本文详细报道了SiBr_4的紫外光电子能谱(PES)及该化合物不同离子态(X~2T_2,A~2T_1,B~2E,C~2T_2等)的电子结构和性质.实验测得对应基态离子态的绝热电离能I_a(X~2T_2←X~1A_1)=10.532eV,X~2T_2离子态的振动频率为(450±30)cm~(-1).结合理论计算对紫外光电子能谱进行了指认和分析,结果表明X~2T_2,A~1T_1两个离子态存在明显的自旋-轨道耦合作用,自旋-轨道耦合导致的分裂分别为:0.27eV和0.53eV.此外,不同计算方法比较显示外层格林函数方法计算得到电离能与实验吻合很好. The electronic structure and properties of SiBr_4 (PES) and its ionic states (X ~ 2T_2, A ~ 2T_1, B ~ 2E, C ~ 2T_2, etc.) have been reported in detail in this paper. (X 2 T 2 ← X ~ 1A 1) = 10.532 eV, and the vibrational frequency of X ~ 2T 2 ion state is (450 ± 30) cm -1 .The binding energy spectra of UV-Vis spectra were identified The results show that there are obvious spin-orbit couplings between X ~ 2T_2 and A ~ 1T_1, and the spin-orbit coupling-induced splits are 0.27eV and 0.53eV, respectively. In addition, comparison of different calculation methods The calculation of the ionization energy by the outer Green’s function method is in good agreement with the experiment.