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Computer modelling of the surface tension of the

gas–liquid and liquid–liquid interface
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Cite this: DOI: 10.1039/c5cs00736d

Aziz Ghoufi,a Patrice Malfreyt*b and Dominic J. Tildesleyc

Received 25th September 2015
DOI: 10.1039/c5cs00736d
www.rsc.org/chemsocrev
This review presents the state of the art in molecular simulations of interfacial systems and of the
calculation of the surface tension from the underlying intermolecular potential. We provide a short
account of different methodological factors (size-effects, truncation procedures, long-range corrections
and potential models) that can affect the results of the simulations. Accurate calculations are presented
for the calculation of the surface tension as a function of the temperature, pressure and composition by
considering the planar gas–liquid interface of a range of molecular fluids. In particular, we consider the
challenging problems of reproducing the interfacial tension of salt solutions as a function of the salt
molality; the simulations of spherical interfaces including the calculation of the sign and size of the
Tolman length for a spherical droplet; the use of coarse-grained models in the calculation of the
interfacial tension of liquid–liquid surfaces and the mesoscopic simulations of oil–water–surfactant
interfacial systems.

1 Introduction
1.1 The surface tension
The surface tension arises from the unbalanced attractive forces
at an interface, where the density of the system is changing
rapidly. The surface appears to be covered with a stretched
elastic membrane. For the vapour–liquid interface of water, the
surface tension is high (72.8 mN m1 at 20 1C), and small
objects that are denser than water are able to float or move along
the surface. An understanding and control of the surface tension
is at the heart of many important industrial and practical
processes, for example: the control of detergency through the
addition of surface active molecules (surfactants);1 enhanced oil
recovery from reservoirs through the injection of dilute solutions
to reduce the surface tension;2 the phenomena of wetting and
spreading in the application of coatings;3 and the separation of
hydrophilic and hydrophobic materials using froth flotation.4
Formally the surface tension of a liquid is the force per unit
length that opposes the expansion of the surface area. For a
system at constant volume, temperature and composition
 
@A
g¼
@A N;V;T
a
Institut de Physique de Rennes, UMR CNRS 6251, Université Rennes 1,
263 avenue du Général Leclerc, 35042 Rennes, France
b
Institut de Chimie de Clermont-Ferrand, ICCF, CNRS, UMR 6296, Université Clermont
Auvergne, Université Blaise Pascal, BP 10448, F-63000 Clermont-Ferrand, France.
E-mail: Patrice.Malfreyt@univ-bpclermont.fr; Tel: +33 473407204
c
CECAM École Polytechnique Fédérale de Lausanne, Batochime BCH 3101,
CH 1015 Lausanne, Switzerland
where A is the Helmholtz free energy and A is the surface area.
The corresponding expression at constant pressure involves the
Gibbs free energy G
 
@G
g¼ : (2)
@A N;P;T
The surface tension can be measured experimentally by a
variety of techniques including the Du Noy ring method, the
pendant drop method and the Wilhelmy plate method.5
However, one of the goals of modern liquid-state theory
has been the accurate prediction of g from a knowledge
of the underlying intermolecular potential functions for
mixtures over a broad range of temperatures and pressures.
The powerful technique of computer simulation can be
brought to bear on this problem and in this review, we will
explore the progress that has been made towards this goal in
the last 40 years.
1.2 Statistical mechanics of the vapour–liquid interface
The connection between the underlying intermolecular potential
and the surface tension of an interface is made through the
(1)
statistical mechanics of inhomogeneous systems.6–8
For an inhomogeneous fluid in the canonical ensemble, the
structure at the interface is essentially described by the singlet
and pair distribution functions. For a fluid of N atoms at a
temperature T
Ð Ð
ð1Þ    expðbVÞdrðN1Þ
r ðr1 Þ ¼ N Ð Ð (3)
   expðbVÞdrðNÞ

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and
Ð Ð
   expðbVÞdrðN2Þ
rð2Þ ðr1 ; r2 Þ ¼ NðN  1Þ Ð Ð (4)
   expðbVÞdrðNÞ
Aziz Ghoufi received his PhD degree
in physical chemistry from the
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University Blaise Pascal, Clermont-
Ferrand, France, in 2006. After two
Postdoctoral stages in Institut
Francais du Pétrole, Paris, France
and in Institut Charles Gerhardt,
Montpellier, France, Aziz Ghoufi
joined in 2008 the physics institute
of Rennes (Institut de Physique de
Rennes, IPR) at the University of
Rennes1 (UR1). Aziz Ghoufi
Aziz Ghoufi currently works in ‘‘Nanosciences
Materials’’ department at IPR. His
research aims at understanding how confinement at the nanoscale
deeply modifies the phase diagram, the molecular dynamics, the flow
or self-assembly conditions of fluids. He aims at gaining a better
understanding of the microscopic mechanisms that control the
nanostructuration of confined fluids. His research interests include the
development and applications of advanced molecular and mesoscale
simulation techniques to model heterogeneous systems and to
understand the confinement effects of liquids and gases in the
nanoporous medium.
Patrice Malfreyt obtained his PhD in
Physical Chemistry on computer
modelling in 1995 from the
University Blaise Pascal, Clermont-
Ferrand, France. After a postdoctoral
stage at Imperial College (London),
he joined the group of
Thermodynamics of Clermont-
Ferrand where he is professor
since 2004. He is the head of the
group of ‘‘Molecular architectures
at interfaces’’ at the Institute of
Patrice Malfreyt Chemistry of Clermont-Ferrand
(ICCF) and he is vice-president
of the Physical Chemistry Division of the French Chemical Society
(SCF). His research is dedicated to the development of
methodologies for simulations of interfacial systems and of multi-
scale simulations for the study of thermodynamic and mechanical
properties of polymers at interfaces.
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where V is the total potential energy of the fluid, dr(N) = dr1  drN,
where dr1 is the volume element for atom 1, and b = 1/kBT, where kB
is the Boltzmann constant. r(1) and r(2) are related through the first
equation in the YBG hierarchy.9
For the planar vapour–liquid interface the cylindrical symmetry
allows us to express these distribution functions in terms of the
height of the atoms zi, and zj, and the distance sij parallel to the
planar interface (or equivalently through the variables {zi, zj, rij}
or {zi, cos yij, rij}). The geometry of the planar interface is shown
in Fig. 1.
In an inhomogeneous system the pressure is a second-rank
tensor. At equilibrium
rp = 0. (5)
Fig. 1 The geometry of the planar interface.
Dominic Tildesley received his BSc
in Chemistry from Southampton
University in 1973 and his DPhil
from Oxford University in 1977.
After postdoctoral positions at
Pennsylvania State University,
Cornell and Oxford, he joined the
Chemistry Department at
Southampton University in 1981.
He was awarded the Chair of
Theoretical Chemistry at
Southampton in 1990. In 1998
Dominic J. Tildesley Dominic joined Unilever Research
Port Sunlight as the Head of the
Physical Sciences Group. In 2003 he became Chief Scientist for
Unilever’s Home and Personal Care Division. He retired from
Unilever in June 2012. He moved to Switzerland in January 2013, to
become Director of CECAM (Centre Européen de Calcul Atomique et
Moléculaire) based in Lausanne in Switzerland. He is currently
Professor Titulaire at the École Polytechnique Fédérale de Lausanne.
His research interests include the statistical mechanics of liquids,
computer modelling of complex fluid, simulation of adsorption and
application of high performance computing to industrial problems.
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The pressure tensor p is diagonal and for a planar interface

it is only a function of z. The independent components are
1 
pN = pzz(z), the normal component, and pT ¼ pxx þ pyy , the
2
tangential component.
Extending the well known virial equation for the pressure of a
homogeneous fluid is not straightforward. There is no unique way
of deciding whether the force between two atoms 1 and 2 con-
tributes to the stress across a microscopic element of the fluid
at a particular z. For pairwise additive potentials Schofield and
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Henderson10 have shown that the pressure tensor can be written as

Fig. 2 The affine transformations required in the test-area method for
*  ð +
N X
X N ra the calculation of g: (a) A decrease in the surface area at constant V to
ij dv rij
pab ðrÞ ¼ kB TrðrÞdab  dl b dðr  lÞ (6) the perturbed system (blue); (b) an increase in the surface area at
r drij Cij
i j 4 i ij constant V, to the perturbed system (red). Note in both cases the atom
positions are scaled between the reference system and the final system,
where Cij is any contour joining ri to rj, dab is the Kronecker delta, v(rij) see eqn (15).
is the potential between atoms i and j and d is the Dirac delta
function. There are infinitely many ways of choosing the contour
from i to j. Irving and Kirkwood11 consider a straight line between the where DV ¼ V 1  V 0 , the potential energy difference between
two atoms. An alternative contour due to Harasima12 extends from i the perturbed and the reference system, is calculated over the
parallel to the plane of the surface and then directly down to j. These states of the reference system. Note that V 1 is calculated by
different contours all lead to the same value of the normal pressure, scaling all of the atom positions with the box. Small scalings of
but can give rise to different values of the tangential pressure. DA=A0  5  104 produce accurate values for g.18 The test-
The surface tension, g can be calculated from the pressure tensor. area method avoids the calculation of the pressure tensor and
ð þ1 is not limited to pairwise additive potentials. This method
g¼ dz½ pN ðzÞ  pT ðzÞ (7) represents then an interesting alternative for the calculation
1 of the surface tension with many body interactions.
where pN and pT are the normal and tangential components of the These formulae for the surface tension can be readily
pressure. The limits of this integral can be truncated at values of z extended to molecular and ionic fluids, where the forces are
within the vapour and liquid where the integrand is zero. g is long-range, and to interfaces of different shapes, such as the
independent of the choice of contour chosen to define p. spherical droplet or the solid–liquid interface. We will discuss
The surface tension can also be obtained directly by calculating the extensions in the later sections of this review or direct the
the change in the free energy or thermodynamic potential13,14 with reader to the original references for the appropriate equations.
surface area at constant volume. Since the planar interface is two dimensional, it is char
ð ð   acterized by a strong asymmetry in the intermolecular forces. In
1 þ1 3z122 0 the bulk phases, there is a force balance between the attractive
g¼ dz1 dr12 r12  v ðr12 Þrð2Þ ðr1 ; r2 Þ (8)
4 1 r12 and repulsive forces due to the symmetry around a given
where v0 (r) is the first derivative of the intermolecular potential molecule. In the liquid–vapour interfacial region, for example,
with respect to r. Eqn (8) is formally equivalent to eqn (7). the surface tension is explained by the pressure anisotropy of
The expressions given in eqn (6) and (8) make the assumption the attractive forces since the repulsive forces are isotropic and
of pairwise additivity. A general statistical expression of the surface not sensitive to the changes in the structure of the liquid
tension15 has been derived by Grant and Desai in 1980 for many around a molecule.19 In the case of water–oil interfaces modified
body interaction potential models. For example, the Kirkwood– by the presence of surfactants for example, the surfactant
Buff expression of eqn (8) has been generalized by Toxvaerd to molecules adsorb at the interface with specific orientations
include the three body contributions.16 and conformations in order to minimize their free energy: the
The third method for calculating g is the test area method of resulting conformation typically has the hydrophilic part of the
Gloor et al.17 From the thermodynamic definition of g, eqn (1), surfactant interacting with the water phase whereas the hydro-
we have phobic part of the surfactant is exposed to the oil phase.
 
