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The hard tetrahedron fluid: a model

for the structure of water?
a a
Jiří Kolafa & Ivo Nezbeda
a
E. Hála Laboratory of Thermodynamics , Institute of
Chemical Process Fundamentals, Acad. Sci. , 165 02, Prague
6—Suchdol, Czech Republic
Published online: 22 Aug 2006.

To cite this article: Jiří Kolafa & Ivo Nezbeda (1995) The hard tetrahedron fluid: a model for
the structure of water?, Molecular Physics: An International Journal at the Interface Between
Chemistry and Physics, 84:2, 421-434, DOI: 10.1080/00268979500100281

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 MOLECULAR PHYSICS, 1995, VOL. 84, NO. 2, 421-434

The hard tetrahedron fluid: a model for the structure of water?

v P

By JIRI K O L A F A and IVO N E Z B E D A

E. H~la Laboratory of Thermodynamics, Institute of Chemical Process
Fundamentals, Acad. Sci., 165 02 Prague 6--Suchdol, Czech Republic

(Received 12 July 1994; revised version accepted 12 October 1994)

The structure and thermodynamic properties of a fluid of regular hard

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tetrahedrons are studied by Monte Carlo simulations in an NP T ensemble. Hard

tetrahedrons exhibit an extreme non-sphericity and their specific way of packing
gives rise to a structure which has several features in common with the structure
of water. It is shown that pentagonal formations of tetrahedrons from 'self-
replicating structures' in the sense that was used by Speedy, R. J. (1984, J. phys.
Chem., 88, 3364) to explain the properties of hydrogen-bonded water molecules.

1. Introduction
In the 1970s and early 1980s a great deal of interest was devoted to fluids of hard
bodies. This was a consequence of the recognition that the structure of fluids is
determined primarily by steep and short-range repulsive forces. Since these forces
mimic, in an approximate way, the size and shape of real molecules, hard body fluids
thus served as one of the simplest models of repulsive forces in real fluids.
There are basically two types o f hard body model: convex bodies (CBs) and
bodies composed of fused hard spheres (FHSs). Whereas the former has several
mathematical advantages and is a reasonable representation of the shape of most
small molecules, the latter is simpler from the computational point of view and offers
a greater flexibility for modelling more complicated molecules. Owing to intensive
computer simulation studies the structure of both types of hard body fluid is well
understood, and accurate equations of state are available. All these results have been
reviewed and assessed critically in [1] and [2]. In the following we will confine our
considerations to CB models only.
A CB is characterized by a non-sphericity parameter ~ which is unity for spheres
and is greater than one otherwise [1]. The parameter ct increases with increasing ratio
of the hard body dimensions, e.g., the length-to-breadth ratio for linear molecules.
However, very large real molecules are inevitably flexible and may thus be poorly
approximated by rigid bodies. In other words, for CB models which model real
molecules reasonably, the parameter ~ varies, roughly, within the range 1 ~< ct < 1.3,
and this is thus the range within which the overwhelming majority of computer
simulations for CB models have been performed. For example, the values of ~ for
very elongated models of molecules of CO 2 and of flexible n-heptane are about 1.23
and 1.45, respectively [3].
However, there is one CB model which does not fit into the above scheme and
which seems to have been ignored thus far: bard tetrahedrons (see figure 1). A regular
hard tetrahedron (HTH) is a symmetric body characterized by a single dimension
(e.g., by the edge length). Its non-sphericity parameter is thus constant regardless of
its size, with a value of ~ = 2"2346. For comparison, this extremely large value of
corresponds to prolate spherocylinders with a length-to-breadth ratio of 5.28 or

0026-8976/95 $10.00 9 1995 Taylor & Francis Ltd.

