The local structure factor near an interface; beyond extended capillary-wave models
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Accepted version
Author(s)
Parry, AO
Evans, R
Rascon, R
Type
Journal Article
Abstract
We investigate the local structure factor S(z; q) at a free liquid-gas interface in systems with
short-ranged intermolecular forces and determine the corrections to the leading-order, capillarywave-like,
Goldstone mode divergence of S(z; q) known to occur for parallel (i.e., measured along
the interface) wavevectors q → 0. We show from explicit solution of the inhomogeneous OrnsteinZernike
equation that for distances z far from the interface, where the profile decays exponentially,
S(z; q) splits unambiguously into bulk and interfacial contributions. On each side of the interface,
the interfacial contributions can be characterised by distinct liquid and gas wavevector dependent
surface tensions, σl(q) and σg(q), which are determined solely by the bulk two-body and three-body
direct correlation functions. At high temperatures, the wavevector dependence simplifies and is
determined almost entirely by the appropriate bulk structure factor, leading to positive rigidity
coefficients. Our predictions are confirmed by explicit calculation of S(z; q) within square-gradient
theory and the Sullivan model. The results for the latter predict a striking temperature dependence
for σl(q) and σg(q), and have implications for fluctuation effects. Our results account quantitatively
for the findings of a recent very extensive simulation study by H¨ofling and Dietrich of the total
structure factor in the interfacial region, in a system with a cut-off Lennard-Jones potential, in
sharp contrast to extended Capillary-Wave models which failed completely to describe the simulation
results.
short-ranged intermolecular forces and determine the corrections to the leading-order, capillarywave-like,
Goldstone mode divergence of S(z; q) known to occur for parallel (i.e., measured along
the interface) wavevectors q → 0. We show from explicit solution of the inhomogeneous OrnsteinZernike
equation that for distances z far from the interface, where the profile decays exponentially,
S(z; q) splits unambiguously into bulk and interfacial contributions. On each side of the interface,
the interfacial contributions can be characterised by distinct liquid and gas wavevector dependent
surface tensions, σl(q) and σg(q), which are determined solely by the bulk two-body and three-body
direct correlation functions. At high temperatures, the wavevector dependence simplifies and is
determined almost entirely by the appropriate bulk structure factor, leading to positive rigidity
coefficients. Our predictions are confirmed by explicit calculation of S(z; q) within square-gradient
theory and the Sullivan model. The results for the latter predict a striking temperature dependence
for σl(q) and σg(q), and have implications for fluctuation effects. Our results account quantitatively
for the findings of a recent very extensive simulation study by H¨ofling and Dietrich of the total
structure factor in the interfacial region, in a system with a cut-off Lennard-Jones potential, in
sharp contrast to extended Capillary-Wave models which failed completely to describe the simulation
results.
Date Issued
2016-04-26
Date Acceptance
2015-12-08
Citation
Journal of Physics: Condensed Matter, 2016, 28
ISSN
1361-648X
Publisher
IOP Publishing
Journal / Book Title
Journal of Physics: Condensed Matter
Volume
28
Copyright Statement
© 2015 IOP Publishing Ltd.
Sponsor
Engineering & Physical Science Research Council (EPSRC)
Grant Number
EP/J009636/1
Subjects
Fluids & Plasmas
0204 Condensed Matter Physics
0912 Materials Engineering
1007 Nanotechnology
Publication Status
Published
Article Number
244013