微孔中简单流体扩散行为的分子动力学模拟研究

用分子动力学模拟方法研究了受限在微孔中的简单流体氩的扩散行为,考察了微孔类型、孔径、温度和密度对微孔中流体扩散系数的影响.研究发现,微孔中流体的扩散系数均小于体相流体,并且随孔径的减小而减小,同时沿孔道或狭缝方向的扩散系数分量远大于沿孔径方向的分量,并且流体在通道型微孔中的扩散系数小于在狭缝型微孔中的扩散系数,温度和密度也是影响微孔中扩散的重要因素.     

Impact of surface roughness on diffusion of confined fluids

Using event-driven molecular dynamics simulations, we quantify how the self diffusivity of confined hard-sphere fluids depends on the nature of the confining boundaries. We explore systems with featureless confining boundaries that treat particle-boundary collisions in different ways and also various types of physically (i.e., geometrically) rough boundaries. We show that, for moderately dense fluids, the ratio of the self diffusivity of a rough wall system to that of an appropriate smooth-wall reference system is a linear function of the reciprocal wall separation, with the slope depending on the nature of the roughness. We also discuss some simple practical ways to use this information to predict confined hard-sphere fluid behavior in different rough-wall systems.     

Surface excess free energy of simple fluids confined in cylindrical pores by isothermal-isobaric Monte Carlo: influence of pore size

Confined fluid properties are mainly determined by interfacial phenomena characterized by surface quantities. Based on a simple model of Lennard-Jones particles confined in a cylindrical pore, this study introduces a grand potential surface quantity to quantify the difference in the thermodynamic pressure between the bulk and the confined fluids. The usual surface tension gamma defined as this grand potential difference for the same chemical potential in both confined and bulk states is generally strongly dependent on both the chemical potential and temperature. It is proposed here to introduce another surface quantity zeta which measures the thermodynamic pressure difference between confined and bulk states for identical densities. It is shown that this quantity is much less dependent on confined fluid density or chemical potential. It is actually constant along the gas-like and liquid-like adsorption/desorption branches for an irreversible isotherm (hysteresis), with a different value for each branch. For reversible supercritical isotherms, zeta is shown to remain constant in the low and high density parts of the isotherm. This independence on chemical potential (or equivalently fluid density) is believed to be of great interest for practical applications when one desires to calculate thermodynamic quantities such as the usual surface tension gamma or the thermodynamic pressure of a confined fluid for any given chemical potential and temperature. Such calculations are required to determine fundamental properties such as metastability or coexistence. The effects of temperature, fluid/substrate interaction strength, and pore size are studied.     

Dynamics and density profile of water in nanotubes as one-dimensional fluid

The transport and structural properties of water confined in nanotubes with different diameters were studied by molecular dynamics (MD) simulation. The effects of pore size, molecule-wall interaction, and the helicity of CNT on the diffusivity, thermal conductivity, and shear viscosity as well as density profile were analyzed. For diffusivity, in model NT > in armchair CNT > in zigzag CNT at similar conditions. However in contrast to the diffusivity, the thermal conductivity and the shear viscosity increase as the pore size decreases, in zigzag CNT > in armchair CNT > (or approximately ) in model NT. The ordered layer distribution of water molecules in nanotubes is clear. It suggests the structure of fluid in the zigzag CNTs is more ordered, and more solidlike. In the nanotubes, where the molecule and the pore dimensions are of similar order of magnitude, the nature of water-water and water-wall interactions, the confinement effect of space, and the helicity of CNT become more significant.     

Does confining the hard-sphere fluid between hard walls change its average properties?

We use grand canonical transition-matrix Monte Carlo and discontinuous molecular dynamics simulations to generate precise thermodynamic and kinetic data for the equilibrium hard-sphere fluid confined between smooth hard walls. These simulations show that the pronounced inhomogeneous structuring of the fluid normal to the confining walls, often the primary focus of density functional theory studies, has a negligible effect on many of its average properties over a surprisingly broad range of conditions. We present one consequence of this insensitivity to confinement: a simple analytical equation relating the average density of the confined fluid to that of the bulk fluid with equal activity. Nontrivial implications of confinement for average fluid properties do emerge in this system, but only when the fluid is both (i) dense and (ii) confined to a gap smaller than approximately three particle diameters. For this limited set of conditions, we find that "in-phase" oscillatory deviations in excess entropy and self-diffusivity (relative to the behavior of the bulk fluid at the same average density) occur as a function of gap size. These paired thermodynamic/kinetic deviations from bulk behavior appear to reflect the geometric packing frustration that arises when the confined space cannot naturally accommodate an integer number of particle layers.     

