Assessment of the van der Waals, Hubbard U parameter and spin-orbit coupling corrections on the 2D/3D structures from metal gold congeners clusters

Detalhes bibliográficos
Autor(a) principal: Piotrowski, Maurício J.
Data de Publicação: 2021
Outros Autores: Orenha, Renato P., Parreira, Renato Luis Tame, Guedes-Sobrinho, Diego
Tipo de documento: Artigo
Idioma: eng
Título da fonte: Repositório Institucional da Universidade Cruzeiro do Sul
Texto Completo: https://repositorio.cruzeirodosul.edu.br/handle/123456789/3932
https://doi.org/10.1002/jcc.26784
Resumo: The coinage-metal clusters possess a natural complexity in their theoretical treatment that may be accompanied by inherent shortcomings in the methodological approach. Herein, we performed a scalar-relativistic density functional theory study, considering Perdew, Burke, and Ernzerhof (PBE) with (empirical and semi empirical) van der Waals (vdW), spin-orbit coupling (SOC), +U (Hubbard term), and their combinations, to treat the Cu13, Ag13, and Au13 clusters in different structural motifs. The energetic scenario is given by the confirmation of the 3D lowest energy configurations for Cu13 and Ag13 within all approaches, while for Au13 there is a 2D/3D competition, depending on the applied correction. The 2D geometry is 0.43 eV more stable with plain PBE than the 3D one, the SOC, +U, and/or vdW inclusion decreases the overestimated stability of the planar configurations, where the most surprising result is found by the D3 and D3BJ vdW corrections, for which the 3D configuration is 0.29 and 0.11 eV, respectively, more stable than the 2D geometry (with even higher values when SOC and/or +U are added). The D3 dispersion correction represents 7.9% (4.4%) of the total binding energy for the 3D (2D) configuration, (not) being enough to change the sd hybridization and the position of the occupied d-states. Our predictions are in agreement with experimental results and in line with the best results obtained for bulk systems, as well as with hybrid functionals within D3 corrections. The properties description undergoes small corrections with the different approaches, where general trends are maintained, that is, the average bond length is smaller (larger) for lower (higher)-coordinated structures, since a same number of electrons are shared by a smaller (larger) number of bonds, consequently, the bonds are stronger (weaker) and shorter (longer) and the sd hybridization index is larger (smaller). Thus, Au has a distinct behavior in relation to its lighter congeners, with a complex potential energy surface, where in addition to the relevant relativistic effects, correlation and dispersion effects must also be considered. Palavras-chave: Au13, Ag13, Cu13, 2D/3D structures, clusters, density functional theory
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spelling 2022-06-28T18:21:59Z2022-06-28T18:21:59Z2021-10-250192-8651https://repositorio.cruzeirodosul.edu.br/handle/123456789/3932https://doi.org/10.1002/jcc.26784The coinage-metal clusters possess a natural complexity in their theoretical treatment that may be accompanied by inherent shortcomings in the methodological approach. Herein, we performed a scalar-relativistic density functional theory study, considering Perdew, Burke, and Ernzerhof (PBE) with (empirical and semi empirical) van der Waals (vdW), spin-orbit coupling (SOC), +U (Hubbard term), and their combinations, to treat the Cu13, Ag13, and Au13 clusters in different structural motifs. The energetic scenario is given by the confirmation of the 3D lowest energy configurations for Cu13 and Ag13 within all approaches, while for Au13 there is a 2D/3D competition, depending on the applied correction. The 2D geometry is 0.43 eV more stable with plain PBE than the 3D one, the SOC, +U, and/or vdW inclusion decreases the overestimated stability of the planar configurations, where the most surprising result is found by the D3 and D3BJ vdW corrections, for which the 3D configuration is 0.29 and 0.11 eV, respectively, more stable than the 2D geometry (with even higher values when SOC and/or +U