拉曼光谱方法研究1,1,3,3-四甲基脲的溶剂效应

测量了1,1,3,3-四甲基脲(TMU)在20种不同溶剂中的拉曼光谱,研究了TMU与溶剂之间的相互作用.将TMU羰基的拉曼频移分别与Kirkwood-Bauer-Magat(KBM)参数(ε-1)/(2ε+1)、溶剂受体数(acceptor number,AN)和线性溶剂自由能关系(linear solvation energy relationships,LSER)进行相关分析.结果表明,TMU的C=O键振动频移与KBM参数没有很好的线性关系,和受体数之间存在比较好的相关性,与LSER参数的线性关系最好.按受体数把溶剂分为质子性溶剂和非质子性溶剂,分别和羰基频移有好的相关性.通过对LSER参数的分析,可以很好地解释溶质和溶剂间的相互作用.     

Effects of Ⅴ/Ⅲ ratio on species diffusion anisotropy inthe MOCVD growth of non-polar a-plane GaN films

Non-polar a-plane (110) GaN films have been grown on r-plane (102) sapphire substrates by metal organic chemical vapour deposition. The influences of Ⅴ/Ⅲ ratio on the species diffusion anisotropy of a-plane GaN films were investigated by scanning electron microscopy, cathodoluminescence and high-resolution x-ray diffraction measurements. The anisotropy of a-plane GaN films may result from the different migration length of adatoms along two in-plane directions. Ⅴ/Ⅲ ratio has an effect on the growth rates of different facets and crystal quality. The stripe feature morphology was obviously observed in the film with a high V/III ratio because of the slow growth rate along the [100] direction. When the Ⅴ/Ⅲ ratio increased from 1000 to 6000, the in-plane crystal quality anisotropy was decreased due to the weakened predominance in migration length of gallium adatoms.     

Kinetic sonication effects in aqueous acetonitrile solutions. Reaction rate levelling by ultrasound

The kinetics of the pH-independent hydrolysis of 4-methoxyphenyl dichloroacetate were investigated with and without ultrasonic irradiation in acetonitrile–water binary mixtures containing 0.008 to 35 wt.% of acetonitrile and the kinetic sonication effects (k_son/k_non) were calculated. Molecular dynamics (MD) simulations of the structure of the solutions were performed with ethyl acetate as the model ester. The ester is preferentially solvated by acetonitrile. The excess of acetonitrile over water in the solvation shell grows fast with an increase in the co-solvent content in the bulk solution. In parallel, the formation of a second solvation shell rich in acetonitrile takes place. Significant kinetic sonication effects for the hydrolysis were explained with facile destruction of the diffuse second solvation shell followed by a rearrangement of the remaining solvent layer under sonication. The rate levelling effect of ultrasound was discussed. In an aqueous-organic binary solvent, independent of the solvent composition, the ultrasonic irradiation evokes changes in the reaction medium which result in an almost identical solvation state of the reagent thus leading to the reaction rate levelling.     

Surface-driven instability and enhanced relaxation in the dynamics of a nonequilibrium interface

We determine the stability of a nonequilibrium interface between two coexisting solid phases in the presence of a weak external field. Starting at the coarsegrained (Cahn-Hilliard) level, we use the method of matched asymptotics to derive the macroscopic interfacial dynamics. We then show that the external field leads to an instability due to flux along the interface, in contrast with the more common Mullins-Sekerka type instability, which involves fluxes normal to the interface. We also find that the external field produces an important modification of the Gibbs-Thomson relation. With these results, we perform the linear stability analysis for an approximately flat interface. If the field is tangent to the interface, the modification of the Gibbs-Thomson relation is important and the interface is stabilized. If the field is normal to the interface, the surface flux is important, and the effect can be stabilizing or destabilizing, but the orientational dependence is opposite what would be obtained if the Mullins-Sekerka instability dominates. Numerical simulations are performed to study the effect of the surface current and are in agreement with our analytical results.     

General synchronization dynamics of coupled Van der Pol–Duffing oscillators

This paper considers the general synchronization dynamics of coupled Van der Pol–Duffing oscillators. The linear and nonlinear stability analysis on the synchronization process is derived through the Whittaker method and the Floquet theory in addition to the multiple time scales method. A stability map displaying different dynamical states of the system is performed. Numerical simulation is carried out to support and to complement the accuracy of the analytical treatment.     

