Seven-Coordinated High-Pressure Phase of CrSb2 and Experimental Equation of State of MSb2 (M = Cr, Fe, Ru, Os).

The MSb2 compounds with M = Cr, Fe, Ru, and Os have been investigated under high pressures by synchrotron powder X-ray diffraction. All compounds, except CrSb2, were found to retain the marcasite structure up to the highest pressures (more than 50 GPa). In contrast, we found that CrSb2 has a structural phase transition around 10 GPa to a metastable, MoP2-type structure with Cr coordinated to seven Sb atoms. In addition, we compared ambient temperature compression with laser-heating experiments and found that laser-heating at pressures below and above this phase transition results in the known CuAl2-type structure. Density functional theory calculations show that this tetragonal structure is the most stable in the whole pressure interval. However, a crossing of the marcasite's and MoP2-like structure's enthalpies occurs between 5 and 7.5 GPa, which is in good agreement with the experimental data. The phase transition to the MoP2-type structure observed in this work opens up for discovering other compounds with this new transition pathway from the marcasite structure.

Singlet Orbital Ordering in Bilayer Sr_{3}Cr_{2}O_{7}.

We perform an extensive study of Sr_{3}Cr_{2}O_{7}, the n=2 member of the Ruddlesden-Popper Sr_{n+1}Cr_{n}O_{3n+1} system. An antiferromagnetic ordering is clearly visible in the magnetization and the specific heat, which yields a huge transition entropy, Rln(6). By neutron diffraction as a function of temperature we have determined the antiferromagnetic structure that coincides with the one obtained from density functional theory calculations. It is accompanied by anomalous asymmetric distortions of the CrO_{6} octahedra. Strong coupling and Lanczos calculations on a derived Kugel-Khomskii Hamiltonian yield a simultaneous orbital and moment ordering. Our results favor an exotic ordered phase of orbital singlets not originated by frustration.

Ba19Cr12O45: A High Pressure Chromate with an Original Structure Solved by Electron Diffraction Tomography and Powder X-ray Diffraction.

We report on the discovery of a Ba-based chromate obtained by high pressure-high temperature treatment of the low pressure orthorhombic Ba2CrO4 phase. By combining transmission electron microscopy and powder X-ray diffraction measurements, we have determined its crystallographic structure. This new Cr-oxide has a cubic lattice with a = 13.3106(6) Å built from a three-dimensional network of two Cr sites, Cr1 and Cr2, both in octahedral environments, with face sharing between Cr1 and Cr2 octahedra and corner-sharing between two Cr1 octahedra. The resulting chemical composition Ba19Cr12O45 and bond valence sum analysis suggest a possible charge disproportion between Cr4+ in the Cr1 site and Cr5+ in the Cr2 site. Finally analysis of magnetization measurements indicates antiferromagnetic correlations between Cr cations and also points toward a probable charge disproportion between Cr sites.