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1.
 The chemical bonding in the ring silicate mineral dioptase is investigated on the basis of accurate single-crystal X-ray diffraction data. A multipole model is used in the refinements. Static deformation electron density is mapped for the silicon tetrahedron, Cu-octahedron and water molecule in different sections. The silicon tetrahedron exhibits peaks resulting from σ-bonds between Si–sp3 hybrid orbitals and O–p orbitals. The excess density is located on bonds between the Si atom and bridge (in ring) O(1)-, O(1′)-oxygens and across the interior of the Si–O–Si angle. In the Jahn-Teller distorted Cu octahedron, in addition to peaks which result from single Cu–O σ-bonds, there are peaks which are due to 3d electrons. The analysis of crystal-field influence on the Cu charge distribution is made using the tetragonal D 4 d approximation for the low-symmetry (C1) Cu octahedron. The calculation of the occupancies of the 3d atomic orbitals shows that the Cu non-bonding orbitals are most populated (˜20%) and the bonding orbitals least populated (14%), as is typical for the Jahn-Teller octahedron. The effective atomic charge on the Cu atom in dioptase determined from the multipoles is +1.23e: closer to the Cu+1 than to the Cu+2 state. The charge on the Si atom has a value +1.17e, which is in the range typical for Si atoms already determined by this method. The accumulation of density on bridge oxygens and across the interior of the Si–O–Si angle may be explained by additional strain in the bond with the decrease of the Si–O–Si angle in dioptase to 132°. The same effect was found earlier in coesite. A single-crystal neutron diffraction study shows that dioptase becomes antiferromagnetic below a Néel temperature of 15.9(1) K, in contrast to the previously reported specific heat anomaly at 21 K. The magnetic propagation vector is (0, 0, 3/2) on the hexagonal triple cell or (1/2, 1/2, 1/2) in rhombohedral indices. The relation between the antiferromagnetic and the charge-density models for dioptase is discussed. The less occupied Cu d x2−y2 orbitals are responsible for the magnetic properties. These lie in the Cu–O squares, which are approximately perpendicular to c hex, but which are alternately inclined to it by a small angle. The magnetic moments of 0.59(1)μ B on the Cu ions in the same level are ordered ferromagnetically, but between ions in alternate levels the coupling is antiferromagnet. Within experimental error the magnetic moments are perpendicular to the square planes, which make an angle ±13(3)° to the triad axis. Received: 8 June 2001 / Accepted: 10 January 2002  相似文献   

2.
 The densification and structural changes in SiO2 glass compressed up to 43.4 GPa by shock experiments are investigated quantitatively by the X-ray diffraction technique. Direct structural data (average Si–O and Si–Si distances and Si–O–Si angles, coordination number of the Si atom) of these shock-densified SiO2 glasses have been obtained by analyzing the radial distribution function curves, RDF(r), calculated with X-ray diffraction data. The coordination number of all densified glasses is about 4 and shows almost no pressure variation. The SiO2 glass has shown density increase of 11% at a shock compression of 26.3 GPa. This density evolution could not be explained by the coordination change. The reduction of the average Si–O–Si angle (144° at 0 GPa to 136° at 26.3 GPa) obtained from RDF(r) data may account for this density increase. This Si–O–Si angle change may be caused by shrinkage of the network structure and the increase of small rings of SiO4 tetrahedra. For higher shock pressure, a decrease in the Si–O–Si angle to 140° was observed. This is consistent with the decrease in density at 32.0 and 43.2 GPa. This decrease in the Si–O–Si angle and density could be attributed to an annealing effect due to high after-shock residual temperature. This pressure dependence of average Si–O–Si angles in shock-densified SiO2 glass agrees with the results of our previous Raman spectroscopic study. On the other hand, the pressure variation for the first sharp diffraction peak (FSDP) was analyzed to estimate the evolution of intermediate range structures. It is suggested that the mean d value (d m ) obtained from the position of FSDP strongly depends on the shock and residual temperature, as well as shock pressure. Received: 29 June 2001 / Accepted: 14 November 2001  相似文献   

