全氮材料基础性能理论研究:Ⅱ.生成焓预测  

Theoretical Investigations on Fundamental Performances of All-nitrogen Materials: Ⅱ.Prediction of Enthalpies of Formation

作　　者：刘英哲[1] 来蔚鹏[1] 尉涛[1] 葛忠学[1] 骆艳娇[2] 徐涛[2] 尹世伟[2] 

机构地区：[1]西安近代化学研究所氟氮化工资源高效开发与利用国家重点实验室,陕西西安710065 [2]陕西师范大学,陕西西安710062

出　　处：《含能材料》2017年第7期552-556,共5页Chinese Journal of Energetic Materials

基　　金：国家自然科学基金资助(21403162;21503160)

摘　　要：为了准确预测全氮材料的生成焓,基于原子化反应,采用B3PW91、B3P86、B3LYP、X3LYP、O3LYP、M052X、M062X、M06HF、B2PLYP 9种密度泛函分别对52种多氮化合物的气相生成焓进行了计算。通过与实验数据对比,双杂化泛函B2PLYP的平均绝对偏差最小,为30.1 k J·mol^(-1),且优于G4方法,选择该泛函计算了N_4(T_d)、_N6(D_(3h))、N_8(O_h)、N_(10)(D_(5h))及N_(12)(D_(6h))5种全氮分子的气相生成焓,计算结果依次为756.4,1338.2,1878.5,2144.3,2787.0 k J·mol^(-1)。To accurately predict the enthalpies of formation of all-nitrogen materials, nine density functionals including B3PW91 , B3P86, B3LYP, X3LYP, O3LYP, M052X, M062X, M06HF, B2PLYP52 were employed to calculate the enthalpies of formation of nitrogen-rich compounds via atomization reaction. The calculation results show that double hybrid functional B2PLYP has the smallest mean absolute deviation of 30.1 kJ · mol-1 , which is more accurate than G4 method. Hence, the enthalpies of formation of five all-nitrogen molecules with cage structure, namely, N4（Td） , N6（D3h）, N8（Oh） , N10（D5h） , and N12（D6h）, were predicted by B2PLYP functional, and the corresponding results were 756.4, 1338.2, 1878.5, 2144.3, 2787.0 kJ · mol-1 , respectively.

关 键 词：密度泛函 笼型结构 原子化反应 全氮材料 

分 类 号：TQ560.1[化学工程—炸药化工]