Molecular Simulation on Transport Properties of Confined Water

The diffusivity and viscosity of water confined in micropores were studied by molecular dynamics simulations. The effects of pore width and density were analyzed at pore widths from 0.9 to 2.6nm. The diffusivity in micropores is lower than that of the bulk, and it decreases as pore width decreases and as density increases. But the viscosity in micropores is much larger than that of the bulk, and it increases as pore width decreases and as density increases. The diffusivity in channel parallel direction is obviously larger than that in channel perpendicular directions.     

The birth of a bubble: a molecular simulation study

We study the nucleation of a bubble in a metastable Lennard-Jones (LJ) fluid, confined to a spherical pore with wetting walls, by a combination of grand canonical, canonical ensemble, and gauge cell Monte Carlo simulation methods complemented by the Voronoi-Delaunay tessellation analysis of statistical geometry of intermolecular cavities. We construct the isotherm of confined fluid in the form of a continuous van der Waals' loop, in which the unstable backward trajectory between the spinodals corresponds to bubble states. We show that as the degree of metastability increases and the fluid becomes progressively stretched, the decrease of fluid density is associated with the evolution of a population of interstitial intermolecular cavities. At the spinodal, the fluid becomes mechanically unstable: Interstitial cavities partly coalesce into a larger cavity located due to the system symmetry around the pore center. This cavity represents a bubble embryo, which grows at the expense of interstitial cavities. The nucleation barrier is calculated by direct thermodynamic integration along the isotherm. We compare our simulation results to the predictions of the classical nucleation theory and experiments on capillary condensation-evaporation of nitrogen in pores of hybrid organic-inorganic mesoporous molecular sieve HMM-3.     

Experimental validation of plugging during drop formation in a T-junction

At low capillary number, drop formation in a T-junction is dominated by interfacial effects: as the dispersed fluid flows into the drop maker nozzle, it blocks the path of the continuous fluid; this leads to a pressure rise in the continuous fluid that, in turn, squeezes on the dispersed fluid, inducing pinch-off of a drop. While the resulting drop volume predicted by this "squeezing" mechanism has been validated for a range of systems, as of yet, the pressure rise responsible for the actual pinch-off has not been observed experimentally. This is due to the challenge of measuring the pressures in a T-junction with the requisite speed, accuracy, and localization. Here, we present an empirical study of the pressures in a T-junction during drop formation. Using Laplace sensors, pressure probes we have developed, we confirm the central ideas of the squeezing mechanism; however, we also uncover other findings, including that the pressure of the dispersed fluid is not constant but rather oscillates in anti-phase with that of the continuous fluid. In addition, even at the highest capillary number for which monodisperse drops can be formed, pressure oscillations persist, indicating that drop formation in confined geometries does not transition to an entirely shear-driven mechanism, but to a mechanism combining squeezing and shearing.     

Transport properties and distribution of water molecules confined in hydrophobic nanopores and nanoslits

The transport properties, including the diffusivity and viscosity, of water confined in hydrophobic nanopores and nanoslits were studied by molecular dynamics simulations. The results show that the diffusion coefficient in nanopores and nanoslits is markedly lower than that in the bulk. But the viscosity is much larger than that in bulk. The parallel diffusion coefficient is obviously larger than the perpendicular ones. The diffusion coefficient in the channel pore is ever less than that in the slit pore at the same pore width, but the viscosity is larger. The temperature and density affect significantly the diffusivity and viscosity in nanopores and nanoslits. Lower density water exhibits some special characteristics on density profiles in nanopores and nanoslits at lower temperatures, and the density profiles show a change from homogeneous to inhomogeneous as the pore width is reduced. Even clusters occurred in micropores.     

A diffusion model for the fluids confined in micropores

The self-diffusion coefficients were calculated by molecular dynamics simulations and the effects of pore width, temperature, and fluid density on diffusion behavior of simple fluid argon and polar fluid water confined in micropores were analyzed and studied. A mathematical model describing diffusion behavior of fluids confined in micropores was proposed from the theories of molecular dynamics and molecular kinematics, and validated on the basis of the simulation results at various conditions. The model indicates that the diffusion coefficient is proportional to the square root of the pore width and to the temperature divided by the density squared. It is applicable to either liquid or gas states and only two parameters are required.     

