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

Abstract

Based on density functional theory (DFT) calculations, the electronic structures and magnetic properties of [Formula: see text] 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 [Formula: see text] symmetry. When there is one Li atom adsorbed on TMPcs directly over (LiTMPc-[Formula: see text]) or slantly above (LiTMPc-[Formula: see text]) the TM atoms, the geometries and electronic structures will be changed. For LiTMPc-[Formula: see text] systems, the central TM atoms will deviate from the molecular plane and the molecules exhibit good [Formula: see text] symmetry. LiTMPc-[Formula: see text] systems are more stable than LiTMPc-[Formula: see text] systems but it do not possess [Formula: see text] and [Formula: see text] symmetries. The total and local magnetic moments and the charge transfer are also presented. Finally, by using the orbit mixing and splitting theory under [Formula: see text] and [Formula: see text] symmetry, we get the ordering of the energy levels of the central TM atoms.