Carlhintzeite, Ca2AlF7•H2O, from the Gigante granitic pegmatite, Córdoba province, Argentina: Description and crystal structure

Carlhintzeite, Ca2AlF7•H2O, has been found at the Gigante pegmatite, Punilla Department, Córdoba Province, Argentina. It occurs as colourless prismatic crystals up to 0.8 mm long, ubiquitously twinned on {001}. Electron microprobe analyses provided the empirical formula Ca1.98Al1.02F6.24(OH) 0.76•H1.62O. A crystal fragment used for the collection of structure data provided the triclinic, C1 cell: a = 9.4227(4), b = 6.9670(5), c = 9.2671(7) Å, α = 90.974(6), β = 104.802(5), γ = 90.026(6)°, V = 558.08(7) Å3 and Z = 4. The crystal structure, solved by direct methods and refined to R 1 = 0.0322 for 723 Fo > 4σF reflections, is made up of linkages of AlF6 octahedra, CaF8 polyhedra and CaF 6(H2O)2 polyhedra. The AlF6 octahedra are isolated from one another, but share polyhedral elements with Ca polyhedra. Most notably, the Al1 octahedron shares trans faces with two CaF 8 polyhedra and the Al2 octahedron shares trans edges with two CaF6(H2O)2 polyhedra. The linkage of the Ca polyhedra alone can be described as a framework in which edge-sharing chains along b are cross-linked by edge-sharing. Edge-sharing chains of Ca polyhedra along b in the carlhintzeite structure are similar to those along c in the structures of gearksutite, CaAlF4(OH)•(H2O), and prosopite, CaAl2F4(OH)4. © 2010 Mineralogical Society.Fil: Kampf, A. R.. Natural History Museum of Los Angeles County; Estados UnidosFil: Colombo, Fernando. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Centro de Investigaciones en Ciencias de la Tierra. Universidad Nacional de Córdoba. Facultad de Ciencias Exactas Físicas y Naturales. Centro de Investigaciones en Ciencias de la Tierra; ArgentinaFil: González Del Tánago, J.. Universidad Complutense de Madrid; Españ

Supersolids in the Bose-Hubbard Hamiltonian

We use a combination of numeric and analytic techniques to determine the groun d state phase diagram of the Bose--Hubbard Hamiltonian with longer range repulsi ve interactions. At half filling one finds superfluidity and an insulating solid phase. Depending on the relative sizes of near--neighbor and next near--neighbor interactions, this solid either follows a checkerboard or a striped pattern. In neither case is there a coexistence with superfluidity. However upon doping ``supersolid'' phases appear with simultaneous diagonal and off--diagonal long range order.Comment: 11 pages, Revtex 3.0, 6 figures (upon request

The Crystal Structure of Tobermorite 14 Å (Plombierite), a C-S-H phase

The crystal structure of tobermorite 14 Å (plombierite) was solved by means of the application of the order-disorder (OD) theory and was refined through synchrotron radiation diffraction data. Two polytypes were detected within one very small crystal from Crestmore, together with possibly disordered sequences of layers, giving diffuse streaks along c*. Only one of the two polytypes, could be refined: it has B11b space group symmetry and cell parameters a = 6.735(2) Å, b = 7.425(2) Å, c = 27.987(5) A, γ = 123.25(1)° . The refinement converged to R = 0.152 for 1291 reflections with F 0>4σ(F 0). The characteristic reflections of the other polytype, F2dd space group, a ≈11.2 Å, b ≈ 7.3 Å, c ≈ 56 Å, were recognized but they were too weak and diffuse to be used in a structure refinement. The structure of tobermorite 14 Å is built up of complex layers, formed by sheets of sevenfold coordinated calcium cations, flanked on both sides by wollastonite-like chains. The space between two complex layers contains additional calcium cations and H 2O molecules; their distribution, as well as the system of hydrogen bonds, are presented and discussed. The crystal chemical formula indicated by the structural results is Ca 5Si 6O 16(OH) 2 ·7H 2O

