六硝基六氮杂三环十二烷的结构和性能——HEDM分子设计

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.     

环四甲撑四硝胺(HMX)结构和性质的DFT研究

用密度泛函理论 (DFT)B3LYP方法 ,取 6 - 31G 基组 ,求得环四甲撑四硝胺分子的几何构型、电子结构、IR谱和 2 98～ 12 0 0K的热力学性质 .全优化几何构型和电子结构均具有Ci 对称性 .在相邻原子之间以N -NO2 键的Mulliken集居数最小 ,表明其间电子分布较少 ,预示其为热解和起爆的引发键 .IR谱与实验结果良好相符     

叠氮乙烷二聚体分子间相互作用的理论研究

用abinitioHF/ 6 3 11+ +G 计算求得叠氮乙烷二聚体势能面上三种优化构型和电子结构 .经MP2电子相关校正和基组叠加误差 (BSSE)以及零点能 (ZPE)校正 ,求得分子间最大相互作用能为 -10 .45kJ/mol.二子体系间的电荷转移很少 .由自然键轨道 (NBO)分析揭示了相互作用的本质 .基于统计热力学求得温度为 2 0 0 .0 0～80 0 .0 0K从单体形成二聚体的热力学性质变化     

(R)-1,3丁二醇的手性不对称性：微分键极化率的研究

本文从(R)-(-)-1,3-丁二醇 ((R)-(-)-1,3-Butanediol) 的拉曼峰强和拉曼旋光峰强, 求得其键极化率和微分键极化率, 得出在拉曼过程中, 电荷主要沿H16 (或H15) O6C3C2C1O5所形成的 (六边) 环向外围的OH键和CH 键流动. 而此环内外化学键的微分键极化率的符号正好相反, 此意味着这个分子具有相当好的手性不对称性质. 关键词： 旋光拉曼 键极化率 微分键极化率 1,3-丁二醇     

{H[Cu(trans-Hcydta)]·2Bzim·1.5H2O·0.5MeOH·HClO4}的合成、结构和量子化学研究

反式 1,2 环已二胺四乙酸与铜离子合成标题配合物 ,经X射线衍射测定配合物的晶体分子结构 ,并用量子化学方法研究配合物的电子结构及分子轨道组成 .该晶体属于单斜晶系 ,空间群为P2 (1) /c ,晶胞参数 :a =1.6 36 0 (6 ) ,b=1.3814 (5 ) ,c=1.5 5 0 3(5 )nm ,β =90 .885 (7) o,V =3.5 0 3(2 )nm3 ,Z =4 ,Dx=1.4 95 g/cm3 ,μ(MoKa) =7.74cm-1,F(0 0 0 ) =16 4 0 ,R1=0 .0 75 0 ,wR =0 .15 2 6 ;配合物中Cu -O键长为 0 .193～ 0 .2 2nm ,中心铜与配基原子形成畸型四棱锥 .     

乙烯在Ni（110）表面吸附的几何结构

用理论计算的方法研究了不同覆盖度的乙烯在Ni（110）表面吸附的位置.乙烯的吸附几何结构在团簇计算中进行了局部优化.在低覆盖度下，单个乙烯分子占据了短桥位和顶位之间的中间位置.乙烯分子的C—C轴大致沿衬底的Ni原子链排列（即沿<110>晶向），C—C轴与衬底Ni（110）表面有10°的倾斜角.乙烯分子的C—C键的键长为0151nm.在高覆盖度下(05ML)，乙烯在Ni (110)上形成了有序的c（2×4）相，在一个表面元胞内的两个乙烯分子的吸附位置类似于低覆盖度时的结果，但乙烯分子的C—C 键键长分别为0142和0143nm.     

