Macromolecular

Chemistry and Physics

Full Paper

A New Coarse Grained Particle-To-Mesh

Scheme for Modeling Soft Matter
Guojie Zhang, Kostas C. Daoulas, Kurt Kremer*
A recently proposed model of high-molecular-weight polymers is employed to develop a gridbased Monte Carlo method for efcient modeling of dense systems, for example, melts. The
polymers are described as chains of soft spheres with uctuating size. The spheres correspond
to Gaussian density distributions of the microscopic segments
and represent whole subchains. Their coordinates and radii
are dened in continuum space and simple potentials keep
the chain connectivity. A density functional denes the nonbonded interactions by mapping the density distributions
onto a grid, without a neighbor list. The high accuracy of the
scheme is demonstrated by comparing with data obtained
from the standard potential-based formulation of the model.
Contrary to most lattice models, the method allows for NPT
simulations.

1. Introduction
One of the strategies currently employed in computer
simulations of soft matter relies on developing coarsegrained models by combining particle-based descriptions
with elements of eld-theoretical representations and
classical density functional theories of liquids. Commonly
such schemes[111] dene the bonded interactions through
explicit particleparticle potentials, while the nonbonded
interactions are formulated through integral functionals of
collective coordinates (e.g., local density). Since these collective degrees of freedom are directly related to the coordinates of the coarse-grained monomers in the system,
the models remain particle based. Therefore, they can
be directly considered within standard particle-based
techniques [e.g., Monte Carlo (MC), dissipative particle
Dr. G. Zhang, Dr. K. C. Daoulas, K. Kremer
Max-Planck-Institut fr Polymerforschung, Ackermannweg 10,
55128 Mainz, Germany
E-mail: kremer@mpip-mainz.mpg.de
K. C. Daoulas
Innovation Lab GmbH, Speyerer Strae 4,
69115 Heidelberg, Germany

214

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dynamics (DPD), and molecular dynamics (MD)], provided

that the connection between the collective variables
and the coordinates of the particles can be incorporated
into the algorithm of the modeling scheme. Conceptually, such hybrid representations are attractive because
their close connection to eld-theoretical representations facilitates more efcient (albeit approximate) treatments through self-consistent Field (SCF) theory schemes
as well as beyond-the-mean-eld techniques, such as the
self-consistent Brownian dynamics (SCBD) simulations,[12]
the single-chain-in-mean-eld (SCMF) simulations,[4,13]
and the Gaussian equivalent representation (GER).[14]
Obtaining quick estimates in the mean-eld limit can be
especially helpful during model parameterization. In a
broader perspective, dual representations are promising as
components of multiscale approaches bridging continuum
and particle-based coarse-grained descriptions.[15,16] In this
sense, these approaches are complementary to purely particle-based scale-bridging methodologies, which typically
consider a bottom-up approach from an all-atom description to a coarser representation.[1719]
Hybrid schemes based on collective variables linked to
the underlying particle coordinates can be very efcient
computationally. In this scope, grid-based methods,[1,4,13,20]

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DOI: 10.1002/macp.201200520

Macromolecular
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A New Coarse Grained Particle-To-Mesh Scheme for Modeling Soft Matter

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in the spirit of particle-to-mesh (PM) techniques used in

electrostatics,[21,22] are particularly attractive. Space is discretized and the collective variables are obtained by mapping the particle coordinates from continuum space onto
the nodes of the grid. This facilitates the implementation
of MC techniques, which do not require neighbor lists and
are, therefore, very fast. It should, however, be kept in
mind that implementing efcient PM techniques violates
the translational invariance and the isotropy of space.
Possible artifacts, for example, registration of interfaces
with the underlying lattice, thus have to be excluded.
Alternatively, one can interpret the density-functionalbased description directly as particleparticle interaction. Typically, the coarse-grained beads are considered
as density clouds and their pairwise potentials can be
obtained from the spatial integration of the density
overlaps.[5,6,10,23,24] In a slightly different approach,[13,9]
one considers point-particles but expresses the effective
energy (free energy in fact) per particle via functionals
of smeared-out local densities. The models derived using
weighting functions should not be seen as hybrid representations, although they are motivated by an underlying functional. They rather belong to the general
class of soft models frequently used when studying soft
matter (details concerning these models can be found,
for example, in refs.[2530]). Due to the explicit pairwise
interactions, they are computationally much more
demanding compared with PM representations.[10] On
the contrary, for lattice-based calculations, the number
of interactions is independent of the density, being
determined only by the number of nodes used for mapping a single particle.
To combine the advantages of the two approaches outlined above, one can retain an explicit density cloud representation for each particle and calculate the spatial density distribution with the help of a high-resolution mesh
where the lattice period is signicantly smaller than the
characteristic size of the soft particle. The density contributed by each particle to a lattice node is given by the
value of the associated density cloud where it overlaps
with the given node. As in standard grid-based methods,
this allows approximating the integral functional via a
discrete sum over the lattice nodes. It is therefore straightforward to obtain the total nonbonded energy of a given
conguration of the studied system and apply a MC sampling scheme. The outlined strategy has similarities with
PM techniques, smearing the density of point particles on
the lattice nodes with high-order polynomials.[21,22] However, one of its advantages is that the exact counterpart
of the discretized version is available in form of pairwise
potentials obtained from the direct, analytical integration. This allows one to perform smaller scale simulations
in the exact limit to validate the discretized version and
obtain error estimates.

