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

TL;DR

This paper investigates how different molecular orbitals derived from various electronic structure methods influence the total electronic energy calculations in multireference problems, emphasizing cost-effective alternatives to traditional CASSCF orbitals.

Contribution

It extends the search for optimal orbitals in post-CI methods by evaluating DFT, Hartree-Fock, CC, and MP orbitals for accurately capturing total correlation energy.

Findings

DFT orbitals improve total energy calculations in post-CI methods.

DFT-based orbitals are a cost-effective alternative to CASSCF.

Application to N₂ dissociation and biradical gaps demonstrates effectiveness.

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 as well as 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 (KS-DFT) to provide improved orbitals for coupled cluster (CC) and M\o ller-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 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 Schr\"odinger equation (ACSE) to the dissociation of N$_2$, the calculation of biradical singlet-triplet gaps and the transition states of the bicylobutane isomerization, we demonstrate DFT provides a cost-effective alternative to CASSCF in providing reference orbitals for post-CI dynamic correlation calculations.