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  • 1
    Electronic Resource
    Electronic Resource
    Springer
    Physics and chemistry of minerals 6 (1980), S. 77-84 
    ISSN: 1432-2021
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences , Physics
    Notes: Abstract The energy levels of MnO 6 9− clusters, with D 4h approximated and C 2v actual symmetry of the M 1 site of Mn3+-bearing andalusite, are calculated using the multiple scattering method. The energies of the electronic d-d transition of Mn3+ in the clusters with D 4h symmetry are calculated to be 6,000–7,000 cm−1 (5 B 1g → 5 A 1g ), ∼18,000 cm−1 (5 B 1g → 5 B 2g ) and ∼19,000 cm−1 (5 B 1g → 5 E g ). Apart from a splitting of the 5 E g -level into two levels separated by 300–350 cm−1, no significant changes of these transition energies are noted for the corresponding cluster with C 2v symmetry. The calculated transition energies give a good fit to the structure of the optical absorption spectra of Mn3+-bearing andalusites and support recent assignments of the major absorption bands observed in these spectra.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    Springer
    Physics and chemistry of minerals 20 (1994), S. 478-482 
    ISSN: 1432-2021
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences , Physics
    Notes: Abstract Electronic absorption spectra have been measured at room temperature and pressure for polycrystalline samples of (Mg, Fe)SiO3 silicate perovskites synthesized by multi-anvil device. One strong near-infrared band at about 7000 cm-1 and several weak bands in the visible region were found. The near-infrared band at 7000 cm-1 is assigned to a spin-allowed transition of Fe2+ at the 8–12 coordinated site in perovskite. However, definite assignments of the weak bands in the visible region are difficult because of their low intensities and the scattering effect at the gain boundaries. Crystal field calculations for Fe2+ at different sites in perovskite have been carried out based on the crystal structure data. The results agree with the assignment of Fe2+ to the 8–12 coordinated site in perovskite. Crystal field stabilization energy of Fe2+ with coordination number of 8 in perovskite is 3332 cm-1 which is small compared to the octahedral site of magnesiowüstite (4320 cm-1), another important lower-mantle mineral.
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    Springer
    Physics and chemistry of minerals 7 (1981), S. 117-123 
    ISSN: 1432-2021
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences , Physics
    Notes: Abstract Room temperature and low temperature Mössbauer and optical absorption spectroscopic data on six natural chloritoids characterized by means of electron microprobe and X-ray powder diffraction techniques are presented. Two narrow quadrupole doublets with widths of 0.25–0.29 mm/s assigned to Fe2+ in a relatively large octahedral site and Fe3+ in a smaller octahedral site, are observed in the Mössbauer spectra. Polarized optical absorption spectra reveal three main absorption bands. A broad absorption band at 16,300 cm−1, which is strongly polarized in E‖X and E‖Y and shows a linear increase in integral absorption with increasing [Fe2+] [Fe3+] concentration product, is assigned to a Fe2++Fe3+→Fe3++Fe2+ charge transfer transition. This band displays also a temperature dependence different from that of single ion d−d transitions. Two absorption bands at 10,900 cm−1 and 8,000 cm−1 are, on the basis of compositional dependence and energy, assigned to Fe2+ in the large M(1B) octahedra of the brucite-type layer in chloritoid. Combined spectroscopic evidence and structural and chemical considerations support a distribution scheme for ferrous and ferric iron which orders the Fe2+ ions in the M(1B) octahedra and the Fe3+ ions in the small M(1A) octahedral sites. Both types of octahedra are found in the brucite type layer of chloritoid.
