High-pressure behavior of perovskite: FeTiO_{3} dissociation into (Fe_{1-delta},Ti_{delta})O and Fe_{1+delta}Ti_{2-delta}O_{5}.

The stability of perovskite-structured materials at high pressure and temperature is of fundamental interest in solid-state physics, chemistry, and the geosciences. As an alternative to decomposition into oxides or transformation of the CaIrO_{3} postperovskite structure, we observe in situ the breakdown of FeTiO_{3} perovskite into a (Fe_{1-delta},Ti_{delta})O + Fe_{1+delta}Ti_{2-delta}O_{5} assemblage beyond 53 GPa and 2000 K. The high-pressure high-temperature phase of Fe_{1+delta}Ti_{2-delta}O_{5} with a new structure (space group C2/c) could be preserved on decompression to 9 GPa, and amorphizes under further pressure release. Our study demonstrates that perovskite-structured materials can undergo chemical changes and form complex oxides with new structures, rather than only transform to denser polymorphs or decompose to simple oxides.

Pressure-induced phase transitions of AX(2)-type iron pnictides: an ab initio study.

An investigation into the high-pressure behavior of AX(2)-type iron pnictides was conducted using first-principles calculations based on density functional theory within the generalized gradient approximation. Our results demonstrate that a phase transition from the marcasite to the CuAl(2) occurs at 108 GPa for FeP(2), at 92 GPa for FeAs(2), and at 38 GPa for FeSb(2), accompanying a semiconductor-to-metal crossover. A linear relationship between bulk moduli and the inverse specific volume is proposed to be B(0) = 17 498/V(0)-45.9 GPa for the marcasite-type phase and B(0) = 31 798/V(0)-67.5 GPa for the CuAl(2)-type phase. According to the observed structural evolutions, we claim that the regular marcasite transforms to the CuAl(2)-type phase and the anomalous marcasite transforms to the pyrite-type phase at high pressures.

Elasticity of iron at the temperature of the Earth's inner core.

Seismological body-wave and free-oscillation studies of the Earth's solid inner core have revealed that compressional waves traverse the inner core faster along near-polar paths than in the equatorial plane. Studies have also documented local deviations from this first-order pattern of anisotropy on length scales ranging from 1 to 1,000 km (refs 3, 4). These observations, together with reports of the differential rotation of the inner core, have generated considerable interest in the physical state and dynamics of the inner core, and in the structure and elasticity of its main constituent, iron, at appropriate conditions of pressure and temperature. Here we report first-principles calculations of the structure and elasticity of dense hexagonal close-packed (h.c.p.) iron at high temperatures. We find that the axial ratio c/a of h.c.p. iron increases substantially with increasing temperature, reaching a value of nearly 1.7 at a temperature of 5,700 K, where aggregate bulk and shear moduli match those of the inner core. As a consequence of the increasing c/a ratio, we have found that the single-crystal longitudinal anisotropy of h.c.p. iron at high temperature has the opposite sense from that at low temperature. By combining our results with a simple model of polycrystalline texture in the inner core, in which basal planes are partially aligned with the rotation axis, we can account for seismological observations of inner-core anisotropy.