On the selective formation of cubic tetrastack crystals from tetravalent patchy particles.

Achieving the formation of target open crystalline lattices from colloidal particles is of paramount importance for their potential application in photonics. Examples of such desired structures are the diamond, tetrastack, and pyrochlore lattices. Here, we demonstrate that the self-assembly of tetravalent patchy particles results in the selective formation of cubic tetrastack crystals, both in the bulk and in the systems subjected to external fields exerted by the solid substrate. It is demonstrated that the presence of an external field allows for the formation of well-defined single crystals with a low density of defects. Moreover, depending on the strength of the applied external field, the mechanism of epitaxial growth changes. For weakly attractive external fields, the crystallization occurs in a similar manner as in the bulk, since the fluid does not wet the substrate. Nonetheless, the formed crystal is considerably better ordered than the crystals formed in bulk, since the surface induces the ordering in the first layer. On the other hand, it is demonstrated that the formation of well-ordered cubic tetrastack crystals is considerably enhanced by the increase in external field strength, and the formation of the thick crystalline film occurs via a series of layering transitions.

The Lattice Model of Particles with Orientation-Dependent Interactions at Solid Surfaces: Wetting Scenarios.

Wetting phenomena in a lattice model of particles having two chemically different halves (A and B) and being in contact with solid substrates have been studied with Monte Carlo methods. The energy of the interaction between a pair of neighboring particles has been assumed to depend on the degree to which the AA, AB and BB regions face each other. In this work, we have assumed that uAA=-1.0 and considered three series of systems with uAB=uBB, uAB=0 and uBB=0. The phase behavior of bulk systems has been determined. In particular, it has been shown that at sufficiently low temperatures the bulk systems order into the superantiferromagnetic (SAF) phase, or into the antiferromagnetic (AF) phase, depending on the magnitudes of AA, AB and BB interaction energies, uAA, uAB and uBB. The SAF structure occurs whenever ϵ=uAA+uBB-2uAB is lower than zero and the AF structure is stable when ϵ is greater than zero. The wetting behavior has been demonstrated to depend strongly on the structure of the bulk condensed phase, the interactions between fluid particles and the strength of the surface potential. In all series, we have found the dewetting transition, resulting from the limited stability of different ordered structures of surface phases. However, in the systems that exhibit the gas-liquid transition in the bulk, the reentrant wetting transition has been observed at sufficiently high temperatures. The mechanism of dewetting and reentrant wetting transitions has been determined. Moreover, we have also demonstrated, how the dewetting transition in the series with uAB=0 is affected by the wall selectivity, i.e., when the interaction between the parts A and B of fluid particles and the solid is different.

Phase Transitions in Two-Dimensional Systems of Janus-like Particles on a Triangular Lattice.

We studied the phase behavior of two-dimensional systems of Janus-like particles on a triangular lattice using Monte Carlo methods. The model assumes that each particle can take on one of the six orientations with respect to the lattice, and the interactions between neighboring particles were weighted depending on the degree to which their A and B halves overlap. In this work, we assumed that the AA interaction was fixed and attractive, while the AB and BB interactions varied. We demonstrated that the phase behavior of the systems considered strongly depended on the magnitude of the interaction energies between the AB and BB halves. Here, we considered systems with non-repulsive interactions only and determined phase diagrams for several systems. We demonstrated that the phase diagram topology depends on the temperature at which the close-packed systems undergo the orientational order-disorder transition.

Lattice Model of Multilayer Adsorption of Particles with Orientation Dependent Interactions at Solid Surfaces.

A simple lattice model has been used to study the formation of multilayer films by fluids with orientation-dependent interactions on solid surfaces. The particles, composed of two halves (A and B) were allowed to take on one of six different orientations. The interaction between a pair of differently oriented neighboring particles was assumed to depend on the degrees to which their A and B parts overlap. Here, we have assumed that the AA interaction was strongly attractive, the AB interaction was set to zero, while the BB interaction was varied between 0 and -1.0. The ground state properties of the model have been determined for the systems being in contact with non-selective and selective walls over the entire range of BB interaction energies between 0 and -1.0. It has been demonstrated that the structure of multilayer films depends on the strengths of surface potential felt by differently oriented particles and the interaction between the B halves of fluid particles. Finite temperature behavior has been studied by Monte Carlo simulation methods. It has been shown that the bulk phase phase diagram is qualitatively independent of the BB interaction energy, and has the swan neck shape, since the high stability of the dense ordered phase suppresses the possibility of the formation of disordered liquid-like phase. Only one class of non-uniform systems with the BB interaction set to zero has been considered. The results have been found to be consistent with the predictions stemming form the ground state considerations. In particular, we have found that a complete wetting occurs at any temperature, down to zero. Furthermore, the sequences of layering transitions, and the structure of multilayer films, have been found to be the same as observed in the ground state.

The effects of confinement in pores built of folded graphene sheets on the equilibrium of nitrogen monoxide dimerisation reaction.

