An analysis of fluctuations in supercooled

TIP4P/2005 water
Cite as: J. Chem. Phys. 138, 184502 (2013); https://doi.org/10.1063/1.4803868
Submitted: 20 February 2013 . Accepted: 22 April 2013 . Published Online: 09 May 2013

S. D. Overduin, and G. N. Patey

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© 2013 AIP Publishing LLC.

 THE JOURNAL OF CHEMICAL PHYSICS 138, 184502 (2013)

An analysis of fluctuations in supercooled TIP4P/2005 water

S. D. Overduin and G. N. Pateya)
Department of Chemistry, University of British Columbia, Vancouver, British Columbia V6T 1Z1, Canada
(Received 20 February 2013; accepted 22 April 2013; published online 9 May 2013)

Large-scale, long-time molecular dynamics simulations are used to investigate fluctuations in the
TIP4P/2005 water model in the supercooled region (240-190 K). Particular attention is focused
in the vicinity of a previously reported liquid-liquid critical point [J. L. F. Abascal and C. Vega,
J. Chem. Phys. 133, 234502 (2010)]. Water is viewed as an equimolar binary mixture with “species”
defined based on a local tetrahedral order parameter. A Bhatia-Thornton fluctuation analysis is used
to show that species concentration fluctuations couple to density fluctuations and completely ac-
count for the anomalous increase in the structure factor at small wave number observed under su-
percooled conditions. Although we find that both concentration and density fluctuations increase
with decreasing temperature along the proposed critical isochore, we cannot confirm the existence
of a liquid-liquid critical point. Our simulations suggest that the parameters previously reported are
not a true liquid-liquid critical point and we find no evidence of two-phase coexistence in its vicin-
ity. It is shown that very long simulations (on the order of 8 μs for 500 molecules) are necessary
to obtain well converged density distributions for deeply supercooled water and this is especially
important if one is seeking direct evidence of a two-phase region. © 2013 AIP Publishing LLC.
[http://dx.doi.org/10.1063/1.4803868]

I. INTRODUCTION There is indirect simulation evidence suggesting that

other water models may have a LL critical point,3, 18 in-
In liquid water there is competition between
cluding the TIP4P/2005 model18 considered here. For ex-
energetically-favored local structures that are highly
ample, by examining pressure as a function of density
tetrahedral and other higher density arrangements that are
along different isotherms in simulations of 500 molecules,
favored by entropy. Competition between different structures
Abascal and Vega18 estimated that the critical temperature
can sometimes lead to a phase transition and it has been
for the TIP4P/2005 model is 193 K. Using data obtained
suggested1–5 that a liquid-liquid (LL) phase transition may
along the line of maximum correlations (Widom line), they
occur in supercooled water, providing possible insight
then estimated that the critical pressure and density are
into water’s well-known anomalous properties. However,
1350 bar and 1.012 g/cm3 , respectively. However, as high-
although any LL transition will involve competition between
lighted previously,16 definitive proof for a LL phase transition
different structures, not all competition between different
is difficult to obtain in simulations of small systems over short
structures must lead to a phase transition, and there are
timescales.
singularity-free explanations of water’s anomalies.6
Recently, we analyzed the TIP4P/2005 water model fol-
Scattering experiments on water under both ambient7 and
lowing the Bhatia-Thornton19 treatment of binary mixtures.
supercooled conditions4 show a rise in the structure factor
In this approach20 water is considered to be a binary mix-
at low wave number, suggesting the presence of anomalous
ture of “species” defined on the basis of a local tetrahe-
density fluctuations. Correlation lengths, obtained from the
dral order parameter. We demonstrated that under ambient
structure factor, experience power law growth with decreas-
conditions, the concentration fluctuations of these species
ing temperature, qualitatively consistent with the presence of
couple to density fluctuations and can quantitatively ac-
a LL critical point in the supercooled region of the phase
count for the behavior of the structure factor at low wave
diagram.4, 7 However, model studies illustrate that power law
number, as well as the isothermal compressibility anomaly.
growth of the correlation length does not necessarily imply
We also showed that concentration fluctuations arise due
LL phase separation. Both the ST28 and mW9 water models
to effective attractive and repulsive interactions between
capture many of water’s anomalies and show signs consistent
like and unlike species (local structures), respectively. Thus,
with the presence of a LL phase transition,3, 10 including, for
coupled concentration-density fluctuations lead to the anoma-
the mW model, power law growth of the correlation length.10
lous properties of the TIP4P/2005 water model under am-
Yet, there is strong, though still controversial,17 evidence that
bient conditions. We note that others have analyzed wa-
the ST211–15 model undergoes a transition, whereas the mW
ter in terms of binary mixture models,21–29 but none have
model does not.16
employed the Bhatia-Thornton19 approach, which allows us
to quantitatively identify the fluctuations at the origin of
anomalous behavior of the structure factor and isothermal
a) patey@chem.ubc.ca compressibility.

