Assessment of the van der Waals, Hubbard U parameter and spin-orbit coupling corrections on the 2D/3D structures from metal gold congeners clusters
Autor(a) principal: | |
---|---|
Data de Publicação: | 2021 |
Outros Autores: | , , |
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 |
id |
UNICSUL-1_b27eaf923ecf2cf380f32d6dd8842471 |
---|---|
oai_identifier_str |
oai:repositorio.cruzeirodosul.edu.br:123456789/3932 |
network_acronym_str |
UNICSUL-1 |
network_name_str |
Repositório Institucional da Universidade Cruzeiro do Sul |
repository_id_str |
|
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) |
instacron_str |
UNICSUL |
institution |
UNICSUL |
reponame_str |
Repositório Institucional da Universidade Cruzeiro do Sul |
collection |
Repositório Institucional da Universidade Cruzeiro do Sul |
bitstream.url.fl_str_mv |
http://dev.siteworks.com.br:8080/jspui/bitstream/123456789/3932/3/license.txt |
bitstream.checksum.fl_str_mv |
8a4605be74aa9ea9d79846c1fba20a33 |
bitstream.checksumAlgorithm.fl_str_mv |
MD5 |
repository.name.fl_str_mv |
Repositório Institucional da Universidade Cruzeiro do Sul - Universidade Cruzeiro do Sul (UNICSUL) |
repository.mail.fl_str_mv |
mary.pela@unicid.edu.br |
_version_ |
1801771127748427776 |