Multiple patterns of diblock copolymer confined in irregular geometries with soft surface

The different confinement shapes can induce the formation of various interesting and novel morphologies, which might inspire potential applications of materials. In this paper, we study the directed self-assembly of diblock copolymer confined in irregular geometries with a soft surface by using self-consistent field theory. Two types of confinement geometries are considered, namely, one is the concave pore with one groove and the other is the concave pore with two grooves. We obtain more novel and different structures which could not be produced in other two-dimensional(2D) confinements. Comparing these new structures with those obtained in regular square confinement, we find that the range of ordered lamellae is enlarged and the range of disordered structure is narrowed down under the concave pore confinement.We also compare the different structures obtained under the two types of confinement geometries, the results show that the effect of confinement would increase, which might induce the diblock copolymer to form novel structures. We construct the phase diagram as a function of the fraction of B block and the ratio of h/L of the groove. The simulation reveals that the wetting effect of brushes and the shape of confinement geometries play important roles in determining the morphologies of the system. Our results improve the applications in the directed self-assembly of diblock copolymer for fabricating the irregular structures.     

Hydrophobic and Ionic-Interactions in Bulk and Confined Water with Implications for Collapse and Folding of Proteins

Water and water-mediated interactions determine the thermodynamics and kinetics of protein folding, protein aggregation and self-assembly in confined spaces. To obtain insights into the role of water in the context of folding problems, we describe computer simulations of a few related model systems. The dynamics of collapse of eicosane shows that upon expulsion of water the linear hydrocarbon chain adopts an ordered helical hairpin structure with 1.5 turns. The structure of dimer of eicosane molecules has two well ordered helical hairpins that are stacked perpendicular to each other. As a prelude to studying folding in confined spaces we used simulations to understand changes in hydrophobic and ionic interactions in nano-sized water droplets. Solvation of hydrophobic and charged species change drastically in nano-scale water droplets. Hydrophobic species are localized at the boundary. The tendency of ions to be at the boundary where water density is low increases as the charge density decreases. The interactions between hydrophobic, polar, and charged residue are also profoundly altered in confined spaces. Using the results of computer simulations and accounting for loss of chain entropy upon confinement we argue and then demonstrate, using simulations in explicit water, that ordered states of generic amphiphilic peptide sequences should be stabilized in cylindrical nanopores.     

Observation of chaotic and regular dynamics in atom-optics billiards

We report on experimental observations of chaotic and regular motion of ultracold atoms confined by a billiard-shaped optical dipole potential induced by a rapidly scanning laser beam. To investigate the dynamics of the atoms confined by such an "atom-optics" billiard we measure the decay of the number of trapped atoms through a hole on the boundary. A fast and purely exponential decay, the clear signature of chaotic motion, is found for a stadium billiard, but not for a circular or an elliptical billiard, in agreement with theory. We also investigated the effects of decoherence, velocity spread, and gravity on regular and chaotic motion.     

椭球与圆球混合胶体体系的玻璃化转变

以椭球与圆球混合的胶体体系为研究对象,通过增加体系的面积分数,从实验上研究了混合体系发生玻璃化转变过程中结构和动力学行为的演变规律.在结构方面,通过计算和分析径向分布函数、泰森多边形以及取向序参量,发现椭球可以有效地抑制圆球结晶,整个体系在结构上始终保持无序.在动力学方面,通过计算体系的均方位移和自散射函数,发现随着面积分数的增加,体系的动力学明显变慢,弛豫时间在接近模耦合理论预测的玻璃化转变点快速增大并发散.通过考察快速粒子参与的协同重排行为,发现协同重排区域形状、大小和位置都与椭球的存在密切关联.     

