Single-crystal elastic properties of alunite, KAl3(SO4)2(OH)6

The single-crystal elastic constants of natural alunite (ideally KAl₃(SO₄)₂(OH)₆) were determined by Brillouin spectroscopy. Chemical analysis by electron microprobe gave a formula KAl₃(SO₄)₂(OH)₆. Single crystal X-ray diffraction refinement with R ₁ = 0.0299 for the unique observed reflections (|F _o| > 4σ _F) and wR ₂ = 0.0698 for all data gave a = 6.9741(3) Å, c = 17.190(2) Å, fractional positions and thermal factors for all atoms. The elastic constants (in GPa), obtained by fitting the spectroscopic data, are C ₁₁ = 181.9 ± 0.3, C ₃₃ = 66.8 ± 0.8, C ₄₄ = 42.8 ± 0.2, C ₁₂ = 48.2 ± 0.5, C ₁₃ = 27.1 ± 1.0, C ₁₄ = 5.4 ± 0.5, and C ₆₆ = ½(C ₁₁–C ₁₂) = 66.9 ± 0.3 GPa. The VRH averages of bulk and shear modulus are 63 and 49 GPa, respectively. The aggregate Poisson ratio is 0.19. The high value of the ratio C ₁₁/C ₃₃ = 2.7 and of the ratio C ₆₆/C ₄₄ = 1.6 are characteristic of an anisotropic structure with very weak interlayer interactions along the c-axis. The basal plane (001) is characterized by 0.1% longitudinal acoustic anisotropy and 0.9–1.1% shear acoustic anisotropy, which gives alunite a characteristic pseudo-hexagonal elastic behavior, and is related to the pseudo-hexagonal arrangement of the Al(O,OH)₆ octahedra in the basal layer. The elastic Debye temperature of alunite is 654 K. The large discrepancy between the elastic and heat capacity Debye temperature is also a consequence of the layered structure.     

High pressure elasticity and phase transformation in brucite, Mg(OH)2

The first pressure derivatives of the second-order elastic constants have been calculated for brucite, Mg(OH)₂ from the second- and third-order elastic constants. The deformation theory and finite strain elasticity theory have been used to obtain the second- and third-order elastic constants of Mg(OH)₂ from the strain energy of the lattice. The strain energy ϕ is calculated by taking into account the interactions up to third nearest neighbors in the Mg(OH)₂ lattice. ϕ is then compared with the strain dependent lattice energy from continuum model approximation to obtain the expressions of elastic constants. The complete set of six second-order elastic constants C _IJ of brucite exhibits large anisotropy. Since C ₃₃ (= 21.6 GPa), which corresponds to the strength of the material along the c-axis direction, is less than the longitudinal mode C ₁₁ (= 156.7 GPa), the interlayer binding forces are weaker than the binding forces along the basal plane of Mg(OH)₂. The 14 nonvanishing components of the third-order elastic constants, C _IJK , of brucite have been obtained. All the C _IJK of brucite are negative except the values of C ₁₁₄ (= 230.36 GPa), C ₁₂₄ (= 75.45 GPa) and C ₁₃₄ (= 36.98 GPa). The absolute values of the C _IJK are, in general, one order of magnitude greater than the C _IJ ’s in the Mg(OH)₂ system as usually expected for a crystalline material. To our knowledge, no previous data are available to compare the pressure derivatives of brucite. The pressure derivatives of the two components viz., C ₁₄ and C ₃₃ become negative indicating an elastic instability in brucite while under pressure. This may be related to the phase transition of brucite largely involving rearrangements of H atoms revealed in the Raman spectroscopic, powder neutron diffraction and synchrotron X-ray diffraction studies.     

