团簇NiCo_(2)S_(4)的极化率与反应活性

Polarizability and Reactivity of Cluster NiCo_(2)S_(4)

通过密度泛函理论(DFT)在B3LYP/Lan12dz水平下对团簇NiCo_(2)S_(4)进行优化计算,确定单、三重态下的12种优化构型,并对其极化率和反应活性进行研究.结果表明:构型2(1)的平均极化率最小,即在外场作用下,结构最稳定;构型3^((1))则最大,即结构最不稳定.此外,平均极化率和极化率各向异性不变量均受自旋多重度和结构多样性的影响.在强吸电子环境中,构型3^((3))、4^((3))和6(1)的反应活性较强,构型2^((3))和4^((1))的较弱;在强给电子环境中,构型2^((3))、3^((1))和5^((1))的反应活性较强,构型1^((1))和4^((3))的较弱;在相对稳定的环境中,构型3^((3))和6^((1))的反应活性较强,构型1^((1))和4^((1))的较弱.

The density functional theory(DFT)was used to optimize the cluster NiCo_(2)S_(4) at the B3LYP/Lan12dz level.Twelve optimized configurations of NiCo_(2)S_(4) in the singlet and triplet states were determined,with their polarizability and reactivity studied.The results show that the average polarizability of configuration 2^((1))is the smallest,that is,its most stable structure,while configuration 3^((1))is the largest,that is,the most unstable structure.In addition,both the average polarizability and the anisotropy invariant of the polarizability are affected by the spin multiplicity,whereas the energy has little effect on them.At the same time,the average polarizability is also related to the structural diversity of the configurations.In strong electron-withdrawing environment,the reactivity of configuration 3^((3)),4^((3))and 6(1)is stronger than that of configurations 2^((3))and 4^((3));in strong electron donating environment,the reactivity of configurations 2^((3)),3^((1))and 5^((1))is stronger than that of configurations 1^((3))and 4^((3));in relatively stable environment,the reactivity of configurations 3^((3))and 6^((1))is stronger than that of configurations 1^((3))and 4^((3)).