Equivalence of nonequilibrium algorithms for simulations of planar Couette flow in confined fluids

Shear flow in fluids confined between planar solid walls is conventionally simulated by moving the walls past each other at constant relative velocity. In infinite fluids (in periodic boundary conditions), it is simulated using one of the "synthetic" nonequilibrium algorithms (the so-called Sllod and Dolls algorithms). Here I formulate the boundary conditions for the motion of confining walls that make these three algorithms equivalent in the weak-field limit.     

Local linear viscoelasticity of confined fluids

In this paper the authors propose a novel method to study the local linear viscoelasticity of fluids confined between two walls. The method is based on the linear constitutive equation and provides details about the real and imaginary parts of the local complex viscosity. They apply the method to a simple atomic fluid undergoing zero mean oscillatory flow using nonequilibrium molecular dynamics simulations. The method shows that the viscoelastic properties of the fluid exhibit dramatic spatial changes near the wall-fluid boundary due to the high density in this region. It is also shown that the real part of the viscosity converges to the frequency dependent local shear viscosity sufficiently far away from the wall. This also provides valuable information about the transport properties in the fluid, in general. The viscosity is compared with predictions from the local average density model. The two methods disagree in that the local average density model predicts larger viscosity variations near the wall-fluid boundary than what is observed through the method presented here.     

Freezing of fluids confined between mica surfaces

Using grand ensemble simulations, we show that octamethyl-cyclo-tetra-siloxane (OMCTS) confined between two mica surfaces can form a variety of frozen phases which undergo solid-solid transitions as a function of the separation between the surfaces. For atomically smooth mica surfaces, the following sequence of transitions 1[triangle up] --> 1[triangle up]b --> 2B --> 2 square --> 2[triangle up] are observed in the one- and two-layered regimes, where n[triangle up], n[square], and nB denote triangular, square, and buckled phases, respectively, with the prefix n denoting the number of confined layers. The presence of potassium on mica is seen to have a strong influence on the degree of order induced in the fluid. The sequence of solid-solid transitions that occurs with the smooth mica surface is no longer observed. When equilibrated with a state point near the liquid-solid transition, a counterintuitive freezing scenario is observed in the presence of potassium. Potassium disrupts in-plane ordering in the fluid in contact with the mica surface, and freezing is observed only in the inner confined layers. The largest mica separations at which frozen phases were observed ranged from separations that could accommodate six to seven fluid layers. The extent of freezing and the square-to-triangular lattice transition was found to be sensitive to the presence of potassium as well as the thermodynamic conditions of the bulk fluid. The implications of our results on interpretation of surface force experiments as well as the generic phase behavior of confined soft spheres is discussed.     

Dielectric permittivity profiles of confined polar fluids

The dielectric response of a simple model of a polar fluid near neutral interfaces is examined by a combination of linear response theory and extensive molecular dynamics simulations. Fluctuation expressions for a local permittivity tensor epsilon(r) are derived for planar and spherical geometries, based on the assumption of a purely local relationship between polarization and electric field. While the longitudinal component of epsilon exhibits strong oscillations on the molecular scale near interfaces, the transverse component becomes ill defined and unphysical, indicating nonlocality in the dielectric response. Both components go over to the correct bulk permittivity beyond a few molecular diameters. Upon approaching interfaces from the bulk, the permittivity tends to increase, rather than decrease as commonly assumed, and this behavior is confirmed for a simple model of water near a hydrophobic surface. An unexpected finding of the present analysis is the formation of "electrostatic double layers" signaled by a dramatic overscreening of an externally applied field inside the polar fluid close to an interface. The local electric field is of opposite sign to the external field and of significantly larger amplitude within the first layer of polar molecules.     

