Theory of surface excess Miesowicz viscosities of planar nematic liquid crystal-isotropic fluid interfaces

An expression for the surface excess stress tensor for planar compressible interfaces between rod-like nematic liquid crystals and isotropic viscous fluids is derived using the classical surface excess theory formalism, adapted to capture the intrinsic anisotropy of the nematic orientational ordering. A required step in the theory is to find the actual stress tensor in the three-dimensional interfacial region, which is obtained by a decomposition of the kinematic fields (rate of deformation tensor and director Jaumann derivative) into tangential, normal, and mixed components with respect to the interface. The viscosity coefficients appearing in the surface excess stress tensor are expressed in terms of interfacial and bulk viscosities for planar, constant orientation, flows. The expressions are used to define the three fundamental surface excess Miesowicz shear viscosities, in analogy with the three bulk Miesowicz shear viscosities. The ordering in the magnitudes of the surface excess Miesowicz shear viscosities is shown to depend on the magnitude of the surface scalar nematic order parameter relative to that of the adjoining bulk nematic phase. When the surface scalar order parameter is greater than in the bulk, the classical ordering in terms of magnitudes of the three bulk Miesowicz shear viscosities is recovered. On the other hand, when the surface scalar order parameter is smaller than in the bulk, the classical ordering in terms of magnitudes of the three viscosities does not hold, and inequality transitions are predicted as the surface scalar order parameter increases towards the bulk value. Received 5 July 1999 and Received in final form 16 November 1999     

Study on spatial dispersion theory of excess conduction loss in normal metals surface below terahertz frequencies

We have developed a rigorous model for analyzing excess conduction loss in normal metals surface by using the spatial dispersion theory. We have used the model to account excess conduction loss and dissect the discrepancies between excess conduction loss measurements and classical theoretical predictions in normal metals surface below terahertz frequencies. Our analysis shows that the conductivity is not only frequency but also wave vector dependent. We demonstrate good quantitative agreement with the published experimental data for the room temperature excess conduction loss of normal metals surface below terahertz frequencies.     

The use of an arbitrary coordinate system in the evaluation of the g-, D- and A- tensors through an electron paramagnetic resonance experiment

The structure and excess energy of the end region of certain one-dimensional systems are investigated. Fowler's expression for the surface excess energy is found to be exact for a Takahashi system with an ideal, fixed end-point. Exact formulae for the local density and the surface energy are derived and discussed for a system with square-well molecules.     

Estimation of friction of a single chemisorbed molecule on a surface using incident atoms

Friction of a single molecule chemisorbed on a surface is a very fundamental property related to the dynamics of the diffusion of the molecule. We used a newly developed method, in which energy-controlled rare gas atoms collide with CO molecules on a stepped surface to displace CO molecules from initial terrace sites to final step sites. The friction coefficient of CO molecules on the surface was determined directly by comparing the experimentally measured increase in the number of CO molecules at step sites with classical molecular dynamics simulation results.     

Suppression of electro-osmotic flow by surface roughness

We show that nanoscale surface roughness, which commonly occurs on microfabricated metal electrodes, can significantly suppress electro-osmotic flows when excess surface conductivity is appreciable. We demonstrate the physical mechanism for electro-osmotic flow suppression due to surface curvature, compute the effects of varying surface conductivity and roughness amplitudes on the slip velocities of a model system, and identify scalings for flow suppression in different regimes of surface conduction. We suggest that roughness may be one factor that contributes to large discrepancies observed between classical electrokinetic theory and modern microfluidic experiments.     

Quantum effects in the electronic polarization energy in molecular systems

Binding energy of the electronic polaron in molecular condensates is examined in a simple model permitting quantum dynamical as well as classical microelectrostatic energy calculations. Quantum effects in the electron (hole) polarization energy due to dipole-dipole correlations (and their distortion by an excess charge) among neutral molecules and molecular ion are studied. It is found that these quantum effects lead to a decrease of the magnitude of the electron (hole) polarization energy in realistic situations.     

用李代数方法构造四原子分子的势能面

把李代数方法得到的四原子分子的代数Hamiltonian，利用相干态经典化之后并找到一个新的变换，将分子的键角引入，而得到四原子分子的势能面.由该势能面计算得到的解离能与力常数与其他方法给出的一致.     