0021-9606/2013/138(18)/184502/8/$30.00 138, 184502-1 © 2013 AIP Publishing LLC

184502-2 S. D. Overduin and G. N. Patey J. Chem. Phys. 138, 184502 (2013)

The TIP4P/2005 model captures many of water’s anoma- species α and β,

lies both under ambient and supercooled conditions.30 In  ∞
addition, excellent agreement with scattering data has been √ sin(kr)
Sαβ (k) = δαβ + 4πρ xα xβ drr hαβ (r), (3)
obtained for this model over a range of temperatures and 0 k
pressures.4 In this paper we show that coupled concentration-
density fluctuations can also completely account for the are related to the total structure factor through
anomalous behavior of the structure factor and isothermal √
compressibility under supercooled conditions, down to the S(k) = xH SH H (k) + xL SLL (k) + 2 xH xL SH L (k), (4)
proposed LL critical point.18 However, we are unable to con-
where xα is the mole fraction of species α.
firm the LL critical point reported by Abascal and Vega18
Following the method of Salacuse et al.,37 we correct
and our results suggest that if such a critical point exists, it
the total and partial structure factors for finite size effects, as
lies elsewhere. Importantly, we also demonstrate that very
discussed previously.20 Briefly, the corrected partial structure
long simulation runs, and likely relatively large systems, are
factors are given by
needed to adequately sample water in the deeply supercooled
region. Sαβ (0) 4
Sαβ (k, R)  Sαβ,N (k, R) + πρR 3 u(kR), (5)
N 3
II. SIMULATION METHOD where
We performed molecular dynamics simulations of the 
√ R
sin(kr)
TIP4P/2005 water model,30 with a 2 fs time step. All simula- Sαβ,N (k, R) = δαβ + 4πρ xα xβ hαβ,N (r).
drr
tions employed the GROMACS 4.5.4 simulation package.31 0 k
(6)
Short-range interactions were truncated at 0.95 nm. Long-
In the above equations, hαβ, N (r) is obtained from an N-
range electrostatic terms were computed using the particle
particle simulation and u(x) = x33 (sin x − x cos x). For suffi-
mesh Ewald method,32 with a grid spacing of 1.2 Å and a
ciently large R, S(k, R)  S(k), and at k = 0, Eq. (5) yields
fourth degree polynomial for interpolation. To maintain con-
stant temperature, we used the Nosé-Hoover thermostat33, 34
with a relaxation time of 0.2 ps. For simulations performed Sαβ,N (0, R)
under constant pressure, the Parrinello-Rahman barostat35 Sαβ (0)  . (7)
1 − N1 43 πρR 3
with a 2 ps relaxation time was used. Constant volume simu-
lations of ∼100–240 ns were carried out along the proposed18 Dropping the subscripts αβ in Eqs. (5)–(7) and setting
critical isochore (1.012 g/cm3 ), for temperatures ranging from √
xα xβ = 1 in Eq. (6) provides an expression for the corrected
190 to 240 K. Unless otherwise stated, all constant vol- total structure factor S(k).
ume simulations employed 32 000 water molecules. Constant Accurate corrections for the structure factor can be ob-
pressure simulations were done with 500, 8000, or 32 000 tained provided all correlations in the system decay within
molecules for ∼400 ns–8 μs, depending on system size. half the box length. The partial pair correlation functions cor-
The current analysis closely follows the method recently rected for finite size effects are then given by
outlined in our paper concerning the anomalous behavior of