激光二极管抽运(Tm,Ho):YLF激光器光谱特性实验分析

Ho：YLF晶体的^5I7和^5I8斯塔克能级分裂数较多。形成2047～2070nm宽的增益谱带,对于可调谐2μm激光及宽带激光放大器研究具有重要意义。理论上分析了(Tm,Ho)：YLF晶体的能级结构。并对晶体掺杂浓度和长度进行了优化。实验研究了激光二极管抽运微片Tm(原子数分数0．06)．Ho(原子数分数0．004)：YLF激光谱线可调谐特性。调谐范围2．0656～2．0671μm。利用(Tm,Ho)：YLF晶体的宽增益谱特性．将其作为激光二极管抽运激光放大器。成功地将2．048μm(Tm,Ho)：GdVO1激光功率放大了2．5倍。实验上测量了(Tm,Ho)：YLF晶体在强抽运条件下480～492nm及530～550nm可见波段的上转换蓝绿光荧光谱。     

MgF2:Mn2+光谱、超精细常数和局部结构的关联

基于电子顺磁共振(EPR)超精细常数As确定键长的新方法和半自洽场d轨道理论,对MgF2:Mn2+光谱和EPR超精细常数作出了统一解释.得到室温下MgF2:Mn2+晶体中杂质中心Mn-F的键长为0.2124±0.0010nm.     

Cr~(3+)在Y_3Ga_5O_(12)晶体中的能级和光谱特性

本文报道用熔盐法生长的Y_3Ga_5O_(12):Cr~(3+)晶体的能级和光谱特性.在室温下;测得~4T_2和~2E能级的有效荧光寿命为205μs,荧光光谱中心波长为727nm.根据Tanabe-Sugano理论计算了晶场能级,并求得了晶场强度参数D_q、Bacah参数B和C以及参数△分别为1626、645、2950和538cm~(-1).     

CO2在中性及带负电Be（n=4, 7, 10, 12, m=0, -1）团簇表面的吸附与解离

运用密度泛函理论,对中性及带负电的BeCO2 (n=4, 7, 10, 12, m=0, -1) 团簇进行了构型优化,稳定性和电子性质分析。结果表明：CO2吸附于Ben和Ben-1团簇表面时,C-O键长均有不同程度的伸长。其中Be4CO2-1,Be12CO2-1中CO2分子的一个C-O键自然断裂(伸长量达到了134%和156%),为典型的解离性吸附。Be团簇表现出了较好的吸附CO2分子的能力,特别是带负电以后,吸附能明显增大(约为3.16eV--5.965eV)。电子性质分析表明,带负电升高了相应团簇的前线轨道能级,使轨道杂化发生在费米能级处附近,从而增强了CO2分子与相应团簇的成键能力。     

Effects of Explosive Particle Microstructure Parameters on NQR Parameters in RDX

The effects of the particle size, density and octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX) content on 1,3,5-trinitroperhydro-1,3,5-triazine (RDX) nuclear quadrupole resonance (NQR) line have been studied at 5, 10, 15 and 20?°C. The RDX line at 3.41?MHz has been measured in 17 different quality lots. The RDX line was not modified in this temperature range but was strongly altered in some lots. No significant correlation was found between line characteristics and particle sizes or particle bulk densities. Correlation coefficients were computed between the HMX content measured using high-performance liquid chromatography and the NQR line intensity and NQR line width. Significant correlations were found. They were based on the study of 11 RDX lots which exhibited 4 different HMX contents from 0 to about 9 percent in weight. Further studies are needed to precise the HMX effect in relation with the HMX location. HMX can be located inside or outside the RDX crystal. Further studies are also needed to determine the line broadening mechanism.     

DFT studies on a high-energy density cage compound 1, 3, 5, 7, 9, 11-hexo(N(CH3)NO2)-2, 4, 6, 8, 10, 12-hexaazatetracyclo[5, 5, 0, 0, 0] dodecane

The infrared and Raman spectra, heat of formation (HOF) and thermodynamic properties were investigated by B3LYP/6-31G^** method for a new designed polynitro cage compound 1,3,5,7,9,11-hexo(N(CH₃)NO₂)-2,4,6,8,10,12-hexaazatetracyclo[5,5,0,0,0]dodecane. The detonation velocity (D) and pressure (P) were predicted by the Kamlet–Jacobs equations based on the theoretical density and condensed HOF. The bond dissociation energies and bond orders for the weakest bonds were analysed to investigate the thermal stability of the title compound. The computational result shows that the detonation velocity and pressure of the title compound are superior to those of hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX), but inferior to those of 1,3,5,7-tetranitro-1,3,5,7-tetraazacyclooctane (HMX) and hexanitrohexaazaisowurtzitane (HNIW). And the analysis of thermal stability shows that the first step of pyrolysis is the rupture of the N₇–NO₂ bond. The crystal structure obtained by molecular mechanics belongs to the P2₁ space group, with the lattice parameters Z = 2, a = 11.8246 Å, b = 10.4632 Å, c = 15.9713 Å, ρ = 1.98 g cm^?3.     

