The origin of the Stokes–Einstein relation in simple dense liquids
Here, we investigate the origin of the universal relation between structural relaxation and diffusion in simple dense liquids, known as the Stokes–Einstein (SE) relation. The fact that this relation, originally derived from a hydrodynamic model of a macroscopic particle in a viscous medium, can describe the microscopic-scale liquid dynamics still eludes understanding. We introduce a new universal measure of structural relaxation in a system of N identical particles based on an explicit decomposition of the configuration space into N! congruent convex polyhedra. This measure makes it possible to quantify the correlation between two distinct particle configurations in terms of their minimal Euclidean distance, optimized with respect to particle permutations. Using this measure alongside a model of independent random walkers under the single-occupancy constraint, we derive a master equation that quantifies the SE relation. It allows us to demonstrate that the universal relation between structural relaxation and diffusion in simple dense liquids is caused by two conditions: (a) the confinement of the dominant density fluctuations to the first coordination shell, manifested by de Gennes narrowing, and (b) Gaussianity of the diffusion process; the former is shown to be violated in low-density fluids, and the latter is known to be violated in supercooled liquids.