Effect of Ion Rigidity on Physical Properties of Ionic Liquids Studied by Molecular Dynamics Simulation

In this work, we have performed molecular dynamics (MD) simulations to compare the structural and dynamical properties of three ionic liquids (ILs), 1-ethyl-3-methyl-imidazolium tetrafluorborate ([EMI+]­[BF4 –]), 1,1′-dimethyl-4,4′-bipyridinium bis­(tetrafluorborate) ([VIO2+]­[BF4 –]2), and 1,1′-dimethyl-4,4′-bipyridinium bis­(trifluoromethylsulfonyl)­imide (bistriflimide in short) ([VIO2+]­[Tf2N–]2), aiming to discover the influence of ion rigidity on the physical properties of ILs. [VIO2+] is more rigid than [EMI+], and [BF4 –] is more rigid than [Tf2N–]. [VIO2+]­[BF4 –]2 has an anion distribution different from the other two by the higher and sharper peaks in the cation–anion radial distribution functions, reflecting a close-packed local structure of anions around cations. [VIO2+]­[BF4 –]2 and [VIO2+]­[Tf2N–]2 have similar dynamics much slower than [EMI+]­[BF4 –], and [VIO2+]­[Tf2N–]2 shows a more isotropic molecular distribution than [VIO2+]­[BF4 –]2 and [EMI+]­[BF4 –]. Additionally, we have simulated two modified viologen-based ILs to reinforce our interpretations. We conclude from the above simulation results that the rigidity of anions influences the alignment of cations and that the rigidity of cations shows a large obstacle to their rotational capacity. Moreover, we have observed a slower diffusion of [VIO2+]­[BF4 –]2 due to the electrostatic correlations, which stabilizes the ion-cage effect.