polytopes are also known to be root systems and thus generate rank-4 Coxeter groups, which can be shown to be a general property of the spinor construction. These considerations thus also apply to other root systems such as A_{1}\oplus I_{2}(n) which induces I_{2}(n)\oplus I_{2}(n), explaining the existence of the grand antiprism and the snub 24-cell, as well as their symmetries. These results are discussed in the wider mathematical context of Arnold's trinities and the McKay correspondence. These results are thus a novel link between the geometries of three and four dimensions, with interesting potential applications on both sides of the correspondence, to real three-dimensional systems with polyhedral symmetries such as (quasi)crystals and viruses, as well as four-dimensional geometries arising for instance in Grand Unified Theories and string and M-theory.