Journal of Chemical Physics, Vol.106, No.8, 3258-3269, 1997
Theoretical-Study of the Valence Ionization Energies and Electron-Affinities of Linear C-2N+1 (N=1-6) Clusters
The valence level hole spectral functions of linear C-2n+1 (n=1-6) clusters are calculated by the ab initio third order algebraic diagrammatic construction [ADC(3)] Green function method and the outer-valence Green function (OVGF) method using an extended basis set. The vertical electron affinities of linear C-2n+1 (n=1-6) clusters are also evaluated by the same methods. With an increase of the number of carbon atoms, the KT energy levels become more closely spaced and start to form quasi-continua. The original spectral strength of the main line becomes distributed over several lines of comparable intensity. With an increase of the number of carbon atoms, the one-electron (or even quasi-particle) picture of the ionization breaks down because of the interaction between the initial single hole level and the final two-hole-one-particle levels. The spectral intensity of the first four ionization levels remains fairly constant independent of the number of carbon atoms. The agreement of the affinities of C-2n+1 (n=1-6) with experiment is in general very good. Two anionic states are found to be bound for C-9, C-11 and C-13.
Keywords:SMALL CARBON CLUSTERS;PROPAGATOR CALCULATIONS;MOLECULAR-STRUCTURE;BINDING ENERGIES;C-6;SPECTROSCOPY;DIANIONS;UPS