In the current work we have used reactive Monte Carlo simulations to systematically study the effects of graphene folding on equilibria of NO dimerisation occurring at isolated surfaces and in porous networks built of corrugated graphene sheets. It has been demonstrated that the folding of isolated graphene sheets significantly improves the yield of reactions occurring on their surface. Then, it has also been shown that in slit-like pores formed by the folded graphene sheets the reaction yield depends on the corrugation and arrangement of the pore walls. It has been found that the reaction yield increases when the walls' corrugation is high because of the appearance of narrow regions and/or wedge-like regions in the pores. The condensation of reacting fluid in such places, where the bulges at both walls are close one to another, leads to much higher reaction yield than on the surface of isolated sheets. Thus, we recommended the highly corrugated graphene to control the chemical reactions.

Carbon Nanohorns as Reaction Nanochambers - a Systematic Monte Carlo Study.

Carbon nanohorns (CNHs, one of the newest carbon allotropes) have been subjected to intensive experimental and theoretical studies due to their potential applications. One of such applications can be their use as reaction nanochambers. However, experimental studies on the reaction equilibria under confinement are extremely challenging since accurate measurements of the concentrations of reacting species in pores are a very hard task. So, the main ways to examine such phenomena are theoretical methods (e.g. the reactive Monte Carlo, RxMC). We have presented the first systematic RxMC study on the influence of the CNH's geometric parameters (the apex angle, the diameter, and the length) on reaction equilibria, taking the nitrogen monoxide dimerisation as an example. All the investigated parameters significantly affect the reaction yield at low and moderate coverages. Short and narrow CNHs have been found to be preferred. However, the key factor influencing the reaction equilibria is the presence of a conical part. Energetics of interactions between the reacting molecules in this fragment of a nanohorn maximises the effects of confinement. In consequence, CNHs have the advantage over their nanotube counterparts of the same diameter. The obtained results have confirmed that CNHs can be considered as potential reaction nanochambers.

Phase behavior of a binary symmetric mixture in slitlike pores with opposing walls: application of density functional approach.

We study adsorption of a symmetric binary Lennard-Jones mixture, which exhibits partial mixing in a bulk phase, in slitlike pores formed by the walls having antisymmetric properties with respect to the components. The calculations are carried out by means of a density functional approach. We show that under suitable conditions the pore filling may occur as a sequence of two first-order transitions. The capillary condensation may lead to an "antisymmetric" liquidlike film, the symmetry of which follows the symmetry of the adsorbing potential, or to a "demixed" film, the symmetry of which is only weakly associated with the symmetry of the adsorption potential. The additional first-order antisymmetric-demixed film transition begins at the triple point temperature and ends at the critical end point temperature.

Capillary condensation of a binary mixture in slit-like pores.

We investigate the capillary condensation of two model fluid mixtures in slit-like pores, which exhibit different demixing properties in the bulk phase. The interactions between adsorbate particles are modeled by using Lennard-Jones (12,6) potentials and the adsorbing potentials are of the Lennard-Jones (9,3) type. The calculations are performed for different pore widths and at different concentrations of the bulk gas, by means of density functional theory. We evaluate the capillary phase diagrams and discuss their dependence on the parameters of the model. Our calculations indicate that a binary mixture confined to a slit-like pore may exhibit rich phase behavior.

Effects of surface nonuniformity and molecular association on mechanism of butanol adsorption from solution.

The paper presents the results of calorimetric measurements and surface excess adsorption isotherms for n-butanol adsorption from n-hexane on a series of controlled porosity glasses characterized by different mean pore diameters. It is demonstrated that, in the region of very low alcohol concentration in solution, the heat of adsorption exhibits sharp maximum, independently of the pore diameter of adsorbent. This rather puzzling result is explained by the heterogeneity of the surface and the effects of molecular association of alcohol molecules in the solution. A simple theoretical model that supports our predictions is presented.

Microscopic structure and properties of an interface between coexisting phases of an associating fluid adsorbed in slitlike pores.

Using density functional theory, we calculate density profiles of an associating fluid in slitlike pores. These profiles characterize an interface between two coexisting, adsorbed phases, e.g., between gaseous and liquid phases formed during capillary condensation. Our study has been carried out for weakly, as well as for strongly, associated fluids confined in pores of different widths. We also investigate the role of the fluid-wall interaction.

Density Functional Study of a Simple Membrane Using the Solvent Primitive Model.

The model membrane, whose surfaces are maintained at the differing surface potentials, V(1) and V(2), on its inner and outer surfaces, that has been studied previously is extended to include explicit solvent molecules. The solvent primitive model, where the solvent molecules are treated as hard spheres, is used. In this study, the electrolyte can interact with the membrane both electrostatically and by means of a short-range van der Waals-like potential that can be attractive or repulsive. The bulk fluid beyond the outer surface is a four-component electrolyte consisting of the hard sphere solvent, two species of cations, and one species of anions. The membrane is impermeable to one of the cation species so that the fluid in the membrane and beyond the inner surface is a three-component electrolyte. Previously, we studied this model membrane by computer simulation and density functional theory (DFT) and found this theory to be quite accurate. Here we report further results, obtained using DFT, from which results can be obtained much more easily than from simulations. The density profiles of the electrolyte near the membrane and the charge-potential relationship of the membrane surfaces under a wider variety of conditions than is possible by simulation are studied. The presence of the solvent molecules leads to a greater excluded volume. As a result, the density profiles are oscillatory, whereas they are monotonic when a molecular model for the solvent is not used. The potential versus charge relationship is strongly influenced by the solvent density. In addition to the electrostatic interactions, the effect of a van der Waals interaction on the solvent molecules is considered. Copyright 2001 Academic Press.