HcnS^—与HSC^—n簇离子的量子化学从头计算

应用量子化学从头计算能量解析梯度法，以ＨＦ６／３１Ｇ为基组优化了ＨＣｎＳ＾－与ＨＳＣ＾－ｎ（ｎ＝１～９）同分异构团簇离子的几何结构，计算了它们的电子总能量，结果显示ＨＣｎＳ＾－比相应的ＨＳＣ＾－ｎ稳定，从相邻簇离子的能量差及簇离子的平均原子结构能可知ｎ为偶数的ＨＣｎＳ＾－与ＨＳＣｎ＾－较ｎ为奇数的簇离子稳定，能量的差异随着ｎ的增加而逐渐减小，计算和实验结果完全相符，还分别计算了ＨＣｎＳ＾－失去Ｈ，

Ab Initio Calculations on HC_nS~- and HSC_n~- Cluster Ions

Ab initio calculations were carried on the cluster anions composed of 1-9 carbon atoms, a sulfur atom and a hydrogen atom. Two structural isomers, HCnS- and HSCn,were considered and HF/6-31Gbasis set was selected for the calculation of the optimum molecular geometry, total electron energy and fragmentation energy of various dissociation paths. The calculated results show that, among the two structural isomers, HCnS- is more stable than HSCn, and the cluster anions with even n are more stable than those with odd n.The calculation result is consistent with the experimental observations.