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1.
Kuniaki Kihara 《Physics and Chemistry of Minerals》1993,19(7):492-501
Temperature factors for oxygen and silicon atoms in β-quartz were calculated on a Born-von Karman lattice dynamical model of an ordered structure. The calculated thermal ellipsoids were in excellent agreements with those of the previous structure refinements of the order model, for both magnitudes and orientations of the principal axes. The temperature factors are contributed mainly by the soft optic modes in Γ-M and the lowest-lying acoustic modes along Γ-A, which are also strongly temperature-dependent. The cusp-shaped temperature dependence of mean square displacements, 〈u2〉, of oxygen atom, observed previously around the α-β transition, are resulted from the softening of these modes. The temperature-dependent modes in Γ-A were also found to cause diffuse scattering extending along ±c* of the fourth hexagon of the hk0 reciprocal lattice plane. The negative expansion known in β-quartz were interpreted in terms of asymmetrical forces exerting on oxygen atoms in Si-O-Si bending modes. In β-quartz, librational motions of oxygen atoms around Si-Si lines with large amplitudes, whose center is just on the β-position of high symmetry, must be possible under the condition that bending tetrahedral O-Si-O angles is energetically more favourable than compressing or stretching Si-O bonds. 相似文献
2.
Compression of MgSiO3 glass in a 6/8 multianvil apparatus to 10.0 ± 0.5 GPa results in demonstrable changes in density and silicon coordination. Under high-pressure, samples were heated over a range of temperatures from 300 to 773 K, quenched to room temperature and decompressed at rates of 10.4 and 0.08 GPa/min. Recovered glasses have bulk densities that are 2.6-11.0% higher than the non-compressed glass. 29Si MAS NMR spectra of compressed glasses show narrowing of the [4]Si peak resulting from a reduction in the spread of the Si-O-Si bond angle distribution. After heating and rapid decompression, 29Si MAS NMR spectra of recovered glasses exhibit peaks assignable to [4]Si, [5]Si, and [6]Si with relative fractions of 0.945, 0.045, and 0.008, respectively. These changes in Si coordination and in Si-O-Si bond angle distribution with pressure only represent part of the structural changes associated with permanent densification of heated and unheated samples. The abundance of [6]Si is found to be insensitive to decompression rate, while [5]Si reverts to [4]Si on slow decompression at room temperature. These observations demonstrate that high-coordinated silicon species in MgSiO3 glass are formed on compression below glass transition temperatures and that pressure-induced structural changes can be preserved with rapid decompression. The ease with which [5]Si reverts to [4]Si during decompression suggests that the conversion of [4]Si → [5]Si principally involves short-range atomic displacement. The reversible and irreversible features of densification of MgSiO3 glass, provide insights into the fundamental structural and rheological properties of refractory silicate melts similar to those found in the Earth’s mantle. 相似文献
3.
The local configurations around sodium ions in silicate glasses and melts and their distributions have strong implications for the dynamic and static properties of melts and thus may play important roles in magmatic processes. The quantification of distributions among charge-balancing cations, including Na+ in aluminosilicate glasses and melts, however, remains a difficult problem that is relevant to high-temperature geochemistry as well as glass science.Here, we explore the local environment around Na+ in charge-balanced aluminosilicate glasses (the NaAlO2-SiO2 join) and its distribution using 23Na magic-angle spinning (MAS) nuclear magnetic resonance (NMR) spectroscopy at varying magnetic fields of 9.4, 14.1, and 18.8 T, as well as triple-quantum (3Q)MAS NMR spectroscopy at 9.4 T, to achieve better understanding of the extent of disorder around this cation. We quantify the extent of this disorder in terms of changes in Na-O distance (d[Na-O]) distributions with composition and present a structural model favoring a somewhat ordered Na distribution, called a “perturbed” Na distribution model. The peak position in 23Na MAS spectra of aluminosilicate glasses moves toward lower frequencies with increasing Si/Al ratios, implying that the average d(Na-O) increases with increasing R. The peak width is significantly reduced at higher fields (14.1 and 18.8 T) because of the reduced effect of second-order quadrupolar interaction, and 23Na MAS NMR spectra thus provide relatively directly the Na chemical shift distribution and changes in atomic environment with composition. Chemical shift distributions obtained from 23Na 3Q MAS spectra are consistent with MAS NMR data, in which deshielding decreases with R. The average distances between Na and the three types of bridging oxygens (BOs) (Na-{Al-O-Al}, Na-{Si-O-Al}, and Na-{Si-O-Si}) were obtained from the correlation between d(Na-O) and isotropic chemical shift. The calculated d(Na-{Al-O-Al}) of 2.52 Å is shorter than the d(Na-{Si-O-Si}) of 2.81 Å, and d(Na-{Al-O-Al}) shows a much narrower distribution than the other types of BOs. 23Na chemical shifts in binary (Al-free) sodium silicate glasses are more deshielded and have ranges distinct from those of aluminosilicate glasses, implying that d(Na-NBO) (nonbridging oxygen) is shorter than d(Na-BO) and that d(Na-{Si-O-Si}) in binary silicates can be shorter than that in aluminosilicate glasses. The results given here demonstrate that high-field 23Na NMR is an effective probe of the Na+ environment, providing not only average structural information but also chemically and topologically distinct chemical shift ranges (distributions) and their variation with composition and their effects on static and dynamic properties. 相似文献
4.
