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

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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...

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Autores principales: Grinberg, H., Capparelli, A.L., Spina, A., Marañon, J., Sorarrain, O.M.
Formato: Artículo publishedVersion
Lenguaje:Inglés
Publicado: 1981
Acceso en línea:http://hdl.handle.net/20.500.12110/paper_00223654_v85_n19_p2751_Grinberg
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Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA) de Universidad de Buenos Aires
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spelling paperaa:paper_00223654_v85_n19_p2751_Grinberg2023-06-12T16:44:43Z 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 Journal of Physical Chemistry 1981;85(19):2751-2759 Grinberg, 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. 1981 info:eu-repo/semantics/article info:ar-repo/semantics/artículo info:eu-repo/semantics/publishedVersion application/pdf eng info:eu-repo/semantics/openAccess http://creativecommons.org/licenses/by/2.5/ar http://hdl.handle.net/20.500.12110/paper_00223654_v85_n19_p2751_Grinberg
institution Universidad de Buenos Aires
institution_str I-28
repository_str R-134
collection Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA)
language Inglés
orig_language_str_mv eng
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.
format Artículo
Artículo
publishedVersion
author Grinberg, H.
Capparelli, A.L.
Spina, A.
Marañon, J.
Sorarrain, O.M.
spellingShingle Grinberg, H.
Capparelli, A.L.
Spina, A.
Marañon, J.
Sorarrain, O.M.
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
author_facet Grinberg, H.
Capparelli, A.L.
Spina, A.
Marañon, J.
Sorarrain, O.M.
author_sort Grinberg, H.
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
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
publishDate 1981
url http://hdl.handle.net/20.500.12110/paper_00223654_v85_n19_p2751_Grinberg
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