High-pressure Single-crystal X-ray Diffraction Study Research Articles

Correlating chemical bonds with glass formation in coordination polymers: a combined X-ray electron density and high-pressure single-crystal X-ray diffraction study

Correlating chemical bonds with glass formation in coordination polymers: a combined X-ray electron density and high-pressure single-crystal X-ray diffraction study

Pressure-Driven Phase Transition in Two-Dimensional Perovskite MHy2PbBr4

The application of high pressure allows tuning physicochemical properties of materials by changing interatomic distances. Pressure may also induce structural phase transitions into new phases with enhanced or novel functional properties. Here, we report complementary high-pressure single-crystal X-ray diffraction, Raman spectroscopy, and optical studies of a two-dimensional (2D) perovskite, MHy2PbBr4, comprising a very small spacer cation (methylhydrazinium, MHy+). This crystal exhibits highly desired ferroelectric and extraordinary multiple linear and nonlinear optical (NLO) properties. Single-crystal X-ray diffraction shows that MHy2PbBr4 undergoes an unusual Pmn21 → P21 phase transition near 4 GPa, associated with the extrusion of some MHy+ cations from the interlayer space into voids located within the inorganic sheets, not reported for any 2D hybrid perovskite. The transport of counter cations leads to a significant increase of Pb–NH2 interactions, an unprecedented threefold increase of positive linear compressibility perpendicular to the polyanionic layers and a large negative linear compressibility of −22.39 TPa–1 within the layers. The Raman data confirm the association of the phase transition with strong distortion of the crystal structure and reorganization of the hydrogen bond network, while the absorption spectra of the compressed ambient-pressure Pmn21 phase show the band gap narrowing, followed by its widening in the high-pressure P21 phase. A similar change in the pressure dependence from a red shift to a blue shift is also observed for the free-exciton (FE) photoluminescence (PL). Furthermore, the pressure-induced phase transition leads to a giant enhancement of PL intensity, especially pronounced for the broad-band emission attributed to the self-trapped excitons (STEx). We attribute the effects, observed in absorption and PL spectra, to the shortening of Pb–Br bonds in the ambient pressure phase and increased distortion of the inorganic layers and tilts of PbBr6 octahedra in the high-pressure phase. Overall, our results for a 2D hybrid compound comprising very small spacer cations extend the understanding of the pressure effect on the properties of 2D hybrid perovskites in general and demonstrate a very different behavior under compression compared to the analogues with large organic cations. They revealed that the structure–strain mechanism can be used for engineering new high-pressure phases with unusual structural, mechanical, and optoelectronic properties.

High-pressure single-crystal synchrotron X-ray diffraction study of lillianite

Abstract In this paper, high-pressure data from a synchrotron X-ray diffraction study on a lillianite (Pb3Bi2S6) single crystal up to ~21 GPa are presented. A phase transition from lillianite (space group Bbmm, LP lillianite) to the high-pressure form β-Pb3Bi2S6 (space group Pbnm, HP lillianite) was confirmed and bracketed between 4.90 and 4.92 GPa. The transition is reversible but of first-order with a hysteresis of ~2.8 GPa. It showed weak effects of pseudo-merohedral twinning that disappeared upon decompression, testifying to a full recovery of the single crystal of lillianite. This makes lillianite an interesting shape-memory material. With a bulk modulus K4.9 = 78(3) GPa and K′ = 5.1(4), β-Pb3Bi2S6 is markedly less compressible than lillianite [K0 = 44(2) GPa, K′ = 7(1)]. Compressional anisotropy increases markedly in β-Pb3Bi2S6 with compressibility along the b axis [M0b = 130(6) GPa and Mb′ = 19(3) in lillianite, M4.9b = 145(4) GPa and Mb′ = 16.0(7) in β-Pb3Bi2S6] significantly larger than that along the other two axes [M0a = 118(5) GPa, Ma′ = 21(3), M0c = 139(12) GPa, and Mc′ = 31(10) in lillianite, M4.9a = 242(12) GPa, Ma′ = 8(1), M4.9c = 242(5) GPa, and Mc′ = 29(1) in β-Pb3Bi2S6]. The behavior of lillianite at high pressure is an interesting case study in relation to non-quenchable ultrahigh-pressure phases likely occurring in the inner Earth, like post-perovskite MgSiO3, the oxide homologue N = 1 of the lillianite series. The β-Pb3Bi2S6 structure, on the other hand, is the N = 3 homologue of the meneghinite series to which the higher-pressure modification of the post-perovskite structure also belongs (homologue N = 1). This makes the two forms of Pb3Bi2S6 potential equivalents of high- and ultrahigh-pressure Mg silicates that could occur both in the deep earth and in other rocky extrasolar planetary bodies.

