团簇Ni_(4)P的催化性质和磁性

Catalytic and magnetic properties of cluster Ni_(4)P

以团簇Ni4P作为二元体系Ni-P非晶态合金的局域结构,采用密度泛函理论,在B3LYP/Lanl2dz水平下分别对不同重态下的构型进行优化计算,从HOMO、LUMO轨道贡献、各轨道未成对电子数、磁矩和自旋态密度角度分析发现:Ni、P原子对轨道贡献率受空间结构的影响,但受自旋多重度的影响极小;Ni原子是前线轨道的主要贡献者,P原子对其贡献亦不可忽略,说明催化活性是以Ni原子为主,P原子为辅所提供,且Ni原子最可能为团簇Ni4P的催化活性位点;构型1(4)~2(2)的磁性由d轨道上的自旋向上的α电子贡献,且四重态贡献较二重态更为显著,构型3(4)~3(2)的磁性主要由p轨道贡献;构型1(4)的磁矩分布范围最大,构型2(4)的磁矩分布次之;电子自旋具有不确定性,导致其α、β电子发生部分偏转。

Cluster Ni4P was used as the local structure of a binary Ni-P amorphous alloy.The density functional theory(DFT)was used to optimize configurations at different heavy states of the B3LYP/Lanl2dz level.The results show that the contribution rates of Ni and P atoms to the orbitals are affected by the spatial structure,but the effect of spin multiplicity is very weak.Ni atoms are the main contributor of the frontier orbitals,but P atoms cannot be ignored.Therefore,the catalytic activity is mainly provided by Ni atoms and supplemented by P atoms,and Ni atoms are most likely the sites for catalytic activity of the cluster Ni4P.The magnetic contribution of the configurations 1(4)~2(2)are mainly fromαelectrons spinning up on the d orbital,and the contribution of quadruple state is more than that of double state.The magnetic properties of the configurations 3(4)~3(2)are mainly contributed by the p orbital.The magnetic moment distribution range of the configuration 1(4)is the largest,followed by the configuration 2(4).The uncertainty of electron spin results in partial deflection ofαandβelectrons.