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Electronic spectroscopy of 1,3,5,7-cyclooctatetraene by low-energy, variable-angle electron impact

Frueholz, Robert P. and Kuppermann, Aron (1978) Electronic spectroscopy of 1,3,5,7-cyclooctatetraene by low-energy, variable-angle electron impact. Journal of Chemical Physics, 69 (8). pp. 3614-3621. ISSN 0021-9606. doi:10.1063/1.437069.

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The electron-impact energy loss spectrum of 1,3,5,7-cyclooctatetraene has been measured at electron impact energies of 30, 50, and 75 eV, and scattering angles varying from 5° to 80°. Three transitions with maxima at 3.05, 4.05, and 4.84 eV are identified as singlet --> triplet excitations. The significance of the lowest lying of these triplet states in the quenching process of dye laser solutions (in particular rhodamine 6G) is discussed and an exciplex mechanism for triplet quenching is suggested. Singlet-->singlet transitions are observed at 4.43, 6.02, and 6.42 eV. These spin-allowed transitions have been observed optically and are assigned as ? 1A1 -->1A2, ? 1A1-->1E, and ? 1A1-->1E excitations. Three new, singlet --> singlet transitions are observed at 6.99, 8.41, and 9.05 eV and are tentatively assigned as the ? 1A1-->1B2, ? 1A1-->1E, and ? 1A1 -->1E, pi-->pi* excitations. Several superexcited features between 10 and 15 eV have been observed and are believed to involve excitations to autoionizing Rydberg states.

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Additional Information:Copyright © 1978 American Institute of Physics. Received 20n February 1978. We wish to thank Professor R. Pettit for providing us with one of our samples of 1,3,5,7-cyclooctatetraene. We also thank Dr. W.M. Flicker for several very helpful discussions. This work was supported by a Contract (No. EY-76-8-03-767) from the Department of Energy. Report Code: CALT-767P4-163. Work performed [by R.P.F.] in partial fulfillment of the requirements for the Ph.D. degree in Chemistry at the California Institute of Technology. Arthur Amos Noyes Laboratory of Chemical Physics, Contribution No. 5732.
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Department of EnergyEY-76-S-03-767
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Arthur Amos Noyes Laboratory of Chemical Physics5732
Issue or Number:8
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ID Code:11384
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Deposited On:11 Aug 2008 20:40
Last Modified:08 Nov 2021 21:58

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