19 April 1996

! ,.. . , -
CHEMICAL
PHYSICS
LETTERS
ELSEVIER Chemical Physics Letters 252 (1996) 384-388

Monte Carlo simulation of an argon cluster confined

in zeolite NaCaA 1
R. Chitra a, S. Yashonath a,b
a Solid State and Structural Chemistry Unit, Indian Institute of Science, Bangalore 560012, India
b Supercomputer Education and Research Centre, Indian Institute of Science, Bangalore 560012, India
Received 29 December 1995; in final form 29 January 1996

Abstract

A Monte Carlo simulation of a thirteen-atom argon cluster in supercages of zeolite NaCaA is reported. The confined
duster undergoes distortion giving a peak in the angle distribution function at around 90°. The structure, energetics and other
properties are dictated by a competition between guest-guest and guest-zeolite interactions. It is found that the duster melts
in the region from 25 to 40 K. The change in 8 during melting is smaller than that observed for bulk matter or that for the
free cluster, which we attribute to confinement.

1. Introduction [11] reported results on small 13-particle argon clus-

Clusters of rare gases have been studied by sev-
eral workers. Berry and co-workers [1,2] as well as
several others [3-7] have found that these clusters
exhibit a solid-liquid like transition, magic numbers,
1 / f spectra and some other interesting features. Our
understanding of these is still incomplete. All the
studies reported earlier relate to free argon clusters.
Clusters confined in a host matrix or porous solid are
important industrially. For example, rare gas clusters
in fl-hydroquinone have potential applications for
storing gases [8]. Zeolites are molecular sieves which
are extensively used for separating hydrocarbon mix-
tures and rare gases [9,10]. Further, the study of the
equilibrium and dynamical properties of rare gas
clusters confined in host lattices is also of great
interest for its own sake. Earlier, Quirke and Sheng
1 Contribution No. 1165 from the Solid State and Structural
Chemistry Unit.
ters confined within a sphere. Their results suggest
that the behaviour of confined clusters deviate con-
siderably from those of free clusters. For this reason,
we have undertaken a study of rare gas clusters
confined in porous media. Specifically, we have
carried out a canonical ensemble Monte Carlo simu-
lation of an Ar13 cluster housed in an a-cage of
zeolite NaCaA.
2. Methods
Details of the guest-guest and guest-zeolite in-
teractions as well as the Monte Carlo method used in
the present study along with the computational de-
tails are discussed below.
2.1. Structural details
The structure of zeolite NaCaA was taken from
the work of Pluth and Smith [12]. The space group is
Fm3c with lattice parameter a = 24.555 A. Each unit

Elsevier Science B.V.