3.
We have explored first-principles molecular dynamics simulation data for hydrous MgSiO3 liquid (with 10 wt% water) to gain insight into its structural and dynamical behavior as a function of pressure (0–150 GPa) and temperature (2,000–6,000 K). By visualizing/analyzing a number of parameters associated with short- and mid-range orders, we have shown that the melt structure changes substantially on compression. The speciation of the water component at low pressures is dominated by the isolated structures (with over 90% hydrogen participated) consisting of hydroxyls, water molecules, O–H–O bridging and four-atom (O–H–O–H and H–O–H–O) groups, where every oxygen atom may be a part of polyhedron or free (i.e., bound to only magnesium atom). Hydroxyls favor polyhedral sites over magnesium sites whereas molecular water is almost entirely bound to magnesium sites, and also interpolyhedral bridging (Si–O–H–O–Si) dominates other types of bridging. Water content is shown to enhance and suppress, respectively, the proportions of hydroxyls and molecular water. As compression increases, these isolated structures increasingly combine with each other to form extended structures involving a total of five or more O and H atoms and also containing threefold coordination species, which together consume over 80% hydrogen at the highest compression studied. Our results show that water lowers the mean coordination numbers of different types including all cation–anion environments. The hydrous melt tends to be more tetrahedrally coordinated but with the Si–Si network being more disrupted compared to the anhydrous melt. Protons increase the content of non-bridging oxygen and decrease the contents of bridging oxygen as well as oxygen triclusters (present at pressures above 10 GPa). The calculated self-diffusion coefficients of all atomic species are enhanced in the presence of water compared to those of the anhydrous melt. This is consistent with the prediction that water depolymerizes the melt structure at all pressures. Our analysis also suggests that proton diffusion involves two processes—the transfer of H atoms (requiring the rupture and formation of O–H bonds) and the motion of hydroxyls as hydrogen carriers (requiring the rupture and formation of Si–O and/or Mg–O bonds). Both the processes are operative at low compression whereas only the first process is operative at high compression.  相似文献   

4.
The experimental multipole electron density, ρ(r), of diopside was derived from high-resolution single-crystal diffraction at room temperature. Its topological analysis revealed predominantly ionic Si–O bonding, as found in electron density studies of other silicates. In particular, the non-bridging Si–O bonds are slightly less ionic in character than the bridging Si–O bonds. The Ca–O and Mg–O bonds are classified as pure closed-shell ionic interactions. An analysis of –∇2ρ(r) showed the presence of maxima around the oxygen atoms, associated to lone pairs domains that are involved in bonds with the surrounding ions. Calculation of atomic basins gave net charges of –1.56(12), 3.11(17), 1.79(13) and 1.88(18) e for O (averaged), Si, Ca and Mg atoms, respectively. O···O interactions between the O atoms at the vertices of the SiO4 tetrahedron were also detected from the topological analysis of ρ(r), and indicate a cooperative interaction among the lone pairs of neighbouring oxygen atoms. All these results were also confirmed by periodic restricted Hartree–Fock (RHF) calculations. Electronic Supplementary Material Supplementary material is available for this article at and is accessible for authorized users.  相似文献   

