二氧化氮催化硝化甘油分解机理的数值计算

Numerical simulation on catalytic decomposition mechanism of NO_2 on nitroglycerin

采用密度泛函理论(DFT)在B3LYP/6-31+G(d,p)水平上模拟计算了NO_2对硝化甘油(NG)催化分解的反应机理。通过与O—NO_2均裂、HNO_2分子内消去反应对比发现,NO_2分子对NG分解反应有显著的催化效应;NG的催化分解途径有α-H夺氢催化和β-H夺氢催化,计算得出2种途径的反应能垒分别为105.337 k J/mol和124.381 k J/mol,说明α-H夺氢催化更容易发生。

The catalytic decomposition mechanism of NO_2 on NG was simulated using density functional theory（ DFT） at the B3 LYP/6-31＋G（ d,p） level. Compared with the homolysis of O—NO_2 and the intra-molecular elimination of HNO_2,NO_2 has significant catalytical effect on the decomposition of NG. There are two possible ways of the catalytic decomposition of NG by NO_2,named α-H catalytic hydrogen abstraction and β-H catalytic hydrogen abstraction. Their energy barriers are 105. 337 k J/mol and124.381 k J/mol,respectively,which indicates that α-H catalytic hydrogen abstraction occurs more easily.