DFT study on the effect of relative positions of methyl-, nitro- and N→oxide groups on the molecular structure,thermal/kinetic stability,crystal density,heat of decomposition and performance characteristics of triazolones

Methyl-, nitro- and N→oxide substituted triazolones are of interest in the contest of high-energy density compounds and have been found to have true local energy minima at the B3LYP/aug-cc-pVDZ level. The optimised structures, harmonic frequencies and thermodynamic values for all the model molecules have been obtained in their ground state. The velocity of detonation (D) and detonation pressure (P) have been evaluated by the Kamlet–Jacob equations using the crystal density and the heat of explosion. The estimated performance properties are higher (D = 9.92–10.27 km/s, P = 48.10–52.52 GPa) compared with 2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane (D = 9.20 km/s, P = 42.0 Gpa). The higher densities are possibly due to the intramolecular hydrogen bonds and the layered structures in the crystal lattice. We speculate that the calculated heat of explosion and the density are for the gas phase compounds and in the reality they should be for the solid phase which would diminish the magnitude of the calculated values. The –N→O and –NO₂ group leads to the desirable consequences of higher heat of explosion and diminished sensitivities. The substituting of N–H hydrogen atom(s) of triazolones for a –CH₃ group decreases melting point, heat of formation and density; however, the methyl group increases the thermal stability.     

用GGA+U法研究稀土掺杂对ZnO电子结构磁性和光学性质的影响

基于自旋密度泛函理论框架下的广义梯度近似平面波模守恒赝势方法,确定了准确计算Zn_(16)O_(16)超晶胞各原子对应的U值;通过计算形成能和化学键的布局分析了掺杂结构的稳定性;通过原子电荷布局和自旋电子态密度的计算分析了掺杂结构的能带结构和磁性状态;讨论了各稀土原子掺杂对ZnO吸收光谱的影响.结果表明:稀土元素的引入使晶格膨胀,Zn-O键最长键增大而最小键减小,导致氧四面体畸变;Y/La/Ce掺杂的ZnO具有亚铁磁性,Th掺杂ZnO则呈弱铁磁性,Ac掺杂ZnO为顺磁体;稀土元素使ZnO的价带和导带下移,费米能级进入导带,增强了体系的电导率;Y/La/Ac掺杂对ZnO带隙宽度的影响较小,吸收光谱略微蓝移,而Ce/Th掺杂则有效提升了ZnO对可见光的吸收.     

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基于Hasegawa-Wakatani湍流模型,数值模拟了托卡马克边缘等离子体中漂移波湍流和相关的反常粒子输运.从等离子体动量守恒方程出发导出了不采用常规的布辛涅斯克近似的带状流方程,论证了大振幅密度扰动和湍性粒子流对激发带状流的贡献可等效地对应于低阶负粘滞阻尼效果.数值模拟表明,大振幅密度扰动的非线性大大增强了带状流饱和振幅,从而有效抑制了湍性粒子输运.研究结果阐明了托卡马克边缘等离子体大振幅密度扰动的非线性对驱动等离子体旋转、动量输运和带状流的重要性.     

利用光泵磁共振曲线测量氢原子密度

本文给出利用光泵磁共振曲线测量氢原子密度的实验.在我们的实验中,当射频源放电功率一定时,在25~61℃的泡温范围内测量到9.2×10¹¹~1.6×10¹¹(原子/厘米³)的氢原子密度.实验结果表明,当放电功率一定时,氢原子密度随泡温升高而下降.     