Short and medium range order of silica and sodium silicate glasses have been investigated from a quantitative analysis of 29Si MAS NMR and 23Na, 17O MQMAS NMR spectra. The method described enables the extraction of the underlying 17O NMR parameter distributions of bridging oxygens (BOs) and non-bridging oxygens (NBOs), and yields site populations which are confirmed by 29Si NMR data. The extracted NMR parameter distributions and their variations with respect to the glass chemical composition can then be analyzed in terms of local structural features (bond angles and bond lengths, coordination numbers) with the help of molecular dynamics simulations combined with first-principles calculations of NMR parameters. Correlations of relevant structural parameters with 23Na, 29Si and 17O NMR interactions (isotropic chemical shift δiso, quadrupolar coupling constant CQ and quadrupolar asymmetry parameter ηQ) are re-examined and their applicability is discussed. These data offer better insights into the structural organization of the glass network, including both chemical and topological disorder. Adding sodium to pure silica significantly diminishes the Si-O-Si bond angles and leads to a longer mean Si-O bond length with a slight decrease of the mean Na-O bond length. Moreover, the present data are in favor of a homogeneous distribution of Na around both oxygen species in the silicate network. Finally, our approach was found to be sensitive enough to investigate the effect of addition of a small quantity of molybdenum oxide (about 1 mol%) on the 17O MAS spectrum, opening new possibilities for investigating the Mo environment in silicate glasses. 相似文献
5.
In order to gain insight into the correlations between 29Si, 17O and 1H NMR properties (chemical shift and quadrupolar coupling parameters) and local structures in silicates, ab initio self-consistent
field Hartree-Fock molecular orbital calculations have been carried out on silicate clusters of various polymerizations and
intertetrahedral (Si-O-Si) angles. These include Si(OH)4 monomers (isolated as well as interacting), Si2O(OH)6 dimers (C2 symmetry) with the Si-O-Si angle fixed at 5° intervals from 120° to 180°, Si3O2(OH)8 linear trimers (C2 symmetry) with varying Si-O-Si angles, Si3O3(OH)6 three-membered rings (D3 and C1 symmetries), Si4O4(OH)8 four-membered ring (C4 symmetry) and Si8O12(OH)8 octamer (D4 symmetry). The calculated 29Si, 17O and 1H isotropic chemical shifts (δi
Si, δi
O and δi
H) for these clusters are all close to experimental NMR data for similar local structures in crystalline silicates. The calculated
17O quadrupolar coupling constants (QCC) of the bridging oxygens (Si-O-Si) are also in good agreement with experimental data. The calculated 17O QCC of silanols (Si-O-H) are much larger than those of the bridging oxygens, but unfortunately there are no experimental data
for similar groups in well-characterized crystalline phases for comparison. There is a good correlation between δi
Si and the mean Si-O-Si angle for both Q
1 and Q
2, where Q
n
denotes Si with n other tetrahedral Si next-nearest neighbors. Both the δ
i
O and the 17O electric field gradient asymmetry parameter, η of the bridging oxygens have been found to depend strongly on the O site
symmetry, in addition to the Si-O-Si angle. On the other hand, the 17O QCC seems to be influenced little by structural parameters other than the Si-O-Si angle, and is thus expected to be the most
reliable 17O NMR parameter that can be used to decipher Si-O-Si angle distribution information. Both the 17O QCC and the 2H QCC of silanols decrease with decreasing length of hydrogen bond to a second O atom (Si-O-H···O), and the δ
i
H increase with the same parameter.