The crystal structure of munakataite, Pb_2Cu_2(Se^(4+)O_3)(SO_4)(OH)_4, from Otto Mountain, San Bernardino County, California, USA

Munakataite, Pb_2Cu_2(Se^(4+)O_3)(SO_4)(OH)_4, has been found in association with a variety of rare secondary Te minerals at Otto Mountain, San Bernardino County, California, USA. It is very rare and occurs as subparallel bundles of blue needles up to 1 mm long. Electron microprobe analyses provided the empirical formula Pb_(1.96)Cu_(1.60)[(Se^(4+)_(0.89)S_(0.11)_(∑1)O_3](SO_4)[(OH)_(3.34)(H_2O)_(0.66)]_(∑4). Munakataite is monoclinic, space group P2_1/m, with cell parameters a = 9.8023(26), b = 5.6751(14), c = 9.2811(25) Å , β = 102.443(6), V = 504.2(2) Å^3 and Z = 2. The crystal structure, solved by direct methods and refined to R_1 = 0.0308 for 544 F_o > 4σF reflections, consists of Jahn-Teller-distorted Cu^(2+)O_6 square bipyramids, which form chains along b by sharing trans edges across their square planes. The chains are decorated by SO_4 tetrahedra and Se^4+O_3 pyramids, which bond to apical corners of adjacent bipyramids. The chains are linked to one another via bonds to two different PbO_9 polyhedra, only one of which exhibits one-sided coordination typical of Pb^(2+) with a stereochemically active 6s^2 lone-electron-pair. Munakataite is isostructural with schmiederite and the structure is closely related to that of linarite

Anorpiment, As_(2)S_(3), the triclinic dimorph of orpiment

The new mineral anorpiment, As_(2)S_(3), the triclinic dimorph of orpiment, has space group P1 and cell parameters a = 5.7577(2), b = 8.7169(3), c = 10.2682(7) Å, α = 78.152(7), β = 75.817(7), γ = 89.861(6)º, V = 488.38(4) Å^3 and Z = 4. It occurs at the Palomo mine, Castrovirreyna Province, Huancavelica Department, Peru. It is a low-temperature hydrothermal mineral associated with dufrénoysite, muscovite, orpiment, pyrite and realgar. It occurs in drusy crusts of wedge-shaped, transparent, greenish yellow crystals. The streak is yellow. The lustre is resinous on crystal faces, but pearly on cleavage surfaces. The Mohs hardness is about 1½. The mineral is sectile with an irregular fracture and one perfect and easy cleavage on {001}. The measured and calculated densities are 3.33 and 3.321 g cm^(-3), respectively. All indices of refraction are greater than 2. The mineral is optically biaxial (—) with 2V = 35-40º and no observed dispersion. The acute bisectrix (X) is approximately perpendicular to the {001} cleavage. Electron microprobe analyses yielded the averages and ranges in wt.%: As 58.21 (57.74-59.03), S 38.72 (38.33-39.00), total 96.94 (96.07-97.75), providing the empirical formula (based on 5 atoms) As_(1.96)S_(3.04). The strongest powder X-ray diffraction lines are [d (hkl) I] 4.867(002) 97, 4.519 (110,111) 77, 3.702 (111) 46, 3.609 (022,112) 82, 2.880 (201,022,121,023) 75, 2.552 (113,131,132) 100, 2.469 (114,130,131) 96. The structure of anorpiment [R_1 = 0.021 for 1484 reflections with F_o > 4σ(F)] consists of layers of covalently bonded As and S atoms. Each S atom bonds to two As atoms at As-S-As angles between 100.45 and 104.15º. Each As atom is strongly bonded to three S atoms at S-As-S angles between 91.28 and 103.59º, forming an AsS_3 pyramid with As at its apex. The As-S linkages within the layers form rings of six AsS_3 pyramids. Interlayer bonding forces are interpreted as van der Waals. The structure of anorpiment is similar to that of orpiment in that it is composed of layers of As2S_3 macromolecules, but arranged in a different stacking sequence

