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I.
INTRODUCTION
l li
lin
Fr
en
ke
en
ke
l
tau
e
lin
Fr
ve
r
lin
VA
F
ss
ov
cro
so
al
cr
os
rm
ic
the
er
0.5
0.6
0.7
triple point
0.4
0.6
tin
g
critical point
el
lin
e
Is
o
ch
or
Iso
ne
0.03
3
ln(temperature)
Institute of Metallurgy, Ural Division of Russian Academy of Sciences, 620016 Yekaterinburg, Russia
2
Institute for High Pressure Physics, Russian Academy of Sciences, 142190 Troitsk, Russia
3
L.D. Landau Institute for Theoretical Physics, Russian Academy of Sciences, 142432, Moscow Region, Chernogolovka, Russia
0.8
0.9
1.0
density
2
0.01
= 0.84
T = 0.7
T = 1.1
T = 2
VAF
1E-3
1E-4
time
10
FIG. 2. (Color online) Z(t) at = 0.84 and different temperature. The straight dashed lines represent a1 t3/2 asymptotics
with appropriate amplitude a1 .
II.
accuracy. To optimize the calculation speed and the operational memory we developed the unique parallel algorithm that was built in the DL POLY Molecular Simulation Package [2931].
Simulating LJ particle system we apply pair potential in the standard form, U (r) = 4[(/r)12 (/r)6 ],
where is the unit of energy, and is the core diameter.
In the remainder of this paper we use the dimensionless
= U/, temperature
quantities for LJ fluid: r = r/, U
p
3
RESULTS
SIMUALTION DETAILS
A.
2
3/2
[4(D + )]
.
3
(1)
3
0 .0 2 5
=
=
=
=
=
=
=
=
=
=
0 .0 0 6
0 .0 0 4
1 M D
1 th e o ry
0 .9 th e o
0 .8 5 M D
0 .8 5 th e
0 .8 th e o
0 .7 5 th e
0 .7 5 M D
0 .7 M D
0 .7 th e o
b )
T = 6
T = 4
T = 3
T = 2 .5
T = 1 .5
0 .0 2 0
ry
o ry
ry
o ry
0 .0 1 5
1
0 .0 0 8
a )
0 .0 1 0
ry
0 .0 0 2
0 .0 0 5
0 .0 0 0
0 .0 0 0
0
1 0
1 5
2 0
2 5
3 0
3 5
4 0
te m p e ra tu re
0 .0 0
0 .2 5
0 .5 0
0 .7 5
1 .0 0
d e n s ity
FIG. 3. (Color online) Dependence of VAF long-time tail amplitude a1 for LJ fluid on temperature (a) and density (b). The
bullets represent result of direct estimation from VAF obtained by molecular dynamic simulation and the stars are the result
of calculation by using formula 1.
B.
4
0 .1
1 0 0
T = 4 0
T = 1 1
1 0
T = 8
6
4
0 .0 1
2
4 0
3 0
2 0
1 0
T = 5
0 .7
0 .8
0 .9
1 .0
d e n s it y
V A F
V A F n o r m a liz e d
T = 1 7
T
8
h y d r o d y n a m ic s c a le , r
c ro s s o v e r te m p e ra tu re
a 1(T ) m a x
c ro s s o v e r
5 0
= 1 , T = 4
1 0
4
5
6
te m p e ra tu re
T = 4
1 E -3
T = 3
1
a )
b )
1 E -4
0 .1
0 .1
1
t im e
0 .1
~ t -7
h c p p e r c o la tio n c lu s te r
1 .0
/4
1 0
t im e
= 1
a 1 , = 1
0 .0 0 8
a 2 , = 1
0 .6
0 .4
0 .0 1
0 .2
5
1 0
1 5
2 0
2 5
3 0
3 5
4 0
V A F
te m p e ra tu re
a 1 , = 0 . 8 4
a 2 , = 0 . 8 4
0 .0 0 6
a 1 , = 0 . 7
a 2 , = 0 . 7
0 .0 0 4
V A F
t e t r a h e d r a p e r c o la t io n c lu s te r
ta il c o e ffic ie n ts
tc
0 .8
= 1 , T = 2 0
~ t -3
/2
0 .0 0 2
1 E -3
c )
0 .1
d )
tc
t im e
1 0
1 5
2 0
2 5
3 0
3 5
4 0
te m p e ra tu re
FIG. 4. (Color online) (a) Master curve of VAFs normalised on corresponding a1 (T ) for = 1. The arrow shows VAF at
crossover temperature Th at which the deviation of VAF from leading asymptotics changes its sign. The insert displays the
dependence of crossover temperature on density. (b) Solid line represents VAF at = 1 T = 4; straight line is the t3/2
asymptotics; dashed line is the integral (1) with adjusted cutoff r0 . (c) Solid line represents VAF at rho = 1, T = 20; dashed
and dot-dashed straight lines are the subleasing term a2 t7/4 and leading asymptotics a1 t3/2 respectively. The arrow shows
the time tc corresponding to crossover to Navier-Stokes hydrodynamics regime. The dependence of this time on temperature at
= 1 is shown in the insert. (d) Temperature dependencies of amplitude a2 of subleasing term corresponding to n = 2 in the
expansion (3) in common with the same dependencies for leading term amplitude a1 . The snapshots demonstrate typical spatial
distribution of atoms with hcp and tetrahedral local order at temperatures corresponding to their percolation thresholds.
