低密度溶液中溶剂的重组织性质

分析了溶液的微观结构 ,结果表明 ,单个溶质粒子影响其周围的溶剂的结构 ,溶质粒子间的相互作用也将影响溶剂的结构 ,溶质对溶剂结构的影响称作溶剂的重组织 .提出了二阶重组织能及二阶重组织熵等概念 ,可以描述在两个溶质粒子发生碰撞时对其周围溶剂结构的影响 .利用二元系的集团展开理论 ,给出了溶剂的一阶、二阶重组织能和重组织熵的表达式 .统计热力学分析给出了溶剂 溶剂径向分布函数与溶质和溶剂化学势之间的关系 ,给出了无限稀溶液模型是否成立的宏观判据 .提出的理论可用于低密度的二元溶液 .     

镱铥共掺杂的氟化镧纳米粒子的亮蓝色上转换发光

采用反胶束法合成镱铥共掺杂的氟化镧纳米粒子.这种反胶束是由微乳液作为合成媒介,这些分散的纳米粒子在化学成分、尺寸分布上是可控的.产物形貌经场发射扫描电镜和透射电镜表征.固态样品分散在乙醇中,在未经超声处理时,样品表现为玉米棒样的聚集.棒的平均直径和长度分别为110,575nm.我们认为这种大量纳米粒子聚集成良好超结构是由于溶剂挥发,分子交叉链接或者表面活性剂分子附着于纳米粒子特殊晶面造成的.当样品经过超声处理后,由于超声振动破坏了上述因素,玉米棒形貌的聚集体转为大量纳米粒子.单个粒子的高分辨电镜显示出该纳米粒子的单晶结构.并且晶面间距约为0.366nm,与纯氟化镧六角相[002]晶面相一致.样品在300℃退火30min后的透射电镜照片显示纳米粒子的平均直径大约为35nm,这与XRD结果相吻合.并且,这些纳米粒子表现出了良好的单分散性,并且在978nm二极管激发下,纳米粒子呈现出亮蓝色上转换发光,这种上转换荧光粉在光电子或生物检测中有潜在的应用前景.     

电子激发和溶剂效应对芴酮-甲醇分子间氢键增强现象的理论研究 (cited: 1)

理论研究了电子激发和溶剂效应导致的芴酮-甲醇复合体系中分子间氢键增强现象．通过基态和激发态性质的计算,不仅展示了分子间氢键键长的变化以及变化在振动光谱中的影响,而且揭示了导致氢键变化的内在物理机制：溶质分子的电子激发及溶剂化效应引起的电子重新分布,增大了溶质和溶剂分子的偶极矩,导致了它们之间的相互作用的增大,并最终加强了分子间氢键的强度．还分别对处于液相及气相中的复合体的基态和激发态的几何结构、红外谱、复合体及构成分子的偶极矩进行了理论计算,结果阐明了电子激发与溶剂化效应对氢键变化的贡献,同时还发现只有进一步引入溶剂化效应,复合体的基态、激发态的性质才能与实验达到精确一致．所有激发态均采用所开发的基于含时密度泛函理论解析计算一阶、二阶激发态能量导数的方法．     

单个纳米粒子对聚合物结晶行为的影响

采用粗粒化模型,应用分子动力学方法研究了单个纳米粒子对聚合物结晶行为的影响.通过改变纳米粒子与聚合物单体之间作用方式(吸引作用或排斥作用)、纳米粒子与聚合物单体之间作用强度和聚合物分子链的长度,计算整个系统和局部区域的有序参数,研究了三个不同因素下纳米粒子对聚合物结晶行为的不同影响.研究表明,在聚合物基体中添加单个纳米粒子,纳米粒子对整个系统的结晶影响不明显,但是纳米粒子对其周围聚合物单体的结晶存在局部强化作用.当纳米粒子与聚合物单体之间为吸引作用且作用强度较大时,纳米粒子对聚合物结晶表现出明显的局部强化作用,聚合物分子链长度也有着一定的影响,在较大吸引作用强度下,长链样本比短链样本有着更为显著的局部强化作用.     

非线性晶体产生的空心光束中大尺寸粒子囚禁与导引

提出了一种基于非线性ZnSe晶体产生的空心光束与光泳力的大尺寸粒子二维囚禁与一维导引、三维囚禁方案.理论上分析并计算了单个非线性ZnSe晶体产生的空心光束内粒子受到的横向与纵向光泳力,纵向光泳力的大小同粒子尺寸与光束尺寸比例的四次方成正比,与空心光束功率成正比,方向与光束传播方向一致.粒子尺寸与空心光束尺寸越接近时,横向光泳力的大小越大.结果表明该光泳力可以实现对大尺寸粒子的二维囚禁,同时可对粒子进行长距离(米量级)一维定向导引;理论上分析并计算了基于双非线性ZnSe晶体产生的局域空心光束内粒子所受横向与纵向光泳力情况,光泳力与系统参数的依赖关系与单个非线性晶体产生的空心光束中的粒子受力情况类似,不同的是该条件下纵向光泳力指向光束中心.结果表明该局域空心光束可以实现大尺寸粒子的三维有效囚禁.基于非线性ZnSe晶体产生的空心光束或者局域空心光束可以作为大尺寸粒子非接触式有效操控的工具,在现代光学以及生物医学中有潜在的应用.     

