The upgraded Polaris powder diffractometer at the ISIS neutron source.

This paper describes the design and operation of the Polaris time-of-flight powder neutron diffractometer at the ISIS pulsed spallation neutron source, Rutherford Appleton Laboratory, UK. Following a major upgrade to the diffractometer in 2010-2011, its detector provision now comprises five large ZnS scintillator-based banks, covering an angular range of 6° ≤ 2θ ≤ 168°, with only minimal gaps between each bank. These detectors have a substantially increased solid angle coverage (Ω âˆ¼ 5.67 sr) compared to the previous instrument (Ω âˆ¼ 0.82 sr), resulting in increases in count rate of between 2× and 10×, depending on 2θ angle. The benefits arising from the high count rates achieved are illustrated using selected examples of experiments studying small sample volumes and performing rapid, time-resolved investigations. In addition, the enhanced capabilities of the diffractometer in the areas of in situ studies (which are facilitated by the installation of a novel design of radial collimator around the sample position and by a complementary programme of advanced sample environment developments) and in total scattering studies (to probe the nature of short-range atomic correlations within disordered crystalline solids) are demonstrated.

Neutron powder diffraction and molecular dynamics study of superionic SrBr2.

The nature of the dynamic ionic disorder within the high-temperature superionic phase of strontium bromide, ß-SrBr2, has been investigated using reverse Monte Carlo (RMC) modelling of neutron powder diffraction data and complementary ab initio molecular dynamics (MD) simulations. The RMC and MD results are in good agreement and indicate the presence of extensive dynamic disorder within the Br(-) sublattice of the cubic fluorite structure. Rapid anion diffusion predominantly occurs as hops between nearest neighbour sites in the 〈100〉 directions, though the trajectories are markedly curved and pass through the peripheries of the octahedral voids in the cation sublattice. In addition, there are extensive correlations between the motions of individual Br(-), often leading to the formation of a short-lived square antiprism co-ordination environment around the Sr(2+). Such polyhedra are observed within the (ambient temperature) ordered tetragonal crystal structure of α-SrBr2. The nature of the ionic disorder in SrBr2 is of particular interest because it is the only known example of a Br(-)-ion superionic. Owing to the large size of this anion, a comparison with the behaviour of other superionic phases gives an insight into the role of ionic size on the conducting properties within these materials.

Total scattering analysis of cation coordination and vacancy pair distribution in Yb substituted δ-Bi2O3.

Reverse Monte Carlo (RMC) modelling of neutron total scattering data, combined with conventional Rietveld analysis of x-ray and neutron data, has been used to describe the cation coordination environments and vacancy pair distribution in the oxide ion conducting electrolyte Bi3YbO6. The thermal variation of the cubic fluorite unit cell volume, monitored by variable temperature x-ray and neutron experiments, reveals significant curvature, which is explained by changes in the oxide ion distribution. There is a significant increase in tetrahedral oxide ion vacancy concentration relative to δ-Bi2O3, due to the creation of Frenkel defects associated with the Yb(3+) cation. The tetrahedral oxide ion vacancy concentration increases from room temperature to 800 °C, but little change is observed in the vacancy pair distribution with temperature. The vacancy pair distributions at both temperatures are consistent with a favouring of [100] vacancy pairs.

KSbO(Ge0.32Si0.68)O4, a KTP isomorph.

A structural model of potassium antimony germanate/silicate (0.32/0.68), KSbO(Ge(0.32)Si(0.68))O(4), has been determined at room temperature. KSbO(Ge(0.32)Si(0.68))O(4) belongs to the KTiOPO(4) (KTP) isomorphic family and is composed of SbO(6) octahedra (site symmetry -1 and 2) arranged in helical chains bridged by (Ge/Si)O(4) tetrahedra. Germanium and silicon have a similar distribution in the crystallographically independent tetrahedra (site symmetry 2). The structure contains large cavities occupied by the K atom. Two partially occupied potassium positions have been identified 1.273 (8) A apart, with an indication of a third potassium position between them. At room temperature, KSbO(Ge(0.32)Si(0.68))O(4) crystallizes in the paraelectric phase of space group Pnan. This phase is found at elevated temperatures for almost all KTiOPO(4) isomorphic compounds and KSbO(Ge(0.32)Si(0.68))O(4) is the second isomorph that is paraelectric at room temperature.

A TiP(2)O(7) superstructure.

A room-temperature structural model of titanium pyrophosphate, TiP(2)O(7), has been determined from synchrotron X-ray data. The structure consists of TiO(6) octahedra and PO(4) tetrahedra sharing corners in a three-dimensional network. The PO(4) tetrahedra form P(2)O(7) groups connecting the TiO(6) octahedra. The 3 x 3 x 3 superstructure differs substantially from the parent AB(2)O(7) structure. The P--O--P bonding angles of the pyrophosphate group are between 141.21 (12) and 144.51 (13) degrees for those groups not located on the threefold axis. The individual TiO(6) octahedra and PO(4) tetrahedra are somewhat distorted.

Crucial influence of solvent and chirality-the formation of helices and three-dimensional nets by hydrogen-bonded biimidazolate complexes.

Deprotonation and recrystallisation of racemic [Co(2,2'-biimidazole)3][NO3]3 by ammonia in water/dimethylformamide solutions gave crystals of [Co(Hbiim)3] x 0.8H2O x 0.5DMF (2: Hbiim = monoanion of 2,2'-biimidazole, DMF = dimethylformamide), a porous material that contains fourfold interpenetrating (10.3) three-dimensional nets formed by neutral, hydrogen-bonded [Co(Hbiim)3] units, with DMF molecules in the narrow channels. Recrystallisation of [delta-Co(2,2'-biimidazolate)3] gave helices instead of the expected (10,3)-a net. These results are discussed in the light of additional density functional theory and molecular mechanics calculations and the X-ray structure of [Co(H2biim)3][NO3]3.