氟代吡啶阳离子的理论研究

利用量子化学密度泛函理论B3LYP方法及 6 31G(d ,p)、6 311G(d ,p)、6 31+G(d ,p)和 6 311+G(d ,p)基组对五氟代吡啶、2 ,6 二氟代吡啶和 2 氟代吡啶分子的阳离子进行了计算研究 .B3LYP构型优化和频率分析计算结果表明这三种氟代吡啶阳离子的结构分别具有C2v、C2v和Cs 对称性 ,电子基态分别为2 A2 、2 A2 和2 A″ .对离子和分子的计算构型做了比较 .利用B3LYP方法和不同的基组对这三种阳离子及其分子进行了自然布居分析计算 .用B3LYP方法对这三种阳离子 (自由基 )中的超精细结构进行了计算 ,对五氟代吡啶、2 ,6 二氟代吡啶和2 氟代吡啶分子的垂直电离势和绝热电离势进行了计算 ,与实验值符合得很好     

Spectral anomalies and spectral switches of partially coherent and polychromatic light diffracted at an aperture

Inrecentyearsanewbranchofmodernphysicalopticscalledsingularoptics[1]hasbeendeveloped.In2002theworkinsingularopticswasextendedfrommonochromaticlighttospatiallyfullycoherentandpolychromaticlightbyGburetal.[2—4].Itwasfoundthat,whenaconverging,spatiallyfullycoherentandpolychromaticsphericalwaveisdiffractedatanaperture,anomalousspectralchangestakeplaceclosetozerosoftheintensityinthefarfield;i.e.thespectrumisredshiftedatsomepoints,blueshiftedatothers,andsplitintotwolineselsewhere.Thepredictionsofsp…     

Real-time visualisation of deformation fields using speckle interferometry and temporal phase unwrapping

A real-time system for analysing data from speckle interferometers, and speckle shearing interferometers, has been developed. Interferograms are continuously recorded by a digital camera at a rate of 60 frames s⁻¹ with temporal phase shifting carried out at the same rate. The images are analysed using a pipeline image processor. With a standard 4-frame phase-shifting algorithm (phase steps of π/2), wrapped phase maps are calculated and displayed at 15 frames s⁻¹. These are unwrapped using a temporal phase unwrapping algorithm to provide a real-time colour-coded display of the relevant displacement component. Each camera pixel (or cluster of pixels) behaves in effect as an independent displacement sensor. The reference speckle interferogram is updated automatically at regular user-defined intervals, allowing arbitrarily large deformations to be measured and errors due to speckle decorrelation to be minimised. The system has been applied to the problem of detecting sub-surface delamination cracks in carbon fibre composite panels.     

Structural study and electrical properties of Zr-doped Nd<Subscript>2</Subscript>Sn<Subscript>2</Subscript>O<Subscript>7</Subscript> pyrochlore compounds

Nd₂Sn₂O₇ pyrochlores with the substitution of Zr⁴⁺ were prepared by conventional ceramic double sintering technique. The single-phase formation was confirmed by X-ray diffraction and neutron diffraction techniques. Relative intensity calculations for X-ray diffraction analysis were performed for oxygen positional parametersx = 0.331 and 0.375, while Rietveld refinements were employed for neutron diffraction data. The neutron diffraction study revealed that there are only two anion sites with 48f and 8b positions. This indicates that the 8a site, i.e. O(3) sublattice, is completely vacant and the structure is a perfect cubic pyrochlore with space group Fd3m (O _h ⁷ ). From the conductivity measurements, it is observed that the electronic conductivity dominates from room temperature up to about 525 K and forT > 525 K, the oxygen ion conduction dominates the charge transport in these compositions. Complex impedance spectroscopy indicates the existence of grain and grain boundary as two separate elements.     

若干具有[(PO_4)_4Mo_6~ⅤO_(15)]~(12-)簇骼的化合物的光谱研究

用FTIR ,NIRFT Raman ,UV VisDRS和荧光光谱等对五个新型具有 [(PO4) 4 MoⅤ6O15]12 -阴离子簇的化合物 :Na·(H4TETA) 3 ·(H3 O) 5·{Zn[(HPO4) 2 (PO4) 2 Mo6O15]2 } (2 ) ,(H2 en) 7·(H3 O) 4 ·{Cu[(HPO4) 2(PO4) 2 Mo6O15]2 }·H2 O (3) ,(H3 DETA) 2 ·(H3 O) 3 ·{Co0 5[(HPO4) 2 (PO4) 2 Mo6O15]}·H2 O (4) ,[Co(H3 TETA) ]2 {Co0 5[(HPO4) (PO4) 3 Mo6O15]}· 3 5H2 O (5 )和 (H3 DETA)· (H3 O ) 4 · {Co1 5[(HPO4) 2(PO4) 2 Mo6O15]}·0 5H2 O (6 ) ,进行研究 ,并探讨其结构和性能的关系。这些化合物具有 {M [(PO4) 4 Mo6O15]2 }二聚体单元 ,化合物 2～ 4的二聚体间通过与有机分子和水分子的氢键形成三维网状结构 ;化合物 5和 6的 {Co[(PO4) 4 Mo6O15]2 }二聚体间是分别通过 [CoH3 TEATA]基团和CoO4四面体组成网状结构。磷钼酸盐的特征振动频率和这些化合物的结构相关 ;化合物的三个UV VisDRS特征谱带分别属于Od→Mo,Oμ→Mo和O→M电荷转移 ;观察到以 2 4 0nm激发 ,在 4 10nm附近出现的由Oμ→Mo跃迁激发引起的较强的荧光发射谱带。     