ambient water.20 We distinguish two types of water molecules hαβ (r) = hαβ,N (r) + Sαβ (0)/ Nα Nβ . (8)
based on the local tetrahedral order parameter,36
The total pair correlation function corrected for finite size ef-
4  
3 
3
1 2 fects in an analogous way is h(r) = hN (r) + S(0)/N. However,
q =1− cos(φij ) + , (1)
8 i=1 j =i+1 3 since S(0) is much smaller in magnitude than Sαβ (0), and N =
32 000, the corrected and uncorrected h(r) are nearly indistin-
where φ ij is the angle between lines connecting the oxygen guishable for all temperatures considered.
atom of a given water molecule to the oxygen atoms of its ith We can obtain additional insight20 into the interactions
and jth neighbors. Molecules are labeled as high-q (H) or low- of H and L molecules (different local structures) from the
q (L), depending on the value of q. As in our earlier work, we density-density, SNN (k), concentration-concentration, SCC (k),
divide the sample in half based on q: for each configuration, and density-concentration, SNC (k), structure factors as defined
molecules with a q value greater than the median q are labeled by Bhatia and Thornton.19 For our system,
H and the remaining molecules are labeled L. The probability √
distribution of q and its dependence on temperature are dis- SCC (k) = xH xL [xH SH H (k) + xL SLL (k) − 2 xH xL SH L (k)],
cussed in Sec. III. For an isotropic fluid, the structure factor is (9)
given by
 ∞  
sin(kr) xL − xH
S(k) = 1 + 4πρ drr h(r), (2) SNC (k) = xH xL SH H (k) − SLL (k) + √ SH L (k) ,
k xH xL
0
(10)
where h(r) = g(r) − 1, g(r) is the radial distribution function and SNN (k) = S(k). SNN (k) and SCC (k) are measures of fluctua-
and ρ is the number density. The partial structure factors of tions in density and concentration, respectively, while SNC (k)
184502-3 S. D. Overduin and G. N. Patey J. Chem. Phys. 138, 184502 (2013)

measures the coupling between the two fluctuations.19 In a
binary mixture at a demixing transition, SCC (0) will diverge
and is the primary indicator of the transition. Both SNC (0) and
SNN (0) will also diverge, provided the partial molar volumes
of the two species differ.
Limmer and Chandler16 recently suggested that some
signs of a LL phase transition may be due to the formation of
small ice nuclei. We check for the presence of ice-like struc-
tures using the CHILL algorithm.38
III. RESULTS AND DISCUSSION
We recently found20 that under ambient conditions there
are effective attractive interactions between water molecules
with similar local structure and effective repulsive interac-
tions between water molecules with different local structures.
These effective interactions give rise to concentration fluctu-
ations that are weakly coupled to density fluctuations. Un-
der ambient conditions, both concentration fluctuations and
their coupling to density grow with decreasing temperature,
leading to the anomalous increase in the isothermal com-
pressibility and the closely related increase in the structure
factor at low wave number. Here, we determine whether cou-
pled density-concentration fluctuations can also completely
account for the anomalous behavior of the structure factor and
isothermal compressibility in the supercooled region and in-
vestigate whether or not the anomalous behavior is related to
an underlying LL critical point.
In order to ensure sufficient equilibration under super-
cooled simulations, long simulations are necessary.16, 17 A
measure of the characteristic relaxation time for translational
motion, τ , can be obtained by fitting the self part of the inter-
mediate scattering function, FS (k, t) (for oxygen atoms), to a
stretched exponential, FS (k, t) ∝ exp ( − t/τ )β , where β is the
stretching exponent.39 We show the long-time part of FS (k,
t) at k = 18.6 nm−1 [the position of the first peak in S(k)]
in Fig. 1. Results obtained at 193 and 195 K are included.
At both temperatures, FS (k, t) decays within 10 ns. We find
0.8
193 K (data)
0.6 195 K (data)
fit
Fs(k,t)
characteristic relaxation times of 1.8 and 1.2 ns, for 193 and
195 K, respectively. As expected, FS (k, t) decays more rapidly
at higher temperatures. The time decay of the distinct part of
the intermediate scattering function (not shown) is very sim-
ilar. The center-of-mass mean-squared displacements (MSD)
for different temperatures are also shown in Fig. 1. At the low-
est temperature, 193 K, it takes ∼80 ns for the molecules to
move 1 nm, roughly four times the position of the first peak
in the oxygen-oxygen pair correlation function. All constant
volume simulations used to obtain the structure factors were
performed for over 100 ns and up to 240 ns at the lowest tem-
peratures, allowing each molecule to sample a region of space
at least several times its diameter. The constant pressure simu-
lations used to search for direct evidence of two liquid phases
were performed for no less than 400 ns and up to 8 μs for
500 molecules.
As noted above, the local tetrahedral order parameter, q,
is used to distinguish two types of water molecules. For each
configuration, molecules with q greater than the median value
are designated H, while the rest are designated L. The P(q)
distribution (Fig. 2) indicates that local tetrahedral structure
becomes more probable with decreasing temperature, as one
would expect. The shoulder associated with less tetrahedral
local structure eventually disappears as the temperature de-
creases.
The partial and total oxygen-oxygen pair correlation
functions along the critical isochore suggested by Abascal and
Vega18 are shown in Fig. 3. As expected, the liquid becomes
more structured with decreasing temperature. Nevertheless,
there is no sign of a diverging length scale in the total corre-
lation function (Fig. 3, bottom panel), despite that 193 K is
estimated to be the critical temperature.
The HH and LL partial correlation functions differ out to
∼2 nm, where most structural features have disappeared. The
partial correlation functions grow slightly in range with de-
creasing temperature. At 193 K, both hHH (r) and hLL (r) are
weakly depressed between ∼2.5 and 3.5 nm, while hHL (r) is
slightly elevated over the same range. These small structural
features do not occur at any other temperature and may sim-
ply be due to very slow convergence at low temperature. In
any case, these correlations (if real) are exactly the opposite

