Order-disorder transition in the prototypical antiferroelectric PbZrO${}_3$

Abstract

The prototypical antiferroelectric PbZrO${}_3$ has several unsettled questions, such as the nature of the antiferroelectric transition, possible intermediate phase and the microscopic origin of the Pbam ground state. Using first principles, we show that no phonon becomes truly soft at the cubic-to-Pbam transition temperature, and the order-disorder character of this transition is clearly demonstrated based on molecular dynamics simulations and potential energy surfaces. The out-of-phase octahedral tilting is an important degree of freedom, which can collaborate with other phonon distortions and form a complex energy landscape with multiple minima. Candidates of the possible intermediate phase are suggested based on the calculated kinetic barriers between energy minima, and the development of a first-principles-based effective Hamiltonian. The use of this latter scheme further reveals that specific bi-linear interactions between local dipoles and octahedral tiltings play a major role in the formation of the Pbam ground state, which contrasts with most of the previous explanations.

References in corpus (4)

• Restoring the density-gradient expansion for exchange in solids and surfaces
• Generalized gradient approximation for solids and their surfaces
• Phase diagram of Pb(Zr,Ti)O3 solid solutions from first principles
• First-principles study of the multi-mode anti-ferroelectric transition of PbZrO3

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• Origin of negative electrocaloric effect in Pnma-type antiferroelectric perovskites
• A new look at the temperature-dependent properties of the antiferroelectric model PbZrO3: an effective Hamiltonian study
• Beware of the water: Hidden hydrogenation of perovskite membranes made by the water-soluble sacrificial layer method