Rapid onset of molecular friction in liquids bridging between the atomistic and hydrodynamic pictures

Abstract

Friction in liquids arises from conservative forces between molecules and atoms. Although the hydrodynamics at the nanoscale is subject of intense research and despite the enormous interest in the non-Markovian dynamics of single molecules and solutes, the emergence of friction from the atomistic scale so far could not be demonstrated. Here, we fill this gap based on frequencyresolved friction data from high-precision simulations of three prototypical liquids, including water. Combining with rigorous theoretical arguments, we show that friction in liquids is non-local in time and emerges abruptly at a characteristic frequency, beyond which viscous liquids appear as non-dissipative, elastic solids. At the same time, the molecules experience Brownian forces that display persistent correlations and long-lasting memory. A critical test of the generalised Stokes–Einstein relation, mapping the friction of single molecules to the viscoelastic response of the macroscopic sample, disproves the relation for Newtonian fluids, but substantiates it exemplarily for a supercooled liquid. The employed approach is suitable to yield novel insights into vitrification mechanisms and the intriguing mechanical properties of soft materials.