Exact Bond Ordered Ground State for the Transition Between the Band and the Mott Insulator

We derive an effective Hamiltonian $H_{eff}$ for an ionic Hubbard chain, valid for $t\ll U,\Delta$, where $t$ is the hopping, $U$ the Coulomb repulsion, and $\Delta$ the charge transfer energy. $H_{eff}$ is the minimal model for describing the transition from the band insulator (BI) ($\Delta -U\gg t$) and the Mott insulator (MI) ($U-\Delta \gg t$). Using spin-particle transformations (Phys. Rev. Lett. \textbf{86}, 1082 (2001)), we map $H_{eff}(U=\Delta)$ into an SU(3) antiferromagnetic Heisenberg model whose exact ground state is known. In this way, we show rigorously that a spontaneously dimerized insulating ferroelectric phase appears in the transition region between the BI and MI

From local to nonlocal Fermi liquid in doped antiferromagnets

The variation of single-particle spectral functions with doping is studied numerically within the t-J model. It is shown that corresponding self energies change from local ones at the intermediate doping to strongly nonlocal ones for a weakly doped antiferromagnet. The nonlocality shows up most clearly in the pseudogap emerging in the density of states, due to the onset of short-range antiferromagnetic correlations.Comment: 4 pages, 3 Postscript figures, revtex, submitted to Phys.Rev.Let

Alcaparrosaite, K_3Ti^(4+)Fe^(3+)(SO_4)_4O(H_2O)_2, a new hydrophobic Ti^(4+) sulfate from Alcaparrosa, Chile

Alcaparrosaite, ideally K_3Ti^(4+)Fe^(3+)(SO_4)_4O(H_2O)_2, is a new mineral from the Alcaparrosa mine, Cerritos Bayos, El Loa Province, Antofagasta, Chile (IMA2011-024). The mineral occurs on and intergrown with coquimbite, and is also associated with ferrinatrite, krausite, pertlikite, pyrite, tamarugite and voltaite. It is a relatively early phase which forms during the oxidation of pyritic masses under increasingly arid conditions. Alcaparrosaite crystallizes from hyperacidic solutions in a chemical environment that is consistent with its association with coquimbite. It occurs as pale yellow blades and tapering prisms up to 4 mm in length, flattened on {010} and elongated along [100]. The observed crystal forms are {010}, {110}, {1.13.0} and {021}. The mineral is transparent and has a white streak, vitreous lustre, Mohs hardness of about 4, brittle tenacity, conchoidal fracture and no cleavage. The measured and calculated densities are 2.80(3) and 2.807 g cm^(−3), respectively. It is optically biaxial (+) with α = 1.643(1), β = 1.655(1), γ = 1.680(1) (white light), 2V_(meas) = 70(2)° and 2V_(calc) = 70.3°. The mineral exhibits strong parallel dispersion, r 2.704 (38) (2İ23,152); 1.9283 (30) (1İ55); 1.8406 (31) (3İ53,206). In the structure of alcaparrosaite (R_1 = 2.57% for 1725 F_o > 4σF), Ti^(4+) and Fe^(3+), in roughly equal amounts, occupy the same octahedrally coordinated site. Octahedra are linked into dimers by corner sharing. The SO_4 tetrahedra link the dimers into chains parallel to [001] and link the chains into undulating sheets parallel to {010}. The sheets link via 10- and 11-coordinated K atoms in the interlayer region. The structure shares some features with that of goldichite

Doping Evolution of Oxygen K-edge X-ray Absorption Spectra in Cuprate Superconductors

