An intermolecular potential model for the simulation of ice and water near the melting

point: A six-site model of

Hiroki Nada, and Jan P. J. M. van der Eerden

Citation: The Journal of Chemical Physics 118, 7401 (2003);

View online: https://doi.org/10.1063/1.1562610
View Table of Contents: http://aip.scitation.org/toc/jcp/118/16
Published by the American Institute of Physics

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JOURNAL OF CHEMICAL PHYSICS VOLUME 118, NUMBER 16 22 APRIL 2003

An intermolecular potential model for the simulation of ice and water

near the melting point: A six-site model of H2 O
Hiroki Nadaa)
National Institute of Advanced Industrial Science and Technology (AIST), Onogawa 16-1,
Tsukuba 305-8569, Japan
Jan P. J. M. van der Eerdenb)
Department of Physical Chemistry of Interfaces, Debye Institute, Utrecht University, Padualaan 8,
3584 CH Utrecht, The Netherlands
共Received 5 November 2001; accepted 29 January 2003兲
An intermolecular potential model of H2 O with six interaction sites is proposed. The model is
developed for the simulation of ice and water near the melting point. Parameters in the potential are
determined to reproduce the real melting point of ice, and densities of ice and water near the melting
point, which are predicted by calculating derivatives of the free energies and volumes of ice and
water against potential parameters. Free energy calculations are carried out for several ice structures
and water, and the results are compared with those obtained in four- and five-site models, which are
currently in use. It is shown that, only in the present six-site model, the proton-disordered hexagonal
ice is the stable structure at the melting point, as in real ice. The melting point of the
proton-disordered hexagonal ice at 1 atm is estimated to be 271⫾9 K in the present model, which
is in good agreement with the real melting point of 273.15 K. Moreover, results of Monte Carlo
simulations of ice and water show that the present six-site model reproduces well the real structural
and thermodynamic properties of ice and water near the melting point. © 2003 American Institute
of Physics. 关DOI: 10.1063/1.1562610兴

I. INTRODUCTION extensive free energy calculations of ice and water. Note

Computer simulations, such as molecular dynamics
共MD兲 and Monte Carlo 共MC兲, provide a lot of physical in-
sight in the molecular-scale structure and thermodynamic
properties of ice and of liquid water. Especially, the simula-
tions of the ice–vapor and the ice–water interfaces at tem-
peratures T just below the melting point T M attract a great
deal of attention in connection with such issues as freezing
of water in biological systems1–3 and pattern formation of
snow and ice crystals.4 – 6
When simulations are applied to studies on ice near T M ,
it is important to select a suitable potential model of H2 O.
Until now, a lot of potential models of H2 O have been pro-
posed. Most of them, however, have been developed for
simulation studies of liquid water, and are hardly tested for
ice. It, therefore, is important to check whether a selected
model is suitable for simulation studies of ice as well.
For a potential model of H2 O to be suitable for simula-
tions of ice and water near T M , it should satisfy the follow-
ing three conditions. 共i兲 The structure of real ice at 1 atm,
that is, the proton-disordered hexagonal ice (I dh ) corresponds
to the free energy minimum near T M of the model. 共ii兲 The
real T M and density of I dh are reproduced in the model. 共iii兲
The structures of real water and ice are reproduced in the
model, at least in the range of 0.9 T M ⬍T⬍1.1 T M . Condi-
tion 共iii兲 can easily be investigated by performing MD or MC
simulation. However, testing conditions 共i兲 and 共ii兲 requires
a兲
Electronic mail: hiroki.nada@aist.go.jp
b兲
Electronic mail: j.p.j.m.vandereerden@chem.uu.nl
that, if for a certain model it turns out that condition 共ii兲 is
poorly satisfied, this can easily be repaired by rescaling of
the relevant energy and length parameters in the potential
function.
As a simulation study that is related to T M of ice, an
upper limit of the mechanical stability of ice has been inves-
tigated by heating a bulk ice until it melts during the
simulation.7–9 However, the upper limit is in practice differ-
ent from T M . 9,10 As far as we know, the upper limit of a
solid is somewhat higher than T M of it. However, the differ-
ence between them is still uncertain. For the present, the only
way to determine the exact T M of ice in a model is to calcu-
late free energies of ice and water.
As far as we know, free energies of ice were investigated
for the SPC/E model,11 which is one of the popular three-site
models, and for the TIP4P model,12 which is the most popu-
lar four-site model and has been used for simulations of
ice.13–20 Báez and Clancy calculated free energies of several
different ice structures for the SPC/E model using the cut-off
of long-range interactions, and concluded that the hexagonal
ice is not stable near T M of real water.21,22 Recently, Ar-
buckle and Clancy indicated that, by including the Ewald
summation method, T M of the hexagonal ice for the SPC/E
model significantly increases to around 280 K.23 However,
including the Ewald method did not provide I dh as the free
energy minimum near T M of the SPC/E model.
Recently, free energy calculations of hexagonal struc-
tures of ice in the TIP4P model were also carried out. Vlot
et al. estimated T M of a proton-ordered hexagonal ice struc-

0021-9606/2003/118(16)/7401/13/$20.00 7401 © 2003 American Institute of Physics

7402 J. Chem. Phys., Vol. 118, No. 16, 22 April 2003 H. Nada and J. P. J. M. van der Eerden

ture 共anti-Ferro electric structure,24 hereafter I oh ) to be 214 II. METHOD

⫾6 K. 25 On the other hand, using a slightly different method A. Free energy calculation of ice
of the free energy calculation, Gao et al. estimated T M of I dh
We calculated free energies of ice crystals by using the
to be 238⫾7 K. 26 These studies demonstrated that the T M of
thermodynamic integration 共TDI兲 共Ref. 10兲 from an Einstein
the hexagonal structures of ices in the TIP4P model are much
reference crystal that has the same structure as the ice crys-
lower than the T M of real water. Moreover, we checked that
tal. In the TDI method, the Helmholtz free energy of the ice
I oh is more stable than I dh near T M , unlike in the real system.
crystal A is calculated using the free energy of the reference
Note that these free energy calculations were carried out us-
crystal A ref as follows:

冕冓 冔
ing the cut-off of long-range interactions. Therefore, includ-
ing the Ewald method would result in different values of
T M . However, as far as we investigated, it can hardly be
A⫽A ref⫹
1

0
dU 共 ␭ 兲
d␭
d␭⫽A ref⫹ 冕具
0
1
U⫺U ref典 d␭, 共1兲
expected that I dh would be provided as the free energy mini-
where
mum near T M for the TIP4P model by including the Ewald
method. Therefore, the TIP4P model is not desirable for U 共 ␭ 兲 ⫽ 共 1⫺␭ 兲 U ref⫹␭U. 共2兲
simulation of real ice near T M , though it gives a good de-
Here, ␭ is a switching parameter connecting the potential
scription of the liquid phase.27,28
energy of the ice crystal U with that of the reference crystal
In addition to three- and four-site models, several five-
U ref linearly. 具 典 means the ensemble average.
site models of H2 O have also been proposed. In this study,
The U ref was calculated using the Einstein potentials for
we investigated both I dh and I oh using the TIP5P model,29 a
the translational motion of the center-of-mass of each mol-
five-site model recently proposed by Mahoney and Jor-
ecule ␾ Tri and for the rotational motion of each molecule
gensen, which successfully reproduces the structure of real
␾ Rot
i . The U ref used was defined as
water. However, in this paper, we will show that the T M of I dh
in the TIP5P model is also much lower than the real T M of it, n

