Formation and photoinduced electron ejection of amminedicyanocuprate(I) and cyano-bridged trinuclear copper(I) complexes in aqueous ammonia solution

UV absorption spectral evidence confirms that a mixed-ligand complex, Cu(CN)(2)(NH(3))(-), is formed in an aqueous solution of KCu(CN)(2) and ammonia. The stepwise stability constant for the reaction, Cu(CN)(2)(-) + NH(3) = Cu(CN)(2)(NH(3))(-), is 2.80 +/- 0.40 in 1 M ionic strength, NaClO(4) medium at 25 degrees C. This amminedicyanocuprate(I) ion readily combines in aqueous solution in a 1:2 and 2:1 molar ratios with Cu(NH(3))(2)(+) to form two trinuclear ionic species, presumably with cyano bridges, with the suggested formulas of Cu(3)(CN)(2)(NH(3))(5)(+) and Cu(3)(CN)(4)(NH(3))(3)(-). The resolved UV absorption spectra of the monomer and two trimers have been determined and exhibit strong bands, presumably metal-ligand charge transfer in nature, in the 200-250-nm region. When solutions of all three complexes absorb a pulse of 266-nm laser light, they photoeject hydrated electrons monophotonically, with quantum yields of 0.41 +/- 0.02, 0.53 +/- 0.02, and 0.50 +/- 0.01 for the monomer, cationic trimer, and anionic trimer, respectively, suggesting that absorption in the charge-transfer-to-solvent bands of these complexes results in an efficient electron ejection process that is enhanced by the existence of a polynuclear structure with cyano bridges. No room-temperature luminescence is observed for these complexes.     

有机硅活性中间体的研究 II. 一些含环丙基的有机硅化合物的合成及其结构

用锂有机物的方法合成了四种含有环丙基有机硅化合物,对上述每种化合物中可能存在着的立体异构进行了分离和和构型测定。     

Spheromak formation by steady inductive helicity injection

A spheromak is formed for the first time using a new steady state inductive helicity injection method. Using two inductive injectors with odd symmetry and oscillating at 5.8 kHz, a steady state spheromak with even symmetry is formed and sustained through nonlinear relaxation. A spheromak with about 13 kA of toroidal current is formed and sustained using about 3 MW of power. This is a much lower power threshold for spheromak production than required for electrode-based helicity injection. Internal magnetic probe data, including oscillations driven by the injectors, agree with the plasma being in the Taylor state. The agreement is remarkable considering the only fitting parameter is the amplitude of the spheromak component of the state.     

Are excimers formed along with hydrated electrons in the UV excitation of cyanocuprate(I) ions in aqueous solution?

The three cyanocuprate(I) complexes, Cu(CN)₂⁻, Cu(CN)₃²⁻, and Cu(CN)₄³⁻, photoeject electrons with high efficiency when excited in aqueous solution by 266 nm laser pulses of 7 ns duration with quantum yields of 0.37±0.06, 0.224±0.021, and 0.240±0.005, for Cu(CN)₂⁻ (at 2 M ionic strength), Cu(CN)₃²⁻, and Cu(CN)₄³⁻ (both measured at 1 M ionic strength). Along with hydrated electrons, two transient intermediates, absorbing at 460 and 340 nm, respectively, form consecutively after excitation through bimolecular reactions with ground-state Cu(I) in solutions of Cu(CN)₂⁻, and Cu(CN)₃²⁻, but not in Cu(CN)₄³⁻. All photoprocesses are essentially monophotonic. A mechanism is proposed that suggests the formation of a dinuclear excited-state complex such as an excimer.     

Mechanism of oxygen transfer in the epoxidation of an olefin by molecular oxygen in the presence of an aldehyde

[reaction: see text] The reaction pathway for peroxide-initiated aldehyde-mediated oxidation of olefins to epoxides by molecular oxygen has been studied. The pathways of reaction via a peroxy acid or an acyl peroxy radical have been differentiated by investigation of the reaction of 4 with oxygen to provide 6 via 8.     

Efficient generation of closed magnetic flux surfaces in a large spherical tokamak using coaxial helicity injection

A method of coaxial helicity injection has successfully produced a closed flux current without the use of the central solenoid in the NSTX device, on a size scale closer to a spherical torus reactor, for a proof-of-principle demonstration of this concept. For the first time, a remarkable 60 times current multiplication factor was achieved. Grad-Shafranov plasma equilibrium reconstructions are used to verify the existence of closed flux current. In some discharges the generated current persists for a surprisingly long time approximately 400 ms.     

Evidence for separatrix formation and sustainment with steady inductive helicity injection

The first sustainment of toroidal plasma current of 50 kA at up to 3 times the injected currents, added in quadrature, using steady inductive helicity injection is described. Separatrix currents-currents not linking the helicity injectors-are sustained up to 40 kA. Decreases in the n=1 toroidal mode of the poloidal magnetic field at higher current amplifications indicate more quiescent, direct toroidal current drive. Results are achieved in HIT-SI (with a spheromak of major radius 0.3 m) during deuterium operations immediately after helium operation. These results represent a breakthrough in the development of this new current drive method for magnetic confinement fusion.     

The microwave heating of two-dimensional slabs with small Arrhenius absorptivity

The microwave heating of two-dimensional slabs in a long rectangularwaveguide propagating the TE₁₀ mode is examined. The temperaturedependency of the electrical conductivity and the thermal absorptivityis assumed to be governed by the Arrhenius law, while both theelectrical permittivity and the magnetic permeability are assumedconstant. The governing equations are the forced heat equationand the steady-state version of Maxwell's equation while theboundary conditions take into account both convective and radiativeheat loss. Approximate analytical solutions, valid for smallthermal absorptivity, are found for the temperature and theelectric-field amplitude using the Galerkin method. As the Arrheniuslaw is not amenable analytically, it is approximated by a rational-cubicfunction. At the steady state the temperature versus power relationshipis found to be multivalued; at the critical power level thermalrunaway occurs when the temperature jumps from the lower (cool)temperature branch to the upper (hot) temperature branch ofthe solution. In the steady-state limit the approximate analyticalsolutions are compared with the numerical solutions of the governingequations for various special cases. These are the limits ofsmall and large heat loss and an intermediate case involvingradiative heat loss. Results are also presented for a case wheredifferential cooling occurs on the different sides on the slab.An alternative heating scenario, where one end of the waveguideis blocked by a short, is also considered. The approximate solutionsare found for this geometry and compared in the small Biot-numberlimit to Kriegsmann (1997). Also, a control process is presented,which allows thermal runaway to be avoided and the desired finalsteady state to be reached. Various special cases of the feedbackparameters associated with the control process are examined.