Decomposition of triacetone triperoxide is an entropic explosion
Decomposition of triacetone triperoxide is an entropic explosion
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DOI：
10.1021/ja0464903
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发表时间：
2005-02-02
影响因子：
15
通讯作者：
Keinan, E
中科院分区：
文献类型：
--
作者：
Dubnikova, F;Kosloff, R;Keinan, E
采用DFT B3LYP方法对三丙酮三过氧物(TATP)和双丙酮二过氧物(DADP)进行了X-射线结晶学和电子结构计算。通过一系列确定过渡态、中间体和最终产物的计算，研究了TATP的热分解途径。与直觉相反的是，这些计算预测，TATP的爆炸并不是一个在热化学上非常有利的事件。相反，它涉及到熵爆发，这是固体状态下每个TATP分子形成一个臭氧和三个丙酮分子的结果。
Both X-ray crystallography and electronic structure calculations using the cc-pVDZ basis set at the DFT B3LYP level were employed to study the explosive properties of triacetone triperoxide (TATP) and diacetone diperoxide (DADP). The thermal decomposition pathway of TATP was investigated by a series of calculations that identified transition states, intermediates, and the final products. Counterintuitively, these calculations predict that the explosion of TATP is not a thermochemically highly favored event. It rather involves entropy burst, which is the result of formation of one ozone and three acetone molecules from every molecule of TATP in the solid state.