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Here, we demonstrate the feasibility of the above

strategy by considering a specic model proposed for
the description of high-molecular-weight polymeric systems.[24] Within this approach, the polymer chains are
described as sequences of soft spheres with uctuating
size, linked by a generic bead-spring type potential. As
described in detail in the original work,[24] the correspondence of the spheres to large blobs of microscopic
segments motivated their consideration as density clouds
with a Gaussian density distribution. This model serves
ideally our purposes of proof-of-concept since: (a) it
contains simultaneously a representation on the level of
density clouds and the corresponding pairwise potentials
and (b) it was especially designed to describe dense systems (concentrated polymer solutions and melts), i.e., the
most demanding regime. The comparison with other softblob-based representations (for representative studies see
refs.[23,26,3136]) will be addressed in further studies.
Our paper is organized as follows. In Section 2, we
briey review the original model of Vettorel et al.[24] and
the parameterization used here. In Section 3, we introduce the representation through collective variables (3.1),
the particle-to-mesh scheme (3.2) and the main technical aspects of the Monte Carlo simulations (3.3). In Section 4, we present results on energetic, conformational,
and liquid-structure properties, and compare them to
reference data obtained from standard potential-based
simulations (Sections 4.14.3). In Section 4.4, the possibility of using the proposed grid-based method for conducting simulations in the isobaric-isothermal ensemble
is illustrated by obtaining the equation of state. Section
5 presents a summary of the current work and an outlook. In Appendix A, we clarify details related to the denition of the stiffness of the mesoscopic bonds, while in
Appendix B we cover technical issues of simulations in
the isobaricisothermal ensemble.

2. Model
2.1. General Description
Since the uctuating soft-sphere approach to polymers has
been discussed in detail in the original work of Vettorel
et al.,[24] here we present only a brief review. Consider a
ne-grained system of n bead-spring or bead-rod chains
with polymerization degree Nin a cubic box of volume V
(i.e., each edge has length L = 3 V ). The nonbonded interactions of the microscopic monomers are described via the
purely repulsive WeeksChandlerAndersen (WCA) potential. As illustrated in Figure 1, the coarse-grained model is
introduced by representing subchains of Nb microscopic
monomers as single, soft spheres. The coordinates of the
spheres and their sizes correspond to the center-of-masses

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distribution of the instantaneous value

of the gyration radius of the underlying
Nb-monomer subchains. For this purpose, a potential originally suggested by
Lhuillier[37] is used:
N

Vsphere =

n 
CG


vsphere (i (s))

(2)

a1 Nb3
a2i2(s)
+
i6(s)
Nb

(3)

i= 1 s = 1

vsphere (i (s)) =

where = 1/kBT. i(s) denotes the radius

of the s-th sphere of the i-th chain. The a1
and a2 are adjustable parameters which,
Figure 1. Schematic of the uctuating soft-sphere model of polymers. The semitrans- for moderate degrees of coarse-graining,
are Nb-dependent (they converge, howparent particles correspond to the soft spheres representing Nb underlying microscopic
segments, shown by the thick solid line. The solid dots and the springs mark the posiever to a constant when Nb >>1). For the
tions of the centers of the soft spheres and the coarse-grained bonds between them, special case, N = 50 we use a = 4.78
b
1
respectively.
104 and a2 = 9.48.[24]
The bond potential, Vbond, ensures
and the gyration radii of the underlying subchains, respecthat the probability distribution of the distance between
tively. These blobs are soft because the chains can intertwo spheres subsequently linked in the same chain reprodigitate[23,26,3136] without violating the excluded volume
duces the one of the distance of the center-of-masses of
constraints. The number of soft spheres, NCG, for each chain
their corresponding subchains. This potential has the
follows from N = NCG(Nb 1) + 1, which takes into account
simple form:
that two connected soft spheres have one common micro1
n N
CG

