We have investigated the structure and electronic properties of ferrimagnetic
double perovskites, A2FeReO6 (A= Ca, Sr, Ba). The A=Ba phase is cubic (Fm3m)
and metallic, while the A=Ca phase is monoclinic (P21/n) and nonmetallic.
57Fe Mossbauer spectroscopy shows that iron is present mainly in the
high-spin (S=5/2) Fe3+ state in the Ca compound, while it occurs in an
intermediate state between high-spin Fe2+ and Fe3+ in the Ba compound. It is
argued that a direct Re t2g - Re t2g interaction is the main cause for the
metallic character of the Ba compound; the high covalency of Ca-O bonds and the
monoclinic distortion (which lifts the degeneracy of t2g states) seem to
disrupt the Re-Re interaction in the case of the Ca compound, making it
non-metallic for the same electron count.Comment: 1 eps fil