Multiconfigurational short-range on-top pair-density functional theory

Abstract

We present the theory and implementation of a novel, fully variational wave function - density functional theory (DFT) hybrid model, which is applicable to many cases of strong correlation. We denote this model the multiconfigurational self-consistent on-top pair-density functional theory model (MC-srPDFT). We have previously shown how the multi-configurational short-range DFT hybrid model (MC-srDFT) can describe many multiconfigurational cases of any spin symmetry, and also state-specific calculations on excited states. However, the srDFT part of the MC-srDFT has some deficiencies that it shares with Kohn-Sham DFT, namely that different MS states have different energies and wrong bond dissociation description of singlet and non-singlet equilibrium states to open-shell fragments. The model we present in this paper corrects these deficiencies by introducing the on-top pair density. Unlike other models in the literature, our model is fully variational and employs a long-range version of the on-top pair density. The implementation is a second-order optimization algorithm ensuring robust convergence to both ground- and excited states. We show how MC-srPDFT solves the mentioned challenges by sample calculations on the ground state singlet curve of H$_2$, N$_2$, and Cr$_2$ and the lowest triplet curves for N$_2$ and Cr$_2$. The calculations show correct degeneracy between the singlet and triplet curves at dissociation and the results are invariant to the choice of MS value for the triplet curves.