Benchmarking the diffusion and viscosity of H-He mixtures in warm dense matter

regime by quantum molecular dynamics simulations

Zhi-Guo Li, Wei Zhang, Zhi-Jian Fu, Jia-Yu Dai, Qi-Feng Chen, and Xiang-Rong Chen

Citation: Physics of Plasmas 24, 052903 (2017); doi: 10.1063/1.4983057

View online: http://dx.doi.org/10.1063/1.4983057
View Table of Contents: http://aip.scitation.org/toc/php/24/5
Published by the American Institute of Physics

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 PHYSICS OF PLASMAS 24, 052903 (2017)

Benchmarking the diffusion and viscosity of H-He mixtures in warm dense

matter regime by quantum molecular dynamics simulations
Zhi-Guo Li,1,2 Wei Zhang,3 Zhi-Jian Fu,4 Jia-Yu Dai,5,a) Qi-Feng Chen,2,a)
and Xiang-Rong Chen1,a)
1
Institute of Atomic and Molecular Physics, College of Physical Science and Technology, Sichuan University,
Chengdu 610064, People’s Republic of China
2
National Key Laboratory for Shock Wave and Detonation Physics Research, Institute of Fluid Physics,
Chinese Academy of Engineering Physics, Mianyang 621900, People’s Republic of China
3
School of Science, Southwest University of Science and Technology, Mianyang 621010,
People’s Republic of China
4
School of Electrical and Electronic Engineering, Chongqing University of Arts and Sciences,
Chongqing 402160, People’s Republic of China
5
Department of Physics, College of Science, National University of Defense Technology, Changsha 410073,
People’s Republic of China
(Received 16 February 2017; accepted 21 April 2017; published online 8 May 2017)
Quantum molecular dynamics simulations for self-diffusion, mutual-diffusion, and viscosities of
hydrogen-helium (H-He) mixtures are investigated to benchmark the standard theoretical models in
the warm dense matter regime. We carefully examine the differences in velocity autocorrelation
functions (VACFs) between the mixtures and pure hydrogen or helium. The VACFs for the mixtures
exhibit oscillatory features, which however are absent for pure species. At low temperatures, the
VACFs of H in H-He mixtures have a negative correlation region, which results in an obviously
smaller self-diffusion of H in H-He mixtures compared to that in a pure H system. The calculated
self-diffusion coefficients of H and He in H-He mixtures show much different behaviors with the
variation of the composition of He (XHe): the self-diffusion coefficients of He increase monoto-
nously with increasing XHe, whereas the self-diffusion coefficients of H generally decrease with the
increase in XHe. The viscosities are smaller for the H-He mixtures with a more helium content.
These diffusion and viscosity coefficients are used as a benchmark to check some analytical models
based on the one component plasma or the Yukawa one component plasma. Published by AIP
Publishing. [http://dx.doi.org/10.1063/1.4983057]

I. INTRODUCTION 7000 K. Ternovo%K et al.11 measured the conductivity of H-

He mixtures up to megabar pressure in their high explosive
Warm dense matter (WDM) has been a burgeoning
shock experiments. Nevertheless, the experimental data
domain of science during the past decade for it is a rather
remain scarce. Quantum molecular dynamics (QMD) or
unique state of matter with partially degenerate electrons and
first-principles molecular dynamics (FPMD) simulations, in
strongly coupled ions lying in between the cold condensed
which electrons are solved using the density functional the-
matter and an ideal gas plasma and existing widely in the
ory (DFT) and ions are treated as classical particles in the
giant planets,1 white dwarfs,2 inertial confinement fusion
Newton equation, are good tools that can be applied to better
(ICF),3 and shock experiments.4–7 A prominent example for
understand the experiments at the microscopic level, as well
a mixture in WDM is hydrogen and helium. This mixture is
as to study the regions that are not accessible experimen-
especially important for astrophysical objects. For example,
tally.12–15 Orbital-free molecular dynamics (OFMD) can also
hydrogen-helium (H-He) mixtures form 70%95% of the
give some validation for the transport properties of hot dense
mass of Jupiter and Saturn, two gas giant planets of our solar
plasmas,16 but it has been limited to relatively high tempera-
system. Our understanding of their compositions, evolutions,
ture regimes until now. A large amount of QMD work has
and interior structures relies on the accurate knowledge
been directed towards H-He mixtures.17–30 The two most
about the equations of state (EOSs) and transport properties
concerned issues of these research studies are the EOSs19–23
of H-He mixtures in the WDM regime.8,9
and H-He phase separation,24–28 which are of significance
Shock-compression experiments are indispensable for
for understanding the interiors of giant planets.
exploring the matter under high pressure and high tempera-
The transport coefficients of H-He mixtures, such as dif-
ture conditions. Gu et al.10 performed multi-shock experi-
fusivities and viscosities, also play a critical role in various
ments for H-He mixtures by using a two-stage gas gun. They
giant planet phenomena. However, the related studies are
measured the EOSs for H-He mixtures up to 30 GPa and
insufficient, especially the studies on the intrinsic physics for
a) the differences in transport coefficients between H-He mix-
Authors to whom correspondence should be addressed. Electronic
addresses: jydai@nudt.edu.cn, chenqf01@gmail.com, and xrchen@scu.edu.cn. tures and pure hydrogen or helium systems. In recent QMD
Tel.: 86-28-85405516. simulations for H-He mixtures, the diffusion and viscosity

