Full Paper

748

Summary: We present and assess the use of non-equilibrium

molecular dynamics (NEMD) simulation method for the
direct study of the linear viscoelastic behavior of polymer
melts. The polymer melt is modeled by a collection of repulsive, anharmonic multibead chains subjected to small amplitude oscillatory shear flow. We present results for chain
lengths below the critical entanglement length and obtain
good agreement with theoretical results for the viscoelastic
behavior of melts of low molecular weight. The range of
oscillation frequencies attainable in the simulation is of a few
decades. Thus we use, as in experiments, a time-temperature
superposition rule to extend the frequency domain. As a side
result, we confirm the so-called Cox-Merz rule.

Snapshot from a non-equilibrium molecular dynamics (3D)

simulation of a polymer melt with 100 chains and 40 beads.

Linear Viscoelastic Behavior of Unentangled Polymer

Melts via Non-Equilibrium Molecular Dynamicsa
Jose Gines Hernandez Cifre,*1b Siegfried Hess,1 Martin Kroger2
1
2

Institut fur Theoretische Physik, Technische Universitat Berlin, D-10623 Berlin, Germany
Polymer Physics, ETH Zurich, Wolfgang-Pauli-Str. 10, CH-8093 Zurich, Switzerland

Received: March 18, 2004; Revised: August 30, 2004; Accepted: October 14, 2004; DOI: 10.1002/mats.200400021
Keywords: linear viscoelasticity; molecular dynamics; non-equilibrium; polymer melt

Introduction
The molecular dynamics (MD) method applied to mesoscopic models for macromolecules is known as a powerful
approach enabling the simulation of the dynamics of polymeric fluids of arbitrary architecture. Often, results are in
remarkable good agreement with known rheological and
structure-resolving experimental findings. Extensive MD
simulations of polymer melts have been performed earlier[1,2] in order to study the different regimes of diffusive
motion of polymer chains in melts. These studies allowed to
determine a critical chain length (/ molecular weight)

a
b

PACS: 83.10.Mj,61.25.Hq,83.50.Ax.
Present address: Dep. de Qumica Fsica, Universidad de
Murcia, Campus Espinardo, 30100 Murcia, Spain.
E-mail: jghc@um.es

Macromol. Theory Simul. 2004, 13, 748753

characterizing the dynamical crossover from the qualitatively different Rouse[3] to reptation[4] regimes. Further, the
flow behavior of polymer melts, subjected to simple
shear,[5,6] uniaxial elongational flow,[7,8] and stress relaxation[9] has been investigated using non-equilibrium molecular dynamics (NEMD). For reviews on this method we
refer to ref.[5,10] In ref.[6], a rheological crossover from
Rouse to reptation had been obtained via NEMD. Based on
these findings, we know that the polymer melts to be studied
in this article (N < 100 beads) should be in the unentangled
regime. The viscoelasticity of unentangled polystyrene
melts has been investigated in detail in ref.[11,12] Computational work devoted to the study of the model polymer melts
under oscillatory shear flow is scarce, although the linear
viscoelastic response is of great practical importance.
Frequency-dependent properties of simple fluids have been
studied via NEMD[1315] (linear viscoelasticity under elongational flow) and extensively discussed in ref.[13,14,16]

DOI: 10.1002/mats.200400021

2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

749

Linear Viscoelastic Behavior of Unentangled Polymer Melts via Non-Equilibrium Molecular Dynamics

(non-linear response under periodic external fields). Experimentally, the linear viscoelastic properties of polymeric
systems are usually obtained by subjecting the sample to a
small strain amplitude oscillatory shear flow characterized
by the dynamic moduli (G0 and G00 ). This article is devoted
to show the use of NEMD to study polymer melts under
oscillatory shear flow. Relaxation time of melts strongly
increases with chain length and therefore frequencies corresponding to the terminal zone of dynamic moduli where
the viscous behavior dominates are such small that direct
simulations targeting this regime are still very time consuming. This work is devoted to summarize our findings
using unapproximated MD. The results should serve to test
approximate methods and single segment theories. Alternate methods (variance reduction,[17] transient time correlation function,[18] average stress fluctuations,[1921]
beyond-equilibrium MD[22]) particularly useful at low
shear rates (and certainly also useful at low frequencies)
have been proposed and should be mentioned, but would
not be employed in this brief article.

