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Please use this identifier to cite or link to this item: http://hdl.handle.net/1942/5779

Title: Valence one-electron and shake-up ionization bands of polycyclic aromatic hydrocarbons: III: coronene, 1.2,6.7-dibenzopyrene, 1.12-benzoperylene, anthanthrene
Authors: DELEUZE, Michael
Issue Date: 2004
Citation: The journal of physical chemistry: A: molecules, spectroscopy, kinetics, environment and general theory, 108(42). p. 9244-9259
Abstract: 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 similar to18 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-zeta 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 [pi(0)* <-- sigma] transition energies in the cations, this approach has led to erroneous identifications of the sigma-ionization onset of the neutral molecules.
URI: http://hdl.handle.net/1942/5779
DOI: 10.1021/jp047224e
ISI #: 000224538900033
ISSN: 1089-5639
Category: A1
Type: Journal Contribution
Validation: ecoom, 2005
Appears in Collections: Center of Molecular and Materials Modelling

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