Reformulation of thermally assisted-occupation density functional theory in the Kohn–Sham framework

Author:

Yeh Shu-Hao123,Yang Weitao3ORCID,Hsu Chao-Ping134ORCID

Affiliation:

1. Institute of Chemistry, Academia Sinica 1 , Taipei 11529, Taiwan

2. Department of Chemistry, National Taiwan University 2 , Taipei 10617, Taiwan

3. Department of Chemistry, Duke University 3 , Durham, North Carolina 27710, USA

4. National Center for Theoretical Sciences 4 , Taipei 10617, Taiwan

Abstract

We reformulate the thermally assisted-occupation density functional theory (TAO-DFT) into the Kohn–Sham single-determinant framework and construct two new post-self-consistent field (post-SCF) static correlation correction schemes, named rTAO and rTAO-1. In contrast to the original TAO-DFT with the density in an ensemble form, in which each orbital density is weighted with a fractional occupation number, the ground-state density is given by a single-determinant wavefunction, a regular Kohn–Sham (KS) density, and total ground state energy is expressed in the normal KS form with a static correlation energy formulated in terms of the KS orbitals. In post-SCF calculations with rTAO functionals, an efficient energy scanning to quantitatively determine θ is also proposed. The rTAOs provide a promising method to simulate systems with strong static correlation as original TAO, but simpler and more efficient. We show that both rTAO and rTAO-1 is capable of reproducing most results from TAO-DFT without the additional functional Eθ used in TAO-DFT. Furthermore, our numerical results support that, without the functional Eθ, both rTAO and rTAO-1 can capture correct static correlation profiles in various systems.

Funder

National Science Foundation

Academia Sinica

Ministry of Science and Technology, Taiwan

Publisher

AIP Publishing

Subject

Physical and Theoretical Chemistry,General Physics and Astronomy

Cited by 6 articles. 订阅此论文施引文献 订阅此论文施引文献,注册后可以免费订阅5篇论文的施引文献,订阅后可以查看论文全部施引文献

1. Entropy is a good approximation to the electronic (static) correlation energy;The Journal of Chemical Physics;2023-11-15

2. Real-Time Extension of TAO-DFT;Molecules;2023-10-24

3. Strong-correlation density functionals made simple;The Journal of Chemical Physics;2023-06-28

4. TAO-DFT with the Polarizable Continuum Model;Nanomaterials;2023-05-10

5. Local Hybrid Functional Applicable to Weakly and Strongly Correlated Systems;Journal of Chemical Theory and Computation;2022-09-28

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