RESUMO
Previous theoretical studies of calamitic (i.e., rod-like) ionic liquid crystals (ILCs) based on an effective one-species model led to indications of a novel smectic-A phase with a layer spacing being much larger than the length of the mesogenic (i.e., liquid-crystal forming) ions. In order to rule out the possibility that this wide smectic-A phase is merely an artifact caused by the one-species approximation, we investigate an extension that accounts explicitly for cations and anions in ILCs. Our present findings, obtained by grand canonical Monte Carlo simulations, show that the phase transitions between the isotropic and the smectic-A phases of the cation-anion system are in qualitative agreement with the effective one-species model used in the preceding studies. In particular, for ILCs with mesogens (i.e., liquid-crystal forming species) carrying charged sites at their tips, the wide smectic-A phase forms, at low temperatures and within an intermediate density range, in between the isotropic and hexagonal crystal phases. We find that in the ordinary smectic-A phase, the spatial distribution of the counterions of the mesogens is approximately uniform, whereas in the wide smectic-A phase, the small counterions accumulate in between the smectic layers. Due to this phenomenology, the wide smectic-A phase could be interesting for applications, which hinge on the presence of conductivity channels for mobile ions.
RESUMO
Ionic liquid crystals (ILCs) are anisotropic mesogenic molecules which additionally carry charges. This combination gives rise to a complex interplay of the underlying (anisotropic) contributions to the pair interactions. It promises interesting and distinctive structural and orientational properties to arise in systems of ILCs, combining properties of liquid crystals and ionic liquids. While previous theoretical studies have focused on the phase behavior of ILCs and the structure of the respective bulk phases, in the present study we provide new results, obtained within density functional theory, concerning (planar) free interfaces between an isotropic liquid L and two types of smectic-A phases (SA or SAW). We discuss the structural and orientational properties of these interfaces in terms of the packing fraction profile η(r) and the orientational order parameter profile S2(r) concerning the tilt angle α between the (bulk) smectic layer normal and the interface normal. The asymptotic decay of η(r) and of S2(r) towards their values in the isotropic bulk is discussed, too.
RESUMO
Ionic liquid crystals (ILCs) are anisotropic mesogenic molecules which carry charges and therefore combine properties of liquid crystals, e.g. the formation of mesophases, and of ionic liquids, such as low melting temperatures and tiny triple-point pressures. Previous density functional calculations have revealed that the phase behavior of ILCs is strongly affected by their molecular properties, i.e. their aspect ratio, the loci of the charges, and their interaction strengths. Here, we report new findings concerning the phase behavior of ILCs as obtained by density functional theory and Monte Carlo simulations. The most important result is the occurrence of a novel, wide smectic-A phase [Formula: see text], at low temperature, the layer spacing of which is larger than that of the ordinary high-temperature smectic-A phase [Formula: see text]. Unlike the ordinary smectic S A phase, the structure of the [Formula: see text] phase consists of alternating layers of particles oriented parallel to the layer normal and oriented perpendicular to it.
RESUMO
The electrostatic interaction in ionic fluids is well known to give rise to a characteristic phase behavior and structure. Sometimes its long range is proposed to single out the electrostatic potential over other interactions with shorter ranges. Here the importance of the range for the phase behavior and the structure of ionic fluids is investigated by means of grandcanonical Monte Carlo simulations of the lattice restricted primitive model (LRPM). The long-ranged electrostatic interaction is compared to various types of short-ranged potentials obtained by sharp and/or smooth cutoff schemes. Sharply cutoff electrostatic potentials are found to lead to a strong dependence of the phase behavior and the structure on the cutoff radius. However, when combined with a suitable additional smooth cutoff, the short-ranged LRPM is found to exhibit quantitatively the same phase behavior and structure as the conventional long-ranged LRPM. Moreover, the Stillinger-Lovett perfect screening property, which is well known to be generated by the long-ranged electrostatic potential, is also fulfilled by short-ranged LRPMs with smooth cutoffs. By showing that the characteristic phase behavior and structure of ionic fluids can also be found in systems with short-ranged potentials, one can conclude that the decisive property of the electrostatic potential in ionic fluids is not the long range but rather the valency dependence.