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1.
J. A. Tossell 《Physics and Chemistry of Minerals》1984,10(3):137-141
Trends in 29Si nuclear magnetic resonance (NMR) chemical shifts in silicates are shown to arise primarily from changes in the paramagnetic contribution to the shift, σpara. Using the average excitation energy approximation, changes in σpara may be correlated with changes in the separation of high energy occupied and low energy unoccupied molecular orbitals. The required molecular orbital (MO) energy differences may be obtained from x-ray emission and absorption spectra. Shifts in σ to high field as silicate polymerization increases are associated with increased occupied to unoccupied MO energy differences. Substitution of Al for Si (and consequent introduction of electropositive cations, such as Na) reduces the occupied to unoccupied orbital energy gap causing shifts of σ to low field. The observed correlation indicates that 29Si NMR is capable of giving information on silicate electronic structure. 相似文献
2.
The effect of the group IA and VIIA ions, as well as Mg2+, and the molecules H2O, CO2, H3O+ and OH? on the energy of the Si-O bond in a H6Si2O7 cluster has been calculated using semiempirical molecular orbital calculations (CNDO/2). Three types of elementary processes, i.e. substitution, addition, and polymerization reactions have been used to interpret data on the dynamic viscosity, surface tension and surface charge, hydrolytic weakening, diffusivity, conductivity, freezing point depression, and degree of polymerization of silicates in melts, glasses, and aqueous solutions. As a test of our calculational procedure, observed X-ray emission spectra of binary alkali silicate glasses were compared with calculated electronic spectra. The well known bondlength variations between the bridging bond [Si-O(br)] and the non-bridging bond [Si-O(nbr)] in alkali silicates are shown to be due to the propagation of oscillating bond-energy patterns through the silica framework. A kinetic interpretation of some results of our calculations is given in terms of the Bell-Evans-Polanyi reaction principle. 相似文献
3.
4.
Ab initio STO-3G molecular orbital theory has been used to calculate energy-optimized Si-O bond lengths and angles for molecular orthosilicic and pyrosilicic acids. The resulting bond length for orthosilicic acid and the nonbridging bonds for pyrosilicic acid compare well with Si-OH bonds observed for a number of hydrated silicate minerals. Minimum energy Si-O bond lengths to the bridging oxygen of the pyrosilicic molecule show a close correspondence with bridging bond length data observed for the silica polymorphs and for gas phase and molecular crystal siloxanes when plotted against the SiOSi angle. In addition, the calculations show that the mean Si-O bond length of a silicate tetrahedron increases slightly as the SiOSi angle narrows. The close correspondence between the Si-O bond length and angle variations calculated for pyrosilicic acid and those observed for the silica polymorphs and siloxanes substantiates the suggestion that local bonding forces in solids are not very different from those in molecules and clusters consisting of the same atoms with the same coordination numbers. An extended basis calculation for H4SiO4 implies that there are about 0.6 electrons in the 3d-orbitals on Si. An analysis of bond overlap populations obtained from STO-3G* calculations for H6Si2O7 indicates that Si-O bond length and SiOSi angle correlations may be ascribed to changes in the hybridization state of the bridging oxygen and (d – p) π-bonding involving all five of the 3d AO's of Si and the lone-pair AO's of the oxygen. Theoretical density difference maps calculated for H6Si2O7 show a build-up of charge density between Si and O, with the peak-height charge densities of the nonbridging bonds exceeding those of the bridging bonds by about 0.05 e Å?3. In addition, atomic charges (+1.3 and ?0.65) calculated for Si and O in a SiO2 moiety of the low quartz structure conform reasonably well with the electroneutrality postulate and with experimental charges obtained from monopole and radial refinements of diffraction data recorded for low quartz and coesite. 相似文献
5.
Using empirical potentials derived from fitting the vibrational frequencies of a group of silicates and oxides (not including the mineral under study), a Born-von Karman rigid ion lattice-dynamical model has been applied to the whole Brillouin zone in phenakite (Be2SiO4), a silicate which can be described as a three-dimensional network of tetrahedral SiO4 and BeO4 groups strictly linked together by sharing the oxygen atoms at their corners. The atomic anisotropic displacement parameters (ADPs) derived from accurate crystal-structure refinement at room temperature agree very well with the corresponding theoretical estimates, thereby confirming the validity of the model and the procedure followed. The experimental values of the bond distances corrected for thermal motion show that the observed invariance of the Si-O bond length with respect to temperature is only apparent. Furthermore, the disagreement with the experimental values of thermodynamic functions such as the specific heat C p and entropy at room temperature is 1.3% and 0.9%, respectively, and such a disagreement remains below 3% for a wide range of temperature (200 to 1000 K). As for many oxides and silicates so far examined, the zero-point contribution to the ADPs of the Si and O atoms amounts to about one half of the corresponding value at room temperature, and that of the Be atoms is even higher (60%). 相似文献
6.
