Sodium trisilicate: A new high-pressure silicate structure (Na2Si[Si2O7])

Crystals of sodium trisilicate (Na₂Si₃O₇) have been grown in the presence of melt at 9 GPa, 1200 °C using the MA6/8 superpress at Edmonton, and the X-ray structure determined at room pressure (R=2.0%). Na₂Si₃O₇ is monoclinic with a=8.922(2) Å, b= 4.8490(5) Å, c=11.567(1) Å, β=102.64(1)° (C2/c), D _x = 3.295 g·cm^-3. Silicon occurs in both tetrahedral and octahedral coordination (^[6]Si∶^[4]Si = l∶2). The SiO₄ tetrahedra form a diorthosilicate [Si₂O₇] group and are linked by the isolated SiO₆ octahedra via shared corners into a framework of 6-membered (^[4]Si-^[4]Si-^[6]Si^[4]Si-^[4] Si-^[6]Si) and 4-membered (^[4]Si-^[6]Si-^[4]Sr-^[6]Si) rings: 〈^[6]Si-O〉=1.789 Å, 〈^[4]Si-O〉= 1.625 Å, ^[4]Si-O-^[4]Si=132.9° and the bridging oxygen is overbonded (s = 2.22). Channels parallel to b-axis and [110] accommodate Na in irregular 6-fold coordination: 〈Na-O〉 = 2.511 Å.     

Sulfur K-edge XANES study of local electronic structure in ternary monosulfide solid solution [(Fe, Co, Ni)0.923S]

 Synchrotron radiation S K-edge XANES spectra and unit-cell parameters are used to investigate the local electronic structure of non-stoichiometric binary and ternary Fe-Co-Ni monosulfide solid solution (mss; M_0.923S, M = Fe, Co, Ni) quenched from 800 °C and low pressure. The prominent absorption edge feature of the XANES spectra represents transition of S 1s core level electrons to unoccupied S 3p σ* antibonding orbitals hybridized with empty metal 3d(e_g) orbitals. There is a progressive increase in area of the edge peak from Fe_0.923S to Ni_0.923S and Co_0.923S, which correlates with progressive decrease in c and a parameters for the NiAs-type subcell and increase in metallic character, and reflects increase in the number and availability of empty e_g ^β orbitals and covalence of metal-S bonds. More generally, the area of the edge peak exhibits an inverse linear correlation with a, c and unit-cell volume of binary and ternary mss. This inverse linear correlation is attributed to progressive increase in covalence and M-S-M bonding interaction in the c-axis direction, through metal-S [M 3d(e_g) - S 3p (or 3d)] π bonding. However, the area of the edge peak does not correlate very well with the average number of 3d electrons per metal atom in these solid solutions, showing that the absorption of synchrotron radiation reflects the local electronic structure of individual absorber atoms (i.e. the SM₆ cluster), and is not a group (crystal energy band) effect. Received: 21 March 2000 / Accepted: 14 July 2000     

S K- and L-edge XANES and electronic structure of some copper sulfide minerals

The S K and L-edge x-ray absorption near-edge structures (XANES) of low bornite, cubanite, chalcocite, covellite, enargite and tetrahedrite have been measured with synchrotron radiation. The near-edge features are interpreted based on comparison with the S K- and L-edge spectra of chalcopyrite and a MO/energy band structure model. The XANES spectra of these sulfides reflect the DOS of unoccupied S s-, p- and d-like states near and above the Fermi level. In tetrahedral Cu-Fe sulfides, the Fe³⁺ 3d crystal field band has much more significant DOS of unoccupied S 3p-and 3s-like states than the Cu⁺ 3d crystal field band. For Cu sulfides, the Cu⁺ 3d crystal field band has the higher DOS of S 3p- and 3 s-like states in tetrahedral structure than in structures with the triangular CuS₃ cluster. The shifts in both S K- and L-edges correlate approximately linearly with the energy gap.     

Synthetic smythite and monoclinic Fe3S4

Smythite and monoclinic Fe₃S₄ have been identified by X-ray diffraction procedures in quenched ironsulfide compositions. Both phases appear to be metastable under the conditions of the experiments and their development is structurally induced. Smythite occurs as a coherent twinned intergrowth with hexagonal 3C pyrrhotite. Individual single crystals contain about 50% smythite. Reciprocal lattice rows with h-k ≠ 3n show continuous diffraction streaks. The available data suggest that smythite forms via a “polytypic” displacive transformation, by the introduction of stacking faults in the hexagonal close-packed layers of S atoms in high-temperature 1C pyrrhotite. This is analogous to the transformation of 2H wurtzite to intermediate ordered and disordered ZnS layer sequences. The ideal formula of smythite appears to be Fe₁₃S₁₆. Monoclinic Fe₃S₄ (a=5.93, b=3.42, c=10.64 Å, β=91.9°) is present in amounts up to 25% of total sulfides. It has a derivative NiAs-type structure, and is isomorphous with monoclinic Cr₃S₄ and Fe₃Se₄. It occurs as small lenticular lamellae within grains of 3C pyrrhotite, and apparently corresponds to the unidentified lamellar phase of Arnold (1962). The lamellae have a rhombohedral morphology, with a habit plane close to {1011}. In single crystal grains of pyrrhotite, monoclinic Fe₃S₄ in twinned in a manner consistent with transformation from high-temperature 1C pyrrhotite. Although Fe₃S₄ lamellae have the general appearance of plate martensite, they do not represent a diffusionless transformation.