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1.
 The cis-vacant configurations of smectites and illites have been studied theoretically by using transferable empirical interatomic potentials. A wide range of compositions of octahedral and tetrahedral cation and interlayer charge has been considered. All results have been compared with the trans-vacant configurations in each sample. The calculated values reproduce the differences in the lattice parameters between the cis- and trans-vacant configurations of experimental studies. Taking into account the cis-/trans-vacant proportion, the calculated structures agree with experiment for the main structural features of the crystal lattice. The effect of the cation substitution in the octahedral and tetrahedral sheets on the cell parameters has been also studied, finding good linear relationships. The calculated cation substitution effects are consistent with experimental results. Although the energy difference between the cis- and trans-vacant configurations is small, the cis-vacant is more stable when the composition of clays is more smectitic, like the experimental behaviour. Similar trends of the cation substitution effect on the cis-/trans-vacant proportion to the experimental results are found. The structure of the hydroxy groups has also been analysed. The OH bond length, the orientation of the O–H bond with respect to the (001) plane and the non-bonding H...O distances have been studied. Received: 4 September 2000 / Accepted: 29 January 2001  相似文献   

2.
 The interaction of γ-rays with smectites induces paramagnetic defects in the structure of these clay minerals. The EPR spectra of three different smectites detect the creation of structural defects and trapping of organic free radicals in the clay structure upon irradiation. The defects are assigned to positive holes or trapped electrons stabilised by existing local charge imbalances in the mineral lattice. The organic radicals are derived from organic compounds present as impurities in the crystal lattice of the clay minerals. In addition, γ-rays cause migration of small interlayer cations (such as Li+) into the layers, as clearly evidenced by EPR and FT-IR reflectance spectroscopies. Received: 20 April 2000 / Accepted: 2 December 2000  相似文献   

3.
 Application of polarized extended X-ray absorption fine structure (P-EXAFS) spectroscopy to thin films of fine-grained minerals is emerging as a powerful method to investigate the in-plane and out-of-plane local structure of phyllosilicates. Mineral platelets have no preferential orientation in the plane of the film, and their c* axes are oriented essentially along the film normal. The angular dependence of the EXAFS amplitude critically depends on the orientation distribution of c* axes due to mosaic spread. The effect of film texture on EXAFS amplitude has been calculated as a function of the mosaic spread, the orientation of the electric field vector, and the crystallographic orientation of the atomic pair. Calculations show that the reduction in amplitude for partially ordered films is more important when the electric field vector is perpendicular to the film plane. For phyllosilicates, no significant deviation from single crystal dichroism occurs when the mosaic spread is less than ±20–25° half-width at half-maximum (HWHM) for parallel measurement, and ±15–20° HWHM for normal measurement. Graphs are given for correcting EXAFS-derived coordination numbers for texture effects. Received: 3 February 2000 / Accepted: 26 July 2000  相似文献   

4.
The maximum entropy method (MEM) is used here to get an insight into the electron density [ρ(r)] of phengites 2M 1 and 3T, paying special attention to the M1-formally empty site and charge distribution. Room temperature single crystal X-ray diffraction data have been used as experimental input for MEM. The results obtained by MEM have been compared with those from conventional structure refinement which, in turn, has provided the prior-electron density to start the entropy maximization process. MEM reveals a comparatively non-committal approach, able to produce information related to the M1-site fractional occupancy, and yields results consistent with those from the difference Fourier synthesis, but free of the uncertainties due to the abrupt truncation of the series. The charge distribution is investigated by means of the notion of ‘‘site basin’’, i.e., those site-centered volumes delimited by a surface such as ∇ρ·n = 0. In particular, we observe: (1) the overall partitioning of the basin total charge between cation and anion sites, and the interlayer site charge seems to depend on sample composition, and (2) the apical-oxygen plane total basin charge and hydroxyl basin charge are presumably related to the polytype. The MEM-determined electron density does not allow full exploration of the critical points for very complex structures as micas, insofar as conventional room temperature experimental diffraction data are used.  相似文献   

