聚丙烯表面的计算机模拟

用计算机模拟的方法详细研究了聚丙烯薄膜表面分子级别的结构 .采用无定形本体聚丙烯产生初始的随机父链 ,将一条随机父链在二维边界条件下进行塌陷 ,研究薄膜在真空中的构型 .用 10 0个重复单元的父链生成厚度为 3 5nm的薄膜 .发现薄膜内部密度等于聚丙烯的本体密度 ,而离自由表面 0 8nm处薄膜的密度开始跌落 .主链键在内部随机取向 ,在自由表面附近则明显沿薄膜表面平面取向 ,键开始有序取向的程度大致与质量密度相对于本体密度的减小一致 .与聚丙烯本体相比 ,薄膜表面中CH2 CH 的反式结构和旁式结构是增加的 ,这是因为分子链能更好的沿薄膜平面舒展 .同时通过聚丙烯无定形本体 (3D周期性 )和薄膜 (2D周期性 )中的链的能量的差异计算了薄膜内部能量对表面能量的贡献 .     

Theory of nanoscale atomic lithography. An ab initio study of the interaction of "cold" Cs atoms with organthiols self-assembled monolayers on Au(111)

This paper deals with the microscopic mechanism of nanolithography of self-assembled monolayers (SAM) of alkanethiol molecules on Au(111) induced by the exposure of the film to a beam of "cold" Cs atoms. Density functional theory calculations have been carried out to elucidate the mechanism of interaction of the Cs atoms with the SAM. We found that the film damage occurs in two steps: the Cs atom penetrates the SAM and at a distance of 10-12 Angstrom from the surface donates one electron to Au, forming a Cs(+) cation which binds strongly to the surface and interacts with the polar head of the SR molecule. The thermal energy released in this process largely exceeds the energy required to stimulate the desorption of RS-SR disulfide molecules from the Au surface with consequent damage of the film. No chemical interaction occurs between Cs or Cs(+) and the hydrocarbon chain of the thiol molecule.     

Thermodynamics of capillary adhesion between rough surfaces

According to the Dupré equation, the work of adhesion is equal to the surface energy difference in the separated versus the joined materials minus an interfacial energy term. However, if a liquid is at the interface between two solid materials, evaporation or condensation takes place under equilibrium conditions. The resulting matter exchange is accompanied by heat flow, and can reduce or increase the work of adhesion. Accounting for the energies requires an open-system control volume analysis based on the first law of thermodynamics. Depending on whether evaporation or condensation occurs during separation, a work term that is negative or positive must be added to the surface energy term to calculate the work of adhesion. We develop and apply this energy balance to several different interface geometries and compare the work of adhesion to the surface energy created. The model geometries include a sphere on a flat with limiting approximations and also with an exact solution, a circular disc, and a combination of these representing a rough interface. For the sphere on a flat, the work of adhesion is one half the surface energy created if equilibrium is maintained during the pull-off process.     

Molecular dynamic simulation of platinum heater and associated nano-scale liquid argon film evaporation and colloidal adsorption characteristics

A novel 'fluid-wall thermal equilibrium model' for the wall-fluid heat transfer boundary condition has been developed in this paper to capture the nano-scale physics of transient phase transition of a thin liquid argon film on a heated platinum surface and the eventual colloidal adsorption phenomenon as the evaporation is diminishing using molecular dynamics. The objective of this work is to provide microscopic characterizations of the dynamic thermal energy transport mechanisms during the liquid film evaporation and also the resulting non-evaporable colloidal adsorbed liquid layer at the end of the evaporation process. A nanochannel is constructed of platinum (Pt) wall atoms with argon as the working fluid. The proposed model is validated by heating liquid argon between two Pt walls and comparing the thermal conductivity and change in internal energy to thermodynamic properties of argon. Later on, phase change process is studied by simulating evaporation of a thin liquid argon film on a Pt wall using the proposed model. Gradual evaporation of the liquid film occurs although the film does not vaporize completely. An ultra-thin layer of liquid argon is noticed to have "adsorbed" on the platinum surface. An analysis similar to the theoretical study by Hamaker (1937) is performed for the non-evaporating film and the value of the Hamaker-type constant falls in the typical range. This analysis is done to quantify the non-evaporating film with an attempt to use molecular dynamics simulation results in continuum mechanics.     

