In this study, we introduce two datasets for nanoscale noncovalent binding, featuring complexes at the hundred-atom scale, benchmarked using coupled cluster with single, double, and perturbative triple [CCSD(T)] excitations extrapolated to the complete basis set (CBS) limit. The first dataset, L14, comprises 14 complexes with canonical CCSD(T)/CBS benchmarks, extending the applicability of CCSD(T)/CBS binding benchmarks to systems as large as 113 atoms. The second dataset, vL11, consists of 11 even larger complexes, evaluated using the local CCSD(T)/CBS method with stringent thresholds, covering systems up to 174 atoms. We compare binding energies obtained from local CCSD(T) and fixed-node diffusion Monte Carlo (FN-DMC), which have previously shown discrepancies exceeding the chemical accuracy threshold of 1 kcal/mol in large complexes, with the new canonical CCSD(T)/CBS results. While local CCSD(T)/CBS agrees with canonical CCSD(T)/CBS within binding uncertainties, FN-DMC consistently underestimates binding energies in π–π complexes by over 1 kcal/mol. Potential sources of error in canonical CCSD(T)/CBS are discussed, and we argue that the observed discrepancies are unlikely to originate from CCSD(T) itself. Instead, the fixed-node approximation in FN-DMC warrants further investigation to elucidate these binding discrepancies. Using these datasets as reference, we evaluate the performance of various electronic structure methods, semi-empirical approaches, and machine learning potentials for nanoscale complexes. Based on computational accuracy and stability across system sizes, we recommend MP2+aiD(CCD), PBE0+D4, and ωB97X-3c as reliable methods for investigating noncovalent interactions in nanoscale complexes, maintaining their promising performance observed in smaller systems.
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Canonical coupled cluster binding benchmark for nanoscale noncovalent complexes at the hundred-atom scale
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21 December 2024
Research Article|
December 16 2024
Canonical coupled cluster binding benchmark for nanoscale noncovalent complexes at the hundred-atom scale
Special Collection:
2024 JCP Emerging Investigators Special Collection
,
JCP and CPR Editors’ Choice 2024
Ka Un Lao
Ka Un Lao
a)
(Conceptualization, Data curation, Formal analysis, Funding acquisition, Investigation, Methodology, Project administration, Resources, Software, Supervision, Validation, Visualization, Writing – original draft, Writing – review & editing)
Department of Chemistry, Virginia Commonwealth University
, Richmond, Virginia 23284, USA
a)Author to whom correspondence should be addressed: [email protected]
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Ka Un Lao
a)
Department of Chemistry, Virginia Commonwealth University
, Richmond, Virginia 23284, USA
a)Author to whom correspondence should be addressed: [email protected]
J. Chem. Phys. 161, 234103 (2024)
Article history
Received:
October 03 2024
Accepted:
November 27 2024
Citation
Ka Un Lao; Canonical coupled cluster binding benchmark for nanoscale noncovalent complexes at the hundred-atom scale. J. Chem. Phys. 21 December 2024; 161 (23): 234103. https://doi.org/10.1063/5.0242359
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