Multiconfigurational short-range on-top pair-density functional theory (2409.05213v2)

Abstract: We present the theory and implementation of a 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 (Hedeg{\aa}rd et al. J. Chem. Phys. 148, 2018, 214103). However, the srDFT part of the MC-srDFT has some deficiencies that it shares with Kohn-Sham DFT; in particular (1) self-interaction errors (albeit reduced because of the range separation), (2) that different M$_S$ states incorrectly become non-degenerate, and (3) that singlet and non-singlet states dissociating to the same open-shell fragments incorrectly lead to different electronic energies at dissociation. The model we present in this paper corrects these deficiencies by introducing the on-top pair density as an auxiliary variable replacing the spin 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$_2$. Furthermore, the rotational barrier for ethene is investigated for the S$_0$ and T$_1$ states. The calculations show correct degeneracy between the singlet and triplet curves at dissociation and the results are invariant to the choice of M$_S$ value for the triplet curves.