First principles calculations of dynamical Born effective charges, quadrupoles and higher order terms from the charge response in large semiconducting and metallic systems

TL;DR

This paper introduces a computational framework for efficiently calculating dynamical Born effective charges, quadrupoles, and higher-order charge response terms in large semiconducting and metallic systems, enhancing the analysis of inelastic scattering processes.

Contribution

It presents a new method to determine charge responses at finite momentum using perturbation theory, applicable to large systems and metals, with implications for material property predictions.

Findings

Efficient computation of Born effective charges and quadrupoles in large systems.

Decomposition of piezoelectric response into localized chemical contributions.

Application to TEM-EELS spectroscopy revealing atomic form-factor limitations.

Abstract

Within the context of first principles techniques we present a theoretical and computational framework to quickly determine, at finite momentum, the self-consistent (longitudinal) charge response to an external perturbation, that enters the determination of the scattering cross section of inelastic scattering processes such as EELS. We also determine the (tranverse) charge response computed in short-circuit condition. The all-order quasimomentum expansion of the tranverse charge response to an atomic displacement are the Born effective charges, quadrupoles, octupoles etc. We demonstrate that the transverse charge response can be related to the longitudinal one via a well-defined long-range dielectric function. Our advancements lead to an efficient use of perturbation theory. Due to its more favorable scaling, our method provides an interesting computational alternative to the use of the 2n+1 theorem, especially for semiconductors and metals with large unit cells. For semiconductors, we compute the piezoelectric properties of a large cell solid-solution of semiconducting hafniun oxide containing 96 atoms. We here show that the clamped ion piezoelectric response can be decomposed into real-space localized contributions that mostly depend on the chemical environment, paving the way for the use of machine-learning techniques in the material search for optimized piezoelectrics. We further apply our methodology to determine the density response of metals. Here, the leading terms of the charge expansion are related to the Fermi energy shift of the potential and by Born effective charges which do not sum to zero over the atoms. We apply our developments to the TEM-EELS spectroscopy of lithium intercalated graphites, where we find that the use of the atomic form-factor in the long-wavelength limit does not take into account for the anisotropy of the atomic chemical bonding.