Critical Drying of Liquids.

Abstract

We report a detailed simulation and classical density functional theory study of the drying transition in a realistic model fluid at a smooth substrate. This transition (in which the contact angle θ→180°) is shown to be critical for both short-ranged and long-ranged substrate-fluid interaction potentials. In the latter case critical drying occurs at exactly zero attractive substrate strength. This observation permits the accurate elucidation of the character of the transition via a finite-size scaling analysis of the density probability function. We find that the critical exponent ν_{∥} that controls the parallel correlation length, i.e., the extent of vapor bubbles at the wall, is over twice as large as predicted by mean field and renormalization group calculations. We suggest a reason for the discrepancy. Our findings shed new light on fluctuation phenomena in fluids near hydrophobic and solvophobic interfaces.