Revisiting Molecular Dissociation in Density Functional Theory: A Simple Model

TL;DR

This paper uses a simple two-electron model to analyze the features of the Kohn-Sham potential during molecular dissociation, revealing how step and peak features develop and their implications for dynamics.

Contribution

It provides a detailed investigation of the development of step and peak features in the Kohn-Sham potential during dissociation using a minimal model, linking them to avoided crossings.

Findings

Step onset coincides with avoided crossing in charge-transfer states

Features develop with increasing bond length in the dissociation process

Features influence molecular dynamics and response despite minimal effect on energetics

Abstract

A two-electron one-dimensional model of a heteroatomic molecule composed of two open-shell atoms is considered. Including only two electrons isolates and examines the effect that the highest occupied molecular orbital has on the Kohn-Sham potential as the molecule dissociates. We reproduce the characteristic step and peak that previous high-level wavefunction methods have shown to exist for real molecules in the low-density internuclear region. The simplicity of our model enables us to investigate in detail their development as a function of bond-length, with little computational effort, and derive properties of their features in the dissociation limit. We show that the onset of the step is coincident with the internuclear separation at which an avoided crossing between the ground-state and lowest charge-transfer excited state is approached. Although the step and peak features have little effect on the ground-state energetics, we discuss their important consequences for dynamics and response.