Hydrogen bonding interactions in phase A [Mg7Si2O8(OH)6] at ambient and high pressure

Neutron powder diffraction data of phase A (Mg₇Si₂O₈(OH)₆) were collected at ambient pressure and 3.2?GPa (calculated from the compressibility of phase A) from the deuterated compound, and the structure was refined using the Rietveld method. The derived crystal structure implies that hydrogen atoms occupy two distinct sites in phase A, both forming hydrogen bonds of different lengths with the same oxygen atom. This picture is supported by IR spectra, which exhibit two absorption bands at 3400 and 3513?cm^?1 corresponding to OH stretching vibrations, and proton NMR spectra, which display two peaks with equal intensities and isotropic chemical shifts of 3.7 and 5?ppm. The D-D distance [D(1)-D(2) distance] at ambient pressure was found to be 2.09?±?0.02?Å from the neutron diffraction data and 2.09?±?0.05?Å from the NMR spectra. At 3.2?GPa, there is no statistically significant increase in the O-D interatomic distance while the hydrogen bonding interaction D···O appears to increase for one of the hydrogen sites, D(1), which has the stronger hydrogen bonding interaction compared with the other hydrogen, D(2), at ambient pressure. The O-D bond valences, determined indirectly from the D···O distances were 0.86 and 0.91 at ambient pressure, and 0.83 and 0.90?at 3.2?GPa, for D(1) and D(2), respectively.     

High-pressure stability, structure and compressibility of Cmcm -MgAl2O4: an ab initio study

 Quantum-mechanical solid-state calculations have been performed on the highest-pressure polymorph of magnesium aluminate (CaTi₂O₄-type structure, Cmcm space group), as well as on the low-pressure (Fd3ˉm) spinel phase and on MgO and Al₂O₃. An ab initio all-electron periodic scheme with localized basis functions (Gaussian-type atomic orbitals) has been used, employing density-functional-theory Hamiltonians based on LDA and B3LYP functionals. Least-enthalpy structure optimizations in the pressure range 0 to 60 GPa have allowed us to predict: (1) the full crystal structure, the pV equation of state and the compressibility of Cmcm-MgAl₂O₄ as a function of pressure; (2) the phase diagram of the MgO–Al₂O₃–MgAl₂O₄ system (with exclusion of CaFe₂O₄-type Pmcn-MgAl₂O₄), and the equilibrium pressures for the reactions of formation/decomposition of the Fd3ˉm and Cmcm polymorphs of MgAl₂O₄ from the MgO + Al₂O₃ assemblage. Cmcm-MgAl₂O₄ is predicted to form at 39 and 57 GPa by LDA and B3LYP calculations, with K ₀=248 (K′=3.3) and 222 GPa (K′=3.8), respectively. Results are compared to experimental data, where available, and the performance of different DFT functionals is discussed. Received: 31 January 2001 / Accepted: 16 May 2001     

P - V - T equation of state of stishovite to the mantle transition zone conditions

In-situ synchrotron X-ray diffraction experiments were conducted using the SPEED-1500 multi-anvil press of SPring-8 on stishovite SiO₂ and pressure-volume-temperature data were collected at up to 22.5 GPa and 1,073 K, which corresponds to the pressure conditions of the base of the mantle transition zone. The analysis of room-temperature data yielded V₀=46.56(1) ų, K_{T 0}=296(5) GPa and K _T =4.2(4), and these properties were consistent with the subsequent thermal equation of state (EOS) analyses. A fit of the present data to high-temperature Birch-Murnaghan EOS yielded (K_T /T) _P =–0.046(5) GPa K^–1 and = a + bT with values of a =1.26(11)×10^–5 K^–1 and b =1.29(17)×10^–8 K^–2. A fit to the thermal pressure EOS gives ₀=1.62(9)×10^–5 K^–1, ( K _T / T) _V =–0.027(4) GPa K^–1 and (²P /T ²) _V =27(5)×10^–7 GPa K^–2. The lattice dynamical approach by Mie-Grüneisen-Debye EOS yielded ₀=1.33(6), q =6.1(8) and ₀=1160(120) K. The strong volume dependence of the thermal pressure of stishovite was revealed by the analysis of present data, which was not detectable by the previous high-temperature data at lower pressures, and this yields ( K _T / T) _V 0 and q 1. The analyses for the fictive volume for a and c axes show that relative stiffness of c axis to a axis is similar both on compression and thermal expansion. Present EOS enables the accurate estimate of density of SiO₂ in the deep mantle conditions.     

