Estudo da Teoria do Funcional da Densidade (DFT) na propriedades estruturais e ópticas de nanoclusters de ouro

Detalhes bibliográficos
Autor(a) principal: Rodrigues, Edna da Silva Machado
Data de Publicação: 2019
Tipo de documento: Tese
Idioma: por
Título da fonte: Repositório Institucional da UFS
Texto Completo: http://ri.ufs.br/jspui/handle/riufs/11730
Resumo: Density Functional Theory (DFT) calculations and its time dependent approach (TDDFT) have been performed to investigate the ligand effect on the structural and optical properties of the Au13 and Au13 3+ clusters. In the first part of this work, it has been investigated through the analysis of the potential energy curves, the most favorable coordination site of the NH3, PH3, SCH3 and SeCH3 ligands on the Au13 cluster. The results show that the NH3 and PH3 ligands bind preferentially on top site, while for the other ligands the coordination to the (111) site is energetically more favorable. In addition, it was studied the ligand influence on the structural, electronic and optical properties of the Au13L, where L = NH3, N(CH3)3, PH3, P(CH3)3, SCH3, SCH2Ph, SCH(CH3)NH2, SCH(CH3)Cl, SPh, SPhCH3 , SPhCOOH and SeCH3. The analysis of the electronic stabilities reveals that the Au13SCH(CH3)Cl and Au13NH3 are the most stable among the other clusters of the thiolate or selenolate and of the phosphine or amine-ligated groups, respectively. The ligand effect on the optical absorption spectra of Au13L is relatively small, in which the main change is observed in the intensity of the highest energy peak. In the second part of this work, it has been developed a systematic structural analysis of Au13L8 3+, where L = SCH3, SeCH3, SCH2OCH3 e S(CH3)2NH2, to exam the influence of different ligands. Binding energy calculations indicate that the gold core is more stabilized by the ligand in the following sequence S(CH3)2NH2 > SCH2OCH3 > SeCH3 > SCH3. Natural Bond Analysis (NBO) shows that the strongest electron donation occurs from a lone pair orbital on the sulfur and selenium atoms to the antibonding acceptor o* (Au−S) and o* (Au−Se), respectively. TDDFT calculations have been performed to simulate the optical absorption spectra of Au13L8 3+ in gas phase and under the effect of solvents with different polarities. The absorption spectrum of [Au13(S(CH2)2NH2)8]3+ shows a spectral profile that differs considerably from the others in gas phase and which is strongly affected by solvent.
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spelling Rodrigues, Edna da Silva MachadoCosta Júnior, Nivan Bezerra daFelicíssimo, Viviane Costa2019-08-14T23:36:44Z2019-08-14T23:36:44Z2019-05-31RODRIGUES, Edna da Silva Machado. Estudo da Teoria do Funcional da Densidade (DFT) na propriedades estruturais e ópticas de nanoclusters de ouro. 2019. 120 f. Tese (Doutorado em Química) - Universidade Federal de Sergipe, São Cristóvão, SE, 2019.http://ri.ufs.br/jspui/handle/riufs/11730Density Functional Theory (DFT) calculations and its time dependent approach (TDDFT) have been performed to investigate the ligand effect on the structural and optical properties of the Au13 and Au13 3+ clusters. In the first part of this work, it has been investigated through the analysis of the potential energy curves, the most favorable coordination site of the NH3, PH3, SCH3 and SeCH3 ligands on the Au13 cluster. The results show that the NH3 and PH3 ligands bind preferentially on top site, while for the other ligands the coordination to the (111) site is energetically more favorable. In addition, it was studied the ligand influence on the structural, electronic and optical properties of the Au13L, where L = NH3, N(CH3)3, PH3, P(CH3)3, SCH3, SCH2Ph, SCH(CH3)NH2, SCH(CH3)Cl, SPh, SPhCH3 , SPhCOOH and SeCH3. The analysis of the electronic stabilities reveals that the Au13SCH(CH3)Cl and Au13NH3 are the most stable among the other clusters of the thiolate or selenolate and of the phosphine or amine-ligated groups, respectively. The ligand effect on the optical absorption spectra of Au13L is relatively small, in which the main change is observed in the intensity of the highest energy peak. In the second part of this work, it has been developed a systematic structural analysis of Au13L8 3+, where L = SCH3, SeCH3, SCH2OCH3 e S(CH3)2NH2, to exam the influence of different ligands. Binding energy calculations indicate that the gold core is more stabilized by the ligand in the following sequence S(CH3)2NH2 > SCH2OCH3 > SeCH3 > SCH3. Natural Bond Analysis (NBO) shows that the strongest electron donation occurs from a lone pair orbital on the sulfur and selenium atoms to the antibonding acceptor o* (Au−S) and o* (Au−Se), respectively. TDDFT calculations have been performed to simulate the optical absorption spectra of Au13L8 3+ in gas phase and under the effect of solvents with different polarities. The absorption spectrum of [Au13(S(CH2)2NH2)8]3+ shows a spectral profile that differs considerably from the others in gas phase and which is strongly affected by solvent.Cálculos da teoria do funcional de densidade (do inglês, Density Functional Theory – DFT) e sua abordagem dependente do tempo (TDDFT) foram realizados para investigar a influência de diferentes ligantes nas propriedades estruturais e ópticas dos clusters de ouro Au13 e Au13 3+. Inicialmente foi investigado, por meio das curvas de energia potencial, o sítio de coordenação mais favorável de diferentes ligantes (NH3, PH3, SCH3 e SeCH3) no cluster de Au13. Os resultados mostram que o ligante aminado e o fosfinado se coordenam preferencialmente ao sítio on top, enquanto que, para os demais ligantes, a coordenação ao sítio da face (111) se mostra energeticamente mais favorável. Em seguida, foi estudada a influência dos ligantes sobre as propriedades estruturais, eletrônicas e ópticas do cluster de Au13L, sendo L = NH3, N(CH3)3, PH3, P(CH3)3, SCH3, SCH2Ph, SCH(CH3)NH2, SCH(CH3)Cl, SPh, SPhCH3, SPhCOOH e SeCH3. A análise dos resultados da estabilidade eletrônica revelou que os clusters de Au13SCH(CH3)Cl e Au13NH3 são os mais estáveis dentre àqueles que pertencem ao grupo dos tiolados ou selenolado e ao grupo dos aminados e fosfinados, respectivamente. Posteriormente, foi avaliada a influência dos ligantes sobre os espectros de absorção do Au13L, onde o principal efeito está na intensidade da banda de mais alta energia. Na segunda parte deste trabalho foi realizada uma análise estrutural do Au13L8 3+, onde L = SCH3, SeCH3, SCH2OCH3 e S(CH3)2NH2. Cálculos de energia de ligação indicam que o Au13 é mais estabilizado pelo ligante de acordo com a sequência: S(CH3)2NH2 > SCH2OCH3 > SeCH3 > SCH3. A análise dos orbitais naturais de ligação (do inglês, Natural Bond Orbitals ‒NBO) mostra que a doação eletrônica mais forte ocorre dos orbitais não ligantes sobre os átomos de enxofre ou selênio para os orbitais antiligantes o* (Au-S) e o* (Au-Se), respectivamente. Além disso, ela permitiu entender a origem da maior estabilidade do [Au13(S(CH2)2NH2)8]3+. Os espectros ópticos de absorção do Au13L8 3+ foram calculados em fase gasosa e sob o efeito de solventes. O espectro de absorção do [Au13(S(CH2)2NH2)8]3+ mostra um perfil espectral que difere dos demais clusters em fase gasosa e o mesmo é fortemente afetado pelo efeito do solvente.Fundação de Apoio a Pesquisa e à Inovação Tecnológica do Estado de Sergipe - FAPITEC/SESão Cristóvão, SEporQuímicaDensidade funcionalÍons complexosPropriedades elétricasPropriedades ópticasSolventesClusters de