Unraveling the electronic structure of transition metal dimers using resonant four‐wave mixing

The potential of two‐color resonant and degenerate four‐wave mixing spectroscopy for investigations of the complex spectra of transition metal dimers is explored. Two‐color resonant and degenerate four‐wave mixing spectroscopy scans of the well‐known A‐X and B‐X transitions in Cu₂ are reported and compared with previous experimental data obtained from standard single‐resonance techniques. The selectivity of the method is shown to enable the measurement of isotopologue pure spectra without the need for isotopically enriched metal targets. Specific subsets of the rovibronic structure are separated in a congested spectral region of overlapping transitions. The sensitivity of the method compares satisfactorily with linear spectroscopic methods such as laser‐induced fluorescence and cavity ring‐down. A new laser vaporization source for the production of transition metal dimers and clusters has been constructed. The new design aims for a high number density and maximum possible shot‐to‐shot stability. The possibilities of further applications of non‐linear four‐wave mixing spectroscopy to Cu₂ and other transition metal dimers are discussed. Copyright © 2015 John Wiley & Sons, Ltd.     

Dynamic polarizability of two‐electron ions under Debye screening

The effect of plasma screening on the dynamic dipole polarizability (DPP) of two‐electron ions Be²⁺, B³⁺, and C⁴⁺ has been investigated using highly correlated exponential wave functions within the framework of pseudostate summation technique and Debye screening concept. Plasma‐screening effect on the oscillator strengths (OS) of the ultraviolet and visible series has also been investigated for the systems Li⁺, Be²⁺, B³⁺, C⁴⁺. The DPP are reported as functions of screening parameters. The OS for S‐P transitions are also reported for various screening parameters. The OS and dynamic polarizability show interesting behavior with increasing screening strength and nuclear charge. © 2015 Wiley Periodicals, Inc.     

Effect of magnesium and titanium on the cathodic behaviour of aluminium in nitric acid

Cathodic polarization of aluminium and Al–0.18 wt.% Mg and Al–0.08 wt.% Ti alloys in 0.24 mol dm^?3 nitric acid solution at 38 °C has been employed to assist understanding of the roles of alloying elements in electrograining. The findings indicate that additions of magnesium and titanium to aluminium accelerate the corrosion of the substrate under the alkalization caused by the cathodic reactions. The accelerated dissolution and the consequent formation of hydrated alumina result in a decreased net cathodic current density in potentiostatic and potentiodynamic polarization conditions relative to the behaviour of aluminium. Copyright © 2014 John Wiley & Sons, Ltd.     

Two‐dimensional reactive scattering with transmitted quantum trajectories

A simple and easy‐to‐implement method is presented for the study of time‐dependent reaction dynamics by propagating an ensemble of transmitted quantum trajectories. During the trajectory evolution, reflected trajectories are gradually removed and all the remaining trajectories represent the transmitted subensemble. The removal process of reflected trajectories avoids numerical instabilities arising from node formation in the reactant region, and allows stable long‐time propagation of transmitted trajectories. This method is applied to a two‐dimensional model chemical reaction. Excellent computational results are obtained for the time‐dependent reaction probabilities evaluated by the time integration of the probability flux. © 2014 Wiley Periodicals, Inc.     

氢氧混合气体爆轰波的真实化学反应模型数值模拟

采用高精度的ENO格式和基于基元化学反应的真实化学反应模型求解氢氧混合气体一维爆轰波的精细结构。采用直接起爆方法得到稳定传播的爆轰波 ,计算的爆轰波阵面参数和实验相当符合。对爆轰波反应区化学反应的研究表明 ,参与反应的不同组分具有不同类型的变化特征。网格尺寸影响的研究表明 ,计算结果的精度随着网格尺寸的增加而增加 ,并能保持较好的收敛性。移动网格研究结果表明 ,网格运动速度和爆轰速度接近时 ,两者的相互作用对计算结果产生一定影响。     

超声波促进手性双酰基氧化膦的合成

以L-薄荷醇为原料,经3步反应制备得到中间体薄荷基二氯化膦.该中间体首先通过与超声波辐射制备的微米级钠粒反应形成薄荷基膦二钠盐,然后依次经过偶联及氧化反应合成了目标产物(-)-双(薄荷基甲酰基)薄荷基氧化膦(BMMPO),并经过1 H NMR、13 C NMR、31P NMR和元素分析进行了表征.     

Six‐wave mixing induced by free‐carrier plasma in silicon nanowire waveguides

Nonlinear wave mixing in mesoscopic silicon structures is a fundamental nonlinear process with broad impact and applications. Silicon nanowire waveguides, in particular, have large third‐order Kerr nonlinearity, enabling salient and abundant four‐wave‐mixing dynamics and functionalities. Besides the Kerr effect, in silicon waveguides two‐photon absorption generates high free‐carrier densities, with corresponding fifth‐order nonlinearity in the forms of free‐carrier dispersion and free‐carrier absorption. However, whether these fifth‐order free‐carrier nonlinear effects can lead to six‐wave‐mixing dynamics still remains an open question until now. Here we report the demonstration of free‐carrier‐induced six‐wave mixing in silicon nanowires. Unique features, including inverse detuning dependence of six‐wave‐mixing efficiency and its higher sensitivity to pump power, are originally observed and verified by analytical prediction and numerical modeling. Additionally, asymmetric sideband generation is observed for different laser detunings, resulting from the phase‐sensitive interactions between free‐carrier six‐wave‐mixing and Kerr four‐wave‐mixing dynamics. These discoveries provide a new path for nonlinear multi‐wave interactions in nanoscale platforms.

     

Simultaneous and Sensitive Detection of Cd(II) and Pb(II) Using a Novel Bismuth Film/Ordered Mesoporous Carbon‐molecular Wire Modified Graphite Carbon Paste Electrode

An electrochemical sensor for the simultaneous and sensitive detection of Cd(II) and Pb(II) is proposed on the basis of square‐wave anodic stripping voltammetry (SWASV) experiments using a novel bismuth film/ordered mesoporous carbon‐molecular wire modified graphite carbon paste electrode (Bi/OMC‐MW/GCPE). Ordered mesoporous carbon (OMC) and molecular wire (MW) (diphenylacetylene) were used as the modifier and binder, respectively. The Bi/OMC‐MW/GCPE was prepared with the addition of graphite powder, OMC and DPA at the ratio of 2 : 1 : 1. The electrochemical properties and morphology of the electrode were characterized by electrochemical impedance spectroscopy (EIS), cyclic voltammetry (CV), SWASV and scanning electron microscopy (SEM). The parameters affecting the stripping current response were investigated and optimized. The experimental results show that the prepared electrode exhibited excellent electrochemical performance, good electrical conductivity and a high stripping voltammetric response. Under optimized conditions, a linear range was achieved over a concentration range from 1.0 to 70.0 μg/L for both Cd(II) and Pb(II) metal ions, with detection limits of 0.07 μg/L for Cd(II) and 0.08 μg/L for Pb(II) (S/N=3) with the deposition time 150 s. Moreover, the sensor exhibited improved sensitivity and reproducibility compared to traditional CPEs. The fabricated electrode was then successfully used to satisfactorily detect Cd(II) and Pb(II) in real soil samples.     

Hyperbolic Yamabe problem

In this paper, we investigate the solutions of the hyperbolic Yamabe problem for the(1 + n)-dimensional Minkowski space-time. More precisely speaking, for the case of n = 1, we derive a general solution of the hyperbolic Yamabe problem; for the case of n = 2, 3, we study the global existence and blowup phenomena of smooth solutions of the hyperbolic Yamabe problem;while for general multi-dimensional case n ≥ 2, we discuss the global existence and non-existence for a kind of exact solutions of the hyperbolic Yamabe problem.