Shedding light on the metal-phthalocyanine EXAFS spectra through classical and ab initio molecular dynamics

Extended X-Ray Absorption Fine Structure (EXAFS) theoretical spectra for some 3d transition metal-phthalocyanines–FePc, NiPc, CuPc, and ZnPc-are presented. Their complexity and rigidity make them a good testbed for the development of theoretical strategies that can complement the difficulties presen...

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Autores: Raposo Hernández, Gema, Sánchez Marcos, Enrique, Rodríguez Pappalardo, Rafael, Martínez Fernández, José Manuel
Tipo de recurso: artículo
Estado:Versión publicada
Fecha de publicación:2023
País:España
Institución:Universidad de Sevilla (US)
Repositorio:idUS. Depósito de Investigación de la Universidad de Sevilla
OAI Identifier:oai:idus.us.es:11441/152714
Acceso en línea:https://hdl.handle.net/11441/152714
https://doi.org/10.1063/5.0135944
Access Level:acceso abierto
Palabra clave:Classical force fields
Born-Oppenheimer molecular dynamics
Classical molecular dynamic simulations
Interference
Extended X-ray absorption fine structure
Time-independent
Schrodinger equation
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spelling Shedding light on the metal-phthalocyanine EXAFS spectra through classical and ab initio molecular dynamicsRaposo Hernández, GemaSánchez Marcos, EnriqueRodríguez Pappalardo, RafaelMartínez Fernández, José ManuelClassical force fieldsBorn-Oppenheimer molecular dynamicsClassical molecular dynamic simulationsInterferenceExtended X-ray absorption fine structureTime-independentSchrodinger equationExtended X-Ray Absorption Fine Structure (EXAFS) theoretical spectra for some 3d transition metal-phthalocyanines–FePc, NiPc, CuPc, and ZnPc-are presented. Their complexity and rigidity make them a good testbed for the development of theoretical strategies that can complement the difficulties present in the experimental spectrum fitting. Classical and ab initio molecular dynamics trajectories are generated and employed as a source of structural information to compute average spectra for each MPc species. The original ZnPc force field employed in the classical molecular dynamics simulations has been modified in order to improve the agreement with the experimental EXAFS spectrum, and the modification strategy–based on MP2 optimized structures–being extended to the rest of MPcs. Both types of trajectories, classical and ab initio, provide very similar results, showing in all cases the main features present in the experimental spectra despite the different simulation timescales employed. Spectroscopical information has been analyzed on the basis of shells and legs contributions, making possible the comparison with the experimental fitting approaches. According to the simulations results, the simple relationships employed in the fitting process to define the dependence of the Debye Waller factors associated with multiple scattering paths with those of single scattering paths are reasonable. However, a lack of multiple backscattering paths contributions is found due to the intrinsic rigidity of the chemical motif (macrocycle). Its consequences in the Debye Waller factors of the fitted contributions are discussed.Ministerio de Ciencia e Innovación y Agencia Estatal de Investigación españoles (10.13039/501100011033) y fondos europeos FEDER - I+D+i nº PGC2018-099366- B-IJunta de Andalucía y Universidad de Sevilla - FEDER US-1264472American Institute of PhysicsQuímica FísicaMinisterio de Ciencia e Innovación (MICIN). EspañaAgencia Estatal de Investigación. EspañaEuropean Commission (EC). Fondo Europeo de Desarrollo Regional (FEDER)Junta de AndalucíaUniversidad de Sevilla2023info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionapplication/pdfapplication/pdfhttps://hdl.handle.net/11441/152714https://doi.org/10.1063/5.0135944reponame:idUS. Depósito de Investigación de la Universidad de Sevillainstname:Universidad de Sevilla (US)InglésThe Journal of Chemical Physics, 158 (6), 064110.I+D+i nº PGC2018-099366- B-I00FEDER US-1264472https://doi.org/10.1063/5.0135944info:eu-repo/semantics/openAccessoai:idus.us.es:11441/1527142026-06-17T12:51:07Z
dc.title.none.fl_str_mv Shedding light on the metal-phthalocyanine EXAFS spectra through classical and ab initio molecular dynamics
title Shedding light on the metal-phthalocyanine EXAFS spectra through classical and ab initio molecular dynamics
spellingShingle Shedding light on the metal-phthalocyanine EXAFS spectra through classical and ab initio molecular dynamics
Raposo Hernández, Gema
Classical force fields
Born-Oppenheimer molecular dynamics
Classical molecular dynamic simulations
Interference
Extended X-ray absorption fine structure
