对称的吡嗪并环脲硝基衍生物结构和性能的量子化学研究(英文)  

Quantum Chemical Studies on the Structures and Properties of Nitro Derivatives of Symmetric Pyrazino-dicycloureas

作　　者：马丛明[1] 刘祖亮[1] 姚其正[1,2] 

机构地区：[1]南京理工大学化工学院,江苏南京210094 [2]中国药科大学药学院,江苏南京210009

出　　处：《含能材料》2014年第6期780-785,共6页Chinese Journal of Energetic Materials

基　　金：National Nature Science Foundation of C hina(21102125)

摘　　要：运用密度泛函理论DFT-B3LYP/6-31G**方法得到了对称的吡嗪并环脲硝基衍生物的分子几何构型和电子结构。用量子化学方法计算了理论密度和生成热,用Kamlet-Jacobs方程计算了爆速和爆压,对这些硝基衍生物的结构-性能关系进行了研究。结果表明,分子中硝基的数量、位置、环境和分子结构的对称性是影响对称吡嗪并环脲硝基衍生物热稳定性和爆轰性能的一些主要因素。1,3,5,7-四硝基-5,7-二氢二咪唑[4,5-b:4',5'-e]吡嗪-2,6(1H,3H)-二酮的理论密度为2.03 g·cm-3,生成热为265.63 k J·mol-1,爆速为9.08 km·s-1,爆压为39.22 GPa。1,3,5,7-四硝基-2,6-二氧杂-1,2,3,5,6,7-六氢二咪唑[4,5-b:4',5'-e]吡嗪-4-氧化物的结构是不稳定的。这些计算结果为新型高能量密度材料的设计和合成提供了基础研究数据。The molecular geometries and electronic structures of nitro derivatives of symmetric pyrazino-dicycloureas were obtained by a density func-tional theory（DFT）method with DFT-B3LYP/6-31G＊＊. Their values of theoretical molecular density（ρ）and heat of formation（HOF）were com-puted by quantum chemical method. The values of detonation velocity（ D）and detonation pressure（ p）were estimated using Kamlet-Jacobs equa-tions. Studies on the relationship between structure and property of these nitro derivatives were performed. Results show that the number,positions, surrounding and symmetry of the nitro group within the molecule and the symmetry of the molecular structure are some principal factors affecting the thermal stabilities and detonation properties of nitro derivatives of symmetric pyrazino-dicycloureas. The values of ρ,HOF,D and p for 1,3,5,7-tetra-nitro-5,7-dihydrodiimidazo[4,5-b：4′,5′-e]pyrazine-2,6（1H,3H）-dione are 2.03 g·cm^-3,265.63kJ·mol^-1,9.08 km·s^-1,and 39.22 GPa, respectively. The structure of 1,3,5,7-tetranitro-2,6-dioxo-1,2,3,5,6,7- hexahydrodiimidazo[4,5-b：4′,5′-e]pyrazine-4-oxide is unstable. These results obtained provide basic research data for molecular design and synthesis of novel high energetic density compounds（ HEDC）.

关 键 词：量子化学 爆轰性能 环脲硝胺 吡嗪环 

分 类 号：TQ560.1[化学工程—炸药化工]