DA
g ¼ lim : (9) 1.3 Computer simulation of c
DA!0 DA NVT

The methods of computer simulation are now widely used to

In a reference system (0) containing an interface of A ¼ 2Lx Ly ,
evaluate the averages discussed in Section 1.2. They include the
we make an imaginary change to the area at constant V of
Metropolis Monte Carlo method and molecular dynamics for
DA ¼ A1  A0 as shown in Fig. 2 then,
atomistic models of the intermolecular forces, and Brownian
kB T dynamics and dissipative particle dynamics for more coarse-
g ¼ lim  lnhexpðbDVÞi0 (10)
DA!0 DA grained models.20,21

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Fig. 3 (a) Radial density profile r(r) of a spherical interface where r is the
distance from the centre of mass; (b) density profile r(z) of a planar
interface where z is the z-position along the axis normal to the surface.
The extension of these simulation methods from the homo-
geneous liquid phase to liquid–vapour and liquid–liquid inter-
faces has been well documented.6–8 For example, to simulate
the fluid–vapour interface, we would begin with the simulation
of the bulk fluid close to the coexisting liquid density in a cubic
box V = Lx3. Additional empty boxes would be added to the top
and bottom of the equilibrated liquid to create a box, Lz = 5Lx, 
Lx  Lx. The new, extended periodic system is simulated
forward until two stable interfaces are established, each of area
A = Lx2. The stability of these interfaces is monitored using
the single particle density profile r(z), see Fig. 3b. Similar
techniques for studying liquid droplets in coexistence with
their vapour can be employed. A droplet can be set up at the
centre of a much larger periodic box and the liquid allowed to
come to equilibrium with its own vapour, or the spherical
droplet and vapour can be surrounded by a soft repulsive wall
of spherical symmetry to confine the droplet. Properties such as
the density and pressure profiles, see Fig. 3a, are calculated
with respect to the centre of mass of the droplet, which can
change during the course of the simulation.
The techniques of establishing a microscopic interface by
simulation works well for temperatures ca. 10% below the
critical point of the fluid. Close to the critical point it is not
possible to stabilise the interface which becomes broader and
more diffuse. Under these circumstances, the technique of
choice is to simulate a single phase in the grand-canonical
ensemble and estimate the distribution function of the number
of atoms as the gas and liquid appear spontaneously in the
same box. g can be calculated for a series of simulations of
different box sizes from the distribution function rmVT(N,L) and
extrapolated to the limit of large box lengths.22 The transition-
matrix Monte Carlo (TMMC) method has also been applied
with the finite-size scaling to calculate the surface tension of
pure Lennard-Jones fluids23 and binary Lennard-Jones mixtures.24
The liquid–vapor interfaces of a mixture of water and butanol
molecules has been investigated by configurational-bias Monte
Carlo simulations in the Gibbs ensemble.25
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Away from the critical point, the surface tension can be
calculated using any one of the three methods described in
Section 2.1.
If the potential is truncated, a long-range correction has to
be added to g often using a mean-field approach. Recent
studies indicate that because of the inhomogeneity in the
density, it may be better to include the long-range correction
at each step in the simulation and we will return to this point.
Considerable progress has been made in the simulation of
surface tension over the last thirty years. The initial simulation
of the gas–liquid interface for atoms has been extended to
molecular fluids including water, and to mixtures, and particularly
ionic liquids. Simulations at the planar interface have been
extended to spherical droplets of atomic and molecular fluids.
Simulations of the solid–liquid and liquid–liquid interfaces have
also been performed. In all of these cases the calculation of g has
proved a useful way of making contact between the experiment
and simulation. We have tried to capture this chronology and the
corresponding references in Fig. 4.
At this point, we have a variety of different routes to g, there
are powerful and generic simulation packages that can be
readily adapted to include these methods, computer speeds
continue to increase following Moore’s law towards exa-flop
computing in 2020. So what is preventing us from achieving our
goal of the prediction of g?
There are essentially three main barriers that we wish to
explore in this review. First, the calculation of g is sensitive to
many of the technical features of the simulation. These include:
the effect of the finite size in the plane of the interface and the
corresponding suppression of the long wavelength capillary
waves; the size of the simulation box in the direction normal
to the surface and the possible interference between liquid
slabs in the periodic boundary conditions; the effect of the cut-off
in the potential functions; and the inclusion of the long-range
corrections when the system contains charges and dipoles. We will
demonstrate that, at least in the case of the planar interface, these
are now under control.
Secondly, once we are certain that is possible to calculate g
accurately and within a predictable error bound, we must be
concerned about the quality of the underlying potential models
that we are using in the simulation. The ability of the potential
model to predict the coexisting liquid and vapour densities is
an essential prerequisite for the accurate prediction of the
surface tension. In some cases, the effective two-body potentials
that have proved so useful in simulating homogeneous liquid
phases may not be appropriate for the highly inhomogeneous
gas–liquid interface.
Thirdly in the simulation of systems containing surfactants,
polymers and proteins it may not be possible to simulate
sufficiently large systems for the appropriate length of time to
establish an equilibrated interface. In these cases, one possible
solution is to use a more coarse-grained model of the system which
avoids the explicit inclusion of all the atoms. We are just beginning
to understand how to use these coarse-grained approaches in the
simulation of g. In the following sections we will address these three
issues for a variety of geometries and systems.
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Fig. 4 A brief history of the computer simulation of surface tension. MC and MD refer to Monte Carlo and molecular dynamics simulations, LJ to
the Lennard-Jones potential, HS to the hard-sphere potential, LV to the liquid–vapour interface, IK to the Irving–Kirkwood method and Ha to
the Harasima version of the surface tension calculation. For water, we indicate in % the percentage of deviation of the simulated surface
tension from experiments and the water model used. CG and MDPD correspond to the coarse-grained model and many-body dissipative particle
dynamics.

2 Planar interfaces where Lz is the dimension of the simulation cell along z. The
element ab of the molecular pressure tensor is
In the case of a planar interface with z perpendicular to the
interface, the surface tension can be calculated using both * +
XX
1 N1 N    
mechanical and thermodynamic definitions. In this section pab ¼ rkB TI þ rij a f ij b (12)
V i¼1 j 4 i
we extend the formal definitions given in Section 1 to more
operational definitions that can be readily used in a simulation.
where I is the unit tensor, T is the input temperature and r = N/
2.1 The Lennard-Jones fluid V is the mean number density. a and b are the Cartesian
In this section the atoms in the fluid, i and j, interact through coordinates. rij is the vector between the atoms i and j and fij
the Lennard-Jones (LJ) potential and the dependencies of the is the intermolecular force between atoms i and j. Note that the
surface tension on properties such as the cutoff are presented sum over i and j 4 i is over all the atoms in the system. If the
in the context of this potential. system is of the form shown in Fig. 3b this will include two
2.1.1 Kirkwood and Buff definition. The surface tension interfaces and the final result for g obtained from eqn (11) will
gKB was introduced by Kirkwood and Buff.48 In terms of need to be divided by 2.
simulated averages, eqn (7) and (8) of Section 1 become 2.1.2 Irving and Kirkwood definition. The method of Irving
and Kirkwood (IK) expresses the surface tension through the z
gKB ¼ hpN  pT iLz dependent local components of the pressure tensor
*  +
X1 XN   (11) ð Lz =2
1 N rij  rij  3zij  zij dvLJ rij
¼ gIK ¼ ð pN ðzÞ  pT ðzÞÞdz: (13)
A i¼1 j¼iþ1 2rij drij Lz =2

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The Lz dimension of the box is divided into slabs of width dz simulations of the surface tension in a slab geometry. Whereas
and the z-dependent pressure tensor is calculated as6,53,54 most of the Monte Carlo simulations of atomistic interfaces use
truncated LJ potentials, the molecular dynamics simulations
pab ðzÞ ¼ hrðzÞikB TI
use the corresponding truncated force. The appropriate integration
*    +
X1 X of the truncated force with distance does not give the truncated
1 N N    
1 zi  z z  zj
þ rij a f ij b  y y potential because of the small step function at the cutoff
A i¼1 j 4 i zij zij zij
distance and as a consequence, MC and MD simulations which
(14) purport to use the same potential are often performed with
slightly different potentials making the comparison between
where y(x) is the unit step function defined by y(x) = 0 when
the two methods problematic. Whereas the subtle truncation
x o 0 and y(x) = 1 when x Z 0. A is the surface area normal to
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effects have little effects on the properties of bulk phases, they

the z axis. r(z) is the total number density calculated in the slab
can significantly affect the interfacial properties. The reader is
at z. The distance zij = zi  zj between two molecular centers of
directed to Trokhymchuk and Alejandre40 and Goujon et al.56
mass is divided into Ns slabs of thickness dz. Following Irving
for a comprehensive discussion of this truncation effect on the
and Kirkwood, the molecules i and j give a local contribution to
surface tension.
the pressure tensor in a given slab if the line joining the atom
There are two ways to obviate this problem. First, one can
i and j crosses, starts or finishes in the slab. Each slab has 1/Ns
use a modified potential and force functions that are contin-
of the total contribution from the i–j interaction.
uous at the cutoff. Using this type of approach Goujon et al.56
2.1.3 Test area definition. The test-area method developed
have shown that the results for the surface tension obtained
by Gloor et al. (TA) is based upon a thermodynamic route and
from MC and MD simulations are identical.56 However, these
expresses the surface tension as a change in the free energy55
results deviate significantly from experiment due to the modification
for an infinitesimal change in the surface area at constant-NVT.
of the underlying LJ potential with a cubic spline function. A
This method uses a perturbation process for which the perturbed
second strategy developed by Trokhymchuk and Alejandre40 in
system (state A þ DA) is obtained from an infinitesimal change
order to match the truncated potential consists in modifying the
DA of the area A of the reference system. The box dimensions

