PHYSICA L R EVIEW LET T ERS week ending

VOLUME 91, N UMBER 2 11 JULY 2003

Monolayer Ice
Ronen Zangi* and Alan E. Mark
Department of Biophysical Chemistry, GBB, University of Groningen, Nijenborgh 4, 9747 AG Groningen, The Netherlands
(Received 4 October 2002; published 8 July 2003)
We report results from molecular dynamics simulations of water under confinement and at ambient
conditions that predict a first-order freezing transition from a monolayer of liquid water to a monolayer
of ice induced by increasing the distance between the confining parallel plates. Since a slab geometry is
incompatible with a tetrahedral arrangement of the sp3 hybridized oxygen of water, the freezing is
coupled to a linear buckling transition. By exploiting the ordered out-of-plane displacement of the
molecules in the buckled phase the distortion of the hydrogen bonds is minimized.

DOI: 10.1103/PhysRevLett.91.025502 PACS numbers: 61.20.Ja, 61.46.+w, 68.15.+e

Bulk ice exhibits a rich polymorphism of phases that [7] was used to describe the water molecules. A system of
are built of tetrahedrally coordinated hydrogen-bonded 780 water molecules was placed between two walls with a
water molecules [1]. While in ordinary ice the tetrahedral triangular arrangement of atoms out-of-registry with
geometry is nearly perfect, in most other ice phases respect to one another. The water-wall interactions were
distortions from ideal geometry occur. This involves represented by a 6 –12 Lennard-Jones (LJ) potential with
bending of the hydrogen bonds at the expense of bond the parameters: Ow W
0:316, Hw W
0:284 nm
strength. Hydrogen bonding interactions are insufficient and Ow W
0:831, Hw W
0:415 kJ=mol. These
to initiate the rehybridization of the sp3 hybridized oxy- parameters represent approximately the van der Waals
gen atom and thus a change in either the molecular H-O- (vdW) interaction between a water molecule and a quartz
H angle or in the spatial distribution of the electron (SiO2 ) surface. The evaluation of the nonbonded interac-
lone pairs. In principle, the tetrahedral arrangement of tions was performed using a twin range cutoff of 0.9 and
water is incompatible with a two-dimensional geometry. 1.4 nm. To account for the neglect of electrostatic inter-
Nevertheless, under confinement a competing phenome- actions beyond the long range cutoff a reaction-field
non comes into play. In general, confinement of a liquid correction assuming a relative dielectric of 78.0 was
to a film thinner than 4 –6 molecular layers will promote applied. Other simulation methodology used was the
solidification. This is because the characteristic transverse same as described previously [8].
density profile of a thin film can induce lateral ordering A first set of simulations was run at constant plate
and result in freezing. The effect is stronger, as evidenced separation, H, with T
300 K and lateral pressure, Pl ,
by an increase in crystalline elastic properties, as coupling. The initial configuration was prepared by tak-
the space in which the system is constrained is reduced ing a thin layer (H
0:41 nm) of water from a bulk
[2 – 4]. However, in experimental studies involving a configuration of the liquid and equilibrating for 30 ns.
mercury/water/mercury tunnel junction (weak wall- At each thermodynamic point (achieved by a sequential
water interactions) at T
265 K it was found that the increase in H) the system was equilibrated for at least
Young’s modulus of two-dimensional ice shows a maxi- 15 ns and data collected for an additional 5 ns. Figure 1(a)
mum value (of 20% of bulk ice Ih ) around a junction shows the lateral diffusion coefficient for plate separa-
separation of 0.58 nm. This discontinuity in the elastic tions in the range 0:41 nm  H  0:59 nm for lateral
modulus raised the possibility of confinement-driven pressures of 1 and 100 bar. No obvious difference in the
order-disorder phase transitions occurring as a function behavior of the system was evident for the two different
of film thickness [5]. lateral pressures. For plate separations in the range
In this study we utilize molecular dynamics (MD) 0:41 nm  H  0:50 nm the monolayer is liquid as in-
simulation techniques to investigate the freezing of a dicated by the large diffusion coefficient and by the fact
water monolayer. Questions addressed include the follow- that the mean square displacement grows linearly with
ing: What is the symmetry of a quasi-two-dimensional time [Fig. 1(b)]. At H
0:51 nm the water molecules of
ice? What is the origin of the anomalous behavior ob- the monolayer transform to a frozen state as indicated by
served for the Young’s modulus of a quasi-two-dimen- a drop of 3– 4 orders of magnitude in the lateral diffusion
sional ice? What is the nature of the melting/freezing coefficient. In this state the dynamics of the molecules is
transition of this system? Can water support buckled best described in terms of small amplitude fluctuations
phases that so far have been observed only in colloidal around fixed positions with occasional cooperative jumps
suspension? rather than as free diffusion [Fig. 1(c)]. Note, the MSD is
The simulations were performed using GROMACS 3.0 not linear in the solid phase. Thus the determination of
[6]. The five-site, tetrahedrally coordinated, TIP5P model the diffusion coefficient from the slope of the MSD plot is

