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Strong correlation effects in the electron binding energies of phthalocyanine



Vertical ionization energies of free-base phthalocyanine are determined with the partial third-order and the third-order algebraic diagrammatic construction approximations of electron propagator theory. A triple-ζ plus polarization basis set is used in calculations performed with semidirect algorithms. Strong correlation effects occur for all final states with π holes. Whereas the Koopmans description of the lowest cationic state retains some qualitative validity, this approximation collapses in the remaining π final states. The results are in good agreement with photoelectron spectra. Two vertical electron affinities correspond to bound 2B1g and 2B2g anionic states of phthalocyanine. © 2009 Wiley Periodicals, Inc. Int J Quantum Chem, 2009