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The Green-Kubo method is a commonly used approach for predicting transport properties in a system from equilibrium molecular dynamics simulations. The approach is founded on the fluctuation dissipation theorem and relates the property of interest to the lifetime of fluctuations in its thermodynamic driving potential. For heat transport, the lattice thermal conductivity is related to the integral of the autocorrelation of the instantaneous heat flux. A principal source of error in these calculations is that the autocorrelation function requires a long averaging time to reduce remnant noise. Integrating the noise in the tail of the autocorrelation function becomes conflated with physically important slow relaxation processes. In this paper we present a method to quantify the uncertainty on transport properties computed using the Green-Kubo formulation based on recognizing that the integrated noise is a random walk, with a growing envelope of uncertainty. By characterizing the noise we can choose integration conditions to best trade off systematic truncation error with unbiased integration noise, to minimize uncertainty for a given allocation of computational resources.
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PHYSICAL REVIEW E 95, 023308 (2017)
Method to manage integration error in the Green-Kubo method
Laura de Sousa Oliveira*and P. Alex Greaney
Mechanical Engineering Department, University of California, Riverside, California, USA
(Received 25 September 2016; revised manuscript received 20 December 2016; published 21 February 2017)
The Green-Kubo method is a commonly used approach for predicting transport properties in a system from
equilibrium molecular dynamics simulations. The approach is founded on the fluctuation dissipation theorem
and relates the property of interest to the lifetime of fluctuations in its thermodynamic driving potential. For heat
transport, the lattice thermal conductivity is related to the integral of the autocorrelation of the instantaneous
heat flux. A principal source of error in these calculations is that the autocorrelation function requires a long
averaging time to reduce remnant noise. Integrating the noise in the tail of the autocorrelation function becomes
conflated with physically important slow relaxation processes. In this paper we present a method to quantify the
uncertainty on transport properties computed using the Green-Kubo formulation based on recognizing that the
integrated noise is a random walk, with a growing envelope of uncertainty. By characterizing the noise we can
choose integration conditions to best trade off systematic truncation error with unbiased integration noise, to
minimize uncertainty for a given allocation of computational resources.
DOI: 10.1103/PhysRevE.95.023308
Transport properties are ubiquitous in materials science and
engineering. Heat sinks and thermal barrier coatings are two
obvious examples where thermal conductivity is paramount for
materials’ performance, but there are also a huge number of
materials applications in which transport properties are folded
in with a number of other properties to dictate performance.
Nanofluids are a promising new material for numerous
applications [13] that include heat dissipation [2,3] for which,
in addition to thermal transport, viscosity calculations are nec-
essary to better our understanding of heat transfer mechanisms.
Moreover, the rheological characterization of fluid materials
has numerous engineering applications beyond cooling (e.g.,
lubrication [4], sheathing [5], or hydraulics [6]), as well as
applications in other fields (e.g., medicine [7], geophysics [8]).
Viscous ionic electrolytes in batteries are an example where
viscosity, diffusion, and ionic conductivity [9] all play an
important role in the materials’ eventual performance. In short,
the ability to reliably predict transport properties is essential in
the search for new materials for a wide variety of applications.
Molecular dynamics (MD) simulations provide a powerful
approach for quickly obtaining atomistic level insight into the
physics of mass, momentum, or energy transport processes in
materials. Two approaches are possible: MD can be used to
(1) simulate systems in equilibrium or (2) perturb and drive
systems out of equilibrium to then measure their response.
Equilibrium molecular dynamics (EMD) calculations are
performed using the well-established Green-Kubo formal-
ism [10,11], which relates transport quantities to the duration
of fluctuations in a microscopic state of the system—the
underlying principle is that the processes that dissipate small
local fluctuations are the same that are responsible for a
material’s feedback to a stimulus. Mathematically this is
achieved by integrating the current autocorrelation function, as
*Also at the Mechanical Engineering Department, University of
California, Riverside, CA, USA.
is shown in the general expression for the Green-Kubo method:
0A(t)A(t+τ)dτ, (1)
where γis the transport property of interest and Ais the
current that drives it. The expression A(t)A(t+τ)is the
autocorrelation function of quantity Aand αis a temperature-
dependent coefficient. For instance, for thermal conductivity,
κ, the Green-Kubo expression becomes
0J(t)J(t+τ)dτ, (2)
where kBis Boltzmann’s constant, Tis the temperature,
Vis the volume of the simulated region, Jis the heat
flux, and J(t)J(t+τ)is the non-normalized heat current
autocorrelation function (HCACF). This method is widely
used by materials scientists, chemists, and physicists. In
addition to thermal conductivity calculations [1215], it has
been used to calculate viscosity [4,8,16], diffusivity [17,18],
and ionic conductivity [9] for a wide range of materials,
by integrating the pressure tensor, velocity, and ionic flux
autocorrelation functions (ACFs), in that order.
There are clear advantages to using an equilibrium ap-
proach: while both equilibrium and nonequilibrium methods
suffer from size artifacts, the use of periodic boundary
conditions in EMD allows for a smaller system size; for
anisotropic systems, one EMD simulation suffices to compute
the full transport tensor; and EMD can be used irregardless
of the linearity of the transport regime with system size.
There is, however, also one major pitfall. Fully converging
the autocorrelation function requires very long simulation
times and often a compromise has to be made between
including the contribution of slow processes and introducing a
random error, or excluding these processes and introducing a
systematic truncation error. In this paper, by recognizing that
the integrated ACF error mimics a random walk, we propose a
method that allows researchers to evaluate this trade-off on the
fly and make better informed decisions about where to truncate
the ACF and how to optimize computational resources. In the
remainder of the paper, we will focus exclusively on thermal
2470-0045/2017/95(2)/023308(11) 023308-1 ©2017 American Physical Society
transport. It is left for the reader to draw the obvious parallels
with other transport properties. The next paragraphs concern
the origin of the oscillations, existing approaches to integrate
the autocorrelation function, and the introduction of the
concept of a random walk in the HCACF. Our proposed method
and its implementation to an example data set are described
next, followed by the discussion and conclusion remarks.