1070-664X/2017/24(5)/052903/12/$30.00 24, 052903-1 Published by AIP Publishing.

052903-2 Li et al. Phys. Plasmas 24, 052903 (2017)

coefficients were studied via the time correlation func- boxes including 120 H atoms, 200 H plus 120 He atoms,
tions.29,30 A simple single exponential fitting method was 120 H plus 200 He atoms, and 120 He atoms, respectively.
used in those works to obtain the diffusion and viscosity The simulation box is repeated with periodic boundary con-
coefficients. It is a good approximation for the weakly cou- ditions, and the sizes of these boxes are fixed once the simu-
pled regime. However, Danel et al.31 and Meyer et al.32 lation density is specified. Furthermore, to obtain the
noted that a single exponential function might not lead to the statistically converged results, especially for viscosity, a suf-
correct diffusion and viscosity parameters for strongly cou- ficiently long time simulation is required. In our simulations,
pled systems such as the WDM, for which the time correla- molecular dynamics are performed for 40 000 steps with a
tion functions exhibit multiple time scales. To arrive at the time step of 0.5 fs. We employed initial conditions based on
true values for the diffusion and viscosity of H-He mixtures a random distribution of hydrogen molecules and helium
in the WDM regime, in this paper, we perform sufficiently atoms, so that the simulations generally reached equilibration
long time QMD simulations to obtain the statistically con- within 5000 steps. We used the configurations after 5000
verged results, as done by Danel et al.31 We systematically steps to obtain thermal properties. Such large supercells and
study the diffusion and viscosity for H-He mixtures with var- simulation time steps are computationally costly for QMD
ious H/He compositions and carefully examine the differ- simulations. Thus, we only consider four simulation
ences between the mixtures and the pure species. Moreover, temperatures between 4000 and 10 000 K and a density of
the QMD results are used as a benchmark to check some ana- 1.0 g/cm3, which are selected to highlight the conditions in
lytical models based on the one component plasma (OCP) or the interiors of giant planets.
the Yukawa one component plasma (YOCP). These models
can be very useful in studying giant planets if they are valid. B. Transport coefficients
The rest of the paper is organized as follows. The theo- The self-diffusion coefficient Da of species a is calcu-
retical method and the computational details are given in lated from the velocity autocorrelation function (VACF)
Section II. The results and discussion are presented in using the Green-Kubo (GK) formula36
Section III. Finally, the conclusions are given in Section IV.
Da ¼ lim Da ðtÞ; (1)
II. THEORETICAL METHOD AND COMPUTATIONAL t!1
DETAILS ðt
1
A. Quantum molecular dynamics Da ðtÞ ¼ dt0 hvai ðt0 Þ  vai ð0Þi; (2)
3 0
QMD simulations have been performed by using the
quickstep code of the CP2K program package.33 Employing where vai ðtÞ is the center-of-mass velocity of the ith atom of
the Born-Oppenheimer approximation, the coupling of the species a at time t, and the angular brackets denote the
ions and electrons is separated. The ions are treated classi- ensemble average. In practice, the average would be com-
cally according to the forces from the electron density and puted for each of the Na particles of species a in the simula-
the ion-ion repulsion, while the electrons are treated quan- tion, and the results are added together and divided by Na, to
tum mechanically through the density functional theory improve statistical accuracy.
(DFT). CP2K adopts the hybrid Gaussian and plane wave The Green-Kubo formula for the mutual-diffusion coef-
(GPW) method to implement fast DFT calculations. The effi- ficient is similar to that for the self-diffusion coefficient,
ciency and accuracy of the GPW method have been illus- which is given by
trated in detail by Vondele et al.33 In our simulations, the
norm-conserving, separable, dual-space pseudopotentials of Dab ¼ lim Dab ðtÞ; (3)
t!1
Goedecker, Teter, and Hutter (GTH)34 are used to describe ðt
the electron-ion interaction. The electron-electron exchange- U
Dab ðtÞ ¼ dt0 hjðt0 Þ  jð0Þi (4)
correlation interaction is represented by the local density 3NXa Xb 0
