Electric Polarization from Nonpolar Phonons

TL;DR

This paper extends the Born effective charge framework to include second-order effects, revealing that nonpolar phonons can induce significant polarization in oxides, which has implications for designing advanced ferroelectric and piezoelectric materials.

Contribution

It introduces the concept of second-order dynamical charge and demonstrates its importance in polarization phenomena in nonpolar phonons using first-principles calculations.

Findings

Nonpolar phonons can induce large second-order polarization.

Second-order mode effective charge is significant in oxides and perovskites.

Microscopic origin linked to bond covalency and electronic rearrangements.

Abstract

Born effective charge (BEC), a fundamental quantity in lattice dynamics and ferroelectric theory, provides a quantitative measure of linear polarization response to ionic displacements. However, it does not account for higher-order effects, which can play a significant role in certain materials, such as fluorite HfO$_2$. In this letter, we extend the BEC framework by introducing the concept of second-order dynamical charge and mode effective charge. Using first-principles calculations, we demonstrate that specific combinations of nonpolar phonon modes in many oxides can induce substantial second-order polarizations, reaching magnitudes comparable to those of intrinsically polar modes. Through a symmetry-based analysis of the charge density, we elucidate the microscopic origin of these effects, tracing them to variations in bond covalency and local electronic rearrangements. We also demonstrate large second-order mode effective charge in well-studied perovskites such as SrTiO$_3$, highlighting the generality of these phenomena. Our results reveal a previously unrecognized mechanism that drives polarization in crystalline solids, offering new insights into the design principles of next-generation ferroelectric, piezoelectric and multifunctional materials.