团簇Co_(3)FeP催化活性位点的研究

Research on the Catalytic Active Site of Cluster Co_(3)FeP

以团簇Co_(3)FeP为局域结构模型,在B3LYP/Lan12dz量子化学水平下,利用拓扑学原理和密度泛函理论分别对团簇Co_(3)FeP三重态和单重态的初始构型进行全参数的优化和频率计算,得到4种单重态优化构型和5种三重态优化构型;利用前线轨道理论和库普曼斯定理研究构型的几何形态和自旋多重度对团簇Co_(3)FeP催化活性的影响。结果表明:构型的几何形态和自旋多重度影响团簇Co_(3)FeP的催化活性,除构型1(3),2(3)和3(3)外,其余构型易催化底物中含有亲电试剂的反应;所有优化构型中,构型3(3)的催化活性最好,Co是团簇Co_(3)FeP唯一有效的催化活性位点。

Taking cluster Co_(3)FeP as the local structure model,at the level of B3LYP/Lan12dz quantum chemistry,the topology principles and density functional theory were used to optimize triplet and singlet states and calculate the frequencies,and 4 singlet optimized configurations and 5 triplet optimized configurations were obtained.The effects of geometry and spin multiplicity on the catalytic activity of cluster Co_(3)FeP were studied by using the frontier orbital theory and Koopmans theorem.The results show that the geometry and spin multiplicity of the configuration affect the catalytic activity.Except for the configurations 1(3),2(3)and 3(3),the other configurations can easily catalyze the reactions with electrophilic reagents in the substrate.Among all the optimized configurations,configuration 3(3)has the best catalytic activity,and Co is the only effective catalytic active site of cluster Co_(3)FeP.