Attempts to extend the capillary-wave theory of fluid interfacial fluctuations to microscopic wavelengths, by introducing an effective wave-vector (q) -dependent surface tension σeff(q), have encountered difficulties. There is no consensus as to even the shape of σeff(q). By analyzing a simple density functional model of the liquid-gas interface, we identify different schemes for separating microscopic observables into background and interfacial contributions. In order for the backgrounds of the density-density correlation function and local structure factor to have a consistent and physically meaningful interpretation in terms of weighted bulk gas and liquid contributions, the background of the total structure factor must be characterized by a microscopic q-dependent length ζ(q) not identified previously. The necessity of including the q dependence of ζ(q) is illustrated explicitly in our model and has wider implications; i.e., in typical experimental and simulation studies, an indeterminacy in ζ(q) will always be present, reminiscent of the cutoff used in capillary-wave theory. This leads inevitably to a large uncertainty in the q dependence of σeff(q).
|Journal||Physical Review E: Statistical, Nonlinear, and Soft Matter Physics|
|Publication status||Published - 11 Mar 2015|