Molecular Origin of Driving-Dependent Friction in Fluids

The friction coefficient of fluids may become a function of the velocity at increased external driving. This non-Newtonian behavior is of general theoretical interest and of great practical importance, for example, for the design of lubricants. Although the effect has been observed in large-scale atomistic simulations of bulk liquids, its theoretical formulation and microscopic origin are not well understood. Here, we use dissipation-corrected targeted molecular dynamics, which pulls apart two tagged liquid molecules in the presence of surrounding molecules, and analyze this nonequilibrium process via a generalized Langevin equation. The approach is based on a second-order cumulant expansion of Jarzynski's identity, which is shown to be valid for fluids and therefore allows for an exact computation of the friction profile as well of the underlying memory kernel. We show that velocity-dependent friction in fluids results from an intricate interplay of near-order structural effects and the non-Markovian behavior of the friction memory kernel. For complex fluids such as the model lubricant C₄₀H₈₂, the memory kernel exhibits a stretched-exponential long-time decay, which reflects the multitude of timescales of the system.