EQCM Study of the Couple Thallium(I)/Thallium Amalgam at a Thin Film Mercury Electrode

EQCM and voltammetric data show that thallium(I) ions, which are adsorbed in the region of the positive surface charge, most probably, in the form of the ionic pairs, are not reduced. In this potential region, thallium(I) ions are reduced directly from the solution. At more negative potentials, the previously adsorbed stable ionic pairs slowly undergo transition into the less stable form. From this form, thallium(I) ions can be reduced or desorbed into the solution. The process is best described by a model of one electron, i.e., full charge transfer.     

Quantitative Depth Profiling of K-Doped Fullerene Films Using XPS and SIMS

 Phenomena accompanying electrochemical doping of solid fullerene films with potassium were studied by sputter ion depth profiling (XPS and SIMS). The potassium distribution was determined, and artifacts associated with possible damage of the layer composition caused by ion impact were investigated and discussed. To compare the charge transfer while reductive doping is taking place at fullerene/solution interface with doping from gas phase, model layers were prepared and doped by potassium under UHV conditions. It was found that sputtering by Ar⁺ primary ions yields both accurate information on the alkaline metal distribution and on its concentration. Sputtering by O⁺ ions led to an enrichment of potassium, apparently due to the reactivity of oxygen with the fullerene matrix. It is shown that the reductive doping starts at the fullerene/solution interface. The concentration of potassium in the doped films was found to be lower than expected from the charge transferred during the electrochemical reduction. Other phase transformations such as hydrogenation are discussed. Received March 4, 2002; accepted July 26, 2002     

Radial and angular correlation in heliumlike ions

In the framework of nonrelativistic variational formalism a new type of basis set is proposed, to estimate separately the effect of radial and angular correlations on the ground‐state energy for helium isoelectronic sequence H^? to Ar¹⁶⁺. Effect of radial correlation is incorporated by using multiexponential functions arising from product basis sets suitably formed out of Slater‐type one‐particle orbitals. The angular correlation can be switched on by incorporating an expansion in terms of basis involving interparticle coordinates. With a set of six‐term Slater‐type one‐particle basis and five‐term interparticle expansion, the ground‐state energy of helium is estimated as ?2.9037236 (a.u.) compared with the multiterm variational estimates ?2.9037244 (a.u.) due to Pekeris and Thakkar and Smith and Drake. Matrix elements of different operators in the ground state have been calculated and found to be in good agreement with available accurate results. © 2003 Wiley Periodicals, Inc. Int J Quantum Chem, 2003     

离子在DMF-水混合溶剂中的体积性质

利用精密数字密度计测定了298．15K氯化氯化铵在N，N－二甲基甲酰胺（DMF）－水混合溶剂中的密度，计算了氯化钾及氯化铵的表观摩尔体积和极限偏摩尔体积，得到了相关离子的极限偏摩尔体积V′I^0和迁移偏摩尔体积△tV′i0，结果表明，当DMF浓度为15％－45％时，K^ 和NH4^ 的极限偏摩尔体积均表现增加趋势，而Cl^－的极限偏摩尔体积在同一DMF浓度范围内则表现为逐渐减小，利用溶质－溶剂和溶剂－溶剂相互作用对结果进行了讨论。     

Influence of the Type of a Ligand on the Intensity of Luminescence of Ln3+ Ions in Aqueous Solutions

The luminescence characteristics of hydrated Ln³⁺ ions and their complexes with some acidic ligands have been investigated. The possibility of determining the stability of the complexes of lanthanides in solutions from the intensity of luminescence bands is shown. The influence of the characteristic features of the f-electron shell of Ln³⁺ on the formation of the spectrochemical series is discussed.     

Lanthanide Complexes for Oligomerization of Phenyl Isocyanate

IntroductionThestudyonthereactivitiesoflanthanidecomplexesto wardisocyanateshasattractedmuchattention .Ithasbeenre portedthatlanthanidealkoxides,1anddivalentdiaza pentadi enyllanthanidecomplexes2 canbeusedasthesinglecompo nentinitiatorsforisocyanatespolymerization .Recentlyourre searchgrouphasalsofoundthatlanthanoceneamide ,3diva lentaryloxideofsamarium4 ,5anddivalentsamarocene6 areallactivefortheoligomerizationofphenylisocyanate,andtheactivespeciesforthesethreesystemswereallsuccessfullyisolat…     

Quantitative assessment of solid oxide electrochemical doping

Quantitative analysis of metal cation doping by solid oxide electrochemical doping (SOED) has been performed under galvanostatic doping conditions. A M–β″-Al₂O₃ (M=Ag, Na) microelectrode (contact radius: about 10 μm) was used as cation source to attain a homogeneous solid–solid contact between the β″-Al₂O₃ and doping target. In Ag doping into alkali borate glass, the measured dopant amount closely matched the theoretical value. High Faraday efficiencies of above 90% were obtained. This suggests that the dopant amount can be precisely controlled on a micromole scale by the electric charge during electrolysis. On the other hand, current efficiencies of Na doping into Bi₂Sr₂CaCu₂O_y (BSCCO) ceramics depended on the applied constant current. Efficiencies of above 80% were achieved at a constant current of 10 μA (1.6 A cm⁻²). The relatively low efficiencies were explained by the saturation of BSCCO grain boundaries with Na. By contrast, excess Na was detected on the anodic surface of ceramics at a constant current of 100 μA (16 A cm⁻²). In the present study, we demonstrate that SOED enables micromole-scale control over dopant amount.     

Stationary entanglement between macroscopic mechanical oscillators

We show that the optomechanical coupling between an optical cavity mode and two movable cavity mirrors is able to entangle two different macroscopic oscillation modes of the mirrors. This continuous variable entanglement is maintained by the light bouncing between the mirrors and is robust against thermal noise. In fact, it could be experimentally demonstrated using present technology. Received 2 September 2002 / Received in final form 10 October 2002 Published online 7 January 2003     

Synthesis and characterization of polyaniline-polyvinyl chloride blends doped with sulfamic acid in aqueous tetrahydrofuran

The temperature dependence of direct current (dc) conductivity was studied for various samples of polyaniline-polyvinylchloride (PANI-PVC) blended films. Polyaniline was doped with different concentrations of sulfamic acid in aqueous tetrahydrofuran (THF) and the blended films were prepared by varying the amount of doped PANI relative to a fixed amount of PVC. The dc conductivity of PANI-PVC blended films was measured to determine the effect of sulfamic acid (dopant) in the temperature range (300–400K). The mechanism of conduction is explained by a two-phase model. In order to evaluate the effect of the dopant, conductivity-derived parameters such as the pre-exponential factor (σ _o) and the activation energy (ΔE) were calculated. The structural changes of polyaniline-PVC blended films were characterized by FTIR spectroscopy that explores information about the suitability of the dopant in the chemical doping process.     

相邻类氢离子电离能关系的研究

根据类氢离子电离能的实验值和相邻元素电离能的相关约束方程,定量地建立了各元素类氢离子电离能与核电荷数的较为精确的递推关系.其推算结果与实验值的相对误差小于0.001%,与相对论自洽场方法计算的结果相比,其相对误差也小于0.001%.