磷原子团簇P_5稳定结构的理论计算  

A THEORETICAL COMPUTATION ON THE STABL STRUCTURES OF PHOSPHORUS CLUSTERS P_(5)

作　　者：李如茵[1] 徐彩霞[1] 张宇蕾[1] 马思渝[1] 

机构地区：[1]北京师范大学化学学院,北京100875

出　　处：《北京师范大学学报（自然科学版）》2006年第3期279-282,共4页Journal of Beijing Normal University(Natural Science)

基　　金：北京市自然科学基金资助项目(2042013)

摘　　要：用MP2和DFT的B3LYP方法,在含有弥散函数的cc-pVDZ基组水平上,对磷原子团簇P5及其正、负离子可能存在的10种同分异构体进行扫描式优化,并通过振动分析对收敛的结果进行验证,以确定是否是稳定的平衡几何构型.结果表明,最稳定的P5为由正四面体的P4演变来的b结构的二重态,P5+和P5-则为由正方形P4演变来的e结构(正四棱锥)和j结构(平面正五边形)的单重态.这些与文献的报道是一致的,不同的是,其他稳定同分异构体的存在形式差别较大.例如,D2h的c结构是不存在的,而C2v的d结构则是新的发现.MP2 and B3LYP methods with AUG-cc-pVDZ basis sets are performed to optimize the 10 kinds of possible isomers of phosphorous clusters P5 and their cations and anions, and the converged results are verified by vibrational analysis in order to get the stable equilibrium geometries. The results show that the most stable P5 is the doublet state of b isomer evolved from regular tetrahedron P4 while the most stable P^＋5 and P^-5 are the singlet state of e, j isomers evolved from square P4, respectively. These are consistent with the reference reports. The distinction is that the existing forms of other stable isomers have lager differences from that of references, for example, c isomer of Dzh does not exist and d isomer of C2v is a new find.

关 键 词：磷原子团簇P5 同分异构体 B3LYP/AUG-cc-pVDZ MP2/AUG-cc-pVDZ 弥散函数 振动分析 

分 类 号：O641.1[理学—物理化学]