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1.
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
2.
M. Zhang G. J. Redhammer E. K. H. Salje M. Mookherjee 《Physics and Chemistry of Minerals》2002,29(9):609-616
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
3.
Y. Shimada M. Okuno Y. Syono M. Kikuchi K. Fukuoka N. Ishizawa 《Physics and Chemistry of Minerals》2002,29(4):233-239
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
4.
V. L. Vinograd O. G. Safonov D. J. Wilson L. L. Perchuk L. Bindi J. D. Gale B. Winkler 《Petrology》2010,18(4):447-459
Atomistic model was proposed to describe the thermodynamics of mixing in the diopside-K-jadeite solid solution (CaMgSi2O6-KAlSi2O6). The simulations were based on minimization of the lattice energies of 800 structures within a 2 × 2 × 4 supercell of C2/c diopside with the compositions between CaMgSi2O6 and KAlSi2O6 and with variable degrees of order/disorder in the arrangement of Ca/K cations in M2 site and Mg/Al in Ml site. The energy
minimization was performed with the help of a force-field model. The results of the calculations were used to define a generalized
Ising model, which included 37 pair interaction parameters. Isotherms of the enthalpy of mixing within the range of 273–2023
K were calculated with a Monte Carlo algorithm, while the Gibbs free energies of mixing were obtained by thermodynamic integration
of the enthalpies of mixing. The calculated T-X diagram for the system CaMgSi2O6-KAlSi2O6 at temperatures below 1000 K shows several miscibility gaps, which are separated by intervals of stability of intermediate
ordered compounds. At temperatures above 1000 K a homogeneous solid solution is formed. The standard thermodynamic properties
of K-jadeite (KAlSi2O6) evaluated from quantum mechanical calculations were used to determine location of several mineral reactions with the participation
of the diopside-K-jadeite solid solution. The results of the simulations suggest that the low content of KalSi2O6 in natural clinopyroxenes is not related to crystal chemical factors preventing isomorphism, but is determined by relatively
high standard enthalpy of this end member. 相似文献
5.
Al-containing MgSiO3 perovskites of four different compositions were synthesized at 27 GPa and 1,873 K using a Kawai-type high-pressure apparatus:
stoichiometric compositions of Mg0.975Si0.975Al0.05O3 and Mg0.95Si0.95Al0.10O3 considering only coupled substitution Mg2+ + Si4+ = 2Al3+, and nonstoichiometric compositions of Mg0.99Si0.96Al0.05O2.985 and Mg0.97Si0.93Al0.10O2.98 taking account of not only the coupled substitution but also oxygen vacancy substitution 2Si4+ = 2Al3+ + VO¨. Using the X-ray diffraction profiles, Rietveld analyses were performed, and the results were compared between the stoichiometric
and nonstoichiometric perovskites. Lattice parameter–composition relations, in space group Pbnm, were obtained as follows. The a parameters of both of the stoichiometric and nonstoichiometric perovskites are almost constant in the X
Al range of 0–0.05, where X
Al is Al number on the basis of total cation of two (X
Al = 2Al/(Mg + Si + Al)), and decrease with further increasing X
Al. The b and c parameters of the stoichiometric perovskites increase linearly with increasing Al content. The change in the b parameter of the nonstoichiometric perovskites with Al content is the same as that of the stoichiometric perovskites within
the uncertainties. The c parameter of the nonstoichiometric perovskites is slightly smaller than that of the stoichiometric perovskites at X
Al of 0.10, though they are the same as each other at X
Al of 0.05. The Si(Al)–O1 distance, Si(Al)–O1–Si(Al) angle and minimum Mg(Al)–O distance of the nonstoichiometric perovskites
keep almost constant up to X
Al of 0.05, and then the Si(Al)–O1 increases and both of the Si(Al)–O1–Si(Al) angle and minimum Mg(Al)–O decrease with further
Al substitution. These results suggest that the oxygen vacancy substitution may be superior to the coupled substitution up
to X
Al of about 0.05 and that more Al could be substituted only by the coupled substitution at 27 GPa. The Si(Al)–O1 distance and
one of two independent Si(Al)–O2 distances in Si(Al)O6 octahedra in the nonstoichiometric perovskites are always shorter than those in the stoichiometric perovskite at the same
Al content. These results imply that oxygen defects may exist in the nonstoichiometric perovskites and distribute randomly. 相似文献
6.