0.4 0.0045
193 K
0.004 195 K
0.2 200 K
210 K
0 0.0035 220 K
0.001 0.01 0.1 1 10 100 240 K
0.003
t (ns)
10 0.0025
P(q)

1 0.002
MSD (nm )
2

0.1
0.0015
0.01 193 K
195 K 0.001
200 K
0.001 220 K
240 K 0.0005
0.0001
0.01 0.1 1 10 100
0
t (ns) 0 0.2 0.4 0.6 0.8 1
q
FIG. 1. The long-time part of the intermediate self-scattering function, FS (k,
t), at k = 18.6 nm−1 for temperatures indicated in the legend (top) and mean- FIG. 2. Normalized probability distribution function of the order parameter q
squared displacements for different temperatures as indicated in the legend (Eq. (1)), for different temperatures obtained with ρ = 1.012 g/cm3 . Vertical
(bottom). lines show the median q values for 193 and 240 K.
184502-4 S. D. Overduin and G. N. Patey J. Chem. Phys. 138, 184502 (2013)

2
0.3 0.005 190 K
193 K
0 195 K
0.2 200 K
r2 hLL(r)

210 K
-0.005 220 K
0.1 1.5 240 K
2 3 4
0 S(k)
-0.1

SCC(k); S(k); SNC(k)

0.3 0.005 1
0
r2 hHH(r)

0.2
-0.005
0.1
2 3 4 0.5
0
SCC(k)
-0.1
0.005 SNC(k)
0.3
0
0
0.2
r2 hHL(r)

-0.005
0.1
2 3 4
0 -0.5
0 10 20 30 40 50 60 70 80
-0.1 k (nm-1)
0.3 0.005
FIG. 4. Density-density, S(k), concentration-concentration, SCC (k), and
0
0.2 density-concentration, SNC (k), structure factors for different temperatures as
r2 h(r)

-0.005 denoted in the legend.

