Please use this identifier to cite or link to this item: http://hdl.handle.net/1942/4957
Title: Valence one-electron and shake-up ionization bands of carbon clusters. III. The Cn (n=5,7,9,11) rings
Authors: DELEUZE, Michael 
GIUFFREDA, Maria 
FRANCOIS, Jean-Pierre
Issue Date: 2002
Publisher: AMER CHEMICAL SOC
Source: JOURNAL OF PHYSICAL CHEMISTRY A, 106(23). p. 5626-5637
Abstract: The 1h (one-hole) and 2h-1p (two-hole; one-particle) shake-up bands in the valence ionization spectrum of odd-membered carbon rings (C-5, C-7, C-9, C-11) are investigated by means of the third-order algebraic diagrammatic construction [ADC(3)] scheme for the one-particle Green's function. Despite a severe dispersion of the sigma- and pi- ionization intensity over intricately dense sets of satellites, the present study undoubtedly confirms that structural fingerprints in ionization spectra could be usefully exploited to discriminate the cyclic C-5, C-7, C-9, and C-11 species from their linear counterparts in plasma conditions. Such spectra could also be used to indirectly trace very fine details of the molecular structure, such as bond length alternations, out-of-plane distortions, or the strength of cyclic strains. Both structurally and electronically, the cyclic isomers of the C-5 and C-9 clusters must be described as even-twisted cumulenic tori, whereas the C-7 and C-11 cyclic species are simply planar polyynic rings. In comparison with their linear counterparts, all species display an intrinsically lower propensity to electronic excitations, marked by a rather significant increase of the fundamental HOMO-LUMO band gap. On the other hand, the lower symmetry of the cyclic clusters, C-5 and C-9 in particular, permits many more configuration interactions in the cation. The ultimate outcome of these two opposite factors is, overall, a severe enhancement of the shake-up fragmentation of ionization bands, compared with the linear isomers.
Keywords: DENSITY-FUNCTIONAL THEORY; EXACT EXCHANGE CONTRIBUTIONS; PARTICLE GREENS-FUNCTION; COUPLED-CLUSTER; PROPAGATOR THEORY; BASIS-SETS; MOLECULES; SPECTRA; ATOMS; SPECTROSCOPY
Document URI: http://hdl.handle.net/1942/4957
ISSN: 1089-5639
e-ISSN: 1520-5215
DOI: 10.1021/jp014
ISI #: 000176161700011
Category: A1
Type: Journal Contribution
Validations: ecoom 2003
Appears in Collections:Research publications

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