and that I oh is more stable than I dh . The fact that the I dh does U ref⫽ 兺 共 ␾ Tri ⫹ ␾ Rot
i⫽1
i 兲
not correspond to the free energy minimum near T M seems
to be a common problem in all three-, four-, and five-site n n
models, which are currently in use. ⫽C Tr 兺
i⫽1
共 r i ⫺r 0i 兲 2 ⫺C Rot
i⫽1
兺 Tr关 M 共 ␣ i , ␤ i , ␥ i 兲兴 , 共3兲
In this paper, we propose a new intermolecular potential
model for H2 O, which is suitable for the simulation of ice where r i and r 0i are the actual and equilibrium center-of-mass
and water near T M . It is a six-site model, with parameters positions of molecule i, respectively. C Tr and C Rot are force
that reproduce T M of real ice. Free energy calculations are constants of the translational and the rotational potentials,
carried out for several ice structures and water. It is shown respectively. Tr关 M 兴 is the trace of the rotation matrix M ,
⫺1
that, in our six-site model, I dh has the minimum free energy. which is defined as M ⫽M ice•M ref , where the M ice and M ref
The T M of I dh is estimated to be 271⫾9 K at a pressure of 1 are the rotation matrices of the molecule in the actual system
atm. MC simulations of ice and water indicate that the struc- and in the reference crystal, respectively. Each matrix de-
tures and thermodynamic properties of the ice and water near pends on the Euler angles ␣ i , ␤ i , and ␥ i of molecule i as
T M compare well with those obtained in the experiment. follows:30

M 共 ␣i ,␤i ,␥i兲⫽ 冉 cos ␣ i cos ␤ i cos ␥ i ⫺sin ␣ i sin ␥ i

sin ␣ i cos ␤ i cos ␥ i ⫹cos ␣ i sin ␥ i
⫺sin ␤ i cos ␥ i
⫺cos ␣ i cos ␤ i sin ␥ i ⫺sin ␣ i cos ␥ i
⫺sin ␣ i cos ␤ i sin ␥ i ⫹cos ␣ i cos ␥ i
sin ␤ i sin ␥ i
cos ␣ i sin ␤ i
sin ␣ i sin ␤ i
cos ␤ i
冊 , 共4兲

Tr关 M 兴 ⫽M 11⫹M 22⫹M 33 .
When the actual system has exactly the same molecular ar-
rangement as the reference system, then M ⫽I and Tr关 M 兴
takes its maximum value of 3. When the actual molecular
orientation deviates from the reference orientation, Tr关 M 兴
decreases toward its minimum value of ⫺1.
An advantage of the present reference potential is that
only one rotational force constant is used instead of two in
the reference potentials proposed until now.21,25 This means
that one can easily choose the optimum values of the force
共5兲 constants in the reference potential. C Tr and C Rot used in this
study are given in Table I.
As the initial molecular arrangement in the reference
crystal, we used time-averaged coordinates and orientations
of molecules of the actual ice crystal, which were obtained
by the MC simulation of the actual ice crystal. This means
that the initial molecular arrangement in the reference crystal
corresponds to the minimum energy arrangement in the ac-
tual system. The Helmholtz free energy of the reference,
A ref , is the sum of the translational and rotational free ener-
gies, A Tr and A Rot , which are given as
J. Chem. Phys., Vol. 118, No. 16, 22 April 2003 A potential model for ice and water 7403

TABLE I. Values of the force constants in the Einstein reference potential, the simulations were all consistent with analytical values,
C Tr and C Rot , used in this study. which were calculated by Eq. 共10兲. Thus, we verified the
T 共K兲 C Tr /k B T (Å ⫺2 ) C Rot /k B T expressions of Z Rot in Eq. 共8兲 and hence A Rot in Eq. 共7兲.
In this study, we also calculated A of ice by the TDI with
175 50.0 64.0 a potential U(␭)⫽(1⫺␭ 2 )U ref⫹␭ 2 U instead of Eq. 共2兲, like
200 40.0 50.0
250 28.0 35.0
in the past works.21,26 However, no significant difference in
275 24.0 30.0 A between the potentials was observed. Moreover, we
checked that A of ice calculated using the present reference
potential was consistent well with A calculated using a ref-
erence proposed by Báez and Clancy,21 and was also consis-
3
A Tr⫽⫺ Nk B T ln
2
冉
2 ␲ 2 mk B2 T 2
C Trh 2
, 冊 共6兲
tent with A calculated using a reference proposed by Vlot
et al.25 共difference of A among the reference potentials was
less than 0.01 kJ/mol兲. This suggests that A of ice calculated
A Rot⫽⫺k B T ln Z Rot共 N,V,T 兲 by the TDI does not significantly depend on the reference
potential used. Hence we expect that the Debye reference
⫽⫺NC Rot⫺Nk B T would also lead to the equivalent A of ice.26 Thus, we con-

再
⫻ln 8 ␲ 2 K A K B K C I 0 冋 冉 冊 冉 冊 册冎
2C Rot
k BT
⫺I 1
2C Rot
k BT
, 共7兲
firmed that the TDI with the present reference potential pro-
vides reliable A of ice.
For the A of I dh , we added a term of ⫺Nk B T ln(3/2),
where which corresponds to the free energy gain due to the (3/2) N

冕 冕 冕
2␲ 2␲ ␲ possible H2 O orientations in the N molecules system,31 to
Z Rot共 N,V,T 兲 ⫽K AN K BN K CN 共 sin ␤ 兲 N d ␤ N d ␣ N d ␥ N the A calculated by the TDI.
0 0 0
Note that rotating a molecule in the present Einstein ref-

⫻exp 冉 N
C Rot兺 i⫽1 Tr关 M 共 ␣ i , ␤ i , ␥ i 兲兴
k BT
冊 erence crystal over ␲ increases the energy by 4C Rot . Hence,
2 N equivalent Einstein reference crystals physically exist, all
leading to equivalent ice configurations. Thus, for a classical

冉 冊
⫽8 ␲ 2N K AN K BN K CN exp
NC Rot
k BT
interpretation where the two hydrogen atoms of a H2 O mol-
ecule are distinguishable, a term ⫺Nk B T ln 2 should be
added to A. We adopt, however, the quantum mechanical

冋 冉 冊 冉 冊册
⫻ I0
2C Rot
k BT
⫺I 1
2C Rot
k BT
N
, 共8兲
interpretation of indistinguishable hydrogen atoms 共symme-
try number p⫽2 for H2 O), in which the 2 N configurations
are indistinguishable and hence correspond to one state.
K A ⫽ 冑h 2 /2␲ I A k B T, K B ⫽ 冑h 2 /2␲ I B k B T,
共9兲
K C ⫽ 冑h 2 /2␲ I C k B T. B. Free energy calculations of water and vapor

Here, I A , I B , and I C are the principal moments of inertia of The Gibbs free energies G of water and vapor were di-
the molecule. N, k B , m, and h are the number of molecules, rectly calculated using the overlapping distribution method
the Boltzmann constant, the molecular mass, and Planck’s 共the f g-sampling method兲 proposed by Shing and
constant, respectively. I 0 and I 1 are the modified Bessel Gubbins.32,33 G is given as
functions of the first kind.
From the partition function for the Einstein rotational
reference Z Rot , which was given in Eq. 共8兲, the mean Ein-
G⫽⫺Nk B T ln 再冉 VK A K B K C 8 ␲ 2
p⌳ 3 N
⫹冊⌬U
k BT
stein rotational potential energy 具 U Rot典 can be derived ana-
lytically as 冎
⫹ln兵 g 共 ⌬U 兲 其 ⫺ln兵 f 共 ⌬U 兲 其 . 共11兲
N
Here, f (⌬U) and g(⌬U) are the distribution functions of the
具 U Rot典 ⫽⫺C Rot 兺 具 Tr关 M 兴 典 potential energy change ⌬U for insertion and removal of the
i⫽1
molecules, respectively. V is the volume of the system. ⌳
⳵ ln Z Rot共 N,V,T 兲 ⫽(h 2 /2␲ mk B T) 1/2 is the Broglie wavelength. p (⫽2) stands
⫽⫺
⳵ 共 1/k B T 兲 for the symmetry number of molecule.

