The excess equimolar radius of liquid drops

Abstract

The curvature dependence of the surface tension is related to the excess equimolar radius of liquid drops, i.e., the deviation of the equimolar radius from that defined with the macroscopic capillarity approximation. Based on the Tolman [J. Chem. Phys. 17, 333 (1949)] approach and its interpretation by Nijmeijer et al. [J. Chem. Phys. 96, 565 (1991)], the surface tension of spherical interfaces is analysed in terms of the pressure difference due to curvature. In the present study, the excess equimolar radius, which can be obtained directly from the density profile, is used instead of the Tolman length. Liquid drops of the truncated-shifted Lennard-Jones fluid are investigated by molecular dynamics simulation in the canonical ensemble, with equimolar radii ranging from 4 to 33 times the Lennard-Jones size parameter sigma. In these simulations, the magnitudes of the excess equimolar radius and the Tolman length are shown to be smaller than sigma/2. Other methodical approaches, from which mutually contradicting findings have been reported, are critically discussed, outlining possible sources of inaccuracy.

References in corpus (4)

• Curvature Dependence of Surface Free Energy of Liquid Drops and Bubbles: A Simulation Study
• Evidence for the role of fluctuations in the thermodynamics of nanoscale drops and the implications in computations of the surface tension
• Modification of the classical nucleation theory based on molecular simulation data for surface tension, critical nucleus size, and nucleation rate
• Hard-Sphere Fluids in Contact with Curved Substrates

Cited by in corpus (9)

• A perspective on the interfacial properties of nanoscopic liquid drops
• Curvature-dependence of the liquid-vapor surface tension beyond the Tolman approximation
• The influence of the liquid slab thickness on the planar vapor-liquid interfacial tension
• Direct Simulations of Homogeneous Bubble Nucleation: Agreement with CNT and no Local Hot Spots
• Density Functional Theory of a Curved Liquid-Vapour Interface: Evaluation of the rigidity constants
• Homogeneous SPC/E water nucleation in large molecular dynamics simulations
• Tolman lengths and rigidity constants from free-energy functionals -- General expressions and comparison of theories
• Steady-State Homogeneous Nucleation and Growth of Water Droplets: Extended Numerical Treatment
• Reexamination of Tolman's law and the Gibbs adsorption equation for curved interfaces