全氮材料基础性能理论研究:Ⅱ.生成焓预测

摘要

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.%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 kJ·mol-1,且优于G4方法,选择该泛函计算了N4(Td)、N6(D3h)、N8(Oh)、N10(D5h)及N12(D6h)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 kJ·mol-1.