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 quasiparticle energies for periodic systems to the thermodynamic limit using increasingly large simulation cells corresponding to increasingly dense integration meshes in reciprocal space. The quasiparticle 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.