Time-independent
Schrodinger equation
title_short Shedding light on the metal-phthalocyanine EXAFS spectra through classical and ab initio molecular dynamics
title_full Shedding light on the metal-phthalocyanine EXAFS spectra through classical and ab initio molecular dynamics
title_fullStr Shedding light on the metal-phthalocyanine EXAFS spectra through classical and ab initio molecular dynamics
title_full_unstemmed Shedding light on the metal-phthalocyanine EXAFS spectra through classical and ab initio molecular dynamics
title_sort Shedding light on the metal-phthalocyanine EXAFS spectra through classical and ab initio molecular dynamics
dc.creator.none.fl_str_mv Raposo Hernández, Gema
Sánchez Marcos, Enrique
Rodríguez Pappalardo, Rafael
Martínez Fernández, José Manuel
author Raposo Hernández, Gema
author_facet Raposo Hernández, Gema
Sánchez Marcos, Enrique
Rodríguez Pappalardo, Rafael
Martínez Fernández, José Manuel
author_role author
author2 Sánchez Marcos, Enrique
Rodríguez Pappalardo, Rafael
Martínez Fernández, José Manuel
author2_role author
author
author
dc.contributor.none.fl_str_mv Química Física
Ministerio de Ciencia e Innovación (MICIN). España
Agencia Estatal de Investigación. España
European Commission (EC). Fondo Europeo de Desarrollo Regional (FEDER)
Junta de Andalucía
Universidad de Sevilla
dc.subject.none.fl_str_mv Classical force fields
Born-Oppenheimer molecular dynamics
Classical molecular dynamic simulations
Interference
Extended X-ray absorption fine structure
Time-independent
Schrodinger equation
topic Classical force fields
Born-Oppenheimer molecular dynamics
Classical molecular dynamic simulations
Interference
Extended X-ray absorption fine structure
Time-independent
Schrodinger equation
description Extended X-Ray Absorption Fine Structure (EXAFS) theoretical spectra for some 3d transition metal-phthalocyanines–FePc, NiPc, CuPc, and ZnPc-are presented. Their complexity and rigidity make them a good testbed for the development of theoretical strategies that can complement the difficulties present in the experimental spectrum fitting. Classical and ab initio molecular dynamics trajectories are generated and employed as a source of structural information to compute average spectra for each MPc species. The original ZnPc force field employed in the classical molecular dynamics simulations has been modified in order to improve the agreement with the experimental EXAFS spectrum, and the modification strategy–based on MP2 optimized structures–being extended to the rest of MPcs. Both types of trajectories, classical and ab initio, provide very similar results, showing in all cases the main features present in the experimental spectra despite the different simulation timescales employed. Spectroscopical information has been analyzed on the basis of shells and legs contributions, making possible the comparison with the experimental fitting approaches. According to the simulations results, the simple relationships employed in the fitting process to define the dependence of the Debye Waller factors associated with multiple scattering paths with those of single scattering paths are reasonable. However, a lack of multiple backscattering paths contributions is found due to the intrinsic rigidity of the chemical motif (macrocycle). Its consequences in the Debye Waller factors of the fitted contributions are discussed.
publishDate 2023
dc.date.none.fl_str_mv 2023
dc.type.none.fl_str_mv info:eu-repo/semantics/article
info:eu-repo/semantics/publishedVersion
format article
status_str publishedVersion
dc.identifier.none.fl_str_mv https://hdl.handle.net/11441/152714
https://doi.org/10.1063/5.0135944
url https://hdl.handle.net/11441/152714
https://doi.org/10.1063/5.0135944
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
dc.relation.none.fl_str_mv The Journal of Chemical Physics, 158 (6), 064110.
I+D+i nº PGC2018-099366- B-I00
FEDER US-1264472
https://doi.org/10.1063/5.0135944
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
eu_rights_str_mv openAccess
dc.format.none.fl_str_mv application/pdf
application/pdf
dc.publisher.none.fl_str_mv American Institute of Physics
publisher.none.fl_str_mv American Institute of Physics
dc.source.none.fl_str_mv reponame:idUS. Depósito de Investigación de la Universidad de Sevilla
instname:Universidad de Sevilla (US)
instname_str Universidad de Sevilla (US)
reponame_str idUS. Depósito de Investigación de la Universidad de Sevilla
collection idUS. Depósito de Investigación de la Universidad de Sevilla
repository.name.fl_str_mv
repository.mail.fl_str_mv
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score 15.301603

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