Valence One-Electron and Shake-Up Ionization Bands of Polycyclic Aromatic Hydrocarbons. III. Coronene, 1.2,6.7-Dibenzopyrene, 1.12-Benzoperylene, Anthanthrene
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...
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Published in | The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory Vol. 108; no. 42; pp. 9244 - 9259 |
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Main Author | |
Format | Journal Article |
Language | English |
Published |
American Chemical Society
21.10.2004
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Online Access | Get full text |
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Summary: | 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. |
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Bibliography: | ark:/67375/TPS-KS593MW8-H istex:145A9AC40951125E72693410535E53C2DD2E21D3 |
ISSN: | 1089-5639 1520-5215 |
DOI: | 10.1021/jp047224e |