Charge disproportionation in RNiO 3 perovskites

Abstract

RNiO 3 perovskites are one of the few families of undoped oxides showing a metal–insulator transition as a function of temperature. The origin of first-order transition has been one of the long-standing questions associated with these compounds. Neutron and synchrotron diffraction data of small rare-earth members of the series provide the first observation of changes in the crystal symmetry at the metal–insulator (MI) transition in RNiO 3 perovskites. At high temperatures, RNiO 3 are orthorhombic and metallic and below T MI they change to a monoclinic insulator. The structural reorganization at T MI gives rise to two crystallographically independent Ni positions and the insulating phase consist of alternating expanded (Ni1O 6) and contracted (Ni2O 6) octahedra along the three directions of the crystal cell. The magnetic structure shows unequal magnetic moments for the two Ni sites. These findings indicate a Ni charge disproportionation.