A. The oscillatory behavior of the autocorrelation function
The HCACF, J(t)J(t+τ), can be numerically
computed as
where Jnis the value of Jat the nth time step, i.e., Jn=J(tn),
for n=0,1,2,...,N, and Jn+mis Jat the (n+m)th time
step, or J(tn+τm), for m=0,1,2,...,M.Nand Mare,
respectively, the maximum numbers of steps in the simulation
and in the HCACF. Analytically, the autocorrelation function
is computed as the inverse Fourier transform of the same
transform of the current multiplied by its complex conjugate,
averaged over Nm. It follows that to obtain good statistical
averaging Mmust be significantly less than N, and that the
error associated with the HCACF increases over time for fixed
N. This is applicable to other transport properties. For a system
in equilibrium, the average current of any property is zero, and
the ACF is expected to decay to zero given sufficient time.
Instead, large oscillations with a significant contribution to the
integral have been observed [15,1922]. Figure 1(a) depicts
an example of fluctuating HCACFs and the growing error in
the corresponding integrals, and Fig. 1(b) shows the longevity
of the fluctuations.
If we were able to sample an infinite system for infinite
time, we should find the system’s true ACF and thus a fixed
true transport quantity. It follows that, for the thermal transport
example we have been using, κ, computed with Eq. (2), is
κ=κtrue ±κ
η(τ)dτ, (4)
where τmax is the maximum time for which the HCACF is
computed, and α=V
3kBT2. The first term in the equation is the
true integrated HCACF, and the second term is the integral
of the HCACF noise that comes about due to insufficient
averaging. As shall be discussed more thoroughly in due
course, at least two sets of different frequency oscillations
can be distinguished that mirror the fast and slow fluctuations
in the heat current.
Accurately predicting the ACF is critical for transport
predictions using the Green-Kubo method. Notwithstanding,
there is little consensus in the literature as to what approach
to take to mitigate the noise, and the cumulative quality of the
integrated noise has seldom been used to inform the choice
of ACF integration approach. The next paragraphs reference
some of the most common ACF integration approaches and a
few less common strategies found in the literature. While it has
been shown that the Green-Kubo approach can be successfully
used with quantum-based calculations [23,24], simulation size
FIG. 1. Panel (a) shows the HCACFs (the decaying functions)
plotted along side their integrals (the curves that rise to a plateau)
computed from nine separate simulations of a 10 648-atom, perfectly
crystalline, and periodically contiguous block of graphite. The data
were taken from a study to determine the influence of Wigner defects
on thermal transport in graphite [22]. The dashed lines correspond to
the heat flux along the [2¯
10] direction and the solid lines correspond
to the heat flux along [01¯
10]. The system was found to be converged
for size, and κis expected to be the same in both directions along the
basal plane. This plot illustrates the increasingly diverging noise of
the HCACF integrals, present even after 50 ps. To the eye, the ACFs
look nicely converged after 10–15 ps. Plot (b) shows the gradual
convergence of the HCACF with increasing averaging time during a
single simulation. The amplitude of the fluctuations in the tail of the
HCACF decays over time, but it is notable that continued averaging
does not remove the pattern of the fluctuations.
and length present a major difficulty in using EMD approaches
within ab initio, and other methods [25,26] continue to offer
greater advantages. However, as computers become faster,
density functional theory (DFT) MD transport calculations
could become more common, and error estimation more
important. Within classical MD, the evolution of computing
means averaging large enough systems for longer will become
less of an issue, thus reducing or even eliminating the error
from these calculations. However, there is an increasing
trend to develop high-throughput approaches for the rapid
screening of materials, which in turn require quick, on-the-fly
approaches for uncertainty quantification. The method
introduced herein meets these requirements.
B. Common autocorrelation function integration approaches
A common strategy to reduce the noise in the ACF is to fit
an exponential to the first few picoseconds (τ<10) [20,21].
The system depicted in Fig. 1exhibits a rapid decay associated
with high-frequency phonons and a slower decay associated
with lower frequency phonons; similar two- or three-stage
decay is observed in many single-element materials and
different authors have modeled κby fitting the HCACF to the
sum of two or more exponentials [20,21,27]. This approach
captures multiple relaxation processes and is therefore more
physically meaningful than a single exponential fit, but it is
ineffective when the HCACF cannot be represented by an
exponential fit [12,22,28] and it forces a behavior description
of the HCACF that might not be accurate. The same is
true of shear relaxation times in viscosity calculations. For
ionic liquid calculations, authors have also fit the pressure
tensor autocorrelation function to Kohlrausch’s law [29,30]
and/or applied weighing factors to their fits [31,32]. Fits to
the frequency domain are also a solution, depending on the
resulting ACF for given data [12,28]. Some strategies include
direct integration of the ACF truncated to various cutoffs.
Whether direct integration is performed or a fit is applied,
the cutoffs are oftentimes arbitrarily selected [3335]. They
can also be more systematically determined, for instance by
taking the running mean of the integrated autocorrelation
at its plateauing region [36,37]. Recently, Chen et al. have
proposed a noise-sensitive mathematical approach: to truncate
the HCACF when the scale of the fluctuations becomes the
same as the mean, i.e., when |σ
E|>1, where σis the standard
deviation and Eis the expected value of the HCACF in an
interval (τ,τ+δτ)[38]. Chen et al. further suggest including
afixedoffsetterm,Y0, to the exponential fitting approach
(e.g., A1eτ/t1+A2eτ/t2+Y0) to the normalized HCACF. In
a study concerning thermal transport in irradiated graphite,
we implemented and compared this and other methods [22].
The method of Chen et al. is a useful, systematic approach,
but it neglects the growing nature of the uncertainty that
results from integrating over the noise. Other approaches that
acknowledge the incremental error of the HCACF integral have
been proposed [31,39]. For instance, Zhang et al. [31]usea
time-decomposition method to compute a growing standard
deviation to which they suggest fitting a power law, and from
which a cutoff can be selected based on a desired percentage er-
ror. With the insight gained from the graphitic systems studied,
we develop here another approach to quantify and mitigate the
noise introduced with the Green-Kubo. This approach is based
on recognizing that the ACF fluctuations around zero integrate
into Brownian noise; i.e., for each simulation a random walk
is effectively added to the integral of the true ACF. Before
proceeding, it is perhaps useful to briefly introduce the notion
of a random walk and how it relates to the noise in the HCACF.