First-order mean spherical approximation for inhomogeneous fluids

The first-order mean-spherical approximation (FMSA) [Y. Tang, J. Chem. Phys., 118, 4140 (2003)] is extended to the studies of inhomogeneous fluids by combining with Rosenfeld's perturbative method [Y. Rosenfeld, J. Chem. Phys. 98, 8126 (1993)]. In the extension, the key input-direct correlation function of FMSA-is applied to constructing the free energy density functional. Preserving its high fidelity at the bulk limit, the FMSA shows satisfactory performance for Yukawa fluids near hard and attractive walls. The results are better than or comparable to several other theories reported before for the geometry. The FMSA is found, in particular, more satisfactory than the traditional mean-field theory for predicting density profiles around hard walls. The FMSA is also compared with the full MSA for inhomogeneous fluids, showing no appreciable differences. The inhomogeneous FMSA goes successfully through the self-consistency test for reproducing the radial distribution function of the bulk Yukawa fluid. As far as the computation is concerned, the FMSA can be executed much faster than any nonmean-field theories, and the speed is virtually identical to that of the mean-field theory.     

Thermodynamic and structural properties of confined discrete-potential fluids

The thermodynamic and structural behaviors of confined discrete-potential fluids are analyzed by computer simulations, studying in a systematic way the effects observed by varying the density, temperature, and parameters of the potentials that characterize the molecule-molecule interactions. The Gibbs ensemble simulation technique for confined fluids [A. Z. Panagiotopoulos, Mol. Phys. 62, 701 (1987)] is applied to a fluid confined between two parallel hard walls. Two different systems have been considered, both formed by spherical particles that differ by the interparticle pair potential: a square well plus square shoulder or a square shoulder plus square well interaction. These model interactions can describe in an effective way pair potentials of real molecular and colloidal systems. Results are compared with the simpler reference systems of square-shoulder and square-well fluids, both under confinement. From the adsorption characterization through the use of density profiles, it is possible to obtain specific values of the interparticle potential parameters that result in a positive to negative adsorption transition.     

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.     

Local structure and density fluctuations in confined fluids

Spatial confinement modifies the microscopic structure of dense fluids, thereby inducing for example structural forces between the confining walls. However, confinement also modifies the fluids' density fluctuations, resulting in more elusive but equally important effects. In this brief review it is shown that both of these phenomena are naturally analyzed using the confined fluid's pair densities, which have recently become also experimentally accessible. Two particular topics are discussed, namely, the mechanisms of oscillatory density profiles and ensuing solvation forces in dense confined fluids as well as the behavior of liquids in solvophobic confinement.     

Density functional theory for inhomogeneous associating chain fluids

We propose a nonlocal density functional theory for associating chain molecules. The chains are modeled as tangent spheres, which interact via Lennard-Jones (12,6) attractive interactions. A selected segment contains additional, short-ranged, highly directional interaction sites. The theory incorporates an accurate treatment of the chain molecules via the intramolecular potential formalism and should accurately describe systems with strongly varying external fields, e.g., attractive walls. Within our approach we investigate the structure of the liquid-vapor interface and capillary condensation of a simple model of associating chains with only one associating site placed on the first segment. In general, the properties of inhomogeneous associating chains depend on the association energy. Similar to the bulk systems we find the behavior of associating chains of a given length to be in between that for the nonassociating chains of the same length and that for the nonassociating chains twice as large.     

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.     

Thermodynamics of d-dimensional hard sphere fluids confined to micropores

We derive an analytical expression of the second virial coefficient of d-dimensional hard sphere fluids confined to slit pores by applying Speedy and Reiss' interpretation of cavity space. We confirm that this coefficient is identical to the one obtained from the Mayer cluster expansion up to second order with respect to fugacity. The key step of both approaches is to evaluate either the surface area or the volume of the d-dimensional exclusion sphere confined to a slit pore. We, further, present an analytical form of thermodynamic functions such as entropy and pressure tensor as a function of the size of the slit pore. Molecular dynamics simulations are performed for d = 2 and d = 3, and the results are compared with analytically obtained equations of state. They agree satisfactorily in the low density regime, and, for given density, the agreement of the results becomes excellent as the width of the slit pore gets smaller, because the higher order virial coefficients become unimportant.     

