The Oxidation of Heterogeneous Tl/Ni/P‐Alloys — Preparation and Crystal Structures of the Thallium Nickel Phosphates TlNi4(PO4)3, Tl4Ni7(PO4)6, and Tl2Ni4(P2O7)(PO4)2

Single crystals of the first anhydrous thallium nickel phosphates were prepared by reaction of heterogeneous Tl/Ni/P alloys with oxygen. TlNi₄(PO₄)₃ (pale‐yellow, orthorhombic, space group Cmc2₁, a = 6.441(2)Å, b = 16.410(4)Å, c = 9.624(2)Å, Z = 4) crystallizes with a structure closely related to that of NaNi₄(PO₄)₃. Tl₄Ni₇(PO₄)₆ (yellow‐brown, monoclinic, space group Cm, a = 10.711(1)Å, b = 14.275(2)Å, c = 6.688(2)Å, β = 103.50(2)°, Z = 8) is isotypic with Na₄Ni₇(PO₄)₆, and Tl₂Ni₄(P₂O₇)(PO₄)₂ (brown, monoclinic, space group C2/c, a = 10.389(2)Å, b = 13.888(16)Å, c = 18.198(3)Å, β = 103.1(2)°, Z = 8) adopts the K₂Ni₄(P₂O₇)(PO₄)₂ structure. Tl₂Ni₄(P₂O₇)(PO₄)₂ could also be prepared in nearly single phase form by reaction of Tl₂CO₃, NiO, and (NH₄)₂HPO₄.     

Photoreduction of o-benzoquinones in the presence of p-bromo-N,N-dimethylaniline

Photoreduction of o-benzoquinones in the presence of p-bromo-N,N-dimethylaniline under irradiation ( > 500 nm) affords the corresponding pyrocatechols and hydroxyphenyl ethers. The latter are unstable and, in turn, decompose in the dark reaction to pyrocatechols. The ratio between pyrocatechol and hydroxyphenyl ether formed upon the photoreaction is determined by the structure of o-quinone, namely, the presence and bulk of substituents in positions 3 and 6 of the ring. The yield of pyrocatechol is maximal (60—65%) if the substituents are the same (H and H, Bu^t and Bu^t) or insignificantly differ (Prⁱ and Bu^t), regardless of its bulk.     

Nonequilibrium fluctuations in μ space

The properties of fluctuations in space in or outside thermal equilibrium are obtained by solving hierarchies of equations derived either from the Liouville or the Master equation. In particular we study the one-, two-, etc., time correlation functions that describe the spatial and temporal behavior of the fluctuations in space. Explicit solutions are obtained for a dilute gas. The Langevin approach is briefly discussed. Our results are compared with those obtained in the extensive literature, which is reviewed in some detail.     

The nonsymmetric pressure tensor in polyatomic fluids

Nonequilibrium molecular dynamics calculations are used to show that polyatomic fluids can support antisymmetric stress. In a homogeneous system where the time dependence of vorticity is a step function, it is shown that the rate at which intrinsic angular velocity approaches its steady-state value ( = 1/2 × u) is determined by the magnitude of the antisymmetric part of the pressure tensor.     

平行光栅对在刻线不平行时的色散研究

 利用三维空间光线追迹法，分析了啁啾脉冲放大系统中的压缩光栅对，在刻线不平行而光栅面平行时光的衍射特性。导出了此时光通过光栅对的群延时，数值计算了系统2阶和3阶色散量，以及这些色散量在光栅对严格平行时的相对误差。得出了中心波长光的接收位置相对于光栅对严格平行时的偏移量，并且分析了它与入射角的变化关系。     

History of Cobaltabis(dicarbollide) in Potentiometry,No Need for Ionophores to Get an Excellent Selectivity

