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Substituent effect on the molecular stability,group interaction,detonation performance,and thermolysis mechanism of nitroamino-substituted cyclopentanes and cyclohexanes

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Science China Chemistry 2008年第12期51卷 1231-1245页

作者： QIU Ling gong xuedong JU XueHai XIAO HeMing Institute for Computation in Molecular and Material Science School of Chemical EngineeringNanjing University of Science and TechnologyNanjing 210094China Key Laboratory of Nuclear Medicine Ministry of HealthJiangsu Institute of Nuclear MedicineWuxi 214063China

Density functional theory (DFT) method has been employed to study the effect of nitroamino group as a substituent in cyclopentane and cyclohexane, which usually construct the polycyclic or caged nitra-mines. Molecular structures were investigated at the B3LYP/6-31G** level, and isodesmic reactions were designed for calculating the group interactions. The results show that the group interactions ac-cord with the group additivity, increasing with the increasing number of nitroamino groups. The dis-tance between substituents influences the interactions. Detonation performances were evaluated by the Kamlet-Jacobs equations based on the predicted densities and heats of formation, while thermal stability and pyrolysis mechanism were studied by the computations of bond dissociation energy (BDE). It is found that the contributions of nitroamino groups to the detonation heat, detonation velocity, detonation pressure, and stability all deviate from the group additivity. Only 3a, 3b, and 9a-9c may be novel potential candidates of high energy density materials (HEDMs) according to the quantitative cri-teria of HEDM (ρ≈ 1.9 g/cm3, D ≈ 9.0 km/s, P ≈ 40.0 GPa). Stability decreases with the increasing number of N-NO2 groups, and homolysis of N-NO2 bond is the initial step in the thermolysis of the title com-pounds. Coupled with the demand of thermal stability (BDE > 20 kcal/mol), only 1,2,4-trinitrotriazacy-clohexane and 1,2,4,5-tetranitrotetraazacyclohexane are suggested as feasible energetic materials. These results may provide basic information for the molecular design of HEDMs.

关键词： density functional theory (DFT) substituent effect monocyclic nitramine high energy density material (HEDM) group interaction detonation performance thermal stability bond dissociation energy (BDE)

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Theoretical studies on new potential high energy density compounds (HEDCs) adamantyl nitrates from gas to solid

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Science China Chemistry 2008年第5期51卷 427-439页

作者： XU XiaoJuan ZHU WeiHua gong xuedong XIAO HeMing Department of Chemistry Nanjing University of Science and TechnologyNanjing 210094China Department of Chemistry Yancheng Teacher’s CollegeYancheng 224002China

A series of adamantyl nitrates have been theoretically studied from gas to solid to search for new po-tential high energy density compounds (HEDCs). The heats of formation (HOFs) for the 26 title com-pounds were calculated by designing isodesmic reactions at the B3LYP/6-31G level. It was found that the HOFs of the 26 isomers with the same number of —ONO2 groups (n) are not correlated well with the corresponding substituted positions. According to the obtained heats of detonation (Q),detonation velocities (D),and detonation pressures (P) using the Kamlet-Jacobs equations,it was found that when n=7～8,the adamantyl nitrates meet the criterion as an HEDC. The calculations on bond dissociation energies of O—N (EO—N) showed that the adamantyl nitrates with gemi —ONO2 always have the worst stability among the isomers,and all the adamantyl nitrates with gemi —ONO2 have similar stability. Due to the complexity of their structures,values of EO—N do not decrease with the increase of the substituent number n obviously,and the stability of adamantyl nitrates is not determined by only one structural parameter. Considering the stability requirement,only 1,2,4,6,8,9,10-adamantyl heptanitrate is recom-mended as a feasible HEDC. Molecular packing searching for 1,2,4,6,8,9,10-adamantyl heptanitrate among 7 most possible space groups (P21/c,P-1,P212121,P21,Pbca,C2/c,and Pna21) using Compass and Dreiding force fields showed that this compound tends to crystallize in P21/c. Ab initio periodic calculations on the electronic structure of the predicted packing showed that the O—NO2 bond is the trigger bond during thermolysis,which agrees with the result derived from the study of dissociation energies of O—N bonds.

