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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:Accurately modeling heterogeneous catalysis requires accurate descriptions of rate-controlling elementary reactions of molecules on metal surfaces, but standard density functionals (DFs) are not accurate enough for this. The problem can be solved with the specific reaction parameter approach to density functional theory (SRP-DFT), but the transferability of SRP DFs among chemically related systems is limited. We combine the MS-PBEl, MS-B86bl, and MS-RPBEl semilocal made simple (MS) meta-generalized gradient approximation (GGA) (mGGA) DFs with rVV10 nonlocal correlation, and we evaluate their performance for the hydrogen (H2) + Cu(111), deuterium (D2) + Ag(111), H2 + Au(111), and D2 + Pt(111) gas-surface systems. The three MS mGGA DFs that have been combined with rVV10 nonlocal correlation were not fitted to reproduce particular experiments, nor has the b parameter present in rVV10 been reoptimized. Of the three DFs obtained the MS-PBEl-rVV10 DF yields an excellent description of van der Waals well geometries. The three original MS mGGA DFs gave a highly accurate description of the metals, which was comparable in quality to that obtained with the PBEsol DF. Here, we find that combining the three original MS mGGA DFs with rVV10 nonlocal correlation comes at the cost of a slightly less accurate description of the metal. However, the description of the metal obtained in this way is still better than the descriptions obtained with SRP DFs specifically optimized for individual systems. Using the Born-Oppenheimer static surface (BOSS) model, simulations of molecular beam dissociative chemisorption experiments yield chemical accuracy for the D2 + Ag(111) and D2 + Pt(111) systems. A comparison between calculated and measured E 1/2(ν, J) parameters describing associative desorption suggests chemical accuracy for the associative desorption of H2 from Au(111) as well. Our results suggest that ascending Jacob's ladder to the mGGA rung yields increasingly more accurate results for gas-surface reactions of H2 (D2) interacting with late transition metals.

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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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