Statistical thermodynamics of isolated rigid rod-like molecules near a surface

The configurational behaviour and thermodynamic properties of a dilute gas of rigid rod-like molecules in the vicinity of a macroscopic planar adsorption surface are investigated using statistical mechanics. The interaction energy between the surface and a rod-like molecule is determined as a function of both its molecular centre of mass separation R and its orientation relative to the surface. In calculating this interaction energy, each rod segment and molecule comprising the surface is assumed to interact through a Lennard-Jones pair potential. The average molecular order parameter is then determined as a function of R. We find that an isolated rod-like molecule tends to align nearly parallel to the surface for small separations. However, as R increases the order parameter first passes through a maximum then decays to zero as R ^-5 for large R. The configurational behaviour of an isolated rod-like molecule located between two parallel adsorption surfaces is also considered briefly. The surface spreading pressure, excess surface energy and entropy are also obtained for a dilute gas of rod-like molecules near a surface. We find that the extent of surface binding increases nearly exponentially with molecular length at constant temperature and surface density, and that the excess surface energy and entropy are essentially proportional to the molecular length.     

STUDY ON EXCESS CONDUCTION LOSS IN NORMAL METALS AT/BELOW SUB-MILLIMETER WAVELENGTHS

We have used the spatial dispersion theory to develop a rigorous model to investigate excess conduction loss in normal metals. We have used the model to account excess conduction loss and dissect the discrepancies between excess conduction loss measurements and classical theoretical predictions in normal metals at/below sub-millimeter wavelengths. Moreover, we have compared the results of this model with the results of the classical skin-effect model and classical relaxation-effect model. Our analysis shows that the conductivity is not only frequency but also wave vector dependent. The results of the calculations indicate a good quantitative agreement with the published experimental data for the room temperature excess conduction loss of normal metals at/below sub-millimeter wavelengths.     

Second-harmonic generation circular dichroism spectroscopy from tripod-like chiral molecular films

The second-harmonic generation (SHG) circular dichroism in the light of reflection from chiral films of tripod-like chiral molecules is investigated.The expressions of the second-harmonic generation circular dichroism are derived from our presented three-coupled-oscillator model for the tripod-like chiral molecules.Spectral dependence of the circular dichroism of SHG from film surface composed of tripod-like chiral molecules is simulated numerically and analysed.Influence of chiral parameters on the second-harmonic generation circular dichroism spectrum in chiral films is studied.The result shows that the second-harmonic generation circular dichroism is a sensitive method of detecting chirality compared with the ordinary circular dichroism in linear optics.All of our work indicates that the classical molecular models are very effective to explain the second-harmonic generation circular dichroism of chiral molecular system.The classical molecular model theory can give us a clear physical picture and brings us very instructive information about the link between the molecular configuration and the nonlinear processes.     

Generation and EPR characterization of color centers at the surface of ionic oxides

The activation of the surface of high surface area alkali-earth oxides to form surface color centers is described in detail. Two methods (the radiative coloring and the additive coloring by means of vapors of low ionization energy metals) have been adopted to form surface electron excess centers of various complexity. The EPR technique is essential to describe the nature and the structural features of the paramagnetic centers. The electron rich surface quickly reacts with a variety of adsorbed molecules forming adsorbed anions and radical anions. Two examples of such reactivity are illustrated in the final part of the paper.     

Transport and free carrier electromagnetic phenomena in semiconductor boundary layer: II. Reflectivity with non-normal incidence and surface plasmons

A classical analysis is given of the reflectivity at oblique incidence on semiconductor surfaces. The theory includes the effect of a space charge boundary layer and yields formulae from which one can obtain the dispersion relation for surface plasmons, for which the effects of the boundary layer are particularly important. An application to experimental data on n-InSb gives satisfactory agreement while yielding a plausible estimate of the surface excess ΔN. The electroreflectance is also studied, including numerical evaluations. It is suggested that measurements at almost grazing incidence could yield valuable information on the surface scattering of carriers.     

Static polarizability effects on counterion distributions near charged dielectric surfaces: A coarse-grained Molecular Dynamics study employing the Drude model

Coarse-grained implicit solvent Molecular Dynamics (MD) simulations have been used to investigate the structure of the vicinal layer of polarizable counterions close to a charged interface. The classical Drude oscillator model was implemented to describe the static excess polarizability of the ions. The electrostatic layer correction with image charges (ELCIC) method was used to include the effects of the dielectric discontinuity between the aqueous solution and the bounding interfaces for the calculation of the electrostatic interactions. Cases with one or two charged bounding interfaces were investigated. The counterion density profile in the vicinity of the interfaces with different surface charge values was found to depend on the ionic polarizability. Ionic polarization effects are found to be relevant for ions with high excess polarizability near surfaces with high surface charge.     