Victor L. Vinograd Julian D. Gale Björn Winkler 《Physics and Chemistry of Minerals》2007,34(10):713-725
Static lattice energy calculations (SLEC), based on empirical interatomic potentials, have been performed for a set of 800
different structures in a 2 × 2 × 4 supercell of C2/c diopside with compositions between diopside and jadeite, and with different states of order of the exchangeable Na/Ca and
Mg/Al cations. Excess static energies of these structures have been cluster expanded in a basis set of 37 pair-interaction
parameters. These parameters have been used to constrain Monte Carlo simulations of temperature-dependent properties in the
range of 273–2,023 K and to calculate a temperature–composition phase diagram. The simulations predict the order–disorder
transition in omphacite at 1,150 ± 20°C in good agreement with the experimental data of Carpenter (Mineral Petrol 78:433–440,
1981). The stronger ordering of Mg/Al within the M1 site than of Ca/Na in the M2 site is attributed to the shorter M1–M1 nearest-neighbor
distance, and, consequently, the stronger ordering force. The comparison of the simulated relationship between the order parameters
corresponding to M1 and M2 sites with the X-ray refinement data on natural omphacites (Boffa Ballaran et al. in Am Mineral
83:419–433, 1998) suggests that the cation ordering becomes kinetically ineffective at about 600°C. 相似文献
7.
Cation tracer diffusion coefficients, DMe *, for Me=Fe, Mn, Co and Ti, were measured using radioactive isotopes in the spinel solid solution (Ti x Fe 1−x )3−δO4 as a function of the oxygen activity. Experiments were performed at different cationic compositions (x=0, 0.1, 0.2 and 0.3) at 1100, 1200, 1300 and 1400 °C. The oxygen activity dependence of all data for DMe * at constant temperature and cationic composition can be described by equations of the type DMe *=D∘ Me[V]. CV·a O2 2/3+DMe[I] ∘·a O2 −2/3·DMe[V] ∘ and DMe[I] ∘ are constants and CV is a factor of the order of unity which decreases with increasing δ. All log DMe * vs. loga O2 curves obtained for different values of x and for different temperatures go through a minimum due to a change in the type of point defects dominating the cation diffusion with oxygen activity. Cation vacancies prevail for the cation diffusion at high oxygen activities while cation interstitials become dominant at low oxygen activities. At constant values of x, DMe[V] ∘ decreases with increasing temperature while DMe[I] ∘ increases. 相似文献
8.
T. Irifune H. Naka T. Sanehira T. Inoue K. Funakoshi 《Physics and Chemistry of Minerals》2002,29(10):645-654
Phase transitions in MgAl2O4 spinel have been studied at pressures 22–38 GPa, and at temperatures up to 1600 °C, using a combination of synchrotron radiation
and a multianvil apparatus with sintered diamond anvils. Spinel dissociated into a mixture of MgO plus Al2O3 at pressures to 25 GPa, while it transformed to the CaFe2O4 (calcium ferrite) structure at higher pressures via the metastably formed oxide mixture upon increasing temperature. Neither
the e-phase nor the CaTi2O4-type MgAl2O4, which were reported in earlier studies using the diamond-anvil cell, were observed in the present pressure and temperature
range. The zero-pressure bulk modulus of the calcium-ferrite-type MgAl2O4 was calculated as K=213 (3) GPa, which is significantly lower than that reported by Yutani et al. (1997), but is consistent with a more recent
result by Funamori et al. (1998) and that estimated by an ab initio calculation by Catti (2001).
