Analyzing cases of significant nondynamic correlation with DFT using the Atomic Populations of Effectively Localized Electrons

TL;DR

This paper introduces APELE, a new size-consistent, cost-effective diagnostic for assessing nondynamic correlation in DFT, demonstrating its effectiveness on various molecular systems and reactions.

Contribution

The study proposes the APELE method as a novel, efficient diagnostic for nondynamic correlation in DFT, improving upon existing methods in accuracy and computational cost.

Findings

APELE agrees well with existing diagnostics

APELE is size-consistent and less costly

Effective in bond stretching and breaking scenarios

Abstract

Multireference effects are associated with degeneracies and near-degeneracies of the ground state and are critical to a variety of systems. Most approximate functionals of density functional theory (DFT) fail to properly describe these effects. A number of diagnostics have been proposed that allow to estimate the reliability of a given single-reference solution in this respect. Some of these diagnostics however lack size-consistency, while remaining computationally expensive. In this work we use the DFT method of determining atomic populations of effectively localized electrons (APELE) as a novel diagnostic in this vein. It is compared with several existing diagnostics of nondynamic correlation on select exemplary systems. We show that the APELE method is on average in good agreement with the existing diagnostics, while being both size-consistent and less costly. It becomes particularly informative in cases involving bond stretching or bond breaking. The APELE method is applied next to organic diradicals like the bis-acridine dimer and the p-quinodimethane molecule which possess unusually high nonlinear optical response, and to the reaction of ethylene addition to Ni dithiolene, where our results shed some more light on how the oxidation state of the Ni center may change when going from the initial reactant to the product.