Partitioning interatomic force constants for first-principles phonon calculations: applications to NaCl, PbTiO3, monolayer CrI3, and twisted bilayer graphene

Abstract

Abstract First-principles phonon calculations have been widely performed for studying vibrational properties of condensed matter, where the dynamical matrix is commonly constructed via supercell force-constant calculations or the linear response approach. With different manners, a supercell can be introduced in both methods. Unless the supercell is large enough, the interpolated phonon property highly depends on the shape and size of the supercell and the imposed periodicity could give unphysical results that can be easily overlooked. Along this line, we discuss how a traditional method can be used to partition the force constants at the supercell boundary and then propose a more flexible method based on the translational symmetry and interatomic distances. The partition method is also compatible with the mixed-space approach for describing LO–TO splitting. We have applied the proposed partition method to NaCl, PbTiO3, monolayer CrI3, and twisted bilayer graphene, where we show how the method can deliver reasonable results. The proper partition is especially important for studying moderate-size systems with low symmetry, such as two-dimensional materials on substrates, and useful for the implementation of phonon calculations in first-principles packages using atomic basis functions, where symmetry operations are usually not applied owing to the suitability for large-scale calculations.