Journal
JOURNAL OF CHEMICAL PHYSICS
Volume 154, Issue 1, Pages -Publisher
AMER INST PHYSICS
DOI: 10.1063/5.0034314
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The research indicates that in ionic liquid crystals with specific properties, a wide smectic-A phase is formed, where the spatial distribution of mesogens with charged sites plays a crucial role in phase transitions, which is important for applications requiring conductivity channels for mobile ions.
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.
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