SCIENCE CHINA

Physics, Mechanics & Astronomy

. Review . May 2014 Vol. 57 No. 5: 810–818
Special Topic: Water Science doi: 10.1007/s11433-014-5451-z

Liquid-liquid phase transition in water

SUN ZhaoRu, SUN Gang, CHEN YiXuan & XU LiMei*
International Center for Quantum Materials, Peking University, Beijing 100871, China

Received November 1, 2013; accepted January 21, 2014; published online March 21, 2014

Water shows anomalies different from most of other materials. Different sceniaros have been proposed to explain water anomalies,
among which the liquid-liquid phase transition (LLPT) is the most discussed one. It attributes water anomalies to the existence of a
hypothesized liquid-liquid critical point (LLCP) buried deep in the supercooled region. We briefly review the recent experimental
and theoretical progresses on the study of the LLPT in water. These studies include the discussion on the existence of the first order
LLPT in supercooled water and the detection of liquid-liquid critical point. Simulational results of different water models for LLPT
and the experimental evidence in confined water are also discussed.

liquid-liquid phase transition, liquid-liquid critical point, water anomalies

PACS number(s): 64.70.Ja, 64.30.+t, 64.10.-i

Citation: Sun Z R, Sun G, Chen Y X, et al. Liquid-liquid phase transition in water. Sci China-Phys Mech Astron, 2014, 57: 810–818, doi: 10.1007/s11433-014-
5451-z

1 Introduction tracting extensive attentions.

Besides density anomaly, water also shows other thermo-
Water is one of the most abundant liquids on Earth. It plays dynamic anomalies [8–10,13,14,16–20], such as isothermal
a crucial role in biological, environmental, geological and compressibility KT related to volume fluctuation, (δV)2  =
chemical processes [1–10], which affect every aspect of our VkB T KT , specific heat C P related to entropy fluctuation,
life. Although consisting of only one oxygen and two hydro- (δS )2  = NkBC P , and thermal expansion coefficient α re-
gen atoms, water is perhaps the most complex liquid in the flecting the correlations between entropy and volume fluctu-
universe. For instance, it has more than 60 anomalies includ- ations, (δS δV) = VkB T α [8,9]. For “normal” liquids, the
ing having more than sixteen crystalline phases, which is very fluctuation of volume and entropy decreases as temperature
different from “normal” liquids [8,9,11]. The particular prop- decreases, however, for water at a certain temperature range,
erties of water that are different from most of other materials these fluctuations increase as temperature decreases [13,17].
are the crucial reason for life prosperous on Earth [7–9,12]. For instance, at atmospheric pressure, KT increases upon
Among all water anomalies, the density anomaly is the most cooling for T < 46◦ C (Figure 1). Similarly, C P increases
well-known one. That is, different from the density behav- upon cooling for T < 35◦ C, and the value of α becomes
ior of most of other materials, the density of bulk water negative indicating volume expansion below 0◦ C (Figure 1).
shows a maximum at temperature 4◦ C under ambient con- These anomalies become more pronounced in the deep su-
ditions (Figure 1), leading to lower density in the solid phase percooled region and tend to diverge at low temperatures.
(e.g., ice floating on top of liquid water) [13–15]. This phe- Different scenarios [21–23] have been proposed to explain
nomenon has been observed centuries ago, however, the rea- the origin of such anomalies, among which the liquid-liquid
son why it happens remains controversial, thus has been at- phase transition (LLPT) scenario [23] is currently the most
*Corresponding author (email: [email protected])
discussed one. According to this scenario, the existence of


c Science China Press and Springer-Verlag Berlin Heidelberg 2014 phys.scichina.com link.springer.com
 Sun Z R, et al. Sci China-Phys Mech Astron May (2014) Vol. 57 No. 5 811

a liquid-liquid critical point (LLCP) is the source of water

anomalies [9,10,23–27]. We note that, besides water, other 300
materials such as, Ge, Si, P, Ce-based alloys and the yttrium TM
oxide-aluminum oxide system [28–36], also exhibit water- 0 Stable water
like anomalies. Therefore, the study of the LLPT in water
is not only important for the understanding of the origin of
TH
water anomaly, but also important for our understanding of
other materials sharing similar features. Supercooled water

