The development of a molecular theory of inhomogeneous fluids and, in particular, of the liquid–gas interface has received enormous interest in recent years; however, long-standing attempts to extend the concept of surface tension in mesoscopic approaches by making it scale dependent, although apparently plausible, have failed to connect with simulation and experimental studies of the interface that probe the detailed properties of density correlations. Here, we show that a fully microscopic theory of correlations in the interfacial region can be developed that overcomes many of the problems associated with simpler mesoscopic ideas. This theory originates from recognizing that the correlation function displays, in addition to a Goldstone mode, an unexpected hierarchy of resonances that constrain severely its structural properties. Indeed, this approach allows us to identify new classes of fully integrable models for which, surprisingly, the tension, density profile and correlation function can all be determined analytically, revealing the microscopic structure of correlations in all generalized van der Waals theories.
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We are grateful to F. Höfling for providing his simulation results and for discussions. A.O.P. acknowledges the EPSRC, UK, for grant EP/L020564/1 (Multiscale Analysis of Complex Interfacial Phenomena). C.R. acknowledges the support of grant FIS2015-66523-P (MINECO/FEDER, UE).
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