C. Random walk
A random walk is a succession of Markovian (uncorrelated)
random steps. This has the property that the expected root
mean square (rms) displacement after Nsteps is xN=
σdN, where σdis the standard deviation of the magnitude
of the steps (i.e., the displacement). Here we argue that
the noise in the HCACF has the statistical properties of a
stream of uncorrelated fluctuations or excursions from zero.
Although these fluctuations have a characteristic duration,
the time integral of a fluctuation equates to one jump in a
random walk. If one determines the time scale over which the
HCACF noise is uncorrelated (the jump frequency δt) and the
typical integrated excursion (jump magnitude, d) then one can
equate the accumulation of noise integration error to the rms
displacement of the equivalent random walk. The equivalence
of the HCACF to a stream of uncorrelated fluctuations that
when integrated yield a random walk is demonstrated in
Figs. 2(a)2(c). In these simulations, the average step size
is σvδt, where σvis the standard deviation of the noise velocity
(d/δt), i.e., the velocity at which the random walk occurs
through time. The standard deviation of the velocity (σv)is
effectively that of the steps. The total number of Markovian
steps over time tis N=t/δt, and so the expected uncertainty
U(t) after integrating to time tis given by
δt =σvtδt. (5)
In this relationship computing σvis straightforward, and so
the remaining challenge is to determine the uncorrelated
fluctuation time δt.
By characterizing the integrated HCACF noise as a random
walk, or as a sum of random walks, in terms of δt and σv,
we propose that one can use Eq. (5) to compute an uncertainty
envelope that informs on how quickly the integrated noise error
in a single simulation grows. From the uncertainty envelope of
asingle simulation one can compute the expected uncertainty
in the average of any number of simulations. The crucial point
is that information about the distribution of error in many
simulations can be obtained from a first, short (a few hundred
picoseconds) simulation, and thus after the first simulation has
been performed, one can decide on an optimal computational
strategy for minimizing uncertainty.
Upon quick inspection, the HCACFs shown in Fig. 1appear
to be converged by 20 ps. Figure 2(e) shows the result of
integrating random fluctuations in the 20–50 ps interval of the
HCACF tail. To parallel Figs. 2(a) and 2(b), which depict an
example of fluctuations [in Fig. 2(a)] that give rise to a random
walk [in Fig. 2(b)], a single HCACF tail is depicted in Fig. 2(d),
but the integrals of 18 HCACFs’ tails are plotted in Fig. 2(e).
The noise in this data [Fig. 2(b)]isnot uncorrelated from point
to point along the data stream but instead has some memory
of itself. To predict the uncertainty from this noise we must
compute the lifetime for this memory to find the time scale at
which the noise becomes uncorrelated. Instead of a jump (or
walk) at every interval in the autocorrelation, jumps are better
described by (some of) its peaks [see the line in magenta in
Fig. 2(d)]. The distribution in Fig. 2(f) corresponds to the
compound HCACF tails for the 18 simulations. Figure 2(g)
was obtained from the peaks as exemplified in Fig. 2(d).A
normal distribution with the standard deviation for each case
and mean zero is shown in red, and the distributions with the
correct mean are in black and magenta for the whole set of tails
FIG. 2. Panel (a) corresponds to the step or velocity fluctuations that give rise to a random walk; in panel (b) a set of 10 random walks is
shown in black and the expected root mean square translation distance at time tis plotted in red; and panel (c) is the distribution of the random
walks shown in panel (b). Panel (d) corresponds to the tail of a HCACF, depicting the noise fluctuations that integrate to a large error akin to a
random walk, shown in panel (e) for all HCACF tails. The black lines correspond to heat-flux measurements along the xdirection ([2¯
10]), and
the blue ones are along the ydirection ([01¯
10]). Both values were measured along the basal plane, and this distinction should not matter. The
data set is explained in the Methods section. For the selected 20–50 ps interval, the distribution of all data points across the multiple simulation
tails is shown in panel (f). A 1-ps moving average was used along with a peak find algorithm to plot major peaks in the HCACF tails, as shown
in panel (d), in magenta. The peak distribution for all data is offered in panel (g). The dashed red lines in panels (f) and (g) correspond to a
normal distribution with the standard deviation of each of the distributions and mean zero. A normal distribution with the mean for each of the
data sets is shown in the solid lines for each case.
and peaks, respectively, in Figs. 2(f) and 2(g). The distributions
will again be addressed in the Results section.
The method developed to quantify the uncertainty that
results from the Green-Kubo approach by treating the noise in
the autocorrelation function as a random walk is introduced in
the Methods section, but not before a more detailed explanation
of the data set used for Figs. 1and 2is offered.
All simulations used to perform error analysis were ob-
tained with the large-scale equilibrium classical molecular dy-
namics software LAMMPS [40], using the adaptive intermolecu-
lar reactive empirical bond-order (AIREBO) potential function
formulated by Stuart et al. [41]. The simulations correspond to
a size-converged 11 ×11 ×11 perfectly crystalline graphite
supercell with 10 648 atoms and a 27.05 ×46.86 ×73.79 ˚
volume in the x,y, and zdirections, respectively. Previous
work has shown that this system is large enough to be size
converged for thermal conductivity [22]. We use data from
nine simulations that were relaxed and equilibrated in the
microcanonical ensemble (NVE), using a standard Velocity-
Verlet quadrature scheme, for 50 ps after being given a thermal
energy equivalent to 300 K before starting to record the
HCACF. Each of the nine runs was simulated for an additional
0.6nswitha0.2-fs time step and periodic boundary conditions.