Log-rolling micelles in sheared amphiphilic thin films

Using molecular dynamics simulations, we show that sheared solutions of cylindrical micelle-forming amphiphiles behave very differently under extreme confinement as compared to the bulk. When confined to ultrathin films, the self-assembled cylindrical micelles roll along the shearing direction and align parallel to each other with their axes along the vorticity direction, as opposed to aligning parallel to the shearing direction in the bulk. It is shown that this new "log-rolling" phase arises due to a strong coupling between the rotational degree of freedom of the micelles and the steady sliding motion of the confining surfaces. We examine the microscopic mechanism of the log-rolling phenomenon and also discuss its dependence on the segregation strength and length of the amphiphile, the shear rate, and the film thickness.     

Polarization anisotropy in the optical properties of silicon ellipsoids

A new real space quantum mechanical approach with local field effects included is applied to the calculation of the optical properties of silicon nanocrystals. Silicon ellipsoids are studied and the role of surface polarization is discussed in details. In particular, surface polarization is shown to be responsible for a strong optical anisotropy in silicon ellipsoids, much more pronounced with respect to the case in which only quantum confinement effects are considered. The static dielectric constant and the absorption spectra are calculated, showing that the perpendicular and parallel components have a very different dependence on the ellipsoid aspect ratio. Then, a comparison with the classical dielectric model is performed, showing that the model only works for large and regular structures, but it fails for thin elongated ellipsoids.     

Structural transitions of solvent-free oligomer-grafted nanoparticles

Novel structural transitions of solvent-free oligomer-grafted nanoparticles are investigated by using molecular dynamics simulations of a coarse-grained bead-spring model. Variations in core size and grafting density lead to self-assembly of the nanoparticles into a variety of distinct structures. At the boundaries between different structures, the nanoparticle systems undergo thermoreversible transitions. This structural behavior, which has not been previously reported, deviates significantly from that of simple liquids. The reversible nature of these transitions in solvent-free conditions offers new ways to control self-assembly of nanoparticles at experimentally accessible conditions.     

Compliant structures with time-varying moment of inertia and non-zero averaged momentum and their application in angular rate microsensors

In this work we introduce a new class of fully compliant structures performing vibratory motion, yet characterized by non-zero averaged momentum, appearing due to time-dependency of the inertial parameters. The work is motivated by microelectromechancial systems (MEMS) applications, where an implementation of unidirectional, non-vibratory motion involving relative motion of parts is not desirable for reliability reasons. Instead of changing the mass, which is challenging on the microscale, the moment of inertia of the proof mass performing tilting vibrations is controlled in such a way that it is higher or lower depending on the sign of the velocity. This results in a non-zero angular momentum averaged over the period. The equations describing the dynamics of a generic structure with a time-varying inertia and in a rotating coordinate frame are derived by using a variational principle. Simple approximate expressions for the averaged momentum and steady tilting angle are obtained and validated numerically. Based on the model results for different operational scenarios, we demonstrate that these devices can be efficiently used in fully compliant actuators and vibratory angular rate sensors (microgyros) with a steady response in a sensing mode (“pseudospinning disk gyros”), as well as in a parametrically excited gyro. The structure can be viewed also as a first step toward the realization of dynamic materials (DM) which are substances with material properties that may change in space and time.     

Confinement-induced novel morphologies of block copolymers

Self-assembly of block copolymers confined in cylindrical nanopores is studied systematically using a simulated annealing technique. For diblock copolymers which form two-dimensional hexagonally packed cylinders with period L0 in the bulk, novel structures such as helices and stacked toroids spontaneously form inside the cylindrical pores. These confinement-induced morphologies have no counterpart in the bulk system and they depend on the pore diameter (D) and the surface-polymer interactions, reflecting the importance of structural frustration and interfacial interactions. On tightening the degree of confinement, transitions from helices to toroids to spheres are observed. Mechanisms of the morphological transitions can be understood based on the degree of structural frustration parametrized by the ratio D/L0.     

