Molecular droplets vs bubbles: Effect of curvature on surface tension and Tolman length

J Wen and D Dini and HB Hu and ER Smith, PHYSICS OF FLUIDS, 33, 072012 (2021).

DOI: 10.1063/5.0057401

Droplets and bubbles are thought to be two sides of the same coin; this work determines how true this is at the molecular scale. Stable cylindrical nanodroplets and nanobubbles are obtained in Molecular Dynamics (MD) simulations with three-phase contact lines pinned by alternate hydrophobic and hydrophilic patterns. The surface tension and Tolman length for both types of curved interfaces are obtained with the Kirkwood-Buff method, based on the difference between normal and tangential pressure components. Both bubble and droplet cases are compared to the flat interface case for reference. Results show that the surface tension decreases linearly while the Tolman length increases linearly with the gas/liquid density ratio. By running a careful parameter study of the flat interface over a range of densities, the effect of the density ratio can be corrected isolating the effects of curvature on the surface tension and Tolman length. It is found that such effects start to be seen when the equimolar curvature radius goes down to 20 reduced Lennard-Jones (LJ) units. They have the same magnitude but act with opposite signs for nanodroplet and nanobubble interfaces. Considering effects of the density ratio and curvature, a fitted Tolman equation was obtained, which predicts the surface tension of a curved interface. Results obtained by the fitted Tolman equation agree well with those obtained by the MD simulations except at very small curvature radius (<10 reduced LJ units) due to the accumulation of the curvature dependence of the Tolman length.

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