Ferroelectric, quantum paraelectric or paraelectric? Calculating the evolution from BaTiO$_3$ to SrTiO$_3$ to KTaO$_3$ using a single-particle quantum-mechanical description of the ions

TL;DR

This paper introduces a cost-effective first-principles method combining DFT and quantum ion treatment to distinguish ferroelectric, paraelectric, and quantum paraelectric materials, and explores effects of isotope substitution and strain.

Contribution

It presents a novel single-particle quantum-mechanical approach for modeling quantum paraelectricity using standard DFT data, applicable to multiple materials.

Findings

The method effectively differentiates between ferroelectric, paraelectric, and quantum paraelectric states.

Isotope substitution has minimal impact on quantum paraelectric behavior.

Strain can significantly alter quantum paraelectric properties.

Abstract

We present an inexpensive first-principles approach for describing quantum paraelectricity that combines density functional theory (DFT) treatment of the electronic subsystem with quantum mechanical treatment of the ions through solution of the single-particle Schr\"odinger equation with the DFT-calculated potential. Using BaTiO$_3$, SrTiO$_3$ and KTaO$_3$ as model systems, we show that the approach can straightforwardly distinguish between ferroelectric, paraelectric and quantum paraelectric materials, based on simple quantities extracted from standard density functional and density functional perturbation theories. We calculate the influence of isotope substitution and strain on the quantum paraelectric behavior, and find that, while complete replacement of oxygen-16 by oxygen-18 has a surprisingly small effect, experimentally accessible strains can induce large changes. Finally, we collect the various choices for the phonon mass that have been introduced in the literature. We identify those that are most physically meaningful by comparing with our results that avoid such a choice through the use of mass-weighted coordinates.