Molecular Dynamics Approach for Predicting Helical Twisting Powers of Metal Complex Dopants in Nematic Solvents

Nematic liquid crystals of small molecules are known to transform into chiral nematic liquid crystals with supramolecular helical structures upon doping with enantiomeric compounds. Although this phenomenon is well established, the basic mechanism is still unclear. We have previously examined metal complexes with Δ and Λ chiralities as dopants in nematic liquid crystals and have found that slight differences in the molecular structure determine the handedness of the induced helical structure. In this study, we investigated the microscopic arrangement of liquid crystal molecules around metal complex dopants with the aid of molecular dynamics (MD) simulations. There are several restrictions to performing MD simulations of the chiral nematic system; for example, one pitch of the helix usually exceeds one side of an applicable periodic boundary box (∼10(2) nm). In view of these simulation problems, we therefore examined racemic systems in which a pair of Δ- and Λ-isomers of the chiral dopant is mixed with liquid crystal molecules. We selected two different octahedral ruthenium complexes as the chiral dopant molecules. As a result, we accurately calculated the ordering matrix that is essential parameter to estimate the helical twisting power of the chiral dopant based on the surface chirality model. Since the microscopic ordering is experimentally hard to be determined, our new approach with using MD simulations accurately deduced the ordering matrix and, with the aid of the surface chirality model, gave reasonable values for the helical twisting powers of each complex.