Using empirical potentials derived from fitting the vibrational frequencies of a group of silicates and oxides (not including
the mineral under study), a Born-von Karman rigid ion lattice-dynamical model has been applied to the whole Brillouin zone
in phenakite (Be2SiO4), a silicate which can be described as a three-dimensional network of tetrahedral SiO4 and BeO4 groups strictly linked together by sharing the oxygen atoms at their corners. The atomic anisotropic displacement parameters
(ADPs) derived from accurate crystal-structure refinement at room temperature agree very well with the corresponding theoretical
estimates, thereby confirming the validity of the model and the procedure followed. The experimental values of the bond distances
corrected for thermal motion show that the observed invariance of the Si-O bond length with respect to temperature is only
apparent. Furthermore, the disagreement with the experimental values of thermodynamic functions such as the specific heat
C
p and entropy at room temperature is 1.3% and 0.9%, respectively, and such a disagreement remains below 3% for a wide range
of temperature (200 to 1000 K). As for many oxides and silicates so far examined, the zero-point contribution to the ADPs
of the Si and O atoms amounts to about one half of the corresponding value at room temperature, and that of the Be atoms is
even higher (60%).
Received: 8 December 1997 / Revised, accepted: 8 May 1998 相似文献
7.
Comparison of measured far-from-equilibrium dissolution rates of natural glasses and silicate minerals at 25 °C and pH 4 reveals the systematic effects of crystallinity and elemental composition on these rates. Rates for both minerals and glasses decrease with increasing Si:O ratio, but glass dissolution rates are faster than corresponding mineral rates. The difference between glass and mineral dissolution rates increases with increasing Si:O ratio; ultra-mafic glasses (Si:O ? 0.28) dissolve at similar rates as correspondingly compositioned minerals, but Si-rich glasses such as rhyolite (Si:O ∼ 0.40) dissolve ?1.6 orders of magnitude faster than corresponding minerals. This behaviour is interpreted to stem from the effect of Si-O polymerisation on silicate dissolution rates. The rate controlling step of dissolution for silicate minerals and glasses for which Si:O > 0.28 is the breaking of Si-O bonds. Owing to rapid quenching, natural glasses will exhibit less polymerisation and less ordering of Si-O bonds than minerals, making them less resistant to dissolution. Dissolution rates summarized in this study are used to determine the Ca release rates of natural rocks at far-from-equilibrium conditions, which in turn are used to estimate their CO2 consumption capacity. Results indicate that Ca release rates for glasses are faster than those of corresponding rocks. This difference is, however, significantly less than the corresponding difference between glass and mineral bulk dissolution rates. This is due to the presence of Ca in relatively reactive minerals. In both cases, Ca release rates increase by ∼two orders of magnitude from high to low Si:O ratios (e.g., from granite to gabbro or from rhyolitic to basaltic glass), illustrating the important role of Si-poor silicates in the long-term global CO2 cycle. 相似文献
8.
?-Na2Si2O5, ζ-Na2Si2O5, Na2Si[Si2O7], and Na6Si3[Si9O27] have been synthesized using an MA6/8 superpress. Densification in high-pressure sodium silicates is effected largely by changes in packing. In the relaxed (1 bar) structures, cation polyhedra and thermal/displacement parameters are similar to those of low-pressure silicates, but the extra-framework cation positions are oversized. The two mixed [4]Si and [6]Si framework silicates of known structure (Na2Si[Si2O7] and Na6Si3[Si9O27]) belong to the limited homologous series Na2mSim[Sin–mO2n+m], with m<n. The structure-composition relationships of wadeite-type, A2Ge4O9-type, and Na6Si3[Si9O27] silicates and germanates depend on T-O distance and size of the large extra-framework cation. Characteristic features of the SiO4 tetrahedral units are present in micro-Raman spectra of mixed [4]Si and [6]Si framework silicates, but bands uniquely attributable to SiO6 octahedra are weak or obscured. However, [6]Si has a profound indirect influence on the Raman spectra, resulting in intense and complex low-frequency bands, assigned to symmetric bending modes with coupled displacements at both bridging oxygens and nonbridging oxygens bonded to [6]Si, and a shift to higher frequency and reduction in intensity of the high-frequency bands assigned to symmetric [4]Si-Onbr stretching vibrations. Raman spectroscopy does not appear to be a useful structural probe for small amounts of [6]Si in silicate glasses and melts. 相似文献
9.