冉 冊
In this study, we applied the f g-sampling method to cal-
2C Rot culate the G of water only at T⭓300 K, because the over-
I1
k BT lapping region was too small to obtain reliable values of G at

冉 冊 冉 冊
⫽NC Rot⫺Nk B T . 共10兲
2C Rot 2C Rot lower T.
I0 ⫺I 1
k BT k BT
C. Monte Carlo simulations
Equation 共10兲 can be used to check the expressions of Eqs.
共7兲 and 共8兲. We carried out MC simulations of Einstein crys- MC simulations of ice and water were carried out using
tals using the present rotational potential and measured a standard Metropolis sampling method at a constant pres-
具 U Rot典 for several C Rot . The values of 具 U Rot典 measured by sure P of 1 atm. The simulations for ice were carried out for
7404 J. Chem. Phys., Vol. 118, No. 16, 22 April 2003
FIG. 1. The G – T curves in the TIP4P model for ice, water, and vapor. The
curves for I oh , water, and vapor were drawn using data reported in Ref. 25.
Each G – T curve was drawn using the Gibbs–Helmholtz relation with H – T
curve and a reference free energy of G 0 at T 0 , which are given in Table II.
I dh and I oh at every 25 K in the T range of 150–300 K. The
simulations of water were carried out at every 12.5 K in the
range of 237.5–350 K, and the simulation of vapor at every
50 K in the range of 350–550 K.
The systems used for I dh and I oh contain 360 H2 O, and
those for water and vapor 500 H2 O. The shape of each sys-
tem was a rectangular parallelepiped, and periodic boundary
conditions were imposed in all three directions. For I dh , six
structures with different proton arrangement were simulated.
All six structures satisfy the Bernal–Fowler rules.34 For the
calculation of the intermolecular interaction energy, a switch-
ing function was used in the intermolecular distance between
9.5 and 10 Å.25
In the MC simulations, the potential energy U and den-
sity ␳ were obtained from 1⫻103 configurations for ice,
from 3⫻103 configurations for water at T⭓300 K and va-
por, and from 5⫻103 configurations for water at T
⬍300 K. For I dh and I oh , 3.6⫻103 configurations, and for
water and vapor 4⫻104 were discarded between each mea-
surement. The averaging was carried out after equilibration
of 3.6⫻106 for I dh and I oh , of 4⫻107 for water at T
⭓300 K and vapor, of 1.2⫻108 for water at 262.5 K⭐T
⬍300 K, and of 2⫻108 for water at T⬍262.5 K. We
checked that the system reached equilibrium for all simula-
tions by monitoring U and volume V.
III. STABLE ICE STRUCTURE AND ITS MELTING
POINT IN THE TIP4P AND TIP5P MODELS
First of all, we discuss the free energy of I dh , I oh , water,
and vapor in the TIP4P and the TIP5P model, to establish the
stable structure of ice and its T M in these models. Figures 1
and 2 show G as a function of T (G – T curve兲 for I dh , I oh ,
water, and vapor, for the TIP4P and TIP5P model, respec-
tively. For the G – T curve of I oh , water and vapor in the
TIP4P model, we refer to the results obtained by Vlot et al.25
Like in that study, the G – T curves are obtained as follows.
At a temperature T 0 , the Gibbs free energy G 0 is calculated
by adding a term PV to the Helmholtz free energy A 0 ,
which is calculated using the TDI method for ice, and the
H. Nada and J. P. J. M. van der Eerden
FIG. 2. The G – T curves in the TIP5P model for ice, water, and vapor.
f g-sampling method for water and vapor. Then, the G – T
curve is obtained with the help of the Gibbs–Helmholtz
relation,
冉 G G0
⫺
T T0 冊 冕
P
⫽⫺
T H
T0 T ⬘
2 dT ⬘ . 共12兲
Here, H (⫽U⫹3Nk B T⫹ PV) is the enthalpy as a function
of T, which is determined by fitting the H obtained from the
MC simulations to a quadratic polynomial for ice and vapor,
and a third-order polynomial for water. The coefficients in
the polynomials of H, and the values of G 0 and T 0 are given
in Table II.
The accuracy of the G – T curve for ice was checked by
an independent calculation of G at 175 K for the TIP4P
model and 200 K for the TIP5P model. Similarly, the accu-
racy of the G – T curve for water was checked by indepen-
dent calculations of G at several different T between 300 and
350 K. Moreover, we confirmed that the G calculated in this
study was equal to the G calculated by Vlot et al.25 Finally,
we again checked the accuracy of the G – T curve by calcu-
lating G of ice at T M estimated.
It can clearly be seen that the G of I oh is lower than that
d
of I h at the T-range displayed in the figures, for both the
TIP4P and TIP5P models. This indicates that I oh is more
stable than I dh in both models at the T-range. The T M of I oh in
the TIP4P model has already been estimated to be 214
⫾6 K by Vlot et al.25 In this study, we estimated the T M of
I dh in the TIP4P model to be 191⫾7 K from the intersection
point of the G – T curves, which is much lower than the real
T M ⫽273.15 K. The T M of I oh in the TIP5P model was esti-
mated to be 270⫾7 K, which is close to the real T M . How-
ever, the T M of I dh in the TIP5P model was estimated to be
213⫾8 K, which is much lower than the real T M , like in the
TIP4P model. In summary, the TIP4P and TIP5P models are
not suitable for the simulation of real ice near T M , because
the real structure of ice, I dh , is not stable near T M . In this
paper, we assume that the free energy minimum structure of
ice near T M at 1 atm for the TIP4P and TIP5P models is I oh .
In addition to T M , the boiling point T B in the TIP5P
model was also estimated to be 348⫾3 K, which underesti-
mates the real T B (⫽373.15 K) by 25 K only.
Our estimation, T M ⫽191⫾7 K of I dh for the TIP4P
model is not consistent with T M ⫽238⫾7 K estimated by
Gao et al.26 They calculated the G of I dh using a Debye ref-
J. Chem. Phys., Vol. 118, No. 16, 22 April 2003 A potential model for ice and water 7405

TABLE II. Coefficients of the enthalpy H as a function of T, H⫽h 0 ⫹h 1 T⫹h 2 T 2 ⫹h 3 T 3 , with the values of G 0 and T 0 for ice, water, and vapor.

T 共K兲 h 0 共kJ/mol兲 h 1 共kJ/mol K兲 h 2 (kJ/mol K2 ) h 3 (kJ/mol K3 ) T 0 共K兲 G 0 (T 0 ) 共kJ/mol兲

