Ab initio studies of phonon softening and high pressure phase transitions of alpha-quartz SiO2

Density functional perturbation theory calculations of alpha-quartz using extended norm conserving pseudopotentials have been used to study the elastic properties and phonon dispersion relations along various high symmetry directions as a function of bulk, uniaxial and non-hydrostatic pressure. The computed equation of state, elastic constants and phonon frequencies are found to be in good agreement with available experimental data. A zone boundary (1/3, 1/3, 0) K-point phonon mode becomes soft for pressures above P=32 GPa. Around the same pressure, studies of the Born stability criteria reveal that the structure is mechanically unstable. The phonon and elastic softening are related to the high pressure phase transitions and amorphization of quartz and these studies suggest that the mean transition pressure is lowered under non-hydrostatic conditions. Application of uniaxial pressure, results in a post-quartz crystalline monoclinic C2 structural transition in the vicinity of the K-point instability. This structure, intermediate between quartz and stishovite has two-thirds of the silicon atoms in octahedral coordination while the remaining silicon atoms remain tetrahedrally coordinated. This novel monoclinic C2 polymorph of silica, which is found to be metastable under ambient conditions, is possibly one of the several competing dense forms of silica containing octahedrally coordinated silicon. The possible role of high pressure ferroelastic phases in causing pressure induced amorphization in silica are discussed.Comment: 17 pages, 8 figs., 8 Table

Growth zoning and strain patterns inside diamond crystals as revealed by Raman maps

The Raman mapping technique provides a non-destructive means of studying internal growth textures and other micro-structural heterogeneity inside diamond single-crystals. Raman maps showing distribution patterns of the bandwidth (FWHM) of the main first-order lattice vibration of diamond (LO=TO phonon at ~1332 cm−1) along two-dimensional planes inside diamond crystals may reveal the internal growth zoning of these crystals. The observed zoning is affected, and in some cases even obscured in micro-areas adjacent to inclusions, by patterns of heterogeneous strain in the diamond. We present Raman maps obtained from diamond crystals containing large, single-crystal graphite inclusions, from the Panda kimberlite, Ekati Diamond Mine, Canada. The diamond growth texture was always found to start from the graphite inclusion. This result implies that graphite must have been the primary phase and was overgrown by diamond, whereas syngenetic growth of diamond and graphite was unlikely