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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Proposed Mechanism of 1,1-Diamino-Dinitroethylene Decomposition: A Density Functional Theory Study
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Proposed Mechanism of 1,1-Diamino-Dinitroethylene Decomposition: A Density Functional Theory Study

机译：提议的1，1-二氨基-二硝基乙烯分解机理：密度泛函理论研究

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摘要

We have investigated the heretofore unknown unimolecular decomposition pathway of the explosive molecule diaminodinitroethylene (DADNE). With the use of DFT methods, whose accuracy has been calibrated by means of ab initio calculations (MP2, MP4, G2) on a simpler but related molecule, nitroethylene, we have been able to characterize the entire decomposition reaction pathway. Importantly, we find that the reaction is initiated by a nitro-to-nitrite rearrangement with a calculated energy barrier of magnitude 59.1 kcal/mol obtained by use of B3LYP (59.7 kcal/mol B3P86) which is very close to the experimental activation energy of 58 kcal/mol. We have been able to characterize every step in the decomposition reaction path leading to fragments NO, HONO, CO, NH_2, and HNC. These may interact to yield final stable products, CO, N_2, H_2O with an energy release that on average is adequate to initiate two additional DADNE molecular decompositions, and thus, sustain a chain reaction. The structural parameters we have calculated for DADNE are consistent with the known experimental crystallographic structure, and also with previous theoretical calculations. Additionally, we have obtained the structural parameters of the initial transition state, as well as each subsequent step along the decomposition pathway. Thus we consider the unimolecular decomposition of DADNE to be well characterized.
机译：我们已经研究了爆炸性分子二氨基二硝基乙烯（DADNE）的迄今未知的单分子分解途径。使用DFT方法，其精度已通过对较简单但相关的分子硝基乙烯进行从头算（MP2，MP4，G2）进行了校准，因此我们能够表征整个分解反应路径。重要的是，我们发现反应是由硝基-亚硝酸根重排引发的，该重排的计算能量垒为通过使用B3LYP（59.7 kcal / mol B3P86）获得的59.1 kcal / mol的能量，非常接近于58 kcal / mol。我们已经能够表征导致片段NO，HONO，CO，NH_2和HNC的分解反应路径中的每个步骤。这些可以相互作用以产生最终稳定的产物CO，N_2，H_2O，其能量释放平均足以引发另外两个DADNE分子分解，并因此维持链反应。我们为DADNE计算的结构参数与已知的实验晶体学结构以及先前的理论计算一致。此外，我们获得了初始过渡态的结构参数，以及分解路径上的每个后续步骤。因此，我们认为DADNE的单分子分解具有良好的特征。

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