Nitric oxide adsorption effects on metal phthalocyanines.

The adsorption of nitric oxide (NO) on various metal phthalocyanines (MPc, M = Mn, Fe, Co) has been studied using first-principles calculations based on density functional theory (DFT). In this study, we investigated the fully optimized geometries and electronic structure of MPc. We found that the electronic structures of metal atoms are essential in shaping the ground-state electronic structure near the Fermi level. These states are defined mostly by the d orbitals of the transition-metal atoms and, to some degree, by the states of nitrogen and carbon atoms of the inner rings. The numerical calculations showed that NO strongly chemisorbs to the metal atom with an end-on configuration and results in a change in geometric and electronic structures of MPc. The N-O bond lengths are slightly longer than that of the isolated NO molecule. The orbital energy levels are shifted with respect to the Fermi level. The HOMO-LUMO gap widens as compared to bare MPc. These changes are attributed to the hybridization of the pi* orbital of NO and the d orbitals of the transition metal. Specifically, the interaction between dpi and the pi* orbital is significant for MnPc-NO, while the hybridization of d(z(2)) and the pi* orbital plays an important role in CoPc-NO.