Orbital driven impurity spin effect on the magnetic order of quasi-three dimensional cupric oxide

Density functional calculations are performed to study the magnetic order of the severely distorted square planar cupric oxide (CuO) and local spin disorder in it in the presence of the transition metal impurities M (= Cr, Mn, Fe, Co and Ni). The distortion in the crystal structure, arisen to reduce the band energy by minimizing the covalent interaction, creates two crisscrossing zigzag spin-1/2 chains. From the spin dimer analysis we find that while the spin chain along [101̅] has strong Heisenberg type antiferromagnetic coupling (J ~ 127 meV), along [101] it exhibits weak, but robust, ferromagnetic coupling (J ~ 9 meV) mediated by reminiscent p-d covalent interactions. The impurity effect on the magnetic ordering is independent of M and purely orbital driven. If the given spin-state of M is such that the dx2−y2 orbital is spin-polarized, then the original long-range ordering is maintained. However, if dx2−y2 orbital is unoccupied, the absence of corresponding covalent interaction breaks the weak ferromagnetic coupling and a spin-flip takes place at the impurity site leading to breakdown of the long range magnetic