2
3 
scopic segment. The average densities of the microscopic
(4)
ri (s + 1) ri (s)
Vbond =
2
2bCG
and the coarse-grained systems are denoted as micro =
i=1 s=1
nN/V and = nNCG/V, respectively. Obviously, the choice
of Nb sets the degree of coarse graining. In the following,
The ri(s) stands for the coordinates of the s-th sphere of
2
without loss of generality, for purposes of method develthe i-th chain, while the bCG
is an adjustable parameter
2
2
opment, we set Nb = 50, since for this case, extensive data
chosen so that bCG = 4 , that is, one ensures that the
on model parameterization are already available from the
average length of the coarse-grained bond equals the
literature.[24]
average diameter of the super-blob, 2 2 . More details
The coarse-grained effective Hamiltonian is formulated
are provided in Appendix A.
assuming that the interactions can be separated into
The third term, Vbend, needs some more explanation.
entropic and excluded-volume contributions, described
It can be shown that choosing the centers-of-mass of the
via the effective Hamiltonians of the bonded, Hb , and
Nb-monomer subchains as mapping centers introduces
the nonbonded, Hnb , interactions, respectively. To comply
angular correlations between two consecutive bonds of
with the original parameterization of the model, all
the overlaying coarse-grained model.[24,38] Thus, Vbend
length scales are expressed in units of the characteristic
in Equation 1 is essential for reproducing correctly
diameter, a, of the microscopic WCA interaction.
the average radius of gyration of the polymer coil and
reads:
2.2. Bonded Interactions

The effective Hamiltonian Hb is subdivided into three

parts:
Hb = Vsphere + Vbond + Vbend

(1)

The rst term, Vsphere, ensures that the radius of the

soft spheres uctuates according to the probability

216

Vbend =

n
CG



1
kbend 1 + cos i (s)
2
i=1 s=1

(5)

where i(s) corresponds to the angle between consecutive

bonds, while kbend is an adjustable parameter which, similarly to a1 and a2, converges to a constant value when Nb >>
1. For Nb = 50 we use kbend = 1.32.

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2.3. Nonbonded Interactions

The effective Hamiltonian Hnb is expressed as:
1 
Hnb =
U (ri (s), i (s); r j (t ), j (t ))
2 i,s j,t
+


i,s

(6)

U (ri (s), i (s); ri (s), i (s))

The function U denotes a pairwise potential, which

depends on the coordinates of the interacting spheres as
well as on their radii and will be discussed in detail below.
The rst term gathers the interactions of all pairs of different
soft spheres [i.e., (i, s) (j, t)], while the second contains contributions from self-interactions of the soft spheres. When
considering polymer solutions, the latter captures the
swelling of the underlying ne-grained subchains because
the excluded-volume interactions between the Nb microscopic monomers are not (or only partially) screened.
The form of the effective potential is obtained in the
spirit of an ansatz introduced by Flory and Krigbaum[31]
where the free-energy cost of the overlap of two soft
spheres is estimated by considering the average distribution in space of the underlying microscopic monomers.
For a given sphere with size i(s) and position ri(s), this
distribution is expressed through a density cloud, i,s(r),
which, following Debye and Bueche,[39] is approximated
by a Gaussian function normalized to unity:

i,s (r) =

2 i2 (s)
3

 3/ 2

3(r ri (s))
2i2 (s)

exp

2

(7)

The effective potential between two spheres is then

calculated from the overlap of their density clouds as:

U (ri (s), i (s); r j (t ), j (t )) =

dri,s (r) j,t (r)

(8)

The parameter controls the magnitude of repulsion

between the different spheres; for Nb = 50, = 4437.[24]
The self-interactions are also obtained from Equation 8.
For i = j, s = t, and Nb = 50, one nds 1 = 2279.[24] The
convolution of the Gaussian density clouds in Equation 8
can be explicitly performed, leading to a pairwise potential of the form:

 3/ 2
2 i2 (s) + 2j (t )

U (ri (s), i (s); r j (t ), j (t )) =

3


exp

 (9)
3(ri (s) r j (t )) 2
2(i2 (s) + 2j (t ))

For the self-interactions, this gives:

Uself (i (s)) = 1

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4 i2 (s)
3

 3/ 2

depending only on the sphere size i(s).

This coarse-grained force-eld allows studying this
model within standard simulation techniques, such as
Monte Carlo.[24] Here, however, we will take advantage of
the density cloud description underlying the nonbonded
interactions (c.f. Equations 7 and 8) and recast them
within an alternative, approximate, particle-to-mesh formulation. The conventional force-elds (i.e., Equations
2, 4, 5, 9, and 10) will be employed only for validating and
establishing the accuracy of the proposed scheme.

3. Particle-to-Mesh Approach
3.1. Collective Densities
To describe the connectivity of polymer chains and the
uctuations of the size of the soft spheres, our particleto-mesh scheme retains the conventional particle-particle
force-elds highlighted above (Equations 2, 4, and 5). At
the same time, using the explicit coordinates of the centers
of the nNCG spheres present in our system, we introduce
the collective variables:
N

(r) =

n 
CG


i,s (r)

(11)

i= 1 s = 1

(r) =


 n NCG
 

(12)

