Interfacial thermodynamics of spherical nanodroplets: Molecular understanding of surface tension via hydrogen bond network

Abstract: Surface tension plays a ubiquitous role in phase transitions including condensation or evaporation of atmospheric liquid droplets. Especially, understanding of interfacial thermodynamics of the critical nucleus of 1 nm scale is important for molecular characterization of the activation energy barrier of nucleation. Here, we investigate surface tension of spherical nanodroplets with both molecular dynamics and density functional theory, and find that surface tension decreases appreciably below 1 nm radius, whose analytic expression is consistently derived from the classic Tolman's equation. In particular, the free energy analysis of nanodroplets shows that the change of surface tension originates dominantly from the configurational energy of interfacial molecules, which is evidenced by the increasingly disrupted hydrogen bond network as the droplet size decreases. Our result can be applied to the interface-related phenomena associated with molecular fluctuations such as biomolecule adsorption at sub-nm scale where the macroscopic thermodynamic quantities are ill-defined.