TIP4P I dh a 150–300 ⫺56.044 4.356⫻10⫺2 3.560⫻10⫺5 250 ⫺50.16⫾0.27

I oh 20–270 ⫺58.060 4.824⫻10⫺2 2.400⫻10⫺5 20 ⫺54.90⫾0.01
Watera 160–510 ⫺57.200 6.679⫻10⫺2 2.891⫻10⫺5 350 ⫺57.78⫾0.14
Vapora 360–710 ⫺4.260 4.682⫻10⫺2 ⫺1.071⫻10⫺5 410 ⫺68.06⫾0.04
TIP5P I dh 150–300 ⫺57.794 4.071⫻10⫺2 4.787⫻10⫺5 250 ⫺49.58⫾0.34
I oh 150–300 ⫺59.755 4.342⫻10⫺2 3.374⫻10⫺5 250 ⫺50.54⫾0.22
Water 225–350 48.167 ⫺1.176 4.636⫻10⫺3 ⫺5.426⫻10⫺6 350 ⫺56.11⫾0.13
Vapor 350–550 ⫺7.338 6.190⫻10⫺2 ⫺2.825⫻10⫺5 350 ⫺56.29⫾0.08
Present model I dh 150–300 ⫺58.590 4.465⫻10⫺2 3.426⫻10⫺5 275 ⫺50.85⫾0.22
I oh 150–300 ⫺58.770 4.330⫻10⫺2 3.727⫻10⫺5 275 ⫺50.31⫾0.21
I co 150–300 ⫺57.334 3.261⫻10⫺2 6.496⫻10⫺5 275 ⫺49.81⫾0.23
Water 237.5–350 ⫺115.792 5.175⫻10⫺1 ⫺1.103⫻10⫺3 9.572⫻10⫺7 350 ⫺55.84⫾0.18
Vapor 350–550 ⫺5.977 5.725⫻10⫺2 ⫺2.397⫻10⫺5 350 ⫺56.45⫾0.07
a
Reference 25.

erence crystal, instead of an Einstein reference crystal, and ice from water in the TIP4P model by MD simulations of an
suggested that the G obtained from the TDI with the Einstein NVT system at 230 K.35 They fixed the density of the system
reference crystal depends on the choice of the force con- to the density of ice at 1 atm, which is much lower than the
stants. However, we checked that different choices of the density of water at 1 atm. This means that the simulations of
force constants led to the same G. water were carried out at a much lower P (Ⰶ0) than 1 atm.
In order to check our estimation of T M for the TIP4P It is well known that T M of ice increases with decreasing P.
model, we carried out an NPT–MC simulation of coexist- Therefore, T M in their NVT system would be much higher
ence of I dh and water at T⫽230 K and P⫽1 atm. As can than T M ⫽214⫾6 K at 1 atm. We inferred T M in their NVT
clearly be seen in Fig. 3, I dh started to melt during the simu- system, from the density of their system, and from the den-
lation. This strongly suggests that, for the TIP4P model in- sity and compressibility of water and ice around 230 K at 1
cluding a switching function with a cut-off radius of 10 Å, atm. Although it was impossible to estimate it exactly, it
T M of I dh is much lower than 230 K. We did not carry out the
simulation at T⬍230 K, because the melting rate at T
⬍230 K was expected to be too small to observe a clear
melting during the simulation run in the present work. How-
ever, the result at 230 K well supports our estimation of
T M ⫽191⫾7 K of I dh for the TIP4P model. We, therefore,
conclude that the G and T M obtained by the TDI with our
Einstein reference crystal are reliable.
It may be noted that there are several differences in the
potential calculation and the system used between the
present and Gao et al.’s studies, which may yield different
estimation of G and T M . For example, the cut-off radius of
the potential, R c ⫽10 Å, used in this study is longer than that
used by them. As will be discussed in Sec. V, G of I dh actu-
ally depends on R c , especially for R c ⬍10 Å. Similarly,
differences in the switching function of the potential and
the size of I dh used may also influence the estimation of G
and T M .
Nada and Furukawa carried out MD simulations of
I oh –water interfaces at T⫽220 and 230 K using the TIP4P
model,17,18 and observed the growth of a molecular layer at
the interfaces. This seems inconsistent with the T M ⫽214
⫾6 K, which was estimated in the free energy calculation.
However, they used R c ⫽10.9 Å, which is longer than R c FIG. 3. Hydrogen-bonded network configurations around interfaces between
I dh and water, which were obtained from a MC simulation of the two phase
⫽10 Å used in this study. Moreover, the system used in the coexistence at T⫽230 K and P⫽1 atm for the TIP4P model; 共a兲 for 5
MD simulations included a fixed ice structure region at a ⫻108 th configuration and 共b兲 for 2⫻109 th configuration after equilibration.
boundary, which may yield some ordering of molecules even Dotted lines show initial positions of interfaces. The shape of the simulation
at T⬎T M . Thus, we conclude that, in addition to effect of system was a rectangular parallelepiped, and three-dimensional periodic
boundary conditions were imposed in the system. The system contained I dh
the longer R c , the fixed structure region in their system
consisted of 720 H2 O and water consisted of 720 H2 O at the beginning of
strongly influenced to yield the growth at the interfaces. the simulation. The hydrogen bonds were defined by an energetic definition
Recently, Matsumoto et al. observed crystallization of 共Ref. 17兲.
7406 J. Chem. Phys., Vol. 118, No. 16, 22 April 2003 H. Nada and J. P. J. M. van der Eerden

In this study, we introduced the six-site model referring

to the spatial distribution of electron densities around a water
molecule. It is known that electrons in a water molecule are
distributed around the H-atoms and L-sites, in addition to
main distribution around the center of mass of the molecule.
Thus, in the present model, point charges are placed on H, L,
and M-sites.
The intermolecular interaction between molecules i and
j, ␾ i j , is represented as the sum of the Coulomb interactions
acting among the charged points and the Lennard-Jones in-
teractions acting on O and H atoms, as follows:

␾i j⫽ 兺
H,L,M
q Iq J
r IJ
ij
⫹4 兺
O,H
␧ IJ 再冉 冊 冉 冊 冎
␴ IJ
r IJ
ij
12
⫺
␴ IJ
r IJ
ij
6
. 共13兲

Here, r IJ
i j is the distance between site I of molecule i and site
J of molecule j. q I shows the charge amount of site I.
FIG. 4. Schematic illustration of the H2 O molecule in the present six-site
model.

B. Potential parameters
turned out that T M in their system might well be somewhat In this study, parameters in the potential function were
higher than 230 K. This is consistent with the fact that they obtained as follows. First, a six-site potential ␾ 0 with tenta-
did not observe crystallization in their NVT system above tive parameters ␰ 0 共that is, parameters included in the ␾ 0
230 K, neither in the NPT system at 230 K and 1 atm. Thus, such as ␧, ␴, and q) was chosen. Using ␾ 0 , the Gibbs free
we conclude that the crystallization at 230 K was due to a energies G 0 and the volumes V 0 of I dh and water at 273 K,
much higher T M in their NVT system than at 1 atm. and the V 0 of water at 298 K were estimated from the MC
Tanaka and Mohanty observed jumping of some mol- simulations. Moreover, the derivatives of G 0 and of V 0
ecules from the ideal lattice sites to other sites at T⭓200 K against each ␰ 0 were calculated as follows:38
during simulations of I dh for the TIP4P model.36 If the jump-
ing corresponded to the ordering of the proton-arrangement
in I dh as they claimed, their result would be consistent with 冉 冊 冓 冔
⳵G0
⳵␰ 0 NPT
⫽
⳵U0
⳵␰ 0 NPT
. 共14兲
the present result that I oh is more stable than that of I dh for the
TIP4P model. Moreover, their result implied that I oh is the
具 V 0 典 NPT 冓 冔 冓
⳵U0
⫺ V0
⳵U0
冔
free energy minimum structure of ice near T M at 1 atm for
the TIP4P model, which is also consistent with our
assumption.
冉 ⳵
⳵␰ 0
具 V 0典 冊 NPT
⫽
⳵␰ 0 NPT
k BT
⳵␰ 0 NPT