Model and Simulation Technique

The dynamical model consists of an ensemble of interacting
linear, multibead polymer (FENE) chains contained in a
cubic box with periodic boundary conditions. Each chain
consists of N beads connected by anharmonic, finitely
extendable non-linear elastic (FENE) springs, U FENE r

12kR20 ln1
r 2 =R20 , between adjacent beads separated by
a distance r. With the choice for the spring coefficient k 30
and the maximum extensibility of the spring R0 1.5, we
follow ref.[1,5,6] The spring coefficient is strong enough to
make bond crossings energetically and virtually impossible. In order to model excluded volume, all beads interact
with a repulsive Lennard-Jones (LJ) potential, U LJ r
4er=~
s
12
r=~
s
6 1=4, for r  rc, and ULJ(r) 0
~
otherwise. Here, r is the distance between pairs of beads, s
is the distance where the LJ energy vanishes, e is the
~ is the cutoff radius.
minimum energy value, and rc 21=6 s
Along this work, all the quantities are reduced to LJ units:
the energy and length parameters of the LJ potential, e and
~, and the particle mass, m. Thus, reference unitsqfor
s
time,

~2 =e,
density, temperature, and pressure are tref m s
~
3 , Tref e/kB, and pref e s
~
3 , respectively. To
rref s
transform our dimensionless results to dimensional results
suitable for comparison with experimental data, our results
must be just rescaled depending on the physical units of the
quantity of interest and the polymer system at hand. For
a representative set of experimental data for different
polymers along with the corresponding simulation data
(FENE model) in dimensionless form, we refer to Table 1 of
ref.[6] In order to study bulk properties, periodic boundary
conditions and the nearest image convention together
with Lees-Edwards boundary conditions are employed.
Macromol. Theory Simul. 2004, 13, 748753

www.mts-journal.de

Newtons equations of motion for the system are integrated

by a velocity-Verlet algorithm and thermostatted using
velocity rescaling as in ref.[5] Thus, the macroscopic velocity of the beads due to oscillatory shear is superimposed to
their peculiar (thermal) velocities. While we employed a
simple velocity rescaling method, we should mention
alternate methods, which for the simulation at hand, lead to
practically the same results. There is the van GunsterenBerendsen thermostat,[23,24] which uses a factor at each
time step that depends on the deviation of the instantaneous
kinetic energy from its average value, corresponding to the
desired temperature. Although this method does not reproduce the canonical ensemble it is widely used, and usually
gives the same results as the rigorous method discussed
below, although caution must be taken using it. It reproduces the correct average energy but the distribution is wrong.
Therefore, averages are usually correct but fluctuations are
not. The Hoover thermostat[25] reproduces the canonical
ensemble, even though it also involves velocity rescaling.
The idea is to introduce an additional degree of freedom
describing the external bath and its corresponding velocity.
Additional kinetic and potential energy terms, coupled to
the particles momenta, are added to the Hamiltonian. The
whole system is conservative and obeys Liouvilles equation. An alternate, similar method called Nose thermostat also uses an additional variable for the momenta
rescaling. It was introduced earlier[26] and works in the scaled coordinates, and reproduces canonical distribution for
positions and scaled momenta. The spring coefficient k
chosen for the present simulations is small enough to use a
reasonable integration time step of typically Dt 0.001
0.005 (LJ units) while integrating Newtons equation of
motion. In practice, we adjust the time step to ensure that the
maximum interparticle force stays below an upper limit,
and sample data for each separate frequency over an interval
of 100 periods.

