季戊四醇四硝酸酯的分子结构和热解机理

The Molecular Structure and Thermolysis Mechanism of Pentaerythritol Tetranitrate

运用SCF-AM1-MO方法,在RHF和UHF水平上分别全优化计算了季成四醇四硝酸酯(太安)的分子结构和热解机理。计算所得三种构象的能量相差很小、且相互转化的能垒也较小。其均裂O-NO_2键(生成双自由基)的热解引发反应活化能较小,而通过α-H转移产生RCHO和HONO的环消除反应需要较高活化能。

The molecular structure and mechanism of thermolysis of pentaerythritol tetranitrate (PETN) have been studied by full optimization calculalions using SCF- AMI -MO method at RHF and UHF levels, respectively. The calculated energy differences and energy barriers of transformations among the three conformers of PETN are small. The initial step of the thermolysis by breaking the O - NO2 bond(into two radicals) has low activation energy. However, cyclo - cleavage reaction via the transfer of a -H with the products RCHO and HONO has much high activation energy.