Thermal Disorder, Fluctuations, Growth and Fragmentation of Finite One-Dimensional Atomic Chains

Ordering in one-dimensional atomic chains is studied using computer simulation. We find that dense ordered chains may exist if the system is cold enough and not macroscopically long. Growth of finite length chains from the vapor and by vapor exchange between chains begins rapidly, then slows down exponentially in time. As temperature rises density fluctuations increase, causing the chains to fragment. Independent of fragmentation, disordering begins at the ends, a condition similar to the precursor of edge and surface melting in two and three dimensions. The chemical potential of finite ordered chains is a function of length and temperature, due to the competition between attraction and internal thermal excitation. Equilibrium of chains coexisting with one-dimensional vapor produces a distribution of sizes, peaked at a temperature dependent chain length. Several results may be relevant to experimental studies of adsorption on carbon nanotubes     

Systematic study of the effect of disorder on nanotribology of self-assembled monolayers

The adhesion and friction between pairs of ordered and disordered self-assembled monolayers on SiO2 are studied using molecular dynamics. The disorder is introduced by randomly removing chains from a well ordered crystalline substrate and by attaching chains to an amorphous substrate. The adhesion force between monolayers at a given separation increases monotonically with chain length at full coverage and with coverage for fixed chain length. Friction simulations are performed at shear velocities between 0.02-2 m/s at constant applied pressures between 200 and 600 MPa. Stick-slip motion is observed at full coverage but disappears with disorder. With random defects, the friction becomes insensitive to chain length, defect density, and substrate.     

多价态高分子链在受体平面上的超选择性吸附

利用三维朗之万动力学模拟研究了多价态高分子链在受体平面上的吸附行为。其在受体平面上的吸附具有超选择性,随着高分子链上配体浓度的增大,发生超选择性吸附时的平面受体浓度范围变窄;而超选择性吸附最显著时的平面受体浓度,即最佳平面受体浓度随着链上配体浓度的增大而减小。对处于吸附态的多价态高分子链的构象性质进行了系统地研究,发现链的平衡回转半径R_g及其水平分量R_g},随着平面受体浓度的增大都存在极大值。其平衡回转半径R_g与其链长N间的标度指数表明当平面受体浓度的增大时,处于吸附态的链构象介于二维链构象和三维链构象之间;随着平面受体浓度的进一步增大,吸附在平面上的多价态高分子链发生轻微的塌缩     

Density functional theory for molecular orientation of hard rod fluids in hard slits

A density functional theory (DFT) is used to investigate molecular orientation of hard rod fluids in a hard slit. The DFT approach combines a modified fundamental measure theory (MFMT) for excluded-volume effect with the first order thermodynamics perturbation theory for chain connectivity. In the DFT approach, the intra-molecular bonding orientation function is introduced. We consider the effects of molecular length (i.e. aspect ratio of rod) and packing fraction on the orientations of hard rod fluids and flexible chains. For the flexible chains, the chain length has no significant effect while the packing fraction shows slight effect on the molecular orientation distribution. In contrast, for the hard rod fluids, the chain length determines the molecular orientation distribution, while the packing fraction has no significant effect on the molecular orientation distribution. By making a comparison between molecular orientations of the flexible chain and the hard rod fluid, we find that the molecular stiffness distinctly affects the molecular orientation. In addition, partitioning coefficient indicates that the longer rodlike molecule is more difficult to enter the confined phase, especially at low bulk packing fractions.     

连续相位板面形的随机特性研究

根据连续相位板面形分布的随机特性,利用自相关函数和相关长度对其面形特性进行了分析.采用一个高斯型随机分布函数推导了相关长度与连续相位板远场分布之间的解析关系.利用数值算法计算了连续相位板远场分布的方差和能量利用率,并计算了不同的相关长度对连续相位板远场分布的具体影响.结果表明,连续相位板的相关长度越小,远场分布均匀性越好,焦斑形态更加接近于目标焦斑,同时具有较高的能量利用率.     

Vapour–liquid phase equilibrium and surface tension of fully flexible Lennard–Jones chains

We report measurements of the vapour–liquid coexistence densities and surface tension of fully flexible Lennard–Jones chain molecules ranging in length from 4 to 60 beads. We demonstrate that the surface tension for all chain lengths collapses to a single master curve when plotted according to the universal parachor correlation. We find a universal parachor exponent 3.79 ± 0.05 for conditions close to the critical point, with a deviation observed for the longest chains far below the critical point.     

One New Method to Obtain the Correlation Length of Solvable Models

We propose a new method to obtain the correlation length of gapped XXZ spin 1/2 antiferromagnetic chains. Following the relativistic quantum field theory in (1+ 1) space-time dimensions, we use the exact dispersion of massive spinon to calculate the correlation length for XXZ spin 1/2 chain. We conjecture that the correlation length for other 1D lattice models can be obtained in the same way. Relation between dispersion and the oscillated correlation of gapped incommensurate lattice models is also discussed.     

