Some Electronic Correlation Effects in the Topological Analysis of the Laplacian of the Electronic Charge Density in C-n-Butonium Cations

Autores
Lobayan, Rosana Maria; Sosa, Gladis Laura; Jubert, Alicia Haydee; Peruchena, Nelida Maria
Año de publicación
2005
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
In this work, we present a topological study of the Laplacian of the electronic density using a 6-311++G** basis set, at Hartree-Fock (HF) and second-order Møller-Plesset (MP2) (full-electron and frozen-core) levels of theory, for the carbocations 2-C-n-butonium generated ugon the insertion of a proton into the secondary C-C bond during the protonation of n-butane. The charge concentration, CC, critical points of the Laplacian distribution at each valence shell, VS, of carbon atoms, and the charge concentration closer to hydrogen atoms are studied. Also, the bonding critical points of the electronic density are analyzed. We analyze some effects that Coulomb correlation has on topological features of the electronic distribution. It is shown that they are mainly reflected in a decreasing of the charge concentrations at the VS and in a contraction of the VS to the nuclei. They are more pronounced over C-C bonds than in C-H bonds. The sensitivity of some parameters derived from this topological analysis to the correlation effect of core electrons and subtle effects related to hyperconjugative interactions are shown. Some consequences of different schemes (double and triple split-valence basis set with diffuse and polarization functions) in the definition of subtle VS charge concentrations at 3c-2e bond paths are presented. It is also demonstrated here how the facts that allow us to understand the MP2 stability order found in the carbocationic species 2-C-n-butonium > 1-C-n-butonium > 2-H-n-butonium > 1-H-n-butonium are similarly depicted at correlated and uncorrelated levels of calculation.
Fil: Lobayan, Rosana Maria. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Nordeste; Argentina. Universidad Nacional del Nordeste. Facultad de Ciencias Exactas y Naturales y Agrimensura; Argentina
Fil: Sosa, Gladis Laura. Universidad Nacional del Nordeste. Facultad de Ciencias Exactas y Naturales y Agrimensura; Argentina
Fil: Jubert, Alicia Haydee. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Centro de Química Inorgánica "Dr. Pedro J. Aymonino". Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Centro de Química Inorgánica "Dr. Pedro J. Aymonino"; Argentina
Fil: Peruchena, Nelida Maria. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Nordeste; Argentina. Universidad Nacional del Nordeste. Facultad de Ciencias Exactas y Naturales y Agrimensura. Departamento de Química. Laboratorio de Estructura Molecular y Propiedades; Argentina
Materia
Aim
Butonium
Laplacian
Charge Density
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:11336/52000
Acceder
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network_acronym_str CONICETDig
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network_name_str CONICET Digital (CONICET)
spelling Some Electronic Correlation Effects in the Topological Analysis of the Laplacian of the Electronic Charge Density in C-n-Butonium CationsLobayan, Rosana MariaSosa, Gladis LauraJubert, Alicia HaydeePeruchena, Nelida MariaAimButoniumLaplacianCharge Densityhttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1In this work, we present a topological study of the Laplacian of the electronic density using a 6-311++G** basis set, at Hartree-Fock (HF) and second-order Møller-Plesset (MP2) (full-electron and frozen-core) levels of theory, for the carbocations 2-C-n-butonium generated ugon the insertion of a proton into the secondary C-C bond during the protonation of n-butane. The charge concentration, CC, critical points of the Laplacian distribution at each valence shell, VS, of carbon atoms, and the charge concentration closer to hydrogen atoms are studied. Also, the bonding critical points of the electronic density are analyzed. We analyze some effects that Coulomb correlation has on topological features of the electronic distribution. It is shown that they are mainly reflected in a decreasing of the charge concentrations at the VS and in a contraction of the VS to the nuclei. They are more pronounced over C-C bonds than in C-H bonds. The sensitivity of some parameters derived from this topological analysis to the correlation effect of core electrons and subtle effects related to hyperconjugative interactions are shown. Some consequences of different schemes (double and triple split-valence basis set with diffuse and polarization functions) in the definition of subtle VS charge concentrations at 3c-2e bond paths are presented. It is also demonstrated here how the facts that allow us to understand the MP2 stability order found in the carbocationic species 2-C-n-butonium > 1-C-n-butonium > 2-H-n-butonium > 1-H-n-butonium are similarly depicted at correlated and uncorrelated levels of calculation.Fil: Lobayan, Rosana Maria. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Nordeste; Argentina. Universidad Nacional del Nordeste. Facultad de Ciencias Exactas y Naturales y Agrimensura; ArgentinaFil: Sosa, Gladis Laura. Universidad Nacional del Nordeste. Facultad de Ciencias Exactas y Naturales y Agrimensura; ArgentinaFil: Jubert, Alicia Haydee. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Centro de Química Inorgánica "Dr. Pedro J. Aymonino". Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Centro de Química Inorgánica "Dr. Pedro J. Aymonino"; ArgentinaFil: Peruchena, Nelida Maria. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Nordeste; Argentina. Universidad Nacional del Nordeste. Facultad de Ciencias Exactas y Naturales y Agrimensura. Departamento de Química. Laboratorio de Estructura Molecular y Propiedades; ArgentinaAmerican Chemical Society2005-01info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/52000Lobayan, Rosana Maria; Sosa, Gladis Laura; Jubert, Alicia Haydee; Peruchena, Nelida Maria; Some Electronic Correlation Effects in the Topological Analysis of the Laplacian of the Electronic Charge Density in C-n-Butonium Cations; American Chemical Society; Journal of Physical Chemistry A; 109; 1; 1-2005; 181-1901089-5639CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/url/https://pubs.acs.org/doi/abs/10.1021/jp0469923info:eu-repo/semantics/altIdentifier/doi/10.1021/jp0469923info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-10T13:10:53Zoai:ri.conicet.gov.ar:11336/52000instacron: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:34982025-09-10 13:10:53.591CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Some Electronic Correlation Effects in the Topological Analysis of the Laplacian of the Electronic Charge Density in C-n-Butonium Cations
title Some Electronic Correlation Effects in the Topological Analysis of the Laplacian of the Electronic Charge Density in C-n-Butonium Cations
spellingShingle Some Electronic Correlation Effects in the Topological Analysis of the Laplacian of the Electronic Charge Density in C-n-Butonium Cations
Lobayan, Rosana Maria
Aim
Butonium
Laplacian
Charge Density
title_short Some Electronic Correlation Effects in the Topological Analysis of the Laplacian of the Electronic Charge Density in C-n-Butonium Cations
title_full Some Electronic Correlation Effects in the Topological Analysis of the Laplacian of the Electronic Charge Density in C-n-Butonium Cations
title_fullStr Some Electronic Correlation Effects in the Topological Analysis of the Laplacian of the Electronic Charge Density in C-n-Butonium Cations
title_full_unstemmed Some Electronic Correlation Effects in the Topological Analysis of the Laplacian of the Electronic Charge Density in C-n-Butonium Cations
title_sort Some Electronic Correlation Effects in the Topological Analysis of the Laplacian of the Electronic Charge Density in C-n-Butonium Cations
dc.creator.none.fl_str_mv Lobayan, Rosana Maria
Sosa, Gladis Laura
Jubert, Alicia Haydee
Peruchena, Nelida Maria
author Lobayan, Rosana Maria
author_facet Lobayan, Rosana Maria
Sosa, Gladis Laura
Jubert, Alicia Haydee
Peruchena, Nelida Maria
author_role author
author2 Sosa, Gladis Laura
Jubert, Alicia Haydee
Peruchena, Nelida Maria
author2_role author
author
author
dc.subject.none.fl_str_mv Aim
Butonium
Laplacian
Charge Density
topic Aim
Butonium
Laplacian
Charge Density
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv In this work, we present a topological study of the Laplacian of the electronic density using a 6-311++G** basis set, at Hartree-Fock (HF) and second-order Møller-Plesset (MP2) (full-electron and frozen-core) levels of theory, for the carbocations 2-C-n-butonium generated ugon the insertion of a proton into the secondary C-C bond during the protonation of n-butane. The charge concentration, CC, critical points of the Laplacian distribution at each valence shell, VS, of carbon atoms, and the charge concentration closer to hydrogen atoms are studied. Also, the bonding critical points of the electronic density are analyzed. We analyze some effects that Coulomb correlation has on topological features of the electronic distribution. It is shown that they are mainly reflected in a decreasing of the charge concentrations at the VS and in a contraction of the VS to the nuclei. They are more pronounced over C-C bonds than in C-H bonds. The sensitivity of some parameters derived from this topological analysis to the correlation effect of core electrons and subtle effects related to hyperconjugative interactions are shown. Some consequences of different schemes (double and triple split-valence basis set with diffuse and polarization functions) in the definition of subtle VS charge concentrations at 3c-2e bond paths are presented. It is also demonstrated here how the facts that allow us to understand the MP2 stability order found in the carbocationic species 2-C-n-butonium > 1-C-n-butonium > 2-H-n-butonium > 1-H-n-butonium are similarly depicted at correlated and uncorrelated levels of calculation.
