本文選題：密度泛函理論 + 晶體缺陷��； 參考：《渤海大學(xué)》2015年碩士論文

【摘要】：含能材料在軍事、工業(yè)、民用以及航空等方面有著廣泛的應(yīng)用,所以含能材料的微觀性能以及含能材料的合成反應(yīng)機理一直人們研究的重點。含能材料中存在的缺陷對于材料的性質(zhì)有著重大的影響;合成高能量密度的含能材料也是當(dāng)今研究的重點之一。本文就對黑索金(RDX)和氧化呋咱這兩種具有代表性的含能材料進行理論研究,主要分為兩部分。第一部分研究了黑索金(RDX)單晶體、超胞和缺陷晶體的優(yōu)化和微觀性質(zhì),微觀性質(zhì)主要包括能帶結(jié)構(gòu)、電子態(tài)密度、前線軌道和缺陷形成能等。計算使用MS軟件并采GGA/PBE泛函,通過對RDX的優(yōu)化得到了RDX晶體的幾何構(gòu)型,分析比較RDX晶體和缺陷晶體的能帶、態(tài)密度、HOMO-LUMO的數(shù)值和缺陷形成能等。并將計算的結(jié)果與實驗值進行對比。結(jié)果表明,使用GGA/PBE方法計算的結(jié)果與實驗值較接近。而且RDX晶體存在缺陷時,從能帶和態(tài)密度圖中可以看出缺陷晶體的帶隙減小、電子態(tài)密度峰值發(fā)生偏移、強度減弱。從HOMO-LUMO的數(shù)值變化圖中發(fā)現(xiàn)缺陷晶體與完整晶體的電子云分布情況也有明顯變化。通過對缺陷形成能的計算可以看出缺陷形成能很低。晶體缺陷的存在使RDX晶體更加活躍,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應(yīng)機理。主要介紹兩種合成反應(yīng),一是乙二肟和硝酸合成二硝基氧化呋咱;二是二硝基甲烷鉀鹽在五氧化二氮和硝酸的作用下合成二硝基氧化呋咱。在氣相和溶液存在的情況下對這兩個反應(yīng)過程中的反應(yīng)物、過渡態(tài)、產(chǎn)物進行優(yōu)化,計算反應(yīng)能壘,過渡態(tài)構(gòu)型和虛頻等,并對反應(yīng)路徑進行確認,最終確定了合理的反應(yīng)機理。
[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.
【學(xué)位授予單位】：渤海大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2015
【分類號】：TB34

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