Solvent-induced Stokes' shift in DCJTB: Experimental and theoretical results

Detalhes bibliográficos
Autor(a) principal: Sousa, Iran da Luz de
Data de Publicação: 2019
Outros Autores: Ximenes, Valdecir Farias [UNESP], Souza, Aguinaldo Robinson de [UNESP], Morgon, Nelson Henrique
Tipo de documento: Artigo
Idioma: eng
Título da fonte: Repositório Institucional da UNESP
Texto Completo: http://dx.doi.org/10.1016/j.molstruc.2019.04.117
http://hdl.handle.net/11449/185747
Resumo: The solvent-induced Stokes' shift, which describes the response at different solvents (acetonitrile, chloroform, dichloromethane, 1,4-dioxane, N,N-dimethylformamide, ethanol, heptanol, tetrahydrofuran, and toluene) to a sudden change in the charge distribution of excited 4-(Dicyanomethylene)-2-tert-butyl-6- (1,1,7,7-tetramethyljulolidin-4-yl-vinyl)-4H-pyran (DCJTB) molecule, was studied through absorption and emission spectra and TD-DFT calculations; the solvent effect was studied trough the IEF-PCM model. The application of IEF-PCM model with TD-DFT methods to obtain the absorption energies provided excellent match with the experimental results. The results observed, for solvents effects on the positions of maxima absorption and emission between experimental data and theoretical calculations, have average absolute deviations of only 0.03 eV and 0.22 eV, respectively. A systematic error was observed by comparing the theoretical and experimental maxima for the emission energies. However, the application of the Lippert-Mataga and Bilot-Kawski equations to the TD-DFT-simulated Stokes' shifts values resulted in excellent correlation coefficients: Lippert-Mataga, R-2 = 0.9982, Bilot-Kawski, R-2 = 0.9908 and R-2 = 0.9795. (C) 2019 Elsevier B.V. All rights reserved.
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spelling Solvent-induced Stokes' shift in DCJTB: Experimental and theoretical resultsDCJTBStokes' shiftLippert-MatagaBilot-Kawski equationsTD-DFTThe solvent-induced Stokes' shift, which describes the response at different solvents (acetonitrile, chloroform, dichloromethane, 1,4-dioxane, N,N-dimethylformamide, ethanol, heptanol, tetrahydrofuran, and toluene) to a sudden change in the charge distribution of excited 4-(Dicyanomethylene)-2-tert-butyl-6- (1,1,7,7-tetramethyljulolidin-4-yl-vinyl)-4H-pyran (DCJTB) molecule, was studied through absorption and emission spectra and TD-DFT calculations; the solvent effect was studied trough the IEF-PCM model. The application of IEF-PCM model with TD-DFT methods to obtain the absorption energies provided excellent match with the experimental results. The results observed, for solvents effects on the positions of maxima absorption and emission between experimental data and theoretical calculations, have average absolute deviations of only 0.03 eV and 0.22 eV, respectively. A systematic error was observed by comparing the theoretical and experimental maxima for the emission energies. However, the application of the Lippert-Mataga and Bilot-Kawski equations to the TD-DFT-simulated Stokes' shifts values resulted in excellent correlation coefficients: Lippert-Mataga, R-2 = 0.9982, Bilot-Kawski, R-2 = 0.9908 and R-2 = 0.9795. (C) 2019 Elsevier B.V. All rights reserved.Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)Univ Estadual Campinas, UNICAMP, Inst Chem, Dept Phys Chem, BR-13083861 Campinas, SP, BrazilSao Paulo State Univ, UNESP, Fac Sci, Dept Chem, BR-17033360 Bauru, SP, BrazilSao Paulo State Univ, UNESP, Fac Sci, Dept Chem, BR-17033360 Bauru, SP, BrazilFAPESP: 2016/20549-5FAPESP: 2015/22338-9FAPESP: 308480/2016-3FAPESP: 2016/04963-6FAPESP: INCT.Bio.Nat 2014/50926-0CNPq: 302793/2016-0CNPq: 306975/2013-0CNPq: 305541/2017-0CNPq: 440503/2014-0Elsevier B.V.Universidade Estadual de Campinas (UNICAMP)Universidade Estadual Paulista (Unesp)Sousa, Iran da Luz deXimenes, Valdecir Farias [UNESP]Souza, Aguinaldo Robinson de [UNESP]Morgon, Nelson Henrique2019-10-04T12:38:15Z2019-10-04T12:38:15Z2019-09-15info:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/article186-191http://dx.doi.org/10.1016/j.molstruc.2019.04.117Journal Of Molecular Structure. Amsterdam: Elsevier Science Bv, v. 1192, p. 186-191, 2019.0022-2860http://hdl.handle.net/11449/18574710.1016/j.molstruc.2019.04.117WOS:000469236000022Web of Sciencereponame:Repositório Institucional da UNESPinstname:Universidade Estadual Paulista (UNESP)instacron:UNESPengJournal Of Molecular Structureinfo:eu-repo/semantics/openAccess2024-04-29T18:16:59Zoai:repositorio.unesp.br:11449/185747Repositório InstitucionalPUBhttp://repositorio.unesp.br/oai/requestopendoar:29462024-08-05T17:25:45.808762Repositório Institucional da UNESP - Universidade Estadual Paulista (UNESP)false
