Institute of Chemical Materials, China Academy of Engineering Physics, P.O. Box 919-311, Mianyang 621900, Sichuan, People's Republic of China.
J Phys Chem B. 2010 Feb 18;114(6):2198-202. doi: 10.1021/jp909404f.
The ZPE-corrected C-NO(2) bond dissociation energies (BDEs(ZPE)) of a series of model C-nitro compounds and 26 energetic C-nitro compounds have been calculated using density functional theory methods. Computed results show that for C-nitro compounds the UB3LYP calculated BDE(ZPE) is less than the UB3P86 using the 6-31G** basis set, and the UB3P86 BDE(ZPE) changes slightly with the basis set varying from 6-31G** to 6-31++G**. For the series of model C-nitro compounds with different chemical skeletons, it is drawn from NBO analysis that the order of BDE(ZPE) is not only in line with that of the NAO bond order but also with that of the energy gap between C-NO(2) bonding and antibonding orbitals. It is found that for the energetic C-nitro compounds whose drop energies (Es(dr)) are below 24.5 J a good linear correlation exists between E(dr) and BDE(ZPE), implying that these compounds ignite through the C-NO(2) dissociation mechanism. After excluding the so-called trinitrotoluene mechanism compounds, a polynomial correlation of ln(E(dr)) with the BDE(ZPE) calculated at density functional theory levels has been established successfully for the 18 C-NO(2) dissociation energetic C-nitro compounds.
使用密度泛函理论方法计算了一系列模型 C-硝基化合物和 26 种含能 C-硝基化合物的 ZPE 校正 C-NO(2)键离解能（BDE（ZPE））。计算结果表明，对于 C-硝基化合物，UB3LYP 计算的 BDE（ZPE）小于使用 6-31G基组的 UB3P86，UB3P86 的 BDE（ZPE）随基组从 6-31G变化到 6-31++G**而略有变化。对于具有不同化学骨架的一系列模型 C-硝基化合物，从 NBO 分析得出，BDE（ZPE）的顺序不仅与 NAO 键序一致，而且与 C-NO(2)成键和反键轨道之间的能隙一致。对于能量为 24.5 J 以下的含能 C-硝基化合物，发现其下落能（Es(dr)）与 BDE（ZPE）之间存在良好的线性相关性，这表明这些化合物通过 C-NO(2)离解机制点火。在排除所谓的三硝基甲苯机制化合物后，成功地为 18 种 C-NO(2)离解能 C-硝基化合物建立了 ln(E(dr))与在密度泛函理论水平上计算的 BDE（ZPE）之间的多项式关系。
