Partitioning interatomic force constants for first-principles phonon calculations: Applications to NaCl, PbTiO$_3$, monolayer CrI$_3$, and twisted bilayer graphene

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, the concept of partition of force constants is discussed, and addressed by NaCl, PbTiO$_3$, monolayer CrI$_3$, and twisted bilayer graphene as examples for illustrating the effects of the imposed supercell periodicity. To diminish the unphysical effects, a simple method of partitioning force constants, which relies only on the translational symmetry and interatomic distances, is demonstrated to be able to deliver reasonable results. The partition method is also compatible with the mixed-space approach for describing LO-TO splitting. 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.