A hybrid meta on-top functional for multiconfiguration pair-density functional theory

Multiconfiguration pair-density functional theory (MC-PDFT) was proposed a decade ago, but it is still in the early stage of density functional development. MC-PDFT uses functionals that are called on-top functionals; they depend on the density and the on-top pair density. Most MC-PDFT calculations to date have been unoptimized translations of generalized gradient approximations (GGAs) of Kohn-Sham density functional theory (KS-DFT). A hybrid MC-PDFT has also been developed, in which one includes a fraction of the complete active space self-consistent-field wave function energy in the total energy. Meta-GGA functionals, which use kinetic-energy densities in addition to GGA ingredients, have shown higher accuracy than GGAs in KS-DFT, yet the translation of meta-GGAs has not been previously proposed for MC-PDFT. In this paper, we propose a way to include kinetic energy density in a hybrid on-top functional for MC-PDFT, and we optimize the parameters of the resulting functional by training with a database developed as part of the present work that contains a wide variety of systems with diverse characters. The resulting hybrid meta functional is called the MC23 functional. We find that MC23 has improved performance as compared to KS-DFT functionals for both strongly and weakly correlated systems. We recommend MC23 for future MC-PDFT calculations.

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Publication Details

Journal
Proceedings of the National Academy of Sciences
Published
2024-12-30
DOI
https://doi.org/10.1073/pnas.2419413121
Citations
10
Primary Topic
Advanced Chemical Physics Studies
Type
article
Field-Weighted Citation Impact
3.38

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article

A hybrid meta on-top functional for multiconfiguration pair-density functional theory

Dayou Zhang, Donald G. Truhlar, Laura Gagliardi, Shaoting Zhang et al.
10 citations
Proceedings of the National Academy of Sciences
Advanced Chemical Physics Studies
3.38
article

A hybrid meta on-top functional for multiconfiguration pair-density functional theory

Dayou Zhang, Donald G. Truhlar, Laura Gagliardi, Shaoting Zhang, Jie J. Bao
article en
10 citations

Abstract

Multiconfiguration pair-density functional theory (MC-PDFT) was proposed a decade ago, but it is still in the early stage of density functional development. MC-PDFT uses functionals that are called on-top functionals; they depend on the density and the on-top pair density. Most MC-PDFT calculations to date have been unoptimized translations of generalized gradient approximations (GGAs) of Kohn-Sham density functional theory (KS-DFT). A hybrid MC-PDFT has also been developed, in which one includes a fraction of the complete active space self-consistent-field wave function energy in the total energy. Meta-GGA functionals, which use kinetic-energy densities in addition to GGA ingredients, have shown higher accuracy than GGAs in KS-DFT, yet the translation of meta-GGAs has not been previously proposed for MC-PDFT. In this paper, we propose a way to include kinetic energy density in a hybrid on-top functional for MC-PDFT, and we optimize the parameters of the resulting functional by training with a database developed as part of the present work that contains a wide variety of systems with diverse characters. The resulting hybrid meta functional is called the MC23 functional. We find that MC23 has improved performance as compared to KS-DFT functionals for both strongly and weakly correlated systems. We recommend MC23 for future MC-PDFT calculations.

Proceedings of the National Academy of SciencesVol. 122(1)
University of Minnesota (US), Nankai University (CN), Pittsburgh Supercomputing Center (US), University of Chicago (US)
Air Force Office of Scientific Research
Affordable and clean energy
Openalex Percentile: Top 7%
Advanced Chemical Physics Studies
3.38
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