Effects of droplet size and surfactants on anchoring in liquid crystal nanodroplets

Liquid crystal (LC) droplets attract scientific attention for many advanced applications, including, but not limited to optical and sensing devices. To aid experimental advancements, theoretical calculations have been conducted to quantify molecular driving forces responsible for the collective behaviour of LC molecules within micrometer-size spherical droplets. To quantify the LC molecular anchoring within spherical physical constraints, molecular simulations at atomistic resolution would be useful. In an attempt to bridge the gap between computational capabilities and experimental interest, coarse-grained simulations are used here to study nematic LC nanodroplets dispersed in water. A LC phase diagram is generated as a function of droplet size and temperature. The effect of adding surfactants on LC anchoring was quantified, considering surfactants of different molecular features. When few surfactants are present, they self-assemble at the droplet boojums regardless of their molecular features. All surfactants tested shifted LC orientation from bipolar to uniaxial. When the surfactants have a hydrophobic tail of sufficient length, they cause deviations from the spherical symmetry of LC droplets. Increasing the concentration of these surfactants enhances such phenomenon. Simulations were also conducted to assess the ability of the surfactants to prevent the agglomeration between two LC droplets. The results showed that coalescence was inevitable at all conditions and suggested that large enough surfactant concentrations can delay the phenomenon. The results presented could be helpful for designing novel surface-active compounds to develop optical and/or sensing devices at conditions in which mutual solubility between water and LCs is low.