Bringing coupled‑cluster theory to the strong-correlation frontier
Accurate prediction of molecular electronic energies is essential yet remains challenging for strongly correlated systems, where conventional coupled-cluster (CC) methods break down. Here we present a generalized valence bond-based block-correlated coupled‑cluster (GVB-BCCC) framework to overcome this limitation. In contrast to standard CC approaches built upon a single-determinant reference, our method employs a multi‑determinantal GVB reference paired with a cluster operator that consistently captures both static and dynamic electron correlation effects, while retaining computational efficiency comparable to single-reference CC theory. With its O ( N ⁷) scaling, GVB‑BCCC delivers chemical accuracy for global potential energy surfaces, reaction barriers, and singlet‑triplet gaps across diverse biradicals and transition-metal complexes. GVB-BCCC thereby enables routine, black-box quantum-chemical predictions for a wide variety of strongly correlated systems, ranging from transition-metal catalysts and organic radicals to functional molecular materials.
Authors
- Feichao Han
- Xiaochuan Ren (ORCID: https://orcid.org/0000-0002-5550-9563)
- Feng Zhang (ORCID: https://orcid.org/0000-0002-1872-1602)
- Shuhua Li (ORCID: https://orcid.org/0000-0001-6756-057X)
- Xixi Hu (ORCID: https://orcid.org/0000-0003-1530-3015)
- Pengfei Ma
- Cong Sun
- Wei Li
- Junyan Wang
Institutions
- Ministry of Education of the People's Republic of China (CN)
- Guangxi University (CN)
- Nanjing University (CN)
Publication Details
- Journal
- ChemRxiv
- Published
- 2026-11-02
- DOI
- https://doi.org/10.26434/chemrxiv.15011511/v1
- Primary Topic
- Advanced Chemical Physics Studies
- Type
- preprint