Received: 2 April 2002 / Accepted: 29 July 2002
Acknowledgements The authors thank Y. Higo, Y. Sueda, T.␣Ueda, Y. Tanimoto, A. Fukuyama, K. Ochi, F. Kurio and T. Kawahara for help in the
in situ X-ray observations at SPring-8 (No: 2000A0061-CD-np and 2000B0093-ND-np). We also thank W.␣Utsumi, J. Ando and O.
Shimomura for advice and encouragement during this study, and N. Funamori and an anonymous reviwer for comments on the article.
The present study is partly supported by the grant-in-aid for Scientific Research (A) of the Ministry of Education, Science,
Sport and Culture of the Japanese government (no: 11694088). 相似文献
9.
We present H2O analyses of MgSiO3 pyroxene crystals quenched from hydrous conditions in the presence of olivine or wadsleyite at 8–13.4 GPa and 1,100–1,400°C.
Raman spectroscopy shows that all pyroxenes have low clinoenstatite structure, which we infer to indicate that the crystals
were high clinoenstatite (C2/c) during conditions of synthesis. H2O analyses were performed by secondary ion mass spectrometry and confirmed by unpolarized Fourier transform infrared spectroscopy
on randomly oriented crystals. Measured H2O concentrations increase with pressure and range from 0.08 wt.% H2O at 8 GPa and 1,300°C up to 0.67 wt.% at 13.4 GPa and 1,300°C. At fixed pressure, H2O storage capacity diminishes with increasing temperature and the magnitude of this effect increases with pressure. This trend,
which we attribute to diminishing activity of H2O in coexisting fluids as the proportion of dissolved silicate increases, is opposite to that observed previously at low pressure.
We observe clinoenstatite 1.4 GPa below the pressure stability of clinoenstatite under nominally dry conditions. This stabilization
of clinoenstatite relative to orthoenstatite under hydrous conditions is likely owing to preferential substitution of H2O into the high clinoenstatite polymorph. At 8–11 GPa and 1,200–1,400°C, observed H2O partitioning between olivine and clinoenstatite gives values of D
ol/CEn between 0.65 and 0.87. At 13 GPa and 1,300°C, partitioning between wadsleyite and clinoenstatite, D
wd/CEn, gives a value of 2.8 ± 0.4. 相似文献
10.
V. P. Solntsev R. I. Mashkovtsev A. V. Davydov E. G. Tsvetkov 《Physics and Chemistry of Minerals》2008,35(6):311-320
It is shown the possibility to determine the coordination of paramagnetic ions in disordered solid structures, e.g., in barium
borate glasses. For this purpose the electron paramagnetic resonance (EPR) method was used to study α-and β-BaB2O4 crystals and glasses of 45·BaO × 55·B2O3 and 40·BaO × 60·B2O3 (mol%) composition activated by Ag+ and Pb2+ ions. After the samples were exposed to X-rays at 77 K, different EPR centers were observed in them. In α-and β-BaB2O4 crystals and glasses the EPR centers Ag2+, Ag0, Pb+, Pb3+, and hole centers of O− type were studied. The EPR parameters of these centers and their arrangement in crystal structure were determined. It is
shown that Pb3+ ions in β-BaB2O4 crystals occupy Ba2+ position in an irregular polyhedron from the eight oxygen, whereas in α-BaB2O4 crystals they occupy Bа2 position in a sixfold coordination. Pb+ ions in α-BaB2O4 crystals occupy Bа1 position in a ninefold coordination from oxygen. In barium borate glasses, Pb3+ ions were studied in coordination polyhedron from six oxygen atoms and in a polyhedron from nine to ten oxygen atoms. It
is assumed that the established difference in the structural position of Pb3+ ions in glasses is due to their previous incorporation in associative cation–anion complexes (AC) and “free” structure-forming
cations (FC). Computer simulations have been performed to analyze the stability of specific associative complexes and to compare
their bond lengths with experimental data. 相似文献
11.
