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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
Received 25th September 2015 molality; the simulations of spherical interfaces including the calculation of the sign and size of the
DOI: 10.1039/c5cs00736d 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
www.rsc.org/chemsocrev interfacial systems.
1 Introduction where A is the Helmholtz free energy and A is the surface area.
The corresponding expression at constant pressure involves the
1.1 The surface tension Gibbs free energy G
The surface tension arises from the unbalanced attractive forces
at an interface, where the density of the system is changing @G
g¼ : (2)
rapidly. The surface appears to be covered with a stretched @A N;P;T
elastic membrane. For the vapour–liquid interface of water, the
surface tension is high (72.8 mN m1 at 20 1C), and small The surface tension can be measured experimentally by a
objects that are denser than water are able to float or move along variety of techniques including the Du Noy ring method, the
the surface. An understanding and control of the surface tension pendant drop method and the Wilhelmy plate method.5
is at the heart of many important industrial and practical However, one of the goals of modern liquid-state theory
processes, for example: the control of detergency through the has been the accurate prediction of g from a knowledge
addition of surface active molecules (surfactants);1 enhanced oil of the underlying intermolecular potential functions for
recovery from reservoirs through the injection of dilute solutions mixtures over a broad range of temperatures and pressures.
to reduce the surface tension;2 the phenomena of wetting and The powerful technique of computer simulation can be
spreading in the application of coatings;3 and the separation of brought to bear on this problem and in this review, we will
hydrophilic and hydrophobic materials using froth flotation.4 explore the progress that has been made towards this goal in
Formally the surface tension of a liquid is the force per unit the last 40 years.
length that opposes the expansion of the surface area. For a
1.2 Statistical mechanics of the vapour–liquid interface
system at constant volume, temperature and composition
The connection between the underlying intermolecular potential
@A and the surface tension of an interface is made through the
g¼ (1)
@A N;V;T statistical mechanics of inhomogeneous systems.6–8
For an inhomogeneous fluid in the canonical ensemble, the
a
Institut de Physique de Rennes, UMR CNRS 6251, Université Rennes 1, structure at the interface is essentially described by the singlet
263 avenue du Général Leclerc, 35042 Rennes, France and pair distribution functions. For a fluid of N atoms at a
b
Institut de Chimie de Clermont-Ferrand, ICCF, CNRS, UMR 6296, Université Clermont temperature T
Auvergne, Université Blaise Pascal, BP 10448, F-63000 Clermont-Ferrand, France.
E-mail: Patrice.Malfreyt@univ-bpclermont.fr; Tel: +33 473407204 Ð Ð
ð1Þ expðbVÞdrðN1Þ
c
CECAM École Polytechnique Fédérale de Lausanne, Batochime BCH 3101, r ðr1 Þ ¼ N Ð Ð (3)
CH 1015 Lausanne, Switzerland expðbVÞdrðNÞ
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and where V is the total potential energy of the fluid, dr(N) = dr1 drN,
Ð Ð where dr1 is the volume element for atom 1, and b = 1/kBT, where kB
expðbVÞdrðN2Þ
rð2Þ ðr1 ; r2 Þ ¼ NðN 1Þ Ð Ð (4) is the Boltzmann constant. r(1) and r(2) are related through the first
expðbVÞdrðNÞ
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}
Aziz Ghoufi received his PhD degree or {zi, cos yij, rij}). The geometry of the planar interface is shown
in physical chemistry from the in Fig. 1.
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Patrice Malfreyt obtained his PhD in Dominic Tildesley received his BSc
Physical Chemistry on computer in Chemistry from Southampton
modelling in 1995 from the University in 1973 and his DPhil
University Blaise Pascal, Clermont- from Oxford University in 1977.