5.
We propose a solid-solution model for dioctahedral aluminous phyllosilicates accounting for the main compositional variations, including hydration, observed in natural smectites, interlayered illite/smectite, illites, and phengites from diagenetic to high-grade metamorphic conditions. The suggested formalism involves dehydrated micas and hydrated pyrophyllite-like thermodynamic end-members. With these end-members, the equilibrium conditions of quartz + water + K-bearing mica-like phyllosilicates of fixed 2:1 composition are represented by a line in P–T space along which the interlayer water content varies. The relevant thermodynamic properties required for the calculation of equilibrium conditions were derived using a set of 250 natural data of known maximal temperature and pressure conditions, which covers a range between 25°C and few MPa to 800°C and 5 GPa. The temperatures calculated at fixed pressure with our model are in fair agreement with those reported in the literature for the 250 natural data. At low temperature and pressure, the amount of interlayer water in K-deficient phengite and illite is predicted to reach 100% of the apparent vacancies, which is consistent with previous values reported in the literature. Although the amount of interlayer water is predicted to decrease with pressure and temperature, it is calculated to be significant in K-deficient phengite from LT–HP pelites metamorphosed at about 350°C, 10 kbar. The presence of molecular water in the interlayer site of such phengites has been confirmed by FTIR mapping. Its implications for P–T estimates are discussed.  相似文献   

6.
层状硅酸盐矿物晶体结构的多体性组装模式与构筑原理   总被引：2，自引：0，他引：2  
将层状硅酸盐矿物晶体结构中属性不同的二维结构单元体看成是不同的结晶学模块,研究了一般层状硅酸盐矿物和间层矿物的多体性组装模式和构筑原理。结果表明,不同二维结构单元体(包括硅氧四面体片、八面体片、层间域(物))的构筑基本符合球体紧密堆积原理,紧密堆积层平行{0001};四面体片与八面体片构筑TO和TOT结构层时采取多种机制消除二者在二维尺寸上的差异;两种模式的结构层与不同类型的层间物(域)组装形成六种组装模式的晶层;并通过二维结构单元体的组合规律的分析,计算出可能存在的28种TOT型间层结构,它们分属于6种间层结构多体性组装模式;间层结构中,结构层对于八面体片是不对称的,并在属性上表现出极性特征;间层矿物的晶层类型可用6种多体性组装模式加以表达。层状硅酸盐矿物结构的多体性分析与组装模式的研究,对于矿物晶体化学研究是非常重要的。  相似文献   

7.
The hydroxy groups of the crystal lattice of dioctahedral 2:1 phyllosilicates were investigated by means of quantum-mechanical calculation. The standard Kohn-Sham self-consistent density functional theory (DFT) method was applied using the generalized gradient approximation (GGA) with numerical atomic orbitals and double-zeta polarized functions as basis set. Isomorphous cation substitution of different cations in the octahedral and tetrahedral sheet was included along with several interlayer cations reproducing experimental crystal lattice parameters. The effect of these substitutions and the interlayer charge on the hydroxyl group properties was also studied. These structures represent different cation pairs among Al3+, Fe3+ and Mg2+ in the octahedral sheet of clays joined to OH groups. The geometrical disposition of the OH bond in the crystal lattice and the hydrogen bonds and other electrostatic interactions of this group were analyzed. The frequencies of different vibrational modes of the OH group [(OH), (OH) and (OH)] were calculated and compared with experimental data, finding a good agreement. These frequencies depend significantly on the nature of cations which are joined with, and the electrostatic interactions with, the interlayer cations. Besides, hydrogen-bonding interactions with tetrahedral oxygens are important for the vibrational properties of the OH groups; however, also the electrostatic interactions of these OH groups with the rest of tetrahedral oxygens within the tetrahedral cavity should be taken into account. The cation substitution effect on the vibration modes of the OH groups was analyzed reproducing the experimental behaviour.Dr. V. Botella passed away last February  相似文献   

