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
- Institución
- Universidad Nacional de La Plata
- OAI Identificador
- oai:sedici.unlp.edu.ar:10915/120321
Ver los metadatos del registro completo
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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 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://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 |
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