关键词： high energy density compound (HEDC) adamantyl nitrate molecular packing periodic calculation energetic property density of states (DOS)

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DFT Studies on Detonation Properties, Pyrolysis Mechanism, and Stability of the Nitro and Hydroxyl Derivatives of Benzene

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Chinese Journal of Chemistry 2011年第3期29卷 455-462页

作者： Du, Hongchen Liu, Hui Liu, Yan Zhang, Jianying Wang, Fang gong, xuedong Department of Chemistry Nanjing University of Science and Technology Nanjing Jiangsu 210094 China State Key Laboratory of Explosion Science and Technology Beijing Institute of Technology Beijing 100081 China

Ninety-one nitro and hydroxyl derivatives of benzene were studied at the B3LYP/6-31G＊ level of density functional theory. Detonation properties were calculated using the Kamlet-Jacobs equation. Three candidates （pentanitrophenol, pentanitrobenzene, and hexanitrobenzene） were recommended as potential high energy density compounds for their perfect detonation performances and reasonable stability. The pyrolysis mechanism was studied by analyzing the bond dissociation energy （BDE） and the activation energy （Ea） of hydrogen transfer （H--T） reaction for those with adjacent nitro and hydroxyl groups. The results show that Ea is much lower than BDEs of all bonds, so when there are adjacent nitro and hydroxyl groups in a molecule, the stability of the compound will decrease and the pyrolysis will be initiated by the H--T process. Otherwise, the pyrolysis will start from the breaking of the weakest C--NO2 bond, and only under such condition, the Mulliken population or BDE of the C--NO2 bond can be used to assess the relative stability of the compound.

关键词： high energy density material nitrobenzene nitrophenol density functional theory

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硝酸甲酯与硝酸乙酯的结构、振动频率和热力学性质的密度函数理论(DFT)研究

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化学学报 1999年第7期57卷 696-705页

作者：贡雪东肖鹤鸣南京理工大学化工学院南京210094

用密度函数理论(DFT)的BLYP和B3LYP方法,取 6-31G,6-31G~*,6-31G^(**),6-311G,6-311G~*和6-311G^(**)六种基组,对硝酸甲酯和硝酸乙酯的几何构型和红外振动频率进行了计算研究.结果表明,B3LYP方法在采用极化基组(6-31G~*,6-31G^(**),6-311G~*和6-311G^(**)时计算得到的结果均较好,适用于硝酸酯类化合物的研究.而BLYP方法无论采用何种基组均不适用;运用校正后的B3LYP/6-31G~*频率(校正因子0.975)计算得到的热力学性质(C_P°,H°和S°)与实验结果较吻合.

关键词：结构 DFT 硝酸甲酯硝酸乙酯振动频率热力学

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A theoretical study on the azido plasticizer TAPE: Structure,properties,and thermal decomposition mechanism

A theoretical study on the azido plasticizer TAPE: Structure...

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中国化学会第十二届全国量子化学会议

作者： Junqing Yang Guixiang Wang xuedong gong Department of Chemistry Nanjing University of Science and Technology

Tetraazido pentaerythritol（TAPE）is a candidate of energetic azido plasticizers with low glass transition temperature and high nitrogen content.A detailed theoretical investigation was carried out using the B3LYP method of density functional theory and the Dreiding force field of molecular mechanics *** bond dissociation energies of several possible trigger bonds were *** show that the thermal decomposition of TAPE starts from the rupture of the N=N bond,which completes via the H transfer to the-N3 group to release N2（Figure 1）.The required activation energy of the pyrolysis process is about 163 k *** crystal structure of TAPE is most likely to belong to the C2/c *** predicted density,detonation velocity,detonation pressure,and specific impulse（1.45 ***-3,7.44 km.s-1,21.44 GPa,and 252.73 s,respectively）are all larger than those of an azido plasticizer with practical applications,1,5-diazido-3-nitrazapentane（DIANP,***-3,7.03 km.s-1,18.91 GPa,and 195.97 s）.This paper provides a wealth of information for TAPE and this theoretical work would be helpful for further studies on energetic azido compounds.

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插烯系硫靛发色体电子光谱的含时密度泛函理论研究

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计算机与应用化学 2007年第7期24卷 949-952页

作者：薛运生贡雪东徐州医学院药学系江苏徐州221004 南京理工大学化工学院江苏南京210094

在密度泛函理论的B3LYP/6-31+G~*水平上对硫靛染料发色体及其插烯系化合物的几何构型进行优化计算;在获得基态稳定结构的基础上,应用含时密度泛函理论在相同水平下计算其电子吸收光谱,探讨了发色体的延伸对电子吸收光谱的影响,得到了与... 详细信息

在密度泛函理论的B3LYP/6-31+G~*水平上对硫靛染料发色体及其插烯系化合物的几何构型进行优化计算;在获得基态稳定结构的基础上,应用含时密度泛函理论在相同水平下计算其电子吸收光谱,探讨了发色体的延伸对电子吸收光谱的影响,得到了与实验值基本一致的变化规律。结果表明,发色体的纵向延伸使光谱产生轻微的红移。通过对前线轨道组成进行自然布居分析,揭示了硫靛染料的发光均源自分子中HOMO-LUMO(π→π^(?))电子跃迁。