Electron bubbles in helium clusters. I. Structure and energetics

In this paper we present a theoretical study of the structure, energetics, potential energy surfaces, and energetic stability of excess electron bubbles in ((4)He)(N) (N=6500-10(6)) clusters. The subsystem of the helium atoms was treated by the density functional method. The density profile was specified by a void (i.e., an empty bubble) at the cluster center, a rising profile towards a constant interior value (described by a power exponential), and a decreasing profile near the cluster surface (described in terms of a Gudermannian function). The cluster surface density profile width (approximately 6 A) weakly depends on the bubble radius R(b), while the interior surface profile widths (approximately 4-8 A) increase with increasing R(b). The cluster deformation energy E(d) accompanying the bubble formation originates from the bubble surface energy, the exterior cluster surface energy change, and the energy increase due to intracluster density changes, with the latter term providing the dominant contribution for N=6500-2 x 10(5). The excess electron energy E(e) was calculated at a fixed nuclear configuration using a pseudopotential method, with an effective (nonlocal) potential, which incorporates repulsion and polarization effects. Concurrently, the energy V(0) of the quasi-free-electron within the deformed cluster was calculated. The total electron bubble energies E(t)=E(e)+E(d), which represent the energetic configurational diagrams of E(t) vs R(b) (at fixed N), provide the equilibrium bubble radii R(b) (c) and the corresponding total equilibrium energies E(t) (e), with E(t) (e)(R(e)) decreasing (increasing) with increasing N (i.e., at N=6500, R(e)=13.5 A and E(t) (e)=0.86 eV, while at N=1.8 x 10(5), R(e)=16.6 A and E(t) (e)=0.39 eV). The cluster size dependence of the energy gap (V(0)-E(t) (e)) allows for the estimate of the minimal ((4)He)(N) cluster size of N approximately 5200 for which the electron bubble is energetically stable.     

Packing density and structure effects on energy-transfer dynamics in argon collisions with organic monolayers

A combined experimental and molecular-dynamics simulation study has been used to investigate energy-transfer dynamics of argon atoms when they collide with n-alkanethiols adsorbed to gold and silver substrates. These surfaces provide the opportunity to explore how surface structure and packing density of alkane chains affect energy transfer in gas-surface collisions while maintaining the chemical nature of the surface. The chains pack standing up with 12 degrees and 30 degrees tilt angles relative to the surface normal and number densities of 18.9 and 21.5 A(2)molecule on the silver and gold substrates, respectively. For 7-kJmol argon scattering, the two surfaces behave equivalently, fully thermalizing all impinging argon atoms. In contrast, these self-assembled monolayers (SAMs) are not equally efficient at absorbing the excess translational energy from high-energy, 35 and 80 kJmol, argon collisions. When high-energy argon atoms are scattered from a SAM on silver, the fraction of atoms that reach thermal equilibrium with the surface and the average energy transferred to the surface are lower than for analogous SAMs on gold. In the case of argon atoms with 80 kJmol of translational energy scattering from long-chain SAMs, 60% and 45% of the atoms detected have reached thermal equilibrium with the monolayers on gold and silver surfaces, respectively. The differences in the scattering characteristics are attributed to excitation efficiencies of different types of surface modes. The high packing density of alkyl chains on silver restricts certain low-energy degrees of freedom from absorbing energy as efficiently as the lower-density monolayers. In addition, molecular-dynamics simulations reveal that the extent to which argon penetrates into the monolayer is related to packing density. For argon atoms with 80-kJmol incident energy, we find 16% and 7% of the atoms penetrate below the terminal methyl groups of C(10) SAMs on gold and silver, respectively.     

Formation of Dissipative Structures in an Amorphous Film

The formation of nanothin spatial dissipative structures (SDSs) of hexagonal selenium with elastic rotational curvature of the lattice about [001] in an amorphous film was considered. It was established that nanothin SDSs form in thermal gradient treatment of an amorphous film by one-side heating of its lower surface at T = 453 K. The state of pseudo-single crystal, which precedes the formation of a nanothin SDS in an amorphous film, is a state with a high concentration of vacancies. Under the action of the temperature difference ΔT, vacancies and selenium atoms undergo thermal diffusion in the direction perpendicular to the surface of the pseudo-single crystal. It was shown that, when ΔT reaches critical values, there is a transition from the structure of a pseudo-single crystal to the structure of a rhombic nanothin SDS of hexagonal selenium. The heat flux through the nanothin SDS in the direction perpendicular to its surface ensures the entropy export to the environment. After the thermal gradient treatment of the amorphous film, the nanothin SDS is quenched by cooling it in air; in this process, there is quenching of nonequilibrium structural defects—atoms and vacancies displaced from equilibrium positions. The quenching makes the nanothin SDS stable. The formation of nanothin SDSs of hexagonal selenium with elastic rotational curvature of the lattice about [001] in an amorphous film occurs under conditions satisfying the theory of the formation of dissipative structures.     

