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  • Springer  (14)
  • Mineralogical Association of Canada  (9)
  • American Association for the Advancement of Science  (4)
  • 1
    Digitale Medien
    Digitale Medien
    Springer
    Physics and chemistry of minerals 20 (1994), S. 617-624 
    ISSN: 1432-2021
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie , Geologie und Paläontologie , Physik
    Notizen: Abstract Molecular orbital calculations completed on fluoride molecules containing first and second row cations have generated bond lengths, R, that match those observed for coordinated polyhedra in crystals to within ∼0.04 Å, on average. The calculated bond lengths and those observed for fluoride crystals can be ranked with the expression R=Kp −0.22, where p=s/r, s is the Pauling strength of the bond, r is the row number of the cation and K=1.34. The exponent -0.22 (≈ -2/9) is the same as that observed for oxide, nitride and sulfide molecules and crystals. Bonded radii for the fluoride anion, obtained from theoretical electron density maps, increase linearly with bond length. Those calculated for the cations as well as for the fluoride anion match calculated promolecule radii to within ∼0.03 Å, on average, suggesting that the electron density distributions in the vicinity of the minima along the bond paths possess a significant atomic component despite bond type. Bonded radii for Si and O ions provided by experimental electron density maps measured for the oxides coesite, danburite and stishovite match those calculated for a series of monosilicic acid molecules. The resulting radii increase with bond length and coordination number with the radius of the oxide ion increasing at a faster rate than that of the Si cation. The oxide ion within danburite exhibits several distinct radii, ranging between 0.9 and 1.2 Å, rather than a single radius with each exhibiting a different radius along each of the nonequivalent bonds with B, Si and Ca. Promolecule radii calculated for the coordinated polyhedra in danburite match procrystal radii obtained in a structure analysis to within 0.002 Å. The close agreement between these two sets of radii and experimentally determined bonded radii lends credence to Slater's statement that the difference between the electron density distribution observed for a crystal and that calculated for a procrystal (IAM) model of the crystal “would be small and subtle, and very hard to determine by examination of the total charge density.”
    Materialart: Digitale Medien
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  • 2
    Digitale Medien
    Digitale Medien
    Springer
    Physics and chemistry of minerals 27 (2000), S. 467-473 
    ISSN: 1432-2021
    Schlagwort(e): Key words Witherite ; High pressure ; Aragonite ; Crystal structure
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie , Geologie und Paläontologie , Physik
    Notizen: Abstract Natural witherite (Ba0.99Sr0.01CO3) has been studied by single-crystal X-ray diffraction in the diamond anvil cell at eight pressures up to 8 GPa. At ambient pressure, cell dimensions are a = 5.3164(12) Å, b = 8.8921(19) Å, c = 6.4279(16) Å, and the structure was refined in space group Pmcn to R(F) = 0.020 from 2972 intensity data. The unit cell and atom position parameters for the orthorhombic cell were refined at pressures of 1.2, 2.0, 2.9, 3.9, 4.6, 5.5, 6.2, and 7.0 GPa. The volume-pressure data are used to calculate equation of state parameters K T0 = 50.4(12) GPa and K′ = 1.9(4). At approximately 7.2 GPa, a first-order transformation to space group P3¯1c was observed. Cell dimensions of the high-pressure phase at 7.2 GPa are a = 5.258(6) Å, c = 5.64(1) Å. The high pressure structure was determined and refined to R(F) = 0.06 using 83 intensity data, of which 15 were unique. This high-pressure phase appears to be more compressible than the orthorhombic phase with an estimated initial bulk modulus (K 7.2GPa) of 10 GPa.
    Materialart: Digitale Medien
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  • 3
    Digitale Medien
    Digitale Medien
    Springer
    Physics and chemistry of minerals 21 (1994), S. 344-349 
    ISSN: 1432-2021
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie , Geologie und Paläontologie , Physik
    Notizen: Abstract Relative compressibilities of five silicate garnets were determined by single-crystal x-ray diffraction on crystals grouped in the same high-pressure mount. The specimens include a natural pyrope [(Mg2.84Fe0.10Ca0,06) Al2Si3O12], and four synthetic specimens with octahedrally-coordinated silicon: majorite [Mg3(MgSi)Si3O12], calcium-bearing majorite [(Ca0.49Mg2.51)(MgSi)Si3012], sodium majorite [(Na1.88Mgp0.12)(Mg0.06Si1.94)Si3O12], and an intermediate composition [(Na0.37Mg2.48)(Mg0.13Al1.07 Si080) Si3O12]. Small differences in the compressibilities of these crystals are revealed because they are subjected simultaneously to the same pressure. Bulk-moduli of the garnets range from 164.8 ± 2.3 GPa for calcium majorite to 191.5 ± 2.5 GPa for sodium majorite, assuming K′=4. Two factors, molar volume and octahedral cation valence, appear to control garnet compression.