Ferrand, France. After a postdoctoral After postdoctoral positions at
stage at Imperial College (London), Pennsylvania State University,
he joined the group of Cornell and Oxford, he joined the
Thermodynamics of Clermont- Chemistry Department at
Ferrand where he is professor Southampton University in 1981.
since 2004. He is the head of the He was awarded the Chair of
group of ‘‘Molecular architectures Theoretical Chemistry at
at interfaces’’ at the Institute of Southampton in 1990. In 1998
Patrice Malfreyt Chemistry of Clermont-Ferrand Dominic J. Tildesley Dominic joined Unilever Research
(ICCF) and he is vice-president Port Sunlight as the Head of the
of the Physical Chemistry Division of the French Chemical Society Physical Sciences Group. In 2003 he became Chief Scientist for
(SCF). His research is dedicated to the development of Unilever’s Home and Personal Care Division. He retired from
methodologies for simulations of interfacial systems and of multi- Unilever in June 2012. He moved to Switzerland in January 2013, to
scale simulations for the study of thermodynamic and mechanical become Director of CECAM (Centre Européen de Calcul Atomique et
properties of polymers at interfaces. 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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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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Table 1 Values of surface tension (mN m1) calculated from Monte Carlo chlorine69 and alkanes.60,70 The long range corrections calculated
simulations using a truncated Lennard-Jones potential and a truncated by this expression are also given in Table 2 for comparison. These
potential modified by a polynomial function (see ref. 58). Different definitions
two tail corrections are added to the intrinsic part of the surface
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 at the end of the simulation but are calculated with a
tension; and each definition, IK, KB and TA has its own expression for the tail density profile that corresponds to the truncated potential without
correction to the surface tension. The reader is directed to ref. 58 for a any tail corrections. By themselves they can only provide a upper
description of the methodology of the calculation. For the MARTINI model, limit to the true tail correction.
the reader is redirected to ref. 59. The subscripts give the accuracy of the last
A third approach used by Alejandre and coworkers64,65,71
decimal(s), i.e., 65.814 means 65.8 1.4
consists in modelling the full LJ potential by calculating the
gKB gIK gTA dispersion term of the LJ potential as a lattice sum such as
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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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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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Finally there are a number of specialised techniques to deal constant-NVT statistical ensemble.57,128–131 The constant-NPT
with 2-D periodic charges such as the methods of Lekner122,123 ensemble is not designed for modelling a two-phase binary
and Hautman and Klein.124 Both these methods require that system because the tangential component, pT, of the pressure
the parameter zij/sij between two charges i and j is small since tensor is not constant along the surface normal, normally
this is used as an expansion parameter in a series expansion of exhibiting a strong minimum in the interfacial region. The
the force. The methods are best applied to physisorbed mono- most appropriate ensemble is at constant-NpN AT where pN is
layers or very thin liquid films. the normal pressure and the A interfacial area. The reader is
directed to the work of Biscay et al.90,132 for a comprehensive
2.3 Mixtures description of the methodology. In this case, the expressions
As discussed in the previous section, the two-phase simulations for the calculation of the long range corrections to the surface
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of liquid–vapour interfaces of pure systems (i.e. a single component) tension through the thermodynamic and mechanical routes are
is well-understood from a methodological viewpoint and the also available.90,132 Fig. 12 shows the surface tension of different
reproduction of the temperature dependence of g for these binary mixtures as a function of the pressure. Fig. 12 shows the
systems is good. For mixtures we need to extend these methods value of the constant-NpN AT simulation method in predicting
to consider additional parameters such as composition and the surface tension. The results of these slab simulations over a
pressure. For example, the long range corrections to the surface large range of pressures for the coexisting densities compare
tension and configurational energy for a mixture is straight- well with the simulated phase diagrams calculated from Gibbs
forward and has been achieved with the approach of Guo and ensemble Monte Carlo (GEMC) simulations.134,135
Lu.76 To our knowledge, the method of Janec̆ek has not been Another challenging aspect of the computer modelling of
applied to the liquid–vapour equilibrium of mixtures but this the surface tension of complex systems is the prediction of the
extension poses no fundamental problems. Fig. 11 shows the dependence of the surface tension on salt concentration. This
surface tension of different mixtures as a function of the calculation may be quite sensitive to the choice of standard
composition. In the case of the liquid–vapour interface of an (non-polarisable) or polarisable models of water and the ions.