Compression of witherite to 8 GPa and the crystal structure of BaCO3II

Natural witherite (Ba_0.99Sr_0.01CO₃) has been studied by single-crystal X-ray diffraction in the diamond anvil cell at eight pressures up to 8 GPa. At ambient pressure, cell dimensions are a?=?5.3164(12) Å, b?=?8.8921(19) Å, c?=?6.4279(16) Å, and the structure was refined in space group Pmcn to R(F)?=?0.020 from 2972 intensity data. The unit cell and atom position parameters for the orthorhombic cell were refined at pressures of 1.2, 2.0, 2.9, 3.9, 4.6, 5.5, 6.2, and 7.0 GPa. The volume-pressure data are used to calculate equation of state parameters K _T0?=?50.4(12) GPa and K′?=?1.9(4). At approximately 7.2 GPa, a first-order transformation to space group P3¯1c was observed. Cell dimensions of the high-pressure phase at 7.2 GPa are a?=?5.258(6) Å, c?=?5.64(1) Å. The high pressure structure was determined and refined to R(F)?=?0.06 using 83 intensity data, of which 15 were unique. This high-pressure phase appears to be more compressible than the orthorhombic phase with an estimated initial bulk modulus (K _7.2GPa) of 10 GPa.     

High-pressure synthesis and properties of magnesiocarpholite,MgAl2[Si2O6] (OH)4

Magnesiocarpholite has been synthesized on its own composition between 15 and 25 kb water pressure and 415°–600° C. Best conditions are 25 kb-550° C, starting from a mixture of oxides and synthetic cordierite. Within the MgO-Al₂O₃-SiO₂-H₂O system, possible substitutions appear to be very limited in magnesiocarpholite. Cell-parameters are a=13.706(3), b= 20.075(3), c=5.107(l) Å, space group Ccca. The larger cell, as compared with the most magnesian natural carpholites, is tentatively ascribed to structural disorder. Preliminary stability data confirm the low-temperature character of this mineral which is shown to be a high-pressure equivalent of sudoite+quartz.     

X-ray diffraction studies of millerite NiS under non-ambient conditions

The high-pressure behaviour of millerite NiS up to 34.7 GPa was studied using single-crystal X-ray diffraction techniques. Under ambient pressure, 8.3, 19.2 and 26.8 GPa crystal-structure determinations were performed. No phase transition was observed and the fit of the Birch-Murnaghan equation of state gave a bulk modulus K=111(1) GPa and a pressure derivative K=5.0(1) at high pressure and room temperature. The high-temperature modification of NiS belongs to the NiAs type and has the smaller volume per formula unit. High-pressure–high-temperature X-ray diffraction studies on NiS powder indicate that the transition temperature is strongly dependent on pressure. Owing to the higher compressibility of millerite compared with that of the high-temperature phase, it is assumed that the NiAs-type is not the stable phase at high pressures.     

葡萄石的热膨胀性与压缩性及其地质意义

利用同步辐射X射线衍射及拉曼光谱技术对葡萄石分别进行了原位高温及原位高压实验。原位高温实验结果表明葡萄石的热膨胀系数为K=1. 77(3)×10~(-5)K~(-1),轴向热膨胀系数具有各向异性(α_aα_bα_c),葡萄石在1073K时开始发生脱水反应,分解为钙长石及硅灰石。原位高压X射线衍射实验结果表明,在大于12. 4GPa时,葡萄石的晶胞参数发生不连续变化,可能发生了相变;在24. 0GPa左右,葡萄石发生不可逆的非晶化转变。原位高压拉曼光谱表明,葡萄石在12. 6GPa左右发生相变,这一相变很可能与其[(Si,Al)O_4]四面体中的Si发生有序排列有关。结合葡萄石的热膨胀性及压缩性,我们确定了葡萄石在高温高压下的稳定范围,这一结果对认识上地幔中含水矿物的状态以及地幔中水的来源有重要意义。     

Ab initio quantum-mechanical modeling of pyrophyllite [Al2Si4O10(OH)2] and talc [Mg3Si4O10(OH)2] surfaces

