Melting point trends and solid phase behaviors of model salts with ion size asymmetry and distributed cation charge.

Abstract

The melting point trends of model salts composed of coarse grain ions are examined using NPT molecular dynamics simulations. The model salts incorporate ion size asymmetry and distributed cation charge, which are two common features in ionic liquids. A series of single-phase and two-phase simulations are done at set temperatures with 50 K intervals for each salt, and the normal melting point is estimated within 50 K. The melting point trends are then established relative to a charge-centered, size symmetric salt with a normal melting point between 1250 K and 1300 K. We consider two sets of size asymmetric salts with size ratios up to 3:1; the melting point trends are different in each set. The lowest melting point we find is between 450 K and 500 K, which is a reduction of over 60% from the charge-centered, size symmetric case. In both sets, we find diversity in the solid phase structures. For all size ratios with small cation charge displacements, the salts crystallize with orientationally disordered cations. When the partial cation charge is far enough off-center in salts with ion size ratios near 1:1, the salts can become trapped in glassy states and have underlying crystal structures that are orientationally ordered. At ion size ratios near 3:1, the salts with large cation charge displacements show premelting transitions at temperatures as low as 300 K. After the premelting transition, these salts exist either as fast ion conductors, where the smaller anions move through a face centered cubic (fcc) cation lattice, or as plastic crystals, where ion pairs rotate on a fcc lattice.