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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
[Image: see text] A hierarchy of wavefunction composite methods (cWFT), based on G4-type cWFT methods available for elements H through Rn, was recently reported by the present authors [J. Chem. Theor. Comput.2020, 16, 4238]. We extend this hierarchy by considering the inner-shell correlation energy...
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
American
Chemical Society
2020
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Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7735707/ https://www.ncbi.nlm.nih.gov/pubmed/33200931 http://dx.doi.org/10.1021/acs.jctc.0c01106 |
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author | Semidalas, Emmanouil Martin, Jan M. L. |
author_facet | Semidalas, Emmanouil Martin, Jan M. L. |
author_sort | Semidalas, Emmanouil |
collection | PubMed |
description | [Image: see text] A hierarchy of wavefunction composite methods (cWFT), based on G4-type cWFT methods available for elements H through Rn, was recently reported by the present authors [J. Chem. Theor. Comput.2020, 16, 4238]. We extend this hierarchy by considering the inner-shell correlation energy in the second-order Møller–Plesset correction and replacing the Weigend–Ahlrichs def2-mZVPP(D) basis sets used with complete basis set extrapolation from augmented correlation-consistent core–valence triple-ζ, aug-cc-pwCVTZ(-PP), and quadruple-ζ, 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 a modest computational cost, as is (for a reduced range of elements) a different variant using MP2-F12/cc-pVTZ-F12 for the MP2 component. |
format | Online Article Text |
id | pubmed-7735707 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2020 |
publisher | American
Chemical Society |
record_format | MEDLINE/PubMed |
spelling | pubmed-77357072020-12-15 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 Semidalas, Emmanouil Martin, Jan M. L. J Chem Theory Comput [Image: see text] A hierarchy of wavefunction composite methods (cWFT), based on G4-type cWFT methods available for elements H through Rn, was recently reported by the present authors [J. Chem. Theor. Comput.2020, 16, 4238]. We extend this hierarchy by considering the inner-shell correlation energy in the second-order Møller–Plesset correction and replacing the Weigend–Ahlrichs def2-mZVPP(D) basis sets used with complete basis set extrapolation from augmented correlation-consistent core–valence triple-ζ, aug-cc-pwCVTZ(-PP), and quadruple-ζ, 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 a modest computational cost, as is (for a reduced range of elements) a different variant using MP2-F12/cc-pVTZ-F12 for the MP2 component. American Chemical Society 2020-11-17 2020-12-08 /pmc/articles/PMC7735707/ /pubmed/33200931 http://dx.doi.org/10.1021/acs.jctc.0c01106 Text en © 2020 American Chemical Society This is an open access article published under a Creative Commons Attribution (CC-BY) License (http://pubs.acs.org/page/policy/authorchoice_ccby_termsofuse.html) , which permits unrestricted use, distribution and reproduction in any medium, provided the author and source are cited. |
spellingShingle | Semidalas, Emmanouil Martin, Jan M. L. 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 |
title | 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 |
title_full | 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 |
title_fullStr | 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 |
title_full_unstemmed | 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 |
title_short | 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 |
title_sort | 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 |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7735707/ https://www.ncbi.nlm.nih.gov/pubmed/33200931 http://dx.doi.org/10.1021/acs.jctc.0c01106 |
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