Mean field kinetic theory for a lattice gas model of fluids confined in porous materials

We consider the mean field kinetic equations describing the relaxation dynamics of a lattice model of a fluid confined in a porous material. The dynamical theory embodied in these equations can be viewed as a mean field approximation to a Kawasaki dynamics Monte Carlo simulation of the system, as a theory of diffusion, or as a dynamical density functional theory. The solutions of the kinetic equations for long times coincide with the solutions of the static mean field equations for the inhomogeneous lattice gas. The approach is applied to a lattice gas model of a fluid confined in a finite length slit pore open at both ends and is in contact with the bulk fluid at a temperature where capillary condensation and hysteresis occur. The states emerging dynamically during irreversible changes in the chemical potential are compared with those obtained from the static mean field equations for states associated with a quasistatic progression up and down the adsorption/desorption isotherm. In the capillary transition region, the dynamics involves the appearance of undulates (adsorption) and liquid bridges (adsorption and desorption) which are unstable in the static mean field theory in the grand ensemble for the open pore but which are stable in the static mean field theory in the canonical ensemble for an infinite pore.     

Optimized ensemble Monte Carlo simulations of dense Lennard-Jones fluids

We apply the recently developed adaptive ensemble optimization technique to simulate dense Lennard-Jones fluids and a particle-solvent model by broad-histogram Monte Carlo techniques. Equilibration of the simulated fluid is improved by sampling an optimized histogram in radial coordinates that shifts statistical weight towards the entropic barriers between the shells of the liquid. Interstitial states in the vicinity of these barriers are identified with unprecedented accuracy by sharp signatures in the quickly converging histogram and measurements of the local diffusivity. The radial distribution function and potential of mean force are calculated to high precision.     

Model for dynamics of inhomogeneous and bulk fluids

An accurate model for the density of states (DOS) for strongly inhomogeneous and bulk fluids has been proposed based on gamma distributions. The contribution to the density of states from the collective dynamics is modeled as an incomplete gamma distribution and the high frequency region is obtained from the solution of the memory equation using a sech memory kernel. Using only the frequency moments as input, the model parameters for the collective dynamics are obtained by matching moments of the resulting distribution. The model results in an analytical expression for the self-diffusivity of the fluid. We present results for soft sphere fluids confined in slit-shaped pores as well as bulk soft sphere liquids. Comparisons of the DOS, velocity autocorrelation functions, and memory kernels with molecular dynamics simulations reveal that the model predicts features in the DOS over the entire frequency range and is able to capture changes in the DOS as a function of fluid density and temperature. As a result the predicted VACFs, memory kernels, and self-diffusivities are accurately predicted over a wide range of conditions. Since the frequency moments for bulk liquids can be obtained from pair correlation functions, our method provides a direct route from fluid structure to dynamics. For fluids confined in slit-shaped pores, where the frequency moments are obtained from molecular dynamics simulations, the predicted self-diffusivities capture the resulting oscillations due to variations in the solvation pressure, and in the case of smooth walled pores, the predictions are superior to those obtained using kinetic theory.     

Reactivity dynamics of a confined molecule in presence of an external magnetic field

Reactivity dynamics and stability of a confined hydrogen molecule in presence of an external magnetic field has been studied using quantum fluid density functional theory. Dynamic profiles of various reactivity parameters such as hardness, electrophilicity, magnetizability, phase volume, entropy, etc. have been studied within a confined environment. Responses in the reactivity parameters as well as the associated electronic structure principles validate the stability of the confined H₂ molecule in ground and excited states in presence of an external magnetic field. Confinement to the system has been imposed by the Dirichlet type boundary condition. Confinement and excitation act in opposite directions. Ground state type dynamics is obtained on simultaneous electronic excitation and confinement. © 2014 Wiley Periodicals, Inc.     

本体柱状的线形嵌段共聚物在受限状态下的自组装结构

综述了使用计算机模拟方法研究在本体状态下形成柱状结构的线形二嵌段和三嵌段共聚物在平行板间和纳米圆孔内的自组装结构.研究发现,嵌段共聚物体系在受限状态下自组装可以得到与本体状态下不同的纳米结构,调整受限状态的物理化学性质可以调控受限体系的相行为,从而诱导体系形成特定的结构.模拟研究还发现不同相分离强度和链结构的体系,在相同的受限状态下表现出不同的相行为.因此在制备纳米结构材料的研究中,人们要根据嵌段共聚物体系的特定性质,选择相应的受限环境,才能够实现有效的控制.     