Linear Viscoelasticity and

Time-Temperature Superposition
Among the several small strain experiments used in rheometry to study linear viscoelasticity phenomena, sinusoidal
(or oscillatory) rheometry is often employed to characterize
the frequency dependence of polymer solutions and
melts.[12] In this controlled-strain test, a sample is deformed
in a oscillatory shearing flow up to reach a maximum strain
g0 (amplitude of strain), which must be small enough to be
in the linear regime, i.e., dynamic moduli are independent
of g0. Then, the time-dependent shear stress s(t) that arises
because of the deformation is monitored. This controlled
strain experiment is usually represented as follows: g g0
sin ot and s s0 sin(ot d) where o is the frequency of
the oscillation and s0 the stress amplitude. For viscoelastic
fluids, the resultant stress is delayed in time with the strain
2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

750

J. G. H. Cifre, S. Hess, M. Kroger

by a phase angle d. The stress wave can be deconvoluted

into two waves of frequency, o, and amplitudes, s00 and s000 ,
the former in-phase and the latter by an angle p/2 out-ofphase with the strain. In the simulation, the instantaneous
shear stress, s, is computed by adding kinetic and potential
contributions (virial formula),[5] due to the peculiar velocities and positions of all the beads. From the stress-strain
relationships, two dynamic moduli are defined: (i) the
elastic, storage, or in-phase modulus related with the elastic
energy stored by the sample, therefore being a measure of
the solid-like behavior of the sample, G0 s00 =g0 , and (ii)
the viscous, loss, or out-of-phase modulus, related with the
energy dissipated by the viscous flow, therefore being a
measure of liquid-like behavior of the sample, G00 s000 =g0 .
Usually, at low frequencies one reveals the liquid-like
behavior and the material has sufficient time to respond to
the perturbation. In practice, the steady-state values of the
dynamic moduli are computed as: G00 (s0/g0)cos d and
G00 G0 tan d, wherein s20 2hsi=p, the brackets h i
standing for time average and the angle d is obtained by a
least squares fit of the stress data. The complex or dynamic
viscosity is then defined as Z* :
iG*/o, where the
complex modulus is defined as G* G0 iG00 .
A practical semi-empirical rule is the so-called timetemperature superposition rule,[11] based on the fact that the
relaxation time of polymeric system is a decreasing function of temperature. The validity and failure of the timetemperature superposition rule for polymers has been
extensively discussed, and related to the molecular parameter, cf. ref.[12,27] In the Rouse model, thermorheological
simplicity holds because all relaxation processes, no matter
how slow, involve relaxations of submolecules each of
which is controlled by the same drag coefficient. The slower
Rouse relaxation processes require the coordinated movement of more submolecules than do faster processes, but
since the degree of coordination does not depend on
temperature, the rates of all modes change proportionately
when the temperature is raised or lowered. For real polymers, time-temperature shifting works for relaxation modes
that involve motions of portions of the chain large enough to
average out small-scale heterogeneities in the chain or in the
viscous environment through which the chain moves.[27]
Thus, increasing the temperature produces identical system
response than decreasing the oscillation frequency and vice
versa. Accordingly, pairs (T, o) exist, that give rise to the
same stress. This allows one to choose the best work
conditions and, after the suitable data manipulation, results
merge into a single curve. More precisely, values of G0 and
G00 measured in a range of frequencies at different temperature are converted into the corresponding values at a given
reference temperature, T0, by making suitable shifts on both
coordinate axis. The vertical shift affecting the complex
modulus reads G*(T0) G*(T)T0V0/(TV), where V is the
volume of the system (simulation box) at the working
temperature T and V0 the analogous volume at T0. Volumes
Macromol. Theory Simul. 2004, 13, 748753

www.mts-journal.de

are slightly different in making experiments on a given

sample at different temperature and same pressure. On the
other hand, the horizontal shift along the frequency
scale reads o(T0) aTo(T). Thus, to make the horizontal
shift we multiply frequencies by the so-called horizontal
shift factor, aT, which depends on the temperature and is
also determined empirically. Following the above procedure, a single master curve corresponding to T0, and comprising a large frequency range can be obtained. Thus, the
time-temperature superposition rule in principle allows to
appreciate all kinds of behavior of polymeric material
(glass, rubber, liquid) from a limited frequency interval.

