Efeitos de inserção do íon de cobre na matriz cristalina do Bi12GeO20 : estudo de primeiros princípios
Autor(a) principal: | |
---|---|
Data de Publicação: | 2018 |
Tipo de documento: | Dissertação |
Idioma: | por |
Título da fonte: | Repositório Institucional da UFS |
Texto Completo: | http://ri.ufs.br/jspui/handle/riufs/10740 |
Resumo: | In this dissertation the effects of insertion of the Cu ion into the Bi12GeO20 (BGO) crystalline matrix were studied by means of the first-order computational techniques based on the density functional theory. The FP-LAPW method implemented in the WIEN2K code was applied. Correlation and exchange effects were treated with the GGA-PBE functional (for structural optimization) and with the TB-mbj potential (for the calculation of the electronic properties). Within the BGO crystalline matrix there are two possible accommodation sites of the impurity, Ge4+ and Bi3+. Experimental studies have shown that most of the transition metal impurities prefer to accommodate at the Ge4+ site. This is surprising, since the impurities are expected to replace the Bi3+ site because it has the more compatible charge state and the larger ionic radius. On the other hand, the Cu ion is one of the few that has a preference for the Bi3+ site. It accommodates at this site with an electronic configuration 3d9 and with oxidation state 2+. In order to understand these facts, not yet explained by the experiments, two distinct systems were simulated: (1) the BGO crystal with Cu impurity at the Ge4+ site, and (2) the BGO crystal with Cu impurity at the Bi3+ site. The defect was studied in the neutral, positively and negatively charged state. The insertion preference was estimated from the calculations of the defect formation energy. Electronic properties were also calculated and the quantum theory of atoms in molecules was applied to estimate the oxidation state of Cu. The results confirmed the preference of accommodation of the Cu ion at the Bi3+ site, in accordance with the results obtained by experimental techniques such as EPR. The electron structure analysis showed that the Cu valence is 2+ (3d9) regardless of the charge state. The changes of the structural, electronic and magnetic properties of the BGO compound in the presence of Cu impurity at both sites of the incorporation were analysed and clarified. |
id |
UFS-2_3d7238e8dfcf54df0df47bc392145163 |
---|---|
oai_identifier_str |
oai:ufs.br:riufs/10740 |
network_acronym_str |
UFS-2 |
network_name_str |
Repositório Institucional da UFS |
repository_id_str |
|
spelling |
Lima, Jailsson SilvaLalic, Milan2019-03-22T12:02:48Z2019-03-22T12:02:48Z2018-02-27LIMA, Jailsson Silva. Efeitos de inserção do íon de cobre na matriz cristalina do Bi12GeO20 : estudo de primeiros princípios. 2018. 114 f. Dissertação (Mestrado em Física) - Universidade Federal de Sergipe, São Cristóvão, SE, 2018.http://ri.ufs.br/jspui/handle/riufs/10740In this dissertation the effects of insertion of the Cu ion into the Bi12GeO20 (BGO) crystalline matrix were studied by means of the first-order computational techniques based on the density functional theory. The FP-LAPW method implemented in the WIEN2K code was applied. Correlation and exchange effects were treated with the GGA-PBE functional (for structural optimization) and with the TB-mbj potential (for the calculation of the electronic properties). Within the BGO crystalline matrix there are two possible accommodation sites of the impurity, Ge4+ and Bi3+. Experimental studies have shown that most of the transition metal impurities prefer to accommodate at the Ge4+ site. This is surprising, since the impurities are expected to replace the Bi3+ site because it has the more compatible charge state and the larger ionic radius. On the other hand, the Cu ion is one of the few that has a preference for the