ouroTeoria do Funcional da Densidade (DFT)Propriedades eletrônicasEspectros ópticosLigantesGold clustersDensity Functional Theory (DFT)Electronic propertyOptical spectraLigandSolventCIENCIAS EXATAS E DA TERRA::QUIMICAEstudo da Teoria do Funcional da Densidade (DFT) na propriedades estruturais e ópticas de nanoclusters de ouroStudy of Density Functional Theory (DFT) in the structural and optical properties of gold nanoclustersinfo:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/doctoralThesisPós-Graduação em QuímicaUFSreponame:Repositório Institucional da UFSinstname:Universidade Federal de Sergipe (UFS)instacron:UFSinfo:eu-repo/semantics/openAccessLICENSElicense.txtlicense.txttext/plain; charset=utf-81475https://ri.ufs.br/jspui/bitstream/riufs/11730/1/license.txt098cbbf65c2c15e1fb2e49c5d306a44cMD51ORIGINALEDNA_SILVA_MACHADO_RODRIGUES.pdfEDNA_SILVA_MACHADO_RODRIGUES.pdfapplication/pdf3916418https://ri.ufs.br/jspui/bitstream/riufs/11730/2/EDNA_SILVA_MACHADO_RODRIGUES.pdf6924ce7078a014d61ed85fb756a869c8MD52TEXTEDNA_SILVA_MACHADO_RODRIGUES.pdf.txtEDNA_SILVA_MACHADO_RODRIGUES.pdf.txtExtracted texttext/plain182562https://ri.ufs.br/jspui/bitstream/riufs/11730/3/EDNA_SILVA_MACHADO_RODRIGUES.pdf.txta8c20a8b6fbaaef86d85ad6232372627MD53THUMBNAILEDNA_SILVA_MACHADO_RODRIGUES.pdf.jpgEDNA_SILVA_MACHADO_RODRIGUES.pdf.jpgGenerated Thumbnailimage/jpeg1414https://ri.ufs.br/jspui/bitstream/riufs/11730/4/EDNA_SILVA_MACHADO_RODRIGUES.pdf.jpg18c5ae90ced66a0490a6c4388154ce9eMD54riufs/117302019-08-14 20:36:44.787oai:ufs.br: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Repositório InstitucionalPUBhttps://ri.ufs.br/oai/requestrepositorio@academico.ufs.bropendoar:2019-08-14T23:36:44Repositório Institucional da UFS - Universidade Federal de Sergipe (UFS)false
dc.title.pt_BR.fl_str_mv Estudo da Teoria do Funcional da Densidade (DFT) na propriedades estruturais e ópticas de nanoclusters de ouro
dc.title.alternative.eng.fl_str_mv Study of Density Functional Theory (DFT) in the structural and optical properties of gold nanoclusters
title Estudo da Teoria do Funcional da Densidade (DFT) na propriedades estruturais e ópticas de nanoclusters de ouro
spellingShingle Estudo da Teoria do Funcional da Densidade (DFT) na propriedades estruturais e ópticas de nanoclusters de ouro
Rodrigues, Edna da Silva Machado
Química
Densidade funcional
Íons complexos
Propriedades elétricas
Propriedades ópticas
Solventes
Clusters de ouro
Teoria do Funcional da Densidade (DFT)
Propriedades eletrônicas
Espectros ópticos
Ligantes
Gold clusters
Density Functional Theory (DFT)
Electronic property
Optical spectra
Ligand
Solvent
CIENCIAS EXATAS E DA TERRA::QUIMICA
title_short Estudo da Teoria do Funcional da Densidade (DFT) na propriedades estruturais e ópticas de nanoclusters de ouro
title_full Estudo da Teoria do Funcional da Densidade (DFT) na propriedades estruturais e ópticas de nanoclusters de ouro
title_fullStr Estudo da Teoria do Funcional da Densidade (DFT) na propriedades estruturais e ópticas de nanoclusters de ouro
title_full_unstemmed Estudo da Teoria do Funcional da Densidade (DFT) na propriedades estruturais e ópticas de nanoclusters de ouro
title_sort Estudo da Teoria do Funcional da Densidade (DFT) na propriedades estruturais e ópticas de nanoclusters de ouro
author Rodrigues, Edna da Silva Machado
author_facet Rodrigues, Edna da Silva Machado
author_role author
dc.contributor.author.fl_str_mv Rodrigues, Edna da Silva Machado
dc.contributor.advisor1.fl_str_mv Costa Júnior, Nivan Bezerra da
dc.contributor.advisor-co1.fl_str_mv Felicíssimo, Viviane Costa
contributor_str_mv Costa Júnior, Nivan Bezerra da
Felicíssimo, Viviane Costa
dc.subject.por.fl_str_mv Química
Densidade funcional
Íons complexos
Propriedades elétricas