5.
 An ab initio Hartree–Fock calculation on beryl structure has been performed and the wave function has been used for an analysis of the electron density. The equilibrium geometry, determined by minimizing the energy with respect to cell parameters and fractional coordinates, is in good agreement with structural experimental measurements; small differences in length between the various Si–O bonds of the structure are well reproduced by the calculation. The two non-equivalent oxygen atoms (O1 and O2) of beryl show different electron distributions. In particular, the valence shell charge concentration (VSCC) of O1 (the bridge between two Si ions) has a torus-like shape, showing a bulge on the external side of the Si–O–Si angle and a thinning on the internal side of it; by contrast O2 has two lone pairs which are approximately located on the line for O2, normal to the plane passing, on average, through the atoms O2, Si, Be and Al. The electron density of each oxygen is strongly polarized toward the Si ions and much less polarized towards the other cations. Such features of the VSCC of the oxygens can be recast in terms of the valence bond theory, to explain the observed differences in bond lengths. By calculating the potential inside the channels of the beryl structure, predictions could be made about the positions occupied by alkali cations, which are often found in natural minerals belonging to the beryl group: results agree in general with experimental findings, but foresee a shift of such cations off the central positions located on the six fold symmetry axis. Additionally, calculations of position and orientation of H2O inside the channel, in the alkali-free beryl, locate the molecule close to the basal plane, with the H⋯H axis parallel to [001] or oriented at 40∘ from it. Received: 12 December 2001 / Accepted: 6 April 2002  相似文献   

6.
Single-crystal W-band electron paramagnetic resonance (EPR) spectra of an electron-irradiated quartz, measured at room temperature, 110 and 77 K, disclose three previously reported hole centers (#1, G and an ozonide radical). The W-band EPR spectra of these three centers clearly resolve six magnetically nonequivalent sites each, whereas previous X- and Q-band EPR studies reported Centers #1 and the ozonide radical to consist of only three symmetry-related components and interpreted them to reside on twofold symmetry axes in the quartz structure. The calculated g matrices of Center #1 and the ozonide radical show that deviations from twofold symmetry axes are <10°, which are probably attributable to distortion related to neighboring charge compensating ions. The W-band EPR spectra of Center G not only result in improved g matrices but also allow quantitative determination of the nuclear hyperfine (A) and quadrupole (P) matrices of its 27Al hyperfine structure that was incompletely resolved before. In particular, the g-maximum and g-minimum principal axes of Center G are approximately along two pairs of O–O edges of the SiO4 tetrahedron, while the unique A principal axis is approximately along a Si–Si direction. These new spin-Hamiltonian parameters suggest that Center G most likely involves trapping of a hole between two oxygen atoms related to a silicon vacancy and stabilized by an Al3+ ion in the neighboring tetrahedron (hence an O2n−–Al3+ defect, where n is either 1 or 3).  相似文献   

7.
 Raman spectra of a single-crystal fragment of hydrous γ-Mg2SiO4, synthesized in a multianvil press, have been measured in a diamond-anvil cell with helium as pressure-transmitting medium to 56.5 GPa at room temperature. All five characteristic spinel Raman modes shift continuously up to the highest pressure, showing no evidence for a major change in the crystal structure despite compression well beyond the stability field of ringwoodite in terms of pressure. At pressures above ∼30 GPa a new mode on the low-frequency site of the two silicate-stretching modes is clearly identifiable, indicating a modification in the spinel structure which is reversible on pressure release. The frequency of the new mode (802 cm−1 extrapolated to 1 bar) suggests the presence of Si–O–Si linkages and/or a partial increase in the coordination of Si. Direct determination of the subtle structural change causing the new Raman mode would require high-pressure, single-crystal synchrotron X-ray diffraction experiments. The Raman modes of hydrous and anhydrous Mg-end-member ringwoodite are nearly identical up to 20 GPa, suggesting that protonation has only minor effect on the lattice dynamics over the entire pressure stability range for ringwoodite in the mantle. Received: 7 December 2001 / Accepted: 16 April 2002  相似文献   

