RESUMEN

Charge transfer in cobalt oxide Co(3)O(4) in the spinel structure is evidenced by experimental results using x-ray diffraction (XRD), x-ray absorption near edge structure (XANES) spectroscopy, and Raman scattering at high pressures up to 42.1, 24.6 and 35.1 GPa, respectively. While the cubic structure was found to persist under pressure up to 42.1 GPa based on the XRD and Raman results, the mode Grüneisen parameter was calculated according to our Raman measurements. Our structural data refinement revealed a structural transition from the normal spinel structure at low pressures to a partially inverse spinel structure at pressures above 17.7 GPa. This transition may be caused by the interaction of charges between tetrahedral and octahedral sites via a charge transfer process. Evidence for the charge transfer process is further supported by changes of the pre-edge features in the XANES data.

RESUMEN

Using synchrotron high-pressure X-ray diffraction at cryogenic temperatures, we have established the phase diagram for calcium up to 110 GPa and 5-300 K. We discovered the long-sought for theoretically predicted ß-tin structured calcium with I4(1)/amd symmetry at 35 GPa in a s mall low-temperature range below 10 K, thus resolving the enigma of absence of this lowest enthalpy phase. The stability and relations among various distorted simple-cubic phases in the Ca-III region have also been examined and clarified over a wide range of high pressures and low temperatures.

Asunto(s)

Calcio/química , Transición de Fase , Estaño/química , Modelos Químicos , Modelos Moleculares , Presión , Temperatura , Difracción de Rayos X/métodos

RESUMEN

Ca-III, the first superconducting calcium phase under pressure, was identified as simple-cubic (sc) by previous X-ray diffraction (XRD) experiments. In contrast, all previous theoretical calculations showed that sc had a higher enthalpy than many proposed structures and had an imaginary (unstable) phonon branch. By using our newly developed submicrometer high-pressure single-crystal XRD, cryogenic high-pressure XRD, and theoretical calculations, we demonstrate that Ca-III is neither exactly sc nor any of the lower-enthalpy phases, but sustains the sc-like, primitive unit by a rhombohedral distortion at 300 K and a monoclinic distortion below 30 K. This surprising discovery reveals a scenario that the high-pressure structure of calcium does not go to the zero-temperature global enthalpy minimum but is dictated by high-temperature anharmonicity and low-temperature metastability fine-tuned with phonon stability at the local minimum.

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.