Development of structural order during supercooling of a fragile oxide melt.

The authors have studied the structural evolution of the fragile glass-forming liquid CaAl2O4 during supercooling from the stable liquid phase to the cold glass below Tg. The evolution is characterized by a sharpening of the first diffraction peak and a shortening of the average nearest-neighbor bond length around 1.25Tg, indicating an increase in the degree of both intermediate-range and short-range orders occurring close to the dynamical crossover temperature. The cooling curve developed a kink at this temperature, indicating a simultaneous change in thermodynamic properties.

Application of a hybrid pixel detector to powder diffraction.

Results obtained using a hybrid pixel photon-counting detector in powder diffraction experiments are presented. The detector works at room temperature and its dynamic response ranges from 0.01 photons pixel(-1) s(-1) up to 10(6) photons pixel(-1) s(-1). The pixel sizes are 0.33 mm x 0.33 mm for a total area of 68 mm x 68 mm. On recording high-resolution diffraction patterns of powders, a reduction of the experimental time by more than a factor of 20 is obtained without loss of data quality. The example of an X-zeolite shows that such detectors can be used for very demanding anomalous experiments. In situ experiments of quenching liquid oxides show that frames of 0.01 s can be achieved for studying such processes.

One-dimensional fluctuating nanodomains in the charge-transfer molecular system TTF-CA and their first-order crystallization.

We report on the direct observation by x-ray diffuse scattering measurements of thermally induced one-dimensional nanoscale ordered fluctuations in the mixed-stack charge-transfer molecular system tetrathiafulvalene-p chloranil (TTF-CA), the prototype for the neutral-ionic phase transition. The unusual physical properties of this compound are considered to be driven by such one-dimensional excitations. The results are discussed in relation to previous experimental and theoretical experiments both at thermal equilibrium and under light irradiation.

Diffraction anomalous fine-structure spectroscopy at beamline BM2 at the European Synchrotron Radiation Facility.

Diffraction anomalous fine-structure (DAFS) spectroscopy uses resonant elastic X-rays scattering as an atomic, shell and site-selective probe that provides information on the electronic structure and the local atomic environment as well as on the long-range-ordered crystallographic structure. A DAFS experiment consists of measuring the Bragg peak intensities as a function of the energy of the incoming X-ray beam. The French CRG (Collaborative Research Group) beamline BM2-D2AM (Diffraction Diffusion Anomale Multi-longueurs d'Onde) at the ESRF (European Synchrotron Radiation Facility) has developed a state-of-the-art energy scan diffraction set-up. In this article the requirements for obtaining reliable DAFS data are presented and recent technical achievements are reported.

Structural evidence for Ta-tetramerization displacements in the charge-density-wave compound (TaSe4)2I from x-ray anomalous diffraction.

We use the anomalous x-ray diffraction technique to investigate the nature of the tantalum displacement pattern in the modulated phase of the charge-density-wave compound (TaSe4)2I. In addition to the known acousticlike modulation, we find the first direct evidence for the condensation of opticlike Ta displacements along the metallic chains corresponding to an LLSS pattern of long and short in-chain Ta-Ta distances (Ta-tetramerization modes). This result confirms a previous model in which the interaction of the electronically coupled optic modes with long-wavelength acoustic shear modes leads to the condensation of a modulation of mixed character.

Resonant "forbidden" reflections in magnetite.

Resonant x-ray scattering was used to investigate electronic fluctuations of the octahedral iron atoms in magnetite. We measured the (002) and (006) "forbidden" x-ray diffraction reflections permitted by the anisotropy of the iron anomalous scattering factor. The energy and azimuthal angle dependencies of these reflections, and the polarization analysis, are shown and discussed. The results clearly show p and d iron empty states ordering in magnetite at room temperature. Moreover, the octahedral iron atoms are electronically equivalent in a time scale lower than 10(-16) sec. Therefore, magnetite should be considered as an itinerant magnet and not as a fluctuating mixed valence material.

D2AM, a beamline with a high-intensity point-focusing fixed-exit monochromator for multiwavelength anomalous diffraction experiments.

D2AM is a french CRG beamline installed at the ESRF (European Synchrotron Radiation Facility) in Grenoble, with half of the time dedicated to biological macromolecule crystallography and half to materials science studies (diffraction, wide-angle and small-angle scattering). It is constructed at the front-end BM02 of the ESRF storage ring, using the X-ray beam from a 0.8 T bending magnet. D2AM entered into routine operation at the end of 1994, and is used either for single-wavelength or for multiwavelength anomalous diffraction studies. The beam is monochromated by an Si[111] two-crystal monochromator with a resolution of about 2 x 10(-4). The first crystal is water cooled. The X-ray photon energy covers the range between 6.5 keV (lambda approximately 1.9 A) and 17 keV (lambda approximately 0.7 A), a domain of energy with many K or L absorption edges of heavy atoms of interest for biological macromolecules studies and in materials science. The X-ray beam is focused in the vertical plane by two long curved mirrors and in the horizontal plane by the second crystal of the monochromator which is given an adjustable sagittal curvature. A spot size of 0.3 x 0.1 mm (FWHM) is measured at the sample position. Both mirrors are cut out of a 6"-diameter 1.1 m-long Si single crystal, polished and coated with a 400 A Pt thin film. The rugosity is better than 4 A r.m.s. and the longitudinal slope error is better than 5 x 10(-6) rad r.m.s. The first mirror is water cooled, the second is not. The beam intensity on the sample is about 10(11) photon s(-1) on a 0.3 x 0.3 mm focus area at 100 mA in the storage ring of the ESRF. The harmonic rejection ratio obtained with the two mirrors is better than 10(-5) for lambda/3. The combined optical system, mirror/monochromating-crystals/mirror, used on D2AM constitutes altogether a high-intensity point-focusing fixed-exit monochromator, which has the additional property that the energy resolution is not dependent on the beam divergence in use. Its stability and resolution are perfectly adapted to multiwavelength anomalous diffraction studies. The alignment of the mirrors and the monochromator is fully automated, taking 5 min, with the exception of the adjustment of the sagittal focusing. During multiwavelength diffraction experiments the wavelength is changed by a fast single monochromator rotation. Neither realignment of the mirrors nor readjustment of the beam focusing are necessary. The stability and reproducibility of the selected X-ray photon energy is better than 0.5 eV.

Coherent small-angle scattering on a bending-magnet beamline at the ESRF.

A coherent X-ray beam is obtained from the D2AM bending-magnet beamline (BM2) of the European Synchrotron Radiation Facility. As this line has permanent convergent optics, monochromated by an Si(111) double monochromator, coherence conditions are satisfied by selecting a part of the beam close to the focal point. Low intensity (10(6) X-rays s(-1)) is partially compensated by a high degree of coherence and by the use of a high-resolution direct-illumination CCD area detector. The stability of the small-angle set-up makes quantitative analysis possible. The calculated and measured degrees of coherence are compared. The distributions of speckle intensities are explained by a beam composed of two-thirds coherent and one-third incoherent parts. This incoherent component is caused by Kapton windows, which will be removed in future experiments.