IV. SIX-SITE POTENTIAL MODEL OF H2 O
We propose a new intermolecular potential model of
rigid H2 O molecule, which has six interaction sites. In this
section, we will see that this six-site model is much more
suitable for the simulations of ice and water near T M than the
TIP4P and TIP5P models.
A. Geometry
Figure 4 shows the molecular geometry of the present
six-site model. A positive point charge is placed on each
hydrogen 共H兲 site, and a negative charge on each lone-pair
共L兲 site, like in the TIP5P model. A negative charge is also
placed on a site M, which is located on the bisector of
⬔HOH, as in the TIP4P model. A different point from the
TIP4P and TIP5P models is that the Lennard-Jones interac-
tion acts not only on the oxygen 共O兲 site but also on the H
sites in the present model. For the OH length (r OH) and
HOH in this model, intermediate values between those of the
real molecule in the ice and vapor phases are taken.37 The
average of ⬔HOH and ⬔LOL in the present model is the
tetrahedral angle of 109.5°.
共15兲
Using these derivatives, values of G and V in the potential ␾
with a new set of potential parameters ␰ ⫽ ␰ 0 ⫹⌬ ␰ 0 were
predicted by linear extrapolation. Next, we chose new pa-
rameter values ␰, which were predicted to satisfy the follow-
ing three conditions: 共a兲 the value of G at 273 K is the same
for both ice and water, that is, T M ⫽273 K, 共b兲 the ␳ of ice
and water, ␳ I and ␳ W , at T M are the same as the experimen-
tal values, and 共c兲 the ␳ W of water at 298 K is equal to the
experimental value. This procedure was iterated until the de-
sired properties were satisfied.
In this way, we deduced optimum values for ␧ OO , ␧ HH ,
␴ OO , ␴ HH , q L , q M , and r OL . At each iteration step, q H was
determined to satisfy the electrically neutral condition of the
molecule, 2q H⫹2q L⫹q M⫽0. ␧ OH and ␴ OH were obtained
from the Lorentz–Berthelot rules, ␧ OH⫽(␧ OO•␧ HH) ⫺1/2 and
␴ OH⫽( ␴ OO⫹ ␴ HH)/2. Furthermore, r OH , r OM , ⬔HOH, and
⬔LOL were kept constant during the iterations. The final
parameter values of the TIP4P, TIP5P and the present six-site
models that we used are given in Table III.
The advantage of this method is that all values of G and
V at each T for both ice and water are predicted simulta-
neously. It turned out that the predicted G and V are usually
J. Chem. Phys., Vol. 118, No. 16, 22 April 2003 A potential model for ice and water 7407

TABLE III. Parameters in the TIP4P, TIP5P, and the present six-site model. TABLE IV. Dependence of G of I oh at 275 K in the present six-site model on
the C Tr and C Rot in the present Einstein reference potential.
TIP4Pa TIP5Pb Present model
C Tr /k B T (Å ⫺2 ) C Rot /k B T G 共kJ/mol兲
r OH 共Å兲 0.9572 0.9572 0.980
r OM 共Å兲 0.15 0.230 32.0 40.0 ⫺50.31⫾0.20
r OL 共Å兲 0.70 0.8892 24.0 30.0 ⫺50.31⫾0.21
⬔HOH 共deg兲 104.52 104.52 108.00 20.0 20.0 ⫺50.30⫾0.21
⬔LOL 共deg兲 109.47 111.00
␧ OO /k B 共K兲 78.0202 80.5147 85.9766
␧ HH /k B 共K兲 13.8817
␴ OO 共Å兲 3.154 3.12 3.115 much higher than the G of I dh . Thus, to the best of our
␴ HH 共Å兲 0.673 knowledge, the present model provides I dh as the most stable
q H (e) 0.52 0.241 0.477
q M (e) ⫺1.04 ⫺0.866
structure, like in the real system.
q L (e) ⫺0.241 ⫺0.044 We estimated T M of I dh in the present six-site model to be
271⫾9 K, which is in quite good agreement with the real T M
a
Reference 12. of 273.15 K. The error in T M was determined on the assump-
b
Reference 29.
tion that the distribution of the H of six I dh structures makes
the error in T M . In addition to T M , the T B was also esti-
mated to be 345⫾3 K, which is about 28 K underestimated
reliable when 兩 ⌬ ␰ / ␰ 兩 ⬍0.05. For ␴, however, predicted val-
from the real T B of 373.15 K.
ues are reliable only when 兩 ⌬ ␴ / ␴ 兩 ⬍0.01. This demonstrates
Here, we will discuss effect of the Ewald summation on
that the structural change of ice and water are sensitive to the
T M for the present model. In this study, we did not estimate
change of the potential parameters, especially for ␴.
T M using the Ewald method. However, we investigated de-
pendence of T M on R c , which we will discuss in Sec. V. We
C. Gibbs free energies of ice and water expect from the result of it that including the Ewald method
would hardly influence the relative stability of I dh and water.
Figure 5 shows the G – T curves of ice, water, and vapor
Hence, the Ewald summation would not significantly influ-
for the present six-site model. The G – T curves were ob-
ence T M of I dh . The same effect of the Ewald summation on
tained in the same manner as described in Sec. III. The co-
T M would also appear for the TIP4P and TIP5P models. For
efficients in the polynomials of H, the values of G 0 and T 0
the present model, we checked that I dh is more stable than I oh
are given in Table II. Moreover, in order to confirm that the
near T M at 1 atm for R c ⭓10 Å. Thus, we believe that, even
G of ice, as calculated by TDI with our Einstein reference
if the Ewald method is used, I dh corresponds to the free en-
crystal, did not depend on the choice of the force constants,
ergy minimum near T M at 1 atm for the present model, and
we calculated the G of I oh at 275 K using three different sets
the T M of it does not significantly change from 271⫾9 K,
of force constants. The results, given in Table IV, show that
which was estimated using R c ⫽10 Å.
fully equivalent G were obtained.
It can clearly be seen that the G of I dh is lower than that
D. Structural and thermodynamic properties
of I h . This indicates that I dh is more stable than I oh , which is
o
of ice and water near the melting point
consistent with the experiment. In order to confirm that I dh is
the most stable structure in the present model, we also cal- 1. Structural properties of ice and water
culated G for the proton-ordered cubic ice I oc , using a system near the melting point
consisting of 512 H2 O molecules. The G – T curve of I oc is The ␳ I and ␳ W , the heat of melting ⌬H M , dT M /d P and
also given in Fig. 5. It is obvious that the G of I oc is much lattice constants of ice for three directions, a, b and c, at T M
higher than that of I dh . Besides, we also tested polar proton- are given in Table V. It can be seen that the experimental ␳ I ,
order hexagonal and cubic ice structures, their G were also a, b, and c are very well reproduced in the present model.
The values of ⌬H M and dT M /d P are close to the experi-
mental values. The ␳ W at T M in the present model is slightly
lower, but still included within the error bar, than the experi-
mental value.
Next, we will compare T-dependence of the densities of
ice and water near T M in the present model with the TIP4P
and TIP5P models. Since T M of the models are different with
each other, we plotted the densities as a function of
T * (⫽T/T M ). Moreover, in order to facilitate comparison
of the density difference between ice and water near T M , we
scaled the densities by ␳ I at T⫽T M , ␳ I (T M ), for all the
models.
Figure 6共a兲 shows ␳ I* and ␳ W * , which are ␳ I and ␳ W
scaled by ␳ I (T M ), as a function of T * . For reference, non-
FIG. 5. The G – T curves in the present six-site model for ice, water, and scaled ␳ – T curves are also given in Fig. 6共b兲. Although, at
vapor. T * ⬍0.9, the slopes of the ␳ I* ⫺T * curve in the TIP5P and
7408 J. Chem. Phys., Vol. 118, No. 16, 22 April 2003 H. Nada and J. P. J. M. van der Eerden

TABLE V. The stable structure of ice at T M ; ␳ I (T M ), the density of stable

ice at T M ; ␳ W (T M ), the density of water at T M ; ⌬H M , the heat of melting
at T M ; the lattice constants, a, b, and c, of stable ice at T M ; and dT M /d P,
which was estimated by the Clapeyron–Clausius relation, dT M /d P
⫽T M ⌬V/⌬H. The ␳ W for the TIP5P and present models were directly
obtained from the MC simulation at T M , whereas other quantities were
obtained from extrapolations using the polynomials, which are given in
Tables II, VI, and VII.

