Crystal structure refinement at high pressures using angle-dispersive powder diffraction techniques

Abstract

The development of area detectors such as the imaging plate (IP) allows the use of angle-dispersive techniques for powder diffraction studies at high pressure. Integration of the 2-d pattern greatly improves the powder averaging and signal-to-noise ratio, making it possible to carry out full Rietveld refinements of crystal structures in high-pressure phases. An IP system is being developed at the Synchrotron Radiation Source (SRS), Daresbury, and the current status of this system -hardware and software -is described. Recent results on La₂CuO₄ and lnSb demonstrate the effectiveness and advantages of the techniques.     

Optics and beamlines for high-pressure research at the european synchrotron radiation facility

Abstract

The European Synchrotron Radiation Facility (ESRF) is the first high-energy, high-brilliance synchrotron radiation source in operation today and it is ideally suited to high pressure research. White-beam and monochromatic diffraction techniques are being optimized in particular for structural studies of low-Z materials and poor scatterers generally, the best example being hydrogen single crystals at very high pressures. Most high pressure measurements are carried out on a versatile beamline equipped with a wiggler and an undulator. Focusing and image plates are used in all monochromatic angle-dispersive studies. The success of the high pressure programme has so far been achieved on a non-optimized beamline, but the next phase of the programme needs an optimized facility. A beamline is being constructed to fully exploit the intrinsic qualities of this unique source and insertion devices for high pressure studies. Its main design concepts are presented.     

Pressure-induced disordering and phase transformations in Eu2Zr2O7 pyrochlore

ABSTRACT

The structural properties of pyrochlore Eu₂Zr₂O₇ under high pressure have been studied by using Raman spectroscopy and in situ angle-dispersive X-ray diffraction (ADXRD). The results of Raman spectra indicate that Eu₂Zr₂O₇ undergoes a reversible structural change around 21.2?GPa. The results of Rietveld refinements from in situ ADXRD data indicate that the ordered pyrochlore structure (Fd-3m) transforms to the defect-cotunnite structure (Pnma) at 26.5?GPa. The phase transition is irreversible and the transformation process is mainly induced by the accumulations of anti-site defects of the cation sublattice and Frenkel defects on the anion sublattice. Besides, the <Zr–O> bonds should play a more important role than the <Eu–O> bonds in the process of the phase transformation.     

Rietveld analysis for energy dispersive x-ray diffraction under high pressure with synchrotron radiation

Abstract

A new program has been developed for the conversion of energy-dispersive x-ray diffraction spectra obtained from powder samples at high pressure in a diamond anvil cell (DAC) into conventional pseudo angle-dispersive data. The program is compatible with a conventional Rietveld program. This allows the determination of the structural parameters of the samples investigated. Results of a synchrotron radiation study of polycrystalline SrFCl in the tetragonal phase at high pressure are presented.

Presented at the IUCr Workshop on ‘Synchrotron Radiation Instrumentation for High Pressure Crystallography’, Daresbury Laboratory 20-21 July 1991     

Design of angle-dispersive spectrometer for xanes under high pressure

Abstract

The angle-dispersive spectrometer with elliptically curved crystal for XANES is proposed. The design is suited to high pressure research with a diamond-anvil cell.

Un spectromètre de dispersion angulaire au cristal elliptiquement courbé pour XANES est proposé. Sa construction est spécialement convenable à la recherche dans le domaine des hautes pressions avec chambre à l'enclume de diamant.     

Axial ratio anomalies and electronic topological transitions in Cd0.80Hg0.20 at high pressures

High-pressure angle-dispersive X-ray diffraction measurements show that Cd_0.80Hg_0.20 alloy remains in the hcp structure up to 50 GPa. We observe subtle anomalies in the pressure variation of the lattice parameters and their ratio, and in normalized stress versus strain. Electronic-structure calculations, as well as experimental and theoretical results for Cd, suggest that these anomalies are related to the occurrence of electronic topological transitions. Our results support Lifshitz's prediction that electronic phase transitions can cause anomalies in structural and elastic properties of materials.     

Anomalous pressure-induced phase transformation in nano-crystalline erbium sesquioxide (Er2O3): partial amorphization under compression

Nanophase materials have novel physical and chemical properties, differing from bulk materials. It is of exceptional interest to investigate the size effect on structural stability in nanocrystals. Here, we investigated pressure-induced phase transitions in nanosized Er₂O₃ using angle-dispersive synchrotron X-ray diffraction up to 40.6 GPa. Nano-Er₂O₃ has enhanced transition pressure and higher bulk modulus (K₀) than its bulk counterparts. Amorphous Er₂O₃ nanoclusters with traces of monoclinic phase are obtained upon compression. This is the first time that partial amorphous structure under compression was observed in nano-Er₂O₃, indicating a kinetic trapping of partial amorphous Er₂O₃ on pressurizing.     

