钝感材料PATO及其衍生物热稳定性质研究  

Quantum Study on Thermal Stability of PATO Derivatives as Insensitive Energetic Material

作　　者：韩新艳[1] 朱佳平[1] 王勇[1] 曹端林[1] 任君[1] 王建龙[1] 

机构地区：[1]中北大学化工与环境学院,山西太原030051

出　　处：《中北大学学报（自然科学版）》2013年第1期45-51,69,共8页Journal of North University of China(Natural Science Edition)

基　　金：山西省自然科学基金资助项目(2009011014)

摘　　要：在密度泛函理论DFT-B3LYP(B3P86)/6-31+G**水平下,对7种PATO及其衍生物体系进行了全优化,几何优化结果表明所有化合物均无虚频,为势能面上的稳定结构;通过不破裂三唑环分子骨架的等键反应设计,比较精确地计算了PATO及其衍生物的气相生成焓,并得到线性方程(ΔfHθ)B3P86=-40.978 98+0.984 65×(ΔfHθ)B3LYP,从而说明了等键反应计算PATO及其衍生物生成焓的精确性、设计的等键反应的合理可行性;计算了PATO及其衍生物的硝基基团的Mulliken最大电荷、最弱键C-NO2键解离能,得到其间的关系BDEC-NO2=273.022 54-52.210 49×(qNO2),BDEC-NO2=-67.148 21-1 432.307 69×(qNO2).运用生成热、C-NO2键解离能和Mulliken电荷(qNO2)等计算结果,阐明了PATO及其衍生物的相对稳定性,为新一代高能量密度材料(HEDM)的分子设计提供了基础数据和规律性.Density functional theory（DFT） calculations were performed for PATO and its derivatives.B3LYP and B3P86 functionals with 6-31＋G＊＊ basis set were used.Vibrational analyses show that the optimized structures have no imaginary frequencies.Heats of formation（HOFs） for PATO derivatives in gas phase are also determined both at two levels using isodesmic work reactions.A good liner equation： ΔfHθ（B3P86）=-40.978 98＋0.984 65×ΔfHθ（B3LYP） is obtained from the calculated accurately values between the two levels.It indicates that designing isodesmic work reactions and calculation accuracy is reliable and feasible.Thermal stabilities are evaluated via bond dissociation energies（BDEs） of the weakest C-NO2 and the biggest Mulliken charges of nitro group in PATO derivatives,and two liner equations are extrapolated： BDEC-NO2=273.022 54-52.210 49×（qNO2）,BDEC-NO2=-67.148 21-1432.307 69×（qNO2）.The relative stability of PATO derivatives is illustrated according to the results calculated by HOFs,C-NO2 bond dissociation energy and Mulliken charge of nitro group（qNO2）.The obtained results provide basic data and regularity for the molecular design of new type of high energetic density materials.

关 键 词：3-苦氨基-1 2 4-三唑 密度泛函理论 气相生成焓 键解离能 Mulliken电荷 

分 类 号：TJ55[兵器科学与技术—军事化学与烟火技术]