Third-order Birch-Murnaghan Equation Of State Research Articles

Compressibility, thermal expansion and Raman scattering of synthetic whitlockite Ca9Mg(PO3OH)(PO4)6 at high pressures and high temperatures

Abstract In-situ X-ray diffraction and 16 Raman scattering of synthetic whitlockite, Ca9Mg(PO3OH)(PO4)6, have been systematically measured at high pressures and high temperatures, respectively. The results show that whitlockite is stable up to ~ 15 GPa at ambient temperature and undergoes a temperature-induced dehydrogenation to merrillite above 973 K at ambient pressure. The obtained pressure-volume data were fitted using a third-order Birch-Murnaghan equation of state to yield the isothermal bulk modulus as K0 = 79(4) GPa with pressure derivative K0' = 4.3(6). When K0' was fixed at 4, the refined isothermal bulk modulus was 81(1) GPa. The volumetric thermal expansion coefficient (αV) is equal to 4.05(8) × 10-5 K-1. The axial thermal expansion coefficients (αa and αc) are 1.07(5) × 10-5 K-1 and 1.91(6) × 10-5 K-1. Both compressibility and thermal expansion show an axial anisotropy. The effects of pressure and temperature on the Raman spectra of whitlockite have been quantitatively analyzed. The isothermal and isobaric mode Grüneisen parameters, and the intrinsic anharmonic mode parameters of whitlockite were calculated. Some amounts of OH--bearing whitlockite may be preserved and could be discovered in meteorites if whitlockite undergoes a low temperature process.

Negative Linear Compressibility and Interlayer Gap Closure in Layered Rare-Earth Hydroxyhalide (YCl(OH)2) under High Pressure.

Layered materials have attracted extensive attention due to their exceptional physical and chemical properties. Understanding the structural evolution of such materials under high pressure is crucial for the development of new functional materials. In this study, the structure evolution of the synthesized layered rare-earth hydroxyhalide YCl(OH)2 under high pressures up to approximately 9.4 GPa was explored by using a diamond anvil cell combined with synchrotron single-crystal X-ray diffraction. Simultaneously, high-pressure Raman spectroscopy experiment was conducted to 10.3 GPa. Our findings indicate that YCl(OH)2 maintains its symmetry within the experimental pressure range. The pressure-volume data of YCl(OH)2 were fitted to the third-order Birch-Murnaghan equation of state (EoS) to derive its EoS parameters including zero-pressure unit-cell volume (VT0), isothermal bulk modulus (KT0), and its pressure derivative (K'T0): VT0 = 142.47 (1) Å3, KT0 = 38.2 (18) GPa, and K'T0 = 9.8 (1). However, the unit-cell parameters a, b, and c exhibit a distinct compressional behavior, with the a-axis being the most compressible and the b-axis being the least. Particularly noteworthy is the observation that YCl(OH)2 displays a negative linear compressibility along the b-axis within the pressure range of 0.4-5.3 GPa. Further detailed structure refinement and Raman spectroscopy analyses indicate that the anomalous behavior of the b-axis could be attributed to the formation of the O-H···O hydrogen bonding chains along the b direction. Moreover, the coordination number of Y3+ increased from 8 to 9 as the pressure reached 5.3 GPa due to the reduction of the interlayer spacing upon compression, ultimately leading to the closure of the interlayer gap.

The intrinsic mechanical properties of hydromagnesite, Mg5(CO3)4(OH)2·4H2O, a key phase of reactive MgO carbonate cement

To potentially enable CO2 sequestration, reactive MgO carbonate cement is emerging as an alternative binder to Portland cement. Understanding the mechanical properties of its binding phase is critical for understanding the strength development and performing materials design for reactive MgO cement systems; however, the intrinsic mechanical properties of hydromagnesite (Mg5(CO3)4(OH)2·4H2O), a key binding phase, remain unexplored. The present study utilized synchrotron-based high-pressure X-ray diffraction to determine the unit cell-scale, intrinsic mechanical properties of hydromagnesite for the first time. Up to hydrostatic loading of 7.7 GPa, the bulk modulus of hydromagnesite was determined as 59 GPa or 71 GPa fitted using the second-order or third-order Birch-Murnaghan equation of state, which we contextualize with binding phases in various cement systems. The experiment results are applicable in materials design of low-carbon concrete and valuable for the validation and calibration of atomistic models.

