Electrostatic interactions in dissipative particle dynamics—simulation of

polyelectrolytes and anionic surfactants

R. D. Groot

Citation: The Journal of Chemical Physics 118, 11265 (2003); doi: 10.1063/1.1574800
View online: http://dx.doi.org/10.1063/1.1574800
View Table of Contents: http://aip.scitation.org/toc/jcp/118/24
Published by the American Institute of Physics

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JOURNAL OF CHEMICAL PHYSICS VOLUME 118, NUMBER 24 22 JUNE 2003

Electrostatic interactions in dissipative particle dynamics—simulation

of polyelectrolytes and anionic surfactants
R. D. Groota)
Unilever Research Vlaardingen, P. O. Box 114, 3130 AC Vlaardingen, The Netherlands
共Received 6 December 2002; accepted 25 March 2003兲
Electrostatic interactions have been incorporated in dissipative particle dynamics 共DPD兲 simulation.
The electrostatic field is solved locally on a grid. Within this formalism, local inhomogeneities in the
electrostatic permittivity can be treated without any problem. Key issues like the screening of the
potential near a charged surface and the Stillinger–Lovett moment conditions are satisfied. This
implies that the method captures the essential features of electrostatic interaction. For the direct
simulation of mixed surfactants near oil–water interfaces, or for the simulation of Coulombic
polymer–surfactant interactions, this method has all the advantages of DPD over full atomistic
molecular dynamics 共MD兲. DPD has proven to be faster than MD by many orders of magnitude,
depending on the precise scaling factor chosen for the simulation. This brings phenomena of
microseconds in reach of routine simulation, while maintaining a fairly accurate representation of
the structure of the molecules. As an example of this simulation tool, the interaction between a
cationic polyelectrolyte and anionic surfactant is discussed. Without a surfactant, the polyelectrolyte
shows a fractal dimensionality that is in line with the theoretical and experimental values cited in
literature, it behaves as a fairly stiff rod, d f ⬃1.1. When salt is replaced by anionic surfactant, the
polymer wraps around one or more discrete surfactant micelles, in line with the current
understanding of these systems, and scaling invariance in the correlation function is broken.
© 2003 American Institute of Physics. 关DOI: 10.1063/1.1574800兴

I. INTRODUCTION dral angles within the same molecule. On a time scale of a

Mesoscopic simulation is a tool that is aimed at model-
ing physical and chemical phenomena at length and time
scales, which are intermediate between the atomic length
scale and the macroscopic length scale. The atomic length
scale here is defined as the length scale to which full mo-
lecular dynamic 共MD兲 simulations are limited, and ‘‘macro-
scopic’’ starts at a length scale where the materials are suffi-
ciently homogeneous to justify a continuum description. In
between these length scales, there is a vast range where nei-
ther continuum methods nor atomic simulation can be ap-
plied. This runs from some 10 nm to about 100 ␮m.
Phenomena that occur at these length scales are polymer
adsorption,1 polymer–surfactant interaction,2 mesophase for-
mation of surface-active materials and block copolymers,3
and the breakup and coalescence of droplets in an emulsion
during processing.4 Furthermore, many biologically relevant
processes occur at this length scale, like transport phenom-
ena through living cells,5 the structuring of cell membranes,
and their perforation under the influence of surfactants or
adsorbing polypeptides.6 Finally, the formation of polymer
networks takes place at this intermediate length scale.7
Apart from this length scale gap, there is also a time
scale gap between the macroscopic world and what can be
reached by conventional MD. If we take the example of lipid
bilayers, we find other phenomena to occur on every next
time scale studied.8 On the shortest time scale of a few pi-
coseconds, lipids show bond and angle fluctuations of dihe-
a兲
Electronic mail: rob.groot@unilever.com
few tens of picoseconds, trans-gauche isomerizations of the
dihedrals occur.9 On a time scale of a few nanoseconds, the
phospholipids rotate around their axis, and on the time scale
of tens of nanoseconds, two lipids switch place within one
bilayer, giving rise to lateral diffusion. Within this time scale,
the individual lipids orient, and lipid membranes show
protrusions.10 Finally, on a time scale of 100 ns peristaltic
motions and undulations occur.11
By virtue of parallelization over several processors or
PC clusters, hardware developments have now pushed the
limit of molecular simulation to 100 ns.11 Nevertheless, there
is a limit beyond which hardware developments cannot help
us. For instance, phenomena, like the cooperative motions in
phase transitions and membrane fusion, occur on much
larger time scales and are well outside the range of current
simulation power. This requires simulation of the microsec-
ond range, while a different set of phenomena could be stud-
ied if we could address the millisecond time scale.
The question thus arises as to how these phenomena can
be modeled. One approach is the dissipative particle dynam-
ics 共DPD兲 method. In this method, a number of atoms are
taken together into one simulation bead, that is used as a
simulation element. The reliability of the result obviously
depends on how the underlying atoms translate into the in-
teraction parameters between the DPD beads. The method
has been used with considerable success to model a wide
range of physical–chemical problems as discussed next.
A brief overview of the DPD method is now given. In
this simulation method, all particles are soft beads that inter-

0021-9606/2003/118(24)/11265/13/$20.00 11265 © 2003 American Institute of Physics

