The contribution of elastic geothermobarometry to the debate on HP versus UHP metamorphism.

Characterizing the pressure and temperature (P-T) histories of eclogite facies rocks is of key importance for unravelling subduction zone processes at all scales. Accurate P-T estimates provide constraints on tectonic and geochemical processes affecting subduction dynamics and help in interpreting the geophysical images of present-day converging plates. Conventional equilibrium geothermobarometers are challenged in ultra high pressure (UHP) metamorphic terranes, as minerals may undergo re-equilibration along their exhumation path. Elastic geobarometry applied to host-inclusion systems is a complementary method to determine P-T conditions of metamorphism independent from chemical equilibrium. Because only a single measurement, the inclusion strain, is made, only a line in P-T space of possible entrapment conditions, the entrapment isomeke, can be determined. Thus, the entrapment pressure along an isomeke can only be determined if the entrapment temperature is known. An alternative is to calculate entrapment conditions for two types of inclusions that are believed, from petrological evidence such as being in the same garnet growth zone, to have been entrapped at the same time. The intersection between the two sets of isomeke calculated on multiple quartz and zircon inclusions demonstrates that measuring different inclusion phases trapped inside a single host allows unique P-T conditions for the host rock to be determined. Here, we combine Zr-in-Rutile thermometry and thermodynamic modelling with micro-Raman measurements on quartz and zircon inclusions trapped in garnet to obtain pressures and temperatures of equilibration of a quartz-garnet vein from the Proterozoic Ulla gneiss basement and of garnet-kyanite gneiss from the Caledonian Blåhø nappe, both in the Fjørtoft UHP terrane, Norway. We find that the quartz-garnet vein formed at high pressure (1.5-2.5 GPa and 750-800°C) and recrystallized at ~1.2 GPa and 880°C. In contrast, the garnet-kyanite gneiss followed an anticlockwise path with peak P-T at 1.2 GPa and 880°C: these estimates are consistent with previous thermodynamic modelling and suggest that the Ulla gneiss and the Blåhø nappe came into contact at these last conditions. We also discuss a new method to detect hydrostatic versus Non-hydrostatic stresses near quartz and zircon inclusions in garnet.

Accurate structures and energetics of neutral-framework zeotypes from dispersion-corrected DFT calculations.

Density-functional theory (DFT) calculations incorporating a pairwise dispersion correction were employed to optimize the structures of various neutral-framework compounds with zeolite topologies. The calculations used the PBE functional for solids (PBEsol) in combination with two different dispersion correction schemes, the D2 correction devised by Grimme and the TS correction of Tkatchenko and Scheffler. In the first part of the study, a benchmarking of the DFT-optimized structures against experimental crystal structure data was carried out, considering a total of 14 structures (8 all-silica zeolites, 4 aluminophosphate zeotypes, and 2 dense phases). Both PBEsol-D2 and PBEsol-TS showed an excellent performance, improving significantly over the best-performing approach identified in a previous study (PBE-TS). The temperature dependence of lattice parameters and bond lengths was assessed for those zeotypes where the available experimental data permitted such an analysis. In most instances, the agreement between DFT and experiment improved when the experimental data were corrected for the effects of thermal motion and when low-temperature structure data rather than room-temperature structure data were used as a reference. In the second part, a benchmarking against experimental enthalpies of transition (with respect to α-quartz) was carried out for 16 all-silica zeolites. Excellent agreement was obtained with the PBEsol-D2 functional, with the overall error being in the same range as the experimental uncertainty. Altogether, PBEsol-D2 can be recommended as a computationally efficient DFT approach that simultaneously delivers accurate structures and energetics of neutral-framework zeotypes.

Experimental and ab Initio Study of Catena(bis(µ2-iodo)-6-methylquinoline-copper(I)) under Pressure: Synthesis, Crystal Structure, Electronic, and Luminescence Properties.

