Unity of Kohn-Sham density-functional theory and reduced-density-matrix-functional theory

2021/01/31 by Neil Qiang Su · 1 citation
Chemical Engineering · Chemistry · Physics and Astronomy · #Advanced Chemical Physics Studies #Catalysis and Oxidation Reactions #Composite material #Density functional theory #Density matrix #Functional theory #Inorganic Chemistry and Materials #Kohn–Sham equations #Materials science #Matrix (chemical analysis) #Orbital-free density functional theory #Physics #Quantum mechanics #Time-dependent density functional theory #physics.chem-ph #quant-ph

paper · pdf · doi:10.1103/physreva.104.052809

published as Phys. Rev. A 104, 052809 (2021)

arxiv created 2021/01/31 · openalex created_date 2021/02/15 · openalex publication_date 2021/11/16 · arxiv updated 2021/11/18 · openalex updated_date 2026/08/05

Abstract

This work presents a rigorous theory to unify the two independent theoretical frameworks of Kohn-Sham (KS) density-functional theory (DFT) and reduced-density-matrix-functional theory (RDMFT). The generalization of the KS orbitals to hypercomplex number systems leads to the hypercomplex KS (HCKS) theory, which extends the search space for the electron density in KS-DFT and reformulates the kinetic energy. The HCKS theory provides a general framework, and different dimensions of the HCKS orbitals lead to different HCKS methods, with KS-DFT and RDMFT being two cases corresponding to the smallest and largest dimensions. Furthermore, a series of tests show that HCKS can capture the multireference nature of strong correlation by dynamically varying fractional occupations, while maintaining the same computational scaling as the KS method. With great potential to overcome the fundamental limitations of the KS method, HCKS creates new possibilities for the development and application of DFT.

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Cited by

• Approximate Functionals in Hypercomplex Kohn-Sham Theory