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PRL 111, 145901 (2013) PHYSICAL REVIEW LETTERS 4 OCTOBER 2013

‘‘Liquid-Gas’’ Transition in the Supercritical Region: Fundamental Changes

in the Particle Dynamics
V. V. Brazhkin,1 Yu. D. Fomin,1 A. G. Lyapin,1 V. N. Ryzhov,1 E. N. Tsiok,1 and Kostya Trachenko2
1
Institute for High Pressure Physics RAS, 142190 Troitsk, Moscow, Russia
2
South East Physics Network and School of Physics, Queen Mary University of London,
Mile End Road, London E1 4NS, United Kingdom
(Received 13 May 2013; published 4 October 2013)
Recently, we have proposed a new dynamic line on the phase diagram in the supercritical region, the
Frenkel line. Crossing the line corresponds to the radical changes of system properties. Here, we focus on
the dynamics of model Lennard-Jones and soft-sphere fluids. We show that the location of the line can be
rigorously and quantitatively established on the basis of the velocity autocorrelation function (VAF) and
mean-square displacements. VAF is oscillatory below the line at low temperature, and is monotonically
decreasing above the line at high temperature. Using this criterion, we show that the crossover of particle
dynamics and key liquid properties occur on the same line. We also show that positive sound dispersion
disappears in the vicinity of the line in both systems. We further demonstrate that the dynamic line bears
no relationship to the existence of the critical point. Finally, we find that the region of existence of
liquidlike dynamics narrows with the increase of the exponent of the repulsive part of interatomic
potential.

DOI: 10.1103/PhysRevLett.111.145901 PACS numbers: [Link], 62.50.
p, [Link]

A liquid near the melting curve has much more in The condition

0 is related to the microscopic dy-
common with a solid than with a gas. For example, a liquid namics at the Frenkel line, although determining the line
supports transverse collective modes at high frequency that using this condition can be done in an approximate way
endow the liquid with shear rigidity at that frequency only. When
and
0 become comparable, particle motion
[1–6]. To denote this state of the liquid, the term ‘‘rigid may not be uniquely separated into oscillations and jumps.
liquid’’ was proposed [7]. In the rigid liquid, particle Besides, the separation of quasiharmonic oscillations in a
motion consists of fairly rare jumps and oscillatory motion liquid into longitudinal and transverse is not rigorously
between the jumps. This is reflected in relaxation time
, defined at high temperature. For this reason, an important
the time between two consecutive particle jumps at one question remains about how to rigorously define the dra-
point in space, being larger than the shortest vibration matic crossover at the Frenkel line.
period
0 (
0 ¼ 2=!0 , where !0 is the maximal fre- The main aim of this work is to identify the dynamic
quency of transverse modes). This description of liquid crossover on the basis of uniquely defined physical char-
dynamics has been proposed by Frenkel [8], and was acteristics: velocity autocorrelation function ZðtÞ and
subsequently rediscovered and used in a number of papers mean-square displacement hr2 ðtÞi. Among other proper-
(see, e.g., Refs. [9–11]). ties, we discuss positive sound dispersion and its behavior
Recently, we have shown that the condition

0 at the Frenkel line.
defines a line, the Frenkel line on the phase diagram that Velocity autocorrelation function (VAF) ZðtÞ is
separates the state of the rigid liquid from the ‘‘nonrigid’’ defined as
gaslike fluid [7,12–14]. Crossing the Frenkel line on tem-
ZðtÞ ¼ hvð0ÞvðtÞi: (1)
perature increase results in the disappearance of shear
rigidity at all frequencies, specific heat reaching 2kB , It is well known that ZðtÞ for the gas is a monotonically
and, importantly, the qualitative change of temperature decaying function, whereas for solids and liquids near
dependence of key system properties [7,12,13]. The line melting it has both oscillatory and decaying components
is universal: it separates two states at arbitrarily high (see Refs. [16,17] and references therein). ZðtÞ for various
pressure and temperature, and exists in systems where liquids was studied in detail. In the early paper [18], it was
liquid-gas transition is absent. found that ZðtÞ for supercritical Lennard-Jones (LJ) fluids
A particularly interesting consequence of crossing the may contain both liquidlike and gaslike features, although
Frenkel line from above is the appearance of positive sound this fact did not attract subsequent attention. Hiwatari and
dispersion (PSD) [7], the increase of the speed of sound at coauthors have found that depending on the density, ZðtÞ is
high frequency [4–6]. Recently, an attempt was made to qualitatively different in soft-sphere (SSp) fluids [19]. This
locate the dynamical line on the basis of molecular dy- was followed by the attempt to relate the oscillations of
namics simulations of PSD for supercritical Ar [15]. ZðtÞ and atomic vibrations in SSp fluid [20]. No detailed

