苯和苯胺类硝基衍生物热解机理和撞击感度的理论研究

A Theoretical Investigation on Pyrolysis Mechanism and Impact Sensitivity of Nitro Derivatives of Benzene and Aminobenzenes

在DFT-B3LYP/6-31G*水平获得苯和苯胺类硝基衍生物的全优化分子几何和电子结构.通过非限制性(U)B3LYP/6-31G*计算求得标题物各化学键离解能(BDE).用UHF-PM3MO方法求得引发键C—NO2键均裂反应的活化能(Ea).以静态指标(键集居数、前线轨道能级差和硝基上净电荷)和动态理论指标(BDE和Ea)阐明了热解引发机理,关联了实验撞击感度.运用SPSS程序关联静态和动态理论指标,表明它们均可以用作预示标题物的热解引发机理和撞击感度.

Nitro derivatives of benzene and aminobenzenes were optimized to obtain their molecular geometries and electronic structures at the DFT-B3LYP/6-31G＊ level. Using the unrestricted B3LYP/6-31G＊ method, bond dissociation energies （BDE） for all kinds of bonds were calculated. The UHF-PM3 MO method was employed to evaluate the thermolysis activation energies of trigger bond C--NO2. The static theoretical indexes （the Mulliken bond population, the gap between the frontier orbital energies and the net charge of the nitro group） and kinetic theoretical indexes （BDE and Ea） illustrate the pyrolysis mechanism and were correlated with the experimental impact sensitivity. Using SPSS program, the static and kinetic theoretical indexes were related with each other. And it was indicated that they can be used to promise the pyrolysis mechanism of the title compounds and the magnitude of impact sensitivity.