Jason B. Burt Nancy L. Ross G. V. Gibbs George R. Rossman Kevin M. Rosso 《Physics and Chemistry of Minerals》2007,34(5):295-306
Potential protonation sites for, kyanite, sillimanite, and andalusite, located in a mapping of the (3, −3) critical points
displayed by their L(r) = −∇2ρ(r) distributions, are compared with polarized single-crystal FTIR spectra of kyanite and sillimanite determined earlier and
with andalusite measured in this study. For andalusite, seven peaks were observed when the electric vector, E, is parallel to [100]: four intense ones at 3,440, 3,460, 3,526, and 3,597 cm−1 and three weaker ones at 3,480, 3,520, and 3,653 cm−1. Six peaks, three intense ones at 3,440, 3,460, and 3,526 cm−1 and three weaker ones at 3,480, 3,520, and 3,653 cm−1 when E parallels [010]. No peaks were observed when E is parallel to [001]. The concentration of water in andalusite varies between 110 and 168 ppm by weight % H2O. Polarized FTIR spectra indicate that the OH vector is parallel to (001) in andalusite and sillimanite and
in kyanite. Examination of the L(r) (3, −3) critical points in comparison with the polarized FTIR indicates that H prefers to bond to the oxygen atoms O1 and
O2 in andalusite and O2 and O4 in sillimanite which correspond to the underbonded oxygen atoms and those with the largest
L(r) maxima. In kyanite, comparison of the FTIR spectrum and the critical points indicates that H will preferentially bond to
the two 4-coordinated O2 and O6 atoms. 相似文献
12.
Shigeto Hirai Yohei Kojima Hiroaki Ohfuji Norimasa Nishiyama Tetsuo Irifune Stephan Klemme Geoffrey Bromiley J. Paul Attfield 《Physics and Chemistry of Minerals》2011,38(8):631-637
Raman spectroscopy and heat capacity measurements have been used to study the post-perovskite phase of CaIr0.5Pt0.5O3, recovered from synthesis at a pressure of 15 GPa. Laser heating CaIr0.5Pt0.5O3 to 1,900 K at 60 GPa produces a new perovskite phase which is not recoverable and reverts to the post-perovskite polymorph
between 20 and 9 GPa on decompression. This implies that Pt-rich CaIr1−xPtxO3 perovskites including the end member CaPtO3 cannot easily be recovered to ambient pressure from high P–T synthesis. We estimate an increase in the thermodynamic Grüneisen
parameter across the post-perovskite to perovskite transition of 34%, of similar magnitude to those for (Mg,Fe)SiO3 and MgGeO3, suggesting that CaIr0.5Pt0.5O3 is a promising analogue for experimental studies of the competition in energetics between perovskite and post-perovskite
phases of magnesium silicates in Earth’s lowermost mantle. Low-temperature heat capacity measurements show that CaIrO3 has a significant Sommerfeld coefficient of 11.7 mJ/mol K2 and an entropy change of only 1.1% of Rln2 at the 108 K Curie transition, consistent with the near-itinerant electron magnetism. Heat capacity results for post-perovskite
CaIr0.5Rh0.5O3 are also reported. 相似文献
13.
For the fibrous zeolites natrolite, Na2[Al2Si3O10]·2H2O, mesolite, Na2Ca2[Al2Si3O10]3·8H2O, and scolecite, Ca[Al2Si3O10]·3H2O, with topologically identical aluminosilicate framework structures, accurate single-crystal X-ray diffraction data have
been analyzed by least-squares refinements using generalized scattering factor (GSF) models. The final agreement indices were
R(F ) = 0.0061, 0.0165, and 0.0073, respectively. Ensuing calculations of static deformation [Δρ(r)], and total, [ρ(r)], model electron density distributions served to study chemical bonding, in particular by topological electron density analyses
yielding bond critical point (bcp) properties and in situ cation electronegativities. The results for 32 SiO, 24 AlO, 14 CaO,
and 12 NaO unique bonds are compiled and analyzed in terms of both mean values and correlations between bond lengths, bonded
oxygen radii, bcp densities, curvatures at the bcps, and electronegativities. Comparison with recent literature data obtained
from both experimental electron density studies on minerals and model calculations for geometry-optimized molecules shows
that the majority of the present findings conforms well with chemical expectation and with the trends observed from molecular
modeling. For the SiO bond, the shared interaction is indicated to increase with decreasing bond length, whereas the AlO bond
is of distinctly more polar nature, as is the NaO bond compared to CaO. Also, the observed ranges of the Si and Al in situ
electronegativities and their mean electronegativities agree well with both Pauling's values and model calculation results,
and statistically significant correlations are obtained which are consistent with trends described for oxide and nitride molecules.