    Materialart: Digitale Medien
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  • 4
    ISSN: 1432-2021
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie , Geologie und Paläontologie , Physik
    Notizen: Abstract  The topological properties of the electron density distributions for more than 20 hydroxyacid, geometry optimized molecules with SiO and GeO bonds with 3-, 4-, 6- and 8-coordinate Si and Ge cations were calculated. Electronegativities calculated with the bond critical point (bcp) properties of the distributions indicate, for a given coordination number, that the electronegativity of Ge (∼1.85) is slightly larger than that of Si (∼1.80) with the electronegativities of both atoms increasing with decreasing bond length. With an increase in the electron density, the curvatures and the Laplacian of the electron density at the critical point of each bond increase with decreasing bond length. The covalent character of the bonds are assessed, using bond critical point properties and electronegativity values calculated from the electron density distributions. A mapping of the (3, −3) critical points of the valence shell concentrations of the oxide anions for bridging SiOSi and GeOGe dimers reveals a location and disposition of localized nonbonding electron pairs that is consistent with the bridging angles observed for silicates and germanates. The bcp properties of electron density distributions of the SiO bonds calculated for representative molecular models of the coesite structure agree with average values obtained in X-ray diffraction studies of coesite and danburite to within ∼5%.
    Materialart: Digitale Medien
    Standort Signatur Erwartet Verfügbarkeit
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  • 5
    Digitale Medien
    Digitale Medien
    Springer
    Physics and chemistry of minerals 25 (1997), S. 39-47 
    ISSN: 1432-2021
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie , Geologie und Paläontologie , Physik
    Notizen: Abstract  The unit-cell dimensions and crystal structure of sillimanite at various pressures up to 5.29 GPa have been refined from single-crystal X-ray diffraction data. As pressure increases, a and b decrease linearly, whereas c decreases nonlinearly with a slightly positive curvature. The axial compression ratios at room pressure are βa:βb:βc=1.22:1.63:1.00. Sillimanite exhibits the least compressibility along c, but the least thermal expansivity along a (Skinner et al. 1961; Winter and Ghose 1979). The bulk modulus of sillimanite is 171(1) GPa with K′=4 (3), larger than that of andalusite (151 GPa), but smaller than that of kyanite (193 GPa). The bulk moduli of the [Al1O6], [Al2O4], and [SiO4] polyhedra are 162(8), 269(33), and 367(89) GPa, respectively. Comparison of high-pressure data for Al2SiO5 polymorphs reveals that the [SiO4] tetrahedra are the most rigid units in all these polymorphic structures, whereas the [AlO6] octahedra are most compressible. Furthermore, [AlO6] octahedral compressibilities decrease from kyanite to sillimanite, to andalusite, the same order as their bulk moduli, suggesting that [AlO6] octahedra control the compression of the Al2SiO5 polymorphs. The compression of the [Al1O6] octahedron in sillimanite is anisotropic with the longest Al1-OD bond shortening by ∼1.9% between room pressure and 5.29 GPa and the shortest Al1-OB bond by only 0.3%. The compression anisotropy of sillimanite is primarily a consequence of its topological anisotropy, coupled with the compression anisotropy of the Al-O bonds within the [Al1O6] octahedron.
    Materialart: Digitale Medien
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  • 6
    Digitale Medien
    Digitale Medien
    Springer
    Physics and chemistry of minerals 25 (1998), S. 585-590 
    ISSN: 1432-2021
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie , Geologie und Paläontologie , Physik
    Notizen: Abstract  The strength of a bond, defined as p=s/r, where s is the Pauling bond strength and r is the row number of an M cation bonded to an oxide anion, is related to a build-up of electron density along the MO bonds in a relatively large number of oxide and hydroxyacid molecules, three oxide minerals and three molecular crystals. As p increases, the value of the electron density is observed to increase at the bond critical points with the lengths of the bonds shortening and the electronegativities of the M cations bonded to the oxide anion increasing. The assertion that the covalency of a bond is intrinsically connected to its bond strength is supported by the electron density distribution and its bond critical point properties. A connection also exists between the properties of the electron density distributions and the connectivity of the bond strength network formed by the bonded atoms of a structure.