Pressure-induced metallization in the absence of a structural transition in the layered transition-metal dichalcogenide ZrSe2.

First-principles calculations were carried out on the ZrSe2 compound, which has been of interest owing to its technologically important physical properties. The structural, electronic and optical properties of this compound were investigated under pressure through the plane wave pseudopotential approach within the framework of density functional theory. A comparison between the computed crystal structure parameters and the corresponding experimental counterparts shows a very good agreement between them. Fitting the pressure-volume data using the third-order Birch-Murnaghan equation of state yielded a bulk modulus B0 = 38.17 GPa and a pressure derivative of bulk modulus B'0 = 8.2 for hexagonal ZrSe2. The relationship between the band structure and pressure is revealed. We calculated the total density of state (TDOS) under different pressures and partial density of state (PDOS) from 0 to 10 GPa. According to our calculations, metallization of hexagonal ZrSe2 is predicted to occur at around 10 GPa and pressure-induced band-gap engineering reveals the transformation of the indirect to direct band gap with increasing pressure. Furthermore, optical properties, such as the complex dielectric function, refractive index and reflectivity spectra of this compound, were studied for incident electromagnetic waves in an energy range up to 45 eV. The contributions to various transition peaks in the optical spectra are analyzed and discussed with the help of the energy-dependent imaginary part of the dielectric function.

Crystallographic structural variations in nano-crystalline Sc2O3 under pressure

The present manuscript reports high-pressure investigations on nano-crystalline Scandium Oxide (Sc2O3) through synchrotron angle dispersive x-ray diffraction technique (ADXRD) up to a pressure of ∼35.4 GPa using a diamond-anvil cell (DAC). The sample, having a cubic bixbyite structure at ambient conditions, underwent substantial changes in crystallographic parameters under the application of external pressure, while exhibiting phase stability i.e. does not undergo any structural phase transition up to 35.4 GPa. The lattice parameters and the unit cell volume decrease significantly with an increase in pressure, revealing the compressible nature of the crystal structure. The pressure-volume data is fitted using the third-order Birch-Murnaghan equation of state to calculate the bulk modulus and its first derivative, which yields zero pressure bulk modulus of 217(35) GPa, with = 12(4) and the corresponding ambient volume per unit molecule comes out to be 59.18(18) Å3.

Crystal structure of calcium-ferrite type NaAlSiO4 up to 45 GPa

Abstract Alkali-rich aluminous high-pressure phases including calcium-ferrite (CF) type NaAlSiO4 are thought to constitute ~20% by volume of subducted mid-ocean ridge basalt (MORB) under lower mantle conditions. As a potentially significant host for incompatible elements in the deep mantle, knowledge of the crystal structure and physical properties of CF-type phases is therefore important to understanding the crystal chemistry of alkali storage and recycling in the Earth’s mantle. We determined the evolution of the crystal structure of pure CF-NaAlSiO4 and Fe-bearing CF-NaAlSiO4 at pressures up to ~45 GPa using synchrotron-based, single-crystal X-ray diffraction. Using the high-pressure lattice parameters, we also determined a third-order Birch-Murnaghan equation of state, with V0 = 241.6(1) Å3, KT0 = 220(4) GPa, and KT0′ = 2.6(3) for Fe-free CF, and V0 = 244.2(2) Å3, KT0 = 211(6) GPa, and KT0′ = 2.6(3) for Fe-bearing CF. The addition of Fe into CF-NaAlSiO4 resulted in a 10 ± 5% decrease in the stiffest direction of linear compressibility along the c-axis, leading to stronger elastic anisotropy compared with the Fe-free CF phase. The NaO8 polyhedra volume is 2.6 times larger and about 60% more compressible than the octahedral (Al,Si)O6 sites, with K0NaO8 = 127 GPa and K0(Al,Si)O6 ~304 GPa. Raman spectra of the pure CF-type NaAlSiO4 sample shows that the pressure coefficient of the mean vibrational mode, 1.60(7) cm–1/GPa, is slightly higher than 1.36(6) cm−1/GPa obtained for the Fe-bearing CF-NaAlSiO4 sample. The ability of CF-type phases to contain incompatible elements such as Na beyond the stability field of jadeite requires larger and less-compressible NaO8 polyhedra. Detailed high-pressure crystallographic information for the CF phases provides knowledge on how large alkali metals are hosted in alumina framework structures with stability well into the lowermost mantle.

