Molecular Orbital Theory of the Electronic Structure of Organic Compounds III : A CNDO/S-CI SCF MO Study on the Lower Electronic States of Large Molecules. Singlet-Singlet Transiti...

Autores
Grinberg, Horacio; Sbarbati Nudelman, Norma; Marañon, Julio; Sorarrain, Oscar M.; Gómez, Carlos F.
Año de publicación
1981
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
The semiempirical molecular orbital CNDO/S-CI spectral parameterization has been used to elucidate the lower electronic states of a series of dioxodiazacycloalkanes. The a₁, b₁, and a' occupied molecular orbitals lie predominantly on the oxygen, while a₂, b₂, and a" are largerly nonbonding orbitals delocalized on the nitrogen and oxygen atoms. The two lowest unoccupied virtual orbitals are predicted to be of b₂, a₂, and a" symmetry. These orbitals are strongly localized on the C = 0 group. The resulting 1 B₂(nₒπ*) and 1 A₂(nₒπ*) spectroscopic states involve intramolecular charge transfer from the oxygen to the carbon atom of the carbonyl group, which is supported by electron density calculations of these excited states. Although the calculated transition energies may not allow for absolute comparisons with experimental values, it appears that the introduction of self-consistency together with solvation energy and configuration interaction, when the elements of the interaction matrix are properly evaluated, lead to a fairly good interpretation of the singlet-singlet transitions. The lowest energy singlet excited state calculated for each structure is comprised almost entirely of the n.π* configuration.
Publicado on line en 2014.
Facultad de Ciencias Exactas
Materia
Química
Física
Electronic States
Large Molecules
Nivel de accesibilidad
acceso abierto
Condiciones de uso
http://creativecommons.org/licenses/by-nc-nd/3.0/
Repositorio
SEDICI (UNLP)
Institución
Universidad Nacional de La Plata
OAI Identificador
oai:sedici.unlp.edu.ar:10915/120321

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repository_id_str 1329
network_name_str SEDICI (UNLP)
spelling Molecular Orbital Theory of the Electronic Structure of Organic Compounds III : A CNDO/S-CI SCF MO Study on the Lower Electronic States of Large Molecules. Singlet-Singlet Transitions of DioxodiazacycloalkanesGrinberg, HoracioSbarbati Nudelman, NormaMarañon, JulioSorarrain, Oscar M.Gómez, Carlos F.QuímicaFísicaElectronic StatesLarge MoleculesThe semiempirical molecular orbital CNDO/S-CI spectral parameterization has been used to elucidate the lower electronic states of a series of dioxodiazacycloalkanes. The a₁, b₁, and a' occupied molecular orbitals lie predominantly on the oxygen, while a₂, b₂, and a" are largerly nonbonding orbitals delocalized on the nitrogen and oxygen atoms. The two lowest unoccupied virtual orbitals are predicted to be of b₂, a₂, and a" symmetry. These orbitals are strongly localized on the C = 0 group. The resulting 1 B₂(nₒπ*) and 1 A₂(nₒπ*) spectroscopic states involve intramolecular charge transfer from the oxygen to the carbon atom of the carbonyl group, which is supported by electron density calculations of these excited states. Although the calculated transition energies may not allow for absolute comparisons with experimental values, it appears that the introduction of self-consistency together with solvation energy and configuration interaction, when the elements of the interaction matrix are properly evaluated, lead to a fairly good interpretation of the singlet-singlet transitions. The lowest energy singlet excited state calculated for each structure is comprised almost entirely of the n.π* configuration.Publicado on line en 2014.Facultad de Ciencias Exactas1981info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionArticulohttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdf494-501http://sedici.unlp.edu.ar/handle/10915/120321enginfo:eu-repo/semantics/altIdentifier/issn/1865-7109info:eu-repo/semantics/altIdentifier/doi/10.1515/zna-1981-0512info:eu-repo/semantics/openAccesshttp://creativecommons.org/licenses/by-nc-nd/3.0/Creative Commons Attribution-NonCommercial-NoDerivs 3.0 Unported (CC BY-NC-ND 3.0)reponame:SEDICI (UNLP)instname:Universidad Nacional de La Platainstacron:UNLP2025-09-29T11:28:29Zoai:sedici.unlp.edu.ar:10915/120321Institucionalhttp://sedici.unlp.edu.ar/Universidad públicaNo correspondehttp://sedici.unlp.edu.ar/oai/snrdalira@sedici.unlp.edu.arArgentinaNo correspondeNo correspondeNo correspondeopendoar:13292025-09-29 11:28:29.672SEDICI (UNLP) - Universidad Nacional de La Platafalse
dc.title.none.fl_str_mv Molecular Orbital Theory of the Electronic Structure of Organic Compounds III : A CNDO/S-CI SCF MO Study on the Lower Electronic States of Large Molecules. Singlet-Singlet Transitions of Dioxodiazacycloalkanes
title Molecular Orbital Theory of the Electronic Structure of Organic Compounds III : A CNDO/S-CI SCF MO Study on the Lower Electronic States of Large Molecules. Singlet-Singlet Transitions of Dioxodiazacycloalkanes
spellingShingle Molecular Orbital Theory of the Electronic Structure of Organic Compounds III : A CNDO/S-CI SCF MO Study on the Lower Electronic States of Large Molecules. Singlet-Singlet Transitions of Dioxodiazacycloalkanes
Grinberg, Horacio
Química
Física
Electronic States
Large Molecules
title_short Molecular Orbital Theory of the Electronic Structure of Organic Compounds III : A CNDO/S-CI SCF MO Study on the Lower Electronic States of Large Molecules. Singlet-Singlet Transitions of Dioxodiazacycloalkanes
title_full Molecular Orbital Theory of the Electronic Structure of Organic Compounds III : A CNDO/S-CI SCF MO Study on the Lower Electronic States of Large Molecules. Singlet-Singlet Transitions of Dioxodiazacycloalkanes
title_fullStr Molecular Orbital Theory of the Electronic Structure of Organic Compounds III : A CNDO/S-CI SCF MO Study on the Lower Electronic States of Large Molecules. Singlet-Singlet Transitions of Dioxodiazacycloalkanes
title_full_unstemmed Molecular Orbital Theory of the Electronic Structure of Organic Compounds III : A CNDO/S-CI SCF MO Study on the Lower Electronic States of Large Molecules. Singlet-Singlet Transitions of Dioxodiazacycloalkanes
title_sort Molecular Orbital Theory of the Electronic Structure of Organic Compounds III : A CNDO/S-CI SCF MO Study on the Lower Electronic States of Large Molecules. Singlet-Singlet Transitions of Dioxodiazacycloalkanes
dc.creator.none.fl_str_mv Grinberg, Horacio
Sbarbati Nudelman, Norma
Marañon, Julio
Sorarrain, Oscar M.
