Spin Symmetry in Thermally-Assisted-Occupation Density Functional Theory

TL;DR

This paper develops a response theory for TAO-DFT showing that using a sufficiently large fictitious temperature can always eliminate unphysical spin-symmetry breaking in multi-reference systems, supported by calculations on various molecules.

Contribution

It introduces a response theory for TAO-DFT demonstrating that higher fictitious temperatures can resolve spin-symmetry issues in multi-reference systems.

Findings

TAO-DFT with large fictitious temperature resolves spin-symmetry breaking.

Calculations on molecules confirm the effectiveness of the approach.

The method improves the physical accuracy of spin densities in MR systems.

Abstract

For electronic systems with multi-reference (MR) character, Kohn-Sham density functional theory (KS-DFT) with the conventional exchange-correlation (xc) energy functionals can lead to incorrect spin densities and related properties. For example, for H2 dissociation, the spin-restricted and spin-unrestricted solutions obtained with the same xc energy functional in KS-DFT can be distinctly different, yielding the unphysical spin-symmetry breaking effects in the spin-unrestricted solutions. Recently, thermally-assisted-occupation density functional theory (TAO-DFT) has been shown to resolve the aforementioned spin-symmetry breaking, when the fictitious temperature is properly chosen. In this work, a response theory based on TAO-DFT is developed to demonstrate that TAO-DFT with a sufficiently large fictitious temperature can always resolve the unphysical spin-symmetry breaking in MR systems. To further support this, TAO-DFT calculations with various fictitious temperatures are performed for the dissociation of H2, N2, He2, and Ne2 as well as the twisted ethylene.