In search of the best DFT functional for dealing wi th organic anionic species

Autores
Borioni, José Luis; Puiatti, Marcelo; Vera, Domingo Mariano Adolfo; Pierini, Adriana Beatriz
Año de publicación
2017
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
Quantum chemical computational methods are thought to have problems in dealing with unstable organic anions. This work assesses the ability of different Density Functional Theory (DFT) functionals to reproduce the electron affinity and reduction potential of organic compounds. The performance of 23 DFT functionals was evaluated by computing the negative electron affinities (from 0 eV to −3.0 eV) and reduction potentials in acetonitrile (from 0 to −2.7 V). In general, most of the hybrid GGA functionals work fine in the prediction of electron affinities, BPW91, B3PW91 and M06 being the best in each class of functionals (pure, hybrid and meta-GGA functionals, respectively). On the other hand, the ab initio post-Hartree–Fock methods, MP2 and coupled-cluster (CCSD(T)), as well as the double hybrid functionals, B2PLYP and mPW2PLYP, usually fail. For compounds with EAs lower than −1.75 eV, a method for stabilizing the anion, based on solvation with the IEFPCM model, was employed. In this case, BPW91, PBE0 and M06-HF could be the recommended option for the pure, hybrid and meta-GGA functionals, respectively. The situation improves for the evaluation and prediction of redox potentials. In this case the performance of the DFT functionals is better, in part because the solvent assists in the stabilization of the anions. Nevertheless, there is a systematic bias in the calculation of absolute redox potentials, which could be corrected by using a redox partner that helps by the cancellation of errors. In this case, the hybrid and meta-GGA functionals B3PW91, PBE0, TPSSh and M06 are also among the best for computing redox potentials with a mean absolute deviation (MAD) lower than 0.13 V.
Fil: Borioni, José Luis. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina
Fil: Puiatti, Marcelo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina
Fil: Vera, Domingo Mariano Adolfo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Mar del Plata. Instituto de Investigaciones en Biodiversidad y Biotecnología; Argentina
Fil: Pierini, Adriana Beatriz. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina
Materia
DFT
COUPLED CLUSTERS
RADICAL ANIONS
NEGATIVE ELECTRON AFFINITIES
TEMPORARY ANIONS
VALENCE ANIONS
NON-VALENCE ANIONS
REDUCTION POTENTIALS
SINGLE ELECTRON TRANSFER (SET)
CORRECTED FUNCTIONALS
Nivel de accesibilidad
acceso abierto
Condiciones de uso
https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
Repositorio
CONICET Digital (CONICET)
Institución
Consejo Nacional de Investigaciones Científicas y Técnicas
OAI Identificador
oai:ri.conicet.gov.ar:11336/40814
Acceder
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oai_identifier_str oai:ri.conicet.gov.ar:11336/40814
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling In search of the best DFT functional for dealing wi th organic anionic speciesBorioni, José LuisPuiatti, MarceloVera, Domingo Mariano AdolfoPierini, Adriana BeatrizDFTCOUPLED CLUSTERSRADICAL ANIONSNEGATIVE ELECTRON AFFINITIESTEMPORARY ANIONSVALENCE ANIONSNON-VALENCE ANIONSREDUCTION POTENTIALSSINGLE ELECTRON TRANSFER (SET)CORRECTED FUNCTIONALShttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1Quantum chemical computational methods are thought to have problems in dealing with unstable organic anions. This work assesses the ability of different Density Functional Theory (DFT) functionals to reproduce the electron affinity and reduction potential of organic compounds. The performance of 23 DFT functionals was evaluated by computing the negative electron affinities (from 0 eV to −3.0 eV) and reduction potentials in acetonitrile (from 0 to −2.7 V). In general, most of the hybrid GGA functionals work fine in the prediction of electron affinities, BPW91, B3PW91 and M06 being the best in each class of functionals (pure, hybrid and meta-GGA functionals, respectively). On the other hand, the ab initio post-Hartree–Fock methods, MP2 and coupled-cluster (CCSD(T)), as well as the double hybrid functionals, B2PLYP and mPW2PLYP, usually fail. For compounds with EAs lower than −1.75 eV, a method for stabilizing the anion, based on solvation with the IEFPCM model, was employed. In this case, BPW91, PBE0 and M06-HF could be the recommended option for the pure, hybrid and meta-GGA functionals, respectively. The situation improves for the evaluation and prediction of redox potentials. In this case the performance of the DFT functionals is better, in part because the solvent assists in the stabilization of the anions. Nevertheless, there is a systematic bias in the calculation of absolute redox potentials, which could be corrected by using a redox partner that helps by the cancellation of errors. In this case, the hybrid and meta-GGA functionals B3PW91, PBE0, TPSSh and M06 are also among the best for computing redox potentials with a mean absolute deviation (MAD) lower than 0.13 V.Fil: Borioni, José Luis. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; ArgentinaFil: Puiatti, Marcelo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; ArgentinaFil: Vera, Domingo Mariano Adolfo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Mar del Plata. Instituto de Investigaciones en Biodiversidad y Biotecnología; ArgentinaFil: Pierini, Adriana Beatriz. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; ArgentinaRoyal Society of Chemistry2017-01info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/40814Borioni, José Luis; Puiatti, Marcelo; Vera, Domingo Mariano Adolfo; Pierini, Adriana Beatriz; In search of the best DFT functional for dealing wi th organic anionic species ; Royal Society of Chemistry; Physical Chemistry Chemical Physics; 19; 13; 1-2017; 9189-91981463-9076CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/doi/10.1039/c6cp06163jinfo:eu-repo/semantics/altIdentifier/url/http://pubs.rsc.org/en/Content/ArticleLanding/2017/CP/C6CP06163Jinfo:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-29T10:34:10Zoai:ri.conicet.gov.ar:11336/40814instacron:CONICETInstitucionalhttp://ri.conicet.gov.ar/Organismo científico-tecnológicoNo correspondehttp://ri.conicet.gov.ar/oai/requestdasensio@conicet.gov.ar; lcarlino@conicet.gov.arArgentinaNo correspondeNo correspondeNo correspondeopendoar:34982025-09-29 10:34:10.297CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv In search of the best DFT functional for dealing wi th organic anionic species
title In search of the best DFT functional for dealing wi th organic anionic species
spellingShingle In search of the best DFT functional for dealing wi th organic anionic species
Borioni, José Luis
DFT
COUPLED CLUSTERS
RADICAL ANIONS
NEGATIVE ELECTRON AFFINITIES
TEMPORARY ANIONS
VALENCE ANIONS
NON-VALENCE ANIONS
REDUCTION POTENTIALS
SINGLE ELECTRON TRANSFER (SET)
CORRECTED FUNCTIONALS
title_short In search of the best DFT functional for dealing wi th organic anionic species
title_full In search of the best DFT functional for dealing wi th organic anionic species
title_fullStr In search of the best DFT functional for dealing wi th organic anionic species
title_full_unstemmed In search of the best DFT functional for dealing wi th organic anionic species
title_sort In search of the best DFT functional for dealing wi th organic anionic species
dc.creator.none.fl_str_mv Borioni, José Luis
Puiatti, Marcelo
Vera, Domingo Mariano Adolfo
Pierini, Adriana Beatriz
author Borioni, José Luis
author_facet Borioni, José Luis
Puiatti, Marcelo
Vera, Domingo Mariano Adolfo
Pierini, Adriana Beatriz
author_role author
author2 Puiatti, Marcelo
Vera, Domingo Mariano Adolfo
Pierini, Adriana Beatriz
author2_role author
author
author
dc.subject.none.fl_str_mv DFT
COUPLED CLUSTERS
RADICAL ANIONS
NEGATIVE ELECTRON AFFINITIES
TEMPORARY ANIONS
VALENCE ANIONS
NON-VALENCE ANIONS
REDUCTION POTENTIALS
SINGLE ELECTRON TRANSFER (SET)
CORRECTED FUNCTIONALS
topic DFT
COUPLED CLUSTERS
RADICAL ANIONS
NEGATIVE ELECTRON AFFINITIES
TEMPORARY ANIONS
VALENCE ANIONS
NON-VALENCE ANIONS
REDUCTION POTENTIALS
SINGLE ELECTRON TRANSFER (SET)
CORRECTED FUNCTIONALS
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv Quantum chemical computational methods are thought to have problems in dealing with unstable organic anions. This work assesses the ability of different Density Functional Theory (DFT) functionals to reproduce the electron affinity and reduction potential of organic compounds. The performance of 23 DFT functionals was evaluated by computing the negative electron affinities (from 0 eV to −3.0 eV) and reduction potentials in acetonitrile (from 0 to −2.7 V). In general, most of the hybrid GGA functionals work fine in the prediction of electron affinities, BPW91, B3PW91 and M06 being the best in each class of functionals (pure, hybrid and meta-GGA functionals, respectively). On the other hand, the ab initio post-Hartree–Fock methods, MP2 and coupled-cluster (CCSD(T)), as well as the double hybrid functionals, B2PLYP and mPW2PLYP, usually fail. For compounds with EAs lower than −1.75 eV, a method for stabilizing the anion, based on solvation with the IEFPCM model, was employed. In this case, BPW91, PBE0 and M06-HF could be the recommended option for the pure, hybrid and meta-GGA functionals, respectively. The situation improves for the evaluation and prediction of redox potentials. In this case the performance of the DFT functionals is better, in part because the solvent assists in the stabilization of the anions. Nevertheless, there is a systematic bias in the calculation of absolute redox potentials, which could be corrected by using a redox partner that helps by the cancellation of errors. In this case, the hybrid and meta-GGA functionals B3PW91, PBE0, TPSSh and M06 are also among the best for computing redox potentials with a mean absolute deviation (MAD) lower than 0.13 V.