Gómez, Carlos F.
author Grinberg, Horacio
author_facet Grinberg, Horacio
Sbarbati Nudelman, Norma
Marañon, Julio
Sorarrain, Oscar M.
Gómez, Carlos F.
author_role author
author2 Sbarbati Nudelman, Norma
Marañon, Julio
Sorarrain, Oscar M.
Gómez, Carlos F.
author2_role author
author
author
author
dc.subject.none.fl_str_mv Química
Física
Electronic States
Large Molecules
topic Química
Física
Electronic States
Large Molecules
dc.description.none.fl_txt_mv The semiempirical molecular orbital CNDO/S-CI spectral parameterization has been used to elucidate the lower electronic states of a series of dioxodiazacycloalkanes. The a₁, b₁, and a' occupied molecular orbitals lie predominantly on the oxygen, while a₂, b₂, and a" are largerly nonbonding orbitals delocalized on the nitrogen and oxygen atoms. The two lowest unoccupied virtual orbitals are predicted to be of b₂, a₂, and a" symmetry. These orbitals are strongly localized on the C = 0 group. The resulting 1 B₂(nₒπ*) and 1 A₂(nₒπ*) spectroscopic states involve intramolecular charge transfer from the oxygen to the carbon atom of the carbonyl group, which is supported by electron density calculations of these excited states. Although the calculated transition energies may not allow for absolute comparisons with experimental values, it appears that the introduction of self-consistency together with solvation energy and configuration interaction, when the elements of the interaction matrix are properly evaluated, lead to a fairly good interpretation of the singlet-singlet transitions. The lowest energy singlet excited state calculated for each structure is comprised almost entirely of the n.π* configuration.
Publicado on line en 2014.
Facultad de Ciencias Exactas
description The semiempirical molecular orbital CNDO/S-CI spectral parameterization has been used to elucidate the lower electronic states of a series of dioxodiazacycloalkanes. The a₁, b₁, and a' occupied molecular orbitals lie predominantly on the oxygen, while a₂, b₂, and a" are largerly nonbonding orbitals delocalized on the nitrogen and oxygen atoms. The two lowest unoccupied virtual orbitals are predicted to be of b₂, a₂, and a" symmetry. These orbitals are strongly localized on the C = 0 group. The resulting 1 B₂(nₒπ*) and 1 A₂(nₒπ*) spectroscopic states involve intramolecular charge transfer from the oxygen to the carbon atom of the carbonyl group, which is supported by electron density calculations of these excited states. Although the calculated transition energies may not allow for absolute comparisons with experimental values, it appears that the introduction of self-consistency together with solvation energy and configuration interaction, when the elements of the interaction matrix are properly evaluated, lead to a fairly good interpretation of the singlet-singlet transitions. The lowest energy singlet excited state calculated for each structure is comprised almost entirely of the n.π* configuration.
publishDate 1981
dc.date.none.fl_str_mv 1981
dc.type.none.fl_str_mv info:eu-repo/semantics/article
info:eu-repo/semantics/publishedVersion
Articulo
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info:ar-repo/semantics/articulo
format article
status_str publishedVersion
dc.identifier.none.fl_str_mv http://sedici.unlp.edu.ar/handle/10915/120321
url http://sedici.unlp.edu.ar/handle/10915/120321
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/issn/1865-7109
info:eu-repo/semantics/altIdentifier/doi/10.1515/zna-1981-0512
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
http://creativecommons.org/licenses/by-nc-nd/3.0/
Creative Commons Attribution-NonCommercial-NoDerivs 3.0 Unported (CC BY-NC-ND 3.0)
eu_rights_str_mv openAccess
rights_invalid_str_mv http://creativecommons.org/licenses/by-nc-nd/3.0/
Creative Commons Attribution-NonCommercial-NoDerivs 3.0 Unported (CC BY-NC-ND 3.0)
dc.format.none.fl_str_mv application/pdf
494-501
dc.source.none.fl_str_mv reponame:SEDICI (UNLP)
instname:Universidad Nacional de La Plata
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reponame_str SEDICI (UNLP)
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