Li Xiaohong, Tang Zhengxin, Zhang Xianzhou, Yang Xiangdong
College of Science, Henan University of Science and Technology, Luoyang, PR China.
J Hazard Mater. 2009 Jun 15;165(1-3):372-8. doi: 10.1016/j.jhazmat.2008.10.003. Epub 2008 Oct 11.
Quantum chemical calculations are used to compute the heats of formation (HOFs) for 24 nitroester (NE) energetic compounds in which only 5 nitroester energetic compounds have the available experimental heats of formation. The heats of formation of the five compounds are calculated from isodesmic reactions by employing the hybrid density functional theory (DFT) (B3LYP, B3PW91, and B3P86) methods with 6-31G** and 6-311G** basis sets. It is demonstrated that B3PW91/6-31G** method can yield reliable HOFs, which has the mean absolute deviation of 1.1kcal/mol. The HOFs of other 19 nitroester energetic compounds are calculated by using B3PW91/6-31G** method. Through the analysis of the calculated result, it is found that the computed heat of formation decreases when the number of methylene (CH(2)) group increases for normal chain nitroester compounds. The further study shows that our results about gas-phase heats of formation of nitroester compounds are better than the results of Muthurajan et al. [H. Muthurajan, R. Sivabalan, M.B. Talawar, M. Anniyappan, S. Venugopalan, Prediction of heat of formation and related parameters of high energy materials, J. Hazard. Mater. A133 (2006) 30-45], and Byrd Edward and Rice Betsy [F.C. Byrd Edward, M. Rice Betsy, Improved prediction of heats of formation of energetic materials using quantum mechanical calculations, J. Phys. Chem. A 110 (2006) 1005-1013]. In addition, the condensed phase heat of formation of the nitroester compounds are computed through the same method of Byrd Edward and Rice Betsy.
量子化学计算用于计算24种硝酸酯（NE）含能化合物的生成热（HOF），其中只有5种硝酸酯含能化合物有可用的实验生成热。通过等键反应，采用杂化密度泛函理论（DFT）（B3LYP、B3PW91和B3P86）方法以及6 - 31G和6 - 311G基组，计算了这五种化合物的生成热。结果表明，B3PW91/6 - 31G方法能够给出可靠的生成热，其平均绝对偏差为1.1kcal/mol。使用B3PW91/6 - 31G方法计算了其他19种硝酸酯含能化合物的生成热。通过对计算结果的分析发现，对于直链硝酸酯化合物，随着亚甲基（CH₂）基团数量的增加，计算得到的生成热降低。进一步的研究表明，我们关于硝酸酯化合物气相生成热的结果优于Muthurajan等人[H. Muthurajan, R. Sivabalan, M.B. Talawar, M. Anniyappan, S. Venugopalan, Prediction of heat of formation and related parameters of high energy materials, J. Hazard. Mater. A133 (2006) 30 - 45]以及Byrd Edward和Rice Betsy[F.C. Byrd Edward, M. Rice Betsy, Improved prediction of heats of formation of energetic materials using quantum mechanical calculations, J. Phys. Chem. A 110 (2006) 1005 - 1013]的结果。此外，通过与Byrd Edward和Rice Betsy相同的方法计算了硝酸酯化合物的凝聚相生成热。