dc.title.none.fl_str_mv Solvent-induced Stokes' shift in DCJTB: Experimental and theoretical results
title Solvent-induced Stokes' shift in DCJTB: Experimental and theoretical results
spellingShingle Solvent-induced Stokes' shift in DCJTB: Experimental and theoretical results
Sousa, Iran da Luz de
DCJTB
Stokes' shift
Lippert-Mataga
Bilot-Kawski equations
TD-DFT
title_short Solvent-induced Stokes' shift in DCJTB: Experimental and theoretical results
title_full Solvent-induced Stokes' shift in DCJTB: Experimental and theoretical results
title_fullStr Solvent-induced Stokes' shift in DCJTB: Experimental and theoretical results
title_full_unstemmed Solvent-induced Stokes' shift in DCJTB: Experimental and theoretical results
title_sort Solvent-induced Stokes' shift in DCJTB: Experimental and theoretical results
author Sousa, Iran da Luz de
author_facet Sousa, Iran da Luz de
Ximenes, Valdecir Farias [UNESP]
Souza, Aguinaldo Robinson de [UNESP]
Morgon, Nelson Henrique
author_role author
author2 Ximenes, Valdecir Farias [UNESP]
Souza, Aguinaldo Robinson de [UNESP]
Morgon, Nelson Henrique
author2_role author
author
author
dc.contributor.none.fl_str_mv Universidade Estadual de Campinas (UNICAMP)
Universidade Estadual Paulista (Unesp)
dc.contributor.author.fl_str_mv Sousa, Iran da Luz de
Ximenes, Valdecir Farias [UNESP]
Souza, Aguinaldo Robinson de [UNESP]
Morgon, Nelson Henrique
dc.subject.por.fl_str_mv DCJTB
Stokes' shift
Lippert-Mataga
Bilot-Kawski equations
TD-DFT
topic DCJTB
Stokes' shift
Lippert-Mataga
Bilot-Kawski equations
TD-DFT
description The solvent-induced Stokes' shift, which describes the response at different solvents (acetonitrile, chloroform, dichloromethane, 1,4-dioxane, N,N-dimethylformamide, ethanol, heptanol, tetrahydrofuran, and toluene) to a sudden change in the charge distribution of excited 4-(Dicyanomethylene)-2-tert-butyl-6- (1,1,7,7-tetramethyljulolidin-4-yl-vinyl)-4H-pyran (DCJTB) molecule, was studied through absorption and emission spectra and TD-DFT calculations; the solvent effect was studied trough the IEF-PCM model. The application of IEF-PCM model with TD-DFT methods to obtain the absorption energies provided excellent match with the experimental results. The results observed, for solvents effects on the positions of maxima absorption and emission between experimental data and theoretical calculations, have average absolute deviations of only 0.03 eV and 0.22 eV, respectively. A systematic error was observed by comparing the theoretical and experimental maxima for the emission energies. However, the application of the Lippert-Mataga and Bilot-Kawski equations to the TD-DFT-simulated Stokes' shifts values resulted in excellent correlation coefficients: Lippert-Mataga, R-2 = 0.9982, Bilot-Kawski, R-2 = 0.9908 and R-2 = 0.9795. (C) 2019 Elsevier B.V. All rights reserved.
publishDate 2019
dc.date.none.fl_str_mv 2019-10-04T12:38:15Z
2019-10-04T12:38:15Z
2019-09-15
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 http://dx.doi.org/10.1016/j.molstruc.2019.04.117
Journal Of Molecular Structure. Amsterdam: Elsevier Science Bv, v. 1192, p. 186-191, 2019.
0022-2860
http://hdl.handle.net/11449/185747
10.1016/j.molstruc.2019.04.117
WOS:000469236000022
url http://dx.doi.org/10.1016/j.molstruc.2019.04.117
http://hdl.handle.net/11449/185747
identifier_str_mv Journal Of Molecular Structure. Amsterdam: Elsevier Science Bv, v. 1192, p. 186-191, 2019.
0022-2860
10.1016/j.molstruc.2019.04.117
WOS:000469236000022
dc.language.iso.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv Journal Of Molecular Structure
dc.rights.driver.fl_str_mv info:eu-repo/semantics/openAccess
eu_rights_str_mv openAccess
dc.format.none.fl_str_mv 186-191
dc.publisher.none.fl_str_mv Elsevier B.V.
publisher.none.fl_str_mv Elsevier B.V.
dc.source.none.fl_str_mv Web of Science
reponame:Repositório Institucional da UNESP
instname:Universidade Estadual Paulista (UNESP)
instacron:UNESP
instname_str Universidade Estadual Paulista (UNESP)
instacron_str UNESP
institution UNESP
reponame_str Repositório Institucional da UNESP
collection Repositório Institucional da UNESP
repository.name.fl_str_mv Repositório Institucional da UNESP - Universidade Estadual Paulista (UNESP)
repository.mail.fl_str_mv
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