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Canonical and DLPNO-based composite wavefunction methods parametrized against large and chemically diverse training sets. 2. Correlation consistent basis sets, core-valence correlation, and F12 alternatives
- Source :
- J. Chem. Theory Comput. 16, 7507-7524 (2020)
- Publication Year :
- 2020
-
Abstract
- A hierarchy of wavefunction composite methods (cWFT), based on G4- type cWFT methods available for elements H through Rn, was recently reported by Semidalas and Martin [J. Chem. Theor. Comput. 2020, 16, 4238]. We extend this hierarchy by considering the inner-shell correlation energy in the second-order Moller-Plesset correction and replacing the Weigend-Ahlrichs def2-mZVPP(D) basis sets used in the aforementioned paper with complete basis set extrapolation from augmented correlation consistent core-valence triple-zeta, aug-cc-pwCVTZ(-PP), and quadruple-zeta, aug-cc-pwCVQZ(-PP), basis sets, thus creating cc-G4- type methods. For the large and chemically diverse GMTKN55 benchmark suite, they represent a substantial further improvement and bring WTMAD2 (weighted mean absolute deviation) down below 1 kcal/mol. Intriguingly, the lion's share of the improvement comes from better capture of valence correlation; the inclusion of core-valence correlation is almost an order of magnitude less important. These robust correlation consistent cWFT methods approach the CCSD(T) complete basis limit with just one or a few fitted parameters. Particularly the DLPNO variants such as cc-G4-T-DLPNO are applicable to fairly large molecules at modest computational cost, as is (for a reduced range of elements) a different variant using MP2-F12/cc-pVTZ-F12 for the MP2 component.<br />Comment: J. Chem. Theor. Comput., ASAP (Open Access under CC)
- Subjects :
- Physics - Chemical Physics
Subjects
Details
- Database :
- arXiv
- Journal :
- J. Chem. Theory Comput. 16, 7507-7524 (2020)
- Publication Type :
- Report
- Accession number :
- edsarx.2008.01591
- Document Type :
- Working Paper
- Full Text :
- https://doi.org/10.1021/acs.jctc.0c01106