Theoretical studies on the structure,sensitivity, density,thermodynamic properties and detonation performance of dinitrobitriazoles

Azodinitro- and dinitroethylene-bridged bitriazoles are of interest in the contest of high explosives, and were found to have true local energy minima at the B3LYP/aug-cc-pVDZ level of theory. The optimised structures, vibrational frequencies and thermodynamic quantities for bitriazoles were obtained in the ground state. Kamlet–Jacobs equations were used to evaluate the performance of bitriazoles based on the predicted density and the calculated heat of explosion. Detonation properties (D = 8.12 to 9.23 km s^?1 and P = 28.0 to 39.83 GPa) of bitriazoles were found to be promising compared with those of hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX, D = 8.75 km s^?1 and P = 34.7 GPa) and octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX, D = 8.96 km s^?1 and P = 35.96 GPa). The fusion of azoles particularly appears to be a promising area for investigation, since it may lead to the desirable consequences of higher heat of explosion, higher density and thus improved detonation performance.     

Comparison of simplified models for nitramine propellant combustion

Although 1,3,5-Trinitroperhydro-1,3,5-triazine (RDX) and Octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX) are very similar molecularly and their burning rates as a function of pressure are nearly identical, it is well known that they differ significantly in temperature sensitivity, especially at low pressures. To understand these differences better, three simple models were applied to HMX and RDX combustion. Both the Denison–Baum–Williams and Li–Williams–Margolis models have previously been calibrated for use with RDX. However, the RDX calibration of the Ward–Son–Brewster model was developed in the present work. All three models were compared with relevant measured data including: burning rate, flame stand-off/thickness, combustion stability, and temperature sensitivity. It was shown that all models are capable of accurately determining the burning rate of HMX and RDX as a function of pressure at the baseline initial temperature, but only two of the models are capable of capturing the variation in temperature sensitivity for both HMX and RDX, and only one model can replicate all the other measured characteristics within experimental uncertainty. Analysis using this model suggests that the surface reaction of RDX is much less exothermic than HMX and that there is a shifting between the gas phase and surface reaction dominance with pressure for HMX. This explains why the temperature sensitivity for RDX is nearly flat for low pressures while the temperature sensitivity for HMX increases significantly as the pressure decreases. Importantly, these trends are achieved without adding significant model complexity or having parameters change with pressure or initial temperature.     

Unreacted equation of states of typical energetic materials under static compression:A review

The unreacted equation of state(EOS) of energetic materials is an important thermodynamic relationship to characterize their high pressure behaviors and has practical importance. The previous experimental and theoretical works on the equation of state of several energetic materials including nitromethane, 1,3,5-trinitrohexahydro-1,3,5-triazine(RDX),1,3,5,7-tetranitro-1,3,5,7-tetrazacyclooctane(HMX), hexanitrostilbene(HNS), hexanitrohexaazaisowurtzitane(HNIW or CL-20), pentaerythritol tetranitrate(PETN), 2,6-diamino-3,5-dinitropyrazine-1-oxide(LLM-105), triamino-trinitrobenzene(TATB), 1,1-diamino-2,2-dinitroethene(DADNE or FOX-7), and trinitrotoluene(TNT) are reviewed in this paper. The EOS determined from hydrostatic and non-hydrostatic compressions are discussed and compared. The theoretical results based on ab initio calculations are summarized and compared with the experimental data.     