2i,s (r)

i = 1 s =1

With the above denitions, the effective Hamiltonian

of the nonbonded interactions presented in the previous section [c.f. Equations (6), (8)] can be equivalently
rewritten as a functional of (r) and (r):




dr 2 (r) 2 (r)
Hnb =
2
(13)
N

n 
CG


Uself i (s)

i= 1 s =1

Subtracting (r) from 2(r) ensures that there are no

self-interactions in the rst term of Equation 13. These
are introduced by the second term so that the original
potential-based formulation of Equations 6 and 8 can be
recovered from Equation 13.
2

3.2. Grid-Based Representation

In order to employ the functional-based nonbonded interactions, we discretize space by a cubic mesh with grid size
L. Then, the two collective densities at each node of the
grid (with a spatial coordinate c) can be written as:
N

(10)

(c) =

n 
CG


i,s (c)

(14)

i = 1 s =1

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 n NCG
 
(c) =
2i,s (c)

(15)


 3 2
L (c) 2 (c)
2 c

Hnb =

i,s s = 1

Thus, the density cloud of each soft sphere [c.f. Equation 7] contributes to the grid-node a portion of density
given by:

i,s (c) =

2 i2 (s)
3

 3/ 2

exp

3(ri (s) c)
2i2 (s)

2

(16)

In practice, the calculation of i, s(c) requires the

introduction of cut-off lengths. The rst cut-off, max,
constrains the maximum allowed radius of the sphere,
which is used during Monte Carlo moves (see Section 3.3). For Nb = 50, we choose max = 10 since in this
case, the corresponding Boltzmann weight [i.e., the exp
[ (vsphere + Uself )], c.f. Equation (3) and (10)] is less than
1010. In addition for each i(s), we introduce a cut-off
length rcut(i(s)) for the corresponding density cloud, i.e.,
we set i, s(c) = 0 if |ri(s) c| > rcut(i(s)). Here, this characteristic length rcut(i(s)) is dened so that i, s(c) 108,
when |ri(s) c| = rcut(i(s)). The above three-dimensional
particle-to-mesh mapping via the density cloud is illustrated in Figure 2 through a simplied two-dimensional
sketch.
Subsequently, the integral functional of Equation 13 is
approximated by the sum over the grid nodes:

grid node
L

rcut

ri
0

c
ii-th
th ssof
soft
offtt sp
ssphere

Figure 2. A two-dimensional cartoon clarifying the three-dimensional scheme used in the simulations for assigning the density
cloud of the i-th sphere onto each grid-node of the lattice. The
coordinate of the center of the sphere is denoted with ri, rcut corresponds to the cut-off length of the density cloud, and c is the
coordinate of a given mesh point.

218

n 
CG


Uself i (s)
+

(17)

i =1 s =1

The lattice spacing, L, is a key parameter of the numerical scheme. The ner the grid, the more accurate is the
approximation and the more expensive is the computation.
Thus, the choice of L constitutes a compromise between
these two factors. Also the simple discretization dened
via Equation 16 only approximately conserves the normalization of the density cloud as dened in continuum space,
that is, ci, s(c)L3 1. Alternatively, the normalization can
be strictly conserved using schemes with correcting prefactors at the expense of additional computations. In Section 4.1, we check the level of approximation needed.
3.3. Simulation Details
3.3.1. NVT Simulations
In the current model, both the radii and the positions of
the soft spheres constitute degrees of freedom, to be sampled by the Monte Carlo algorithm. For this purpose, two
separate Monte Carlo moves are implemented: changing
of the size of the sphere (CSS) and slithering snake moves
(reptation or REP). When performing a single CSS move,
one of the nNCG soft spheres is randomly selected, the
old radius, old, of the selected soft sphere is replaced by
a new one new (0, max], being drawn according to the
Boltzmann weight exp [ vsphere(new)], using the standard
method proposed by von Neumann[40] (for the denition
of vsphere see Equation 3).
For the REP move, a chain is randomly selected as well
as the direction of the move along the chain contour. One
sphere is cut from the one end of the chain and attached
to the opposite. During this procedure, the size of the
sphere is retained, while the length of the bond is drawn
according to the Boltzmann weight of the harmonic
potential dened in Equation 4.
To obtain the change of the nonbonded energy by the
attempted moves, the new values of the collective variables, new(c) and new(c), are calculated for the nodes of
the lattice affected by the proposed move. For the CSS
move, these will be the nodes overlapping with the density cloud of the sphere for the old and the new values of
i(s); in the case of REP, these will be the nodes overlapping with the density cloud at the old and the new position of the sphere. Then Hnb is given by

Hnb =




2new 2old 2new 2old L3
2 c
a

(18)

+ Uself

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where the summation is performed only over the affected

grid-points ca. Uself is the energy difference of self-interaction
involved during CSS, that is, Uself = 0, for REP while Uself =
Uself(new) Uself(old) for CSS. The moves are then accepted with probability pacc (CSS) = min[1, exp( Hnb )]
and pacc (REP) = min[1, exp( ( Vbend + Hnb ))]. Those
Boltzmann factors that are already taken into account
during the biased selection of the proposed conguration
are omitted from the Metropolis acceptance criterion. A
typical mix of moves consists of 50% CSS and 50% REP. In
all cases, we employ periodic boundary conditions.
It is helpful to compare[10] roughly the efciencies of the
simulations using the PM scheme and the conventional
formulation of interactions through pair potentials. For
example, in the reptation move, where only one sphere is
moved at a time, the computational time, g, of the gridbased method should be proportional to the total number
of grid nodes affected by the sphere during the move. This


