 Square-gradient theory of a liquid interface

A diffuse-interface free energy balances the bulk preference for coexisting compositions against a positive penalty for sharp composition gradients. For dimensionless composition $\varphi$, $f_b$ is a bulk energy density and $K$ has units of energy per length. Subtract the bulk coexistence common tangent to define $\Delta \omega (\varphi )$, with equal zero minima at the two compositions. A planar equilibrium profile obeys $K{\varphi }^{\prime \prime }=\Delta {\omega }^{\prime }(\varphi )$ and $K({\varphi }^{\prime }{)}^2/2=\Delta \omega (\varphi )$. Its surface tension is $\int K({\varphi }^{\prime }{)}^{2}dz$. As a thermodynamic critical point is approached, the composition contrast and bulk curvature vanish, the correlation length grows, and the intrinsic interface broadens. A scalar quartic domain wall gives the mean-field hyperbolic-tangent profile. Thermally excited capillary waves can broaden a measured profile further.