Local atomic and electronic structure in the LiVPO4(F,O) tavorite-type materials from solid-state NMR combined with DFT calculations

⁷Li, ³¹P, and ¹⁹F solid-state nuclear magnetic resonance (NMR) spectroscopy was used to investigate the local arrangement of oxygen and fluorine in LiVPO₄F_1-yO_y materials, interesting as positive electrode materials for Li-ion batteries. From the evolution of the 1D spectra versus y, 2D ⁷Li radiofrequency-driven recoupling (RFDR) experiments combined, and a tentative signal assignment based on density functional theory (DFT) calculations, it appears that F and O are not randomly dispersed on the bridging X position between two X–VO₄–X octahedra (X = O or F) but tend to segregate at a local scale. Using DFT calculations, we analyzed the impact of the different local environments on the local electronic structure. Depending on the nature of the VO₄X₂ environments, vanadium ions are either in the +III or in the +IV oxidation state and can exhibit different distributions of their unpaired electron(s) on the d orbitals. Based on those different local electronic structures and on the computed Fermi contact shifts, we discuss the impact on the spin transfer mechanism on adjacent nuclei and propose tentative signal assignments. The O/F clustering tendency is discussed in relation with the formation of short V^IVO vanadyl bonds with a very specific electronic structure and possible cooperative effect along the chain.     

Mixed Boron(III) and Phosphorous(V) Complexes of meso‐Triaryl 25‐Oxasmaragdyrins

Two unprecedented mixed B^III/P^V complexes of meso‐triaryl 25‐oxasmaragdyrins were synthesized in appreciable yields under mild reaction conditions. These unusual 25‐oxasmaragdyrin complexes containing one or two seven‐membered heterocyclic rings comprised of five different atoms (B, C, N, O, and P) were prepared by reacting B(OH)(Ph)‐smaragdyrin and B(OH)₂‐smaragdyrin complexes, respectively, with POCl₃ in toluene at reflux temperature. The products were characterized by HRMS and 1D‐ and 2D‐NMR spectroscopy. X‐ray crystallography of one of the mixed B^III/P^V smaragdyrin complexes indicated that the macrocycle is significantly distorted and contains a stable seven‐membered heterocyclic ring within the macrocycle. The bands in the absorption and emission spectra were bathochromically shifted with reduced quantum yields and singlet‐state lifetimes relative to the free base, meso‐triaryl 25‐oxasmaragdyrin. The mixed B^III/P^V complexes were difficult to oxidize but easier to reduce than the free base. The DFT‐optimized structure of the 25‐oxasmaragdyrin complex with two seven‐membered heterocycles indicated that it was a bicyclic spiro compound with two half‐chair‐like conformers. This was in contrast to the chair‐like conformation of the complex with a single seven‐membered heterocyclic ring. Moreover, incorporation of a second phosphate group in the former case stabilized the bonding geometry and resulted in higher stability, which was reflected in the bathochromic shift of the absorption spectra, more‐positive oxidation potential, and less‐negative reduction potential.     

NMR 77Se, 125Te, 31P and Structure of Seleno-and Telluro-Phosphorus Compounds

Spectra of a nuclear magnetic resonance of seleno- and telluro-phosphorus compounds on nuclei ⁷⁷Se, ¹²⁵Te, ³¹P are described. The dependences of spectral parameters on a structure of the substitutes at phosphorus atom in these compounds are discussed.     

Band alignment in organic light emitting diodes - On the track of thickness dependent onset voltage shifts

In this paper we report on an unclear effect in the IV characteristics of organic light emitting diodes (OLEDs). When the thickness of the emitter layer based on a modified phenyl carbozole triplet host material (TH) in the device is increased, a significant shift of the onset voltage to higher values can be noticed. The voltage shift is not observed if the TH is substituted by an isomer with only minor variation of the molecular structure. In a previous publication we could already show that an electric interface field is necessary to describe the onset voltage behaviour. To find the origin of this interface field in the present publication the two isomers are characterized and the band alignment at the interfaces to the emitter layer is investigated using photoelectron spectroscopy. The interface energy diagrams have been measured on stepwise prepared model interfaces. A further simplification of the bipolar to a hole only device stack proofs, that band bending at the hole injecting interface to the TH layer is the origin of the interface field. In contrast an entire flat band situation is measured in case of the device using the other isomer showing no onset voltage shift.     