Phase behaviors in a binary mixture of diblock copolymers confined between two parallel walls

The phase behaviors in a binary mixture of diblock copolymers confined between two parallel walls are investigated by using a cell dynamics simulation of the time-dependent Ginzburg-Landau theory.The morphological dependence of the wall-block interaction and the distance between walls(confinement degree) has been systematically studied,and the effect of repulsive interactions between different monomers is also discussed.It is interesting that multiple novel morphological transitions are observed by changing these factors,and various multilayered sandwich structures are formed in the mixture.Furthermore,the parametric dependence and physical reasons for the microdomain growth and orientational order transitions are discussed.From the simulation,we find that much richer morphologies can form in a binary mixture of diblock copolymers than those in a pure diblock copolymer.Our results provide an insight into the phase behaviors under parallel wall confinement and may provide guidance for experimentalists.This model system can also give a simple way to realize orientational order transition in soft materials through confinement.     

Molecular motion in restricted geometries

Molecular dynamics in restricted geometries is known to exhibit anomalous behaviour. Diffusion, translational or rotational, of molecules is altered significantly on confinement in restricted geometries. Quasielastic neutron scattering (QENS) offers a unique possibility of studying molecular motion in such systems. Both time scales involved in the motion and the geometry of motion can be studied using QENS. Molecular dynamics (MD) simulation not only provides insight into the details of the different types of motion possible but also does not suffer limitations of the experimental set-up. Here we report the effect of confinement on molecular dynamics in various restricted geometries as studied by QENS and MD simulations. An example where the QENS technique provided direct evidence of phase transition associated with change in the dynamical behaviour of the molecules is also discussed.      

Phase behaviors in binary mixture of diblock copolymers confined between two parallel walls

The phase behaviors in binary mixture of diblock copolymers confined between two parallel walls are investigated by using cell dynamics simulation of the time-dependent Ginzburg-Landau theory. The morphological dependence of the wall-block interaction and the distance between walls (confinement degree) has been systematically studied, and the effect of repulsive interactions between different monomers is also discussed. It is interesting that multiple novel morphological transitions are observed by changing these factors, and various multilayered sandwich structures are formed in the mixture. Furthermore, the parametric dependence and physical reasons for the microdomain growth and orientational order transitions are discussed. From the simulation, we find that much richer morphologies can form in binary mixture of diblock copolymers than those in pure diblock copolymer. Our results provide an insight into the phase behaviors under parallel walls confinement and may provide guidance for experimentalists. This model system can also give a simple way to realize orientational order transition in soft materials through confinement.     

聚乙烯在碳受限空间中的结晶

认识聚合物在受限空间内的结晶行为和特点对于开发高储热性能复合相变材料有着重要意义.本文对聚乙烯在限域空间下的结晶行为进行了分子动力学模拟,并与自由空间下的聚乙烯结晶进行了对比.针对单层石墨烯片构成的一维限制、无定形碳圆形孔道构成的二维限制,分别计算了聚乙烯的径向分布函数、势能、回转半径及其与壁面的相互作用能.结果 表明...     

A single trapped ion in a finite range trap

This paper presents a method to describe dynamics of an ion confined in a realistic finite range trap. We model this realistic potential with a solvable one and we obtain dynamical variables (raising and lowering operators) of this potential. We consider coherent interaction of this confined ion in a finite range trap and we show that its center-of-mass motion steady state is a special kind of nonlinear coherent states. Physical properties of this state and their dependence on the finite range of potential are studied.     

Ionic liquid confined in silica nanopores: molecular dynamics in the isobaric–isothermal ensemble

Molecular dynamics simulations in the isobaric–isothermal ensemble are used to investigate the structure and dynamics of an ionic liquid confined at ambient temperature and pressure in hydroxylated amorphous silica nanopores. The use of the isobaric–isothermal ensemble allows estimating the effect of confinement and surface chemistry on the density of the confined ionic liquid. The structure of the confined ionic liquid is investigated using density profiles and structural order parameters while its dynamics is assessed by determining the mobility and ionic conductivity of the confined phase. Despite the important screening of the electrostatic interactions (owing to the small Debye length in ionic liquids), the local structure of the confined ionic liquid is found to be mostly driven by electrostatic interactions. We show that both the structure and dynamics of the confined ionic liquid can be described as the sum of a surface contribution arising from the ions in contact with the surface and a bulk-like contribution arising from the ions located in the pore centre; as a result, most properties of the confined ionic liquid are a simple function of the surface-to-volume ratio of the host porous material. In contrast, the ionic conductivity of the confined ionic liquid, which is a collective dynamical property, is found to be similar to the bulk. This study sheds light on the complex behaviour of hybrid materials made up of ionic liquid confined in inorganic porous materials.     

