A molecular-dynamics study of sliding liquid nanodrops: Dynamic contact angles and the pearling transition

Hypothesis: That the behavior of sliding drops at the nanoscale mirrors that seen in macroscopic experiments, that the local microscopic contact angle is velocity dependent in a way that is consistent with the molecular-kinetic theory (MKT), and that observations at this scale shed light on the pearling transition seen with larger drops. Methods: We use large-scale molecular dynamics (MD) to model a nanodrop of liquid sliding across a solid surface under the influence of an external force. The simulations enable us to extract the shape of the drop, details of flow within the drop and the local dynamic contact angle at all points around its periphery. Findings: Our results confirm the macroscopic observation that the dynamic contact angle at all points around the drop is a function of the velocity of the contact line normal to itself, U(cm)Sin phi, where U-cm is the velocity of the drop's center of mass and 4) is the slope of the contact line with respect to the direction of travel. Flow within the drop agrees with that observed on the surface of macroscopic drops. If slip between the first layer of liquid molecules and the solid surface is accounted for, the velocity dependence of the dynamic contact angle is identical with that found previous MD simulations of spreading drops, and consistent with the MKT. If the external force is increased beyond a certain point, the drop elongates and a neck appears between the front and rear of the drop, which separate into two distinct zones. This appears to be the onset of the pearling transition at the tip of a macroscopic drop. The receding contact angle at the tip of the drop is far removed from its equilibrium value but non -zero and approaches a more-or-less constant critical value as the transition progresses. (C) 2019 Published by Elsevier Inc.