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Mn(I) in an extended oxide: the synthesis and characterization of La1–xCaxMnO2+δ (0.6 ≤ x ≤ 1)

DOI: 10.1021/ja207616c DOI Help

Authors: Edward Dixon (University of Oxford) , Joke Hadermann (University of Antwerp) , Silvia Ramos (Diamond Light Source) , Andrew L. Goodwin (University of Oxford) , Michael A. Hayward (University of Oxford)
Co-authored by industrial partner: No

Type: Journal Paper
Journal: Journal Of The American Chemical Society , VOL 133 (45)

State: Published (Approved)
Published: October 2011
Diamond Proposal Number(s): 2122

Abstract: Reduction of La1–xCaxMnO3 (0.6 ? x ? 1) perovskite phases with sodium hydride yields materials of composition La1–xCaxMnO2+?. The calcium-rich phases (x = 0.9, 1) adopt (La0.9Ca0.1)0.5Mn0.5O disordered rocksalt structures. However local structure analysis using reverse Monte Carlo refinement of models against pair distribution functions obtained from neutron total scattering data reveals lanthanum-rich La1–xCaxMnO2+? (x = 0.6, 0.67, 0.7) phases adopt disordered structures consisting of an intergrowth of sheets of MnO6 octahedra and sheets of MnO4 tetrahedra. X-ray absorption data confirm the presence of Mn(I) centers in La1–xCaxMnO2+? phases with x < 1. Low-temperature neutron diffraction data reveal La1–xCaxMnO2+? (x = 0.6, 0.67, 0.7) phases become antiferromagnetically ordered at low temperature.

Subject Areas: Chemistry, Materials

Instruments: B18-Core EXAFS

Other Facilities: POLARIS at ISIS

Added On: 31/10/2011 09:59

Discipline Tags:

Chemistry Materials Science Inorganic Chemistry

Technical Tags:

Spectroscopy X-ray Absorption Spectroscopy (XAS) X-ray Absorption Near Edge Structure (XANES)