8.
The configurational heat capacity, shear modulus and shear viscosity of a series of Na2O–Fe2O3–Al2O3–SiO2 melts have been determined as a function of composition. A change in composition dependence of each of the physical properties is observed as Na2O/(Na2O + Al2O3) is decreased, and the peralkaline melts become peraluminous and a new charge-balanced Al-structure appears in the melts. Of special interest are the frequency dependent (1 mHz–1 Hz) measurements of the shear modulus. These forced oscillation measurements determine the lifetimes of Si–O bonds and Na–O bonds in the melt. The lifetime of the Al–O bonds could not, however, be resolved from the mechanical spectrum. Therefore, it appears that the lifetime of Al–O bonds in these melts is similar to that of Si–O bonds with the Al–O relaxation peak being subsumed by the Si–O relaxation peak. The appearance of a new Al-structure in the peraluminous melts also cannot be resolved from the mechanical spectra, although a change in elastic shear modulus is determined as a function of composition. The structural shear-relaxation time of some of these melts is not that which is predicted by the Maxwell equation, but up to 1.5 orders of magnitude faster. Although the configurational heat capacity, density and shear modulus of the melts show a change in trend as a function of composition at the boundary between peralkaline and peraluminous, the deviation in relaxation time from the Maxwell equation occurs in the peralkaline regime. The measured relaxation times for both the very peralkaline melts and the peraluminous melts are identical with the calculated Maxwell relaxation time. As the Maxwell equation was created to describe the timescale of flow of a mono-structure material, a deviation from the prediction would indicate that the structure of the melt is too complex to be described by this simple flow equation. One possibility is that Al-rich channels form and then disappear with decreasing Si/Al, and that the flow is dominated by the lifetime of Si–O bonds in the Al-poor peralkaline melts, and by the lifetime of Al–O bonds in the relatively Si-poor peralkaline and peraluminous melts with a complex flow mechanism occurring in the mid-compositions. This anomalous deviation from the calculated relaxation time appears to be independent of the change in structure expected to occur at the peralkaline/peraluminous boundary due to the lack of charge-balancing cations for the Al-tetrahedra.  相似文献   

9.
 Cordierite precursors were prepared by a sol-gel process using tetraethoxysilane, aluminum sec.-butoxide, and Mg metal flakes as starting materials. The precursors were treated by 15-h heating steps in intervals of 100 °C from 200 to 900 °C; they show a continuous decrease in the analytical water content with increasing preheating temperatures. The presence of H2O and (Si,Al)–OH combination modes in the FTIR powder spectra prove the presence of both H2O molecules and OH groups as structural components, with invariable OH concentrations up to preheating temperatures of 500 °C. The deconvolution of the absorptions in the (H2O,OH)-stretching vibrational region into four bands centred at 3584, 3415, 3216 and 3047 cm−1 reveals non-bridging and bridging H2O molecules and OH groups. The precursor powders remain X-ray amorphous up to preheating temperatures of 800 °C. Above this temperature the precursors crystallize to μ-cordierite; at 1000 °C the structure transforms to α-cordierite. Close similarities exist in the pattern of the 1400–400 cm−1 lattice vibrational region for precursors preheated up to 600 °C. Striking differences are evident at preheating temperatures of 800 °C, where the spectrum of the precursor powder corresponds to that of conventional cordierite glass. Bands centred in the “as-prepared” precursor at 1137 and 1020 cm−1 are assigned to Si–O-stretching vibrations. A weak absorption at 872 cm−1 is assigned to stretching modes of AlO4 tetrahedral units and the same assignment holds for a band at 783 cm−1 which appears in precursors preheated at 600 °C. With increasing temperatures, these bands show a significant shift to higher wavenumbers and the Al–O stretching modes display a strong increase in their intensities. (Si,Al)–O–(Si,Al)-bending modes occur at 710 cm−1 and the band at 572 cm−1 is assigned to stretching vibrations of AlO6 octahedral units. A strong band around 440 cm−1 is essentially attributed to Mg–O-stretching vibrations. The strongly increasing intensity of the 872 and 783 cm−1 bands demonstrates a clear preference of Al for a fourfold-coordinated structural position in the precursors preheated at high temperatures. The observed band shift is a strong indication for increasing tetrahedral network condensation along with changes in the Si–O and Al–O distances to tetrahedra dimensions similar to those occurring in crystalline cordierite. These structural changes are correlated to the dehydration process starting essentially above 500 °C, clearly demonstrating the inhibiting role of H2O molecules and especially of OH groups. Received: 1 March 2002 / Accepted: 26 June 2002  相似文献   

