Adsorbate-adsorbate interactions and the ordering of organic monolayers on metal surfaces

To study the ordering of molecules adsorbed on single-crystal substrates, a molecular cross-section (MCS) is defined, which measures the surface area occupied by each molecule. With this MCS, a two-dimensional packing coefficient C_2D is then defined for ordered arrays of adsorbed molecules. Values and trends for MCS and C_2D are discussed for known surface structures, especially for benzene adsorbed on metal surfaces. The packing is found to be generally less dense at surfaces than one would expect from comparison with packing in three-dimensional organic crystals. The Van der Waals packing energy and the repulsive dipole-dipole energy are also computed to study this issue. The lack of close-packing is attributed to the need to respect structural coincidence with the substrate and/or co-adsorption of small molecules like CO. These concepts are then applied to the prediction of the long-range order that a monolayer of adsorbed molecules may adopt: thereby possible adsorption structures can be defined, restricting the number of possibilities in a further structural determination.     

The re-entrant cholesteric phase of DNA

The character of packing of double-stranded DNA molecules in particles of liquid-crystal dispersions formed as a result of the phase exclusion of DNA molecules from aqueous salt polyethylene glycol solutions has been estimated by comparing the circular dichroism (CD) spectra of these dispersions recorded at different osmotic pressures and temperatures. It is shown that the first cycle of heating of dispersion particles with hexagonally packed double-stranded DNA molecules leads to the occurrence of abnormal optical activity of these particles, which manifests itself in the form of a strong negative CD band, characteristic of DNA cholesterics. Moreover, subsequent cooling is accompanied by a further increase in the abnormal optical activity, which indicates the existence of the “hexagonal → cholesteric packing” phase transition, controlled by both the osmotic pressure of the solution and its temperature. The result obtained can be described in terms of “quasi-nematic” layers composed of orientationally ordered DNA molecules in the structure of dispersion particles. There are two possible ways of packing for these layers, which determine their hexagonal or cholesteric spatial structure. The second heating → cooling cycle confirms these results and is indicative of possible differences in the packing of double-stranded DNA molecules in the hexagonal phase, which depend on the osmotic pressure of the solution.     

Molecular packing for planar molecules

The crystal packing of five planar molecules is considered in this paper. Each unit cell contains two non-equivalent molecules whose planes are inclined to each other. It is shown that the angle of inclination between the planes is completely determined by a simple geometrical criterion. A simple sequential arrangement of the four molecules defining the elementary parallelopiped of which the entire crystal is built leads to various configurations from which the one which has the least interaction energy can be picked out. Using a crude Lennard-Jones potential for the non-bonded interaction and a hard sphere model for the atoms, one can compute the crystal structure from the minimum energy criterion and this is found to be in fair agreement with the observed structure. This simple sequential packing with some modifications can provide an useful model for calculating the radial distribution function in amorphous solids involving planar groups.     

应变层超晶格InAs/InP界面的平均键能行为与价带边不连续性

采用LMTO能带方法,对两种不同应变状态下(自由形变和以InP为衬底),应变层超晶格(InAs)₁(InP)₁(001)和与应变层超晶格的分子层相对应的应变体材料,以及无应变的体材料进行了第一原理计算,并采用冻结势方法求出了两种超晶格各分子层的平均键能。结果表明,能存在应变的情况下,异质界面两边的平均键能非常一致,且这种一致性受应变状态的影响很小,因而可以把它用来作为确定应变层超晶格价带边不连续值(△E_v)的普遍适用的参考能级。研究了应变对 关键词：     

Packing configurations for methane storage in carbon nanotubes

In this paper we investigate methane packing in single-walled carbon nanotubes. We employ classical applied mathematical modelling using the basic principles of mechanics to exploit the Lennard-Jones potential function and the continuous approximation, which assumes that intermolecular interactions can be approximated by average atomic surface densities. We consider both zigzag and spiral configurations formed by packing methane molecules into (9, 5), (8, 8) and (10, 10) carbon nanotubes, and we derive analytical expressions for the interaction potential energy of these configurations. Our findings indicate that for the zigzag configuration for a (9, 5) tube, the potential energy of the system is minimized when the methane molecules simply form a linear chain along the tube axis, but genuine zigzag patterns are found as the tube size increases such as for the (8, 8) and (10, 10) tubes. For the spiral configuration, the potential energy of the system is minimized when the angular spacing is approximately equal to π for the (9, 5) and (8, 8) tubes, and π/2 for the (10, 10) tube. Overall, our results are in good agreement with molecular dynamics simulations in the literature and show that the most energetically efficient packing configuration of the three tubes studied, occurs for a (10, 10) tube with a zigzag packing, while a (10, 10) tube with a spiral packing configuration has the largest free-cavity volume for methane adsorption at higher temperatures.     

How do smectic liquid crystals of different molecular length mix in thin films?

