Mintz, Donald M. and Kuppermann, Aron (1979) Photoelectron spectroscopy of ethylene, isobutylene, trimethylethylene, and tetramethylethylene at variable angles. Journal of Chemical Physics, 71 (8). pp. 3499-3513. ISSN 0021-9606. http://resolver.caltech.edu/CaltechAUTHORS:20120726-111639575
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Using a HeI line 58.4 nm source lamp, photoelectron angular distributions were measured for the series of four olefins: ethylene, isobutylene (2‐methyl‐propene), trimethylethylene (2‐methyl‐2‐butene), and tetramethylethylene (2,3‐dimethyl‐2‐butene). From these, the asymmetry parameter β as a function of photoelectron energy was obtained for each of these molecules. The following important effects in the behavior of β are observed: (a) In the π orbital ionization regions of the spectrum of each molecule, β increases with increasing electron energy across the vibrational envelopes. (b) With increasing methyl substitution (and at a fixed photoelectron enegy) β for this band decreases. (c) In the region of the spectra of each of the methyl‐substituted ethylenes involving several 2pσ bands, this energy dependence of β behaves as if they constituted a single band, in spite of the widely differing orbital symmetries. (d) Over most of the 2pσ region of each molecule, β decreases with increasing photoelectron energy, except for the high ionization potential end of this region, where β increases instead. We attribute effects (b) and (d) to σ–π orbital mixing.
|Additional Information:||© 1979 American Institute of Physics. Received 13 November 1978. Online Publication Date: 25 July 2008. This work was supported in part by a contract (EY-76-S-03-767) from the Department of Energy. Report Code: CALT- 767P4-178. Work performed in partial fulfillment of the requirements for the Ph. D. degree in Chemistry at the California Institute of Technology. Contribution No. 5884.|
|Subject Keywords:||PHOTOELECTRON SPECTROSCOPY, ETHYLENE, 2−METHYLPROPENE, PINACOL, BUTENES, ANGULAR DISTRIBUTION|
|Other Numbering System:|
|Classification Code:||PACS: 33.60.+q|
|Official Citation:||Photoelectron spectroscopy of ethylene, isobutylene, trimethylethylene, and tetramethylethylene at variable angle Donald M. Mintz and Aron Kuppermann J. Chem. Phys. 71, 3499 (1979); http://dx.doi.org/10.1063/1.438739|
|Usage Policy:||No commercial reproduction, distribution, display or performance rights in this work are provided.|
|Deposited By:||Ruth Sustaita|
|Deposited On:||26 Jul 2012 21:48|
|Last Modified:||26 Dec 2012 15:44|
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