Self‐doping PPV oligomers – electrochemistry and structure of the self‐doped systems

A novel class of self‐doping conjugated oligomers, E,E‐2‐(sulfoalkoxy)‐5‐alkoxy‐1,4‐bis[2‐(2,4,6‐trimethoxyphenyl) ethenyl]benzenes, is presented. The synthesis and spectroscopic characterisation of five such oligomers are described, and an electrochemical analysis using cyclic voltammetry is performed to determine the anodic peak potentials. A structural study is performed on six self‐doping oligomers in which the structures and energies of the possible mono‐molecular forms of the electrically conducting doped material are described and evaluated using Hirshfeld charges and the Quantum Theory of Atoms In Molecules. Copyright © 2009 John Wiley & Sons, Ltd.     

On the structure of 3‐acetylamino‐5‐methyl‐1,2,4‐oxadiazole and on the fully degenerate rearrangements (FDR) of its anion: a stimulating comparison between the results of ‘in‐silicon chemistry’ and ‘laboratory chemistry’

An accurate crystal structure determination has provided evidence for a planar conformation for 3‐acetylamino‐5‐methyl‐1,2,4‐oxadiazole ( 5 ), in agreement with quantum‐mechanical calculations in the gas phase. In the crystal, a series of strong intermolecular N7H7^….O9 hydrogen bonds link the amido groups of different molecules, causing the formation of infinite parallel ordered chains. The effect of the DMSO solvent on the energy and charge distribution of compound 5 and on its relevant 5 ^? anion, involved in a fully degenerate rearrangement (FDR), has been deepened by quantum‐mechanical DFT calculations. The calculated energy barrier for the FDR increases in going from in vacuo to DMSO, in agreement with previsions based on the Hughes and Ingold rules concerning the nucleophilic substitution of an anionic reagent (the deprotonated amido group in the side chain) on a neutral substrate (the 1,2,4‐oxadiazole ring). Copyright © 2009 John Wiley & Sons, Ltd.     

Nondestructive elemental depth profiling of Japanese lacquerware ‘Tamamushi‐nuri’ by confocal 3D‐XRF analysis in comparison with micro GE‐XRF

We have applied recently two XRF (micro x‐ray fluorescence) methods [micro‐Grazing Exit XRF (GE‐XRF) and confocal 3D‐XRF] to Japanese lacquerware ‘Tamamushi‐nuri.’ A laboratory grazing‐exit XRF (GE‐XRF) instrument was developed in combination with a micro‐XRF setup. A micro x‐ray beam was produced by a single capillary and a pinhole aperture. Elemental x‐ray images (2D images) obtained at different analyzing depths by micro GE‐XRF have been reported. However, it was difficult to directly obtain depth‐selective x‐ray spectra and 2D images. A 3D XRF instrument using two independent polycapillary x‐ray lenses and two x‐ray sources (Cr and Mo targets) was also applied to the same sample. 2D XRF images of a Japanese lacquerware showed specific distributions of elements at the different depths, indicating that ‘Tamamushi‐nuri’ lacquerware has a layered structure. The merits and disadvantages of both the micro GE‐XRF and confocal micro XRF methods are discussed. Copyright © 2009 John Wiley & Sons, Ltd.     

Effect of K doping on the physical properties of La0.65Ca0.35−xKxMnO3 (0?x?0.2) perovskite manganites

The effects of K doping in the A-site on the structural, magnetic and magnetocaloric properties in La_0.65Ca_0.35−xK_xMnO₃ (0?x?0.2) powder samples have been investigated. Our samples have been synthesized using the solid-state reaction method at high temperature. The parent compound La_0.65Ca_0.35MnO₃ is an orthorhombic (Pbnm space group) ferromagnet with a Curie temperature T_C of 248 K. X-ray diffraction analysis using the Rietveld refinement show that all our synthesized samples are single phase and crystallize in the orthorhombic structure with Pbnm space group for x?0.1 and in the rhombohedral system with R3¯c space group for x=0.2 while La_0.65Ca_0.2K_0.15MnO₃ sample exhibits both phases with different proportions. Magnetization measurements versus temperature in a magnetic applied field of 50 mT indicate that all our investigated samples display a paramagnetic-ferromagnetic transition with decreasing temperature. Potassium doping leads to an enhancement in the strength of the ferromagnetic double-exchange interaction between Mn ions, and makes the system ferromagnetic at room temperature. Arrott plots show that all our samples exhibit a second-order magnetic-phase transition. The value of the critical exponent, associated with the spontaneous magnetization, decreases from 0.37 for x=0.05 to 0.3 for x=0.2. A large magnetocaloric effect (MCE) has been observed in all samples, the value of the maximum entropy change, |ΔS_m|_max, increases from 1.8 J/kg K for x=0.05 to 3.18 J/kg K for x=0.2 under a magnetic field change of 2 T. For x=0.15, the temperature dependence of |ΔS_m| presents two maxima which may arise from structural inhomogeneity.     

