On the notion of strong correlation in electronic structure theory
Brad Ganoe, James Shee
Abstract
, H-He-H, and benzene - and the half-filled Hubbard model over a range of correlation regimes. Various quantities are examined including the extent of spin symmetry breaking in correlated single-reference wave functions, energetic ratios inspired by the Hubbard model and the Virial theorem, and metrics derived from the one- and two-electron reduced density matrices (RDMs). The trace and the square norm of the cumulant of the two-electron reduced density matrix capture what may well be defined as strong correlation. Accordingly, strong correlation is understood as a statistical dependence between two electrons, and is distinct from the concepts of "correlation energy" and more general than entanglement quantities that require a partitioning of a quantum system into distinguishable subspaces. This work enables us to build a bridge between a rigorous and quantifiable regime of strong electron correlation and more familiar chemical concepts such as anti-aromaticity in the context of Baird's rule.