Green's function study of the one-electron and shake-up ionization spectra of unsaturated hydrocarbon cage compounds.
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 pi-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.
Knippenberg
S
S
Group of Theoretical Chemistry, Department SBG, Hasselt University, Agoralaan, Gebouw D, B-3590 Diepenbeek, Belgium.
François
J-P
JP
Deleuze
M S
MS
D000475:Alkenes / Q000737:chemistry*; D001643:Bridged Bicyclo Compounds / Q000737:chemistry*; D001952:Bridged-Ring Compounds / Q000737:chemistry*; D003198:Computer Simulation; D004583:Electrons; D007659:Ketones / Q000737:chemistry*; D015394:Molecular Structure; D011789:Quantum Theory; D012680:Sensitivity and Specificity; D021241:Spectrometry, Mass, Electrospray Ionization / Q000379:methods
D000475:Alkenes; D001643:Bridged Bicyclo Compounds; D001952:Bridged-Ring Compounds; D007659:Ketones; C521608:bicyclo(2.2.1)heptane-2,5-dione; C521607:bicyclo(2.2.2)octane-2,5-dione; C521605:stella-2,6-diene; C521606:stella-2,6-dione