Volcano-Like Ferroic Transitions Deviating from the Model of Landau Theory

TL;DR

This paper predicts novel volcano-like temperature dependencies of polarization and magnetization in certain ferroic materials, deviating from classical Landau theory, supported by first-principles calculations on specific systems.

Contribution

It introduces new models of ferroic transitions with volcano-like behavior, expanding understanding beyond traditional Landau theory, and demonstrates these phenomena through computational studies.

Findings

Volcano-like polarization and magnetization temperature dependence predicted.

Metastable phases influence switching pathways and properties.

First-principles calculations confirm the proposed phenomena.

Abstract

We predict the existence of abnormal volcano-like temperature dependence of polarization or magnetization with maxima located at elevated temperature, distinct from classical model based on Landau theory. One case is ferroelectricity with long ion displacements and quantized polarizations that cannot be used for expansion in Landau model, and the switching pathway involves various metastable phases where the polar phase is higher both in energy and entropy compared with non-polar phase. Another case is compensated antiferromagnets with two opposite spin lattices of different spin exchange constants. Such difference can be utilized for a unique type of temperature differentiated multiferroicity, where large magnetizations can be reversed upon ferroelectric switching between two Curie temperature with alternating half of spins in paramagnetic state. We demonstrate these proposals by first-principles calculations on several paradigmatic systems, including magnetic bilayers intercalated by Ag ions or metal molecules.