In 29Si-NMR, it has so far been accepted that the chemical shifts of Qn species (SiO4 units containing n bridging oxygens) were equivalent between alkali borosilicate and boron-free alkali silicate glasses. In the sodium borosilicate glasses with low sodium content, however, a contradiction was confirmed in the estimation of alkali distribution; 11B NMR suggested that Na ions were entirely distributed to borate groups to form BO4 units, whereas a −90 ppm component was also observed in 29Si-NMR spectra, which has been attributed to Q3 species associated with a nonbridging oxygen (NBO). Then, cluster molecular orbital calculations were performed to interpret the −90 ppm component in the borosilicate glasses. It was found that a silicon atom which had two tetrahedral borons (B4) as its second nearest neighbors was similar in atomic charge and Si2p energy to the Q3 species in boron-free alkali silicates. Unequal distribution of electrons in Si-O-B4 bridging bonds was also found, where much electrons were localized on the Si-O bonds. It was finally concluded that the Si-O-B4 bridges with narrow bond angle were responsible for the −90 ppm 29Si component in the borosilicate glasses. There still remained another interpretation; the Q3 species were actually present in the glasses, and NBOs in the Q3 species were derived from the tricluster groups, such as (O3Si)O(BO3)2. In the glasses with low sodium content, however, it was concluded that the tricluster groups were not so abundant to contribute to the −90 ppm component. 相似文献
10.
The
∞
2
[Si2O
5
2−
] frame in phyllosilicate minerals is distorted through the rotation and tilting of the silicate tetrahedra and interacts
with octahedral cations through its apical oxygens. Qualitative perturbation theory and extended Hückel band structure calculations
demonstrate that rotation and tilting distortions of the
∞
2
[Si2O
5
2−
] frame have little influence on orbital interactions within the frame. The effects which are observed can be traced to next-nearestneighbor,
oxygen-oxygen interactions. Analysis of band widths and crystal-orbital-overlap-populations demonstrate the importance of
O(2s) orbitals in the silicate bond. Interactions between Si(3s, 3p) and O(2s) atomic orbitals account for about half of the bonding overlap in the Si-O bond. Crystal orbitals within the
∞
2
[Si2O
5
2−
] frame are perturbed in kaolinite, lizardite, pyrophyllite and talc through interactions of the apical oxygens with octahedrally
coordinated Al(III) and Mg(II). These interactions appear to involve states that are non-bonding in an isolated frame, having
little effect on the Si-Oapical bond while significantly reducing the apical-oxygen atomic population. 相似文献
11.
J. A. Tossell 《Physics and Chemistry of Minerals》1992,19(5):338-342
29Si NMR studies on synthetic single crystal forsterite have shown an isotropic NMR shift of –63.2 ppm relative to tetramethyl silane and shift tensor components of –24.4, –7.9 and +32.2 ppm relative to this isotropic value. The most shielded component (+32.2 ppm) lies close to the Si-O1 vector, where Si-O1 is the shortest bond, R(Si-O1)=1.614Å (Weiden and Rager, Z. Naturforsch 40a, 126 (1985)). Ab initio self consistent field molecular orbital calculations using the Random Phase Approximation Localized-Orbital Local-Origin (RPA LORG) method and a polarized split valence basis set yield shift tensor components of –28.9, +2.3 and +26.6 ppm relative to the isotropic value, with the most shielded component 17.6° from the Si-O1 axis. This good agreement is obtained for a SiO
4
4–
cluster with forsterite local geometry stabilized by four +1 point charges, PC, with the 相似文献
12.
David A. McKeown 《Physics and Chemistry of Minerals》1989,16(7):678-683
Al X-ray absorption K-edge spectra were calculated for atom clusters which simulate Al surrounded by oxygens in tetrahedral and octahedral environments in five minerals, and are compared with experimental Al K-edge spectra from the same minerals. The experimental data show simple edges, for Al tetrahedra, that are shifted to lower energy by 2 eV compared with more complicated edges for Al octahedra. The calculated edge itself is due to a strong 1s to 3p resonance in the μ0 for Al. The shifting of the calculated edges is due to different molecular potentials used and different types of atomic scattering. The calculated edge features for tetrahedral Al are all similar, and are due primarily to single scattering from the tetrahedral oxygens. Calculated edge features for octahedral Al are more complicated and are dominated by multiple scattering. The calculated edge features resemble the experimental data, but are much larger in amplitude than their experimental counterparts. 相似文献
13.
