Atomic contributions to the valence band photoelectron spectra of metal-free, iron and manganese phthalocyanines

The present work reports a photoelectron spectroscopy study of the low-energy region of the valence band of metal-free phthalocyanine (H2Pc) compared with those of iron phthalocyanine (FePc) and manganese phthalocyanine (MnPc). Density Functional Theory calculations have been used to resolve the atomic orbital composition of the valence spectra of all the phthalocyanines (Pcs) analyzed in this study. Moreover we show how the atomic character of the Highest Occupied Molecular Orbital (HOMO) is reflected on the outermost valence band binding energy region. The intensity related to the C 2p contributions, resulting in the HOMO for H2Pc and FePc and in the HOMO-1 for MnPc as described by the theoretical predictions is in very good agreement with the experimental results. The DFT simulations, discerning the atomic contribution to the density of states, indicate how the central metal atom interacts with the C and N atoms of the molecule, giving rise to different partial and total density of states for these three different Pc molecules