0031-9007=13=111(14)=145901(5) 145901-1 Ó 2013 American Physical Society

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PRL 111, 145901 (2013) PHYSICAL REVIEW LETTERS 4 OCTOBER 2013

1 .0
analysis of ZðtÞ was performed up to date to distinguish the 0.2 T=10
(a) T=15
dynamics between systems in the liquid and gaslike fluid 0.8
0.1 T=20
states.

< v (0)v (t ) >

0.6 0.0
T=30
Similarly, the time dependence of the mean-square dis- T=40
placement hr2 ðtÞi is qualitatively different in liquids and 0.4 -0.1 T=50
solids. Consequently, the behavior of hr2 ðtÞi at long times 0.2 0.05 0.10 0.15
T=60
T=70
can be used to calculate the diffusion coefficient in liquids
0.0
and determine melting and crystallization or vitrification
points. At the long time limit, the diffusion coefficient D is 0.00 0.05 0.10 0.15 0.20 0.25
related to the mean-square displacement as D ¼ hr2 ðtÞi=6t. Time
Evidently, the time dependence of hr2 ðtÞi in liquids and 10
100
gases should be different at short times, yet no detailed (b)

2
(1/6D)d < r >/dt
analysis of hr2 ðtÞi was performed in this time regime. 5 10

<r >
We note that the second time derivative of hr2 ðtÞi is

2
1
0

2
proportional to ZðtÞ. Indeed, using the well-known 0.1
equation (see, for example, Ref. [16]) -5 0.01 Time
Zt
hr2 ðtÞi ¼ 6 ðt
sÞZðsÞds; -10
0.01 0.1 1 10
0
0.1 1
one has Time
@2 =@t2 hr2 ðtÞi ¼ 6ZðtÞ: (2) 1.0
0.1 n =12 T=0.57
Therefore, the analysis of the second derivative of hr2 ðtÞi T=1
T=2
and ZðtÞ is formally equivalent. < v (0)v (t ) > T=4
0.0
We have studied LJ liquid and SSp liquids with different 0.5 T=6
exponent n and in a wide range of parameters. The phase T=8
T=10
diagram of the SSp system corresponds to the equation -0.1 T=20.57
0.1 0.2 0.3
 ¼ 3 ð"=kB TÞ3=n ¼ const. Here, the values of  ¼ 0.0
2:33 for n ¼ 6;  ¼ 1:15 for n ¼ 12, and  ¼ 0:942 for (c)
n ¼ 36 have been calculated using the data obtained in
0.0 0.2 0.4 0.6
Ref. [21]. In the simulations of the LJ liquid, the system Time
size varied depending on the density reaching 4000 parti-
1.0
cles at the highest density. The equations of state were 0.02 T=2.06
n =36
integrated using the velocity Verlet algorithm; the systems T=4.06
0.00 T=8.06
were simulated in the number of particles-volume-energy T=16.06
< v (0)v (t ) >

