高能硝酸酯化合物生成焓的计算

Calculation of Heats of Formation of Nitroester Energetic Materials

利用等键反应,以密度泛函方法对24种硝酸酯化合物的生成焓进行了计算,并将其中5种化合物的计算结果与实验值作了对比。计算中采用的基组为6-31G**和6-311G**。计算结果表明:B3PW91/6-31G**方法可以得到可信的生成焓,平均绝对偏差为4.5 k J/mol。进一步利用B3PW91/6-31G**方法计算了其他19种硝酸酯化合物的生成焓。计算结果表明:对于直链硝酸酯化合物,当亚甲基基团数目增加时,计算得到的生成焓减少,放出的热量更多。

The heats of formation( HOFs) of 24 nitroester compounds were calculated by density functional theory method,in which the calculated HOFs of 5 nitroester compounds were compared with the experimental HOFs by isodesmic reactions. The used basis sets was 6-31G**and 6-311G**. The results show that B3PW91 /6-31G**method can obtain reliable HOFs,with the mean absolute deviation of 4. 5 k J / mol. The HOFs of other 19 nitroester energetic compounds were further calculated by using B3PW91 /6-31G**method.Through the analysis of the calculated results,the computed HOF decreases when the number of methylene( CH2) group increases for normal chain nitroester compounds.