Theoretical Study On Sc Atom And Super Alkali Metal Doped X₁₂Y₁₂ Tetrahedral Clusters And Graphdiyne

In the past half century,the theoretical research of nanoclusters has great prospects in the fields of adsorption,catalyst,gas sensor,chemical storage,semiconductor,nonlinear optics and so on.Compared with other conformations of X₁₂Y₁₂clusters,their spherical tetrahedral structure is the most stable.The tetrahedral structure of X₁₂Y₁₂nanoclusters is a truncated octahedron composed of eight hexagons and six quadrilaterals.The cluster structure is perfect and has high symmetry and stability.Graphdiyne(GDY),as an allotrope of carbon,is characterized by abundant carbon chemical bonds,large conjugation system and wide interlayer spacing.Therefore,it shows various characteristics,such as conductivity,nonlinear optical sensitivity,heat resistance,etc.These characteristics make GDY widely used in electronic devices,detectors,gas storage,water purification and cancer treatment.Super atom is a kind of special cluster,which is composed of several or even dozens of atoms.It has similar chemical properties or the same electronic structure as the elements in the periodic table.As a very important part of the superatom,the superalkali has a lower ionization potential than the alkali metal,so it has a stronger reducibility.In this paper,GDY and X₁₂Y₁₂clusters were doped to obtain a new complex.The following three groups of doping systems have been studied by quantum chemical theoretical calculations.(1)Theoretical study of Sc doped X₁₂Y₁₂tetrahedral nanoclustersIn this study,we theoretically studied the geometric,electronic and nonlinear optical properties of 13 groups of X₁₂Y₁₂clusters and Sc doped clusters.We calculated the energy gap,ionization potential,chemical potential,chemical hardness and some nonlinear optical properties of the 13 groups of nanoclusters.The chemical stability,conductivity and nonlinear optical(NLO)properties of Sc doped nanoclusters were compared.The results show that the?₀of the doped cluster is greatly improved,which indicates that it can be used as a good nonlinear optical material.(2)Theoretical study of superalkali doped Mg₁₂O₁₂tetrahedral nanoclustersIn this study,we theoretically studied the geometric,electronic and nonlinear optical properties of Mg₁₂O₁₂complexes doped with superalkalis(Li₂F,Li₂Cl,Li₂Br,Li₂I,K₃O,CLi₅,NLi₄).The results show that the energy gap and chemical hardness of the doped nanoclusters decrease,and the reactivity of the doped nanoclusters increases.The?₀of Mg₁₂O₁₂nanoclusters doped with superalkalis increases obviously.Among these complexes,the strongest nonlinear optical response is Mg₁₂O₁₂@Li₂Br.(3)Theoretical study on superalkali doped graphite diyne complexesIn this part,we systematically studied the geometric,electronic and nonlinear optical(NLO)properties of the complexes formed by doping GDY with the superalkalis(Cs₂Cl,Cs₂F,PLi₄,NLi₄and NH₄)theoretically.We judge the stability of the complexes by interaction energy and vertical ionization energy,analyze the electronic properties by NBO analysis,energy gap value and charge transfer,the?and the?were analyzed by Multiwfn software,and use the two-level formula to analyze the relationship between the?and the time-dependent properties.The theoretical calculation results show that the study of GDY doped with superalkali is helpful to promote the potential application of new electronic nano devices and nonlinear optical materials.