ensemble. The usual equilibration and production runs -0.02 T=24.06

0.5
consisted of 1:5  106 steps, with the time step of 0.001 T=30.06
T=34.06
in LJ units. The SSp system consisted of 1000 particles, -0.04
T=40.06
with the time step of 0.0005 in reduced units. The follow- 0.0 0.1 0.2
ing critical parameters, averaged from literature sources, (d)
0.0
were used for the LJ system: c ¼ 0:314, Tc ¼ 1:31, and
Pc ¼ 0:13. The temperature corresponding to cV ¼ 2:0 0.0 0.1 0.2 0.3
Time
was determined from the dependence of the isochoric
heat capacity on temperature along the isochors. The dis- FIG. 1 (color online). Time dependences of VAF ZðtÞ for the LJ
persion of the longitudinal collective excitations !L ðqÞ has liquid (P ¼ 200, pressure is in the LJ units) (a) SSp systems with
been calculated for both LJ and SSp systems using the n ¼ 12 (c) and n ¼ 36 (d) ( ¼ 1, density is in the standard soft-
same approach as in Ref. [15]. The dispersion has been sphere units), and the second derivative of the mean-square dis-
analyzed at different temperatures along several isochors. placement (b) for the LJ liquid (P ¼ 200, pressure is in the LJ
We analyze the temperature dependence of ZðtÞ and units). Insets in (a),(c), and (d) show detailed pictures; inset in panel
hr2 ðtÞi along several isochors and isobars. We show ZðtÞ, (b) shows time dependences of mean-square displacement. The
hr2 ðtÞi and its second derivatives at several temperatures for vertical arrows correspond to the disappearance of oscillations.
both LJ and SSp systems in Fig. 1, and observe that they
qualitatively change with temperature. ZðtÞ is oscillatory at More specifically, the presence of both decreasing and
low temperature, but decreases monotonically at high. We increasing parts of ZðtÞ implies that the projection of
propose that this qualitative change can be used as a velocity on the direction of motion changes its sign on
mathematically rigorous criterion to define the Frenkel line. average, i.e., it signifies the presence of an oscillatory

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PRL 111, 145901 (2013) PHYSICAL REVIEW LETTERS 4 OCTOBER 2013

component of motion. Consequently, the temperature at system at high pressure, the temperature of the Frenkel
the Frenkel line can be naturally chosen at the ‘‘critical’’ line exceeds the melting temperature by a factor of 4–5 on
temperature at which minima and maxima of the function the isobar.
in question disappear. We observe that the second deriva- Importantly, we observe in Fig. 2(b) that the calculated
tives of hr2 ðtÞi have the same functional time dependence line perfectly agrees with all other experimental and theo-
as ZðtÞ, consistent with Eq. (2). The coincidence of retical criteria of the Frenkel line proposed previously [7].
@2 =@t2 hr2 ðtÞi and ZðtÞ and their temperature evolution We therefore find that the phase diagram of the LJ system
serves as a self-consistency check in our calculations. contains a sharp boundary separating the states of the rigid
The line corresponding to the change of dynamics liquid and nonrigid gaslike state.
according to the above criterion is shown in Fig. 2. For both LJ and SSp systems, we study the dispersion of
In Fig. 2(a) we observe that the temperature of the calcu- the longitudinal collective mode !L ðqÞ. We detect PSD in
lated line is about 1.5–1.7 times lower than the line both LJ and SSp systems at low temperature, and find that
approximately defined from one of the previous criterion, PSD disappears on temperature increase quite close to the


0 . The difference is related to the uncertainty in calculated Frenkel line. The existence of PSD in the SSp
determining high-frequency longitudinal and transverse system at low temperatures (Fig. 3) is an important result.
oscillations on the basis of visual analysis of trajectories It means that the presence or absence of PSD is not related
made in Refs. [7,12,13]. We also note that for the LJ to the continuation of the boiling curve and the critical
point whatsoever, contrary to the previous discussions
100 Calculation for LJ liquid [6,15]. Rather, PSD and its crossover are purely dynamic
Tm Liquid
in origin.
liquid-gas
Definition of Frenkel line In Figs. 4 we show the calculated Frenkel line on the
from PRE (2012) (τ =τ0)
II I phase diagrams for the SSp system with n ¼ 6, 12, and 36.
from < v (0)v (t ) >
We note that the terms gas and liquid are not appropriate
T/Tc