Investigation of the crystal structure of a low water content hydrous olivine to 29.9 GPa: A high-pressure single-crystal X-ray diffraction study

AbstractOlivine is the most abundant mineral in the Earth's upper mantle and subducting slabs. Studying the structural evolution and equation of state of olivine at high-pressure is of fundamental importance in constraining the composition and structure of these regions. Hydrogen can be incorporated into olivine and significantly influence its physical and chemical properties. Previous infrared and Raman spectroscopic studies indicated that local structural changes occur in Mg-rich hydrous olivine (Fo ≥ 95; 4883–9000 ppmw water) at high-pressure. Since water contents of natural olivine are commonly <1000 ppmw, it is inevitable to investigate the effects of such water contents on the equation of state (EoS) and structure of olivine at high-pressure. Here we synthesized a low water content hydrous olivine (Fo95; 1538 ppmw water) at low SiO2 activity and identified that the incorporated hydrogens are predominantly associated with the Si sites. We performed high-pressure single-crystal X-ray diffraction experiments on this olivine to 29.9 GPa. A third-order Birch-Murnaghan equation of state (BM3 EoS) was fit to the pressure-volume data, yielding the following EoS parameters: VT0 = 290.182(1) Å3, KT0 = 130.8(9) GPa, and K′T0 = 4.16(8). The KT0 is consistent with those of anhydrous Mg-rich olivine, which indicates that such low water content has negligible effects on the bulk modulus of olivine. Furthermore, we carried out the structural refinement of this hydrous olivine as a function of pressure to 29.9 GPa. The results indicate that, similar to the anhydrous olivine, the compression of the M1-O and M2-O bonds are comparable, which are larger than that of the Si-O bonds. The compression of M1-O and M2-O bonds of this hydrous olivine are comparable with those of anhydrous olivine, while the Si-O1 and Si-O2 bonds in the hydrous olivine are more compressible than those in the anhydrous olivine. Therefore, this study suggests that low water content has negligible effects on the EoS of olivine, though the incorporation of water softens the Si-O1 and Si-O2 bond.

A Cr3+ luminescence study of natural topaz Al2SiO4(F,OH)2 up to 60 GPa

Abstract Topaz [Al2SiO4(F,OH)2] is a subduction-related mineral that is found in metasediments and has a large pressure and temperature stability field. Here, we use luminescence spectroscopy of Cr3+ to probe the Al site in topaz at pressures up to ~60 GPa, which corresponds to a depth of ~1400 km in the Earth. This technique allows us to probe all three unique Al environments (i.e., [AlO4(OH)2]7–, [AlO4(F)2]7–, and [AlO4OH,F]7–) simultaneously under high pressure. We find that the R-line luminescence from all three Al environments shift linearly to longer wavelength to ~40 GPa. Above ~40 GPa, they shift nonlinearly and begin to flatten out at ~48 GPa, with a pressure shift of ~0 cm–1/GPa from ~48–55 GPa. Our results, combined with previous high-pressure single-crystal X-ray diffraction studies to ~45 GPa, strongly indicate that there is a change in the compression mechanism in topaz above ~40 GPa. Our high-pressure room-temperature results show that the metastable persistence of topaz on compression represents one of the most extreme cases among tetrahedrally coordinated silicates.