3
would be about 4rcut
/3L3 ; it is reminded that the rcut
stands for a cut-off length of the density cloud. At the
same time in the simulations using the potential-based
formulation of the interactions, the computational time,
p, will be determined by the number of potentially interacting neighbors. For the simplest cell-list method,[40]
3
it will be p 27rcut
, where rcut is the cut-off length of
the pairwise potential, which determines the minimum
allowed size of the cells in the cell-list. As will be demonstrated in Section 4.1 for Nb = 50, the PM scheme
becomes accurate for L = 2.5. For this Nb, the maximum
allowed radius of the spheres will be max = 10 leading to
a rcut 26.4 (c.f. Section 3.2). Substituting i = j = max into
the pairwise potential, Equation 9, one obtains rcut 33.8
requiring that U ( rcut ) 104 . Thus g p when 4.7
103, corresponding to micro 0.24. In can be seen that the
grid-based method becomes indeed favorable (i.e., g <
p) for modeling polymeric systems in the high-density
regime, > 4.7 103 (concentrated solution or melts).
Although the chains are distributed on a grid, the
memory requirements are rather modest. Already a computer with main memory of 4G, for L = 2.5 can handle
a system of soft spheres with lateral dimensions L = 625
(discretized with Ngrid = 250 nodes at each side). For the
melt-density micro 0.85, such a box will contain 4 106
super-blobs (when Nb = 50).
3.3.2. NPT Simulations
In general, performing simulations of lattice-based models
within the isobaricisothermal ensemble is rather complicated. Thus obtaining, for instance, the equation of state
requires more elaborated approaches, like the thermodynamic integration schemes described in Refs.[41,42]. Within
the current PM scheme the situation is different, due to
the high accuracy with which the continuum limit is

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approximated. More specically, in addition to the CSS and

the REP moves, we implement a volume-changing move,
which is very similar to volume-changing algorithms
used in the NPT simulations of standard potential-based
models.[43]
To do so, a volume change of the box,
from V to V

(the edges of the box change from L = 3 V to L = 3 V  ,

correspondingly) is proposed. The new particle coordinates ri (s) , are obtained from the old coordinates ri(s) as
ri (s) = ri (s)L /L , while the radii of all the spheres are conserved. The move is accepted with probability:
pacc = min[1, exp[ (H H
+ P(V  V ) 1 nNCG ln(V  / V ))]]

(19)

where P is the pressure, while H and H represent the total

energy (i.e., the sum of the bonded and nonbonded interactions) of the old and the new conguration, respectively.
This approach becomes very accurate (see the following
sections) provided that the grid spacing L is smaller than
some threshold value, Lo, (for Nb = 50, Lo = 2.5). Further
technical details can be found in the Appendix B.

4. Results and Discussion

4.1. The Nonbonded Energy
To maintain computational efciency, it is essential to
implement the crudest discretization of space, which guarantees the required accuracy. For a given lattice-spacing, L,
this is checked by comparing key properties as obtained in
the grid-based, PM, scheme and in a standard potentialbased simulation using the force-eld described by Equations 2, 4, 5, 9, and 10. Since the nonbonded interactions
are directly related to the density clouds of the super-blobs
[see Equations 7, 8], we expect that a difference in these
energies will provide a very sensitive measure. We have
considered systems of coarse-grained molecules with NCG =
10 (i.e., the polymerization degree of the underlying microscopic polymer chains is N = 491 for Nb = 50) at various densities . From the denition of micro and , it follows micro
Nb. Thus for example, the coarse-grained density = 0.017
corresponds to micro 0.85, deep in the dense
 melt regime.
 o
o 
/Enb
Figure 3 illustrates the relative deviation Enb Enb
of the ensemble-averaged nonbonded energy calculated
in the PM scheme, Enb, and in the potential-based method,
o
Enb
, as a function of the lattice spacing, L. It can be seen
that for all densities there is a well-dened value of L
where the relative error becomes on the order of 104. Most
notably, at lower densities, high accuracy can be already
achieved at larger values of L. This is due to the swelling
of the super-blobs in the dilute regime; these enlarged
objects can be discretized using cruder lattices.

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1.2

0.8

2.510

= 0.002
= 0.006
= 0.012
= 0.017

-4

2.010

-4

1.510

-4

1.010

-5

5.010

0.0

|Enb - Enb |/ Enb

-4

0.6

2.2

2.4

2.6

2.8

0.4
0.2
0

Figure 3. The relative differences of the nonbonded energies calculated in simulations

o
, for
performed with the grid-based approach, Enb, and the potential-based method, Enb
different densities of coarse-grained particles, = nNCG/V. L denotes the lattice spacing
in the grid-based method.

