A mechanism is suggested which can modify in certain cases the Goodenough-Kanamori-Anderson rules determining the character of superexchange in magnetic insulators; namely, side groups coupled to ligands, which are often present but are usually ignored, may contribute significantly, and may in certain cases even lead to a change in sign of the superexchange interaction. Thus this factor can make the 90° superexchange of half-filled shells antiferromagnetic, in contrast to the usual case. Qualitative arguments and numerical estimates show that this mechanism may be important in the inorganic spin-Peierls compound ${\mathrm{CuGeO}}_3$. © 1996 The American Physical Society.

• Received 29 November 1995

DOI:https://doi.org/10.1103/PhysRevB.54.3011