In search for an optimal methodology to calculate the valence electron affinities of temporary anions

Recently, we have proposed an approach for finding the valence anion ground state, based on the stabilization exerted by a polar solvent; the methodology used standard DFT methods and relatively inexpensive basis sets and yielded correct electron affinity (EA) values by gradually decreasing the diel...

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Authors: Puiatti, Marcelo, Vera, Domingo Mariano Adolfo, Pierini, Adriana Beatriz
Format: article
Status:Published version
Publication Date:2009
Country:Argentina
Institution:Consejo Nacional de Investigaciones Científicas y Técnicas
Repository:CONICET Digital (CONICET)
Language:English
OAI Identifier:oai:ri.conicet.gov.ar:11336/76445
Online Access:http://hdl.handle.net/11336/76445
Access Level:Open access
Keyword:Negative Electron Affinity
Radical Anions
Dft
Td-Dft
https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
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oai_identifier_str oai:ri.conicet.gov.ar:11336/76445
network_acronym_str AR
network_name_str Argentina
repository_id_str
dc.title.none.fl_str_mv In search for an optimal methodology to calculate the valence electron affinities of temporary anions
title In search for an optimal methodology to calculate the valence electron affinities of temporary anions
spellingShingle In search for an optimal methodology to calculate the valence electron affinities of temporary anions
Puiatti, Marcelo
Negative Electron Affinity
Radical Anions
Dft
Td-Dft
https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
title_short In search for an optimal methodology to calculate the valence electron affinities of temporary anions
title_full In search for an optimal methodology to calculate the valence electron affinities of temporary anions
title_fullStr In search for an optimal methodology to calculate the valence electron affinities of temporary anions
title_full_unstemmed In search for an optimal methodology to calculate the valence electron affinities of temporary anions
title_sort In search for an optimal methodology to calculate the valence electron affinities of temporary anions
dc.creator.none.fl_str_mv Puiatti, Marcelo
Vera, Domingo Mariano Adolfo
Pierini, Adriana Beatriz
author Puiatti, Marcelo
author_facet Puiatti, Marcelo
Vera, Domingo Mariano Adolfo
Pierini, Adriana Beatriz
author_role author
author2 Vera, Domingo Mariano Adolfo
Pierini, Adriana Beatriz
author2_role author
author
dc.subject.none.fl_str_mv Negative Electron Affinity
Radical Anions
Dft
Td-Dft
https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
topic Negative Electron Affinity
Radical Anions
Dft
Td-Dft
https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
description Recently, we have proposed an approach for finding the valence anion ground state, based on the stabilization exerted by a polar solvent; the methodology used standard DFT methods and relatively inexpensive basis sets and yielded correct electron affinity (EA) values by gradually decreasing the dielectric constant of the medium. In order to address the overall performance of the new methodology, to find the best conditions for stabilizing the valence state and to evaluate its scope and limitations, we gathered a pool of 60 molecules, 25 of them bearing the conventional valence state as the ground anion and 35 for which the lowest anion state found holds the extra electron in a diffuse orbital around the molecule (non valence state). The results obtained by testing this representative set suggest a very good performance for most species having an experimental EA less negative than -3.0 eV; the correlation at the B3LYP/6-311+G(2df,p) level being y = 1.01x + 0.06, with a correlation index of 0.985. As an alternative, the time dependent DFT (TD-DFT) approach was also tested with both B3LYP and PBE0 functionals. The methodology we proposed shows a comparable or better accuracy with respect to TD-DFT, although the TD-DFT approach with the PBE0 functional is suggested as a suitable estimate for species with the most negative EAs (ca.-2.5 to -3.5 eV), for which stabilization strategies can hardly reach the valence state. As an application, a pool of 8 compounds of key biological interest with EAs which remain unknown or unclear were predicted using the new methodology.
publishDate 2009
dc.date.none.fl_str_mv 2009-08
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/11336/76445
Puiatti, Marcelo; Vera, Domingo Mariano Adolfo; Pierini, Adriana Beatriz; In search for an optimal methodology to calculate the valence electron affinities of temporary anions; Royal Society of Chemistry; Physical Chemistry Chemical Physics; 11; 40; 8-2009; 9013-9024
1463-9076
CONICET Digital
CONICET
url http://hdl.handle.net/11336/76445
identifier_str_mv Puiatti, Marcelo; Vera, Domingo Mariano Adolfo; Pierini, Adriana Beatriz; In search for an optimal methodology to calculate the valence electron affinities of temporary anions; Royal Society of Chemistry; Physical Chemistry Chemical Physics; 11; 40; 8-2009; 9013-9024
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/b908870a
info:eu-repo/semantics/altIdentifier/url/https://pubs.rsc.org/en/content/articlelanding/2009/CP/b908870a#!divAbstract
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
instname_str Consejo Nacional de Investigaciones Científicas y Técnicas
reponame_str CONICET Digital (CONICET)
collection CONICET Digital (CONICET)
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
_version_ 1799195964751216640
spelling In search for an optimal methodology to calculate the valence electron affinities of temporary anionsPuiatti, MarceloVera, Domingo Mariano AdolfoPierini, Adriana BeatrizNegative Electron AffinityRadical AnionsDftTd-Dfthttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1Recently, we have proposed an approach for finding the valence anion ground state, based on the stabilization exerted by a polar solvent; the methodology used standard DFT methods and relatively inexpensive basis sets and yielded correct electron affinity (EA) values by gradually decreasing the dielectric constant of the medium. In order to address the overall performance of the new methodology, to find the best conditions for stabilizing the valence state and to evaluate its scope and limitations, we gathered a pool of 60 molecules, 25 of them bearing the conventional valence state as the ground anion and 35 for which the lowest anion state found holds the extra electron in a diffuse orbital around the molecule (non valence state). The results obtained by testing this representative set suggest a very good performance for most species having an experimental EA less negative than -3.0 eV; the correlation at the B3LYP/6-311+G(2df,p) level being y = 1.01x + 0.06, with a correlation index of 0.985. As an alternative, the time dependent DFT (TD-DFT) approach was also tested with both B3LYP and PBE0 functionals. The methodology we proposed shows a comparable or better accuracy with respect to TD-DFT, although the TD-DFT approach with the PBE0 functional is suggested as a suitable estimate for species with the most negative EAs (ca.-2.5 to -3.5 eV), for which stabilization strategies can hardly reach the valence state. As an application, a pool of 8 compounds of key biological interest with EAs which remain unknown or unclear were predicted using the new methodology.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; ArgentinaFil: Vera, Domingo Mariano Adolfo. 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: 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 Chemistry2009-08info: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/11336/76445Puiatti, Marcelo; Vera, Domingo Mariano Adolfo; Pierini, Adriana Beatriz; In search for an optimal methodology to calculate the valence electron affinities of temporary anions; Royal Society of Chemistry; Physical Chemistry Chemical Physics; 11; 40; 8-2009; 9013-90241463-9076CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/doi/10.1039/b908870ainfo:eu-repo/semantics/altIdentifier/url/https://pubs.rsc.org/en/content/articlelanding/2009/CP/b908870a#!divAbstractinfo:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2024-05-08T14:10:02Zoai:ri.conicet.gov.ar:11336/76445instacron: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:34982024-05-08 14:10:02.535CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
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