10 2 2
and d < r >/dt
2

(calculation at P =const) for the SSp system with no vapor-liquid coexistence curve;
from < v (0)v (t )> nevertheless, the qualitative change of the particle dynam-
(calculation at ρ =const)
Solid ics from the liquidlike to gaslike takes place in this system
1
(a)
1 10 100 1000
25 (a) ρ =1, T=2
P/Pc
20
100
Calculation for LJ liquid
Tm Liquid 15
ω

10
Frenkel line
cV =2kB 9
Vs =2Vth
10
CL
8
loss of PSD II I
7
10 Experiment 5
T/Tc

Ar, cV =2kB 6 Q
Ar, Vs~2Vth 0 1 2 3 4
N2, Vs~2Vth 0
Solid 60
(b)
1 50 ρ =1, T=40
(b)
40
ω

1 10 100 1000
P/Pc 30

20
FIG. 2 (color online). (P, T) phase diagram of the LJ liquid in
the relative critical coordinates. Panel (a) compares previous 10
criteria of the Frenkel line from Ref. [7]. The shaded region 0
covers all experimental and calculated curves from Ref. [7], 0 1 2 3 4
together with the Frenkel line calculated in this work. Panel Q
(b) compares positions of the Frenkel line found in this work
with calculated and experimental curves and points defined by FIG. 3 (color online). Dispersion curves !ðQÞ (blue circles
different criteria (see Ref. [7] and references therein). Black with bars) for the simulated soft-sphere systems with n ¼ 12 at
circles correspond to the disappearance of PSD under heating low (a) and high (b) temperatures. The inset shows the longitu-
calculated in the present work. Red dashed line in panel (b) dinal velocity CL ¼ !=Q vs wave vector Q dependence for the
shows the dynamic line proposed in Ref. [15]. In all cases I case (a), illustrating the PSD. Thick solid lines in panels (a) and
corresponds to the rigid liquid state and II to the nonrigid gaslike (b) and the triangle in the inset correspond to the adiabatic sound
state. velocity at Q ¼ 0.

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(a) n =6 Interestingly, the increase of the exponent n results in the

II narrowing of the P, T region where the quasiharmonic
10
rigid liquid exists. For the SSp system, the ratio of the
Temperature

I temperature at the Frenkel line to that at the melting line

1 on the isobar is 11.2 for n ¼ 6; 5.3 for n ¼ 12, and 2.2 for
Liquid n ¼ 36 (see Fig. 4). This behavior is consistent with our
earlier findings [7,12] that for n  50–60, the line corre-
0.1 sponding to cv ¼ 2kB moves under the melting line; i.e.,
Solid the region of existence of quasiharmonic rigid liquid above
10 100 the melting line disappears. It should be mentioned that for
Pressure large values of exponents governing the repulsion n the
criterion of the dynamic crossover based on ZðtÞ no longer
100
(b) n =12 applies. The oscillation amplitude becomes extremely
II
small for n > 50, and the oscillations become irregular
I
Temperature

themselves. Physically, this means that particles of the fluid

10 Liquid spend most of their time outside the field of action of the
Tm potential, and move ballistically as in a gas. This is also the
1
cV=2k B reason for a slight discrepancy of the Frenkel line calcu-
Frenkel line
from < v (0)v (t ) >
lated from ZðtÞ and cv ¼ 2kB for n ¼ 36 [see Figs. 4(c)].
Solid
2 2
from d < r >/dt
2
As discussed earlier [7,12–14], the Frenkel line and
linear fit
0.1 related physics bear no relationship to various versions of
10 100 1000 a ‘‘thermodynamic’’ continuation of the boiling line, the
Pressure
Widom line. This is particularly apparent in our finding
100 (c) n =36 that the dynamic crossover at the Frenkel line, including
II I the crossover of PSD, exists in the SSp system where the
liquid-gas transition and the critical point are absent
Temperature

