Structure transitions of polymer-mediated colloidal crystals

The self-assembled colloidal crystals with structure transitions were realized experimentally on substrates with polymer brushes. Such polymer-mediated colloidal crystals were found to experience a series of in-layer structure transitions including stable columnar, polycrystalline, mixed square-hexagonal, square, hexagonal structures when the mass ratio of colloidal particles to free polymers was adjusted from 0.125 to 10. Among these structures, a large area interfacial square structure was proved to be a body-centered tetragonal (BCT) structure in three dimensions in the polymer-mediated colloidal crystals.     

不对称二聚物粒子在两嵌段共聚物形成的支撑膜上的自组装

结合自洽场理论和密度泛函理论,研究了不对称的二聚物粒子在AB两嵌段共聚物形成的支撑膜上的自组装行为. 不对称的二聚物粒子是由两个不同的球组成的两性分子. 其中一个球与A嵌段相亲,另外一个喜欢B嵌段. 不对称粒子能在支撑膜上形成一个双层结构. 由于衬底的存在,所形成的支撑膜上下两叶的对称性被破坏,导致了二聚物粒子在膜上形成的结构也变的不对称. 随着二聚物粒子浓度的增加,在膜上的二聚物粒子的结构将发生变化,从稀四方、六角、密四方再到圆柱结构. 在一个高浓度的密堆积下,二聚物粒子将形成弯曲的圆柱结构. 在支撑膜     

Nature of the transition from two- to three-dimensional ordering in a confined colloidal suspension

We report the results of extensive molecular dynamics simulations of solid-to-solid transitions in two- to six-layer colloidal suspensions confined between two smooth parallel walls. The studies are designed to elucidate the ordered particle packings that interpolate between the structures of two- and three-dimensional crystals in a confined space. At a fixed density per layer, as the wall separation increases we find a sequence of stable phases, each characterized by uniform amplitude buckling along the normal to the layer planes. The buckling is coupled to an in-plane ordering transition. The buckled phases alternate with phases whose structures contain only parallel planes of particles. The relative densities of the positively and negatively displaced particles in a buckled layer, the in-plane structures, and the behavior with respect to increasing wall separation of the split density distribution that characterizes a buckled layer, clearly identify these layers as intermediates in the reconstructive transformations ntriangle up-->(n+1) square that occur when the character of the constrained space evolves from being two dimensional to being three dimensional (triangle up denotes layers with hexagonal packing symmetry, while square denotes layers with square packing symmetry). The two transitions, ntriangle up-->n-buckled-->(n+1) square, are found to be first order.     

Isosteric heat of adsorption for repulsive interactions

The isosteric heat of adsorption of particles with repulsive nearest-neighbour interactions on a square lattice is calculated using the transfer matrix method. A significant diminution of enhancement of this repulsion is observed around half-coverage and at temperatures below and near the order-disorder transition. Consequences for thermal desorption are examined.     

Cyclotron resonance in bilayer graphene

We present the first measurements of cyclotron resonance of electrons and holes in bilayer graphene. In magnetic fields up to B=18 T, we observe four distinct intraband transitions in both the conduction and valence bands. The transition energies are roughly linear in B between the lowest Landau levels, whereas they follow square root[B] for the higher transitions. This highly unusual behavior represents a change from a parabolic to a linear energy dispersion. The density of states derived from our data generally agrees with the existing lowest order tight binding calculation for bilayer graphene. However, in comparing data to theory, a single set of fitting parameters fails to describe the experimental results.     

Shape-induced frustration of hexagonal order in polyhedral colloids

The effect of a nonspherical particle shape and shape polydispersity on the structure of densely packed hard colloidal particles was studied in real space by confocal microscopy. We show that the first layer at the wall of concentrated size-monodisperse but shape-polydisperse polyhedral colloids exhibits significant deviations from a hexagonal lattice. These deviations are identified as bond-orientational fluctuations which lead to percolating "mismatch lines." While the shape-induced geometrical frustration of the hexagonal symmetry suppresses translational order, bond-orientational order is clearly retained, indicating a hexaticlike structure of the polyhedral colloids.     

NaCl structure in a mixture of silica and gold sols

The formation of an NaCl structure in a mixture of a monodisperse silica sol with particle diameter of 5300 A and a gold sol with average particle size of 800 A is described. The mixture was left still for a month, and the particles settled to form a dense layer at the bottom, where phase separation appeared. In the ordered phase only gold particles were observed microscopically as bright spots at their individual lattice points, being arranged in hexagonal or in square pattern. From the distance between the particles in the square pattern and hexagonal pattern, the lattice type for gold particles was concluded to be fcc. Further, it was known that four gold particles forming a square hold one silica particle in its center. On these grounds, the entire lattice was concluded to be of the NaCl-type.     

Morphological diversity of DNA-colloidal self-assembly

We study theoretically a binary system in which an attraction of unlike particles is combined with a type-independent soft-core repulsion. The possible experimental implementation of the system is a mixture of DNA-covered colloids, in which both the repulsion and the attraction may be induced by DNA solution. The system is shown to exhibit surprisingly diverse and unusual morphologies. Among them are the diamond lattice and the membrane phase with in-plane square order, a striking example of spontaneous compactification.     

二维荷电粒子维格纳晶格:边界效应

采用一种非线性的优化方法,研究了处于硬壁限制势下二维带电多粒子系统的基态,分析不同形状边界对系统基态构型的影响.由于圆形边界对称性高,基态结构和抛物限制势下情况相似.在正方形边界下,当系统粒子数N<66时,荷电粒子形成方形晶格;当N≥66时,由于边界影响被削弱,内层粒子形成六角维格纳晶格.进一步分析了椭圆和矩形边界对维格纳晶格的影响.     

