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

•In detail comparison between the valence band structure of H2Pc, FePc and MnPc.•Comparison between the gas phase samples and thin evaporated films on Au (111).•Detailed analysis of the atomic orbital contributions to the valence band features.•DFT/HSE06 study of the valence band electronic structure of H2Pc, FePc and MnPc. 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). We have analysed in detail the atomic orbital composition of the valence band both experimentally, by making use of the variation in photoionization cross-sections with photon energy, and theoretically, by means of density functional theory. The atomic character of the Highest Occupied Molecular Orbital (HOMO), reflected on the outermost valence band binding energy region, is different for MnPc as compared to the other two molecules. The peaks related to the C 2p contributions, result in the HOMO for H2Pc and FePc and in the HOMO-1 for MnPc as described by the theoretical predictions, 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 Pc molecules.