Elucidating the molecular orbital dependence of the total electronic energy in multireference problems

Abstract

The accurate resolution of the chemical properties of strongly correlated systems, such as biradicals, requires the use of electronic structure theories that account for both multi-reference and dynamic correlation effects. A variety of methods exist that aim to resolve the dynamic correlation in multi-reference problems, commonly relying on an exponentially scaling complete-active-space self-consistent-field (CASSCF) calculation to generate reference molecular orbitals (MOs). However, while CASSCF orbitals provide the optimal solution for a selected set of correlated (active) orbitals, their suitability in the quest for the resolution of the total correlation energy has not been thoroughly investigated. Recent research has shown the ability of Kohn–Shan density functional theory to provide improved orbitals for coupled cluster (CC) and Møller–Plesset perturbation theory (MP) calculations. Here, we extend the search for optimal and more cost effective MOs to post-configuration-interaction [post-(CI)] methods, surveying the ability of the MOs obtained with various density functional theory (DFT) functionals, as well as Hartree–Fock and CC and MP calculations to accurately capture the total electronic correlation energy. Applying the anti-Hermitian contracted Schrödinger equation to the dissociation of N2, the calculation of biradical singlet–triplet gaps, and the transition states of bicylobutane isomerization, we demonstrate that DFT provides a cost-effective alternative to CASSCF in providing reference orbitals for post-CI dynamic correlation calculations.