220

is plotted in Figure 5 with open squares.

On the contrary, for the lattice spacing
L = 2.5 the g(r) calculated in the gridbased simulations follows closely the
reference result obtained using the
potential-based simulations (solid circles), even more clearly demonstrated in
the inset. The pair distribution function
indicates that in the exact limit there is
still some overlap between the superblobs. However in this case, this is not
an artifact but a physical property of a
dense polymer system.
It is also instructive to compare
the average size of the soft spheres,
2 1/ 2 , as a function of density ,
Figure 6. At low densities, the superblobs are signicantly swollen, while
in the limit of typical polymer melt
densities, the strong overlap of the soft
spheres leads to a signicant contraction. Again this compares extremely
well to the potential-based simulations,
also shown in Figure 6.

4.2. Local Conformational Properties And Structure

4.3. Global Conformational Properties

Taking the comparison of nonbonded energies presented

in Figure 3, we expect that lattices with L 2.5 will yield
very accurate results for all densities. This is conrmed by
Figure 4, where we compare the PM-based results for probability distributions of (a) the bond length, P(rAB), (b) the
angle between consecutive bonds, P(), and (c) the radius
of the soft spheres, P(), with the potential based simulations with NCG = 10 at density = 0.01 (micro 0.5). The
distributions obtained via the grid-based method with
L = 2.5 (open circles) follow closely that of the reference
potential-based method (solid circles). Especially, the excellent agreement for the distribution of the sphere radiia
quantity most directly determined by the form of the density cloudis encouraging.
Increasing the lattice-spacing reduces the accuracy of
the grid-based method and for large Ls signicant artifacts are observed. As an illustration, we only show one
result (in Figure 4) obtained from simulations conducted
with a grid-spacing L = 7.29 (open squares). For example,
the distribution P(rAB) (see Figure 4a) becomes strongly
bimodal. This is because for large L, the soft spheres can
avoid intersecting the nodes of the lattice. Avoiding the
grid-nodes is energetically favorable, since in this case,
the spheres do not contribute to the density, i.e., the nonbonded energy is reduced. This ideal-gas-like behavior of
the soft spheres within large lattice cells can be observed
after calculating the pair distribution function g(r), which

For a more conclusive validation of the grid-based

approach, it is essential to demonstrate that the global conformational properties of the polymer chains are correctly
reproduced, as well. This can be quantied on all scales via
the static structure factor:
2 
 N

CG

1 
S(q) =
exp( iqri (s)) 
(20)
NCG  s= 1

where the angular brackets denote an average over the
chain conformations and the directions of the vector q. In
Figure 7, we present the S(q)s calculated in the grid-based
(for L = 2.5) and the potential-based simulations at two
different densities = 0.001 (micro 0.05) and = 0.016
(micro 0.8). Again the comparison of the curves obtained
with the two approaches (open and solid symbols, respectively) conrms that the grid-based method with the above
discretization reproduces faithfully the reference results.
4.4. Equation of State
Finally, let us shortly turn to the NPT simulations. Figure 8
shows the equation of state (EOS) obtained from the potential- and the grid-based (L 2.5) methods as a function
of the packing fraction of the soft spheres, = 403 / 3
(0 stands for the average radius of the spheres in the
ideal case, that is, when the nonbonded interactions are

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12

0.15

(a)

potential-based method
grid-based method, L=2.50
grid-based method, L=7.29

potential-based method
grid-based method, L=2.50
grid-based method, L=7.29

10

1.5

g(r)

g(r)

P(rAB)

0.1

0.5

0.05

10

0.012

15

rAB

20

0
0

30

25

P()

0.009

0.006

potential-based method
grid-based method, L=2.50
grid-based method, L=7.29

1.25

30

60

(c)

120

150

180

10

10

15

15

turned off). For all densities, the two results are in excellent mutual agreement. It is instructive to compare these
results with the EOS of the same systems obtained within
a mean-eld approximation (dashed line):

P =

1
+ 2
NCG
2

(21)

This result can be obtained through a formal

self-consistent eld theory treatment, largely inspired by
refs. [4446]. For details, we refer to a subsequent more
formal analysis of the method presented here.[47]

potential-based method
grid-based method, L=2.50
grid-based method, L=7.29

P()

90

Figure 5. Pair distribution function, g(r), calculated from simulations of systems containing soft-sphere polymer chains with
polymerization degree NCG = 10 at density = 0.01. Open circles
and open squares show the results obtained from grid-based simulations with a lattice spacing L = 2.5 and L = 7.29, respectively.
The reference data (calculated with very small statistical error)
from potential-based simulations are plotted with solid circles.
A smaller scale plot showing the excellent agreement between
the grid-based method with L = 2.5 and the reference results is
shown in the inset.

