Interconversion of Metallabenzenes and Cyclic η2‐Allene‐Coordinated Complexes

Treatment of the osmabenzene [Os{CHC(PPh₃)CHC(PPh₃)CH} Cl₂(PPh₃)₂]Cl ( 1 ) with excess 8‐hydroxyquinoline produces monosubstituted osmabenzene [Os{CH C(PPh₃) CHC(PPh₃)CH}(C₉H₆NO)Cl(PPh₃)]Cl ( 2 ) or disubstituted osmabenzene [Os{CHC(PPh₃)CHC(PPh₃)CH} (C₉H₆NO)₂]Cl ( 3 ) under different reaction conditions. Osmabenzene 2 evolves into cyclic η²‐allene‐coordinated complex [Os{CH?C(PPh₃)CH=(η²‐C?CH₂)}(C₉H₆NO)(PPh₃)₂]Cl ( 4 ) in the presence of excess PPh₃ and NaOH, presumably involving a P? C bond cleavage of the metallacycle. Reaction of 4 with excess 8‐hydroxyquinoline under air affords the S_NAr product [(C₉H₆NO)Os{CHC(PPh₃)CHCHC} (C₉H₆NO)(PPh₃)]Cl ( 5 ). Complex 4 is fairly reactive to a nucleophile in the presence of acid, which could react with water to give carbonyl complex [Os{CH?C(PPh₃)CH?CH₂}(C₉H₆NO) (CO)(PPh₃)₂]Cl ( 6 ). Complex 4 also reacts with PPh₃ in the presence of acid and results in a transformation to [Os {CHC(PPh₃)CHCHC}(C₉H₆NO)Cl (PPh₃)₂]Cl ( 7 ) and [Os{CH?C(PPh₃) CH=(η²‐C?CH(PPh₃))}(C₉H₆NO) Cl(PPh₃)]Cl ( 8 ). Further investigation shows that the ratio of 7 and 8 is highly dependent on the amount of the acid in the reaction.     

Differential loop for measuring 1 MA/1O0 ns pulsed high current

“强光一号”加速器能输出上升沿约100 ns、幅值约2 MA的电流脉冲.实验中通常采用自积分式Rogowski线圈监测负载电流.为与该线圈比对校验,研制了一种快响应、结构简单、抗电磁干扰性能较好的微分环.标定实验给出,微分环测量的响应时间约1.2 ns,频谱响应范围10 kHz～100 MHz,灵敏度为6.13×10-11(V· s)/A.其快时间响应将有助于监测与负载物理特性有关的瞬态电流变化.在加速器二极管短路状态对微分环和积分式Rogowski线圈进行了实验比对,数值积分给出的电流波形与后者基本相符,峰值偏差小于10％,表明微分环的设计合理,同时校验了电流测量的可信度.     

Room-temperature structures of solid hydrogen at high pressures

By employing first-principles metadynamics simulations, we explore the 300 K structures of solid hydrogen over the pressure range 150-300 GPa. At 200 GPa, we find the ambient-pressure disordered hexagonal close-packed (hcp) phase transited into an insulating partially ordered hcp phase (po-hcp), a mixture of ordered graphene-like H(2) layers and the other layers of weakly coupled, disordered H(2) molecules. Within this phase, hydrogen remains in paired states with creation of shorter intra-molecular bonds, which are responsible for the very high experimental Raman peak above 4000 cm(-1). At 275 GPa, our simulations predicted a transformation from po-hcp into the ordered molecular metallic Cmca phase (4 molecules∕cell) that was previously proposed to be stable only above 400 GPa. Gibbs free energy calculations at 300 K confirmed the energetic stabilities of the po-hcp and metallic Cmca phases over all known structures at 220-242 GPa and >242 GPa, respectively. Our simulations highlighted the major role played by temperature in tuning the phase stabilities and provided theoretical support for claimed metallization of solid hydrogen below 300 GPa at 300 K.     