025502-1 0031-9007=03=91(2)=025502(4)$20.00  2003 The American Physical Society 025502-1

 PHYSICA L R EVIEW LET T ERS week ending
VOLUME 91, N UMBER 2 11 JULY 2003

a b
4

radial distribution
a
lateral diffusion coefficient (cm /s) 50
2 -4
10 3 H = 0.47 nm
H = 0.45 nm H = 0.53 nm
H = 0.47 nm H = 0.58 nm
H = 0.49 nm 2
H = 0.50 nm
-5
40 H = 0.51 nm

relative intensity
10 H = 0.53 nm 1
H = 0.58 nm

pl = 1 bar 30 0 1 4
0 2 3
-6 pl = 100 bar r (nm)
10 c

relative intensity
20 9 H = 0.47 nm
H = 0.53 nm
H = 0.58 nm
-7
10 6
10
3
-8
10 0.41 0.43 0.45 0.47 0.49 0.51 0.53 0.55 0.57 0.59 0 0
H (nm) -0.2 -0.1 0.0 0.1 0.2 100 120 140 160 180
O
z-axis (nm) O--H--O angle ( )
b 0.04
c
100
lateral MSD (nm )
lateral MSD (nm )

2
2

80 H = 0.47 nm
H = 0.57 nm 0.03
H = 0.53 nm
FIG. 2 (color). (a) Transverse distribution of the density of
60 oxygen atoms for different plate separations, H. (b) Oxygen-
0.02
40 oxygen radial distribution function. Most of the curve at H

20 0.01 0:47 nm is hidden due to overlap with the distribution at H

0
0 1 2 3 4 5 0.00 0:58 nm. (c) Hydrogen bond angle distribution. The ratio of the
0 1 2 3 4 5
t (ns) t (ns) area under each plot corresponds to the ratio of the average
number of hydrogen bonds per molecule, namely, 2:8:3:8:3:5
FIG. 1 (color online). (a) Inplane diffusion coefficients as a for H
0:47, 0.53, 0.58 nm, respectively.
function of the distance between the confining parallel plates at
T
300 K. (b) Inplane mean square displacement as a func-
tion of time in the simulations with lateral pressure coupling of indicates that the system has the characteristics of an
1 bar for a monolayer and a bilayer of liquid water. (c) Lateral ordered crystalline phase. This freezing transition occurs
MSD as a function of time for a frozen water monolayer. at a temperature (T
300 K) well above the freezing
temperature of a bulk TIP5P water (T < 270 K) [9].
A transformation from a homogenous to a split normal
not strictly appropriate. However, the values obtained density distribution of each layer in confined solids as a
from such a procedure, shown in Fig. 1(a), provide a function of plate separation is a fingerprint of a buckling
measure of the relative magnitude of the particles’ dis- transition. Buckled phases were first observed in mono-
placement. At H
0:57 nm the monolayer transforms layers [10 –13] and later in multilayers [14,15] of colloidal
into a bilayer of liquid water [see Fig. 2(a)]. The value particles. The transition to a bimodal distribution of the
of the lateral diffusion coefficient of liquid water in the transverse density is coupled to an inplane order-disorder
monolayer is higher than in the bilayer due to the pres- transition. The lateral ordering takes the form of linear or
ence of interlayer hydrogen bonds in the bilayer resulting zigzag rows of particles buckled against each other. The
in an increase in connectivity and a decrease in mobility. manifestation of the buckling transition enhances as the
Examination of the transverse density profile [Fig. 2(a)] number of layers decreases.
reveals that the liquid state of the monolayer is charac- Figure 3 shows a configuration after equilibration from
terized by a unimodal distribution. As H approaches the a simulation of monolayer water (H
0:47 nm), mono-
transition point (H
0:51 nm), the distribution starts to layer ice (H
0:53 nm), and bilayer water (H

develop two peaks adjacent to the walls. There is a clear 0:58 nm). The ice monolayer has an inplane rhombic
bimodal character for H  0:51 nm. The origin of this symmetry with respect to the positions of the oxygen
phenomenon is an excluded volume effect and is not due atoms. The out-of-plane positions correspond to a linear
to a particular interaction between the molecules and the buckled phase. Figure 2(c) shows that this out-of-plane
walls. The bimodal character of the normal density profile displacement, together with the rhombic arrangement of
for 0:51 nm  H  0:56 nm is due to a monolayer con- the nearest neighbors, results in a hydrogen bond angle
figuration which is buckled and only at H
0:57 does the distribution with maxima at 164 and 139 . At the same
system transform to a bilayer where the normal density time it allows each water molecule to be involved in four
profile is also bimodal. The degree of spatial order of the hydrogen bonds (in the liquid phase the unimodal distri-
oxygen atoms as indicated by the O–O radial distribution bution has a maximum at 159 for the monolayer and at
function for H
0:47, 0.53, and 0.58 nm are shown in 157 for the bilayer). Each water molecule donates to and
Fig. 2(b). The short range order in the plots corresponding accepts from its nearest neighbors present in the other
to H
0:47 and 0.58 nm reflect the disorder of the liquid vertical plane one hydrogen bond (this corresponds to the
phase. However, the long range order at H
0:53 nm lower degree of the hydrogen bond bending, the peak at

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VOLUME 91, N UMBER 2 11 JULY 2003

FIG. 3 (color). Snapshots from the MD simulations. Lateral and transverse views of (a) a water monolayer, H
0:47 nm, (b) an
ice monolayer, H
0:53 nm, and (c) a water bilayer, H
0:58 nm. Hydrogens are depicted in white. Oxygen atoms that lie above
and below the midplane along the normal axis are depicted in magenta and cyan, respectively. Note, the phases are homogenous and
the same degree of ordering is present throughout the entire box.