T (°C)
200

T (K)
(Pc, Tc)

2 Liquid-liquid phase transition

−100
“No man’s land”
TX
One experimental evidence linked to the first-order LLPT LDL HDL

is the observation of two amorphous phases of water, the Ultraviscous

high-density amorphous (HDA) and the low-density amor-
phous (LDA) water. By compressing Ice Ih at 77 K, Mishima Tg

et al. [37,38] found an abrupt change in volume, that is, wa- Glassy water 100

ter undergoes a first-order-like phase transition from LDA to LDA HDA

HDA upon compression (Figure 2). The LLPT hypothesis −200

0 0.2
is that this first-order phase transition line in the amorphous
P (GPa)
state of water can extend to lower pressure and higher tem-
perature region and terminate at a LLCP as shown in Figure 2
Figure 2 The phase diagram of water (adapted from ref. [25]). A first order
[23–26]. LLPT line is shown between HDL and LDL. The LLPT ends with a LLCP
Using molecular dynamics simulations on ST2 model of at Pc , T c . T m , T g and T H represent the melting temperature, glass transition
water, Poole et al. [23] investigated the structure and equation temperature, and homogeneous nucleation temperature, respectively.
of state for supercooled bulk water. They found a first-order
phase transition between two liquids, the low density liq- in other classical water models (e.g. TIP4P, TIP5P) [24,45–
uid (LDL) and the high density liquid (HDL), above the 52], Monte Carlo simulation on lattice model [53,54], and ab
LDA-HDA transition. The HDL and LDL are suggested to initio simulations [55,56] as well as thermodynamic models
correspond to the two experimentally observed glass states for supercooled water [57–62]. The location of the LLCP for
of water, HDA and LDA, respectively [37–44]. This LLPT different models is summarized in Table 1. It should be men-
terminates at a liquid-liquid critical point (LLCP) located tioned that not all water models exhibit LLPT, though they
at T c ∼ 235 K and Pc ∼ 200 MPa (Figure 2) [24]. Be- display water anomalies [63–65].
sides the study on ST2 water, the LLPT was also investigated Structural difference between the two phases of su-
percooled water is observed experimentally [17,25,66–72].
Simple liquid
Simple liquid For instance, using neutron diffraction experiment, Soper
et al. [66] verified the structure transformation in liquid water
from low density water (LDW) to high density water (HDW)
ρ

4°C 4°C α=0 upon compression. By comparing the oxygen-oxygen radial

Water Water distribution function shown in Figure 3(a), they found that the
main difference between LDW (density 0.0295 molecules per
T T
Å3 ) and HDW (0.0402 molecules per Å3 ) lies in the second
shell. Though having the same overall orientational symme-
Water
try, the second shell√of LDW sits at approximately the tetra-
Simple liquid
Water hedral distance (∼ 8/3 times the near neighbor distance),
while the second shell of HDW has substantially collapsed to
KT

cp

a point where it is almost coincident with the first shell, lead-

35°C
ing to the break of hydrogen bonds in HDW (Figure 3(b)).
46°C Simple liquid Using similar techniques mentioned above, Bellissent-
T T Funel et al. [41,42] showed that the structure of liquid water
Figure 1 Anomalous thermodynamic properties of water compared to nor-
changes to the HDA structure when water is cooled at high
mal liquids (adapted from ref. [8]). A schematic comparison of the isobaric pressures, while it changes to the LDA structure when wa-
temperature dependence of the density ρ, thermal expansion coefficient α, ter is cooled at low pressures, indicative of the continuation
isothermal compressibility KT , and isobaric heat capacity c p for water and a of the LDA-HDA transition to the LLPT as shown in Fig-
simple liquid. ure 2. This is consistent with the results obtained by using
812 Sun Z R, et al. Sci China-Phys Mech Astron May (2014) Vol. 57 No. 5