Bulk and slab geometry optimizations and calculations of the electrostatic potential at the surface of both pyrophyllite [Al₂Si₄O₁₀(OH)₂] and talc [Mg₃Si₄O₁₀(OH)₂] were performed at Hartree–Fock and DFT level. In both pyrophyllite and talc cases, a modest (001) surface relaxation was observed, and the surface preserves the structural features of the crystal: in the case of pyrophyllite the tetrahedral and octahedral sheets are strongly distorted with respect to the ideal hexagonal symmetry (and basal oxygen are located at different heights along the direction normal to the basal plane), whereas the structure of talc deviates slightly from the ideal hexagonal symmetry (almost co-planar basal oxygen). The calculated distortions are fully consistent with those experimentally observed. Although the potentials at the surface of pyrophyllite and talc are of the same order of magnitude, large topological differences were observed, which could possibly be ascribed to the differences between the surface structures of the two minerals. Negative values of the potential are located above the basal oxygen and at the center of the tetrahedral ring; above silicon the potential is always positive. The value of the potential minimum above the center of the tetrahedral ring of pyrophyllite is ?0.05 V (at 2 Å from the surface), whereas in the case of talc the minimum is ?0.01 V, at 2.7 Å. In the case of pyrophyllite the minimum of potential above the higher basal oxygen is located at 1.1 Å and it has a value of ?1.25 V, whereas above the lower oxygen the value of the potential at the minimum is ?0.2 V, at 1.25 Å; the talc exhibits a minimum of ?0.75 V at 1.2 Å, above the basal oxygen.     

Tilting and distortion of CaSnO<Subscript>3</Subscript> perovskite to 7 GPa determined from single-crystal X-ray diffraction

The structural changes of CaSnO₃, a GdFeO₃-type perovskite, have been investigated to 7 GPa in a diamond-anvil cell at room temperature using single-crystal X-ray diffraction. Significant changes are observed in both the octahedral Sn–O bond lengths and tilt angles between the SnO6 octahedra. The octahedral (SnO6) site shows anisotropic compression and consequently the distortion of SnO6 increases with pressure. Increased pressure also results in a decrease of both of the inter-octahedral angles, Sn–O1–Sn and Sn–O2–Sn, indicating that octahedral tilting increases with increasing pressure, chiefly equivalent to rotation of the SnO6 octahedra about the pseudocubic <001>_p axis. The distortion in the CaO12 and SnO6 sites, along with the octahedral SnO6 tilting, is attributed to the SnO6 site being less compressible than the CaO12 site.Acknowledgments The authors acknowledge with gratitude the financial support for this work from NSF grant EAR-0105864. Ruby pressure measurements were conducted with the Raman system in the Vibrational Spectroscopy Laboratory in the Department of Geosciences at Virginia Tech with the help of Mr. Charles Farley.     

Quantum-mechanical modeling of minerals at high pressures. The role of the Hamiltonian in a case study: the beryl (Al4Be6Si12O36)

Ab initio calculations of the beryl structure at room and higher pressures, and of its equation of state, have been performed both at the Hartree–Fock (HF) and density functional (DFT) level. In the latter case, three different hybrid HF/DFT Hamiltonians have been employed, in which the exact non-local exchange contribution increases from 20% (B3LYP Hamiltonian, indicated with the symbol F20) to 50% (F50) and 60% (F60). Within the DFT series, the equilibrium volume (V ₀) increases as the HF exchange contribution decreases; with respect to the experimental datum, F20 overestimates V ₀ by 2.9%, whereas F60 underestimates it by 0.9%; F50 (and HF) volume is very close to the experimental datum (error less than −0.1%). All four Hamiltonians overestimate the bulk modulus (K ₀); with respect to the experimental datum (obtained in the present work) [K ₀=179(1) GPa], the F20 Hamiltonian leads to the smallest error (+2.7%); the corresponding errors for the F50, F60 and HF Hamiltonians are +13.2, +16.2 and +16.3%, respectively. In the case of F20, in spite of the small error in K ₀, the relatively large error in V ₀ leads to an incorrect P(V) equation of state, which significantly overestimates the pressure at a given volume, compared to the experimental one at the same volume; the maximum error in the pressure range investigated is at the largest pressure (P _max=26.4 GPa) and amounts to +34.8%. The corresponding errors for the F50, F60 and HF Hamiltonians are +12.9, +5.7 and +15.5%.     