Simulation of fluid-solid coexistence in finite volumes: a method to study the properties of wall-attached crystalline nuclei

The Asakura-Oosawa model for colloid-polymer mixtures is studied by Monte Carlo simulations at densities inside the two-phase coexistence region of fluid and solid. Choosing a geometry where the system is confined between two flat walls, and a wall-colloid potential that leads to incomplete wetting of the crystal at the wall, conditions can be created where a single nanoscopic wall-attached crystalline cluster coexists with fluid in the remainder of the simulation box. Following related ideas that have been useful to study heterogeneous nucleation of liquid droplets at the vapor-liquid coexistence, we estimate the contact angles from observations of the crystalline clusters in thermal equilibrium. We find fair agreement with a prediction based on Young's equation, using estimates of interface and wall tension from the study of flat surfaces. It is shown that the pressure versus density curve of the finite system exhibits a loop, but the pressure maximum signifies the "droplet evaporation-condensation" transition and thus has nothing in common with a van der Waals-like loop. Preparing systems where the packing fraction is deep inside the two-phase coexistence region, the system spontaneously forms a "slab state," with two wall-attached crystalline domains separated by (flat) interfaces from liquid in full equilibrium with the crystal in between; analysis of such states allows a precise estimation of the bulk equilibrium properties at phase coexistence.     

Quantitative link between single-particle dynamics and static structure of supercooled liquids

We present evidence via molecular simulation that the supercooled fluid states of SPC/E water as well as the "repulsive" and "attractive" supercooled fluid states of a recently introduced model for colloids with short-ranged attractions are characterized by the same functional relationship between self-diffusivity and the pair correlation function. We discuss how this simple relationship connects to an earlier finding that the temperature dependency of a supercooled fluid's single-particle dynamics tracks that of its excess entropy (relative to ideal gas). The generality of this observed structure-property relationship is supported by its ability to successfully describe the nontrivial behaviors of these very different types of model systems.     

Transport Properties of Fluids in Micropores by Molecular Dynamics Simulation

The transport properties of fluid argon in micropores, i.e. diffusivity and viscosity, were studied by molecular dynamics simulations. The effects of pore width, temperature and density on diffusivity and viscosity were analyzed in micropores with pore widths from 0.8 to 4.0 nm. The results show that the diffusivity in micropores is much lower than the bulk diffusivity, and it decreases as the pore width decreases; but the viscosity in micropores is significantly larger than the bulk one, and it increases sharply in narrow micropores. The diffusivity in channel parallel direction is obviously larger than that in channel perpendicular direction. The temperature and density are important factors that obviously affect diffusivity and viscosity in micropores.     

Relaxation and short time dynamics of bulk liquids and fluids confined in spherical cavities and slit pores

The density of states for bulk and confined fluids have been modeled using a recently proposed gamma distribution (Krishnan, S. H.; Ayappa, K. G. J. Chem. Phys. 2004, 121, 3197). The gamma distribution results in a closed form analytical expression for the velocity autocorrelation function and the relaxation time of the fluid. The two parameters of the gamma distribution are related analytically to the second and fourth frequency moments of the fluid using short time expansions. The predictions by the proposed gamma model are compared with the velocity autocorrelation functions obtained using the theory of instantaneous normal modes (INMs) and from molecular dynamics simulations. The model is applied to a bulk soft sphere liquid and fluids confined in a spherical cavity and slit-shaped pores. The gamma model is able to capture the resulting changes in relaxation time due to changes in density and temperature extremely well for both the bulk liquid and confined inhomogeneous fluid situations. In all cases, the predictions by the gamma model are superior to those obtained from the INM theory. In the case of the fluid confined in a slit pore, the loadings were obtained from a grand canonical Monte Carlo simulation where the pore is equilibrated with a bulk fluid. This is similar to a confinement situation in a surface force apparatus. The predicted relaxation times vs pore widths from the gamma model are seen to accurately capture the oscillations due to formation and disruption of layers within the slit pore.     

Modeling velocity autocorrelation functions for confined fluids using gamma distributions

We propose a model for the short-time dynamics of fluids confined in slit-shaped pores. The model has been developed from the observation that the real lobe of the instantaneous normal mode density of states (INM DOS) closely follows a gamma distribution. By proposing that the density of states of the confined fluid can be represented by a gamma distribution, the resulting velocity autocorrelation function (VACF) is constructed such that it is accurate upto the fourth frequency moment. The proposed model results in an analytical expression for the VACF and relaxation times. The VACFs obtained from the model have been compared with the VACFs obtained from molecular dynamic simulations and INM analysis for fluids confined in slit-shaped pores over a wide range of confinement and temperatures. The model is seen to capture the short-time behavior of the VACF extremely accurately and in this region is superior to the predictions of the VACF obtained from the real lobe of the INM DOS. Although the model predicts a zero self-diffusivity, the predicted relaxation times are in better agreement with the molecular dynamics results when compared with those obtained from the INM theory.