Borates consisting of diverse fundamental building blocks (FBB) formed from complex polymerization of planar triangular [Bϕ3] groups and tetrahedral [Bϕ4] groups, where ϕ = O and OH, provide an excellent opportunity for investigation of correlations between the NMR parameters
and local structures. However, previous studies suggested that the 11B NMR parameters in borates are insensitive to local structural environments other than the B coordination number, in contrast
to those documented for 29Si, 23Na and 27Al in silicates, and no correlation between 11B chemical shifts and the sum of bond valences has been established for borate minerals with hydroxyl groups or molecular
water in the structures. In this study, high-resolution NMR spectra have been acquired at the ultra high field of 21 T as
well as at 14 T for selected borate and borosilicate minerals, and have been used to extract high-precision NMR parameters
by using combined ab initio theoretical calculations and spectral simulations. These new NMR parameters reveal subtle correlations
with various structural characters, especially the effects of the 11B chemical shifts from the bridging oxygen atom(s), site symmetry, symmetry of FBB, the sum of bond valences, as well as the
next-nearest-neighbor cations and hydrogen bonding. Also, these results provide new insights into the shielding mechanism
for 11B in borate and borosilicate minerals. In particular, this study demonstrates that the small variation in 11B chemical shifts can still be used to probe the local structural environments and that the established correlations can be
used to investigate the structural details in borates and amorphous materials. 相似文献
14.
《Chemical Geology》2006,225(3-4):373-387
Rock-forming zeolites often exhibit complex solid solutions reflecting isomorphous substitutions between Si and Al in tetrahedral framework sites, between charge-balancing extraframework cations, and between water molecules and vacancies. Although the number of moles of charge on extraframework cations in a zeolite must equal the moles of Al in order to maintain charge balance, the relationships between Si–Al and extraframework substitutions vary considerably across this mineral group. Review of available compositional data suggests that there are three main modes of Si–Al substitution in zeolites: 1) coupled CaAl–NaSi substitution; 2) coupled substitution of a single extraframework cation plus Al for Si; and 3) completely uncoupled substitution among extraframework cations and Si and Al on tetrahedral sites. Among zeolites that exhibit the latter two modes of solid solution, Si–Al substitution can be described by an SiO2 (± H2O) compositional exchange vector from a hypothetical, pure-silica endmember composition. Recent calorimetric, structural, and theoretical investigations suggest that Si–Al substitution follows a non-ideal, athermal solution model characterized by no excess enthalpies of mixing and negative excess entropies of mixing. Because Si–Al exchange in these minerals can be explicitly or implicitly described by exchange of an SiO2 component, the Si/Al ratio in their framework can be predicted solely as a function of temperature, pressure, and the chemical potential of SiO2. Application of this model leads to calculated Si/Al ratios in stilbite (coexisting with albite), analcime, and chabazite consistent with observed mineral compositions and parageneses in very low-grade metamorphic environments. Coexistence of silica polymorphs with zeolites containing SiO2·nH2O exchange vectors potentially provides a means of performing thermobarometric calculations in very low-grade metamorphic and diagenetic environments. 相似文献
15.
Far-infrared, mid-IR, and Raman powder spectra were measured on six phases (bromellite, chrysoberyl, phenakite, bertrandite, beryl, and euclase) in the system BeO-Al2O3-SiO2-H2O. A single-crystal absorption spectrum of IR fundamentals in beryl is also presented, which more closely resembles the powder absorption spectrum than it does absorption spectra calculated from single-crystal reflection data. Assignments of the SiO4 and BeO4 internal vibrations are made in accordance with each mineral's symmetry and composition and by comparison to structural analogs. Heat capacities C v calculated for these partial band assignments agree with C v derived from experimental C p for all six phases, provided that Kieffer's (1979c) model is slightly modified to correctly enumerate both Si-O and Be-O stretching modes in the high frequency region (>750 cm?1). Si-O stretching bands were found to out-number Be-O stretching modes in the high-energy region of the vibrational spectra with two exceptions: (1) For those phases containing oxygen ions not coordinated to silicon, vibrations occurring at v>1,080 cm?1 that are attributable to Be-O (H) stretching must be treated separately in the model in order to calculate C v accurately. (2) Minerals consisting entirely of interlocking Si and Be tetrahedra (i.e., phases without Al or OH) can be modeled by one optic continuum representing all optical modes. These results, along with the occurrence of very low energy lattice vibrations for Be-silicates within Al, suggests that although Be-O bonds are generally weaker than neighboring Si-O bonds, Be mimics the network-forming characteristic of Si to a limited extent. 相似文献
16.
