Structural and thermal properties of LaMnO3 from neutron diffraction and first principles studies

Neutron diffraction experiments have been performed on powder samples of LaMnO(3) below and above the Jahn-Teller transition temperature of 750 K. Experimental investigations are assisted by density functional theory calculations. Theoretical studies are carried out for the orbitally ordered state of LaMnO(3) which allows one to compare the behavior of the orbitally ordered and disordered structures as a function of temperature. The temperature dependences of the structural parameters characterizing the Jahn-Teller distortions are reported and discussed. A gradual departure of the experimental data from theoretical predictions is observed above 650 K. In this range of temperatures, anions surrounding the Jahn-Teller active cations perform more isotropic thermal motion. The onset of structural phase transition induces a reduction of the crystal volume by about 0.4% which follows from the structural transformations yielding more regular oxygen octahedra formed above the phase transformation. It is found that above the Jahn-Teller transition the distortions of the MnO(6) octahedra are not completely removed. The non-vanishing distortions are accompanied by the lifted degeneracy of the Mn e(g) states. Weak residual distortions can be assigned to the short-range orbital order that persists within a local scale but it seems quenched on average giving rise to a disappearance of the long-range order coherency of the Jahn-Teller effect.