Vibronic Magnetoelectric Effects in the Bi-Based Multiferroics

The detailed magneto-electron-lattice (vibronic) theory of ferroelectricity in the Bi-based multiferroics (BiFeO₃ etc.) is developed further. The vibronic admixture of the empty oxygen 2p states to the Bi 6s lone electron pair state leads to ferroelectricity. These interactions are the driving and restoring forces of the structural phase transformations of the Bi-based multiferroics. The free energy of the BiFeO₃-type multiferroics with the ferroelectric and the G-type antiferromagnetic phase transitions are derived. The Zeeman splitting and spin-transversal optical phonon couplings are also important.