Transition from highly to fully stretched polymer brushes in good solvent

The stretching of brushes of long polymers grafted to a planar surface is investigated by Monte Carlo simulations in the limit of very high grafting densities, as achieved in recent experiments. The monomer density profiles are shown to deviate considerably from the parabolic limiting form predicted by self-consistent field theory. A rapid transition is observed from parabolic to fully stretched polymers, characterized by a dramatic change in the end-monomer height distribution and by a clear crossover in the slope of the brush height versus scaled grafting density.     

锥形纳米孔内的电压整流及流体流动

文章以生物纳米通道及纳米孔中的离子传输及化学反应为背景,以离子流整流、电渗流整流、离子积累耗散模型为理论基础,使用有限元数值计算方法研究压力及电场交互作用下的锥形纳米孔孔内离子浓度分布及速度场分布现象.分析了不同电压下压力和电场的交互作用对锥形纳米孔中速度场、流场及浓度分布的影响.结果表明纳米孔孔内氢离子运动方向主要受电场方向影响.由于静电吸附效应,沿着孔壁流动的电渗流中的氢离子浓度会高于体溶液中的氢离子浓度.当电压较小时,流场方向主要受压力流的影响,当电压较大时,流场流动方向由电渗流带动的流体流动和压力驱动的流体流动共同决定.      

Grafted polymers with annealed excluded volume: A model for surfactant association in brushes

We present an analytical self-consistent-field (SCF) theory for a neutral polymer brush (a layer of long polymer chains end-grafted to a surface) with annealed excluded volume interactions between the monomer units. This model mimics the reversible adsorption of solute molecules or aggregates, such as small globular proteins or surfactant micelles, on the grafted chains. The equilibrium structural properties of the brush (the brush thickness, the monomer density profile, the distribution of the end segments of the grafted chains) as well as the overall adsorbed amount and the adsorbate density profile are analyzed as a function of the grafting density, the excluded volume parameters and the chemical potential (the concentration) of the adsorbate in the solution. We demonstrate that, when the grafting density is varied, the overall adsorbed amount always exhibits a maximum, whereas the root-mean-square brush thickness either increases monotonically or passes through a (local) minimum. At high grafting densities the chains are loaded by adsorbed aggregates preferentially in the distal region of the brush, whereas in the region proximal to the grafting surface depletion of aggregates occurs and the polymer brush retains an unperturbed structure. Depending on the relative strength of the excluded volume interactions between unloaded and loaded monomers both the degree of loading of the chains and the polymer density profile are either continuous or they exhibit a discontinuity as a function of the distance from the grafting surface. In the latter case intrinsic phase separation occurs in the brush: the dense phase consists of unloaded and weakly extended chains and occupies the region proximal to the surface, whereas a more dilute phase consisting of highly loaded and strongly extended chains forms the periphery of the brush. Received 26 November 1998 and Received in final form 2 April 1999     

Ionenbewegung unter dem Einfluß von Umladungsstößen

The motion of ions under the influence of an electric field and a density gradient is investigated by taking into account only charge-transfer collisions between the ions and a neutral gas background. The two model cases of constant mean free path and constant mean free time are considered. For weak electric fields the Boltzmann equation can be solved using a special expansion of the velocity distribution. The expansion in Sonine polynomials as given by Chapman and Cowling does not converge. For medium and high electric fields the velocity distribution is calculated by collecting the contributions of the different paths of the ions. The inhomogeneous drift in high electric fields is investigated for a small perturbation by gradients of the electric field, the ion density and of the mean free path.     

双尺度疏油结构纳米通道滑移效应的研究

针对双尺度结构表面疏油特性的优异性,采用分子动力学的方法建立油液流体正十六烷烃分子模型,研究双尺度结构壁面润湿性影响下的纳米通道内流体的流动特性,通过对通道壁面亲疏油性下的双尺度结构的构建,与光滑壁面和单尺度壁面进行比较来探究双尺度纳米通道表面结构影响下油液流体在纳米通道内密度分布、速度分布、速度滑移和滑移长度的影响.模拟结果表明:对于亲油通道壁面,双尺度结构壁面亲油性明显加强,主流区域流体密度、流体速度和速度滑移都减小,甚至出现负滑移;而对于疏油通道壁面,双尺度分层结构能加强壁面的疏油性,通道内壁面形成稳定的气层使流体主流区域的密度增大,并且通道内流体的速度、速度滑移和滑移长度明显大于光滑和单尺度结构壁面.因此,纳米通道内双尺度结构能改变通道壁面的润湿性,并且能够加强流体在纳米疏油通道内的滑移减阻效应,为纳米通道内油液运输以及润滑薄膜减阻提供了设计基础.     