truncated force with a d-function like impulsive contribution.57
ðAþDAÞ ðAþDAÞ
Lx ; Ly ; LzðAþDAÞ in the perturbed system are obtained Even using the same simulation method, truncation of the
using the following transformations potential can also create differences between the mechanical
pffiffiffiffiffiffiffiffiffiffiffi and thermodynamic routes to g when calculating the direct or
LðAþDAÞ
x ¼ LðAÞ
x 1þx intrinsic part of the surface tension in a simulation. The thermo-
pffiffiffiffiffiffiffiffiffiffiffi dynamic route of Section 2.1.3 uses the potential functions,
LyðAþDAÞ ¼ LðAÞ
y 1þx (15) whereas the mechanical route of Sections 2.1.1 and 2.1.2 uses its
. first derivative. However, when truncated potential and forces are
LzðAþDAÞ ¼ LðAÞ
z ð1 þ xÞ
used, the differences between the mechanical and thermodynamic
routes are exactly compensated by the differences associated with
where x { 1, see Fig. 2. The area ðA þ DAÞ of the perturbed
ðAÞ ðAÞ ðAÞ ðAÞ
the long range corrections (see line 1 of Table 1).38,60
state is Lx Ly ð1 þ xÞ and DA is equal to Lx Ly x. These Table 1 demonstrates the equivalence of the Kirkwood Buff,
transformations conserve the volume of the box in the per- Irving Kirkwood and test area methods for calculating g for
turbed state. This means that it is possible to express the three different systems. The first line of the table also shows the
surface tension as a ratio of partition function between the difference in the calculation of the intrinsic part of the surface
perturbed and reference states. V ðAÞ ðrN Þ and V ðAþDAÞ ðr0N Þ are tension by mechanical and thermodynamic routes and the way
the configurational energies of the systems with an area A this is balanced by different long-range corrections.
and a configurational space rN and an area A þ DA and a 2.1.5 Long range corrections. Since most of the molecular
configurational space r 0 N, respectively. The transformations simulations use a pair potential with a spherical cutoff at a
used in the perturbation process lead to the following equality distance rc, long range corrections must be added to the thermo-
dr 0 N = drN. This equality allows us to write the surface tension as dynamic properties such as energy, pressure, stress tensor,
the average of expðDV=kB T Þ at constant-NVT, i.e. chemical potential and surface tension to compensate for the
  missing long-range part of the potential. In the case of bulk
@A
gTA ¼ simulations,20 these long range corrections assume a uniform
@A N;V;T
density r and a radial distribution function equal to unity
  ðAþDAÞ 0N 
kB T V ðr Þ  V ðAÞ ðrN Þ beyond rc. For example, for the homogeneous Lennard-Jones
¼ lim  ln exp 
x!0 DA kB T A
fluid, the contribution of the tail corrections to the total energy
(16) decreases from 12% to 0.4% as the cutoff increases from 2.1s to
6.4s where s represents the effective atomic diameter of the LJ
particle. The usual expressions of the long range corrections to
2.1.4 Truncation effects. It is often appropriate and useful the energy and pressure are not applicable in two-phase systems
to combine and compare Monte Carlo and molecular dynamics and different approaches have been developed. The development

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Table 1 Values of surface tension (mN m1) calculated from Monte Carlo
simulations using a truncated Lennard-Jones potential and a truncated
potential modified by a polynomial function (see ref. 58). Different definitions
are used to calculate the intrinsic part of the surface tension, gI, i.e. the part
within the simulation cut off. gLRC is the long range correction to the surface
tension; and each definition, IK, KB and TA has its own expression for the tail
correction to the surface tension. The reader is directed to ref. 58 for a
description of the methodology of the calculation. For the MARTINI model,
the reader is redirected to ref. 59. The subscripts give the accuracy of the last
decimal(s), i.e., 65.814 means 65.8  1.4
gKB gIK gTA
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chlorine69 and alkanes.60,70 The long range corrections calculated
by this expression are also given in Table 2 for comparison. These
two tail corrections are added to the intrinsic part of the surface
tension at the end of the simulation but are calculated with a
density profile that corresponds to the truncated potential without
any tail corrections. By themselves they can only provide a upper
limit to the true tail correction.
A third approach used by Alejandre and coworkers64,65,71
consists in modelling the full LJ potential by calculating the
dispersion term of the LJ potential as a lattice sum such as

gI gLRC gTOT gI gLRC gTOT gI gLRC gTOT using the Ewald method,28 the particle-particle-mesh Ewald
Truncated LJ potential
method72,73 or one of the multilevel summation methods74 that
9.512 3.61 13.113 9.512 3.81 13.313 10.611 2.61 13.211 have been proposed to reduce the computational cost of the full
lattice sum. In these methods atoms in the central box interact
Cubic spline modified LJ potential
8.58 0 8.58 8.58 0 8.58 8.58 0 8.58
with one another and with all of their periodic images. Recent
studies72,73 have established that the simulations of the liquid–
MARTINI force field – n-hexadecane–water liquid–liquid interface vapour interface of the LJ fluid can be performed accurately
43.210 0 43.210 43.210 0 43.210 43.210 0 43.210
with both the Ewald and the PPPM approach. Changes in the
intrinsic surface tension with the cutoff are balanced by
of these long range corrections for the two-phase simulations and changes in the long range part of the dispersion interaction
the interfacial properties has been an area of active research for the which is calculated in reciprocal space.
past two decades.38,41,42,61–66 These tail corrections are important A fourth and important set of approaches is based on the
because they range from 50% to 7% of the intrinsic surface tension introduction of the local configurational energy38,41,63,66,76–80 or
as the cutoff changes from 2.1–6.4s. An accurate estimate of these local force77,78 in each slab, dz of the simulation box. As first
tail contributions of the surface tension can be critical in obtaining proposed by Guo and Lu41,63,76 the tail contribution to the
accurate simulated values of g when the Lennard-Jones potential is configurational energy depends on the position of the molecule
involved. in the direction normal to the interface, and is specifically
The first operational expression for correcting g was developed included at each step of the Monte Carlo simulation. The tail
from the work of Fowler67 and used in simulations from 1973 correction changes the Markov chain of states generated during
onwards.42,61,68 This expression is based on the use of a step the simulation. This long range correction to the configurational
function for the density profile r(z) and thus an interface of energy comprises two contributions: the first one is similar to that
zero-thickness. Values of g calculated by this route are given corresponding to a bulk (homogeneous) system with a local
in Table 2 as a function of the cutoff radius at two different density r(z). The second contribution corrects for the density
temperatures. inhomogeneity by considering an integral over a series of
A second approach based upon the Kirkwood–Buff expression48 density differences. This second contribution has usually been
for the surface tension, proposed initially by Chapela et al. and neglected due to the high computational cost of its calculation.
corrected later by Blokhuis et al., assumes that the density profile The approximate approach of Guo and Lu, with the inclusion of
r(z) can be fitted to a hyperbolic tangent function with an interface only the first term at each step, has been widely used in the
of non-zero thickness. The resulting operational expression has calculation of the surface tension of different fluids.56,58,70,81–85
been widely used with the truncated Lennard-Jones potential for An alternative approach based on a local long range correction to
the calculation of the surface tension of water,18,28,29,38 hexane and the energy was proposed by Janec̆ek66 in 2006. The original
formulation66 has been revisited by MacDowell and Blas79 in
order to avoid the need for the recalculation of the complete
Table 2 Values of the reduced surface tensions (intrinsic, gI, and long-
density profile at each step in the simulation. The method of
range correction contributions, gLRC), calculated from configurations Janec̆ek has also been widely applied to different liquid–vapor
obtained with the LJ potential truncated at rc = 3.2s at T* = 0.67 and systems: LJ fluids,79,80,86 cyclic hydrocarbons,87 alkanes,88
T* = 0.83. The long-range corrections to the surface tension are calcu- water and CO238 and argon.89
lated from different expressions: gFOW
LRC is calculated from the expression of
Recently,75 the full version of the Guo and Lu method (both
Fowler,67 gBLO
LRC from Blokhuis et al.,
62 JAN
gLRC from Janec̆ek et al.66 and gGL
LRC
from Guo and Lu.41 The subscripts give the accuracy of the last decimal
terms) was compared directly with the Janec̆ek method by studying
places, i.e., 0.9239 means 0.923  0.009 the cutoff dependence of the surface tension and the results are
presented in Fig. 5. The reduced surface tension is the sum of
rc gI gFOW
LRC gBLO
LRC gJAN
LRC gGL
LRC
the intrinsic and long-range parts. In the figure we have also
T* = 0.67 included the results for g using a truncated LJ potential and
3.2 0.9239 0.327 0.296 0.293 0.297 shifted LJ potential (where the Lennard-Jones potential is shifted
T * = 0.83 to zero at rc). For the shifted Lennard-Jones potential, there is no
3.2 0.59511 0.270 0.222 0.221 0.225 long range correction to the surface tension.