0.1
2 3 4
0
-0.1
1 2 3 4
r (nm)
FIG. 3. Partial oxygen-oxygen pair correlation functions, r2 hLL (r) (top
panel), r2 hHH (r) (2nd panel), r2 hHL (r) (3rd panel), and the total pair correla-
tion function, r2 h(r) (bottom panel), for 193 K (red), 195 K (black), 200 K
(yellow), and 240 K (dark blue).
(k)]2 SCC (k) , (11)
of the like attractions and unlike repulsions one would ex-
(k) = SNC (k)/SCC (k) is called the dilation factor. In the
pect to signal an approaching demixing transition. It is possi-
ble that the growth of long-range correlations expected near a
(k) = 0 and S(k) = θ (k). Therefore, θ (k) provides
critical point (thought to be at 193 K) is somehow suppressed
in our constant volume simulations, despite the large system
size. However, results obtained from constant pressure simu-
lations performed at 1350 bar (the previously reported critical
pressure18 ) and 195 K are very similar to those obtained from
constant volume simulations at the same temperature and the
corresponding density.
As noted above, S(k) and SCC (k) provide measures of den-
(k)]2 SCC (k), which directly measures the contribu-
sity and concentration fluctuations, respectively, while SNC (k)
measures the coupling between the two fluctuations. The
structure factor obtained from simulations of the TIP4P/2005
water model agrees well with experimental small angle scat-
tering results at ambient pressure.4, 5, 40 Scattering experi-
ments have not been reported at high pressure in the temper-
ature range of interest, so we cannot directly compare our re-
sults with experiment. Nevertheless, it has been shown that
the isothermal compressibility obtained for the TIP4P/2005
model under higher pressure agrees reasonably well with ex-
perimental measurements.5, 30
(0)]2 SCC (0)/ρkB T , (12)
In Fig. 4, S(k), SCC (k), and SNC (k) are shown for dif-
ferent temperatures. It can be seen that both density and
concentration fluctuations grow with decreasing temper-
ature, as does the coupling between them. Also, the
concentration fluctuations are noticeably stronger than the
density fluctuations. We note that increasing density fluctua-
tions with decreasing temperature is consistent with previous
experimental4, 41 and simulation5, 18 studies.
Following Bhatia and Thornton,19 we divide the structure
factor into two terms,20
S(k) = θ (k) + [
where
absence of coupling between density and concentration fluc-
tuations,
an estimate of how the structure factor might behave if cou-
pled concentration and density fluctuations were not present.
The functions θ (k) and S(k) are shown in Fig. 5 for small
wave number. As occurs at higher temperatures under ambi-
ent pressure,20 θ (k) monotonically decreases with decreasing
wave number over the small wave number region shown in
the figure. The discrepancy between S(k) and θ (k) is due to
the term [
tion made by coupled concentration and density fluctuations.
Thus, coupled concentration-density fluctuations account for
the anomalous low wave number increase in S(k) throughout
the supercooled region.
In contrast with most liquids, the isothermal compress-
ibility κ T = S(0)/ρkB T of liquid water increases with de-
creasing temperature below some pressure-dependent thresh-
old temperature. As with S(k) above, we can determine how
fluctuations influence the isothermal compressibility by writ-
ing
κT = κT + [
where κT = θ (0)/ρkB T .
184502-5 S. D. Overduin and G. N. Patey J. Chem. Phys. 138, 184502 (2013)

0.16 relationship,43
193 K
195 K
c
= ξ −2 + k 2 ,
0.14 200 K
210 K (13)
0.12
220 K S A (k)
240 K
where c is a temperature-dependent constant and ξ is corre-
S(k); θ(k)

0.1
0.08
0.06
0.04
0.02
0 2 4 6 8 10
k (nm-1)
(k)]2 SCC (k).
FIG. 5. The functions S(k) (thick lines) and θ (k) (thin lines), at small wave
number, for different temperatures as denoted in the legend.
Both κ T and κT are plotted in Fig. 6. The error bars
are estimated standard deviations obtained using at least four
simulation runs, each of 20 ns. Over the temperature range
considered, κT decreases, while κ T increases, with decreas-
ing temperature. Thus, coupled concentration-density fluc-
tuations account entirely for the anomalous behavior of the
isothermal compressibility, providing another demonstration
that the local tetrahedral order parameter is sufficient to dis-
tinguish structural fluctuations throughout the temperature
range.
If the TIP4P/2005 water model indeed approaches a LL
critical point as the temperature is decreased, then increasing
concentration and density fluctuations are expected. In partic-
ular, the relevant correlation length is expected to experience
power law growth along the critical isochore, with a critical
exponent of ∼0.63.43 Both SCC (k) and S(k) can be used to es-
timate correlation lengths.
In investigations of possible critical behavior in water,
it is usual4, 5, 7, 41, 42 to attempt to separate the structure fac-
tor into so-called normal and anomalous contributions, SN (k)
and SA (k), respectively. Temperature-dependent correlation
lengths are then estimated using the Ornstein-Zernike (OZ)
lation length. Various approximate methods for distinguish-
ing SA (k) and SN (k) have been employed.4, 5, 7, 42 As discussed
above, in the present analysis, θ (k) provides an estimate for
S(k) in the absence of coupled concentration-density fluctu-
ations and shows no sign of anomalous behavior at small
wave number. Thus, setting SN (k) = θ (k) is an obvious choice.
The anomalous scattering is then the difference, SA (k) = S(k)
− θ (k) = [
Alternatively, we can consider the concentration fluctu-
ations as is done in analysis of binary mixtures approaching
a demixing transition.44 Correlation lengths can then be esti-
mated by simply replacing SA (k) with SCC (k) in Eq. (13), with
c of course being a different constant in this case.
The small wave number behavior of both SA (k) and
SCC (k) is well described by the OZ expression, as shown in
Fig. 7. At 195 K, we find correlation lengths of 0.58 and
0.42 nm from the SA (k) and SCC (k) routes, respectively.
As the critical temperature, TC , is approached along the
critical isochore, ξ (T) is expected to follow43
 −ν
T
ξ (T ) = ξ0 −1 , (14)
TC
with ν ≈ 0.63. The behavior of ξ with (T/TC ) − 1 is shown
in Fig. 8. We have also included a data point at 190 K, below
the estimated18 critical temperature (193 K). As the system
approaches 193 K, we do observe apparent power law growth
of the correlation lengths calculated using both the S(k) and
SCC (k) routes, in qualitative agreement with results obtained
by Wikfeldt et al.5 along various isobars. Fitting the simu-
lation results to Eq. (14) using data points between 195 and
1.7
1.6

