含能材料分子反应机理研究

发布时间：2018-07-12 19:34

本文选题：密度泛函理论 + 晶体缺陷　；参考：《渤海大学》2015年硕士论文

【摘要】：含能材料在军事、工业、民用以及航空等方面有着广泛的应用,所以含能材料的微观性能以及含能材料的合成反应机理一直人们研究的重点。含能材料中存在的缺陷对于材料的性质有着重大的影响;合成高能量密度的含能材料也是当今研究的重点之一。本文就对黑索金(RDX)和氧化呋咱这两种具有代表性的含能材料进行理论研究,主要分为两部分。第一部分研究了黑索金(RDX)单晶体、超胞和缺陷晶体的优化和微观性质,微观性质主要包括能带结构、电子态密度、前线轨道和缺陷形成能等。计算使用MS软件并采GGA/PBE泛函,通过对RDX的优化得到了RDX晶体的几何构型,分析比较RDX晶体和缺陷晶体的能带、态密度、HOMO-LUMO的数值和缺陷形成能等。并将计算的结果与实验值进行对比。结果表明,使用GGA/PBE方法计算的结果与实验值较接近。而且RDX晶体存在缺陷时,从能带和态密度图中可以看出缺陷晶体的带隙减小、电子态密度峰值发生偏移、强度减弱。从HOMO-LUMO的数值变化图中发现缺陷晶体与完整晶体的电子云分布情况也有明显变化。通过对缺陷形成能的计算可以看出缺陷形成能很低。晶体缺陷的存在使RDX晶体更加活跃,也更加容易引爆。第二部分研究了3,4-二硝基氧化呋咱的合成反应机理。主要介绍两种合成反应,一是乙二肟和硝酸合成二硝基氧化呋咱;二是二硝基甲烷钾盐在五氧化二氮和硝酸的作用下合成二硝基氧化呋咱。在气相和溶液存在的情况下对这两个反应过程中的反应物、过渡态、产物进行优化,计算反应能垒,过渡态构型和虚频等,并对反应路径进行确认,最终确定了合理的反应机理。
[Abstract]:Energetic materials have been widely used in military, industrial, civil and aeronautical fields. So the micro properties of energetic materials and the synthesis reaction mechanism of energetic materials have been the focus of research. The defects in the energetic materials have great influence on the properties of the materials; and the energetic materials with high energy density are also today. One of the key points of this study is the theoretical study of the two representative energetic materials of RDX and furozan. The first part is divided into two parts. The first part studies the optimization and microscopic properties of the single crystal, supercell and defect crystals of RDX, including the band structure, the electron density of state, the frontier orbit. The MS software is used and the GGA/PBE functional is used. The geometric configuration of the RDX crystal is obtained by optimizing the RDX. The energy band, the density of state, the value of HOMO-LUMO and the formation energy of the defect are compared and compared with the RDX crystal and the defective crystal. The results of the calculation are compared with the experimental values. The results show that the GGA/PBE method is used to calculate the results. The results are close to the experimental values. And when there are defects in the RDX crystal, the band gap in the energy band and the state density diagram can be seen to reduce the band gap of the defective crystals, the peak shift of the electron state density and the intensity weaken. It is found that the distribution of the electric sub cloud of the defective crystal and the complete crystal is also obviously changed from the numerical change of the HOMO-LUMO. The calculation of the formation energy shows that the formation energy of the defects is very low. The existence of the crystal defects makes the RDX crystal more active and easier to detonate. The second part studies the synthesis reaction mechanism of the 3,4- two nitro oxidizing furan. The main introduction of the two synthesis reactions, the one is the two nitro nitration of the two oxime and the nitric acid, and the two is two nitromethane potassium. Two nitro oxidizing furzan was synthesized under the action of nitrogen pentoxide and nitric acid. In the presence of gas and solution, the reactant, transition state and product in the two reactions were optimized, the reaction energy barrier, the transition state configuration and the virtual frequency were calculated, and the reaction path was confirmed, and the rational reaction mechanism was finally determined.
【学位授予单位】：渤海大学
【学位级别】：硕士
【学位授予年份】：2015
【分类号】：TB34

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