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Fig. 5 Values of surface tension (g* = gs/e) as a function of the reduced
cutoff distance (rc* = rc/s) for different potential models. For T* = 0.80 ,
Janec̆ek method;38 For T* = 0.83 , simplified version of Guo and Lu;75 ,
full version of Guo and Lu;75 , Janec̆ek method;75 , truncated LJ
potential;75 n, truncated and shifted LJ potential.75 For T* = 0.85 ,
dispersion interaction calculated with the Ewald method;72 , dispersion
interaction calculated with the PPPM method.72
Some limited results have also been included for the Ewald
and PPPM lattice sums,72 which used a cutoff of 4s. The resulting
simulation time is increased by a factor of 5 for the Ewald method
and a factor of 2 for the PPPM approach as compared to a
simulation with a simple real-space cutoff, rc = 4s.
The full correction of Guo and Lu and the method of Janec̆ek
give almost identical results for the interfacial properties when
applied to the same set of configurations.75 Although not
shown in the plot, the convergence of the coexisting densities
as a function of the potential cutoff is slower than for the
surface tension. We would recommend using a cutoff of at least
4.5s to obtain accurate values of these densities even with
the long-range correction included at each step. The surface
tension and coexisting densities can be calculated without
using the long-range correction at each step. In this approach
we would recommend using rc Z 5.5s. Even though the
intrinsic part of the calculation of g converges for rc Z 4s,
there is still the issue of accurately adding the long-range
correction by the Blokhuis method62 and this requires an
accurate estimate of the coexisting densities and rc Z 5.5s.
Even in the case where the electrostatic interactions play a
major role, the long-range correction to the dispersion inter-
action remains important18 and it is necessary to add a correc-
tion for each term in the site–site dispersion potential. These
conclusions will also be valid for fluid mixtures. However, in
this case the density profile of a particular component may not
be well represented by a hyperbolic tangent function, e.g. where
one component is adsorbed at the gas–liquid interface of the
other component as is the case for CO2/H2O in ref. 90. In this
case, we would recommend avoiding the Blokhuis correction
and using the Janec̆ek correction during the course of the run.
We note that the method of Janec̆ek can be readily extended to
more complicated functional forms than the Lennard-Jones
Chem. Soc. Rev.
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potential. For more accurate two-body potentials (for example,
the Barker Fisher Watts potential89), the decay at large r is
faster than r6 and the conclusions that we make for the LJ
fluid are equally valid. The use of a truncated and shifted
potential for the surface tension does not produce a converged
result for any of the cutoffs and should be avoided. Shifting the
potential to zero at rc certainly avoids the long range corrections
but the results show that this truncated and shifted potential
produces values of surface tensions that are dependent on the
cutoff. This type of potential is not able to produce quantitative
predictions because the cutoff is an adjustable parameter.
Our overall conclusion is that an efficient accurate method
for adding the long-range correction in these slab simulations
is to use the Janec̆ek method66 to estimate the long-range
correction at each step of the simulation with an update of
the density profile at every ten Monte Carlo cycles. The long
range correction to g should also be calculated at each step
using the Janec̆ek method and added to the intrinsic calculation
of g. A cutoff of between 3.0 and 4.0s can be employed.
2.1.6 Size effects. It is now well-established that the calculation
39,60,91
of the surface tension
 is dependent on both the surface
area A ¼ Lx Ly and the box dimension (Lz) along the normal
to the surface. Indeed, several studies have shown that the
surface tension exhibits an oscillatory behaviour as a function
of Lx (for Ly = Lx). The precise nature of these oscillations in g(Lx)
depends on the potential model employed.60 Typical oscillations
are shown in Fig. 6 for several potential models at different
reduced temperatures.
The origin of these oscillations has been attributed to the stress
anisotropy39,60,92 in the liquid phase induced by the use of periodic
boundary conditions and small box dimensions. Interestingly, the
modification of the truncated LJ potential using a cubic spline
significantly reduces the stress anisotropy in the liquid phase and
as a result the dependence of the surface tension on the surface
area. When the long range correction to the energy is included at
each step, we see that one peak of oscillation is removed and the
amplitude of these oscillations is reduced. We also note the same
oscillatory behaviour60 of the surface tension as we change the Lz
dimension of the box. We conclude that in order to avoid any size-
effects dependence of the surface tension, a surface area of 11 
11s2 and a value of Lz = 60s must be used for simulations carried
out with the truncated LJ potential. These box dimensions can be
reduced to A = 99s2 and Lz = 50s when the long range corrections
to the energy are included directly in the simulation. With these
box dimensions, the vapour and liquid densities show no size-effect
dependence.71
For the planar liquid–vapour interface, the surface tension
also depends on the slab thickness, D, of the liquid phase.93 As
the slab thickness decreases, the surface tension decreases
from its limiting value (D - N) as shown for a number of
systems in Fig. 7. For the LJ-like potentials, we recommend a
value of D* Z 10 to ensure that the two interfaces are quite
independent. When the potential is more strongly attractive,
the surface tension is higher and the interface sharper. In this
case, smaller values of D* can be used as shown for the slabs of
the metallic liquids, copper and tin94 in Fig. 7.
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Fig. 6 Reduced surface tensions calculated for different values of Lx for
different potential models and temperatures. For T* = 0.8 , truncated LJ
potential;60 , truncated LJ potential modified by local range corrections
of Guo and Lu;60 , truncated and shifted potential;39 , truncated LJ
potential modified by a cubic spline function from ref. 60; T* = 0.85 m,
truncated LJ potential;39 T* = 0.9 , truncated LJ potential.91
Fig. 7 Ratio of the surface tension to the surface tension glim calculated at
the largest value of D* = D/s. UT,JAN represents the truncated LJ potential
modified by the addition of the long range corrections to the energy
calculated with the Janec̆ek method; UT and UTS denote the truncated and
truncated and shifted LJ potentials. UEAM corresponds to Embedded
Atoms Models applied to slabs of liquid copper.94 The EAM potential has
the advantage to be decomposable into pairwise contributions for the
calculation of the pressure. The description of the methodology for the
calculation of the surface tension can be found in ref. 95.
In the case of atoms interacting though the Lennard-Jones
type potentials, the impact of the size-effects is now well-
understood and can be controlled. As systems approach to
within 10% of the critical point, the interfaces become more
delocalised and the periodic slabs will interact making this
approach to g inappropriate.
2.1.7 Close to the critical point. The calculation of the
surface tension of liquid–vapour interfaces using a slab geometry
is accurate when the density between the vapour and the liquid
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phases differs by several orders of magnitude and the interface
is well-defined. As the temperature approaches the critical
temperature (T 4 0.9Tc), the two-phase simulations with explicit
interface must be carried out with caution to obtain an accurate
estimate of g.35,89 The previous recommendations concerning
the box dimensions and the cutoff radius are no longer valid.
Potoff and Panagiotopoulos use the grand canonical Monte
Carlo simulations and histogram-reweighting techniques to
calculate the free energy barrier height at different system-sizes.
The surface tension can then be obtained by using the methodology
of Binder.96 This method works well for predicting the surface
tension of temperatures above 0.7Tc. For lower temperatures,
Potoff and Panagiotopoulos concluded that this methodology is
too time-consuming. The grand-canonical transition-matrix
Monte Carlo (TMMC) method23 developed by Errington is then
applicable to the entire liquid–vapour coexistence curve and
performs better than equivalent Gibbs ensemble calculations.22
2.1.8 Potential model. Now that the methodological questions
have been addressed, we can ask if a simple Lennard-Jones potential
can reproduce the surface tension of liquid argon. In fact, it is hard
to get within 15% of the experimental values using any reason-
able, effective two-body potential. It is possible to approach the
experimental values of g using a truncated and shifted Lennard-
Jones potential.35 In this case, the simulated surface tensions
are strongly cutoff-dependent. The shifted potentials bear little
resemblance to the true intermolecular potentials between
argon atoms and these shifted potentials are not transferable.
A more appealing approach is to include a three-body
interactions97
 
  n 1 þ 3 cos yi cos yj cos yk
vð3BÞ ri ; rj ; rk ¼ (17)
rij3 rik3 rjk3
where yi is the internal angle of the triangle, ijk, centered on
atom i. This potential must be added to the accurate two-body
interactions such as the BFW potential98 or the NLD potential99
for argon–argon interactions. This three-body contribution to
the surface tension can be readily calculated in a Monte Carlo
simulation.89,100,101 The intrinsic part of the surface tension has
been calculated using the Kirkwood–Buff approach16 developed to
include the three body contributions. The reader is directed to
ref. 89 for a comprehensive description of the calculation. Care
needs to be taken to properly include the corresponding long
range corrections to the surface tension form both the two-body
and three-body potentials. This approach leads to a good agree-
ment for g with experiments as shown in Fig. 8.
Whereas the two-body effective LJ potential overestimates
the surface tension along the liquid–vapour equilibrium curve
with a maximum difference of 33% approaching the critical
point, the best agreement with the experiment is obtained with
the NLD + AT potential which shows a relative deviation of less
than 3% over the whole temperature range. This is a good
example of how simulation can be used predictively in model-
ling the surface tension. The ability of a particular model to
reproduce g along the coexistence curve is a useful test, since
these interfacial properties are not normally used in fitting the
parameters of a given model.
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the surface tensions over this range. Considerable attention has

been paid to polarisable models of water, and in Fig. 9 we show
the surface tensions of two polarisable models POL4108 and
SWM4-DP106 at different temperatures. These models show
their limits in the prediction of g at temperatures greater than
400 K. Tables 3 and 4 also shows some values of surface
tensions calculated using the TIP4P/2005 model and confirms
the quantitative agreement with the experiments independently
of the method used for considering the long range corrections
to the energy41,66 and to the surface tension. These results are
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in line with the conclusions drawn by Mı́guez et al. from a

cutoff of 3s. To conclude, the best performance in reproducing
the surface tension of water over a large range of temperature is
Fig. 8 Surface tensions calculated from the two-body Lennard-Jones
given by the TIP4P/2005 model.
potential,89 the three-body BFW98 and NLD99 potentials.

