Sampling the reciprocal Coulomb potential in finite and anisotropic cells

Abstract

We present a robust strategy to numerically sample the Coulomb potential in reciprocal space for periodic Born-von Karman cells of general shape. Our approach tackles two common issues of plane-wave based implementations of Coulomb integrals under periodic boundary conditions, the treatment of the singularity at the Brillouin-zone center, as well as quadrature errors, which can cause severe convergence problems in anisotropic cells, necessary for the calculation of low-dimensional systems. We apply our strategy to the Hartree-Fock (HF) and coupled cluster (CC) theory and discuss the consequences of different sampling strategies on the different theories. We show that sampling the Coulomb potential via the widely used probe-charge Ewald method is unsuitable for CC calculations in anisotropic cells. To demonstrate the applicability of our developed approach, we study two representative, low-dimensional use cases: the infinite carbon chain, for which we report the first periodic CCSD(T) potential energy surface, as well as a surface slab of lithium hydride, for which we demonstrate the impact of different sampling strategies for calculating surface energies. We find that our Coulomb sampling strategy serves as a vital solution, addressing the critical need for improved accuracy in plane-wave based CC calculations for low-dimensional systems.

7 pages, 3 figures

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Cited by in corpus (3)

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• Finite-size Effects in periodic EOM-CCSD for Ionization Energies and Electron Affinities: Convergence Rate and Extrapolation to the Thermodynamic Limit
• Ground-States for Metals from Converged Coupled Cluster Calculations