alcohol–water mixture, the simulations accurately predict the Fig. 13 shows the increase of the relative surface tension
significant decrease of the surface tension with the alcohol defined by Dg = gsalt gwater where gsalt and gwater are the
mole fraction.125,126 In the water–alcohol mixtures, the long surface tensions of the salt solution and pure water. Different
range corrections to the surface tension contribute between 5% methods have been employed to include electronic polarisation
and 10% of the total surface tension depending on the alcohol into simple atom–atom potentials. Three of the most widely-used
concentration and must be accurately included. The molecular techniques are the induced dipole model,136–138 the fluctuation
description of the mixture in terms of density profiles and charge model139,140 and the classical Drude oscillator model.106
hydrogen bond profiles has been used convincingly to interpret The Drude oscillator model, with the simple functional form of
the decrease of the surface tension with the alcohol concentration. the pairwise additive interactions and the ability to account for
The dependence of the surface tension on the composition is well the electronic polarisability, is particularly useful since it intro-
reproduced for other mixtures127 where the variation is less duces only a small computational overhead. Different polarisable
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
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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. 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
Drop size can be defined from the radius of the equimolar
the droplet where gN is the surface tension of the planar limit. , FMT
dividing surface (Re) which can be derived from the radial (a nonlocal DFT using functional measure theory).33 Thermodynamic
density profile r(r) routes: , grand canonical Monte Carlo simulations;152 , Monte
ð1 Carlo simulations using a thermodynamic route of Homman et al.;32 ,
1 drðrÞ
Re3 ¼ drr3 (19) the simulated surface tension calculated from TA ellipsoidal deforma-
ðrv rl Þ 0 dr tions.33 Mechanical routes: , molecular dynamics simulations using the
mechanical route;35 , Monte Carlo simulations using the IK definition.32
where rv and rl are the vapour and liquid densities. 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 where x is a small, dimensionless variable and Z represents the
the last 30 years.155 Although the DFT method allows a direct box length and the atom coordinate vectors, so that the
and unambiguous calculation of g, its application to realistic transformation preserves the spherical symmetry of the droplet.
systems with complex interactions is more difficult and it does V 0r and V 1r are the local configurational energy in the radial
not provide exact results. On the other hand molecular simulation element dr at r when the local volume is changed from V 0r to V1r .
is exact, can be readily applied to complex intermolecular forces The expression for the tangential component of the local
but the calculation of surface tension for a well-defined model pressure157 is
remains ambiguous. More recently Sampayo et al.,33 Lau et al.156
kB T
and Homman et al.32 have provided a macroscopic thermodynamic 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 The Tolman length calculated by this approach is normally
tension at Rs and Dp the pressure difference between the vapour small and negative153,162 but some carefully performed simulations
and liquid phases separated by the surface of tension. Usually, still suggest a positive value.162,163 This remains an unsolved issue.
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 4 Coarse-grained (CG) models
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 All the computer simulations discussed up until this point have
separated by a dividing surface of radius R. Thermodynamic been performed using atomistic force fields with different UA
equilibrium implies that (United Atom) and AA (All Atom) models. These atomistic
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using the Mie-generalized Lennard-Jones potential.196 All these potential, is not sufficiently steep to sustain a liquid–vapour
force fields can be readily used with standard MC and MD equilibrium. It is necessary to adapt the model so that coefficient a
methods. Other CG potentials can be used with mesoscopic depends on the local density to form a stable liquid–vapour
methods such as dissipative particle dynamics (DPD).26,197–199 interface (MDPD). A direct comparison between atomistic MC
The first simulations of the liquid–vapour interface of water and MDPD simulations has been performed to compare the
with the MARTINI CG force field187 gave values of surface surface tension, coexisting densities and profiles of the normal
tensions of 45 and 30 mN m1 at 298 K depending on the and tangential components of the pressure tensor along the
system-sizes (see Fig. 15). For the polarisable version of the surface normal for water. This MDPD method has also been
water MARTINI model,191 the simulated surface tension is extended to the case of the liquid–vapour interface of mixtures201
30 mN m1. This significant deviation from experiments (gexp. = and electrolytes.173 Calculations of g and the rl for water at room
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73 mN m1) can be explained by the absence of significant temperature agree with the results of atomistic simulation and
ordering of the dipoles of the CG water particles in the inter- experiment to within ca. 5% and the coarse grained parameters are
facial region191 unlike the behaviour observed for the atomistic transferable over a range of 50 K.