 422 J. Kolafa and I. Nezbeda

/
Figure 1. Regular tetrahedron inscribed in a cube; L = 2, and a = x/8.
Downloaded by [McGill University Library] at 10:35 03 December 2014

to oblate spherocylinders (plate-like molecules) with a diameter-to-breadth ratio

of 6.56.
The aforementioned 'anomalies' of HTH suggest also that the properties of the
HTH fluid may be unusual, and probably will not obey the theoretical or semi-
theoretical results given in [1]. This might be a good reason for studying this fluid
but there is an even more appealing motivation: intuitive speculations suggest that
there may be a close similarity between the structural properties of the HTH fluid
and another 'anomalous' fluid, namely, water.
Liquid water is known to exhibit a number of anomalies [4], which result from
a well-developed hydrogen-bond network with a more or less regular tetrahedral
symmetry. A number of attempts have been made to provide a deeper insight into
the structure of the hydrogen-bond network and hence to explain the anomalous
properties of water qualitatively [5-8]. From these, a purely geometrical theory due
to Speedy [8], based on pentagonal (and higher) formations of hydrogen-bonded
molecules, seems to be the 'deepest' one, although we are aware that our criterion
is mainly aesthetic.
The main stream of modern investigations of liquid water follows the concept of
an intermolecular potential which must reflect, among other things, the tetrahedral
symmetry. A number of water potentials have been developed, ranging from
complicated realistic potentials to simple model ones.
The older realistic potentials BNS [9] and ST2 [10] take into account the
tetrahedral symmetry, considering explicitly four interaction sites, two positively
charged (hydrogens) and two negatively charged (lone electron pairs). Newer
potentials [11-14] have usually one negative charge. A question arises (which we are
not going to solve here) as to what extent the observed tetrahedral structure is a
consequence of the tetrahedral nature of the potential itself and to what extent the
cooperative effect of other water molecules is important.
The simple model potentials rely on the concept of four interaction sites. They
differ in the way the short-range hydrogen bonds are modelled in order to simplify
theoretical investigations [15-19], to what extent the (exact) tetrahedral arrangement
is actually used in the theory [20-22], and how other forces (dipole-dipole, attractive
background) are eventually accounted for.
Although the underlying mechanisms leading to the spatial arrangement of
particles in the HTH fluid and in water are completely different, there are good
reasons to assume that the final results will be very similar. The HTH fluid thus
might serve as a prototype for the structure of water and, due to its simplicity, might
eventually play a significant role in developing a molecular theory of water.
 Hard tetrahedron fluid 423

In order to discover to what extent the above physical considerations are correct,
we carried out Monte Carlo (MC) simulations on the H T H fluid. A geometrical
definition of a 'hydrogen bond' in the H T H fluid has been introduced and the
hydrogen bond network has been investigated in detail with the special attention
paid to the occurrence of various polygons. Standard quantities, e.g. the pressure and
correlation functions, have also been evaluated. The results are presented and
discussed in section 3, where they are compared also with available theoretical results.
It is shown that the fluid of H T H indeed possesses structural properties which are
closely related to those observed for real liquid water.

2. Theory
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2.1. Properties of convex body fluids

Throughout the paper we use units which correspond to a regular tetrahedron
which is inscribed in a cube of edge length 2, see figure 1. The edge length of the
tetrahedron is ~/8, its volume is ~ = 8/3, its surface area 50 = 8~/3, and its mean
curvature ~ = (3~/2/2) a r c c o s ( - 1/3) [1].
The non-sphericity parameter ct is given by the ratio of these three geometrical
functionals,
-- ~ 5 e / 3 ~ , (1)

and hence
= 2-2346. (2)

For a CB, the second virial coefficient BE is defined uniquely in terms of ~ regardless
of the actual shape of the body and is given by

B2/"//" = 1 + 3~ = 7.7037. (3)

For higher virial coefficients there are currently no exact results available. From the
available numerical results of B3 and/34 (and exact B 2 ) for prolate spherocylinders,
Nezbeda [23] derived the following approximate expression which, for i ~< 4, is quite
accurate even for large values of e:
~2 -it- 4~t
B / ~ i-1 ~ 1 + 3~(i -- 1) + -- 2 (i -- 1)(i - 2) ~(5~t-- 4) (i -- 2)(i - 3).
2 2
(4)
Assuming that this formula holds true for all i, the virial expansion can be summed
to give the equation of state (EOS) in closed form as
tiP 1 + (3c~ - 2)~/+ ((Z2 -{- (X- - 1)q 2 -- ~(5~ -- 4)q 3
- (5)
p (1 - - /1)3

Here, fl = 1/kB T, T is the absolute temperature, k8 is the Boltzmann constant, and

q = p ~ is the packing fraction. Equation (5) is the most accurate available
approximate EOS for large non-sphericities, and therefore will be used below for the
H T H fluid also.
The structure of hard body fluids is described conveniently by a set of average
correlation functions which are the (000) spherical harmonic expansion coefficients
 424 J. Kolafa and I. Nezbeda

of the full pair correlation function g(1, 2) in the appropriate coordinate frames
[24, 25]:

gooo(r) = ~ O(1, 2) d(1) d(2), (6)

