Zn(NCN)单轴的负热膨胀性及机理研究

负热膨胀(NTE)是一种反常的物理现象, 已在合金和框架结构化合物等材料中被观察到, 但NTE材料的种类仍然有限. 本文合成了一种单轴NTE材料Zn(NCN), 该材料在c轴方向及在100~475 K下的热膨胀系数为-3.35×10^?6 K^?1, 而a轴和b轴方向则呈低热膨胀性, 体积具有低的热膨胀系数[6.13×10^?6 K^?1(100~475 K)]. 通过同步辐射X射线衍射、 扩展X射线吸收精细结构和拉曼光谱等方法, 研究了Zn(NCN)的NTE机理. 结果表明, Zn—N键具有明显的横向振动, 一些低频振动模Grüneisen参数为负值. 直接的实验证据表明, N=C=N的横向振动以及准刚性ZnN₄四面体的耦合旋转和扭摆导致了c轴方向的NTE.     

Ab initio potential energy surface and vibration‐rotation energy levels of silicon dicarbide,SiC2

The accurate ground‐state potential energy surface of silicon dicarbide, SiC₂, has been determined from ab initio calculations using the coupled‐cluster approach. Results obtained with the conventional and explicitly correlated coupled‐cluster methods were compared. The core‐electron correlation, higher‐order valence‐electron correlation, and scalar relativistic effects were taken into account. The potential energy barrier to the linear SiCC configuration was predicted to be 1782 cm^?1. The vibration‐rotation energy levels of the SiC₂, ²⁹SiC₂, ³⁰SiC₂, and SiC¹³C isotopologues were calculated using a variational method. The experimental vibration‐rotation energy levels of the main isotopologue were reproduced to high accuracy. In particular, the experimental energy levels of the highly anharmonic vibrational ν₃ mode of SiC₂ were reproduced to within 6.7 cm^?1, up to as high as the v₃ = 16 state.     

Density Functional Theory Study on the Adsorption of Dioxygen on Small Pt-Pd Clusters

1 INTRODUCTION The bimetallic nanoclusters are of standing inte- rest since they can exhibit catalytic, electronic and optical properties distinct from those of corre- sponding pure nanoclusters[1～4]. Palladium and pla- tinum, well known for their catalytic properties, are often used as the catalyst in different fuel cells[5～8]. Several experimental results illustrate that for the oxygen reduction reaction (ORR), which is one of the primary reactions taking place in many fuel cells and…     

Are the pyrazolines formed from the reaction of [60]fullerene with alkyl diazoacetates unstable?

[60]Fullerene-fused pyrazolines 1 were prepared by the reaction of C₆₀ with alky diazoacetates under the solid-state high-speed vibration milling conditions as well as in toluene solution. Pyrazolines 1 were stable in refluxing toluene and its thermolysis process in 1,2-dichlorobenzene was investigated, the decomposition rates and activation energies of pyrazolines 1 were obtained. The current work demonstrated that the liquid-phase reaction of C₆₀ with alkyl diazoacetates undergoes via 1,3-dipolar cycloaddition pathway at room temperature, or proceeds via carbene mechanism at a temperature of refluxing toluene, thus clarifies the previous ambiguity of its reaction mechanism.     

Energy transfer rates and impact sensitivities of two classes nitramine explosives molecules

Some explosives are stable molecules with large energy barriers to chemical reaction, and in shock or impact initiation, a sizable amount of phonon energy must be converted to the molecular internal higher vibrations by multiphonon up pumping. To investigate the relationship between impact sensitivities and energy transfer rates, the number of doorway modes of explosive molecules is estimated by a simple theory in which the rate is proportional to the number of normal mode vibrations. We evaluated frequencies of normal mode vibrations of 13 explosive molecules which are CHNO nitramine-contained and have not been analyzed previously. The number of doorway modes in the regions of 200–700 cm⁻¹ was evaluated by the direct counting method. For more clear investigation of the relationship we have classified these 13 nitramine explosive molecules, by the number of nitramine group they contained, into two groups. There are eight molecules that contained one nitramine group and five molecules that contained poly-nitramine groups. It is found that the number of doorway modes shows a linearly correlation to the impact sensitivities derived from drop hammer tests. This result is in agreement with that of several previous works. Besides, it is also noted in our study that in those nitramine explosives molecules with similar molecular structure (similar number nitramine group they contained) and similar molecular weight, the correlation between the sensitivity and the number of doorway modes is higher. We found that the vibrational frequency of ω corresponds to nitro group motions of every molecule is contributed to the number of doorway modes in the regions of 200–700 cm⁻¹.     

Ab initio study of the structure and conformations of 2-fluoroethanal in the ground and lowest excited electronic states

The structure of the conformationally flexible 2-fluoroethanal molecule (CH₂FCHO, FE) in the ground (S₀) and lowest excited triplet (T₁) and singlet (S₁) electronic states was investigated by ab initio quantum-chemical methods. The FE molecule in the S₀ state was found to exist as two conformers, viz., as cis (the F—C—C—O angle is 0°) and trans (the F—C—C—O angle is 180°) conformers. On going both to the T₁ and S₁ states, the FE molecule undergoes substantial structural changes, in particular, the CH₂F top is rotated with respect to the core and the carbonyl CCHO fragment becomes nonplanar. The potential energy surfaces for the T₁ and S₁ states are qualitatively similar, viz., six minima in each of the excited states of FE correspond to three pairs of mirror-symmetrical conformers. Based on the potential energy surfaces calculated for the FE molecule in the T₁ and S₁ states, the one-dimensional problems on the torsion and inversion nuclear motions as well as the two-dimensional torsion-inversion problems were solved.     

共线散射体系A+BC的平-振能量传递──无限维李代数处理方法

利用无限维李代数方法处理了在BC分子能谱中含有二级与三级非简谐项的散射体系A＋BC的平-振能量传递问题，获得了散射过程的含有主要动力学参量的跃迁矩阵元和跃迁几率的解析表达式     

Free vibration of functionally graded sandwich plates using four-variable refined plate theory

This paper uses the four-variable refined plate theory (RPT) for the free vibration analysis of functionally graded material (FGM) sandwich rectangular plates.Unlike other theories, there are only four unknown functions involved, as compared to five in other shear deformation theories. The theory presented is variationally consistent and strongly similar to the classical plate theory in many aspects. It does not require the shear correction factor, and gives rise to the transverse shear stress variation so that the transverse shear stresses vary parabolically across the thickness to satisfy free surface conditions for the shear stress. Two common types of FGM sandwich plates are considered, namely, the sandwich with the FGM facesheet and the homogeneous core and the sandwich with the homogeneous facesheet and the FGM core. The equation of motion for the FGM sandwich plates is obtained based on Hamilton's principle. The closed form solutions are obtained by using the Navier technique. The fundamental frequencies are found by solving the eigenvalue problems. The validity of the theory is shown by comparing the present results with those of the classical, the first-order, and the other higher-ordex theories. The proposed theory is accurate and simple in solving the free vibration behavior of the FGM sandwich plates.     

航空发动机旋转叶片振动监测系统研究

介绍了叶尖定时测量旋转叶片的原理，设计的光纤柬式传感结合光电接收实现了高精度的弱光检测。基于“5＋2”传感器均布方案，利用双速率对叶片振动信号进行采样，通过“5＋2”处理算法实现了振动频率的准确辨识，并在某航空设备上进行了高速模拟转子实验，实验表明测得频率与应变仪结果一致。