Synchrotron IR study of hydrous ringwoodite (γ-Mg2SiO4) up to 30 GPa

High-pressure synchrotron infrared (IR) absorption spectra were collected between 650 and 4,000 cm⁻¹ at ambient temperature for hydrous Mg-ringwoodite (γ-Mg₂SiO₄) up to 30 GPa. The main feature in the OH⁻ stretching region is an extremely broad band centred at 3,150 cm⁻¹. The hydrogen bond is strong for most protons and the most probable site for protonation is the tetrahedral edge. With increasing pressure, this band shifts downward while decreasing its integrated intensity until disappearance at a pressure of 25 GPa. Only one band at 2,450 cm⁻¹ and an absorption plateau persist with a maximum wavenumber of 3,800 cm⁻¹. This behaviour is reversible upon pressure release. We interpret this as a second-order phase transition occurring in hydrated Mg-ringwoodite at high pressure (beyond ∼ 25 GPa). This result is compatible with the observation by Kleppe et al. (Phys Chem Miner 29:473–476, 2002a) who suggested the presence of Si–O–Si linkages and/or partial increase in the coordination of Si. Beyond the phase transition, the protons are delocalized and their environment on the ringwoodite structure is probably quite different from that at low pressure. Data obtained in situ at high pressures and temperatures are needed to better understand the effect of protonation on the structure and to better constrain this phase transition.     

Atomistic simulation of the structure and elastic properties of pyrite (FeS2) as a function of pressure

Interatomic potential parameters have been derived at simulated temperatures of 0 K and 300 K to model pyrite FeS₂. The predicted pyrite structures are within 1% of those determined experimentally, while the calculated bulk modulus is within 7%. The model is also able to simulate the properties of marcasite, even though no data for this phase were included in the fitting procedure. There is almost no difference in results obtained for pyrite using the two potential sets; however, when used to model FeS₂ marcasite, the potential fitted at 0 K performs better. The potentials have also been used to study the high-pressure behaviour of pyrite up to 44 GPa. The calculated equation of state gives good agreement with experiment and shows that the Fe–S bonds shorten more rapidly that the S–S dimer bonds. The behaviour of marcasite at high pressure is found to be similar to that of pyrite.     

Determination of cation distribution in (Co,Ni,Zn)2SiO4 olivine by synchrotron X-ray diffraction

 The cation distribution of Co, Ni, and Zn between the M1 and M2 sites of a synthetic olivine was determined with a single-crystal diffraction method. The crystal data are (Co_0.377Ni_0.396Zn_0.227)₂SiO₄, M _r  = 212.692, orthorhombic, Pbnm, a = 475.64(3), b = 1022.83(8), and c = 596.96(6) pm, V = 0.2904(1) nm³, Z = 4, D _x  = 4.864 g cm⁻³, and F(0 0 0) = 408.62. Lattice, positional, and thermal parameters were determined with MoKα radiation; R = 0.025 for 1487 symmetry-independent reflections with F > 4σ(F). The site occupancies of Co, Ni, and Zn were determined with synchrotron radiation employing the anomalous dispersion effect of Co and Ni. The synchrotron radiation data include two sets of intensity data collected at 161.57 and 149.81 pm, which are about 1 pm longer than Co and Ni absorption edges, respectively. The R value was 0.022 for Co K edge data with 174 independent reflections, and 0.034 for Ni K edge data with 169 reflections. The occupancies are 0.334Co + 0.539Ni + 0.127Zn in the M1 sites, and 0.420Co + 0.253Ni + 0.327Zn in the M2 sites. The compilation of the cation distributions in olivines shows that the distributions depend on ionic radii and electronegativities of constituent cations, and that the partition coefficient can be estimated from the equation: ln [(A/B)_M1/(A/B)_M2] = −0.272 (IR _A -IR _B ) + 3.65 (EN _A −EN _B ), where IR (pm) and EN are ionic radius and electronegativity, respectively. Received: 8 April 1999 / Revised, accepted: 7 September 1999     