Jr = eonst

where r is the distance between selected reference points within the hard body, and
the integration is performed over all orientations. For the HTH fluid the functions
of main interest are the centre-to-centre gcc, and vertex-to-vertex gvv correlation
functions. These functions give the probability of finding the chosen reference points
of two bodies at separation r regardless of the mutual orientation of the two bodies
and of the orientation and positions of all remaining particles in the system.
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For CB fluids the theory which gives the best overall results for g(1, 2)is the
RAM perturbation theory due to Smith and Nezbeda [25]. Within this theory the
(000) spherical harmonic expansion coefficients are approximated by the radial
distribution function go of a simple reference fluid whose potential Uo is given by the
average Boltzmann factor of the molecular fluid with respect to the reference points
of interest (for details see [25]). Thus,

gooo = go (7)
and
fluo(r) = - ln(exp [ - flu(l, 2)]) (8)
where u(1, 2) is the potential defining the molecular fluid and ( ) denotes an angular
average at fixed r.
From the practical point of view, a sufficiently accurate result for go of a simple
fluid can be obtained from the RHNC theory [26], which will be used later.
Both the centre-to-centre and vertex-to-vertex average Boltzmann factors and the
corresponding reference-fluid potentials ur162and Uvv are shown in figure 2. ur162is a
simple Kihara-type potential with a hard core corresponding to the shortest
centre-to-centre separation, while uvv is a typical site-site potential with a finite value
at the core (which has zero diameter in this case) and exhibiting a cusp (slope
discontinuity) at rvv = 4/x/3 = 2.3094.
The RAM theory is exact at low densities and is known to yield accurate results
for both the structural and thermodynamic properties of molecular fluids of
small-to-medium non-sphericity for all densities [25, 27]. For large ~ the theory
rapidly deteriorates with increasing density, which is a consequence of the inadequacy
of the approximation utilizing a spherically symmetric reference system.

2.2. Hydrogen bond networks

2.2.1. Water
The concept of an irregular distorted but locally tetrahedral network of hydrogen
bonds (HBs) has become a standard tool for describing properties and anomalies of
liquid water. This view has been supported by molecular simulations using different
potential models and has allowed the study of phenomena such as polygons (cycles)
in the HB network or the occurrence of various polyhedrons.
In water, the hydrogen bond is defined using either geometric (mutual orientation
and separation between two molecules) or energetic arguments [4]. Despite the
qualitative difference between the two approaches and the variety of intermolecular
 Hard tetrahedron fluid 425

centre-to-centre vertex-to-vertex
!
I" ' I ' I "'i I I U I I I I n I u.

0.4

Uo(r)
0.2

II , I
' 0.0
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1.0 1.0

0.8
e(r) 0.5

0.6
n ~ I o I I I, In I tl nil
0,0
0 t 2 3 4 0 2 4 6
r r
Figure 2. The centre-to-centre and vertex-to-vertex average Boltzmann factors e(r) and the
corresponding RAM reference potentials uo(r).

water-water potential models used in computer simulations, similar qualitative

results have been obtained. These may be summarized as follows 1-28-32-1.
(1) There is a high probability that an arbitrarily selected molecule has four
neighbours which are tetrahedrally arranged.
(2) The hydrogen-bond network is fully connected (percolated). Two-, three-, and
four-bonded molecules are the most probable.
(3) The conformation of a hydrogen bonded pair of molecules is more likely to
be staggered [dihedral angle q~ = (2n + 1)~/3, n e {0, 1, 2}] than eclipsed
(4~ = 2nrc/3) [33].
(4) Of all bridgeless (non-short-circuited) polygons made from hydrogen-bonded
molecules, pentagons and hexagons are the most probable, although neither
longer polygons are negligible.
(5) Pentagonal rings of bonded molecules form self-replicatin9 structures [8, 34],
i.e., it is more probable to find a pentagon in the vicinity of another pentagon
than at a random place. A similar (but weaker) phenomenon occurs for
hexagons.
(6) Water at low temperatures (supercooled water) contains bulky polyhedrons
with pentagonal and hexagonal faces. These polyhedrons are bound by their
faces in an irregular way.

