Rotational spectra of the diastereomers of Soman

The pure rotational spectrum of the nerve agent Soman has been recorded using a pulsed-molecular-beam Fourier-transform microwave spectrometer. The spectrum consists of transitions from two different isomers. The two distinguishable isomers are likely the [SS] (or [RR]) and the [RS] (or [SR]) diastereomers that result from the two chiral centers in the molecule. The rotational constants determined for the A internal rotor states of the [SS, RR] and [RS, SR] isomers are A=1645.39765(9) MHz, B=591.97752(3) MHz, and C=547.58168(3) MHz, and A=1635.0580(1), B=600.14889(6), and C=556.45840(6) MHz, respectively, where type A, k=1 or 1σ standard uncertainties are given. Structural assignments of the diastereomers were made based on comparisons of the calculated electric dipole moments at the MP2/6-311G level of theory with the observed selection rules. Many of the rotational transitions are split into doublets and correspond to the A- and E-state transitions arising from internal rotation of the methyl top attached to the phosphorus atom. These splittings have been used to obtain the V₃ barriers of the methyl groups for both diastereomers. This work is part of an ongoing project aimed at generating a spectral database of chemical agents and related families of compounds.     

PVP对Nylon 6形貌及结晶行为影响的研究

采用变温红外光谱、示差扫描量热（DSC）和偏光显微镜（POM）等方法研究了聚乙烯吡咯烷酮（PVP）与尼龙6（nylon 6）分子间的相互作用及其对nylon 6热行为及结晶形貌的影响。DSC结果表明PVP的加入明显影响了nylon 6的熔融和结晶行为：随着PVP含量增加,PVP/nylon 6共混物的结晶温度、熔融温度及结晶度均逐渐降低;POM观察显示：随着PVP含量增多,nylon 6的球晶尺寸变小、球晶逐渐变得不完善。变温红外光谱结果表明,无定形PVP分子的羰基能够与nylon 6分子的N—H基团形成新的氢键,部分破坏了nylon 6分子之间的氢键结构,从而阻碍了nylon 6分子的规整排列,使其结晶度降低并导致nylon 6结晶形貌的变化。     

Infrared studies of poly[3,3-bis(chloromethyl)oxacyclobutane]. I. Single crystals

Infrared spectra of poly[3,3-bis(chloromethyl)oxacyclobutane] (Penton) single crystals indicate that annealing perfects the crystals in a manner not involving a change in the relative amount of side-group rotational isomers. Other spectral and nonspectral considerations indicate that Penton has a highly crystalline but imperfect paracrystalline structure. The spectral differences between the two polymorphic forms are associated with differences in the magnitude of crystalline interactions rather than differences in relative amounts of side-group rotational isomers. An explanation for the nonthickening annealing behavior of Penton single crystals is offered.     

Electrical conductance properties for magnetic tunnel junctions with MgO barriers

We measured inelastic electron tunneling (IET) spectra and conductance for MgO tunneling magnetoresistance (TMR) films to obtain information on the ferromagnetic/barrier layer interface. The IET spectra showed the difference between amorphous and crystalline structures in the barrier. In the magnetic tunnel junction (MTJ) with a crystalline barrier the IET spectra indicated an Mg-O phonon peak at a low bias voltage by measurement with a parallel magnetization configuration. On the other hand, no peak was observed in the MTJ with an amorphous barrier.     

Review on applications of synchrotron-based X-ray techniques in materials characterization

Synchrotron radiation (SR), as a result of its high-intensity, brilliant, monochromatic, and collimated beams, is becoming one of the most crucial components of research in various fields of materials science such as nanomaterials, biomaterials, and energy materials. SR-based characterization methods can be employed to analyze different systems such as powders, thin films, and bulk forms having complex crystalline or amorphous structures. In this review, peculiarities of SR are briefly explained. Moreover, various techniques carried out utilizing this instrument for material characterization such as X-ray powder diffraction, grazing-incidence X-ray diffraction, small/wide-angle X-ray scattering, X-ray absorption spectroscopy, different techniques of X-ray imaging, X-ray photoelectron spectroscopy, and X-ray microprobes/nanoprobes are presented. As a result, by shedding light on the advantages of SR and its superiority to the equivalent laboratory experiments, researchers are recommended to exploit the capabilities of this invaluable tool in their materials characterization.     