One New Method to Obtain the Correlation Length of Solvable Models

We propose a new method to obtain the correlation length of gapped XXZ spin 1/2 antiferromagnetic chains.Following the relativistic quantum field theory in (1 1) space-time dimensions,we use the exact dispersion of massive spinon to correlation length for XXZ spin 1/2 chain.We conjecture that the correlation length for other 1D lattice models can be obtained in the same way.Relation between dispersion and the oscillated correlation of gapped incommensurate lattice models is also discussed.     

Formation and structural phase transition in Co atomic chains on a Cu(775) surface

The formation of Co atomic chains on a Cu(775) surface is investigated by the kinetic Monte Carlo method. It is found that the length of Co atomic chains formed as a result of self-organization during epitaxial growth is a random quantity and its mean value depends on the parameters of the experiment. The existence of two structural phases in atomic chains is detected using the density functional theory. In the first phase, the separations between an atom and its two nearest neighbors in a chain are 0.230 and 0.280 nm. In the second phase, an atomic chain has identical atomic spacings of 0.255 nm. It is shown that the temperature of the structural phase transition depends on the length of the atomic chain.     

链间耦合对聚乙炔多链体系中电子极化子再激发态的影响

采用拓展紧束缚Su-Schrieffer-Heeger(SSH)模型,研究了链间耦合对反式聚乙炔多链体系中电子极化子再激发态的晶格位形、净电荷密度、局域能级波函数和态密度的影响.结果发现:对于两条链体系,当链间耦合很小(t⊥≤0.01 e V)时,注入到系统中的电子只会在第一条链上诱发产生一个晶格缺陷,形成电子极化子再激发态,这和单链体系是一致,而第二条链仍是二聚化基态.随着链间耦合的增大,第一条链上缺陷的局域度减少而第二条链上的缺陷局域度相应增加,直至两条链上的位形相同;对于多条链(5条链和6条链)体系,当耦合很小(t⊥≤0.05 e V)时,电子极化子再激发态也只会存在于一条链上,当链间耦合较强时,极化子再激发态会在链间层次性地扩展开来,并不会出现多条链位形相同;从两条链的能级图上可以看到随着链间耦合t⊥的增大,体系的带隙不断的增大和电子态密度显示的是完全吻合的,体系的导电性减弱.通过分析两条链体系在t⊥=0 e V和t⊥=0.1 e V的能级态密度,发现链间耦合越强,则中间局域能级的态密度越小,最后没有中间局域态.     

链间耦合对聚乙炔多链体系中电子极化子再激发态的影响

从拓展紧束缚模型出发,研究了链间耦合对反式聚乙炔多链体系中电子极化子再激发态的晶格位形、净电荷密度、局域能级波函数和态密度的影响。结果发现：对于两条链体系,当链间耦合很小（eV）时,注入到系统中的电子只会在第一条链上诱发产生一个晶格缺陷,形成电子极化子再激发态,这和单链体系是一致,而第二条链仍是二聚化基态。随着链间耦合的增大,第一条链上缺陷的局域度减少而第二条链上的缺陷局域度相应增加,直至两条链上的位形相同。对于多条链（5条链和6条链）体系,当耦合很小（0.05eV）时,电子极化子再激发态也只会存在于一条链上,当链间耦合较强时,极化子再激发态会在链间层次性地扩展开来,并不会出现多条链位形相同。从两条链的能级图上可以看到随着链间耦合的增大,体系的带隙不断的增大和电子态密度显示的是完全吻合的,体系的导电性减弱。通过分析两条链体系在eV和eV的能级态密度,发现链间耦合越强,则中间局域能级的态密度越小,最后没有中间局域态。     

Directed self-avoiding walks and statistics of rigid-chain polymer molecules

The statistics of rigid-chain polymer conformations is described on the basis of a model of directed self-avoiding walks. The generating functions for the distribution function of a chain in one-, two-, and three-dimensional spaces are constructed. It is shown that the statistics of the conformational states of chains with finite interunit flexural stiffness can differ strongly from Gaussian statistics. If the chain length is comparable to the Kuhn segment length, then the molecule is strongly anisotropic (almost rectilinear), but as the chain length increases, the molecule starts to bend and ultimately coils up. However, since a coil contains extended, almost rectilinear, chain sections, the coil is not truly Gaussian, even though the squared average size of the coil is directly proportional to the chain length. It is shown that under certain conditions the existence of almost rectilinear chain sections results in the appearance of orientational order in the system.     

Partial crystallinity in alkyl side chain polymers dictates surface freezing

We have studied the structure of a novel crystalline surface monolayer on top of a disordered melt of the same material [poly(n-alkyl acrylate)s] using grazing incidence x-ray diffraction. The grazing incidence x-ray diffraction, surface tension, and bulk latent heat results show that side chains crystallize except the nine methylene units of the alkyl side chains closest to the polymer backbone. The partial crystallinity along with a thicker surface layer, due to the additional length of the linker group, explains why the difference between the surface order-to-disorder transition temperature and bulk melting temperature increases with a decrease in the length of the alkyl side chain.     

