An unusual high-spin ground state of Co3+ in octahedral coordination in brownmillerite-type cobalt oxide.

The crystal and magnetic structures of brownmillerite-like Sr(2)Co(1.2)Ga(0.8)O(5) with a stable Co(3+) oxidation state at both octahedral and tetrahedral sites are refined using neutron powder diffraction data collected at 2 K (S.G. Icmm, a = 5.6148(6) Å, b = 15.702(2) Å, c = 5.4543(6) Å; R(wp) = 0.0339, R(p) = 0.0443, χ(2) = 0.775). The very large tetragonal distortion of CoO(6) octahedra (1.9591(4) Å for Co-O(eq) and 2.257(6) Å for Co-O(ax)) could be beneficial for the stabilization of the long-sought intermediate-spin state of Co(3+) in perovskite-type oxides. However, the large magnetic moment of octahedral Co(3+) (3.82(7)µ(B)) indicates the conventional high-spin state of Co(3+) ions, which is further supported by the results of a combined theoretical and experimental soft X-ray absorption spectroscopy study at the Co-L(2,3) edges on Sr(2)Co(1.2)Ga(0.8)O(5). A high-spin ground state of Co(3+) in Sr(2)Co(1.2)Ga(0.8)O(5) resulted in much lower in comparison with a LaCoO(3) linear thermal expansion coefficient of 13.1 ppm K(-1) (298-1073 K) determined from high-temperature X-ray powder diffraction data collected in air.

From antiferromagnetic insulator to correlated metal in pressurized and doped LaMnPO.

Widespread adoption of superconducting technologies awaits the discovery of new materials with enhanced properties, especially higher superconducting transition temperatures T(c). The unexpected discovery of high T(c) superconductivity in cuprates suggests that the highest T(c)s occur when pressure or doping transform the localized and moment-bearing electrons in antiferromagnetic insulators into itinerant carriers in a metal, where magnetism is preserved in the form of strong correlations. The absence of this transition in Fe-based superconductors may limit their T(c)s, but even larger T(c)s may be possible in their isostructural Mn analogs, which are antiferromagnetic insulators like the cuprates. It is generally believed that prohibitively large pressures would be required to suppress the effects of the strong Hund's rule coupling in these Mn-based compounds, collapsing the insulating gap and enabling superconductivity. Indeed, no Mn-based compounds are known to be superconductors. The electronic structure calculations and X-ray diffraction measurements presented here challenge these long held beliefs, finding that only modest pressures are required to transform LaMnPO, isostructural to superconducting host LaFeAsO, from an antiferromagnetic insulator to a metallic antiferromagnet, where the Mn moment vanishes in a second pressure-driven transition. Proximity to these charge and moment delocalization transitions in LaMnPO results in a highly correlated metallic state, the familiar breeding ground of superconductivity.

Magnetic field induced orbital polarization in cubic YbInNi4: determining the quartet ground state using x-ray linear dichroism.

We have been able to induce a linear dichroic signal in the Yb M(5) x-ray absorption white line of cubic YbInNi(4) by the application of a magnetic field. The nonzero integrated intensity of the magnetic field induced dichroic spectrum indicates a net noncubic 4f orbital polarization. A quantitative analysis of the temperature and field strength dependence establishes that the crystal-field ground state is a Γ(8) quartet. The results demonstrate the potential of magnetic field induced linear dichroism as a new powerful approach for the investigation of the degeneracy and orbital degrees of freedom of cubic heavy-fermion and Kondo systems.

Spin blockade, orbital occupation, and charge ordering in La1.5Sr0.5CoO4.

Using Co-L2,3 and O-K x-ray absorption spectroscopy, we reveal that the charge ordering in La1.5Sr0.5CoO4 involves high spin (S=3/2) Co2+ and low spin (S=0) Co3+ ions. This provides evidence for the spin-blockade phenomenon as a source for the extremely insulating nature of the La2-xSrxCoO4 series. The associated e{g}{2} and e{g}{0} orbital occupation accounts for the large contrast in the Co-O bond lengths and, in turn, the high charge ordering temperature. Yet, the low magnetic ordering temperature is naturally explained by the presence of the nonmagnetic (S=0) Co3+ ions. From the identification of the bands we infer that La1.5Sr0.5CoO4 is a narrow band material.