团簇NiMo3P极化率与催化性质的研究

为了探究团簇NiMo₃P各优化构型的形变情况，并寻找催化性能最优异的团簇NiMo₃P构型，根据拓扑学原理，在B3LYP泛函条件下，采用Lan12dz基组运用密度泛函理论对团簇NiMo₃P进行优化计算，得到4种四重态、5种二重态共9种稳定构型。对团簇NiMo₃P的变形性能进行分析发现：团簇极化率对于几何结构具有很强的依赖性，构型1^（2）的结构最为紧凑，不易发生形变。对前线轨道进行分析发现：金属原子与非金属原子相比具有更好的催化活性；在Ni、Mo、P 3种原子中，Mo原子最有可能是团簇潜在的催化活性位点；在催化反应中，团簇NiMo₃P具有强的电子接受能力，但其提供电子的能力亦不可忽略；构型2^（2）的能隙差值最小，亲电指数值最高，反应活性最强。

Polarizability and catalytic properties of NiMo3P clusters

We have studied the deformation of each optimized configuration of the NiMo₃P cluster, in order to find the cluster configuration with the best catalytic performance. According to the topological principle, using the B3LYP functional, and the Lan12dz basis set, density functional theory has been employed to optimize the structure of the NiMo₃P cluster. Four quartet states and five doublet states were obtained, giving nine stable configurations in total. The deformation performance of the NiMo₃P cluster was analyzed. It was found that the cluster polarizability has a strong dependence on its geometry. The structure of configuration 1⁽²⁾ is the most compact and is not easily deformed. Analysis of the frontier molecular orbitals showed that the metal atoms have better catalytic activity than the non-metal atom, and the Mo atoms are the most likely catalytic site in the cluster. In the catalytic reaction, the cluster NiMo₃P has strong electron acceptor ability, but its additional ability to donate electrons can not be ignored. Configuration 2⁽²⁾ has the smallest HOMO-LUMO energy gap, the highest electrophilic index value, and the highest reactivity.