用密度泛函理论研究多硝基吡嗪氮氧化物的结构和爆轰性能

在DFT-B3LYP(B3P86)/6-31+G**水平上优化了多硝基吡嗪氮氧化物的几何构型。用线性方程式H50=-23.16597+(73.60873×BDE/E)×104,计算了14种炸药的撞击感度,通过设计等键反应,计算了气相生成焓。用Monte-Carlo方法理论估算了标题化合物的密度,用Kamlet-Jacobs经验公式预测了爆速、爆压。结果表明,多硝基吡嗪环具有芳香性,所设计的系列硝基吡嗪类化合物的爆速在7.38～9.77km/s之间,是具有潜力的含能材料的候选物。     

Acetonitrile (CH3CN) and methyl isocyanide(CH3NC)adsorption on Pt(111) surface: a DFT study

The adsorption of CH3CN and CH3NC on the Pt(111)surface at the 1/4 monolayer(ML)coverage has been carried out at the level of density functional theory for understanding hydrogenation processes of nitriles.The most favored adsorption structure for CH3CN is the C-N bond almost parallel to the surface with the C-N bond interaction with adjacent surface Pt atoms.For CH3NC,the most stable configuration is the CH3NC locates at the face center cubic(fcc)site with the C-atom bonded to three Pt atoms.In addition,the HCN and HNC adsorption has been computed,and the adsorption pattern is nearly similar to the CH3CN and CH3NC,respectively.The adsorbed molecules rehybridize on the surface,becoming non-linear with a bent C-C-N or C-N-C angle.Furthermore,the binding mechanism of these molecules on the Pt(111)surface is also analyzed.     

钝感材料PATO及其衍生物热稳定性质研究

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.