The crystal chemistry and Fe<Superscript>II</Superscript>–site properties of aluminosilicate garnet solid solutions as revealed by Mössbauer spectroscopy and electronic structure calculations

The three binary garnet solid solutions Fe^II₃Al₂Si₃O₁₂–X^II₃Al₂Si₃O₁₂ (X^II= Mg^II, Mn^II, Ca^II) have been investigated by ⁵⁷Fe Mössbauer spectroscopy at 298 and 77 K and by electronic structure calculations in the local spin density approximation. The spectra yield isomer shifts and quadrupole splittings that are typical for Fe^II in the dodecahedral X-site of 222 point symmetry and are similar for each of the three binaries recorded. Conversely, electronic structure calculations based on the experimental crystal structure of the different end-member garnets exhibit pronounced variations in some of the electronic properties of Fe^II that are not reflected in the spectroscopic data. These results are interpreted as indicating that the different X–O bonds in garnet solid solutions retain to a large degree the intrinsic lengths that they possess in their respective end members, and that the Fe–O bond does not change greatly as a function of composition. This is evidence for the state of alternating bonds and not for the virtual crystal approximation in describing the X–O bond types or lengths in aluminosilicate garnet solid solutions. The observed degree and behavior of the Fe^II doublet asymmetry in the Mössbauer spectra for the three solid solution series do not indicate major variations in the anisotropic recoil-free fraction of Fe^II. Variations in doublet asymmetry are more likely a result of complex next-nearest X-site neighbor interactions and/or some degree of short-range cation ordering, though doublets representing different local X-site cation configurations cannot be resolved or fitted to the experimental spectra.     

Multipole-refined charge density study of diopside at ambient conditions

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.     

The assemblage diaspore+quartz in metamorphic rocks: a petrological, experimental and thermodynamic study

The upper pressure limit of pyrophyllite is given by the equilibria (i) pyrophyllite=diaspore+quartz and (ii) pyrophyllite=diaspore+coesite. High- P experimental investigations carried out to locate equilibrium (i) yield brackets between 497 °C/24.8  kbar and 535 °C/25.1  kbar, and between 500 °C/23  kbar and 540 °C/23  kbar. Equilibrium (ii) was bracketed at 550 °C between 26.0 and 28.3  kbar. In the experimental P–T  range, equilibria (i) and (ii) are metastable with respect to kyanite. A stable P–T  grid is calculated using thermodynamic data derived under consideration of the present experimental results. According to these data, the lower pressure limit of the assemblage diaspore+quartz according to equilibrium (i) range from about 12  kbar/300 °C to 20  kbar/430 °C (in the presence of pure water). The upper stability of diaspore+quartz is limited by the reaction diaspore+quartz=kyanite+H₂O at about 450 °C (nearly independent of pressure) and, to higher pressure, by the quartz=coesite transition. Equilibrium (ii) is metastable over the whole P–T  range.
Natural occurrences600.S of the diaspore–quartz assemblage in metamorphic rocks in Sulawesi, New Caledonia, Amorgos and the Vanoise are characterized by minerals indicative of high- P such as ferro-magnesiocarpholite, glaucophane, sodic pyroxene and lawsonite. The metamorphic P–T  conditions of these rocks are estimated to be in the range 300–400 °C, >8  kbar. These data are compatible with the derived P–T  stability field of the diaspore+quartz assemblage. We conclude that, in metamorphic rocks, diaspore+quartz is, as ferrocarpholite, an indicator for unusual low- T  /very high- P settings.     

Accurate area determination in the cadaster: case study of Slovenia

This paper discusses methodological problems of accurate area determination in the cadaster. The paper contrasts the ambiguous legal definition of the parcel boundary and parcel area in relation to the theoretically well-defined geodetic parcel boundary and the geodetic parcel area on the reference ellipsoid. To align with the real world, parcel area must account for terrain elevation. Various approximate methods for area determination which can be used in the cadaster are tested. A highly accurate method for parcel area computation is proposed, based on an equal-area projection. Considering the geodetic parcel area as a reference, the achievable accuracy of different methods is evaluated. For this analysis, the coordinates of the parcel boundary points are treated as error-free. Finally, the relevance of various systematic errors is discussed in relation to the statistical uncertainty of the parcel area, which could be gained by an a real-time kinematic GNSS survey. A case study is presented for the territory of Slovenia, its georeferencing rules, land demarcation pattern, and characteristics of its topography. Based on the results of this study, some general recommendations for the parcel area determination are given.     

The generation and evolution of the Archean continental crust: The granitoid story in southeastern Brazil

The Archean Eon was a time of geodynamic changes. Direct evidence of these transitions come from igneous/metaigneous rocks, which dominate cratonic segments worldwide. New data for granitoids from an Archean basement inlier related to the Southern São Francisco Craton (SSFC), are integrated with geochronological, isotopic and geochemical data on Archean granitoids from the SSFC. The rocks are divided into three main geochemical groups with different ages: (1) TTG (3.02–2.77 Ga); (2) medium- to high-K granitoids (2.85–2.72 Ga); and (3) A-type granites (2.7–2.6 Ga). The juvenile to chondritic (Hf-Nd isotopes) TTG were divided into two sub-groups, TTG 1 (low-HREE) and 2 (high-HREE), derived from partial melting of metamafic rocks similar to those from adjacent greenstone belts. The compositional diversity within the TTG is attributed to different pressures during partial melting, supported by a positive correlation of Dy/Yb and Sr/Zr, and batch melting calculations. The proposed TTG sources are geochemically similar to basaltic rocks from modern island-arcs, indicating the presence of subduction processes concomitant with TTG emplacement. From ～2.85 Ga to 2.70 Ga, the dominant rocks were K-rich granitoids. These are modeled as crustal melts of TTG, during regional metamorphism indicative of crustal thickening. Their compositional diversity is linked to: (i) differences in source composition; (ii) distinct melt fractions during partial melting; and (iii) different residual mineralogies reflecting varying P–T conditions. Post-collisional (～2.7–2.6 Ga) A-type granites reflect rifting in that they were closely followed by extension-related dyke swarms, and they are interpreted as differentiation or partial melting products of magmas derived from subduction-modified mantle. The sequence of granitoid emplacement indicates subduction-related magmatism was followed by crustal thickening, regional metamorphism and crustal melting, and post-collisional extension, similar to that seen in younger Wilson Cycles. It is compelling evidence that plate tectonics was active in this segment of Brazil from ～3 Ga.     

