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PreprintCC BY-NC-NDChemRxiv

Basis-Set Limit Wavefunction Energies of Massive Water Clusters: Resolution of a Challenge for Many-Body Expansion

  • Yuhong Jiang1,2
  • Jiarui Wang1,2
  • Giuseppe M. J. Barca3,4,5
  • Junming Ho1,2
5 affiliations
  1. 1School of Chemistry
  2. 2University of New South Wales
  3. 3School of Computing
  4. 4Australian National University
  5. 5Monash Institute of Pharmaceutical Sciences
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Abstract

The many-body expansion (MBE) offers a route to high-level wavefunction energies of systems beyond the reach of conventional calculations, but its practical convergence is entangled with basis set superposition error (BSSE), electrostatic embedding, and the scarcity of direct supersystem benchmarks at large size. Here, we show that as the complete-basis-set (CBS) limit is approached, electrostatically embedded three-body MBE, EE-MBE(3), provides accurate absolute and relative HF, RI-MP2, and CCSD(T) energies across water clusters of varying sizes. Critically, the largesystem conclusions are tested against direct same-level supersystem references rather than lowerlevel or extrapolated benchmarks. A distributed canonical RI-MP2 implementation enables a systematic HF/RI-MP2 campaign for 64 and 128 waters with cc-pVXZ and aug-cc-pVXZ basis sets (X = D, T, Q), with three configurations at each cluster size/basis set point. The largest calculation, (H2O)128/aug-cc-pVQZ, contains 22,016 spherical primary basis functions and, to our knowledge, is the largest reported MP2 calculation performed without a local-correlation approximation. At augcc-pVQZ, EE-MBE(3) maintains per-water errors within the 0.09 kcal mol-1 dynamical-accuracy

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Cite

BibTeXRIS
BibTeX
@misc{jiang2026basisset,
  title = {{Basis-Set Limit Wavefunction Energies of Massive Water Clusters: Resolution of a Challenge for Many-Body Expansion}},
  author = {Yuhong Jiang and Jiarui Wang and Giuseppe M. J. Barca and Junming Ho},
  howpublished = {ChemRxiv},
  year = {2026},
  month = oct,
  doi = {10.26434/chemrxiv.15009940/v1},
  url = {https://chemrxiv.org/doi/full/10.26434/chemrxiv.15009940/v1},
  note = {CC BY-NC-ND},
}
RIS
TY  - UNPB
TI  - Basis-Set Limit Wavefunction Energies of Massive Water Clusters: Resolution of a Challenge for Many-Body Expansion
AU  - Yuhong Jiang
AU  - Jiarui Wang
AU  - Giuseppe M. J. Barca
AU  - Junming Ho
PY  - 2026
DA  - 2026/10/05
PB  - ChemRxiv
DO  - 10.26434/chemrxiv.15009940/v1
UR  - https://chemrxiv.org/doi/full/10.26434/chemrxiv.15009940/v1
AB  - The many-body expansion (MBE) offers a route to high-level wavefunction energies of systems beyond the reach of conventional calculations, but its practical convergence is entangled with basis set superposition error (BSSE), electrostatic embedding, and the scarcity of direct supersystem benchmarks at large size. Here, we show that as the complete-basis-set (CBS) limit is approached, electrostatically embedded three-body MBE, EE-MBE(3), provides accurate absolute and relative HF, RI-MP2, and CCSD(T) energies across water clusters of varying sizes. Critically, the largesystem conclusions are tested against direct same-level supersystem references rather than lowerlevel or extrapolated benchmarks. A distributed canonical RI-MP2 implementation enables a systematic HF/RI-MP2 campaign for 64 and 128 waters with cc-pVXZ and aug-cc-pVXZ basis sets (X = D, T, Q), with three configurations at each cluster size/basis set point. The largest calculation, (H2O)128/aug-cc-pVQZ, contains 22,016 spherical primary basis functions and, to our knowledge, is the largest reported MP2 calculation performed without a local-correlation approximation. At augcc-pVQZ, EE-MBE(3) maintains per-water errors within the 0.09 kcal mol-1 dynamical-accuracy
ER  -