(b)

0.003

0.75

4.8

0.5

potential-based method
grid-based method, L=2.5

4.6

0.25

4.4

Figure 4 . The probability distributions of the bond length,

P(rAB), bending angle, P(), and radius of the soft spheres, P(),
are shown in panels (a), (b), and (c), respectively. The data were
calculated from simulations of systems containing soft-sphere
polymer chains with polymerization degree NCG = 10 at density
= 0.01. The results obtained from grid-based simulations with a
lattice spacing L = 2.5 and L = 7.29 are shown with open circles
and squares, respectively. The reference data for the considered
model, calculated from potential-based simulations are plotted
with solid circles.

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4.2

4
0

0.003

0.006

0.009

0.012

0.015

, of the soft
Figure 6. The gure shows the average radius,
spheres as a function of density, . The open circles denote the
results obtained using the grid-based method with a lattice
spacing L = 2.5, while the reference data obtained from the
potential-based simulations are shown with solid circles.

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S(q)

10

=0.001, potential-based method

=0.001, grid-based method
=0.016, potential-based method
=0.016, grid-based method

0.01

0.1

Figure 7. The plot shows the single-chain structure factor, S(q),

of soft sphere polymers with a polymerization degree NCG = 10.
The open circles and squares mark the results obtained from the
grid-based method using a lattice spacing L = 2.5 at densities =
0.001 and = 0.016, respectively. The corresponding reference
data obtained from the potential-based simulations are shown
with solid circles and solid squares.

30
25

potential-based method
grid-based method
mean-field prediction

P/

20
15
10
5
0
0

0.2

0.4

0.6

0.8

1.2

Figure 8. The equation of state of a system of soft-sphere polymers with NCG = 10 is shown as a function of the packing fraction,
, of the soft spheres in the system. The results obtained from the
grid-based method using a lattice spacing L = 2.5 and the potential-based simulations (both performed in the isobaricisothermal
ensemble) are shown with open and solid circles, respectively. The
equation of state obtained from a mean-eld analysis is plotted
with the dashed line.

5. Conclusions and Outlook

Our work has been inspired by the general interest in
developing efcient simulation techniques for the treatment of a special class of coarse-grained models, gaining
popularity[111] in describing soft matter. These are descriptions combining explicit particle-based representations
with nonbonded interactions dened through functionals
of a few collective variables (e.g., local densities).
In this context, we focused on a model recently proposed for the description of high-molecular-weight polymeric systems.[24] It belongs to the family of soft-blob
models[23,26,3136] and achieves a signicant reduction

222

of the degrees of freedom by mapping subchains of Nb

microscopic segments onto single soft spheres with uctuating size. Within this representation, the coarse-grained
polymer chains can be seen as sequences of Gaussian density clouds (super-blobs) with uctuating variance connected through simple bonded interactions, chosen so that
the global conformational properties of the underlying
ne-grained chains are reproduced. The nonbonded interactions between such clouds are determined by the amount
of their overlap, expressed through a simple quadratic
density functional, and mapped onto a discretized background. Thus, the coordinates and the radii of the blobs are
dened in continuum space and the bonded interactions
are calculated via explicit particleparticle bonded potentials. For the nonbonded interactions, no neighbor-lists
are needed and the computational cost of calculating the
change of the non-bonded energy during a Monte Carlo
move becomes density independent. Therefore, the proposed scheme is particularly attractive for modeling dense
systems, for example, melts of long polymers.
To validate this approach, we calculated in parallel
accurate reference values for energetic, conformational,
and liquid-structure properties of the system at various
densities, using conventional simulations.[24] The detailed
comparison with the same quantities as obtained from the
grid-based approach showed that the latter can be made
very accurate even for rather moderate grid-resolutions.
Most notably, the presented particle-to-mesh approach
allows for simulations in the isobaricisothermal
ensemble, which is not straightforward, in most cases, of
lattice-based models.
Here, we have addressed a coarse-grained description
corresponding to a quadratic density functional motivated by an underlying microscopic model of a polymeric
system with only repulsive, athermal, excluded volume
interactions. Considering more elaborated microscopic
models (e.g., with LennardJonnes potentials) would
require the implementation of more complex functionals;
for their choice, the classical density functional theory
of liquids can offer important insights. Possible choices
include functionals which are: (a) high order polynomials
of density (such approaches have been used to describe
polymer/poor-solvent[48] and polymer/vapor[13] interfaces) or/and (b) nonlocal. Our expectation is that for the
rst case, extending the modeling strategy highlighted
here should be rather straightforward. Conceptually, the
approach could also handle non-local functionals, however it remains to be explored whether this is numerically
feasible when using moderate mesh-resolutions.
Conceptually, the particle-to-mesh approach was developed here in the framework of Monte Carlo schemes
aimed to deliver structural properties. The softness of
the interactions relaxes topological constraints (i.e.,
chains can cross through each other); thus, Monte Carlo