Structure and compressibility of Fe-bearing Al-phase D

Abstract Due to its large thermal stability, Al-phase D, the (Al,Fe3+)2SiO6H2 member of the dense hydrous magnesium silicate (DHMS) phase D, may survive along hot subduction geotherms or even at ambient mantle temperatures in the Earth’s transition zone and lower mantle, therefore potentially playing a major role as a water reservoir and carrier in the Earth’s interior. We have investigated the crystal structure and high-pressure behavior of Fe-bearing Al-phase D with a composition of Al1.53(2)Fe0.22(1) Si0.86(1)O6H3.33(9) by means of single-crystal X-ray diffraction. While the structure of pure Al-phase D (Al2SiO6H2) has space group P63/mcm and consists of equally populated and half-occupied (Al,Si)O6 octahedra, Fe-incorporation in Al-phase D seems to induce partial ordering of the cations over the octahedral sites, resulting in a change of the space group from P63/mcm to P6322 and in well-resolved diffuse scattering streaks observed in X-ray images. The evolution of the unit-cell volume of Fe-bearing Al-phase D between room pressure and 38 GPa, determined by means of synchrotron X-ray diffraction in a diamond anvil cell, is well described by a third-order Birch-Murnaghan equation of state having an isothermal bulk modulus KT0 = 166.3(15) GPa and first pressure derivative KT0′ = 4.46(12). Above 38 GPa, a change in the compression behavior is observed, likely related to the high-to-low spin crossover of octahedrally coordinated Fe3+. The evolution of the unit-cell volume across the spin crossover was modeled using a recently proposed formalism based on crystal-field theory, which shows that the spin crossover region extends from approximately 30 to 65 GPa. Given the absence of abrupt changes in the compression mechanism of Fe-bearing Al-phase D before the spin crossover, we show that the strength of H-bonds and likely their symmetrization do not greatly affect the elastic properties of phase D solid solutions, independently of their compositions.

High-Pressure, High-Temperature Studies of Phase Transitions in SrOsO3─Discovery of a Post-Perovskite.

Using a recently developed method for in situ high-pressure, laser heating experiments in diamond anvil cells, we obtained a novel post-perovskite phase of SrOsO3. The phase transition from perovskite SrOsO3 was induced at 44 GPa and 1350 K in a diamond anvil cell and characterized with synchrotron powder X-ray diffraction. The newly obtained post-perovskite is quenchable and Le Bail refinements under ambient conditions yielded the unit cell parameters: a = 3.152(9) Å, b = 10.82(2) Å, c = 7.27(1) Å, V = 248.1(1) Å3. In addition, the compression of perovskite SrOsO3 at ambient temperature was investigated up to 66 GPa in a diamond anvil cell using synchrotron powder X-ray diffraction. The compression at ambient temperature showed that pressure alone does not induce the first-order phase transition to the post-perovskite structure. However, at 36 GPa, a continuous phase transition to monoclinic (P21/n) symmetry was detected, persistent up to 58 GPa, where the perovskite transitioned back to orthorhombic (Pbnm) symmetry. Fitting a third-order Birch-Murnaghan equation of state to the obtained P-V data for perovskite SrOsO3 yielded a bulk modulus of K0 = 187.4(15) GPa. Density functional theory calculations were performed to support the experimental findings in the compression study at ambient temperature. This work shows that transformations to the post-perovskite structure can be obtained for a wider range of perovskites than simple empirical rules otherwise suggest.

Structural behavior of C2/m tremolite to 40 GPa: A high-pressure single-crystal X-ray diffraction study

