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Green's function study of the one‐electron and shake‐up ionization spectra of unsaturated hydrocarbon cage compounds
Author(s) -
Knippenberg S.,
François J.P.,
Deleuze M. S.
Publication year - 2006
Publication title -
journal of computational chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.907
H-Index - 188
eISSN - 1096-987X
pISSN - 0192-8651
DOI - 10.1002/jcc.20461
Subject(s) - chemistry , ionization , ionization energy , spectral line , valence (chemistry) , valence electron , electron , atomic physics , computational chemistry , physics , quantum mechanics , organic chemistry , ion
The valence one‐electron and shake‐up ionization spectra of stella‐2,6‐diene, stella‐2,6‐dione, bicyclo‐[2.2.2]‐octane‐2,5‐dione, and bicyclo‐[2.2.1]‐heptane‐2,5‐dione have been exhaustively studied, up to the double ionization threshold and beyond, by means of one‐particle Green's function theory. This study is based on calculations employing the outer‐valence Green's function and the third‐order algebraic diagrammatic construction schemes, along with a variety of basis sets. A comparison is made with available ultraviolet (He I) photoelectron and (e, 2e) electron‐impact ionization spectra, with main focus on the identification of spectral fingerprints for cyclic strains and through‐bond π‐conjugation. As a byproduct, our results demonstrate that it is impossible to reliably assign complex (e, 2e) ionization spectra by resorting only to Hartree–Fock or Kohn–Sham orbital energies and to the related electron momentum distributions. © 2006 Wiley Periodicals, Inc. J Comput Chem, 2006