SIMULACAO DA ESTRUTURA MOLECULAR E ELETRÔNICA DE POLIMEROS CONDUTORES

Detalhes bibliográficos
Autor(a) principal: Andrade, Ageo Meier de
Data de Publicação: 2016
Tipo de documento: Dissertação
Idioma: por
Título da fonte: Biblioteca Digital de Teses e Dissertações da UEPG
Texto Completo: http://tede2.uepg.br/jspui/handle/prefix/2045
Resumo: The search for materials with conductive capacity has been gaining attention in the scienti c community for its many technological applications. Moreover, understanding the charge transport phenomena in these materials it is still seen as a challenge to the scientic community. Poly (3,4-ethylenedioxythiophene), PEDOT features desirable characteristics where planar molecular structure ensures process of charge transfer and charge separation. In the investigation of these properties, computational tools emerge as an alternative with low nancial cost when compared to experimental techniques. Knowing that several semi-empirical methodologiess are available and the class of conductive polymers exhibit unique macromolecular characteristics; the objective of this study was to investigate the structural properties of 1-EDOT to 10-EDOT by the latest methodologies available in MOPAC2012 program, that is, PM6, PM7 and RM1. It was found that among them, PM6 methodology provided good results, especially for presenting the planar polymer chain to oligomers of 2-EDOT to 10-EDOT. DFT calculations have been used for organic polymeric systems with conductive characteristics and has evolved as a major computational tools for electronic properties. Thus, for 1-EDOT to 10-EDOT optimized by PM6 methodology, single point calculations were applied using DFT B3LYP/6-31++G(d,p) obtaining information related to the charge transport, especially reducing band-gap energy, border orbital location and formation of an intramolecular charge hall. From these informations, were investigated electrostatic potential map and Density of States (DOS) based on energy levels. In computational analysis of excited states, calculations based on TDDFT using B3LYP/6-31+G were applied to molecular systems, where it was possible to investigate discrete levels of excitation energy in the UV-visible range. In small oligomers of 1-EDOT to 6-EDOT using PM6 optimized structures such calculations showed the possibility of investigating the main configuration related to discrete levels, showing the reduction in energy required for excitation with increasing polymer chain for this material. Having noted both the reduction of energy band-gap and the singlet excitation energy, relatedto increasing polymeric chain, it was investigated these properties for a macromolecular system considering infinite oligomers. In this analysis, linear regression applied to the results of 2-EDOT to 6-EDOT had the lowest band-gap energy. Subsequently, band-gap energy was related to the wavelength of maximum absorption of the singlet excitation energy. It was concluded that it is possible to apply semi-empirical calculations followed by single-pint DFT and TDDFT calculations in the investigation of conductive properties of polymeric materials providing significant results to understand charge transport and the prediction of structural and electronic properties.
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spelling Lazaro, Sérgio Ricardo deCPF:26128947808http://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4700975U6Camilo Junior, AlexandreCPF:08449668867http://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4785298U2Lavarda, Francisco CarlosCPF:32323417053http://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4782181J8Fiorin, Barbara CelâniaCPF:02347764985http://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4771983Z7CPF:06841950976http://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4415090E2Andrade, Ageo Meier de2017-07-24T19:37:54Z2016-06-292017-07-24T19:37:54Z2016-02-22ANDRADE, Ageo Meier de. SIMULACAO DA ESTRUTURA MOLECULAR E ELETRÔNICA DE POLIMEROS CONDUTORES. 2016. 