Results
We studied the linear viscoelastic behavior of FENE polymer melts, characterized by bead number density n 0.84
and (reference) temperature T 1 (LJ units). Concerning
initial conditions, a total number of Nt 3 500 beads
allocated to FENE chains of length N are placed into the
periodic simulation box along the lines indicated in ref.[28]
As in experimental works, a suitable working strain amplitude, g0, must be chosen; low enough in order to be in the
linear regime but not so low that values of the properties
are largely affected by noise. A good value turned out to be
g0 0.1 which is also a common value used in experiments.
The inset of Figure 1 shows the amplitude dependence of
the loss modulus, G00 , for a melt of linear FENE chains of
N 20 using a value of oscillatory frequency o 0.1. As
observed, for g0 0.1, we are fully in the linear region but
far from the noisy region appearing at very low g0. Thus, all
plots presented in this work correspond to that selected g0.
Figure 2 shows the frequency dependence of the storage
modulus, G0 (black symbols) and G00 (empty symbols) for
different melts of linear FENE chains with N 5, 20, 70.

Figure 1. Loss modulus, G00 , versus strain amplitude, g0, for a

melt of linear multibead chains with N 20 beads each, at the
particular frequency o 0.1. Search of suitable work strain
amplitude.
2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

751

Linear Viscoelastic Behavior of Unentangled Polymer Melts via Non-Equilibrium Molecular Dynamics

Figure 2. Effect of chain length, N (/ molecular weight) on

frequency dependence of the dynamic moduli, G0 and G00 for melts
of linear finitely extendable non-linear elastic (FENE) chains.

This kind of representation helps to appreciate the frequency evolution of the solid-like and liquid-like behaviors
of the material under study as well as their relative importance. The chain lengths simulated in this work are below
the critical entanglement length Nc  100.[6] For chain
lengths below the rheological crossover length, the G0 and
G00 in the low frequency zone are expected to conform well
to the modified Rouse theory for undiluted polymer solutions as long as the temperature is well above the glass
transition temperature, cf. ref.[11] In addition, when entanglements are not formed, there is a transition from the
terminal zone (smallest o values in our dynamic moduli
curves) directly to the glassy zone, without an intermediate
rubbery range.[11] Let us first compare the behavior of G0
(i.e., black symbols only) by varying the chain length N.
Figure 2 shows that at the low frequency range swept, the
shorter the chain, the smaller is the value of G0 , while at high
frequencies all G0 curves tend to converge. Differences in
the G0 curves start to occur in reaching the terminal zone
(predominant liquid-like behavior). In the transition zone to
the glassy consistency, viscoelastic properties are dominated by configurational rearrangements of chain segments
which are not very extended (chains remain near the coil
equilibrium conformation because of the small g0 applied).
There possible crosslinks play a minor role. As a result, the
behavior is not much affected by differences in chain
length. For N 20 and N 70, because of their relatively
large relaxation times,[1] the simulated frequencies are
located above the terminal zone and therefore their G0
curves in general, superimpose. For N 5, however, the
work frequencies are close to the terminal liquid-like region
and at the lowest frequencies simulated its G0 values diverge
from those of the larger chains. In contrast, the quantity G00
(empty symbols only) is much less sensitive to the transition
from the glassy to the terminal zone since the characteristic
slopes of each zone in the log-log plot are closer than in the
Macromol. Theory Simul. 2004, 13, 748753

