A re-examination of antiferroelectric PbZrO${}_3$ and PbHfO${}_3$: an 80-atom $Pnam$ structure

Abstract

First principles density functional theory (DFT) simulations of antiferroelectric (AFE) PbZrO${}_3$ and PbHfO${}_3$ reveal a dynamical instability in the phonon spectra of their purported low temperature $Pbam$ ground states. This instability doubles the $c$-axis of $Pbam$ and condenses five new small amplitude phonon modes giving rise to an 80-atom $Pnam$ structure. Compared with $Pbam$, the stability of this structure is slightly enhanced and highly reproducible as demonstrated through using different DFT codes and different treatments of electronic exchange & correlation interactions. This suggests that $Pnam$ is a new candidate for the low temperature ground state of both materials. With this finding, we bring parity between the AFE archetypes and recent observations of a very similar AFE phase in doped or electrostatically engineered BiFeO${}_3$.

14 pages, 3 figures and 4 tables