Bi3+ site. It accommodates at this site with an electronic configuration 3d9 and with oxidation state 2+. In order to understand these facts, not yet explained by the experiments, two distinct systems were simulated: (1) the BGO crystal with Cu impurity at the Ge4+ site, and (2) the BGO crystal with Cu impurity at the Bi3+ site. The defect was studied in the neutral, positively and negatively charged state. The insertion preference was estimated from the calculations of the defect formation energy. Electronic properties were also calculated and the quantum theory of atoms in molecules was applied to estimate the oxidation state of Cu. The results confirmed the preference of accommodation of the Cu ion at the Bi3+ site, in accordance with the results obtained by experimental techniques such as EPR. The electron structure analysis showed that the Cu valence is 2+ (3d9) regardless of the charge state. The changes of the structural, electronic and magnetic properties of the BGO compound in the presence of Cu impurity at both sites of the incorporation were analysed and clarified.Nessa dissertação foram estudados os efeitos da inserção do íon de Cu na matriz cristalina do Bi12GeO20 (BGO) utilizando técnicas computacionais de primeiros princípios baseadas na teoria do funcional da densidade. Foi aplicado o método FP-LAPW implementado no código WIEN2K. Os efeitos de correlação e troca foram tratados com o funcional GGA-PBE (para optimização estrutural) e com o potencial TB-mbj (para o cálculo das propriedades eletrônicas). Dentro da matriz cristalina há dois possíveis sítios de acomodação da impureza, Ge4+ e Bi3+. Os estudos experimentais têm mostrado que a maioria das impurezas de metais de transição tem mais preferência em se acomodar no sítio Ge4+. Este fato surpreende, pois espera-se que as impurezas substituam o sítio do Bi3+, por ele ter o estado de carga mais compatível e maior raio iônico. Por outro lado, o íon de Cu é um dos poucos que tem preferência pelo sítio do Bi3+. Ele se acomoda neste sítio com configuração eletrônica 3d9 e com estado de oxidação 2+. Então, com o objetivo de compreender estes fatos não explicados ainda pelos experimentos, foram simuladas dois sistemas distintos: (1) o cristal BGO com impureza de Cu no sítio de Ge4+, e (2) o cristal BGO com impureza de Cu no sítio de Bi3+. O defeito foi estudado nos estados de carga neutro, carregado positivamente e negativamente. A preferência da inserção foi estimada a partir dos cálculos da energia de formação dos defeitos. Também foram calculadas propriedades eletrônicas e aplicada a teoria quântica de átomos em moléculas com objetivo de estimar o estado de oxidação do Cu. Os resultados confirmaram a preferência de acomodação do íon de Cu no s tio do Bi3+, em acordo com os resultados obtidos por técnicas experimentais como a EPR. A análise da estrutura eletrônica mostrou que a valência do Cu e 2+ (3d9) independentemente do estado de carga. Foram analisadas e esclarecidas as mudanças nas propriedades estruturais, eletrônicas e magnéticas do composto BGO na presença da impureza de Cu em ambos os sítios da incorporação.Coordenação de Aperfeiçoamento de Pessoal de Nível Superior - CAPESSão Cristóvão, SEporComposto Bi12GeO20Física dos defeitosCálculos DFTPropriedades eletrônicasEnergias de formação do defeitoCompound Bi12GeO20Physics of defectsDFT calculationsElectronic propertiesDefect formation energiesCIENCIAS EXATAS E DA TERRA::FISICAEfeitos de inserção do íon de cobre na matriz cristalina do Bi12GeO20 : estudo de primeiros princípiosEffects of insertion of the copper ion on the crystalline matrix of the Bi12GeO20 : first principles studyinfo:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/masterThesisPós-Graduação em FísicaUniversidade Federal de Sergipereponame:Repositório Institucional da UFSinstname:Universidade