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Assessment of SAPT(DFT) with meta-GGA functionals.

ABSTRACT: This work examines the suitability of meta-GGA functionals for symmetry-adapted perturbation theory (SAPT) calculations. The assessment is based on the term-by-term comparison with the benchmark SAPT variant based on coupled-cluster singles and doubles description of monomers, SAPT(CCSD). Testing systems include molecular complexes ranging from strong to weak and the He dimer. The following nonempirical meta-GGAs are examined: TPSS, revTPSS, MVS, SCAN, and SCAN0 with and without the asymptotic correction (AC) of the exchange-correlation potential. One range-separated meta-GGA functional, LC-PBETPSS, is also included. The AC-corrected pure meta-GGAs (with the exception of MVS) represent a definite progress in SAPT(DFT) compared to pure GGA, such as PBEAC, with their more consistent predictions of energy components. However, none of the meta-GGAs is better than the hybrid GGA approach SAPT(PBE0AC). The SAPT(DFT) electrostatic energy offers the most sensitive probe of the quality of the underlying DFT density. Both SCAN- and TPSS-based electrostatic energies agree with reference to within 5% or better which is an excellent result. We find that SCAN0 can be used in SAPT without the AC correction. The long-range corrected LC-PBETPSS is a reliable performer both for the components and total interaction energies.

SUBMITTER: Hapka M

PROVIDER: S-EPMC7256086 | biostudies-literature | 2020 Apr

REPOSITORIES: biostudies-literature

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Assessment of SAPT(DFT) with meta-GGA functionals.

Hapka Michał M Modrzejewski Marcin M Chałasiński Grzegorz G Szczęśniak Małgorzata M MM

Journal of molecular modeling 20200415 5

This work examines the suitability of meta-GGA functionals for symmetry-adapted perturbation theory (SAPT) calculations. The assessment is based on the term-by-term comparison with the benchmark SAPT variant based on coupled-cluster singles and doubles description of monomers, SAPT(CCSD). Testing systems include molecular complexes ranging from strong to weak and the He dimer. The following nonempirical meta-GGAs are examined: TPSS, revTPSS, MVS, SCAN, and SCAN0 with and without the asymptotic c ...[more]

PMID: 32296948

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Project description:Researchers carrying out calculations using the DFT method face the problem of the correct choice of the exchange-correlation functional to describe the quantities they are interested in. This article deals with benchmark calculations aimed at testing various exchange-correlation functionals in terms of a reliable description of the electron density distribution in molecules. For this purpose, 30 functionals representing all rungs of Jacob's Ladder are selected and then the values of some QTAIM-based parameters are compared with their reference equivalents obtained at the CCSD/aug-cc-pVTZ level of theory. The presented results show that the DFT method undoubtedly has the greatest problems with a reliable description of the electron density distribution in multiple strongly polar bonds, such as C=O, and bonds associated with large electron charge delocalization. The performance of the tested functionals turned out to be unsystematic. Nevertheless, in terms of a reliable general description of QTAIM-based parameters, the M11, SVWN, BHHLYP, M06-HF, and, to a slightly lesser extent, also BLYP, B3LYP, and X3LYP functionals turned out to be the worst. It is alarming to find the most popular B3LYP functional in this group. On the other hand, in the case of the electron density at the bond critical point, being the most important QTAIM-based parameter, the M06-HF functional is especially discouraged due to the very poor description of the C=O bond. On the contrary, the VSXC, M06-L, SOGGA11-X, M06-2X, MN12-SX, and, to a slightly lesser extent, also TPSS, TPSSh, and B1B95 perform well in this respect. Particularly noteworthy is the overwhelming performance of double hybrids in terms of reliable values of bond delocalization indices. The results show that there is no clear improvement in the reliability of describing the electron density distribution with climbing Jacob's Ladder, as top-ranked double hybrids are also, in some cases, able to produce poor values compared to CCSD.

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Assessment of SAPT(DFT) with meta-GGA functionals.

Publications

Assessment of SAPT(DFT) with meta-GGA functionals.

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