85 f. Dissertação (Mestrado em Química) - UNIVERSIDADE ESTADUAL DE PONTA GROSSA, Ponta Grossa, 2016.http://tede2.uepg.br/jspui/handle/prefix/2045The search for materials with conductive capacity has been gaining attention in the scienti c community for its many technological applications. Moreover, understanding the charge transport phenomena in these materials it is still seen as a challenge to the scientic community. Poly (3,4-ethylenedioxythiophene), PEDOT features desirable characteristics where planar molecular structure ensures process of charge transfer and charge separation. In the investigation of these properties, computational tools emerge as an alternative with low nancial cost when compared to experimental techniques. Knowing that several semi-empirical methodologiess are available and the class of conductive polymers exhibit unique macromolecular characteristics; the objective of this study was to investigate the structural properties of 1-EDOT to 10-EDOT by the latest methodologies available in MOPAC2012 program, that is, PM6, PM7 and RM1. It was found that among them, PM6 methodology provided good results, especially for presenting the planar polymer chain to oligomers of 2-EDOT to 10-EDOT. DFT calculations have been used for organic polymeric systems with conductive characteristics and has evolved as a major computational tools for electronic properties. Thus, for 1-EDOT to 10-EDOT optimized by PM6 methodology, single point calculations were applied using DFT B3LYP/6-31++G(d,p) obtaining information related to the charge transport, especially reducing band-gap energy, border orbital location and formation of an intramolecular charge hall. From these informations, were investigated electrostatic potential map and Density of States (DOS) based on energy levels. In computational analysis of excited states, calculations based on TDDFT using B3LYP/6-31+G were applied to molecular systems, where it was possible to investigate discrete levels of excitation energy in the UV-visible range. In small oligomers of 1-EDOT to 6-EDOT using PM6 optimized structures such calculations showed the possibility of investigating the main configuration related to discrete levels, showing the reduction in energy required for excitation with increasing polymer chain for this material. Having noted both the reduction of energy band-gap and the singlet excitation energy, relatedto increasing polymeric chain, it was investigated these properties for a macromolecular system considering infinite oligomers. In this analysis, linear regression applied to the results of 2-EDOT to 6-EDOT had the lowest band-gap energy. Subsequently, band-gap energy was related to the wavelength of maximum absorption of the singlet excitation energy. It was concluded that it is possible to apply semi-empirical calculations followed by single-pint DFT and TDDFT calculations in the investigation of conductive properties of polymeric materials providing significant results to understand charge transport and the prediction of structural and electronic properties.A busca por materiais com capacidades condutoras vem ganhando atenção na comunidade científica por suas inúmeras aplicações tecnológicas. Além disso, o entendimento do fenômeno de transporte de carga continua sendo visto como um desafio para a comunidade cientifica. Poli (3,4-etilenodioxitiofeno), PEDOT apresenta caracteristicas condutoras desejáveis porque sua estrutura molecular planar garante que haja o processo de transferência e separação de carga. Na investigação dessa propriedade, ferramentas computacionais surgem como uma alternativa de baixo custo financeiro quando comparados a técnicas experimentais. Sabendo que diversas metodologias semi-empíricas estão disponíveis e que a classe de polímeros condutores apresentam caracteressticas macromoleculares únicas; objetivou-se neste estudo a investigação das propriedades estruturais de 1-EDOT a 10-EDOT pelas mais recentes metodologias disponíveis no programa MOPAC2012, isto é, PM6, PM7 e RM1. Verificou-se que dentre elas, a metodologia PM6 forneceu bons resultados em relação aos resultados experimentais, principalmente por apresentar a cadeia polimérica planar para oligômeros de 2-EDOT a 10-EDOT. Cálculos em DFT tem sido usados para sistemas poliméricos orgânicos com características condutoras e evoluiu como uma das principais ferramentas computacionais para propriedades eletrônicas. Sendo assim, foram aplicados cálculos pontuais em DFT usando B3LYP/6-31++G(d,p)) de 1-EDOT a 10-EDOT a partir de estruturas otimizadas em PM6 obtendo-se informações relevantes ao transporte de carga, principalmente, redução da energia de band-gap, localizaçãoo dos orbitais de fronteiras e formação de um corredor de carga intramolecular. Investigou-se a partir destas informações o mapa de potencial eletrostático e a Densidade de Estados (DOS) por meio dos níveis discretos de energia. Na análise computacional de estados excitados, cálculos baseados em TDDFT usando B3LYP/6-31+G foram aplicados a sistemas moleculares, onde é possível investigar níveis discretos de excitação na faixa do UV-Visível. Nos pequenos oligomeros de 1-EDOT a 6-EDOT, utilizando a estrutura otimizada em PM6, tais cálculos mostraram a