Croatica Chemica Acta, Vol. 57 No. 5, 1984.
Original scientific paper
Breakdown of the One-Electron Picture of Ionization for Hydrocarbon n Systems
Jens Spanget-Larsen
; Royal Danish School of Educational Studies, Department of Chemistry, Emdrupvej 115 B, DK-2400 Copenhagen NV, Denmark
Abstract
The photoelectron spectra of a number of characteristic hydrocarbon
n systems are analyzed in terms of Koopmans' and non-
Koopmans' contributions within a< limited configuration interaction ·
(CI) framework. The results for several compounds, including quinodimethanes,
fulvenes, annulenes, and related systems, suggest
frequent invalidity of the one-electron picture of ionization even
in the outer valence region. A similar situation may apply for the
corresponding anion spectra, as indicated by the electron transmission
spectrum of p-benzoquinone. This and sever a'l recent
investigations demonstrate a general need for the introduction of
a more realistic excited state concept than the one implied by
Koopmans' approximation.
Keywords
Hrčak ID:
194069
URI
Publication date:
14.1.1985.
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