SSDI 0 0 0 9 - 2 6 1 4 ( 9 6 ) 0 0 1 9 3 - 5
 R. Chitra, S. Yashonath / Chemical Physics Letters 252 (1996) 384-388
cell of zeolite NaCaA contains 192 silicon, 384
oxygen, 32 sodium and 32 calcium atoms. There are
eight a-cages in one crystallographic (1 × 1 x 1)
unit cell of zeolite NaCaA. The diameter of each
a-cage is about 11.4 A. Each a-cage in the zeolite A
framework is octahedrally connected to six neigh-
bouring cages via 8-ring windows which have diam-
eters of approximately 4.5 ,A [12].
2.2. Intermolecular potential functions
The interactions between the argon atoms were
modelled in terms of a (6-12) Lennard-Jones poten-
tial:
q~(r) = 4 ~ [ ( o r / r ) 12- (or/r)6],
where r denotes the interatomic separation and
and or are the well depth and the diameter for the
interacting atoms. The guest-guest interaction en-
ergy is, therefore, given by
1N N 1N
t:~=~ E E ~'(r,)=~ Eug~(r~), (2)
i=l j=l,j~i i=1
where i and j denote guest atoms. Though the
parameters for argon are well known, there are small
variations in the values of e and or chosen by
different workers. We have adopted those used by
Davis et al. [1].
It is assumed that the argon atoms interact only
with the oxygen atoms and the extra-framework
cations of the zeolite framework, i.e. we neglect the
interaction of the Ar atoms with the Si and Al atoms
of the zeolite lattice since these are rendered inacces-
sible to the argon atoms by the presence of the
bulkier oxygen atoms. The guest-zeolite interactions
were also assumed to be of Lennard-Jones form. We
denote this by ¢kiz(riz), where z = O, Na or Ca and
i = 1 to 13. The guest-zeolite interaction energy is
given by
N N
Ugh = E E c~(r,z) = E Ugh(ri),
i = 1 z = O,Na,Ca i= 1
The self-interaction parameters for the zeolite atoms
were taken from Kiselev and Du [13] and from
Englesfield [14]. The parameters for the guest-zeolite
interactions were calculated using the Lorentz-
Berthelot combination rules [15]. The potential pa-
rameters used in our calculations are listed in Table
385
Table 1
Potential parameters for guest-guest and guest-zeolite interac-
tions
Type o- e
(.A) (kJ/mol)
Ar-Ar 3.4 1.00568
Ar-O 3.095 1.33038
Ar-Na 3.33 0.29920
Ar-Ca 3.375 3.09831
1. The potentials were shifted so as to have zero
energy at the cut-off radius.
2.3. Monte Carlo method
(1) Monte Carlo canonical ensemble simulations were
carried out on a cluster of thirteen argon atoms
confined to the void space within zeolite NaCaA
using the Metropolis algorithm [15,16]. The zeolite
atoms were not included in the Monte Carlo simula-
tion; they provided the force field in which the argon
atoms evolved. Each Monte Carlo step consisted of a
sequence of N ( = 13) attempted displacements of
each cluster atom in turn. If the attempted displace-
ments were found to be greater than 40" from the
cluster centre of mass (corn), then such a move was
rejected. Periodic boundary conditions were im-
posed. The minimum image convention was used in
the calculation of guest-guest and gu.est-zeolite in-
teractions. A spherical cut-off of 10 A was used for
both guest-guest and guest-zeolite interactions.
Also, the coordinates and energies were stored every
100 MC steps from which all properties were calcu-
lated.
The starting configuration consisted of an icosa-
hedral cluster of thirteen argon atoms placed at the
centre of an a-cage. At each temperature, the equili-
bration run consisted of 13 × 106 configurations or
106 MC steps, which was followed by a production
run of 7 × 10 6 MC steps. The configuration of the
cluster at the first step after the equilibration run at a
(3) given temperature was used as the starting configura-
tion for the MC run at the next higher temperature.
3. Results and discussion
The starting configuration for the simulation was
an icosahedral cluster placed at the centre of one of
386 R. Chitra, S. Yashonath / Chemical Physics Letters 252 (1996) 384-388

Table 2
V a r i a t i o n o f the a v e r a g e potential e n e r g y w i t h t e m p e r a t u r e 30K

r (u> (u~> (ug.>

(K) (kJ/mol) (kJ/mol) (kJ/mol)
0
15 - 17.35 -2.72 - 14.63
2
20 - 17.29 - 2.70 - 14.59
25 - 17.52 - 2.75 - 14.77
30 - 17.44 - 2.64 - 14.80 f(e)
35 - 17.38 - 2.60 - 14.78
40 - 17.51 - 2.38 - 15.12 0
2 2