the transition between VHDA and HDA in experiment. Us-

Table 1 Critical temperature T c , pressure Pc and density ρc reported using
different water potentials
ing X-ray diffraction, Loerting et al. found that the transition
between HDA and VHDA is continuous, while the transi-
Potential T c (K) Pc (MPa) ρc (g/cm3 ) tion between HDA and LDA is reversible and discontinu-
ST2 [24,45] 235 200 1 ous [74,75,84–86]. This suggests that the transition between
SPC/E [45] 160 200 1.07 the HDL and LDL is a first-order LLPT, while the transi-
TIP5P [46] 217±3 340±20 1.13±0.04
tion between HDL and VHDL is a continuous one, thus the
existence of a multiple liquid-liquid transition is unfavor-
ST2 [47] 245 180 0.94
able [87].
TIP5P-E [49] 210 310 1.09
TIP4PEW [50] 210 310 1.09
3 Detection of the LLCP from supercritical re-
ST2 [51] 237±4 167±24 0.99±0.02 gion
TIP4P2005 [52] 193 135 1.012
WAIL [55] 207 50 Since the prediction of the LLPT in the supercooled liquid of
ST2 water [23], it attracts extensive attentions to experimen-
tally verify the existence of the LLCP [25,26,88–90]. How-
ever, this is challenging because the hypothesized LLCP of
(a)
3
liquid water is located in the deep supercooled region of the
HDL
LDL phase diagram below the homogeneous nucleation line. This
2 region is also called “no-man’s land” [25,26], which is unable
goo

to reach for bulk liquid because either heating amorphous

1 ice from temperatures below the crystallization temperature
T X or cooling liquid water from temperatures above the ho-
0
3 4 5 6 7 mogeneous nucleation temperature T H leads to spontaneous
Å crystallization (Figure 2). Therefore, alternative methods to
(b)
detect the LLCP are necessary.
Using molecular dynamics simulations on a ramp model
with a LLCP, Xu et al. [91–94] investigated the critical phe-
nomenon in the supercritical region. They found that, for wa-
ter, when the system is cooled isobarically along a path in the
supercritical region (below the liquid-liquid critical pressure
Pc as shown in Figure 4), the thermodynamic response func-
HDL LDL tions undergo a continuously change from the values char-
Figure 3 (Color online) Structural difference between high density water acterizing the high-temperature phase (HDL) to those char-
and low density water. (a) Radial distribution functions of oxygen atoms for acterizing the low-temperature phase (LDL). The thermody-
HDL and LDL. (b) Spatial density functions for HDL and LDL. This figure namic response functions, such as isobaric heat capacity C P
is adapted from ref. [66] and isothermal compressibility KT , show maxima upon cool-
ing at constant pressure. Remarkably, these maxima are still
dilatometry and powder x-ray diffractions [73,74]. Loerting prominent far below the critical pressure Pc [47,95–98]. The
et al. [73–75] studied the reversible transformation of HDA loci of the response functions, e.g., C Pmax and KTmax as shown
and LDA by controlling pressure. They showed the transfor- in Figure 4, asymptotically approach one another and con-
mation from HDW to LDW upon decompression at 140 K, verge to a line (also called the Widom line) as the LLCP is
suggesting a first-order transition in the ultraviscous liquid approached from the supercritical region [91].
region just above the glass transition temperature. As temperature decreases, the Widom line converges to the
Recently, a new form of amorphous water, very high den- LLCP, where the correlation length as well as the response
sity amorphous (VHDA) ice, is observed in experiments and functions diverges. The temperature at which different re-
simulations by compressing HDA [76–81]. A new liquid sponse functions converge gives an upper limit of the critical
state, very high density liquid (VHDL) corresponding to the temperature. Thus, by tracing the loci of response function
observed VHDA, and the possibility of a second liquid-liquid extrema from supercritical region, that is, the Widom line,
transition between VHDL and HDL were proposed and in- one can locate the LLCP. In the cases of water and other ma-
vestigated [50,82,83]. However, using molecular dynamics terials sharing water-like anomalies, this is very important be-
simulations on pair potentials Buldyrev et al. [82] found that cause the hypothesized LLCP is typically buried deep in the
the structural difference between VHDL and HDL is much supercooled region [23,99], which is difficult to detect along
less pronounced than that between HDL and LDL. Simi- the coexistence line in the two-phase region but is possible to
larly, the transition between VHDL and HDL depends on locate along the Widom line in the supercritical region .
 Sun Z R, et al. Sci China-Phys Mech Astron May (2014) Vol. 57 No. 5 813

