Spectroscopic properties of polyenes. I. The lowest energy allowed singlet-singlet transition for cis- and trans- 1,3,5-hexatriene
- 15 April 1973
- journal article
- Published by AIP Publishing in The Journal of Chemical Physics
- Vol. 58 (8) , 3160-3165
- https://doi.org/10.1063/1.1679637
Abstract
The absorption spectra of cis‐ and trans‐ 1,3,5‐hexatriene are reported for the region of the first allowed singlet‐singlet electronic transition, 2600 to 2100 A. A least‐squares procedure in which a Lorentzian line shape is assumed for each band was used to fit the spectra. Progressions are found of 408, 1262, and 1626 cm−1 for the cis isomer and of 350, 1232, and 1628 cm−1 for the trans isomer. The 0–0 transition for the cis compound, 39668 cm−1, lies about 130 cm−1 lower than that for the trans, 39800 cm−1. The fact that the 0–0 transition energy for cis is less than that for trans is interpreted as evidence that the cis isomer has a non‐planar geometry in the electronic ground state. The extinction coefficient for the 0–0 band of the trans isomer is about 1.5 times that for the cis.Keywords
This publication has 13 references indexed in Scilit:
- On the origin of a low-lying forbidden transition in polyenes and related moleculesChemical Physics Letters, 1972
- The Single and Double Bonds between sp2-Hybridized Carbon Atoms, as studied by the Gas Electron Diffraction Method. II. The Molecular Structure of 1,3,5-trans, trans, trans-Hexatriene.Acta Chemica Scandinavica, 1968
- The Single and Double Bonds between sp2-Hybridized Carbon Atoms, as Studied by the Gas Electron Diffraction Method. III. The Molecular Structure of 1,3,5-cis-Hexatriene.Acta Chemica Scandinavica, 1968
- The photochemical and macromolecular aspects of visionProgress in Biophysics and Molecular Biology, 1967
- Organic Quantum Chemistry. VII. Calculation of the Near-Ultraviolet Spectra of PolyolefinsJournal of the American Chemical Society, 1964
- The Vibrational Spectra and Geometric Configuration of cis-1,3,5-HexatrieneJournal of the American Chemical Society, 1962
- A New Preparation of 1,3,5-Hexatriene and the Separation of its Geometrical IsomersJournal of the American Chemical Society, 1960
- The Vibrational Spectra and Geometrical Configuration of 1,3,5-Hexatriene1Journal of the American Chemical Society, 1958
- The absorption spectra of hexatriene and divinyl acetylene in the vacuum ultra-violetProceedings of the Royal Society of London. Series A. Mathematical and Physical Sciences, 1946
- Syntheses of Polyenes. I. Hexatriene and its PolymersJournal of the American Chemical Society, 1939