掺钌硅原子簇的结构及其稳定性研究  

Structures and Stabilities of the Ruthenium-Doped Silicon Clusters

作　　者：刘源[1] 李国良[1] 陈红雨[1] 李前树[1] 

机构地区：[1]华南师范大学化学与环境学院,环境理论化学省部共建教育部重点实验室,广州市能源转化与储能材料重点实验室,广州510006

出　　处：《华南师范大学学报（自然科学版）》2014年第1期56-64,共9页Journal of South China Normal University(Natural Science Edition)

基　　金：国家重点基础研究发展计划项目(2009CB226109);广东省自然科学基金项目(10151063101000041)

摘　　要：采用密度泛函理论中的B3LYP方法,结合6311SDD基组,系统地研究了掺钌硅原子簇RuSi n(n=1~14)的几何结构、稳定性以及电子性质.结果表明,当n>3时,RuSi n的基态由平面结构转为三维立体结构.随着硅原子数由1增长到14,RuSi n原子簇中Ru原子的位置逐渐从原子簇表面转移到原子簇内部.当n=12时,Ru原子完全陷入原子簇结构中,形成一个以Ru为中心的硅笼结构.自然键轨道分析表明RuSi n(n=2~14)的基态结构中都存在三中心键,有利于这些结构的稳定性.此外,RuSi n(n=1~14)原子簇各基态结构的平均结合能、二阶差分能、HOMO-LUMO能隙、电离势、电子亲合势等数据都表明RuSi12的基态结构的稳定性很高.该文研究结果有望对今后有关掺钌硅原子簇的质谱和光电子能谱等研究提供指导和帮助.The geometries, stabilities and electronic properties of the ruthenium-doped silicon clusters RuSin （ n = 1 ~ 14） have been systematically investigated using density functional theory method at the B3LYP/6311 SDD level. The results show that the ground state structures of RuSin change from planar to three-dimensional for n 〉 3. The e- quilibrium site of the Ru atom in RuSin gradually changes from convex, surface, to interior of the cluster as the number of Si atoms varying from 1 to 14. Starting from n = 12, the Ru atom completely falls into the center of the Sin frame, forming Ru-centered Sin cage-like structures. Natural bond orbital analysis shows that there are three- centered bonds in the ground state structures of the RuSin clusters, which should account for their higher stability. Furthermore, average binding energies, second order energy differences, HOMO-LUMO gaps, vertical ionization potentials, vertical electron affinities and charge transfers are also discussed for the lowest-lying RuSin isomers. Ac- cording to its relatively large Eh and A2E values, the RuSi^2 cluster with Ru-centered perfect hexagonal prism struc- ture has higher stability.

关 键 词：掺钌硅原子簇 结构 稳定性 密度泛函理论 B3LYP方法 

分 类 号：O64[理学—物理化学]