Closed-loop liquid-vapor equilibrium in a one-component system

We report Monte Carlo simulations that show closed-loop liquid-vapor equilibrium in a pure substance. As far as we know, this is the first time that such a topology of the phase diagram has been found for one-component systems. This finding has been achieved on a two-dimensional lattice model for patchy particles that can form network fluids. We have considered related models with a slightly different patch distribution in the order to understand the features of the distribution of patches on the surface of the particles that make possible the presence of the closed-loop liquid-vapor equilibrium, and its relation with the phase diagram containing the so-called empty liquids. Finally we discuss the likelihood of finding the closed-loop liquid-vapor equilibria on related models for three dimensional models of patchy particles in the continuum, and speculate on the possible relationship between the mechanism behind the closed-loop liquid vapor equilibrium of our simple lattice model and the salt-induced reentrant condensation found in complex systems.Comment: 5 pages (two columns); 7 Figures (Submitted to Physical Review

Phase behaviour of the confined lattice gas Lebwohl-Lasher model

The phase behaviour of the Lebwohl-Lasher lattice gas model (one of the simplest representations of a nematogenic fluid) confined in a slab is investigated by means of extensive Monte Carlo simulations. The model is known to yield a first order gas-liquid transition in both the 2D and 3D limits, that is coupled with an orientational order-disorder transition. This latter transition happens to be first order in the 3D limit and it shares some characteristic features with the continuous defect mediated Berezinskii-Kosterlitz-Thouless transition in 2D. In this work we will analyze in detail the behaviour of this system taking full advantage of the lattice nature of the model and the particular symmetry of the interaction potential, which allows for the use of efficient cluster algorithms.Comment: 6 pages, 5 figure

Phase behaviour of attractive and repulsive ramp fluids: integral equation and computer simulation studies

Using computer simulations and a thermodynamically self consistent integral equation we investigate the phase behaviour and thermodynamic anomalies of a fluid composed of spherical particles interacting via a two-scale ramp potential (a hard core plus a repulsive and an attractive ramp) and the corresponding purely repulsive model. Both simulation and integral equation results predict a liquid-liquid de-mixing when attractive forces are present, in addition to a gas-liquid transition. Furthermore, a fluid-solid transition emerges in the neighbourhood of the liquid-liquid transition region, leading to a phase diagram with a somewhat complicated topology. This solidification at moderate densities is also present in the repulsive ramp fluid, thus preventing fluid-fluid separation.Comment: 29 pages, 10 figure

Theory and simulation of the confined Lebwohl-Lasher model

We discuss the Lebwohl-Lasher model of nematic liquid crystals in a confined geometry, using Monte Carlo simulation and mean-field theory. A film of material is sandwiched between two planar, parallel plates that couple to the adjacent spins via a surface strength $\epsilon_s$. We consider the cases where the favoured alignments at the two walls are the same (symmetric cell) or different (asymmetric or hybrid cell). In the latter case, we demonstrate the existence of a {\it single} phase transition in the slab for all values of the cell thickness. This transition has been observed before in the regime of narrow cells, where the two structures involved correspond to different arrangements of the nematic director. By studying wider cells, we show that the transition is in fact the usual isotropic-to-nematic (capillary) transition under confinement in the case of antagonistic surface forces. We show results for a wide range of values of film thickness, and discuss the phenomenology using a mean-field model.Comment: 40 pages 19 figures (preprint format). Part of the text and some figures were modified. New figure was include

Three-dimensional patchy lattice model: ring formation and phase separation

We investigate the structural and thermodynamic properties of a model of particles with $2$ patches of type $A$ and $10$ patches of type $B$. Particles are placed on the sites of a face centered cubic lattice with the patches oriented along the nearest neighbor directions. The competition between the self-assembly of chains, rings and networks on the phase diagram is investigated by carrying out a systematic investigation of this class of models, using an extension of Wertheim's theory for associating fluids and Monte Carlo numerical simulations. We varied the ratio $r\equiv\epsilon_{AB}/\epsilon_{AA}$ of the interaction between patches $A$ and $B$, $\epsilon_{AB}$, and between $A$ patches, $\epsilon_{AA}$ ($\epsilon_{BB}$ is set to $0$) as well as the relative position of the $A$ patches, i.e., the angle $\theta$ between the (lattice) directions of the $A$ patches. We found that both $r$ and $\theta$ ($60^\circ,90^\circ,$ or $120^\circ$) have a profound effect on the phase diagram. In the empty fluid regime ($r < 1/2$) the phase diagram is re-entrant with a closed miscibility loop. The region around the lower critical point exhibits unusual structural and thermodynamic behavior determined by the presence of relatively short rings. The agreement between the results of theory and simulation is excellent for $\theta=120^\circ$ but deteriorates as $\theta$ decreases, revealing the need for new theoretical approaches to describe the structure and thermodynamics of systems dominated by small rings.Comment: 26 pages, 10 figure

Reply to "Comment on 'Effect of polydispersity on the ordering transition of adsorbed self- assembled rigid rods'"

We comment on the nature of the ordering transition of a model of equilibrium polydisperse rigid rods on the square lattice, which is reported by Lopez et al. to exhibit random percolation criticality in the canonical ensemble, in sharp contrast to (i) our results of Ising criticality for the same model in the grand canonical ensemble [Phys. Rev. E 82, 061117 (2010)] and (ii) the absence of exponent(s) renormalization for constrained systems with logarithmic specific-heat anomalies predicted on very general grounds by Fisher [Phys. Rev. 176, 257 (1968)]

Bistability in a self-assembling system confined by elastic walls: Exact results in a one-dimensional lattice model

© 2015 AIP Publishing LLC. The impact of confinement on self-assembly of particles interacting with short-range attraction and long-range repulsion potential is studied for thermodynamic states corresponding to local ordering of clusters or layers in the bulk. Exact and asymptotic expressions for the local density and for the effective potential between the confining surfaces are obtained for a one-dimensional lattice model introduced by J. Pękalski et al. [J. Chem. Phys. 138, 144903 (2013)]. The simple asymptotic formulas are shown to be in good quantitative agreement with exact results for slits containing at least 5 layers. We observe that the incommensurability of the system size and the average distance between the clusters or layers in the bulk leads to structural deformations that are different for different values of the chemical potential μ. The change of the type of defects is reflected in the dependence of density on μ that has a shape characteristic for phase transitions. Our results may help to avoid misinterpretation of the change of the type of defects as a phase transition in simulations of inhomogeneous systems. Finally, we show that a system confined by soft elastic walls may exhibit bistability such that two system sizes that differ approximately by the average distance between the clusters or layers are almost equally probable. This may happen when the equilibrium separation between the soft boundaries of an empty slit corresponds to the largest stress in the confined self-assembling system.Peer Reviewe