Accurate and efficient localized basis sets for two-dimensional materials

Abstract

First-principles density functional theory (DFT) codes which employ a localized basis offer advantages over those which use plane-wave bases, such as better scaling with system size and better suitability to low-dimensional systems. The trade-off is that care must be taken in order to generate a good localized basis set which is efficient and accurate in a variety of environments. Here we develop and make freely available optimized local basis sets for two common two-dimensional materials, graphene and hexagonal boron nitride, for the SIESTA DFT code. Each basis set is benchmarked against the ABINIT plane-wave code, using the same pseudopotentials and exchange-correlation functionals. We find that a significant improvement is obtained by including the l + 2 polarization orbitals (4 f ) in the basis set, which greatly improves angular flexibility. The optimized basis sets yield much better agreement with plane-wave calculations for key features of the physical system, including total energy, lattice constant, and cohesive energy. The optimized basis sets also result in a speedup of the calculations with respect to the nonoptimized, native choices.