Pseudo Jahn–Teller origin of ferroelectric instability in BaTiO3 type perovskites: The Green's function approach and beyond

Abstract

The local origin of dipolar distortions in ABO3 perovskite crystals is reexamined by means of a novel approach, the Green's function method augmented by DFT computations. The ferroelectric distortions are shown to be induced by the pseudo Jahn–Teller effect (PJTE). The latter involves vibronic hybridization (admixture) of the ground state to same-spin opposite-parity excited electronic bands. Similar to numerous molecular calculations, the PJT approach provides a deeper insight into the nature of chemical bonding in the octahedral cluster [BO6] and, in particular, reveals the local origin of its polar instability. This allows predicting directly which transition ions can create ferroelectricity. In particular, the necessary conditions are established when an ABO3 perovskite crystal with an electronic dn configuration of the complex ion [BO6] can possess both proper ferroelectric and magnetic properties. Distinguished from the variety of cluster approaches to local properties, the Green's function method includes the influence of the local vibronic-coupling perturbation on the whole crystal via the inter-cell interaction responsible for creation of electronic and vibrational bands. Calculated Green's functions combined with the corresponding numeric estimates for the nine electronic bands, their density of states, and the local adiabatic potential energy surface (APES) confirm the eight-minimum form of this surface and feasibility of the PJT origin of the polar instability in BaTiO3. We show also that multicenter long-range dipole–dipole interactions critically depend on the PJTE largely determining the magnitude of the local dipoles. DFT calculations for the bulk crystal and its clusters confirm that the dipolar distortions are of local origin, but become possible only when their influence on (relaxation of) the whole lattice is taken into account. The results are shown to be in full qualitative and semiquantitative agreement with the experimental data for this crystal.