Charge density distribution of KMnF3 under high pressure

The charge density distributions of KMnF3 under high pressure (0.3, 1.0, 1.7, 2.7, 3.4, 4.0, 4.8, 5.7, and 6.3 GPa) were determined from the synchrotron-radiation powder-diffraction data by the maximum entropy method (MEM). The difference-MEM charge density, which represents deformations from the spherical atomic charge density for each atom, is changed by applying pressure. The excess electrons on the Mn-F bond suggesting a Mn3d-F2p orbital hybridization were found in the difference-MEM charge densities at 0.3 GPa. The excess electrons are localized near Mn nuclei by increasing pressure. Two types of Mn-F bonds were found in the high-pressure tetragonal phase. One is parallel and another is perpendicular to the rotation axis of the F6 octahedra (i.e., c axis). The number of electrons for K, F, and Mn atoms was estimated from the MEM charge densities. The valence statuses of K atom were +1.02e at 0.3 GPa and +0.20e at 6.3 GPa. The valence statuses of F atom were -0.96e at 0.3GPa and -0.60 and -0.77e at 6.3 GPa. On the other hand, the valence status of Mn atom was virtually unchanged with pressure. This fact suggests that the electron charge transfer from F to K atom occurs with increasing pressure.