Abstract The high-pressure structure and stability of the calcic amphibole tremolite [Ca2Mg5Si8O22(OH)2] was investigated to ~40 GPa at 300 K by single-crystal X-ray diffraction using synchrotron radiation. C2/m symmetry tremolite displays a broader metastability range than previously studied clinoamphiboles, exhibiting no first-order phase transition up to 40 GPa. Axial parameter ratios a/b and a/c, in conjunction with finite strain vs. normalized pressure trends, indicate that changes in compressional behavior occur at pressures of ~5 and ~20 GPa. An analysis of the finite strain trends, using third-order Birch-Murnaghan equations of state, resulted in bulk moduli (K0T) of 72(7), 77(2), and 61(1) GPa for the compressional regimes from 0–5 GPa (regime I), 5–20 GPa (II), and above 20 GPa (III), respectively, and accompanying pressure-derivatives of the bulk moduli (K0T′) of 8.6(42), 6.0(3), and 10.0(2). The results are consistent with first-principle theoretical calculations of tremolite elasticity. The axial compressibility ratios of tremolite, determined as βa:βb:βc = 2.22:1.0:0.78 (regime I), 2.12:1.0:0.96 (II), and 1.03:1.0:0.75 (III), demonstrate a substantial reduction of the compressional anisotropy of tremolite at high pressures, which is a notable contrast with the increasingly anisotropic compressibility observed in the high-pressure polymorphs of the clinoamphibole grunerite. The shift in compression-regime at 5 GPa (I–II) transition is ascribed to stiffening along the crystallographic a-axis corresponding to closure of the vacant A-site in the structure, and a shift in the topology of the a-oriented surfaces of the structural I-beam from concave to convex. The II–III regime shift at 20 GPa corresponds to an increasing rate of compaction of the Ca-polyhedra and increased distortion of the Mg-octahedral sites, processes which dictate compaction in both high-pressure compression-regimes. Bond-valence analyses of the tremolite structure under pressure show dramatic overbonding of the Ca-cations (75% at 30 GPa), with significant Mg-cation overbonding as well (40%). These imply that tremolite’s notable metastability range hinges on the calcium cation’s bonding environment. The eightfold-coordinated Ca-polyhedron accommodates significant compaction under pressure, while the geometry of the Ca-O polyhedron becomes increasingly regular and inhibits the reorientation of the tetrahedral chains that generate phase transitions observed in other clinoamphiboles. Peak/background ratio of diffraction data collected above 40 GPa and our equation of state determination of bulk moduli and compressibilities of tremolite in regime III, in concert with the results of our previous Raman study, suggest that C2/m tremolite may be approaching the limit of its metastability above 40 GPa. Our results have relevance for both the metastable compaction of tremolite during impact events, and for possible metastable persistence of tremolite within cold subduction zones within the Earth.

X-ray diffraction reveals two structural transitions in szomolnokite

AbstractHydrated sulfates have been identified and studied in a wide variety of environments on Earth, Mars, and the icy satellites of the solar system. The subsurface presence of hydrous sulfur-bearing phases to any extent necessitates a better understanding of their thermodynamic and elastic properties at pressure. End-member experimental and computational data are lacking and are needed to accurately model hydrous, sulfur-bearing planetary interiors. In this work, high-pressure X-ray diffraction (XRD) and synchrotron Fourier-transform infrared (FTIR) measurements were conducted on szomolnokite (FeSO4·H2O) up to ~83 and 24 GPa, respectively. This study finds a monoclinic-triclinic (C2/c to P1) structural phase transition occurring in szomolnokite between 5.0(1) and 6.6(1) GPa and a previously unknown triclinic-monoclinic (P1 to P21) structural transition occurring between 12.7(3) and 16.8(3) GPa. The high-pressure transition was identified by the appearance of distinct reflections in the XRD patterns that cannot be attributed to a second phase related to the dissociation of the P1 phase, and it is further characterized by increased H2O bonding within the structure. We fit third-order Birch-Murnaghan equations of state for each of the three phases identified in our data and refit published data to compare the elastic parameters of szomolnokite, kieserite (MgSO4·H2O), and blödite (Na2Mg(SO4)2·4H2O). At ambient pressure, szomolnokite is less compressible than blödite and more than kieserite, but by 7 GPa both szomolnokite and kieserite have approximately the same bulk modulus, while blödite’s remains lower than both phases up to 20 GPa. These results indicate the stability of szomolnokite’s high-pressure monoclinic phase and the retention of water within the structure up to pressures found in planetary deep interiors.