Concentrated second‐harmonic generation from a single Al‐covered ZnS nanobelt

Here we report on the hybrid nanostructures where a single ZnS nanobelt was half‐covered with an aluminum (Al) film, which is an ideal platform for studying the second‐harmonic generation (SHG) enhancement effects of the Al coating. It was fabricated by the lift‐off process and allowed for the accurate comparison of the SHG intensity between the Al‐covered and the same bare ZnS nanobelt under consistent test conditions. The results indicate that the Al coating in the hybrid nanostructures not only confines the pumping laser in the ZnS effectively, but also concentrates the emitted SHG signal greatly, increasing the signal collection efficiency. By the combination of these two effects, ∼60 times enhancement of the SHG intensity is achieved at the optimized geometry size (width and thickness) of the ZnS nanobelts. The Al‐based hybrid nanostructures open up new possibilities for low‐cost, highly efficient and directional coherent nanolight sources at short wavelengths.

     

Short Terahertz Pulse Generation from a Dispersion Compensated Modelocked Semiconductor Laser

Dispersion compensation is vital for the generation of ultrashort and single cycle pulses from modelocked lasers across the electromagnetic spectrum. It is typically based on addition of an extra dispersive element to the laser cavity that introduces a chromatic dispersion opposite to that of the gain medium. To date, however, no dispersion compensation schemes have been successfully applied to terahertz (THz) quantum cascade lasers for short and stable pulse generation in the THz range. In this work, a monolithic on‐chip compensation scheme is realized for a modelocked QCL, permitting THz pulses to be considerably shortened from 16ps to 4ps. This is based on the realization of a small coupled cavity resonator that acts as an ‘off resonance’ Gires‐Tournois interferometer (GTI), permitting large THz spectral bandwidths to be compensated. This novel application of a GTI opens up a direct and simple route to sub‐picosecond and single cycle pulses in the THz range from a compact semiconductor source.     

Dynamic Thermal Emission Control Based on Ultrathin Plasmonic Metamaterials Including Phase‐Changing Material GST

Dynamic thermal emission control has attracted growing interest in a broad range of fields, including radiative cooling, thermophotovoltaics and adaptive camouflage. Previous demonstrations of dynamic thermal emission control present disadvantages of either large thickness or requiring sustained electrical or thermal excitations. In this paper, an ultrathin (∼0.023λ, λ is the emission peak wavelength) metal‐insulator‐metal plasmonic metamaterial‐based zero‐static‐power mid‐infrared thermal emitter incorporating phase‐changing material GST is experimentally demonstrated to dynamically control the thermal emission. The electromagnetic modes can be continuously tuned through the intermediate phases determined by controlling the temperature. A typical resonance mode, which involves the coupling between the high‐order magnetic resonance and anti‐reflection resonance, shifts from 6.51 to 9.33 μm while GST is tuned from amorphous to crystalline phase. This demonstration will pave the way towards the dynamical thermal emission control in both the fundamental science field and a number of energy‐harvesting applications.     

硼掺杂单壁碳纳米管吸附甲醛的电子结构和光学性能研究

应用基于第一性原理的密度泛函理论研究了硼原子取代掺杂的（8,0）碳纳米管吸附甲醛气体分子的束缚能、电子结构以及光吸收和反射性质.研究发现,硼原子掺杂的碳纳米管对甲醛气体具有较强的敏感性,其束缚能大大增加,电荷转移更加显著,吸收峰和反射峰增多,峰值减小,且在低能区发生蓝移现象,在能量约为172 eV处均出现一特征峰.对计算结果进行了讨论,期望利用硼掺杂碳管来制作检测甲醛的纳米传感器和光电器件. 关键词： 碳纳米管 甲醛 硼原子取代掺杂 光学性能     

LAMOST光纤单元定位参数研究

大天区多目标光纤光谱天文望远镜LAMOST是世界上光谱获取量最大的望远镜,4000个双回转光纤单元的精确定位是关键因素之一。根据对星像观测的要求以及单元的定位方式,确立了所需的7个定位参数,研究了在复杂现场环境下获取定位参数的具体流程和可行性算法,包括光重心法、摄像机快速标定算法、基于最小二乘拟合圆算法、空间坐标旋转算法等。通过模拟星像观测仿真测试和现场星像试观测证明,定位参数精度能很好地满足观测需求。目前LAMOST望远镜观测光谱获取率已达到90%以上。     

碳原子1s~22s~22pns~3P态精细结构的理论计算

提出了构造碳原子1s~22s~22pns ~3P态波函数的新方法,以多电子原子精细结构哈密顿的球张量形式和不可约张量理论为基础,开发了一套计算碳原子1s~22s~22pns ~3P态精细结构的Mathemtica程序,具体计算了碳原子1s~22s~22pns ~3P(n=3～6)态的精细结构(包括自旋-轨道相互作用、自旋-其它轨道相互作用和自旋-自旋相互作用),计算结果与实验值非常接近.