Federal de Sergipe (UFS)instacron:UFSinfo:eu-repo/semantics/openAccessTEXTJAILSSON_SILVA_LIMA.pdf.txtJAILSSON_SILVA_LIMA.pdf.txtExtracted texttext/plain213927https://ri.ufs.br/jspui/bitstream/riufs/10740/3/JAILSSON_SILVA_LIMA.pdf.txt33ef5a4376b26c783416d69c726dcaf4MD53THUMBNAILJAILSSON_SILVA_LIMA.pdf.jpgJAILSSON_SILVA_LIMA.pdf.jpgGenerated Thumbnailimage/jpeg1220https://ri.ufs.br/jspui/bitstream/riufs/10740/4/JAILSSON_SILVA_LIMA.pdf.jpg6bc05ffe08a974120cc0ec797116a69dMD54LICENSElicense.txtlicense.txttext/plain; charset=utf-81475https://ri.ufs.br/jspui/bitstream/riufs/10740/1/license.txt098cbbf65c2c15e1fb2e49c5d306a44cMD51ORIGINALJAILSSON_SILVA_LIMA.pdfJAILSSON_SILVA_LIMA.pdfapplication/pdf1704919https://ri.ufs.br/jspui/bitstream/riufs/10740/2/JAILSSON_SILVA_LIMA.pdf655b8616b6e71ff49cd68cbb880de336MD52riufs/107402019-03-22 09:02:48.881oai:ufs.br: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Repositório InstitucionalPUBhttps://ri.ufs.br/oai/requestrepositorio@academico.ufs.bropendoar:2019-03-22T12:02:48Repositório Institucional da UFS - Universidade Federal de Sergipe (UFS)false |
dc.title.pt_BR.fl_str_mv |
Efeitos de inserção do íon de cobre na matriz cristalina do Bi12GeO20 : estudo de primeiros princípios |
dc.title.alternative.eng.fl_str_mv |
Effects of insertion of the copper ion on the crystalline matrix of the Bi12GeO20 : first principles study |
title |
Efeitos de inserção do íon de cobre na matriz cristalina do Bi12GeO20 : estudo de primeiros princípios |
spellingShingle |
Efeitos de inserção do íon de cobre na matriz cristalina do Bi12GeO20 : estudo de primeiros princípios Lima, Jailsson Silva Composto Bi12GeO20 Física dos defeitos Cálculos DFT Propriedades eletrônicas Energias de formação do defeito Compound Bi12GeO20 Physics of defects DFT calculations Electronic properties Defect formation energies CIENCIAS EXATAS E DA TERRA::FISICA |
title_short |
Efeitos de inserção do íon de cobre na matriz cristalina do Bi12GeO20 : estudo de primeiros princípios |
title_full |
Efeitos de inserção do íon de cobre na matriz cristalina do Bi12GeO20 : estudo de primeiros princípios |
title_fullStr |
Efeitos de inserção do íon de cobre na matriz cristalina do Bi12GeO20 : estudo de primeiros princípios |
title_full_unstemmed |
Efeitos de inserção do íon de cobre na matriz cristalina do Bi12GeO20 : estudo de primeiros princípios |
title_sort |
Efeitos de inserção do íon de cobre na matriz cristalina do Bi12GeO20 : estudo de primeiros princípios |
author |
Lima, Jailsson Silva |
author_facet |
Lima, Jailsson Silva |
author_role |
author |
dc.contributor.author.fl_str_mv |
Lima, Jailsson Silva |
dc.contributor.advisor1.fl_str_mv |
Lalic, Milan |
contributor_str_mv |
Lalic, Milan |
dc.subject.por.fl_str_mv |
Composto Bi12GeO20 Física dos defeitos Cálculos DFT Propriedades eletrônicas Energias de formação do defeito |
topic |
Composto Bi12GeO20 Física dos defeitos Cálculos DFT Propriedades eletrônicas Energias de formação do defeito Compound Bi12GeO20 Physics of defects DFT calculations Electronic properties Defect formation energies CIENCIAS EXATAS E DA TERRA::FISICA |
dc.subject.eng.fl_str_mv |
Compound Bi12GeO20 Physics of defects DFT calculations Electronic properties Defect formation energies |
dc.subject.cnpq.fl_str_mv |
CIENCIAS EXATAS E DA TERRA::FISICA |
description |