are added). The D3 dispersion correction represents 7.9% (4.4%) of the total binding energy for the 3D (2D) configuration, (not) being enough to change the sd hybridization and the position of the occupied d-states. Our predictions are in agreement with experimental results and in line with the best results obtained for bulk systems, as well as with hybrid functionals within D3 corrections. The properties description undergoes small corrections with the different approaches, where general trends are maintained, that is, the average bond length is smaller (larger) for lower (higher)-coordinated structures, since a same number of electrons are shared by a smaller (larger) number of bonds, consequently, the bonds are stronger (weaker) and shorter (longer) and the sd hybridization index is larger (smaller). Thus, Au has a distinct behavior in relation to its lighter congeners, with a complex potential energy surface, where in addition to the relevant relativistic effects, correlation and dispersion effects must also be considered. Palavras-chave: Au13, Ag13, Cu13, 2D/3D structures, clusters, density functional theoryengUniversidade de FrancaUNIFRANBrasilJournal of Computational ChemistryCNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICAAu13Ag13Cu132D/3D structuresclustersdensity functional theoryAssessment of the van der Waals, Hubbard U parameter and spin-orbit coupling corrections on the 2D/3D structures from metal gold congeners clustersinfo:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/article43230243Piotrowski, Maurício J.Orenha, Renato P.Parreira, Renato Luis TameGuedes-Sobrinho, Diegoinfo:eu-repo/semantics/openAccessreponame:Repositório Institucional da Universidade Cruzeiro do Sulinstname:Universidade Cruzeiro do Sul (UNICSUL)instacron:UNICSULLICENSElicense.txtlicense.txttext/plain; charset=utf-81748http://dev.siteworks.com.br:8080/jspui/bitstream/123456789/3932/3/license.txt8a4605be74aa9ea9d79846c1fba20a33MD53123456789/39322022-06-29 13:26:39.008oai:repositorio.cruzeirodosul.edu.br: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Repositório InstitucionalPRIhttps://repositorio.cruzeirodosul.edu.br/oai/requestmary.pela@unicid.edu.bropendoar:2022-06-29T16:26:39Repositório Institucional da Universidade Cruzeiro do Sul - Universidade Cruzeiro do Sul (UNICSUL)false
dc.title.pt_BR.fl_str_mv Assessment of the van der Waals, Hubbard U parameter and spin-orbit coupling corrections on the 2D/3D structures from metal gold congeners clusters
title Assessment of the van der Waals, Hubbard U parameter and spin-orbit coupling corrections on the 2D/3D structures from metal gold congeners clusters
spellingShingle Assessment of the van der Waals, Hubbard U parameter and spin-orbit coupling corrections on the 2D/3D structures from metal gold congeners clusters
Piotrowski, Maurício J.
CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA
Au13
Ag13
Cu13
2D/3D structures
clusters
density functional theory
title_short Assessment of the van der Waals, Hubbard U parameter and spin-orbit coupling corrections on the 2D/3D structures from metal gold congeners clusters
title_full Assessment of the van der Waals, Hubbard U parameter and spin-orbit coupling corrections on the 2D/3D structures from metal gold congeners clusters
title_fullStr Assessment of the van der Waals, Hubbard U parameter and spin-orbit coupling corrections on the 2D/3D structures from metal gold congeners clusters
title_full_unstemmed Assessment of the van der Waals, Hubbard U parameter and spin-orbit coupling corrections on the 2D/3D structures from metal gold congeners clusters
title_sort Assessment of the van der Waals, Hubbard U parameter and spin-orbit coupling corrections on the 2D/3D structures from metal gold congeners clusters
author Piotrowski, Maurício J.
author_facet Piotrowski, Maurício J.
Orenha, Renato P.
Parreira, Renato Luis Tame
Guedes-Sobrinho, Diego
author_role author
author2 Orenha, Renato P.
Parreira, Renato Luis Tame
Guedes-Sobrinho, Diego
author2_role author
author
author
dc.contributor.author.fl_str_mv Piotrowski, Maurício J.
Orenha, Renato P.