结晶PMMA的NMR研究

用NMR方法和DSC技术研究了结晶聚甲基丙烯酸甲酯(PMMA)性质和玻璃化转变温度,并与无定形PMMA作了比较.通过¹³C CPMAS谱,观察到了结晶PMMA与无定形PM MA的谱的线形,线宽,化学位移都十分类似,其中α-CH₃分裂为两个峰,我们将它归属为γ旁式效应所对应的反式和旁式构象.而反门控碳谱显示PMMA中有四种状态,即等规PMMA结晶态和无定形态,间规PMMA结晶态和无定形态.通过测定T₂(H)和旋转坐标系中质子的自旋晶格弛豫时间T_1ρ(H),我们分别得到了两T₂(H)值和两个T_1ρ(H)值,对应于晶区与非晶区,而且其含量分别与反门控碳谱积分所得含量一致.     

Octaethylporphin films. II absorption and emission of amorphous films

Amorphous thin films octaethylporphin have been prepared and are observed to crystallize over time if thicker than about 100 nm. Transmission spectra of amorphous films have a sharper Soret band than transmission spectra of crystalline films and lack the exciton band seen in crystalline films. The exciton band can be resolved in amorphous films by taking a difference spectrum between two amorphous films of different thickness. Fluorescence is observed from one impurity in amorphous films as compared to two impurities in crystalline films. This indicates a smaller exciton diffusion length in amorphous films as compared to crystalline films, consistent with the differences in the transmission spectra of the two kinds of film.     

Controlling growth of ZnO rods by polyvinylpyrrolidone (PVP) and their optical properties

ZnO rods with different morphologies were synthesized through a wet chemical method by addition of polyvinylpyrrolidone (PVP). By adjusting the concentration of the additive in the growth solution, we can control the diameter, ratio of length to diameter and density of ZnO rods. FESEM images showed that the rods in nanoscale could be obtained at the polyvinylpyrrolidone concentration of 1.0 mM. Meanwhile, the resonant Raman scattering and photoluminescence spectra showed that the crystalline quality and the optical property of ZnO rods were improved through moderate addition of polyvinylpyrrolidone (concentration of 1.0 mM) in the growth solution. In addition, the possible mechanism of the PVP effect on the growth of ZnO rods was discussed based on the FT-IR spectra.     

Initial growth of intrinsic microcrystalline silicon thin film: Dependence on pre-hydrogen glow discharge and substrate surface morphology

We found the decreases of amorphous incubation volume from Raman spectra and surface roughness from AFM in hydrogenated microcrystalline silicon (μc-Si:H) films deposited with a pre-hydrogen glow discharge. The above phenomena are attributed to the increase in the nuclei density as observed by AFM measurements. Substrate surface morphology of eagle2000 glass modified by wet etching also has a positive effect on the nucleation and crystalline formation. In addition, μc-Si:H doped layer is also beneficial for decreasing the amorphous incubation layer thickness because of surface roughness and crystallinity in the μc-Si:H doped layer.     

Electroreflectance and Raman scattering investigation of glow-discharge amorphous Si:F:H

The electroreflectance and Raman scattering spectra of several samples of glow-discharge amorphous Si:F:H films have been investigated. We have observed for the first time modulated optical spectroscopy structure above the absorption edge for a disordered semiconductor. The energy positions of these structures, at 3.4 and 4.5 eV, correspond to peaks seen in crystalline silicon. In particular, the latter feature can be related to the degree of disorder in the material. Also we have seen for the first time in disordered silicon (except for ion-damaged, laser annealed samples) peaks in the Raman spectra intermediate between amorphous (465 cm^-1) and crystalline materials (522 cm^-1). These experimental results provide strong evidence that a-Si:F:H possesses “microcrystalline” or some other intermediate range order (i.e., an improved connectivity between the elements of the random network.)     

Modelling of multifrequency ESR spectra of Fe3+ ions in crystalline and amorphous materials: A Simplified approach to determine statistical distributions of spin-spin coupling parameters

Focussed on the understanding of the complex Fe³⁺ electron spin resonance (ESR) spectra in crystalline and amorphous systems, the simulation program ESR-MAKRO-1 was developed, which allows the calculation of powder spectra of paramagnetic centers with 1/2 ≤S ≤7/2. For the reproduction of the ESR spectra of amorphous systems Gaussian distributions of the zero-field-splitting parameters of second and fourth order (D, E, a, F) were implemented into the program. Applications of ESR-MAKRO-l are given both for crystalline powders and for glassy systems. A stepwise analysis of the ESR spectra, allowing an approach to Fe³⁺ ESR spectra of amorphous matrices and showing the influence ofD, E, a, andF as well as their distributions, is given.     