石墨相C_3N_4压致结构相变研究

将有机物三聚氰胺(C3N6H6)高温热解,得到了石墨相C3N4(g-C3N4)。利用同步辐射X射线衍射和金刚石对顶砧(DAC)高压技术,在室温下对g-C3N4进行了结构变化研究。实验结果表明,在16.57 GPa压力范围内,g-C3N4发生了压致结构相变,在6.6 GPa压力下,晶体结构由原来的石墨相转变为三斜相。使用Birch-Murnagha等温状态方程拟合出了样品的等温状态方程。     

Kinetics and systematics of structural phase transitions in the regular lanthanide metals under pressure

Abstract

Techniques and results of studies on the kinetics and hysteresis of the structural phase transitions in lanthanides under pressures up to 58 GPa and temperatures between 200 K and 520 K are presented. The transformation rates show the same time dependence as for diffusion controlled transitions, however, other interpretations of this time dependence are also possible. Estimates of the 0 K equilibrium transition pressures are derived from the pressure and temperature dependence of the activation free energies A, G. A comparison of critical radius ratios, R_ux/R_5p for all the regular lanthanides at the various phase transitions shows simple systematics in the high pressure behaviour of the lanthanides.     

Pressure induced lattice instability and phase separation in the cuprates

High pressure structural studies using a synchrotron source and Raman measurements on various cuprates reveal several structural modifications. The data have shown strong deviations from the normal equation of state at characteristic pressures, hysteresis, and the appearance of additional peaks that can be attributed to a new phase. The combined data of synchrotron angle-dispersive experiments with the optical measurements indicate that at some critical pressures, at least for certain compounds, non-linear effects are observed together with phase separation that affect the distribution of the carriers and the transition temperature. The comparison of the data with those induced by an internal pressure by an atomic substitution indicates that the effect is related to the existence of carriers within the CuO₂ superconducting planes.     

The application of neutron powder diffraction techniques for crystallographic studies at high pressures

Abstract

For phase transition studies, neutron powder diffraction offers a number of important advantages over x-ray based techniques, for example ab-initio structural determination. There are two distinct methods using either monochromatic angular dispersive geometry on a reactor cold source or time-of-flight energy-dispersive techniques requiring a pulsed neutron source. Both techniques offer comparable resolution but have differing advantages for high pressure studies. Recent studies illustrate the benefits of the two methods and the application of these to solve unknown crystal structures.     

Discussion of the generalized phase diagram for ‘regular’ lanthanides under pressure (Abstract)

Abstract

X-ray diffraction studies on the kinetics and hysteresis of the structural phase transitions in lanthanides under pressures up to 58 GPa and temperatures between 200 and 520 K are presented. Estimates of the 0 K equilibrium transition pressures are derived from the pressure and temperature dependence of the activation free energies Δ_aG. A comparison of critical radius ratios, R_ws/R_5p, for all the regular lanthanides at the various phase transitions shows simple systematics in the high pressure behaviour of the lanthanides. The “volume collapse” transitions in lanthanides are compared with the behaviour of the actinides and discussed with respect to f-electron delocalization.     

High pressure neutron diffraction studies using the Paris-Edinburgh cell

Abstract

Neutron diffraction was until recently confined to pressures below ～ 3 GPa. This restricted range has limited the high-pressure structural information that is available for a wide range of phenomena for which neutron diffraction is the technique of choice. But now the recently-developed Paris-Edinburgh cell can achieve pressures up to ～ 30 GPa with a sample volume large enough to allow accurate structural studies with neutrons. After a period of development of the neutron scattering techniques needed to obtain the best possible results using the cell, a variety of successful structural studies have been performed. These illustrate the value of neutron diffraction in important areas such as locating hydrogen and other low-Z atoms in structures, the measurement of accurate structural pressure dependence and the examination of the changes in atomic thermal motion with pressure.     

Shape co-existence and structural evolution of thevi13/2 band in157Yb

The high-spin states of¹⁵⁷Yb have been studied via the reaction of¹⁴⁴Sm(¹⁶O, 3n) at¹⁶O energy of 90 MeV using techniques of in-beam γ-ray spectroscopy. Measurement of γ-γ-t coincidences was performed with 11 BGO(AC)HPGe detectors. Based on the γ-γ coincidence relationships and the measured results of γ-ray anisotropies and DCO ratios, the level scheme for¹⁵⁷Yb was established. The shape co-existence and structural evolution of thevi_13/2 band with increasing angular momentum in¹⁵⁷Yb have been discussed. The systematics of thevi_13/2 bands in theN=87 odd-A isotones have been compared.     

