Valence one-electron and shake-up ionization bands of fluorene, carbazole and dibenzofuran

A comprehensive study of the He (I) ultra-violet photoelectron spectra of fluorene, carbazole and dibenzofuran is presented with the aid of one-particle Green's Function calculations employing the outervalence Green's Function (OVGF) approach and the third-order algebraic diagrammatic construction [ADC(3)] scheme, along with Dunning's correlation consistent basis sets of double and triple zeta quality (cc-pVDZ, cc-pVTZ). Extrapolations of the ADC(3) results for the outermost one-electron pi-ionization energies to the cc-pVTZ basis set enable theoretical insights into He (I) measurements within similar to 0.15 eV accuracy, up to the sigma-ionization onset. The lower ionization energy of carbazole is the combined result of mesomeric and electronic relaxation effects. OVGF/cc-pVDZ or OVGF/cc-pVTZ pole strengths smaller than 0.85 systematic ally corroborate a breakdown of the orbital picture of ionization at the ADC(3) level. Comparison is made with calculations of the lowest doublet-doublet excitation energies of the radical cation of fluorene, by means of time-dependent density functional theory (TDDFT). (c) 2013 Elsevier B.V. All rights reserved.