摘要
采用密度泛函理论(DFT)中的B3LYP方法,在6 311G(d)水平上对AlmPn(m+n=2～6)团簇及其阴 离子的几何构型、电子结构和振动光谱等性质进行了理论研究.计算预测一些过去未知的团簇(例如Al3P-和 AlmPn(m+n≥5)),并认为单聚和二聚的AlP和(AlP)2团簇呈类似Si2和Si4团簇的平面和立体结构,而较大的 AlP团簇则完全不同于含相同电子数的Sin团簇.计算结果表明,单线态稳定结构的对称性比二重态稳定结构的 高.并在相同水平下计算了AlmPn-(m+n=2～6)的垂直电离能和AlmPn(m+n=2～6)的绝热电子亲合能,该结 果合理的解释了最近由Gomez等人报道的磷化铝团簇的阴离子光电子能谱.
The geometries, electronic states and energies of Al mP n (m+n=2～6) neutral and anionic clusters have been investigated using the density functional theory (DFT) method of Becke’s three-parameter hybrid exchange functional with the nonlocal correlation of B3LYP. Structural optimization and frequency analyses are performed with the basis of 6-311G(d). The calculations predict the existence of a number of previously unknown isomers (i.e., Al 3P – and Al mP n(m+n≥5)). The calculations have also predicted that small AlP and (AlP) 2 clusters adopt two-and three-dimensional structures characteristic of Si 2 and Si 4 clusters, while the structures of the larger AlP clusters are different completely from those of Si n clusters with the same electrons. The results show that the structures with the singlet have higher symmetries, while those with the doublet have lower symmetries. The vertical detachment energy of Al mP n (m+n=2～6) are also discused and the adiabatic electron affinities of Al mP n (m+n=2～6) and also discussed at the same level. The results agree satisfactorily with the anion photoelectron spectroscopy of aluminum phosphide clusters reported recently by Gomez et al.
