The ferromagnetic and anti-ferromagnetic phases (cubic, tetragonal, orthorhombic) of KMnF3. A quantum mechanical investigation

Many space groups are proposed in the literature for the KMnF3 perovskite (see, for example, Knight et al., J. Alloys Compd., 2020, 842, 155935), ranging from cubic (C) (Pmm) to tetragonal (T) ( or I4/m) down to orthorhombic (O) (Pbnm). The relative stability ΔE of these phases, both ferromagnetic (FM) and antiferromagnetic (AFM), has been investigated quantum mechanically by using both the B3LYP hybrid functional and the Hartree–Fock Hamiltonian, an all-electron Gaussian type basis set and the CRYSTAL code. The O phase is slightly more stable than the T phase which in turn is more stable than the C phase, in agreement with experimental evidence. The C to T to O transition is accompanied by a volume reduction. The mechanism of stabilization of the AFM solution with respect to the FM one is discussed. Spin density maps and profiles, Mulliken charges, magnetic moments and bond population data are used for supporting the proposed mechanism. The IR and Raman spectra of the FM and AFM C, T and O cells are discussed; the only noticeable difference between the C, T and O spectra appears at wavenumbers lower than 150 cm−1. The effect of pressure is also explored in the 0–20 GPa interval. The stability order (O > T > C) at 0 GPa persists also at high pressure, and the differences between the phases increase.