Copper(I) iodine compounds can exhibit interesting mechanochromic and thermochromic luminescent properties with important technological applications. We report the synthesis and structure determination by X-ray diffraction of a new polymeric staircase copper(I) iodine compound catena(bis(µ2-iodo)-6-methylquinoline-copper(I), [C10H9CuIN]. The structure is composed of isolated polymeric staircase chains of copper-iodine coordinated to organic ligands through Cu-N bonds. High pressure X-ray diffraction to 6.45 GPa shows that the material is soft, with a bulk modulus K0 = 10.2(2)GPa and a first derivative K'0 = 8.1(3), typical for organometallic compounds. The unit-cell compression is very anisotropic with the stiffest direction [302] arising from a combination of the stiff CuI ladders and the shear of the planar quinolone ligands over one another. Full structure refinements at elevated pressures show that pressures reduce the Cu···Cu distances in the compound. This effect is detected in luminescence spectra with the appearance of four sub-bands at 515, 600, 647, and 712 nm above 3.5 GPa. Red-shifts are observed, and they are tentatively associated with interactions between copper(I) ions due to the shortening of the Cu···Cu distances induced by pressure, below twice the van der Waals limit (2.8 Å). Additionally, ab initio simulations were performed, and they confirmed the structure and the results obtained experimentally for the equation of state. The simulation allowed the band structure and the electronic density of states of this copper(I) iodine complex to be determined. In particular, the band gap decreases slowly with pressure in a quadratic way with dEg/dP = -0.011 eV/GPa and d(2)Eg/dP(2) = 0.001 eV/GPa(2).

High-pressure crystal structure of elastically isotropic CaTiO3 perovskite under hydrostatic and non-hydrostatic conditions.

The structural evolution of orthorhombic CaTiO3 perovskite has been studied using high-pressure single-crystal x-ray diffraction under hydrostatic conditions up to 8.1 GPa and under a non-hydrostatic stress field formed in a diamond anvil cell (DAC) up to 4.7 GPa. Under hydrostatic conditions, the TiO6 octahedra become more tilted and distorted with increasing pressure, similar to other 2:4 perovskites. Under non-hydrostatic conditions, the experiments do not show any apparent difference in the internal structural variation from hydrostatic conditions and no additional tilts and distortions in the TiO6 octahedra are observed, even though the lattice itself becomes distorted due to the non-hydrostatic stress. The similarity between the hydrostatic and non-hydrostatic cases can be ascribed to the fact that CaTiO3 perovskite is nearly elastically isotropic and, as a consequence, its deviatoric unit-cell volume strain produced by the non-hydrostatic stress is very small; in other words, the additional octahedral tilts relevant to the extra unit-cell volume associated with the deviatoric unit-cell volume strain may be totally neglected. This study further addresses the role that three factors--the elastic properties, the crystal orientation and the pressure medium--have on the structural evolution of an orthorhombic perovskite loaded in a DAC under non-hydrostatic conditions. The influence of these factors can be clearly visualized by plotting the three-dimensional distribution of the deviatoric unit-cell volume strain in relation to the cylindrical axis of the DAC and indicates that, if the elasticity of a perovskite is nearly isotropic as it is for CaTiO3, the other two factors become relatively insignificant.

The structural state of lead-based relaxor ferroelectrics under pressure.

The exceptional properties of lead-based perovskite-type (ABO(3)) relaxor ferroelectrics are due to their structural inhomogeneities. At ambient conditions, the average structure is pseudocubic but rich in ferroic nanoregions too small to be directly studied by conventional diffraction analysis. However, combining in situ temperature and pressure diffraction and Raman scattering allows us to resolve the structural complexity of relaxors. Because of the different length and time scales of sensitivity, diffraction probes the long-range order, i.e., the structure averaged over time and space, whereas Raman spectroscopy can detect local structural deviations from the average structure via the anomalous Raman activity of the phonon modes that, when the symmetry of the average structure is considered, should not generate Raman peaks. Hence, the combined analysis of the long-range order induced at low temperatures or high pressures and of the phonon anomalies enhanced on temperature decrease or pressure increase can reveal the energetically preferred structural nanoclusters existing at ambient conditions. In this regard, high-pressure experiments are vital for understanding the nanoscale structure of relaxors. Using X-ray diffraction, neutron diffraction, and Raman scattering on stoichiometric and doped PbSc(0.5)Ta(0.5)O(3) and PbSc(0.5)Na(0.5)O(3), we demonstrate the existence of a pressure-induced cubic-to-rhombohedral continuous phase transition. The high-pressure structure has suppressed polar shifts of B-site cations, enhanced correlation of Pb-O ferroic species, and long-range ordered antiphase BO(6) octahedral tilts. The critical pressure is preceded by an intermediate pressure at which the coupling between off-centered Pb and B-cations is suppressed and octahedral tilting detectable by neutron diffraction is developed.