    Type of Medium: Electronic Resource
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  • 4
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 18 (1980), S. 1473-1477 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The ground state and the first few excited states of an MnO69- cluster are calculated in the unrestricted Hartree-Fock model. The state ordering is 5B1 g, 5A1 g, 5B2 g, and 5Eg as can be expected from simpler models. Consistent with the results by the same method for copper complexes, we obtain d-d transition energies about one half or less of the experimental energies. The charge transfer spectrum is subject to a large spin polarization in the sense that the lowest charge transfer state (5Eu) has five unpaired spins on Mn.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
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  • 5
    Publication Date: 2023-06-27
    Keywords: 22-216; 92-597C; Arsenic; Calcium; Chlorine; Copper; Deep Sea Drilling Project; DRILL; Drilling/drill rig; DSDP; DSDP/ODP/IODP sample designation; Event label; Glomar Challenger; Indian Ocean//RIDGE; Iron; Leg22; Leg92; Manganese; Number; Oxygen; PIXE, Particle induced x-ray emission; Potassium; Sample code/label; Silicon; South Pacific
    Type: Dataset
    Format: text/tab-separated-values, 31 data points
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  • 6
    Publication Date: 2023-06-27
    Keywords: 11-105; 129-801C; 185-1149A; 185-1149C; 22-216; 40-364; 92-597C; Comment; Copper; Deep Sea Drilling Project; DRILL; Drilling/drill rig; DSDP; DSDP/ODP/IODP sample designation; Event label; Glomar Challenger; Indian Ocean//RIDGE; Joides Resolution; Leg11; Leg129; Leg185; Leg22; Leg40; Leg92; North Atlantic/HILL; North Pacific Ocean; Number; Sample code/label; Sample material; South Atlantic/SYNCLINE; South Pacific; δ65Cu; δ65Cu, standard deviation
    Type: Dataset
    Format: text/tab-separated-values, 102 data points
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  • 7
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    Unknown
    PANGAEA
    In:  Supplement to: Dekov, Vesselin M; Rouxel, Olivier J; Asael, Dan; Hålenius, Ulf; Munnik, Kate (2013): Native Cu from the oceanic crust: Isotopic insights into native metal origin. Chemical Geology, 359, 136-149, https://doi.org/10.1016/j.chemgeo.2013.10.001
    Publication Date: 2024-01-09
    Description: Ocean drilling has revealed that, although a minor mineral phase, native Cu ubiquitously occurs in the oceanic crust. Cu isotope systematics for native Cu from a set of occurrences from volcanic basement and sediment cover of the oceanic crust drilled at several sites in the Pacific, Atlantic and Indian oceans constrains the sources of Cu and processes that produced Cu**0. We propose that both hydrothermally-released Cu and seawater were the sources of Cu at these sites. Phase stability diagrams suggest that Cu**0 precipitation is favored only under strictly anoxic, but not sulfidic conditions at circum-neutral pH even at low temperature. In the basaltic basement, dissolution of primary igneous and potentially hydrothermal Cu-sulfides leads to Cu**0 precipitation along veins. The restricted Cu-isotope variations (delta 65Cu = 0.02-0.19 per mil) similar to host volcanic rocks suggest that Cu**0 precipitation occurred under conditions where Cu+-species were dominant, precluding Cu redox fractionation. In contrast, the Cu-isotope variations observed in the Cu**0 from sedimentary layers yield larger Cu-isotope fractionation (delta 65Cu = 0.41-0.95 per mil) suggesting that Cu**0 precipitation involved redox processes during the diagenesis, with potentially seawater as the primary Cu source. We interpret that native Cu precipitation in the basaltic basement is a result of low temperature (20°-65 °C) hydrothermal processes under anoxic, but not H2S-rich conditions. Consistent with positive delta 65Cu signatures, the sediment cover receives major Cu contribution from hydrogenous (i.e., seawater) sources, although hydrothermal contribution from plume fallout cannot be entirely discarded. In this case, disseminated hydrogenous and/or hydrothermal Cu might be diagenetically remobilized and reprecipitated as Cu**0 in reducing microenvironment.
    Keywords: Deep Sea Drilling Project; DSDP; Ocean Drilling Program; ODP
    Type: Dataset
    Format: application/zip, 2 datasets
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  • 8
    Publication Date: 2016-09-15
    Print ISSN: 0236-5731
    Electronic ISSN: 1588-2780
    Topics: Chemistry and Pharmacology , Energy, Environment Protection, Nuclear Power Engineering
    Published by Springer
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  • 9
    Publication Date: 2019
    Print ISSN: 0026-461X
    Electronic ISSN: 1471-8022
    Topics: Geosciences
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  • 10
    Publication Date: 2011-04-01
    Description: Six synthetic single crystals of spinel phases with different compositions along the ZnAl2O4-ZnCr2O4 solid solution were structurally and chemically characterized by X-ray diffraction and electron microprobe techniques. As predicted, unit-cell parameters and octahedral bond lengths (M-O) increase with increasing replacement of Al3+ by Cr3+. Despite the constant occupancy of the T site by Zn, also the tetrahedral bond length TZn-O shows significant variations along this binary. These variations are positively correlated with variations in M-O bond lengths. The present data in conjunction with data from literature provide a basis for quantitative analyses of the variation in TZn-O in normal spinel structures. A negative correlation between TZn-O and the ionic potential at M (MIP) suggests that increasing MIP is related to a stronger electrostatic cation-cation repulsion across the shared octahedral edge M(O-O)shared of the structure. An observed negative correlation between MIP and M(O-O)shared suggests that a decrease of M(O-O)shared provides a more efficient shielding effect to reduce the octahedral cation interactions. In normal ZnB2O4 spinels (where B = Al3+, Cr3+, Ga3+, V3+, Fe3+, and Mn3+) cations with a smaller size provides a higher charge density. Increasing charge density at the M site causes shortening of M(O-O)shared, which in turn results in shorter TZn-O bond length. In general, variations in TZn-O are required by the structure to better provide an oxygen shielding effect to the octahedral cation-cation repulsion.
    Print ISSN: 0003-004X
    Electronic ISSN: 1945-3027
    Topics: Geosciences
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