Hole-mixing effects in the ionization of some unsaturated oxo-compounds |
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Authors: | W Von Niessen G Bieri J Schirmer LS Cederbaum |
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Institution: | Institut für Physikatische Chemie, Technische Universität Braunschweig, D-3300 Braunschweig, West Germany;The Royal Institute of Technology, Physics Department, S-100 44 Stockholm, Sweden;Theoretische Chemie, Institut für Physikalische Chemie, Universität Heidelberg, D-6900 Heidelberg, West Germany |
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Abstract: | The He(II) photoelectron spectra of acrolein, propynal, propynol and propiolic acid are interpreted with the aid of ab initio many-body Green's function calculations in the outer and inner valence region. Koopmans' approximation fails to supply the correct ordering of electronic states in the radical cation if the lone pair orbital on the oxygen atom is of a′ symmetry. In the case of propynal the ordering of two ionic states o f equal symmetry is interchanged with respect to the Koopmans' orderin. A strong mixing of hole configurations occurs for outer valence states of propynol and propiolic acid. The implications of this mixing are briefly discussed. |
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