Pressure-induced phase transition in 1,3,5-triamino-2,4,6-trinitrobenzene (TATB)

Determining the unreacted equation of state of 1,3,5-triamino-2,4,6-trinitrobenzene (TATB) is challenging because it exhibits low crystal symmetry and low X-ray scattering strength. Here, we present the first high-pressure single-crystal X-ray diffraction (SXD) study of this material. Our SXD results reveal a previously unknown transition to a monoclinic phase above 4 GPa. No abrupt change of the volume occurs but the compressibility changes. Concomitant first principles evolutionary crystal structure prediction USPEX calculations confirm this transition and show that it involves a pressure-induced in-plane shift of the layers of TATB molecules with respect to the ambient-pressure phase.

High-pressure single-crystal X-ray diffraction study of a model Rh complex exhibiting metallophilic interactions in the solid state

High-pressure single-crystal X-ray diffraction study of a model Rh complex exhibiting metallophilic interactions in the solid state

Armstrongite at non-ambient conditions: An in-situ high-pressure single-crystal X-ray diffraction study

Abstract The high-pressure behavior of a natural armstrongite [(Ca0.96Ce0.01Yb0.01)Zr0.99Si6O14.97·2.02H2O, a∼14.03 A, b∼14.14 A, c∼7.85 A, β∼109.4°, Sp. Gr. C2/m], a microporous heterosilicate, has been studied by single-crystal X-ray diffraction with a diamond-anvil cell up to 8 GPa, using the methanol:ethanol:H2O = 16:3:1 mixture as a pressure-transmitting fluid. A first-order phase transition, characterized by a triplication of the unit-cell volume, was detected between 4.01 (5) and 5.07 (5) GPa. The isothermal bulk modulus (KV0 = -V (∂P/∂V)) of the high-pressure polymorph was found to be ∼50% higher than that obtained for the low-pressure one (i.e., KV0 = 45 (1) GPa for the high-pressure polymorph, KV0 = 31.2 (6) GPa for the low-pressure polymorph), indicating a remarkable change in the structure compressibility. The mechanisms at the atomic scale, which govern the structure deformation of the low-P polymorphs, are described based on a series of structure refinements up to 4 GPa, and a comparison with those experienced by the structure at high temperature is provided. As observed for other microporous silicates, the polyhedral tilting is the main deformation mechanism able to accommodate the effects of the applied pressure. No evidence of crystal-fluid interaction, with a selective sorption of molecules of the pressure-transmitting fluid through the cavities, was observed at high pressure.

High-Pressure Transformations and the Resonance Structure of Thiourea

High pressure increases intermolecular interactions in the crystal environment and affects the molecular dimensions of thiourea, CS(NH2)2, consistently with changing contributions of the thione and zwitterionic mesomers. The ambient-pressure phase V (space-group Pnma, Z = 4) at 0.34 GPa transforms to phase VI, of the same space-group symmetry, but with the larger unit-cell trifold (Z = 12). Another pressure-induced transition to phase VII was previously postulated for thiourea at 0.54 GPa; however, no associated structural transformations were identified. Our high-pressure single-crystal X-ray diffraction study reveals that following the transition at 0.34 GPa the lattice parameters and crystal structure strongly and monotonically change to about 0.65 GPa while the crystal symmetry is retained.

High-pressure Single-crystal X-ray Diffraction Study on Minerals Related to the Earth's Mantle:

High-pressure Single-crystal X-ray Diffraction Study on Minerals Related to the Earth's Mantle:

A closer look into close packing: pentacoordinated silicon in a high-pressure polymorph of danburite.

Due to their high technological and geological relevance, silicates are one of the most studied classes of inorganic compounds. Under ambient conditions, the silicon in silicates is almost exclusively coordinated by four oxygen atoms, while high-pressure treatment normally results in an increase in the coordination from four- to sixfold. Reported here is a high-pressure single-crystal X-ray diffraction study of danburite, CaB2Si2O8, the first compound showing a step-wise transition of Si coordination from tetrahedral to octahedral through a trigonal bipyramid. Along the compression, the Si2O7 groups of danburite first transform into chains of vertice-sharing SiO5 trigonal bipyramids (danburite-II) and later into chains of edge-sharing SiO6 octahedra (danburite-III). It is suggested that the unusual formation of an SiO5 configuration is a consequence of filling up the pentacoordinated voids in the distorted hexagonal close packing of danburite-II.