TIP4Pa TIP5P Present model Expt.

Stable structure I oh I oh I dh I dh
T M 共K兲 214⫾6 270⫾7 271⫾9 273.15
␳ I (T M ) (g/cm3 ) 0.966 0.982⫾0.002 0.917⫾0.002 0.917b
␳ W (T M ) (g/cm3 ) 1.037 1.000⫾0.011 0.989⫾0.012 0.999c
⌬H M /k B T M 2.84 3.23⫾0.06 2.84⫾0.07 2.646d
⫺dT M /d P 共K/MPa兲 0.054 0.014⫾0.002 0.064⫾0.002 0.074b
a 共Å兲 4.81 4.75⫾0.01 4.52⫾0.01 4.523b
b 共Å兲 7.31 7.27⫾0.01 7.82⫾0.01 7.834b
c 共Å兲 7.02 7.08⫾0.01 7.37⫾0.01 7.368b
a
Reference 25.
b
Reference 39.
c
Reference 40.
d
Reference 41.

the present models are slightly larger than in experiment, the

experimental ␳ I* ⫺T * curve near T M (T * ⬎0.9) is well re-
produced by all models. The ␳ W * ⫺T * curve, however, is sig-
nificantly better reproduced by the present model than by the
other models. This indicates that the present model suffi-
ciently reproduces the real density difference between ice
and water near T M . Moreover, the maximum of the ␳ W * ap-
pears around T * ⫽1.06 in the present model, which is com-
parable with the maximum of the ␳ W * in the experiment at
T * ⫽1.0145.
It can be noted that the slope of the ␳ W * ⫺T * curve at
T * ⬍1 in the present model is much larger than in the ex-
periment. The ␳ W * , however, showed a large fluctuation, es-
pecially in the range of T * between 0.95 and 1.03, as can be
seen in the error bars of ␳ W* in Fig. 6共a兲. This suggests that
structural fluctuations take place, possibly related to the tran-
sition to a low-density amorphous structure,43– 46 or to the
nucleation of ice. More intensive studies are required to elu-
cidate the structure of the supercooled water in the present
model. Nevertheless, it is obvious that the reproduction of
the ␳ I* ⫺T * and ␳ W * ⫺T * curves near T M is better in the
present model than in the TIP4P and TIP5P models.
FIG. 6. 共a兲 Scaled ␳ – T relationships: ␳ I* ⬅ ␳ I / ␳ I (T M ) for the most stable
ice structure and ␳ W* ⬅ ␳ W / ␳ I (T M ) as a function of T * ⬅T/T M . Solid tri-
angles, squares, and circles show ␳ I* for the TIP4P, TIP5P, and the present
models for the most stable structure, respectively. Open triangles, squares,
and circles show ␳ W * for the TIP4P, TIP5P, and the present models, respec-
tively. Dotted lines are experimental data 共Ref. 40兲. 共b兲 Nonscaled ␳ – T
relationships: ␳ I and ␳ W as a function of T.
In addition, coefficients of quadratic polynomials for a,
b, c, ␳ I , ␳ W , and ␳ for vapor as a function of T are given in
Tables VI and VII, respectively.
2. Pair correlation functions and thermodynamic
properties of water near the melting point
Most of the potential models for H2 O have been pro-
posed and tested for the simulation of water at 25 °C (T
⫽298.15 K, in the real system兲. Thus, the structure of water
in the simulation has often been compared with the experi-
ment at 298.15 K. However, in the real system, the tempera-

TABLE VI. Coefficients in the polynomials of the lattice constant a, b, and c of the stable ice as a function of
T, a⫽I 0 ⫹I 1 T⫹I 2 T 2 .

T 共K兲 I 0 共Å兲 I 1 共Å/K兲 I 2 (Å/K2 )

TIP4Pa I oh a 共Å兲 20–290 4.722 0.98⫻10⫺4 4.4⫻10⫺7

b 共Å兲 20–290 7.335 ⫺3.5⫻10⫺4 1.2⫻10⫺6
c 共Å兲 20–290 6.910 5.4⫻10⫺4 8.0⫻10⫺8
TIP5P I oh a 共Å兲 150–300 4.692 ⫺1.049⫻10⫺5 8.120⫻10⫺7
b 共Å兲 150–300 7.151 3.557⫻10⫺4 7.229⫻10⫺8
c 共Å兲 150–300 6.889 6.538⫻10⫺4 ⫺5.457⫻10⫺8
Present model I dh a 共Å兲 150–300 4.442 1.571⫻10⫺4 4.648⫻10⫺7
b 共Å兲 150–300 7.671 5.270⫻10⫺4 1.200⫻10⫺7
c 共Å兲 150–300 7.258 2.063⫻10⫺4 8.800⫻10⫺7
a
Reference 25.
J. Chem. Phys., Vol. 118, No. 16, 22 April 2003 A potential model for ice and water 7409

TABLE VII. Coefficients in the polynomials of the densities of ice ␳ I , water ␳ W , and vapor ␳ V , as a function
of T, ␳ ⫽ ␳ 0 ⫹ ␳ 1 T⫹ ␳ 2 T 2 .

T 共K兲 ␳ 0 (g/cm3 ) ␳ 1 (g/cm3 K) ␳ 1 (g/cm3 K2 )

TIP4P I dh 150–300 0.977 ⫺1.215⫻10⫺4 ⫺1.780⫻10⫺7

I oa
h 20–290 0.989 ⫺5.3⫻10⫺5 ⫺2.5⫻10⫺7
Watera 160–510 0.897 1.38⫻10⫺3 ⫺3.4⫻10⫺6
Vapora 360–710 1.5⫻10⫺3 ⫺3.0⫻10⫺6 1.9⫻10⫺9
TIP5P I dh 150–300 1.040 ⫺1.718⫻10⫺4 ⫺3.882⫻10⫺7
I oh 150–300 1.031 ⫺1.308⫻10⫺4 ⫺1.945⫻10⫺7
Water 250–287.5 1.324⫻10⫺3 1.660⫻10⫺2 ⫺2.957⫻10⫺5
Water 287.5–350 0.529 3.675⫻10⫺3 ⫺7.027⫻10⫺6
Vapor 350–500 ⫺0.002 ⫺4.426⫻10⫺6 3.546⫻10⫺9
Present model I dh 150–300 0.968 ⫺1.377⫻10⫺4 ⫺1.834⫻10⫺7
I oh 150–300 0.981 ⫺1.963⫻10⫺4 ⫺6.952⫻10⫺8
I co 150–300 0.941 1.716⫻10⫺4 ⫺9.655⫻10⫺8
Water 237.5–287.5 ⫺0.054 6.376⫻10⫺3 ⫺9.403⫻10⫺6
Water 287.5–350 0.623 2.760⫻10⫺3 ⫺5.031⫻10⫺6
Vapor 350–500 1.742⫻10⫺3 ⫺4.391⫻10⫺6 3.539⫻10⫺9
a
Reference 25.

