Metallic and nonmetallic double perovskites: A case study of {A_2FeReO_6} (A=Ca, Sr, Ba)

We have investigated the structure and electronic properties of ferrimagnetic double perovskites, {A_2FeReO_6} (A = Ca, Sr, Ba). The A = Ba phase is cubic (Fm3m) and metallic, while the A = Ca phase is monoclinic {P2_1 /n} and nonmetallic. Fe{^57 Mossbauer} spectroscopy shows that iron is present mainly in the high spin S = (5/2) {Fe^3+} state in the Ca compound, while it occurs in an intermediate state between high spin {Fe^2+ and Fe^3+} in the Ba compound. It is argued that a direct {Re t_2g-Re_ t2g} interaction is the main cause for the metallic character of the Ba compound; the smaller size of Ca and the monoclinic distortion (which lifts the degeneracy of {t_2g} states seem to disrupt the Re-Re interaction in the case of the Ca compound, making it nonmetallic for the same electron count.