The ν4 and ν2 + ν5 high resolution infrared bands of FClO3 and FClO3

The high resolution infrared spectra of monoisotopic F³⁵Cl¹⁸O₃ and F³⁷Cl¹⁸O₃ have been studied in the region of the ν₄ fundamentals, centered at 1278.3 and 1263.3 cm⁻¹, respectively. Large perturbations are observed in both bands due to a Fermi type anharmonic resonance with the ν₂ + ν₅ combination bands, centered at 1270.7 cm⁻¹ in F³⁵Cl¹⁸O₃ and 1257.3 cm⁻¹ in F³⁷Cl¹⁸O₃. In particular, they affect the kl > 0 levels of the v₄ = 1 and v₂ = v₅ = 1 states which cross at kl ? 18 in F³⁵Cl¹⁸O₃ and kl ? 3 in F³⁷Cl¹⁸O₃, due to the opposite values of and . The Δl = Δk = ±2 and Δl = 0, Δk = ±3 essential resonances are also effective in the excited states of the dyad in F³⁵Cl¹⁸O₃, while in F³⁷Cl¹⁸O₃ only the Δl = Δk = ±2 one is active. In the spectrum of F³⁵Cl¹⁸O₃ 3423 transitions have been assigned, 10% of them belonging to ν₂ + ν₅. The rovibrational parameters and the interaction constants between the v₄ = 1 and v₂ = v₅ = 1 levels have been obtained. The depertubed band origins of ν₄ and ν₂ + ν₅ are 1277.310567(165) and 1271.753733(195) cm⁻¹, respectively, and the anharmonic resonance constant is 2.804416(153) cm⁻¹. For F³⁷Cl¹⁸O₃, 3022 transitions have been assigned, 38% belonging to the ν₂ + ν₅ combination band. The depertubed band origins are 1260.856338(123) and 1259.872338(134) cm⁻¹, for ν₄and ν₂ + ν₅ and the constant is 2.9350669(405) cm⁻¹. The equilibrium geometry of perchloryl fluoride, r_e (ClO) = 139.7(3) pm, r_e (ClF) = 161.0(5) pm, and α_e (OClO) = 115.7(4) degree, has been determined using the A_e and B_e equilibrium constants of the four symmetric isotopologues of perchloryl fluoride, F^35/37Cl¹⁶O₃ and F^35/37Cl¹⁸O₃.     

Tomographic analysis of the central magnetohydrodynamic oscillations on the HT-7 tokamak

Multi-channel soft x-ray (SX) detectors are applied to generate images of magnetohydrodynamic (MHD) oscillation on the HT-7 tokamak, and the data from SX cameras are analysed by using the Fourier--Bessel harmonic reconstruction method and the singular value decomposition. The image reconstruction of SX emissivity is obtained on the assumption of plasma rigid rotation. One of the important phenomena in the HT-7 discharge is the transition from the sawtooth oscillations to the MHD oscillations when the plasma density grows higher. The MHD structure observed in the SX tomography is featured as follows: the magnetic surface of MHD structure is made up of the crescent-shaped ``hot core' and the circular ``cold bubble'. The structure of the magnetic surface is relatively stable. It rotates in the direction of the electron diamagnetic drift at a frequency being the oscillation frequency of the MHD oscillations.     

Effects of initial frequency chirp on the linear propagation characteristics of the exponential optical pulse

In this paper, the linear propagation characteristics of the exponential optical pulse with initial linear and nonlinear frequency chirp are numerically studied in a single mode fibre for \be₂<0. It can be found that the temporal full width at half maximum and time-bandwidth product of exponential pulse monotonically increase with the increase of propagation distance and decrease with the increase of linear chirp C for C<0.5, go through an initial decreasing stage near \zeta=1, then increase with the increase of propagation distance and linear chirp C for C\geq0.5. The broadening of pulses with negative chirp is faster than that with positive chirp. The exponential pulse with linear chirp gradually evolves into a near-Gaussian pulse. The effect of nonlinear chirp on waveform of the pulse is much greater than that of linear chirp. The temporal waveform breaking of exponential pulse with nonlinear chirp is first observed in linear propagation. Furthermore, the expressions of the spectral width and time-bandwidth product of the exponential optical pulse with the frequency chirp are given by use of the numerical analysis method.     

Expressions for Entropy Production Rate of Fuel Cells

基于燃料电池的一般模型,应用电化学和热力学理论导出燃料电池系统在不同条件下熵产生率的表示式．为了分析存在实际燃料电池中不可逆损失的影响,引进燃料电池的等效电路,直接将燃料电池的不可逆因子表示为内电阻、漏电阻和负载电阻的函数．进而计算燃料电池的最大输出功率和效率,讨论燃料电池的优化运行,确定负载电阻的匹配条件,从而得到一些有意义的结果．     

多晶AlN光学性质研究

运用X射线衍射仪和拉曼光谱仪,测量了物理气相输运(PVT)方法生长的AlN多晶材料的X射线衍射和常温拉曼光谱。常温拉曼光谱研究了晶界、晶面方向与拉曼频率的关系,观察到了E和E峰位基本不随测量位置变化,与晶界无关,但是E1(TO),A1(LO)和Quasi-LO声子峰位却明显与晶界有关,为研究晶粒间、晶粒内应力提供了有效手段。