Phase equilibria and transport in polymer colloids

Colloidal dispersions of uniform spherical particles, achievable through special emulsion polymerization techniques, show order-disorder transitions in which the ordered phase consists of particles spaced on a close-packed lattice. This colloidal phenomenon is an example of condensation of a hard-sphere gas, the so-called Kirkwood-Alder transition. The colloid transition can be simulated by using the DLVO pair potential either in numerical integration of Newton's equations o r in a Monte Carlo method. Although suitable for equilibrium properties, these methods can not yield transport properties of colloids, due to neglect of interactions between particle and medium, Substitution of Langevin's equation for Newton's introduces both frictional and stochastic forces on the particles. Computer simulation of particle motions by integration of Langevin's equation yields correct equilibrium properties, and permits the calculation of transport properties as well. Some results of computer simulation of diffusion are presented.     

Continuous freezing in three dimensions

We analyze the freezing transition in a system of hard particles with a very long-ranged repulsion. The long-range repulsion makes first-order freezing transitions continuous, but leaves the initial stages of the crystallization unchanged: the crystal phase must still nucleate. The coexistence between bulk phases is replaced by microphase separation.     

Classical molecules in two dimensions

The ground-state configurations and spectrum of two parallel two-dimensional classical atoms are obtained as a function of the inter-atomic distance ( ). The classical particles are confined by parabolic potentials and repel each other through a Coulomb potential. As a function of we find several configurational transitions which are of first or second order. For first- (second-) order transitions the first (second) derivative of the energy with respect to is discontinuous, the radial position of the particles changes discontinuously (continuously) and the frequency of the eigenmodes exhibit a jump (softening of a mode). In the limit of an infinite number of electrons the Wigner bilayer system is recovered which moves through five different stable crystalline phases as a function of . For unequal strength of parabolic confinement we find that the number of configurational transitions increases.     

Formation of two-dimensional crystal-like structures from inclusions in smectic C films

The structures formed by inclusions in smectic C (SmC) free-standing films are investigated using polarized light microscopy. The domains confined in these two-dimensional (2D) systems induce distortion of the inplane orientational order, which governs the elastic interaction between the inclusions. The balance between long-range quadrupolar attraction and short-range repulsion gives rise to a nontrivial collective behavior of domains. Various 2D structures are created as a function of the concentration and size of inclusions. We observe the formation of chains and then a 2D square lattice when the concentration of domains increases. Further increase in the domain size leads to the transition from square to hexagonal close-packed structure.     

Equilibrium configurations and phase transitions in dipole lattices

Two-dimensional square and hexagonal lattices of magnetic dipoles with the number of rows 1–4 have been studied. Based on the numerical analysis, equilibrium stable domain configurations, including the minimum number of lattice dipoles, have been revealed; the conditions for the creation and destruction of domains have been determined; and their associated changes in the magnetic moment of the lattice and in the energy of the dipole interaction have been found. The conditions for the occurrence of phase transitions that change the configuration of the lattices have been investigated and the conditions for unidirectional propagation of the front of the phase transition have been established. A comparative analysis of different square and hexagonal lattices has been performed in terms of the specific features of the formed domains and the observed orientation phase transitions.     

Effect of lateral interactions on tunnel diffusion of adsorbed particles

A way of calculating the chemical diffusion coefficient for tunnel diffusion is discussed. It is shown that the famous “jump rate” formula may be used to describe the tunnel diffusion of interacting particles in the region of coverages and temperatures where phase transitions in the adsorbed overlayer are absent. The dependence of the tunnel diffusion coefficient on coverage is calculated for the square lattice taking into consideration the repulsive lateral interactions of nearest-neighbour particles.     

Charged particles on a two-dimensional lattice subject to anisotropic Jahn-Teller interactions

The properties of a system of charged particles on a 2D lattice, subject to an anisotropic Jahn-Teller-type interaction and 3D Coulomb repulsion, are investigated. In the mean-field approximation without Coulomb interaction, the system displays a phase transition of first order. When the long-range Coulomb interaction is included, Monte Carlo simulations show that the system displays very diverse mesoscopic textures, ranging from spatially disordered pairs to ordered arrays of stripes, or charged clusters, depending only on the ratio of the two interactions (and the particle density). Remarkably, charged objects with an even number of particles are more stable than with an odd number of particles. We suggest that the diverse functional behavior-including superconductivity-observed in oxides can be thought to arise from the self-organization of this type.     

Dynamic colloidal stabilization by nanoparticle halos

We explore the conditions under which colloids can be stabilized by the addition of smaller particles. The largest repulsive barriers between colloids occur when the added particles repel each other with soft interactions, leading to an accumulation near the colloid surfaces. At lower densities these layers of mobile particles (nanoparticle halos) result in stabilization, but when too many are added, the interactions become attractive again. We systematically study these effects--accumulation repulsion, reentrant attraction, and bridging--by accurate integral equation techniques.     

Dynamics of the field-induced formation of hexagonal zipped-chain superstructures in magnetic colloids

Combining nuclear magnetic resonance and molecular dynamics simulations, we unravel the long-time dynamics of a paradigmatic colloid with strong dipole-dipole interactions. In a homogeneous magnetic field, ionic ferrofluids exhibit a stepwise association process from ensembles of monomers over stringlike chains to bundles of hexagonal zipped-chain patches. We demonstrate that attractive van der Waals interactions due to charge-density fluctuations in the magnetic particles play the key role for the dynamical stabilization of the hexagonal superstructures against thermal dissociation. Our results give insight into the dynamics of self-organization in systems dominated by dipolar interactions.