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Lattice parameters and orthorhombic distortion of CaMnO3

Published online by Cambridge University Press:  29 February 2012

Wojciech Paszkowicz*
Affiliation:
Institute of Physics, Polish Academy of Sciences, Lotnikow 32/46, 02-668 Warsaw, Poland
Jarosław Piętosa
Affiliation:
Institute of Physics, Polish Academy of Sciences, Lotnikow 32/46, 02-668 Warsaw, Poland
Scott M. Woodley
Affiliation:
Department of Chemistry, University College London, 3rd Floor, Kathleen Lonsdale Building, Gower Street, London WC1E 6BT, United Kingdom
Piotr A. Dłużewski
Affiliation:
Institute of Physics, Polish Academy of Sciences, Lotnikow 32/46, 02-668 Warsaw, Poland
Mirosław Kozłowski
Affiliation:
Institute of Physics, Polish Academy of Sciences, Lotnikow 32/46, 02-668 Warsaw, Poland
Christine Martin
Affiliation:
Laboratoire CRISMAT-ENSICAEN, UMR CNRS 6805, CNRS, 6, Bld. Maréchal Juin, 14050 Caen Cedex 04, France
*
a)Author to whom correspondence should be addressed. Electronic mail: paszk@ifpan.edu.pl

Abstract

CaMnO3 is a parent compound for numerous multicomponent manganese perovskite oxides. Its crystallographic data are of primary importance in the science and technology of functional CaMnO3-based materials. In the present study, data were collected for a CaMnO3 sample at 302 K. The crystal structure refinement yields accurate absolute values of lattice parameters, a=5.281 59(4) Å, b=7.457 30(4) Å, and c=5.267 48(4) Å, leading to orthorhombic distortion of (c/a, √2c/b)=(0.997 33,0.998 95). The orthorhombic distortion of the CaMnO3 structure is discussed on the basis of comparison of our unit-cell size with data already published. At a graphical representation of the distortion, it is observed that there is a considerable scatter of the distortion values among the literature data but, interestingly, a considerable fraction of experimental results (including the present one) for stoichiometric samples are grouped around the distortion (c/a, √2c/b)=(0.9973,0.9990), which lies close to a maximum in the extent of orthorhombicity. The influence of off-stoichiometry on the orthorhombic distortion is discussed on the basis of available experimental data. Simulations, employing a mean-field approach for low temperatures, predict an increase in cell volume and structural distortions with the concentration of oxygen vacancies when the additional electrons are localized on the manganese. A simple model of delocalization produced the opposite effect, which is expected to combine with lattice vibrations to recover the cubic phase at high temperatures.

Type
Technical Articles
Copyright
Copyright © Cambridge University Press 2010

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