Received: 10 May 1999 / Revised, accepted: 14 September 1999 相似文献
14.
Dmytro M. Trots Alexander Kurnosov Leonid Vasylechko Marek Berkowski Tiziana Boffa Ballaran Daniel J. Frost 《Physics and Chemistry of Minerals》2011,38(7):561-567
A single crystal X-ray diffraction study on lithium tetraborate Li2B4O7 (diomignite, space group I41
cd) has been performed under pressure up to 8.3 GPa. No phase transitions were found in the pressure range investigated, and
hence the pressure evolution of the unit-cell volume of the I41
cd structure has been described using a third-order Birch–Murnaghan equation of state (BM-EoS) with the following parameters:
V
0
= 923.21(6) Å3, K
0
= 45.6(6) GPa, and K′ = 7.3(3). A linearized BM-EoS was fitted to the axial compressibilities resulting in the following parameters a
0
= 9.4747(3) Å, K
0a
= 73.3(9) GPa, K′
a
= 5.1(3) and c
0
= 10.2838(4) Å, K
0c
= 24.6(3) GPa, K′
c
= 7.5(2) for the a and c axes, respectively. The elastic anisotropy of Li2B4O7 is very large with the zero-pressure compressibility ratio β
0c
/β
0a
= 3.0(1). The large elastic anisotropy is consistent with the crystal structure: A three-dimensional arrangement of relatively
rigid tetraborate groups [B4O7]2− forms channels occupied by lithium along the polar c–axis, and hence compression along the c axis requires the shrinkage of the lithium channels, whereas compression in the a direction depends mainly on the contraction of the most rigid [B4O7]2− units. Finally, the isothermal bulk modulus obtained in this work is in general agreement with that derived from ultrasonic
(Adachi et al. in Proceedings-IEEE Ultrasonic Symposium, 228–232, 1985; Shorrocks et al. in Proceedings-IEEE Ultrasonic Symposium, 337–340, 1981) and Brillouin scattering measurements (Takagi et al. in Ferroelectrics, 137:337–342, 1992). 相似文献
15.
Taku Okada Takehiko Yagi Daisuke Nishio-Hamane 《Physics and Chemistry of Minerals》2011,38(4):251-258
The phase relations and compression behavior of MnTiO3 perovskite were examined using a laser-heated diamond-anvil cell, X-ray diffraction, and analytical transmission electron
microscopy. The results show that MnTiO3 perovskite becomes unstable and decomposes into MnO and orthorhombic MnTi2O5 phases at above 38 GPa and high temperature. This is the first example of ABO3 perovskite decomposing into AO + AB2O5 phases at high pressure. The compression behavior of volume, axes, and the tilting angle of TiO6 octahedron of MnTiO3 perovskite are consistent with those of other A2+B4+O3 perovskites, although no such decomposition was observed in other perovskites. FeTiO3 is also known to decompose into two phases, instead of transforming into the CaIrO3-type post-perovskite phase and we argue that one of the reasons for the peculiar behavior of titanate is the weak covalency
of the Ti–O chemical bonds. 相似文献
16.