氮气射频放电与直流放电PIC/MC模拟的比较

建立氮气容性射频等离子体过程的PIC/MC模型,将模拟结果与直流放电进行比较.结果表明:射频等离子体粒子(e,N₂⁺,N⁺)的平均密度较直流放电约大-个量级,在射频电极附近粒子(e,N₂⁺,N⁺)的平均能量比直流放电阴极附近的能量低3倍左右;密度偏低的原子离子N⁺在两电极附近具较高的能量,能量较低的分子离子N₂⁺在放电空间具较高密度,N₂⁺的密度大约是N⁺的6倍;计算的电子能量几率分布与测量结果-致.     

聚集效应对银纳米粒子的二阶非线性光学特性的影响研究

运用超瑞利散射(HRS)技术,对由KNO3诱导聚集的银纳米粒子的二阶光学非线性特性进行了实验研究.通过粒子尺寸测量和透射电镜观察，表明银纳米粒子的聚集方式为链状聚集.当聚集体平均尺寸为120nm时，银纳米粒子聚集体的HRS信号强度比聚集前增大了约15倍.分析表明，聚集导致银纳米粒子表面电场极化强度的增强和极化分布的改变，并通过表面和体贡献机理对二阶非线性极化过程产生影响. 关键词： 银纳米粒子 超瑞利散射 二阶光学非线性 聚集     

混合中子星内强子-夸克退禁闭相变

高密度物质环境内可能存在多种相互竞争的粒子相.利用包含ω²ρ²相互作用项的相对论平均场理论中FSUGold参数组描述强子相物质,夸克质量密度相关的有效质量口袋模型描述夸克相物质,再通过Gibbs相平衡条件构建强子-夸克混合相物质,研究了处于β平衡的混合中子星性质.计算口袋常数B对混合中子星性质的影响,结果表明B对混合中子星内强子-夸克退禁闭相变始末点、粒子分布均有较大影响,且相较于相变开始点,相变结束点受B的影响会更加明显.随着B的增大,混合中子星物质状态方程变硬,质量-半径关系曲线上升,极限质量在1.3-1.4倍太阳质量(M_⊙)范围内,半径在9-12 km之间.此外,还研究了吸引和排斥的∑势对混合中子星性质的影响,结果表明不同∑势对混合中子星内的粒子种类影响较大,且相较于∑引力势,混合中子星在∑斥力势下拥有更大的极限质量.计算得到吸引和排斥的∑势下混合中子星的极限质量分别为1.38M_⊙和1.41M_⊙.     

紫外光谱溶剂效应的SPT研究

本文根据定标粒子理论的模型导得了紫外光谱溶剂效应的理论公式。对苯酚，硝基苯、苯胺及氯苯分别在８种纯溶剂的π→π跃迁紫外吸收波数进行了理论计算。与Ｍｃａｒｅ理论的结果相比，计算精度提高了近一个数量级。最后对理论模型、溶质的结构参量及各相互作用项的贡献进行了简要讨论。     

SPH方法气-液界面边界条件研究

针对界面附近粒子光滑函数截断和非物理穿透问题,提出一种气-液界面边界条件的处理方法.当界面附近支持域出现不同材料粒子,每步计算可在支持域设置虚粒子,按照密度分配方法给虚粒子物理量赋值,并对界面附近粒子引入气-液两相阻力.采用SPH方法和Level-Set方法,计算运动激波对气-液界面作用问题,两者计算结果一致,初步验证了气-液界面边界条件处理的适用性.用SPH方法分别计算超声速气流中的圆截面液柱绕流和下落问题,界面两侧粒子压力和法向速度连续,给出弓形激波、回流区和下游回流区等定性合理结果.表明本文方法可适度避免界面附近流体粒子光滑截断和粒子非物理穿透现象、界面附近流场数值振荡.     