We present a model for the structure of binary mixtures of smectic compounds in freely suspended films of 2-7 layers. The compounds are the hexyl (6AB) and dodecyl (10AB) homologues of p, p'-dialkylazoxybenzene that differ by about 40% in molecular length. X-ray reflectivity indicates that no demixing occurs between 6AB and 10AB molecules, while also there is no indication found of increased roughness at the film surfaces. However, the surface layers are somewhat expanded compared to the interior layers. This can be explained by backfolding of the dodecyl end chains of 10AB molecules at the surface via two gauche kinks, which ensures dense packing. This model is supported by surface tension measurements that indicate an increased amount of alkyl groups at the surfaces.     

Interface and contact structures for nanoelectronic devices using assemblies of metallic nanoclusters,conjugated organic molecules and chemically stable semiconductor layers

Self-assembly (‘building’) approaches can provide well-controlled structures and assemblies at the nanometer scale, but typically do not provide the specific structures or functionalities required for robust nanoelectronic circuits. One approach to realize high-density nanoelectronic circuits is to combine self-assembly techniques with more conventional semiconductor device and circuit approaches (‘chiseling`) in order to provide suitable functionality and arbitrary circuit functions. An interesting challenge is to find approaches where these techniques can be combined to realize suitable device structures. This paper describes recent work which combines self-assembly techniques involving metal nanoclusters and conjugated organic molecules with semiconductor interface and device structures to form structures of interest for nanoelectronics. One key requirement for this approach is the availability of a chemically stable semiconductor surface layer, which can provide a low-resistance interface between the metallic nanostructure and the semiconductor device layers following room-temperature, ex situ processing. As an illustration of the structures which can be realized, we describe a nanometer-scale ohmic contact to n-type GaAs which utilizes low-temperature-grown GaAs as the chemically stable interface layer. Contact structures have been realized using both isolated (sparse) clusters and using close-packed arrays of clusters on the surface. The low-resistance contacts between the nanoclusters and the semiconductor device layers indicates that relatively low surface barriers and high doping densities have been achieved in these ex situ structures. The general conduction model for this contact structure is described in terms of the interface electrical properties and the contributions from the various components are discussed.     

Phase transitions in the adsorbed molecular chains

Rotational excitations of molecular adsorbed layers are studied theoretically. Nonlinear dynamical equations are obtained with accounting of quadrupolar interactions between molecules and freezing of translational degrees of freedom. The equilibrium positions of the molecules are found to be experimentally observed structures with alternating rotational ordering of planar rotors along the direction to the nearest neighbor (for linear or square structures) under low temperature. Dynamical analysis gives an integral of motion (energy) of the chain that in the long-wave limit leads consequently to the existence of four phases. The first one corresponds to oscillations near equilibrium ordered states. The second phase corresponds to low-energy rotational excitations along ‘valleys’ (easy directions in the effective potential) that do not destroy strong correlations between molecules while structural data can show rotational disorder (melting). The third phase corresponds to an energy that is enough to travel between ‘valleys’; only some ‘islands’ in the angle space are forbidden. Complete destruction of correlation when the energy is over the peaks of the effective potential corresponds to the fourth phase. Therefore rotational melting is a complex phenomenon that has several stages. Presented at the 2nd International Conference “Physics of Liquid Matter: Modern Problems” (September 2003, Kyiv, Ukraine).     

Formation of Zero Density Regions During the Dissolving of C60 and C70

Based on a comprehensive review of the calculated and experimental data obtained in this and previous articles by the authors, a phenomenological model of the supramolecular structure of fullerene solutions is proposed. The model suggests the development in the fullerene solutions of some zero density regions due to poor packing of spheroidal fullerene molecules C₆₀ and C₇₀, on the one hand, and columnar or ribbon supramolecular structures formed by solvent molecules, on the other. It is assumed that the source of the long-range energy of fullerenes is a physical vacuum, concentrated not only in the cavities of the fullerene molecules but also in new regions forming outside the fullerenes during their dissolving in single-ring aromatic solvents.     

Packing state in bilayer membranes of diacylphosphatidylcholines with varying acyl chain lengths under high pressures

The bilayer packing states of a series of diacylphosphatidylcholines (CnPC) containing linear saturated acyl chains were examined by a high-pressure fluorescence method. We revealed from the second derivatives of Prodan fluorescence spectra for all bilayer membranes that the Prodan molecules can be distributed into multiple sites in these bilayer membranes and move around the head-group region, depending on the phase state. The hydrophobicity of the PC molecules markedly affected the distribution quantities of the Prodan molecules between the gel and liquid crystalline phases. The distribution of the Prodan molecules into the gel phase decreased with the increasing acyl chain length while that into the liquid crystalline phase conversely increased. The present study suggests that Prodan can sensitively recognize the packing states and strengths in the bilayer membranes and becomes a good packing indicator.     