Octahedral tilts, symmetry-adapted displacive modes and polyhedral volume ratios in perovskite structures.

The structures of tilted perovskites in each of the 15 tilt systems have been decomposed into the amplitudes of symmetry-adapted modes in order to provide a clear and unambiguous definition of the tilt angles. A full expression in terms of the mode amplitudes for the ratio of the volumes of the two polyhedra within the perovskite structure for each of the 15 tilt systems is derived, along with more general expressions in terms of either mode amplitudes or tilt angles that can be used to estimate this ratio when the distortions of the octahedra are small.

Comparison between beryllium and diamond-backing plates in diamond-anvil cells: application to single-crystal x-ray diffraction high-pressure data.

A direct comparison between two complete intensity datasets, collected on the same sample loaded in two identical diamond-anvil pressure cells equipped, respectively, with beryllium and diamond-backing plates was performed. The results clearly demonstrate that the use of diamond-backing plates significantly improves the quality of crystal structure data. There is a decrease in the internal R factor for averaging, structure refinement agreement factors, and in the errors and uncertainties of the atomic coordinates, atomic displacement parameters, and individual bond lengths.

The structural variation of rhombohedral LaAlO3 perovskite under non-hydrostatic stress fields in a diamond-anvil cell.

The structural variation of LaAlO(3) perovskite under non-hydrostatic stress developed in the pressure medium within a diamond-anvil cell was determined using single-crystal x-ray diffraction. The experimental results show that the lattice of LaAlO(3) becomes more distorted and deviates from the hydrostatic behavior as pressure is increased up to 7.5 GPa. The determination of the crystal structure further confirms that the octahedral AlO(6) groups become more distorted, but the octahedral rotation around the threefold axis decreases as under hydrostatic conditions. These experimental results can be reproduced from knowledge of the elastic tensor of the sample at ambient conditions and the stress state within the pressure medium. Further calculations for two other orientations also indicate that non-hydrostatic stress has only a small effect on the rotation of the AlO(6) octahedra towards zero, but non-hydrostatic stress inevitably leads to distortions in the crystal lattice and the AlO(6) octahedra. As a result, the crystal structure is eventually driven away from cubic symmetry under non-hydrostatic conditions, whereas it evolves towards cubic symmetry under hydrostatic pressure.

Detailed study of the phase transition in [Ni(H2O)6](NO3)2·(15-crown-5)·H2O and analysis in terms of mean-field theory.

The transition between 190 and 200 K in [Ni(H(2)O)(6)](NO(3))(2)·(15-crown-5)·H(2)O has been followed by determining the structure at 22 temperatures in the range 90-273 K. The structural change is a zone-boundary transition with a critical point at (½, 0, ½) in the Brillouin zone of the high-temperature phase; both phases have space-group symmetry P2(1) but the volume of the unit cell is halved when a crystal is heated through the transition. The only obvious disorder in the high-temperature phase is of the lattice water molecule, which occupies two sites; some disorder persists below the transition. The greatest changes in the structure below the transition are the rotations of one of the two 15-crown-5 molecules and of one of the two nitrate ions; above the transition the two molecules are related by symmetry as are the two ions. Below the transition these two rotation angles evolve linearly with one another, and can thus be associated with a single order parameter that describes the structural evolution. The evolution of the spontaneous strain arising from the transition does not, however, follow the same evolution as the structural order parameter. This observation indicates that the transition cannot be described in terms of a Landau-type expansion that is characterized by a single order parameter, perhaps because the potential-energy surface for this essentially molecular crystal is more complicated than for the inorganic and framework structures in which such simple behaviour is observed.

