The electronic structure of bond-alternating and nonalternant conjugated hydrocarbons

Diphenylpolyenes and azulene

Kwok L. Yip, N. O. Lipari, C. B. Duke, Bruce S Hudson, James Diamond

Research output: Contribution to journalArticle

32 Citations (Scopus)

Abstract

The electronic structures of the first four diphyenylpolyenes (stilbene, diphenylbutadiene, diphenylhexatriene, and diphenyloctatetraene) and of azulene are evaluated using the new "spectroscopic" SCF CNDO/S2 molecular orbital model. In the case of the diphenylpolyenes the higher-energy π and σ ionization potentials and the strong allowed 1Bu optical transitions (in the vicinity of hv=3-4 eV) are predicted to within about 0.1 eV by this model. In addition, the inclusion in our analysis of σ as well as π electronic orbitale permits the detailed interpretation of the electronic origin of all prominent maxima in their ultraviolet photoemission spectra. In the case of azulene, all major peaks in the photoemission and absorption spectra are predicted to within ΔE ≤ 0.4 eV. The predicted dipole moment is 2.1 D, as compared with a Pariser-Parr-Pople value of 1.9 D. We conclude that the CNDO/S2 model can describe the electronic structure of nonalternant and bond-alternating alternant hydrocarbons, as well as that of the symmetric alternant hydrocarbons considered earlier.

Original languageEnglish (US)
Pages (from-to)4020-4026
Number of pages7
JournalThe Journal of Chemical Physics
Volume64
Issue number10
StatePublished - 1976
Externally publishedYes

Fingerprint

azulene
Hydrocarbons
Electronic structure
hydrocarbons
Photoemission
electronic structure
photoelectric emission
Diphenylhexatriene
Stilbenes
Optical transitions
stilbene
Ionization potential
Dipole moment
Molecular orbitals
electronics
optical transition
ionization potentials
self consistent fields
Absorption spectra
molecular orbitals

ASJC Scopus subject areas

  • Atomic and Molecular Physics, and Optics

Cite this

Yip, K. L., Lipari, N. O., Duke, C. B., Hudson, B. S., & Diamond, J. (1976). The electronic structure of bond-alternating and nonalternant conjugated hydrocarbons: Diphenylpolyenes and azulene. The Journal of Chemical Physics, 64(10), 4020-4026.

The electronic structure of bond-alternating and nonalternant conjugated hydrocarbons : Diphenylpolyenes and azulene. / Yip, Kwok L.; Lipari, N. O.; Duke, C. B.; Hudson, Bruce S; Diamond, James.

In: The Journal of Chemical Physics, Vol. 64, No. 10, 1976, p. 4020-4026.

Research output: Contribution to journalArticle

Yip, KL, Lipari, NO, Duke, CB, Hudson, BS & Diamond, J 1976, 'The electronic structure of bond-alternating and nonalternant conjugated hydrocarbons: Diphenylpolyenes and azulene', The Journal of Chemical Physics, vol. 64, no. 10, pp. 4020-4026.
Yip, Kwok L. ; Lipari, N. O. ; Duke, C. B. ; Hudson, Bruce S ; Diamond, James. / The electronic structure of bond-alternating and nonalternant conjugated hydrocarbons : Diphenylpolyenes and azulene. In: The Journal of Chemical Physics. 1976 ; Vol. 64, No. 10. pp. 4020-4026.
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AU - Hudson, Bruce S

AU - Diamond, James

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N2 - The electronic structures of the first four diphyenylpolyenes (stilbene, diphenylbutadiene, diphenylhexatriene, and diphenyloctatetraene) and of azulene are evaluated using the new "spectroscopic" SCF CNDO/S2 molecular orbital model. In the case of the diphenylpolyenes the higher-energy π and σ ionization potentials and the strong allowed 1Bu optical transitions (in the vicinity of hv=3-4 eV) are predicted to within about 0.1 eV by this model. In addition, the inclusion in our analysis of σ as well as π electronic orbitale permits the detailed interpretation of the electronic origin of all prominent maxima in their ultraviolet photoemission spectra. In the case of azulene, all major peaks in the photoemission and absorption spectra are predicted to within ΔE ≤ 0.4 eV. The predicted dipole moment is 2.1 D, as compared with a Pariser-Parr-Pople value of 1.9 D. We conclude that the CNDO/S2 model can describe the electronic structure of nonalternant and bond-alternating alternant hydrocarbons, as well as that of the symmetric alternant hydrocarbons considered earlier.

AB - The electronic structures of the first four diphyenylpolyenes (stilbene, diphenylbutadiene, diphenylhexatriene, and diphenyloctatetraene) and of azulene are evaluated using the new "spectroscopic" SCF CNDO/S2 molecular orbital model. In the case of the diphenylpolyenes the higher-energy π and σ ionization potentials and the strong allowed 1Bu optical transitions (in the vicinity of hv=3-4 eV) are predicted to within about 0.1 eV by this model. In addition, the inclusion in our analysis of σ as well as π electronic orbitale permits the detailed interpretation of the electronic origin of all prominent maxima in their ultraviolet photoemission spectra. In the case of azulene, all major peaks in the photoemission and absorption spectra are predicted to within ΔE ≤ 0.4 eV. The predicted dipole moment is 2.1 D, as compared with a Pariser-Parr-Pople value of 1.9 D. We conclude that the CNDO/S2 model can describe the electronic structure of nonalternant and bond-alternating alternant hydrocarbons, as well as that of the symmetric alternant hydrocarbons considered earlier.

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