locally tetrahedrally coordinated hydrogen-bond network is

ST2 potential
300 not fully developed, while the low-temperature liquid cor-
responds to the LDL where the more open, locally ice-like
200 C hydrogen-bond network is fully developed. As the temper-
ature lowers along constant pressure P, the cusplike fragile-
P (MPa)

to-strong transition observed in experiment occurs when the

100
Widom line is crossed in the one-phase region [91]. Thus,
KT
max
this dynamic crossover line (the loci of the dynamic crossover
0
max
temperature T L ) can be considered as the extension of the
Cp
liquid-liquid transition line into the supercritical region (Fig-
220 240 260 280 300 ure 6), which is also predicted by MD simulations of wa-
T (K) ter [91]. These results provide experimental evidence for the
LLPT with a LLCP estimated at Pc = (1600 ± 400) bar and
Figure 4 (Color online) Phase diagram of ST2 potential (adapted from T c = (200 ± 10) K, the terminal point of the Widom line (Fig-
ref. [91]), showing the coexistence of LLCP at Pc ≈ 186 MPa and T c ≈ 246
K, the line of isobaric specific heat maxima C max
ure 6).
P , the line of isothermal
compressibility maxima KTmax . According to the experimental measurements on confined
water in the supercritical region [102,105–107,109–111], if a
LLCP exists, we are able to trace this LLCP along the Widom
Across the Widom line, the structure response function line. However, one important question is to what extent the
also changes. Xu et al. [100] showed that the populations phase diagram of confined water is a good representation of
of LDL-like and HDL-like structures change upon cooling that of bulk water? As we know that both the confinement
at constant pressure (Figure 5). The maximal change in lo- and the surface chemistry may play a role in the phase dia-
cal structures occurs at the temperature where the Widom gram of confinement geometries [118–132]. Xu et al. [133]
line is crossed, which is confirmed by IR-fred, Nuclear Mag-
netic Resonance (NMR), and Quasi-Electric Neutron Scatter-
(a)
ing (QENS) experiments on confined water [101,102]. Sim- 0.8 HDA-like
ilarly, Wikfeldt et al. [103,104] found a strong dependence
with the HDL structure dominating (3:1 of HDL vs. LDL)
Relative population

under ambient conditions in agreement with estimates from 0.6

analysis of X-ray spectroscopy measurements, while the state

points with 1:1 population of HDL and LDL coincide with
0.4
the Widom and coexistence lines in the model, where indeed
fluctuations are expected to be maximal [100].
0.2 LDA-like

4 Dynamic crossover in confined water 150 200 250 300 350 400
T (K)
As the instability of the liquid results from its crystallization,
the direct experimental confirmation of the existence of the (b)
LLCP in bulk water, especially in the “no man’s land” re-
Derivative of relative population