2.2 Molecular systems

2.2.1 Molecular forces. Many simulations of molecular
systems are based on additive site–site potentials, where the
total force on molecule i from j, fij, is given by
nj nj  
Xni X Xni X
riajb dv riajb
f ij ¼ fiajb ¼  (18)
a¼1 b¼1
r
a¼1 b¼1 iajb
driajb

where v(riajb) is the potential between site a in molecule i and

site b in molecule j and ni and nj are the number of sites in
molecules i and j, respectively.
The definition of the molecular pressure tensor20,102–105 for
Fig. 9 Simulated values of the surface tension of water. The experimental
molecular systems with forces given by eqn (18) is given by a values are shown as a solid black line. , TIP4P/2005 using both the
straightforward extension of eqn (12). Recall that this approach mechanical and thermodynamic definitions18 and with the Guo and Lu
is only valid for pair-additive potentials. For molecular systems methodology.41 , TIP4P/2005 water using the Ewald summation tech-
containing partial charges the electrostatic interactions are nique for the calculation of the dispersion interaction;71 , SPCE model;29
, TIP4P water model calculated using the test-area method;17,28 E,
usually calculated using an Ewald sum. In this case, the
TIP4P/2005 water model calculated using the test-area method;28 ,
contribution to the potential in the real space is pairwise- TIP4P/2005 water model calculated using the test-area method and the
additive whereas the contribution in the reciprocal space is Janec̆ek methodology;38 , the Drude oscillator model SWM4-DP;106,107
not. The appropriate expressions for the Lennard-Jones and , the polarizable POL4 model.108
electrostatic contributions to the pressure tensor have been
considered in detail.18,29,85
Whereas the size effects have been thoroughly investigated
for the LJ liquid–vapor interfaces, the study of the impact of the Table 3 The surface tension from simulation: CH4 using the truncated LJ
potential UT,58 with the LRC of Guo and Lu,58 and with the LRC of
cutoff value and size effects of molecular systems is not so
Janec̆ek;38 H2O using the truncated LJ potential,28 with the LRC of Guo
extensive. Mı́guez et al.38 have established the dependence of and Lu,18 and with the LRC of Janec̆ek;38 CO2.18,38 The subscripts give the
the surface tension of water on rc when the electrostatic accuracy of the last decimal(s), i.e., 65.814 means 65.8  1.4
interactions are calculated by the reaction field and the long
UT + ULRC
range corrections to the dispersion interactions are included
during the course of the simulation. For rc Z 3s, the surface UT Guo and Lu – LRC Janec̆ek-LRC
tension of water is independent of the cutoff radius when long T (K) gKB gTA gKB gTA gKB gTA Exp.
range corrections to the surface tension are properly applied. Methane
Fig. 9 shows the temperature dependence of the surface 120 13.51 13.51 13.112 13.212 13.81 13.81 11.3
tension of water calculated using different methodologies and
Water – TIP4P/2005
models such as SPC/E,109 TIP4P110 and TIP4P/2005.111 Whereas 388 55.840 55.540 55.9
the TIP4P model shows significant deviations from experi- 400 52.57 52.27 52.010 52.010 53.6
ments with values of surface tensions underestimated by 17% 418 49.720 51.020 49.8
to 45% over the temperature range from 300 K to 500 K, the SPC/ CO2
E and the TIP4P/2005 models exhibit quantitative predictions of 270 4.82 5.77 5.610 5.12 5.5

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Table 4 Contributions of surface tensions (mN m1) derived from the recent work Zubillaga et al.49 which reports the values of surface
Lennard-Jones contribution (gLJ), the real part (gR) and the two terms tensions calculated for 61 molecular systems with the OPLS/AA
(gK,1,gK,2) of the reciprocal space part of the Ewald contribution, the LRC
force field.115,116 Again, in this study, the simulated surface
term (gLRC). The terms are calculated from the pressure tensor.18 The total
(g) is the sum of all of these contributions calculated with a real-space tensions are within 10% to 20% of the experimental values.
cutoff radius of 12 Å However, other force fields87 can lead to significant difference
from experiments. These differences cannot be understood
gLJ gR gK,1 gK,2 gLRC g
a priori, that is before the simulation has been conducted and
H2O-TIP4P/2005 (T = 478 K) more systematic work is required in this area. Interestingly,
87.6 112.1 6.4 12.0 3.5 33.6
when the coexisting liquid and vapour density are accurately
CO2 (T = 238 K) predicted by a model, in most cases, the surface tension is also
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6.1 2.0 0.8 1.7 2.5 11.5 accurately predicted.

H2S (T = 187 K)
21.0 8.0 1.5 2.8 8.0 38.3
C6H6 (T = 409 K)
7.5 3.5 0.3 0.5 2.7 13.9
We now focus on the ability of the two-phase simulations to
reproduce the temperature dependence of surface tension of
various molecular systems as shown in Fig. 10. As shown in the
legend of Fig. 10, various molecular systems such as the linear
alkanes (n-pentane70 and n-heptadecane112), branched alkanes
(2,3-dimethylpentane70), cyclic alkanes (cyclohexane87), aromatics
(benzene87 and phenol113), acid gases (CO218,38 and H2S18)
incondensable gases114 (O2, SO2, and N2) have been modelled
by using different force field models. Table 3 shows the
calculation of the surface tension of CO2 from simulations
using truncated LJ potentials, and truncated potentials modified
by the addition of long range corrections according to the Guo and
Lu and Janec̆ek methods. Within the statistical fluctuations, the
simulated surface tensions are equal and indeed independent
of the definition used for the calculation. We can conclude that
the prediction of the surface tension of many molecular systems
can be calculated to within 15% of the experimental values
along much of the orthobaric curve. This view is supported by
Fig. 10 Surface tensions of molecular systems calculated from two-phase
simulations. The reader is directed to the original paper for a description
of the methodology used for the calculation of g. CO2,18,38 H2S,18 n-C5H12,
n-C10H22,70 N2, O2,114 C6H6, C6H12,87 2,3-DMP,70 C6H5OH,113 n-C17H36,112
and monoethanolamine (MEA).117 The experimental surface tensions,
represented in dotted lines, can be found in the original papers.
In most of the simulations reported in Fig. 10, the electro-
static interactions are calculated using the Ewald summation
technique.29,118 Table 4 lists different contributions to the
surface tension calculated in systems differing in the relative
magnitudes of the dispersion–repulsion and electrostatic inter-
actions. Since the simulation boxes for these slabs are not
normally cubic, the Ewald summation requires a large number
of k-vectors in the longer z-direction.29 Interestingly, the contribution
to the dispersion–repulsion term is negative for water due to
the strong electrostatic interactions in this system. When the
electrostatic interactions become less strong, the dispersion–
repulsion term of the surface tension is again positive for CO2,
H2S and C6H6.
We note that the reaction field has also been employed in
the calculation of the surface tension.38,119 Since the dielectric
constant depends on the z-position along the normal to the
surface, the use of the dielectric constant corresponding to a
homogeneous bulk phase is not ideal. However, the authors
report the results of surface tensions38,119 that compare well
with those calculated using the Ewald method.
The Ewald sum is the method of choice for including long-
range interactions in simulations. Its accuracy can be improved
by extending the number of k-vectors in the reciprocal space
sum and balancing the real and reciprocal contributions to the
sum. The easiest way to use the Ewald method for a 3-D system
with 2-D periodicity is to surround the slab (both the liquid and
vapour phases or the liquid between solid walls) with a number
of empty boxes along the z-direction and to make this extended
box periodic. This empty space helps to prevent any interaction
between periodic slabs in the z-direction. The Ewald sum can
then be applied to the extended cell. As always, there is an
additional term in the energy since the infinite array of images
in the Ewald sum is eventually surrounded by a vacuum. In this
case, there is a correction proportional to Mz (the z component
of the overall dipole of the central box).120 As the system size
increases beyond ca. 500 charges it is often more efficient to
assign the charges to a fine regular mesh and use a direct fast
Fourier transform to calculate the reciprocal sum. These techniques
such as the particle mesh Ewald method have been applied to
slab geometries121 with good effect. Recently a new technique
has been developed to periodically reproduce the spherical
cut-off sphere around a charge. The isotropic periodic sum
method has been applied to bulk fluids, liquid/liquid and
liquid/vapour interfaces, and lipid bilayers and monolayers
and is capable of outperforming the mesh lattice methods.121