2.2.2. Hard tetrahedrons

Their geometrical shape suggests that at high density two tetrahedrons prefer a
face-to-face arrangement in order to minimize the excluded volume. Since each
 426 J. Kolafa and I. Nezbeda

l
(a] (b] [c)
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Figure 3. Configuration of a pair of tetrahedrons used to define the hydrogen bond:

(a) arrangement at the closest centre-to-centre separation; (b) arrangement correspond-
ing to a double 'hydrogen bond'; and (c) arrangement corresponding to the maximum
centre-to-centre separation for which the 'hydrogen bond' can be defined.

tetrahedron has four faces, one may expect that tetrahedrons in the neighbour-
hood of an arbitrarily chosen tetrahedron and under these conditions also will
be preferentially arranged tetrahedrally. We thus see a clear analogy with the
structure of liquid water, where the tetrahedral arrangement is caused by hydrogen
bonds. The problem remains of how to define a 'hydrogen bond' for a pair of
tetrahedrons.
Since the interaction energy between two tetrahedrons is infinity or zero, we
cannot define the 'hydrogen bond' using an interaction energy and have to use a
geometric definition. The simplest way is to express the HB in terms of the
centre-to-centre distance rcc between two tetrahedrons: we say that two tetrahedrons
are 'hydrogen bonded' if their centre-to-centre distance is less than a certain limit
ms. In the next paragraph, we try to draw criteria for this limit and give its geometrical
interpretation.
The shortest centre-to-centre distance between two tetrahedrons (tetrahedrons A
and B in figure 3(a) is 2/x/3, and corresponds to a face-to-face configuration. For a
range of slightly larger centre-to-centre separations there is no room for the face of
a third tetrahedron to approach closely the engaged faces o f either tetrahedron A or
tetrahedron B. We say that A and B in this configuration form a single hydrogen
bond. This ceases to hold true at rc~ = x/2 (the configuration shown in figure 3(b)).
For this and slightly larger separations two tetrahedrons can be 'hydrogen bonded'
to one face of a third tetrahedron. We say that tetrahedrons B and C form a double
hydrogen bond with tetrahedron A. Our simple definition of the hydrogen bond loses
its meaning if it is not possible to decide on the basis of rcr which 'interaction site'
(face of the tetrahedron) is 'bonded'. This happens first for the arrangement shown
in figure 3(c) for r~ = 1 + 1/~/3 = 1"577.
Strictly speaking, this limiting separation defines mathematical boundaries separ-
ating regions of different physical meaning. If we find in an equilibrated fluid
configuration two tetrahedrons slightly more than ~/2 apart from one tetrahedron,
they will very probably form two different HBs and not a double HB. Similarly, if
we find a pair of tetrahedrons slightly more than 1 + 1/~/3 apart, it is highly
improbable that this ' b o n d ' does not have the proper tetrahedral arrangement. From
the physical point of view we may thus choose slightly larger values of the separations
 Hard tetrahedron fluid 427

Table 1. Virial coefficients of hard tetrahedrons where ~e~ is the tetrahedron volume.

i Bi/~i- 1 Equation (4)

2 7"7031(15) 7-7037"
3 33"038(9) 26-34
4 80"77(10) 40"88
5 84"3(9) 51'32

a Equation (4) gives the exact value

of n 2.
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defining the HB. Three different thresholds will be used: rHR = 1.5, 1.6, and 1.7. The
final decision as to which one is more appropriate must be made a posteriori.
We will show that most of the properties of the HB network of water are also
exhibited by the H T H fluid using this definition of the hydrogen bond. Differences
are found for items 3 and 4 only.

3. Results and discussion

3.1. Bulk and structural properties
The virial coefficients up to the fifth were calculated numerically using the
R e e - H o o v e r representation [35] and the chain MC method [36]. The results are
summarized in table 1, along with the approximate values given by equation (4). It
is seen, not surprisingly, that the higher coefficients are poorly described by the
prolate-spherocylinder-based values of equation (4).
To avoid using the inaccurate approximate expressions for B 3 and B4 in
developing the EOS, it may be tempting to derive an EOS on the basis of the
knowledge of the first five virial coefficients (which is, in fact, a typical way to derive
an EOS for hard body fluids, see [1]). Examination of table 1 shows that B,~ ~ B~.
Using an ansatz that B* = B* for all i > 5, we obtain

