High pressure behavior of Fe2O3has been a long-standing subject of research due to its high importance for understanding Earth's interiors. At pressures from 40 to 60 GPa it undergoes a series of transformations, such as structural changes with a large volume discontinuity (~10 %), a drop of the resistivity, a spin crossover of Fe3+, and a disappearance of the ordered magnetic state. The crystal structure of the phase(s) observed on compression at ambient temperature above 50 GPa is still under question since only powder X-ray diffraction (XRD) data were available so far. Mössbauer and Raman spectroscopy studies cannot provide definitive structural information. Applying laser heating to Fe2O3, compressed up to 70 GPa and above, results in a distinct reconstructive phase transition to the CaIrO3-type structure, according to powder XRD. Poverty of the available structural data encouraged us to perform a series of high-pressure and high-temperature XRD experiments on single crystals of Fe2O3in diamond anvil cells. We have studied the behavior of Fe2O3at pressures up to 100 GPa and temperatures up to 2500 K. Here we report crystal structures of two novel high-pressure Fe2O3polymorphs, as well as the relations between a spin state of iron atoms and the crystal chemistry of the iron compound. In our compression experiments initially hematite-structured Fe2O3transformed to a new phase at ~54 GPa with 10 % of the volume reduction. This phase has a triclinic distorted perovskite-type structure. The second reconstructive transition occurred at 66–70 GPa with 3 % of the volume discontinuity and resulted in formation of an orthorhombic phase. Laser heating to ~21001100 K at pressures above 70 GPa promoted a transition to a Cmcm CaIrO3-type phase, whose crystal structure was refined by means of single crystal XRD to R1~ 9.7 %. Decompression experiments showed that the Cmcm phase transforms back to hematite at pressures between ~25 and 15 GPa.
Crystal structure and Raman spectra of molecular complex [{Cd(Et2dtc)}2• DABCO]• C60• (DABCO)2 at high pressure
