The energetics and structure of the hydrogarnet defect in grossular: A computer simulation study

We have used computer simulation methods to model the structure and energetics of the hydrogarnet defect in grossular. The predicted structure is in good agreement with experimental data. The calculated energy for the reaction of water with grossular to form the hydrogarnet defect is 1.02 Ev (98 kJ mol^-1). This low energy of reaction suggests that such defects will be common in garnets where they could play an important role in effecting processes such as atomic transport.     

Periodic ab initio Hartree-Fock study of trigonal and orthorhombic phases of boric oxides

The structure and electronic properties of trigonal and orthorhombic boric oxide (B₂O₃) are studied using periodic ab initio Hartree-Fock method. The optimised structural parameters for two B₂O₃ polymorphs are in good agreement with experimental data. The analyses of their electronic structures provide insights into the chemical nature of the B–O bond and the way in which it changes with the coordination number around boron and oxygen. Our quantum-chemical study suggests that the orthorhombic form is more ionic than the trigonal form and that the coordination number of boron around oxygen plays a more dominant role than that of oxygen around boron in B₂O₃ crystals.     

Formation of H2 on an olivine surface: a computational study

The formation of H₂ on a pristine olivine surface [forsterite (010)] is investigated computationally. Calculations show that the forsterite surface catalyzes H₂ formation by providing chemisorption sites for H atoms. The chemisorption route allows for stepwise release of the reaction exothermicity and stronger coupling to the surface, which increases the efficiency of energy dissipation. This suggests that H₂ formed on a pristine olivine surface should be much less rovibrationally excited than H₂ formed on a graphite surface. Gas-phase H atoms impinging on the surface will first physisorb relatively strongly  ( E _phys= 1240 K)  . The H atom can then migrate via desorption and re-adsorption, with a barrier equal to the adsorption energy. The barrier for a physisorbed H atom to become chemisorbed is equal to the physisorption energy, therefore there is almost no gas-phase barrier to chemisorption. An impinging gas-phase H atom can easily chemisorb  ( E _chem= 12 200 K)  , creating a defect where a silicate O atom is protonated and a single electron resides on the surface above the adjacent magnesium ion. This defect directs any subsequent impinging H atoms to chemisorb strongly (39 800 K) on the surface electron site. The two adjacent chemisorbed atoms can subsequently recombine to form H₂ via a barrier (5610 K) that is lower than the chemisorption energy of the second H atom. Alternatively, the adsorbed surface species can react with another incoming H atom to yield H₂ and regenerate the surface electron site. This double chemisorption 'relay mechanism' catalyzes H₂ formation on the olivine surface and is expected to attenuate the rovibrational excitation of H₂ thus formed.     

Crystal morphology and surface structures of orthorhombic MgSiO3 perovskite

Orthorhombic MgSiO₃ perovskite is thought to be the most abundant mineral in the mantle of the Earth. Its bulk properties have been widely studied, but many geophysical and rheological processes are also likely to depend upon its surface and grain boundary properties. As a first step towards modelling these geophysical properties, we present here an investigation of the structures and energetics of the surfaces of MgSiO₃-perovskite, employing both shell-model atomistic effective-potential simulations, and density-functional-theory (DFT) calculations. Our shell-model calculations predict the {001} surfaces to be the energetically most stable surfaces: the calculated value of the surface energy being 2.2 J/m² for the MgO-terminated surface, which is favoured over the SiO₂-terminated surface (2.7 J/m²). Also for the polar surfaces {111}, {101} and {011} the MgO-terminated surfaces are energetically more stable than the Si-terminated surfaces. In addition we report the predicted morphology of the MgSiO₃ perovskite structure, which is dominated by the energetically most stable {001} and {110} surfaces, and which appears to agree well with the shape of grown single crystals.     

An ab-initio Hartree-Fock study of α-quartz and stishovite

-quartz and stishovite have been studied using a periodic ab-initio Hartree-Fock method in order to characterize the chemical nature of the Si-O bond and the way in which it changes with the coordination number of Si. Structural properties, including unit cell volume and c/a ratio have been optimized in order to evaluate the reliability of the method and the effect of the basis set. Density of states and electron charge density maps have been taken into account to investigate the electronic properties of the two systems and the rôle played by different orbitals. We also present comparisons with experimental X-ray emission data. The importance of d orbitals is stressed by our calculations, and a possible interpretation of the Si-O bond proposed. Quartz is found to be more covalent than stishovite.     

Calculations on the energetics of water dissolution in wadsleyite

Physics and Chemistry of Minerals - Computer simulation techniques are used to investigate the energetics and mechanisms of dissolution of water in the upper mantle mineral wadsleyite (β(Mg,...     

数字河流数据的组织和制图综合

本文概略地介绍了通过使数据合理化和溪流顺序排列的软件的研制,把某些结构引入TIS已拥有的河流数据里所进行的工作。这项工作不仅施惠于水文学和地理学,而且可用于制图。它便于根据重新组织过的数据在逻辑上的联结,借助计算机生产各种比例尺的制图综合过的地图。综合样图以英格兰西南部的水系加以说明。     

A computer simulation study of (OH) defects in olivine

Recent experiments (Miller et al. 1987; Bell and Rossman 1992; Bai and Kohlstedt 1992) have shown that olivine, the dominant mineral in the Earth's upper mantle, can contain substantial amounts of water in the form of OH. There is uncertainty, however, as to the mechanisms by which water dissolves into the mineral structure and as to the site it occupies in the host lattice. We have therefore used atomistic computer simulation techniques based on the Born model of solids, to investigate the structures and energies of OH defects in olivine. Our calculations suggest that the most favourable route for incorporation of OH into olivine involves reactions with water accompanied by the reduction of ferric iron for which we obtain a solution energy of 0.46 eV. We propose therefore that the OH content will be largely controlled by the concentration of Fe³⁺.     

Silica grain catalysis of methanol formation

The specific catalytic effect of a silica grain on the formation of methanol via the sequential addition of H atoms to CO adsorbed on the surface is investigated. A negatively charged defect on a siliceous edingtonite surface is found to reduce the gas phase barriers for the H + CO_ads and H + H₂C=O_ads reactions by 770 and 399 K, respectively, when compared to the same reactions in the gas phase. The catalytic effect of negatively charged surface sites could also be applicable to the hydrogenation of other adsorbed unsaturated species. However, the activation energies on the surface defect are still too large (1150 and 2230 K) for CH₃OH to form efficiently at 10–20 K in the interstellar medium via a classical mechanism. It is therefore suggested that quantum mechanical tunnelling through the activation barrier is required for these hydrogen addition reactions to proceed at such temperatures. The calculations show that because the adsorption energies of CO and H₂C=O on the negatively charged defect are substantial, CH₃OH may form efficiently during the warm-up period in star-forming regions.     

Ab initio potentials for the calculation of the dynamical and elastic properties of α-quartz

Ab initio LDF theory has been used to derive interatomic potentials for the Si-O and O-O interaction in α-quartz. The potentials have been used to study the lattice dynamical properties of α-quartz from 1 atm to 12.5 Gpa pressure. The results are compared with other calculated and experimentally derived potentials.