approximation (LDA) functional.34 The plane-wave cutoff
energy is set to 500 Ry, whereas the cutoff energy of the j(t) is the mutual-diffusion current, which is given by
Gaussian type basis set (Double Zeta Valence, DZV) is
X
Na Nb
X
40 Ry. The Brillouin-zone sampling we used is the C point
only. These parameters are carefully tested and sufficient to jðtÞ ¼ Xb vai  Xa vbj ; (5)
i¼1 j¼1
lead well-converged energies and forces.
Molecular dynamics simulations have been performed where Xa and Na represent the concentrationPand the particle
in the canonical ensemble using Nose-Hoover thermostats.35 number of species a, respectively, and N ¼ a Na is the total
Four H-He systems are considered in the present work, i.e., particle number. The factor U is the thermodynamic factor,
XHe ¼ 0, 0.375, 0.625, and 1, where XHe is the composition which can be chosen to be unity here.
of He defined by XHe ¼ NHe/(NH þ NHe) with N being the par- The viscosity g is computed from the stress autocorrela-
ticle number. In order to obtain adequate statistics for each tion function (SACF) using the Green-Kubo formula
species in the mixture, the particle number of each species
should not be smaller than 120 in the cubic simulation box g ¼ lim gðtÞ; (6)
according to our tests. Therefore, we use four simulation t!1
052903-3 Li et al.
ðt
V
gðtÞ ¼ dt0 hP12 ðt0 Þ  P12 ð0Þi;
kB T 0 A. Self- and mutual-diffusion
where P12 represents the averaged result for five independent
components of the stress tensor Pxy, Pyz, Pzx, (Pxx–Pyy)/2, and
(Pyy–Pzz)/2. The stress tensor is a property of the whole sys-
tem, including no additional averaging over Na particles.
Consequently, the viscosity coefficients are subject to
much greater statistical imprecision than the self-diffusion
coefficients, and therefore, much longer trajectories are
needed. Fig. 1 shows the normalized SACFs of the H-He
mixtures with He compositions of XHe ¼ 0, 0.375, 0.625,
and 1 for a density of 1.0 g/cm3 and a temperature of
4000 K, obtained by QMD simulations using different
time lengths. We can see that the normalized SACFs
using 30 000 and 40 000 time steps already show reason-
ably good convergence. Therefore, using 40 000 time
steps in our simulations can prove a relatively good con-
vergence for the results.
By the way, a sliding time window should be considered
in calculating the time correlation functions to skip the
highly correlated steps that may introduce systematic errors.
We used time windows of tw ¼ 5 fs for viscosity and tw ¼ 20
fs for diffusion, which were chosen to be slightly larger
than the effective decay time given in Ref. 32.
FIG. 1. Sensitivity of the normalized SACFs to simulation steps for H-He mixtures with He compositions of XHe ¼ 0, 0.375, 0.625, and 1, at 1.0 g/cm3 and
4000 K.
Phys. Plasmas 24, 052903 (2017)
III. RESULTS AND DISCUSSION
(7)
Time correlation functions are of great interest in com-
puter simulations because they give a clear picture of the
dynamics in a fluid system. In Fig. 2, we display the normal-
ized VACFs of H and He in H-He mixtures with various XHe
values, at a density of 1.0 g/cm3 and temperatures from 4000
to 10 000 K. The upper panels of Fig. 2 show the VACFs for
H and lower panels show those for He. We notice that the
VACFs of H in pure hydrogen systems are really different
from those in H-He mixtures. The VACFs of H in H-He mix-
tures show obvious oscillatory features at low temperatures.
Moreover, a negative correlation region can be found from
the VACFs. The oscillations and negative correlation
become weak with the increase in temperature. In a pure
hydrogen system, however, the VACFs of H show no obvi-
ous oscillation within the whole temperature range. This
illustrates that the presence of He has a strong influence on
the dynamic behavior of H and is responsible for the forma-
tion of oscillation and negative correlation. The VACFs of
He have no negative correlation and have a little and system-
atic change as XHe is changed. At low temperatures, the
VACFs of He in H-He mixtures also exhibit oscillations
although weak compared to those of H.
052903-4 Li et al. Phys. Plasmas 24, 052903 (2017)

FIG. 2. The normalized VACFs of H (first row) and He (second row) in H-He mixtures with various XHe values, at a density of 1.0 g/cm3 and temperatures
from 4000 to 10 000 K.

