RESUMEN
The mineralogical constitution of the Earth's mantle dictates the geophysical and geochemical properties of this region. Previous models of a perovskite-dominant lower mantle have been built on the assumption that the entire lower mantle down to the top of the Dâ³ layer contains ferromagnesian silicate [(Mg,Fe)SiO3] with nominally 10 mole percent Fe. On the basis of experiments in laser-heated diamond anvil cells, at pressures of 95 to 101 gigapascals and temperatures of 2200 to 2400 kelvin, we found that such perovskite is unstable; it loses its Fe and disproportionates to a nearly Fe-free MgSiO3 perovskite phase and an Fe-rich phase with a hexagonal structure. This observation has implications for enigmatic seismic features beyond ~2000 kilometers depth and suggests that the lower mantle may contain previously unidentified major phases.
RESUMEN
Using high-pressure synchrotron x-ray absorption spectroscopy, we observed the Ce 4f electron in Ce(75)Al(25) metallic glass transform from its ambient localized state to an itinerant state above 5 GPa. A parallel x-ray diffraction study revealed a volume collapse of about 8.6%, coinciding with 4f delocalization. The transition started from a low-density state below 1.5 GPa, went through continuous densification ending with a high-density state above 5 GPa. This new type of electronic polyamorphism in densely packed metallic glass is dictated by the Ce constituent, and is fundamentally distinct from the well-established structural polyamorphism in which densification is caused by coordination change and atomic rearrangement.
RESUMEN
The formation of substitutional alloys has been restricted to elements with similar atomic radii and electronegativity. Using high-pressure at 298 K, we synthesized a face-centered cubic disordered alloy of highly dissimilar elements (large Ce and small Al atoms) by compressing the Ce(3)Al intermetallic compound >15 GPa or the Ce(3)Al metallic glass >25 GPa. Synchrotron X-ray diffraction, Ce L(3)-edge absorption spectroscopy, and ab initio calculations revealed that the pressure-induced Kondo volume collapse and 4f electron delocalization of Ce reduced the differences between Ce and Al and brought them within the Hume-Rothery (HR) limit for substitutional alloying. The alloy remained after complete release of pressure, which was also accompanied by the transformation of Ce back to its ambient 4f electron localized state and reversal of the Kondo volume collapse, resulting in a non-HR alloy at ambient conditions.