10 altogether. Furthermore, as is seen in Fig. 2(b), the

Liquid
Frenkel line for the LJ system lies in the range of tempera-
tures that are lower than the critical temperature, and starts
1 from the boiling region at temperature T  0:7–0:8Tc .
Solid
In relation to this, we note that at temperature higher
than 0:75–0:85Tc , a fluid, as a rule, does not possess a
10 100 1000 cohesive state (the dependence of the free energy on vol-
Pressure
ume has no minimum), implying that the upper region of
FIG. 4 (color online). (P, T) phase diagrams of the simulated the boiling curve should be rather considered as the gas-gas
soft-sphere systems with n ¼ 6 (a), n ¼ 12 (b), and n ¼ 36 (c), transition (see, e.g., Ref. [24]).
comparing the location of the Frenkel lines with the lines As mentioned above, there has been a recent attempt
calculated from the criteria cV ¼ 2kB . The black circle corre- [15] to determine the dynamic line for supercritical Ar on
sponds to the calculated in present work disappearance of PSD the basis of molecular dynamics simulations of the PSD [it
under heating. In all cases I corresponds to the rigid liquid state is shown in Fig. 2(b) as a dashed line]. The line proposed in
and II to the nonrigid gaslike state. Ref. [15] is notably different from the Frenkel line calcu-
lated in our work. The PSD is not a fundamental phenome-
too. Importantly, we observe that the dynamic crossover non on its own: as was discussed a long time ago [8], the
line calculated on the basis of ZðtÞ perfectly coincides with existence of PSD is simply the result of the presence of
the line that corresponds to cv ¼ 2kB , one of the main high-frequency transverselike collective excitations. These
criteria of the Frenkel line [7]. Indeed, as discussed earlier excitations disappear at the Frenkel line. The disappear-
[7,22,23], liquid specific heat reduces from 3kB to 2kB ance of PSD is therefore only one of many consequences of
when

0 , corresponding to the potential energy of the dynamic crossover at the Frenkel line rather than its
shear modes becoming zero due to the loss of shear modes origin. The PSD in the SSp system additionally points to
at all frequencies. The perfect coincidence of the crossover the inconsistency of using the combination of thermody-
lines calculated on the basis of ZðtÞ and cv ¼ 2kB serves as namic continuation of the boiling line. Moreover, quanti-
an important self-consistency check of our theory of the fying PSD in molecular dynamics simulations suffers from
dynamic crossover at the Frenkel line. We also note that the large uncertainty, and cannot be, in our view, used as a
calculated line corresponds to the appearance of PSD at convenient criterion to establish the location of the
low temperature [see Fig. 4(b)]. dynamic line. It suffices to note that calculated parameters

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PRL 111, 145901 (2013) PHYSICAL REVIEW LETTERS 4 OCTOBER 2013

at which PSD disappears for Ar, calculated by the same [5] F. Gorelli, M. Santoro, T. Scopigno, M. Krisch, and
authors [6,15], differ widely. Indeed, at T ¼ 3:8Tc , PSD G. Ruocco, Phys. Rev. Lett. 97, 245702 (2006).
disappears at P < 80Pc according to Ref. [6], and at [6] G. G. Simeoni, T. Bryk, F. A. Gorelli, M. Krisch, G.
P < 30Pc according to Ref. [15]. Ruocco, M. Santoro, and T. Scopigno, Nat. Phys. 6, 503
(2010).
In summary, we proposed a criterion to locate the
[7] V. V. Brazhkin, Yu. D. Fomin, A. G. Lyapin, V. N. Ryzhov,
dynamic Frenkel line on the phase diagram of fluids that and K. Trachenko, Phys. Rev. E 85, 031203 (2012).
is both mathematically rigorous and convenient for simu- [8] J. Frenkel, Kinetic Theory of Liquids, edited by R. H.
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systems coincides with various experimental data for rare- Press, Oxford, 1947).
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been supported by the RFBR (Grants No. 11-02-00303, [15] F. A. Gorelli, T. Bryk, M. Krisch, G. Ruocco, M. Santoro,
No. 11-02-00341, and No. 13-02-01207) and by the and T. Scopigno, Sci. Rep. 3, 1203 (2013).
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EPSRC. (Elsevier, Amsterdam, Boston, 2007).
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