New polaronic excitons in ferroelectric oxides: phenomenological theory

It is shown that three types of new polaronic excitons exist in ferroelectric oxides–charge transfer vibronic excitons (CTVEs). The electron-hole bipolaron pairs are common in all these cases, the difference having to do with the origin of charge transfer–lattice instabilities. These are the cases of the charge transfer and lattice distortions and their vibronic interactions induced in the harmonic (i) and anharmonic (ii) regimes both in the electronic excited state on the one hand, and the (iii) case of the CTVE excited vibronic state induced in the anharmonic regime but related with electronic ground state on the other. All these CTVEs are characterized by strong coupling with good self-localization conditions in separate orientation wells of their multi-well potentials. The relevant phenomenological theory is developed. While the (i) type CTVE is confirmed by luminescence experiments, the (iii) type CTVE with low excitation energy and with metastable intrinsic defect behaviour can be a candidate for the explanation of an order-disorder effect in the classical ferroelectric oxides discovered recently [Phys. Rev. Lett. 90 (2003) 037601].