Precisely computing phonons via irreducible derivatives

TL;DR

This paper introduces new irreducible derivative methods for more precise and efficient first-principles phonon calculations, addressing inaccuracies in sensitive systems like AuZn and lithium.

Contribution

It presents the LID, BID, and hybrid approaches with a CNO basis, improving accuracy and efficiency in phonon computations from finite displacements.

Findings

Demonstrated improved phonon accuracy in AuZn and lithium

Developed a hybrid LID-BID method for optimized precision

Provided a fully automated approach suitable for high throughput

Abstract

Computing phonons from first-principles is typically considered a solved problem, yet inadequacies in existing techniques continue to yield deficient results in systems with sensitive phonons. Here we circumvent this issue using the lone irreducible derivative (LID) and bundled irreducible derivative (BID) approaches to computing phonons via finite displacements, where the former optimizes precision via energy derivatives and the latter provides the most efficient algorithm using force derivatives. A condition number optimized (CNO) basis for BID is derived which guarantees the minimum amplification of error. Additionally, a hybrid LID-BID approach is formulated, where select irreducible derivatives computed using LID replace BID results. We illustrate our approach on two prototypical systems with sensitive phonons: the shape memory alloy AuZn and metallic lithium. Comparing our resulting phonons in the aforementioned crystals to calculations in the literature reveals nontrivial inaccuracies. Our approaches can be fully automated, making them well suited for both niche systems of interest and high throughput approaches.