大别硬玉石英岩中金红石原位高温高压下晶体结构和OH的研究

本文通过金刚石对顶砧与拉曼光谱、红外光谱联用技术,原位模拟了金红石在高温高压下晶体结构及其OH的变化,从而了解俯冲带流体中金红石在地质过程中的行为及作用。实验证明,金红石在压力的作用下经历两次相变,分别为金红石型TiO₂结构→斜锆石型TiO₂结构（P=23.43GPa）→萤石型TiO₂结构（P=34.98GPa）,其结构在经历过超深俯冲后、折返过程中则以ɑ-PbO₂型TiO₂结构稳定存在。并且金红石晶体中的OH红外特征峰强度随着压力的增加而降低,从而显示在加压过程中金红石中OH含量降低,但直至地球深部超过600km（37.28GPa,约1200km）,其晶体中的OH也并未完全脱去。在高温高压实验中,金红石样品从常温常压条件加压、加温至P=4.01~4.08GPa和T=700℃时,金红石晶体的有序度、OH含量随着温度增加而降低,但至实验最高温压,晶体内部仍保留OH,其结构也稳定存在,因此金红石可以将水携带至深部约120km处。在降至常温常压的过程中,金红石中OH含量虽然增加,但并未恢复至实验开始时的含量,因此经历过快速俯冲、折返后的金红石中的OH含量无法代表金红石形成时的OH含量。

     

Thermodynamic properties,low-temperature heat-capacity anomalies,and single-crystal X-ray refinement of hydronium jarosite, (H<Subscript>3</Subscript>O)Fe<Subscript>3</Subscript>(SO<Subscript>4</Subscript>)<Subscript>2</Subscript>(OH)<Subscript>6</Subscript>

Crystals of hydronium jarosite were synthesized by hydrothermal treatment of Fe(III)–SO₄ solutions. Single-crystal XRD refinement with R₁=0.0232 for the unique observed reflections (|F_o| > 4_F) and wR₂=0.0451 for all data gave a=7.3559(8) Å, c=17.019(3) Å, V^o=160.11(4) cm³, and fractional positions for all atoms except the H in the H₃O groups. The chemical composition of this sample is described by the formula (H₃O)_0.91Fe_2.91(SO₄)₂[(OH)_5.64(H₂O)_0.18]. The enthalpy of formation (H^o_f) is –3694.5 ± 4.6 kJ mol^–1, calculated from acid (5.0 N HCl) solution calorimetry data for hydronium jarosite, -FeOOH, MgO, H₂O, and -MgSO₄. The entropy at standard temperature and pressure (S^o) is 438.9±0.7 J mol^–1 K^–1, calculated from adiabatic and semi-adiabatic calorimetry data. The heat capacity (C_p) data between 273 and 400 K were fitted to a Maier-Kelley polynomial C_p(T in K)=280.6 + 0.6149T–3199700T^–2. The Gibbs free energy of formation is –3162.2 ± 4.6 kJ mol^–1. Speciation and activity calculations for Fe(III)–SO₄ solutions show that these new thermodynamic data reproduce the results of solubility experiments with hydronium jarosite. A spin-glass freezing transition was manifested as a broad anomaly in the C_p data, and as a broad maximum in the zero-field-cooled magnetic susceptibility data at 16.5 K. Another anomaly in C_p, below 0.7 K, has been tentatively attributed to spin cluster tunneling. A set of thermodynamic values for an ideal composition end member (H₃O)Fe₃(SO₄)₂(OH)₆ was estimated: G^o_f= –3226.4 ± 4.6 kJ mol^–1, H^o_f=–3770.2 ± 4.6 kJ mol^–1, S^o=448.2 ± 0.7 J mol^–1 K^–1, C_p (T in K)=287.2 + 0.6281T–3286000T^–2 (between 273 and 400 K).     