HL—1装置密度极限破裂分析

HL-1装置上观测到大量的密度极限破裂放电。其主要特性是破裂前偏离几何中心的磁面位移很小,中心区总是观测到锯齿现象,破裂后,其电流中断时间大于20ms。本文详细分析了出现在电流上升段,坪段及下降段密度极限破裂的特征。其中一类是由于辐射功率超过加热功率所确定的村上极限,没有观测到先兆振荡;另一类是由于约束变坏所确定的赫吉尔极限,可观测到驰豫几毫秒的先兆振荡,这类放电破裂后多数能恢复。该装置运行的最大村上参数是0.35×10~(20)m~(-2).T~(-1)。     

溴化苄及其阳离子红外光谱的理论研究

利用密度泛函理论（DFT）在B3LYP/6-311G++（d,p）水平上对溴化苄分子进行了结构优化和频率计算,得到了该分子的稳定构型和全部振动模式。计算得到的几何参数通过与苯分子的实验值相比,发现理论值与其相吻合;理论计算和实验测得的红外光谱数据的比较分析表明,理论计算与实验测量结果符合得较好,并对其振动模式进行了归属。最后,在B3LYP/6-311G++（d,p）水平上计算得到了溴化苄阳离子的红外光谱,并与溴化苄进行了比较,计算表明电离对振动偶极距产生了较大影响。     

First-principles study on the electronic structures of iron phthalocyanine monolayer

The electronic band structure and magnetic properties of iron phthalocyanine (FePc) monolayer were investigated by using the first-principles all-electron full-potential linearized augmented plane wave energy band method. It is found that the ferromagnetic FePc monolayer is energetically more stable than the paramagnetic one. The exchange interaction, which splits the majority and minority bands, influences strongly on the electronic structure near the Fermi level (E_F). Magnetic moment of the central Fe atom is calculated to 1.95 μ_B. The range of the positive polarization of Fe site is larger in the out-of-plane than in the in-plane direction. The FePc ligand remains paramagnetic. The presence of states at E_F indicates the metallic character of FePc monolayer both for the paramagnetic and ferromagnetic states. However, the large density of states at E_F of the majority spins in the ferromagnetic state is expected to cause a phase transition to insulating antiferromagnetic state from the metallic ferromagnetic one.     

Surface core level shift observed on NiAl(1 1 0)

Using high resolution core level spectroscopy, a surface core level shift towards lower binding energy of −0.13 eV is determined for the 2p level of the outwardly relaxed Al surface atoms on NiAl(1 1 0). Density functional theory based calculations with inclusion of final state effects yield a value of −0.14 eV for this shift in excellent agreement with experiment. We show that the initial state approximation yields a value of +0.09 eV, i.e. the inclusion of final state relaxation effects is vital not only to obtain the correct value but even the correct sign for this shift.     

封装椭圆形C70的手性纳米管的理论表征

应用第一性原理计算,研究了椭圆形的C₇₀分子在碳纳米管中的可能取向．采用(14,7)单壁纳米管为原型材料,发现纳米管和C₇₀分子的弱化学相互作用是决定分子取向的决定因素．通过模拟扫描隧道显微镜图像和计算光学性质,发现封装的椭圆体C₇₀分子的局域电子结构敏感地依赖于分子取向     

锰氧化物团簇正离子与硫化氢反应的实验与理论研究 (cited: 2)

采用激光溅射法制备了同位素标记的氧化锰团簇正离子Mn_m¹⁸O_n⁺,并研究了其在快速流动反应管中与硫化氢在热碰撞条件下的反应,氧化锰团簇正离子与硫化氢反应前后的质量分布与强度变化由飞行时间质谱仪检测．实验表明,绝大多数氧化锰团簇正离子可与硫化氢发生氧-硫交换反应产生水分子,反应通式为：Mn_m¹⁸O_n⁺+H₂S→Mn_m¹⁸O_n-1S⁺+H₂¹⁸O．通过密度泛函理论计算了氧化锰团簇正离Mn₂O₂⁺、Mn₂O₃⁺和Mn₂O₄⁺与H₂S反应的机理,结果显示,在这些反应体系中氧-硫交换反应通道同时具有热力学和动力学优势,印证了实验中观察到的现象．气相团簇研究发现的氧-硫交换反应与相关凝聚相体系反应结果一致