1.5
1/SCC(k)

1.4
22
κT
20 κ´T 1.3
195 K
18 1.2 200 K
210 K

16 1.1
30
14
28
κT,κ´T

12
26
10
1/SA(k)

24
8
22
6
20
4
18
2 16
190 200 210 220 230 240
Temperature (K)
2.5 3 3.5 4 4.5 5
2 -2
FIG. 6. The isothermal compressibility, κ T , and κT
= θ (k)/(ρkB T ). kT
pro- k (nm )
vides a measure of the structure factor in the absence of concentration fluc-
tuations. The error bars represent estimated standard deviations, which are FIG. 7. The functions 1/SCC (k) and 1/SA (k) with k2 , along with fits (lines) to
smaller than the symbols for κT . Eq. (13), for the temperatures denoted in the legend.
184502-6 S. D. Overduin and G. N. Patey J. Chem. Phys. 138, 184502 (2013)

from S(k)
0.06
1.2
from SCC(k)
0.05
1
Correlation Length (nm)

0.04

P(density)
0.8
0.03
0.6
0.02
0.4
0.01
0.2
0
0 0.96 0.98 1 1.02 1.04 1.06 1.08 1.1
-0.05 0 0.05 0.1 0.15 0.2 0.25 3
density (g/cm )
(T/TC)-1
FIG. 9. Density distributions obtained at 1400 bar and 191 K, initially started
FIG. 8. Correlation lengths, ξ obtained from Eq. (13), along with fits (lines) from a density of ρ = 1.000 g/cm3 , calculated over different 500 ns time
to Eq. (14). The black and red curves are as denoted in the legend. The error windows. Density distribution shapes and average densities calculated from
bars represent estimated standard deviations. different time windows vary significantly.

240 K, we obtain the exponents ν = 0.19 and 0.26, from the
S(k) and SCC (k) routes, respectively, both well below the ex-
pected value of 0.63. This suggests that the LL critical point,
if one in fact exists, does not lie on the isochore predicted
by the earlier simulations of Abascal and Vega.18 The NPT
simulations discussed below provide further support for this
conclusion.
Before turning to the constant pressure results, a brief dis-
cussion of how the sample is divided into H and L molecules
is in order, since both SA (k) and SCC (k) can depend on how
the division is done. As noted above, the results presented
in this paper are obtained by identifying H and L based on
the median value of q. However, to ensure that our qualita-
tive observations are not strongly dependent on this particu-
lar choice, we did consider other selection criteria. For ex-
ample, for some temperatures we labeled molecules with q-
values above the 70th percentile H and the remainder L. This
choice gave results similar to those presented here and pro-
density distributions determined over 500 ns intervals (the
total length of the simulation runs reported by Abascal and
Vega18 ) vary significantly, with uni- and bimodal distributions
possible, as shown in Fig. 9. However, averaged over 8 μs,
the density distributions from both simulations appear uni-
modal as shown in Fig. 10 (top panel), with a maximum at
1.013 g/cm3 , suggesting that only a single liquid phase is
present at this pressure and temperature. Note that, despite
these lengthy runs, the density distributions from the two
simulations are not identical, though they are very similar,
demonstrating that at this temperature extremely long runs are
required for adequate density sampling. Similar results were
obtained at 1450 bar, as shown in Fig. 11 (top panel).
high - 6500 ns
500
low - 6500 ns
0.03 combined
P(density)