Because κcan be computed in all lattice directions from a
single simulation using the Green-Kubo formalism, there are
18 HCACFs along the basal plane of the graphite supercell
with which to perform data analysis (nine each along xand
y, that is, [2¯
10] and [01¯
10]). These data were obtained for a
previous publication on the thermal conductivity of irradiated
FIG. 3. The noise of a HCACF tail in the 30–50 ps interval is shown (a) decomposed into high-frequency (blue) and low-frequency (red)
noise. The autocorrelations of the noise (black) and the high-frequency (blue) and low-frequency (red) components of the noise are shown in
panel (b), along with fits through the high-frequency (cyan) and the low-frequency (magenta) autocorrelations. In panel (c) the integrated tail
appears in black and the uncertainty envelope for δt equal to the interval of the HCACFs is shown in dashed red; the uncertainty envelopes
corresponding to the high-frequency and low-frequency noise are in cyan and magenta, respectively. The dashed black line that follows along
the magenta is the combined uncertainty envelope of the high- and low-frequency noises, i.e., the square root of the sum of their squares.
graphite [22]. A longer 8.0-ns simulation with a 0.4-fs time
step was also performed, under the same conditions. Based on
the premise that the noise of the integrated HCACF is akin to
a random walk, we can use Eq. (5) to compute the root mean
squared of the noise integrated up to time τmax.Thisisthe
expected deviation (or error) from the mean for each random
walk, and we can thus compute the standard deviation of said
error at time τmax in an average of Nrandom walks, with the
same characteristic δt and σv,asSN=σvτmaxδt
Decomposing the noise into uncorrelated fluctuations is
the first step required to discern between a single random
walk or the sum of varying frequency random walks. Then,
to characterize the random walks, one must determine the
standard deviation of these fluctuations and the average
interval between them. If the random fluctuations occurred
at the same interval that the HCACF is recorded, the expected
noise uncertainty envelope would be as indicated in Fig. 3(c),in
the dashed red line. This largely underestimates the integrated
noise. A moving average low-pass filter with a 0.4-ps window
applied to the noise reveals that at least two distinct sets of
noise frequencies are present [see Fig. 3(a)]. This indicates
that instead of a single random walk with the same time step
as that of the HCACF, the noise is best described by the sum
of different frequency random walks. Finding the contribution
of each random walk to the expected error can be difficult, but
a series of frequency passes (see Fig. 4) can help examine the
contribution of varying frequencies in the noise to the expected
error. The subsequent analysis is performed with the separate
sets of noise identified as having the largest contribution to
the expected error and shown in Fig. 3(a). While the noise
behaves similarly to a random walk, the system has a memory
of itself and the fluctuations should be correlated with each
other. The correlation time obtained from the autocorrelation
function of the noise gives the average time interval, δt,at
which the fluctuations are Markovian. This method is applied
to a single simulation as detailed in the following steps, with
the aid of Fig. 3:
(i) The first step is to isolate the noise from the data. This
is easily done by selecting a portion of the tail; if it is clear the
HCACF is converged after some time. Otherwise, a fit could
be used to extract the noise. Using the tail of the HCACF
to analyze the noise is generally preferable to using a fit,
as it removes the uncertainty that arises from guessing the
behavior of the HCACF. The choice of interval (30–50 ps) to
characterize the noise is explained in the Results section.
(ii) The second step is to filter the noise for different
frequencies. This step is exemplified in Fig. 3(a). A low-pass
filter allows us to distinguish two main sets of oscillations, in
red and in blue. While only one pass, separating frequencies
below and above 2.5 THz, is illustrated in Fig. 3(a),more
could be applied (see Fig. 4) to gain a better understanding
of the noise. This is discussed more thoroughly in the Results
section. The contribution of each set of data is considered as
described next.
(iii) The third step consists in computing the autocorrela-
tion of the different frequency noise components. For the low-
and high-frequency noise found in step (ii) and depicted in
FIG. 4. This graph shows the application of multiple pass filters
to isolate existing frequencies in the HCACF noise. The first filter
applied selects out data below a 0.04-ps interval (the blue high-
frequency line at the bottom of the graph) and leaves the remaining
frequencies. The next filter has a 0.08-ps window and is used to filter
the low-frequency data remnant from the first pass. This procedure is
performed for 0.04-ps intervals up to a filter with a 0.56-ps window.
Fig. 3(a), the ACFs are shown in red and blue, respectively, in
Fig. 3(b).
(iv) The fourth step is to fit a single exponential aiet
to each of the above autocorrelations. The fits are shown in
magenta and cyan, for the low- and high-frequency cases, in
that order. The fitting parameter τprovides an estimate of the
interval of our near-random walk noise. The autocorrelation
of the low-frequency noise (in red) is comparable to that
of the whole system (in black). It is already clear that the
contribution of the low-frequency HCACF noise explains most
of the random walk uncertainty.
(v) The fifth step is to compute the standard deviation, σ,
of each of the noise contributions.
(vi) The sixth and final step is to compute the uncertainty
envelope by using the calculated τand σin Eq. (5). In
Fig. 3(c), the magenta uncertainty envelope corresponds to the
low-frequency oscillations, and the cyan envelope corresponds
to the contribution of the high-frequency noise. As anticipated,
the high-frequency noise envelope is not much greater than
the envelope calculated with the HCACF interval (in dashed
red). The combined error of high- and low-frequency noise (in
dashed black) is barely distinguishable from that of the low-
frequency noise (in magenta). As expected, the contribution
of low-frequency oscillations largely explains the noise.
τand σare all that is necessary to characterize the random
walk. This means a simulation could be undergoing and its
data used to evolve the uncertainty envelope on the fly. An
example of this is shown in the results. For the present data
set, the low-frequency oscillations explain nearly all of the
noise, and it would suffice to consider the autocorrelation of the
whole, unfiltered noise, to obtain an estimate for the integrated
noise envelope. A more thorough discussion of the filtering is
offered in the Results section. Also in the Results section, this
approach is applied to the 18 HCACFs, thus allowing us to
obtain an error estimate of the uncertainty envelope.Wealso
show that a frequency decomposition analysis similar to that
applied to the HCACF can be used directly on the heat flux to
determine a suitable simulation time step to optimize HCACF
We applied steps (i)–(vi) to all HCACFs. The second
step involves identifying different noise frequencies. It is
worthwhile to remark on the difficulty of extricating individual
random walks from a sum of random walks. For instance,
applying a filter (as in Fig. 4) can syphon out data that belongs
to a lower frequency random walk. In Fig. 4, frequency filters
are applied with windows ranging between 0.04 and 0.56 ps
at a 0.04-ps interval. Each time, the data filtered are removed
from the overall noise. One might be tempted to say, from
evaluation of Fig. 4, that there are multiple high-frequency
random walks, with time fluctuations τ=0.04, 0.08, and
0.12 ps, for instance, and that might be correct or the
sets of filtered data might belong to a single random walk.
