Quantum-mechanical modeling of minerals at high pressures. The role of the Hamiltonian in a case study: the beryl (Al4Be6Si12O36)

Ab initio calculations of the beryl structure at room and higher pressures, and of its equation of state, have been performed both at the Hartree–Fock (HF) and density functional (DFT) level. In the latter case, three different hybrid HF/DFT Hamiltonians have been employed, in which the exact non-local exchange contribution increases from 20% (B3LYP Hamiltonian, indicated with the symbol F20) to 50% (F50) and 60% (F60). Within the DFT series, the equilibrium volume (V ₀) increases as the HF exchange contribution decreases; with respect to the experimental datum, F20 overestimates V ₀ by 2.9%, whereas F60 underestimates it by 0.9%; F50 (and HF) volume is very close to the experimental datum (error less than −0.1%). All four Hamiltonians overestimate the bulk modulus (K ₀); with respect to the experimental datum (obtained in the present work) [K ₀=179(1) GPa], the F20 Hamiltonian leads to the smallest error (+2.7%); the corresponding errors for the F50, F60 and HF Hamiltonians are +13.2, +16.2 and +16.3%, respectively. In the case of F20, in spite of the small error in K ₀, the relatively large error in V ₀ leads to an incorrect P(V) equation of state, which significantly overestimates the pressure at a given volume, compared to the experimental one at the same volume; the maximum error in the pressure range investigated is at the largest pressure (P _max=26.4 GPa) and amounts to +34.8%. The corresponding errors for the F50, F60 and HF Hamiltonians are +12.9, +5.7 and +15.5%.     

镓的部分溶解富集-电感耦合等离子体发射光谱法测定高纯氧化铕中非稀土杂质

基于液态金属镓为球形,其表面具有等电位的特性,且利用EθGa3+/Ga(-0.56V)、EθEu3+/Eu(-2.407V)与EθMen+/Me(>-0.56V)之间Eθ的不同,提出一种借助镓的部分溶解富集高纯Eu2O3中标准电位比镓更正的杂质元素(如Cu、Pb、Fe、Co、Ni等)的方法,然后用电感耦合等离子体发射光谱法测定。方法用于实际样品分析,结果与等离子体质谱法相符,6次测定的相对标准偏差为0.4%～3.3%,加标回收实验的回收率为92%～106%。     

Characterization of beryl (aquamarine variety) by Mössbauer spectroscopy

The Mössbauer spectra of several blue beryls have been obtained in the temperature range of 4.2–500 K. A common feature observed in all room-temperature spectra is the presence of an asymmetric Fe²⁺ doublet (ΔE _Q ?～?2.7?mm?s^?1, δ?～?1.1?mm?s^?1), with a very broad low-velocity peak. This asymmetry seems to be related to a relaxation process involving ferrous ions and water molecules in the structural channels, as suggested by Price et?al. (1976). Surprisingly, the spectrum at 500?K also shows a broad, but symmetrical, doublet, with a clear splitting of the lines indicating the presence of at least two Fe²⁺ components. The room-temperature spectrum obtained after the 500?K run shows the same features as prior to the heating. At 4.2?K the spectrum of a deep blue beryl was well fitted with four symmetrical doublets, one of which could be related to Fe²⁺ in the structural channels. Ferrous ion was also found to occupy the octahedral and tetrahedral sites, whereas ferric ion is most probably located in the octahedral site. A meaningful fit of the room-temperature spectrum, as well as an explanation for the temperature dependence of the Mössbauer spectra, are discussed. Finally, it is believed that the color in beryl will be dictated by the relative proportions of Fe³⁺ in the octahedral sites and of Fe²⁺ in the channels.     

Channel constituents in synthetic beryl: ammonium

 The infrared spectra and electron paramagnetic resonance (EPR) of channel constituents in beryls synthesized hydrothermally in the presence of NH₄Cl were investigated. Two forms of ammonium ion were observed to be incorporated into the c -channel. IR-spectra show the double band at 3295 and 3232 cm⁻¹ and two broad bands between 2600 and 3000 cm⁻¹ which were assigned to the NH₃ molecule and NH₄ ⁺ ion, respectively. Similar N–H stretching vibrations are also observed in Regency hydrothermal synthetic beryls and can be used to separate these synthetic beryls from their natural counterparts. After γ-irradiation of hydrothermally grown samples at 77 K, the EPR of the NH₃ ⁺(I) radical was observed. The NH₃ ⁺(II) radical replaces the NH₃ ⁺(I) radical when the sample is heated to room temperature. Both the NH₃ molecule and the NH₃ ⁺ radical have their C₃ symmetry axes perpendicular to the crystal c-axis. The spin Hamiltonian parameters of the NH₃ ⁺(I) are axial-symmetric due to the rapid rotation of the radical about the c-axis. The NH₃ ⁺(II) radical has a low symmetry and shows a hindered rotation because of its shift from the c-axis position and an interaction with the proton in the near neighbourhood. Possible models for the paramagnetic centres are discussed. Received: 16 May 2000 / Accepted: 5 July 2001     

