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Photoelectron spectroscopy of ethylene, isobutylene, trimethylethylene, and tetramethylethylene at variable angles

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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Abstract

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.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1063/1.438739DOIUNSPECIFIED
http://jcp.aip.org/resource/1/jcpsa6/v71/i8/p3499_s1PublisherUNSPECIFIED
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.
Funders:
Funding AgencyGrant Number
Department of Energy (DOE)EY-76-S-03-0767
Subject Keywords: PHOTOELECTRON SPECTROSCOPY, ETHYLENE, 2−METHYLPROPENE, PINACOL, BUTENES, ANGULAR DISTRIBUTION
Other Numbering System:
Other Numbering System NameOther Numbering System ID
Caltech Arthur Amos Noyes Laboratory of Chemical Physics5884
Caltech Report CodeCALT-767P4-178
Classification Code:PACS: 33.60.+q
Record Number:CaltechAUTHORS:20120726-111639575
Persistent URL:http://resolver.caltech.edu/CaltechAUTHORS:20120726-111639575
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.
ID Code:32746
Collection:CaltechAUTHORS
Deposited By: Ruth Sustaita
Deposited On:26 Jul 2012 21:48
Last Modified:26 Dec 2012 15:44

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