8.
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   

9.
Atomic models involving the dehydroxylation process of dioctahedral phyllosilicates without interlayer charge were used to calculate energies and explore the reaction paths of the possible mechanisms of this reaction at a quantum mechanical level. The geometrical features and electronic structure of a molecular cluster model of two edge-sharing octahedrally coordinated cations coupled to a ring of six silicate tetrahedra was evaluated by ab initio molecular orbital calculations with Hartree-Fock approximation. Two dehydroxylation mechanisms are considered. One mechanism involves two contiguous hydroxyl that are on an octahedron shared edge that joins a pair of octahedral cations. The other model considered involves OH loss from across an octahedral vacant. The substitution effect of Al3+ by Fe3+ in the octahedral sheet on the activation energy and structural transformations is compared by minimization of the critical points of the Potential Energy Surface (PES) for the reactant, transition state and product along the reaction path of the dehydroxylation process. The calculated energy differences and vibration frequencies are according to previous experimental results. The dehydroxylation mechanism involving OH across the octahedral hole, is less energetically favorable and is endothermic.  相似文献   

10.
The method of crystal static deformation, including inner strain effects, was applied to calculate the structure configuration and the elastic constants of forsterite under anisotropic and isotropic pressure. A Born type interatomic potential is used, with optimized atomic charges and repulsive radii; SiO4 tetrahedra are approximated as rigid units. Computations were carried out in the range 1–8 GPa, with steps of 1 GPa, for the three uniaxial stresses τ1, τ2, τ3 and for pressure p. By interpolation of results, interatomic distances and elastic tensor components are shown to depend quadratically on stress. A non-linear behaviour generally appears above 4 GPa; the importance of inner strain and non-linear effects is analyzed. Mg-O bond lengths and O-O edges of coordination polyhedra respond differently to anisotropic and to isotropic stresses, according to the topological features of the structure. Elastic and structural results for hydrostatic pressure are compared to experimental literature data, discussing the range of validity of the rigid body approximation for SiO4 groups.  相似文献   

11.
Neutron powder diffraction studies of calcite on heating towards the orientational order–disorder phase transition show that the phase transition is not a simple analogue of an Ising-like transition, but more similar to a rotational analogue of Lindemann melting. The transition is precipitated by the librational amplitude of the carbonate molecular ions exceeding a critical value rather than a result of a statistical entropy of ‘wrong’ orientations. Using tested interatomic potentials the single-particle orientational potential and nearest-neighbour orientational interactions have been calculated.  相似文献   

12.
The crystal structures of the two hydrous wadsleyite crystals with formulae, Mg1.75SiH0.50O4 (0.5H–β) and Mg1.86SiH0.28O4 (0.3H–β) have been analyzed in this study. The single-crystal X-ray diffraction data showed that the unit cells of the 0.3H–β and the 0.5H–β are metrically monoclinic with a slight distortion from the orthorhombic cell but their intensity distributions conform to the orthorhombic symmetry within the limit of experimental errors. The Fourier and the difference Fourier syntheses were calculated. Small but significant Fourier peaks were found at the site, Si2, in a normally vacant tetrahedral void adjacent to Mg3 site as reported for the monoclinic hydrous wadsleyite by Smyth et al.. From the comparison of the hydrous and anhydrous wadsleyite structures, the Mg-vacant structural modules were found to be the building units for the structure of hydrous wadsleyite. The dilution of symmetry from orthorhombic to monoclinic in the hydrous wadsleyite structure is interpreted qualitatively due to lack of mirror perpendicular to the a axis in the module. The mode of arrangement of the Mg-vacant structural modules interprets the symmetry and hydrogen content of the hydrous wadsleyite and gives the structural relationship between hydrous wadsleyite and hydrous ringwoodite. Received: 8 May 1998 / Revised, accepted: 3 October 1998  相似文献   