Propriedades ópticas
Solventes
Clusters de ouro
Teoria do Funcional da Densidade (DFT)
Propriedades eletrônicas
Espectros ópticos
Ligantes
topic Química
Densidade funcional
Íons complexos
Propriedades elétricas
Propriedades ópticas
Solventes
Clusters de ouro
Teoria do Funcional da Densidade (DFT)
Propriedades eletrônicas
Espectros ópticos
Ligantes
Gold clusters
Density Functional Theory (DFT)
Electronic property
Optical spectra
Ligand
Solvent
CIENCIAS EXATAS E DA TERRA::QUIMICA
dc.subject.eng.fl_str_mv Gold clusters
Density Functional Theory (DFT)
Electronic property
Optical spectra
Ligand
Solvent
dc.subject.cnpq.fl_str_mv CIENCIAS EXATAS E DA TERRA::QUIMICA
description Density Functional Theory (DFT) calculations and its time dependent approach (TDDFT) have been performed to investigate the ligand effect on the structural and optical properties of the Au13 and Au13 3+ clusters. In the first part of this work, it has been investigated through the analysis of the potential energy curves, the most favorable coordination site of the NH3, PH3, SCH3 and SeCH3 ligands on the Au13 cluster. The results show that the NH3 and PH3 ligands bind preferentially on top site, while for the other ligands the coordination to the (111) site is energetically more favorable. In addition, it was studied the ligand influence on the structural, electronic and optical properties of the Au13L, where L = NH3, N(CH3)3, PH3, P(CH3)3, SCH3, SCH2Ph, SCH(CH3)NH2, SCH(CH3)Cl, SPh, SPhCH3 , SPhCOOH and SeCH3. The analysis of the electronic stabilities reveals that the Au13SCH(CH3)Cl and Au13NH3 are the most stable among the other clusters of the thiolate or selenolate and of the phosphine or amine-ligated groups, respectively. The ligand effect on the optical absorption spectra of Au13L is relatively small, in which the main change is observed in the intensity of the highest energy peak. In the second part of this work, it has been developed a systematic structural analysis of Au13L8 3+, where L = SCH3, SeCH3, SCH2OCH3 e S(CH3)2NH2, to exam the influence of different ligands. Binding energy calculations indicate that the gold core is more stabilized by the ligand in the following sequence S(CH3)2NH2 > SCH2OCH3 > SeCH3 > SCH3. Natural Bond Analysis (NBO) shows that the strongest electron donation occurs from a lone pair orbital on the sulfur and selenium atoms to the antibonding acceptor o* (Au−S) and o* (Au−Se), respectively. TDDFT calculations have been performed to simulate the optical absorption spectra of Au13L8 3+ in gas phase and under the effect of solvents with different polarities. The absorption spectrum of [Au13(S(CH2)2NH2)8]3+ shows a spectral profile that differs considerably from the others in gas phase and which is strongly affected by solvent.
publishDate 2019
dc.date.accessioned.fl_str_mv 2019-08-14T23:36:44Z
dc.date.available.fl_str_mv 2019-08-14T23:36:44Z
dc.date.issued.fl_str_mv 2019-05-31
dc.type.status.fl_str_mv info:eu-repo/semantics/publishedVersion
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dc.identifier.citation.fl_str_mv RODRIGUES, Edna da Silva Machado. Estudo da Teoria do Funcional da Densidade (DFT) na propriedades estruturais e ópticas de nanoclusters de ouro. 2019. 120 f. Tese (Doutorado em Química) - Universidade Federal de Sergipe, São Cristóvão, SE, 2019.
dc.identifier.uri.fl_str_mv http://ri.ufs.br/jspui/handle/riufs/11730
identifier_str_mv RODRIGUES, Edna da Silva Machado. Estudo da Teoria do Funcional da Densidade (DFT) na propriedades estruturais e ópticas de nanoclusters de ouro. 2019. 120 f. Tese (Doutorado em Química) - Universidade Federal de Sergipe, São Cristóvão, SE, 2019.
url http://ri.ufs.br/jspui/handle/riufs/11730
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