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Finally there are a number of specialised techniques to deal
with 2-D periodic charges such as the methods of Lekner122,123
and Hautman and Klein.124 Both these methods require that
the parameter zij/sij between two charges i and j is small since
this is used as an expansion parameter in a series expansion of
the force. The methods are best applied to physisorbed mono-
layers or very thin liquid films.
2.3 Mixtures
As discussed in the previous section, the two-phase simulations
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of liquid–vapour interfaces of pure systems (i.e. a single component)
is well-understood from a methodological viewpoint and the
reproduction of the temperature dependence of g for these
systems is good. For mixtures we need to extend these methods
to consider additional parameters such as composition and
pressure. For example, the long range corrections to the surface
tension and configurational energy for a mixture is straight-
forward and has been achieved with the approach of Guo and
Lu.76 To our knowledge, the method of Janec̆ek has not been
applied to the liquid–vapour equilibrium of mixtures but this
extension poses no fundamental problems. Fig. 11 shows the
surface tension of different mixtures as a function of the
composition. In the case of the liquid–vapour interface of an
alcohol–water mixture, the simulations accurately predict the
significant decrease of the surface tension with the alcohol
mole fraction.125,126 In the water–alcohol mixtures, the long
range corrections to the surface tension contribute between 5%
and 10% of the total surface tension depending on the alcohol
concentration and must be accurately included. The molecular
description of the mixture in terms of density profiles and
hydrogen bond profiles has been used convincingly to interpret
the decrease of the surface tension with the alcohol concentration.
The dependence of the surface tension on the composition is well
reproduced for other mixtures127 where the variation is less
pronounced with the composition.
The situation is still more delicate when we examine the
pressure dependence of binary systems. To date, most of the
simulations of binary systems have been performed in the
Fig. 11 Surface tensions of water–methanol and water–propan-2-ol
mixtures as a function of the mole fraction of alcohol126 and surface
tensions of hexane–decane and CO2–decane mixtures as a function of
the liquid mole fraction.127 The dotted lines are the experimental values.
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constant-NVT statistical ensemble.57,128–131 The constant-NPT
ensemble is not designed for modelling a two-phase binary
system because the tangential component, pT, of the pressure
tensor is not constant along the surface normal, normally
exhibiting a strong minimum in the interfacial region. The
most appropriate ensemble is at constant-NpN AT where pN is
the normal pressure and the A interfacial area. The reader is
directed to the work of Biscay et al.90,132 for a comprehensive
description of the methodology. In this case, the expressions
for the calculation of the long range corrections to the surface
tension through the thermodynamic and mechanical routes are
also available.90,132 Fig. 12 shows the surface tension of different
binary mixtures as a function of the pressure. Fig. 12 shows the
value of the constant-NpN AT simulation method in predicting
the surface tension. The results of these slab simulations over a
large range of pressures for the coexisting densities compare
well with the simulated phase diagrams calculated from Gibbs
ensemble Monte Carlo (GEMC) simulations.134,135
Another challenging aspect of the computer modelling of
the surface tension of complex systems is the prediction of the
dependence of the surface tension on salt concentration. This
calculation may be quite sensitive to the choice of standard
(non-polarisable) or polarisable models of water and the ions.
Fig. 13 shows the increase of the relative surface tension
defined by Dg = gsalt  gwater where gsalt and gwater are the
surface tensions of the salt solution and pure water. Different
methods have been employed to include electronic polarisation
into simple atom–atom potentials. Three of the most widely-used
techniques are the induced dipole model,136–138 the fluctuation
charge model139,140 and the classical Drude oscillator model.106
The Drude oscillator model, with the simple functional form of
the pairwise additive interactions and the ability to account for
the electronic polarisability, is particularly useful since it intro-
duces only a small computational overhead. Different polarisable
Fig. 12 Surface tensions of different binary mixtures as a function of the
pressure. Water–methane132 (T = 373 K), water–CO290 (T = 383 K) and
water–H2S90 (T = 393 K), water–N285 (T = 298 K), decane–CO284 (T = 344
K), pentane–H2S84 (T = 344 K), hexane–N2133 (T = 333 K), and ethanol–
N2133 (T = 333 K) systems.
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Fig. 13 Relative surface tensions defined as Dg = gsalt  gwater as a function
of the molal concentration of NaCl for different nonpolarisable and
polarisable models for ions and water at T = 298 K. The dashed lines
represent the experimental linear dependence of the surface tension on
molality. , TIP4P2005 + OPLS models;107 , SPC/E + ion models;143 .,
polarisable Drude models;107 J, nonpolarisable + electronic continuum
models;144 and , polarisable POL3 model.145
water models: SWM4-DP;106 SWM4-NDP;141 and SWM6142 based on
classical Drude oscillators, have been proposed. Fig. 13 shows that the
nonpolarizable models perform well in reproducing a monotonic
increase of the surface tension with the molality.
The polarisable force field based upon the Drude oscillator
model leads to some scattering in the predicted surface tensions
and the POL3 model145 underestimates the increase of the
surface tension with the salt concentration. The electronic
continuum model (EC),146,147 an alternative method of adding
electronic polarisation into a simple nonpolarisable model,
produces a fluctuating change in the surface tensions with the
molality. The structure of the interface is significantly different
between the polarisable and non-polarisable models: without
polarisation the structure corresponds to a profile resembling a
simple LJ fluid; with polarisation the ions occupy preferential
layers at the aqueous interface.
3 Spherical interfaces
While the calculation of surface tension by simulation for
planar interfaces is essentially under control, for spherical
droplets there are still open questions about the dependence
of the surface tension on the drop size, and the validity of the
mechanical definition of the local pressure.6,10,33,148,149 The
methodology is still being developed and there are very few
comparisons with real experimental systems.
Drop size can be defined from the radius of the equimolar
dividing surface (Re) which can be derived from the radial
density profile r(r)
ð1
1 drðrÞ
Re3 ¼ drr3 (19)
ðrv  rl Þ 0 dr
where rv and rl are the vapour and liquid densities.
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In particular, the arbitrariness in the choice of contour
connecting two atoms that contribute to the stress leads to an
ambiguity in the definition of the local elements of the pressure
tensor in a spherical geometry. Indeed, in relation to the planar
interfaces, the curvature complicates the definition of the local
stress149 and amplifies the difference in the different routes to g
(see Section 3.1). Despite this ambiguity, the Irving–Kirkwood
(IK)48 and Harasima150 definitions are widely used in the
calculation of p and g for droplets. Recently, Nakamura
et al.151 have also proposed a novel method for computing
the pressure tensor along the radial direction of a molecular
system with spherical symmetry. The method uses the slice-
averaged pressure to improve the numerical stability and the
precision of the calculation significantly. Although this approach is
numerically useful, the ambiguity in the contour remains.
Density functional theory calculations (DFT) provide a
straightforward, if approximate, estimate of g(Re) with respect
to the drop size (Re).148,149,152–154 Fig. 14 compares the results of
g for the simulation of spherical Lennard-Jones droplets from
simulation and from the DFT methods. The main conclusions are:
(i) there is a maximum in g with respect to the drop size in
DFT but a variety of different behaviours for this curve from
different simulation approaches;
(ii) a number of different simulation approaches produce
g(Re) values of different magnitudes to the DFT results, while
some simulation results are quite similar to DFT;
(iii) DFT predicts a negative Tolman length (d) while negative
and positive values can be found in different simulations of the
same system using different approaches.
Fig. 14 Curvature dependence of the liquid–vapour surface tension of
the LJ fluid at a temperature T* = 0.8. g/gN is plotted against the radius of
the droplet where gN is the surface tension of the planar limit. , FMT
(a nonlocal DFT using functional measure theory).33 Thermodynamic
routes: , grand canonical Monte Carlo simulations;152 , Monte
Carlo simulations using a thermodynamic route of Homman et al.;32 ,
the simulated surface tension calculated from TA ellipsoidal deforma-
tions.33 Mechanical routes: , molecular dynamics simulations using the
mechanical route;35 , Monte Carlo simulations using the IK definition.32
The inset shows a magnification in the region of the maximum of g(Re)/gN.
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These disagreements have been noted in many studies over
the last 30 years.155 Although the DFT method allows a direct
and unambiguous calculation of g, its application to realistic
systems with complex interactions is more difficult and it does
not provide exact results. On the other hand molecular simulation
is exact, can be readily applied to complex intermolecular forces
but the calculation of surface tension for a well-defined model
remains ambiguous. More recently Sampayo et al.,33 Lau et al.156
and Homman et al.32 have provided a macroscopic thermodynamic
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where x is a small, dimensionless variable and Z represents the
box length and the atom coordinate vectors, so that the
transformation preserves the spherical symmetry of the droplet.
V 0r and V 1r are the local configurational energy in the radial
element dr at r when the local volume is changed from V 0r to V1r .
The expression for the tangential component of the local
pressure157 is
kB T
pT ðrÞ ¼ lim
x!0 xVr0
route to compute the surface tension through a revised version of   1 0 

V r ðr Þ  V 0r ðrÞ
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N
the test-area method (TA) (see Section 2.1.3). These TA results for  ln ð1 þ xÞ exp  (24)
kB T mVr0 T
g(Re), shown in Fig. 14, are in much better agreement than the
results from the mechanical route via the pressure tensor with where m is the chemical potential. Eqn (24) provides the
the results obtained from surface free energy change,154 Landau r-dependent tangential component, pT. The normal component
free energy approach152 and density functional theory.153 is calculated through the condition of mechanical equilibrium.
In the following sections we shall consider these results A more convenient form of eqn (24) for use in a simulation of N
more carefully. molecules is
3.1 Mechanical routes to the local pressure tensor and surface X
N X
N
kB T
tension pT ðrÞ ¼ lim Fðr  ri Þ
x!0
i j4i
xVr0
As for the planar interfaces, two methods have been used to *  1 0   ! +
compute the local elements of the pressure: the Irving–Kirkood Nvr rij  v0r rij
 ln ð1 þ xÞ exp 
definition (IK)48 and the method of Harasima (Ha).150 For the kB T
mVr0 T
Ha method the transverse component is calculated directly and
(25)
the radial (normal) component is deduced from the condition
of mechanical equilibrium. Whereas, in the IK method, pN where F is the Heaviside step function and v(rij) the pair
is calculated directly and pT is deduced from rp = 0. potential.
More, recently, a thermodynamic route has been proposed for Lau et al.156 have recently extended the test-area method
droplets based on the calculation of the local energy, to with g  DA=DA, where A is the free energy and the surface area
compute the local components of the pressure tensor.157 to compute the surface tension of spherical interfaces.33,156 In
Several thermodynamic and statistical mechanics definitions order to conserve the volume of phase space, a spherical to
are available to compute the surface tension.6,10,34,158 Rowlinson6 elliptical transformation was employed. The expression for g is
and Lovett et al. suggest a mechanical route that is invariant to the  
5 b 2 
form of pressure tensor. From the condition of the mechanical g¼ hbi  a (26)
8pR2 2
stability, rp = 0, they showed that
ð1 where
g¼ drðRs =rÞðpN ðrÞ  pT ðrÞÞ; (20)  
0 1 @ 2 DV   1 @DV 2
hbi ¼ ; and a2 ¼
where Rs is the radius of tension6 2 @e2 2 @e
ð1 ð 1
and DV ¼ V 1r ðr0 Þ  V 0r ðrÞ. For the operational version of eqn (26)
Rs ¼ drrðdpN ðrÞ=drÞ drðdpN ðrÞ=drÞ: (21)
0 0 the reader is directed to the original paper.156 An entropic
  (gentropic) and energetic (genergetic) component of the total surface
From eqn (20), Lovett159 showed that to O R2 , where R is the tension (g = genergetic  gentropic) have been identified (see
size of the droplet, g is independent of Rs and is given by eqn (25) and (26) of Lau et al.156). By applying the test-area
ð1 method with the elliptical transformation, a small curvature
g¼ dr½ pN ðrÞ  pT ðrÞ: (22) dependence of the surface tension of the LJ system was found
0
while a strong curvature dependence of g was observed for small
water clusters.
3.2 Thermodynamic routes to the local pressure and surface
tension 3.3 Surface tension from the surface of tension
To obtain a the local pressure for a droplet, we assume a local The surface tension of the droplet can also be calculated in
partition function in the grand canonical ensemble.44,58 An isotropic simulation from the surface of tension (which is the radius at
change in the volume of the system is made by modifying the which the tension acts6) through the Laplace equation6,36,160
coordinates and the box dimensions in Cartesian space
ðDpÞRs
g¼ (27)
Z1a = Z0a(1 + x)1/3 (23) 2

