Generalizing Density Functional Theory with a Particle-Hole Expansion

Strong electron correlation remains difficult to describe within conventional density functional approximations, particularly when natural-orbital occupations become strongly fractional. We introduce a systematic particle-hole expansion that generalizes density functional theory (DFT) through an explicit functional of the one-electron reduced density matrix. The previously derived cumulant-based correction emerges as the leading term and the thermal (entropic) correction as an infinite-order member whose coefficients are fixed by a single parameter. The expansion can be formulated as a moment problem solved by semidefinite programming with computational scaling comparable to DFT. We show that both the first- and second-order corrections yield closed-form natural-orbital occupations. Applications to periacenes and Fe-porphyrin demonstrate that the second-order correction substantially reduces excessive orbital fractionalization, yielding natural-orbital occupations and fundamental gaps in improved agreement with correlated calculations.

Source: arXiv:2610.40621v1 - http://arxiv.org/abs/2610.40621v1 PDF: https://arxiv.org/pdf/2610.40621v1 Original Link: http://arxiv.org/abs/2610.40621v1