In our considered density and temperature range, the
structures in VACFs are mainly due to the bonding effects.37
In Fig. 3, we display the pair distribution functions (PDFs)
of H-H, He-He, and H-He for H-He mixtures with He com-
positions of XHe ¼ 0, 0.375, 0.625, and 1, at 1.0 g/cm3 and
4000–10 000 K. It can be seen that the PDFs of H-H for the
pure H system show no obvious peaks within the whole tem-
perature range. This means that the hydrogen molecules
have totally dissociated and the system is typically a corre-
lated atomic liquid. With the addition of He, the PDFs of

FIG. 3. The PDFs of H-H, He-He, and H-He for H-He mixtures with He compositions of XHe ¼ 0, 0.375, 0.625, and 1, at 1.0 g/cm3 and 400010 000 K.
052903-5 Li et al.
H-H exhibit a high peak at around 0.75 Å (the bond length of
a hydrogen molecule) followed by a deep valley at a low
temperature of 4000 K, which suggests the presence of a
large number of hydrogen molecules in the H-He system. In
this case, the diffusion of the H atom will be strongly
affected by its neighbor atom bound to a molecule, which
may lead to the oscillations and even negative correlation in
VACFs. The peaks get weak with the increase in tempera-
ture, which is the same trend as the structures in VACFs.
These sets of evidence strongly suggest that the structures in
VACFs are mainly caused by the bonding effect. The PDFs
of He-He also exhibit peaks at around 1.8 Å, which suggests
that there will be short-lived dimers of He. This may be the
reason for the existence of structures in the VACFs of He.
The PDF of H-He shows a peak at a low temperature of
4000 K. The peak is really weak and disappears at high
temperature.
Motivated by shortening the length of the simulation
and avoiding the noise in the long time behavior of time cor-
relation functions, some authors used functions to describe
the temporal behavior of time correlation functions.32,38–40 A
widely used function is a simple single exponential for-
mula.38–40 Recently, Meyer et al.32 developed a function
with multiple time scales to fit the VACFs
t=s0
hvðtÞ  vð0Þi ¼ a0 e
X seen from Fig. 4 that the self-diffusion coefficients obtained
þ ai et=si ½cos ðxi tÞ þ ai sin ðxi tÞ;
i
where s0 and si are the decay times and xi describe the fre-
quencies of oscillations. They tested this formula for dense
plasmas of copper and carbon-hydrogen mixtures,32 as well
as the warm dense mixture of methane, ammonia, and
water.37 Here, we use the QMD VACFs as a benchmark to
examine the validity of these fitting forms for H-He mixtures
in the investigated regime. In Fig. 4, the QMD VACFs of H
and He in the H-He mixture with a He composition of
FIG. 4. VACFs of H and He in the H-He mixture with a He composition of XHe ¼ 0.375 at 1.0 g/cm3 and 4000 K: the present QMD data are compared with the
fitting results by a formula with multiple time scales, i.e., Eq. (8), and a single exponential fit. D and DMSD represent the self-diffusion coefficients derived
using Eq. (9) and the mean square displacement, respectively. The VACFs are in atomic units.
Phys. Plasmas 24, 052903 (2017)
XHe ¼ 0.375, at 1.0 g/cm3 and 4000 K, are compared with the
fits by Eq. (8) with i ¼ 1 and the single exponential formula
(i.e., a0 et=s0 ). It can be seen that the fit by Eq. (8) well
reproduces the VACFs for both H and He. However, in both
the H and He cases, it is clear that a single exponential fit is
insufficient to correctly describe the VACFs. Using Eq. (8)
with i ¼ 1, one can immediately find the diffusion constant
1 þ a1 s1 x1
D ¼ a0 s0 þ a1 s1 : (9)
1 þ s21 x21
The statistical error derived by Meyer et al.32 is written as
sffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
 