Microstructure and surface roughness of graphite‐like carbon films deposited on silicon substrate by molecular dynamic simulation

Molecular dynamics simulations are performed on the atomic origin of the growth process of graphite‐like carbon film on silicon substrate. The microstructure, mass density, and internal stress of as‐deposited films are investigated systematically. A strong energy dependence of microstructure and stress is revealed by varying the impact energy of the incident atoms (in the range 1–120 eV). As the impact energy is increased, the film internal stress converts from tensile stress to compressive stress, which is in agreement with the experimental results, and the bonding of C‐Si in the film is also increased for more substrate atoms are sputtered into the grown film. At the incident energy 40 eV, a densification of the deposited material is observed and the properties such as density, sp³ fraction, and compressive stress all reach their maximums. In addition, the effect of impact energy on the surface roughness is also studied. The surface morphology of the film exhibits different characteristics with different incident energy. When the energy is low (<40 eV), the surface roughness is reduced with the increasing of incident energy, and it reaches the minimum at 50 eV. Copyright © 2012 John Wiley & Sons, Ltd.     

Density functional theory of size-dependent surface tension of Lennard-Jones fluid droplets using a double well type Helmholtz free energy functional

A double well type Helmholtz free energy density functional and a model density profile for a two phase vapor-liquid system are used to obtain the size-dependent interfacial properties of the vapor-liquid interface at coexistence condition along the lines of van der Waals and Cahn and Hilliard density functional formalism of the interface. The surface tension, temperature-density curve, density profile, and thickness of the interface of Lennard-Jones fluid droplet-vapor equilibrium, as predicted in this work are reported. The planar interfacial properties, obtained from consideration of large radius of the liquid drop, are in good agreement with the results of other earlier theories and experiments. The same free energy model has been tested by solving the equations numerically, and the results compare well with those from the use of model density profile.     

Application of the level-set method to the implicit solvation of nonpolar molecules

A level-set method is developed for numerically capturing the equilibrium solute-solvent interface that is defined by the recently proposed variational implicit solvent model [Dzubiella, Swanson, and McCammon, Phys. Rev. Lett. 104, 527 (2006); J. Chem. Phys. 124, 084905 (2006)]. In the level-set method, a possible solute-solvent interface is represented by the zero level set (i.e., the zero level surface) of a level-set function and is eventually evolved into the equilibrium solute-solvent interface. The evolution law is determined by minimization of a solvation free energy functional that couples both the interfacial energy and the van der Waals type solute-solvent interaction energy. The surface evolution is thus an energy minimizing process, and the equilibrium solute-solvent interface is an output of this process. The method is implemented and applied to the solvation of nonpolar molecules such as two xenon atoms, two parallel paraffin plates, helical alkane chains, and a single fullerence C(60). The level-set solutions show good agreement for the solvation energies when compared to available molecular dynamics simulations. In particular, the method captures solvent dewetting (nanobubble formation) and quantitatively describes the interaction in the strongly hydrophobic plate system.     

Surface Properties of Fluorinated Acrylate Polymer Latex Films

The surface chemical compositions of fluorinated latex films and the dynamic contact angles of water were determined using X-ray photoelectron spectroscopy (XPS) and a Kruss interface tension measurement, respectively. The surface tensions of the films were calculated by the equation of state approach using the dynamic contact angles, and the effect of temperature on the wetting behavior of these films was investigated. It was shown that the F 1s signal intensity from the outermost surface of these fluorinated latex films was stronger than that from the interior surface of the film and that the surface tension showed a linear decrease with the increase of density of fluorine atoms on the latex film surface to a certain extent. The surface tension rapidly decreased with the increase of fluorinated lateral chains (Rf) content in the copolymer with longer Rf (carbon atom number n>6). The water receding contact angles (θr) on the latex films sharply decreased with the increase of n value, then leveled off nearly at n=10, and remained almost unchanged when n>10. In addition, θr increased more remarkably with the increase of F content in the poly (protonated acrylate- co-fluorinated acrylate) with short hydrocarbon side chains. The water wetting ability of the fluorinate latex films became slightly better only when temperature was more than 40°C.     

