The effect of different energy portions on the 2D/ 3D stability swapping for 13-atom metal clusters†
Autor(a) principal: | |
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Data de Publicação: | 2022 |
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/123456789/3933 https://doi.org/10.1039/D2CP00148A |
Resumo: | The complexity of Cu13, Ag13, and Au13 coinage-metal clusters was investigated through their energy contributions via a density functional theory study, considering improvements in the PBE functional, such as van der Waals (vdW) corrections, spin–orbit coupling (SOC), Hubbard term (+U), and their combinations. Investigating two-dimensional (planar 2D) and three-dimensional (distorted 3D, CUB – cuboctahedral, and ICO – icosahedral) configurations, we found that vdW corrections are dominant in modulating the stability swapping between 2D and ICO (3D) for Ag13 (Au13), whereas for Cu13 its role is increasing the relative stability between 2D (least stable) and 3D (most stable), setting ICO as the reference. Among the energy portions that constitute the relative total energy, the dimensionality difference correlates with the magnitude of the relative dispersion energy (large for 2D/ICO and small for 3D/ICO) as the causal factor responsible for an eventual stability swapping. For instance, empirical vdW corrections may favor Ag13 as ICO, while semi empirical ones tend to swap the stability by favoring 2D. The same tendency is observed for Au13, except when SOC is included, which enlarges the stability of 3D over 2D. Energy decomposition analysis combined with the natural orbitals for the chemical valence approach confirmed the correlations between the dimensionality difference and the magnitude of the relative dispersion energies. Our structural analysis protocol was able to capture the local distortion effects (or even their absence) through the quantification of the Hausdorff chirality measure. Here, ICO, CUB, and 2D are achiral configurations for all coinage-metal clusters, whereas Cu13 as 3D presents a slight chirality when vdW correction based on many body dispersion is used, at the same time Ag13 as 3D turned out to be chiral for all calculation protocols as evidence of the role of the chemical composition. Palavras-chave: metal clusters, Au13, Ag13, Cu13, 2D/3D stability |
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2022-06-28T19:31:06Z2022-06-28T19:31:06Z2022-06-131463-9076https://repositorio.cruzeirodosul.edu.br/handle/123456789/3933https://doi.org/10.1039/D2CP00148AThe complexity of Cu13, Ag13, and Au13 coinage-metal clusters was investigated through their energy contributions via a density functional theory study, considering improvements in the PBE functional, such as van der Waals (vdW) corrections, spin–orbit coupling (SOC), Hubbard term (+U), and their combinations. Investigating two-dimensional (planar 2D) and three-dimensional (distorted 3D, CUB – cuboctahedral, and ICO – icosahedral) configurations, we found that vdW corrections are dominant in modulating the stability swapping between 2D and ICO (3D) for Ag13 (Au13), whereas for Cu13 its role is increasing the relative stability between 2D (least stable) and 3D (most stable), setting ICO as the reference. Among the energy portions that constitute the relative total energy, the dimensionality difference correlates with the magnitude of the relative dispersion energy (large for 2D/ICO and small for 3D/ICO) as the causal factor responsible for an eventual stability swapping. For instance, empirical vdW corrections may favor Ag13 as ICO, while semi empirical ones tend to swap the stability by favoring 2D. The same tendency is observed for Au13, except when SOC is included, which enlarges the stability of 3D over 2D. Energy decomposition analysis combined with the natural orbitals for the chemical valence approach confirmed the correlations between the dimensionality difference and the magnitude of the relative dispersion energies. Our structural analysis protocol was able to capture the local distortion effects (or even their absence) through the quantification of the Hausdorff chirality measure. Here, ICO, CUB, and 2D are achiral configurations for all coinage-metal clusters, whereas Cu13 as 3D presents a slight chirality when vdW correction based on many body dispersion is used, at the same time Ag13 as 3D turned out to be chiral for all calculation protocols as evidence of the role of the chemical composition. Palavras-chave: metal clusters, Au13, Ag13, Cu13, 2D/3D stabilityengUniversidade de FrancaUNIFRANBrasilPhysical Chemistry Chemical PhysicsCNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICAmetal clustersAu13Ag13Cu132D/3D stabilityThe effect of different energy portions on the 2D/ 3D stability swapping for 13-atom metal clusters†info:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/article241165156524Guedes-Sobrinho, DiegoOrenha, Renato P.Parreira, Renato Luis TameNagurniak, Glaucio R.Silva, Gabriel Reynald daPiotrowski, Maurício J.info: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/123456789/3933/2/license.txt8a4605be74aa9ea9d79846c1fba20a33MD52123456789/39332022-06-29 13:27:12.318oai:repositorio.cruzeirodosul.edu.br: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Repositório InstitucionalPRIhttps://repositorio.cruzeirodosul.edu.br/oai/requestmary.pela@unicid.edu.bropendoar:2022-06-29T16:27:12Repositório Institucional da Universidade Cruzeiro do Sul - Universidade Cruzeiro do Sul (UNICSUL)false |
