Molecular theory of surface tension

A molecular theory of surface tension is developed for a liquid–gas interface of a one component system. The Helmholtz free energy, the quantity minimized in the van der Waals approach, is obtained here from a rigorous expansion in powers of derivatives of density ρ and is minimized by the calculus of variations. The coefficient A (ρ) of the term in the square of the density gradient is (kT/6) ℱdr r2C (r,ρ), C being the direct correlation function. In the case in which ρ varies in one direction x only, the solution of the Euler–Lagrange differential equation is analyzed in detail. This describes the cases of a single phase and of two coexisting phases and leads to the equal area Maxwell construction. The effect of an external field on the solution is discussed. The Euler–Lagrange differential equation provides a differential statement of Bernoulli’s theorem. In a three dimensional treatment the stress tensor formula is obtained from the corresponding Euler–Lagrange partial differential equation. A (differential) generalization of the Young–Laplace equation for a spherical interface is also derived. In addition, metastable regions are described and interpreted. The stress tensor for a system in the presence of any kind of conservative force field is also obtained.