关键词：硫靛染料发色体密度泛函理论含时密度泛函理论电子吸收光谱

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提高大红山铜矿铜回收率及降低介耗的研究

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铜业工程 2024年第3期 54-60页

作者：肖庆飞王国彬金赛珍骆忠田厚源周强刘向阳朱有军龚学东昆明理工大学国土资源工程学院云南昆明650093 玉溪矿业有限公司云南玉溪653100 矿物加工科学与技术国家重点实验室北京102628

针对玉溪矿业有限公司大红山铜矿一选厂浮选给矿产品中合格粒级含量过低、过磨粒级含量较高、铜选别回收率较低等问题,在研究选厂给矿性质的基础上,基于球径半理论公式推导了该段磨矿作业中钢球的最佳配比,并将该方案分别在实验室和现... 详细信息

针对玉溪矿业有限公司大红山铜矿一选厂浮选给矿产品中合格粒级含量过低、过磨粒级含量较高、铜选别回收率较低等问题,在研究选厂给矿性质的基础上,基于球径半理论公式推导了该段磨矿作业中钢球的最佳配比,并将该方案分别在实验室和现场进行验证。对于推导出的一段球磨机初装方案m(Φ70 mm)︰m(Φ50 mm)︰m(Φ40 mm)︰m(Φ30 mm)=15︰25︰35︰25,在实验室试验和工业试验中进行验证,结果表明:该方案能够提高-0.020+0.010 mm可选粒级及-0.074+0.018 mm易选粒级的含量,有效减少了过粉碎现象,降低了介质消耗,提高了铜精矿回收率,实现了降本增效。

关键词：大红山铜矿回收率磨矿钢球介耗

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六硝基六氮杂三环十二烷的结构和性能——HEDM分子设计

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Chinese Journal of Chemical Physics 2005年第4期18卷 541-546页

作者：邱玲肖鹤鸣居学海贡雪东南京理工大学化学系南京210094

用密度泛函理论B3LYP方法,在631G基组水平下设计和计算了高能量密度化合物六硝基六氮杂三环十二烷的结构和性质.由分子总能量、前线轨道能级和键集居数等电子结构参数,判别船式(α)比椅式(β)构象稳定.求得其IR谱频率和强度并作归属,报... 详细信息

用密度泛函理论B3LYP方法,在631G基组水平下设计和计算了高能量密度化合物六硝基六氮杂三环十二烷的结构和性质.由分子总能量、前线轨道能级和键集居数等电子结构参数,判别船式(α)比椅式(β)构象稳定.求得其IR谱频率和强度并作归属,报道了200～800K体系的热力学性质.基于理论计算密度和生成热,运用Kamlet公式预示了标题物的爆速和爆压,α构象的爆速和爆压分别为9.46km/s和41.74GPa,β构象则稍低些,分别为9.34km/s和40.02GPa.

关键词：六硝基六氮杂三环十二烷密度泛函理论电子结构 IR谱热力学性质爆轰性质

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粘土的分子力学力场优化及结构、性能研究

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无机化学学报 1998年第2期14卷 175-180页

作者：贡雪东肖鹤鸣南京理工大学化学系

以ＤＥＬＰＨＩ分子力学程序优化了粘土力场。计算研究了高岭石、地开石、珍珠陶土、叶蜡石１Ｔｃ和叶蜡石２Ｍ等五种粘土的结构、电荷分布和红外光谱等性质，所得结果与实验结果比较相符。

关键词：粘土分子力学电荷分布红外光谱结构

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Theoretical study on tetrazole and its derivatives (Ⅰ)──Ab initio study on chlorotetrazole

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Chinese Science Bulletin 1998年第6期43卷 480-483页

作者： XIAO Heming, CHEN Zhaoxu and gong xuedong Department of Chemistry, Nanjing University of Science and Technology, Nanjing 210094, China

Molecular geomitries and electronic structures of four chlorotetrazoles are calculated with ab initio method at MP2/6-311G ** level. The results show that all the titled compounds are planar and aromatic. The skeletal bond lengths of the ring tend to be uniformized. Compared with 1- and 2-substituted chlorotetrazoles, 5-substituted chlorotetrazoles are more acidic and lower in total energy. 5-chloro-2H-tetrazole has the lowest energy and is the most stable.

关键词： chlorotetrazole ab initio geometry electronic structure acidity aromaticity stability.

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