Longitudinal and volume viscosities of fluids confined in nanochannel

Longitudinal and volume viscosities of Lennard-Jones fluid, argon–krypton binary mixture and isotopic fluid mixture confined to nanochannels of different widths are calculated by employing theoretical technique based on Green–Kubo formula. A significant enhancement is observed in longitudinal and volume viscosities when width of the nanochannel is less than 10 nm. Effect of mass ratio of two species on longitudinal and volume viscosities is also studied for equimolar isotopic fluid mixture. It is found that enhancement in viscosity is more for larger mass ratios. It is also noted that enhancement in longitudinal and shear viscosities is more than volume viscosity.     

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.     

Probing memory effects in confined fluids via diffusion measurements

Confinement of fluids in porous materials is widely exploited in a variety of technologies, including chemical conversion by heterogeneous catalysis and adsorption separations. Important fundamental phenomena associated with many-molecule interactions occur in such systems, including a remarkably long "memory" of the past when the actual amount of molecules in the pores dramatically depends on the history of how the external conditions have been changed. We demonstrate that the intrinsic diffusivity as measured by NMR serves as an excellent probe of the history-dependent states of the confined fluid. A remarkable feature of our results are differences in diffusivity between out-of-equilibrium states with the same density within the hysteresis loop. This reflects different spatial distributions of the confined fluid that accompany the arrested equilibration of the system in this region.     

The structure of fluids confined in crystalline slitlike nanoscopic pores

Grand canonical and canonical ensemble Monte Carlo simulation methods are used to study the structure and phase behavior of Lennard-Jones fluids confined between the parallel (100) planes of the face centered cubic crystal. Thin slit pores with a width allowing for the formation of only up to five atomic layers are considered. The phase diagrams of the systems characterized by different pore width as well as by different strength of the fluid-pore walls potential are determined. It is shown that an enormously large number of different phase diagram topologies can occur, depending on the parameters of the problem (pore width, strength of the fluid-pore walls potential, etc).     

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.     

Molecular modeling of freezing of simple fluids confined within carbon nanotubes

We report Monte Carlo simulation results for freezing of Lennard-Jones carbon tetrachloride confined within model multiwalled carbon nanotubes of different diameters. The structure and thermodynamic stability of the confined phases, as well as the transition temperatures, were determined from parallel tempering grand canonical Monte Carlo simulations and free-energy calculations. The simulations show that the adsorbate forms concentric molecular layers that solidify into defective quasi-two-dimensional hexagonal crystals. Freezing in such concentric layers occurs via intermediate phases that show remnants of hexatic behavior, similar to the freezing mechanism observed for slit pores in previous works. The adsorbate molecules in the inner regions of the pore also exhibit changes in their properties upon reduction of temperature. The structural changes in the different regions of adsorbate occur at temperatures above or below the bulk freezing point, depending on pore diameter and distance of the adsorbate molecules from the pore wall. The simulations show evidence of a rich phase behavior in confinement; a number of phases, some of them inhomogeneous, were observed for the pore sizes considered. The multiple transition temperatures obtained from the simulations were found to be in good agreement with recent dielectric relaxation spectroscopy experiments for CCl(4) confined within multiwalled carbon nanotubes.     

Torsion-induced phase transitions in fluids confined between chemically decorated substrates

In this paper we investigate the phase behavior of a "simple" fluid confined to a chemically heterogeneous slit pore of nanoscopic width s(z) by means of Monte Carlo simulations in the grand canonical ensemble. The fluid-substrate interaction is purely repulsive except for elliptic regions of semiaxes A and B attracting fluid molecules. On account of the interplay between confinement (i.e., s(z)) and chemical decoration, three fluid phases are thermodynamically permissible, namely, gaslike and liquidlike phases and a "bridge phase" where the molecules are preferentially adsorbed by the attractive elliptic patterns and span the gap between the opposite substrate surfaces. Because of their lack of cylindrical symmetry, bridge phases can be exposed to a torsional strain 0相似文献