Mechanical Properties of a Calcium Dietary Supplement, Calcium Fumarate Trihydrate.

The mechanical properties of calcium fumarate trihydrate, a 1D coordination polymer considered for use as a calcium source for food and beverage enrichment, have been determined via nanoindentation and high-pressure X-ray diffraction with single crystals. The nanoindentation studies reveal that the elastic modulus (16.7-33.4 GPa, depending on crystallographic orientation), hardness (1.05-1.36 GPa), yield stress (0.70-0.90 GPa), and creep behavior (0.8-5.8 nm/s) can be rationalized in view of the anisotropic crystal structure; factors include the directionality of the inorganic Ca-O-Ca chain and hydrogen bonding, as well as the orientation of the fumarate ligands. High-pressure single-crystal X-ray diffraction studies show a bulk modulus of ∼ 20 GPa, which is indicative of elastic recovery intermediate between small molecule drug crystals and inorganic pharmaceutical ingredients. The combined use of nanoindentation and high-pressure X-ray diffraction techniques provides a complementary experimental approach for probing the critical mechanical properties related to tableting of these dietary supplements.

High-pressure single-crystal X-ray diffraction study of jadeite and kosmochlor

The crystal structures of natural jadeite, NaAlSi2O6, and synthetic kosmochlor, NaCrSi2O6, were studied at room temperature, under hydrostatic conditions, up to pressures of 30.4 (1) and 40.2 (1) GPa, respectively, using single-crystal synchrotron X-ray diffraction. Pressure–volume data have been fit to a third-order Birch–Murnaghan equation of state yielding V0 = 402.5 (4) A3, K0 = 136 (3) GPa, and K0′ = 3.3 (2) for jadeite and V0 = 420.0 (3) A3, K0 = 123 (2) GPa and K0′ = 3.61 (9) for kosmochlor. Both phases exhibit anisotropic compression with unit-strain axial ratios of 1.00:1.95:2.09 for jadeite at 30.4 (1) GPa and 1:00:2.15:2.43 for kosmochlor at 40.2 (1) GPa. Analysis of procrystal electron density distribution shows that the coordination of Na changes from 6 to 8 between 9.28 (Origlieri et al. in Am Mineral 88:1025–1032, 2003) and 18.5 (1) GPa in kosmochlor, which is also marked by a decrease in unit-strain anisotropy. Na in jadeite remains six-coordinated at 21.5 (1) GPa. Structure refinements indicate a change in the compression mechanism of kosmochlor at about 31 GPa in both the kinking of SiO4 tetrahedral chains and rate of tetrahedral compression. Below 31 GPa, the O3–O3–O3 chain extension angle and Si tetrahedral volume in kosmochlor decrease linearly with pressure, whereas above 31 GPa the kinking ceases and the rate of Si tetrahedral compression increases by greater than a factor of two. No evidence of phase transitions was observed over the studied pressure ranges.

On the high-pressure behavior of gobbinsite, the natural counterpart of the synthetic zeolite Na–P2

An in situ high-pressure single-crystal X-ray diffraction study of gobbinsite, the natural counterpart of the synthetic zeolite Na–P2, was carried out up to 4.3GPa. No evidence of amorphization was observed within pressure-range investigated. Using a non-penetrating P-medium, two changes of the elastic behavior occur: the first at 1.1–1.3GPa and the second at 2.7–3.2GPa. Birch-Murnaghan equations of state truncated to the second order were used to fit the experimental P–V data within the three P-ranges (i.e. 0.0001–1.1, 1.3–2.7 and 3.2–4.3GPa), giving the following isothermal bulk moduli (KV0): 46.3(9), 52(8) and 28(6) GPa, respectively. The unit-cell compression is significantly anisotropic. In response to the applied pressure, the 8-membered ring channel parallel to [100] undergoes a significant increase of ellipticity, whereas the channel parallel to [010] undergoes a shrinking towards a circular shape at P≥1.3GPa. A partial re-organization of the H2O sites occurs between 1.1 and 1.3GPa, and new framework deformational modes onset at P≥3.2GPa, coupled with a change in the coordination environment of the extraframework cations.