High-pressure phase transition and behavior of protons in brucite Mg(OH)2: a high-pressure–temperature study using IR synchrotron radiation

 Infrared absorption spectra of brucite Mg (OH)₂ were measured under high pressure and high temperature from 0.1 MPa 25 °C to 16 GPa 360 °C using infrared synchrotron radiation at BL43IR of Spring-8 and a high-temperature diamond-anvil cell. Brucite originally has an absorption peak at 3700 cm⁻¹, which is due to the OH dipole at ambient pressure. Over 3 GPa, brucite shows a pressure-induced absorption peak at 3650 cm⁻¹. The pressure-induced peak can be assigned to a new OH dipole under pressure. The new peak indicates that brucite has a new proton site under pressure and undergoes a high-pressure phase transition. From observations of the pressure-induced peak under various P–T condition, a stable region of the high-pressure phase was determined. The original peak shifts to lower wavenumber at −0.25 cm⁻¹ GPa⁻¹, while the pressure-induced peak shifts at −5.1 cm⁻¹ GPa⁻¹. These negative dependences of original and pressure-induced peak shifts against pressure result from enhanced hydrogen bond by shortened O–H···O distance, and the two dependences must result from the differences of hydrogen bond types of the original and pressure-induced peaks, most likely from trifurcated and bent types, respectively. Under high pressure and high temperature, the pressure-induced peak disappears, but a broad absorption band between 3300 and 3500 cm⁻¹ was observed. The broad absorption band may suggest free proton, and the possibility of proton conduction in brucite under high pressure and temperature. Received: 16 July 2001 / Accepted: 25 December 2001     

Sulfur K-edge XANES study of local electronic structure in ternary monosulfide solid solution [(Fe, Co, Ni)0.923S]

 Synchrotron radiation S K-edge XANES spectra and unit-cell parameters are used to investigate the local electronic structure of non-stoichiometric binary and ternary Fe-Co-Ni monosulfide solid solution (mss; M_0.923S, M = Fe, Co, Ni) quenched from 800 °C and low pressure. The prominent absorption edge feature of the XANES spectra represents transition of S 1s core level electrons to unoccupied S 3p σ* antibonding orbitals hybridized with empty metal 3d(e_g) orbitals. There is a progressive increase in area of the edge peak from Fe_0.923S to Ni_0.923S and Co_0.923S, which correlates with progressive decrease in c and a parameters for the NiAs-type subcell and increase in metallic character, and reflects increase in the number and availability of empty e_g ^β orbitals and covalence of metal-S bonds. More generally, the area of the edge peak exhibits an inverse linear correlation with a, c and unit-cell volume of binary and ternary mss. This inverse linear correlation is attributed to progressive increase in covalence and M-S-M bonding interaction in the c-axis direction, through metal-S [M 3d(e_g) - S 3p (or 3d)] π bonding. However, the area of the edge peak does not correlate very well with the average number of 3d electrons per metal atom in these solid solutions, showing that the absorption of synchrotron radiation reflects the local electronic structure of individual absorber atoms (i.e. the SM₆ cluster), and is not a group (crystal energy band) effect. Received: 21 March 2000 / Accepted: 14 July 2000     

Crystal structure and compression of an iron-bearing Phase A to 33 GPa

Fe-bearing dense hydrous magnesium silicate Phase A, Mg_6.85Fe_0.14Si_2.00O₈(OH)₆ has been studied by single-crystal X-ray diffraction at ambient conditions and by high-pressure powder diffraction using synchrotron radiation to 33 GPa. Unit cell parameters at room temperature and pressure from single crystal diffraction are a=7.8678 (4) Å, c=9.5771 (5) Å, and V=513.43 (4) ų. Fitting of the P–V data to a third-order Birch-Murnaghan isothermal equation of state yields V ₀=512.3 (3) ų, K _T,0=102.9 (28) GPa and K′=6.4 (3). Compression is strongly anisotropic with the a-axes, which lie in the plane of the distorted close-packed layers, approximately 26% more compressible than the c-axis, which is normal to the plane. Structure refinement from single-crystal X-ray intensity data reveals expansion of the structure with Fe substitution, mainly by expansion of M-site octahedra. The short Si2–O6 distance becomes nearly 1% shorter with ~2% Fe substitution for Mg, possibly providing additional rigidity in the c-direction over the Mg end member. K _T obtained for the Fe-bearing sample is ~5.5% greater than reported previously for Fe-free Phase A, despite the larger unit cell volume. This study represents a direct comparison of structure and K _T–ρ relations between two compositions of a F-free dense hydrous magnesium silicate (DHMS) phase, and may help to characterize the effect of Fe substitution on the properties of other DHMS phases from studies of the Fe-free end-members.