Grand ensemble Monte Carlo calculation of the thermodynamic properties of a solid/vapour interface

Lane, J. E.; Spurling, Thomas H.

doi:10.1071/ch9762103

Cited by 66 publications

(14 citation statements)

References 0 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Stratification diminishes rapidly with increasing distance from the substrates, because of the decay of the fluid-substrate interaction; beyond a few molecular diameters f , the fluid is essentially homogeneous, as computer simulations have repeatedly demonstrated. 4,5,[7][8][9][10][11] We therefore expect Eq. ͑18͒ to be reasonable for mesoscopic pores (s z տ10 fw ).…”

Section: B Mean-field Theory Of Pore Fluidmentioning

confidence: 98%

“…It is well established 4,5,[7][8][9][10][11]34 that fluid confined to a slit-pore is stratified ͑i.e., the fluid molecules order themselves in strata parallel with the substrates͒. Stratification diminishes rapidly with increasing distance from the substrates, because of the decay of the fluid-substrate interaction; beyond a few molecular diameters f , the fluid is essentially homogeneous, as computer simulations have repeatedly demonstrated.…”

Section: B Mean-field Theory Of Pore Fluidmentioning

confidence: 99%

“…In essence most methods involve the calculation of the ͑grand͒ free energy approximately. Perhaps the most exacting, and computationally most laborious, procedure is the grand canonical ensemble Monte Carlo method, [4][5][6][7][8][9][10][11] in which the trajectories of fluid molecules are generated stochastically ͑by means of a pseudo-randomnumber generator͒ so that the phase of the trajectory is weighted according to the probability density function of the grand canonical ensemble and the properties of the pore fluid are expressed as phase averages over the trajectory. Less a͒ Electronic mail: schoen@wpta2.physik.uni-wuppertal.de b͒ Electronic mail: agro016@unlvm.unl.edu exacting, as well as less intensive computationally, are methods that invoke the mean-field approximation for the fluidfluid interactions.…”

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Analytical treatment of a simple fluid adsorbed in a slit-pore

Schoen

Diestler

1998

The Journal of Chemical Physics

View full text Add to dashboard Cite

A model for a simple fluid confined to a slit-pore (fluid sandwiched between two plane-parallel substrates with infinitesimally smooth surfaces) is presented. The analysis is based on thermodynamic perturbation theory, in which the free energy is split into a zero-order (unperturbed) contribution from a hard-sphere fluid reference system and a correction accounting for both fluid-fluid and fluid-substrate attractions. The correction is evaluated in the mean-field approximation and the (unperturbed) local density is assumed uniform in order to obtain a closed expression for the correction. The resulting equation of state has the same temperature and density dependence as the van der Waals equation of state for the bulk fluid, although it differs from the latter in that the a parameter (ap) is a function of the separation sz of the substrate surfaces. The inequality ap(sz)⩽ab holds, from which it follows that the critical temperature of the pore fluid is lower than that of the bulk fluid. For mesoscopic pores, the lowering is in semi-quantitative agreement with experiment. The excess coverage Γ is calculated for bulk isochoric paths T→T0b, where T0b is the bulk liquid-gas coexistence temperature for a given isochore. If the fluid-substrate attraction is great enough, Γ vs T may exhibit a discontinuity reflecting pore condensation. The model predicts pore condensation over a density range comparable with the experimental one.

show abstract

Section: B Mean-field Theory Of Pore Fluidmentioning

confidence: 98%

Section: B Mean-field Theory Of Pore Fluidmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Analytical treatment of a simple fluid adsorbed in a slit-pore

Schoen

Diestler

1998

The Journal of Chemical Physics

View full text Add to dashboard Cite

show abstract

“…This fundamental difference from the bulk liquid, which has only recently been investigated (7)(8)(9)(10)(11)(12)(13)(14), is discussed below. proven to be one of the most b&ng aspects of liquids, in spite of long-standing interest (15,16).…”

mentioning

confidence: 99%

Motions and Relaxations of Confined Liquids

Granick

1991

Science

951

697

View full text Add to dashboard Cite

When a liquid is confined in a narrow gap (as near a cell membrane, in a lubricated contact between solids, or in a porous medium), new dynamic behavior emerges. The effective shear viscosity is enhanced compared to the bulk, relaxation times are prolonged, and nonlinear responses set in at lower shear rates. These effects are more prominent, the thinner the liquid film. They appear to be the manifestation of collective motions. The flow of liquids under extreme confinement cannot be understood simply by intuitive extrapolation of bulk properties. Practical consequences are possible in areas from tribology and materials processing to membrane physics.

show abstract

“…As a consequence, the fluid appears to be stratified; that is, the centres of mass of fluid molecules arrange themselves preferentially in individual layers parallel with the substrate surfaces. Stratification of confined fluid phases is a well-known feature that has been noted many times in the previous literature for various systems and confinement scenarios such as hard spheres between hard surfaces [30,31], or soft spheres between atomically smooth [32] or structured substrates [33,34]. In addition, the substrates may be chemically patterned [15,35] or nonplanar [36 -38].…”

Section: Structural Aspectsmentioning

confidence: 99%

Sorption strains and their consequences for capillary condensation in nanoconfinement

Günther

Schoen

2009

Molecular Simulation

View full text Add to dashboard Cite

We employ Monte Carlo simulations in a semi-grand canonical ensemble to investigate the impact of pore deformation on capillary condensation in nanoconfined fluids. The fluid is composed of 'simple' spherically symmetric molecules of the Lennard-Jones type. These molecules are confined to a slit pore, where the pore walls consist of a single layer of atoms distributed according to the (100) plane of the face-centred cubic lattice. The atoms are bound to their equilibrium lattice sites by harmonic potentials such that they can depart to some extent from these sites on account of their thermal energy and the interaction with the fluid molecules. Under experimentally realistic conditions, our results show that, upon filling with fluid, the effective average pore size first increases, and then drops sharply at capillary condensation. The pore eventually expands again when the density of the confined liquid-like phase is further enhanced. Compared with the ideal case of perfectly rigid substrates, deformability of the pore causes capillary condensation to shift to higher bulk pressures; that is, the liquid-like phases are destabilised relative to the confined gas-like phases.

show abstract

Grand ensemble Monte Carlo calculation of the thermodynamic properties of a solid/vapour interface

Cited by 66 publications

References 0 publications

Analytical treatment of a simple fluid adsorbed in a slit-pore

Analytical treatment of a simple fluid adsorbed in a slit-pore

Motions and Relaxations of Confined Liquids

Sorption strains and their consequences for capillary condensation in nanoconfinement

Contact Info

Product

Resources

About