Negative Linear Compressibility of a Metal–Organic Framework

A 3D hybrid zinc formate framework, [NH(4)][Zn(HCOO)(3)], possessing an acs topology, shows a high degree of mechanical anisotropy and negative linear compressibility (NLC) along its c axis. High-pressure single-crystal X-ray diffraction studies and density functional theory calculations indicate that contraction of the Zn-O bonds and tilting of the formate ligands with increasing pressure induce changes in structure that result in shrinkage of the a and b axes and the NLC effect along c.

High-pressure behavior of zoisite

A high-pressure single-crystal X-ray diffraction (XRD) study has been carried out on two natural zoisite samples Ca 2 Al 3-x FexSi 3 O 12 OH, one Fe-free (x = 0) and one Fe-rich (x = 0.12). The unit-cell parameters were determined for the Fe-free sample at 18 different pressures up to 7.76 GPa and for the Fe-rich sample at 13 different pressures up to 7.63 GPa. The P(V) data for both of the samples were fitted by a third-order Birch-Murnaghan equation of state (BM3 EoS). The equation of state coefficients are: V 0 = 903.39(5) Å 3 , K T0 = 122.1(7) GPa, and K 0 ′ = 6.8(2) for the Fe-free sample and V 0 = 906.95(5) Å 3 , K T0 = 119.1(7) GPa, and K 0 ′ = 7.3(2) for the Fe-rich sample. This shows that the addition of Fe in to the crystal structure of zoisite leads to a slight softening of the structure. Both compositions exhibit axial compressibilities β c > β a >> β b , with the compressibilities of the a and b axes of the two samples being indistinguishable. The softening of the bulk modulus of zoisite with Fe content follows from softening of the c-axis of the structure. A high-pressure structural study of the Fe-free sample showed that the main compression mechanisms in the structure are the compression of soft inter-octahedral distance along [001] and soft intra-octahedral distances along [010] directions, while along [100] the main compression occurs because of the compression of stiff intra-octahedral distances. The substitution of Fe on to the M3 octahedral site of the structure leads to an increase of the intra-octahedral distance of the M3 that triggers the rotation of M12 and therefore leads to the softening of the M12 inter-octahedral distances that accounts for the softening of the c-axis of the structure.

High-pressure displacive phase transition of a natural Mg-rich pigeonite

A high-pressure single-crystal X-ray diffraction study has been carried out on a P21/c natural Mg-rich pigeonite sample with composition ca. Wo6En76Fs18 using a diamond anvil-cell. The unit-cell parameters were determined at 14 different pressures to 7.14 GPa. The sudden disappearance of the b-type reflections (h + k = odd) and a strong discontinuity (about 2.8%) in the unit-cell volume indicated a first-order P21/c–C2/c phase transition between 4.66 and 4.88 GPa. The P(V) data of the P21/c phase were fitted to 4.66 GPa by a third-order Birch–Murnaghan equation of state (BM3 EoS), whereas the limited number of experimental data collected within the C2/c phase between 4.88 and 7.14 GPa were fitted using the same equation of state but with K′ constrained to the value obtained for the P21/c fitting. The equation of state coefficients are V0 = 424.66(6) A3, KT0 = 104(2) GPa and K′ = 8(1) for the P21/c phase, and V0 = 423.6(1) A3, KT0 = 112.4(8) GPa, and K′ fixed to 8(1) for the C2/c phase. The axial moduli for a, b, and c for the P21/c phase were obtained using also a BM3-EoS, while for the C2/c phase only a linear calculation could be performed, and therefore the same approach was applied for comparison also to the P21/c phase. In general the C2/c phase exhibits axial compressibilities (βc > βa >> βb) lower than those of the P21/c phase (βb > βc ≈ βa; similar to those found in previous studies in clinopyroxenes and orthopyroxenes). The lower compressibility of the C2/c phase compared with that of the P21/c could be ascribed to the greater stiffness along the b direction. A previously published relationship between Pc and M2 average cation radius (i.r.) has been updated using all the literature data on P21/c clinopyroxene containing large cations at M2 site and our new data. The following weighted regression was obtained: Pc (GPa) = 26(4) − 28(5) × i.r (A), R2 = 0.97. This improved equation can be used to predict the critical pressure of natural P21/c clinopyroxene samples just knowing the composition at M2 site.