Fil: Lobayan, Rosana Maria. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Nordeste; Argentina. Universidad Nacional del Nordeste. Facultad de Ciencias Exactas y Naturales y Agrimensura; Argentina
Fil: Sosa, Gladis Laura. Universidad Nacional del Nordeste. Facultad de Ciencias Exactas y Naturales y Agrimensura; Argentina
Fil: Jubert, Alicia Haydee. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Centro de Química Inorgánica "Dr. Pedro J. Aymonino". Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Centro de Química Inorgánica "Dr. Pedro J. Aymonino"; Argentina
Fil: Peruchena, Nelida Maria. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Nordeste; Argentina. Universidad Nacional del Nordeste. Facultad de Ciencias Exactas y Naturales y Agrimensura. Departamento de Química. Laboratorio de Estructura Molecular y Propiedades; Argentina
description In this work, we present a topological study of the Laplacian of the electronic density using a 6-311++G** basis set, at Hartree-Fock (HF) and second-order Møller-Plesset (MP2) (full-electron and frozen-core) levels of theory, for the carbocations 2-C-n-butonium generated ugon the insertion of a proton into the secondary C-C bond during the protonation of n-butane. The charge concentration, CC, critical points of the Laplacian distribution at each valence shell, VS, of carbon atoms, and the charge concentration closer to hydrogen atoms are studied. Also, the bonding critical points of the electronic density are analyzed. We analyze some effects that Coulomb correlation has on topological features of the electronic distribution. It is shown that they are mainly reflected in a decreasing of the charge concentrations at the VS and in a contraction of the VS to the nuclei. They are more pronounced over C-C bonds than in C-H bonds. The sensitivity of some parameters derived from this topological analysis to the correlation effect of core electrons and subtle effects related to hyperconjugative interactions are shown. Some consequences of different schemes (double and triple split-valence basis set with diffuse and polarization functions) in the definition of subtle VS charge concentrations at 3c-2e bond paths are presented. It is also demonstrated here how the facts that allow us to understand the MP2 stability order found in the carbocationic species 2-C-n-butonium > 1-C-n-butonium > 2-H-n-butonium > 1-H-n-butonium are similarly depicted at correlated and uncorrelated levels of calculation.
publishDate 2005
dc.date.none.fl_str_mv 2005-01
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/11336/52000
Lobayan, Rosana Maria; Sosa, Gladis Laura; Jubert, Alicia Haydee; Peruchena, Nelida Maria; Some Electronic Correlation Effects in the Topological Analysis of the Laplacian of the Electronic Charge Density in C-n-Butonium Cations; American Chemical Society; Journal of Physical Chemistry A; 109; 1; 1-2005; 181-190
1089-5639
CONICET Digital
CONICET
url http://hdl.handle.net/11336/52000
identifier_str_mv Lobayan, Rosana Maria; Sosa, Gladis Laura; Jubert, Alicia Haydee; Peruchena, Nelida Maria; Some Electronic Correlation Effects in the Topological Analysis of the Laplacian of the Electronic Charge Density in C-n-Butonium Cations; American Chemical Society; Journal of Physical Chemistry A; 109; 1; 1-2005; 181-190
1089-5639
CONICET Digital
CONICET
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/url/https://pubs.acs.org/doi/abs/10.1021/jp0469923
info:eu-repo/semantics/altIdentifier/doi/10.1021/jp0469923
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
dc.publisher.none.fl_str_mv American Chemical Society
publisher.none.fl_str_mv American Chemical Society
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 12.993085

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