Zhang Chaoyang, Shu Yuanjie, Huang Yigang, Zhao Xiaodong, Dong Haishan
Institute of Chemical Materials, China Academy of Engineering Physics (CAEP), P.O. Box 919-311, 621900 Mianyang, Sichuan, PR China.
J Phys Chem B. 2005 May 12;109(18):8978-82. doi: 10.1021/jp0512309.
A new method of calculating the Mulliken net charges of the nitro group, Q(NO)()2, to assess impact sensitivities for nitro compounds is established. All calculations including optimizations and Mulliken population and frequency analyses are performed by density functional theory (DFT) and the general gradient approximation (GGA) method in Acceryls' code Dmol(3) with the Beck-LYP hybrid functional and the DNP basis set. As a result, the charges on nitro group can be regarded as a structural parameter to estimate the impact sensitivity on the bond strength, oxygen balance, and molecular electrostatic potential. The compound with more -Q(NO)()2 will be insensitive and gives a large value of impact sensitivity H(50)(). This method considering the molecular structure is applicable for almost all nitro compounds when the C-NO(2), N-NO(2), or O-NO(2) bond is the weakest in the molecule. According to the results in this paper, the compounds with -Q(NO)()2 >0.23e show H(50)() </= 0.4 m.
建立了一种计算硝基 Mulliken 净电荷 Q(NO)₂ 以评估硝基化合物撞击感度的新方法。所有计算，包括优化、Mulliken 布居和频率分析，均采用密度泛函理论 (DFT) 和广义梯度近似 (GGA) 方法，在 Acceryls 的代码 Dmol(3) 中使用 Beck-LYP 混合泛函和 DNP 基组进行。结果表明，硝基上的电荷可作为一个结构参数，用于估计对键强度、氧平衡和分子静电势的撞击感度。具有更多 -Q(NO)₂ 的化合物将不敏感，且撞击感度 H(50) 的值较大。当 C-NO₂、N-NO₂ 或 O-NO₂ 键是分子中最弱的键时，这种考虑分子结构的方法几乎适用于所有硝基化合物。根据本文的结果，-Q(NO)₂ > 0.23e 的化合物显示 H(50) ≤ 0.4 m。
