Structures,Electronic And Magnetic Properties Of Transition Metal Doped Zinc Sulfide

As a common metal sulfide,Zn S has a wide range of applications and great research values.Due to the defects of pure Zn S materials themselves,doping is an important method to improve the physical and chemical properties of metal sulfide materials.The structures,electronic and magnetic properties of the transition metal（TM）embedded Zn₁₂S₁₂clusters have been studied by first principles.The Sc,V,Fe,Ni,Zn,Nb,Rh,Ta and Pt atoms prefer to interact with the Zn₁₂S₁₂clusters by the binding energy per atom and the embedding energy.The maximum values（0.331|e|,1.032|e|and 0.436|e|）of the Mülliken charges occur at Sc,Y and Lu,the minimum values（-0.111|e|,-0.301|e|and-0.462|e|）of the Mülliken charges occur at Cu,Rh and Pt.The maximum spin densities（5.484|e|,5.039|e|,1.565|e|and 4.201|e|）of the TM atoms for the TM@Zn₁₂S₁₂clusters appear as Cr,Mo,Ru and Re embedded.The structures,electronic and magnetic properties of the TM substituted cage-like Zn₁₂S₁₂clusters have been analyzed by first principles.According to the different electronic affinity of TM and Zn atoms,the Rh,Pd,Ir,Pt and Au atoms prefer to enter the interior of the Zn₁₁S₁₂clusters.The maximums（0.700|e|,1.250|e|and 0.845|e|）of the Mülliken charges of the TMZn₁₁S₁₂clusters appear at Sc,Y and Lu,the minimums（-0.042|e|,-0.257|e|and-0.344|e|）of the Mülliken charges of the TMZn₁₁S₁₂clusters appear at Mn,Rh and Pt.Spin densities of all TMZn₁₁S₁₂clusters degenerate to zero.The structures,electronic and magnetic properties of the TM_n@Zn₁₈S₁₈（n=1-3）clusters have been investigated by using first-principles.The structure of pristine Zn₁₈S₁₈clusters is distorted obviously as the TM_nclusters embedded.The Ni₂@Zn₁₈S₁₈,Ti₃@Zn₁₈S₁₈,V₃@Zn₁₈S₁₈,Co₃@Zn₁₈S₁₈,and Ni₃@Zn₁₈S₁₈clusters are more structural stabilities than pristine Zn₁₈S₁₈cages by the binding energy per atom.The spin densities of the TM_n@Zn₁₈S₁₈（TM=Mn,Fe,Co and Ni,n=1-3）clusters are obviously affected by the number of the encapsulated TM atoms.The structures,electronic properties and dipole magnitudes of the TMZn₂₃S₂₄clusters have been investigated by using first-principles.The TMZn₂₃S₂₄（TM=Ti and Ni）clusters are more structurally stable than their neighbors by the binding energy per atom.Due to the TM（TM=Ti,Ni and Cu）atom locates at the edge of the ground-state TMZn₂₃S₂₄clusters,the hybridization between TM d orbitals and S p orbital near the Fermi level is less.And then the dipole magnitudes of the TMZn₂₃S₂₄（TM=Ti,Ni and Cu）clusters are larger than other clusters.