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algorithms invoking local displacement moves[49] will

reproduce Rouse dynamics. In principle entanglements
could be captured after augmenting the current soft
model with phenomenological mechanisms, for example,
slip-links[50,51] or transient forces.[52] In general the extent
to which similar grid-based strategies could be combined
with truly dynamical coarse-grained models[5356] based
on MD, Langevin, and DPD schemes presents an interesting question. For instance, the grid-based strategy
could be invoked for calculating forces[8,12] corresponding
to coarse-grained potentials motivated by a density-functional description. At the same time, one might still need
to develop approaches for calculating, e.g., dissipative
forces without invoking explicit information on relative
dynamics of each neighbor pair.[50]
In the future, we are planning to apply the model of
uctuating soft spheres to study high-molecular weight
polymer melts in the context of a general multiscale
framework. For this purpose, the grid-based scheme presented in the current work should be a central tool to
equilibrate systems of very long polymer chains.
Acknowledgements: It is a pleasure to thank Burkhard Dnweg
for a careful reading of our manuscript and Thomas Vettorel for
enjoyable and fruitful discussions. We are grateful to Torsten
Sthn for his help with respect to computational issues. Financial
support by the German Federal Ministry for Education and
Research BMBF within the MORPHEUS Project (FKZ 13N11701) is
gratefully acknowledged.

Appendix A: Calculating the Bond Stiffness

Parameter
The stiffness parameter kbond = 3/2b2CG in Equation 4 is
determined according to the average value of the bond
length, bCG, to be reproduced. As mentioned in the main
text, in the model of Vettorel et al.,[24] the average bond
length is connected to the average radius of the soft spheres,
<2>, as b2CG = 42 . This is motivated by the fact that the
density clouds introduced in the model for describing the
distribution of the Nb microscopic segments within a superblob are approximated by a Gaussian for all blob-sizes and
density regimes (see Equation 7). Due to the form of this
distribution, for each instantaneous radius i(s) of the soft
sphere, the average squared distance of the underlying
Nb monomers from the center of the cloud will be i2(s).
Therefore, the characteristic
average radius of the clouds in

the system will be 2 , and the average square distance
of their centers, that is, the b2CG , given by b2CG = 42 . This
implies that for each density, the b2CG must be reparameterized according to the average radius of the soft spheres
in this regime. Taking into account, the dependence of
the size of the underlying Nb-monomer subchains on the

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2
density of the system, the change in the values of bCG
can
[
57
,
58
]
be substantial. For example
in a dilute solution (at
good solvent conditions), each soft sphere can be seen as
a self-avoiding chain of Nb/gT thermal blobs of size T. Each
thermal blob will be composed of gT microscopic monomers, so that T bg1/2
T , where b denotes the monomer
size. Then in good solutions, in the dilute regime: bCG
T(Nb/gT)3/5. However, in the case of ideal chains, the soft
spheres will correspond to a random walk of the underlying thermal blobs, that is, bCG T(Nb/gT)1/2.
In practice, exactly because the b2CG is connected to the
average size of the spheres a self-consistent procedure
is required for its determination. This can be anticipated
taking into account that the 2 is determined by an intricate interplay between all the bonded and the nonbonded
interactions in the system. Hence it will be also affected by
the bonding potential Vbond, which, however, is a function
of the undetermined parameter b2CG . In this scope, we use
the following iterative approach: (a) an initial value for
the b2CG is selected and simulations are performed, after
which a new b2CG is obtained from the ensemble average
of the radius of the spheres as: b2CG = 42 (b) We return
to step (a) using the new b2CG as an initial value for the
next simulation. The above cycle continues until the b2CG
on the input and the b2CG on the output are the same.

Appendix B: Volume Changing Move

During the volume uctuations, the number of the grid
points, Ngrid, discretizing each dimension of the simulation
cell remains xed, provided that L = L/Ngrid is smaller than
Lo. If, for example, during a proposed increase of volume
the L = L/Ngrid exceeds Lo, the number of lattice nodes
is increased before calculating the nonbonded energy
contribution to H . Similarly, in the case of a signicant
contraction of the volume, the number of lattice nodes can
be reduced for reasons of computational efciency. In case
of NPT simulations, volume changes are attempted with
probability 1/nNCG, that is, on the average, we perform
one single volume change per nNCG standard NVT moves
(i.e., CSS and REP). Since each volume change requires the
computation of the nonbonded energy of nNCG particles,
this choice of frequency ensures[43] that the computational
cost of sampling the volume space and the coordinates of
the particles via the NVT moves is roughly the same (it is
reminded that each of our NVT moves invokes only one
particle at a time).
Received: August 30, 2012; Revised: October 11, 2012; Published
online: November 22, 2012; DOI: 10.1002/macp.201200520
Keywords: coarse-grained models; computer modeling; hybrid
methods; Monte Carlo simulation; polymer melts

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