0.01
gion between the homogeneous nucleation temperature of ice HDL-like
T H ≈ 232 K and the glass transition temperature T g ≈ 136 K
for ambient pressure (Figure 2), remains an issue. However,
by confining water in narrow nanopores, the liquid state can 0 Tmax

be studied down to very low temperatures. This is because

confinement lowers the crystallization temperature of water, LDL-like
which makes it possible to study the structural transformation
−0.01
of the cooled water in the stable state.
Recent experiments on MCM-41 nano-confined water by
QENS and NMR [102,105–112] studied the crossover in the 150 200 250 300 350 400
T (K)
supercritical region. Liu et al. [106,113–117] observed a cus-
Figure 5 (Color online) IR-fred experiment results for structural change
plike dynamic transition (“fragile”) behavior at high temper- of confined water upon crossing the Widom line (adapted from ref. [100]).
atures to Arrhenius (“strong”) behavior at low temperatures, (a) Relative population of HDA-like and LDA-like water species with re-
by confining water in nanopores of silica glass [107]. This spect to temperatures. (b) Derivative of the relative population for HDA-like
transition is also called fragile-to-strong (FS) transition. The and LDA-like water species. The maximal change occurs at the temperature
high-temperature liquid corresponds to the HDL where the T max where the Widom line is crossed.
814 Sun Z R, et al. Sci China-Phys Mech Astron May (2014) Vol. 57 No. 5

−120 −100 −80 −60 −40 −20 0 (°C) ter (Figure 7). In addition, Kesselring et al. [141,142] demon-
1.25
2.5 2.22 kbar 2.42 kbar 2.74kbar
ICE II ICE III 1.20
Liquid
1.15
2.0 ICE I

ρ (g/cm3)
L-L coexistence line? 1.10
Pressure (kbar)

1.05
1.5
1.00
TMD TM
0.95
1.0 TL
TX 0.90

TH 0.03 0.06 0.09 0.12 0.03 0.06 0.09 0.12 0.03 0.06 0.09 0.12
0.5 Q6

Figure 7 (Color online) Reversible free energy surface in ST2 water

0.0 (adopted from ref. [139]) in the (ρ, Q6 ) plane at 228.6 K, 2.42 kbar. Each
140 160 180 200 220 240 260 280
contour line represents 1 KB T . Note the presence of two basins correspond-
T (K)
ing to the LDL and HDL.
Figure 6 (Color online) Phase diagram in the P-T plane (adapted from
ref. [107]), showing the pressure dependence of the fragile-to-strong dy- strated the existence of LLPT of ST2-RF with the “phase
namic transition temperature, T L . The homogeneous nucleation temperature
flipping” between the HDL and LDL on microseconds time
line, denoted as T H , crystallization temperatures of amorphous solid water,
denoted as T X , and the temperature of maximum density line, denoted as scales. For the missing minimum of LDL in the energy land-
TMD are also shown. scape by ref. [134], Liu et al. [137] point out that the con-
ducting boundary condition for Ewald summation used by
studied the anomalous behavior of nano-confined mW wa- ref. [134] leads to rapid crystallization to a high-density ice
ter by removing the surface interaction. They found that the phase which causes the LDL beyond its limit of stability un-
density anomaly in confined water follows the same trend as der the state conditions investigated by Chandler [134].
that of bulk water, indicating that confinement itself may not To summarize, the simulation studies and experimental re-
significantly affect density anomaly. However, confinement sults of water showed some supportive evidence for the ex-
smears first-order transitions, thus direct evidence of a first- istence of LLPT [75,103,143–145]. However, the discussion
order LLPT in confined water may not be found in strongly on the LLPT of water may continue until we have more di-
confined water, even though it does not mean that there is no rect experimental proofs. More advanced experimental tech-
LLPT without well-defined first-order structural transforma- niques are still needed to detect the “no-man’s land” region
tion. and directly verify the hypothesized LLCP of water located
in supercooled region.

5 Recent progresses and prospects

This work was supported by the National Natural Science Foundation of
Recently, Limmer and Chandler have questioned the LLPT China (Grant Nos. 11290162/A040106, 10974238, 11274012, 91021007
hypothesis in water, especially in ST2 water with Ewald and 11174006) and the National Basic Research Program of China (Grant
summation (ST2-Ew) treatment of long-ranged Coulomb No. 2012CB921404).
forces [134]. Using Monte Carlo (MC) umbrella sampling,
they calculated the free energy landscape as function of den-
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