Hydration structure of Na+ and K+ from ab initio molecular dynamics based on modern density functional theory

Molecular dynamics (Born–Oppenheimer) simulations based on density functional theory have been carried out to investigate the solvation structure of monovalent Na⁺ and K⁺ cations in water under ambient conditions. Four recently proposed van der Waals (vdW) density functionals (LMKLL, DRSLL, DRSLL-PBE, DRSLL-optB88), the semiempirical vdW method of Grimme (BLYP-D3) and conventional gradient-corrected (GGA-BLYP) density functionals are applied in order to evaluate their accuracy in describing the hydration structure of alkali metal ions. Theoretical results are compared to available experimental data. Our results indicate that addition of corrections accounting for dispersion forces significantly improves the agreement between predicted and measured coordination numbers for both Na⁺ and K⁺ cations. Analysis of radial distribution functions brings further support to the notion that the choice of the generalised gradient approximation density functional impacts crucially on the computed structural properties. DRSLL-optB88 and BLYP-D3 provide the best agreement with experiment.     

少模光纤放大器中的准静态模式不稳定实验研究

模式不稳定发现于2010年,是影响高功率光纤激光器功率提升的重要限制因素.当前模式不稳定主要有两类,一类是动态模式不稳定,一类是准静态模式不稳定.本文研究了纤芯/内包层直径为25μm/400μm掺镱双包层光纤后向抽运放大器中的模式不稳定效应.通过对功率、光束质量和时域数据的分析,发现在该放大器中出现了准静态模式不稳定的现象,随着抽运功率的增加,放大器输出光束质量逐步退化,而时域上没有发现明显的动态模式不稳定特性.实验上对不同种子功率下放大器的输出特性进行研究,结果表明,通过提高种子激光功率可以较为有效地提高模式不稳定阈值,在种子功率为528 W时,当输出功率大于3000 W,输出激光效率没有明显下降.     

Selective nonspecific solvation under dielectric saturation and fluorescence spectra of dye solutions in binary solvents

The influence of selective nonspecific solvation on the fluorescence spectra of three substitutedN-methylphthalimides in a binary solvent system consisting of a nonpolar (n-heptane) and a polar (pyridine) component has been studied under conditions close to dielectric saturation. The substantially nonlinearity of the effect is confirmation that the spectral shifts of fluorescence bands depend on the number of polar solvent molecules involved in solvating the dye molecule. The measured fluorescence spectral shifts determined by substituting one nonpolar solvent molecula with a polar one in the proximity of the dye molecule agree quantitatively with the forecasts of the previously proposed semiempirical theory which describes this nonlinear solvation phenomenon.     

Study of the stability of polarization mode dispersion in fibre

Polarization mode dispersion (PMD) is the ultimate limitation to high bit-rate fibre communication system. The stability of PMD is very important to its measurement and compensation. This paper puts forward a method to measure the stability of PMD by measuring the stability of the state of polarization (SOP) and introduces the conception of time evolution vector (TEV) of SOP. We observe the fact that the regularity of the principal state of polarization changing with time is the same as other SOPs‘‘, if we neglect the dependence of TEV on wavelength. We also measure the SOP‘‘s stability of some fibres with different lengths, and obtain results of PMD changing with time.     

UV-spectral changes for some azo compounds in the presence of different solvents

The electronic absorption spectra of four azo dyes with different substituents (such as Cl, I, OH) are determined at room temperature in twenty-one solvents with different polarities. The electronic transitions of azo dyes are interpreted. Linear solvation energy relationships have been investigated for solvatochromic behaviors and solute-solvent interactions of azo dyes. Linear solvation energy relationships were performed by multiple linear regression analysis using dielectric function, refractive index function and Kamlet-Taft parameters. We have observed that the hydrogen bonding acceptor ability and the induction-dispersive forces of solvent molecules have caused the bathochromic shift in absorption maxima of azo dyes.     

