Valence one-electron and shake-up ionization bands of fluorene, carbazole and dibenzofuran (vol 417, pg 17, 2013)

Abstract

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 p-ionization energies to the cc-pVTZ basis set enable theoretical insights into He (I) measurements within 0.15 eV accuracy, up to the r-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 systematically 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).