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

Journal Article · 27 March 2024 · Physical Review. X

DOI: https://doi.org/10.1103/PhysRevX.14.011059 · OSTI ID:2329559

Xing, Xin ; Lin, Lin

Coupled cluster theory is one of the most popular post-Hartree-Fock methods for 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. Published by the American Physical Society 2024

• Sponsoring Organization: USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Science (SC), Advanced Scientific Computing Research (ASCR)
• Grant/Contract Number: SC0022364
• OSTI ID: 2329559
• Alternate ID(s): OSTI ID: 2426901
• Journal Information: Physical Review. X, Journal Name: Physical Review. X Journal Issue: 1 Vol. 14; ISSN PRXHAE; ISSN 2160-3308
• Publisher: American Physical SocietyCopyright Statement
• Country of Publication: United States
• Language: English