A novel atomistic effective Hamiltonian scheme, incorporating an original and simple bilinear energetic coupling, is developed and used to investigate the temperature-dependent physical properties of the prototype antiferroelectric ${\mathrm{PbZrO}}_3$ (PZO) system. This scheme reproduces very well the known experimental hallmarks of the complex Pbam orthorhombic phase at low temperatures and the cubic paraelectric state of $\mathrm{Pm}\overline{3}\mathrm{m}$ symmetry at high temperatures. Unexpectedly, it further predicts a novel intermediate state also of Pbam symmetry, but in which antiphase oxygen octahedral tiltings have vanished with respect to the Pbam ground state. Interestingly, such a new state exhibits a large dielectric response and thermal expansion that remarkably agrees with previous experimental observations and the x-ray experiments we performed. We also conducted direct first-principles calculations at 0 K, which further support such a low-energy phase. Within this fresh framework, a reexamination of the properties of PZO is thus called for.

• Received 26 August 2022
• Revised 27 October 2022
• Accepted 29 November 2022

DOI:https://doi.org/10.1103/PhysRevB.106.214108