    Materialart: Digitale Medien
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  • 7
    Publikationsdatum: 2015-10-17
    Beschreibung: Four factors contribute to the roles played by chance and necessity in determining mineral distribution and diversity at or near the surfaces of terrestrial planets: (1) crystal chemical characteristics; (2) mineral stability ranges; (3) the probability of occurrence for rare minerals; and (4) stellar and planetary stoichiometries in extrasolar systems. The most abundant elements generally have the largest numbers of mineral species, as modeled by relationships for Earth's upper continental crust (E) and the Moon (M), respectively: Log(NE)=0.22 Log(CE)+1.70(R2=0.34)(4861 minerals,72 elements) Log(NM)=0.19 Log(CM)+0.23(R2=0.68)(63 minerals,24 elements), where C is an element's abundance in ppm and N is the number of mineral species in which that element is essential. Several elements that plot significantly below the trend for Earth's upper continental crust ( e.g. , Ga, Hf, and Rb) mimic other more abundant elements and thus are less likely to form their own species. Other elements ( e.g ., Ag, As, Cu, Pb, S, and U) plot significantly above the trend, which we attribute to their unique crystal chemical affinities, multiple coordination and oxidation states, their extreme concentration in some ore-forming fluids, and/or frequent occurrence with a variety of other rare elements—all factors that increase the diversity of mineral species incorporating these elements. The corresponding diagram for the Moon shows a tighter fit, most likely because none of these elements, except Cu and S, are essential constituents in lunar minerals. Given the similar slopes for Earth and the Moon, we suggest that the increase in mineral diversity with element abundance is a deterministic aspect of planetary mineral diversity. Though based on a limited number of collecting sites, the Moon's observed mineralogical diversity could be close to the minimum for a rocky planet or moon comparable in size—a baseline against which diversity of other terrestrial planets and moons having radii in the same range as Earth and its Moon can be measured. Mineral-forming processes on the Moon are limited to igneous activity, meteor impacts, and the solar wind—processes that could affect any planet or moon. By contrast, other terrestrial planets and moons have been subjected to more varied physical, chemical, and (in the case of Earth) biological processes that can increase mineral diversity in both deterministic and stochastic ways. Total mineral diversity for different elements is not appreciably influenced by the relative stabilities of individual phases, e.g. , the broad pressure-temperature-composition stability ranges of cinnabar (HgS) and zircon (ZrSiO 4 ) do not significantly diminish the diversity of Hg or Zr minerals. Moreover, the significant expansion of near-surface redox conditions on Earth through the evolution of microbial oxygenic photosynthesis tripled the available composition space of Earth's near-surface environment, and resulted in a corresponding tripling of mineral diversity subsequent to atmospheric oxidation. Of 4933 approved mineral species, 34% are known from only one or two localities, and more than half are known from five or fewer localities. Statistical analysis of this frequency distribution suggests that thousands of other plausible rare mineral species await discovery or could have occurred at some point in Earth's history, only to be subsequently lost by burial, erosion, or subduction— i.e. , much of Earth's mineral diversity associated with rare species results from stochastic processes. Measurements of stellar stoichiometry reveal that stars can differ significantly from the Sun in relative abundances of rock-forming elements, which implies that bulk compositions of some extrasolar Earth-like planets likely differ significantly from those of Earth, particularly if the fractionation processes in evolving stellar nebulas and planetary differentiation are factored in. Comparison of Earth's upper continental crust and the Moon shows that differences in element ratios are reflected in ratios of mineral species containing these elements. In summary, although deterministic factors control the distribution of the most common rock-forming minerals in Earth's upper continental crust and on the Moon, stochastic processes play a significant role in the diversity of less common minerals. Were Earth's history to be replayed, and thousands of mineral species discovered and characterized anew, it is probable that many of those minerals would differ from species known today.
