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The Stokes-Einstein-Sutherland equation at the nanoscale revisited
The Stokes-Einstein-Sutherland (SES) equation is at the foundation of
statistical physics, relating a particle's diffusion coefficient and size with
the fluid viscosity, temperature and the boundary condition for the
particle-solvent interface. It is assumed that it relies on the separation of
scales between the particle and the solvent, hence it is expected to break down
for diffusive transport on the molecular scale. However, a number of
experimental studies showed a remarkable small, if any, violation of this
equation down to the size of a nm, where there is no scale separation. To
resolve this puzzle we combine analytical ultracentrifugation experiments and
molecular dynamics simulations to study the transport of buckminsterfullerene
C suspended in toluene at infinite dilution. We show that this system
clearly violates the conditions of slow momentum relaxation. Yet, through a
linear response to a constant force, we show both in experiments and in
simulations that the SES equation can be recovered in the long time limit with
no more than 4% uncertainty. This nonetheless requires partial slip on the
particle interface, extracted consistently from all the data. Our results,
thus, resolve a long-standing discussion on the validity and limits of the SES
equation at the molecular scale