硅基过渡金属掺杂MSi_(12)^(-)(M=V,Cr,Mn)团簇的结构和性质

Structure and property of transition metal-doped silicon-based clusters of MSi_(12)^(-)(M=V,Cr,Mn)

基于密度泛函理论结合粒子群优化算法程序卡利普索,对硅基过渡金属掺杂团簇MSi_(12)^(-)(M=V,Cr,Mn)的几何结构、电子和光谱特性、热力学性质进行系统研究.结果表明,MSi_(12)^(-)(M=V,Cr,Mn)团簇的基态结构为M位于中心的鼓状高对称性(D_(3d),D_(3d)和C_(2h)点群对称)结构.基于该基态结构,讨论了体系的分子轨道、电荷转移和极化率等电子特性.此外,拟合出了体系的光电子能谱、红外和拉曼光谱,对主要特征峰进行了归属分析.最后,分析了体系的热力学性质.以期该研究能为过渡金属掺杂硅基纳米材料的实验制备和表征提供重要理论参考.

In this paper,the geometric structure,electronic and spectral properties,thermodynamic properties of MSi_(12)^(-)(M=V,Cr,Mn)clusters using density functional theory and crystal structure analysis by particle swarm optimization(CALYPSO)structure searching method.The results showed that the drum-shaped MSi_(12)^(-)clusters favored for M with high symmetry of D_(3d),D_(3d) and C_(2h) symmetry respectively.Based on the lowest energy structures,the electronic properties were analyzed by calculating the molecular orbitals,charge transfer and polarizability.In addition,the photoelectron spectra,infrared spectra and Raman spectra were predicted and could be used to identify the structures of these isomers from experiments.At last,thermodynamic properties were studied for the lowest energy structures of MSi_(12)^(-)(M=V,Cr,Mn)clusters.The authors hoped that the researches could supply powerful guidelines for future experimental synthesis and measurements of the transition metal-doped silicon based nanomaterials.