Structural studies and vibrational analyses of stable and less stable conformers of 1,3,5-hexatriene based on ab initio MO calculations

H. Yoshida, Yukio Furukawa, M. Tasumi

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42 Citations (Scopus)

Abstract

For 3-trans and 3-cis isomers of 1,3,5-hexatriene, structure parameters of not only the stable (trans about the CC single bonds) but also less stable conformers have been optimized by restricted Hartree-Fock calculations at the 6-31G level. The less stable conformers are found to have torsional angles about the CC single bonds in the range between 32° and 48° from the planar s-cis conformation. Force constants in the Cartesian-coordinate space have been calculated and transformed into the group-coordinate force constants, which have then been adjusted to obtain good agreement between the calculated and observed vibrational frequencies. Vibrational assignments for the stable conformers are reexamined in view of the latest experimental data. Infrared bands of less stable conformers previously reported by two of the present authors are reasonably assigned on the basis of the results of normal-coordinate calculations. Characteristics features of some normal modes of individual conformers are discussed in detail.

Original languageEnglish
Pages (from-to)279-299
Number of pages21
JournalJournal of Molecular Structure
Volume194
Issue numberC
DOIs
Publication statusPublished - 1989
Externally publishedYes

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Cartesian coordinates
Vibrational spectra
Isomers
Conformations
isomers
Infrared radiation
1,3,5-hexatriene
single bond

ASJC Scopus subject areas

  • Structural Biology
  • Organic Chemistry
  • Physical and Theoretical Chemistry
  • Spectroscopy
  • Materials Science (miscellaneous)
  • Atomic and Molecular Physics, and Optics

Cite this

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abstract = "For 3-trans and 3-cis isomers of 1,3,5-hexatriene, structure parameters of not only the stable (trans about the CC single bonds) but also less stable conformers have been optimized by restricted Hartree-Fock calculations at the 6-31G level. The less stable conformers are found to have torsional angles about the CC single bonds in the range between 32° and 48° from the planar s-cis conformation. Force constants in the Cartesian-coordinate space have been calculated and transformed into the group-coordinate force constants, which have then been adjusted to obtain good agreement between the calculated and observed vibrational frequencies. Vibrational assignments for the stable conformers are reexamined in view of the latest experimental data. Infrared bands of less stable conformers previously reported by two of the present authors are reasonably assigned on the basis of the results of normal-coordinate calculations. Characteristics features of some normal modes of individual conformers are discussed in detail.",
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T1 - Structural studies and vibrational analyses of stable and less stable conformers of 1,3,5-hexatriene based on ab initio MO calculations

AU - Yoshida, H.

AU - Furukawa, Yukio

AU - Tasumi, M.

PY - 1989

Y1 - 1989

N2 - For 3-trans and 3-cis isomers of 1,3,5-hexatriene, structure parameters of not only the stable (trans about the CC single bonds) but also less stable conformers have been optimized by restricted Hartree-Fock calculations at the 6-31G level. The less stable conformers are found to have torsional angles about the CC single bonds in the range between 32° and 48° from the planar s-cis conformation. Force constants in the Cartesian-coordinate space have been calculated and transformed into the group-coordinate force constants, which have then been adjusted to obtain good agreement between the calculated and observed vibrational frequencies. Vibrational assignments for the stable conformers are reexamined in view of the latest experimental data. Infrared bands of less stable conformers previously reported by two of the present authors are reasonably assigned on the basis of the results of normal-coordinate calculations. Characteristics features of some normal modes of individual conformers are discussed in detail.

AB - For 3-trans and 3-cis isomers of 1,3,5-hexatriene, structure parameters of not only the stable (trans about the CC single bonds) but also less stable conformers have been optimized by restricted Hartree-Fock calculations at the 6-31G level. The less stable conformers are found to have torsional angles about the CC single bonds in the range between 32° and 48° from the planar s-cis conformation. Force constants in the Cartesian-coordinate space have been calculated and transformed into the group-coordinate force constants, which have then been adjusted to obtain good agreement between the calculated and observed vibrational frequencies. Vibrational assignments for the stable conformers are reexamined in view of the latest experimental data. Infrared bands of less stable conformers previously reported by two of the present authors are reasonably assigned on the basis of the results of normal-coordinate calculations. Characteristics features of some normal modes of individual conformers are discussed in detail.

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