Influence of Solvent-Solvent and Solute-Solvent Interaction Properties on Solvent-Mediated Potential

A recently proposed universal calculational recipe for solvent-mediated potential is applied to calculate excess potential of mean force between two large Lennard-Jones (LJ) or hard core attractive Yukawa particles immersed in small LJ solvent bath at supercritical state. Comparison between the present prediction with a hypernetted chain approximation adopted for solute-solute correlation at infinitely dilute limit and existing simulation data shows high accuracy for the region with large separation, and qualitative reliability for the solute particle contact region. The calculational simplicity of the present recipe allows for a detailed investigation on the effect of the solute-solvent and solvent-solvent interaction details on the excess potential of mean force. The resultant conclusion is that gathering of solvent particles near a solute particle leads to repulsive excess PMF, while depletion of solvent particles away from the solute particle leads to attractive excess PMF, and minor change of the solvent-solvent interaction range has large influence on the excess PMF.     

Influence of Solvent-Solvent and Solute-Solvent Interaction Properties on Solvent-Mediated Potential

A recently proposed universal calculational recipe for solvent-mediated potential is applied to calculate excess potential of mean force between two large Lennard-Jones （LJ） or hard core attractive Yukawa particles immersed in small LJ solvent bath at supercritical state. Comparison between the present prediction with a hypernetted chain approximation adopted for solute-solute correlation at infinitely dilute limit and existing simulation data shows high accuracy for the region with large separation, and qualitative reliability for the solute particle contact region. The calculational simplicity of the present recipe allows for a detailed investigation on the effect of the solute-solvent and solvent-solvent interaction details on the excess potential of mean force. The resultant conclusion is that gathering of solvent particles near a solute particle leads to repulsive excess PMF, while depletion of solvent particles away from the solute particle leads to attractive excess PMF, and minor change of the solvent-solvent interaction range has large influence on the excess PMF.     

Microscopic theory of intrinsic shear and bulk viscosities

A microscopic theory of intrinsic shear and bulk viscosities of solutions is given for a model of particles that interact with hard-sphere cores and weak longrange attraction. The approximation considered (the velocity chaos assumption of the Enskog theory) can be expected to yield quantitatively useful values for viscosities of the model solute-solvent system when the solute particles are not much larger than the solvent particles. Under solute-solvent mixing conditions of constant pressure and temperature we find that the intrinsic viscosities of a hard-sphere solute in a hard-sphere solvent can be positive or negative, depending upon size and mass ratios; for solute and solvent particles whose mass ratio equals their volume ratio, the intrinsic shear and bulk viscosities are always positive for solute particles larger than solvent particles: in the opposite case, the intrinsic shear viscosity is always negative while the intrinsic bulk viscosity is for the most part negative, becoming positive again when the solute particle is sufficiently small. For solute particles smaller than solvent particles, this result is sensitive to change in mass ratio. The addition of solvent-solvent attraction is found to lower the intrinsic viscosities substantially; the addition of solute-solvent attraction raises it. Detailed quantitative analysis of these effects is given.     

Behavior of a quantum particle in contact with a classical heat bath

We investigate the behavior of a two-level quantum system in contact with a classical heat bath, e.g., a solute particle with internal degrees of freedom immersed in a solvent of massive particles. Using a combination of analytical and numerical methods, we obtain precise information about localization, time-displaced correlation functions, and the frequency-dependent susceptibility of such solute particles. We find that these quantities can have a strong dependence on the density of the solvent fluid, with the maximum changes from the behavior of the corresponding isolated quantum system occurring in many cases at very low densities. We compare the exact results with those obtained by path integral Monte Carlo. There is good agreement with the imaginary time correlations, but analytic continuation to real time proves elusive: even with the best numerical data on the former, we can only get very gross features of the latter.     

Phase behaviour of a dispersion of charge-stabilised colloidal spheres with added non-adsorbing interacting polymer chains

We present a theory for the phase behaviour of mixtures of charge-stabilised colloidal spheres plus interacting polymer chains in good and θ -solvents within the framework of free-volume theory. We use simple but accurate combination rules for the depletion thickness around a colloidal particle and for the osmotic pressure up to the semi-dilute concentration regime. Hence, we obtain expressions for the free energy for mixtures of charged colloidal particles and non-adsorbing interacting polymers. From that, we calculate the phase behaviour, and discuss its topology in dependence on the competition between the charge-induced repulsion and the polymer-induced attraction. The homogeneous mixture of colloids and polymers becomes more stabilised against demixing when increasing the electrostatic repulsion. This charge-induced stabilisation is strongest for small polymer-to-colloid size ratios and is more pronounced for charged colloids mixed with polymers in a good solvent than for polymers in a θ -solvent. For the weakly charged regime we find that the phase diagram becomes salt-concentration-independent in the protein limit for charged colloids plus polymers in a θ -solvent. The liquid window, i.e., the concentration regimes where a colloidal liquid exists, is narrowed down upon increasing the charge-induced repulsion. Also this effect is more pronounced when charged colloids are mixed with polymer chains in a good solvent. In summary, we demonstrate that the solvent quality significantly influences the phase behaviour of mixtures of charged colloids plus non-adsorbing polymers if the range of the screened electrostatic repulsion becomes of the order of the range of the depletion-induced attraction.     

