Vibrational and dielectric properties of La2Hf2O7 : Experiment and theory

The physical origin of the static dielectric constant and its relationship with lattice dynamics of La2Hf2O7are studied by combining infrared spectroscopy and density functional perturbation theory (DFPT). Both La and Hf show obvious effective charge anomaly which is attributed to the hybridization between 2p states of the oxygen and 5d states of the cations, indicating a mixed covalent–ionic bonding between the cations and the oxygen. The dielectric response is determined by seven infrared phonon modes and the static dielectric constant extracted from infrared reflection spectrum is in close agreement with DFPT calculation. Both experiment and theory reveal that most of the contributions to the static dielectric constant are dominated by three infrared phonon modes at 137, 172 and 297 cm−1. Two of them (172 and 297 cm−1) are from the displacements of oxygen atoms inside HfO6 octahedra and the other one (137 cm−1) is from the bending of La2O′ chain. This result indicates that the origin of the static dielectric constant of La2Hf2O7 is directly connected with the two interpenetrating sub-networks of pyrochlore structure (HfO6 octahedra and La2O′ chain).

► The physical origin of the static dielectric constant of La2Hf2O7 is studied.
► The static dielectric constant is related to the La2O′ chain and HfO6 octahedron.
► The effective charge anomaly is attributed to the hybridization between O-2p and 5d cations.