Spectral properties of contact matrix: Application to proteins

A protein can be modelled by a set of points representing its amino acids. Topologically, this set of points is entirely defined by its contact matrix (adjacency matrix in graph theory). The contact matrix characterizing the relation between neighboring amino acids is deduced from Voronoi or Laguerre decomposition. This method allows contact matrices to be defined without any arbitrary cut-off that could induce arbitrary effects. Eigenvalues of these matrices are related with elementary excitations in proteins. We present some spectral properties of these matrices that reflect global properties of proteins. The eigenvectors indicate participation of each amino acids to the excitation modes of the proteins. It is interesting to compare the protein modelled as a close packing of amino acids, with a random close packing of spheres. The main features of the protein are those of a packing, a result that confirms the importance of the dense packing model for proteins. Nevertheless there are some properties, specific to the hierarchical organization of the protein: the primary chain order, the secondary structures and the domain structures.     

Pulsed laser heating calculations incorporating vapourization

We present a scheme for solution of the heat flow equation in one-dimension incorporating melting and vapourization produced under pulsed laser irradiation. The method can be applied to pure materials as well as multilayered structures such as deposited films. The variation of physical properties with temperature can be easily taken into account. Results of calculation are presented for aluminium and for chromium and antimony layers deposited on aluminium. As a consequence of excessive vapourization at high energy densities, the melt depth and the melt duration do not increase beyond a certain limit. The resolidification front velocity is strongly dependent on energy density and can be controlled in an experiment by a careful choice of laser parameters. Some recent experimental data on laser treated chromium films are discussed in light of our calculations.     

气相沉积技术在原子制造领域的发展与应用

随着未来信息器件朝着更小尺寸、更低功耗和更高性能方向的发展,构建器件的材料尺寸将进一步缩小.传统的"自上而下"技术在信息器件发展到纳米量级时遇到瓶颈,而气相沉积技术由于其能在原子尺度构筑纳米结构引起极大关注,被认为是最有潜力突破现有制造极限进而在原子尺度构造、搭建物质形态的"自下而上"方法.本文重点讨论适用于低维材料的原子尺度制造的分子束外延技术和原子层沉积/刻蚀技术.简要介绍相关技术中蕴含的科学原理及其在纳米信息器件加工和制造领域的应用,并探讨如何在原子尺度实现对低维功能材料厚度和微观形貌的精密控制.     

The Special Features of the Electronic Structure of Imperfect and Interacting Low-Dimensional Nanoparticles

A new method for constructing analytic exactly solvable models of the electronic structure of imperfect and interacting low-dimensional nanoparticles is suggested. The method uses the approach based on multiple scattering theory. It allows characteristic equations to be written specifying the contributions of exchange interactions between separate atoms, nanoparticle fragments, or interacting nanoparticles. The possibilities of the method are demonstrated for the example of one-dimensional and quasi-one-dimensional finite regular structures with monovacancies and isolated attached atoms and diatomic molecules. We also consider regular structures composed of two interacting low-dimensional nanoparticles. The general characteristic of the electronic spectra of the systems under consideration is qualitative changes in the system of energy levels and electron density distributions as a result of the formation of defects or new bonds between subsystems. These changes can substantially influence all the physical and chemical properties of nanoparticles.     

β-1,3,5,7-四硝基-1,3,5,7-四氮杂环辛烷热膨胀各向异性的量子化学计算与分子动力学模拟

在303～383 K和NPT系综和COMPASS力场下对β-1,3,5,7-四硝基-1,3,5,7-四氮杂环辛烷(HMX)超晶胞初始结构的分子动力学模拟,得到常压下各温度的晶体平衡构型并发现分子的堆积方式不变;通过线性拟合求算出线膨胀系数与实验值相近,体现出明显的各向异性. 采用密度泛函理论方法对沿各晶轴方向膨胀率变化(100%～105%)的HMX单胞模型进行了总能计算,得到的能量变化率体现各向异性并与热膨胀系数值关联,建立了关联方程. 由此阐 释了HMX晶体热膨胀各向异性的本质即特定的分子堆积模式.     

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.     

Tailoring the structure of water at a metal surface: a structural analysis of the water bilayer formed on an alloy template

Recent studies show that structures based on the traditional "icelike" water bilayer are not stable on flat transition metal surfaces and, instead, more complex wetting layers are formed. Here we show that an ordered bilayer can be formed on a SnPt(111) alloy template and determine the structure of the water layer by low energy electron diffraction. Close agreement is found between experiment and the structure calculated by density functional theory. Corrugation of the alloy surface allows only alternate water molecules to chemisorb, stabilizing the H-down water bilayer by reducing the metal-hydrogen repulsion compared to a flat surface.     

Cu87团簇在升温与急冷过程中结构变化的原子尺度模拟

本文采用基于嵌入原子法的正则系综分子动力学方法在原子尺度上计算了包含87个原子的Cu87金属团簇在连续升温和急冷降温时的结构演化过程。根据原子平均势能、对分布函数、原子堆积结构和主要原子键对数目随温度的变化表明,温度的不同极大地影响团簇内的原子堆积结构。在升温过程中,随着温度的升高,团簇内原子堆积结构出现由密排六方、二十面体直到无序堆积的变化。在急冷降温过程中,随着急冷温度的降低,团簇内由出现的一定数量的二十面体和面心立方的局域结构、数量不一的HCP,FCC和二十面体局域结构,直到急冷温度较低时的一定数量的二十面体局域结构。