在应用ＤＶ－Ｘａ自洽场方法研究Ｃｕｎ、Ａｇｎ、Ａｕｎ原子簇电子结构基础上，分析了原子簇中原子轨道间的相互作用及其大小随几何构型的变化，并讨论了原子簇的Ｘａ总能量与原子簇几何构型的关系。采用单、双过渡态理论方法分别计算原子簇分子轨道的电离能和分子轨道的电子跃迁能，结果表明Ａｇｎ的电离能计算值与实验值符合较好，而Ａｕｎ原子簇则有一定偏差，这可能是由Ａｕｎ的较大相对论效应引起的，Ａｇ４的电子跃迁能与实验值亦符合较好。 Based on the study of the electronic structure of Cun, Agn and Aun clusters by using DV-Xa self-consistent field method, the interaction between atomic orbits and the variation of their size with geometric configuration have been analyzed. The Xa The Relationship Between Total Energy and Cluster Geometry. Single and double transition state theory were used to calculate the ionization energies and molecular orbital energies of the molecular clusters, respectively. The results show that the calculated ionization energy of Agn is in good agreement with the experimental data, while the Aun cluster has a certain deviation It may be caused by the larger relativistic effect of Aun. The electron transition energy of Ag4 is also in good agreement with the experimental data.