If the former is true, the contribution of the independent
sets of high-frequency data were calculated to be negligible
compared to the low-frequency data, in the same way the
high-frequency data obtained with a single (0.4-ps) filter, as
shown in Fig. 3(a), does not significantly contribute to the
overall noise [see Fig. 3(c)]. Similarly, the low-frequency noise
could be considered as the sum of its parts, but this would
remove the underlaying characteristics of the noise. For this
reason, having identified distinct frequency ranges in the noise,
and having determined that their contribution is remarkably
unequal, we proceed with the analysis performed as described
in steps (i)–(vi).
For all simulations, τwas computed as to minimize the
standard deviation, with the caveat that the maximum allowed
value for τwas limited by the lowest intercept with zero
between all noise autocorrelation functions. This is because
we fit to the natural logarithm of the noise autocorrelation.
This does befit us, however, in that we aim to calculate the
effect of the fast rate of decay of the systems’ memory reflected
in the noise. Moreover, a similar argument to there being a
true autocorrelation function for the heat flux can be made
with regards to the noise. If the frequency of the noise is the
same across samples, there is one true autocorrelation function
that describes the interval for which the noise is correlated,
FIG. 5. In panel (a) the tail of the HCACFs, their integral, the uncertainty envelope (cyan) calculated as described in the text, and its error
(blue) are all plotted. In the inset in panel (b), instead of only considering the noisy tails of the HCACFs, the whole HCACFs are represented. In
both panel (a) and the inset in panel (b) the solid black lines correspond to results along the ydirection, and the dashed black lines correspond
to results along the xdirection. The bold red line in the inset in panel (b) is the integral of the average of the HCACFs; the solid green line is
the standard error computed for the 18 HCACF integrals; and the dashed green line is the standard error of the 216 50-ps HCACF integrals that
can be obtained from the 18 sets of data with 600 ps each. These lines are shown in the inset in panel (b) for perspective, but also in the larger
plot in panel (b) for a clearer distinction between them and the cyan line, which shows the uncertainty calculated as described in the text, using
the random walk approach.
FIG. 6. Panel (a) is the normal distribution over all J. Panel (b) is the distribution of the noise from the tails in the 30–50ps interval. Panel
(c) is the distribution of the peaks fit to the noise from the tails in the 30–50 ps interval, as shown in Fig. 2(d).
i.e., before it becomes random. For the high-frequency noise,
τH=0.27 ±0.02 ps and is one order of magnitude greater
than the interval of the HCACF (δt =0.02 ps), but, as depicted
in Fig. 3(c) for the calculated uncertainty envelope of a single
HCACF tail, it has a low impact in the overall uncertainty
envelope. For the low-frequency noise, τLis 4.6±0.78 ps.
The standard deviation for the high-frequency noise, σH,is
8.06 ±.11 ×108eV2/˚
A4ps2and for the low-frequency noise
σLis 2.89 ±16 ×107eV2/˚
A4ps2. Figure 5(a) shows how the
noise integrals compare to the envelope (in cyan) computed
from the mean τLand σLobtained from the 18 HCACF
tails, using Eq. (5), including the error (in blue) obtained by
propagating the standard error of each quantity; the above
stated uncertainties for τH,τL,σH, and σLare the standard
error. In Fig. 5(b) in the inset the envelope is compared with
the full HCACF integrals. The standard error computed over of
the 18 HCACF integrals is also depicted in Fig. 5(b) (in solid
green), including in the inset, as is the standard error computed
over the set of 216 sets of 50-ps HCACF integrals to which
the 18 sets can be reduced (in dashed green) by splitting each
600-ps set of Jvalues in 12 sets of 50 ps. This method of
splitting the heat current data into many small parcels and
computing the HCACF independently for each parcel means
that the individual HCACF’s are more noisy, but there are
more data sets from which to infer the standard error in the
integral. This method predicts an uncertainty slightly smaller
that the random walk method. The approach is appealing
because it is simple and it appears to provide a narrow estimate
of uncertainty. Unfortunately, the tails of HCACFs computed
from neighboring data windows are found to be correlated and
so the approach underestimates the error, providing a false
degree of certainty. It can be seen in Fig. 5(b) that nearing
30 ps the error defined as the standard error of the HCACF
integrals becomes more ill defined. Again, this is because
over time each of the HCACFs has less data to average over.
The possibility that Jis still correlated after the length of
the HCACF implies that, unlike the method proposed herein,
a correct noise estimate with the standard error approach
requires multiple simulations with differing starting points. As
seen in Fig 10, with the random walk approach a few hundred
picoseconds suffice to characterize the error and obtain an
uncertainty envelope.
In Figs. 2(f) and 2(g) it can be observed that for the
20–50 ps interval selected the HCACF tails have a nonzero
mean. This suggests that the HCACFs might not have been
fully relaxed by 20 ps. In Fig. 6we consider the distributions
of J[Fig. 6(a)], the noise in the 30–50 ps interval for the entire
data [Fig. 6(b)], and for the case where the peaks are computed
from a moving average with a 1-ps interval [Fig. 6(c)]asshown
in Fig. 2(d). Figures 6(b) and 6(c) correspond to Figs. 2(e) and
2(f) for the smaller interval. Figure 6reassures us that over all
simulations the system is close to relaxed by 30 ps. However,
not all individual simulations seem to have converged by
30 ps. While the distribution of Jfor each simulation reveals a
consistently normal distribution with mean zero, the mean of
the distribution of individual HCACF tails fluctuates around
but is not consistently at zero. This is not an issue because
the random walk approach to estimate the uncertainty of the
Green-Kubo method is largely insensitive to prevailing steady
deviations from zero and it considers these variations as real
slow decay processes.
Figure 7evidences that the random walk method is robust
to slow decay processes affecting the characterization of the
FIG. 7. Panel (a) shows two extremes both in terms of their total integrated value and the interval, τL, of their low-frequency oscillations.
The uncertainty envelope for the integrated HCACF in purple is slightly above the maximum standard error (blue), whereas that of the HCACF
integral in brown is below. The corresponding noise and noise integrals for these extrema are shown in panel (b).
