在密度泛函理论B3LYP/6-31G弊水平下，对3，7-二硝基-1，3，5，7-四氮杂双环[33．1．]壬烷（DPT ）硝解制备1，3，5，7-四硝基-1，3，5，7-四氮杂环辛烷（HMX）的过程进行量子化学研究，主要计算了DPT 以及重要反应中间体的电子云密度、键长、键级和二阶微扰能。结果表明，由于受键长和键解离能的影响，DPT 在硝解过程中可能同时生成八元环和六元环的中间体；八元环中间体受键解离能与二阶微扰能的影响，在硝解制备 HMX的同时有副产物产生。因此，DPT硝解制备 HMX不仅受实际实验过程影响，还受到分子本身结构的影响，通过计算可以看出，量子化学参数在微观上体现了HMX的总收率不理想的内在原因。%The nitration process of 3 ,7-dinitro-1 ,3 ,5 ,7-tetrazabicyclo [3 3. 1.]nonane (DPT ) to 1 ,3 ,5 ,7-Tet-ranitro-1 ,3 ,5 ,7-tetraazacyclooctane (HMX) was studied using density functional theory at the B3LYP/6-31G" level . Several important factors such as the electron density ,bond length ,bond order and second-order perturbation ener-gy were calculated .The results show that ,because of the influence of bond length and bond dissociation energy ,the nitration of DPT not only leads to the intermediate with eight-membered ring but also six-membered ring .Besides that ,byproducts would generate in the nitrolysis of the eight-membered ring products to HMX ,which was affected by the bond dissociation energies and the second-order perturbation energy .Therefore ,the nitration process is af-fected both by experiment and molecular structure .Through calculation ,the quantum chemical parameters micro-scopically provide the intrinsic reasonable explanation why the yield of HMX is limited in industrial production .
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