Solute size effects on the solvation structure and diffusion of ions in liquid methanol under normal and cold conditions

Abstract

We have performed a series of molecular dynamics simulations of alkali metal (Li⁺, Na⁺, K⁺, Rb⁺, and Cs⁺) and halide (F^-, Cl^-, Br^-, and I^-) ions in liquid methanol at two different temperatures to investigate the effects of ion size on the hydration structure and diffusion of ions in methanol under normal and cold conditions. Simulations are also carried out for some of the larger cations such as I⁺, (CH₃)₄N⁺, and (C₂H₅)₄N⁺ and also neutral alkali metal atoms in methanol at both temperatures. With the increase of ion size, the diffusion coefficients of both positive and negative ions are found to show anomalous behavior. For cations, it is found that the maximum of the diffusion coefficient versus ion size curve occurs at the rather large cation of (CH₃)₄N⁺ unlike in water where the maximum occurs at the relatively smaller ion of Rb⁺. For halide ions, the anomalous behavior, i.e., the increase of diffusion with ion size, continues up to iodide ion and no maximum is observed. These results are in good agreement with experimental observations. The diffusion coefficients of neutral atoms are found to be greater in methanol than that in water and they decrease monotonically with solute size, whereas the diffusion coefficients of the corresponding ions are found to be smaller in methanol. Accordingly, an ion experiences a smaller Stokes friction and a higher dielectric friction in methanol than in water. These contrasting effects are believed to be responsible for the shift of the maximum of ion diffusion toward a larger ion size when compared with similar anomalous size dependence in liquid water.