Inverse Volume Scaling of Finite-Size Error in Periodic Coupled Cluster Theory

Abstract

Coupled cluster theory is one of the most popular post-Hartree-Fock methods for ab initio molecular quantum chemistry. The finite-size error of the correlation energy in periodic coupled cluster calculations for three-dimensional insulating systems has been observed to satisfy the inverse volume scaling, even in the absence of any correction schemes. This is surprising, as simpler theories that utilize only a subset of the coupled cluster diagrams exhibit much slower decay of the finite-size error, which scales inversely with the length of the system. In this study, we review the current understanding of finite-size error in quantum chemistry methods for periodic systems. We introduce new tools that elucidate the mechanisms behind this phenomenon in the context of coupled cluster doubles calculations. This reconciles some seemingly paradoxical statements related to finite-size scaling. Our findings also show that singularity subtraction can be a powerful method to effectively reduce finite-size errors in practical quantum chemistry calculations for periodic systems.

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Cited by in corpus (4)

• Periodic Local Coupled-Cluster Theory for Insulators and Metals
• Interacting-bath dynamical embedding for capturing non-local electron correlation in solids
• Finite-size Effects in periodic EOM-CCSD for Ionization Energies and Electron Affinities: Convergence Rate and Extrapolation to the Thermodynamic Limit
• Resolving Finite-Size Errors in EOM-CCSD Band Gaps of Solids with Interacting-Bath Dynamical Embedding Theory