Understanding Atomic-Scale Behavior of Liquid Crystals at Aqueous Interfaces

The ordered environment presented by liquid crystals at interfaces enables a range of novel functionalities that is only now beginning to be exploited in applications ranging from light focusing devices to biosensors. One key feature of liquid crystals is that molecular events occurring at an interface propagate over large distances through the bulk. In spite of their importance, our fundamental understanding of liquid crystal–water and liquid crystal–air interfaces remains limited. In this work, we present results from large-scale atomistic molecular dynamics simulations on the organization of the nematic and isotropic phases of the nitrile-containing mesogenic molecule 4-cyano-4′-pentylbiphenyl (5CB) in the vicinity of vacuum and aqueous interfaces. Hybrid boundary conditions are imposed by confining 5CB films between vacuum and an aqueous medium to examine how those two types of interfaces influence the specific structural arrangement and ordering of 5CB. Consistent with experiments, our results indicate that 5CB exhibits homeotropic anchoring at the vacuum interface, and planar alignment at aqueous interfaces. Two-dimensional molecular dynamics potential of mean force calculations and average polarization densities show that the polar nitrile group of 5CB remains hydrated near the aqueous interface, where it modulates the orientation of water molecules. Estimates of the anchoring strength reveal an oscillatory decay and a semilinear decay with distance from the interface in vacuum and water, respectively