tiP - 1 + B~q + B*~l2 + B*q 3 + B*q~ (9)

p 1- 7

However, as we will see later, this equation performs (with the exception of the lowest
densities) even more poorly than the general Nezbeda equation (5).
To obtain the properties of the H T H fluid at medium and high densities, we used
the usual MC simulation in an N P T ensemble and cubic periodic box, see, e.g. [37].
The number N of particles in the basic cell was 343 for all pressures but the lowest,
where we used also N = 125. Most of the technical details of our particular
experimental arrangement are given in [38]. Three types of trial MC move were
attempted randomly: a displacement, with a probability of approximately 0-4; a
rotation, with a probability of approximately 0.6; and a volume change, with a
probability of 1IN. The parameters of the moves were set so as to maintain,
approximately, acceptance ratios of about 0-3.
The simulation runs started from a simple cubic lattice with lattice constant 2.5,
which gives a low packing fraction of q = 0.171. The pressure tiP was then increased
gradually to attain higher densities. Convergence profiles for the volume and the
 428 J. Kolafa and I. Nezbeda

Table 2. MC simulation results for the equation of state, m denotes the number of one-step
MC configurations, N is the number of particles,/~P is the reduced pressure, and q is
the packing fraction.

10-6m N tiP ~/

6 125 0"5 0"2325(15)

11 343 0'5 0"2346(5)
73 343 1 0.3026(6)
181 343 1.5 0'3531(9)
91 343 2"5 0.4468(9)
96 343 3:5 0-5348(8)
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0.~ ' I ' I ; I

0.4

0.2 ~

0,0 i I , I i I ,

0 i 2 3 4

Figure 4. Equation of state of the hard tetrahedron fluid. Circles are the MC results (error
bars are smaller than the symbol size), the solid curve is the Nezbeda EOS (5), and the
dashed curve is the virial EOS (9).

number of H B for the three aforementioned distances reB were monitored to follow
the approach of the system towards its equilibrium state.
The raw M C results for the equation of state are show in table 2. They are
compared with the Nezbeda and virial equations of state in figure 4. It is seen that
the virial EOS matches the simulation data well only at the lowest densities, which
is in accordance with our expectations. The good performance of the Nezbeda
equation (5) extends t o moderate densities. At high densities both equations
overestimate the pressure significantly. This means that the thermodynamics (EOS)
of the H T H fluid are more complicated than those of other hard-body fluids, and
cannot be described by the summation of a virial-like expansion that leads to the
derivation of the Nezbeda EOS. This is analogous to the case of liquid water,
 Hard tetrahedron fluid 429

2 , i , i ~ i , i , i l , I ~ I , I , I , I ,

[3P=J __ [3P=J . 5
te , I
e ~ ! ,
i i
i js--- _.

(P)
/

L.
I I I
Ii 1
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' I ' I ' I ' I ~ I '

,
i t

\
6P=2.5 _ .

I/" P-3.5 i
g. (P)
a
!

I , lJ, I i I i I l I i

0 2 4 0 2 4 6
Figure 5. The centre-to-centre correlation functions qcc at four different reduced pressures
tiP. The solid curve is the simulation result, and the dashed curve is the RAM/RHNC
result for the fluid defined by equation (8).

where the EOS cannot be described by an approach based on making the potential
spherical [20].
The radial distribution functions for the four highest densities considered are
shown in figures 5 and 6. It is seen from figure 5 that for low densities the structure
of the H T H fluid is similar to that of a fluid of spherically symmetric soft-repulsive
atoms. This observation is supported by the qualitative success of the RAM theory
which is based on a spherically averaged potential. As one would expect, with
increasing density/pressure the specific way of packing of the H T H s begins to
dominate (the number of hydrogen bonds increases) and the structures of the simple
fluid reference and of the H T H fluid become different, see figures 5 for/~P = 2-5. For
/~P = 2"5, 9cc resembles the oxygen-oxygen correlation function of real water,
characterized by one pronounced (first) peak only. 9c~ for the highest density is similar
to the corresponding function for models of liquid water like ST2, which exaggerate
the role of hydrogen bonds: the high second peak corresponds to the tetrahedral
arrangement and the coordination number of the first shell (the number of particles
in the shell up to the first minimum) is 3"5, which is even lower than the value of
about 4.5 found in real water.
In figure 6 we show the vertex-to-vertex correlation functions 9vv. They are
characterized by the cusp located at 4/~/3, corresonding to a configuration in which
a vertex of one tetrahedron touches the centre of a face of a second tetrahedron (cf.
 430 J. Kolafa and I. Nezbeda

