Reaching the thermodynamic limit of periodic CCSD cohesive energies and band gaps with denser Brillouin zone sampling

Abstract

The high computational cost of periodic coupled-cluster theory has limited the density of Brillouin zone sampling, yielding finite-size errors that need to be removed by extrapolation. Here we report the development and application of a distributed-memory software implementation of periodic coupled-cluster theory with single and double excitations (CCSD) that runs efficiently on up to 12 nodes with 96 cores each. This new implementation allows ground-state and excited-state calculations in which the Brillouin zone is sampled with up to $6^3=216$ $k$-points, allowing us to reliably extrapolate to the thermodynamic limit. For eight simple semiconductors and insulators, we report the cohesive energy and band gap, which are converged to 0.1 eV, providing definitive benchmark numbers for the CCSD level of theory. Compared to experimental values, average errors for the cohesive energy are 0.1-0.2 eV (typically an underestimate), and average errors for the band gap are about 0.4 eV (typically an overestimate).