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where Rs is the radius of the surface of tension, g the surface
tension at Rs and Dp the pressure difference between the vapour
and liquid phases separated by the surface of tension. Usually,
Rs is determined from eqn (27) once the surface tension has
been determined by, say a mechanical route. However, Rs can
be calculated directly from a simulation using the approach of
Hill.36 In this method, the system is modelled by a sphere of
liquid (a) surrounded by a vapour phase (b). The two phases are
separated by a dividing surface of radius R. Thermodynamic
equilibrium implies that
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   models, often associated with Monte Carlo (MC) or molecular
@A 
 dynamics (MD) methods, have been extensively used to study
 ¼0 (28)
@R Ra ;Rb ;N;T 
R¼Rs
where Ra and Rb are radii inside the two phases at which the
density has reached its limiting values and Rs corresponds to
the minimum in the free energy.32 Simulations in the canonical
ensemble are performed using different trial values of Rt for the
surface of tension. The free energy derivative in eqn (28) is
estimated using a perturbation approach, another application
of the test area method. In this case Rt is displaced with Ra and
Rb fixed. The system on one side of Rt expands while on the
other side it contracts with an overall conservation of volume.
The full expression for the derivative is given in eqn (12) of
Homman et al.32 Rt = Rs when the free energy derivative is zero.
The extraction of the surface tension from Laplace’s equation
follows once Dp = pl  pv is computed. There are no ambiguities in
calculating the limiting pressures in the two bulk phases.34 As
shown in Fig. 14 the surface tensions calculated from thermo-
dynamic approaches are in good agreement with analytical theory.
3.4 Tolman length
The Tolman length (d) is a measure of the deviation of the
surface tension with respect to the planar limit. It can be
expressed as the limit in the planar case (R - +N) of the
difference between the surface of tension Rs and the Gibbs
equimolar dividing surface Re:
d ¼ lim dðRÞ  ze  zs ; dðRÞ ¼ Re  Rs : (29)
R!1
where ze and zs, respectively, are the positions of the Gibbs
equimolar surface and the surface of tension of planar interface
(with the surface normal along the z). While ze can be obtained
by a fit of the density profile using an error function,161 zs is
more difficult to extract.
A straightforward modification of the previous approach for
planar interfaces allows us to obtain the Tolman length32 for
the droplet. This approach is based on the evaluation of the free
energy derivative with respect to R using a test area approach.
This method gives a Tolman length of d = 0.04  0.01. This
value is in fair agreement with the DFT calculation obtained
by van Giessen and Blokhuis (d = 0.1).162 An alternative
simulation approach to calculate d is to fit to the defining
equation.153,157
g 2d
¼1 : (30)
g1 Rs
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The Tolman length calculated by this approach is normally
small and negative153,162 but some carefully performed simulations
still suggest a positive value.162,163 This remains an unsolved issue.
4 Coarse-grained (CG) models
All the computer simulations discussed up until this point have
been performed using atomistic force fields with different UA
(United Atom) and AA (All Atom) models. These atomistic
the behaviour of simple and complex systems on time scales
extending over hundreds of nanoseconds. They are predicated
on atomistic force fields that perform well in terms of accuracy
and computational cost for the prediction of the surface tension
of the liquid–vapour interfaces of pure systems and mixtures.
This approach is less obvious when we plan to use these force
fields to model liquid–liquid interfaces or more complex systems
such as vesicles, membrane-bound proteins, polymers, or micelles.
These systems often relax over times that are longer than a
microsecond. In this case, we need to simplify the interactions
by employing a coarse-grained (CG) model, in which the CG
particle (often called the ‘bead’) may correspond to many atoms
or molecules. Reducing the number of degrees of freedom in
this way averages the structure of the component monomers but
it is normally possible to preserve the geometry (architecture)
and the overall charge distribution of the polymer and to
increase the time-step of the simulation by an order of magnitude.
The reader is directed to a number of discussions of the
advantages and drawbacks of the CG models.164–169
There are two approaches to developing coarse-grained force
fields. The top-down approach derives the parameters from
macroscopic properties (compressibility, diffusion, surface tension,
bulk density, and enthalpy of vaporisation)170–175 and requires
the use of an extensive, experimental database. The bottom-up
approaches use an integration over the atomistic degrees of
freedom and the corresponding atomistic force-field to develop
the mesoscopic model.176–181 Useful bottom-up CG strategies
include the iterative Boltzmann inversion (IBI)164,182,183 and
force matching (FM)184,185 schemes.
Different CG force fields171,172,174,175,179,186–189 use different
mappings as they develop beads from the underlying atoms.
These mappings can range from 4 : 1 (a CG particle represents
four heavy atoms plus associated hydrogen atoms)186 to 20 : 1
(one CG particle corresponds to 20 united atoms).179–181 Some
models such as the MARTINI force field186–188,190–193 developed
by Marrink et al. model the dispersion and overlap interactions
with a 12-6 shifted Lennard-Jones potential, while Klein and
co-workers171 prefer a 9-6 LJ potential, and Chiu et al.172 have
employed a Morse potential to study alkanes and water. The
MARTINI model has been developed from the calculation of the
free energy of hydration, the free energy of vaporization, and
the partitioning free energies between water and a number of
organic phases. Again, Avendano et al.174,175 have developed
the (SAFT-g) CG field from the SAFT equation of state,194,195
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using the Mie-generalized Lennard-Jones potential.196 All these
force fields can be readily used with standard MC and MD
methods. Other CG potentials can be used with mesoscopic
methods such as dissipative particle dynamics (DPD).26,197–199
The first simulations of the liquid–vapour interface of water
with the MARTINI CG force field187 gave values of surface
tensions of 45 and 30 mN m1 at 298 K depending on the
system-sizes (see Fig. 15). For the polarisable version of the
water MARTINI model,191 the simulated surface tension is
30 mN m1. This significant deviation from experiments (gexp. =
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73 mN m1) can be explained by the absence of significant
ordering of the dipoles of the CG water particles in the inter-
facial region191 unlike the behaviour observed for the atomistic
models.202 The MARTINI model performs better in the case
of the liquid–vapour interface of alkanes.187 These types of
molecules are the best candidate for a coarse-grained approach
since they are formed by a number of identical groups that
interact predominantly through dispersion–repulsion inter-
actions. Another coarse-graining strategy, based on the models
of Mie196 segments, has been successfully applied to calculate
the surface tension of liquid–vapour interfaces174,175 of CO2, SF,
CH4, and long linear alkanes including n-C10H22 and n-C20H42.
The surface tension of water26 has also been calculated
from the many-body dissipative particle dynamics (MDPD)
method199 by considering a top-down approach for the devel-
opment of the potential parameters. We note the standard
version of DPD has a short-ranged conservative force usually
represented by a linear ramp
fij = a(1  rij/rc)r̂ij rij r rc (31)
where a determines the interaction between the DPD beads.
While this model gives rise to a perfectly satisfactory liquid–
liquid interface, this force, and the corresponding quadratic
Fig. 15 The interfacial tensions, g of: n-hexane–water, n-octane–water,
n-decane–water, n-dodecane–water, n-hexadecane–water, cyclohexane–
water, benzene–water, chloroform–water, octan-1-ol-water;59 cyclohexane–
water and benzene–water calculated using the DPD method;200 mixtures such
as water–methanol, hexane–benzene, and water + NaCl salt calculated with
the DPD model;173,201 the liquid–vapour interfaces of pure water and pure
dodecane calculated using the MARTINI force field;187 the liquid–vapour
interfaces of the CF4 SF6 and n-eicosane systems;175 the liquid–vapour interface
of water using a CG model with the Morse potential.172
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potential, is not sufficiently steep to sustain a liquid–vapour
equilibrium. It is necessary to adapt the model so that coefficient a
depends on the local density to form a stable liquid–vapour
interface (MDPD). A direct comparison between atomistic MC
and MDPD simulations has been performed to compare the
surface tension, coexisting densities and profiles of the normal
and tangential components of the pressure tensor along the
surface normal for water. This MDPD method has also been
extended to the case of the liquid–vapour interface of mixtures201
and electrolytes.173 Calculations of g and the rl for water at room
temperature agree with the results of atomistic simulation and
experiment to within ca. 5% and the coarse grained parameters are
transferable over a range of 50 K.
As discussed, the computer modelling of micellar systems203–207
is a particularly challenging problem due to the microsecond
time-scale for the micellar relaxation and the length scale (the
simulation of tens of micelles of C12E6 in aqueous solution
might require ca. a million atoms). Although leading-edge
computers can perform simulations of this size and length, it
is difficult to use atomistic simulation in a routine way to fit
models to experimental data and a coarse-grained approach is
required. In the case of the study of water–surfactant–oil
complex systems, the prediction of the interfacial tension of
the oil–water liquid–liquid interface represents a good test for
these CG models. Fig. 15 shows the interfacial tension of some
water–alkanes, water–benzene and water–chloroform calculated
from the CG MARTINI force field.59 This figure shows that we
cannot expect a prediction of the interfacial tension of some
liquid–liquid systems with the CG MARTINI force field to be
better than 10 mN m1. The calculation of the surface tension
with the MARTINI force field is less accurate when the interfaces
are characterized by strong local orientational ordering or
hydrogen bonding.59 The definition of the CG element must
also consider if the atomic groups representing the bead are
undergoing internal changes.
Nevertheless, the interfacial tension of oil–water systems is
reasonably reproduced with the MARTINI model.59 The DPD
mesoscale simulations of water–benzene and water–cyclohexane200
systems predict interfacial tensions to an accuracy of 10 mN m1.
These CG models (MARTINI and DPD) also reproduce accurately
the dependence of the interfacial tension of these oil–water systems
with temperature200 and alkane chain length.59
The simulation of oil–surfactant–water mixtures needs large
systems, so that the results do not depend on the area of the
surface, and also long simulations since the equilibration of the
surfactant between the bulk and surface regions is slow. The
modelling of oil–surfactant–water systems has been investigated
by DPD simulations209–216 and using the MARTINI models.208,217
These simulations accurately reproduce the dependence of the
interfacial tension as a function of the surfactant concentration
at the interface. Fig. 16 shows the calculated interfacial tension of
the dodecane–water modified by the addition of SDS (sodium
dodecyl sulfate) surfactants. Three different models have been
compared: the standard MARTINI force field187 with explicit
water molecules,191 an implicit-solvent-version of the MARTINI
model,217 and CG potentials206 used with the DPD method.
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Fig. 16 g/g0 ratio as a function Cs, the number of surfactants at the
surface divided by the surface area. g0 is the interfacial tension of the
water–dodecane interface (with no surfactant). The values of the inter-
facial tensions are calculated with the DRY MARTINI model;208 the MAR-
TINI model with explicit solvent molecules and the DPD method.
In order to allow the comparison between the different methods, we
report the results of interfacial tension as the ratio g/g0 where g0 is
the interfacial tension of the oil–water system without any
surfactants. All the simulated interfacial tensions as a function
of surface coverage fall on one simple curve in Fig. 16; i.e., the
interfacial tension decreases in a concave down fashion as the
surfaces are covered by more dodecyl sulphate anions. g reaches
a minimum finite value corresponding to the interfacial tension
at the point of surfactant micellisation. At this point, the interface
is fully saturated with surfactant molecules. The mesoscopic (DPD)
simulations and MARTINI coarse-grained force fields correctly
reproduce the dependence of interfacial tension on surfactant
concentration. Fig. 17a shows a typical configuration of the oil/
water/SDS surfactant mixtures below the critical micelle concen-
tration (cmc) calculated from the MARTINI CG model whereas
Fig. 17b presents a configuration of the same system near the cmc
where we observe the formation of surfactant micelle in the bulk
water phase.
Mesoscopic simulation of CG models can be used to make
quantitative prediction of interfacial properties of complex
Fig. 17 Snapshots of the n-dodecane–water + surfactants at different
SDS concentrations (a) obtained from the MARTINI model at concentra-
tions well below the cmc for the model. (b) For the DPD model at
concentrations well above the cmc for the model.
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systems involving the self-assembly of amphiphiles. So far this
work has not been extended to nanoscopic droplet interface,
to design new surfactants of new surfactants for industrial
applications, of to understand how solid surface modifies g at
a neighbouring liquid–vapour interface.
5 Conclusions
The slab geometry is a useful technique for modelling liquid–
liquid and liquid–vapour planar interfaces and for calculating
the surface tensions from the triple point to within ca. 10%
of the critical point. For the system close to the critical point
the best route is to employ grand canonical Monte Carlo
simulations and histogram-reweighting techniques to calculate g.
There are a number methods for accurately calculating the
surface tension from a slab geometry simulation. The mechanical
route to g involves the calculation of the pressure tensor, p. For the
planar interface, the transverse component of p cannot be deter-
mined uniquely as a function of z but all reasonable definitions
will lead to the same surface tension. In addition, the test area
method is a simple and reliable thermodynamic method for the
calculation of g which involves scaling the surface area of the slab
at constant volume. These two routes are consistent once the
appropriate long-range corrections are added to the intrinsic
surface tension. The test area method has the advantage that it
can be used with non-pair additive potentials.
For the planar interface the computational procedures used
in the Monte Carlo and molecular dynamics simulations of the
slab geometry are now under control and we have given some
clear recommendations in this review which should lead to
accurate calculations of g for a particular model.
In particular, the long-range corrections to the pressure are
particularly important and can amount to as much as 30% of gI
for a cut-off rc = 3.0s for the Lennard-Jones fluid. The Janec̆ek66
method provides an accurate calculation of the long range
correction for the pressure tensor when applied at each step
in the calculation and in terms of its implementation and
speed, is the most promising approach. However, it is also
possible to calculate these corrections by applying the Ewald
sum in the slab geometry for the dispersion term of the
Lennard-Jones potential.
Once these methodological issues are properly addressed,
the simulations will be predictive if the underlying potential
models are accurate. Most straightforward effective pairwise
potentials are not fitted to the surface tension so that its
calculation can be a severe test of such potentials. For example
for modelling g for argon, simulations with the LJ potential
exhibit systematic differences between experiment and simula-
tion of 20% for g and it requires the introduction of the 3-body
forces and an accurate 2-body potential to reduce this difference
to 2% along most of the orthobaric curve. One can argue that
given the accuracy in the experimental determination of g the
simulation is predictive for the liquid–vapour interface of argon.
However, even for an approximately spherical molecule such as
CH4, where the polarisability is low, the agreement between the
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simulated and experimental values of g is not satisfactory
(although in this case the difference may be due to the neglect
of the octopole–octopole electrostatic interaction). Even for
atomic liquids the intrinsic planar surface is not smooth and
g will be a function of the wave vector describing the periodicity
of the surface. g(k) can be calculated in simulations218 but to
date this k-dependence has not been observed experimentally
to the best of our knowledge. The calculation of interfacial
properties of intrinsic surfaces will be an interesting area for
future simulations.
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For a large range of molecular liquids the prediction of the
surface tension is to within 15% of experiment. This includes
small molecules such as N2, H2S, alcohols, alkanes (up to C12),
and aromatics. In these simulations, it is necessary to introduce
the electrostatic interaction either as point multipoles, distributed
multipoles or partial charges. For long-range interactions (where
the potential falls off more slowly than the dimensionality) these
are included using an Ewald sum or one of the other techniques
for handling long range force. The real and reciprocal-space
contributions to the pressure tensor are well understood and can
be calculated as a function of z through the interface. The first
simulations of water were performed in 198031 and since then
there have been over 1000 papers reporting simulations of various
water interfaces. Currently one of the best predictive model for the
surface tension is TIP4P2005111 with an average deviation of 5%
along the coexistence curve and a maximum deviation of 15% at
600 K (Tcritical = 645 K). It is important to have this model under
control since water is an important solvent in many industrial
applications of surfactancy.
The simulation of mixtures allows us to extend the variables
that we consider from temperature to concentration and pressure.
(The Gibbs rule tells us that for a single component systems at
each temperature there is a single point on the coexistence line but
for mixtures there are many coexistence points on higher
dimensional surfaces.) The development of good potentials for
complex mixture requires not just an understanding of the
single component interactions in a molecular fluid but also
the mixing rules between the unlike components. Most simulations
to date have been performed using the venerable Lorentz–Berthelot
mixing rule219,220 and future work will involve accurately para-
metrising cross interactions between important components
such as CO2 and H2O. This is true for the important dispersion
interaction, while on the other hand the electrostatic interac-
tions are quite transferable between like and unlike species.
The preferred ensemble for these simulations is constant-
NpN AT. For two component mixtures such as C5H12/H2S and
H2O/CO2 good predictions of g as a function of pressure are
obtained for pressure up to 40 MPa. The results are important
for the storage of CO2. The risk of leakage through the cap rock
is governed by the water acid gas interfacial tension through the
Laplace equation.90 The simulation of the interfacial properties of
the salt solution is also a challenging and interesting problem.
The driving force for this work is an understanding of water
purification by osmosis. We observe that the increase in g with
molality is well described by non-polarisable effective pair
potentials but the arrangement of the molecules at the interface
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is better described by the more realistic polarisable model.
These polarisable model do not do such a good job on the
surface tension. The underlying reasons for this are not well
understood and further experimental work and further work on
model building for these systems is required.
Another challenging topic is the calculation of the interfacial
tension of chemically reacting mixtures such as CO2 + NO2/
N2O4221 by coupling the reaction ensemble Monte Carlo (RxMC)
method222–224 with the explicit modeling of the interface.
A knowledge of g for surface tensions of droplet on surfaces
is critical for the determination of spreading and wetting.149 In
reality all interfaces are curved, the planar interface is the limit
of the spherical droplet with an infinite radius of curvature and
we expect to see important differences in g for small droplets.
However, there are still fundamental problems in defining the
local components of the pressure tensor in an isolated spherical
droplet. This results in a number of reasonable yet different
definitions of g through the mechanical route. As is clear from
Fig. 14 there are also differences between the mechanical and
thermodynamic routes as exemplified by the extensions of the
test area method. Although this is not a proof of the superiority
of one approach over the other, the thermodynamic route in
simulation is in much better agreement with the density
functional-like theories than the mechanical route. The test
area method itself is quite complicated to apply to spherical
droplet because we need to identify a linear transformation that
is volume conserving. However, at this time, we would recommend
the TA33 approach for the calculation of g for droplets. The
methodological problems for the small spherical droplets have
not been sufficiently resolved to perform meaningful, routine
simulation on molecular systems and their mixtures in this
geometry. For example it would be difficult to use simulation to
ask if there is a significant difference in the Tolman length of a
water or CO2 droplet. The whole area of long-range corrections
for these finite systems, which is so important for the calculation
of g in the planar slab, has not been addressed. An understanding
of the effects of system-size and cut-off dependence is difficult
mainly because we expect the properties of the droplet to change
with size and droplet radius. These difficulties mean that many
simulations of the droplet are run with truncated and shifted
Lennard-Jones potentials, which we know to be problematic for
planar interfaces.
The simulation of coarse-grained models for the calculation
of interfacial properties is an important area of active research.
We are still seeking of the correct level of coarse-graining for
different problems (such as surface wetting, polymer micelle
interaction and lubrication). An important feature of the problem
is to build a mesoscale model from an underpinning atomistic
model. This is not straightforward because techniques such as
iterative Boltzmann inversion or force-matching while applicable
to homogeneous fluid are difficult to use in interfacial simulations
because the effective potential may depend strongly on the local
density. In multi-scale simulation we have a loose coupling of the
levels by transfer of parameters, such as g calculated at, say, the
atomistic to the mesoscale (i.e. the levels are independent). In an
alternative approach it is possible to have a close-coupling of the
This journal is © The Royal Society of Chemistry 2016