FIG. 8. Panel (a) shows the averaged HCACFs for all simulations along x(cyan) and y(magenta), the HCAFCs for x(blue) and y(red)
for the large, 8-ns, simulation and the corresponding integrals in the same color. To observe the effect of a single outlier, all HCACFs except
the purple one (see Fig. 7) are averaged. The resulting HCACF and integral are plotted in dashed yellow. Panel (b) shows the integrals [using
the same color scheme as in panel (a)] with the corresponding uncertainty envelope around them.
noise. Upon first impression the integral in purple, in Figs. 5(b)
and 7(a), stands out as having a large noise—it is well above the
mean of all integrals [shown in red in the inset in Fig. 5(b)].
Yet, since its value is large, the error is a smaller fraction
of the total integral value. There are possibly three factors
at play here. (1) A random walk is, well, random, and the
uncertainty envelope is merely an estimate of the expected
value of any random walk for a given σand τ. (2) Figure 7(a)
includes the individual uncertainty envelopes computed with
the random walk approach for each simulation. In both cases
A4ps2. However, τLis 1.24 ps for the
simulation in brown, and 6.32 ps for the simulation in purple,
so some of the error does seems to be due to a lower noise
frequency and it is accounted for in the envelope. (3) A closer
look at this HCACF reveals that it is not yet converged [see
Fig. 7(b)]. In this particular case, the noise due to the random
walk is not the main cause for the discrepancy between this
HCACF integral and the remainder. This is in agreement
with the above discussion of the individual simulations’
distribution. The uncertainty envelope for this simulation
being below the integrated HCACF is thus consistent with
FIG. 9. This shows the integrated HCACF average for all
simulations along x(cyan) and y(magenta) for the subset of
800-ps simulations resulting from the 8-ns simulation, the integrated
HCAFCs for x(blue) and y(red) for the large, 8-ns, simulation and
the corresponding uncertainty envelope around them.
the random walk method being broadly agnostic to slow
decay processes. To reinforce this idea, we computed τLafter
displacing the HCACF tail by the mean so it oscillates around
zero and it equals 6.28 ps, not noticeably different from
τL=6.32 ps as calculated above. In other words, because
we are interested in the rapid decay process of the HCACFs,
slow-rate processes in the HCACF are not mistaken for noise.
The random walk uncertainty quantification approach could
be a valuable tool for guiding researchers on how the noise
varies over time or across simulations. To test this, a simulation
of the same system was performed along xand yfor 8.0 ns. For
the 8.0-ns simulation data was collected at 0.04-ps intervals.
The set of 18 simulations of 600 ps each adds to 10.8ns, or
5.4 ns if we consider the xand yindependently, with data
collected every 0.02 ps. A total of 200 000 data points are
available for averaging over the single simulation, and 270 000
for a nine-simulations set. As expected, the final HCACF
for the 8.0-ns simulation is much smoother than any of the
HCACFs from the 600-ps simulations, but as shown in Fig. 8it
continues to retain some of its oscillatory features. In Fig. 8,the
integrated mean HCACFs for xand yfor each of the two sets of
nine simulations are compared to the xand yHCACF integrals
obtained from the 8.0-ns simulation and their corresponding
uncertainty envelopes. Figure 8(a) also shows the impact of
a single outlier on the integrated HCACF average. Strikingly,
the noise obtained from a single large simulation with fewer
data points is lower than that obtained by averaging multiple
simulations over a greater number of data points.
Recall that each simulation was performed from scratch
by replicating a unit cell and conferring each system a
temperature using individual seeds for each simulation. To
determine if the discrepancy between the cross-autocorrelation
averaging and the single-simulation autocorrelation averaging
was maintained over a similar simulation length for the
same seed, we subdivided the 8-ns simulation into a set of
10 800 ps simulations and averaged over them (see Fig. 9).
Cross-simulation averaging with the same amount of data
actually seems to reduce the error slightly. Most importantly,
the smaller interval selected for a larger simulation is a
worthwhile trade-off.
An example of an on-the-fly application of the suggested
approach is given in Fig. 10(a), which shows the running
mean of the evolving random walk uncertainty envelope as
FIG. 10. In panel (a), in addition to the HCACF, the moving average of the uncertainty envelope computed using the random walk approach
is also propagated through the simulation time. In panel (b) the percentage error is computed as the uncertainty envelope over the total integral.
the simulation progresses. The correlation (R) between τand
the evolving envelope is 0.52, and that between σand the
envelope is 0.56, both with a zero Pvalue. This indicates a
strong dependence of the envelope variance on both variables.
The percentage error is computed throughout the simulation as
the ratio between the envelope and the integral of the HCACF
[see Fig. 10(b)]. It is interesting to notice that around 4 ns there
is a steep decrease in the expected HCACF integrated noise,
after which point the variation in the uncertainty diminishes.
To determine if there was an apparent direct correspondence
between the system’s Lyapunov memory and the system’s
energy fluctuation memory, we computed the Lyapunov
instability, λ, which was found to be around 0.55 THz. Several
simulation intervals for the system size were considered,
including the 0.2-fs interval used for our simulations. The
systems lose coherence between 15–20 ps. The distance, d(t),
between systems was computed as |(X)A(X)B|, where (X)A
are the coordinates of system A, started an approximate 105˚
distance away from system B.
To evaluate the hypothesis that the origin of the noise in the
tails results from larger peaks in Jthat have not been averaged
out due to insufficient data, we performed an autocorrelation
through Jwith both a gradual and a rough cutoff of these peaks
[see Fig. 11(a)]. The results obtained [see Figs. 11(b)11(e)]
indicate otherwise. A cut, soft—i.e., such that the value of J
is reduced by a higher fraction the further away from zero
Jit is—or abrupt—i.e., removing peaks above and below a
cutoff—through Jreveals the importance of the peaks to set the
shape of the HCACF [see Fig. 11(b)], but it provides evidence
contrary to our hypothesis that the correlation between a few
wider peaks were at the origin of the random-walk-type noise.
