对Li,Na和K叠氮盐晶体进行DFT-B3LYP计算研究,求得其能带和电子结构,探讨了结构-性能关系.从带隙约为0.23～0.25（a.u.）和前沿能带较平伏推知碱金属叠氮盐晶体为绝缘体.原子间重叠布居和电荷密度分析表明,碱金属离子与叠氮离子以典型离子键相结合.经基组叠加误差（BSSE）校正求得LiN3,α-NaN3和 KN3的晶格能分别为-852.30,-771.45和-614.78kJ·mol-1,与文献值相近.晶体前沿轨道主要由叠氮根端位氮原子轨道组成,金属离子对LUMO贡献极小;电子由HOMO向LUMO跃迁难于进行,根据“最易跃迁原理”可预测碱金属叠氮盐均较钝感. DFT-B3LYP calculations of Li, Na and K azide crystals were carried out to study their energy bands and electronic structures, and the structure-property relationship was discussed. From the band gap of about 0.23-0.25 (au) It is deduced that the alkali metal azide crystal is an insulator.The intermolecular overlap population and charge density analysis show that the alkali metal ion and azide ion are bound by typical ionic bond.The LiN3, The lattice energies of NaN3 and KN3 are -852.30, -771.45 and -614.78kJ · mol-1, respectively, which are close to the values ​​reported in the literature.The frontier orbital of crystal mainly consists of the terminal azide orbitals of azide, and the metal ions contribute minimally to LUMO ; The transition from HOMO to LUMO is difficult to proceed. According to “the easiest transition principle”, the alkali metal azide salt is more insensitive.