www.mts-journal.de

case of G0 . Therefore, in the whole frequency region, values

for different chain lengths practically superimpose.
Let us compare the relative behavior of G0 and G00 for a
given chain length (i.e., black and empty symbols of a given
type). As appreciated G00 > G0 for the whole frequency
range and all chain lengths. It means that the liquid-like
(viscous) behavior predominates over the elastic behavior
for the chain model simulated and, as expected for polymers
of low molecular weight, there is no intermediate rubbery
region and therefore no crossover between the G0 and G00
curves. However, in increasing the chain length, the behavior seems to tend progressively to that of entangled polymer melts. Thus, it can be appreciated that for the chains
with N 70 (triangles), curves of G0 and G00 tend to
converge at the small frequency corresponding to the
crossover between a hypothetical rubbery region and the
glassy one. It also indicates that, at the frequencies employed, these melts are fully in the glassy zone. On the other
hand, for the shortest chains, N 5 (circles), the work
frequency region is in transition between the terminal zone
and the glassy zone. In this case, the expected Rouse
behavior in the terminal zone, i.e., G0 / o2 and G00 / o
tends to hold, as is better visible in Figure 3. It is interesting
to observe how the dynamic moduli in the frequency range
0.01 < o < 10 (cf. plots showing results for N 5) are
similar to those reported for dilute polymer solutions.[11,29]
Thus, not only in the terminal zone (obtained for N 5)
slopes of G00 and G0 tend to be 1 and 2, respectively, but in
the transition to the glassy region their curves tend to reach
slopes about 2/3 (lower frequencies) and 1/2 (higher
frequencies) similar to the theoretical values predicted for
dilute polymer solutions.[11] This finding is established
through the G00 curve (N 20), which is fully in the transition to the glassy region. Accordingly, we confirm[12] that
the Rouse behavior of dilute solutions is applicable, with
slight modifications, to melts of low molecular weight. This
is not surprising since for the amplitude and frequencies
studied, chains are merely non-stretched and a Hookean

Figure 3. Application of the time-temperature superposition

rule for a melt of linear FENE chains with N 5.
2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

752

J. G. H. Cifre, S. Hess, M. Kroger

bond potential rather than a FENE potential should yield

similar results. Because hydrodynamic interaction is not
relevant for polymer melts, Rouse rather than Zimm model
is expected to be more suitable in describing the investigated system.
An informative picture is obtained by plotting the dynamic viscosity versus the oscillatory frequency in a log-log
plot, cf. Figure 4. Only for the melt with N 5, the Newtonian plateau is fully reached and the zero-shear viscosity,
Z0, can be extracted. The onset of shear thinning occurs at a
frequency (inverse of the small relaxation time) inside
the range explored. Viscosity values of melts formed by the
longer polymer chains (N > 20) fall inside the shear thinning region. In Figure 4, we observe the validity of the
empirical Cox-Merz rule jZ*(o)j Z(o). Notice how the
dashed line in Figure 4 (corresponding to values of the shear
viscosity obtained via NEMD with N 20 subjected to a
simple shear flow) superimposes with the empty circles
(oscillatory flow). As appreciated in the steady simple shear
experiment, we can get values in the Newtonian plateau
because these simulations are less time consuming. All
curves superimpose in the shear thinning region with a slope
of 
0.55, in overall agreement with experimental findings.[11] By subjecting samples with N 2, 5, 10, and 20 to
simple shear flow, we obtained the dependence of Z0 on
the chain length (i.e., molecular weight). As observed in
Figure 5, the slope in the log-log plot of Z0 versus N, i.e., the
exponent of the power law Z0 / Na, is a 0.91  0.02
close to the value 1 expected for Rouse-like behavior of the
polymer chain. That scaling relationship and the Z0 values
obtained agree well with previous results for short chains
using the same methodology.[6] If chains were longer, reptation behavior sets in and the power law exponent increases
to about three (experimentally the value 3.4 is found).[1]
The representation in the complex plane of Z00 versus Z0
(Cole-Cole plot) gives a circular arc for a simple Maxwell

Figure 4. Both (absolute) dynamic viscosity jZ*j and steadyshear viscosity, Z, versus frequency, o, and shear rate, g_ ,
respectively (both in reduced Lennard-Jones (LJ) units). CoxMerz rule verified.
Macromol. Theory Simul. 2004, 13, 748753

www.mts-journal.de

Figure 5. Effect of chain length on the Newtonian shear

viscosity of polymer melts with chain length N 2, 5, 10, and
20 in the unentangled regime. Data obtained from steady shear
flow NEMD simulations.

