Finite-size Effects in periodic EOM-CCSD for Ionization Energies and Electron Affinities: Convergence Rate and Extrapolation to the Thermodynamic Limit

Abstract

We investigate the convergence of quasi-particle energies for periodic systems to the thermodynamic limit using increasingly large simulation cells corresponding to increasingly dense integration meshes in reciprocal space. The quasi-particle energies are computed at the level of equation-of-motion coupled-cluster theory for ionization (IP-EOM-CC) and electron attachment processes (EA-EOM-CC). By introducing an electronic correlation structure factor, the expected asymptotic convergence rates for systems with different dimensionality are formally derived. We rigorously test these derivations through numerical simulations for trans-Polyacetylene using IP/EA-EOM-CCSD and the G0W0@HF approximation, which confirm the predicted convergence behavior. Our findings provide a solid foundation for efficient schemes to correct finite-size errors in IP/EA-EOM-CCSD calculations.

16 pages, 9 figures

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Cited by in corpus (4)

• Analytic $G_0{W}_0$ gradients based on a double-similarity transformation equation-of-motion coupled-cluster treatment
• Low-scaling \textit{GW} calculations of quasi-particle energies for extended systems within the numerical atomic orbital framework
• Resolving Finite-Size Errors in EOM-CCSD Band Gaps of Solids with Interacting-Bath Dynamical Embedding Theory
• Quantitative Description of Strongly Correlated Materials by Combining Downfolding Techniques and Tensor Networks