Yu. P. Dikov E. I. Debolsky Yu. N. Romashenko S. P. Dolin A. A. Levin 《Physics and Chemistry of Minerals》1977,1(1):27-41
The Si, Al LII, III and OKα emission and quantum yield spectra were obtained for 24 silicates. It was found that in minerals of a homogeneous anion composition the Si LII, III line has double-humped structure, and when in addition to SiO 4 4? ions of other composition (BeO 4 6? , AlO 4 5? etc.) are present it has triple-humped structure. The process of crystal-glass transition was studied by X-ray spectroscopy. The result is that in spite of the original form of the Si LII, III line of the mineral this line changes its structure in glass and exhibits a typical double-humped structure. The CNDO/2 approach was used to calculate the electronic structure of basic structural groups of silicates from SiO 4 4? to Si5O 16 12? by replacing one or two of the Si atoms by Be, B, Al and P. A qualitative interpretation of the X-ray spectra is presented. 相似文献
17.
27Al,29Si MAS NMR studies of kaolinite and its thermal transformation products show that in the kaolinite-mullite reaction series
there is an extensive segregation of Al2O3 and SiO2 and the reaction of Al2O3 with SiO2 to form mullite is the main path of mullite formation. At about 850° C, the peak intensity of A1(V) reaches its maximum and
with the further rise of temperature the A1(V) signal completely disappears. At about 950°C, γ-Al2O3 accounts for about 71% of the material phases containing Al atoms. In the series there is no obvious presence of Al-Si spinel.
The27Al and29Si MAS NMR spectra show that there is an obvious difference between the temperature points for Al-O2(OH)4 octahedral sheet collapsing and Si-O4 tetrahedral sheet breaking down. 相似文献
18.
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
19.
Several important equilibrium Si isotope fractionation factors among minerals, organic molecules and the H4SiO4 solution are complemented to facilitate the explanation of the distributions of Si isotopes in Earth’s surface environments. The results reveal that, in comparison to aqueous H4SiO4, heavy Si isotopes will be significantly enriched in secondary silicate minerals. On the contrary, quadra-coordinated organosilicon complexes are enriched in light silicon isotope relative to the solution. The extent of 28Si-enrichment in hyper-coordinated organosilicon complexes was found to be the largest. In addition, the large kinetic isotope effect associated with the polymerization of monosilicic acid and dimer was calculated, and the results support the previous statement that highly 28Si-enrichment in the formation of amorphous quartz precursor contributes to the discrepancy between theoretical calculations and field observations. With the equilibrium Si isotope fractionation factors provided here, Si isotope distributions in many of Earth’s surface systems can be explained. For example, the change of bulk soil δ30Si can be predicted as a concave pattern with respect to the weathering degree, with the minimum value where allophane completely dissolves and the total amount of sesqui-oxides and poorly crystalline minerals reaches their maximum. When, under equilibrium conditions, the well-crystallized clays start to precipitate from the pore solutions, the bulk soil δ30Si will increase again and reach a constant value. Similarly, the precipitation of crystalline smectite and the dissolution of poorly crystalline kaolinite may explain the δ30Si variations in the ground water profile. The equilibrium Si isotope fractionations among the quadra-coordinated organosilicon complexes and the H4SiO4 solution may also shed light on the Si isotope distributions in the Si-accumulating plants. 相似文献
20.
CNDO/2 MO calculations on H12Si5O16 clusters modeling silicate tetrahedral linkage in the silica polymorphs show total energy minima at bent SiOSi angles and a correlation between the Si-O bond lengths, d(Si-O), used in the calculation and the minimum energy value of the SiOSi angle. Calculations on hydrogen saturated Si5O16 clusters isolated from the structures of low quartz, low cristobalite and coesite which were adjusted by DLS methods so that all d(Si-O) equal 1.61 Å and all L OSiO equal 109.47° yield Mulliken bond overlap populations, n(Si-O), and Si-O two-center energies, E(Si-O), which correlate with observed bond lengths; shorter bonds involve larger n(Si-O) values and more negative E(Si-O) values.
相似文献