13.
Static lattice energy calculations, based on empirical pair potentials, were performed for a large set of structures differing in the arrangement of octahedral cations within the garnet 2 × 2 × 2 supercell. The compositions of these structures varied between Ca3Fe2Ge3O12 and Ca4Ge4O12. The energies were cluster expanded using pair and quaternary terms. The derived ordering constants were used to constrain Monte Carlo simulations of temperature-dependent mixing properties in the ranges of 1,073–3,673 K and 0–10 GPa. The free energies of mixing were calculated using the method of thermodynamic integration. The calculations predict a wide miscibility gap between Fe-rich (cubic) and Fe-pure (tetragonal) garnets consistent with recent experimental observations of Iezzi et al. (Phys Chem Miner 32:197–207, 2005). It is shown that the miscibility gap arises due to a very strong cation ordering at the Fe-pure composition, driven by the charge difference between Ca2+ and Ge4+ cations. The structural and thermodynamic analogies between Ca–Ge and Mg–Si systems suggest that a similar miscibility gap should exist between pyrope and Mg–Si-majorite.  相似文献   

14.
 The surface structure of the tetrahedral sheet of dioctahedral mica muscovite was compared to that of the tetrahedral sheet of trioctahedral mica phlogopite using atomic force microscopy (AFM). AFM revealed distinct structural differences between the tetrahedral sheet surfaces of the two micas. The hexagonal ring in the AFM image of muscovite elongates in the [3 1 0] direction, and the groove runs perpendicular to the [3 1 0] direction. On the phlogopite surface, the hexagonal ring contracts slightly in the a axis direction, but the groove is not apparent. These results were consistent with the bulk structure data of the two micas determined by X-ray diffraction (XRD). The degree of surface relaxation was much larger in muscovite than in phlogopite. In muscovite, the interlayer K reduces the amount of tetrahedral rotation that actually occurs, since the interlayer K is too large for its hexagonal hole after full tetrahedral rotation. Thus, it is naturally expected that muscovite will show more tetrahedral rotation after removal of the interlayer K. It is also expected that muscovite will show more tilting of SiO4 tetrahedra after cleaving, since an attractive force between the hydrogen in the OH group and the lower basal oxygen should be in operation, due to the decreased distance between them following interlayer K removal. Received: 14 March 2000 / Accepted: 29 July 2000  相似文献   

15.
Numerical simulations, using empirical interatomic potentials within the framework of lattice dynamics and quasi-harmonic approximation, have been carried out to model the behaviour of the structure and of some thermoelastic properties of pyrope at high pressure and high temperature conditions (0–50 GPa, 300–1500 K). Comparison with observed data, available as a function either of P or of T, suggests that the pressure effects are satisfactorily modelled, whilst the effect of T on the simulations is underestimated. The cell edge, bond lengths and polyhedral volumes have been studied as a function of P along five isotherms, spaced by 300 K steps. These isotherms tend to converge at high pressure, which demonstrates that the pressure effects become dominant compared to those of thermal origin in affecting the structural properties far from ambient conditions. The cell parameter, bond distances, and other structural and thermoelastic quantities determined through simulations have been parametrised as a function of P and T by polynomial expansions. Bulk modulus and thermal expansion have been discussed in the light of the high-temperature-Birch-Murnaghan and of the Vinet P – V – T equations of state. The predictions of the bulk modulus versus P and T from the present calculations and from the Vinet-EOS agree up to 10 GPa, but they differ at higher pressure. Received: 23 October, 1998 / Revised, accepted: 23 April, 1999  相似文献   

16.
A quasi-harmonic model has been used to simulate the thermodynamic behaviour of the CaCO3 polymorphs, by equilibrating their crystal structures as a function of temperature so as to balance the sum of inner static and thermal pressures against the applied external pressure. The vibrational frequencies and elastic properties needed have been computed using interatomic potentials based on two-body Born-type functions, with O-C-O angular terms to account for covalency inside the CO3 molecular ion. A good agreement with experimental data is generally shown by simulated heat capacity and entropy, while the thermal expansion coefficient seems to be more difficult to reproduce. The results obtained for aragonite are less satisfactory than those of calcite, but they are improved by using a potential specifically optimized on properties of that phase itself.  相似文献   

