氢在金刚石结构中的自陷模型

氢在金刚石结构中是自陷的。可以稳定存在的自陷形式有成键氢、反键心氢、键心氢及四面体空隙氢四种模型，而且氢在其中的相对稳定程度依上述顺序渐次递减。     

金刚石中氢的研究及其意义

含氢对于天然与高温高压合成金刚石体内而言是固有的，但是对CVD金刚石来说并非固有。氢可以稳定存在于晶格位、键心、反键心及四面体空隙等金刚石的结构属性中，也可以存在于显微流体包裹体中。即便是在 1473K下淬火，氢在金刚石中也并不发生迁移或扩散，表明氢在金刚石结构中是自陷的。金刚石中的氢的研究对于地幔矿物学及材料科学等均有重要理论意义和实际意义。     

氢——地球深部流体的重要源泉

介绍了近年来金刚石包裹体中流体研究结果，特别是分子氢和羟基的发现。基于地幔中氢的发现，论证了氢在地球内部的赋存形式。地核和地幔中有氢化物存在得到高压低温实验、地球物理和天文物理测定的支持。从而提出，氢是地幔羽中的原始热物质。核幔边界或地幔中氢化物释放出的氢，发生化学反应，形成地幔流体，推动地球演化。地幔羽应称为氢羽。     

天然金刚石结构中氢的赋存状态

利用振动光谱（IR、RAMAM）研究金刚石结构中的含氢物相，发现金刚石结构中存在晶格氢和间隙氢两种。其中HF的存在为首次提出。同时不同的含氢物相在金刚石结构中的赋存状态不尽相同。     

金刚石中的成键氢

金刚石中杂质相的研究一直倍受关注,但大多集中在B、N两种杂质的研究上,而对于氢在其中的赋存状态研究则刚刚开始。从振动谱学（IR、Raman）的角度对氢在金刚石中的一种赋存状态--成键氢进行的研究表明,成键氢在金刚石中可以以碳氢键、H2及 O-H键的形式存在。     

明溪蓝刚玉的水热溶液改色实验初步研究

明溪蓝刚中Fe主要以Fe^3 形式存在，Fe^3 的d-d电子跃迁和Fe^2 -Ti^4 /Fe^3 -Ti^3 、O^2-Fe^3 间电荷转移是致色的主要因素；浓度差可以作为扩散动力；氢含量的提高可以促进蓝色致因子的形成。采用高温高压水溶液方法对蓝刚玉进行改色处理，可消除刚玉中的杂色调，使颜色向纯蓝色方向变化。     

金刚石中分子氢的赋存状态研究

金刚石中分子氢的定向红外光谱研究表明在垂直于(100),(110)和(111)三个方向上所测得分子氢的浓度是不相同的,且不同样品中的变化趋势也不同,即分子氢在金刚石中的定向性不明显;MNDO法计算结果显示分子氢在金刚石中的稳定程度大小关系依次为沿〈111〉定向的键心与反键心组合(a.b+b.c)〉六角体空隙(H)〉四面体空隙(T1)〉菱形中心(C1＝C2)〉四面体空隙(T2).     

氢的地球化学——幔汁氢化迁移律

氢乃是自然界中最小、最轻、迁移最快、反应能最强的气相元素。笔者(1989)曾经提出,氢主要储存于外地核液态铁之中[1],其在巨大的压力梯度、温度梯度、质量梯度及黏度梯度中自发向上、强力喷射,构成了最伟大的地球内动因。本文系统探讨了氢的种种地球化学特性,特别是氢流对地球深部物质成分氢化迁移的特殊功能。     

金刚石中的氢及其在金刚石高温高压合成中的意义

氢在金刚石中往往以一定的化学态形式存在,不同类型的金刚石中氢会以不同的电荷状态进行迁移与扩散,也可以与其他杂质元素N、B、P等作用,形成(N,H)、(B,H)、(P,H)对;为高温高压合成金刚石的物质体系中引入氢,有利于提高高温高压合成金刚石的产量、粒度及品级,也将为模拟天然金刚石的形成与探讨地球深部的动力学过程提供科学线索。     

德清序村萤石矿的同位素研究

本文公布序村萤石矿的氢和锶同位素分析结果.讨论了成矿溶液和成矿物质Sr、Ba、Ca的来源,指出成矿溶液中存在有HF和SiF_4.     