First-principles molecular dynamics simulation of biased electrode/solution interface

First-principles molecular dynamics simulations have been carried out for water in contact with Pt(1 1 1) surface. To apply negative bias potential to the water/Pt interface, excess electrons were added to our slab model using the recently developed computational scheme called “effective screening medium (ESM)”. Water molecules located away from the surface reoriented themselves to screen the electric field, but they responded differently near the surface. Water molecules nearest to the surface, forming a distinct layered structure with the hydrogen atom directed to the surface, increased the density with increasing field. On these bases, we discuss microscopic aspects of the electric double layer.     

Vaporization of Small Spherical Drops in a Gas

The process of vaporization of a small (compared to the free path of molecules in the medium) spherical liquid drop in an infinite nonabsorbing gaseous medium is considered. Analytical expressions for the time dependence of the drop radius are derived under assumption that vaporized molecules escape from the drop in the asymptotic diffusion regime, and the thermal energy flux toward the vaporizing drop is formed as a result of collisions of vaporized and gas molecules. It is demonstrated that consideration of unsaturated vapor at the surface of the evaporating drop increases the estimated vaporization time of submicron drops by several orders of magnitude compared to the Maxwell classical model.     

Renormalization of molecular electronic levels at metal-molecule interfaces

The electronic structure of benzene on graphite (0001) is computed using the GW approximation for the electron self-energy. The benzene quasiparticle energy gap is predicted to be 7.2 eV on graphite, substantially reduced from its calculated gas-phase value of 10.5 eV. This decrease is caused by a change in electronic correlation energy, an effect completely absent from the corresponding Kohn-Sham gap. For weakly coupled molecules, this correlation energy change can be described as a surface polarization effect. A classical image potential model illustrates the impact for other conjugated molecules on graphite.     

一种针对弱场搜寻态冷极性分子的可控静电表面囚禁方案

提出一种使用带电金属环和六个球电极和一个外加偏置电场实现对冷极性分子静电囚禁的新方案.计算装载和囚禁时空间电场分布.囚禁中心距离芯片表面的高度可以通过外电场和环形电极所加电压来操控.蒙特卡罗模拟表明对于中心速度为15 m·s^-1的ND₃分子束,装载效率可以达到70%,得到冷分子的温度大约为45 mK.当继续增加偏置电场强度时,单阱分裂为对称的两个阱.如果同时改变球形电极上所加电压,得到不对称的两个阱,可以借此来调节两个阱中所囚禁的冷分子数目的比例.为了易于理解,用蒙特卡罗方法模拟了装载、囚禁、分裂冷分子波包的动力学过程.     

Trapping excess electrons in molecular charge pockets on surfaces

This work considers the use of theoretical ab initio calculations to design a novel molecular trap for excess electrons. The basic principle is to develop a model by which these electrons can be stabilized by charge pockets on the surface of molecules. Calculations reveal that systems with OH groups can form stable hydrogen-bonded networks on one side of a hydrocarbon surface (i.e. cyclohexane sheets), while the hydrogen atoms on the opposite side of this surface form a pocket of positive charge that attracts the extra negative charge.     

Investigation of vapour--liquid nucleation properties for spherical and chain-like fluids by density functional theory

The excess Helmholtz free energy functional for nonpolar chain-like molecules is formulated in terms of a weighted density approximation （WDA） for short-range interactions and a Weaks Chandler Andersen （WCA） approximation and a Barker Henderson （BH） theory for long-range attraction. Within the framework of density functional theory （DFT）, vapour liquid interracial properties including density profile and surface tension, and vapour-liquid nucleation properties including density profile, work of formation and number of particles are investigated for spherical and chain- like molecules. The obtained vapour liquid surface tension and the number of particles in critical nucleus for Lennard- Jones （L J） fluids are consistent with the simulation results. The influences of supersaturation, temperature and chain length on vapour liquid nucleation properties are discussed.[第一段]     

Oxygen vacancy pairs on CeO2(110): A DFT + U study

Oxygen vacancy pairs have been suggested to play a role in the reduction of NO molecules on ceria and for the oxidation processes of reducible rare-earth oxides. The formation energy of the oxygen vacancy pairs and the changes in the structural and electronic properties of the ceria (110) surface with oxygen vacancy pairs are investigated using density-functional theory (DFT + U) methodology within the generalized gradient approximation. It is found that the excess electrons localize on the Ce ions neighbouring the vacancies, and the most stable structure for the oxygen vacancy pairs on the ceria (110) surface is at next-nearest-neighbour site.