vided no additional evidence suggesting a nearby LL critical 0.02

point. Thus, the median q criterion appears sufficient to cap-
0.01
ture the essential underlying physics. We note that different
methods of distinguishing water molecules in binary mixture- 0
like analyses have been used by other researchers.23, 28, 29 0.15 8000
high - 1200 ns
low - 1200 ns
The strongest evidence obtained by Abascal and Vega18 combined
P(density)

for a LL phase transition in the TIP4P/2005 water model is 0.1

bimodal density distributions obtained at some pressures and
temperatures less than 193 K. The authors report that two in- 0.05

dependent simulations both at 1400 bar and 191 K produced

0
liquid phases with two different densities. The densities of 0.4 high - 600 ns
32000 low - 360 ns
each simulation remained stable and distinct for 400 ns. For combined
0.3
P(density)

the same temperature at 1450 bar, Abascal and Vega obtained

a bimodal density distribution in a 500 ns simulation, which 0.2
they attribute to a system undergoing transitions between two
0.1
liquid states.
We attempted to reproduce the bimodal density distribu- 0
0.96 0.98 1 1.02 1.04 1.06 1.08 1.1 1.12
tions obtained by Abascal and Vega,18 and investigated the in- density (g/cm3)
fluences of run length and finite system size. At 1400 bar and
191 K, two 500 molecule NPT simulations (the system size FIG. 10. Density distributions obtained at 1400 bar and 191 K with 500 (top
used by Abascal and Vega18 ) were each run for over 8 μs, panel), 8000 (middle panel), and 32 000 (bottom panel) molecules. In all
panels, density distributions from two different simulations are shown, one
with the initial configurations taken from equilibrated N V T
started with ρ = 1.000 g/cm3 (black) and the other with ρ = 1.029 g/cm3 .
simulations with densities of 1.000 or 1.029 g/cm3 , selected The average density distribution from the two runs is also shown. Simulation
based on the results of Abascal and Vega.18 We observe that times, excluding equilibration, are given in the legend.
184502-7 S. D. Overduin and G. N. Patey
500 high - 6500 ns
0.03
low - 6500 ns
combined
P(density)
0.02
0.01
0 nal ice-like molecules. We find that, although more ice-like
0.2 high - 960 ns
8000 low - 960 ns
combined
P(density)
0.15
0.1
0.05
0
0.25 32000
600 ns
P(density)
0.2
0.15
0.1
0.05
0
0.96 0.98 1 1.02 1.04 1.06 1.08 1.1 1.12
density (g/cm )
3 state.
FIG. 11. Density distributions obtained at 1450 bar and 191 K with 500 (top
panel), 8000 (middle panel), and 32 000 (bottom panel) molecules. In the top
two panels, density distributions from two different simulations are shown,
one started at lower density, either ρ = 1.000 g/cm3 (for 8000 molecules), or
ρ = 1.012 g/cm3 (for 500 molecules), and the other with ρ = 1.029 g/cm3 .
The average density distribution from the two runs is also shown. Simulation
times, excluding equilibration, are given in the legend.
NPT simulations with 8000 and 32 000 molecules were
also performed at 191 K and both 1400 and 1450 bar. At
1400 bar, two simulations were performed for each system
size, with initial configurations for each simulation taken
from equilibrated N V T simulations with densities of 1.000
or 1.029 g/cm3 . The density distributions (Fig. 10) for both
larger systems are much narrower than the 500 molecule
case. Unimodal density distributions are found for both larger
systems. The density distributions obtained from simulations
started with different initial densities move together over
time, suggesting a single liquid state at 191 K and 1400 bar
(Fig. 10). Although the density distributions are much nar-
rower for the larger samples than for the 500 molecule sys-
tems, long simulations are still necessary to generate equilib-
rium density distributions, as demonstrated by small but visi-
ble differences from independent simulations.
Similarly, at 1450 bar, NPT simulations performed with
8000 and 32 000 molecules show unimodal density distribu-
tions as shown in Fig. 11. The average density obtained with
8000 molecules lies between the two densities found by Abas-
cal and Vega18 with 500 molecules. Only one simulation was
performed with 32 000 molecules at 1450 bar. There is no sign
in this large simulation of two density states and the average
density agrees well with that obtained for 8000 molecules.
Our results strongly suggest that only a single liquid state is
present at 1450 bar and 191 K.
It has been suggested that the formation of small ice nu-
clei may account for some of the density fluctuations observed
in supercooled water.16 We monitored for the presence of
molecules that are part of ice-like structures using the CHILL
J. Chem. Phys. 138, 184502 (2013)
algorithm.38 The algorithm classifies molecules as ice-like
or liquid-like, depending on the orientation of a molecule
with respect to its neighbors, and also distinguishes be-