3 I ' I ' I ' I i | ' ~ I ' I ' I ' I ' I '

E
2

g,, (r)

i i i I ~ I I I i I ,.i I I I i I i I I 1
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g,, (r)

0 , I , I I I I I I I I I I I I 1 I I t I ,

0 2 4 0 2 4 6
Figure 6. The vertex-to-vertex correlation functions gvv at four different reduced pressures
tiP. The solid curve is the simulation result, and the dashed curve is the RAM/HNC
result for the fluid defined by equation (8).

the RHS of figure 2). For the two lowest pressures, the RAM theory results (obtained
by using R H N C theory [26] which, in the case of the core of zero diameter, is identical
to common H N C theory) are also shown, but they disagree completely with the
simulation data even for the lowest pressure of/~P = 1. We recall that the packing
fraction corresponding to this pressure is about 0.3, which means that the H T H fluid
is well outside the range of low densities where the theory performs well.

3.2. The H T H hydrooen-bond network

The simplest quantities describing the structure of the HB network are the
concentration of different bonded states, i.e. the average number of HB per molecule
and average cluster size. We investigate them at different densities and three different
values of the distances rnB which define the HB (see section 2.2.2).
The concentration of different bonded states cne is the probability that a H T H
has nHB 'hydrogen bonds' bonded to other molecules. As seen from figure 7, these
distributions resemble the distributions for liquid water at different temperatures and
hydrogen-bond definitions [30, 31]. The fact that the number of five (and more)
bonded molecules is negligible even for the least stringent definition of the HB (longest
rnB) justifies a posteriori our geometrical definition of the HB.
 Hard tetrahedron fluid 431

I I I I I I l l I I I I I I

0.4
O
0.4 ~13P 3 5
/ t :
o" /
c~ 0.2 / 0.2 .." i
- t
- t
:" t
./ .0

0.0 0.0
I I I I I I I I I I I I I I
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0 2 4 6 0 2 4 6

nile hie
Figure 7. Concentrations cnB of molecules according to the number nab of attached
'hydrogen bonds' for three different values of distances defining the hydrogen bond:
rHB = 1"5 (dotted curve), 1"6 (dashed curve), and 1'7 (solid curve).

Table 3. MC simulation results for hydrogen-bond clusters, rr~B is the centre-to-centre

distance limit defining the hydrogen bond, (nnB> is the average number of HB per one
HTH, and (no1> is the average cluster size.

rnB < 1"5 rn~ < 1"6 rnB < 1"7

tiP <nxB> <n~l> <nnB > <nr > <nxB> <no86

>

1 0-164(1) 1-18 0.356(3) 1.47 0-657(4) 2.18

1.5 0.352(5) 1.45 0.675(7) 2.23 1.111(9) 5-49
2.5 1.085(11) 5.22 1.658(12) 73-76 2.242(13) 293.34
3.5 2.127(9) 258.83 2-749(8) 332.61 3.216(9) 341.92

The average number of HB per molecule,

<nHB > = ~ nHBCHB , (10)

/IHB

is shown in table 3 along with the average size of the cluster calculated in the same
way from the distribution of clusters of different sizes. It is seen that the water-like
properties of the HB network (the mean number of HB per molecule is greater than
2 and an 'infinite' cluster, i.e., a cluster with (no,) ~ N = 343, is present [28, 29])
are reached only for the two highest pressures of [3P = 2"5 and 3.5; for the lower
pressure tip = 2"5 this is true only with the least stringent definition of a HB. We
have seen in section 3.1 that at these pressures the centre-to-centre correlation
function (see figure 5) becomes water-like, while at lower pressures no HB network
is found, and the structure is to be that of a simple fluid.
A deeper insight into the structure of the HB network can be obtained by
examining concentrations cpoly of polygons (n-cycles) of bonded molecules [28, 32].
We consider only bridgeless polygons [28], also called non-short-circuited polygons
[32], i.e. polygons which do not contain a bridge (short circuit) that would create a
 432 J. Kolafa and I. Nezbeda

