High-pressure synthesis, crystal structure determination, and a Ca substitution study of the metallic rhodium oxide NaRh2O4

The sodium rhodate NaRh2O4 was synthesized for the first time and characterized by neutron and x-ray diffraction studies, measurements of magnetic susceptibility, specific heat, electrical resistivity, and the Seebeck coefficient. NaRh2O4 crystallizes in the CaFe2O4-type structure, which is comprised of a characteristic RhO6 octahedra network. The compound is metallic in nature, probably reflecting the 1 to 1 mixed valence character of Rh(III) and Rh(IV) in the network. For further studies of the compound, the Rh valence was varied significantly by means of an aliovalent substitution: the full range solid solution between NaRh2O4 and CaRh2O4 was achieved and characterized as well. The metallic state was dramatically altered, and a peculiar magnetism developed in the low Na concentration range.