Ge0.57Ti0.43O2: a new high-pressure material with rutile-type crystal structure.

Single crystals of a GeO2-TiO2 solid solution with the corresponding composition Ge0.57Ti0.43O2 (germanium titanium tetra-oxide) were obtained by devitrification of germania-titania glass at high pressure and temperature. The new compound crystallizes in the rutile structure type (space group P42/mnm), where Ge and Ti share the same position M (site symmetry m.mm), with occupancy values of 0.57 (3) and 0.43 (3), respectively, and one O-atom position (m.2m). The M site is in a sixfold O-atom coordination and, as in the original TiO2 rutile structure, an elongation of the O-M-O bonds along the c-axis direction of the coordination polyhedron and deviation of the angles from 90° lead to a decrease in the coordination symmetry from octa-hedral to tetra-gonal. The Ge and Ti atoms are fully disordered in the structure, which indicates that the rutile structure is surprisingly pliant given the differing sizes of the two cations.

Ultrahydrous stishovite from high-pressure hydrothermal treatment of SiO2.

Stishovite (SiO(2) with the rutile structure and octahedrally coordinated silicon) is an important high-pressure mineral. It has previously been considered to be essentially anhydrous. In this study, hydrothermal treatment of silica glass and coesite at 350-550 °C near 10 GPa produces stishovite with significant amounts of H(2)O in its structure. A combination of methodologies (X-ray diffraction, thermal analysis, oxide melt solution calorimetry, secondary ion mass spectrometry, infrared and nuclear magnetic resonance spectroscopy) indicate the presence of 1.3 ± 0.2 wt % H(2)O and NMR suggests that the primary mechanism for the H(2)O uptake is a direct hydrogarnet-like substitution of 4H(+) for Si(4+), with the protons clustered as hydroxyls around a silicon vacancy. This substitution is accompanied by a substantial volume decrease for the system (SiO(2) + H(2)O), although the stishovite expands slightly, and it is only slightly unfavorable in energy. Stishovite could thus be a host for H(2)O at convergent plate boundaries, and in other relatively cool high-pressure environments.

SrZn(11): a new binary compound with the BaCd(11) structure.

Single crystals of strontium undecazinc, SrZn(11), were obtained when decomposing SrZn(2) under conditions of high pressure and high temperature. The new binary Sr-Zn compound crystallizes in the space group I4(1)/amd (BaCd(11) structure type) with one Sr position (\overline{4}m2) and three Zn sites (\overline{4}m2, .2/m., 1). The structure is described in terms of all-face-capped Zn(8) tetrahedra as the central building unit, defined by the Zn atoms on .2/m. and 1. The building units are condensed into chains by the central tetrahedra sharing edges, and the chains are interconnected by shared capping atoms. The resulting three-dimensional framework of Zn atoms yields channels that are occupied by Sr and Zn atoms on the high-symmetry \overline{4}m2 positions.