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Assessment of DLPNO-MP2 Approximations in Double-Hybrid DFT
[Image: see text] The unfavorable scaling (N(5)) of the conventional second-order Møller–Plesset theory (MP2) typically prevents the application of double-hybrid (DH) density functionals to large systems with more than 100 atoms. A prominent approach to reduce the computational demand of electron co...
Autores principales: | , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
American Chemical Society
2023
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Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10653103/ https://www.ncbi.nlm.nih.gov/pubmed/37862406 http://dx.doi.org/10.1021/acs.jctc.3c00896 |
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author | Neugebauer, Hagen Pinski, Peter Grimme, Stefan Neese, Frank Bursch, Markus |
author_facet | Neugebauer, Hagen Pinski, Peter Grimme, Stefan Neese, Frank Bursch, Markus |
author_sort | Neugebauer, Hagen |
collection | PubMed |
description | [Image: see text] The unfavorable scaling (N(5)) of the conventional second-order Møller–Plesset theory (MP2) typically prevents the application of double-hybrid (DH) density functionals to large systems with more than 100 atoms. A prominent approach to reduce the computational demand of electron correlation methods is the domain-based local pair natural orbital (DLPNO) approximation that is successfully used in the framework of DLPNO-CCSD(T). Its extension to MP2 [Pinski P.; Riplinger, C.; Valeev, E. F.; Neese, F. J. Chem. Phys.2015, 143, 034108.] paved the way for DLPNO-based DH (DLPNO-DH) methods. In this work, we assess the accuracy of the DLPNO-DH approximation compared to conventional DHs on a large number of 7925 data points for thermochemistry and 239 data points for structural features, including main-group and transition-metal systems. It is shown that DLPNO-DH-DFT can be applied successfully to perform energy calculations and geometry optimizations for large molecules at a drastically reduced computational cost. Furthermore, PNO space extrapolation is shown to be applicable, similar to its DLPNO-CCSD(T) counterpart, to reduce the remaining error. |
format | Online Article Text |
id | pubmed-10653103 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2023 |
publisher | American Chemical Society |
record_format | MEDLINE/PubMed |
spelling | pubmed-106531032023-11-16 Assessment of DLPNO-MP2 Approximations in Double-Hybrid DFT Neugebauer, Hagen Pinski, Peter Grimme, Stefan Neese, Frank Bursch, Markus J Chem Theory Comput [Image: see text] The unfavorable scaling (N(5)) of the conventional second-order Møller–Plesset theory (MP2) typically prevents the application of double-hybrid (DH) density functionals to large systems with more than 100 atoms. A prominent approach to reduce the computational demand of electron correlation methods is the domain-based local pair natural orbital (DLPNO) approximation that is successfully used in the framework of DLPNO-CCSD(T). Its extension to MP2 [Pinski P.; Riplinger, C.; Valeev, E. F.; Neese, F. J. Chem. Phys.2015, 143, 034108.] paved the way for DLPNO-based DH (DLPNO-DH) methods. In this work, we assess the accuracy of the DLPNO-DH approximation compared to conventional DHs on a large number of 7925 data points for thermochemistry and 239 data points for structural features, including main-group and transition-metal systems. It is shown that DLPNO-DH-DFT can be applied successfully to perform energy calculations and geometry optimizations for large molecules at a drastically reduced computational cost. Furthermore, PNO space extrapolation is shown to be applicable, similar to its DLPNO-CCSD(T) counterpart, to reduce the remaining error. American Chemical Society 2023-10-20 /pmc/articles/PMC10653103/ /pubmed/37862406 http://dx.doi.org/10.1021/acs.jctc.3c00896 Text en © 2023 The Authors. Published by American Chemical Society https://creativecommons.org/licenses/by/4.0/Permits the broadest form of re-use including for commercial purposes, provided that author attribution and integrity are maintained (https://creativecommons.org/licenses/by/4.0/). |
spellingShingle | Neugebauer, Hagen Pinski, Peter Grimme, Stefan Neese, Frank Bursch, Markus Assessment of DLPNO-MP2 Approximations in Double-Hybrid DFT |
title | Assessment of DLPNO-MP2
Approximations in Double-Hybrid
DFT |
title_full | Assessment of DLPNO-MP2
Approximations in Double-Hybrid
DFT |
title_fullStr | Assessment of DLPNO-MP2
Approximations in Double-Hybrid
DFT |
title_full_unstemmed | Assessment of DLPNO-MP2
Approximations in Double-Hybrid
DFT |
title_short | Assessment of DLPNO-MP2
Approximations in Double-Hybrid
DFT |
title_sort | assessment of dlpno-mp2
approximations in double-hybrid
dft |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10653103/ https://www.ncbi.nlm.nih.gov/pubmed/37862406 http://dx.doi.org/10.1021/acs.jctc.3c00896 |
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