The effect of TiN nanoparticles deposition with different number of shots on SS316L by plasma focus device

In this paper, we present the result of TiN nanocrystalline deposition on SS316L, using a 4 kJ plasma focus (PF) device for 10, 20, and 30 focus shots. The effect of different number of focus shots on micro-structural changes of thin film is characterized by field emission scanning electron microscope. Existence of grains in different size confirms the formation of TiN nanocrystals on the surface of SS316L substrate. X-ray diffraction (XRD) reveals the formation of a nanocrystalline titanium nitride coating on the surface of SS316L samples. The crystalline size of TiN obtained from XRD data is strongly dependent on the number of focus shots. Thickness of the elements found on the surface of the treated sample that obtain by Rutherford backscattering spectroscopy (RBS) analysis is in the range of 150×10¹⁵?200×10¹⁵ atoms/cm². All the existence elements in the coated samples are identified by Particle Induced X-ray Emission (PIXE) spectra. Investigation on the corrosion resistance of TiN coatings was performed using an electrochemical potentiodynamic polarization. Our results suggest that TiN nanocrystalline implantation with proper ion fluences using PF can significantly improve the corrosion resistance of SS316L.     

Muon study of the intermetallic hydrides Zr2NiH x

Zero-field μSR experiments have been carried out in crystalline and amorphous hydrides of Zr₂Ni using the pulsed muon beam available at the Rutherford Appleton Laboratory. The main result of this study is the fact that the motion of the muon relative to the protons (hydrogen) appears to be significantly slower than the hydrogen motion observed by¹⁸¹Ta PAC or¹H NMR. An explanation of this paradoxical effect is suggested. Affiliated to the Centre National de la Recherche Scientifique.     

Experimental study of the amorphous phases of group-IV semiconductors by the119mSn Mössbauer probe

The amorphous phases of silicon, germanium, and -tin have been studied by Mössbauer emission spectroscopy on ion-implanted, radioactive^119mSn. Amorphous samples have been produced by ion implantations of various elements and by vacuumevaporation techniques. The same well-defined type of complex spectrum is observed for all investigated amorphous samples. These spectra are characterized by an increase in average isomer shift of (0.15±0.03) mm/s, a line broadening of 20±2%, and the same Debye temperature as compared with spectra of substitutional Sn in the respective crystalline host lattices. The spectra are proposed to originate from Sn atoms incorporated substitutionally in the amorphous host with distorted local surroundings. The recrystallization of the amorphous phase upon thermal and laser annealing has been monitored. After appropriate annealing, spectra characteristic of crystalline materials are observed for most samples. An exception are high-dose, inert-gas implanted samples where different complex defects seem to be formed in the annealing process.     

过渡区p型氢化硅氧薄膜结构和光电特性的研究

采用射频等离子体增强化学气相沉积技术,利用二氧化碳(CO_2)、氢气(H_2)、硅烷(SiH_4)和乙硼烷(B_2H_6)作为气源,制备出一系列p型氢化硅氧薄膜.利用拉曼光谱、傅里叶变换红外光谱和暗电导测试,研究了不同二氧化碳流量对薄膜材料结构和光电特性的影响,获得了从纳米晶相向非晶相转变的过渡区P层.研究表明:随着二氧化碳流量从0增加到1.2 cm~3·min~(-1),拉曼光谱的峰值位置从520 cm~(-1)逐渐移至480 cm~(-1).材料红外光谱表明,随着二氧化碳流量的增加,薄膜中的氧含量逐渐增加,氢键配置逐渐由硅单氢键转换为硅双氢键.P层SiO:H薄膜电导率从3S/cm降为8.3×10~(-6)S/cm.所有p型SiO:H薄膜的光学带隙(Eopt)都在1.82—2.13 eV之间变化.在不加背反射电极的条件下,利用从纳米晶相向非晶相转变的过渡区P层作为电池的窗口层,且在P层和I层之间插入一定厚度的缓冲层,制备出效率为8.27%的非晶硅薄膜电池.     