25K

the a-cages. Within a few MC steps the cluster

underwent a distortion in which the distance between
0
one of the six pairs of diagonally, opposite surface
0 30 60 90 120 150 180 30 60 ~ 120 150 180
atoms increased from 7.4 to 10.9 A. The guest-guest
e (degrees)
and guest-zeolite energies for the starting configura-
tion - the icosahedral cluster at the cage centre - are F i g . 1. T h e a n g l e d i s t r i b u t i o n f u n c t i o n ( a d f ) f o r the Ar13 c l u s t e r in
the a - c a g e o f zeolite N a C a A is s h o w n at d i f f e r e n t t e m p e r a t u r e s .
- 3.4 and - 6.4 k J / m o l respectively. For the cluster
confined in the zeolite, the distorted icosahedron is
Fig. 1 shows the angle distribution function (adf)
the stable configuration and at 15 K, the guest-guest
for the confined cluster at different temperatures.
and guest-zeolite interaction energies are - 2 . 7 and
Here 0 is the angle subtended at the cluster com by
- 14.6 k J / m o l respectively. Jameson and co-workers
any two atoms lying within a distance of 1.3o'. For
[17] have reported several minimum energy struc-
the icosahedral cluster the adf has no peak around
tures for xenon clusters in zeolite NaA for cluster
90 ° whereas there is a prominent peak at this angle
sizes ranging from Xe 2 to Xe 8.
for the confined cluster. Clearly, although the icosa-
Table 2 gives the average potential energy of the
hedral geometry is the preferred one for free clusters,
system at various temperatures along with the contri-
this is not so for confined clusters even at low
bution due to guest-guest and guest-host interac-
temperatures. With increasing temperature, it is found
tions. The results indicate that the total potential
that the peaks in the adf become somewhat diffuse.
energy is lower at higher temperatures which is not
what is normally found in either free clusters or bulk
0.6 0.6
liquids. For example, Davis et al. [1] find that for a
free mrl3 cluster, the average value of the potential
energy increases from - 3 . 2 5 kJ/mol at 15 K to
- 2.98 k J / m o l at 30 K for the solid-like phase. Even 0 0

Quirke and Sheng [11] who investigated a 13-atom 0.0 ..................... 0.0

cluster confined to a spherical pore find that the total 35~

potential energy increases with temperature. In our f(r)

case, the a-cage in the zeolite defines a structured
0 0
cavity in which the argon cluster is confined. As has 0.6 ............ 0.6
been already noted by Li and Berry [18], it is not 2514 40K
unreasonable to expect that the properties of clusters
confined inside a structured cavity would be differ-
ent from those of free clusters or those confined to
homogeneous structureless pores. We find that the
0

0 ' o 1 2 " 0.4 ' :0 6 ' 0.8

' '
2 0

0.2 0.4 0.6 0.8

total potential energy of the system changes from r(A)
- 17.35 k J / m o l at 15 K to - 17.44 k J / m o l at 30 K. Fig. 2. T h e d i s t r i b u t i o n o f the c l u s t e r c e n t r e o f m a s s to a - c a g e
We will see later why this behaviour is obtained. c e n t r e d i s t a n c e s is s h o w n f o r d i f f e r e n t t e m p e r a t u r e s .
 R. Chitra, S. Yashonath / Chemical Physics Letters 252 (1996) 384-388 387

Fig. 2 shows the distribution of the cluster com to

cage centre distances. At 15 K the cluster corn is
quite close ( = 0.4 ,~) to the cage centre. At 25 K we
find a slight shift of the cluster com away from the
cage centre. Fig. 3 shows the distribution of the
guest-zeolite interaction energy for a single argon
atom. This was obtained by averaging over the whole
simulation and over all cluster atoms. The curves
exhibit five prominent peaks at all temperatures in-
dicative of the differing environments sampled by (a) z5 K (b) 40 K
the guest atoms inside the zeolite. The number of
cluster atoms under each peak is also indicated. We
found that the peak near - 4 k J / m o l is due to the
argon atom near the cluster com which is also the
atom nearest to the cage centre. This atom is not in
contact with any zeolite atom. The peak near - 1 6
k J / m o l is due to the two atoms located close to the
8-ring windows interconnecting any two e-cages.
The number of atoms under the third peak near - 15 (c) (d) 15 K
k J / m o l increases from 5 to 6 when the temperature
Fig. 4. Typical configurations of the confined cluster (a) at 25 K
increases from 20 to 25 K. Simultaneously, the
clearly showing the presence of a central atom and (b) at 40 K in
fourth peak near - 1 2 k J / m o l shows a correspond- which the central atom has moved towards the surface of the
ing decrease. This is accompanied by the shift of the a-cage so as to optimize its interactions with the zeolite frame-
cluster com away from the cage centre and is related work. (c) The starting configuration - an icosahedral cluster at the
to the increase in the magnitude of the guest-zeolite centre of an e-cage. (d) A typical configuration at 15 K showing
the distorted icosahedron with two argon atoms located at the
interaction energy. The peak around - 4 k J / m o l
&ring windows.
remains intact during this. However, there is a de-
crease in the intensity of the peak near - 4 k J / m o l