Received: 18 July 1997 / Revised, accepted: 23 February 1998 相似文献
6.
Revealing the atomic structure and disorder in oxide glasses, including sodium silicates and aluminosilicates, with varying degrees of polymerization, is a challenging problem in high-temperature geochemistry as well as glass science. Here, we report 17O MAS and 3QMAS NMR spectra for binary sodium silicate and ternary sodium aluminosilicate glasses with varying degrees of polymerization (Na2O/SiO2 ratio and Na2O/Al2O3 ratio), revealing in detail the extent of disorder (network connectivity and topological disorder) and variations of NMR parameters with the glass composition. In binary sodium silicate glasses [Na2O-k(SiO2)], the fraction of non-bridging oxygens (NBOs, Na-O-Si) increases with the Na2O/SiO2 ratio (k), as predicted from the composition. The 17O isotropic chemical shifts (17O δiso) for both bridging oxygen (BO) and NBO increase by about 10-15 ppm with the SiO2 content (for k = 1-3). The quadrupolar coupling products of BOs and NBOs also increase with the SiO2 content. These trends suggest that both NBOs and BOs strongly interact with Na; therefore, the Na distributions around BOs and NBOs are likely to be relatively homogenous for the glass compositions studied here, placing some qualitative limits on the extent of segregation of alkali channels from silica-enriched regions as suggested by modified random-network models. The peak width (in the isotropic dimension) and thus bond angle and length distributions of Si-O-Si and Na-O-Si increase with the SiO2 content, indicating an increase in the topological disorder with the degree of polymerization. In the ternary aluminosilicate glasses [Na2O]x[Al2O3]1−xSiO2, the NBO fraction decreases while the Al-O-Si and Al-O-Al fractions apparently increase with increasing Al2O3 content. The variation of oxygen cluster populations suggests that deviation from “Al avoidance” is more apparent near the charge-balanced join (Na/Al = 1). The Si-O-Si fraction, which is closely related to the activity coefficient of silica, would decrease with increasing Al2O3 content at a constant mole fraction of SiO2. Therefore, the activity of silica may decrease from depolymerized binary silicates to fully polymerized sodium aluminosilicate glasses at a constant mole fraction of SiO2. 相似文献
7.
We have performed X-ray Raman scattering (XRS) measurements on the oxygen K and silicon L absorption edges of four silica minerals: α-quartz, α-cristobalite, coesite, and stishovite. We have also calculated the
partial electron densities of states (DOSs) and compared these with the XRS spectra. This study demonstrates that the short-range
structure around the atom of interest strongly influences the XRS spectral features. Importantly, the oxygen K-edge XRS spectra are found to reflect the p-orbital DOS while the silicon L-edge spectra reflect the s- and d-orbital DOSs, even when a product of a momentum transfer and a mean radius of a electron orbit (1s for oxygen and 2p for silicon), Qr, is close to or larger than unity. Building on this, calculations of the partial DOSs for other silica phases are presented,
including ultra-high-pressure phases, which provide a good reference for further XRS study of silica and silicate minerals.
XRS measurements should be performed on not only either of oxygen or silicon but also on many kinds of constituent elements
to reveal the structural change of glasses/melts of silicates under extreme conditions. 相似文献
8.