    Print ISSN: 0008-4476
    Thema: Geologie und Paläontologie
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  • 8
    Publikationsdatum: 2017-06-27
    Beschreibung: A new mineral, petersite-(Ce), ideally Cu 2+ 6 Ce(PO 4 ) 3 (OH) 6 ·3H 2 O (IMA2014-002), has been found in the Cherry Creek District of Yavapai County, Arizona, USA. It is a secondary alteration mineral associated with malachite, chlorite, a biotite phase, quartz, albite, orthoclase, hematite, chalcopyrite, and an uncharacterized hisingerite-like mineral. Petersite-(Ce) occurs as sprays of yellowish-green, acicular crystals approximately 20 x 20 x 50 μm in size. It has a white streak with vitreous luster. The mineral is brittle and has a Mohs hardness of ~3.5; no cleavage or parting was observed. The calculated density is 3.424 g/cm 3 . An electron microprobe analysis resulted in an empirical chemical formula of Cu 6.05 (Ce 0.18 Y 0.16 La 0.12 Nd 0.09 Gd 0.03 Pr 0.02 Dy 0.01 Sm 0.01 Ca 0.42 ) 1.04 [(PO 4 ) 2.54 (SiO 4 ) 0.14 (PO 3 OH) 0.32 (OH) 6 ]·3.65H 2 O. Petersite-(Ce) is hexagonal, with space group P 6 3 / m and unit-cell parameters a 13.2197(18) Å, c 5.8591(9) Å, and V 886.8(4) Å 3 , Z = 2. It is the Ce analogue of petersite-(Y) and exhibits the mixite structure type. The mixite group can be expressed by the general formula Cu 2+ 6 A ( T O 4 ) 3 (OH) 6 · 3H 2 O, where nine-coordinated A is a rare earth element, Al, Ca, Pb, or Bi, and T is P or As. The structure of petersite-(Ce) is characterized by chains of edge-sharing CuO 5 square-pyramids along c . These chains are connected in the a-b plane by edge-sharing CeO 9 polyhedra and corner-sharing PO 4 tetrahedra. Hydroxyl groups occupy each corner of the CuO 5 polyhedra not shared by a neighboring P or Ce atom. Each CeO 9 polyhedron is surrounded by three zeolitic channels. The walls of the channels, parallel to c , are six-membered, hexagonal rings composed of CuO 5 and PO 4 polyhedra in a ratio of 2:1, respectively, and contain H 2 O molecules. In our model of petersite-(Ce), we defined one distinct H 2 O site positioned to form a ring inside the channel, although there are many statistically possible locations.
    Print ISSN: 0008-4476
    Thema: Geologie und Paläontologie
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  • 9
    Publikationsdatum: 2017-04-06
    Beschreibung: A new mineral species, raygrantite, ideally Pb 10 Zn(SO 4 ) 6 (SiO 4 ) 2 (OH) 2 , has been found in the Big Horn Mountains, Maricopa County, Arizona, USA. Associated minerals are galena, anglesite, cerussite, lanarkite, leadhillite, mattheddleite, alamosite, hydrocerussite, caledonite, and diaboleite. Raygrantite crystals are bladed with striations parallel to the elongated direction (the c axis). Twinning (fish-tail type) is pervasive on (1 2 ). The mineral is colorless, transparent with white streak, and has a vitreous luster. It is brittle and has a Mohs hardness of ~3; cleavage is good on {120} and no parting was observed. The calculated density is 6.374 g/cm 3 . Optically, raygrantite is biaxial (+), with n α = 1.915(7), n β = 1.981(7), n = 2.068(9), 2V meas = 76(2)°, and 2V calc = 85°. It is insoluble in water, acetone, or hydrochloric acid. An electron microprobe analysis yielded the empirical formula Pb 2+ 9.81 Zn 2+ 0.93 (S 1.00 O 4 ) 6 (Si 1.05 O 4 ) 2 (OH) 2 . Raygrantite is a new member of the iranite mineral group. It is triclinic, with space group P and unit-cell parameters a 9.3175(4), b 11.1973(5), c 10.8318(5) Å, α 120.374(2), β 90.511(2), 56.471(2)°, and V 753.13(6) Å 3 . Its crystal structure, refined to R 1 = 0.031, is characterized by slabs that lie parallel to (120) of SO 4 and SiO 4 tetrahedra with ZnO 4 (OH) 2 octahedra, held together by Pb 2+ cations displaying a wide range of Pb–O bond distances. The discovery of raygrantite indicates that, in addition to complete OH–F and Cu–Zn substitutions, there is also a complete substitution between (CrO 4 ) 2– and (SO 4 ) 2– in the iranite group of minerals, pointing to the possible existence of a number of other (SO 4 ) 2– -bearing iranite-type phases yet to be found or synthesized.
    Print ISSN: 0008-4476
    Thema: Geologie und Paläontologie
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  • 10
    Publikationsdatum: 2003-02-01
    Print ISSN: 0008-4476
    Digitale ISSN: 1499-1276
    Thema: Geologie und Paläontologie
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