11266 J. Chem. Phys., Vol. 118, No. 24, 22 June 2003
act with the pair-wise force f i ⫽⌺ j (F Ci j ⫹F Ri j ⫹F D
i j ) where the
sum runs over all neighboring particles within a certain dis-
tance R c . All forces depend on coordinate differences. The
conservative force is chosen as12
再
⫺a i j 共 1⫺ 兩 ri j 兩 /R c 兲 r̂i j if 兩 ri j 兩 ⬍R c
F Ci j ⫽
if 兩 ri j 兩 ⬎R c ,
0
where a i j is a maximum repulsion between particle i and
particle j, ri j ⫽r j ⫺ri and r̂i j ⫽ri j / 兩 ri j 兩 . Between neighboring
particles on a chain, an extra spring force is defined that
binds the particles together, given by
F Si j ⫽4ri j if i is connected to j.
The drag force F D R
i j and the random force F i j act as heat sink
and source, respectively, so their combined effect is a ther-
mostat. They are given by F Ri j ⫽ ␴␻ (r i j )r̂i j ␨ / 冑␦ t and F D ij
⫽⫺1/2␴ 2 ␻ (r i j ) 2 /kTr̂i j (vi j "r̂i j ), where ␨ is a random vari-
able with zero mean and variance 1, and ␻ (r)⫽(1⫺r) for
r⬍1 and ␻⫽0 for r⬎1.
In this article, a fixed noise amplitude ␴⫽3 is used, fol-
lowing Groot and Warren.13 The precise value of the noise
amplitude and friction in this range has little influence on the
efficiency of the simulation algorithm, it merely provides an
efficient thermostat. This particular thermostat is special in
that it conserves 共angular兲 momentum, which leads to a cor-
rect description of hydrodynamics.14 The particle mass, tem-
perature, and interaction range are chosen as units of mass,
energy, and length, hence m⫽kT⫽R c ⫽1 so that the simu-
lated time is expressed in the natural unit of time
␶ ⫽R c 冑m/kT.
The DPD method, in general, has been shown to produce a
correct 共NVT兲 ensemble as the fluctuation–dissipation rela-
tion is satisfied.13,15 At every time step, the set of positions
and velocities, 兵 ri ,vi 其 is updated from the positions and ve-
locities at earlier time using a modified version of the
velocity-Verlet algorithm:
r i 共 t⫹ ␦ t 兲 ⫽r i 共 t 兲 ⫹ ␦ t v i 共 t 兲 ⫹ 21 ␦ t 2 f i 共 t 兲 ,
ṽ i 共 t⫹␭ ␦ t 兲 ⫽ ṽ i 共 t 兲 ⫹␭ ␦ t f i 共 t 兲 ,
f i 共 t⫹ ␦ t 兲 ⫽ f i 共 r i 共 t⫹ ␦ t 兲 , ṽ i 共 t⫹␭ ␦ t 兲兲 ,
v i 共 t⫹ ␦ t 兲 ⫽ v i 共 t 兲 ⫹ 21 ␦ t 共 f i 共 t 兲 ⫹ f i 共 t⫹ ␦ t 兲兲 .
As the masses of the particles are put at 1, the force acting on
a particle equals its acceleration. The force is updated once
per iteration. Because the force depends on the velocities, the
velocity in the next time step has to be estimated by a pre-
dictor method. This is done in the second step of the algo-
rithm. The velocity is corrected in the last step. If parameter
␭ is put at ␭⫽0.5, this scheme equals the velocity-Verlet
algorithm.16 However, here we use ␭⫽0.65, where we find a
very accurate temperature control even at the time-step ␦ t
⫽0.06␶ that is used. A more systematic study into the influ-
ence of parameter ␭ was presented by Den Otter and
Clarke.17
To find, in practice, the interaction parameters for this
model, one needs to match the liquid structure function in the
R. D. Groot
limit k→0, as this determines the free-energy change asso-
ciated with density fluctuations. This, in turn, is, related to
the compressibility and solubilities of the components. Note
that the pressure itself drops out in an NVT ensemble, as this
is a linear variation of the free energy. This condition implies
共1兲 that the system should satisfy
冉 冊 冉 冊冉 冊
1 ⳵p 1 ⳵n ⳵p
⫽ •
kT ⳵␳ kT ⳵␳ ⳵n
simulation experiment
⫽ 冉 冊
Nm ⳵p
kT ⳵ n experiment
, 共5兲
共2兲
where N m is the number of water molecules, e.g., that each
DPD bead represents. N m can been chosen freely in general,
it is a real-space renormalization factor of the simulation. For
the choices N m ⫽1 and N m ⫽3, the compressibility of water
at room temperature is matched if the repulsion parameter in
Eq. 共1兲 between particles of the same type is given by a ii
⫽25 and by a ii ⫽78, respectively.13,18
Groot and Rabone recently showed18 that the effective
time scale ␶ of the simulation can be found by matching the
bead diffusion constant in the simulation to that of pure wa-
ter. Following their analysis for a fixed repulsion parameter
a ii ⫽25, we have
N m D simR 2c
␶⫽ ⫽25.7⫾0.1N m
5/3
关 ps兴 . 共6兲
D water
In Eq. 共6兲, it is implicitly assumed that the repulsion param-
eter between equal beads is fixed at the value of a⫽25, and
共3兲 that the bead density is fixed at ␳⫽3. In practical terms, this
means that time steps of 9.6 ps are taken when N m ⫽3 and
a ii ⫽25. A comprehensive table of all parameter values used
is given in Sec. IV.
At this point, we can understand why the DPD method is
so much faster than straightforward MD. There are two com-
bined effects that lead to speedup. In an ordinary liquid, like
water, the interaction potential contains a hard core repul-
sion. This hard core leads to a caging effect, so that an atom
undergoes many collisions before it is actually transported.
The soft potential used here removes this caging effect, so
共4兲 that the diffusivity of particles is increased by a factor of
1000. The second factor leading to fast simulation is the
scaling of the physical time with the renormalization factor
N m as in Eq. 共6兲. On top of the power 5/3 by which the
physical time scale increases, the amount of central process-
ing unit 共CPU兲 time will decrease inversely proportional to
N m if we want to simulate a given volume, simply because
we have to update the position of fewer objects. Thus, for a
given system volume, DPD can be expected to be faster than
MD by a factor of roughly 1000 N m 8/3
⬇2⫻104 for N m ⫽3
and about 10 for N m ⫽6, independent of hardware and dis-
5
regarding the CPU time spent on evaluating the 共relatively
long-ranged兲 Lennard-Jones potential.
After Hoogerbrugge and Koelman12 introduced this
simulation method and a physical basis was given by Es-
pañol and Warren,15 and by Groot and Warren,13 it has been
applied to a range of mesoscopic problems. Some examples
are polymer–polymer surface tension and block copolymer
J. Chem. Phys., Vol. 118, No. 24, 22 June 2003 Electrostatics in dissipative particle dynamics 11267

mesophase formation,19,20 and polymer–surfactant interac-
tions in bulk solution.21 The scaling laws of the polymer
endpoint distribution have been checked by Kong et al.22 and
by Spenley.23 The method has been applied to describe sur-
factant mesophases by Jury et al.24 Clark et al.25 further ap-
plied this method to the breakup of liquid droplets by hydro-
dynamic interactions, while Novik and Coveney26 used this
method to study spinodal decomposition. The rheology of a
colloidal suspension was simulated by Boek et al.,27 the
structure and rheology of biomembranes was studied by
Groot and Rabone18 and, finally, the spontaneous formation
of vesicles was studied recently by Yamamoto et al.28
DPD is thus demonstrated to be a versatile method that
can be applied to modeling on various length and time
scales. When the problem is defined on a large length scale,
In Eq. 共7兲, express the charge density ␳ e (r)⫽⌺ i e i ␦ (r⫺r i )
was substituted for the sum of individual charges, and e i
⫽eq i is the charge of ion i. Some care must be taken to
subtract the self-energy of the charges, but this issue will not
be addressed here.
The idea behind a field formulation is that all charges
interact with a local field, ␾ (r), which propagates from one
charge to another. To find this field, we first re-express the
charge density by its Fourier transform ␳ e (k)
⫽ 兰 exp(ik"r) ␳ e (r)d 3 r. The Fourier transform of the interac-
tion 1/(4 ␲ ⑀ 0 ⑀ r r) is obtained as 1/⑀ 0 ⑀ r k2 and, hence, the en-
ergy of the system follows as
U⫽
1
2
冕␳ e 共 k 兲 ␳ e 共 ⫺k 兲

⑀ 0⑀ rk 2
d 3 k. 共8兲
e.g., the breakup of droplets in viscous flow, the method can
be used effectively by matching surface tensions and liquid Now, the electrostatic field is introduced as the function that
viscosities. However, when modeling specific molecules, we maximizes the following functional:

冕冋 册
still lack a quantitative relation that links atoms and mol- 1
ecules to the DPD beads. An initial link to molecules was ⍀⫽max ⑀ ⑀ ␾ 共 r 兲 ⌬ ␾ 共 r 兲 ⫹ ␾ 共 r 兲 ␳ e共 r 兲 d 3r
␾ 2 0 r
given by Groot and Warren,13 who showed that the thermo-

冕冋
dynamics of the simulation model is very close to that of the 1
Flory–Huggins model, and a method to determine the rel- ⫽max ⫺ ⑀ 0 ⑀ r k 2 ␾ 共 k 兲 ␾ 共 ⫺k 兲
2
evant Flory–Huggins ␹-parameters from experimental data ␾

册
has been described.18 An alternative way to coarse-grain the
1 1
potential is to start with MD simulated pair-correlation func- ⫹ ␾ 共 k 兲 ␳ e 共 ⫺k 兲 ⫹ ␾ 共 ⫺k 兲 ␳ e 共 k 兲 d 3 k
tions, and extract an effective potential for a coarse-grained 2 2

