Valence One-Electron and Shake-Up Ionization Bands of Polycyclic Aromatic Hydrocarbons. III. Coronene, 1.2,6.7-Dibenzopyrene, 1.12-Benzoperylene, Anthanthrene

• Published in: The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory Vol. 108; no. 42; pp. 9244 - 9259
• Main Author: Deleuze, Michael S
• Format: Journal Article
• Language: English
• Published: American Chemical Society 21.10.2004
• ISSN: 1089-5639; 1520-5215
• DOI: 10.1021/jp047224e

A comprehensive theoretical study of the He(I) UV photoionization spectra of coronene, 1.2,6.7-dibenzopyrene, 1.12-benzoperylene, and anthanthrene up to electron binding energies of ∼18 eV is presented with the aid of one-particle Green's function calculations performed using the outer-valence Green's function (OVGF) approach and the third-order algebraic-diagrammatic construction [ADC(3)] scheme, using Dunning's correlation-consistent polarized valence basis set of double-ζ quality and the 6-31G basis set, respectively. The deviations from the one-electron OVGF/cc-pVDZ binding energies and experimental results most generally do not exceed 0.3 eV. OVGF/cc-pVDZ pole strengths smaller than 0.85 systematically corroborate a breakdown of the orbital (or one-electron) picture of ionization at the ADC(3)/6-31G level. A comparison has been made with calculations of the lowest doublet−doublet excitation energies of the related radical cations, by means of time-dependent density functional theory (TDDFT) and the Becke−Lee−Yang−Parr (BLYP) functional: Because of systematic and significant underestimations of the lowest [π0* ← σ] transition energies in the cations, this approach has led to erroneous identifications of the σ-ionization onset of the neutral molecules.