Quenching of lamellar ordering in an n-alkane embedded in nanopores

We present an X-ray diffraction study of the normale alkane nonadecane C_{19}H_{40} embedded in nanoporous Vycor glass. The confined molecular crystal accomplishes a close-packed structure by alignment of the rod-like molecules parallel to the pore axis while sacrificing one basic principle known from the bulk state, i.e. the lamellar ordering of the molecules. Despite this disorder, the phase transitions observed in the confined solid mimic the phase behavior of the 3D unconfined crystal, though enriched by the appearance of a true rotator phase known only from longer alkane chains.Comment: 7 pages, 3 figure

Percolation, depinning, and avalanches in capillary condensation of gases in disordered porous solids

We propose a comprehensive theoretical description of hysteresis in capillary condensation of gases in mesoporous disordered materials. Applying mean-field density functional theory to a coarse-grained lattice-gas model, we show that the morphology of the hysteresis loops is influenced by out-of-equilibrium transitions that are different on filling and on draining. In particular, desorption may be associated to a depinning process and be percolation-like without explicit pore-blocking effects.Comment: 4 pages, 5 figure

Liquid-liquid coexistence in the phase diagram of a fluid confined in fractal porous materials

Multicanonical ensemble sampling simulations have been performed to calculate the phase diagram of a Lennard-Jones fluid embedded in a fractal random matrix generated through diffusion limited cluster aggregation. The study of the system at increasing size and constant porosity shows that the results are independent from the matrix realization but not from the size effects. A gas-liquid transition shifted with respect to bulk is found. On growing the size of the system on the high density side of the gas-liquid coexistence curve it appears a second coexistence region between two liquid phases. These two phases are characterized by a different behaviour of the local density inside the interconnected porous structure at the same temperature and chemical potential.Comment: 5 pages, 4 figures. To be published in Europhys. Letter

Soft disks in a narrow channel

The pressure components of "soft" disks in a two dimensional narrow channel are analyzed in the dilute gas regime using the Mayer cluster expansion and molecular dynamics. Channels with either periodic or reflecting boundaries are considered. It is found that when the two-body potential, u(r), is singular at some distance r_0, the dependence of the pressure components on the channel width exhibits a singularity at one or more channel widths which are simply related to r_0. In channels with periodic boundary conditions and for potentials which are discontinuous at r_0, the transverse and longitudinal pressure components exhibit a 1/2 and 3/2 singularity, respectively. Continuous potentials with a power law singularity result in weaker singularities of the pressure components. In channels with reflecting boundary conditions the singularities are found to be weaker than those corresponding to periodic boundaries

Structural properties of hard disks in a narrow tube

Positional ordering of a two-dimensional fluid of hard disks is examined in such narrow tubes where only the nearest-neighbor interactions take place. Using the exact transfer-matrix method the transverse and longitudinal pressure components and the correlation function are determined numerically. Fluid-solid phase transition does not occur even in the widest tube, where the method just loses its exactness, but the appearance of the dramatic change in the equation of state and the longitudinal correlation function shows that the system undergoes a structural change from a fluid to a solid-like order. The pressure components show that the collisions are dominantly longitudinal at low densities, while they are transverse in the vicinity of close packing density. The transverse correlation function shows that the size of solid-like domains grows exponentially with increasing pressure and the correlation length diverges at close packing. It is managed to find an analytically solvable model by expanding the contact distance up to first order. The approximate model, which corresponds to the system of hard parallel rhombuses, behaves very similarly to the system of hard disks.Comment: Acceped in Journal of Statistical Mechanics: Theory and Experimen

Does Young's equation hold on the nanoscale? A Monte Carlo test for the binary Lennard-Jones fluid

When a phase-separated binary ($A+B$) mixture is exposed to a wall, that preferentially attracts one of the components, interfaces between A-rich and B-rich domains in general meet the wall making a contact angle $\theta$. Young's equation describes this angle in terms of a balance between the $A-B$ interfacial tension $\gamma_{AB}$ and the surface tensions $\gamma_{wA}$, $\gamma_{wB}$ between, respectively, the $A$- and $B$-rich phases and the wall, $\gamma _{AB} \cos \theta =\gamma_{wA}-\gamma_{wB}$. By Monte Carlo simulations of bridges, formed by one of the components in a binary Lennard-Jones liquid, connecting the two walls of a nanoscopic slit pore, $\theta$ is estimated from the inclination of the interfaces, as a function of the wall-fluid interaction strength. The information on the surface tensions $\gamma_{wA}$, $\gamma_{wB}$ are obtained independently from a new thermodynamic integration method, while $\gamma_{AB}$ is found from the finite-size scaling analysis of the concentration distribution function. We show that Young's equation describes the contact angles of the actual nanoscale interfaces for this model rather accurately and location of the (first order) wetting transition is estimated.Comment: 6 pages, 6 figure

Evidence for a disorder driven phase transition in the condensation of 4He in aerogels

We report on thermodynamic and optical measurements of the condensation process of $^4$He in three silica aerogels of different microstructures. For the two base-catalysed aerogels, the temperature dependence of the shape of adsorption isotherms and of the morphology of the condensation process show evidence of a disorder driven transition, in agreement with recent theoretical predictions. This transition is not observed for a neutral-catalysed aerogel, which we interpret as due to a larger disorder in this case.Comment: 11 page

Lattice-gas Monte Carlo study of adsorption in pores

A lattice gas model of adsorption inside cylindrical pores is evaluated with Monte Carlo simulations. The model incorporates two kinds of site: (a line of) ``axial'' sites and surrounding ``cylindrical shell'' sites, in ratio 1:7. The adsorption isotherms are calculated in either the grand canonical or canonical ensembles. At low temperature, there occur quasi-transitions that would be genuine thermodynamic transitions in mean-field theory. Comparison between the exact and mean-field theory results for the heat capacity and adsorption isotherms are provided

Fast Ensemble Smoothing

Smoothing is essential to many oceanographic, meteorological and hydrological applications. The interval smoothing problem updates all desired states within a time interval using all available observations. The fixed-lag smoothing problem updates only a fixed number of states prior to the observation at current time. The fixed-lag smoothing problem is, in general, thought to be computationally faster than a fixed-interval smoother, and can be an appropriate approximation for long interval-smoothing problems. In this paper, we use an ensemble-based approach to fixed-interval and fixed-lag smoothing, and synthesize two algorithms. The first algorithm produces a linear time solution to the interval smoothing problem with a fixed factor, and the second one produces a fixed-lag solution that is independent of the lag length. Identical-twin experiments conducted with the Lorenz-95 model show that for lag lengths approximately equal to the error doubling time, or for long intervals the proposed methods can provide significant computational savings. These results suggest that ensemble methods yield both fixed-interval and fixed-lag smoothing solutions that cost little additional effort over filtering and model propagation, in the sense that in practical ensemble application the additional increment is a small fraction of either filtering or model propagation costs. We also show that fixed-interval smoothing can perform as fast as fixed-lag smoothing and may be advantageous when memory is not an issue