model from these, by requiring that the DPD simulated pair-
correlation matches the MD result.29–31 However, so far,
electrostatic interactions have not been considered in combi-
nation with the soft DPD potential. One practical reason for
this is that the soft particles are allowed to overlap, which
may give rise to strong ion pairing.
For many molecular problems, however, electrostatics
are of paramount importance, e.g., for the description of
biomembranes. Therefore, a method to tackle this problem is
described here. In Sec. II, a review is given of the interrela-
tion between 1/r interactions and a field theoretic descrip-
tion. How to apply this theory to mesoscopic simulations,
particularly the DPD model, is described in Sec. III and vali-
dated in Sec. IV, and a brief example of an application is
given in Sec. V to demonstrate the potential of the method.
II. FIELD FORMALISM
In this section, the basic electrostatic field theory is
briefly reviewed. The aim of this work is to describe the
behavior of an ensemble of ions, polyelectrolytes, and
charged particles in a mesoscopic simulation. For this pur-
pose, two options are open: Either all interactions between
all charges are summed in real space or, instead, all particles
are coupled to a local electrostatic field, for which the field
equations are solved separately. The first option comes down
to the following expression for the internal 共electrostatic兲 en-
ergy:
⫽ 冕 冕
ee 1 ␳ 共 r 兲␳ 共 r⬘兲
U⫽ 兺 i j
i⬍ j 4 ␲ ⑀ 0 ⑀ r 兩 r i ⫺r j 兩 2
e e
4 ␲ ⑀ 0 ⑀ r 兩 r⫺r ⬘ 兩
d 3 rd 3 r ⬘ .
共7兲
冕
1
⫽ 关 ␳ e 共 k 兲 ␳ e 共 ⫺k 兲 / ⑀ 0 ⑀ r k 2 兴 d 3 k. 共9兲
2
This functional is maximized by the field
k 2␾ 共 k 兲 ⫽ ␳ e共 k 兲 / ⑀ 0⑀ r or ⌬ ␾ 共 r 兲 ⫽⫺ ␳ e 共 r 兲 / ⑀ 0 ⑀ r ,
共10兲
which is, in fact, Poisson’s equation for the electrostatic field
E⫽⫺ⵜ ␾ . At this point, the correspondence between the
charge–charge interaction in Eq. 共7兲 and the field formula-
tion in Eq. 共9兲 is made.
In many practical cases, the dielectric permittivity that
appears in Eq. 共10兲 is not constant throughout space, for
instance, when a water/oil interface is considered. Therefore,
the dielectric displacement D was introduced by Maxwell,
which he defined by D⫽ ⑀ r E, and which satisfies the field
equation
ⵜ•D 共 r 兲 ⫽ ␳ e 共 r 兲 / ⑀ 0 . 共11兲
The field D incorporates the local polarization of the me-
dium, P⫽( ⑀ r ⫺1)E. Variations in the local value of ⑀ r sig-
nify a change in the local polarization that, in itself, become
a source for the electrostatic E field, but not for the D field. If
we substitute the relation between D, ⑀ r , and ␾ into Eq. 共11兲,
we find
ⵜ• 共 ⑀ r 共 r 兲 ⵜ ␾ 共 r 兲兲 ⫽⫺ ␳ e 共 r 兲 / ⑀ 0 . 共12兲
One advantage of using a field formulation is that it is quite
straightforward to do simulations for liquids with different
dielectric permittivity, whereas a summation over explicit
charge interactions involves summations over mirror image
charges as well 共Sec. IV D兲.
11268 J. Chem. Phys., Vol. 118, No. 24, 22 June 2003 R. D. Groot

III. HOW TO APPLY FIELD THEORY TO MESOSCOPIC ␶ ⫽25.7N m5/3 ps⫽160 ps for N m ⫽3, a⫽25, ␴ ⫽3.
SIMULATION 共20兲
A. Scaling the parameters The pressure near a charged wall follows from the contact
The dimensionless electrostatic field that will be used in theorem by Hendersom, Blum, and Lebowitz,32 which, in
simulations is turn, follows from a force balance argument near a hard wall.
This contact theorem states that
␺⫽␤e␾. 共13兲
␴2
The Poisson equation for this field is p⫽kT 兺 ␳ contact⫺
2⑀
ⵜ• 共 ⑀ ⵜ ␺ 兲 ⫽⫺ ␤ e ␳ . 2
共14兲
1
In DPD, liquid elements are represented by beads that ⇒p * ⫽ pR 3c /kT⫽ 兺 ␳ contact
* ⫺ ⌫ ␴ *2,
2
共21兲
interact with each other up to a cutoff distance R c . It is
convenient to take this distance as the unit of length where ␴ is the surface charge in Cm⫺2 and ␴* is the surface
in the simulations, and to take kT as unit of energy. To make charge in unit charges per R 2c . For a bulk system, the pres-
Eq. 共14兲 dimensionless, we will extract the dielectric sure follows from the virial theorem, which can be expressed
permittivity ⑀ ⫽ ⑀ 0 ⑀ r (r) by defining a permittivity rela- as16
tive to the value in pure water: ⑀⫽⑀ 0 ⑀ r p(r). Here, ⑀ 0 1
⫽8.854 187 82 10⫺12 C2 J⫺1 m⫺1 , the dielectric constant of p⫽kT 兺␮ ␳ ␮ ⫹ 3V 兺i 共 x i f x,i ⫹y i f y,i ⫹z i f z,i 兲 , 共22兲
vacuum, ⑀ r ⫽78.3 is the relative permittivity of water at
25 °C, and p⫽1 for water and p⬇0.025 for hydrocarbons. where ␮ runs over all particle types, and i runs over all
Multiplying Eq. 共14兲 by R 2c and dividing by ⑀ 0 ⑀ r , we find particles in the system, (x i ,y i ,z i ) is the position of particle i,
the dimensionless equation and ( f x,i , f y,i , f z,i ) is the conservative force acting on par-
ticle i. This is the sum of the conservative forces given in
e 2 ␳ R 3c
R 2c ⵜ• 共 p 共 r 兲 ⵜ ␺ 兲 ⫽⫺ Eqs. 共1兲 and 共2兲, and the electrostatic forces acting on the
kT ⑀ 0 ⑀ r R c particles that will be discussed in Sec. III C. Even when the
⇒ⵜ * • 共 p 共 r 兲 ⵜ * ␺ 兲 ⫽⫺⌫ ␳ * . 共15兲 polarizability is a function of (x,y,z), the same expression
applies, as the effect of polarizability and therefore mirror
Here, ␳* is the concentration of cations minus that of anions charge effects are included in the field and therefore also
or per R 3c , ⵜ* is the gradient in DPD units, and p(r) is the included in the forces. This expression also contains all
local polarizability relative to pure water: forces caused by image charges that result from the periodic
p 共 r 兲 ⫽ 具 p i 典 i苸cell . 共16兲 boundary conditions used. Note that the virial equation here
does not contain coordinate differences but the absolute co-
The average runs over all particles in a cell near r, and p i is ordinates. However, the center of mass of the system drops
the polarizability of particle i in this cell. The precise details out of the equation because the sum of all forces vanishes.
are given in Appendix II.
The unit of length R c can be related to the volume of a
DPD bead. Let N m be the number of water molecules that B. Smearing out the charges
each DPD bead represents. Then, by matching the volume of Before we can solve the field equations, we need to
a bead to that of N m water molecules,18 we find at bead choose a model for the density distribution that corresponds
density ␳⫽3 with a charged bead. Point charges would collapse on top of
R c ⫽0.448 14N m
1/3
关 nm兴 ⫽0.64 633 关 nm兴 for N m ⫽3. 共17兲 each other, forming infinitely strongly bound ion pairs. This
is a consequence of the soft core interaction presently used in
This relation implies that the coupling constant at room tem- DPDs. Therefore, we need to spread out the charge. For each
perature is given by unit charge in the simulation, we choose the charge distribu-
e2 tion
⫺1/3
⌫⫽ ⫽20.00N m ⫽13.87 for N m ⫽3, 共18兲
kT ⑀ 0 ⑀ r R c 3
f 共 r 兲⫽ 共 1⫺r/R e 兲 for r⬍R e , 共23兲
and, likewise, the unit of concentration is ␲ R 3e
R ⫺3 ⫺1
c ⫽11.11N m
⫺1
关 nm⫺3 兴 ⫽18.45N m 关 Mol/l兴 where R e is the electrostatic smearing radius, and f (r)⫽0
for r⬎R e . The interaction potential between two of these
⫽6.150 关 Mol/l兴 for N m ⫽3. 共19兲
charge clouds is worked out in Appendix I. A plot of the
⫺2
Hence, if a salt concentration of 10 M is to be simulated, exact potential between two smeared-out charges and its first
the concentration in DPD units should be 10⫺2 /6.15⫽1.63 derivative is given in Fig. 1.
⫻10⫺3 , leading to a screening length in DPD units of ␬ ⫺1 The depth of the potential well between two unlike
⫽1/冑 (2⌫c)⫽4.71 R c ⫽3.0 nm. As discussed by Groot and charges is 52/35 ⌫/4␲ R e ⬇1.64/R e when we take the ex-
Rabone,18 the time scale is fixed by matching the diffusion ample of N m ⫽3 for which in water ⌫⫽13.87. Now if the
constant of water. For the repulsion parameter a⫽25, we interaction potential between two ions at contact is much
have lower than ⫺kT they may form an ion pair, whereas they are
J. Chem. Phys., Vol. 118, No. 24, 22 June 2003 Electrostatics in dissipative particle dynamics 11269

the coupling constant ⌫ does not appear in this expression

for the energy, as the coupling constant is already accounted
for in the solution of the field. The force that is exerted on an
ion in this field is given by

i 共 r 兲 ⫽⫺q i
F el 冕 f 共 r⫺r ⬘ 兲 ⵜ ␺ 共 r ⬘ 兲 d 3 r ⬘ . 共26兲

The field equations, in turn, are solved by maximizing the

functional 关see Eq. 共9兲兴

⍀⫽ 冕 ⫺ p共 r 兲
共 ⵜ * ␺ 共 r 兲兲 2
2⌫
⫹ ␺¯␳ d 3 r. 共27兲

This free energy also implies a force on the neutral particles,

FIG. 1. Electrostatic potential between linearly smeared-out charges. The which is given by