High-pressure phase transition of a natural pigeonite

High-pressure and room-temperature single-crystal X-ray diffraction (XRD) studies have been performed on crystals of a natural pigeonite sample with composition ca. Wo10En43Fs47 using diamondanvil cells. The unit-cell parameters were determined at 18 different pressures up to about 6 GPa. A first-order P21/c-C2/c phase transition was found between 3.5 and 3.6 GPa, associated with the disappearance of the b-type reflections (h + k = odd) and a strong discontinuity (about 1.7%) in the unit-cell volume. At the transition, a small hysteresis (~0.3 GPa) was observed. A third-order Birch-Murnaghan equation of state (BM3-EoS) fit to the 10 P-V data of the low-P phase yielded V0 = 431.93(2) Å3, KT0 = 96.8(8) GPa and K′ = 8.5(6). A second-order Birch-Murnaghan EoS fit to the 8 P-V data (between 3.6 and 6 GPa) of the C2/c high-P phase yielded V0 = 423.6(1) Å3 and KT0 = 112.4(8), indicating that the high-P C2/c phase is significantly stiffer than the low-P phase.

Compressibility trends of the clinopyroxenes, and in-situ high-pressure single-crystal X-ray diffraction study of jadeite

The crystal structure of a natural jadeite, NaAlSi2O6, was studied at room temperature over the pressure range 0–9.17 GPa using single-crystal X-ray diffraction. Unit-cell data were determined at 16 pressures, and intensity data were collected at nine of these pressures. A third-order Birch-Murnaghan equation of state fit to the P-V data yielded V = 402.03(2) A3, K = 136.5(14) GPa, and K ′ = 3.4(4) Jadeite exhibits strongly anisotropic compression with unit strain axial ratios of 1.00:1.63:2.10. Silicate chains become more O-rotated with pressure, reducing ∠O3-O3-O3 from 174.7(1)° at ambient pressure to 169.2(6)° at 9.17 GPa and bringing the anions of jadeite closer to a cubic closest-packed arrangement. No evidence of a phase transition was observed over the studied pressure range. In an effort to understand pyroxene compressibilities, selected clinopyroxene bulk moduli were plotted against ambient unit-cell volumes. Two trends were identified and are explained in terms of differences in M2-O3 bonding topologies and the geometric relationship of the bonds with tetrahedral rotation in the silicate chains. Bonds positioned to favor the tetrahedral rotation upon compression are termed “sympathetic,” whereas bonds positioned to resist the rotation are termed “antipathetic.” Examination of the different pyroxene structures indicates that structures containing antipathetic M2-O3 bonds are less compressible than those with only sympathetic M2-O3 bonds. This behavior has not been previously recognized.

High-pressure single-crystal X-ray diffraction study of YAlO 3 perovskite

The equation of state and structural changes of YAlO 3 perovskite, a GdFeO 3-type perovskite with Pbnm symmetry, have been investigated to 8.5 GPa in a diamond-anvil cell at room temperature using single-crystal X-ray diffraction. A fit of a third-order Birch-Murnaghan equation of state to the P– V data yields values of K T0 =192(2) GPa and K′ 0=7.3(4), with compressional moduli of the axes, K a0 =220(7) GPa, K b0 =157(3) GPa and K c0 =212(2) GPa, and their pressure derivatives, K′ a0 =12(2), K′ b0 =4.4(6)(6) and K′ c0 =8.7(4). The evolution of the structure with pressure shows that compression of the YO12 site is strongly anisotropic with the four longest Y–O separations more compressible than the eight shorter Y–O bond lengths. Consequently the distortion of the YO12 site decreases with increasing pressure. In contrast, the AlO6 site undergoes nearly isotropic compression and is more compressible than the YO12 site. The interoctahedral angles, ∠Al–O1–Al and ∠Al–O2–Al, show a significant increase with pressure, reflected in the movement of O1 along 〈100〉. The structure of YAlO 3 perovskite therefore becomes less distorted with increasing pressure, in contrast with other Pbnm perovskites such as CaSnO 3.