1,2,3三唑类衍生物与Na^+形成分子-离子相互作用对其感度的密度泛函理论研究

DFT computational studies on explosive sensitivity upon the formation of the molecule-cation interaction between derivatives of 1,2,3-triazole and Na^+

采用B3LYP和MP2(full)方法,在6-311++G**,6-311++G(2d,p)与aug-cc-pVTZ水平上对单硝基1,2,3-三唑类衍生物的硝基与Na^+离子形成分子-离子相互作用后,分子-离子相互作用与引发键N–NO_2离解能的变化值进行系统研究。研究结果表明,在形成分子-离子相互作用后,引发键增强,感度降低。引发键离解能的变化(ΔBDE)与分子-离子相互作用(Eint.)成良好的线性关系(R=0.9952)。原子-分子理论(AIM)也表明:在形成分子-离子相互作用时电子云密度向引发键转移,导致引发键强度加强,爆炸感度降低。

The changes of the bond dissociation energy of the trigger bond (N–NO2) upon the formation of the molecule- cation interaction between the nitro group of derivatives of 1,2,3-triazole and cation (Na+) have been systematically investigated using the B3LYP and MP2(full) methods with the 6-311++G**, 6-311++G(2d,p) and aug-cc-pVTZ basis sets. The strength of the trigger bond is enhanced and the explosive sensitivity is reduced upon the formation of molecule-cation interaction. The increment of the trigger bond dissociation energy (ΔBDE) in comparison with the monomer correlates well with the molecule-cation interaction energy (Eint.) (R=0.9952) The analyses of AIM shows that the electron density shifts toward the trigger bond upon the formation of the molecule-cation interaction. Thus, the trigger bond is strengthened and the sensitivity is reduced.