models.202 The MARTINI model performs better in the case As discussed, the computer modelling of micellar systems203–207
of the liquid–vapour interface of alkanes.187 These types of is a particularly challenging problem due to the microsecond
molecules are the best candidate for a coarse-grained approach time-scale for the micellar relaxation and the length scale (the
since they are formed by a number of identical groups that simulation of tens of micelles of C12E6 in aqueous solution
interact predominantly through dispersion–repulsion inter- might require ca. a million atoms). Although leading-edge
actions. Another coarse-graining strategy, based on the models computers can perform simulations of this size and length, it
of Mie196 segments, has been successfully applied to calculate is difficult to use atomistic simulation in a routine way to fit
the surface tension of liquid–vapour interfaces174,175 of CO2, SF, models to experimental data and a coarse-grained approach is
CH4, and long linear alkanes including n-C10H22 and n-C20H42. required. In the case of the study of water–surfactant–oil
The surface tension of water26 has also been calculated complex systems, the prediction of the interfacial tension of
from the many-body dissipative particle dynamics (MDPD) the oil–water liquid–liquid interface represents a good test for
method199 by considering a top-down approach for the devel- these CG models. Fig. 15 shows the interfacial tension of some
opment of the potential parameters. We note the standard water–alkanes, water–benzene and water–chloroform calculated
version of DPD has a short-ranged conservative force usually from the CG MARTINI force field.59 This figure shows that we
represented by a linear ramp cannot expect a prediction of the interfacial tension of some
liquid–liquid systems with the CG MARTINI force field to be
fij = a(1 rij/rc)r̂ij rij r rc (31)
better than 10 mN m1. The calculation of the surface tension
where a determines the interaction between the DPD beads. with the MARTINI force field is less accurate when the interfaces
While this model gives rise to a perfectly satisfactory liquid– are characterized by strong local orientational ordering or
liquid interface, this force, and the corresponding quadratic 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
Fig. 15 The interfacial tensions, g of: n-hexane–water, n-octane–water,
These simulations accurately reproduce the dependence of the
n-decane–water, n-dodecane–water, n-hexadecane–water, cyclohexane– interfacial tension as a function of the surfactant concentration
water, benzene–water, chloroform–water, octan-1-ol-water;59 cyclohexane– at the interface. Fig. 16 shows the calculated interfacial tension of
water and benzene–water calculated using the DPD method;200 mixtures such the dodecane–water modified by the addition of SDS (sodium
as water–methanol, hexane–benzene, and water + NaCl salt calculated with
dodecyl sulfate) surfactants. Three different models have been
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
compared: the standard MARTINI force field187 with explicit
interfaces of the CF4 SF6 and n-eicosane systems;175 the liquid–vapour interface water molecules,191 an implicit-solvent-version of the MARTINI
of water using a CG model with the Morse potential.172 model,217 and CG potentials206 used with the DPD method.
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5 Conclusions
The slab geometry is a useful technique for modelling liquid–
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simulated and experimental values of g is not satisfactory is better described by the more realistic polarisable model.
(although in this case the difference may be due to the neglect These polarisable model do not do such a good job on the
of the octopole–octopole electrostatic interaction). Even for surface tension. The underlying reasons for this are not well
atomic liquids the intrinsic planar surface is not smooth and understood and further experimental work and further work on
g will be a function of the wave vector describing the periodicity model building for these systems is required.
of the surface. g(k) can be calculated in simulations218 but to Another challenging topic is the calculation of the interfacial
date this k-dependence has not been observed experimentally tension of chemically reacting mixtures such as CO2 + NO2/
to the best of our knowledge. The calculation of interfacial N2O4221 by coupling the reaction ensemble Monte Carlo (RxMC)
properties of intrinsic surfaces will be an interesting area for method222–224 with the explicit modeling of the interface.
future simulations. A knowledge of g for surface tensions of droplet on surfaces
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For a large range of molecular liquids the prediction of the is critical for the determination of spreading and wetting.149 In
surface tension is to within 15% of experiment. This includes reality all interfaces are curved, the planar interface is the limit
small molecules such as N2, H2S, alcohols, alkanes (up to C12), of the spherical droplet with an infinite radius of curvature and
and aromatics. In these simulations, it is necessary to introduce we expect to see important differences in g for small droplets.
