Journal of Electron Spectroscopy and Related Phenomena 94 (1998) 243-252
Isomeric sensitivity of the C ls spectra of xylenes
I.G. Eustatiu, B. Huo, S.G. Urquhart', A.P. Hitchcock*
Department of Chemistry, McMaster University, Hamilton, L8S 4M1, Canada
Received 1 December 1997; revised 10 March 1998; accepted 10 March 1998

Oscillator strengths for C ls inner-shell excitation of the isomeric xylenes (ortho-, meta- and para-) have been derived from electron energy loss spectra recorded under scattering conditions dominated by electric dipole transitions. The lineshape of the C ls ® p * transition is found to be dependent on the substitution pattern, with para-xylene exhibiting two components, ortho-xylene a single asymmetric peak, and meta-xylene a single symmetric peak at an instrumental resolution of 0.35 eV. Improved orbital ab imtio calculations were carried out on all three species, providing spectral shapes in reasonable agreement with experiment. 'The calculations indicate that the transition responsible for the splitting which is observed only in the C ls spectrum of para-xylene is associated with the methyl-substitlited ring carbons, for which there is a somewhat larger chemical shift in the para relative to the ortho- or meta-isomers. These results are compared to other recent studies of C ls spectroscopy of di-substituted benzenes (dimethylphthalates and nitroanilines) in order to investigate trends in the sensitivity of C ls spectroscopy to isomeric substitution patterns.

Keywords: EELS; C ls excitation spectra; Xylenes; Isomeric effects; Ab initio calculations

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