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Peer-reviewedCC BY-NC-NDNature communications

Improving coupled cluster theory for strongly correlated molecules with Kohn-Sham density encoding.

  • Abdulrahman Y Zamani1
  • Barbaro Zulueta2
  • Andrew M Ricciuti1
  • John A Keith3
  • Kay Carter-Fenk4
4 affiliations
  1. 1Department of Chemistry, University of Pittsburgh, Pittsburgh, PA, USA.
  2. 2Department of Chemical and Petroleum Engineering, University of Pittsburgh, Pittsburgh, PA, USA.
  3. 3Department of Chemical and Petroleum Engineering, University of Pittsburgh, Pittsburgh, PA, USA. [email protected].
  4. 4Department of Chemistry, University of Pittsburgh, Pittsburgh, PA, USA. [email protected].
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Abstract

Coupled cluster theory using a Kohn-Sham density functional reference can dramatically outperform the standard Hartree-Fock-based approach for strongly correlated systems, but the origin of these improvements has remained unclear. We show these improvements arise from differences in the one-particle density as encoded into the Fock matrix, not from the nature of the orbitals themselves, as is commonly assumed. Exploiting this insight, Kohn-Sham references enable near-chemical accuracy for electronic and thermochemical properties of transition metal dimers and main group compounds. Notably, Kohn-Sham coupled cluster qualitatively recovers the entire chromium dimer potential energy surface, a notorious failure case for conventional methods. We further introduce a density difference diagnostic that detects multireference character and guides the selection of optimal references at mean-field cost. Together, these results establish a practical route to treating strong correlation within quantum chemistry's "gold standard" framework, with immediate implications for machine learning potential development and materials research, which rely heavily on density functional theory.

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Cite

BibTeXRIS
BibTeX
@article{zamani2026improving,
  title = {{Improving coupled cluster theory for strongly correlated molecules with Kohn-Sham density encoding.}},
  author = {Abdulrahman Y Zamani and Barbaro Zulueta and Andrew M Ricciuti and John A Keith and Kay Carter-Fenk},
  journal = {Nature communications},
  year = {2026},
  month = sep,
  doi = {10.1038/s41467-026-77540-x},
  url = {https://europepmc.org/article/MED/42875438},
  note = {CC BY-NC-ND},
}
RIS
TY  - JOUR
TI  - Improving coupled cluster theory for strongly correlated molecules with Kohn-Sham density encoding.
AU  - Abdulrahman Y Zamani
AU  - Barbaro Zulueta
AU  - Andrew M Ricciuti
AU  - John A Keith
AU  - Kay Carter-Fenk
PY  - 2026
DA  - 2026/09/11
JO  - Nature communications
DO  - 10.1038/s41467-026-77540-x
UR  - https://europepmc.org/article/MED/42875438
AB  - Coupled cluster theory using a Kohn-Sham density functional reference can dramatically outperform the standard Hartree-Fock-based approach for strongly correlated systems, but the origin of these improvements has remained unclear. We show these improvements arise from differences in the one-particle density as encoded into the Fock matrix, not from the nature of the orbitals themselves, as is commonly assumed. Exploiting this insight, Kohn-Sham references enable near-chemical accuracy for electronic and thermochemical properties of transition metal dimers and main group compounds. Notably, Kohn-Sham coupled cluster qualitatively recovers the entire chromium dimer potential energy surface, a notorious failure case for conventional methods. We further introduce a density difference diagnostic that detects multireference character and guides the selection of optimal references at mean-field cost. Together, these results establish a practical route to treating strong correlation within quantum chemistry's "gold standard" framework, with immediate implications for machine learning potential development and materials research, which rely heavily on density functional theory.
SN  - 2041-1723
ER  -