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P-Analysis of Uncertainties in Polymer Viscoelastic Properties
P-Analysis of Uncertainties in Polymer Viscoelastic Properties
We critically evaluate the uncertainties in the stress autocorrelation function obtained from
equilibrium molecular dynamics simulation of model polymer melts. This quantity is central to
evaluating transport properties, e.g., the complex modulus and the viscosity. In contrast to the
intuitive expectation that simulations have to be run five to six orders of magnitude longer than the
chain relaxation time to reduce uncertainties to acceptable levels, our analysis shows that the
majority of the uncertainty is associated with rapidly oscillating bonded interactions. These
fluctuations occur on time scales which are approximately 104 times shorter than the relaxation time
of a chain of length 80. Consequently, the effects of these oscillations on the stress autocorrelation
function can be dramatically reduced by 共i兲 conducting long simulations 共typically 106 times longer
than the bond relaxation times or only 102 chain relaxation times兲 and 共ii兲 by performing running
averages with time windows whose time scales are much longer than these oscillations. Conducting
such long simulations also allows for the accurate determination of the melt viscosity and the
low-frequency complex modulus, but performing running averages do not impact these quantities
since they are time integrals of the stress autocorrelation function. © 2006 American Institute of
Physics. 关DOI: 10.1063/1.2186637兴
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144909-2 Sen, Kumar, and Keblinski J. Chem. Phys. 124, 144909 共2006兲
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144909-3 Analysis of uncertainties in polymer viscoelastic properties J. Chem. Phys. 124, 144909 共2006兲
Downloaded 03 May 2006 to 165.123.34.86. Redistribution subject to AIP license or copyright, see http://jcp.aip.org/jcp/copyright.jsp
144909-4 Sen, Kumar, and Keblinski J. Chem. Phys. 124, 144909 共2006兲
FIG. 4. Short time scale behavior of the error autocorrelation function ex-
FIG. 5. Viscosity integrals of the stress autocorrelation function showing
hibiting oscillatory decay similarly as the stress autocorrelation function
that both “raw” data and running averages of the stress autocorrelation func-
shown in Fig. 1共a兲.
tion 关see Fig. 1共b兲兴 yield the same results upon integration.
DISCUSSION
used fixed length bonds, the relevant quantity on the right
Our analysis of the uncertainty in the stress autocorrela- side of Eq. 共2兲 would be much smaller, 冑R具共R兲共0兲典. The
tion function calculated for the bead-spring polymer melt uncertainty in the stress autocorrelation function would thus
demonstrates that it is dominated by the stress associated be even smaller in these cases, emphasizing again that equi-
with high-frequency bond oscillations. To further understand librium MD simulations can yield reliable estimates of trans-
these issues we show the uncertainty autocorrelation function port properties in these cases.
in Fig. 4. This function is characterized by short time decay- Finally, we note another important point that integrated
ing oscillations, with the oscillation period being the same as quantities such as the viscosity and the complex modulus
the one characterizing the stress autocorrelation function 关see 共for frequencies much smaller than the bond fluctuation兲 are
Fig. 1共a兲兴. The relaxation time constant estimated from the not affected by running average procedures. For example, the
data in Fig. 4 is about 0.15t*. If we take this short time, viscosity is obtained via Eq. 共1兲. To illustrate the uncertainty
rather than the polymer relaxation time, as c, our estimate propagation in this quantity we plot the viscosity integrals
for the uncertainty following Eq. 共2兲 becomes 共Fig. 5兲,
␦共具共t*兲共0兲典兲 = 冑 2 ⫻ 0.15 2
200 000
具 典 ⬇ 0.08, 共4兲 共t兲 =
V
k BT
冕
0
t
具共t⬘兲共0兲典dt⬘ , 共5兲
0
具共t⬘兲共0兲典errordt⬘ . 共6兲
the bond fluctuations then determine the ultimate uncertainty
in the transport properties determined from an equilibrium The second term in Eq. 共6兲 can be considered as an integral
simulation. An alternative means of understanding the suc- over a random walk. By analogy to molecular diffusion, the
cess of equilibrium calculations in estimating the stress au- diffusion constant of the random walker can be evaluated as
tocorrelation function is that Vladkov and Barrat incorrectly D = 兰⬁0 具V共t兲V共0兲典dt, where V共t兲 is the “velocity” of the stress
suggest that the run time independent part of Eq. 共2兲 is pro- autocorrelation function error defined as V共t兲 = 共V / kBT兲
portional to 冑R具共0兲2典: rather they should have employed ⫻关d共具共t兲共0兲典error兲 / dt兴. Figures 6共a兲 and 6共b兲 show running
冑bond具共0兲2典. In the absence of bond fluctuations, e.g., if one integrals corresponding to the D values. We calculated two
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144909-5 Analysis of uncertainties in polymer viscoelastic properties J. Chem. Phys. 124, 144909 共2006兲
Downloaded 03 May 2006 to 165.123.34.86. Redistribution subject to AIP license or copyright, see http://jcp.aip.org/jcp/copyright.jsp
144909-6 Sen, Kumar, and Keblinski J. Chem. Phys. 124, 144909 共2006兲
1
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