Octahedral tilting in Pb-based relaxor ferroelectrics at high pressure.

We have employed a combination of powder neutron diffraction and single-crystal synchrotron X-ray diffraction to characterize the pressure-induced phase transitions that occur in the perovskite-type relaxor ferroelectric PbSc(0.5)Ta(0.5)O(3) (PST) and Pb(0.78)Ba(0.22)Sc(0.5)Ta(0.5)O(3) (PST-Ba). At ambient pressure the symmetry of the average structure for both compounds is Fm3m as a result of partial ordering of the Sc and Ta cations on the octahedral sites. At pressures above the phase transition both the neutron and X-ray diffraction patterns exhibit an increase in the intensities of h,k,l = all odd reflections and no appearance of additional Bragg reflections. Synchrotron single-crystal X-ray diffraction data show that the intensity of hhh peaks, h = 2n + 1, does not change with pressure. This indicates that the structural distortion arising from the phase transition has a glide-plane pseudo-symmetry along the 111 cubic directions. Rietveld refinement to the neutron powder data shows that the high-pressure phase has either R3c or R3 symmetry, depending on whether the presence of 1:1 octahedral cation ordering is neglected or taken into account, and comprises octahedral tilts of the type a(-)a(-)a(-) that continuously evolve with pressure. The cubic-to-rhombohedral transition is also marked by a large increase in the anisotropy of the displacement ellipsoids of the Pb cations, indicating larger displacements of Pb cations along the rhombohedral threefold axis rather than within the perpendicular plane. For PST the anisotropy of the Pb displacement parameters decreases at approximately 3 GPa above the phase-transition pressure. For both PST and PST-Ba the average magnitudes of Pb-cation displacements expressed in terms of isotropic displacement ellipsoids gradually decrease over the entire pressure range from ambient to 7.35 GPa.

Pressure-induced cooperative bond rearrangement in a zinc imidazolate framework: a high-pressure single-crystal X-ray diffraction study.

The pressure-dependent structural evolution of a neutral zinc-imidazolate framework [Zn(2)(C(3)H(3)N(2))(4)](n) (ZnIm) has been investigated. The as-synthesized three-dimensional ZnIm network (alpha-phase) crystallizes in the tetragonal space group I4(1)cd (a = 23.5028(4) A, c = 12.4607(3) A). The ZnIm crystal undergoes a phase transition to a previously unknown beta-phase within the 0.543(5)-0.847(5) GPa pressure range. The tetragonal crystal system is conserved during this transformation, and the beta-phase space group is I4(1) (a = 22.7482(3) A, c = 13.0168(3) A). The physical mechanism by which the transition occurs involves a complex cooperative bond rearrangement process. The room-temperature bulk modulus for ZnIm is estimated to be approximately 14 GPa. This study represents the first example of a high-pressure single-crystal X-ray diffraction analysis of a metal-organic framework.

High-pressure crystallography of rhombohedral PrAlO(3) perovskite.

The evolution of the crystal structure of rhombohedral PrAlO(3) perovskite with pressure has been investigated by single-crystal x-ray diffraction and Raman scattering experiments. The structural evolution as indicated by lattice strains, octahedral tilts, and the distortions of the octahedral AlO(6) and polyhedral PrO(12) groups with increasing pressure, is controlled by the relative compressibilities of the AlO(6) octahedra and the PrO(12) site. Because the AlO(6) octahedra are more compressible than the PrO(12) sites, up to 7.4 GPa the structure evolves towards the high-symmetry cubic phase like any other rhombohedral perovskite. The variation of volume of the rhombohedral phase with pressure can be represented by a third-order Birch-Murnaghan equation of state with bulk modulus K(0) = 193.0(1.2) GPa and K' = 6.6(4). Above 7.4 GPa the evolution towards a cubic phase is interrupted by a phase transition. Observations are consistent with the assignment of Imma symmetry to the high-pressure phase. Comparison with the low-temperature [Formula: see text] to Imma transition confirms that electronic interactions stabilize the Imma phase.

