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.
Authors
- Dayou Zhang (ORCID: https://orcid.org/0000-0002-5393-657X)
- Donald G. Truhlar (ORCID: https://orcid.org/0000-0002-7742-7294)
- Laura Gagliardi (ORCID: https://orcid.org/0000-0001-5227-1396)
- Shaoting Zhang (ORCID: https://orcid.org/0000-0002-8719-448X)
- Jie J. Bao (ORCID: https://orcid.org/0000-0003-0197-3405)
Institutions
- University of Minnesota (US)
- Nankai University (CN)
- Pittsburgh Supercomputing Center (US)
- University of Chicago (US)
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
Funders
- Air Force Office of Scientific Research