Metal adsorption on oxide polar ultrathin films

The adsorption of Au and Pd atoms on two nanostructured titania monolayers grown on the Pt(111) surface is investigated via a computational approach. These phases present compact regions (zig-zag-like stripes) with titanium atoms at the oxide-metal interface and oxygen in the top-most overlayer, sometimes intercalated by point defects, i.e. holes exposing the bare metal support, and give rise to very regular patterns extending for large distances. A Pd atom experiences a rather flat energy landscape on the compact regions whereas it is strongly bound to the defects which act as nucleation centers, whence the interest of these substrates as nanotemplates for the growth of metal clusters. The interaction of a Au atom with these phases is peculiarly different: a charge transfer from the underlying Pt(111) support occurs so that Au gets negatively charged and strongly interacts with a titanium atom extracted from the interface in the compact regions, whereas it penetrates less easily than Pd into the defective holes due to its larger size. These results are discussed as paradigmatic examples of the interaction of metals with polar ultrathin films of oxides grown on metal supports, a novel and promising field in materials science.     

First-principles study on the adhesive and electronic property of c-BN(111)/Cu(111) interface

The interface properties of c-BN/Cu composite play an important role in its application. In this work, we employed first-principles calculation to investigate the bonding properties and electronic characteristics of the c-BN(111)/Cu(111) interface. The adhesion properties, partial density of states (PDOS), charge density, and charge density difference of different interfaces were analyzed. The results show that the interface of B-termination “OT” stacking mode is the most stable one. The density of states at the c-BN(111)/Cu(111) interface is similar to that of c-BN bulk phase, indicating that the electronic states of the c-BN layer are not affected by the Cu atoms. The PDOS diagram shows that the 2p orbital of B atoms and the 2p orbital of N atoms are hybridized in the c-BN layer. Besides, 2p orbital of B(N) atoms and 3d orbital of Cu atoms are hybridized in the interface. The covalent bonds and ionic bonds in the interface of N-termination and B-termination OT stacking mode structures are stronger than that of “SL” and “TL” stacking mode. So, the OT stacking mode has larger adhesive energy. Furthermore, Cu and c-BN can form a good coherent interface, which can be used to prepare c-BN/Cu composites and functional materials with excellent mechanical properties.     

升温烧结过程中TiO2纳米颗粒的原子分类分析(Ⅰ):表面原子识别

开发表面原子识别模型,对单个TiO₂颗粒升温烧结过程中表面原子进行分类研究。模型对颗粒空间立方体网格化,利用标准球形颗粒体积积分法确定最佳网格尺寸为0.3 nm。通过表面网格识别实现表面原子分类,采用近邻网格中外部网格数量(N_ext)作为准则数判断目标网格是否为表面网格,确定最佳N_ext=9。基于LAMMPS软件模拟了半径为0.75 nm颗粒的升温过程,发现系统能量弛豫速度明显高于结构弛豫速度;利用表面识别模型分类分析原子特性,表面原子平均位移大于内部原子,且表面O原子迁移活性高于Ti原子;表面原子配位数低于内部原子,佐证表面结构规律性较差。研究结果为深入分析纳米材料活性位等结构分布奠定基础。     

Argon–water system at low temperatures

The molecular dynamics method is used to simulate argon solutions in water and a thin water film–argon system at low temperatures. The correlation in motions of two closely spaced argon atoms is of another nature than the correlation of two neon atoms in a neon solid solution in ice II. The structure of hydrate shells of argon atoms contains five-membered rings composed of water molecules. The solubility of argon in a water film at low temperatures is noticeably higher than at room temperature. If a water film is first cooled to the glassy state and then argon atoms are added to it, then approximately as many argon atoms are absorbed on the film surface as they are present in a cooled film in equilibrium with the argon atmosphere. Argon atoms migrate from one pit to another on the rough surface of a solid water film.     

Molecular dynamics study of thermal phenomena in an ultrathin liquid film sheared between solid surfaces: the influence of the crystal plane on energy and momentum transfer at solid-liquid interfaces

A molecular dynamics study has been performed on a liquid film sheared between moving solid walls. Thermal phenomena that occur in the Couette-like flow were examined, including energy conversion from macroscopic flow energy to thermal energy, i.e., viscous heating in the macroscopic sense, and heat conduction from the liquid film to the solid wall via liquid-solid interfaces. Four types of crystal planes of fcc lattice were assumed for the surface of the solid wall. The jumps in velocity and temperature at the interface resulting from deteriorated transfer characteristics of thermal energy and momentum at the interface were observed. It was found that the transfer characteristics of thermal energy and momentum at the interfaces are greatly influenced by the types of crystal plane of the solid wall surface which contacts the liquid film. The mechanism by which such a molecular scale structure influences the energy transfer at the interface was examined by analyzing the molecular motion and its contribution to energy transfer at the solid-liquid interface.     

