Interaction between hydrophobic surfaces with metastable intervening liquid

Molecular simulation is used to elucidate hydrophobic interaction at atmospheric pressure where liquid water between apolar walls is metastable with respect to capillary evaporation. The steep increase of the estimated activation barrier of evaporation with surface–surface separation explains the apparent stability of the liquid at distances more than an order of magnitude below the thermodynamic threshold of evaporation. Solvation by metastable liquid results in a short-ranged oscillatory repulsion which gives rise to an irreversible potential barrier between approaching walls. The barrier increases with external pressure in accord with measured pressure-induced slowing of conformational transitions of biopolymers with strong hydrophobic interactions. At a sufficiently small separation, the force abruptly turns attractive signaling nucleation of the vapor phase. This behavior is consistent with the cavitation-induced hysteresis observed in a number of surface–force measurements for strongly hydrophobic surfaces at ambient conditions. © 2001 American Institute of Physics. @DOI: 10.1063/1.1386926#