Electron structure and spin dynamical properties of crystalline and amorphous rare-earth intermetallics from Mössbauer and μSR experiments

A comparative study of crystalline and amorphous DyAg using¹⁶¹Dy Mössbauer spectroscopy is presented as a way to gain insight into the changes in electronic structure and spin dynamical properties of the rare-earth ion when its local surrounding is randomly distorted. It can be seen, especially in the paramagnetic regime, that the influence of the lowering of local symmetry is significant in both the electronic ground state of Dy³⁺ and the fluctuation rate of the local magnetic moment. At high-spin fluctuation rates, Mössbauer spectroscopy rapidly becomes insensitive, while muon spin relaxation (μSR) has still a high power of resolution. μSR measurements on Laves phase intermetallics are used to demonstrate the presence of paramegnetic spin correlations far above the Curie temperature. First measurements of this kind on crystalline and amorphous DyAg will also be discussed.     

聚合物PVP表面修饰CdS纳米棒的制备及其光谱特性

用水热合成方法制备了PVP表面修饰CdS纳米棒,用XRD,TEM,TG-DTA,IR,UV-Vis,PL等光谱技术进行了表征。与未修饰的CdS纳米棒相比,PVP修饰后的CdS纳米棒具有更均匀的尺寸分布,吸收光谱具有结构峰特征,其荧光发射谱增强。     

Magnetic hyperfine properties in FeZrB‐type nanocrystalline metallic alloys

Transmission Mössbauer spectra were performed on FeZrB nanocrystalline alloys with high crystalline fraction (≈60%)at temperatures comprised within the range 77–600 K. We report the temperature dependencies of the magnetic hyperfine data of the three contributions: the crystalline bcc‐Fe grains, the residual amorphous phase, and the interface intermediate between the bulk of crystalline and amorphous phases. The evolution of the average value of the hyperfine field characteristic of the residual amorphous phase is discussed in terms of interactions between crystalline grains transmitting through the intergranular phase.     

纳米硅薄膜光吸收谱的研究

用恒定光电导法测量了纳米硅(其晶粒尺寸为3-5nm,晶态成分比X_c为45％—50％)薄膜在0.9—2.5eV范围的光吸收谱。分析了在不同光子能量范围可能存在的对光电导作主要贡献的几种光跃迁过程,以及随着X_c的增加,材料由非晶、微晶转变为纳米硅薄膜时光吸收谱的变化。发现纳米硅晶粒之间的界面区(平均厚度约为1nm)中载流子的跃迁及传输过程对整个范围的光吸收谱起主导作用。联系纳米硅的这种特殊结构解释了有关实验结果。 关键词：     

Solid-state NMR studies of the crystalline and amorphous domains within PEO and PEO: LiTf systems

Solid polymer electrolytes (SPEs) contain amorphous and crystalline regions, each of which have unique contributions to the ¹³C NMR spectrum. Understanding and assigning the ¹³C NMR signals are vital to interpreting the NMR data collected for each phase. The ¹³C CPMAS solid-state NMR spectrum of poly(ethylene oxide), a common polymer electrolyte host material, has superimposed broad and narrow components. Previously, the narrow component has been assigned to the amorphous region and the broad component to the crystalline PEO fraction. These assignments for pure PEO have been applied to various PEO:salt systems. Using lithium triflate salt dissolved in PEO, we revisit the spectral assignments and discover that the narrow component is due to crystalline PEO:LiTf component, which is reversed from the previous pure PEO assignment. This paradigm shift is based on data collected from a 100% crystalline PEO:LiTf with a 3:1 oxygen:lithium ratio sample, which exhibited only the narrow peak. For dilute electrolytes, such as 20:1 PEO:LiTf, the ¹³C CPMAS spectra contain the narrow peak superimposed on a broad peak as seen with pure PEO. As dilute electrolytes are heterogeneous with crystalline and amorphous regions of both pure PEO and PEO:LiTf complex, peak assignments for pure PEO and PEO:LiTf are important. Thus, we reexamine the previous assignment for pure PEO using samples of pure powdered PEO, thermally treated pure powdered PEO, and a thin film PEO cast from an acetonitrile solution. With these different samples, we observed the growth of the narrow peak under conditions that favor crystallization. Therefore, for pure PEO, we have reassigned the narrow peak to the crystalline region and the broad peak to the amorphous region. In light of our observations, previous NMR studies of pure PEO and PEO SPEs should be reinvestigated. We also use rotational echo double resonance (REDOR) to study the 20:1 PEO:LiTf created from 2 and 100 kDa PEO. We find that the lithium environment is similar in the respective microcrystalline domains. However, the 100 kDa samples have a larger fraction of pure crystalline PEO.