Shear Thinning and Nonlinear Structural Deformation of Ionic Liquids with Long Alkyl Chains Studied by Molecular Dynamics Simulation

Nonequilibrium molecular dynamics (MD) simulation was performed on imidazolium-based ionic liquids of two different alkyl chain lengths, and shear-rate-dependent viscosity was evaluated. Compared with the frequency-dependent linear shear viscosity determined by equilibrium MD simulation, shear thinning occurs at the shear rate several times lower than that predicted by the Cox-Merz rule. The deformation of the structure factor was also evaluated as the function of shear rate. The onset of shear thinning corresponds to that of the nonlinearity in the deformation of the charge-alternation mode in both ionic liquids, which is in harmony with the result of our previous work that the shear relaxation of ionic liquids is mainly coupled to the structural relaxation of the charge-alternation mode. In the presence of the polar-nonpolar domain structure characteristic to ionic liquids with a long alkyl chain, in particular, the nonlinearity in the domain mode begins within the Newtonian regime of shear viscosity.