Brian L. Phillips John G. Thompson Yuehui Xiao R. James Kirkpatrick 《Physics and Chemistry of Minerals》1993,20(5):341-352
Nuclear magnetic resonance spectroscopic data are presented for the cristobalite polymorphs of AlPO4 and SiO2 from RT to 770 K, through their respective α-β transitions. The nuclear magnetic resonance (NMR) data include chemical shifts for 31P, 27Al, and 29Si, 27Al quadrupole coupling parameters, and 31P and 27Al spin-lattice relaxation rates. Also presented are electron diffraction patterns of β-cristobalite AlPO4 that show diffuse scattering similar to that reported previously for SiO2. For the α-phases of both AlPO4 and SiO2, the chemical shifts decrease approximately linearly with increasing temperature from RT to Tc and discontinuously by -2 to -3 ppm from α to β. This result is consistent with a small, continuous increase in the mean T-O-T angle (〈θ〉) of the α-phases with increasing T and an increase of 〈θ〉 by about 4° across the α-β transition for both cristobalite and its AlPO4 analogue. Based on the 29Si chemical shifts, the mean Si-O-Si angle for β-cristobalite is 152.7±1° near Tc. For AlPO4-cristobalite, the 27Al nuclear quadrupole coupling constant (CQ) decreases approximately linearly from 1.2 MHz at RT to 0.94 MHz near Tc (493±10 K). At the α-β transition the 27Al CQ approaches zero, in agreement with the cubic average structure observed by diffraction. The satellite transitions retain a small frequency distribution above the α-β transition from electric field gradients attributed to defects. The short-range cubic symmetry of the Al-site and non-linear Al-O-P angle support a dynamically disordered model of the β-cristobalite structure. Complete averaging of the 27Al quadrupole coupling in the β-phase indicates that the lifetime of any short-range ordered domains must be shorter than about 1 μs. 相似文献
9.
Stable isotope fractionation between mollusc shells and marine waters from Martinique Island 总被引：1，自引：0，他引：1
Forty-nine aragonitic and calcitic shells from 14 species of marine tropical molluscs (Bivalvia, Gastropoda, Polyplacophora) and ambient waters from Martinique have been analyzed for their carbon and oxygen isotope compositions. Mineralogy of shells was systematically determined by Raman spectroscopy that reveals composite shell structures and early processes of diagenetic alteration. In mangrove, brackish waters result from the mixing between 89±1% of seawater and 11±1% of freshwater, a hydrological budget quantified by both oxygen isotope and salinity mass balance calculations. Mollusc shells from the mangrove environment (S=31‰; δ18O=0.5‰) are characterized by mean δ13C values (−1.2‰) lower than those (+2.6‰) living in the open sea (S=35‰; δ18O=1‰). These low carbon isotope compositions result from the oxidation of organic matter into bicarbonate ions used in the building of mollusc shells. The oxygen isotope compositions of the studied mollusc species are mainly controlled by the temperature and composition of seawater whereas the role of the so-called “vital effects” is negligible. Contrasting with carbon isotopes, variability in the δ18O values among and within species of mollusc shells is very low (1σ=0.15) for a given littoral environment. Using ambient temperatures of seawater (28-30 °C), oxygen isotope fractionations between all studied living species and environmental waters match those extrapolated from the fractionation equation established for molluscs by Grossman and Ku [Chem. Geol., Isot. Geosci. Sect. 59 (1986) 59] in the range 3-20 °C. By analyzing calcite and aragonite layers from the same shell or by comparing shells from different species living in the same environment, there is no evidence that oxygen isotope fractionation between aragonite and water differs from that between calcite and water. On the basis of these results, we conclude that the oxygen isotope compositions of shells from most fossil mollusc species are suitable to estimate past seawater temperatures at any paleolatitude. 相似文献
10.
André C. Colonese Giovanni Zanchetta Catherine Perlès Russell N. Drysdale Giuseppe Manganelli Ilaria Baneschi Elissavet Dotsika Hélène Valladas 《Quaternary Research》2013
This paper investigates the stable isotopic composition from late Pleistocene–Holocene (~ 13 to ~ 10.5 cal ka BP) shells of the land snail Helix figulina, from Franchthi Cave (Greece). It explores the palaeoclimatic and palaeoenvironmental implications of the isotope palaeoecology of archaeological shells at the time of human occupation of the cave. Modern shells from around the cave were also analysed and their isotopic signatures compared with those of the archaeological shells. The carbon isotope composition of modern shells depicts the consumption of C3 vegetation. Shell oxygen isotopic values are consistent with other Mediterranean snail shells from coastal areas. Combining empirical linear regression and an evaporative model, the δ18Os suggest that modern snails in the study area are active during periods of higher relative humidity and lower rainfall δ18O, probably at night. Late glacial and early Holocene δ18Os show lower values compared to modern ones. Early Holocene δ18Os values likely track enhanced moisture and isotopic changes in the precipitation source. By contrast, lower late glacial δ18O could reflect lower temperatures and δ18Op, compared to the present day. Shell carbon isotope values indicate the presence of C3 vegetation as main source of carbon to late glacial and early Holocene snails. 相似文献
11.
