ABSTRACT
A novel perovskite oxide, CaCu3Rh4O12, has been synthesized under high-pressure and high-temperature conditions (15 GPa and 1273 K). Rietveld refinement of synchrotron X-ray powder diffraction data indicates that this compound crystallizes in a cubic AA'3B4O12-type perovskite structure. Synchrotron X-ray absorption and photoemission spectroscopy measurements reveal that the Cu and Rh valences are nearly trivalent. The spectroscopic analysis based on calculations suggests that the appropriate ionic model of this compound is Ca(2+)Cu(â¼2.8+)3Rh(â¼3.4+)4O12, as opposed to the conventional Ca(2+)Cu(2+)3Rh(4+)4O12. The uncommon valence state of this compound is attributed to the relative energy levels of the Cu 3d and Rh 4d orbitals, in which the large crystal-field splitting energy of the Rh 4d orbitals is substantial.
Subject(s)
Calcium Compounds/chemical synthesis , Oxides/chemistry , Calcium Compounds/chemistry , Hot Temperature , Oxides/chemical synthesis , Powder Diffraction , Pressure , Titanium/chemistry , X-Ray Absorption SpectroscopyABSTRACT
An A-site-ordered perovskite LaCu3Pt(3.75)O12 was synthesized by replacing Ca(2+) with La(3+) in a cubic quadruple AA'3B4O12-type perovskite CaCu3Pt4O12 under high-pressure and high-temperature of 15 GPa and 1100 °C. In LaCu3Pt(3.75)O12, 1/16 of B-site cations are vacant to achieve charge balance. The B-site deficiencies were evidenced by crystal structure refinement using synchrotron X-ray powder diffraction, hard X-ray photoemission spectroscopy, and soft X-ray absorption spectroscopy, leading to the ionic model La(3+)Cu(2+)3Pt(4+)(3.75)O(2-)12. Magnetic susceptibility data for this compound indicated a spin-glass-like behavior below T(g) = 3.7 K, which is attributed to disturbance of the antiferromagnetic superexchange interaction by the B-site deficiencies.