2 1 þ a1 s1 x1
e¼ c0 s0 þ c1 s1 ; (10)
Na Ttraj 1 þ s21 x21
P
pffiffiffiffiffiffi weights of ai, ci ¼ ai = i ai . The
where ci are the relative
additional factor 1= Na is from averaging the VACFs over
all the particles of species a. Moreover, the self-diffusion
coefficient can also be computed from the trajectory using
the mean-square displacement (MSD)36
1
Da ¼ hjRai ðtÞ  Rai ð0Þj2 i; (11)
6t
where Rai ðtÞ is the position of the ith atom of species a at
time t. This provides a check for the fitting results. It can be
(8)
using Eq. (9) show reasonably good agreement with those
obtained using MSD (DMSD), and the deviations are only
3% and 2% for H and He, respectively. Therefore, it is
appropriate to use this fitting procedure to derive the values
of diffusion.
We also test Eq. (8) for denser regimes. In Fig. 5, the
QMD VACFs of H and He in the H-He mixture with a He
composition of XHe ¼ 0.375, at 5.0 g/cm3 and 4000 K, are
compared with the fits by Eq. (8). It can be seen that the fit
by Eq. (8) can also reproduce the VACFs for both H and He
052903-6 Li et al. Phys. Plasmas 24, 052903 (2017)

FIG. 5. VACFs of H and He in the H-He mixture with a He composition of XHe ¼ 0.375 at 5.0 g/cm3 and 4000 K: the present QMD data are compared with the
fitting results by a formula with multiple time scales, i.e., Eq. (8). The VACFs are in atomic units.

well. It should be mentioned that the VACF of He under
5.0 g/cm3 shows more than three decay times, and therefore,
we need to use Eq. (8) with i ¼ 2 at least.
The calculated self-diffusion coefficients of H and He,
as a function of XHe, at a density of 1.0 g/cm3 and tempera-
tures from 4000 K to 10 000 K, are presented in Figs. 6(a)
and 6(b), respectively. The self-diffusion coefficients of H
and He increase with increasing temperature but exhibit very
different behaviors with respect to XHe. In Fig. 6(a), the self-
diffusion coefficients of H in the H-He mixtures are obvi-
ously smaller than those in the pure hydrogen system. This is
mainly due to the bonding effect existing in the H-He mix-
tures as described above. The self-diffusion coefficients of H
in H-He mixtures generally decrease with the increase in
XHe, which suggests that a more helium content will lead to a
stronger bonding effect for H. This can be found from Fig. 3
that the more helium content in the mixture leads to a higher
molecule peak for H. In Fig. 6(b), the self-diffusion coeffi-
cients of He increase monotonously with increasing XHe. It is
due to the fact that the peak in He-He PDF decreases as XHe
increases, so that the self-diffusion coefficients of He
increase with increasing XHe, as can be seen from Fig. 3.
The time correlation function of the mutual-diffusion
current j(t) for the H-He mixture with XHe ¼ 0.375, at 1.0 g/
cm3 and 4000 K, is shown in Fig. 7. It is noticed that the
time correlation function of the mutual-diffusion current j(t)
also exhibits a negative correlation. This negative correlation
is to be expected because the diffusion of H into He would
also be obstructed by the bonding effect. Moreover, the com-
parison between the QMD data and the fitting results sug-
gests that the formula in the study by Meyer et al.32 can also
characterize well the time correlation function of mutual-