An all-digital coherent-like BFSK demodulator

An all-digital coherent-like binary frequency shift keying (BFSK) demodulation based on the use of a multi-bit shift register, two multi-bit XOR gates and a mean value filter is presented. The demodulator is fabricated in SMIC 65-nm CMOS process with a die area of 0.015 mm². The demodulator consumes 1.44 mW with 1.2 V of voltage supply and 32 MHz of sample clock. The measured bit error ratio (BER) performance is better than that of other non-coherent demodulators. The proposed demodulator exhibits better performance in terms of composite indicator compared to other demodulators. Another advantage of the all-digital demodulator defined using Verilog HDL is that it can also be implemented on Field Programmable Gate Array (FPGA) platform rapidly to recover FSK signals with different carrier frequencies and data rates. These results make the all-digital demodulator suitable for the application in communication and consumer electronics.     

The structure factor for liquid lead

Abstract

The structure factor for liquid lead at the temperatures 613 K, 643 K, 863 K and 1163 K are measured by neutron diffraction. Extensive comparisons to earlier measurements are made as well as comparisons to different hard-core models.     

Off-resonance frequency filtered magnetic resonance imaging

One of the main problems with rapid magnetic resonance imaging (MRI) techniques is the artifacts that result from off-resonance effects. The proposed off-resonance frequency filtered MRI (OFF-MRI) method focuses on the elimination of off-resonance components from the image of the observed object. To maintain imaging speed and simultaneously achieve good frequency selectivity, MRI is divided into two steps: signal acquisition and post-processing.     

Variable antenna‐space shift keying for high spectral efficiency in exponentially correlated channels

In space shift keying (SSK), all information bits are transmitted by antenna indices rather than transmitting symbols. To obtain high spectral efficiency, exponentially increasing number of antennas is used, which is generally not practical. Less number of antennas can only be possible by using more than one active antenna, such as generalized SSK, but this type of solutions result in excessive degradation in bit error ratio in correlated channels. In this study, variable number of active antennas for each codeword is proposed and called variable antenna‐SSK. First of all, pairwise error probability is obtained for variable number of antennas in the case of correlated channels. Then, to reduce the correlation effect, a novel antenna codeword construction method that minimizes the pairwise error probability is introduced for exponentially correlated channels. Codeword sets are obtained for k = 3 and 8 bits/s/Hz for 7 and 13 transmit antennas. Simulation results show that variable antenna‐SSK gets better performance according to its counterparts with increasing effect of correlation. Copyright © 2014 John Wiley & Sons, Ltd.     

诱导无线定位系统在行移台车上的运用

连铸机所配备的专用精确诱导无线位置检测系统必须具备高精度和高可靠性。文章通过对某钢厂实际工程应用，证明诱导无线定位在横移台车上使用，定位准确，误差满足设计要求，不大于10mm。     

联合Kalman和自适应Meanshift的稳健相关视频跟踪方法

相关视频跟踪器存在计算量大、模板漂移、对机动目标,杂波影响大以及遮挡情况无法跟踪的问题,而Kalman滤波能通过利用相关跟踪器的输出结果来预测目标在下一帧里在图像中的坐标,可以在高概率的小范围内对目标进行搜索,以大幅减小计算量和杂波的影响.然后,当跟踪器由于受到杂波或遮挡的影响而提供了错误的测量信息时,跟踪的性能将大幅下降.大量研究表明,Mean-Shift跟踪器具有运算速度快和跟踪性能好的特点,而当目标柱状图和待选图像区域相近时,其跟踪性能也将大幅下降,甚至无法进行跟踪.为了解决该问题,结合上述3种思想提出了一种改进的、稳健的视频目标跟踪方法,并通过理论分析和仿真结果表明了算法的有效性和优越性.