The onset of hydrous partial melting in the mantle above the transition zone is dictated by the H2O storage capacity of peridotite, which is defined as the maximum concentration that the solid assemblage can store at P and T without stabilizing a hydrous fluid or melt. H2O storage capacities of minerals in simple systems do not adequately constrain the peridotite water storage capacity because
simpler systems do not account for enhanced hydrous melt stability and reduced H2O activity facilitated by the additional components of multiply saturated peridotite. In this study, we determine peridotite-saturated
olivine and pyroxene water storage capacities at 10–13 GPa and 1,350–1,450°C by employing layered experiments, in which the
bottom ~2/3 of the capsule consists of hydrated KLB-1 oxide analog peridotite and the top ~1/3 of the capsule is a nearly
monomineralic layer of hydrated Mg# 89.6 olivine. This method facilitates the growth of ~200-μm olivine crystals, as well
as accessory low-Ca pyroxenes up to ~50 μm in diameter. The presence of small amounts of hydrous melt ensures that crystalline
phases have maximal H2O contents possible, while in equilibrium with the full peridotite assemblage (melt + ol + pyx + gt). At 12 GPa, olivine and
pyroxene water storage capacities decrease from ~1,000 to 650 ppm, and ~1,400 to 1,100 ppm, respectively, as temperature increases
from 1,350 to 1,450°C. Combining our results with those from a companion study at 5–8 GPa (Ardia et al., in prep.) at 1,450°C,
the olivine water storage capacity increases linearly with increasing pressure and is defined by the relation
C\textH2 \textO\textolivine ( \textppm ) = 57.6( ±16 ) ×P( \textGPa ) - 169( ±18 ). C_{{{\text{H}}_{2} {\text{O}}}}^{\text{olivine}} \left( {\text{ppm}} \right) = 57.6\left( { \pm 16} \right) \times P\left( {\text{GPa}} \right) - 169\left( { \pm 18} \right). Adjustment of this trend for small increases in temperature along the mantle geotherm, combined with experimental determinations
of
D\textH2 \textO\textpyx/olivine D_{{{\text{H}}_{2} {\text{O}}}}^{\text{pyx/olivine}} from this study and estimates of
D\textH2 \textO\textgt/\textolivine D_{{{\text{H}}_{2} {\text{O}}}}^{{{\text{gt}}/{\text{olivine}}}} , allows for estimation of peridotite H2O storage capacity, which is 440 ± 200 ppm at 400 km. This suggests that MORB source upper mantle, which contains 50–200 ppm
bulk H2O, is not wet enough to incite a global melt layer above the 410-km discontinuity. However, OIB source mantle and residues
of subducted slabs, which contain 300–1,000 ppm bulk H2O, can exceed the peridotite H2O storage capacity and incite localized hydrous partial melting in the deep upper mantle. Experimentally determined values
of
D\textH2 \textO\textpyx/\textolivine D_{{{\text{H}}_{2} {\text{O}}}}^{{{\text{pyx}}/{\text{olivine}}}} at 10–13 GPa have a narrow range of 1.35 ± 0.13, meaning that olivine is probably the most important host of H2O in the deep upper mantle. The increase in hydration of olivine with depth in the upper mantle may have significant influence
on viscosity and other transport properties. 相似文献
17.
Planewave pseudopotential calculations of supercell total energies were used as bases for first-principles calculations of
the CaCO3–MgCO3 and CdCO3–MgCO3 phase diagrams. Calculated phase diagrams are in qualitative to semiquantitative agreement with experiment. Two unobserved
phases, Cd3Mg (CO3)4 and CdMg3(CO3)4, are predicted. No new phases are predicted in the CaCO3–MgCO3 system, but a low-lying metastable Ca3Mg(CO3)4 state, analogous to the Cd3Mg(CO3)4 phase is predicted. All of the predicted lowest-lying metastable states, except for huntite CaMg3(CO3)4, have dolomite-related structures, i.e. they are layer structures in which A
m
B
n
cation layers lie perpendicular to the rhombohedral [111] vector.
Received: 6 May 2002 / Accepted: 23 October 2002
Acknowledgements This work was partially supported by NSF contract DMR-0080766 and NIST. 相似文献
18.
