Hydrophobic Drying and Hysteresis at Different Length Scales by Molecular Dynamics Simulations

YJ Lei and YS Leng, LANGMUIR, 28, 3152-3158 (2012).

DOI: 10.1021/la203646f

We performed molecular dynamics simulations to investigate hydrophobic interactions between two parallel hydrophobic plates immersed in water. The two plates are separated by a distance D ranging from contact to a few nanometers. To mimic the attractive hydrophobic force measurement in a surface force experiment, a driving spring is used to measure the hydrophobic force between two hydrophobic plates. The force distance curves, in particular the force variations from spontaneous drying to hydrophobic collapse are obtained. These details are usually not accessible in the surface force measurement due to the unstable jump into contact. The length scale effect on the hydrophobic drying during normal approach and the hydrophobic hysteresis during retraction has been studied. We find that the critical distance at which a spontaneous drying occurs is determined by the shorter characteristic dimension of the plate, whereas the hydrophobic hysteresis is determined by the longer characteristic dimension of the plate. The variations of the potential of mean force versus separation during approach and retraction are also calculated. The results show that water confined between two parallel hydrophobic plates is in a thermodynamic metastable state. This comparably high energy state leads to the spontaneous drying at some critical distance.

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