Ab initio quantum chemical investigation of arsenic sulfide molecular diversity from As4S6 and As4

The structural diversity of arsenic sulfide molecules in compositions between As₄S₆ and As₄ was investigated using ab initio quantum chemical calculations. The As₄S₆ molecule consists of four trigonal pyramid coordinations of As atoms bonding to three S atoms. In the As₄S₅ composition, only one type of molecular configuration corresponds to an uzonite-type molecule. In the As₄S₄ composition, two molecular configurations exist with realgar-type and pararealgar-type molecules. Three molecular configurations are in the As₄S₃ composition. The first configuration comprises trigonal pyramidal As atom coordinations of two types: bonding to two S atoms and one As atom, and bonding to one S atom and two As atoms. The second is the molecular configuration of dimorphite. The third comprises trigonal pyramidal As atom coordinations of two types: bonding to three As atoms, and bonding to one As atom and two S atoms. The As₄S₂ composition allows molecular configurations of two types. One is comprised of trigonal pyramidal As atom configurations of one type bonding to two As atoms and one S atom. The other comprises trigonal pyramidal As atom coordinations of three types: bonding to two S atoms and one As atoms, bonding to one S atom and two As atoms, and bonding to three As atoms. The As₄S molecule has trigonal pyramidal As atom coordinations of two types: bonding to one S atom and two As atoms, and bonding to three As atoms. The As₄S composition permits only one molecular configuration, which suggests that the mineral duranusite comprises the As₄S molecular geometry. In all, ten molecular configurations are predicted in the molecular hierarchy of the arsenic sulfide binary system. The simulated Raman spectral profiles are helpful in searching for undiscovered arsenic sulfide minerals.     

A modeling of the structure and favorable H-docking sites and defects for the high-pressure silica polymorph stishovite

Employing first-principles methods, the docking sites for H were determined and H, Al, and vacancy defects were modeled with an infinite periodic array of super unit cells each consisting of 27 contiguous symmetry nonequivalent unit cells of the crystal structure of stishovite. A geometry optimization of the super-cell structure reproduces the observed bulk structure within the experimental error when P1 translational symmetry was assumed and an array of infinite extent was generated. A mapping of the valence electrons for the structure displays mushroom-shaped isosurfaces on the O atom, one on each side of the plane of the OSi₃ triangle in the nonbonded region. An H atom, placed in a cell near the center of the super cell, was found to dock upon geometry optimization at a distance of 1.69 Å from the O atom with the OH vector oriented nearly perpendicular to the plane of the triangle such that the OH vector makes a angle of 91° with respect to [001]. However, an optimization of a super cell with an Al atom replacing Si and an H atom placed nearby in a centrally located cell resulted in an OH distance of 1.02 Å with the OH vector oriented perpendicular to [001] as observed in infrared studies. The geometry-optimized position of the H atom was found to be in close agreement with that (0.44, 0.12, 0.0) determined in an earlier study of the theoretical electron density distribution. The docking of the H atom at this site was found to be 330 kJ mol^–1 more stable than a docking of the atom just off the shared OO edge of the octahedra as determined for rutile. A geometry optimization of a super cell with a missing Si generated a vacant octahedra that is 20% larger than that of the SiO₆ octahedra. The valence electron density distribution displayed by the two-coordinate O atoms that coordinate the vacant octahedral site is very similar to those displayed by the bent SiOSi angles in coesite. The internal distortions induced by the defect were found to diminish rather rapidly with distance, with the structure annealing to that observed in the bulk crystal to within about three coordination spheres.     

Atomic ordering around the oxygen vacancies in sillimanite

Computer simulation is used to investigate the short range ordering around an isolated oxygen vacancy in sillimanite. The static lattice energy with the use of empirical potentials is calculated, for different Al/Si distributions around a vacancy in a supercell of sillimanite. A parametrisation of the total energy is built up and used to deduce the best Al/Si ordering around the oxygen vacancy. It is found that a strong ordering about the vacancy occurs. In the ab-plane two sets of aluminium cluster are found besides the vacancy, surrounded above and below by silicon atoms, a configuration that promotes local charge balance. By placing two vacancies on sites directly adjacent to the same oxygen, the central oxygen site is bonded to four cations: this situation is found to be energetically unfavourable.     

Hydrogen Incorporation in Crystalline Jadeite: Insight from First Principles Calculations

Hydrogen incorporation is critical for explaining defect energies, structure parameters and other physical characteristics of minerals and understanding mantle dynamics. This work analyzed the hydrogen complex defects in jadeite by the plane-wave pseudo-potential method based on density functional theory, and optimized the atomic positions and lattice constants in all configurations(different defective systems). Incorporation mechanisms considered for hydrogen(H) in jadeite include:(1) hydrogen incorporating with the O2 site oxygen and coexisting with M2 vacancy;(2) one H atom combined with an Al atom replacing Si in tetrahedron;(3) 4H atoms directly replacing Si in tetrahedron and(4) 3H atoms replacing Al on the M1 site. The four incorporation mechanisms mentioned above form the corresponding V_(Na)-H_i, Al_(Si)-H_i, V_(Si)-4H_i and V_(Al)-3H_i point defects. The molecular dynamics simulation to the ideal, V_(Na)-H_i, Al_(Si)-H_i, V_(Si)-4H_i and V_(Al)-3H_i point defects under the P-T conditions of 900 K, 2 GPa, the V_(Na)-H_i and Al_(Si)-H_i point defects under different pressures at T = 900 K, and Al_(Si)-H_i point defects under different temperatures at P = 3 GPa was performed to examine the preferential mode of hydrogen incorporation in jadeite by means of first-principles calculations. The calculations show that the averaged O–H bond-length in the hydrogen point defects system decreased in the order of Al_(Si)-H_i, V_(Na)-H_i, V_(Si)-4H_i and V_(Al)-3H_i. V_(Na)-H_i complex defects result in a contraction of the jadeite volume and the presence of Al_(Si)-H_i, V_(Si)-4H_i and V_(Al)-3H_i defects could increase the supercell volume, which is the most obvious in the V_(Al)-3H_i defects. The energy of formation of Al_(Si)-H_i and V_(Al)-3H_i complex defects was much lower than that of other defect systems. The V_(Al)-3H_i defects system has the lowest energy and the shortest O–H bond-length, suggesting that this system is the most favorable. The analytical results of vacancy formation energy, O–H bondlength, and the stability of the hydrogen defects in jadeite have suggested that the preferred hydration incorporation mode in jadeite is V_(Al)-3H_i complex defect.     

