FORTE - a multipurpose high-vacuum diffractometer for tender X-ray diffraction and spectroscopy at the SIRIUS beamline of Synchrotron SOLEIL.

A new high-vacuum multipurpose diffractometer (called FORTE from the French acronyms of the project) has recently been installed at the tender/hard X-ray SIRIUS beamline of Synchrotron SOLEIL, France. The geometry chosen allows one to work either in the classical Eulerian four-circle geometry for bulk X-ray diffraction (XRD) or in the z-axis geometry for surface XRD. The diffractometer nicely fits the characteristics of the SIRIUS beamline, optimized to work in the 1.1-4.5 keV range, and allows one to perform unprecedented diffraction anomalous fine structure (DAFS) experiments in the tender X-ray region, also around non-specular reflections, covering a large reciprocal-space volume. Installation of an X-ray fluorescence detector on a dedicated flange allows simultaneous DAFS and X-ray absorption (XAS) measurements. The access to the tender X-ray region paves the way to resonant investigations around the L-edges of second-row transition elements which are constituents of functional oxide materials. It also enables access to several edges of interest for semiconductors. Finally, the control architecture based on synchronized Delta Tau units opens up exciting perspectives for improvement of the mechanical sphere of confusion.

Size effects in a relaxor: further insights into PMN.

Dielectric measurements of PbMg1/3Nb2/3O3 (PMN) powder and dense ceramics with grain sizes between 15 nm and two microns were carried out in a broad frequency range (20 Hz-1 GHz). Clear grain size dependence of relaxor behavior was evidenced. A progressive transformation from Vogel-Fulcher behavior towards the Arrhenius process in the PMN with reduction of grain size in both ceramics and powder was observed. In the case of ceramics we were able to extract deeper information from the distributions of relaxation times and an analysis using the Vogel-Fulcher law, revealing two main contributions: a fast part of distribution of relaxation times with a maximum close to 10(-11) s, which is almost grain-size independent and has a non-polar origin; whereas, a process with long relaxation times (in the time range of 10(-8) to 10(-5) s) is associated with the dynamics of the polar nanoregions and is strongly suppressed with reduction of grain size. The results of dielectric investigations are confirmed by Nuclear Magnetic Resonance experiments.

An ordered low-temperature phase of barium nitroprusside trihydrate studied by neutron diffraction.

Crystals of barium pentacyanonitrosylferrate trihydrate (barium nitroprusside trihydrate), Ba[Fe(CN)(5)(NO)].3H(2)O, have been studied by neutron diffraction in order to examine the structural behaviour of the compound in the 20-120 K temperature range and to determine the structure at 105 K. The results show the existence of a new crystal phase of the compound at 80 K (with a duplicated a parameter), which still exists at 20 K. The crystal structure at 105 K shows a rearrangement of the water molecules, which results in an ordered structure with P1 symmetry. Two of the four independent nitroprusside cations are rotated by 4.5 degrees around the [100] direction.

A new crystal phase of barium nitroprusside trihydrate studied by neutron diffraction at 20 K.

The crystal of barium pentacyanonitrosylferrate trihydrate [barium nitroprusside trihydrate, Ba[Fe(CN)5(NO)] x 3H2O] has been studied by neutron diffraction at 20 K. The study was performed to characterize the structural phase generated by the phase transition undergone by the crystals at 80 K, at which temperature the unit-cell volume doubles. This crystal phase still exists at 20 K. The crystal structure, in space group P1, is completely ordered. The positional changes of the water molecules in the present structure with respect to those of the compound at 105 K are presented.

Structure of the X-phase of 38% brominated betaine calcium chloride dihydrate.

The structures of the high- and low-temperature phases of 38% brominated BCCD [betaine (trimethylammonioacetate) calcium chloride dihydrate], the latter being known as the X-phase, have been determined by single-crystal neutron diffraction at 295 and 20 K, respectively. The symmetry of the X-phase is described by the P2(1)2(1)2(1) space group. The distortion with respect to the high-temperature Pnma phase is characterized by anti-symmetric displacements of the betaine molecules as well as of the Ca octahedra. On the basis of a symmetry-mode analysis, we propose an interpretation of the direct phase transition that occurs around 80 K between these two phases.