10.
 As part of a wider study of the nature and origins of cation order–disorder in micas, a variety of computational techniques have been used to investigate the nature of tetrahedral and octahedral ordering in phengite, K2 [6](Al3Mg)[4](Si7Al)O20(OH)4. Values of the atomic exchange interaction parameters J n used to model the energies of order–disorder were calculated. Both tetrahedral Al–Si and octahedral Al–Mg ordering were studied and hence three types of interaction parameter were necessary: for T–T, O–O and T–O interactions (where T denotes tetrahedral sites and O denotes octahedral sites). Values for the T–T and O–O interactions were taken from results on other systems, whilst we calculated new values for the T–O interactions. We have demonstrated that modelling the octahedral and tetrahedral sheets alone and independently produces different results from modelling a whole T–O–T layer, hence justifying the inclusion of the T–O interactions. Simulations of a whole T–O–T layer of phengite indicated the presence of short-range order, but no long-range order was observed. Received: 8 August 2002 / Accepted: 14 February 2003 Acknowledgements The authors are grateful to EPSRC (EJP) and the Royal Society (CIS) for financial support. Monte Carlo simulations were performed on the Mineral Physics Group's Beowulf cluster and the University of Cambridge's High Performance Computing Facility.  相似文献   

11.
 The charge density and bond character of the rutile-type structure of SiO2 (stishovite) under compression to 30 GPa were investigated by X-ray diffraction study using synchrotron radiation and AgKα rotating anode X-ray generator through a newly devised diamond-anvil cell. The valence electron density was determined by least-squares refinement including the κ parameter and the electron population in the X-ray atomic scattering parameters. The oxygen κ-parameter of SiO2 is 0.94 under ambient conditions and 1.11 at 29.1 GPa and the silicon valence changes from +2.12(8) at ambient pressure to +2.26(15) at 29.1 GPa. These values indicate that the electron distributions are more localized with increasing pressure. The difference Fourier map shows the deformation of the valence electron distribution and the bonding electron population in residual electron densities. The bonding electron observed from the X-ray diffraction study is interpreted by molecular orbital calculations. The deformation of SiO6octahedra and the bonding electron density of stishovite structures are elucidated from the overlapping electron orbits. The O–O distances of shared and unshared edge of SiO6 octahedra change with the cation ionicity. The repulsive force between the two cations in the adjacent octahedron makes its shared edge shorter. The pressure changes of the apical and equatorial Si–O interatomic distances are explained by the electron density of state (DOS) of Si and electron configuration. Received: 7 January 2002 / Accepted: 6 May 2002  相似文献   

12.
The synthetic LiGaSi2O6 clinopyroxene is monoclinic C2/c at room-T. Its experimental electron density, ρ(r), has been derived starting from accurate room-T single-crystal diffraction data. Topological analysis confirms an intermediate ionic-covalent character for Si–O bonding, as found by previous electron-density studies on other silicates such as diopside, coesite and stishovite. The non-bridging Si–O bonds have more covalent character than the bridging ones. The Ga–O bonds have different bonding characters, the Ga–O2 bond being more covalent than the two Ga–O1 bonds. Li–O bonds are classified as pure closed-shell ionic interactions. Similar to spodumene (LiAlSi2O6), Li has sixfold coordination, but the bond critical points associated to the two longest bonds are characterized by very low electron density values. Similar to what previously found in spodumene and diopside, O···O interactions were detected from the topological analysis of ρ(r), and indicate a cooperative interaction among the lone pairs of neighbouring oxygen atoms. In particular, this kind of interaction has been obtained for the O1···O1 edge shared between two Ga octahedra. Integration over the atomic basins gives net charges of −1.39(10), 2.82(10), 1.91(10) and 0.82(8) e for O (averaged), Si, Ga and Li atoms, respectively. Periodic Hartree–Fock and DFT calculations confirm the results obtained by multipole refinement of the experimental data. Moreover, the theoretical topological properties of the electron density distribution on the Si2O6 group are very similar to those calculated for spodumene. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.  相似文献   