Mineral-specific IR absorption coefficients were calculated for natural and synthetic olivine, SiO2 polymorphs, and GeO2 with specific isolated OH point defects using quantitative data from independent techniques such as proton–proton scattering,
confocal Raman spectroscopy, and secondary ion mass spectrometry. Moreover, we present a routine to detect OH traces in anisotropic
minerals using Raman spectroscopy combined with the “Comparator Technique”. In case of olivine and the SiO2 system, it turns out that the magnitude of ε for one structure is independent of the type of OH point defect and therewith
the peak position (quartz ε = 89,000 ± 15,000
\textl \textmol\textH2\textO-1 \textcm-2\text{l}\,\text{mol}_{{\text{H}_2}\text{O}}^{-1}\,\text{cm}^{-2}), but it varies as a function of structure (coesite ε = 214,000 ± 14,000
\textl \textmol\textH2\textO-1 \textcm-2\text{l}\,\text{mol}_{{\text{H}_2}\text{O}}^{-1}\,\text{cm}^{-2}; stishovite ε = 485,000 ± 109,000
\textl \textmol\textH2\textO-1 \textcm-2\text{l}\,\text{mol}_{{\text{H}_2}\text{O}}^{-1}\,\text{cm}^{-2}). Evaluation of data from this study confirms that not using mineral-specific IR calibrations for the OH quantification in
nominally anhydrous minerals leads to inaccurate estimations of OH concentrations, which constitute the basis for modeling
the Earth’s deep water cycle. 相似文献
19.
Thirty spodumene samples of distinct paragenetic types (primary magmatic, secondary after petalite and hydrothermal) from variety of granitic pegmatites were characterized by electron microprobe, polarized FTIR spectroscopy and Mössbauer spectroscopy. The FTIR spectra of OH (weak sharp pleochroic bands at 3,425, 3,410, 3,395 cm−1 and in the 3,500–3,470 spectral region) are strongly polarized with maximum absorption parallel to nγ. The majority of OH dipoles are presumably generated by a partial replacement of O2 oxygen atoms with an orientation pointing above the Li vacancy site. The separation of the bands probably resulted from a replacement of the coordinating Al by Fe and Si by Al. Homogeneous spodumene mostly close to its ideal formula LiAlSi2O6 shows Fe (0.00–0.10 apfu as Fe3+; Fe3+ >> Fe2+) and Na (0.00–0.04 apfu) as the only minor cations and Fe3+Al−1 substitution up to 10 mol% of the LiFe3+Si2O6 component. Hydrogen concentrations (from 0.1 up to <5 ppm H2O by weight) vary as a function of genetic type with the highest amounts in high-temperature magmatic spodumene. Differences among particular genetic types of spodumene are related to maximum solubility of OH in spodumene structure at given P–T conditions and at actual chemical composition of spodumene. OH defect concentrations in spodumene follow a trend, LT/LP pyroxenes containing lower hydrogen contents compared to HT/HP ones. The hydrogen contents in particular genetic types of spodumene and their decrease with decreasing T and P are consistent with petrologic models of the pegmatite (sub)types formations. 相似文献
20.
Boris Kolesov 《Physics and Chemistry of Minerals》2008,35(5):271-278
Single-crystal polarized Raman spectra (3,000–4,000 cm−1 at 3 ≤ T ≤ 300 K) were measured for synthetic alkali-free and natural beryl, Be2Al3Si6O18·xH2O, to determine the behavior of H2O molecules of both Type I and Type II in the cavities. At low temperature, the H2O molecules of Type I displace from the center of cavity and give rise to very weak hydrogen bonding with the host lattice.
The H2O Type I translational motion is characterized by substantial anharmonicity and looks like a motion of “a particle in the
box” with a frequency of 6.3 cm−1. Water Type II is characterized by a free rotation with respect to the C
2 molecule axis, and it makes possible the water nuclear isomers (i.e. ortho- and para-) to be observed at low temperature.
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Boris KolesovEmail: |