Application of Multi-well Subsidence Analysis of the Beryl Embayment,Viking Graben, Northern North Sea

1 Introduction A series of studies have indicated that there were two extensional phases in the North Sea (Fig. 1). An earlier period (Late Permian-Early Triassic) of rifting occurred widely in these areas, with predominant extension direction of W-E (F?rseth, 1996; F?rseth et al., 1997). In contrast to the widely distributed Permo-Triassic extension, Jurassic extension in the North Sea were generally much more localized into the three main rift arms (Fig. 1): the Viking Graben, Moray…     

X射线荧光滤纸片法测定纯氧化铥中主量氧化铥及相邻稀土氧化物杂质

本文拟定了一种采用滤纸片法制样,X射线荧光直接测定纯氧化铥中氧化铥主量以及氧化钬、氧化铒、氧化镱、氧化镥和氧化钇等稀土杂质含量的分析方法。其测定下限为:Tm_2O_30.11％、Ho_2O_30.20％、Er_2O_3 0.05％、Yb_2O_3 0.20％、Lu_2O_3 0.07％、Y_2O_3 0.40％。方法精度为0.2％～8.0％,对人工合成样品及试样分析结果表明方法准确度良好。方法操作简便快速、试剂耗费少、可用于稀土生产中低纯氧化铥产品的分析。     

感耦等离子体质谱法测定高纯氧化钪中15个痕量稀土杂质的研究

文章报道了用感耦等离子体质谱法测定高纯氧化钪中１５个痕量稀土杂质的研究，考察了测定中的各种干扰和影响因素，选择Ｃｓ为内标元素补颈体抑制效应和灵敏度漂移。各稀土元素的检出限在０．００５－０．０２７ｎｇ／ｍｌ范围，标准加入回收率为９４．５％－１０３．７％，精密度为０．８５％－１．９５％，称取１０ｍｇ样品，酸溶解后可直接测定高纯氧化钪中总量低于２μｇ／ｇ的１５个稀土杂质。     

Influence of annealing conditions on impurity species in arsenic-doped HgCdTe grown by molecular beam epitaxy

Based on our previous work, the influence of annealing conditions on impurity species in in-situ arsenic (As)-doped Hg_1-xCd_xTe (x≈ 0.3) grown by molecular beam epitaxy has been systematically investigated by modulated photoluminescence spectra. The results show that (i) the doped-As acting as undesirable shallow/deep levels in as-grown can be optimized under proper annealing conditions and the physical mechanism of the disadvantage of high activation temperature, commonly assumed to be more favourable for As activation, has been discussed as compared with the reports in the As-implanted HgCdTe epilayers (x≈ 0.39), (ii) the density of V_textrmHg has an evident effect on the determination of bandgap (or composition) of epilayers and the excessive introduction of V_Hg will lead to a short-wavelength shift of epilayers, and (iii) the V_textrmHg prefers forming the V_Hg-As_Hg complex when the inactivated-As (As_Hg or related) coexists in a certain density, which makes it difficult to annihilate V_Hg in As-doped epilayers. As a result, the bandedge electronic structures of epilayers under different conditions have been drawn as a brief guideline for preparing extrinsic p-type epilayers or related devices.     

Light-absorbing impurities on Keqikaer Glacier in western Tien Shan: concentrations and potential impact on albedo reduction

Light-absorbing impurities on glaciers are important factors that influence glacial surface albedo and accelerate glacier melt. In this study, the quantity of light-absorbing impurities on Keqikaer Glacier in western Tien Shan, Central Asia, was measured. We found that the average concentrations of black carbon was 2,180 ng/g, with a range from 250 ng/g to more than 10,000 ng/g. The average concentrations of organic carbon and mineral dust were 1,738 ng/g and 194 μg/g, respectively. Based on simulations performed with the Snow Ice Aerosol Radiative model simulations, black carbon and dust are responsible for approximately 64% and 9%, respectively, of the albedo reduction, and are associated with instantaneous radiative forcing of 323.18 W/m2(ranging from 142.16 to 619.25 W/m2) and 24.05 W/m2(ranging from 0.15 to69.77 W/m2), respectively. For different scenarios, the albedo and radiative forcing effect of black carbon is considerably greater than that of dust. The estimated radiative forcing at Keqikaer Glacier is higher than most similar values estimated by previous studies on the Tibetan Plateau, perhaps as a result of black carbon enrichment by melt scavenging. Light-absorbing impurities deposited on Keqikaer Glacier appear to mainly originate from central Asia, Siberia, western China(including the Taklimakan Desert) and parts of South Asia in summer, and from the Middle East and Central Asia in winter.A footprint analysis indicates that a large fraction(60%) of the black carbon contributions on Keqikaer Glacier comes from anthropogenic sources. These results provide a scientific basis for regional mitigation efforts to reduce black carbon.     

双向晶体旋转仪的研制及其在矿物学研究中的应用

本文介绍了双向晶体旋转仪的原理及研究情况，以及应用它研究金刚石，红宝石处在非立方对称时的杂质氮和铬的实验结果。