Electronic structure of incipient ferroelectric CaTiO3

CaTiO3 is widely used in electronic ceramic materials, it is also a key component of Synroc, a synthetic rock form used to immobilize nuclear waste. There has been considerable interest in the structure phase transitions of this typical perovskite oxide. As reported by Kennedy et al., CaTiO3 is orthorhombic with space group Pbnm below 1380 K and belongs to another orthorhombic space group Cmcm between 1380 K and 1500 K. At 1500 K, it transforms into tetragonal with space group 14/mcm. Above 1580 K, it becomes cubic with space group Pm (3) over barm. Lemanov et al. measured the dielectric properties of CaTiO3 at low temperature, and classified it as an incipient ferroelectric or a quantum paraelectric. CaTiO3 is Called a "higher" quantum paraelectric because its dielectric constant saturates at higher temperature than that for other quantum paraelectrics such as SrTiO3 and KTaO3. To understand the physics underlying these properties, first - principles calculation of the electronic structure is desirable. In order to understand the tendency of the CaTiO3 cubic perovskite to suffer a ferroelectric transition, we calcutated the electronic properties of CaTiO3 for different displacement of Ti in the [001] direction. At the experiment equilibrium volume ( V/V-0 = 1.0), CaTiO3 is not energetically favored with the proposed ferroelectric distortion. However, with a 10% volume expansion( V/V-0 = 1.1), the same displacement results in a shallow, but well defined double well. It implies that there is a tendency to ferroelectricity in cubic CaTiO3 crystal. This is consistent with the experimental results that point out that CaTiO3 is an incipient ferroelectric. From our calculation, the ferroelectric state can be induced by a negative pressure. The DOS of Ti d and O p at Deltaz = 0.03 for V = V-0 shows there is a weak hybridization between Ti d and O p. While for a 10% volume expansion, this hybridization becomes stronger. Like other perovskites, it is this hybridization between Ti 3d and O 2p that weakens the short range repulsions and stabilizes the ferroelectricity. The strong hybridization implies that the interaction between Ti and O is highly covalent. This is consistent with the analysis of the total energy. From the calculated total energy, it is shown that CaTiO3 has a tendency to a ferroelectric state in which the atom Ti displaces in the [001] direction. An analysis of the DOS and electric field gradients reveals that there is a hybridization between Ti 3d and O 2p. This hybridization is essential leading to the incipient ferroelectricity.