The structure of the interface in the solvent-mediated interaction of dipolar surfaces

Summary Interaction of two dipolar surfaces separated by a polar medium is considered within the framework of nonlocal electrostatics. The dipolar-surface layers are modelled as regular lattices with fixed orientation of dipoles which are immersed into the solvent; solvent response is characterized by nonlocal dielectric function. The model is elaborated in order to reveal the role of the dipolar-layer discreteness in the electric field produced by one surface and the interaction between two surfaces (which gives rise to the so-called ?hydration? or ?structural? force acting between mineral surfaces and phospholipid bilayers). The discreteness effects are present only for commensurate lattices. Their special mutual arrangement then may lead to considerable reduction of structural forces,viz. the usual repulsion regime may change at short distances to attraction. Conditions are considered when repulsion is entirely replaced by attraction,i.e. the ?hydration barrier? disappears. In appended note we discuss the role of solvation of surface dipolar groups. We propose an explanation of why two modes of decay (one with oscillative fine structure) may be present in the dependence of the force upon distance, if the surface dipolar groups are immersed deep enough in the solvent, and how the long-range oscillative mode disappears when the surface is but weakly solvated. To speed up publication, the authors of this paper have agreed to not receive the proofs for correction.     

用积分方程方法决定胶粒之间的空耗势

用硬球模中性胶体粒子 ,数值求解双组分Ornstein Zernike积分方程 (当大的中性胶体粒子的浓度为零时 ) ,用来决定悬浮在溶剂 (用小的硬球模拟 )中两个胶粒之间的空耗势 .所预言的空耗势与文献的模拟数据和实验数据能很好地符合 .研究发现 ,基于空耗势的有效一组分Hansen Verlet一相相变标准完全不能预言双组分系统的液 固相变 .讨论了导致这种现象的原因 :Hansen Verlet一相相变标准不能自地处理有效一组分系统中固相与液相的体积能     

A classical density functional approach to depletion interaction of Lennard-Jones binary mixtures

In this article, we apply classical density functional theory to investigate the characteristics of depletion interaction in Lennard-Jones (LJ) binary fluid mixtures. First, to confirm the validity of our adopted density functional formalism, we calculate the radial distribution functions using a theoretical approach and compare them with results obtained by molecular dynamics simulation. Then, this approach is applied to two colloids immersed in LJ solvent systems. We investigate the variation of depletion interaction with respect to the distance of two colloids in LJ binary systems. We find that depletion interaction may be attractive or repulsive, mostly depending on the bulk density of the solvent and the temperature of the binary system. For high bulk densities, the repulsive barrier of depletion force is remarkable when the total excluded volume of colloids touches each other and reaches a maximum. The height of the repulsive barrier is related to the parameters of the LJ potential and bulk density. Moreover, the depletion force may exhibit attractive wells if the bulk density of the solvent is low. The attractive well tends to appear when the surface–surface distance of colloids is half of the size of the polymer and deepens with temperature lowering in a fixed bulk density. In contrast with the hard-sphere system, no oscillation of depletion potential around zero is observed.     

Adsorption of hydrophobic polyelectrolytes onto oppositely charged surfaces

We present a scaling theory for the adsorption of a weakly charged polyelectrolyte chain in a poor solvent onto an oppositely charged surface. Depending on the fraction of charged monomers and on the solvent quality for uncharged monomers, the globule in the bulk of the solution has either a spherical conformation or a necklace structure. At sufficiently high surface charge density, a chain in the globular conformation adsorbs in a flat pancake conformation due to the Coulombic attraction to the oppositely charged surface. Different adsorption regimes are predicted depending on two screening lengths (the Debye screening length monitored by the salt concentration and the Gouy-Chapman length monitored by the surface charge density), on the degree of ionization of the polymer and on the solvent strength. At low bulk ionic strength, an increase in the surface charge density may induce a transition from an adsorbed necklace structure to a uniform pancake due to the enhanced screening of the intra-chain Coulombic repulsion by the counterions localized near the surface. Received 12 April 2001     

Long-range interactions in polymer melts: the anti-Casimir effect

It is well known that small neutral particles normally tend to aggregate due to the van der Waals forces. We discover a new universal long-range interaction between solid objects in polymer media that is directly opposite the van der Waals attraction. The new force could reverse the sign of the net interaction, possibly leading to the net repulsion. This universal repulsion comes from the subtracted soft fluctuation modes, which are not present in the real polymer system, but rather are in its ideal counterpart. The predicted effect has a deep relation to the classical Casimir interactions, providing an unusual example of fluctuation-induced repulsion instead of normal attraction. That is why it is referred to as the anti-Casimir effect. We also find that the correlation function of monomer units in a concentrated solution of infinite polymer chains follows a power-law rather than an exponential decay at large distances.