13.
The reverse Monte Carlo (RMC) method was used for modelling the three-dimensional structure of sodium tetrasilicate glass (Na2Si4O9, NS4). Neutron diffraction data over a large momentum transfer range and nuclear magnetic resonance results (Q-species distribution) as well as chemical bonding considerations have been used to constrain the RMC simulations. Very good agreement with the experimental structure factor was achieved. The three-dimensional model is analysed in terms of partial pair distribution functions, bond-angle distributions, short-range order (SRO) clusters and ring statistics. The average Si–O–Si bridging angle is different for the different Qi–Qj units. The effect of different Q species on the network connectivity is analysed by comparison with statistical SRO distributions. While the Q2 species are randomly distributed, a high preference for the formation of Q4–Q4 units in three-membered rings is found. This explains why during the initial stages of hydration of NS4 glass, Si–OH groups are preferentially formed by breaking Q4–Q4 linkages. The RMC model also provides an independent test for the assignment of bands in the Si–O stretching region of the Raman spectrum. It is shown that the bands at about 1050 and 1100 cm−1 are probably due to Q3 units surrounded by different numbers of Q4 units. Received: 7 April 1997 / Revised, accepted: 5 July 1997  相似文献   

14.
Summary ?Sheet silicates of the serpentine–kaolin-group (serpentine, kaolinite, dickite, nacrite, halloysite), the talc–pyrophyllite-group (talc, pyrophyllite), the smectite-group (montmorillonite), and illite (as a mineral of the mica-group) were investigated to obtain information concerning their cathodoluminescence behaviour. The study included analyses by cathodoluminescence (CL microscopy and spectroscopy), electron paramagnetic resonance (EPR), X-Ray diffraction (XRD), scanning electron microscopy (SEM) and trace element analysis. In general, all dioctahedral clay minerals exhibit a visible CL. Kaolinite, dickite, nacrite and pyrophyllite have a characteristic deep blue CL, whereas halloysite emission is in the greenish-blue region. On the contrary, the trioctahedral minerals (serpentine, talc) and illite do not show visible CL. The characteristic blue CL is caused by an intense emission band around 400 nm (double peak with two maxima at 375 and 410 nm). EPR measurements indicate that this blue emission can be related to radiation induced defect centres (RID), which occur as electron holes trapped on apical oxygens (Si–O centre) or located at the Al–O–Al group (Al substituting Si in the tetrahedron). Additional CL emission bands were detected at 580 nm in halloysite and kaolinite, and between 700 and 800 nm in kaolinite, dickite, nacrite and pyrophyllite. Time-resolved spectral CL measurements show typical luminescence kinetics for the different clay minerals, which enable differentiation between the various dioctahedral minerals (e.g. kaolinite and dickite), even in thin section. Received December 3, 2001; revised version accepted February 27, 2002  相似文献   

15.
This study examines the electron localization function (ELF) isosurfaces of the Al2SiO5 polymorphs kyanite, sillimanite, and andalusite to see how differences in coordination and geometry of the cations and anions affect the ELF isosurfaces. Examination of the ELF isosurfaces indicates that their shapes are dependent on the coordination and geometry of the oxygen atoms and are not sensitive to coordination of the surrounding cations. Of the 18 crystallographically distinct oxygen atoms in the Al2SiO5 polymorphs, 13 are bonded to two aluminum atoms and one silicon atom (Al2–O–Si) and are associated with two different ELF isosurface shapes. The shape of the ELF isosurface is dependent on the distance at which the oxygen atom lies from a plane defined by the three surrounding cations: at a distance greater than 0.2 Å the ELF can be defined as horseshoe-shaped and at a distance less then 0.2 Å it can be described as concave hemispherical. This feature is also seen in the ELF isosurfaces for the oxygens bonded to three aluminum atoms (Al3–O) where the isosurfaces can be defined as trigonally toroidal and uniaxially trigonally toroidal. The changes in the ELF isosurfaces for the three coordinated oxygens are also indicative of changes in hybridization. The ELF isosurface for the two-fold coordinated oxygen (Al–O–Si) has a large mushroom-shaped isosurface along the Al–O bond and a concave hemispherical isosurface along the Si–O. The four-fold coordinated oxygen (Al4–O) contains two concave hemispherical isosurfaces along the shorter Al–O bonds and a banana-shaped isosurface, which encompasses the longer Al–O bonds. In addition, this study shows the homeomorphic relationship between the ELF isosurfaces and electron density difference maps with respect to number and arrangement of domains.  相似文献   

