Molecular Dynamics Simulation Study on Heterogeneous Structure, Rheology, and Dynamic Correlation of Concentrated Aqueous Solutions of a Lithium Salt.

Molecular dynamics simulation of an aqueous solution of lithium bis(trifluoromethanesulfonyl)amide, LiTFSA, was performed at various concentrations to relate its liquid structure with frequency-dependent shear viscosity. The structure factor exhibited a low-q peak that represents a heterogeneous structure composed of water and anion domains, and the lithium ion existed in the water domain due to its strong hydration. The frequency-dependent shear viscosity showed bimodal relaxation, and the relative contribution of the slower mode increased with an increase in the salt concentration. The cross-correlation between the shear stress and the two-body density revealed that the slower viscoelastic mode is assigned to the dynamics of the heterogeneous structure, and the assignment was also confirmed by the comparison between the viscoelastic and structural relaxations. The collective translational motions of the cation and the anion showed a strong negative correlation in a concentrated solution, reflecting the heterogeneous domain structure.