Variational projector-augmented wave method: A full-potential approach for electronic structure calculations in solid-state physics

Highlights: • New variational method for periodic electronic eigenvalue problems with Coulomb singularities. • Faster plane-wave convergence with a priori bounds. • Theoretical convergence rates validated by numerical tests. In solid-state physics, energies of crystals are usually computed with a plane-wave discretization of Kohn-Sham equations. However the presence of Coulomb singularities requires the use of large plane-wave cut-offs to produce accurate numerical results. In this paper, an analysis of the plane-wave convergence of the eigenvalues of periodic linear Hamiltonians with Coulomb potentials using the variational projector-augmented wave (VPAW) method is presented. In the VPAW method, an invertible transformation is applied to the original eigenvalue problem, acting locally in balls centered at the singularities. In this setting, a generalized eigenvalue problem needs to be solved using plane-waves. We show that cusps of the eigenfunctions of the VPAW eigenvalue problem at the positions of the nuclei are significantly reduced. These eigenfunctions have however a higher-order derivative discontinuity at the spheres centered at the nuclei. By balancing both sources of error, we show that the VPAW method can drastically improve the plane-wave convergence of the eigenvalues with a minor additional computational cost. Numerical tests are provided confirming the efficiency of the method to treat Coulomb singularities.