16.
 Linear anisotropic elasticity has been applied to interpret the dislocation stability and ease of slip in wadsleyite. It is shown that wadsleyite is very isotropic from the elastic point of view. The influence of crystal chemistry and bonding on the choice of the slip plane is discussed. It is shown that slip is predominantly achieved on planes that do not shear Si–O bonds. It is suggested that dissociation of dislocations is essential in determining the ease of slip among the various slip systems. Received: 15 July 2002 / Accepted: 14 February 2003 Acknowledgements High-pressure experiments were performed at the Bayerisches Geoinstitut under the EU IHP – Access to Research Infrastructures Programme (Contract no. HPRI-1999-CT-00004 to D.C. Rubie). Enlightening discussions with A. Coujou and J. Rabier are gratefully acknowledged.  相似文献   

17.
 Synthetic aegirine LiFeSi2O6 and NaFeSi2O6 were characterized using infrared spectroscopy in the frequency range 50–2000 cm−1, and at temperatures between 20 and 300 K. For the C2/c phase of LiFeSi2O6, 25 of the 27 predicted infrared bands and 26 of 30 predicted Raman bands are recorded at room temperature. NaFeSi2O6 (with symmetry C2/c) shows 25 infrared and 26 Raman bands. On cooling, the C2/c–P21/c structural phase transition of LiFeSi2O6 is characterized by the appearance of 13 additional recorded peaks. This observation indicates the enlargement of the unit cell at the transition point. The appearance of an extra band near 688 cm−1 in the monoclinic P21/c phase, which is due to the Si–O–Si vibration in the Si2O6 chains, indicates that there are two non-equivalent Si sites with different Si–O bond lengths. Most significant spectral changes appear in the far-infrared region, where Li–O and Fe–O vibrations are mainly located. Infrared bands between 300 and 330 cm−1 show unusually dramatic changes at temperatures far below the transition. Compared with the infrared data of NaFeSi2O6 measured at low temperatures, the change in LiFeSi2O6 is interpreted as the consequence of mode crossing in the frequency region. A generalized Landau theory was used to analyze the order parameter of the C2/c–P21/c phase transition, and the results suggest that the transition is close to tricritical. Received: 21 January 2002 / Accepted: 22 July 2002  相似文献   

18.
Raman spectra of monoclinic Fo90 hydrous wadsleyite with 2.4 wt% H2O have been measured in a diamond-anvil cell with helium as a pressure-transmitting medium to 58.4 GPa at room temperature. The most intense, characteristic wadsleyite modes, the Si–O–Si symmetric stretch at 721 cm−1 and the symmetric stretch of the SiO3 unit at 918 cm−1, shift continuously to 58.4 GPa showing no evidence of a first order change in the crystal structure despite compression well beyond the stability field of wadsleyite in terms of pressure. The pressure dependence of these two modes is nearly identical for Fo90 hydrous and Fo100 anhydrous wadsleyite. A striking feature in the high-pressure Raman spectra of Fo90 hydrous wadsleyite is the appearance of new Raman modes above 9 GPa in the mid-frequency range (300–650 cm−1 at 1-bar and shifted to 500–850 cm−1 at 58.4 GPa) accompanied by a significant growth in their intensities under further compression. In the OH stretching frequency range Fo90 hydrous wadsleyite exhibits a larger number of modes than the Mg end-member phase. The higher number of modes may be due to either additional protonation sites or simply that we observe a different subset of all possible OH modes for each sample. The high-pressure behaviour of the OH stretching modes of Fo90 and Fo100 hydrous wadsleyite is consistent: OH stretching modes with frequencies <3,530 cm−1 decrease with increasing pressure whereas the higher-frequency OH modes show a close to constant pressure dependence to at least 13.2 GPa. The approximately constant pressure dependence of the OH modes above 3,530 cm−1 is consistent with protons being located at the O1···O edges around M3.  相似文献   