FIG. 6. The self-diffusion coefficients of H (a) and He (b) in the H-He mixtures as a function of XHe, for a density of 1.0 g/cm3 and temperatures from 4000 to
10 000 K.
052903-7 Li et al.
FIG. 7. The time correlation function of the mutual-diffusion current j(t) for
the H-He mixture with a He composition of XHe ¼ 0.375 at 1.0 g/cm3 and
4000 K: the present QMD data are compared with the fitting result by a for-
mula with multiple time scales, i.e., Eq. (8), and a single exponential fit. The
VACF is in atomic units.
diffusion current j(t) for warm dense H-He mixtures. The
mutual-diffusion coefficients of H-He mixtures obtained
using Eq. (9), as a function of temperature, at a density of
1.0 g/cm3 are presented in Fig. 8. The general tendency of
the mutual-diffusion coefficients for different compositions
of H-He mixtures is similar, i.e., increase with increasing
temperature. The more helium content gives rise to a larger
mutual-diffusion coefficient because the He atoms diffuse
more freely than the H atoms in the mixture. The mutual-
diffusion coefficient can also be obtained in terms of the
self-diffusion coefficient using the Darken relation,41 i.e.,
Dab ¼ Xb Da þ Xa Db : (12)
Here, we examine the validity of the Darken relation for
warm dense H-He mixtures. It is clearly seen from Fig.
8 that the mutual-diffusion coefficients obtained using the
Darken relation show obvious discrepancies with the results
by the time correlation functions of mutual-diffusion current
FIG. 9. The normalized SACFs for the H-He mixtures with various XHe values, at a density of 1.0 g/cm3 and two different temperatures of 4000 and 8000 K.
Phys. Plasmas 24, 052903 (2017)
FIG. 8. The mutual-diffusion coefficients of H-He mixtures as a function of
temperature at 1.0 g/cm3, obtained using the time correlation functions of
mutual-diffusion current and obtained in terms of the self-diffusion coeffi-
cients using the Darken relation, respectively.
j(t). This illustrate that the Darken relation is not appropriate
for the present warm dense H-He mixtures.
B. Viscosity
Systems that display multiple decay times in the VACF
might also have multiple decay times in the SACF. The nor-
malized SACFs for the H-He mixtures with various XHe val-
ues at a density of 1.0 g/cm3 and two different temperatures
of 4000 K and 8000 K are given in Fig. 9. The SACFs decay
to zero in a few tens of femtoseconds and then slightly fluc-
tuate around zero, indicating that the systems have reached
the final viscosity value. The SACFs do not exhibit obvious
oscillations. Nevertheless, they are still not in a single expo-
nential manner according to the small differences between
the QMD data and the single exponential fit as shown in
Fig. 10. Here, we use a two exponential formula designed by
Guo et al.42 to fit the SACF
052903-8 Li et al.
FIG. 10. The SACF for the H-He mixture with a He composition of
XHe ¼ 0.375 at 1.0 g/cm3 and 8000 K: the present QMD data are compared
with the fitting results by a formula with multiple time scales, i.e., Eq. (13),
and a single exponential fit. The SACF is in atomic units.
b0 b1
hP12 ðtÞ  P12 ð0Þi ¼ b0 eðt=s0 Þ þ b1 eðt=s1 Þ cos ðx1 tÞ; (13)
where b0 and b1 are the free parameters. With this formula,
we reproduce well the QMD data in Fig. 10, and the viscos-
ity can be derived by a numerical integral.
The calculated viscosity coefficients of H-He mixtures
with various XHe values as a function of temperature for a
density of 1.0 g/cm3 are displayed in Fig. 11. In general, the
viscosity coefficients are smaller for the H-He mixtures with
a more helium content. For the case of XHe ¼ 0, 0.375, and
0.625, the viscosity coefficients seem to have a local mini-
mum within the present temperature range. In fluids, the vis-
cosity arises from the transport of momentum, which is
governed by not only the bodily movement of particles but
also the action of interparticle forces at a distance. The two
mechanisms have a competitive relation with temperature.
As a consequence, the viscosity may have a local minimum
along temperature. For the case of XHe ¼ 1, the local mini-
mums are located at very low temperature, which is beyond
the present investigation region.
FIG. 11. The viscosity coefficients of H-He mixtures with various XHe val-
ues, as a function of temperature for a density of 1.0 g/cm3.
Phys. Plasmas 24, 052903 (2017)
C. Comparison with the Yukawa one component
plasma model
Although QMD is a promising approach for computing
the diffusion and viscosity for WDM, it remains too compu-
tationally expensive to provide a large amount of data over a
wide range. An alternative method is to map the WDM onto
a similar system for which the transport properties are well-
known. Murillo suggested that the WDM can be mapped
onto the Yukawa one component plasma (YOCP) model,
which is a screened version of the one component plasma
(OCP) model. Previous work has examined the transport
properties of YOCP.43–48 The present QMD data provide a
check for these models. A YOCP can be fully characterized
by two dimensionless parameters: (1) the ionic coupling
parameter
Z 2 e2
C¼ ; (14)
akB T
where Z is the ion charge, e is the electron charge, kB is the
Boltzmann constant, and
 1=3
3
a¼ (15)
4pn
is the Wigner-Seitz radius of the ions for ion number density
n; and (2) the inverse screening length j, which can be com-
puted via the Fermi screening length, j ¼ 1/kTF,39,49 where
 1=3
p pffiffiffiffi
kTF ¼ rs (16)
12Z
with rs ¼ a/a0 (a0  h2/mee2 is the Bohr radius) is the reduced
Wigner-Seitz radius.
As mentioned above, the WDM is characterized by par-
tial ionization. Therefore, we need to know the effective ion-
ization state Z* of the ions to replace Z. In this work, Z* is
obtained by an average atom (AA) model,50,51 which solves
the Dirac equation in a self-consistent field approximation
assuming a finite temperature and considering the energy
level broadening effect in dense environments. As an
illustration, we plot in Fig. 12 the effective ionizations of H
and He in H-He mixtures as a function of temperature at
1.0 g/cm3. It can be seen that the effective ionization changes
a little with temperatures within the present temperature
range. The effective ionization of H changes a little with
XHe, whereas the effective ionization of He decreases rapidly
as XHe is increased.
Daligault44 generated an empirical function for the
dimensionless self-diffusion coefficient D* in the strongly
coupled liquid-like regime according to the MD results for
the YOCP
AðjÞ BðjÞC
D ¼ e ; (17)
C
where the coefficients are the parameter function of j
AðjÞ ¼ a0 þ a1 ja2 ; (18)
052903-9 Li et al. Phys. Plasmas 24, 052903 (2017)

