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Excited electronic states of cyclohexene, 1,4-cyclohexadiene, norbornene, and norbornadiene as studied by electron-impact spectroscopy

Frueholz, Robert P. and Flicker, Wayne M. and Mosher, Oren A. and Kuppermann, Aron (1979) Excited electronic states of cyclohexene, 1,4-cyclohexadiene, norbornene, and norbornadiene as studied by electron-impact spectroscopy. Journal of Chemical Physics, 70 (4). pp. 1986-1993. ISSN 0021-9606. http://resolver.caltech.edu/CaltechAUTHORS:FRUjcp79a

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Abstract

The excited electronic states of cyclohexene, 1,4-cyclohexadiene, norbornene (bicyclo[2.2.1]-2-heptene), and norbornadiene (bicyclo-[2.2.1]-2,5-heptadiene) have been studied by electron impact at scattering angles from 5° to 80°, and impact energies of 30 and 50 eV. Low-lying features with intensity maxima at 4.24 eV in cyclohexene and 4.10 eV in norbornene are identified as singlet --> triplet transitions. Similar features in the spectra of 1,4-cyclohexadiene and norbornadiene extending from 3.4 to 5.4 eV and 2.9 to 4.5 eV, respectively, are believed to result from superposition of two low-lying singlet --> triplet transitions in each molecule. In norbornadiene these features have estimated intensity maxima at 3.4 and 3.9 eV, while in 1,4-cyclohexadiene they appear to be more highly overlapped, yielding a single intensity maximum at 4.29 eV. The singlet --> singlet excited state spectra of these molecules are discussed from the point of view of a model in which ethylene units interact via through-bond and through-space effects. In each of these four molecules, transitions to several superexcited states are observed.


Item Type:Article
Additional Information:Copyright © 1979 American Institute of Physics. (Received 13 June 1978) This work was supported in part by a contract (EY-76-S-03-767) from the Department of Energy. Report Code: CALT-767P4-173. Work performed in partial fulfillment of the requirements for [R.P.F.'s] Ph.D. degree in Chemistry at the California Institute of Technology, Pasadena, CA. Arthur A. Noyes Laboratory of Chemical Physics, Contribution No. 5807.
Subject Keywords:EXCITATION, ELECTRON–MOLECULE COLLISIONS, CYCLOALKENES, ENERGY–LEVEL TRANSITIONS, ALKENES
Record Number:CaltechAUTHORS:FRUjcp79a
Persistent URL:http://resolver.caltech.edu/CaltechAUTHORS:FRUjcp79a
Alternative URL:http://dx.doi.org/10.1063/1.437624
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:10257
Collection:CaltechAUTHORS
Deposited By: Archive Administrator
Deposited On:18 Apr 2008
Last Modified:26 Dec 2012 09:58

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