Multi-state pair-density functional theory

Abstract

Multi-configuration pair-density functional theory (MC-PDFT) has previously been applied successfully to carry out ground-state and excited-state calculations. However, because they include no interaction between electronic states, MC-PDFT calculations in which each state’s PDFT energy is calculated separately can give an unphysical double crossing of potential energy surfaces (PESs) in a region near a conical intersection. We have recently proposed state-interaction pair-density functional theory (SI-PDFT) to treat nearly degenerate states by creating a set of intermediate states with state interaction; although this method is successful, it is inconvenient because two SCF calculations and two sets of orbitals are required and because it puts the ground state on an unequal footing with the excited states. Here we propose two new methods, called extended-multi-state-PDFT (XMS-PDFT) and variational-multi-state-PDFT (VMS-PDFT), that generate the intermediate states in a balanced way with a single set of orbitals. The former uses the intermediate states proposed by Granovsky for extended multi-configuration quasi-degenerate perturbation theory (XMC-QDPT); the latter obtains the intermediate states by maximizing the sum of the MC-PDFT energies for the intermediate states. We also propose a Fourier series expansion to make the variational optimizations of the VMS-PDFT method convenient, and we implement this method (FMS-PDFT) both for conventional configuration-interaction solvers and for density-matrix-renormalization-group solvers. The new methods are tested for eight systems, exhibiting avoided crossings among two to six states. The FMS-PDFT method is successful for all cases for which it has been tested (all cases in this paper except O₃ for which it was not tested), and XMS-PDFT is successful for all eight cases except the mixed-valence case. Since both XMS-PDFT and VMS-PDFT are less expensive than XMS-CASPT2, they will allow well-correlated calculations on much larger systems for which perturbation theory is unaffordable.