ABSTRACT
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.
ABSTRACT
The origin of both the Ising chain magnetism and ferroelectricity in Ca3CoMnO6 is studied by ab initio electronic structure calculations and x-ray absorption spectroscopy. We find that Ca3CoMnO6 has alternate trigonal prismatic Co2+ and octahedral Mn4+ sites in the spin chain. Both the Co2+ and Mn4+ are in the high-spin state. In addition, the Co2+ has a huge orbital moment of 1.7micro_{B} which is responsible for the significant Ising magnetism. The centrosymmetric crystal structure known so far is calculated to be unstable with respect to exchange striction in the experimentally observed upward arrow upward arrow downward arrow downward arrow antiferromagnetic structure for the Ising chain. The calculated inequivalence of the Co-Mn distances accounts for the ferroelectricity.
ABSTRACT
Sr3(Ru(1-x)Mnx)2O7, in which 4d-Ru is substituted by the more localized 3d-Mn, is studied by x-ray dichroism and spin-resolved density functional theory. We find that Mn impurities do not exhibit the same 4+ valence of Ru, but act as 3+ acceptors; the extra eg electron occupies the in-plane 3d(x2-y2) orbital instead of the expected out-of-plane 3d(3z2-r2). We propose that the 3d-4d interplay, via the ligand oxygen orbitals, is responsible for this crystal-field level inversion and the material's transition to an antiferromagnetic, possibly orbitally ordered, low-temperature state.
ABSTRACT
Using soft x-ray absorption spectroscopy and magnetic circular dichroism at the Co-L(2,3) edge, we reveal that the spin state transition in LaCoO3 can be well described by a low-spin ground state and a triply degenerate high-spin first excited state. From the temperature dependence of the spectral line shapes, we find that LaCoO3 at finite temperatures is an inhomogeneous mixed-spin state system. It is crucial that the magnetic circular dichroism signal in the paramagnetic state carries a large orbital momentum. This directly shows that the currently accepted low- or intermediate-spin picture is at variance. Parameters derived from these spectroscopies fully explain existing magnetic susceptibility, electron spin resonance, and inelastic neutron data.
ABSTRACT
Using x-ray absorption spectroscopy at the Ru-L2,3 edge we reveal that the Ru4+ ions remain in the S=1 spin state across the rare 4d-orbital ordering transition and spin-gap formation. We find using local spin density approximation + Hubbard U band structure calculations that the crystal fields in the low-temperature phase are not strong enough to stabilize the S=0 state. Instead, we identify a distinct orbital ordering with a significant anisotropy of the antiferromagnetic exchange couplings. We conclude that La4Ru2O10 appears to be a novel material in which the orbital physics drives the formation of spin-singlet dimers in a quasi-two-dimensional S=1 system.
