Generalized Uniform Singlet- and Triplet-Pair Extrapolation of the Correlation Energy to the One Electron Basis Set Limit
Main Author: | |
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Publication Date: | 2008 |
Format: | Article |
Language: | eng |
Source: | Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) |
Download full: | http://hdl.handle.net/10316/10360 https://doi.org/10.1021/jp710477t |
Summary: | The relationship between the triplet- and singlet-pair interaction coefficients in the uniform singlet- and triplet-pair extrapolation method recently suggested for extrapolating ab initio energies to the one-electron basis set limit is analyzed. Based on the premise that such a ratio is invariant over the configuration space of the molecule, generalizations of the method are investigated and their performance tested on extrapolations with MP2, CCD, CCSD, and MRCI(Q) energies. The best variant requires raw energies calculated using augmented correlated consistent basis sets with cardinal numbers up to X = 6 at a single geometry. A scheme is also suggested that performs better than the traditional X-3 law and possibly the original uniform singlet- and triplet-pair extrapolation method but requires data only up to X = Q. |
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Generalized Uniform Singlet- and Triplet-Pair Extrapolation of the Correlation Energy to the One Electron Basis Set LimitThe relationship between the triplet- and singlet-pair interaction coefficients in the uniform singlet- and triplet-pair extrapolation method recently suggested for extrapolating ab initio energies to the one-electron basis set limit is analyzed. Based on the premise that such a ratio is invariant over the configuration space of the molecule, generalizations of the method are investigated and their performance tested on extrapolations with MP2, CCD, CCSD, and MRCI(Q) energies. The best variant requires raw energies calculated using augmented correlated consistent basis sets with cardinal numbers up to X = 6 at a single geometry. A scheme is also suggested that performs better than the traditional X-3 law and possibly the original uniform singlet- and triplet-pair extrapolation method but requires data only up to X = Q.American Chemical Society2008-02-28info:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/articlehttp://hdl.handle.net/10316/10360http://hdl.handle.net/10316/10360https://doi.org/10.1021/jp710477tengThe Journal of Physical Chemistry A. 112:8 (2008) 1841-18501089-5639Varandas, A. J. C.info:eu-repo/semantics/openAccessreponame:Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos)instname:Agência para a Sociedade do Conhecimento (UMIC) - FCT - Sociedade da Informaçãoinstacron:RCAAP2019-06-02T10:38:05Zoai:estudogeral.uc.pt:10316/10360Portal AgregadorONGhttps://www.rcaap.pt/oai/openaireopendoar:71602024-03-19T21:01:14.706888Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) - Agência para a Sociedade do Conhecimento (UMIC) - FCT - Sociedade da Informaçãofalse |
dc.title.none.fl_str_mv |
Generalized Uniform Singlet- and Triplet-Pair Extrapolation of the Correlation Energy to the One Electron Basis Set Limit |
title |
Generalized Uniform Singlet- and Triplet-Pair Extrapolation of the Correlation Energy to the One Electron Basis Set Limit |
spellingShingle |
Generalized Uniform Singlet- and Triplet-Pair Extrapolation of the Correlation Energy to the One Electron Basis Set Limit Varandas, A. J. C. |
title_short |
Generalized Uniform Singlet- and Triplet-Pair Extrapolation of the Correlation Energy to the One Electron Basis Set Limit |
title_full |
Generalized Uniform Singlet- and Triplet-Pair Extrapolation of the Correlation Energy to the One Electron Basis Set Limit |
title_fullStr |
Generalized Uniform Singlet- and Triplet-Pair Extrapolation of the Correlation Energy to the One Electron Basis Set Limit |
title_full_unstemmed |
Generalized Uniform Singlet- and Triplet-Pair Extrapolation of the Correlation Energy to the One Electron Basis Set Limit |
title_sort |
Generalized Uniform Singlet- and Triplet-Pair Extrapolation of the Correlation Energy to the One Electron Basis Set Limit |
author |
Varandas, A. J. C. |
author_facet |
Varandas, A. J. C. |
author_role |
author |
dc.contributor.author.fl_str_mv |
Varandas, A. J. C. |
description |
The relationship between the triplet- and singlet-pair interaction coefficients in the uniform singlet- and triplet-pair extrapolation method recently suggested for extrapolating ab initio energies to the one-electron basis set limit is analyzed. Based on the premise that such a ratio is invariant over the configuration space of the molecule, generalizations of the method are investigated and their performance tested on extrapolations with MP2, CCD, CCSD, and MRCI(Q) energies. The best variant requires raw energies calculated using augmented correlated consistent basis sets with cardinal numbers up to X = 6 at a single geometry. A scheme is also suggested that performs better than the traditional X-3 law and possibly the original uniform singlet- and triplet-pair extrapolation method but requires data only up to X = Q. |
publishDate |
2008 |
dc.date.none.fl_str_mv |
2008-02-28 |
dc.type.status.fl_str_mv |
info:eu-repo/semantics/publishedVersion |
dc.type.driver.fl_str_mv |
info:eu-repo/semantics/article |
format |
article |
status_str |
publishedVersion |
dc.identifier.uri.fl_str_mv |
http://hdl.handle.net/10316/10360 http://hdl.handle.net/10316/10360 https://doi.org/10.1021/jp710477t |
url |
http://hdl.handle.net/10316/10360 https://doi.org/10.1021/jp710477t |
dc.language.iso.fl_str_mv |
eng |
language |
eng |
dc.relation.none.fl_str_mv |
The Journal of Physical Chemistry A. 112:8 (2008) 1841-1850 1089-5639 |
dc.rights.driver.fl_str_mv |
info:eu-repo/semantics/openAccess |
eu_rights_str_mv |
openAccess |
dc.publisher.none.fl_str_mv |
American Chemical Society |
publisher.none.fl_str_mv |
American Chemical Society |
dc.source.none.fl_str_mv |
reponame:Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) instname:Agência para a Sociedade do Conhecimento (UMIC) - FCT - Sociedade da Informação instacron:RCAAP |
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Agência para a Sociedade do Conhecimento (UMIC) - FCT - Sociedade da Informação |
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RCAAP |
institution |
RCAAP |
reponame_str |
Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) |
collection |
Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) |
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Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) - Agência para a Sociedade do Conhecimento (UMIC) - FCT - Sociedade da Informação |
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1799133904776462336 |