an t1/2
(3)
n>0
5
6
= 1 ,
= 0 . 9 ,
= 0 . 8 ,
5
= 0 . 9 5
= 0 . 8 5
= 0 . 7 5
D , T
D , T
D , T
D , T
, T
, T
, T
, T
1 0
D ,
D ,
3
2
0 .5
= 1 ,
= 0 . 9 ,
= 0 . 8 ,
0 .4
= 0 . 9 5
= 0 . 8 5
= 0 . 7 5
= 1 .5
= 2 .5
= 4
= 6
= 1 .5
= 2 .5
= 4
= 6
0 .3
0 .2
0 .1
0 .1
a )
b )
2
0 .0
0 .5
1 .0
d e n s it y
te m p e ra tu re
FIG. 5. (Color online) The dependencies of self-diffusion coefficient D and kinematic shear viscosity on temperature (a)
and density (b). The data were taken from [35, 36]. The insert shows difference between density dependence of dynamic and
kinematic viscosity.
DISCUSSION
6
consider typical temperature dependencies for dense fluids and gases. In liquids and dense fluids, shear viscosity
decreases with temperature. The simplest model to show
it is based on the assumption that the fluid flow obeys
the Arrhenius equation for molecular kinetics. That gives
exponential Arrhenius law exp(E/T ) which works
well for dense simple liquids and even for many liquid
metals and alloys. In gases, one can easily find using the Boltsman equation within the -approximation
that = P (for onecomponent gas). Pressure P increases
with temperature like T , while decreases like
p
l/ kB T /m. So increases with temperature in gases
at fixed . In supercritical fluid, distinct liquid and gas
phases do not exist this is some intermediate state.
So it is rather obvious that there the liquid-like decrease
of with temperature turns into the increase of with
temperature like in gases.
Now, we turn to the density dependencies of () and
D() (Fig. 5b). We see that the self-diffusion coefficient
decreases with density monotonously but viscosity has
minimum. This minimum stands behind maximum on
a1 (). It should be noted that minimum on () curve
is the spatial characteristic of kinematic viscosity; the
dynamic viscosity increases with density monotonously
(see the insert in Fig. 5b).
Fluid kinematic viscosity can be qualitatively identified with the resistance to flow and shear under the force
of gravity. This quantity is proportional to dynamic viscosity (resistance to shear stress deformation) and inverse
to the density which promotes flowing. At very low densities, has very large value dilute gas hardly flows
due to gravity. That is why the kinematic viscosity diverges at 0 whereas dynamic viscosity tends to zero.
The decrease of in low density region is mostly due
to the increase as far as is small. But, at intermediate densities, the grow of dominates and so the
starts to increase developing the minimum. Thus we see
that isothermal hydrodynamic anomaly reflects crossover
from dilute gas-like to fluid-like behavior in respect to
flowing features. Note that this anomaly takes place at
low density region.
B.
We must note that crossover from liquid-like to gaslike behaviour expressed by minimum on (T ) (or (T ))
has already been discussed in the context of so called
dynamical (Frenkel) line [26, 39]. It was written that
minimum viscosity locus should coincide with dynamical
crossover line defined by the criterion, 0 where is
the liquid relaxation time and 0 is the minimal period
of transverse quasiharmonic waves. Despite of qualitative soundness of the arguments presented, quantitatively
these lines are located far away from each other (see tau
Frenkel line in Fig. 1). Later, the same authors proposed
another criterium for dynamical crossover line based on
features of VAF at atomic time scales [27]; similar argu-
C.
V.
CONCLUSIONS
7
extremuma (see Fig. 1). These hydrodynamic anomaly
lines separate regions of phase diagram where fluid shows
different behaviour related to collective particle motion.
The comparison of our results with data obtained earlier
suggests that there is no universal criterium describing
the evolution of supercritical fluid system from liquid to
gas. Each property evolves with temperature and density in various way and so there is a continuous multistage
process of transformation from liquid-like to gas-like behaviour.
VI.
ACKNOWLEDGMENTS
This work was supported by Russian Scientific Foundation (grant RNF 14-12-01185). We are grateful to Supercomputer Center of Ural Branch of Russian Academy
of Sciences for access to Uran cluster.