Oscillatory surface tension due to finite-size

effects
Cite as: J. Chem. Phys. 123, 114702 (2005); https://doi.org/10.1063/1.2018640
Submitted: 18 March 2005 . Accepted: 13 July 2005 . Published Online: 19 September 2005

Pedro Orea, Jorge López-Lemus, and José Alejandre

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J. Chem. Phys. 123, 114702 (2005); https://doi.org/10.1063/1.2018640 123, 114702

© 2005 American Institute of Physics.

 THE JOURNAL OF CHEMICAL PHYSICS 123, 114702 共2005兲

Oscillatory surface tension due to finite-size effects

Pedro Orea
Ingeniería Molecular, Instituto Mexicano del Petróleo, Eje Central Lázaro Cárdenas 152, México DF
07730, México
Jorge López-Lemus
Facultad de Ciencias, Universidad Autónoma del Estado de México, Avenida Instituto Literario 100, Toluca
CP 50000, México
José Alejandrea兲
Departamento de Química, Universidad Autónoma Metropolitana-Iztapalapa, Avenida San Rafael Atlixco
186, Col. Vicentina, México DF 09340, México
共Received 18 March 2005; accepted 13 July 2005; published online 19 September 2005兲

The simulation results of surface tension at the liquid-vapor interface are presented for fluids
interacting with Lennard Jones and square-well potentials. From the simulation of liquids we have
reported 关M. González-Melchor et al., J. Chem. Phys. 122, 4503 共2005兲兴 that the components of
pressure tensor in parallelepiped boxes are not the same when periodic boundary conditions and
small transversal areas are used. This fact creates an artificial oscillatory stress anisotropy in the
system with even negative values. By doing direct simulations of interfaces we show in this work
that surface tension has also an oscillatory decay at small surface areas; this behavior is opposite to
the monotonic decay reported previously for the Lennard Jones fluid. It is shown that for small
surface areas, the surface tension of the square-well potential artificially takes negative values and
even increases with temperature. The calculated surface tension using a direct simulation of
interfaces might have two contributions: one from finite-size effects of interfacial areas due to box
geometry and another from the interface. Thus, it is difficult to evaluate the true surface tension of
an interface when small surface areas are used. Care has to be taken to use the direct simulation
method of interfaces to evaluate the predicted surface tension as a function of interfacial area from
capillary-wave theory. The oscillations of surface tension decay faster at temperatures close to the
critical point. It is also discussed that a surface area does not show any important effect on
coexisting densities, making this method reliable to calculate bulk coexisting properties using small
systems. © 2005 American Institute of Physics. 关DOI: 10.1063/1.2018640兴

I. INTRODUCTION simulation methods. By using the Gibbs ensemble Monte

González-Melchor et al. have found1 in simulations of
liquids and ionic fluids that the finite-size effect and periodic
boundary conditions introduce an artificial oscillatory stress
anisotropy in bulk phases when the simulations are per-
formed on parallelepiped boxes. This box shape is regularly
used to directly simulate the liquid-vapor and liquid-liquid
interfaces. The stress anisotropy is important when the trans-
versal area of the parallelepiped is small and when the liquid
density is close to that of phase equilibrium conditions.
González-Melchor et al. used the same definition of surface
tension to calculate the stress anisotropy and found positive
and negative values. At small transversal areas this unphysi-
cal stress anisotropy has the same order of magnitude with
that calculated in a liquid-vapor interface. An oscillatory be-
havior of surface tension with surface area was also obtained
by direct molecular-dynamics 共MD兲 simulations at the
liquid-vapor interface of ionic fluids.2
The liquid-vapor equilibrium of Lennard Jones 共LJ兲 flu-
ids have been widely studied in the last three decades using
a兲
Author to whom correspondence should be addressed. Electronic mail:
jra@xanum.uam.mx
Carlo simulations Smit3 found that the phase diagram is very
sensitive to long-range interactions. The critical temperature
increases by around 20% when the Lennard Jones potential
is spherically truncated and shifted 共LJSTS兲 at a distance of
2.5␴ compared with the full interaction. The phase equilib-
rium properties can also be obtained by direct simulation of
interfaces, and, for the same potential model, the results are
the same as those obtained using methods without
interfaces.4,5 Most simulations to obtain surface tension have
used periodic systems having two liquid-vapor interfaces
where a liquid slab is surrounded by vapor; however, other
setups have also been used,6 for instance, confining the in-
terfaces between flat surfaces. The surface tension has also
been obtained using bulk simulations combined with
histogram-reweighting Monte Carlo 共MC兲 and finite-size
scaling techniques.7–9 In direct simulations of interfaces the
system is not homogeneous and the long-range corrections
are not in general easy to include; however, the problem is
eliminated by using a lattice sum method to calculate the
long-range interactions.5
During the last two decades the effect that the number
of particles,10 the range of interaction,4,5 and the amount of

0021-9606/2005/123共11兲/114702/6/$22.50 123, 114702-1 © 2005 American Institute of Physics

114702-2 Orea, López-Lemus, and Alejandre J. Chem. Phys. 123, 114702 共2005兲

liquid in the slab11 have on the surface tension ␥ has been When two particles are apart a distance r the LJSTS
analyzed. Trockymchuk and Alejandre4 showed that when potential USTS共r兲 is defined as
the surface tension of a truncated LJ potential is obtained by
MC or MD techniques, the forces at the discontinuity of the
potential have to be included. Ignoring that contribution
USTS共r兲 = 再 ULJ共r兲 − ULJ共Rc兲, r 艋 Rc
0, r ⬎ Rc ,
冎 共1兲

gives a nonconstant normal pressure profile. Recently, Duque

where Rc is the distance where the potential is truncated and
and Vega analyzed12 how the long-range corrections can be
ULJ共r兲 is the Lennard-Jones function given by
added consistently in a simulation to calculate interfacial
properties. By using lattice sum expressions for the disper-
sion interactions of the LJ potential López-Lemus and
Alejandre5 showed that phase equilibria and interfacial prop-
ULJ共r兲 = 4␧ 冋冉 冊 冉 冊 册
␴
r
12
−
␴
r
6
, 共2兲

erties can be obtained for the full interaction, avoiding the where ␴ is the diameter of a LJ particle and ⑀ the well depth.
use of long-range corrections. On the other hand, the surface The full LJ potential is obtained by using a lattice sum
tension of square-well 共SW兲 fluids of different interaction method 共LSM兲 in the dispersion interactions.5,19,20 The at-
ranges has previously been reported using methods with and tractive term in Eq. 共2兲 for one-component systems can be
without interfaces. The agreement between results obtained written as
using both methods was excellent.13–15 N−1 N
␭
Some simulations have been performed to analyze the
effect that surface area has on surface tension. Direct MD
U6 = 兺 兺
i=1 j⬎i r
ij
6 =U
real
+ Urecip + Uself , 共3兲
ij
simulations at the liquid-vapor interface of LJ fluids and
molten salts were performed by Chen16 and Aguado et al.,17 where N is the number of molecules and ␭ij = −␭i␭ j with
respectively. Monte Carlo simulations of bulk systems using ␭ j = 2冑⑀␴3. The real term is

冉 冊
histogram reweighting and finite-size techniques have also N−1 N
been applied8,9 to calculate the surface tension. All of these a−2 −a2
studies found that surface tension decayed monotonically
Ureal = ␯6 兺 兺
L i=1 j⬎i
兺 ␭ij a−6 + a−4 + 2
e , 共4兲
with surface area as predicted by the capillary-wave theory18
共CWT兲. where L is the lattice vector of the periodic array of image
The main goal of this work is to show that the surface cells, a = 兩ri − r j − RL兩␯, where ri is the position of molecule i
tension of LJ and SW fluids at the liquid-vapor interface and RL is the lattice translation vector. The quantity ␯ is an
oscillates with surface area. The origin of the oscillatory be- adjustment parameter which indicates how fast the real term
havior discussed in this work comes from the use of a par- is damped.
allelepiped shape of the simulation box with a small surface The reciprocal contribution is
area and periodic boundary conditions. Thus, the calculation N N
␲3/2 ␲3/2␯3
of the total surface tension contains an artificial contribution
due to box geometry and has to be taken into account in the
U recip
=− 兺
24V h⫽0
S共h兲S共− h兲B共h兲 + 兺 兺 ␭ij ,
6V i=1 j=1
computer simulation of interfaces. The true surface tension is
共5兲
not properly computed when direct simulations of interfaces
are performed with small surface areas, and it is difficult to where

冋 冉 冊 册
evaluate the results predicted by the capillary-wave theory
using this simulation method. We will show that Chen acci- 1 1 −b2
B共h兲 = h3 ␲1/2 erfc共b兲 + 3 − e , 共6兲
dentally performed16 simulations of LJ fluids at the liquid- 2b b
vapor interface on boxes with dimensions where it is not
possible to observe the oscillation on surface tension. The with b = h / 2␯. In Eq. 共5兲, V is the volume of the unit cell, h
simulations were performed using squared interfacial areas, is the reciprocal lattice vector with magnitude h = 兩h兩, and
and the results are analyzed in terms of the box length where S共h兲 is the structure factor defined as
it is easier to look at the wavelength of the oscillations. N
The remainder of the paper is organized as follows: In S共h兲 = 兺 ␭ jeih·r j . 共7兲
Sec. II is given the potential models and the definition of j=1
calculated properties. The details about MD and MC simula-
The second term in Eq. 共5兲 arises from the reciprocal space
tions are presented in Sec. III. The results of the simulations
when h = 0.
are presented and discussed in Sec. IV. Finally, conclusions
Finally, the self-correction term comes from the exclu-
from our findings are given in Sec. V.
sion of i = j when L = 0 and it is written as
N
␯6
U self
= − 兺 ␭ii . 共8兲
II. POTENTIAL MODELS AND PROPERTIES 12 i=1

In this work we used the LJSTS and the full LJ and SW Expressions for forces and components of the pressure
potentials to simulate the liquid-vapor interface at different tensor are found in Refs. 5 and 20
temperatures and surface areas. The SW potential is defined as
114702-3 Oscillatory surface tension due to finite size effects
冦 冧
⬁ if r ⬍ ␴
u共r兲 = − ⑀ if ␴ 艋 r ⬍ ␭␴
0 if r 艌 ␭␴ ,
where ␴ is the diameter of a hard-sphere particle, ⑀ is the
well depth, and ␭ is the range of the attractive interaction.
Hereafter, the ␴ and ⑀ parameters have the same value in all
the interaction potentials.
In liquid-vapor interfaces the vapor pressure by hydro-
static equilibrium is related with the normal component Pzz
which can be calculated using the mechanical definition
N−1 N
1
Pzz = ␳kBT + 兺
V i=1
兺
j⬎i
zijFzij , 共10兲
where zij = zi − z j, zi being the z coordinate of atom i. The
force component between atoms i and j in the z direction is
du共r兲 zij
Fzij = − . 共11兲
dr r
The derivative of the potential for the LJSTS and full LJ
potentials were calculated using Eqs. 共1兲 and 共2兲; in the latter
case Eq. 共3兲 was used to calculate the dispersion interactions.
The du共r兲 / dr of the square-well potential was calculated in
every discontinuity by
du共r兲
= − kBT␦共r − ␴兲, 共12兲
dr
where kB is the Boltzmann’s constant, T is the absolute tem-
perature and ␦ is a delta function. We have shown that the
derivative of discontinuous potentials can be obtained during
MC simulations13,21 if the ␦ function is calculated numeri-
cally.
The surface tension of a planar interface was calculated
from the average components of the pressure tensor by using
the mechanical definition
Lz
␥= 兵具Pzz典 − 0.5关具Pxx典 + 具Pyy典兴其, 共13兲
2 ⌬␴ → 0.
where Lz is the box length in the z direction and the factor
1 / 2 is because there are two interfaces in the system.
The liquid and vapor densities were calculated at the end
of simulations from the average density profiles.
III. SIMULATION DETAILS
The interfacial properties at the liquid-vapor interface of
the LJSTS and full LJ potentials were calculated using MD
simulations, while the MC method was used to simulate the
SW model. The simulation cell was parallelepiped in shape
with sides Lz ⬎ Lx = Ly and surface area A = Lx ⫻ Ly. The dis-
tance is made dimensionless by dividing it by ␴. In simula-
tions of LJSTS and full LJ potentials Lz* = 50. The initial
setup of the simulation consisted of a liquid slab surrounded
by two vacuum regions. The particles in the liquid region
were allocated using a fcc crystalline array. Simulations at
different surface areas were performed, and the amount of
liquid in the simulation cell, around 20␴ in the z direction,
was kept constant by increasing the number of molecules in
J. Chem. Phys. 123, 114702 共2005兲
the system. The LSM was used to evaluate the dispersion
共9兲 forces of the full LJ model. The truncation distance was 2.5␴
for the LJSTS model and for the short-range forces of the
full LJ. In the LSM, the reciprocal lattice vectors in the long-
est direction were chosen according to kzmax = 共Lz / Lx兲kmax x ,
with a typical value of kmax x = 6. The error in the reduced
energy of dispersion interactions for the full LJ model was
less than 10−3. A multiple time-step scheme was used to re-
duce the computational cost of the simulation.22 The interac-
tions in the real part were calculated using a reduced time
step ⌬t* = ⌬t共⑀ / m␴2兲1/2 = 0.005 共where m is the mass of each
particle兲; for the reciprocal part ⌬t* = 0.05 was used. The ca-
nonical molecular-dynamics simulations were performed us-
ing the Nosé-Hoover chain thermostat,23 one thermostat per
atom. The thermostat parameter was one hundred times the
smaller time step. In all cases, the reduced temperatures T*
= kBT / ⑀ varied from the triple to the critical points. The sys-
tem was equilibrated for at least 5 ⫻ 105 time steps, and after
this period the coexisting densities, pressure, and surface ten-
sion were calculated every 20 configurations in 10 blocks of
105. The error 共=␴ / N1/2 b 兲 in the simulation was calculated
using these Nb blocks, where ␴ is a standard deviation.
The range of interaction for the SW potential was
␭ = 1.5. The simulations of the SW model were performed
using a standard MC in the canonical ensemble with a neigh-
bor list to speed up the code.24 The setup of the system was
similar to that of the LJSTS and full LJ potentials. In this
case Lz* = 40 for all the MC simulations and the total reduced
density was kept constant to ␳* = ␳␴3 = 0.35. The simulations
were performed in cycles; in every cycle it was attempted to
move the particles within the neighbor list. The system was
equilibrated for 106 cycles and after this period the proper-
ties were calculated every 20 cycles in 10 blocks of 106.
Equation 共12兲 was used to calculate the components of the
pressure tensor. The approximated ␦ function was
calculated13 using ⌬␴ / ␴ = 0.005, 0.010, 0.015, and 0.020.
The results obtained using these ⌬␴s were used to extrapo-
late the pressure components and surface tension when
The reduced coexisting densities were calculated via the
density profile ␳共z兲 = 具N共z兲典 / ⌬V, where N共z兲 is the average
number of molecules in every slab and ⌬V is its volume.
IV. RESULTS
The main result of this work is the surface tension as a
function of surface area for LJSTS, full LJ and SW poten-
tials. The effect of the surface area on coexisting densities is
also discussed for the LJSTS model. The three models have
different triple and critical points. The reduced critical tem-
perature is around 1.3 for the full LJ, 1.1 for the LJSTS
truncated at 2.5␴, and 1.22 for the SW model with interac-
tion ␭ = 1.5.
A. LJSTS potential
Figure 1 shows the surface tension as a function of L*x
for the LJSTS model at three temperatures. The results ob-
tained by Chen16 are also shown at T* = 0.72. Chen per-
formed his calculations to show that surface tension decayed
114702-4 Orea, López-Lemus, and Alejandre
FIG. 1. Surface tension of the LJSTS fluid as a function of Lx*. The reduced
temperature is shown in the figure. The open circles are results from this
work and 共 *兲 joined by a dashed line are results of Chen 共Ref. 16兲. The
continuous lines are guides to the eye. The filled circles are results from
Sides et al. 共Ref. 25兲. The errors in the results from this work are “less than”
symbols.
monotonically with surface area according to CWT predic-
tions. The dashed line is a fit of the simulation data of Chen
to a function according to a Gaussian model of the CWT,
␥共L*x 兲 = ␥共L*x = ⬁兲 + a/L*2
x ,
where ␥共L*x = ⬁兲
is the surface tension of an infinite system.
The results from this work do not follow the same trend;
instead, an oscillatory function was found. Chen accidentally
performed simulations using integer values of L*x , and it was
a casualty that the surface tension decayed monotonically. If
he would have chosen noninteger values of L*x , for instance,
5.5 and 6.5, his surface tensions would have increased. His
simulations are correct and his results are in good agreement
with those from this work at the same value of L*x . In a recent
work we have found1 that when bulk simulations are per-
formed on parallelepiped boxes, the system has an artificial
stress anisotropy when the transversal area is small. The an-
isotropy was calculated for simple liquids and ionic fluids
using the same definition that is used to calculate the surface
tension of an interface, and as a result it was observed that it
oscillates around zero. For small surface areas it has the
same order of magnitude compared with the surface tension
in a real liquid-vapor interface. The stress anisotropy in liq-
uids oscillates due to finite size in transversal areas and pe-
riodic boundary conditions, the so called periodic error. The
oscillations of surface tension shown in Fig. 1 are also due to
the fact that simulations are performed in parallelepiped cells
and the true surface tension of the interface cannot be iso-
lated when small surface areas are used. It is seen in Fig. 1
that oscillations decay faster with surface area and tempera-
ture. In Fig. 1 are also shown results for larger systems
共L*x ⬎ 12 and Lz* ⬎ 127兲 obtained by Sides et al.25 The results
J. Chem. Phys. 123, 114702 共2005兲
FIG. 2. Coexisting densities as a function of Lx* at T* = 0.72 共open circles兲,
0.8 共open squares兲, and 0.9 共open triangles兲. 共a兲 Liquid and 共b兲 Vapor. The
errors in the results from this work are less than symbols.
from this work tend to the same value. Sides et al. used their
results to calculate the width of the interface and test the
predictions of the capillary-wave theory for surface tension.
They found that when finite size effects are negligible, the
width of the interface ⌬ follows a function,
冉 冊
k BT Lx
⌬2 = ⌬20 + ln , 共15兲
2␲␥ ␰
共14兲
where ␰ is the correlation length.
The value of ⌬ was obtained by fitting the calculated
density profile to an error function and to a hyperbolic tan-
gent function. The surface tension calculated using ⌬ fitted
to an error function was in good agreement with that ob-
tained through the pressure tensor components. From Fig. 1
we can see that it is not possible to validate, using Eq. 共14兲
with small surface areas, the predictions of the CWT about
how surface tension decays with surface area using direct
interface simulations.
The coexisting densities are essentially independent of
surface area. Figure 2 shows the liquid and vapor densities as
functions of L*x for the LJSTS model at three temperatures. It
is seen that for systems having L*x ⬎ 6 is enough to obtain the
correct densities for the potential model. This means that
small systems can be used to obtain coexistence properties
using direct simulation of interfaces. The same conclusion
can be drawn from the interface simulations of Chen.
B. Full LJ potential
The effect of long-range forces on the oscillations of
surface tension is analyzed by using the full LJ model. Fig-
ure 3 shows the surface tension as a function of L*x for this
potential at different temperatures. As expected, the ampli-
tude due to larger correlations is higher in this model than in
the LJSTS model, as can be seen at T* = 0.72. This is ex-
pected because at this temperature the full LJ is closer to the
114702-5 Oscillatory surface tension due to finite size effects
FIG. 3. Surface tension of the full LJ fluid as a function of Lx*. The reduced
temperatures are shown in the figure. The errors in the results from this work
are less than symbols.
triple point. As the temperature increased, the oscillation de-
cays faster and the maxima and minima are slightly shifted
to larger values of L*x . It was not our interest to obtain the
surface tension of the infinite system but to show that surface
tension in this model also oscillates with surface area. We
would like to emphasize that T* = 0.72 is close to the triple
point.
C. SW potential
As an example of a discontinuous potential, the SW
model was chosen to estimate the surface tension varying the
interfacial area and temperature. The results are shown in
Fig. 4 for values of L*x changing in steps of 0.5. The same
trend was found compared with that of LJSTS and full LJ
models. The amplitude on the oscillating function decreases
with temperature. Actually, the oscillation is damped faster at
FIG. 4. Surface tension of the SW fluid as a function Lx* for ␭ = 1.5. The
reduced temperatures are shown in the figure. The 共 *兲 are results taken from
Orea et al. 共Ref. 13兲. The errors in the results from this work are less than
symbols.
J. Chem. Phys. 123, 114702 共2005兲
FIG. 5. Surface tension of the square-well fluid as a function temperature.
The range of interaction is ␭ = 1.5. The values of Lx* used to calculate the
surface area are shown in the figure. The critical point 共Ref. 15兲 is shown
with 共 *兲. The errors in the results from this work are less than symbols.
high temperature. It is interesting to note that although this
potential is very short ranged, the oscillation at T* = 0.9 per-
sists up to L*x = 10. The surface tension for systems using
L*x = 12 are shown with star symbols.13 The results from this
work decay at the same value. At L*x = 5 the surface tension is
negative, certainly this is not a real surface tension but the
result of using a small surface area in a parallelepiped cell
with periodic boundary conditions.
The effect of temperature on surface tension at a con-
stant surface area is shown in Fig. 5 for the SW model. The
values of ␥* decreases monotonically except in systems with
the smallest area, A = 5 ⫻ 5␴2, where the surface tension
shows an anomalous increase. This fact is due to the use of
periodic boundary conditions in a cuboid cell; a similar ef-
fect was found in bulk simulations using the same geometry
in the simulation box. It is interesting to see that at T* = 0.9
the surface tension changes from −0.2 to 0.8 when L*x varies
from 5 to 5.5, respectively. The surface tension as a function
of interfacial area and temperature has a triangle shape with
one vertex in the critical point. Its value up and down with L*x
at a given T* and the result for the largest system are almost
in the middle of the side opposite to that vertex. Most of the
results, as a function of surface area, tend to the critical
point, shown with a star.15
V. CONCLUSIONS
We have used the direct simulation of interfaces to show
that periodic boundary conditions and small surface areas
have a strong effect on surface tension. An oscillatory func-
tion of ␥* as a function of L*x was found in the three potential
models used in this work; i.e., the range of interaction is not
responsible for such oscillations. The wavelength of the os-
cillating function is around ␴ for all the potential models.
The oscillation comes from the use of periodic boundary
conditions in a noncubic cell with small surface areas. The
geometry of the simulation box introduces an artificial con-
tribution to the components of the pressure tensor, and it
114702-6 Orea, López-Lemus, and Alejandre J. Chem. Phys. 123, 114702 共2005兲

6
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ACKNOWLEDGMENTS 17
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All the authors are grateful to CONACyT for financial 共2001兲.
18
M. P. Gelfand and M. E. Fisher, Physica A 166, 1 共1990兲.
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FE03/2005. P.O. thanks IMR-Mexico for Grant No. 20
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