冕 ␦␦ ␳
lower curve gives the force; the dashed curve gives the 1/r potential be-
tween point charges. ⳵ ␦⍀ ⳵ p 共 r ⬘ 兲 共 ⵜ * ␺ 共 r ⬘ 兲兲 2 3
f m ⫽⫺ ⫽ d r ⬘.
⳵ r i ␦ ␳ i共 r 兲 ⳵ r i i共 r 兲 2⌫
共28兲
unlikely to pair if the potential well is shallower. This im-
This force is the Maxwell force on the dielectric medium. Its
plies that ion pairing might occur if R e ⬍1.64, whereas the
effect is that a medium of low dielectric permittivity 共e.g.,
electrolyte will completely dissociate if R e ⬎1.64. Since, in
oil兲 is displaced by a medium of high dielectric permittivity
practice, there is also a short-range ion–ion repulsion in the
共e.g., water兲 if a strong electric field is applied. Since this is
DPD potential that counteracts ion pairing, a reasonable
a second-order effect in the field, it has been neglected in the
choice for the smearing radius is R e ⫽1.6.
simulations described next but, in principle, this effect can be
Following the method by Beckers et al.,33 the electro-
taken into account in the present method.
static field is solved on a lattice. In their algorithm, the
Rather than using a Fourier transform method to solve
charges are spread out over the lattice nodes, and the long-
the field equations, a real-space successive overdamped re-
range part of the interaction potential is calculated by solving
laxations method is used here. This method has been applied
the Poisson equation on the grid. Details on how the charges
successful by Beckers et al.33 to solve the far field on a lat-
are spread out and how derivatives on the lattice are taken
tice. The basic idea behind this is that the field is updated via
are given in Appendix II. Beckers et al.33 refer to this
method as the particle–particle particle–mesh 共PPPM兲 algo-
rithm, though in the original PPPM algorithm the far field
d␺
dt
⫽␨
D⍀
␦␺
⫽␨
␦⍀
␦␺
⫺ⵜ•
␦⍀
␦ⵜ␺冋 册
⫽ ␨ 关 ⌫¯␳ e ⫹ⵜ• 共 pⵜ ␺ 兲兴 .
was solved using a fast Fourier transform.34 The accuracy of 共29兲
this method was analyzed critically by Deserno and Holm.35
This evolution equation is analogous to that of a particle in a
The present method to solve the field equation is close to the
potential well of energy ⫺⍀, where ␨ is the analog of a
multigrid methods described by Sagui and Darden.36 Another
friction factor. However, the sign is different, because the
alternative is not to solve the field equation, but to make the
solution is not a minimum of the grand potential ⍀, but a
field a dynamic variable such that its correlation matches the
maximum. The maximum is reached by iterating
electrostatic potential,37 and to update these variables during
the simulation using the Monte Carlo algorithm. d␺
␺ new⫽ ␺ old⫹ . 共30兲
dt
C. Solving the field equations
Since the smallest wave that fits the lattice is sin(␲x), ␨
To solve the field equations for an ensemble of smeared should be of the order 1/␲ 2 ⫽0.1 for a one-step convergence
charges, we first consider the energy of a charge density ␳ e of the highest-frequency modes. Larger values of ␨ lead to a
in a field ␺. This is given by faster convergence of the longer waves, but if ␨⬎0.2, the

冕冕 ␺
smallest wave does not converge anymore. Therefore,
U⫽ 共 r 兲 f 共 r⫺r ⬘ 兲 ␳ e 共 r ⬘ 兲 d 3 rd 3 r ⬘ ␨⫽0.15 is a good compromise.
To monitor how accurate the field is solved, the root-

⫽ 冕␺ 共 r 兲¯␳ e 共 r 兲 d 3 r, 共24兲
mean-square value of the right-hand side of Eq. 共29兲, which
should converge to zero, is compared to the root-mean-
square value of the divergence of the field. This gives the
where the locally averaged density is defined by relative error

¯␳ e 共 r 兲 ⫽ 冕 f 共 r⫺r ⬘ 兲 ␳ e 共 r ⬘ 兲 d 3 r ⬘ , 共25兲
err⫽ 冑 兺 cells关 ⌫¯␳ e ⫹ⵜ• 共 pⵜ ␺ 兲兴 2
. 共31兲
兺 cells关 ⵜ• 共 pⵜ ␺ 兲兴 2
and where ␳ e (r) is the nonsmeared charge density, ␳ e (r)
⫽⌺ i q i ␦ (r⫺r i ). Here, i runs over all charges in the system, If the previous solution to the field, or a time extrapolation
and q i ⫽⫾1 is the number of unit charges of ion i. Note that thereof, is taken as initial guess for the field, some six to
11270 J. Chem. Phys., Vol. 118, No. 24, 22 June 2003 R. D. Groot

TABLE I. Summary of parameters used, unless stated otherwise.

Parameter Value Meaning

a ii 25 Repulsion between identical particle types

err 0.03 Relative error to which field equation is solved, Eq. 共31兲
kT 1 Temperature
m 1 Particle mass
Nm 3 Number of water molecules represented by one bead
Rc 0.646 33 nm Range of soft repulsive interaction, Eq. 共17兲
Re 1.6 R c Range over which charges are smeared, Eq. 共23兲
Rn 2 Rc Range over which neighboring grid points are searched
⌫ 13.87 Electrostatic coupling, Eqs. 共15兲 and 共18兲
␦t 0.06␶ Time step
␭ 0.65 Velocity prediction parameter in update algorithm, Eq. 共4兲
␴ 3 Noise amplitude
␶ 160 ps Characteristic time scale, Eqs. 共3兲 and 共6兲
␨ 0.15 Friction factor in solving field equations, Eq. 共29兲

