The Missing Relationship between the Miscibility of Chiral Dopants and the Microscopic Dynamics of Solvent Liquid Crystals: A Molecular Dynamics Study

Nematic liquid crystals (LCs) are known to undergo a phase transition to chiral nematic LCs possessing helices upon doping with enantiomeric molecules known as chiral dopants. The relationship between the helical pitch ( p), the molar fraction (x), and the power of the chiral dopant to induce a helix in a nematic solvent ( beta M) is expressed as p = 1/(x center dot beta M). The helical pitch is easily controlled by the concentration of the chiral dopant when the dopant molecule is miscible with the host nematic LC. However, it has not yet been clarified what the miscibility of the chiral dopant molecules with the nematic LCs depends. Therefore, we performed all-atom molecular dynamics (MD) simulations for the system composed of both D and L isomers of a chiral dopant molecule dispersed in a nematic LC and investigated the relationship between the microdynamics of the chiral molecules and their miscibility with the nematic solvent. The miscibility of the chiral dopant molecules with the LC solvent was found to correlate with the diffusion coefficient of the LC solvent. In the system where the chiral dopant molecules with high miscibility were added, the diffusion coefficient of the LC solvents was comparable to that of the system in which the chiral molecule was not doped. Furthermore, it was confirmed that more elongated chiral dopants were more miscible with the nematic solvent consisting of calamitic molecules, and that these dopant molecules did not have a significant effect on the diffusion behavior of the LC molecules.