fluid. From this plot, Z0 is extracted as the intercept of the

circular arc with the Z0 axis. Figure 6 presents such a representation for melts with chains of N 5 and N 20. For
N 5, for which some values in the Newtonian regime are
available, the interception is observed, giving Z0  4.5.
However, for N 20, we are still in the uprise of the curve
(non-Newtonian part in the flow curve, Figure 4). Another
parameter that can be extracted from the Cole-Cole plot is a
characteristic relaxation time of the melt, t0, corresponding
to omax, where the function Z00 approaches its maximum:
t0 1/omax. From Figure 5 we can get that relaxation time
for the melt of chains with N 5 and t0 7. This value
compares well with the one obtained for the Rouse relaxation time of a FENE melt in ref.[1] It is worth mentioning
that the shape of graphs in the Cole-Cole and related
representations, e.g., so-called Van Gurp-Palmen plot,
have been used to classify polymeric fluids by their
architecture (linear, branched, star etc.).[30]
Similarly to experiments, the frequency range available
for simulation is limited. This is because simulations at very
small frequencies are prohibitively time consuming and at

Figure 6. Cole-Cole plots of melts of linear FENE chains of

lengths N 5 and N 20.
2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

753

Linear Viscoelastic Behavior of Unentangled Polymer Melts via Non-Equilibrium Molecular Dynamics

high frequencies become unstable, both resulting in large

inaccuracy. Therefore, analogously to experiments, we decided to perform simulations at temperatures lower and
higher than the reference one (T 1) and make use of the
time-temperature superposition rule exposed in the theoretical section to extend slightly the range of frequencies
embraced. Figure 3 shows the resulting master plot obtained
for the melt with N 5 at different temperatures after the
shift to the reference temperature T 1. Black and empty
symbols correspond to G0 and G00 values, respectively, and
different symbol types were used to distinguish values of a
given modulus obtained originally at different temperatures. Simulation parameters were considered independent
of the temperature provided that the temperature range used
was very small. Care was also taken to keep the system at
approximately the same pressure in varying the temperature. Thus, by shifting the corresponding curves along the
coordinate axis (as outlined in the previous section) we got
the plot in Figure 3. In that plot, the shift factor, aT, was
determined in order to get a nice superposition of the
curves obtained at different temperatures. Extension of the
curve at higher frequencies by lowering the work temperature gave better results than extension at lower frequencies. In the terminal zone, Z0 can be obtained from the slope
of the G00 curve since G00 Z0o. In this case, in agreement
with the result obtain from the Cole-Cole plot (Figure 6) and
from the extrapolation in the Newtonian regime in Figure 4,
Z0  4.5.

Conclusion
Small strain oscillatory rheometry is widely used to characterize the mechanical behavior of viscoelastic systems.
Nevertheless, computational studies devoted to reproduce
this experimental setup are scarce. We have shown the
adequacy of NEMD of a coarse-grained polymer (FENE)
model to simulate oscillatory flow in spite of its limitations
in sweeping a broad frequency range due to the enormous
CPU time required to get results in the terminal zone. In
order to extend the frequency range, we make use of the
time-temperature superposition rule, widely used in experimental works. In simulations, care must be taken if applying
that empirical rule, because variations of the work temperature entail changes in the temperature-dependent model
parameters (for instance, the spring coefficient) and in the
thermodynamic properties of the system (pressure, volume,
density). We think that as long as temperature keeps closed
to T0, these changes play a negligible role in simulation
results.
Results obtained for chain lengths under the critical
entanglement length give rise to results which, at least
qualitatively, agree with experimental findings for melts of
low molecular weight.[12] Furthermore, we were able to
check the validity of the empirical Cox-Merz rule. Apart
from CPU time requirements, NEMD has, in principle, no
Macromol. Theory Simul. 2004, 13, 748753

www.mts-journal.de

limitations to simulate and thus study and understand the

dynamics and conformational evolution of melts formed by
polymer chains of arbitrary topology, such as branched
polymers.[31] Therefore, beside studying longer chains, the
next step is to investigate melts composed of chains with
different topology as well as polydisperse melts with the
methodology outlined here.

