Capillary waves and the decay of density correlations at liquid surfaces

Wertheim predicted strong density-density correlations at free liquid surfaces, produced by capillary wave fluctuations of the interface [M. S. Wertheim, J. Chem. Phys. 65, 2377 (1976)JCPSA60021-960610.1063/1.433352]. That prediction has been used to search for a link between capillary wave (CW) theory and density functional (DF) formalism for classical fluids. In particular, Parry et al. have recently analyzed the decaying tails of these CW effects moving away from the interface as a clue for the extended CW theory [A. O. Parry, J. Phys.: Condens. Matter 28, 244013 (2016)JCOMEL0953-898410.1088/0953-8984/28/24/244013], beyond the strict long-wavelength limit studied by Wertheim. Some apparently fundamental inconsistencies between the CW and the DF theoretical views of the fluid interfaces arose from the asymptotic analysis of the CW signal. In this paper we revisit the problem of the CW asymptotic decay with a separation of local non-CW surface correlation effects from those that are a truly nonlocal propagation of the CW fluctuations from the surface towards the liquid bulk.We acknowledge support from the Spanish Secretariat for Research, Development and Innovation (Grants No. FIS2013-47350-C5 and No. FPU2015/0248) and the “Maria de Maeztu” Programme for Units of Excellence in R&D (Grant No. MDM-2014-0377)