Heterogeneous Rotational Dynamics of Imidazolium-Based Organic Ionic Plastic Crystals

Organic ionic plastic crystals (OIPCs) are a unique class of materials that undergo orientational and conformational motions while maintaining a long-range ordered lattice structure. OIPCs have attracted attention because the rotational motions were known to accelerate the diffusion of mobile ions such as lithium ions. However, only a small number of combinations of cations and anions lead to OIPCs because the rotational motion may be restricted by both the molecular structure and the crystal class. In this work, we perform molecular dynamics simulations to study the effects of the molecular structure and the crystal class on the rotational motion and the phase transitions. We investigate four imidazolium-based ionic crystals: (1) 1-methyl-3-methylimidazolium hexafluorophosphate ([MMIM][PF₆]), (2) 1-methyl-3-methylimidazolium chloride ([MMIM][Cl]), (3) monoclinic 1-butyl-3-methylimidazolium chloride ([BMIM][Cl]), and (4) orthorhombic [BMIM][Cl] ionic crystals. We construct initial configurations of OIPCs by employing experimental crystalline structures. Then, we increase the temperature gradually and monitor the density and the radial distribution functions. We estimate the rotational van Hove correlation functions and find that molecules in plastic crystal phases undergo rotational hopping motions and OIPCs exhibit rotational dynamic heterogeneity significantly. The structure of anions and cations affect the phase transition of OIPCs. And the crystal class is also critical to the phase transition of OIPCs because the rotational motion of ions depends on the crystal class.