Acknowledgements: J. G. H. C. is the recipient of a postdoctoral

fellowship from the Spanish Ministerio de Educacion Cultura y
Deportes. This work has been performed under the auspices of the
Sfb 448 Mesoskopisch strukturierte Verbundsysteme, Deutsche
Forschungsgemeinschaft (DFG).

[1] K. Kremer, G. S. Grest, J. Chem. Phys. 1990, 92, 5057.

[2] M. Putz, K. Kremer, G. S. Grest, Europhys. Lett. 2000, 49,
735.
[3] P. E. Rouse, J. Chem. Phys. 1953, 21, 1272.
[4] P. G. de Gennes, J. Chem. Phys. 1971, 55, 572.
[5] M. Kroger, W. Loose, S. Hess, J. Rheol. 1993, 37, 1057.
[6] M. Kroger, S. Hess, Phys. Rev. Lett. 2000, 85, 1128.
[7] P. J. Daivis, M. L. Matin, B. D. Todd, J. Non-Newtonian
Fluid Mech. 2003, 111, 1.
[8] M. Kroger, C. Luap, R. Muller, Macromolecules 1997, 30,
526.
[9] J. Gao, J. H. Weiner, Macromolecules 1992, 25, 1348.
[10] M. Kroger, Phys. Rep. 2004, 390, 453.
[11] J. D. Ferry, Viscoelastic Properties of Polymers, 3rd
edition, Wiley, New York 1980.
[12] J.-C. Majeste, J.-P. Montfort, A. Allal, G. Marin, Rheol. Acta.
1998, 37, 486.
[13] P. J. Daivis, B. D. Todd, Int. J. Thermophys. 1998, 19, 1063.
[14] B. D. Todd, P. J. Daivis, J. Chem. Phys. 1997, 107, 1617.
[15] G. Rickayzen, J. G. Powles, D. M. Heyes, J. Chem. Phys.
2003, 118, 11048.
[16] J. Petravic, D. J. Evans, Phys. Rev. Lett. 1997, 78, 1199.
[17] G. Ciccotti, G. Jacucci, I. R. McDonald, J. Stat. Phys. 1979,
21, 1.
[18] G. P. Morriss, D. J. Evans, Phys. Rev. A 1987, 35, 792.
[19] S. Hess, D. J. Evans, Phys. Rev. E 2001, 64, 11207.
[20] S. Hess, M. Kroger, D. J. Evans, Phys. Rev. E 2003, 67,
42201.
[21] C. P. Calderon, W. T. Ashurst, Phys. Rev. E 2002, 66, 13201.
ttinger, J. Non-Newtonian Fluid Mech.
[22] M. Kroger, H. C. O
2004, 120, 175.
[23] H. J. C. Berendsen, J. P. M. Postma, W. F. van Gunsteren,
A. DiNola, J. R. Haak, J. Chem. Phys. 1984, 81, 3684.
[24] M. P. Allen, D. J. Tildsley, Computer Simulation of
Liquids, 1st edition, Clarendon Press, Oxford 1987.
[25] W. G. Hoover, Phys. Rev. A 1985, 31, 1695.
[26] S. Nose, J. Chem. Phys. 1984, 81, 511.
[27] R. G. Larson, The Structure and Rheology of Complex
Fluids, Oxford University Press, New York 1999, p. 126.
[28] M. Kroger, Comput. Phys. Commun. 1995, 90, 381.
[29] C. Tiu, K. C. Tam, J. Non-Newtonian Fluid Mech. 1989, 33,
165.
[30] S. Trinkle, P. Walter, C. Friedrich, Rheol. Acta 2002, 41, 103.
[31] P. J. Daivis, D. J. Evans, G. P. Morriss, J. Chem. Phys. 1992,
97, 616.
2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim