Semiempirical quantum-mechanical calculation of the electronic structure of DNA. Double-minimum potential curves of the singlet and triplet excited electronic states, tunneling and...

Autores
Grinberg, H.; Capparelli, A.L.; Spina, A.; Marañon, J.; Sorarrain, O.M.
Año de publicación
1981
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
The excited states of the double hydrogen bond in the adenine-thymine nucleotide base pair has been investigated in the semiempirical CNDO/S-CI approximation. Double-minimum potential curves are obtained for several nuclear configurations characterizing simultaneous tautomeric rearrangements of the NH⋯N and O⋯HN bonds. The energy profiles for the coupled movement of the hydrogen bonding show that the Watson-Crick configuration of the adenine-thymine base pair is the most stable for all of the excited states studied. Estimates are made within the WKB approximation of the tunneling rate and tunneling probability. The results indicate that increasing the energy of the excited states would increase the probability of double protonic transfer by tunnel effect and thus for irreversible mutation. A comparison of the composition of the potentials for the single movement of the protons with the double-minimum potential of the concerted movement shows that the potential is nonseparable. The shortcomings that follow from the WKB approximation as applied to the present problem are discussed. © 1981 American Chemical Society.
Fil:Grinberg, H. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales; Argentina.
Fuente
Journal of Physical Chemistry 1981;85(19):2751-2759
Nivel de accesibilidad
acceso abierto
Condiciones de uso
http://creativecommons.org/licenses/by/2.5/ar
Repositorio
Biblioteca Digital (UBA-FCEN)
Institución
Universidad Nacional de Buenos Aires. Facultad de Ciencias Exactas y Naturales
OAI Identificador
paperaa:paper_00223654_v85_n19_p2751_Grinberg
Acceder
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oai_identifier_str paperaa:paper_00223654_v85_n19_p2751_Grinberg
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repository_id_str 1896
network_name_str Biblioteca Digital (UBA-FCEN)
spelling Semiempirical quantum-mechanical calculation of the electronic structure of DNA. Double-minimum potential curves of the singlet and triplet excited electronic states, tunneling and tautomeric equilibrium of the NH⋯N and O⋯HN bonds in the adenine-thymine base pairGrinberg, H.Capparelli, A.L.Spina, A.Marañon, J.Sorarrain, O.M.The excited states of the double hydrogen bond in the adenine-thymine nucleotide base pair has been investigated in the semiempirical CNDO/S-CI approximation. Double-minimum potential curves are obtained for several nuclear configurations characterizing simultaneous tautomeric rearrangements of the NH⋯N and O⋯HN bonds. The energy profiles for the coupled movement of the hydrogen bonding show that the Watson-Crick configuration of the adenine-thymine base pair is the most stable for all of the excited states studied. Estimates are made within the WKB approximation of the tunneling rate and tunneling probability. The results indicate that increasing the energy of the excited states would increase the probability of double protonic transfer by tunnel effect and thus for irreversible mutation. A comparison of the composition of the potentials for the single movement of the protons with the double-minimum potential of the concerted movement shows that the potential is nonseparable. The shortcomings that follow from the WKB approximation as applied to the present problem are discussed. © 1981 American Chemical Society.Fil:Grinberg, H. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales; Argentina.1981info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfhttp://hdl.handle.net/20.500.12110/paper_00223654_v85_n19_p2751_GrinbergJournal of Physical Chemistry 1981;85(19):2751-2759reponame:Biblioteca Digital (UBA-FCEN)instname:Universidad Nacional de Buenos Aires. Facultad de Ciencias Exactas y Naturalesinstacron:UBA-FCENenginfo:eu-repo/semantics/openAccesshttp://creativecommons.org/licenses/by/2.5/ar2025-10-23T11:18:28Zpaperaa:paper_00223654_v85_n19_p2751_GrinbergInstitucionalhttps://digital.bl.fcen.uba.ar/Universidad públicaNo correspondehttps://digital.bl.fcen.uba.ar/cgi-bin/oaiserver.cgiana@bl.fcen.uba.arArgentinaNo correspondeNo correspondeNo correspondeopendoar:18962025-10-23 11:18:29.911Biblioteca Digital (UBA-FCEN) - Universidad Nacional de Buenos Aires. Facultad de Ciencias Exactas y Naturalesfalse
dc.title.none.fl_str_mv Semiempirical quantum-mechanical calculation of the electronic structure of DNA. Double-minimum potential curves of the singlet and triplet excited electronic states, tunneling and tautomeric equilibrium of the NH⋯N and O⋯HN bonds in the adenine-thymine base pair
title Semiempirical quantum-mechanical calculation of the electronic structure of DNA. Double-minimum potential curves of the singlet and triplet excited electronic states, tunneling and tautomeric equilibrium of the NH⋯N and O⋯HN bonds in the adenine-thymine base pair
spellingShingle Semiempirical quantum-mechanical calculation of the electronic structure of DNA. Double-minimum potential curves of the singlet and triplet excited electronic states, tunneling and tautomeric equilibrium of the NH⋯N and O⋯HN bonds in the adenine-thymine base pair
Grinberg, H.
title_short Semiempirical quantum-mechanical calculation of the electronic structure of DNA. Double-minimum potential curves of the singlet and triplet excited electronic states, tunneling and tautomeric equilibrium of the NH⋯N and O⋯HN bonds in the adenine-thymine base pair
title_full Semiempirical quantum-mechanical calculation of the electronic structure of DNA. Double-minimum potential curves of the singlet and triplet excited electronic states, tunneling and tautomeric equilibrium of the NH⋯N and O⋯HN bonds in the adenine-thymine base pair
title_fullStr Semiempirical quantum-mechanical calculation of the electronic structure of DNA. Double-minimum potential curves of the singlet and triplet excited electronic states, tunneling and tautomeric equilibrium of the NH⋯N and O⋯HN bonds in the adenine-thymine base pair
title_full_unstemmed Semiempirical quantum-mechanical calculation of the electronic structure of DNA. Double-minimum potential curves of the singlet and triplet excited electronic states, tunneling and tautomeric equilibrium of the NH⋯N and O⋯HN bonds in the adenine-thymine base pair
title_sort Semiempirical quantum-mechanical calculation of the electronic structure of DNA. Double-minimum potential curves of the singlet and triplet excited electronic states, tunneling and tautomeric equilibrium of the NH⋯N and O⋯HN bonds in the adenine-thymine base pair
dc.creator.none.fl_str_mv Grinberg, H.
Capparelli, A.L.
Spina, A.
Marañon, J.
Sorarrain, O.M.
author Grinberg, H.
author_facet Grinberg, H.
Capparelli, A.L.
Spina, A.
Marañon, J.
Sorarrain, O.M.
author_role author
author2 Capparelli, A.L.
Spina, A.
Marañon, J.
Sorarrain, O.M.
author2_role author
author
author
author
dc.description.none.fl_txt_mv The excited states of the double hydrogen bond in the adenine-thymine nucleotide base pair has been investigated in the semiempirical CNDO/S-CI approximation. Double-minimum potential curves are obtained for several nuclear configurations characterizing simultaneous tautomeric rearrangements of the NH⋯N and O⋯HN bonds. The energy profiles for the coupled movement of the hydrogen bonding show that the Watson-Crick configuration of the adenine-thymine base pair is the most stable for all of the excited states studied. Estimates are made within the WKB approximation of the tunneling rate and tunneling probability. The results indicate that increasing the energy of the excited states would increase the probability of double protonic transfer by tunnel effect and thus for irreversible mutation. A comparison of the composition of the potentials for the single movement of the protons with the double-minimum potential of the concerted movement shows that the potential is nonseparable. The shortcomings that follow from the WKB approximation as applied to the present problem are discussed. © 1981 American Chemical Society.
Fil:Grinberg, H. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales; Argentina.
description The excited states of the double hydrogen bond in the adenine-thymine nucleotide base pair has been investigated in the semiempirical CNDO/S-CI approximation. Double-minimum potential curves are obtained for several nuclear configurations characterizing simultaneous tautomeric rearrangements of the NH⋯N and O⋯HN bonds. The energy profiles for the coupled movement of the hydrogen bonding show that the Watson-Crick configuration of the adenine-thymine base pair is the most stable for all of the excited states studied. Estimates are made within the WKB approximation of the tunneling rate and tunneling probability. The results indicate that increasing the energy of the excited states would increase the probability of double protonic transfer by tunnel effect and thus for irreversible mutation. A comparison of the composition of the potentials for the single movement of the protons with the double-minimum potential of the concerted movement shows that the potential is nonseparable. The shortcomings that follow from the WKB approximation as applied to the present problem are discussed. © 1981 American Chemical Society.
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
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/20.500.12110/paper_00223654_v85_n19_p2751_Grinberg
url http://hdl.handle.net/20.500.12110/paper_00223654_v85_n19_p2751_Grinberg
dc.language.none.fl_str_mv eng
language eng
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
http://creativecommons.org/licenses/by/2.5/ar
eu_rights_str_mv openAccess
rights_invalid_str_mv http://creativecommons.org/licenses/by/2.5/ar
dc.format.none.fl_str_mv application/pdf
dc.source.none.fl_str_mv Journal of Physical Chemistry 1981;85(19):2751-2759
reponame:Biblioteca Digital (UBA-FCEN)
instname:Universidad Nacional de Buenos Aires. Facultad de Ciencias Exactas y Naturales
instacron:UBA-FCEN
reponame_str Biblioteca Digital (UBA-FCEN)
collection Biblioteca Digital (UBA-FCEN)
instname_str Universidad Nacional de Buenos Aires. Facultad de Ciencias Exactas y Naturales
instacron_str UBA-FCEN
institution UBA-FCEN
repository.name.fl_str_mv Biblioteca Digital (UBA-FCEN) - Universidad Nacional de Buenos Aires. Facultad de Ciencias Exactas y Naturales
repository.mail.fl_str_mv ana@bl.fcen.uba.ar
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score 12.982451

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