Molecular simulation study of the glass transition in a soft primitive model for ionic liquids

In this paper, we present a molecular dynamics study of the glass transition for a soft-core primitive model for ionic liquids, in which cations are fully flexible chains of tangent soft spherical monomers, being the positively charged monomer at one of the ends of the chain, and anions as charged soft spheres. We have monitored transport coefficients such as the self-diffusion coefficients and the shear viscosity, as well as correlation functions such as the mean-square displacement, the self-intermediate scattering function, and probes of heterogeneous dynamics such as the van Hove distribution function and the four-points susceptibility. The analysis of these properties indicates that, for a given pressure, the glass transition shows a weak temperature dependence on the cation length, occurring first for short-chain than for long-chain ionic liquids.     

Measurement of surface roughness properties using speckle patterns with non-gaussian statistics

The surface roughness properties (i.e. the rms surface roughness and the correlation length) of strong diffuse objects are investigated by using the speckle patterns which obeys the non-gaussian statistics. The intimate linear relation is found to exist between the rms surface roughness of objects and the maximum contrast obtained from the varying curves of the average image speckle contrast as a function of the point spread of an optical imaging system. The correlation length of surface roughness of objects is related to the averaged intensity distribution of speckle patterns produced at the far-field diffraction plane. It now becomes clear that the rms roughness and the correlation length of strong diffuse objects are determined, respectively, from the maximum speckle contrast at the image plane and the averaged speckle intensity distribution at the far-field diffraction plane.     

Modeling dislocation — segment length distributions

The influence of intermolecular interaction between point defects, which are moving pinning points for dislocations, on the length distribution of dislocation segments is discussed. The distribution function is analyzed by Monte Carlo numerical modeling. It is shown that a length distribution can be described in the absence of external stresses by an exponential function that may differ from the Köhler function at high defect concentrations. Intermolecular interaction of defects changes the distribution function, which, with time, also becomes nearly exponential, but with different values of the parameters.     

Monte-Carlo study of correlations in quantum spin chains at non-zero temperature

Antiferromagnetic Heisenberg spin chains with various spin values (S=1/2,1,3/2,2,5/2) are studied numerically with the quantum Monte-Carlo method. Effective spin S chains are realized by ferromagnetically coupling n=2S antiferromagnetic spin chains with S=1/2. The temperature dependence of the uniform susceptibility, the staggered susceptibility, and the static structure factor peak intensity are computed down to very low temperatures, . The correlation length at each temperature is deduced from numerical measurements of the instantaneous spin-spin correlation function. At high temperatures, very good agreement with exact results for the classical spin chain is obtained independent of the value of S. For the S=2 chain which has a gap , the correlation length and the uniform susceptibility in the temperature range are well predicted by the semi-classical theory of Damle and Sachdev. Received: 23 December 1997 / Revised and Accepted: 11 March 1998     

A time-dependent density functional theory investigation of plasmon resonances of linear Au atomic chains

We report theoretical studies on the plasmon resonances in linear Au atomic chains by using ab initio time-dependent density functional theory. The dipole responses are investigated each as a function of chain length. They converge into a single resonance in the longitudinal mode but split into two transverse modes. As the chain length increases, the longitudinal plasmon mode is redshifted in energy while the transverse modes shift in the opposite direction (blueshifts). In addition, the energy gap between the two transverse modes reduces with chain length increasing. We find that there are unique characteristics, different from those of other metallic chains. These characteristics are crucial to atomic-scale engineering of single-molecule sensing, optical spectroscopy, and so on.     

Binary N-step Markov chains and long-range correlated systems

A theory of systems with long-range correlations based on the consideration of binary N-step Markov chains is developed. In our model, the conditional probability that the ith symbol in the chain equals zero (or unity) is a linear function of the number of unities among the preceding N symbols. The correlation and distribution functions as well as the variance of number of symbols in the words of arbitrary length L are obtained analytically and numerically. If the persistent correlations are not extremely strong, the variance is shown to be nonlinearly dependent on L. A self-similarity of the studied stochastic process is revealed. The applicability of the developed theory to the coarse-grained written and DNA texts is discussed.     

摩擦导致的聚合物表层微观结构改变

应用大规模分子动力学方法, 模拟了锥形探头在非晶态聚合物薄膜表面的滑动摩擦过程, 研究了摩擦导致的聚合物薄膜表层微观结构改变, 以及探头与基体间黏着作用、滑动速度和分子链长度对基体表层微观结构改变的影响. 当探头与基体之间为黏着作用时, 摩擦导致基体表面滑痕区域的键取向沿滑动方向重新取向, 导致表层分子链回转半径沿滑动方向伸长, 并且这些表层微观结构的改变程度随滑动速度的减小而增大. 在摩擦导致结构改变的过程中, 链端单体和链中单体的贡献作用不同, 形成了不同的分子链拉伸变形机制. 当样本缠结度较大或探头滑动速度较小时, 相比于链中单体, 探头对链端单体的拖曳作用使更多分子链发生拉伸变形. 研究还发现, 在探头与聚合物薄膜系统中, 使薄膜表层微观结构发生改变是摩擦能量耗散的重要途径.