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Abstract:

The double hydrogen bonding in the adenine-thymine nucleotide base pair has been investigated in the CNDO/S semiempirical approximation. Correlation of the molecular orbitals for the double proton transfer in the normal and tautomeric configurations shows that the π molecular orbitals are only slightly perturbed, whereas the σ molecular orbitals are delocalized on both units of the base pair. Analysis via perturbation theory in order to elucidate the formation of the hydrogen-bonded complex has been performed. The results suggest that an unsymmetrical charge transfer is involved in the double proton transfer process. The first-order contribution to the perturbed orbital energies of the σ and π molecular orbitals localized on the same unit of the base pair, is predominantly from exchange repulsion energy, whereas the second-order contributor is mainly polarization energy. In the normal configuration of the base pair, the contribution of the deepest σ molecular orbitals (up to -30 eV) to the energy of formation of the hydrogen-bonded complex shows a stabilizing character, whereas at higher energies the opposite trend predominates. The behaviour of the molecular orbitals of the tautomeric configuration is quite different since only some of the σ orbitals (those laying between -40 and -30 eV) localized on thymine help stabilize the complex, whereas the remainder contribute to destabilization of the configuration. Hence the normal configuration of the base pair is more stable than the tautomeric configuration. © 1982.

Registro:

Documento: Artículo
Título:Semiempirical quantum mechanical calculation of the electronic structure of DNA. Molecular orbitals correlation and orbital energy shifts in the double hydrogen bonding of the adenine-thymine base pair
Autor:Marañon, J.; Grinberg, H.
Filiación:Laboratorio de Física Teórica, Departamento de Física, Facultad de Ciencias Exactas, C.C. No 67, 1900 La Plata, Argentina
Departamento de Química Orgánica, Facultad de Ciencias Exactas y Naturales, Universidad de Buenos Aires, 1428 Buenos Aires, Argentina
Año:1982
Volumen:88
Número:3-4
Página de inicio:283
Página de fin:293
DOI: http://dx.doi.org/10.1016/0166-1280(82)80178-4
Título revista:Journal of Molecular Structure: THEOCHEM
Título revista abreviado:J. Mol. Struct. THEOCHEM
ISSN:01661280
CODEN:THEOD
Registro:https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_01661280_v88_n3-4_p283_Maranon

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Citas:

---------- APA ----------
Marañon, J. & Grinberg, H. (1982) . Semiempirical quantum mechanical calculation of the electronic structure of DNA. Molecular orbitals correlation and orbital energy shifts in the double hydrogen bonding of the adenine-thymine base pair. Journal of Molecular Structure: THEOCHEM, 88(3-4), 283-293.
http://dx.doi.org/10.1016/0166-1280(82)80178-4
---------- CHICAGO ----------
Marañon, J., Grinberg, H. "Semiempirical quantum mechanical calculation of the electronic structure of DNA. Molecular orbitals correlation and orbital energy shifts in the double hydrogen bonding of the adenine-thymine base pair" . Journal of Molecular Structure: THEOCHEM 88, no. 3-4 (1982) : 283-293.
http://dx.doi.org/10.1016/0166-1280(82)80178-4
---------- MLA ----------
Marañon, J., Grinberg, H. "Semiempirical quantum mechanical calculation of the electronic structure of DNA. Molecular orbitals correlation and orbital energy shifts in the double hydrogen bonding of the adenine-thymine base pair" . Journal of Molecular Structure: THEOCHEM, vol. 88, no. 3-4, 1982, pp. 283-293.
http://dx.doi.org/10.1016/0166-1280(82)80178-4
---------- VANCOUVER ----------
Marañon, J., Grinberg, H. Semiempirical quantum mechanical calculation of the electronic structure of DNA. Molecular orbitals correlation and orbital energy shifts in the double hydrogen bonding of the adenine-thymine base pair. J. Mol. Struct. THEOCHEM. 1982;88(3-4):283-293.
http://dx.doi.org/10.1016/0166-1280(82)80178-4