Efficacious symmetry-adapted atomic displacement method for lattice dynamical studies

TL;DR

This paper introduces a symmetry-adapted atomic displacement method for lattice dynamical studies that optimizes displacement directions based on group theory, improving accuracy and robustness especially for low-symmetry crystals.

Contribution

The authors propose a systematic, symmetry-based approach for selecting atomic displacement directions in small displacement methods, enhancing accuracy and efficiency in lattice dynamical calculations.

Findings

Method maintains maximum triple product V to reduce roundoff errors.

Robustness demonstrated on systems like Si, graphene, Sb2S3.

Effective for low-symmetry and large aspect ratio cells.

Abstract

Small displacement methods have been successfully used to calculate the lattice dynamical properties of crystals. It involves displacing atoms by a small amount in order to calculate the induced forces on all atoms in a supercell for the computation of force constants. Even though these methods are widely in use, to our knowledge, there is no systematic discussion of optimal displacement directions from the crystal's symmetry point of view nor a rigorous error analysis of such methods. Based on the group theory and point group symmetry of a crystal, we propose displacement directions, with an equivalent concept of the group of $k$, deduced directly in the Cartesian coordinates rather than the usual fractional coordinates, that maintain the theoretical maximum for the triple product $V$ spanned by the three displacements to avoid possible severe roundoff errors. The proposed displacement directions are generated from a minimal set of irreducible atomic displacements that keep the required independent force calculations to a minimum. We find the error in the calculated force constant explicitly depends on the inverse of $V$ and inaccuracy of the forces. Test systems such as Si, graphene, and orthorhombic Sb2S3 are used to illustrate the method. Our displacement method is shown to be very robust in treating low-symmetry cells with a large `aspect ratio' due to huge differences in lattice parameters, use of a large vacuum height, or a very oblique unit cell due to unconventional choice of primitive lattice vectors. It is expected that our displacement strategy can be used to address higher-order interatomic interactions to achieve good accuracy and efficiency.