Ab initio исследования влияния давления на структуру, электронные и упругие свойства карбонатов щелочных--щелочно-земельных металлов

Density functional theory with a gradient PBE functional and dispersion correction D3(BJ) in the basis of localized orbitals of the CRYSTAL17 package was used to study the effect of pressure on the structural, electronic, and elastic properties of K2Ca(CO3)2, K2Mg(CO3)2, Na2Ca2(CO3)3, Na2Mg(CO3)2. The parameters of the third-order Birch-Murnaghan equation of state are determined, and it is shown that the equilibrium volume and compressibility modulus depend linearly on the average cation radius. Under pressure, the widths of the upper valence bands increase maximally in K2Ca(CO3)2 and minimally in Na2Ca2(CO3)3, while the centers of gravity of the cationic states shift by ~0.2 eV. Elastic constants and polycrystalline moduli are calculated, which increase with decreasing average cation radius. The shear modulus for K2Ca(CO3)2 and K2Mg(CO3)2 decreases with increasing pressure, and this leads to anomalous behavior of the longitudinal and transverse acoustic wave velocities.

Thermodynamic, elastic, and vibrational (IR/Raman) behavior of mixed type-AB carbonated hydroxylapatite by density functional theory

Abstract The present investigation reports the equation of state, thermodynamic, and thermoelastic properties of type AB carbonated apatite [CAp-AB, Ca10(CO3)B(PO4)5(CO3)A, space group P1], as obtained from density functional theory simulations and the quasi-harmonic approximation. The static (0 K) third-order Birch-Murnaghan equation of state resulted in the parameters K0 = 104.3(8) GPa, K′ = 4.3(1), and V0 = 517.9(2) Å3, whereas at room temperature (300 K) they were KT = 101.98 GPa, K′ = 4.12, and V0 = 524.486 GPa. Thermodynamics and thermoelasticity were calculated in the temperature range 0–800 K and between 0 and 30 GPa. Furthermore, the dependence of the infrared/Raman spectra of type-AB carbonated apatite with pressure is also reported, which could be useful for researchers interested in vibrational spectroscopy. The theoretical results corroborate the few experimental ones on a similar type-AB carbonated hydroxylapatite and provide further details over wide pressure and temperature ranges on the elastic, thermodynamic, and infrared/Raman properties of this important mineral found in both geological and biological environments.

Stability and Thermoelasticity of Diaspore by Synchrotron X-ray Diffraction and Raman Spectroscopy

The thermoelasticity and stability of diaspore (α-AlOOH, Al1.002Fe0.003OOH) were investigated in this study by in situ synchronous X-ray diffraction (XRD) and Raman spectroscopy methods at high pressure and high temperature conditions. The results indicate that diaspore is stable within the pressure and temperature (P-T) region examined in this study. With increasing pressure, the Raman peaks move toward the high wave number direction, the intensity of the Raman peaks increases, and the vibration mode of diaspore changes linearly. Pressure-volume data from in situ high-pressure XRD experiments were fitted by the third-order Birch-Murnaghan equation of state (EoS) with the zero-pressure unit-cell volume V0 = 118.15 (4) Å3, the zero-pressure bulk modulus KV0 = 153 (2) GPa, and its pressure derivative K'V0 = 2.4 (3). When K'V0 was fixed at 4, the obtained KV0 = 143 (1) GPa. The axial compressional behavior of diaspore was also fitted with a linearized third-order Birch-Murnaghan EoS, showing slight compression anisotropy with Ka0 = 137 (5) GPa, Kb0 = 169 (7) GPa and Kc0 = 178 (6) GPa. In addition, the temperature-volume data from in situ high-temperature XRD experiments were fitted by Fei’s thermal equation with the thermal expansion coefficients αV = 2.7 (2) × 10–5 K−1, αa = 1.13 (9) × 10–5 K−1, αb = 0.77 (5) × 10–5 K−1, and αc = 0.85 (9) × 10–5 K−1 for diaspore, which shows that diaspore exhibits slightly anisotropic thermal expansion. Furthermore, in situ synchrotron-based single-crystal XRD under simultaneously high P-T conditions indicates that the P-T stability of diaspore is up to ∼10.9 GPa and 700 K. Combined with previous results, we infer that diaspore can be subducted to ∼390 km under cold subduction conditions based on existing experimental data and is a good candidate for transporting water to the deep Earth.