0.06 t t t t t t t o t ! 0.6 i , , , , , , , , , ,

r ~P=3.5
0.04 0.4F

Cpoly
0.02
0"2i
- ~ " ~ ..0.. ', A
0.00 ,o---o. . . . . o-.o:.~...-o.-...o,.-o.-.o 0.0 ~' ~o~...o...~.~
I I I I I I I I I I I I I I I I I I I
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2 4 6 8 10 12 2 4 6 8 10 12
n ll
Figure 8. Concentrations Cpoly of polygons as a function of the polygon size n. The curves
are the same as in figure 7. Note the different scales of the two figures.

Figure 9. Typical arrangement of two pentagons sharing a side corresponding to the first
maximum on the pentagon-pentagon correlation function. The dashed line connects
centres of 'hydrogen bonded' tetrahedrons.

smaller polygon. Concentrations of these polygons for the two highest densities and
three HB definitions are shown in figure 8. A sharp peak at n = 5 is observed. The
abundance of pentagons means that there exists a formation of five tetrahedrons
which is packed efficiently. Such a formation is caused by the similarity between the
angle of two faces of the tetrahedron 70.5 ~ and the pentagonal angle 72 ~ All five
tetrahedrons lie (almost) face-to-face and the final compact structure resembles a lens
(see figure 9).
We note in passing that if all polygons are considered (i.e., including those with
possible bridges), the results for n ~< 7 remain almost unchanged. The value of epoxy
 Hard tetrahedron fluid 433

30 ~ )i I ' I ' I '

)))i I ' I i I ' I ' 1
iO
~P=2.5 ~P--3.5
J3
;I I
gss (r) I
5

I::" I
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0 t 2 3 4 5 0 '1 2 3 4 5
r r
Figure 10. The pentagon-pentagon correlation functions. The curves are the same as in
figure 7.

for n = 8 increases, reflecting the occurrence of two pentagons sharing one edge (cf.
figure 9).
The polygon structure of the H T H may be compared with the structure of water
1-28, 32], where both pentagons and hexagons are present in approximately equal
numbers; their ratio depends on the temperature and on the energy limit defining
the hydrogen bond; only for the lowest temperatures and most stringent hydrogen-
bond definitions is a tiny abundance of pentagons observed. The reason for this
difference between water and hard tetrahedrons can be explained by the tendency of
a pair of bonded water molecules to be in a staggered conformation [33], whereas
a pair of face-to-face tetrahedrons prefers an eclipsed conformation.
Speedy and Mezei [34] studied pentagons in liquid water by means of computer
simulations. Since the role of pentagons in the HTH fluid is even more pronounced
than in water, we also followed this approach, and calculated the pentagon-pentagon
correlation function (see figure 10). A clear first maximum (or a group of spikes for
tip = 2.5 and rHB = 1"5 where only a few pentagons are found in the system)
corresponds to conformations shown in figure 9. We can thus conclude that
pentagonal rings in the HTH fluid form 'self-replicating structures' [8]: when we
consider any edge (pair of 'hydrogen bonded' tetrahedrons) of a pentagon, the
eclipsed conformation of these two tetrahedrons makes it easier for the other three
tetrahedrons to form an additional pentagon containing this edge.

4. Conclusion
Despite the fact that there are no attractive forces acting between hard tetra-
hedrons, their shape induces, at high densities, a structure which resembles the
structure of liquid water. These intuitive speculations have been proved to be correct
by computer simulations. By introducing a suitable geometric definition of a
'hydrogen bond' for the HTH fluid it has been shown that the HB network exhibits
similar properties to those found for the real HB network of water. In the light of
this fact it is not surprising that the thermodynamic properties and structure of the
 434 J. Kolafa and I. Nezbeda

HTH fluid are not described well by known theories of hard body fluids, which are
based more or less on a fluid of hard spheres, just as the structure of water cannot
be explained by any theory which is based on a spherically averaged intermolecular
potential. These results might give rise to a renewed interest in fluids of hard bodies
of considerable non-sphericity, and might also be used to explore the structure of
water.

This work was supported by grant 203/93/2284 of the Grant Agency of the Czech
Republic and by grant 472406 of the Grant Agency of the Academy of Sciences.

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Downloaded by [McGill University Library] at 10:35 03 December 2014

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