Approximate Functionals in Hypercomplex Kohn-Sham Theory

TL;DR

This paper explores approximate functionals in hypercomplex Kohn-Sham theory, demonstrating improved handling of strong correlation effects over traditional DFT through the use of hierarchical correlation orbitals and HCO-dependent exchange.

Contribution

It introduces a new perspective on functional development in HCKS, highlighting the benefits of HCOs for better correlation treatment compared to KS-DFT.

Findings

HCKS outperforms KS-DFT in triplet-singlet gap calculations.

Including HCO-dependent HF exchange reduces systematic errors.

HCKS offers a promising approach to address strong electron correlation.

Abstract

The recently developed hypercomplex Kohn-Sham (HCKS) theory shows great potential to overcome the static/strong correlation issue in density functional theory (DFT), which highlights the necessity of further exploration of the HCKS theory toward better handling many-electron problem. This work mainly focuses on approximate functionals in HCKS, seeking to gain more insights into functional development from the comparison between Kohn-Sham (KS) DFT and HCKS. Unlike KS-DFT, HCKS can handle different correlation effects by resorting to a set of auxiliary orbitals with dynamically varying fractional occupations. These orbitals of hierarchical correlation (HCOs) thus contain distinct electronic information for better considering the exchange-correlation effect in HCKS. The test on the triplet-singlet gaps shows that HCKS has much better performance as compared to KS-DFT in use of the same functionals, and the systematic errors of semi-local functionals can be effectively reduced by including appropriate amount of the HCO-dependent Hartree-Fock (HF) exchange. In contrast, KS-DFT shows large systematic errors, which are hardly reduced by the functionals tested in this work. Therefore, HCKS creates new channels to address to the strong correlation issue, and further development of functionals that depend on HCOs and their occupations is necessary for the treatment of strongly correlated systems.