Lattice parameters and orthorhombic distortion of CaMnO3

Abstract

CaMnO3is 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 CaMnO3sample 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, andc=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 CaMnO3structure 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.