We study oxygen K-edge x-ray absorption spectroscopy (XAS) and investigate the validity of the Zhang-Rice singlet (ZRS) picture in overdoped cuprate superconductors. Using large-scale exact diagonalization of the three-orbital Hubbard model, we observe the effect of strong correlations manifesting in a dynamical spectral weight transfer from the upper Hubbard band to the ZRS band. The quantitative agreement between theory and experiment highlights an additional spectral weight reshuffling due to core-hole interaction. Our results confirm the important correlated nature of the cuprates and elucidate the changing orbital character of the low-energy quasi-particles, but also demonstrate the continued relevance of the ZRS even in the overdoped region.Comment: Original: 5 pages, 4 figures. Replaced: 6 pages and 4 figures, with updated title and conten

Bobmeyerite, a new mineral from Tiger, Arizona, USA, structurally related to cerchiaraite and ashburtonite

Bobmeyerite, Pb_4(Al_(3)Cu)(Si_(4)O_12)(S_(0.5)Si_(0.5)O_4)(OH)_(7)Cl(H_(2)O)_3, is a new mineral from the Mammoth - Saint Anthony mine, Tiger, Pinal County, Arizona, USA. It occurs in an oxidation zone assemblage attributed to progressive alteration and crystallization in a closed system. Other minerals in this assemblage include atacamite, caledonite, cerussite, connellite, diaboleite, fluorite, georgerobinsonite, hematite, leadhillite, matlockite, murdochite, phosgenite, pinalite, quartz, wulfenite and yedlinite. Bobmeyerite occurs as colourless to white or cream-coloured needles, up to 300 mm in length, that taper to sharp points. The streak is white and the lustre is adamantine, dull or silky. Bobmeyerite is not fluorescent. The hardness could not be determined, the tenacity is brittle and no cleavage was observed. The calculated density is 4.381 g cm^(-3). Bobmeyerite is biaxial (-) with a ≈ b = 1.759(2), γ = 1.756(2) (white light), it is not pleochroic; the orientation is X = c; Y or Z = a or b. Electron-microprobe analyses provided the empirical formula Pb_(3.80)Ca_(0.04)Al_(3.04) Cu^(2+)_(0.96)Cr^(3+)_(0.13)Si_(4.40)S_(0.58)O_(24.43) Cl_(1.05)F_(0.52)H_(11.83). Bobmeyerite is orthorhombic (pseudotetragonal), Pnnm with unit-cell parameters a = 13.969(9), b = 14.243(10), c = 5.893(4) Å, V = 1172.5(1.4) Å 3 and Z = 2. The nine strongest lines in the X-ray powder diffraction pattern, listed as [d_(obs)(Å )(I)(hkl)], are as follows: 10.051(35)(110); 5.474(54)(011,101); 5.011(35)(220); 4.333(43)(121,211); 3.545(34)(040,400); 3.278(77)(330,231,321); 2.9656(88)(141,002,411); 2.5485(93)(051,222,501); 1.873(39)(multiple). Bobmeyerite has the same structural framework as cerchiaraite and ashburtonite. In the structure, which refined to R_1 = 0.079 for 1057 reflections with F > 4σF, SiO_4 tetrahedra share corners to form four-membered Si_(4)O_12 rings centred on the c axis. The rings are linked by chains of edge-sharing AlO_6 octahedra running parallel to [001]. The framework thereby created contains large channels, running parallel to [001]. The Cl site is centred on the c axis alternating along [001] with the Si_(4)O_12 rings. Two non-equivalent Pb atoms are positioned around the periphery of the channels. Both are elevencoordinate, bonding to the Cl atom on the c axis, to eight O atoms in the framework and to two O (H_(2)O) sites in the channel. The Pb atoms are off-centre in these coordinations, as is typical of Pb^2+ with stereo-active lone-electron pairs. A (S, Si, Cr)O_4 group is presumed to be disordered in the channel. The name honours Robert (Bob) Owen Meyer, one of the discoverers of the new mineral