二硝酰胺铵热分解机理的理论研究进展

Review on Theoretical Investigations of the Thermal Decomposition of Ammonium Dinitramide

介绍了二硝酰胺铵(ADN)热分解反应的基本性质。总结了ADN分解反应的理论研究结果。分析了溶剂对DN-模型中ADN分解行为的影响,比较了二硝酰胺酸(HDN)、二硝酰胺酸二聚体(HDN2)及其二硝酰胺铵二聚体(ADN2)簇模型中不同质子转移异构体分解的优势路径,以及分子内和分子间双质子转移过程对不同异构体的形成和分解反应的影响。讨论了微量水在(H2O)n…NH4+[ON(O)NNO2]-(n=1,2,3)和ADN2簇模型中对ADN反常分解行为的原因。不同理论模型在一定程度上揭示了ADN分解反应的本质,在较大ADNn簇中获得的动力学参数与实验结果吻合更好。研究认为,对ADN体系分解产生的各中间体之间的交叉反应以及将QM-MM方法用于较大ADNn簇和溶剂化模型的研究,对理解ADN复杂分解反应以及获得其应用过程所涉及的相关热力学和动力学参数具有重要作用。

Basic properties of the thermal decomposition reaction of ammonium din itramide （ADN） were introduced. Theoretical investigation results of ADN decomposition reactions were summarized. The effect of solvent on the decomposition behavior of AND in the DN- model was analyzed. The advantage of path for decomposition of different proton transfer isomers in dinitramide acid （HDN）, HDN2 and ADN2 cluster model and the effects of the double proton transfer process of the intramolecular and intermolecular on the formation and decomposition reaction of different isomers were compared. The reason of trace water in （H20） , .NH4 ION（O） NNO2 ]-（n=l ,2,3）and ADN2 cluster model on the abnormal decomposition behavior of ADN was discussed. Different theoretical model reveals the essence of the decomposition reaction of ADN to a certain extent, the kinetic parameters obtained in the larger ADN, clusters agree with the experimental results well. Study shows that the introduction of the QM-MM method, which is suitable for the larger ADNn clusters and solvation model in the liquid phase and gas phase, will play an impor- tant role to obtain the relevant thermodynamic and kinetic parameters of ADN involved in the application process.