Published online by Cambridge University Press: 26 March 2008
It is now well-established that the liquid adjacent to a solid need not be stationary – it can slip. How this slip occurs is unclear. We present molecular-dynamics (MD) simulation data and results from an analytical model which support two mechanisms of slip. At low levels of forcing, the potential field generated by the solid creates a ground state which the liquid atoms preferentially occupy. Liquid atoms hop through this energy landscape from one equilibrium site to another according to Arrhenius dynamics. Visual evidence of the trajectories of individual atoms on the solid surface supports the view of localized hopping, independent of the dynamics outside a local neighbourhood. We call this defect slip. At higher levels of forcing, the entire layer slips together, obviating the need for localized defects and resulting in the instantaneous motion of all atoms adjacent to the solid. The appearance of global slip leads to an increase in the number of slipping atoms and consequently an increase in the slip length. Both types of slip observed in the MD simulations are described by a dynamical model in which each liquid atom experiences a force from its neighbouring liquid atoms and the solid atoms of the boundary, is sheared by the overlying liquid, and damped by the solid. In agreement with the MD observations, this model predicts that above a critical value of forcing, localized slipping occurs in which atoms are driven from low-energy sites, but only if there is a downstream site which has been vacated. Also as observed, above a second critical value, all the liquid atoms adjacent to the wall slip. Finally, the dynamical equation predicts that at extremely large values of forcing, the slip length approaches a constant value, in agreement with the MD simulation results.