Pyrite oxidation: a state-of-the-art assessment of the reaction mechanism

The oxidation of pyrite to release ferrous iron and sulfate ions to solution involves the transfer of seven electrons from each sulfur atom in the mineral to an aqueous oxidant. Because only one or, at most, two electrons can be transferred at a time, the overall oxidation process is quite complex. Furthermore, pyrite is a semiconductor, so the electrons are transferred from sulfur atoms at an anodic site, where oxygen atoms from water molecules attach to the sulfur atoms to form sulfoxy species, through the crystal to cathodic Fe(II) sites, where they are acquired by the oxidant species. The reaction at the cathodic sites is the rate-determining step for the overall process. This paper maps out the most important steps in this overall process.     

Radiation induced lattice defects in natural zircon (ZrSiO4) observed at atomic resolution

Fission tracks and point defects in natural zircon are directly observed by a 1 MV electron microscope at atomic resolution for three types of samples adjusted to the 100 orientation. Lattice planes intersecting the fission tracks at high angles are distorted in a rather irregular manner over a wide region up to more than 100 Å wide. Diameter of the tracks, ranging from 25 Å to 40Å, is much narrower than those so far reported for the U-doped synthetic zircon (100–200 Å), UO₂ thin film (100 Å), mica (66 Å, 240 Å) or fluorophlogopite (150 Å). The fact that fairly long tracks thousands of angstroms in length are observed in thin 100-oriented sample hundreds of angstroms in thickness and that some of them are nearly parallel to a low index lattice plane suggest a possible occurrence of channelling in the process of track formation. Parallel tracks often observed in chemically etched specimens support the idea of channelling. Slightly bent tracks are sometimes observed. It is concluded from computer simulation that many contrast anomalies of bright and dark spots in the lattice image are due to point defects of vacancies and interstitial atoms, mainly produced by the direct atomic collision with α-particles or by passage of ionizing nuclear particles. Optimum conditions of the observation of point defects with highest contrast are studied. One interstitial Zr atom or one Zr ion vacancy will give very low contrast and will be not detectable unless the crystal is less than two unit cells thick. A pair of Zr ion vacancies, however, yields extended detectable limit of thickness. Some of the observed defects are in good accordance with those simulated.     

A comment on diffusion and the displacement of atoms in metamorphic transformations

Experimental data on diffusion in olivine , are used to define certain terms – diffusion coefficient, jump frequency, characteristic distance, random walk – that are useful in a discussion of atom displacements under natural conditions. Examples of atom displacements in two metamorphic terranes of the Canadian Precambrian Shield are then examined, as follows. (i) In a high‐grade metamorphic terrane in the Mid‐Proterozoic Grenville Province (Otter Lake Area), Mg concentration gradients about dolomite microcrystals in calcite and Na gradients about albite microcrystals in K‐feldspar are viewed as stranded Mg–Ca and Na–K interdiffusion gradients, formed by exsolution during slow cooling from ~700 to ~400 °C. (ii) In the Archean Slave Province (Yellowknife area), the crystallization of sillimanite, near andalusite but within crystals of quartz, possibly occurred by coupled Al–Si and oxygen–vacancy interdiffusion in quartz at ~550 °C. And the crystallization of garnet from chlorite occurred by the two‐way crystal‐boundary diffusion of several kinds of atoms across distances ranging to 3 mm. (iii) In the Otter Lake area, the crystallization of orthopyroxene–hornblende–spinel reaction zones at boundaries between crystals of olivine and plagioclase in metagabbro, evidently occurred by the mechanism of interstitial diffusion, that transported Mg, Fe, Mn and O atoms across the reaction zone from olivine to the plagioclase–(hornblende+spinel) boundary, and Si, Al, Ca and Na atoms from plagioclase to the olivine–orthopyroxene boundary, accompanied by NaSi–CaAl interdiffusion in plagioclase, and the addition of hydrogen and minor Ti, Zn, F, Cl and K from beyond the reaction zone. Also, centimetric reaction zones, with abundant biotite and plagioclase, at boundaries between K‐feldspar gneiss and deformed amphibolite dykes, evidently formed by the reaction, strained hornblende (in amphibolite) + K‐feldspar (in gneiss)→biotite (in amphibolite) + plagioclase (in gneiss), with crystal‐boundary diffusion of (Na + Ca) atoms and of K atoms across the reaction zone.