ture of T⫽298.15 K corresponds to T * ⫽1.09. Therefore, if
the water structure near T M is compared with the experiment,
the comparison should be carried out at T * ⫽1.09, rather
than 298.15 K.
Figures 7–9 shows the pair correlation functions for
O–O (g OO), O–H (g OH) and H–H atoms (g HH) in water at
T * ⫽1.09, respectively. For reference, the pair correlation
functions at T⫽298 K are also shown as dotted lines, though
there are few differences in the functions between T *
⫽1.09 and T⫽298 K for the TIP5P and the present models.
It can be seen that the TIP5P and the present models repro-
duce the experimental g 兵 OO其 quite well, whereas the correla-
tion that appears in the g OO in the TIP4P model at T *
⫽1.09 is stronger than that in the experiment. This suggests
that water near T M in the TIP4P model has a more highly
ordered structure than real water. All models reproduce g OH
and g HH equally well. Thus, the real structure of water near
T M is well reproduced in the present model.
In Table VIII, some of the thermodynamic variables of
water at T * ⫽1.09 are shown. Although the heat capacity C P
and the isothermal compressibility ␬ in the present model are
somewhat overestimated, the experimental heat of vaporiza-
tion ⌬H vap and ␳ W are well reproduced, as well as in the
TIP5P model. The thermal expansion coefficient ␣ is much
better reproduced in the present model than in the TIP4P and
TIP5P models. Thus, overall, the present model provides bet-
ter thermodynamic quantities of real water at T * ⫽1.09 than
the TIP4P and TIP5P models. Consequently, we conclude
that the structure and thermodynamic properties of real water
near T M are sufficiently reproduced in the present six-site
model, in addition to the structure of real ice with the real
T M of it. This strongly suggests that the present model is
suitable for simulations of ice and water near T M .
Additionally, the dielectric constant of water at 298 K in
the present model was estimated using the same method as
described in Ref. 29. The estimated dielectric coefficient was
33⫾7, which is much lower than the experimental value of
78.48 This small dielectric coefficient in the present model
would be mainly due to smaller dipole moment of the mol-
ecule of 1.89 D in the present model than 2.18 D in the
TIP4P model and 2.29 D in the TIP5P model.
Furthermore, the mean square displacements 共MSD兲 of

FIG. 7. O–O pair correlation functions at T * ⫽1.09 for the TIP4P model, FIG. 8. O–H pair correlation functions at T * ⫽1.09 for the TIP4P model,
the TIP5P model, the present model, and the experiment 共Ref. 47兲. Dotted the TIP5P model, the present model, and the experiment 共Ref. 47兲. Dotted
lines are the functions at 298 K. lines are the functions at 298 K.
7410 J. Chem. Phys., Vol. 118, No. 16, 22 April 2003 H. Nada and J. P. J. M. van der Eerden

TABLE IX. The U 共in kJ/mol兲 as a function of the cut-off radius R cut .

R c 共Å兲 8.0 9.0 10.0 11.0

TIP4P I dh ⫺48.59 ⫺48.94 ⫺49.19 ⫺49.28

I oh ⫺48.72 ⫺49.59 ⫺50.74 ⫺50.06
TIP5P I dh ⫺50.32 ⫺50.69 ⫺50.87 ⫺50.98
I oh ⫺51.06 ⫺51.78 ⫺53.05 ⫺53.76
Present model I dh ⫺50.97 ⫺51.29 ⫺51.52 ⫺51.64
I oh ⫺51.07 ⫺51.95 ⫺51.87 ⫺52.28
I co ⫺51.92 ⫺52.95 ⫺51.41 ⫺51.20
Water ⫺41.44 ⫺41.55 ⫺41.48 ⫺41.58

nificant for water. As we are interested in the stable I dh and

FIG. 9. H–H pair correlation functions at T * ⫽1.09 for the TIP4P model,
the TIP5P model, the present model, and the experiment 共Ref. 47兲. Dotted
lines are the functions at 298 K.
molecules in water at 298 K as a function of MC steps in the
present model were compared with those in the TIP4P and
TIP5P models, to infer the diffusion coefficient, D s , in the
present model. Although it was difficult to estimate the exact
value of D s by the MC simulation, the slope of MSD in the
present model was quite similar to that in the TIP5P model,
under the same simulation conditions. We, therefore, expect
that the D s in the present model is close to the experimental
value as well as in the TIP5P model, in which the experi-
mental D s is well reproduced.49
V. DISCUSSION
A. Dependence of the melting point
on the cut-off radius
In this study, the G of ice and water were calculated
using R c of 10 Å with a switching function for the estimation
of the intermolecular interaction. However, the estimation of
G depends on the choice of R c . Table IX shows the U of ice
at 250 K and water at 300 K using R c ⫽8, 9, 10, and 11 Å.
It can be seen that the U of I oh strongly depends on R c ,
most for R c ⭐9 Å in the present model, and for R c ⭐10 Å in
the TIP4P and TIP5P models. On the other hand, the depen-
dence of U on R c is much weaker for I dh and is quite insig-
water phases, the choice of R c ⫽10 Å seems a sensible com-
promise. The stronger dependence of U on R c for I oh than for
I dh and for water reflects the long-range correlation of spatial
charge distribution in I oh , while there is no significant long-
range correlation of the charge distribution in I dh and water.
The difference in the correlation can be found in the pair
correlation function between the dipole moments of
molecules.
Supposing that the variation of G with R c is mainly due
to the variation of U, the shift of T M depends mainly on the
shift of U of ice. Consequently, for I oh , the T M drastically
increases with increasing R c , especially for R c ⭐9 Å in the
present model, and for R c ⭐10 Å in the TIP4P and TIP5P
models. For I dh , T M increases only slowly with increasing
R c . For example, if R c ⫽11 Å is chosen in the present
model, the T M of I dh is estimated to be 275 K, which is fully
included in the error bar of T M ⫽271⫾9 K for R c ⫽10 Å.
Even if infinitely long R c is chosen, we do not expect that
T M of I dh is beyond the error bar of T M for R c ⫽10 Å, be-
cause the variation of G with R c is thought to be negligibly
small for R c ⭓11 Å. Moreover, we also checked that G of I dh
never is higher than that of I oh at T M for R c ⫽12, 13, 14, and
20 Å in the present model, and also that I oc is not stable for
R c ⭓10 Å. Thus, our choice of R c ⫽10 Å is sufficient to pro-
vide I dh as a stable structure. It, however, would be more
desirable to discuss the effect of the infinitely long-range
interaction by including the Ewald summation method. We,
therefore, intend to include it in future research.
Since T M depends on R c , the relationship between T M

TABLE VIII. Some thermodynamic variables of water at T * ⫽1.09; the scaled water density ␳ W , the heat of
vaporization ⌬H vap , the heat capacity C P , the isothermal compressibility ␬, and the thermal expansion coef-
ficient ␣. The ⌬H vap was estimated by the approximation, ⌬H vapⱌU W ⫹Nk B T, where U W is the potential
energy of water. The C P and ␣ were estimated using the same method as described in Ref. 42. The ␬ was
estimated by the fluctuation formula, ␬ ⫽( 具 V 2 典 ⫺ 具 V 典 2 )/k B T 具 V 典 . The thermodynamic variables at T⫽298 K are
given in parentheses.