Quantum shape effects and novel thermodynamic behaviors at nanoscale

Thermodynamic properties of confined systems depend on sizes of the confinement domain due to quantum nature of particles. Here we show that shape also enters as a control parameter on thermodynamic state functions. By considering specially designed confinement domains, we demonstrate how shape effects alone modify Helmholtz free energy, entropy and internal energy of a confined system. We propose an overlapped quantum boundary layer method to analytically predict quantum shape effects without even solving Schrödinger equation or invoking any other mathematical tools. Thereby we reduce a thermodynamic problem into a simple geometric one and reveal the profound link between geometry and thermodynamics. We report also a torque due to quantum shape effects. Furthermore, we introduce isoformal, shape preserving, process which opens the possibility of a new generation of thermodynamic cycles operating at nanoscale with unique features.     

Vibration confinement and energy harvesting in flexible structures using collocated absorbers and piezoelectric devices

We propose an optimal design for supplementing flexible structures with a set of absorbers and piezoelectric devices for vibration confinement and energy harvesting. We assume that the original structure is sensitive to vibrations and that the absorbers are the elements where the vibration energy is confined and then harvested by means of piezoelectric devices. The design of the additional mechanical and electrical components is formulated as a dynamic optimization problem in which the objective function is the total energy of the uncontrolled structure. The locations, masses, stiffnesses, and damping coefficients of these absorbers and capacitances, load resistances, and electromechanical coupling coefficients are optimized to minimize the total energy of the structure. We use the Galerkin procedure to discretize the equations of motion that describe the coupled dynamics of the flexible structure and the added absorbers and harvesting devices. We develop a numerical code that determines the unknown parameters of a pre-specified set of absorbers and harvesting components. We input a set of initial values for these parameters, and the code updates them while minimizing the total energy in the uncontrolled structure. To illustrate the proposed design, we consider a simply supported beam with harmonic external excitations. Here, we consider two possible configurations for each of the additional piezoelectric devices, either embedded between the structure and the absorbers or between the ground and absorbers. We present simulations of the harvested power and associated voltage for each pair of collocated absorber and piezoelectric device. The simulated responses of the beam show that its energy is confined and harvested simultaneously.     

Dynamics of wing cracks and nanoscale damage in glass

We investigate initiation, growth, and healing of wing cracks in confined silica glass by molecular dynamics simulations. Under dynamic compression, frictional sliding of precrack surfaces nucleates nanovoids which evolve into nanocrack columns at the precrack tip. Nanocrack columns merge to form a wing crack, which grows via coalescence with nanovoids in the direction of maximum compression. Lateral confinement arrests the growth and partially heals the wing crack. Growth and arrest of the wing crack occur repeatedly, as observed in dynamic compression experiments on brittle solids under lateral confinement.     

Thomas-Fermi equation with non-spherical boundary conditions

The confined atom Thomas-Fermi equation with non-spherical boundary conditions is considered. A 2-D finite element code for solving the Thomas-Fermi equation with general boundary conditions is demonstrated. Results for both Dirichlet and Neumann boundary conditions for ellipsoids of revolution are presented.     

C36团簇自组装的分子动力学研究

提出了利用C36团簇在气相条件下自组装制备新纳米团簇的设想，并利用分子动力学方法模 拟了包括真实氦气氛作用的碳团簇生长过程，发现环境气体温度是影响最后所生成的团簇结 构的关键因素：C36团簇在1000?K到2000?K的温度范围内，自组装形成保持C36线径特征的 蚕茧状新纳米团簇；在高于2000?K的温度下，最后形成的团簇趋于球状. 关键词： 分子动力学模拟 纳米碳团簇