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X-ray diffraction and density functional theory studies of R(Fe0.5Co0.5)O3 (R = Pr, Nd, Sm, Eu, Gd)

Published online by Cambridge University Press:  20 September 2016

W. Wong-Ng ,
G. Liu ,
I. Levin ,
I. Williamson ,
P. Ackerman ,
K. R. Talley ,
J. Martin ,
K. AlHamdan ,
W. Badegaish  and
J. A. Kaduk
...Show all authors
W. Wong-Ng*
Affiliation:
Materials Measurement Science Division, National Institute of Standards and Technology, Gaithersburg, Maryland 20899
G. Liu
Affiliation:
Science Research Institute, China University of Geosciences, Beijing 100083, China
I. Levin
Affiliation:
Materials Measurement Science Division, National Institute of Standards and Technology, Gaithersburg, Maryland 20899
I. Williamson
Affiliation:
Micron School of Materials Science and Engineering, Boise State University, Boise, Idaho 83725
P. Ackerman
Affiliation:
Department of Materials Science and Engineering, Carnegie Melon University, Pittsburgh, Pennsylvania 15213
K. R. Talley
Affiliation:
Micron School of Materials Science and Engineering, Boise State University, Boise, Idaho 83725
J. Martin
Affiliation:
Materials Measurement Science Division, National Institute of Standards and Technology, Gaithersburg, Maryland 20899
K. AlHamdan
Affiliation:
Department of Materials Science and Engineering, The Catholic University of America, Washington, DC 20064
W. Badegaish
Affiliation:
Department of Materials Science and Engineering, The Catholic University of America, Washington, DC 20064
J. A. Kaduk
Affiliation:
Department of Chemistry, Illinois Institute of Technology, Chicago, Illinois 60616
L. Li
Affiliation:
Micron School of Materials Science and Engineering, Boise State University, Boise, Idaho 83725 Center for Advanced Energy Studies, Idaho Falls, Idaho 83401
*
a)Author to whom correspondence should be addressed. Electronic mail: [email protected]
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Abstract

The structure of a series of lanthanide iron cobalt perovskite oxides, R(Fe0.5Co0.5)O3 (R = Pr, Nd, Sm, Eu, and Gd), have been investigated. The space group of these compounds was confirmed to be orthorhombic Pnma (No. 62), Z = 4. From Pr to Gd, the lattice parameter a varies from 5.466 35(13) Å to 5.507 10(13) Å, b from 7.7018(2) to 7.561 75(13) Å, c from 5.443 38(10) to 5.292 00(8) Å, and unit-cell volume V from 229.170(9) Å3 to 220.376(9) Å3, respectively. While the trend of V follows the trend of the lanthanide contraction, the lattice parameter “a” increases as the ionic radius r(R3+) decreases. X-ray diffraction (XRD) and transmission electron microscopy confirm that Fe and Co are disordered over the octahedral sites. The structure distortion of these compounds is evidenced in the tilt angles θ, ϕ, and ω, which represent rotations of an octahedron about the pseudocubic perovskite [110]p, [001]p, and [111]p axes. All three tilt angles increase across the lanthanide series (for R = Pr to R = Gd: θ increases from 12.3° to 15.2°, ϕ from 7.5° to 15.8°, and ω from 14.4° to 21.7°), indicating a greater octahedral distortion as r(R3+) decreases. The bond valence sum for the sixfold (Fe/Co) site and the eightfold R site of R(Fe0.5Co0.5)O3 reveal no significant bond strain. Density Functional Theory calculations for Pr(Fe0.5Co0.5)O3 support the disorder of Fe and Co and suggest that this compound to be a narrow band gap semiconductor. XRD patterns of the R(Fe0.5Co0.5)O3 samples were submitted to the Powder Diffraction File.

Keywords

R(Fe0.5Co0.5)O3 (R = Pr, Nd, Sm, Eu, and Gd)DFT calculationsTEMcrystal structureX-ray powder diffraction patterns
Type
Technical Articles
Information
Powder Diffraction , Volume 31 , Issue 4 , December 2016 , pp. 259 - 266
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Copyright
Copyright © International Centre for Diffraction Data 2016 

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