Perturbation bounds for weighted polar decomposition in the weighted unitarily invariant norm

In this paper, by generalizing the ideas of the (generalized) polar decomposition to the weighted polar decomposition and the unitarily invariant norm to the weighted unitarily invariant norm, we present some perturbation bounds for the generalized positive polar factor, generalized nonnegative polar factor, and weighted unitary polar factor of the weighted polar decomposition in the weighted unitarily invariant norm. These bounds extend the corresponding recent results for the (generalized) polar decomposition. In addition, we also give the comparison between the two perturbation bounds for the generalized positive polar factor obtained from two different methods. Copyright © 2008 John Wiley & Sons, Ltd.     

A General Route to Prepare Low-Ruthenium-Content Bimetallic Electrocatalysts for pH-Universal Hydrogen Evolution Reaction by Using Carbon Quantum Dots

A challenging but pressing task to design and synthesize novel, efficient, and robust pH-universal hydrogen evolution reaction (HER) electrocatalysts for scalable and sustainable hydrogen production through electrochemical water splitting. Herein, we report a facile method to prepare an efficient and robust Ru-M (M=Ni, Mn, Cu) bimetal nanoparticle and carbon quantum dot hybrid (RuM/CQDs) for pH-universal HER. The RuNi/CQDs catalysts exhibit outstanding HER performance at all pH levels. The unexpected low overpotentials of 13, 58, and 18 mV shown by RuNi/CQDs allow a current density of 10 mA cm⁻² in 1 m KOH, 0.5 m H₂SO₄, and 1 m PBS, respectively, for Ru loading at 5.93 μgRu cm⁻². This performance is among the best catalytic activities reported for any platinum-free electrocatalyst. Theoretical studies reveal that Ni doping results in a moderate weakening of the hydrogen bonding energy of nearby surface Ru atoms, which plays a critical role in improving the HER activity.     

Isoreticular Linker Substitution in Conductive Metal–Organic Frameworks with Through-Space Transport Pathways

The extension of reticular chemistry concepts to electrically conductive three-dimensional metal–organic frameworks (MOFs) has been challenging, particularly for cases in which strong interactions between electroactive linkers create the charge transport pathways. Here, we report the successful replacement of tetrathiafulvalene (TTF) with a nickel glyoximate core in a family of isostructural conductive MOFs with Mn²⁺, Zn²⁺, and Cd²⁺. Different coordination environments of the framework metals lead to variations in the linker stacking geometries and optical properties. Single-crystal conductivity data are consistent with charge transport along the linker stacking direction, with conductivity values only slightly lower than those reported for the analogous TTF materials. These results serve as a case study demonstrating how reticular chemistry design principles can be extended to conductive frameworks with significant intermolecular contacts.     

SR分解的乘法扰动界

In this paper, we present the first order perturbation bounds for the SR factorization with respect to left multiplicative perturbation, and the first order and rigorous perturbation bounds for this factorization with respect to right multiplicative perturbation.Moreover, taking the properties of SR factors into consideration, we also provide some refined perturbation bounds.     

3 MV感应电压叠加器的磁感应腔研制

 根据脉冲驱动源和负载参数,提出了3 MV感应电压叠加器磁感应腔的设计指标为1.2 MV/70 ns。由感应腔的电流传输效率和真空同轴线绝缘要求,确定了磁芯的几何尺寸;研制了矩形比为0.5的预退火非晶磁环,明确磁环数量不少于6只;在30 T/s时,实验测量的最大脉冲相对磁导率与饱和波模型计算结果相当;估算磁感应腔的等效激磁电感约为7.3 μH,涡流损耗电阻约为139 Ω。根据临界击穿场强的经验公式,采用电场数值分析方法,确定了磁感应腔的电气结构;实验验证了磁感应腔设计有效性;建立了基于磁感应腔的3 MV感应电压叠加器全电路模型,阳极杆箍缩二极管电压、电流计算波形,与实验结果基本相符。     

JEMS- FDTD超大规模并行计算测试

 介绍了JEMS- FDTD在大规模并行计算机上进行的并行性能测试,包括网格片大小对性能的影响、单节点MPI/OPENMP混合并行性能、多节点MPI/OPENMP混合并行性能、大规模并行性能等。同时,也给出了一个包含电大尺寸复杂、真实结构模型的算例,并对其进行了计算、分析。测试表明,JEMS- FDTD可高效使用数万个处理器核进行并行计算。大型算例测试表明：JEMS- FDTD可针对电大尺寸复杂、真实结构模型进行有效的计算、分析。