Kohn-Sham density encoding rescues coupled cluster theory for strongly correlated molecules

Abstract

Coupled cluster theory with a Kohn-Sham reference (KS-CC) can dramatically outperform its Hartree-Fock counterpart for strongly correlated systems, but the origin of these improvements has remained unclear. Here we demonstrate that these improvements arise from differences in the one-particle density matrix that are encoded into the non-canonical Fock matrix and not from the nature of the KS orbitals, as is commonly assumed. Equipped with this insight, KS-CCSD(T) can be leveraged to achieve near-chemical-accuracy for electronic and thermochemical properties of transition-metal dimers and main-group compounds. Most strikingly, KS-CCSD(T) qualitatively recovers the entire Cr$_2$ potential energy surface, a notorious failure case for HF-CCSD(T) and single-reference density functional theory. We further introduce a density difference diagnostic that identifies multireference character and guides practitioners toward rational selections of optimal references at mean-field cost. These results establish KS-CCSD(T) as a practical route to treat strong correlation within the "gold standard" framework, and this has immediate implications for machine learning potential development and materials research, areas that heavily rely on KS-DFT for model-parameter fitting.