Influence of submonolayer sodium adsorption on the photoemission of the Cu(111)/water ice surface

Photoemission from an ice film deposited on Cu(111) as a function of thickness has been observed in the presence and absence of sodium atoms at the surface-vacuum interface. For either adsorbate alone and photon energies below 4 eV, two-photon photoemission from the Cu(111) substrate dominates. The Cu(111) photoelectron spectrum is perturbed by low coverages of Na, and its intensity is strongly attenuated by a few monolayers of ice. For a low density amorphous ice film, strong charging effects are observed. For ice films annealed to yield either the dense amorphous or crystalline phase, this effect is absent. Deposition of only 0.02 monolayer of Na leads to a dramatic decrease in the threshold for photoemission to 2.3+/-0.2 eV. Thus, photoelectrons are generated by visible radiation in a one-photon process with a cross section that exceeds 10(-18) cm(2). The initial state for the photoemission is identified as a metastable surface trapped electron, which decays thermally with an activation energy of 10+/-2 kJ mol(-1). Quantum calculations are described which support this model and show that the Na atom is accommodated in the first layer of the ice surface.     

Structural and shear characteristics of adsorbed sodium caseinate and monoglyceride mixed monolayers at the air-water interface

The structural and shear characteristics of mixed monolayers formed by an adsorbed Na-caseinate film and a spread monoglyceride (monopalmitin or monoolein) on the previously adsorbed protein film have been analyzed. Measurements of the surface pressure (pi)-area (A) isotherm and surface shear viscosity (eta(s)) were obtained at 20 degrees C and at pH 7 in a modified Wilhelmy-type film balance. The structural and shear characteristics of the mixed films depend on the surface pressure and on the composition of the mixed film. At surface pressures lower than the equilibrium surface pressure of Na-caseinate (at pipi(e)(CS) have important repercussions on the shear characteristics of the mixed films.     

Molecular Dynamics Study of Ionic Liquid Film Based on [emim][Tf2N] and [emim][TfO] Adsorbed on Highly Oriented Pyrolytic Graphite

Molecular dynamics simulation was used to study the ionic liquid(IL) crystalline film based on 1-ethyl-3-methylimidazolium bis[trifluoromethylsulfonyl]imide([emim][Tf₂N]) and 1-ethyl-3-methylimidazolium trifluoromethanesulfonate([emim][TfO]) on the graphite surface. Our results show that the cations are parallelly distributed to the surface in the 1/2 monolayer(ML) crystalline film. The [Tf₂N]^- anions are parallel to the surface with the oxygen atoms at the bottom, whereas the [TfO]^- anions are perpendicularly distributed to the surface also with the oxygen atoms at the bottom in the 1/2 ML crystalline film. It has been found that the IL-vapor interface strongly influences the arrangement of ions at the interface. The anions in the top layer with the oxygen atoms outmost turn over to make themselves with the F atoms outmost so as to form C-H···O hydrogen bonds with the cations. The calculated orientational ordering shows that in the outmost layer at the IL-vapor interface, the cation rings present either parallel or perpendicular to the surface at 350 K.     

Dynamics and kinetics of heat transfer at the interface of model diamond [111] nanosurfaces

A molecular dynamics simulation was performed to study the effect of an applied force on heat transfer at the interface of model diamond [111] nanosurfaces. The force was applied to a small, hot nanosurface at 800, 1000, or 1200 K brought into contact with a larger, colder nanosurface at 300 K. The relaxation of the initial nonequilibrium interfacial force occurs on a subpicosecond time scale, much shorter than that required for heat transfer. Heat transfer occurs with exponential kinetics and a rate constant that increases linearly with the interfacial force according to 7 x 10(-4) ps(-1)/nN. This rate constant only increases by at most 10% as the temperature of the hot surface is increased from 800 to 1200 K. Replacing the interfacial H-atoms on both surfaces by D atoms also has a very small effect on the heat transfer. However, if one nanosurface has H atoms on its interface and the other nanosurface's interface has D atoms, then there is a marked 25% decrease in the rate constant for heat transfer. Increasing the size of the hot surface, and, thus, the interfacial contact area, increases the rate of heat transfer but not the rate constant. For the same interfacial force, different anharmonic models for the nanosurfaces' potential energy function give the same heat transfer rate constant. The possibility of quantum effects for heat transfer across the diamond interface is considered.