Fil: Borioni, José Luis. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina
Fil: Puiatti, Marcelo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina
Fil: Vera, Domingo Mariano Adolfo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Mar del Plata. Instituto de Investigaciones en Biodiversidad y Biotecnología; Argentina
Fil: Pierini, Adriana Beatriz. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina
description Quantum chemical computational methods are thought to have problems in dealing with unstable organic anions. This work assesses the ability of different Density Functional Theory (DFT) functionals to reproduce the electron affinity and reduction potential of organic compounds. The performance of 23 DFT functionals was evaluated by computing the negative electron affinities (from 0 eV to −3.0 eV) and reduction potentials in acetonitrile (from 0 to −2.7 V). In general, most of the hybrid GGA functionals work fine in the prediction of electron affinities, BPW91, B3PW91 and M06 being the best in each class of functionals (pure, hybrid and meta-GGA functionals, respectively). On the other hand, the ab initio post-Hartree–Fock methods, MP2 and coupled-cluster (CCSD(T)), as well as the double hybrid functionals, B2PLYP and mPW2PLYP, usually fail. For compounds with EAs lower than −1.75 eV, a method for stabilizing the anion, based on solvation with the IEFPCM model, was employed. In this case, BPW91, PBE0 and M06-HF could be the recommended option for the pure, hybrid and meta-GGA functionals, respectively. The situation improves for the evaluation and prediction of redox potentials. In this case the performance of the DFT functionals is better, in part because the solvent assists in the stabilization of the anions. Nevertheless, there is a systematic bias in the calculation of absolute redox potentials, which could be corrected by using a redox partner that helps by the cancellation of errors. In this case, the hybrid and meta-GGA functionals B3PW91, PBE0, TPSSh and M06 are also among the best for computing redox potentials with a mean absolute deviation (MAD) lower than 0.13 V.
publishDate 2017
dc.date.none.fl_str_mv 2017-01
dc.type.none.fl_str_mv info:eu-repo/semantics/article
info:eu-repo/semantics/publishedVersion
http://purl.org/coar/resource_type/c_6501
info:ar-repo/semantics/articulo
format article
status_str publishedVersion
dc.identifier.none.fl_str_mv http://hdl.handle.net/11336/40814
Borioni, José Luis; Puiatti, Marcelo; Vera, Domingo Mariano Adolfo; Pierini, Adriana Beatriz; In search of the best DFT functional for dealing wi th organic anionic species ; Royal Society of Chemistry; Physical Chemistry Chemical Physics; 19; 13; 1-2017; 9189-9198
1463-9076
CONICET Digital
CONICET
url http://hdl.handle.net/11336/40814
identifier_str_mv Borioni, José Luis; Puiatti, Marcelo; Vera, Domingo Mariano Adolfo; Pierini, Adriana Beatriz; In search of the best DFT functional for dealing wi th organic anionic species ; Royal Society of Chemistry; Physical Chemistry Chemical Physics; 19; 13; 1-2017; 9189-9198
1463-9076
CONICET Digital
CONICET
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/doi/10.1039/c6cp06163j
info:eu-repo/semantics/altIdentifier/url/http://pubs.rsc.org/en/Content/ArticleLanding/2017/CP/C6CP06163J
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
eu_rights_str_mv openAccess
rights_invalid_str_mv https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
dc.format.none.fl_str_mv application/pdf
application/pdf
application/pdf
application/pdf
dc.publisher.none.fl_str_mv Royal Society of Chemistry
publisher.none.fl_str_mv Royal Society of Chemistry
dc.source.none.fl_str_mv reponame:CONICET Digital (CONICET)
instname:Consejo Nacional de Investigaciones Científicas y Técnicas
reponame_str CONICET Digital (CONICET)
collection CONICET Digital (CONICET)
instname_str Consejo Nacional de Investigaciones Científicas y Técnicas
repository.name.fl_str_mv CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicas
repository.mail.fl_str_mv dasensio@conicet.gov.ar; lcarlino@conicet.gov.ar
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score 13.070432

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