Theoretical study of point defects in crystalline zircon

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     

Mössbauer and molecular orbital study of chlorites

The different Fe²⁺ lattice sites in iron-rich chlorites have been characterized by Mössbauer spectroscopy and molecular orbital calculations in local density approximation. The Mössbauer measurements were recorded at 77?K within a small velocity range (±3.5?mm?s^?1) to provide high energy resolution. Additionally, measurements were recorded in a wider velocity range (±10.5?mm?s^?1) at temperatures of 140, 200, and 250?K in an applied field (7?T) parallel to the γ-beam. The zero-field spectra were analyzed with discrete Lorentzian-shaped quadrupole doublets to account for the Fe²⁺ sites M1, M2, and M3 and with a quadrupole distribution for Fe³⁺ sites. Such a procedure is justified by the results obtained from MO calculations, which reveal that different anion (OH^?) distributions in the first coordination sphere of M1, M2, and M3 positions have more influence on the Fe²⁺ quadrupole splitting than cationic disorder. The spectra recorded in applied field were analyzed in the spin-Hamiltonian approximation, yielding a negative sign for the electric field gradient (efg) of Fe²⁺ in the M1, M2, and M3 positions. The results of the MO calculations are in quantitative agreement with experiment and reveal that differences in the quadrupole splittings (ΔE _Q ), their temperature dependence and in the isomer shifts (δ) of Fe²⁺ in M1, M2, and M3 positions can theoretically by justified. Therefore, the combined Mössbauer and MO investigation shows that the three Fe²⁺ lattice sites in the chlorites investigated here can be discriminated according to their ΔE _Q -δ parameter pairs. With the calculated average iron-oxygen bond strength, the MO study provides an explanation for the observed trend that the population of the three lattice sites by Fe²⁺ increases according to the relation M1?相似文献   

Ab initio calculations on the O<Subscript>2</Subscript><Superscript>3−</Superscript>-Y<Superscript>3+</Superscript> center in CaF<Subscript>2</Subscript> and SrF<Subscript>2</Subscript>: its electronic structure and hyperfine constants

The O₂ ^3?-Y³⁺ center in fluorite-type structures (CaF₂ and SrF₂) has been investigated at the density functional theory (DFT) level using the CRYSTAL06 code. Our calculations were performed by means of the hybrid B3PW method in which the Hartree–Fock exchange is mixed with the DFT exchange functional, using Becke’s three parameter method, combined with the non-local correlation functionals by Perdew and Wang. Our calculations confirm the stability and the molecular character of the O₂ ^3?-Y³⁺ center. The unpaired electron is shown to be almost exclusively localized on and equally distributed between the two oxygen atoms that are separated by a bond distance of 2.47 Å in CaF₂ and 2.57 Å in SrF₂. The calculated ¹⁷O and ¹⁹F hyperfine constants for of the O₂ ^3?-Y³⁺ center are in good agreement with their corresponding experimental values reported by previous electron paramagnetic resonance and electron nuclear double resonance studies, while discrepancies are notable for the ⁸⁹Y hyperfine constants.     

Numerical analysis of the response of battered piles to inclined pullout loads

This paper presents a three‐dimensional finite element analysis of the response of battered piles to the combined lateral and vertical pullout loads. Analyses are carried out using an elastoplastic constitutive law based on the non‐associated Mohr–Coulomb criterion. The influence of the contact condition at the pile–soil interface is also investigated. Analyses show that the load's inclination with regard to the pile's axis affects both the lateral and axial response of the battered piles. Analyses also show that the pullout capacity of battered piles is affected by the pile's inclination regarding the vertical axis as well as the load's inclination regarding the pile's axis. The investigation of the influence of the contact condition at the soil–pile interface shows that the possibility of sliding at the soil–pile interface affects the response of battered piles subjected to loads with low inclination regarding the pile's axis. Copyright © 2008 John Wiley & Sons, Ltd.     

掺杂Fe、Cd闪锌矿电子结构的第一性原理计算

采用基于密度泛函理论的第一性原理计算方法,对掺Fe和(或)Cd的闪锌矿型Zn S的电子结构进行了计算。计算结果表明,纯闪锌矿的禁带宽度为2.85 e V;掺Fe浓度为3.125%的闪锌矿禁带宽度为2.58 e V,且Fe的3d和S的3p轨道杂化在禁带中引入了两条杂质能级;随着掺Fe量的增加,杂质能级的宽度和峰高也随之增大;掺Cd闪锌矿的禁带宽度为2.68 e V,并在下价带底引入一条杂质能级;Fe/Cd共掺杂的闪锌矿禁带宽度为2.49 e V,在禁带中出现的两条施主杂质能级可提高闪锌矿的可见光响应及催化能力。计算结果为深入探讨天然闪锌矿的可见光催化机制提供了理论支持。