TIP4P TIP5P Present model Expt.b

T (⫽1.09 T M ) 共K兲 234 295 296 298.15

␳ W (g/cm3 ) 1.034a 共1.006a兲 1.002⫾0.007 (1.000) 1.000⫾0.008 (0.999) 0.997
⌬H vap /k B T 24.55a 共18.01a兲 18.05⫾0.02 (17.73) 17.98⫾0.03 (17.80) 17.74
C P 共J/mol deg兲 80a 共84a兲 125⫾3 (122) 102⫾3 (101) 75.3
106 ␬ (atm⫺1 ) 30⫾9 共58兲 50⫾8 (46) 55⫾8 (56) 45.8
105 ␣ (deg⫺1 ) 20a 共64a兲 60⫾4 (67) 24⫾3 (28) 25.7
a
Reference 25.
b
Reference 42.
J. Chem. Phys., Vol. 118, No. 16, 22 April 2003
and T at which the maximum of ␳ W appears, which was
described in Sec. IV D, may also depend on R c . Similarly,
relationship between T M and the structure of the supercooled
water may also be influenced by the choice of R c . 27,28 There-
fore, if we focused on such relationships, it would be neces-
sary to investigate dependence of the ␳ W – T curve and the
water structure on R c in more detail for each model, as well
as the dependence of T M on R c . We, however, emphasize
that the purpose of this study is to propose a model that has
I dh as the stable structure near T M . Note that a good model to
describe the structural properties of water around T M should
reproduce both T M and T at which the maximum of ␳ W
appears accurately. Therefore, investigations of the depen-
dence of T M on R c and/or those of the effect of the Ewald
summation on T M in a model will help provide a thorough
understanding of the structural properties of water
around T M .
B. Stability of hydrogen-bonded configurations in ice
Finally, we will discuss why only the present six-site
model provides I dh as a stable structure near T M . Suppose
that the dominant contribution to the U of I dh is from the first
nearest neighbors. Then, the stability of I dh will be related to
the distribution of the energy E dim of the water dimer. Figure
10共b兲 shows the E dim as a function of the tilt angle ␶ at the
rotation angle ␪ ⫽0 and 60°. The definitions of ␶ and ␪ are
given in Fig. 10共a兲. The E dim shown there is the lowest en-
ergy of the water dimer upon changing the O–O distance of
the dimer at each ␶ and ␪.
All molecules in ice are connected by a hydrogen bond.
In Fig. 10, four plausible different hydrogen-bonded configu-
rations of water dimers are shown, which we refer to as A
( ␶ ⫽⫺55°, ␪ ⫽0°), B (55°,0°), C (⫺55°,60°), and D
(55°,60°). All four water dimer configurations occur in I dh ,
only B and D occur in I oh , and arbitrary values of ␶ and ␪
occur in water. If all A, B, C, and D are energetically roughly
equally stable, then I dh may appear as a stable structure.
For the present model, local minima appear in the E dim
around A, B, C, and D, and the E dim of them are close to
each other. This indicates that all four water dimer configu-
rations are energetically stable, and hence the present model
provides I dh as a stable structure. For the TIP5P model, the
E dim of A and C are much higher than the E dim of B and D.
This explains why I dh is not provided as a stable structure,
and explains why T M of I oh is much higher than that of I dh in
the TIP5P model 共270 K versus 213 K兲. For the TIP4P
model, local minima appear only around B and D, again
explains why I dh is not stable in the TIP4P model.
In order to infer whether the TIP4P or TIP5P model with
modified potential parameters provides the stable I dh , we cal-
culated derivatives of G against ␧, ␴ or q in the TIP4P and
TIP5P models, for I dh and I oh . However, the derivatives for I dh
and I oh were very similar, like in the present model 共see Table
X兲. This suggests that these models with modified param-
eters can hardly have the stable I dh , even if the present
method to obtain optimum parameters is applied. Moreover,
we tested several four- and five-site models with different
r OH , r OM , r OL , ⬔HOH, and ⬔LOL from the TIP4P and
A potential model for ice and water 7411
FIG. 10. 共a兲 The definitions of the tilt angle ␶ and the rotation angle ␪ of the
molecule. 共b兲 The minimum energy of the water dimer, E dim , as a function
of ␶ for ␪ ⫽0° 共the upper兲 and for ␪ ⫽60° 共the lower兲. Illustrations of four
hydrogen-bonded configurations of the water dimer A, B, C, and D in ice are
also given.
TIP5P models. However, for all models that we tested, I dh
was not stable at T M , and the E dim of A and C were much
higher than those of B and D. Thus, we expect that the stable
structure of ice in a model is essentially independent of the
potential parameter values, and that introduction of a six-site
model is required to have the stable I dh .
In our calculation, the simulation of the present six-site
model needed about 2.3 times longer cpu time than the
TIP4P model. This seems to be a reasonable price for the
simple model, which is suitable for the simulation of ice and
water near T M . Currently new potential models of H2 O are
being developed: a polarizable model50–54 and a flexible
model.55,56 However, at this point, we cannot speculate
whether these models are superior to the present six-site
model. Note, however, that they are developed mainly for the
simulation of water above T M .
A fluctuating charge model 共TIP4P-FQ model兲 proposed
by Rick et al. reproduces well the dielectric properties of
water and ice, and the density curve of water.54,57 A recent
simulation study implied that I dh is stable at the T M of real ice
in the TIP4P-FQ model.57 Therefore, if I dh corresponds to the
free energy minimum near the T M at 1 atm, such a fluctuat-
ing charge model may be the future model, which is suitable
for the simulation of real ice and water near T M . Note, how-
ever, that G and T M of ice structures for the fluctuating
charge model have not been established yet.
The potential parameters in the present model were de-
termined to reproduce the real T M of ice, ␳ I and ␳ W near
T M , by using derivatives of G and V against the potential
parameters. It turned out that the G and V are quite sensitive
to the choice of potential parameters. Even if the parameters
7412 J. Chem. Phys., Vol. 118, No. 16, 22 April 2003 H. Nada and J. P. J. M. van der Eerden

TABLE X. Derivatives of G against the parameters in the present model for at 275 K and water at 300 K.
具 ⳵ G/ ⳵ q M 典 LP stands for the derivative of G against q M , with keeping q L constant, and with keeping the sum of
charges in a molecule constant.

I dh 共275 K兲 I oh 共275 K兲 I co 共275 K兲 Water 共300 K兲

具 ⳵ G/ ⳵ ␧ OO典 P 13.992 14.246 13.462 8.145

具 ⳵ G/ ⳵ ␧ OH典 P 3.312 3.466 2.994 ⫺0.515
具 ⳵ G/ ⳵ ␧ HH典 P ⫺1.325⫻10⫺2 ⫺1.326⫻10⫺2 ⫺1.343⫻10⫺2 ⫺1.477⫻10⫺2
具 ⳵ G/ ⳵␴ OO典 P 共K/Å兲 8.043⫻103 8.156⫻103 7.836⫻103 6.215⫻103
具 ⳵ G/ ⳵␴ OH典 P 共K/Å兲 2.122⫻103 2.167⫻103 2.031⫻103 1.056⫻103
具 ⳵ G/ ⳵␴ HH典 P 共K/Å兲 ⫺1.639 ⫺1.640 ⫺1.661 ⫺1.827
具 ⳵ G/ ⳵ q M 典 LP (K/e C) 1.312⫻104 1.322⫻104 1.298⫻104 1.021⫻104
具 ⳵ G/ ⳵ q M 典 HP (K/e C) ⫺2.623⫻104 ⫺2.644⫻104 ⫺2.545⫻104 ⫺1.821⫻104

deviate a few percent only from the optimum parameters, the simulations of ice surfaces and/or ice–water interfaces near
resulting G and V are largely influenced. It, therefore, should T M using the present model to confirm the suitability of the
be emphasized that the method to determine the potential model to the studies of ice and water near T M . We believe
parameters using the derivatives helped greatly to provide that the present model largely contributes to the understand-
the optimum parameters in the present model. The depen- ing of microscopic properties of ice and water near T M .
dence of G on the parameters can be appreciated from Table
X, where the derivatives against several parameters in the
present model are given. ACKNOWLEDGMENTS
The authors are grateful to Professor G.-J. Kroes, of
VI. CONCLUSIONS Leiden University, for providing us initial coordinates of
We proposed a new potential model of H2 O for the proton-disordered hexagonal ice. The authors also are
simulation of the ice and water near T M of ice, a six-site grateful to M. Louwerse for his helpful discussions about
rigid model of the H2 O molecule. The parameters in the the free energy of the proton-disordered ice in the TIP4P
potential model were determined to reproduce the real T M of model, and to J. Makkinje for his help regarding computer
ice, and the real structure and density of ice and water near programming.
T M , which were predicted from the derivatives of G and V
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