tween cubic, hexagonal, and intermediate ice-like molecules.
Intermediate ice-like molecules are ice-like molecules that
do not strictly meet the requirements for cubic or hexago-
molecules are present at low density, in the smallest systems
(500 molecules), only 1%–8% of the molecules are ice-like,
of which over 80% are classified as intermediate. In larger
systems (8000 and 32 000 molecules), the density distribu-
tions are much narrower and fewer than 4% of the molecules
are ice-like. Furthermore, by visual inspection of configura-
tional snapshots, we find that the ice-like molecules are dis-
tributed throughout the sample, rather than clustered together
to form a larger ice nucleus. Thus, the presence of small ice
nuclei does not appear to be a significant factor in the den-
sity fluctuations observed for the TIP4P/2005 water model.
Rather, the observed density fluctuations are consistent with
a broad free energy minimum associated with a single liquid
IV. SUMMARY AND CONCLUSIONS
Large-scale, long-time molecular dynamics simulations
are employed in order to analyze fluctuations in the
TIP4P/2005 water model in the deeply supercooled region.
As in our earlier work,20 we treat water as an equimolar
mixture of two “species” distinguished by means of a local
tetrahedral order parameter. Concentration and density fluc-
tuations are then analyzed following the Bhatia-Thornton19
approach for binary mixtures. Under supercooled conditions,
along the critical isochore identified by Abascal and Vega,18
we find that concentration and density fluctuations increase
with decreasing temperature. Additionally, the coupling be-
tween these fluctuations grows with decreasing temperature.
These effects explain the anomalous behavior of the structure
factor in the supercooled regime.
While increasing fluctuations (correlation lengths) with
decreasing temperature are consistent with an approaching
LL critical point, our simulations do not confirm the exis-
tence of a critical point at 1350 bar and 193 K, as previously
reported.18 Correlation lengths along the proposed critical iso-
chore can be calculated and fitted to the usual power law form,
but the estimated exponent is much lower than the expected
critical value. Moreover, we find no direct evidence, such as
bimodal density distributions, for the existence of two liquid
phases below the supposed critical point. Our results demon-
strate that very long simulations are necessary to obtain true
equilibrium density distributions in deeply supercooled water
and that poorly converged results from shorter runs can some-
times appear to be bimodal. We believe that this is the likely
explanation of the bimodal density distributions reported
by Abascal and Vega18 for the same model under identical
conditions.
Finally, we would like to emphasize the following per-
spective. Although increasing fluctuations with decreasing
temperature suggest the possibility of a LL phase transition,
such a transition need not actually exist. In contrast with a true
184502-8 S. D. Overduin and G. N. Patey
two-component mixture, the “species” (local structures) in
water obviously change their nature as the temperature is de-
creased. In particular, as the TIP4P/2005 water approaches the
critical point expected on the basis of fluctuation maxima,18
the q-distribution becomes more tetrahedral and differences
between the two structural “species” become smaller. Thus,
as the temperature is decreased, fluctuations increase, but the
differences between the two species decrease, perhaps pre-
empting any phase transition. This would explain why based
on fluctuations the TIP4P/2005 model looks as if it should
have a LL critical point, but appears not to have one, or at least
not at the location expected from “extrapolation” of fluctua-
tion data.18 Of course, it is always possible that a LL critical
point does exist somewhere in the phase diagram, so the ques-
tion obviously remains open.
Nevertheless, whether or not a LL transition occurs in
supercooled water, for the TIP4P/2005 model our results
demonstrate that incommensurate local structures give rise
to coupled concentration and density fluctuations, which in
turn account for the anomalous behavior of the structure fac-
tor and isothermal compressibility, under both ambient20 and
supercooled conditions.
ACKNOWLEDGMENTS
We thank Jingyi Yan for implementation of the CHILL
algorithm. The financial support of the Natural Science and
Engineering Research Council of Canada is gratefully ac-
knowledged. This research has been enabled by the use of
WestGrid and Compute/Calcul Canada computing resources,
which are funded in part by the Canada Foundation for In-
novation, Alberta Innovation and Science, BC Advanced Ed-
ucation, and the participating research institutions. WestGrid
and Compute/Calcul Canada equipment is provided by IBM,
Hewlett Packard, and SGI.
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