seven iterations are sufficient to solve the equation up to ⫹a exp(␬(x⫺20))⫹ ␺ ⬁ , where a, ␬, and ␺ ⬁ are free fit pa-
relative error 0.03 in a box of size 20⫻20⫻20 containing rameters. Over the range 2⬍x⬍18, this led to a screening
1600 ions. The total CPU time necessary to distribute the parameter ␬⫽0.572⫾0.009, i.e., an exact match with the
charges, solve the field equation, and calculate the forces on value it should have 共see Fig. 2兲.
the particles is small compared to the rest of the CPU time To check this further, the density profiles and field were
used per time step. In theory, the sum of all forces that act on checked for consistency with the Poisson–Boltzmann equa-
all charges should vanish. However, in practice, a small re- tion. If this equation is valid, the concentration of positive
sidual force per ion still appears to be left over that fluctuates and negative ions should follow ␳ ⫹ ⫽c exp(⫺␺) and ␳ ⫺
with an amplitude of order 0.000 05, even if the charge dis- ⫽c exp(␺). Therefore, ⫺ln(␳⫹ /c) and ln(␳⫺ /c) are plotted
tribution around each particle is balanced as described in together with the field in Fig. 2. It is clear from Fig. 2 that
Appendix II. To conserve total momentum, this residual the match is very good. The only deviations occur near the
force is, therefore, subtracted again from all charges. This is charged plates as a result of the smearing of the charges. As
a minor correction of the order 10⫺5 relative to the electro- a technical point, it should be noted that to arrive at this
static force. comparison, the field has first been shifted upward by sub-
tracting the constant ␺ ⬁ so that the field extrapolates to ␺⫽0
IV. VALIDATION far away from the charged wall. Such a shift is known as a
The 共implicit兲 parameters used in the validation runs de- gauge transformation. The right gauge follows from the re-
scribed next are summarized in Table I. When other param- quirement that ␳ ⫹ ⫽ ␳ ⫺ ⫽c when ␺⫽0.
eters are used this is stated explicitly.
B. Bulk electrolyte
A. Electric double layers
Bulk electrolytes satisfy two exact relations for the pair
As a first test to validate the method, a salt solution near
correlation function, known as the Stillinger–Lovett moment
a charged plate was studied. In this particular simulation, the
conditions.38 For a symmetric electrolyte, these can be sum-
plate was completely permeable for all particles in the sys-
marized by
tem, and also the electrostatic field was calculated with full
periodic boundary conditions. Thus, the charged plate is rep-
resented by a two-dimensional 共2D兲 array of fixed charges at
x⫽0. The box size was 20⫻10⫻10 in DPD units, which is
12.9⫻6.5⫻6.5 nm3 in physical units. Taking N m ⫽3, the cou-
pling constant ⌫⫽13.87 was used. The plate was charged by
ten unit charges, i.e., ␴*⫽0.1 which corresponds to ␴⫽0.038
Cm⫺2. The box contained 30 counterions, 20 co-ions and
5950 neutral 共water兲 particles. The system was evolved over
5⫻105 time steps, corresponding to 5 ␮s.
To analyze the data, the mean salt concentration c
⫽( ␳ ⫹ ⫹ ␳ ⫺ )/2 was averaged between 4⬍x⬍16. Over this
interval, the concentration was c⫽0.011 836⫾0.000 017, in-
dependent of x. According to Eq. 共19兲, this corresponds to a
concentration of 0.0728 Mol/l. At this concentration, the in-
verse screening length should be ␬ ⫽ 冑 2⌫c⫽0.5730
FIG. 2. Density profiles of positive charges 共⫹兲 and negative charges 共䊊兲,
⫾0.0004. To test this prediction, the field ␺ (x) was fitted to and the mean electrostatic field near a charged plate 共diamond symbols兲. The
a three-parameter function of the form ␺ (x)⫽a exp(⫺␬x) full curve is a fit to a cosh function.
J. Chem. Phys., Vol. 118, No. 24, 22 June 2003
FIG. 3. Pair-correlation functions between equal and unequal ion pairs in
aqueous solution at 0.6 M, and between neutral particles, in a box of 6.5
⫻6.5⫻6.5 nm3, averaged over 1 ␮s physical time.
k2
lim ch D 共 k 兲 ⫽h 0 ⫹h 2 k 2 ⫹O 共 k 4 兲 ⫽⫺1⫹ ⫹O 共 k 4 兲 ,
2⌫c
k→0
共32兲
where c is the salt concentration and h D (r)⫽g ⫹⫹ (r)
⫺g ⫹⫺ (r). The physical meaning of the first Stillinger–
Lovett relation (h 0 ⫽⫺1) is that each charge is exactly
screened by a counter charge. The implication of the second
condition (h 2 ⫽1/关 2⌫c 兴 ) is that the direct correlation be-
tween two charges at large separation is exactly given by
minus the electrostatic potential divided by kT. The pair-
correlation functions g ⫹⫹ (r) and g ⫹⫺ (r) are shown in Fig.
3 for salt concentration c⫽0.1 共i.e., 0.6 M兲 and ⌫⫽13.87.
The box size is 10⫻10⫻10, and the pair-correlation func-
tions are averaged over 105 simulation steps, corresponding
to 1 ␮s physical time. The liquid density is ␳⫽3 and the
repulsion parameter between all particles is a⫽25. Figure 3
also gives the pair-correlation function for uncharged par-
ticles. It is found that for the present parameters the correla-
tion function between charged particles to a high degree of
accuracy satisfies g ⫹⫹ (r)g ⫹⫺ (r)⫽g(r) 2 , where g(r) is the
pair correlation function between neutral particles. The im-
plication is that g ⫹⫹ (r) and g ⫹⫺ (r) satisfy
g ⫹⫹ 共 r 兲 ⫽g 共 r 兲 exp关 ⫺ ␸ 共 r 兲兴
and 共33兲
g ⫹⫺ 共 r 兲 ⫽g 共 r 兲 exp关 ⫹ ␸ 共 r 兲兴 ,
where ␸ (r) is an effective electrostatic interparticle poten-
tial. For this reason, the perturbation theory may be applied,
e.g., reference hypernetted chain theory. This is outside the
scope of this article.
To check the Stillinger–Lovett moment conditions, the
charge structure function has been determined at a range of k
values for four different salt concentrations, c⫽0.025, 0.05,
0.1, and 0.2, which correspond to a range from 0.15 to 1.2
M. The simulation box size was L 3 ⫽20⫻20⫻20, so the
simulations contained, respectively, 400, 800, 1600, and
3200 ions. For these simulations, the electrostatic field was
solved up to a relative accuracy err⫽0.005. To obtain the
structure function, the Fourier transform of the charge den-
sity distribution
Electrostatics in dissipative particle dynamics 11271
FIG. 4. Structure function simulated at ⌫⫽13.87 for salt concentrations c
⫽0.025 共䉱兲, c⫽0.05 共䊊兲, c⫽0.1 共䉭兲 and c⫽0.2 共䊉兲. For comparison, the
dashed curves have the exact limiting slopes 0.18, 0.36, 0.72, and 1.44,
respectively.
␳ e 共 k兲 ⫽ 兺j q j exp共 ik"rj 兲 ⫽ 兺j q j exp共 2 ␲ in"rj /L 兲 ,
共34兲
was determined first. Here, n is an integer vector to which
the wave vector is related as k⫽2 ␲ n/L, and q j ⫽⫾1 is the
charge of ion j expressed in unit charges. The charge struc-
ture function, in turn, is obtained as the ensemble average of
共see e.g., Hansen and McDonald兲39
S 共 k兲 ⫽ 具 ␳ e 共 k兲 ␳ e 共 ⫺k兲 典 /N⫽1⫹ch D 共 k兲 , 共35兲
where N is the total number of ions in the system. All 924
modes for which n2 ⭐36 have been monitored from which
the angle-average structure function was averaged over 105
time steps for each system.
For an ideal ion gas, the charge structure function takes
the form39 S(k)⫽k 2 /(2⌫c⫹k 2 ). However, since the soft
short-range DPD interaction and the extended charge per ion
effectively excludes ion overlap, the structure function must
contain k 4 terms. Therefore, the structure functions are fitted
to a function of the form
a 0 k 2 ⫹a 2 k 4
S共 k 兲⫽ . 共36兲
2⌫c⫹a 1 k 2 ⫹a 2 k 4
These fits are shown in Fig. 4, together with the exact limit-
ing laws given by k 2 /2⌫c. Parameter a 0 in Eq. 共36兲 should
take on the value of 1. The fit values actually are a 0 ⫽1.03
⫾0.02, 1.04⫾0.02, 1.04⫾0.03, and 1.01⫾0.03 for c
⫽0.025 up to c⫽0.2, respectively. Hence, the second mo-
ment and, therefore, the long-range direct correlation is cor-
rect up to about 3%, which is also the accuracy by which the
slope was determined.
C. Electrostatic force
In Appendix I, the force between two smeared-out
charges is calculated. In this section, the actual force, as
obtained from the lattice method, will be compared with the
theoretical curve. Toward this end, a simulation with just two
ions immersed in water was run in a box of size 10⫻10⫻10.
The electrostatic force exerted on the ions as a function of
11272 J. Chem. Phys., Vol. 118, No. 24, 22 June 2003
FIG. 5. Force between two ions as function of distance. The dashed curve
gives the theoretical force for R e ⫽1.6, the full curve is the force for R e
⫽1.725.
radial distance was averaged over the simulation run. This
leads to the angle-averaged force which, for an infinitely
large system, should be given by the derivative of the poten-
tial given in Appendix I. The charge smearing radius R e was
taken at R e ⫽1.6.
In a short run (104 steps兲 some fluctuations in the force
are seen to occur at short separation (1⬍r⬍2). Some points
fall on the theoretical curve and others fall below. Appar-
ently, there is a different force depending on the orientation.
One possible cause of this is the nonspherical charge distri-
bution, another cause could be the breaking of spherical
and translational symmetry of the field by the lattice.
An average over a longer run (105 steps兲 gives the mean
共spherically averaged兲 force as function of distance, which is
shown in Fig. 5. Because the force in some directions is
below the theoretical curve, the overall average is below the