CoSO4·H2O and its continuous transition compared to the compression properties of isostructural kieserite-type polymorphs

Abstract The kieserite-type compound cobalt(II) sulfate monohydrate, CoSO4·H2O, has been investigated under isothermal (T = 295 K) hydrostatic compression up to 10.1 GPa in a diamond anvil cell by means of single-crystal X-ray diffraction and Raman spectroscopy. The monoclinic α-phase (space group C2/c) undergoes a second-order ferroelastic phase transition at P c = 2.40(3) GPa to a triclinic β-phase (space group P 1 ‾ $‾{1}$ ). Lattice elasticities derived from fitting third-order Birch-Murnaghan equations of state to the pressure dependent unit-cell volume data yield V 0 = 354.20(6) Å3, K 0 = 53.0(1.7) GPa, K′ = 5.7(1.8) for the α-phase and V 0 = 355.9(8) Å3, K 0 = 45.2(2.6) GPa, K′ = 6.6(6) for the β-phase. Crystal structure data of the high-pressure polymorph were determined at 2.98(6) and 4.88(6) GPa. The most obvious structural feature and thus a possible driving mechanism of the phase transition, is a partial rearrangement in the hydrogen bonding system. However, a comparative analysis of pressure-induced changes in the four kieserite-type compounds investigated to date suggests that the loss of the point symmetry 2 at the otherwise rather rigid SO4 tetrahedron, allowing symmetrically unrestricted tetrahedral rotations and edge tiltings in the β-phase, could be the actual driving mechanism of the phase transition.

Equation of State for Natural Almandine, Spessartine, Pyrope Garnet: Implications for Quartz-In-Garnet Elastic Geobarometry

The equation of state (EoS) of a natural almandine74spessartine13pyrope10grossular3 garnet of a typical composition found in metamorphic rocks in Earth’s crust was obtained using single crystal synchrotron X-ray diffraction under isothermal room temperature compression. A third-order Birch-Murnaghan EoS was fitted to P-V data and the results are compared with published EoS for iron, manganese, magnesium, and calcium garnet compositional end-members. This comparison reveals that ideal solid solution mixing can reproduce the EoS for this intermediate composition of garnet. Additionally, this new EoS was used to calculate geobarometry on a garnet sample from the same rock, which was collected from the Albion Mountains of southern Idaho. Quartz-in-garnet elastic geobarometry was used to calculate pressures of quartz inclusion entrapment using alternative methods of garnet mixing and both the hydrostatic and Grüneisen tensor approaches. QuiG barometry pressures overlap within uncertainty when calculated using EoS for pure end-member almandine, the weighted averages of end-member EoS, and the EoS presented in this study. Grüneisen tensors produce apparent higher pressures relative to the hydrostatic method, but with large uncertainties.

Phase transformations of zircon-type DyVO4 at high pressures up to 36.4 GPa: X-ray diffraction measurements

The compression behavior of zircon-type DyVO4 has been investigated in a diamond anvil cell by angle-dispersive X-ray diffraction (ADXRD) at high pressures up to 36.4 GPa. Under quasi-hydrostatic compression with argon as the pressure transmitting medium, DyVO4 underwent a sluggish zircon-to-scheelite phase transformation that started at approximately 8.0 GPa and was completed at 15.3 ± 0.9 GPa. The scheelite-type phase remained stable at pressures up to 25.3 GPa and during the process of decompression to ambient conditions, implying that the zircon-to-scheelite transformation is irreversible. Fitting the pressure-volume data using the third-order Birch-Murnaghan equation of state yielded a bulk modulus B0 = 129 (7) GPa and a pressure derivative of bulk modulus B′ = 3.4 (4) for the zircon-type phase, and B0 = 184 (10) GPa and B′ = 5.3 (8) for the scheelite-type phase. When compressed in a methanol-ethanol (4:1) pressure transmitting medium, DyVO4 was transformed into the scheelite-type phase at a pressure of 8.8 ± 1.1 GPa and then transformed into a fergusonite-type phase at 21.3 ± 1.6 GPa. The scheelite-to-fergusonite transformation was reversible during decompression. Our study indicates that DyVO4 under compression experiences a sequential zircon-scheelite-fergusonite phase transformation and that the scheelite-fergusonite transformation is sensitive to nonhydrostatic conditions.

