Efficacious symmetry-adapted atomic displacement method for lattice dynamical studies

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 constants 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 symmetry-adapted atomic 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 atomic displacement strategy can be used to address higher-order interatomic interactions to achieve good accuracy and efficiency. (C) 2020 Elsevier B.V. All rights reserved.

Automated summary

Small displacement methods are widely used in calculating lattice dynamical properties of crystals, but there is currently no systematic discussion on optimal displacement directions and rigorous error analysis. By utilizing group theory and point group symmetry, a new method with proposed displacement directions is introduced for better accuracy and efficiency in treating low-symmetry cells.