We have studied the electronic structure of unoccupied states measured by O K-edge and Cu L-edge x-ray absorption spectroscopy (XAS), combined with crystal structure studied by high resolution powder x-ray diffraction (HRPXRD), of charge-compensated layered superconducting CaxLa(1-x)Ba(1.75-x)La(0.25+x)Cu3Oy (0<x<0.4, 6.4<y<7.3) cuprate. A detailed analysis shows that, apart from hole doping, chemical pressure on the electronically active CuO2 plane due to the lattice mismatch with the spacer layers greatly influences the superconducting properties of this system. The results suggest chemical pressure to be the most plausible parameter to control the maximum critical temperatures (Tcmax) in different cuprate families at optimum hole density.
We present a combined experimental and theoretical study on the local magnetism of the Co ions in the spin-chain compound CoV2O6, which crystallizes in two different allotropic phases, alpha- and gamma-CoV2O6. Using x-ray magnetic circular dichroism, we have found a very large and a moderate orbital contribution to the magnetism in alpha- and gamma-CoV2O6, respectively. Full-multiplet calculations indicate that the differences in the magnetic behavior of alpha- and gamma-CoV2O6 phases originate from different local distortions of the CoO6 octahedra. In particular, the strong compression of the CoO6 octahedra in alpha-CoV2O6 lead to a strong mixture of t2g and eg orbitals which, via the local atomic Coulomb and exchange interactions, results in an exceptionally large orbital moment.
Using powder neutron diffraction we have discovered an unusual magnetic order-order transition in the Ising spin chain compound Ca3Co2O6. On lowering the temperature an antiferromagnetic phase with propagation vector k=(0.5,-0.5,1) emerges from a higher temperature spin density wave structure with k=(0, 0, 1.01). This transition occurs over an unprecedented time-scale of several hours and is never complete.
We present single-crystal neutron-diffraction data for the spin-chain compound Ca3Co2O6. The intensity and line shapes of the two families of Bragg peaks characterising both the antiferromagnetic and the ferromagnetic components of the magnetic order present in this material have been measured as a function of temperature and applied magnetic fields of up to 5 T. We have studied the microscopic nature of the magnetic order at each step seen in the bulk magnetisation and investigated the evolution of the long and short-range components of the magnetic order in Ca3Co2O6.
X-ray absorption spectroscopy (XAS) and high resolution X-ray diffraction are combined to study the interplay between electronic and lattice structures in controlling the superconductivity in cuprates with a model charge-compensated CaxLa1-xBa1.75-xLa0.25+xCu3Oy (0<x<0.5, y=7.13) system. In spite of a large change in Tc, the doped holes, determined by the Cu L and O K XAS, hardly show any variation with the x. On the other hand, the CuO2 plaquette size shows a systematic change due to different size of substituted cations. The results provide a direct evidence for the chemical pressure being a key parameter for controlling the superconducting ground state of the cuprates.
We have performed a resonant x-ray scattering (RXS) study near the Co K edge on a single crystal of Ca3Co2O6. In the magnetically ordered phase a new class of weak reflections appears at the magnetic propagation vector tau (1/3,1/3,1/3). These new reflections allow direct access to the dipolar-quadrupolar E1E2 scattering channel. The theoretical possibility of observing isolated E1E2 electromagnetic multipoles has attracted a lot of interest in the recent years. Unfortunately in many system of interest, parity even and parity odd tensor contributions occur at the same positions in reciprocal space. We demonstrate that in Ca3Co2O6 it is possible to completely separate the parity even from the parity odd terms. The possibility of observing such terms even in globally centrosymmetric systems using RXS has been investigated theoretically; Ca3Co2O6 allows a symmetry based separation of this contribution.