This work is a mini-review highlighting the relevance of the θ metallabis(dicarbollide) [3,3′-Co(1,2-C₂B₉H₁₁)₂]⁻ with its peculiar and differentiating characteristics, among them the capacity to generate hydrogen and dihydrogen bonds, to generate micelles and vesicles, to be able to be dissolved in water or benzene, to have a wide range of redox reversible couples and many more, and to use these properties, in this case, for producing potentiometric membrane sensors to monitor amine-containing drugs or other nitrogen-containing molecules. Sensors have been produced with this monoanionic cluster [3,3′-Co(1,2-C₂B₉H₁₁)₂]⁻. Other monoanionic boron clusters are also discussed, but they are much fewer. It is noteworthy that most of the electrochemical sensor species incorporate an ammonium cation and that this cation is the species to be detected. Alternatively, the detection of the borate anion itself has also been studied, but with significantly fewer examples. The functions of the borate anion in the membrane are different, even as a doping agent for polypyrrole which was the conductive ground on which the PVC membrane was deposited. Apart from these cases related to closo borates, the bulk of the work has been devoted to sensors in which the θ metallabis (dicarbollide) [3,3′-Co(1,2-C₂B₉H₁₁)₂]⁻ is the key element. The metallabis (dicarbollide) anion, [3,3′-Co(1,2-C₂B₉H₁₁)₂]⁻, has many applications; one of these is as new material used to prepare an ion-pair complex with bioactive protonable nitrogen containing compounds, [YH]_x[3,3′-Co(1,2-C₂B₉H₁₁)₂]_y as an active part of PVC membrane potentiometric sensors. The developed electrodes have Nernstian responses for target analytes, i.e., antibiotics, amino acids, neurotransmitters, analgesics, for some decades of concentrations, with a short response time, around 5 s, a good stability of membrane over 45 days, and an optimal selectivity, even for optical isomers, to be used also for real sample analysis and environmental, clinical, pharmaceutical and food analysis.     

M+AsF6-(M=Li,Na,K,Rb和Cs)离子对的结构和振动光谱

利用abinitio计算方法研究了AsF6-阴离子和M AsF6-(M =Li ,Na ,K ,Rb 和Cs )直接接触离子对的结构和光谱行为。结果表明,具有C3V结构三齿相互作用的M AsF6-最稳定,二齿配位的结构只有在特定条件下才可能稳定存在。当形成离子对后,阳离子与AsF6-的相互作用将改变AsF6-的结构,这其中Li 的影响最大。另外,AsF6-光谱的变化可用来指认溶液中离子的缔合和离子对的种类。     

利用全元素矩张量反演方法识别地下核爆炸

将震源矩张量中的各分量作为权重因子,利用基本Green函数的线性组合可以对地震波场进行描述,本文利用水平分层模型下的广义反射-透射系数方法的地震波场正演公式,反演了苏联东哈萨克斯坦地下核试验场的7次地下核爆炸、3次震中位置相近的天然地震的震源矩张量,反演结果表明地下核爆炸震源明显含有爆炸源成分,同时包含双力偶成分（DC）和线性偶极补偿源成分（CLVD）,且CLVD成分比重大,CLVD的存在可用层裂机制来解释;天然地震震源矩张量的反演结果表明,DC源为主要成分,符合剪切位错震源模式。

     

多重短程有序准化学模型:有序原子对的对立与统一

在准化学模型框架下, 假设有序原子对同时具有可区分与不可区分的双重属性, 首先构造了双重短程有序准化学模型, 然后讨论了该模型所能满足的各类理论极限. 经总结提炼, 提出了有序原子对的对立统一理论. 基于该理论, 进一步将双重短程有序准化学模型做了一般化推广, 开发了多重短程有序准化学模型. 该模型能够有效描述二元熔体中存在多重短程有序构型时的热力学行为. 选取了至少存在两重短程有序构型的Bi-K熔体来检验模型的合理性和可靠性. 结果表明, 除配位数外, 只需4个模型参数就能合理再现该二元熔体所有的热化学数据.