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Peer-reviewedCC BY 4.0The Journal of Physical Chemistry. a

Sub-kJ/mol Precision at Practical Cost for Molecular Solids through Local Coupled-Cluster Approaches

  • Khanh Ngoc Pham1
  • Marcin Modrzejewski2
  • Péter R. Nagy3,4,5
  • Jiří Klimeš1
5 affiliations
  1. 1Department of Chemical Physics and Optics, Faculty of Mathematics and Physics, Charles University, Ke Karlovu 3, Prague 2 CZ-12116, Czech Republic
  2. 2Faculty of Chemistry, University of Warsaw, Pasteura 1, Warsaw 02-093, Poland
  3. 3Department of Physical Chemistry and Materials Science, Faculty of Chemical Technology and Biotechnology, Budapest University of Technology and Economics, Műegyetem rkp. 3., Budapest H-1111, Hungary
  4. 4HUN-REN−BME Quantum Chemistry Research Group, Műegyetem rkp. 3., Budapest H-1111, Hungary
  5. 5MTA−BME Lendület Quantum Chemistry Research Group, Muegyetem rkp. 3., Budapest H-1111, Hungary
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Abstract

Generation of numerically converged coupled-cluster reference energies of molecular crystals remains highly non-routine. Yet, such data points are critically needed as computational methodologies strive to reach correlated wave-function accuracy in condensed-phase systems. Localized-orbital coupled-cluster approaches applied within the many-body expansion promise a scalable route to these reference results. Here, we report solutions to a technical challenge when using this methodologyat long intermolecular distances, the numerical noise due to local approximations can accumulate for some molecular crystals into a large-scale drift of the correlation energy, especially in the nonadditive three-body contributions. Within the local natural orbital (LNO) coupled-cluster method, we suggest well-balanced approaches to overcome this issue. At the benchmark level, we propose more accurate LNO-CCSD­(T) settings that remove the artifacts at long distances and attain a numerical precision of 0.2 kJ/mol (maximum error) in the lattice energy, with a practical cost that is orders of magnitude lower than that of canonical CCSD­(T). As an even more scalable solution, we propose a multi-level strategy that utilizes the established routine LNO-CCSD­(T) precision tiers (Tight, vTight) but retains the numerical stability of the benchmark level by treating long-distance three-body systems with the random-phase approximation (RPA).

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Cite

BibTeXRIS
BibTeX
@article{pham2026subkjmol,
  title = {{Sub-kJ/mol Precision at Practical Cost for Molecular Solids through Local Coupled-Cluster Approaches}},
  author = {Khanh Ngoc Pham and Marcin Modrzejewski and Péter R. Nagy and Jiří Klimeš},
  journal = {The Journal of Physical Chemistry. a},
  year = {2026},
  month = oct,
  doi = {10.1021/acs.jpca.6c05975},
  url = {https://doi.org/10.1021/acs.jpca.6c05975},
  note = {CC BY 4.0},
}
RIS
TY  - JOUR
TI  - Sub-kJ/mol Precision at Practical Cost for Molecular Solids through Local Coupled-Cluster Approaches
AU  - Khanh Ngoc Pham
AU  - Marcin Modrzejewski
AU  - Péter R. Nagy
AU  - Jiří Klimeš
PY  - 2026
DA  - 2026/10/14
JO  - The Journal of Physical Chemistry. a
DO  - 10.1021/acs.jpca.6c05975
UR  - https://doi.org/10.1021/acs.jpca.6c05975
AB  - Generation of numerically converged coupled-cluster reference energies of molecular crystals remains highly non-routine. Yet, such data points are critically needed as computational methodologies strive to reach correlated wave-function accuracy in condensed-phase systems. Localized-orbital coupled-cluster approaches applied within the many-body expansion promise a scalable route to these reference results. Here, we report solutions to a technical challenge when using this methodologyat long intermolecular distances, the numerical noise due to local approximations can accumulate for some molecular crystals into a large-scale drift of the correlation energy, especially in the nonadditive three-body contributions. Within the local natural orbital (LNO) coupled-cluster method, we suggest well-balanced approaches to overcome this issue. At the benchmark level, we propose more accurate LNO-CCSD­(T) settings that remove the artifacts at long distances and attain a numerical precision of 0.2 kJ/mol (maximum error) in the lattice energy, with a practical cost that is orders of magnitude lower than that of canonical CCSD­(T). As an even more scalable solution, we propose a multi-level strategy that utilizes the established routine LNO-CCSD­(T) precision tiers (Tight, vTight) but retains the numerical stability of the benchmark level by treating long-distance three-body systems with the random-phase approximation (RPA).
SN  - 1089-5639
SN  - 1520-5215
ER  -