Affordable Access

deepdyve-link
Publisher Website

Approximate functionals in hypercomplex Kohn–Sham theory

Authors
  • Su, Neil Qiang1
  • 1 Nankai University, People’s Republic of China
Type
Published Article
Journal
Electronic Structure
Publisher
IOP Publishing
Publication Date
Mar 01, 2022
Volume
4
Issue
1
Identifiers
DOI: 10.1088/2516-1075/ac5756
Source
ioppublishing
Keywords
Disciplines
  • Emerging Leaders 2021
License
Unknown

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 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.

Report this publication

Statistics

Seen <100 times