Microscopic Marangoni Flows Cannot Be Predicted on the Basis of Pressure Gradients

A concentration gradient along a fluid-fluid interface can cause flow. On a microscopic level, this so-called Marangoni effect can be viewed as being caused by a gradient in the pressures acting on the fluid elements or as the chemical-potential gradients acting on the excess densities of different species at the interface. If the interface thickness can be ignored, all approaches should result in the same flow profile away from the interface. However, on a more microscopic scale, the different expressions result in different flow profiles, only one of which can be correct. Here we compare the results of direct nonequilibrium molecular dynamics simulations with the flows that are generated by pressure and chemical-potential gradients. We find that the approach based on the chemical-potential gradients agrees with the direct simulations, whereas the calculations based on the pressure gradients do not.