Resolving Finite-Size Errors in EOM-CCSD Band Gaps of Solids with Interacting-Bath Dynamical Embedding Theory
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, 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.
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BibTeX
@misc{li2026resolving,
title = {{Resolving Finite-Size Errors in EOM-CCSD Band Gaps of Solids with Interacting-Bath Dynamical Embedding Theory}},
author = {Jiachen Li and Christopher Hillenbrand and Christian Venturella and Enzhi Chen and Tianyu Zhu},
howpublished = {arXiv},
year = {2026},
month = aug,
doi = {10.48550/arxiv.2606.12621},
eprint = {2606.12621},
archivePrefix = {arXiv},
url = {https://arxiv.org/abs/2606.12621},
}
RIS
TY - UNPB
TI - Resolving Finite-Size Errors in EOM-CCSD Band Gaps of Solids with Interacting-Bath Dynamical Embedding Theory
AU - Jiachen Li
AU - Christopher Hillenbrand
AU - Christian Venturella
AU - Enzhi Chen
AU - Tianyu Zhu
PY - 2026
DA - 2026/08/17
PB - arXiv
DO - 10.48550/arxiv.2606.12621
UR - https://arxiv.org/abs/2606.12621
AB - 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 G_0W_0@PBE, G_0W_0@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, lower than that of G_0W_0@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.
ER -