possibilidade de investigar as principais configurações de excitação do estado singlete em níveis discretos, mostrando a redução da energia necessária para excitação com o aumento da cadeia polimérica para esse material. Por ter verificado tanto a redução da energia de band-gap quanto da energia de excitação de singlete, e que ambos s~ao relacionados ao aumento da cadeia polimérica, investigou-se a previsão por extrapolação para um sistema macromolecular com infinitos oligômeros. Nessa análise, a regressão linear aplicada aos resultados de 2-EDOT a 6-EDOT apresentou a menor energia de band-gap. Posteriormente, o band-gap foi relacionado ao comprimento de onda máximo da absorção de singlete. Concluiu-se que é possível aplicar cálculos semi-empíricos em conjunto com cálculos pontuais em DFT e TDDFT na investigação de propriedades condutoras de materiais poliméricos proporcionando resultados expressivos para entender o transporte de carga e a prediação de propriedades estruturais e eletrônicas.Made available in DSpace on 2017-07-24T19:37:54Z (GMT). No. of bitstreams: 1 Ageo Meier Andrade.pdf: 3358892 bytes, checksum: c2798e568b2f1bcb11fc21644c783df2 (MD5) Previous issue date: 2016-02-22Coordenação de Aperfeiçoamento de Pessoal de Nível Superiorapplication/pdfporUNIVERSIDADE ESTADUAL DE PONTA GROSSAPrograma de Pós-Graduação em Química AplicadaUEPGBRQuímicaPM6PM7RM1DFTTDDFTEDOTtransporte de cargaPM6PM7RM1DFTTDDFT, PEDOT, Charge transport.CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICASIMULACAO DA ESTRUTURA MOLECULAR E ELETRÔNICA DE POLIMEROS CONDUTORESinfo:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/masterThesisinfo:eu-repo/semantics/openAccessreponame:Biblioteca Digital de Teses e Dissertações da UEPGinstname:Universidade Estadual de Ponta Grossa (UEPG)instacron:UEPGORIGINALAgeo Meier Andrade.pdfapplication/pdf3358892http://tede2.uepg.br/jspui/bitstream/prefix/2045/1/Ageo%20Meier%20Andrade.pdfc2798e568b2f1bcb11fc21644c783df2MD51prefix/20452017-07-24 16:37:54.854oai:tede2.uepg.br:prefix/2045Biblioteca Digital de Teses e Dissertaçõeshttps://tede2.uepg.br/jspui/PUBhttp://tede2.uepg.br/oai/requestbicen@uepg.br||mv_fidelis@yahoo.com.bropendoar:2017-07-24T19:37:54Biblioteca Digital de Teses e Dissertações da UEPG - Universidade Estadual de Ponta Grossa (UEPG)false
dc.title.por.fl_str_mv SIMULACAO DA ESTRUTURA MOLECULAR E ELETRÔNICA DE POLIMEROS CONDUTORES
title SIMULACAO DA ESTRUTURA MOLECULAR E ELETRÔNICA DE POLIMEROS CONDUTORES
spellingShingle SIMULACAO DA ESTRUTURA MOLECULAR E ELETRÔNICA DE POLIMEROS CONDUTORES
Andrade, Ageo Meier de
PM6
PM7
RM1
DFT
TDDFT
EDOT
transporte de carga
PM6
PM7
RM1
DFT
TDDFT, PEDOT, Charge transport.
CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA
title_short SIMULACAO DA ESTRUTURA MOLECULAR E ELETRÔNICA DE POLIMEROS CONDUTORES
title_full SIMULACAO DA ESTRUTURA MOLECULAR E ELETRÔNICA DE POLIMEROS CONDUTORES
title_fullStr SIMULACAO DA ESTRUTURA MOLECULAR E ELETRÔNICA DE POLIMEROS CONDUTORES
title_full_unstemmed SIMULACAO DA ESTRUTURA MOLECULAR E ELETRÔNICA DE POLIMEROS CONDUTORES
title_sort SIMULACAO DA ESTRUTURA MOLECULAR E ELETRÔNICA DE POLIMEROS CONDUTORES
author Andrade, Ageo Meier de
author_facet Andrade, Ageo Meier de
author_role author
dc.contributor.advisor1.fl_str_mv Lazaro, Sérgio Ricardo de
dc.contributor.advisor1ID.fl_str_mv CPF:26128947808
dc.contributor.advisor1Lattes.fl_str_mv http://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4700975U6
dc.contributor.advisor-co1.fl_str_mv Camilo Junior, Alexandre
dc.contributor.advisor-co1ID.fl_str_mv CPF:08449668867
dc.contributor.advisor-co1Lattes.fl_str_mv http://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4785298U2
dc.contributor.referee1.fl_str_mv Lavarda, Francisco Carlos
dc.contributor.referee1ID.fl_str_mv CPF:32323417053
dc.contributor.referee1Lattes.fl_str_mv http://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4782181J8
dc.contributor.referee2.fl_str_mv Fiorin, Barbara Celânia
dc.contributor.referee2ID.fl_str_mv CPF:02347764985
dc.contributor.referee2Lattes.fl_str_mv http://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4771983Z7
dc.contributor.authorID.fl_str_mv CPF:06841950976
dc.contributor.authorLattes.fl_str_mv http://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4415090E2
dc.contributor.author.fl_str_mv Andrade, Ageo Meier de
contributor_str_mv Lazaro, Sérgio Ricardo de
Camilo Junior, Alexandre
Lavarda, Francisco Carlos
Fiorin, Barbara Celânia
dc.subject.por.fl_str_mv PM6
PM7
RM1
DFT
TDDFT
EDOT
transporte de carga
topic PM6
PM7
RM1
DFT
TDDFT
EDOT
transporte de carga
PM6
PM7
RM1
DFT
TDDFT, PEDOT, Charge transport.
CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA
dc.subject.eng.fl_str_mv PM6
PM7
RM1
DFT
TDDFT, PEDOT, Charge transport.
dc.subject.cnpq.fl_str_mv CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA
description The search for materials with conductive capacity has been gaining attention in the scienti c community for its many technological applications. Moreover, understanding the charge transport phenomena in these materials it is still seen as a challenge to the scientic community. Poly (3,4-ethylenedioxythiophene), PEDOT features desirable characteristics where planar molecular structure ensures process of charge transfer and charge separation. In the investigation of these properties, computational tools emerge as an alternative with low nancial cost when compared to experimental techniques. Knowing that several semi-empirical methodologiess are available and the class of conductive polymers exhibit unique macromolecular characteristics; the objective of this study was to investigate the structural properties of 1-EDOT to 10-EDOT by the latest methodologies available in MOPAC2012 program, that is, PM6, PM7 and RM1. It was found that among them, PM6 methodology provided good results, especially for presenting the planar polymer chain to oligomers of 2-EDOT to 10-EDOT. DFT calculations have been used for organic polymeric systems with conductive characteristics and has evolved as a major computational tools for electronic properties. Thus, for 1-EDOT to 10-EDOT optimized by PM6 methodology, single point calculations were applied using DFT B3LYP/6-31++G(d,p) obtaining information related to the charge transport, especially reducing band-gap energy, border orbital location and formation of an intramolecular charge hall. From these informations, were investigated electrostatic potential map and Density of States (DOS) based on energy levels. In computational analysis of excited states, calculations based on TDDFT using B3LYP/6-31+G were applied to molecular systems, where it was possible to investigate discrete levels of excitation energy in the UV-visible range. In small oligomers of 1-EDOT to 6-EDOT using PM6 optimized structures such calculations showed the possibility of investigating the main configuration related to discrete levels, showing the reduction in energy required for excitation with increasing polymer chain for this material. Having noted both the reduction of energy band-gap and the singlet excitation energy, relatedto increasing polymeric chain, it was investigated these properties for a macromolecular system considering infinite oligomers. In this analysis, linear regression applied to the results of 2-EDOT to 6-EDOT had the lowest band-gap energy. Subsequently, band-gap energy was related to the wavelength of maximum absorption of the singlet excitation energy. It was concluded that it is possible to apply semi-empirical calculations followed by single-pint DFT and TDDFT calculations in the investigation of conductive properties of polymeric materials providing significant results to understand charge transport and the prediction of structural and electronic properties.
publishDate 2016
dc.date.available.fl_str_mv 2016-06-29
2017-07-24T19:37:54Z
dc.date.issued.fl_str_mv 2016-02-22
dc.date.accessioned.fl_str_mv 2017-07-24T19:37:54Z
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dc.identifier.uri.fl_str_mv http://tede2.uepg.br/jspui/handle/prefix/2045
identifier_str_mv ANDRADE, Ageo Meier de. SIMULACAO DA ESTRUTURA MOLECULAR E ELETRÔNICA DE POLIMEROS CONDUTORES. 2016. 85 f. Dissertação (Mestrado em Química) - UNIVERSIDADE ESTADUAL DE PONTA GROSSA, Ponta Grossa, 2016.
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