as the temperature increases from 35 to 40 K. This is

0.1 5 0.1 attributed to the movement of the central atom away
l 6.5 30K
3212 15K from the cage centre so as to optimize its interactions
311.9~ 1 with the atoms of the zeolite framework. Now there
is no atom which is in contact only with other guest
atoms. The decrease in the total potential energy
0.1 O~
20K 6.7 35K suggests that it is more favourable for all cluster
f(u~) 2 2 1
atoms to be in contact with zeolite atoms rather than
1.8
other guest atoms. See Fig. 4a and 4b where we
show the configurations corresponding to these two
::C- ... ° °
o. situations. This explains the general decrease in the
7 40K
I 3 1"1 251< guest-zeolite interaction and consequently the over-
/ il'gfl 1 all potential energy with increasing temperature: there
0.5
is a competition between the guest-guest and
..... ! o guest-zeolite interaction energies and the system
-20 -15 -10 -5 -20 -15 -10 -5 tries to optimize the sum of the two interactions. At
u ~ (k J/tool) the lowest temperature, the distortion of the icosahe-
Fig. 3. The distribution of Ugh, [(Ugh), is shown as a function of dral geometry (see Fig. 4c and 4d) leads to a large
temperature. gain in the guest-zeolite interaction energy which
388 R. Chitra, S. Yashonath / Chemical Physics Letters 252 (1996) 384-388
0.08
0.07
0.06
8 0.05
0.04
0.03
0.02
10 20 30 40 50
T(K)
Fig. 5. Variation of the root-mean-square bond length fluctuation,
8, as a function of temperature.
more than offsets the loss in the g u e s t - g u e s t interac-
tion energy. At higher temperatures the argon atoms
have sufficient kinetic energy to be able to sample
regions of the zeolite cage which are more favourable
with respect to the guest-zeolite interaction. This
leads to a lowering of the total potential energy with
increasing temperature. This explains the behaviour
reported in Table 2.
In Fig. 5 we show the rms bond length fluctuation
( 8 ) as a function of temperature. It is seen that the
cluster begins to melt around 25 K. This may be
compared with the ' melting' of the free cluster which
begins at 26 K and continues up to 37 K. One
prominent difference we find is that the value of 8
after ' m e l t i n g ' is only 0.08 which is small when
compared with the value for the free cluster ( = 0.3).
This is also less than 0.1 which corresponds to the
Lindemann criterion for the melting of bulk matter.
W e attribute this to the effect of confinement; the
volume of the a-cages is roughly comparable to the
volume of the cluster, thereby constraining the
movement of the argon atoms. It is worthwhile
noting that Quirke and Sheng [11] have also ob-
served that the expansion is less in the constrained
cluster.
W e have reported Monte Carlo results for the
melting of a cluster of thirteen argon atoms when
confined in an a - c a g e of zeolite NaCaA. The results
suggest that the equilibrium properties and, in all
likelihood, the dynamics of the cluster are dictated
by the competition between g u e s t - g u e s t and g u e s t -
zeolite interactions. The cluster corn is reasonably
close to the cage centre at all temperatures. At higher
temperatures, the central atom of the cluster moves
to the periphery of the cluster. The d u s t e r eventually
splits around 45 K. The effect of confinement is
reflected in the small change in the rms bond length
fluctuation during melting.
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