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Abstract:

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' oc-cupied 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(no π*) and 1 A2(n0 π*) spectroscopic states involve intra-molecular 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 nn* configuration. © 1981, Walter de Gruyter. All rights reserved.

Registro:

Documento: Artículo
Título:Molecular Orbital Theory of the Electronic Structure of Organic Compounds III. A CNDO/S-CI SCF MO Study on the Lower Electronic States o! Large Molecules. Singlet-Singlet Transitions of Dioxodiazacycloalkanes
Autor:Grinberg, H.; Nudelman, N.S.; Marañón, J.; Sorarrain, O.M.; Gómez, C.F.
Filiación:MCIC CONICET, Argentina
MCIC CIC, Provincia de Buenos Aires, Argentina
Departamento de Quimiea Organica, Universidad de Buenos Aires, Ciudad Universitaria, 1428 Buenos Aires, Argentina
Año:1981
Volumen:36
Número:5
Página de inicio:494
Página de fin:501
DOI: http://dx.doi.org/10.1515/zna-1981-0512
Título revista:Zeitschrift fur Naturforschung - Section A Journal of Physical Sciences
Título revista abreviado:Z. Naturforsch. Sect. A J. Phys. Sci.
ISSN:09320784
Registro:https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_09320784_v36_n5_p494_Grinberg

Referencias:

  • Marañón, J., Sorarrain, O., Grinberg, H., ; Marañó, J., Sorarrain, O., Grinberg, H., Lamdan, S., Gaozza, C.H., (1978) Tetrahedron, 34 (53)
  • Pople, J.A., (1953) Trans. Faraday Soc., 49 (1375)
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  • Roothaan, C.C.J., (1951) Rev. Mod. Phys., 23 (69)
  • Calculations were performed on a IBM 360/50 Computer with a QCPE program CNDO/S-CI, , The modi-fied closed-shell CNDO/S-CI program (QCPE N° 315) was obtained from the Quantum Chemistry Program Exchange, Indiana University, Bloomington, IN 47401. The molecular symmetry groups were auto-matically generated from the cartesian coordinates
  • Parr, R.G., (1952) J. Chem. Phys., 20 (1499)
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  • The dielectric constants used to calculate the solvation energy are intended to be the limiting values at low frequencies, the so-called static values Solvents used are given in [25]
  • Grinberg, H., Lamdan, S., Gaozza, C.H., (1975) J. Hetero-cyclic Chem., 12 (763)
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Citas:

---------- APA ----------
Grinberg, H., Nudelman, N.S., Marañón, J., Sorarrain, O.M. & Gómez, C.F. (1981) . Molecular Orbital Theory of the Electronic Structure of Organic Compounds III. A CNDO/S-CI SCF MO Study on the Lower Electronic States o! Large Molecules. Singlet-Singlet Transitions of Dioxodiazacycloalkanes. Zeitschrift fur Naturforschung - Section A Journal of Physical Sciences, 36(5), 494-501.
http://dx.doi.org/10.1515/zna-1981-0512
---------- CHICAGO ----------
Grinberg, H., Nudelman, N.S., Marañón, J., Sorarrain, O.M., Gómez, C.F. "Molecular Orbital Theory of the Electronic Structure of Organic Compounds III. A CNDO/S-CI SCF MO Study on the Lower Electronic States o! Large Molecules. Singlet-Singlet Transitions of Dioxodiazacycloalkanes" . Zeitschrift fur Naturforschung - Section A Journal of Physical Sciences 36, no. 5 (1981) : 494-501.
http://dx.doi.org/10.1515/zna-1981-0512
---------- MLA ----------
Grinberg, H., Nudelman, N.S., Marañón, J., Sorarrain, O.M., Gómez, C.F. "Molecular Orbital Theory of the Electronic Structure of Organic Compounds III. A CNDO/S-CI SCF MO Study on the Lower Electronic States o! Large Molecules. Singlet-Singlet Transitions of Dioxodiazacycloalkanes" . Zeitschrift fur Naturforschung - Section A Journal of Physical Sciences, vol. 36, no. 5, 1981, pp. 494-501.
http://dx.doi.org/10.1515/zna-1981-0512
---------- VANCOUVER ----------
Grinberg, H., Nudelman, N.S., Marañón, J., Sorarrain, O.M., Gómez, C.F. Molecular Orbital Theory of the Electronic Structure of Organic Compounds III. A CNDO/S-CI SCF MO Study on the Lower Electronic States o! Large Molecules. Singlet-Singlet Transitions of Dioxodiazacycloalkanes. Z. Naturforsch. Sect. A J. Phys. Sci. 1981;36(5):494-501.
http://dx.doi.org/10.1515/zna-1981-0512