Chem Soc Rev
levels where the behaviour at, say, the mesoscale demands that the
simulation be carried forward at the atomistic scale. To date, we
are unaware of simulations of surface tension that involve this
second kind of close coupling and this will be an important
development for the future. Another interesting topic that could
be addressed by using the theoretical background of the spherical
interfaces and the use of GC models157 is the question of the
prediction of the spontaneous curvature and elasticity of inter-
facial films225,226 in the case of phase equilibria of water-in-oil
microemulsions.
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Simulations of g are also important in the oil and gas industry
because we can predict the temperature and pressure dependence
in regions that are not readily accessible in laboratory experiment.
The general extension of these methods to multi-component
mixtures is straightforward. Many important detergency problems
in industry are tackled using 5–7 component mixtures of
surfactants and simulation will be an important part in the
optimisation of these products. In the future, we will need a
large system to include a significant number of molecules of
each species and longer times to ensure equilibration of the
species between the phases, but the principles discussed in the
review remain the same. Fortunately computer power continue
to increase and it is likely that leading-edge machines of 1018
Flops will become available in the next five years and more
general machine of this power available five years beyond that.
These speed increases will occur because of the parallelisation
of the algorithms and all of the techniques discussed in this
review can be run on parallel machines using domain decom-
position and other techniques. We can envisage a powerful code
for the calculation of the surface tension and other interfacial
properties of multi-component mixtures that will widely be used
to guide the experimental design of multi-component surfactant
mixtures. While the quantitative prediction of the exact surface
tension of multi-component may still be a difficult problem,
these simulation codes will enable us to study the changes and
trends in g with the addition of minor components.
Acknowledgements
We wish to thank Florent Goujon, University Blaise Pascal,
Véronique Lachet, IFPen, Emeric Bourasseau, CEA, Massimo
Noro and Patrick Warren, Unilever Research, for useful discussions
in the preparation of this review.
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