dc.title.pt_BR.fl_str_mv |
The effect of different energy portions on the 2D/ 3D stability swapping for 13-atom metal clusters† |
title |
The effect of different energy portions on the 2D/ 3D stability swapping for 13-atom metal clusters† |
spellingShingle |
The effect of different energy portions on the 2D/ 3D stability swapping for 13-atom metal clusters† Guedes-Sobrinho, Diego CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA metal clusters Au13 Ag13 Cu13 2D/3D stability |
title_short |
The effect of different energy portions on the 2D/ 3D stability swapping for 13-atom metal clusters† |
title_full |
The effect of different energy portions on the 2D/ 3D stability swapping for 13-atom metal clusters† |
title_fullStr |
The effect of different energy portions on the 2D/ 3D stability swapping for 13-atom metal clusters† |
title_full_unstemmed |
The effect of different energy portions on the 2D/ 3D stability swapping for 13-atom metal clusters† |
title_sort |
The effect of different energy portions on the 2D/ 3D stability swapping for 13-atom metal clusters† |
author |
Guedes-Sobrinho, Diego |
author_facet |
Guedes-Sobrinho, Diego Orenha, Renato P. Parreira, Renato Luis Tame Nagurniak, Glaucio R. Silva, Gabriel Reynald da Piotrowski, Maurício J. |
author_role |
author |
author2 |
Orenha, Renato P. Parreira, Renato Luis Tame Nagurniak, Glaucio R. Silva, Gabriel Reynald da Piotrowski, Maurício J. |
author2_role |
author author author author author |
dc.contributor.author.fl_str_mv |
Guedes-Sobrinho, Diego Orenha, Renato P. Parreira, Renato Luis Tame Nagurniak, Glaucio R. Silva, Gabriel Reynald da Piotrowski, Maurício J. |
dc.subject.cnpq.fl_str_mv |
CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA |
topic |
CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA metal clusters Au13 Ag13 Cu13 2D/3D stability |
dc.subject.por.fl_str_mv |
metal clusters Au13 Ag13 Cu13 2D/3D stability |
description |
The complexity of Cu13, Ag13, and Au13 coinage-metal clusters was investigated through their energy contributions via a density functional theory study, considering improvements in the PBE functional, such as van der Waals (vdW) corrections, spin–orbit coupling (SOC), Hubbard term (+U), and their combinations. Investigating two-dimensional (planar 2D) and three-dimensional (distorted 3D, CUB – cuboctahedral, and ICO – icosahedral) configurations, we found that vdW corrections are dominant in modulating the stability swapping between 2D and ICO (3D) for Ag13 (Au13), whereas for Cu13 its role is increasing the relative stability between 2D (least stable) and 3D (most stable), setting ICO as the reference. Among the energy portions that constitute the relative total energy, the dimensionality difference correlates with the magnitude of the relative dispersion energy (large for 2D/ICO and small for 3D/ICO) as the causal factor responsible for an eventual stability swapping. For instance, empirical vdW corrections may favor Ag13 as ICO, while semi empirical ones tend to swap the stability by favoring 2D. The same tendency is observed for Au13, except when SOC is included, which enlarges the stability of 3D over 2D. Energy decomposition analysis combined with the natural orbitals for the chemical valence approach confirmed the correlations between the dimensionality difference and the magnitude of the relative dispersion energies. Our structural analysis protocol was able to capture the local distortion effects (or even their absence) through the quantification of the Hausdorff chirality measure. Here, ICO, CUB, and 2D are achiral configurations for all coinage-metal clusters, whereas Cu13 as 3D presents a slight chirality when vdW correction based on many body dispersion is used, at the same time Ag13 as 3D turned out to be chiral for all calculation protocols as evidence of the role of the chemical composition. Palavras-chave: metal clusters, Au13, Ag13, Cu13, 2D/3D stability |
publishDate |
2022 |
dc.date.accessioned.fl_str_mv |
2022-06-28T19:31:06Z |
dc.date.available.fl_str_mv |
2022-06-28T19:31:06Z |
dc.date.issued.fl_str_mv |
2022-06-13 |
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/123456789/3933 |
dc.identifier.issn.pt_BR.fl_str_mv |
1463-9076 |
dc.identifier.doi.pt_BR.fl_str_mv |
https://doi.org/10.1039/D2CP00148A |
identifier_str_mv |
1463-9076 |
url |
https://repositorio.cruzeirodosul.edu.br/handle/123456789/3933 https://doi.org/10.1039/D2CP00148A |
dc.language.iso.fl_str_mv |
eng |
language |
eng |
dc.relation.ispartof.pt_BR.fl_str_mv |
Physical Chemistry Chemical Physics |
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 |
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Universidade Cruzeiro do Sul (UNICSUL) |
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UNICSUL |
institution |
UNICSUL |
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Repositório Institucional da Universidade Cruzeiro do Sul |
collection |
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) |
repository.mail.fl_str_mv |
mary.pela@unicid.edu.br |
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1801771133852188672 |