Parreira, Renato Luis Tame
Guedes-Sobrinho, Diego
dc.subject.cnpq.fl_str_mv CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA
topic CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA
Au13
Ag13
Cu13
2D/3D structures
clusters
density functional theory
dc.subject.por.fl_str_mv Au13
Ag13
Cu13
2D/3D structures
clusters
density functional theory
description The coinage-metal clusters possess a natural complexity in their theoretical treatment that may be accompanied by inherent shortcomings in the methodological approach. Herein, we performed a scalar-relativistic density functional theory study, considering Perdew, Burke, and Ernzerhof (PBE) with (empirical and semi empirical) van der Waals (vdW), spin-orbit coupling (SOC), +U (Hubbard term), and their combinations, to treat the Cu13, Ag13, and Au13 clusters in different structural motifs. The energetic scenario is given by the confirmation of the 3D lowest energy configurations for Cu13 and Ag13 within all approaches, while for Au13 there is a 2D/3D competition, depending on the applied correction. The 2D geometry is 0.43 eV more stable with plain PBE than the 3D one, the SOC, +U, and/or vdW inclusion decreases the overestimated stability of the planar configurations, where the most surprising result is found by the D3 and D3BJ vdW corrections, for which the 3D configuration is 0.29 and 0.11 eV, respectively, more stable than the 2D geometry (with even higher values when SOC and/or +U are added). The D3 dispersion correction represents 7.9% (4.4%) of the total binding energy for the 3D (2D) configuration, (not) being enough to change the sd hybridization and the position of the occupied d-states. Our predictions are in agreement with experimental results and in line with the best results obtained for bulk systems, as well as with hybrid functionals within D3 corrections. The properties description undergoes small corrections with the different approaches, where general trends are maintained, that is, the average bond length is smaller (larger) for lower (higher)-coordinated structures, since a same number of electrons are shared by a smaller (larger) number of bonds, consequently, the bonds are stronger (weaker) and shorter (longer) and the sd hybridization index is larger (smaller). Thus, Au has a distinct behavior in relation to its lighter congeners, with a complex potential energy surface, where in addition to the relevant relativistic effects, correlation and dispersion effects must also be considered. Palavras-chave: Au13, Ag13, Cu13, 2D/3D structures, clusters, density functional theory
publishDate 2021
dc.date.issued.fl_str_mv 2021-10-25
dc.date.accessioned.fl_str_mv 2022-06-28T18:21:59Z
dc.date.available.fl_str_mv 2022-06-28T18:21:59Z
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 https://repositorio.cruzeirodosul.edu.br/handle/123456789/3932
dc.identifier.issn.pt_BR.fl_str_mv 0192-8651
dc.identifier.doi.pt_BR.fl_str_mv https://doi.org/10.1002/jcc.26784
identifier_str_mv 0192-8651
url https://repositorio.cruzeirodosul.edu.br/handle/123456789/3932
https://doi.org/10.1002/jcc.26784
dc.language.iso.fl_str_mv eng
language eng
dc.relation.ispartof.pt_BR.fl_str_mv Journal of Computational Chemistry
dc.rights.driver.fl_str_mv info:eu-repo/semantics/openAccess
eu_rights_str_mv openAccess
dc.publisher.none.fl_str_mv Universidade de Franca
dc.publisher.initials.fl_str_mv UNIFRAN
dc.publisher.country.fl_str_mv Brasil
publisher.none.fl_str_mv Universidade de Franca
dc.source.none.fl_str_mv reponame:Repositório Institucional da Universidade Cruzeiro do Sul
instname:Universidade Cruzeiro do Sul (UNICSUL)
instacron:UNICSUL
instname_str Universidade Cruzeiro do Sul (UNICSUL)
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institution UNICSUL
reponame_str Repositório Institucional da Universidade Cruzeiro do Sul
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repository.name.fl_str_mv Repositório Institucional da Universidade Cruzeiro do Sul - Universidade Cruzeiro do Sul (UNICSUL)
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