Effect of Metal−Ligand Bond Lengths on Superexchange Interactions in Jahn−Teller d⁴ Ion Systems:  Spin Dimer Analysis of the Magnetic Structure of Marokite CaMn₂O₄

Abstract

In marokite CaMn(2)O(4), all six Mn-O bonds of each MnO(6) octahedron are different because of the Jahn-Teller distortion so that every Mn(3+) (d(4)) ion has six different superexchange interactions with its neighboring Mn(3+) ions. The spin exchange interactions of CaMn(2)O(4) were examined on the basis of spin dimer analysis to find what geometrical parameters of the Mn-O-Mn superexchange paths control the signs and strengths of their spin exchange interactions. Our work correctly describes the magnetic structure of CaMn(2)O(4) observed from neutron powder diffraction measurements and shows that the antiferromagnetic interactions of the Mn-O-Mn paths depend primarily on the asymmetry and the Mn-O bond length of the Mn-O-Mn bridge, but not on the 90 degree angle Mn-O-Mn bond angle.