First-principle study of the electronic structure and magnetism of lithium-adsorbed 3d transition-metal phthalocyanines

Based on density functional theory (DFT) calculations, the electronic structures and magnetic properties of 3d transition-metal phthalocyanine (TMPc, TM = Ti, V, Cr, Mn, Fe, Co, Ni and Cu), as well as Li -adsorbed phthalocyanines have been studied. The results show that the pristine TMPcs all have a good D-4h symmetry. When there is one Li atom adsorbed on TMPcs directly over (LiTMPc-alpha) or slantly above (LiTMPc-beta) the TM atoms, the geometries and electronic structures will be changed. lug LiTMPc-alpha systems, the central TM at orris will deviate from the molecular plane and the molecules exhibit good C-4v Symmetry. LiTMPc-beta systems are more stable than LiTMPc-alpha systems but it do not possess D46 and C4, symmetries. The total and local magnetic moments and the charge transfer are also presented. Finally, by using the orbit mixing and splitting theory under D-4h and C-4v symmetry, we get the ordering of the energy levels of the central TM atoms.