Collapse of polyelectrolyte brushes: Scaling theory and simulations

We investigate polyelectrolyte brushes using both scaling arguments and molecular dynamics simulations. As a main result, we find a novel collapsed brush phase. In this phase, the height of the brush results from a competition between steric repulsion between ions and monomers and an attractive force due to electrostatic correlations. As a result, the monomer density inside the brush is independent of the grafting density and the polymerization index. For small ionic and monomer radii (or for large Bjerrum length) the brush undergoes a first-order phase transition from the osmotic into the collapsed state. Received 26 September 2000     

非对称纳米通道内流体流动与传热的分子动力学

采用分子动力学方法研究了流体在非对称浸润性粗糙纳米通道内的流动与传热过程,分析了两侧壁面浸润性不对称对流体速度滑移和温度阶跃的影响,以及非对称浸润性组合对流体内部热量传递的影响.研究结果表明,纳米通道主流区域的流体速度在外力作用下呈抛物线分布,但是纳米通道上下壁面浸润性不对称导致速度分布不呈中心对称,同时通道壁面的纳米结构也会限制流体的流动.流体在流动过程中产生黏性耗散,使流体温度升高.增强冷壁面的疏水性对近热壁面区域的流体速度几乎没有影响,滑移速度和滑移长度基本不变,始终为锁定边界,但是会导致近冷壁面区域的流体速度逐渐增大,对应的滑移速度和滑移长度随之增大.此时,近冷壁面区域的流体温度逐渐超过近热壁面区域的流体温度,流体出现反转温度分布,流体内部热流逆向传递.随着两侧壁面浸润性不对称程度增加,流体反转温度分布更加明显.     

粗糙纳通道内流体流动与传热的分子动力学模拟研究

为研究粗糙表面对纳尺度流体流动和传热及其流固界面速度滑移与温度阶跃的影响,本文建立了粗糙纳通道内流体流动和传热耦合过程的分子动力学模型,模拟研究了粗糙通道内流体的微观结构、速度和温度分布、速度滑移和温度阶跃并与光滑通道进行了比较,并分析了固液相互作用强度和壁面刚度对界面处速度滑移和温度阶跃的影响规律. 研究结果表明,在外力作用下,纳通道主流区域的速度分布呈抛物线分布,由于流体流动导致的黏性耗散使得纳通道内的温度分布呈四次方分布. 并且,在固体壁面处存在速度滑移与温度阶跃. 表面粗糙度的存在使得流体剪切流动产生了额外的黏性耗散,使得粗糙纳通道内的流体速度水平小于光滑通道,温度水平高于光滑通道,并且粗糙表面的速度滑移与温度阶跃均小于光滑通道. 另外,固液相互作用强度的增大和壁面刚度的减小均可导致界面处速度滑移和温度阶跃程度降低. 关键词： 速度滑移 温度阶跃 流固界面 粗糙度     

Conductivity of composites containing ferromagnetic nanoparticles: The role of a magnetic field

A theory of conductivity is developed for metal-containing nanocomposites. An expression is obtained for the tunneling rate of an electron between nanoparticles. Three regimes of current flow are possible: the cases of weak, strong, and superstrong electric fields. In the weak-field regime, the electrons generated as a result of ionization of neutral nanoparticles are characterized by a nearly equilibrium distribution. The conductivity in this regime is calculated with the use of this nearly equilibrium distribution of electrons and the relationship between the spacing of neighboring particles and their radii. An expression is obtained for the electric conductivity as a function of temperature and a magnetic field (for ferromagnets) with regard to the distribution of nanoparticles with respect to radius and their volume density.     

Electron drift velocity and mobility in graphene

We present a theoretical study of the electric transport properties of graphene-substrate systems. The drift velocity, mobility, and temperature of the electrons are self-consistently determined using the Boltzmann equilibrium equations. It is revealed that the electronic transport exhibits a distinctly nonlinear behavior. A very high mobility is achieved with the increase of the electric fields increase. The electron velocity is not completely saturated with the increase of the electric field. The temperature of the hot electrons depends quasi-linearly on the electric field. In addition, we show that the electron velocity, mobility, and electron temperature are sensitive to the electron density. These findings could be employed for the application of graphene for high-field nano-electronic devices.     