Structural Disorder in Supercritical Aqueous Ionic Solutions as seen by MD-EXAFS

Because of their inherent structural disorder, liquids are challenging systems for structural studies. This is even more so for high temperature/high pressure fluids such as supercritical (SC) ones. By combining Molecular Dynamics simulations with Extended X-ray Absorption Fine Structure spectroscopy, we have recently elucidated the structure of the Br m hydration shell in low concentrated solutions from ambient to supercritical conditions [1]. The densities explored correspond to pressures up to 450 bar. In this paper, we show that this combination of techniques has been an essential tool to correctly interpret the experimental signals. Indeed, the occurrence of drastic different local environment of the ions in solutions, typical of liquids and magnified in supercritical conditions, can be seriously misleading if not taken into account.     

Effects of doping on the surface energies of nanocrystals and evidence from studies at high pressure

Zn_1−XMn_XS (X=0.85% and 1.26%) nanoparticles have been synthesized using a specially designed equipment and we have studied the influence of doping Mn²⁺ on the surface energy of ZnS. The high pressure behaviors of ZnS nanocrystals with different dopant contents have been investigated using angle-dispersive synchrotron X-ray powder diffraction up to 45.1 GPa. Theoretical calculations show that doping with Mn²⁺ increases the surface energy of the nanocrystals. The theoretical result has been further corroborated by our experimental observation of an increase in the phase transition pressure of Mn²⁺ doped ZnS nanocrystals in diamond-anvil-cell studies.     

Strength and equation of state of molybdenum triboride under 80 GPa pressure,using radial X-ray diffraction

The strength and equation of state of molybdenum triboride have been determined under nonhydrostatic compression up to 80?GPa, using an angle-dispersive radial X-ray diffraction technique in a diamond anvil cell (DAC). The RXD data yield a bulk modulus and its pressure derivative as K_0?=?342(6)?GPa with K₀′?=?2.11(17) at ψ?=?54.7°. Analysis of diffraction data using the strain theory indicates that the ratio of differential stress to shear modulus (t/G) ranges from 0.002 to 0.050 at pressures of 4–80?GPa. Together with theoretical results on the high pressure shear modulus, our results here show that molybdenum triboride sample under uniaxial compression can support a differential stress of ～10?GPa when it started to yield with plastic deformation at ～30?GPa. In addition, we draw a conclusion that MoB₃ is not a superhard material but a hard material.     

Correlation lengths in quasi-one-dimensional systems via transfer matrices

ABSTRACT

Using transfer matrices up to next-nearest-neighbour interactions, we examine the structural correlations of quasi-one-dimensional systems of hard disks confined by two parallel lines and hard spheres confined in cylinders. Simulations have shown that the non-monotonic and non-smooth growth of the correlation length in these systems accompanies structural crossovers [Fu et al., Soft Matter 13, 3296 (2017)]. Here, we identify the theoretical basis for these behaviours. In particular, we associate kinks in the growth of correlation lengths with eigenvalue crossing and splitting. Understanding the origin of such structural crossovers answers questions raised by earlier studies, and thus bridges the gap between theory and simulations for these reference models.     

Laser Raman Investigation of Solid State Reactions

Abstract

Traditionally, molecular ions have been studied by mass spectrometers or ion-counting techniques. The great sensitivity and versatility of these techniques are clearly attested to by the vast amount of mass spectrometric literature. However, it is equally true that mass spectroscopy has its limitations; basically, it provides one only with a charge-to-mass ratio for an ion. Obviously, all quantum state information is lost, particularly the vibrational and rotational, and usually even the electronic distributions of the ions. Similarly, no structural information such as bond lengths and angles is obtained. Indeed, in some cases the information obtained is so slight that one cannot even write a structural formula for the ion or distinguish between different chemical isomers.     

Shape co-existence and structural evolution of the yrast band in 157Yb

The high-spin states of ¹⁵⁷Yb have been studied via the ¹⁴⁴Sm(¹⁶O, 3n) reaction at ¹⁶O energy of 90 MeV using techniques of in-beam γ-ray spectroscopy. Measurement of γ-γ-t coincidences was performed with 11 BGO(AC)HPGe detectors. Based on the measured results of γ-γ coincidences, γ-ray anisotropies and DCO ratios, the level scheme for ¹⁵⁷Yb was established. The shape co-existence and structural evolution of the νi _13/2 band with increasing angular momentum in ¹⁵⁷Yb have been discussed. The systematics of the νi _13/2 bands in the N = 87 odd-A isotones have been compared. Received: 7 January 2002 / Accepted: 10 April 2002