Shear banding instability in wormlike micellar solutions

Using NMR velocimetry and mechanical measurements we study the flow dynamics, within a cone-and-plate rheometer, of the wormlike micelle system, cetylpyridinium chloride/sodium salicylate (CPyCl/NaSal) at 100 mM/60 mM concentration in distilled water. Depending on precise conditions within the system, two classes of behaviour are observed, one in which the boundary between different shear rate phases fluctuates rapidly (on the order of tens of milliseconds) and one in which it migrates slowly with a time constant of many seconds. These modes of behaviour may depend on minor solution impurities, which presumably affect the detailed constitutive properties, but also on the externally applied shear rate within a given system. We argue that the slow migrations are governed by stress relaxation effects while the rapid migrations are flow driven and arise from interfacial instability. Received: 2 June 1998 / Received in final form and Accepted: 27 July 1998     

Gibbs energy of cooperative hydrogen‐bonding interactions in aqueous solutions of amines and pyridines

A method to determine the Gibbs energy of specific (hydrogen bonding) interactions of a solute with water is proposed. The energies of hydrogen bonding in bulk water are very difficult to determine by any method. The Gibbs energy of hydration of substances forming hydrogen bonds with water is considered as the sum of contributions due to non‐specific interactions, the hydrophobic effect, and specific interactions. The first two terms were found to be rather accurately described by empirical equations. The Gibbs energies of hydrogen bonding of aliphatic amines and pyridines in bulk water are determined, and the results are compared with the energies of their complexes with one molecule of water. The cooperativity of hydrogen bonding is proved in aqueous solutions of amines and pyridines. To use our equations, experimental values of the Gibbs energies of solvation in 'standard' solvents need to be known. The Gibbs energies of solvation of ten amines and pyridines in dimethyl sulfoxide are determined experimentally using chromatographic head space analysis. The tendencies observed for the series of amines and pyridines are in agreement with other studies. Copyright © 2009 John Wiley & Sons, Ltd.     

一类时滞非线性相对转动系统的Hopf分岔与周期解的稳定性

讨论了一类时滞非线性相对转动系统的Hopf分岔现象,给出了系统产生Hopf分岔的临界时滞条件,利用多尺度法研究了系统在主共振情况下时滞参数对分岔方向和周期解稳定性的影响,最后,用数值模拟对所得结论进行验证.     

Solitary wave solutions as a signature of the instability in the discrete nonlinear Schrödinger equation

The effect of instability on the propagation of solitary waves along one-dimensional discrete nonlinear Schrödinger equation with cubic nonlinearity is revisited. A self-contained quasicontinuum approximation is developed to derive closed-form expressions for small-amplitude solitary waves. The notion that the existence of nonlinear solitary waves in discrete systems is a signature of the modulation instability is used. With the help of this notion we conjecture that instability effects on moving solitons can be qualitative estimated from the analytical solutions. Results from numerical simulations are presented to support this conjecture.     

Effect of dipole-dipole interaction in a solvent on the electronic spectra of three-component solutions

Electronic spectra of three-component solutions are calculated on the basis of a model, which makes it possible to incorporate the interaction between the molecules of a polar solvent, including the case of dielectric saturation. It is shown that the use of the theory of three-component solutions, which disregards the interaction between the molecules of a polar solvent, can lead to an overestimation of the efficiency with which an activator interacts with the molecules of a polar solvent. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 67, No. 1, pp. 38–41, January–February, 2000.     

Stability of travelling wave solutions for coupled surface and grain boundary motion

We investigate the spectral stability of the travelling wave solution for the coupled motion of a free surface and grain boundary that arises in materials science. In this problem a grain boundary, which separates two materials that are identical except for their crystalline orientation, evolves according to mean curvature. At a triple junction, this boundary meets the free surfaces of the two crystals, which move according to surface diffusion. The model is known to possess a unique travelling wave solution. We study the linearization about the wave, which necessarily includes a free boundary at the location of the triple junction. This makes the analysis more complex than that of standard travelling waves, and we discuss how existing theory applies in this context. Furthermore, we compute numerically the associated point spectrum by restricting the problem to a finite computational domain with appropriate physical boundary conditions. Numerical results strongly suggest that the two-dimensional wave is stable with respect to both two- and three-dimensional perturbations.     