17.
Quantum mechanical calculations based on the density functional theory (DFT) are used to study the crystal structures of dioctahedral 2:1 phyllosilicates. The isomorphous cation substitution is investigated by exploring different substitutions of octahedral Al3+ by Mg2+ or Fe3+, tetrahedral substitution of Si4+ by Al3+, and different interlayer cations (IC) (Na+, K+, Ca2+, and Mg2+). Samples with different kinds of layer charges are studied: only tetrahedrally charged, only octahedrally charged, or mixed octahedral/tetrahedral charged. The effect of the relative arrangements of these substitutions on the lattice parameters and total energy is studied. The experimental observation of segregation tendency of Fe3+ and dispersion tendency of Mg2+ in the octahedral sheet is reproduced and explained with reference to the relative energies of the octahedral cation arrangements. These energies are higher than those due to the IC/tetrahedral and IC/octahedral relative arrangements. The tetrahedral and octahedral substitutions that generate charged layers also tend to be dispersed. The octahedral cation exchange potentials change with the IC-charge/ionic radius value.  相似文献   

18.
We present a numerical study of point defects in crystalline zircon (ZrSiO4). Vacancies and interstitials of all the constituents of zircon have been considered. For each defect, the structure and the formation energies have been calculated. Calculations, using the supercell method, are based on the Density Functional Theory in the Local Density Approximation. Empirical potentials have also been considered for comparison with electronic structure results. We find a formation energy for the oxygen interstitial of 1.7 eV. This value is compatible with the experimental activation energy for oxygen diffusion in zircon, which proves an interstitial mechanism for the diffusion of oxygen in zircon. For all other defects the calculated formation energies lead to negligible thermal concentration at equilibrium. Received: 8 January 1999 / Revised, accepted: 14 May 1999  相似文献   

19.
A two-body interatomic potential model for GeO2 polymorphs has been determined to simulate the structure change of them by semi-empirical procedure, total lattice energy minimization of GeO2 polymorphs. Based on this potential, two polymorphs of GeO2; α-quartz-type and rutile-type, have been reproduced using the molecular dynamics (MD) simulation techniques. Crystal structures, bulk moduli, volume thermal expansion coefficients and enthalpies of these polymorphs of GeO2 were simulated. In spite of the simple form of the potential, these simulated structural values, bulk moduli and thermal expansivities are in excellent agreement with the reliable experimental data in respect to both polymorphs. Using this potential, MD simulation was further used to study the structural changes of GeO2 under high pressure. We have investigated the pressure-induced amorphization. As reported in previous experimental studies, quartz-type GeO2 undergoes pressure-induced crystalline-to-amorphous transformation at room temperature, the same as other quartz compounds; SiO2, AlPO4. Under hydrostatic compression, in this study, α-quartz-type GeO2 transformed to a denser amorphous state at 7.4 GPa with change of the packing of oxygen ions and increase of germanium coordination. At higher pressure still, rutile-type GeO2 transformed to a new phase of CaCl2-type structure as a post-rutile candidate. Received: 29 July 1996 / Revised, accepted: 30 April 1997  相似文献   

20.
 The electronic structure of the three polymorphs of Al2SiO5, andalusite, sillimanite, and kyanite, is studied by linearized-augmented-plane-wave (LAPW) calculations using the WIEN code. Total energy calculations verify, in agreement with recent pseudopotential calculations, that andalusite is the most stable phase, followed by sillimanite and kyanite.We determine the electronic charge density distribution and find strong polarizations on all oxygen ions. We identify different polarizations due to Al or Si neighbors which depend on their respective distances to the oxygen atom. The chemical bonding is not purely ionic in nature but has important covalent contributions. Electric field gradients (EFGs) at all sites are calculated and agree well (within 10%) with available experimental data on Al. We identify the origin of the EFGs and demonstrate its relation to the nearest-neighbor coordination and the resulting anisotropy of the electronic charge distribution. Received: 22 March 2000 / Accepted: 3 August 2000  相似文献   

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