Phase coexistence in [C22/C1MIm]+[NO3]- ionic-liquid mixtures and first-order phase transitions from homogeneous liquid to smectic B by varying the cation ratio

We perform molecular dynamics simulations to investigate the transition processes of [C-22/C(1)MIm](+)[NO3](-) binary mixtures by varying the cation ratio of C-22 to C-1 at a fixed temperature of 400 K. The cation ratio is tuned by ranging C-22 percentage from 0% to 100% with a fixed number of 4096 total simulated ion pairs. Our simulated-annealing results indicate that, at 400 K, pure C-1 is a homogeneous liquid whilst pure C-22 is an ionic liquid crystal (ILC) of smectic-B (SmB) type. With increasing C-22 percentage, the system goes through a first-order phase transition from homogeneous liquid to nano-fragment liquid in the range from 15% to 17.5%, during which some of the individual cationic alkyl side chains locally aggregate to form small bundles "floating" in the polar "solvent" composed of anions and cationic head groups. Although the side chains in each bundle are parallelly aligned, the bundles distribute randomly without a global orientation. As the C-22 percentage further increases, another first-order phase transition occurs to bring the system into the SmB ILC phase. Particularly, when the C-22 percentage is in the range from 45% to 50%, the SmB phase coexists with the liquid phase containing both individual and bundled alkyl side chains.