Laser-induced crystallization and phase transitions of As2Se3 under high pressure

Utilizing the synchrotron x-ray powder diffraction ${\mathrm{As}}_{2}{\mathrm{Se}}_{3}$ has been investigated under high pressure in a diamond anvil cell with hydrogen and neon applied as the pressure media. For both systems the amorphous samples were compressed to ca. 2--3 GPa and heated in situ by a laser, which led to their crystallization in the $R$-3 $m, {\mathrm{Bi}}_{2}{\mathrm{Te}}_{3}$-type phase. During further compression this phase transforms to the $C2/m, \ensuremath{\beta}\text{\ensuremath{-}}{\mathrm{Sb}}_{2}{\mathrm{Te}}_{3}$-type structure, and they coexist within the pressure range of 21.5--33.0 GPa. The latter phase is observed up to the highest achieved pressure of 52.0 GPa, revealing no signs of reaction with the hydrogen pressure-transmitting medium. The pressure evolution of the volume of the reported phases has been described by the third-order Birch-Murnaghan equation of state. The relative stability of the experimentally detected crystalline phases is confirmed by the density functional theory calculations. The pressure-driven evolution of the As--Se distances and coordination number has been discussed in comparison to the recent findings concerning the amorphous $a\text{\ensuremath{-}}{\mathrm{As}}_{2}{\mathrm{Se}}_{3}$ phase.

Constraining the density evolution during destruction of the lithospheric mantle in the eastern North China Craton

The thermoelastic properties of minerals in mantle xenoliths combined with the thermal states can provide an integrated understanding of the petrophysics of the lithospheric mantle. Here, we conducted high-pressure and high-temperature experiments on the main minerals (e.g. olivine, orthopyroxene, clinopyroxene, spinel, and garnet) in peridotite xenoliths from basalt of the eastern North China Craton (NCC) using in situ synchrotron single-crystal X-ray diffraction combined with diamond anvil cells. The pressure-temperature-volume data were fitted to the third-order Birch-Murnaghan equations of state and yielded the thermoelastic parameters that included bulk modulus, pressure and temperature derivatives, and thermal expansion coefficients. The density profiles of the eastern NCC during the destruction process since the Mesozoic are presented from the temporal and spatial aspects. The lithospheric density dramatically decreased during destruction, and high heat flow may have been a trigger. The spatially distributed density profile also provides firm evidence for lateral heterogeneities in the eastern NCC. This may suggest that the present mantle is characterized by heterogeneous destruction of the NCC.

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.

P21/c Postorthopyroxene γ-LiScGe2O6, a New Dense High-Pressure Polymorph and Its Direct Transformation from the Pbca Structure.

Orthorhombic β-LiScGe2O6 single crystals were compressed hydrostatically up to 10.35 GPa using a diamond anvil cell and investigated in situ by means of X-ray diffraction and Raman spectroscopy. Crystal-structure investigations at ambient conditions and at high pressure show a structural transition from an orthopyroxene-type Pbca structure (a ≈ 18.43 Å, b ≈ 8.85 Å, and c ≈ 5.34 Å at 8.6 ± 0.1 GPa) to a postorthopyroxene type P21/c structure of the new dense γ-LiScGe2O6 (a ≈ 18.62 Å, b ≈ 8.85 Å, c ≈ 5.20 Å, and β ≈ 93.1° at 9.5 ± 0.1 GPa). The structure refinements reveal displacive shifts of O atoms associated with a rotation of every other tetrahedral-chain unit from the O- to S-type position similar to the postorthopyroxene-type MgSiO3. As a consequence of the oxygen displacement, the coordination number of Li atoms is changing from [5 + 1] to a proper 6-fold coordination. The transition around Pc = 9.0 ± 0.1 GPa is associated with a volume discontinuity of ΔV = −1.6%. This orthopyroxene (OEn-Pbca) to postorthopyroxene (pOEn-P21/c) transition is the second example of this type of transformation. Precise lattice parameters have been determined during isothermal compression. The fit of the unit-cell volumes of β-LiScGe2O6, using a third-order Birch–Murnaghan equation of state, yields V0 = 943.63 ± 0.11 Å3, K0 = 89.8 ± 0.6 GPa, and dK/dP = 4.75 ± 0.18 as parameters. Evaluation of the data points beyond the critical transition pressure using a second-order Birch–Murnaghan equation suggests V0 = 940.6 ± 4.4 Å3 and K0 = 82.4 ± 4.8 GPa. A series of high-pressure Raman spectra confirm the symmetry-related structural transition, with band positions shifting in a noncontinuous manner, thus confirming the proposed first-order transition.