FIG. 12. The effective ionizations of H (a) and He (b) in H-He mixtures as a function of temperature at 1.0 g/cm3 calculated by the AA model.

BðjÞ ¼ b0 þ b1 jb2 (19) Cmod ¼ AðjÞ þ BðjÞC þ CðjÞC2 ; (22)

with a0 ¼ 1.525, a1 ¼ 0.167, and a2 ¼ 2.25636 and where the coefficients are a parameter function of the inverse
b0 ¼ 0.0081, b1 ¼ 0.292124, and b2 ¼ 1.74659. The self- screening length j, with
diffusion coefficient can be obtained by
0:46j4
 2 AðjÞ ¼ ; (23)
D ¼ D xp a : (20) 1 þ 0:44j4

The plasma frequency xp is given by BðjÞ ¼ 1:01e0:92j ; (24)

xp ¼ ð4pn=MÞ1=2 Z e:
Murillo45 proposed a simple way to describe the dynamical
properties of YOCP systems in terms of the OCP models by
substituting into OCP’s formulas a modified ionic coupling
parameter Cmod
CðjÞ ¼ 3:7  105 þ 9:0  104 j  2:9  104 j2 : (25)
(21)
In Fig. 13, the self-diffusion coefficients for pure H and
He systems from QMD are compared with the YOCP model
of Daligault44 and the YOCP models of Murillo based on the
OCP models of Daligault52 and Hansen et al.53 It can be
seen that the YOCP models based on Daligault and Hansen’s

FIG. 13. The self-diffusion coefficients for pure H (a) and He (b) systems as a function of temperature at 1.0 g/cm3: the present QMD data are compared with
the YOCP model of Daligault44 and the YOCP models of Murrilo based on the OCP models of Daligault52 and Hansen et al.53 Dash-dot-dotted lines represent
the YOCP model of Daligault using an effective ionization calculated by the AA model without the consideration of the energy level broadening effect.
052903-10 Li et al. Phys. Plasmas 24, 052903 (2017)

FIG. 14. The viscosity coefficients of H-He mixtures with various XHe values, as a function of temperature at 1.0 g/cm3: the present QMD data are compared
with the YVM model46 and the YOCP models of Murillo based on the OCP models of Daligault,52 Bastea,54 and Wallenborn-Baus.55 Dash-dot-dotted lines
represent the YVM model using an effective ionization calculated by the AA model without the consideration of the energy level broadening effect.

