Ferroelectricity and chirality in the Pb$_5$Ge$_3$O$_{11}$ crystal

Abstract

We study from first-principles calculations the ferroelectric structural phase transition of Pb$_5$Ge$_3$O$_{11}$ crystal. The calculations of phonons and Born effective charges of the paraelectric phase allow us to identify a polar instability that is unstable in both transverse-optic and longitudinal-optic versions, giving rise to an entire branch of instability along a propagation vector parallel to the mode polarization (the hexagonal axe). This is the hint of hyperferroelectricity and the stable head-to-head and tail-to-tail domain, as recently reported from both experiments and theory. Then, our analysis of the ferroelectric phase shows that the polarization of Pb$_5$Ge$_3$O$_{11}$ is uniaxial along the hexagonal axes and with small in-plane components due to a piezoelectric effect. The symmetry-adapted mode analysis shows that the total ferroelectric ground state distortion comes mainly from polar distortions of the unstable polar phonon mode but also from an invariant, cooperative mode that amplifies the polar deformation. We also build a phenomenological model that highlights how the coupling between these modes is at play and helps us understand how to reproduce the second-order phase transition. At last, we also quantify the structural chirality through the continuous symmetry measure method and trace its origin to the polar unstable mode itself. By extending our approach to the phonon states we further show that the chirality is poorly affected by the relaxation but could also be enhanced by activating high frequency modes with polar symmetry. Finally we study the phonon angular momentum (AM) distribution in both phases and identify trends in the AM behaviour across the Brillouin zone.