If we consider a moving average (in red) through J,we
find that it perfectly captures the trend of the HCACF [see
Fig. 11(b)]. The normalized HCACF obviates that the trend of
the data is more acutely captured by the moving average. The
FIG. 11. The heat flux (black), J,a0.4-ps moving average of J(red), and a gradual cutoff of the higher peaks of J(green) are shown in
panel (a). The HCACF and integral for each of the above cases is shown in panel (b) as is, and is normalized in panel (c). Panels (d) and (e)
are close-ups of panels (b) and (c), respectively. The color coding is maintained throughout the figures.
FIG. 12. Panel (a) shows J(black), a transform on Jthat keeps its higher peaks and replaces data between the peaks with a zero value
(blue), and a line at 550 ps representing a cutoff of the Jdata above it. Panel (b) shows the normalized HCACF for the above cases, including
those depicted in Fig. 11(a). The HCACF as is shown in panel (c). The color code is kept constant between Figs. 11 and 12.
normalized HCACF discrepancy between the moving average
and the actual data could be omitted by normalizing the moving
average autocorrelation function by the first element of the true
If we, conversely, only consider the data from the highest
peaks, setting all other data to zero (in blue in Fig. 12), some
of the noise fades away, but so does the overall trend of the
HCACF. A cut through the data increases the noise as expected
(in yellow in Fig. 12), by reducing the amount of data to
average over. In as far as we can ascertain, the noise is coupled
to the overall fluctuations of J.
In this paper we propose a method for quantifying the
uncertainty of the autocorrelation function and thus that of
transport properties computed using the Green-Kubo ap-
proach. This method is based on the premise that the noise
of the autocorrelation function is akin to discrete white noise
and it integrates into a random walk. The value of this method
goes beyond estimating the error of a single simulation and
it can be used to determine the minimum duration of a
simulation to achieve a desired error threshold, as evidenced
in Fig. 10. Most valuably, for a stipulated error, this method
can be used to determine the optimal simulation time on
the fly. While we have not found conclusive evidence for
the origin of the noise, we have determined it is coupled to
the overall trend of the measured flux and that the error is
largely the result of fluctuations at frequencies below terahertz.
Moreover, our results indicate that it is preferable to trade
off a smaller time step for a longer total simulation time
with a wider time step, to smooth the long-term oscillatory
behavior of the HCACF, provided the time step is large
enough to account for the relevant physics of the simulated
system. Transport properties computed with equilibrium MD
can be optimized by combining (1) performing a single
simulation to determine the minimum required simulation
time to reach a desired Markovian error with (2) performing
multiple independent simulations with which to obtain a
robust average autocorrelation function and standard error. The
suggested approach can also be used to determine if slow decay
processes are present in the autocorrelation by comparing the
noise distribution to a normal with the mean and standard
deviation found to characterize the noise. The method herein is
suitable for high-throughput approaches for which expeditious
simulations and uncertainty quantification are paramount.
L.d.S.O. thanks Daniel McCoy and Trevor Howard for
useful discussions. This work used the Extreme Science
and Engineering Discovery Environment (XSEDE), which is
supported by National Science Foundation Grant No. OCI-
1053575, this work was supported in part by the National
Science Foundation under Award No. 1403423.
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The shear viscosity, η, of model liquids and solids is investigated within the framework of the viscuit and Fluctuation Theorem (FT) probability distribution function (PDF) theories, following Heyes et al. [J. Chem. Phys. 152, 194504 (2020)] using equilibrium molecular dynamics (MD) simulations on Lennard-Jones and Weeks–Chandler–Andersen model systems. The viscosity can be obtained in equilibrium MD simulation from the first moment of the viscuit PDF, which is shown for finite simulation lengths to give a less noisy plateau region than the Green–Kubo method. Two other formulas for the shear viscosity in terms of the viscuit and PDF analysis are also derived. A separation of the time-dependent average negative and positive viscuits extrapolated from the noise dominated region to zero time provides another route to η. The third method involves the relative number of positive and negative viscuits and their PDF standard deviations on the two sides for an equilibrium system. For the FT and finite shear rates, accurate analytic expressions for the relative number of positive to negative block average shear stresses is derived assuming a shifted Gaussian PDF, which is shown to agree well with non-equilibrium molecular dynamics simulations. A similar treatment of the positive and negative block average contributions to the viscosity is also shown to match the simulation data very well.
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An atomistic level understanding of how varying types and numbers of irradiation induced defects affect thermal resistance in graphite is vital in designing accident tolerant fuels for next-generation nuclear reactors. To this end we performed equilibrium molecular dynamics simulations and computed the change to thermal conductivity due to a series of clustering and non-clustering point defects using the Green–Kubo method. In addition, we present a comprehensive discussion of several approaches to converge the integral of the heat current autocorrelation function. Our calculations show that more energetically favorable clustering defects exhibit fewer low frequency modes and increase the anisotropic nature of graphite selectively exerting a significant effect on thermal resistance along the c-axis.
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In the warm dense matter (WDM) regime, material properties like diffusion and viscosity can be obtained from lengthy quantum molecular dynamics simulations, where the quantum behavior of the electrons is represented using either Kohn-Sham or orbital-free density functional theory. To reduce the simulation duration, we fit the time dependence of the autocorrelation functions (ACFs) and then use the fit to find values of the diffusion and viscosity. This fitting procedure avoids noise in the long time behavior of the ACFs. We present a detailed analysis of the functional form used to fit the ACFs, which is always a more efficient means to obtain mass transport properties. We use the fits to estimate the statistical error of the transport properties. We apply this methodology to a dense correlated plasma of copper and a mixture of carbon and hydrogen. Both systems show structure in their ACFs and exhibit multiple time scales. The mixture contains different structural forms of the ACFs for each component in the mixture.
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Since the past decade, rapid development in nanotechnology has produced several aspects for the scientists and technologists to look into. Nanofluid is one of the incredible outcomes of such advancement. Nanofluids (colloidal suspensions of metallic and nonmetallic nanoparticles in conventional base fluids) are best known for their remarkable change to enhanced heat transfer abilities.Earlier research work has already acutely focused on thermal conductivity of nanofluids. However, viscosity is another important property that needs the same attention due to its very crucial impact on heat transfer. Therefore, viscosity of nanofluids should be thoroughly investigated before use for practical heat transfer applications. In this contribution, a brief review on theoretical models is presented precisely. Furthermore, the effects of nanoparticles’ shape and size, temperature, volume concentration, pH, etc. are organized together and reviewed.