Modulation instability analysis,optical and other solutions to the modified nonlinear Schrödinger equation

This paper studies the new families of exact traveling wave solutions with the modified nonlinear Schrödinger equation, which models the propagation of rogue waves in ocean engineering. The extended Fan sub-equation method with five parameters is used to find exact traveling wave solutions. It has been observed that the equation exhibits a collection of traveling wave solutions for limiting values of parameters. This method is beneficial for solving nonlinear partial differential equations, because it is not only useful for finding the new exact traveling wave solutions, but also gives us the solutions obtained previously by the usage of other techniques (Riccati equation, or first-kind elliptic equation, or the generalized Riccati equation as mapping equation, or auxiliary ordinary differential equation method) in a combined approach. Moreover, by means of the concept of linear stability, we prove that the governing model is stable. 3D figures are plotted for showing the physical behavior of the obtained solutions for the different values of unknown parameters with constraint conditions.     

Methodology for the solutions of some reduced Fokker‐Planck equations in high dimensions

In this paper, a new methodology is formulated for solving the reduced Fokker‐Planck (FP) equations in high dimensions based on the idea that the state space of large‐scale nonlinear stochastic dynamic system is split into two subspaces. The FP equation relevant to the nonlinear stochastic dynamic system is then integrated over one of the subspaces. The FP equation for the joint probability density function of the state variables in another subspace is formulated with some techniques. Therefore, the FP equation in high‐dimensional state space is reduced to some FP equations in low‐dimensional state spaces, which are solvable with exponential polynomial closure method. Numerical results are presented and compared with the results from Monte Carlo simulation and those from equivalent linearization to show the effectiveness of the presented solution procedure. It attempts to provide an analytical tool for the probabilistic solutions of the nonlinear stochastic dynamics systems arising from statistical mechanics and other areas of science and engineering.     

黏滞等离子体中双撕裂模不稳定性的数值模拟研究

本文采用磁流体力学模型,数值研究了平板位形下双撕裂模线性增长率关于等离子体电阻η和黏滞v的定标关系.结果表明,对于有理面间距较大的情况,线性增长率关于电阻和黏滞的指数定标率随着黏滞的增加逐渐由γ∝ η3/5v0的定标变化到γ∝η5/6v-1/6的定标;而对于有理面间距较小的情况,其指数定标率随着黏性的增加从γ∝η 1/3 v0的定标逐渐变化到γ∝η2/3v-1/3的定标.本文还给出了初始阶段对称的双撕裂模的非线性演化,发现在非线性阶段对称的双撕裂模将转化为反对称的双撕裂模,并解释了相应的物理机理.     

The structure,dynamics and solvation mechanisms of ions in water from long time molecular dynamics simulations: a case study of CaCl2 (aq) aqueous solutions

Systematic long time (5–20 ns) molecular dynamics (MD) simulations have been carried out to study the structural and dynamical properties of CaCl₂ aqueous solutions over a wide range of concentrations (≤9.26 m) in this study. Our simulations reveal totally different structural characteristics of those yielded from short time (≤1 ns) MD simulations [A.A. Chialvo and J.M. Simonson, J. Chem. Phys. 119, 8052 (2003); T. Megyes, I. Bako, S. Balint, T. Grosz, and T. Radnai, J. Mol. Liq. 129, 63 (2006)]. An apparent discontinuity was found at 4–5 m of CaCl₂ in various properties including ion–water coordination number and self-diffusion coefficient of ions, which were first noticed by Phutela and Pitzer in their thermodynamic modelling [R.C. Phutela and K.S. Pitzer, J. Sol. Chem. 12, 201 (1983)]. In this study, residence time was first taken into consideration in the study of Ca²⁺–Cl^? ion pairing, and it was found that contact ion pair and solvent-sharing ion pair start to form at the CaCl₂(aq) concentrations of about 4.5 and 4 m, respectively, which may be responsible for the apparent discontinuity. In addition, the residence time of water molecules around Ca²⁺ or Cl^? showed that the hydration structures of Ca²⁺ and Cl^? are flexible with short residence time (<1 ns). It needs to be pointed out that it takes much longer simulation time for the CaCl₂–H₂O system to reach equilibrium than what was assumed in previous studies.