Variations in the 17O nuclear quadrupole coupling constant, NQCC, and the 17O NMR shielding constant, σO, are evaluated for bridging oxygens in H3T-O-T′H3 linkages (with T, T′=Al, Si, P), and for nonbridging O in SiH3O?, SiH3OH and SiH3OMg+ and the 19F NMR shielding constant, σF, is evaluated for bridging F in H3SiFSiH 3 ? using Hartree-Fock methods with large, flexible Gaussian basis sets. Trends in 17O NQCC as a function of T and T′ identity agree with experiment but the value for the Si-O-Al case is underestimated, indicative of neglected contributions from charge compensating cations. For H3SiOSiH3 the decrease in NQCC over the range from 180° to 140° is substantial but somewhat slower than the variation of -cosSi and σO decrease as Si of the nonbridging oxygen of SiH3O? compared to the bridging oxygen of H3SiOSiH3 but the calculated σSi in H3SiOAlH 3 ? is too large and σO too small, indicative of important contributions from counter ions. By contrast, σO for PH3OAlH3 compared to SiH3OSiH3 is consistent with experiment. In H3SiFSiH 3 + (a model for bridging F in amorphous Si:H:F) the value of σSi is smaller and the NQCC at F is considerably larger than for H3SiF, suggesting distinctive 29Si and 19F NMR spectra for this species. 相似文献
12.
Extended Hückel molecular orbital theory (EHT) and simple, approximate Self-Consistent-Field MO methods are employed to explain the geometries of nontransition metal bearing minerals and inorganic compounds. The spectra of such minerals and the electronic structure of transition metal oxidic minerals are explained using the Self-Consistent-Field X α MO method. EHT provides an objective algorithm for rationalizing and correlating bond length and angle data for insular and polymerized TO 4 ?n tetrahedral oxyanions where T=Be, B, Al, Si, P, S, Ge, As and Se. Calculated bond overlap populations n(T-O), correlate linearly with the observed T-O bond lengths with shorter bonds tending to involve larger n(T-O) values. Such calculations show that n(T-O) is strongly dependent upon the average of the three O-T-O angles associated with a common bond, larger n(T-O) values involving wider angles. Calculations of n(T-O) as a function of the T-O-T angles in T 2O 7 ?n ions, indicate that the n(T-O) values for the bonds to the bridging oxygen atoms increase nonlinearly with increasing T-O-T angle whereas those the nonbridging oxygens decrease slightly as the angle widens. In agreement with the experimental data, these results predict that shorter T-O bonds should involve wider O-T-O and T-O-T angles. The SCF-X α MO cluster model is then applied to silica and FeO. The calculations yield a satisfactory interpretation of the visible, UV and X-ray emission and X-ray photoelectron spectra of these materials. Theoretical and empirical MO diagrams are constructed and the electronic structures of the materials are discussed. 相似文献
13.
Study of the carbon and oxygen isotopic composition of the foraminifera shells of different species from the Callovian-Oxfordian undershale rocks in the Unzha River basin near the town of Makar’ev (Central Volga region) has shown that the δ18O values of the epistomina shells correspond to relatively low temperatures and their δ13C values indicate the high productivity of the basin in this period. The Lenticulina tumida shells register low δ13C and δ18O values, which probably reflect the biological effect of fractionation during their formation. The Jurassic lagenids (Lenticulina tumida and Citharina chanika) were characterized by a wider habitat areal or ecological niche. We established the importance of isotopic studies of foraminifers of the same genus, and even better of the same species. Most likely, the foraminifera shells may be applied for study of Mesozoic sedimentation conditions. 相似文献
14.
Xianyu Xue Jonathan F. Stebbins Masami Kanzaki 《Physics and Chemistry of Minerals》1993,19(7):480-485
Stishovite, a high-pressure SiO2 polymorph in which each Si is coordinated by six O atoms, transforms to an amorphous phase when undergoing heat treatment below the glass transition temperature at ambient pressure. We have applied 29Si magic angle spinning nuclear magnetic resonance spectroscopy (MAS NMR) to study this amorphization process. We found that the amorphous phase generated after heating stishovite for up to 3 days at around 600 ° C consisted exclusively of four-coordinate Si, similar to glasses quenched from melts at ambient pressure. Furthermore, our data suggest that there are subtle structural differences between the amorphous phase transformed from stishovite at 600 ° C and glasses quenched from melts at ambient pressure: the amorphous phase from stishovite had a smaller mean Si-O-Si angle initially, and it gradually relaxed toward the latter with increasing heating time. There was no detectable change in the stishovite structure even after about 80% of it had been converted to the amorphous phase. The mechanism of the amorphization of stishovite is discussed in light of these results. 相似文献
15.
Variations of stable isotopic ratios of carbon (13C/12C) and oxygen (18O/16O) were investigated in modern shells of two species of Rabdotus land snails (R. dealbatus and R. alternatus) in the southern Great Plains. Geographic variation in relation to climate and vegetation, microgeographic variation, variability among individuals, and detailed records of seasonal variations within individual shells were studied. Stable carbon isotopic ratios in shell carbonate are primarily a function of the isotopic composition of the diet of the snails, as represented by the isotopic composition of shell organic matter. This in turn reflects the presence or absence of CAM (Crassulacean Acid Metabolism) or C4 plants. Vegetation density may have a small effect on the carbon isotope ratios. Microgeographic variation (samples within 25 to 300 m) is greater than that seen across different climatic regions and points to very local control of isotopic variations, predominantly related to vegetation. Seasonal variations, as assessed through serial analysis of individual shells (up to 35 samples per shell), may provide a means for distinguishing between isotopic influences of perennial CAM vs. annual C4 plants. Carbon isotopic variations in time-series of shells from a site provide a means of reconstructing temporal changes in environment and climate.Oxygen isotopic values of shell carbonate are uniform across the region and also show no significant microgeographic variation. The oxygen isotopic composition appears to be mainly a function of the rainwater isotopic composition, with no direct influence of rainfall amount or evaporative effects. The δ18O values are only 2‰ enriched relative to estimated equilibrium with rainwater. Variability is low (SD of 0.8‰ among sites), so the isotopic composition of fossil Rabdotus shells can provide a precise record of changes in the isotopic composition of rain over time. 相似文献
16.
Kimberly E. Kelsey Jonathan F. Stebbins Gordon E. Brown Jr. Jed L. Mosenfelder 《Geochimica et cosmochimica acta》2009,73(13):3914-2191
We examined aluminosilicate glasses containing a variety of network modifying to intermediate cations (Li, La, Sc, and Fe), quenched from melts at 1 atm to 8 GPa, to further investigate the role of cation field strength in Al coordination changes and densification. 27Al Nuclear Magnetic Resonance Spectroscopy (NMR) reveals that the mean Al coordination increases with increasing pressure in the Li-containing glasses, which can be explained by a linear dependence of fractional change in Al coordination number on cation field strengths in similar K-, Na-, and Ca-containing aluminosilicate glasses (K < Na < Li < Ca). Measured recovered densities follow a similar linear trend. In contrast, the La-containing glasses have significantly lower mean Al coordination numbers at given pressures than the cation field strength of La and glass density would predict. La L3 X-ray absorption fine structure (XAFS) spectroscopy results indicate a significant increase with pressure in average La-O bond distances, suggesting that La and Al may be “competing” for higher coordinated sites and hence that both play a significant role in the densification of these glasses, especially in the lower pressure range. However, in Na aluminosilicate glasses with small amounts of Sc, 45Sc NMR reveals only modest Sc coordination changes, which do not seem to significantly affect the mean Al coordination values. For a Li aluminosilicate glass, 17O MAS and multiple quantum magic angle spinning (3QMAS) NMR data are consistent with generation of more highly coordinated Al at the expense of non-bridging oxygen (NBO), whereas La aluminosilicate glasses have roughly constant O environments, even up to 8 GPa. Finally, we demonstrate that useful 23Na and 27Al MAS NMR spectra can be collected for Ca-Na aluminosilicate glasses containing up to 5 wt.% Fe oxide. We discuss the types of structural changes that may accompany density increases with pressure and how these structural changes are affected by the presence of different cations. 相似文献
17.
Kuniaki Kihara 《Physics and Chemistry of Minerals》1995,22(4):223-232
Disorder models of oxygen positions in P63/ mmc, C2221 and P212121 tridymites were given in applying geometrical and lattice dynamical calculations. Sixmembered rings of rigid SiO4 units are all collapsed in these forms; with silicon atoms fixed, SiO4 units can take six different orientations in forming tridymite frameworks in both the P63/mmc and C2221 forms, and three orientations in the P212121 form. Atomic distances and angles obtained from the distance least-squares method are about equal for the three forms: 〈Si-O〉 (mean Si-O) = 1.611 Å, 〈O-O〉 = 2.629 Å, and 〈Si-O-Si〉 = 147°. Domain formation models are given for the three forms. The tridymite framework structures may possibly undergo lattice vibrations with low frequencies in two kinds of pair-wise rotational modes of SiO4 units joined by the apical oxygen atoms, at the Γ-point: one is around 〈100〉 (or 〈210〉 for the hexagonal case), and the other is around 〈010〉. As temperature approaches the hexagonal-orthorhombic transition from below, the rotational mode around 〈100〉 remarkably softens at the Γ-point. The behavior of the atoms at the hexagonal-orthorhombic transition is explained in terms of a coupled softening of the two rotational modes of neighboring local domains in different orientations. 相似文献
18.
Magnetization, susceptibility and Mössbauer spectra are reported for representative chlorite samples with differing iron content. The anisotropy of the susceptibility and magnetization of a clinochlore crystal is explained using the trigonal effective crystal-field model developed earlier for 1:1 and 2:1 layer silicates, with a splitting of theT 2g triplet of 1,120K. Predominant exchange interactions in the iron-rich samples are ferromagnetic withJ=1.2 K, as for other trioctahedral ferrous minerals. A peak in the susceptibility of thuringite occurs atT m=5.5 K, and magnetic hyperfine splitting appears at lower temperatures in the Mössbauer spectrum. However neutron diffraction reveals no long-range magnetic order in thuringite (or biotite, which behaves similarly). The only magnetic contribution to the diffraction pattern at 1.6 K is increased small angle scattering (q<0.4 Å?1). A factor favouring this random ferromagnetic ground state over the planar antiferromagnetic state of greenalite and minnesotaite is the presence of pairs of ferric ions on adjacent sites, in conjunction with magnetic vacancies in the octahedral sheets. Monte Carlo simulations of the magnetic ground state of the sheets illustrate how long range ferromagnetic order may be destroyed by vortices forming around the Fe3+-Fe3+ pairs. 相似文献
19.
J. Purton R. Jones M. Heggie S. Öberg C. R. A. Catlow 《Physics and Chemistry of Minerals》1992,18(6):389-392
Ab initio LDF theory has been used to study the structure of the hydrogarnet defect in α-quartz. The predicted structure is in good agreement with the available sexperimental data. The techniques employed also yield a good model for the structure of α-quartz, giving an average Si-O bond length of 1.62 Å and average Si-O-Si angle of 142°. 相似文献
20.
Christine Latal Werner E. Piller Mathias Harzhauser 《International Journal of Earth Sciences》2006,95(1):95-106
The Korneuburg Basin, with mainly upper Lower Miocene (Karpatian) sediment filling, is divided by the Mollmannsdorf–Obergänserndorf Swell into two sub-basins characterised by different environmental settings. Paleoecological data indicate a marine northern part and a mainly estuarine southern part. Nevertheless, short-termed marine ingressions from the north allowed marine faunas (ostracods, molluscs, and echinoids) to temporarily settle the southern part of the basin. The carbon and oxygen isotopic composition of gastropod shells from these different environmental settings were investigated. Highest δ18O and δ13C values are found in Turritella shells from the northern part of the basin, and in Turritella shells from layers interpreted as a marine ingression in the south. Generally, components of the mudflat fauna (Tympanotonos cinctus, Granulolabium bicinctum, Terebralia bidendata, and Ocenebra crassilabiata) have slightly lower isotope values. Considerable freshwater influx in the southern part is documented by abundant freshwater genera such as Melanopsis, which show low carbon and oxygen isotope values. Data of identical taxa, especially Turritella and Granulolabium, reflect a trend from higher isotope values at the marine northern part to slightly lower values in the mainly estuarine southern part of the basin. Differences in δ18O between the marine and the estuarine assemblages are interpreted to be caused by changes in salinity and isotopic composition of ambient water rather than by temperature. Paleotemperature estimates derived from oxygen isotope data are in good agreement with existing paleoclimatic proxies for the Korneuburg Basin. Hence, an annual range of the sea-surface temperature from 13 to 26°C can be predicted within that protected basin. 相似文献