In this dissertation the effects of insertion of the Cu ion into the Bi12GeO20 (BGO) crystalline matrix were studied by means of the first-order computational techniques based on the density functional theory. The FP-LAPW method implemented in the WIEN2K code was applied. Correlation and exchange effects were treated with the GGA-PBE functional (for structural optimization) and with the TB-mbj potential (for the calculation of the electronic properties). Within the BGO crystalline matrix there are two possible accommodation sites of the impurity, Ge4+ and Bi3+. Experimental studies have shown that most of the transition metal impurities prefer to accommodate at the Ge4+ site. This is surprising, since the impurities are expected to replace the Bi3+ site because it has the more compatible charge state and the larger ionic radius. On the other hand, the Cu ion is one of the few that has a preference for the Bi3+ site. It accommodates at this site with an electronic configuration 3d9 and with oxidation state 2+. In order to understand these facts, not yet explained by the experiments, two distinct systems were simulated: (1) the BGO crystal with Cu impurity at the Ge4+ site, and (2) the BGO crystal with Cu impurity at the Bi3+ site. The defect was studied in the neutral, positively and negatively charged state. The insertion preference was estimated from the calculations of the defect formation energy. Electronic properties were also calculated and the quantum theory of atoms in molecules was applied to estimate the oxidation state of Cu. The results confirmed the preference of accommodation of the Cu ion at the Bi3+ site, in accordance with the results obtained by experimental techniques such as EPR. The electron structure analysis showed that the Cu valence is 2+ (3d9) regardless of the charge state. The changes of the structural, electronic and magnetic properties of the BGO compound in the presence of Cu impurity at both sites of the incorporation were analysed and clarified. |
publishDate |
2018 |
dc.date.issued.fl_str_mv |
2018-02-27 |
dc.date.accessioned.fl_str_mv |
2019-03-22T12:02:48Z |
dc.date.available.fl_str_mv |
2019-03-22T12:02:48Z |
dc.type.status.fl_str_mv |
info:eu-repo/semantics/publishedVersion |
dc.type.driver.fl_str_mv |
info:eu-repo/semantics/masterThesis |
format |
masterThesis |
status_str |
publishedVersion |
dc.identifier.citation.fl_str_mv |
LIMA, Jailsson Silva. Efeitos de inserção do íon de cobre na matriz cristalina do Bi12GeO20 : estudo de primeiros princípios. 2018. 114 f. Dissertação (Mestrado em Física) - Universidade Federal de Sergipe, São Cristóvão, SE, 2018. |
dc.identifier.uri.fl_str_mv |
http://ri.ufs.br/jspui/handle/riufs/10740 |
identifier_str_mv |
LIMA, Jailsson Silva. Efeitos de inserção do íon de cobre na matriz cristalina do Bi12GeO20 : estudo de primeiros princípios. 2018. 114 f. Dissertação (Mestrado em Física) - Universidade Federal de Sergipe, São Cristóvão, SE, 2018. |
url |
http://ri.ufs.br/jspui/handle/riufs/10740 |
dc.language.iso.fl_str_mv |
por |
language |
por |
dc.rights.driver.fl_str_mv |
info:eu-repo/semantics/openAccess |
eu_rights_str_mv |
openAccess |
dc.publisher.program.fl_str_mv |
Pós-Graduação em Física |
dc.publisher.initials.fl_str_mv |
Universidade Federal de Sergipe |
dc.source.none.fl_str_mv |
reponame:Repositório Institucional da UFS instname:Universidade Federal de Sergipe (UFS) instacron:UFS |
instname_str |
Universidade Federal de Sergipe (UFS) |
instacron_str |
UFS |
institution |
UFS |
reponame_str |
Repositório Institucional da UFS |
collection |
Repositório Institucional da UFS |
bitstream.url.fl_str_mv |
https://ri.ufs.br/jspui/bitstream/riufs/10740/3/JAILSSON_SILVA_LIMA.pdf.txt https://ri.ufs.br/jspui/bitstream/riufs/10740/4/JAILSSON_SILVA_LIMA.pdf.jpg https://ri.ufs.br/jspui/bitstream/riufs/10740/1/license.txt https://ri.ufs.br/jspui/bitstream/riufs/10740/2/JAILSSON_SILVA_LIMA.pdf |
bitstream.checksum.fl_str_mv |
33ef5a4376b26c783416d69c726dcaf4 6bc05ffe08a974120cc0ec797116a69d 098cbbf65c2c15e1fb2e49c5d306a44c 655b8616b6e71ff49cd68cbb880de336 |
bitstream.checksumAlgorithm.fl_str_mv |
MD5 MD5 MD5 MD5 |
repository.name.fl_str_mv |
Repositório Institucional da UFS - Universidade Federal de Sergipe (UFS) |
repository.mail.fl_str_mv |
repositorio@academico.ufs.br |
_version_ |
1802110807537876992 |