19.
 The solubility of hydroxyl in coesite was investigated in multianvil experiments performed at 1200 °C over the nominal pressure range 5–10 GPa, at an f O2 close to the Ni-NiO buffer. The starting material for each experiment was a cylinder of pure silica glass plus talc, which dehydrates at high P and T to provide a source of water and hydrogen (plus enstatite and excess SiO2). Fourier-transform infrared (FTIR) spectra of the recovered coesite crystals show five sharp bands at 3606, 3573, 3523, 3459, and 3299 cm−1, indicative of structurally bonded hydrogen (hydroxyl). The concentration of hydrogen increases with pressure from 285 H/106 Si (at 5 GPa) to 1415 H/106 Si (at 10 GPa). Assuming a model of incorporation by (4H)Si defects, the data are fit well by the equation C OH=Af 2 H2<\INF>Oexp(−PΔV/RT), with A=4.38 H/106 Si/GPa, and ΔV=20.6 × 10−6 m3 mol−1. An alternative model entailing association of hydrogen with cation substitution can also be used to fit the data. These results show that the solubility of hydroxyl in coesite is approximately an order of magnitude lower than in olivines and pyroxenes, but comparable to that in pyropic garnet. However, FTIR investigations on a variety of ultrahigh pressure metamorphic rocks have failed in all cases to detect the presence of water or hydrogen in coesite, indicating either that it grew in dry environments or lost its hydrogen during partial transformation to quartz. On the other hand, micro-FTIR investigations of quartz crystals replacing coesite show that they contain varying amounts of H2O. These results support the hypothesis that preservation of coesite is not necessarily linked to fast exhumation rates but is crucially dependent on limited fluid infiltration during exhumation. Received: 23 August 1999 / Accepted: 10 April 2000  相似文献   

20.
Chalcedony is a spatial arrangement of hydroxylated nanometre-sized α-quartz (SiO2) crystallites that are often found in association with the silica mineral moganite (SiO2). A supplementary Raman band at 501 cm−1 in the chalcedony spectrum, attributed to moganite, has been used for the evaluation of the quartz/moganite ratio in silica rocks. Its frequency lies at 503 cm−1 in sedimentary chalcedony, representing a 2 cm−1 difference with its position in pure moganite. We present a study of the 503 cm−1 band’s behaviour upon heat treatment, showing its gradual disappearance upon heating to temperatures above 300 °C. Infrared spectroscopic measurements of the silanole (SiOH) content in the samples as a function of annealing temperature show a good correlation between the disappearance of the 503 cm−1 Raman band and the decrease of structural hydroxyl. Thermogravimetric analyses reveal a significant weight loss that can be correlated with the decreasing of this Raman band. X-ray powder diffraction data suggest the moganite content in the samples to remain stable. We propose therefore the existence of a hitherto unknown Raman band at 503 cm−1 in chalcedony, assigned to ‘free’ Si–O vibrations of non-bridging Si–OH that oscillate with a higher natural frequency than bridging Si–O–Si (at 464 cm−1). A similar phenomenon was recently observed in the infrared spectra of chalcedony. The position of this Si–OH-related band is nearly the same as the Raman moganite band and the two bands may interfere. The actually observed Raman band in silica rocks might therefore be a convolution of a silanole and a moganite vibration. These findings have broad implications for future Raman spectroscopic studies of moganite, for the assessment of the quartz/moganite ratio, using this band, must take into account the contribution from silanole that are present in chalcedony and moganite.  相似文献   

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