the electrostatic interaction either as point multipoles, distributed However, there are still fundamental problems in defining the
multipoles or partial charges. For long-range interactions (where local components of the pressure tensor in an isolated spherical
the potential falls off more slowly than the dimensionality) these droplet. This results in a number of reasonable yet different
are included using an Ewald sum or one of the other techniques definitions of g through the mechanical route. As is clear from
for handling long range force. The real and reciprocal-space Fig. 14 there are also differences between the mechanical and
contributions to the pressure tensor are well understood and can thermodynamic routes as exemplified by the extensions of the
be calculated as a function of z through the interface. The first test area method. Although this is not a proof of the superiority
simulations of water were performed in 198031 and since then of one approach over the other, the thermodynamic route in
there have been over 1000 papers reporting simulations of various simulation is in much better agreement with the density
water interfaces. Currently one of the best predictive model for the functional-like theories than the mechanical route. The test
surface tension is TIP4P2005111 with an average deviation of 5% area method itself is quite complicated to apply to spherical
along the coexistence curve and a maximum deviation of 15% at droplet because we need to identify a linear transformation that
600 K (Tcritical = 645 K). It is important to have this model under is volume conserving. However, at this time, we would recommend
control since water is an important solvent in many industrial the TA33 approach for the calculation of g for droplets. The
applications of surfactancy. methodological problems for the small spherical droplets have
The simulation of mixtures allows us to extend the variables not been sufficiently resolved to perform meaningful, routine
that we consider from temperature to concentration and pressure. simulation on molecular systems and their mixtures in this
(The Gibbs rule tells us that for a single component systems at geometry. For example it would be difficult to use simulation to
each temperature there is a single point on the coexistence line but ask if there is a significant difference in the Tolman length of a
for mixtures there are many coexistence points on higher water or CO2 droplet. The whole area of long-range corrections
dimensional surfaces.) The development of good potentials for for these finite systems, which is so important for the calculation
complex mixture requires not just an understanding of the of g in the planar slab, has not been addressed. An understanding
single component interactions in a molecular fluid but also of the effects of system-size and cut-off dependence is difficult
the mixing rules between the unlike components. Most simulations mainly because we expect the properties of the droplet to change
to date have been performed using the venerable Lorentz–Berthelot with size and droplet radius. These difficulties mean that many
mixing rule219,220 and future work will involve accurately para- simulations of the droplet are run with truncated and shifted
metrising cross interactions between important components Lennard-Jones potentials, which we know to be problematic for
such as CO2 and H2O. This is true for the important dispersion planar interfaces.
interaction, while on the other hand the electrostatic interac- The simulation of coarse-grained models for the calculation
tions are quite transferable between like and unlike species. of interfacial properties is an important area of active research.
The preferred ensemble for these simulations is constant- We are still seeking of the correct level of coarse-graining for
NpN AT. For two component mixtures such as C5H12/H2S and different problems (such as surface wetting, polymer micelle
H2O/CO2 good predictions of g as a function of pressure are interaction and lubrication). An important feature of the problem
obtained for pressure up to 40 MPa. The results are important is to build a mesoscale model from an underpinning atomistic
for the storage of CO2. The risk of leakage through the cap rock model. This is not straightforward because techniques such as
is governed by the water acid gas interfacial tension through the iterative Boltzmann inversion or force-matching while applicable
Laplace equation.90 The simulation of the interfacial properties of to homogeneous fluid are difficult to use in interfacial simulations
the salt solution is also a challenging and interesting problem. because the effective potential may depend strongly on the local
The driving force for this work is an understanding of water density. In multi-scale simulation we have a loose coupling of the
purification by osmosis. We observe that the increase in g with levels by transfer of parameters, such as g calculated at, say, the
molality is well described by non-polarisable effective pair atomistic to the mesoscale (i.e. the levels are independent). In an
potentials but the arrangement of the molecules at the interface alternative approach it is possible to have a close-coupling of the
Chem. Soc. Rev. This journal is © The Royal Society of Chemistry 2016
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levels where the behaviour at, say, the mesoscale demands that the 5 S. Hartland, Surface and Interfacial Tension: Measurement,
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27 A. E. Ismail, G. S. Grest and M. J. Stevens, J. Chem. Phys.,
We wish to thank Florent Goujon, University Blaise Pascal,
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