四硝基并哌嗪(TNAD)与一些含能材料混合体系熔点的分子动力学模拟

利用分子动力学模拟方法预测了TNAD/HMX、TNAD/RDX、TNAD/DINA和TNAD/DNP四种混合体系的熔点, 利用比容与温度的曲线拐点决定了四种混合体系的熔点． 结果是TNAD/HMX、TNAD/RDX、TNAD/DINA的熔点分别为500、536、488 K．而TNAD/DNP体系没有明显的熔点,表明此体系是不相容的．利用熔点进一步预测了四种体系的相容性,分析了它们的径向分布函数．TNAD与HMX、RDX、DINA和DNP之间的分子间相互作用是近距离相互作用,且相容性越好,分子间相互作用越强     

Factors affecting the NQR line width in nitramine explosives

A number of factors associated with crystal quality contribute to the nuclear quadrupole resonance (NQR) line width. Imperfections such as dislocations, voids, strain and impurities can be electrical sources that distort the electric field gradient at nearby quadrupolar nuclei and broaden the observed NQR line. We measured the¹⁴N NQR line widths in powdered samples of the nitramine explosives hexahydro-1,3,5-trinitro-s-triazine (RDX), octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX) and 2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane and show correlations with sample purity, particle size distribution and density. Cast plastic-bonded explosives containing either RDX or HMX were also studied and their line widths compared with those of the powdered samples.     

含能材料中键离解能的密度泛函理论计算

通过计算一个包括臭氧,硝基甲烷以及1,3,5 -三硝基-1,3,5-三氮杂环已烷(RDX)在内的典型系统的键离解能,对由四种交换/相关函数(BLYP,B3LYP,B3PW91和B3P86)加上不同的基函数组合而成的多种密度泛函方法的准确性进行了比较研究.结果表明:B3P86/6-31G**是计算该系统C-NO2,O-O和N-NO2键离解能的最可靠的方法.     

Structural,elastic, thermodynamic and electronic properties of LuX (X = N,Bi and Sb) compounds: first principles calculations

ABSTRACT

The structural, electronic, elastic and thermodynamic properties of LuX (X = N, Bi and Sb) based on rare earth into phases, Rocksalt (B1) and CsCl (B2) have been investigated using full-potential linearized muffin-tin orbital method (FP-LMTO) within density functional theory. Local density approximation (LDA) for exchange-correlation potential and local spin density approximation (LSDA) are employed. The structural parameters as lattice parameters a₀, bulk modulus B, its pressure derivate B’ and cut-off energy (E_c) within LDA and LSDA are presented. The elastic constants were derived from the stress–strain relation at 0 K. The thermodynamic properties for LuX using the quasi-harmonic Debye model are studied. The temperature and pressure variation of volume, bulk modulus, thermal expansion coefficient, heat capacities, Debye temperature and Gibbs free energy at different pressures (0–50 GPa) and temperatures (0–1600 K) are predicted. The calculated results are in accordance with other data.     

Structure and detonation performance of a novel HMX/LLM‐105 cocrystal explosive

Intermolecular interactions and properties of octahydro‐1,3,5,7‐tetranitro‐1,3,5,7‐ tetrazocine (HMX) / 2,6‐diamino‐3,5‐dinitropyrazine‐1‐oxide (LLM‐105) cocrystal were studied by using the dispersion‐corrected density functionals (ωB97XD, B97D) and meta‐hybrid functional (M062x) methods. Binding energies, heats of formation, thermodynamic properties, atoms in molecules, and natural bond orbital analysis were performed to investigate HMX/LLM‐105 complexes. Results show that the main intermolecular interactions between HMX and LLM‐105 are CH…O, NH…O, N…O, and O…O interactions. In addition, Monte Carlo simulation was employed to predict the crystal structure of HMX/LLM‐105 cocrystal. The HMX/LLM‐105 cocrystal is most likely to crystallize in C2/c space group, and its corresponding cell parameters are Z = 8, a = 41.63 Å, b = 6.77 Å, c = 45.63 Å, ß = 164.55°, and ρ = 1.99 g/cm³. Detonation velocity and pressure of HMX/LLM‐105 cocrystal are 8.95 km/s, 37.69GPa, a little lower than those of HMX (9.10 km/s, 37.76GPa). However, according to the net charges of nitro group, HMX/LLM‐105 cocrystal exhibits less sensitive than HMX. Finally, bond dissociation energy calculation shows that HMX/LLM‐105 complexes are thermally stable. Considering thermal stability, sensitivity, and detonation performance, HMX/LLM‐105 cocrystal meets the requirements of insensitive high energy density materials. Copyright © 2013 John Wiley & Sons, Ltd.