Dynamics of domain-wall motion in ferroelectric liquid crystals in an electric field

The director reorientation in smectic liquid crystals with ferroelectric properties has been considered in the case where the interaction of liquid-crystal molecules with the surface leads to a partial unwinding of the helical structure of the liquid crystal and the reorientation occurs as a result of the domain-wall motion. The dependences of the velocity of domain-wall motion on the electric field strength, electric field variation frequency, boundary conditions, spontaneous polarization, and viscosity of the liquid crystal have been determined. It has been demonstrated that an increase in the electric field variation frequency or the polar part of the anchoring energy and the spontaneous polarization of the liquid crystal at a constant field frequency results in an increase of the velocity of domain-wall motion. As a consequence, the time of the electro-optic response of the liquid crystal in weak electric fields (from 0.4 to 2.0 V/μm) decreases by a factor of more than three.     

场致爆炸发射阴极表面微凸起热效应的数值研究

研究场致发射电流密度与阴极表面微凸起顶部的温度之间的高度非线性关系,用数值方法计算在外加宏观电场条件下,不同顶底半径比微凸起的热效应.结果表明:当微凸起顶底半径比值不同时,由于微凸起的微观电场增强因子不同,当微凸起顶部温度达到阴极材料的熔点时,微凸起内部温度分布差异显著;当外加宏观电场相同时,微凸起的顶底半径比越小,爆炸发射延迟时间越短;对于顶底半径比确定的微凸起而言,爆炸电子发射延迟时间随外加宏观电场强度的减小而成指数规律增长.     

Molecular dynamic simulation of Copper and Platinum nanoparticles Poiseuille flow in a nanochannels

In this paper, simulation of Poiseuille flow within nanochannel containing Copper and Platinum particles has been performed using molecular dynamic (MD). In this simulation LAMMPS code is used to simulate three-dimensional Poiseuille flow. The atomic interaction is governed by the modified Lennard–Jones potential. To study the wall effects on the surface tension and density profile, we placed two solid walls, one at the bottom boundary and the other at the top boundary. For solid–liquid interactions, the modified Lennard–Jones potential function was used. Velocity profiles and distribution of temperature and density have been obtained, and agglutination of nanoparticles has been discussed. It has also shown that with more particles, less time is required for the particles to fuse or agglutinate. Also, we can conclude that the agglutination time in nanochannel with Copper particles is faster that in Platinum nanoparticles. Finally, it is demonstrated that using nanoparticles raises thermal conduction in the channel.     

Optical and electrophysical properties of nanocomposites based on PEDOT: PSS and gold/silver nanoparticles

The absorption spectra in the visible region and current-voltage characteristics in a wide range of electric fields have been investigated at the macroscopic level (planar structures) and at the microscopic level (using a conductive atomic force microscope) in films based on the electroactive polymer PEDOT: PSS and gold/silver nanoparticles (PEDOT: PSS + Au/AgNP). It has been shown that the behavior of the current-voltage characteristics of the nanocomposite films depends significantly on the electric field strength. It has been found that the introduction of gold nanoparticles into PEDOT: PSS in weak electric fields leads to an increase in the bulk conductance by almost two orders of magnitude (due to donor-acceptor interactions), a 50% decrease in the conduction activation energy, and an increase in the sensitivity to adsorbed oxygen. It has been demonstrated that electrical conduction of PEDOT: PSS + AuNP films is provided by hopping charge transfer both in the system of intrinsic localized states and in the system of impurity states of adsorbed oxygen. In strong electric fields, the current-voltage characteristics exhibit a different behavior in the forward and reverse scanning modes.     

