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arXiv:2606.12621 · The Journal of Chemical Physics

Resolving finite-size errors in EOM-CCSD band gaps of solids with interacting-bath dynamical embedding theory

Jiachen Li, Christopher Hillenbrand, Christian Venturella, Enzhi Chen, Tianyu Zhu

Published Sep 1, 2026• 0 citations
arXivHTMLPDF

Abstract

Periodic equation-of-motion coupled-cluster theory with single and double excitations (EOM-CCSD) has shown promise for quantitative calculations of band structures in solids. However, its steep computational scaling has limited calculations to relatively coarse k-point meshes, leading to sizable finite-size errors and discrepant estimates of thermodynamic-limit band gaps in recent benchmarks. In this work, we revisit EOM-CCSD band gaps for ten semiconductors and insulators using interacting-bath dynamical embedding theory (ibDET), a systematically improvable Green's function embedding framework that enables dense Brillouin-zone sampling at modest computational cost. By pushing the k-point sampling up to 10 × 10 × 10, well beyond the system sizes accessible in canonical periodic EOM-CCSD calculations, we significantly reduce finite-size errors and obtain stable thermodynamic-limit extrapolations. We further compare G0W0@PBE, G0W0@HF, and EOM-CCSD on an equal footing using the same numerical settings in PySCF. We find that EOM-CCSD yields a mean absolute error of 0.32 eV relative to experimental band gaps for a test set of ten semiconductors and insulators, which is lower than that of G0W0@PBE. For ZnO, EOM-CCSD also accurately describes the Zn 3d-band binding energy, despite overestimating the band gap. These results demonstrate that ibDET offers a practical route to high-accuracy many-body electronic structure calculations in periodic systems.

DOI
10.1063/5.0347878

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