Equilibrium molecular dynamics is often used in conjunction with a Green-Kubo integral of the pressure tensor autocorrelation function to compute the shear viscosity of fluids. This approach is computationally expensive and is subject to a large amount of variability because the plateau region of the Green-Kubo integral is difficult to identify unambiguously. Here, we propose a time decomposition approach for computing the shear viscosity using the Green-Kubo formalism. Instead of one long trajectory, multiple independent trajectories are run and the Green-Kubo relation is applied to each trajectory. The averaged running integral as a function of time is fit to a double-exponential function with a weighting function derived from the standard deviation of the running integrals. Such a weighting function minimizes the uncertainty of the estimated shear viscosity and provides an objective means of estimating the viscosity. While the formal Green-Kubo integral requires an integration to infinite time, we suggest an integration cutoff time tcut, which can be determined by the relative values of the running integral and the corresponding standard deviation. This approach for computing the shear viscosity can be easily automated and used in computational screening studies where human judgment and intervention in the data analysis are impractical. The method has been applied to the calculation of the shear viscosity of a relatively low-viscosity liquid, ethanol, and relatively high-viscosity ionic liquid, 1-n-butyl-3-methylimidazolium bis(trifluoromethane-sulfonyl)imide ([BMIM][Tf2N]), over a range of temperatures. These test cases show that the method is robust and yields reproducible and reliable shear viscosity values.
Metal-organic-framework materials (MOFs) are the most porous materials known to humanity and thus are promising materials for gas storage and absorption refrigerators-reducing the overall size of the absorption bed. Central to the performance of the MOF is its ability to withdraw heat from the absorbed working gas. Here we use a suite of molecular dynamics simulations to relate structural features of the MOF-5 framework to its thermal transport properties. These were performed for the purpose of establishing design principles that can be used in the development of new MOFs with tailored thermal conductivity. The last part of the paper examines thermal transport in MOF-5 when loaded with hydrogen and deuterium which increases thermal conductivity.
Quantum simulation methods based on density-functional theory are currently deemed to be unfit to cope with atomic thermal transport in materials within the Green-Kubo formalism. In contrast with this belief, we derive an expression for the adiabatic energy flux from density-functional theory, that permits the ab initio simulation of atomic thermal transport using equilibrium molecular dy- namics. The resulting thermal conductivity is shown to be unaffected by the inherent ill-definedness of quantum mechanical energy densities and currents. Our new methodology is demonstrated by comparing results from ab-initio and classical molecular-dynamics simulations of a model liquid- Argon system, for which accurate inter-atomic potentials are derived by the force-matching method, and finally applied to compute the thermal conductivity of heavy water at ambient conditions.
Transport properties of five room-temperature ionic liquids based on the 1-butyl-3-methylimidazolium cation with any of the following anions, [PF6]−, [BF4]−, [CF3SO3]−, [NTf2]−, and [NO3]−, were determined from classical molecular dynamics simulations. The force field employed fractional ion charges whose magnitude were determined using condensed phase quantum calculations. Integrals of appropriate equilibrium time correlation functions within the Green-Kubo approach were employed to predict shear viscosity and electrical conductivity of these liquids. Computed shear viscosity values reproduce experimental data with remarkable accuracy. Electrical conductivity calculated for [BMIM][PF6] and [BMIM][BF4] showed impressive agreement with experiment while for [BMIM][CF3SO3] and [BMIM][NTf2] the agreement is fair. The current approach shows considerable promise in the prediction of collective transport quantities of room temperature ionic liquids from molecular simulations.
Effect of nanoparticle aggregation on the transport properties that include thermal conductivity and viscosity of nanofluids is studied by molecular dynamics (MD) simulation. Unlike many other MD simulations on nanofluids which have only one nanoparticle in the simulation box with periodic boundary condition, in this work, multiple nanoparticles are placed in the simulation box which makes it possible to simulate the aggregation of the nanoparticles. Thermal conductivity and viscosity of the nanofluid are calculated using Green-Kubo method and results show that the nanoparticle aggregation induces a significant enhancement of thermal conductivity in nanofluid, while the increase of viscosity is moderate. The results also indicate that different configurations of the nanoparticle cluster result in different enhancements of thermal conductivity and increase of viscosity in the nanofluid.
We present a Green-Kubo method to spatially resolve transport coefficients in compositionally heterogeneous mixtures. We develop the underlying theory based on well-known results from mixture theory, Irving-Kirkwood field estimation, and linear response theory. Then, using standard molecular dynamics techniques, we apply the methodology to representative systems. With a homogeneous salt water system, where the expectation of the distribution of conductivity is clear, we demonstrate the sensitivities of the method to system size, and other physical and algorithmic parameters. Then we present a simple model of an electrochemical double layer where we explore the resolution limit of the method. In this system, we observe significant anisotropy in the wall-normal vs. transverse ionic conductances, as well as near wall effects. Finally, we discuss extensions and applications to more realistic systems such as batteries where detailed understanding of the transport properties in the vicinity of the electrodes is of technological importance.
Ability to encapsulate molecules is one of the outstanding features of nanotubes. The encapsulation alters physical and chemical properties of both nanotubes and guest species. The latter normally form a separate phase, exhibiting drastically different behavior compared to bulk. Ionic liquids (ILs) and apolar carbon nanotubes (CNTs) are disparate objects; nevertheless, their interaction leads to spontaneous CNT filling with ILs. Moreover, ionic diffusion of highly viscous ILs can increase 5-fold inside CNTs, approaching that of molecular liquids, even though the confined IL phase still contains exclusively ions. We exemplify these unusual effects by computer simulation on a highly hydrophilic, electrostatically structured, and immobile 1-ethyl-3-methylimidazolium chloride, [C2C1IM][Cl]. Self-diffusion constants and energetic properties provide microscopic interpretation of the observed phenomena. Governed by internal energy and entropy rather than external work, the kinetics of CNT filling is characterized in detail. The significant growth of the IL mobility induced by nanoscale carbon promises important advances in electricity storage devices.