expected force. By taking the derivative of the potential in
Appendix A as a fit function, the simulated force–distance
curve can be reinterpreted as the force of charge clouds with
R e ⫽1.725.
Hence, even though the force does not exactly fit
the force of the distribution that we aimed to describe,
this analysis shows that the electrostatic force is reasonably
well reproduced by the lattice method. The deviations
from the force profile given in the Appendix show up at
short distance and are due to lattice artifacts. This difference
will fall away when the force field is parameterized
properly.
D. Mirror image effects
In general, the electrostatic interaction can be treated in
two ways. Either all charges are coupled to a local field that
is the solution of the Poisson equation, or an explicit sum-
mation over all other charges is done using the appropriate
Green’s function. This Green’s function is the solution of the
Poisson equation for a point charge. When the Green’s func-
tion method is used, mirror image charges need to be con-
sidered explicitly, because in the presence of inhomogeneous
dielectric media, the solution of the Poisson equation takes
the form of a sum over image charges. To check if, indeed,
the effect of mirror image charges in the presence of inho-
R. D. Groot
mogeneous media is described correctly in the simulation
method, therefore, comes down to the question: Is the Pois-
son equation solved correctly if a dielectric discontinuity is
present? Two examples are now described to demonstrate
this. The first problem is that of the field between two fixed
walls, and the second is the interaction between a wall and an
ion in the presence of a dielectric discontinuity. In the former
problem, a box is considered of sizes 80⫻10⫻10, with full
periodic boundary conditions. Two charged walls perpen-
dicular to the x axis are defined, of charge density ␴⫽0.1
共⫽0.038 cm⫺2兲 at x⫽0, and ␴⫽⫺0.1 at x⫽40. Two slabs of
low dielectric oil are inserted at 0⬍x⬍20 and at 60⬍x
⬍80, and one slab of water is inserted at 20⬍x⬍60. The
polarizability of the water phase is defined as p⫽1 共or ⑀ r
⫽78.3) and the polarizability of the oil is p⫽0.5 共or ⑀ r
⫽39.15). The phases are represented by soft beads with re-
pulsion a ii ⫽25 between particles of the same type, and with
repulsion a i j ⫽57.7 between water and oil, which corre-
sponds to ␹⫽10.
The electric field was solved to an error of err⫽0.001
关see Eq. 共31兲兴, and averaged over 650 time steps after an
equilibration of 350 steps. The mean electrostatic field thus
contains an average over the fluctuations of the water–oil
interface, and it incorporates the width of the interface. The
average field gradient is shown in Fig. 6. Indicated in Fig. 6
are the locations of the charge planes and the areas where the
dielectric permittivity is inhomogeneous. For this geometry,
the field can easily be solved analytically, in the low dielec-
tric medium, the field should be ⵜ␺ ⫽⫾⌫ ␴ /2p⫽⫾1.387,
and in the high dielectric medium, it should be ⵜ␺⫽⫾⌫␴/2
⫽⫾0.6935. The actual values found in the simulation are
ⵜ␺⫽1.385⫾0.001 and ⵜ␺⫽0.6941⫾0.0004, respectively,
hence, the field in simulation deviates from the exact value
by 0.1%, which is indeed the error tolerance used in solving
the field.
In the second example studied, a single ion of charge ⫺1
is enclosed in a box of sizes 40⫻10⫻10, with full periodic
boundary conditions for the electrostatic field, but all par-
ticles interact with soft impenetrable walls at x⫽0 and at x
⫽40. At x⫽0, a surface charge ␴⫽0.01 is positioned, so that
overall charge neutrality is maintained. Again a slab of lower
dielectric oil (p⫽0.5) surrounds this wall, which ranges over
0⬍x⬍10 and over 30⬍x⬍40. The mean electrostatic force
on the ion was monitored over 105 time steps as the ion was
moved randomly through the system, and is shown in Fig. 7.
The natural system to compare these simulations with, is that
of a point ion immersed in a box of size L⫻R⫻R, interact-
ing with a charged wall at x⫽0, in the presence of dielectric
medium that has infinitely sharp jumps in the permittivity at
x⫽L/4 and at x⫽3L/4.
To solve the Poisson equation for this system, the field ␺
can be expanded in Fourier modes parallel to the yz plane,
hence ␺ (x,y,z)⫽⌺ k ␺ k (x)exp(i2␲k"r/R), where R⫽10 is
the width of the simulation box, k is a 2D integer vector, and
r is the (y,z) coordinate relative to the particle. The Poisson
equation 关Eq. 共15兲兴 has two cases, one for k⫽0, and one for
k⫽0:
J. Chem. Phys., Vol. 118, No. 24, 22 June 2003
FIG. 6. The electrostatic field in a periodic 80⫻10⫻10 box with charged
plates at x⫽0 and x⫽40, in the presence of a dielectric discontinuity at x
⫽20 and at x⫽60. The charged plane at x⫽40 is indicated by the dashed
line.
共 1⫺p 兲关 ␦ 共 x⫺ 41 L 兲 ⫺ ␦ 共 x⫺ 43 L 兲兴 ␺ ⬘0 ⫹p 共 x 兲 ␺ ⬙0
⫽⫺⌫ ␦ 共 x 兲 /R ⫹⌫ ␦ 共 x⫺x c 兲 /R ,
2 2
共37兲
共 1⫺p 兲关共 ␦ 共 x⫺ 41 L 兲 ⫺ ␦ 共 x⫺ 43 L 兲兴 ␺ k⬘ ⫹p 共 x 兲 ␺ ⬙k
⫹p 共 x 兲 ␺ k 4 ␲ 2 k 2 /R 2 ⫽⌫ ␦ 共 x⫺x c 兲 /R 2 .
Here, p is the ratio of the dielectric permittivity in the oil
phase relative to that of water, and x c is the x coordinate of
the particle. The k⫽0 case is equal to the case of two
charged planes as just described, but now the planes are situ-
ated at x⫽0 and at x⫽x c . This equation can be solved
straightforwardly, giving the following expression for the
再
force on the particle:
p 共 1⫺2x c /L 兲
⫺ •⌫/R 2 for L/4⬍x c ⬍3L/4
共 1⫹p 兲
0⫽
f el
共 1⫹p⫺4x c /L 兲
⫺ •⌫/R 2 for 0⬍x c ⬍L/4.
2p 共 1⫹ p 兲
共38兲
This k⫽0 force is shown in Fig. 7 by the dashed curve, and
gives an excellent match with the simulated force far away
from x⫽10, where the discontinuity in the permittivity is
located. Closer to this point, mirror image charge effects oc-
cur, which arise from the k⫽0 modes.
For an infinitely large system (R,L→⬁), ions to the
right-hand side of L/4 interact with a mirror image charge of
size (1⫺p)/(1⫹ p)q⫽1/3 q, located at the opposite of the
plane of dielectric discontinuity. Charges located to the left-
hand side of this plane interact with the opposite charge
⫺1/3 q. This leads to the mirror image force ⌫/(48␲ p(x c
⫺L/4) 2 ), where p⫽1 to the right-hand side and p⫽1/2 to
the left-hand side of the discontinuity. In a finite system,
however, the lowest k⫽0 mode is screened, see Eq. 共37兲. The
solution takes on the form ␺ k (x)⫽A exp(⫺2␲kx/R)
⫹B exp(2␲kx/R), with discontinuities in the first derivative
of ␺ k at x⫽L/4, at x⫽3L/4 and at x⫽x c . Since the lowest
lateral mode is screened on a distance of R/2␲ , the total
electrostatic force near the dielectric discontinuity takes on
the form
Electrostatics in dissipative particle dynamics 11273
FIG. 7. Force on an ion in a system with a dielectric discontinuity at x
⫽10, and a charged wall at x⫽0. The dashed curve is the exact k⫽0
contribution to the force, the full curve is a one parameter fit. Deviations
near x⫽10 result from the smearing of the ion charge.
exp共 ⫺2 ␲ 兩 x⫺L/4兩 /R 兲
f el共 x 兲 ⫽ f el
0 共 x 兲 ⫹A , 共39兲
p 共 x 兲共 x⫺L/4兲 2
where the numerical value of A is the same on both sides of
x⫽L/4. The full curves in Fig. 7 are one-parameter fits to the
function in Eq. 共39兲. On the left- and right-hand sides of the
discontinuity, the fit values A⫽0.24⫾0.01 and A⫽0.245
⫾0.002 are obtained. Deviations from this curve occur
within 2R c from the discontinuity and for x⬍1.6R c , which
can be attributed to the smearing of the charge over a dis-
tance of R e ⫽1.6R c , and to the width of the interface.
V. APPLICATION: POLYELECTROLYTE–SURFACTANT
INTERACTIONS
This simulation method described has all capabilities of
ordinary DPD, but includes applications where electrostatics
is essential and that were previously inaccessible. One key
example is the interaction between surfactants and polymers.
Often polymer–surfactant interactions occur via electrostatic
interactions,2 and to predict the phase behavior of mixtures
of cationic, anionic, and nonionic surfactants, and their inter-
action with polyelectrolytes, electrostatic interaction cannot
be neglected.40 To illustrate the potential of this method,
some qualitative aspects are discussed here.
For a typical anionic surfactant, like sodium dodecylsul-
phonate, the surfactant is modeled by a dimer, and the inter-
action parameter between hydrocarbon tails 共c兲 and water 共w兲
is taken as ␹ cw ⫽ 18, following earlier work.21 This means that
the tail size is roughly N m ⫽9 carbon atoms. Hence, we have
R c ⫽0.93 nm, ⌫⫽9.615, and ␶⫽1.00 ns. The head groups 共h兲
carry a charge ⫺1, and are parameterized by ␹ ch⫽6 and
␹ wh⫽0. One polymer of 50 beads and 75 surfactant mol-
ecules are simulated in a box of size 15⫻15⫻15. In physical
units, this is a volume of some 2700 nm3. Each polymer bead
共p兲 carries a charge ⫹1/2, and has a solubility parameter
␹ pw⫽0.65, so that it would be in a ␪-solution if it had no
charge. This corresponds to a polymer of molecular weight21
M w ⬃8000. The other parameters for the polymer are: ␹ cp
⫽ ␹ ch⫽6 and ␹ ph⫽0. Counterions of a charge of ⫺1 are
added to preserve charge neutrality, and have the
11274 J. Chem. Phys., Vol. 118, No. 24, 22 June 2003 R. D. Groot

␹-parameters of water. The polarizabilities are chosen as

p w ⫽p h ⫽1, p p ⫽0.35, and p c ⫽0.025. In this context, the
Flory–Huggins ␹-parameter equals the excess repulsion be-
tween unlike bead types, up to a constant. Following Groot
and Warren,13 the expression for the repulsion parameter,
a i j ⫽25⫹ ␹ i j /0.306, is used.
A typical conformation is shown in Fig. 8. In this con-
formation, the polymer wraps around two discrete micelles.
This is the accepted state of an electrostatically interacting
flexible polymer.41 In other conformations 共not shown兲, the
polymer wraps around a single micelle. Already from this
picture, one can see that a relatively high fraction of surfac-
tant molecules is in solution as a monomer or dimer. When
similar interaction parameters are used without a surfactant,
the monomer concentration is much lower.21 This reflects the
general trend that the critical micelle concentration of an-
ionic surfactants is higher than that of nonionic surfactants.
For the present amount of surfactant, the polymer end-
point distribution is close to a Gaussian, i.e., the distribution
that the polymer would have without charge and without
surfactant. However, if we study the pair-correlation func-
tions, a different picture emerges. In Fig. 9, the radial distri-
bution functions between head groups 共h兲 and polymer beads FIG. 8. 共Color兲 Typical conformation of cationic polyelectrolyte interacting
with anionic surfactant. Green dots are counterions.
共p兲 are shown. The polymer–polymer pair-correlation func-
tion shows a distinct shoulder at a length scale of 3 nm, i.e.,
the size of a micelle, when compared to the pair-correlation
obtained by scaling theory,42,43 which predicts fully extended
function for a noninteracting neutral polymer. Also, the sur-
chains, but experimental results44 indicate a similar fractal
factant head group–head group and the head group–polymer
dimension of d f ⬃1.2. MD simulations at a vanishing salt
correlation function show structures on the length scale of a
concentration45 show a continuous crossover from d f ⫽1.1
micelle.
up to d f ⫽2, depending on polymer concentration. These re-
For comparison, the dots in Fig. 9 give the polymer–
sults are in line with the present simulation results for poly-
polymer radial distribution function for the case where all
electrolytes.
surfactant molecules are replaced by salt ions. This is a poly-
To put this result into perspective a comparison should
electrolyte solution at a salt concentration of 0.045 M. A
be made with uncharged polymers. Polymers in a melt gen-
typical conformation is shown in Fig. 10. A quantitative mea-
erally follow Gaussian statistics, r⬀M ␯ ⫽M 1/2 or d f ⫽2.
sure of the structure is found by analyzing the pair-
Polymers in a bad solvent coil up to form a globule, hence,
correlation functions that are shown in Fig. 9. For the poly-
␯⫽1/3 or d⫽3, and polymers in a good solvent swell to ␯
mer in the presence of anionic surfactant, we find an initial
⫽0.588 (d f ⫽1.7) according to the renormalization theory,46
zone r⬍1 nm where the correlation is dominated by bead–
bead repulsion. For 1⬍r⬍3 nm, we have a small scaling
regime, and for r⬎3 we see a terminal correlation range. In
contrast, the polyelectrolyte without a surfactant shows scal-
ing behavior over the entire range from r⬎1 nm. The mea-
surement of the correlation function was truncated at r
⫽7.5, half of the box size.
In general, when scaling applies, the mass M within a
sphere of radius r is M ⬀r d f , where d f is the fractal dimen-
sion, which is related to the swelling exponent by d f ⫽1/␯ .
The correlation function scales with the local density, hence,
g(r)⬀r d f ⫺3 . By fitting the correlation function to a power
law, for the polyelectrolyte in salt solution a fractal dimen-
sion d f ⫽1.10 was found, which holds over about a decade in
length scale. On the other hand, the same polyelectrolyte in
anionic surfactant solution gives a slope corresponding to a
fractal dimension d f ⫽1.82 over a limited range but, in real- FIG. 9. Intramolecular polymer–polymer, polymer–head group, and head
ity, one should say that scaling invariance is broken. These group–head group pair-correlation functions 共full curves兲 for a polyelectro-
lyte interacting with surfactant micelles, see Fig. 8. The dots give the in-
differences are very significant. Whereas in surfactant solu- tramolecular polyelectrolyte pair-correlation function without surfactant
tion the polymer is folded around the surfactant micelle, it is present, see Fig. 10. The drawn curves are lines of slope ⫺1.18 and ⫺1.90,
strongly stretched in salt solution. The stretching is less than corresponding to fractal dimensions d f ⫽1.82 and d f ⫽1.10, respectively.
J. Chem. Phys., Vol. 118, No. 24, 22 June 2003
FIG. 10. 共Color兲 Typical conformation of a cationic polyelectrolyte in salt
solution of 0.045 M.
or to ␯ ⫽3/5 (d f ⫽5/3) according to the Flory theory. The
transition from globule to swollen chain has been observed
in DPD simulation,22 which shows that indeed ␯ increases
continuously from ␯⫽1/3 to ␯⫽3/5 as the quality of the sol-
vent increases. From a simple argument, it can be seen that a
short-range repulsive interaction can never produce a swell-
ing exponent larger than ␯⫽3/5. The free energy of a chain
of M segments in mean field is given by F⬃R 2 /M
⫹bM 2 /R 3 , where R is the polymer endpoint separation and
b is the second virial coefficient. Minimizing F with respect
to R gives R⬃b 1/5M 3/5. So, irrespective of how large the
second virial coefficient is, in this simple mean-field analy-
sis, the swelling exponent is always ␯⫽3/5 as long as b is
positive.
Finding a swelling exponent ␯⫽0.9 as in these simula-
tions is, therefore, very special. It effectively means that the
chains are stiff, with a persistence length of at least ten
beads, as the scaling is observed over a decade in length
scale. To generate such polymer conformations without long-
range interactions would require a strong bond–angle inter-
action, i.e., a three-body interaction. Such a three-body inter-
action produces stiff polymers or wormlike chains. Over
distances smaller than the persistence length, the correlation
function of these polymers shows an apparent swelling ex-
ponent close to ␯⫽1, but beyond a distance of a persistence
length, the polymers behave as self-avoiding walk again,
␯⫽3/5. Such a bond–angle interaction was not included
here, however, and it would exclude a realistic interaction of
the polymer with surfactant micelles. Stiff polymers with a
persistence length as seen in the present simulations cannot
bend around the micelle for realistic interactions between the
polymer and surfactant, as this is excluded by the stiffness of
the polymer. The transition from ␯⫽0.9 without a surfactant,
to a breaking of scale invariance in the presence of a surfac-
Electrostatics in dissipative particle dynamics 11275
tant is, therefore, intricately linked to the presence of a long-
range electrostatic interaction.
VI. CONCLUSIONS
Electrostatic interactions can be incorporated in mesos-
copic DPD simulation. The grid method used here proved to
work efficiently if the grid size is taken equal to the particle
size. Within this formalism, local inhomogeneities in the
electrostatic permittivity can be treated without any problem.
The rather large grid size used here causes some slight arti-
facts in the ion–ion force at short distances. However, the
short-range DPD repulsion dominates the pair-correlation at
short length scales, therefore, this effect is not very impor-
tant. Moreover, it can be compensated by a short-range pair
interaction if required. When the grid size is reduced, the
accuracy of the electrostatic interaction at short distance
would be improved, but this will be achieved at the cost of
increased CPU time. Key issues like the screening of the
potential near a charged surface and the Stillinger–Lovett
moment conditions are satisfied. Since the electrostatic field
is solved explicitly, effects caused by dielectric inhomogene-
ities, like image charge effects, are included in the method.
Also, the Maxwell force on dielectric media can be readily
incorporated. This implies that the method captures the es-
sential features of electrostatic interaction.
For the direct simulation of mixed surfactants near oil–
water interfaces, or for the simulation of Coulombic
polymer–surfactant interactions, this method has all the ad-
vantages of DPD over full atomistic MD. DPD has proved to
be faster than MD by many orders of magnitude,18 depend-
ing on the precise scaling factor chosen for the simulation.
This brings phenomena of microseconds in reach of simula-
tions that still contain a fairly accurate representation of the
structure of the molecules.
As an example of the method, a cationic polyelectrolyte
solution was studied. The polyelectrolyte shows a fractal di-
mensionality that is in line with theoretical and experimental
values cited in literature, it behaves as a fairly stiff rod of
fractal dimension d f ⫽1.1. When salt is replaced by an an-
ionic surfactant, the polymer wraps around one or more dis-
crete surfactant micelles, in line with current understanding
of these systems. In short, the present simulation method,
which includes long-range electrostatic interactions, pro-
duces realistic results for polymer–surfactant systems, with-
out the need of introducing effective short-range potentials to
force the simulation to a desired result. This makes the
method a powerful, predictive simulation tool, which can be
applied to polyelectrolytes, surfactant systems, biological
membranes, and interactions between these.
APPENDIX A: THE CHARGE–CHARGE INTERACTION
For charge clouds centralized around the points 0 and r,
the potential is given by
冕冕
⌫
U共 r 兲⫽ f 共r1兲 f 共 r⫺r 2 兲 d 3 r 1 d 3 r 2 , 共A1兲
4 ␲ 共 r 1 ⫺r 2 兲
when we take R c as unit of length (R e ⫽R phys e /R c ).
The double convolution is easiest evaluated by first consid-
11276 J. Chem. Phys., Vol. 118, No. 24, 22 June 2003 R. D. Groot

ering the Fourier transform, which is given by U(k)

⫽⌫ f (k) 2 /k 2 . Substituting the Fourier transform of f (r)
⫽3(1⫺r/R e )/ ␲ R 3e the interaction is obtained as

U 共 r 兲 /⌫⫽
1
2␲ r 2 冕0
⬁
k sin共 kr 兲 f 共 k 兲 2 /k 2 dk

⬇
52 4 r
⫺
35 5 R e 冉 冊 冉 冊 2
⫹
2 r
5 Re
4
⫺..
, 共A2兲
4␲Re
where the series was found by expanding the sine in a Taylor
series, and evaluating the resulting moment integrals. The
numerically calculated back transform was fitted to the
asymptotic expansion plus a power law, which gives a very
good description at r⬍R e :

4 ␲ R e U 共 r 兲 /⌫⫽
52 4 r
⫺
35 5 R e 冉 冊 冉 冊 2
⫹
2 r
5 Re
4
FIG. 11. Grid points within neighbor distance R n are checked for their
distance from the particle, those within a distance R e are actually used for

冉 冊 5.145 smearing out the ion charge. The arrows point at the lattice sites over which
r the charge of the ion is spread.
⫺0.135 87 . 共A3兲
Re
In the range R e ⬍r⬍2R e , the potential is empirically very
well described by cides with the particle center. Toward this end, a dipole and a

冉 冊
Re r charges coincides with the particle position. The correction
4 ␲ R e U 共 r 兲 /⌫⫽ ⫺3.2100 1⫺
r 2R e
and finally for r⬎2R e , the potential is exactly given by
U(r)⫽⌫/4␲ r. Over the entire range 0⬍r⬍2R e , the error
in the fit is of the order 10⫺4 . Assuming power laws as in
Eqs. 共A3兲 and 共A4兲, the coefficients follow analytically from
the power 5.145, and from the conditions that the potential
and its first derivative must be continuous in r⫽R e .
APPENDIX B: CHARGE REDISTRIBUTION
AND DIFFERENTIATION ON THE LATTICE
In principle, the lattice grid size can be chosen at any
value, but as we want to have a fast implementation and
describe local polarizability effects, it is prudent to choose
the lattice cells equal to the cells that are used for the linked
cell administration. The charges are smeared out over all
lattice nodes that are closer by than a distance R e . Therefore,
at forehand, a neighbor list is made of all nodes within a
distance R n of the central cell 共see Fig. 11兲. Then during the
simulation, all nodes within the outer circle are checked for
their distance from the ion. The nodes that are found within
a distance R e from the ion are used for smearing.
The actual smearing is done in two steps. First, a charge
proportional to f (r)⫽1⫺r/R e is assigned to each of the
nodes i, normalized such that the sum of all these charges
equals the charge of the ion, hence,
1⫺ 兩 ri ⫺rc 兩 /R e
f i 共 rc 兲 ⫽ , 共B1兲
兺 i ⬘ 1⫺ 兩 ri ⬘ ⫺rc 兩 /R e
where ri is the position of node i, rc is the position of the ion,
and the sum over i ⬘ runs over all nodes within a distance R e
from rc .
In the second step of the smearing operation, the distri-
bution is balanced such that its center of mass exactly coin-
6
quadrupole moment are added such that the center of lattice
, 共A4兲
to the charge distribution has the form
␦ f i ⫽ f i • 关 1⫹␭ x 共 x i ⫺x c 兲 ⫹ ␮ x 共 x i ⫺x c 兲 2 ⫹ 共 x→y 兲
⫹ 共 x→z 兲兴 , 共B2兲
where x i is the x coordinate of a lattice position, x c is the x
coordinate of the particle, and the last two terms are analo-
gous expressions for the y and z direction. The redistributed
charge is calculated from the conditions
兺i 共 x i ⫺x c 兲共 f i ⫹ ␦ f i 兲 ⫽0 and 兺i ␦ f i ⫽0. 共B3兲
To solve Eq. 共B3兲, the following moments of the charge dis-
tribution are calculated first:
S xn ⫽ 兺i 共 x i ⫺x c 兲 n ␦ f i , 共B4兲
for n⫽1, 2, and 3, and analogous expressions for the y and z
directions are determined. If the charge redistribution in the x
direction would not influence the moments in the other di-
rection, ␭ x and ␮ x appearing in Eq. 共B2兲 could directly be
solved as
␭ x ⫽⫺S x1 S x2 / 关共 S x2 兲 2 ⫺S x1 S x3 兲 ]
and 共B5兲
␮ x ⫽ 共 S x1 兲 2 / 关共 S x2 兲 2 ⫺S x1 S x3 兲 ].
However, since the moments in the y direction also change
when the distribution in the x direction is balanced, Eqs.
共B2兲, 共B4兲, and 共B5兲 have to be iterated three to four times to
satisfy Eq. 共B3兲 up to six decimal places.
To enable the simulation of a surface charge of a wall at
x⫽0, the grid points at which the field and charge density are
defined, are taken at integer multiples of the cell size used for
J. Chem. Phys., Vol. 118, No. 24, 22 June 2003 Electrostatics in dissipative particle dynamics 11277

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