Disorder and pseudo-symmetry in octakis(trivinylsilyl)octasilicate.

Octakis(trivinylsilyl)octasilicate was prepared by capping octaspherosilicate cubes, [Si(8)O(20)](8-), with trivinylsilyl groups in methanol solution. Crystals grown from CCl(4) crystallize in the tetragonal space group I4(1). Systematic absences are consistent with the space group I4(1)/amd, although the R(int) values clearly indicate 4/m rather than 4/mmm Laue symmetry. Structure solution and refinement show that the pseudo a-glide results from the approximate m\bar 3m symmetry of the core (Si(8)O(12))O(8)(8-) unit. The positions of the molecules conform to a {110} d-glide that is broken by the small rotations of all the molecules in the same direction about [001]. Crystals grown from toluene give a diffraction pattern consisting of sharp peaks that can be indexed on the same ca 7200 A(3) unit cell, but with h + k even, and l even only. The l = odd layers contain no Bragg spots, but instead exhibit diffuse sheets of intensity. Within the sheets of diffuse scattering are streaks parallel to r* = 110* that cross at the h + k odd Bragg positions. This diffuse scattering pattern arises from well ordered rods of molecules parallel to c with frequent faults in the stacking sequence of molecules parallel to 110, with displacement vectors of [00(1/2)].

High-pressure- and low-temperature-induced changes in [(CH3)2NH(CH2)2NH3][SbCl5].

The structure of N,N-dimethylethylenediammonium pentachloroantimonate(III), [(CH3)2NH(CH2)2NH3][SbCl5], NNDP, was investigated at 100 and 15 K at ambient pressure, as well as at pressures up to 4.00 GPa at room temperature in the diamond-anvil cell. The stable structure at low temperatures and low pressures consists of isolated [SbCl5]2- anions and [(CH3)2NH(CH2)2NH3]2+ cations. The inorganic anions have a distorted square pyramidal geometry. They are arranged in linear chains parallel to the c axis. In contrast to the low-temperature studies, where no phase transition was detected, pressure induces a P2(1)/c --> P2(1)/n phase transition between 0.55 and 1.00 GPa, accompanied by a doubling of the a unit-cell parameter. This solid-solid transition results from changes in the electron configuration of the Sb(III) atom and formation of the Sb-Cl bridging bonds between inorganic polyhedra to form, at approximately 1.0 GPa, isolated [Sb2Cl10]4- units consisting of [SbCl6]3- octahedra and [SbCl5]2- square pyramids connected by a common corner. The intermolecular distances continuously decrease with further increase in pressure, and at approximately 3.1 GPa, zigzag [{SbCl5}n]2n- chains containing corner-sharing [SbCl6]3- octahedra are formed. The unit-cell volume of NNDP decreases by 18.15% between room pressure and 4.00 GPa. The linear distortions of the [SbCl5]2- and [SbCl6]3- polyhedra decrease with increasing pressure and decreasing temperature and indicate a reduction in the stereochemical activity of the lone electron pair on the Sb(III) atom.

Single-crystal synchrotron X-ray diffraction study of wüstite and magnesiowüstite at lower-mantle pressures.

This study demonstrates the use of monochromatic synchrotron X-ray radiation of 40 keV for high-precision equation-of-state studies on sets of single crystals analysed individually in the same diamond-anvil pressure cell. Angle-dispersive zone-axis diffraction patterns were obtained from crystals of wustite-Fe0.93O and magnesiowüstite-(Mg0.73Fe0.27)O to 51 GPa in a hydrostatic helium pressure medium. The rhombohedral phase of Fe0.93O was observed above 23 GPa, and its isothermal bulk modulus (K0) was determined to be 134 (+/-4) GPa, assuming K'=4. The rhombohedral phase of Fe(0.93)O is more compressible than B1-structured Fe0.93O, with K0=146 (+/-2) GPa. Magnesiowüstite-(Mg0.73Fe0.27)O remains cubic over the experimental pressure range, and has a bulk modulus of 154 (+/-3) GPa with K'=4.0 (+/-0.1).