OCP models strongly overestimate the self-diffusion coeffi- in the investigated regime, the ionization of pure He calcu-
cients in both the H and He cases. This overestimation was lated by the AA model is really small, which leads to the
also recognized for deuterium by Clerouin and Dufr^eche.49 results in the YOCP diffusion for pure He that are obviously
The YOCP model of Daligault shows better agreement with larger than QMD data.
the QMD data. We also calculated the effective ionization Murillo46 generated a “Yukawa viscosity model” (YVM)
using the AA model without the consideration of energy according to the MD results of Saigo and Hamaguchi.47 The
level broadening. It can be seen from Fig. 13 that the self- viscosity was written in terms of the characteristic viscosity
diffusion coefficients of H calculated by the effective ioniza- pffiffiffi
tion with and without the energy level broadening are close, g0 ¼ 3xE Mna2 ; (26)
whereas the self-diffusion coefficients of He calculated with
and without the energy level broadening show obvious dif- where xE is the Einstein frequency, which can be written
ferences. The results with the energy level broadening seem approximately in terms of xp as
to be in better agreement with the QMD results. The consid-
pffiffiffi 1:62
eration of energy level broadening can include the effect of 3xE ¼ xp e0:2j : (27)
the continuum lowering effect caused by density, which will
introduce higher ionization states for WDM. More electrons The viscosity coefficient g is given by
in the system should introduce more obvious effects of the
energy level broadening. Therefore, using YOCP models in g Cm C
¼ 0:0051 þ 0:374 þ 0:022; (28)
WDM strongly depends on the calculation of effective ioni- g0 C Cm
zation, which should be treated with caution. Even we con-
sider the energy level broadening effect, we should note that where Cm is the melt boundary
052903-11 Li et al.
1:38
Cm ¼ 171:8 þ 82:8ðe0:565j  1Þ: (29)
Moreover, Murillo suggested a simple approach to treat mix-
P
¼
tures, i.e., using M a Xa Ma in g0 and an effective cou-
pling parameter in the YVM
hðZ  Þ
5=3
ihZ  i1=3 e2
Cef f ¼ ; (30)
akB T
P ACKNOWLEDGMENTS
where hZ  i ¼ a Xa Za , and Ma and Za represent the mole
mass and the effective ionization for species a.
In Fig. 14, the QMD viscosity coefficients of H-He mix-
tures with various XHe values are compared with the results
from YVM, together with the YOCP models based on the
OCP models of Daligault,52 Bastea,54 and Wallenborn-
Baus.55 Similar to the situation for self-diffusion, the YOCP
models based on Daligault and Bastea’s OCP models
strongly overestimate the viscosity coefficients, whereas the
YOCP models based on Wallenborn-Baus’s OCP model
show better agreement with QMD data. The YVM generally
shows reasonable agreement with QMD data at high temper-
atures (except for pure He) because the AA model is more
suitable for elevated temperatures. The differences between
the viscosity coefficients calculated by YVM with and with-
out the consideration of energy level broadening are small
for pure H and generally increase with XHe. The viscosity
coefficient is a difficult quantity to extract the from QMD
simulation because it requires very long time simulations to
get rid of statistical noise. Therefore, the YVM provides, to
some extent, an alternative approach to calculate the viscos-
ity of warm dense H-He systems.
IV. CONCLUSION
We have performed extensive QMD simulations for
investigating the diffusion and viscosity of H-He mixtures in
the WDM regime, which benchmark some standard popular
models. A sufficiently long simulation time was used to
achieve statistically converged results. We carefully exam-
ined the differences in VACFs between the mixtures and
pure hydrogen or helium. The VACFs for the mixtures
exhibit oscillatory features, which however are absent for
pure species. Moreover, at low temperatures, the VACFs of
H in H-He mixtures have a negative correlation region,
which results in an obviously smaller self-diffusion of H in
H-He mixtures compared to that in a pure H system. The
oscillations and negative correlation in VACFs are mainly
due to the bonding effect according to the PDFs. The VACF
data are compared with some fitting models. It is found that
a fitting form with multiple time scales developed by Meyer
et al. can reasonably describe the features of VACFs. Then,
we systematically study the diffusion and viscosity coeffi-
cients of H-He mixtures with various H/He compositions.
The self-diffusion of H and He in H-He mixtures shows very
different behavior with the composition of He: the self-
diffusion of He increases monotonously with increasing XHe,
whereas the self-diffusion coefficients of H generally
decrease with the increase in XHe. The viscosity coefficients
Phys. Plasmas 24, 052903 (2017)
are smaller for the H-He mixtures with a more helium con-
tent. Also, the viscosity coefficients have a local minimum
along temperature in the investigated region, and the location
of the local minimum tends to low temperatures as XHe is
increased. Finally, the QMD diffusion and viscosity coeffi-
cients are used as a benchmark to check some analytical
models based on the one component plasma (OCP) or the
Yukawa one component plasma (YOCP).
This work was supported by the National Natural
Science Foundation of China (Grant Nos. 11674292,
11504352, and 11422432), the Science Challenge Project
(Grant No. JCKY2016212A501), the Science and Technology
Development Foundation of China Academy of Engineering
Physics (Grant Nos. 2013A0101001 and 2015B0102001), the
President Foundation of China Academy of Engineering
Physics (201501032), and the Foundation of Laboratory of
Shock Wave and Detonation Physics of China Academy of
Engineering Physics (Grant No. 9140C670103150C67289).
DJY thanks the support of the Advanced Research Foundation
of NUDT under Grant No. JQ14-02-01.
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