外场下丙烯酸甲酯的激发特性研究

采用密度泛函B3LYP方法在6-311+ +G* *基组上优化了不同外电场作用下丙烯酸甲酯分子的基态几何结构、电偶极矩和分子的总能量,并且分析了分子的HOMO-3到LUMO+3轨道的能量变化,然后利用杂化CIS-DFT方法(CIS-B3LYP)在相同基组下探讨了无电场时丙烯酸甲酯分子前9个激发态的激发能、波长和振子强度和外电场对丙烯酸甲酯分子激发态的影响规律.结果表明,分子的几何构型与外电场大小有着较强的依赖关系.随着外电场的增大,分子总能量先增大后减小,电偶极矩μ先减小后增大,激发能随电场 关键词： 丙烯酸甲酯 外电场 振子强度 激发能     

High-field transport in semiconductor superlattices for interacting Wannier–Stark levels

We developed a microscopic theory of electron transport in superlattices within the Wannier–Stark approach by including the interaction associated with Zener tunneling between the energy levels pertaining to adjacent quantum wells. By using a Monte Carlo technique we have simulated the hopping motion associated with absorption and emission of polar optical phonons and determined the main transport parameters for the case of a GaAs/GaAlAs structure at room temperature. Interaction between the levels is found to be responsible for a systematic increase of the level energy with respect to the bottom of the quantum well at electric fields above about 20 kV/cm. When compared with the non-interacting case, at the highest fields the average carrier energy evidences a consistent increase, which leads to a significant softening of the negative slope of both the drift velocity and diffusivity versus electric field behavior.     

外电场作用下乙酸乙烯酯的分子结构和激发态

采用密度泛函B3LYP方法在6-31G(d)基组水平上,计算了乙酸乙烯酯分子在不同外电场(0.000 a.u.~0.030 a.u.)作用下的基态几何结构、电偶极距、电荷分布及分子总能量,然后利用杂化CIS-DFT方法在相同基组下研究了外电场对乙酸乙烯酯分子前8个激发态的激发能、波长和振子强度的影响.结果表明,分子的几何结构、电荷分布与外电场的大小呈现强烈的依赖关系.随着外电场的不断增加,分子的总能量逐渐减小,偶极距逐渐增大,激发能随电场的增加总体上呈减小的趋势,表明在外电场作用下,乙酸乙烯酯分子易于激发,激发态波长随电场的增加总体上呈增大的趋势,且电子跃迁光谱都集中在紫外区.     

Solving the Boltzmann equation in a 2-D-configuration and2-D-velocity space for capacitively coupled RF discharges

A new kinetic scheme, the generalized Monte Carlo flux (GMCF) method, provides the electron particle distribution function in phase space, f(ν, μ, r, z, t) (ν: speed, μ: velocity angle, r: radial position, z: axial position, and t: time), for solving the Boltzmann equation in modeling capacitively coupled RP discharges. For a simulation with spatial- and temporal-varying fields in RF discharges, the GMCF method handles the collision terms of the Boltzmann equation by using one transition matrix to compute the collision transition between velocity space cells. An anti-diffusion flux transport scheme is developed to overcome the numerical diffusion in the velocity and configuration spaces. The major advantages of the GMCF method are the increase in resolution in the tail of distribution functions and the decrease of computation time. The GMCF calculation results in terms of microscopic electron distribution function and macroscopic quantities of density, electric field and ionization rate, are presented for RF discharges and compared with other kinetic and fluid simulation and experimental results. The effects of the induced radial electric field in the sheath close to the radial wall in a cylindrically symmetric parallel-plate geometry are discussed     

氯乙烯在外电场下的激发态结构研究

采用密度泛函B3P86方法在6-311G基组上优化了不同外电场作用下氯乙烯分子的基态几何结构、电偶极矩和分子的总能量,然后利用杂化CIS-DFT方法(CIS-B3P86)在相同基组下探讨了无电场时氯乙烯分子前9个激发态的激发能、波长和振子强度和外电场对氯乙烯分子激发态的影响规律.结果表明,分子的几何构型与外电场大小有着强烈的依赖关系.随着外电场的增大,分子总能量先增大后减小,电偶极矩μ先减小后增大.激发能随电场增加快速减小,表明在外电场作用下,氯乙烯分子易于激发和离解.激发态波长随电场的增大而不断增大,且其电子跃迁光谱都集中在紫外区.     

Polymer brushes near the crystallization density

In this paper, polymer brushes are studied via molecular-dynamics simulations at very high grafting densities, where the crossover between the brush regime and the polymer-crystal regime is taking place. This crossover is directly observed with the structure factor and pair-correlation function. With increasing grafting density, this crystallization is progressing from the core layer of the brush towards the surface layer. The same process is analyzed using the lateral fluctuations of the monomers as a signature of their diminishing mobility. Additionally, bond forces and the chain excess free energy indicate a transition from the brush regime to the overstretched regime, which is in agreement with predictions of a modified self-consistent field theory.