团簇NiPS3光谱性质的密度泛函分析

运用密度泛函理论，在B3LYP/def2-tzvp水平下，对团簇NiPS₃的初始构型进行优化计算，获得9种优化构型。从红外光谱、偶极矩、拉曼光谱和极化率这4个方面对团簇NiPS₃的光谱学性质进行分析，结果表明：团簇NiPS₃的所有优化构型均为C1对称，二重平面非对称构型1^（2）最为稳定；二重立体戴帽三角锥构型5^（2）和四重立体戴帽三角锥构型3^（4）的红外活性和拉曼活性均相近；二重立体三角双锥构型2^（2）、四重立体三角双锥构型1^（4）的红外特征振动最高峰以及二重平面非对称构型4^（2）、四重立体戴帽三角锥构型3^（4）的拉曼特征振动最高峰均发生了红移现象；团簇NiPS₃的红外活性受其几何形态的影响，拉曼活性受其极化率张量大小的影响。

Density functional analysis of the spectral properties of the NiPS3 cluster

Using density functional theory, the initial configuration of the NiPS₃ cluster was optimized at the B3LYP/def2-tzvp level, and nine optimized configurations were obtained. The spectroscopic properties of the NiPS₃ cluster were analyzed by infrared spectroscopy, dipole moment values, Raman spectroscopy and polarizability values. The results show that all the optimized configurations of the NiPS₃ cluster have C1 symmetry, and the double plane asymmetric configuration 1⁽²⁾ is the most stable. The infrared and Raman activities of the double stereoscopic capped triangular cone configuration 5⁽²⁾ and the quadruplet stereoscopic capped triangular cone configuration 3⁽⁴⁾ are similar. The strongest infrared characteristic vibration peaks of the double stereoscopic triangular bicone configuration 2⁽²⁾ and the quadruple stereoscopic triangular bicone configuration 1⁽⁴⁾, as well as the strongest Raman characteristic vibration peaks of the double plane asymmetric configuration 4⁽²⁾ and the quadruplet stereoscopic capped triangular cone configuration 3⁽⁴⁾, are all redshifted. The infrared activity of the NiPS₃ cluster is affected by its geometric shape, and the Raman activity is affected by its polarization tensor.