164 ). In addition each water molecule donates to and that of the melting transition in three dimensions.
accepts from its nearest neighbors present in the same According KTHNY theory two-dimensional solid melts
vertical plane one hydrogen bond (this corresponds to the via a two-stage process: first a continuous transition to a
higher degree of the hydrogen bond bending, the peak at hexatic state, followed by a continuous transition to the
139 ). Following the treatment proposed by Pauling to liquid state [17].
estimate the residual entropy of ice Ih [16], the above Figure 4(a) shows an isotherm of the lateral pressure as
connectivity pattern allows only two equivalent orienta- a function of the area, A, in a second set of simulations at
tions of the water molecule with respect to its nearest constant N; T; A; H. The initial configuration was a
neighbors (instead of six for ice Ih ). However, since the monolayer of liquid water taken from the first set and
probability that a given orientation of the central water is equilibrated for 30 ns at an area of A
60:7 nm2 . The
permitted by the orientations of the neighboring mole- area of the system was then increased or decreased in
cules is only 1=4, the total number of configurations for N small incremental steps and simulated for time periods
molecules is W
2=4N . Thus, there is no residual the same as in the first set of simulations. However, in the
entropy, S0
kB lnW, arising from the disorder in the critical coexistence region the system was equilibrated
hydrogen positions, characterizing ice Ih . Therefore, the for 30 ns and an additional 10 ns were run for data
hydrogen positions must be ordered as is evident collection. For A > 60:4 nm2 the phase is monolayer
in Fig. 3(b). The density of the ice monolayer is in the water while for A < 54:0 nm2 the phase is monolayer
range 0:90–0:91 g=ml. This is higher than the density of ice with the same symmetry and degree of ordering as
the water monolayer (0:79–0:87 g=ml) but lower than the observed in the simulations at constant lateral pressure.
density of the bilayer water examined in this study For 54:0 nm2  A  60:4 nm2 there is a coexistence of
(1:11–1:16 g=ml). the two phases. The vdW loop of the lateral pressure area
The abrupt change in the dynamics and in the range of isotherm [Fig. 4(a)], the sharp linear decrease (resulting
structural ordering during the freezing process suggests from lever rule partitioning) of the energy [Fig. 4(b)], and
that the transition is first order. Simulations with tempera- the phase separation of the two coexisting phases shown
ture and lateral pressure coupling are the most appropri- in Fig. 4(c) all indicate that the transition is first order.
ate to mimic experimental studies of confined system Experimental studies infer that water stratifies into
in mechanical equilibrium with the bulk, they do not layers and exhibits an increased oscillatory stress re-
allow, however, the simulation of phase coexistence. sponse as the film is reduced to thickness less than four
Determining the order of the transition in the present molecular diameters [4]. However, it was also found that
study is necessary since the nature of the melting tran- the viscosity of water remains comparable to its bulk
sition in two-dimensions is as yet unresolved. It has been value even within films down to one or two monolayers
argued that 2D solids lack a long range translational order thick [18]. It is likely that freezing in confined geometry,
in the limit r ! 1. One of the consequences of this which depends on the ability of the molecules to establish
phenomenon is that the character of the melting transition inplane interparticle connections, is influenced by com-
in two dimensions can be fundamentally different from peting interfacial interactions.

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VOLUME 91, N UMBER 2 11 JULY 2003

3.0
a b ducted at a T
265 K, we believe the origin of this
-44
2.0 behavior is due to confinement induced freezing and

Upot (kJ/mol)
-46
Pl (kbar)

1.0 -48 melting as predicted by the simulations. In addition, the

0.0 -50 discontinuous transition observed indicates that the
-1.0 -52 KTHNY scenario is preempted by a first-order transition
-2.0 -54 similar to that found in three dimensions. The buckled
51 53 55 57 59 61 63 65 51 53 55 57 59 61 63 65 phase that we find for the ice monolayer was observed
2 2
A (nm ) A (nm ) before only for (spherical) colloidal particles. The theo-
C ries that have been proposed to account for such transi-
tions are based on a hard sphere description and have lead
to the conclusion that buckling transitions are entropy
induced [12]. Our results show that for water this is not
the case and that buckling transitions can also be en-
thalpically driven.
We thank Dr. Uri Raviv for stimulating discussions.

*Corresponding author.
Email address: R.Zangi@chem.rug.nl
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