Volume 177, number I CHEMICAL PHYSICS LETTERS 8 February 1991

Adsorption of xenon in zeolite Y: a molecular dynamics study *

S. Yashonath
Solid State andStructural Chemistry Unit, Indian Institute of Science, Bangalore, 560 012, India

Received 13 March 1990; in final form I9 November 1990

A molecular dynamics calculation of a realistic model of xenon adsorprion in sodium-Y zeolite is reported. The equilibrium
properties such as the energy distribution function, the centre-of-cage-centre-of-mass radial distribution function, and the cage-
occupancy distribution function are obtained. The results are in reasonable agreement with those of earlier calculations. The
dynamics is significantly slower than that observed for other small organic molecules. Xenon exhibits anisotropic motion in the
large cavity.

1. Introduction and computational details. The results and discus-

sion are presented in section 3.

Adsorption in zeolites has attracted much atten-

tion in recent times. The problem is complicated by
the large number of factors influencing the adsorp-
tion in the channels and cages of the zeolites. Among
these, geometrical as well as the chemical state of the
zeolite determined by the %/Al ratio and the nature
of the extraframework cations play important roles
in determining the adsorption characteristics. Ad-
sorption of xenon in faujasites has been studied by
Rowlinson and co-workers by direct calculation of
partition functions, and by a grand canonical Monte
Carlo method [ 1,2]. These results have yielded in-
teresting insights into the structure of the adsorbed
fluid, distribution of occupancies and thermody-
namic behaviour. Recently, some work on adsorp-
tion of small organic molecules in faujasites has also
been reported [ 3-51.
Here, we report a molecular dynamics calculation
of xenon adsorbed in faujasite. Our interest is to study
the equilibrium and the dynamical behaviour of the
adsorbed xenon in faujasite and to compare our re-
sults with those of earlier calculations. In section 2,
we discuss the details of the intermolecular potential
2. The details of calculation
The crystal structure of faujasite has been deter-
mined by several workers [ 6-8 1. The space group is
Fd3m. In the present calculation, the atomic coor-
dinates and the lattice parameter a=24.85 8, re-
ported by Fitch et al. have been used [ 81. The zeo-
lite lattice was kept rigid and only the xenon
coordinates were included in the integration. The
number of extraframework sodium cations were 48
per unit cell corresponding to a Si/AI ratio of 3.0. Of
the 48 cations, 16 are in Si sites and the remaining
32 occupy S,, sites [ 4,8]. In the present calculation,
we have adopted the model of Kiselev and co-work-
ers [ 91 for the zeolite-xenon interaction. The inter-
action between the adsorbed xenon and the zeolite
is confined to the oxygens and the sodiums. This is
a reasonable assumption in view of the fact that the
silicon and the aluminium are buried within the ox-
ygen lattice, thus preventing the close approach of
the xenon to these atoms. The xenon-(oxygen, so-
dium) interaction was taken to be of the Lennard-
Jones form [ 91,

* Contribution
istry Unit.
No. 691 from Solid State and Structural Chem-
@ik=-A$+$,i=Xe,k=O,Na.

54 0009-2614/91/$ 03.50 0 1991 - Elsevier Science Publishers B.V. (North-Holland)

Volume 177,number 1 CHEMICALPHYSICS LETTERS
Table I
Potential parameters for xenon-Nay zeolite at T= 375 K
Atom A ( IO'kJ mol-’ A6) B ( lo6 kJ mol-’ A’*)
0 Na 0 Na
Xe 8.2793 Il.1345 7.9079
2.9143
The dispersion parameters Aik were obtained from
the Kirkwood-Muller expression and the repulsion
parameters Blk by imposition of the constraint that
the force should be zero at the equilibrium distance.
The details are given in ref. [ lo]. The polarization
energy is taken into account in the present calcula-
tion since this is a many-body term and would result
in a considerable increase in the computational time.
The xenon-xenon interaction was modelled by a
Lennard-Jones potential,
(2)
with a=4.10 8, and e/k=221 K [lo].
Molecular dynamics calculations were performed
in the microcanonical ensemble with periodic
boundary conditions. The system consisted of one
unit cell of faujasite consisting of 384 oxygen, 48 so-
dium and eight xenon atoms. The xenon atoms were
uniformly distributed at the start of the simulation
in the large cavities or the supercages. A time step of
1.0 fs was employed for the integration. Equilibra-
tion was performed over a period of about 20 ps and
averages accumulated over a fairly long period of 0.1
ns. A shifted potential with a potential truncation of
IO A has been employed. Integration was carried out
by means of a simple Verlet scheme [ 121.
3. Results and discussion
The average temperature of the system is 375.9 K.
The total interaction energy of a xenon atom is
( U) = ( U,) + ( Ugh), where ( V,) is the guest-
guest and ( Ugh) is the guest-host contribution. We
have obtained a value of - 12.33 kJ/mol for ( U) .
The guest-guest contribution to the total interaction
energy was found to be small. The isosteric heat of
adsorption, qa, is 15.46 kJ/mol. This compares rea-
sonably with the experimentalvalue of 180.0 kJ/mol
8 February 199I
and the calculated value of 17.25 kJ/mol obtained
by Kiselev and Du [ 91 in view of the fact that the
Si/Al ratio employed by us here is higher and qs,de-
creases with an increase in the Si/Al ratio [ 13 1. Part
of the discrepancy is due to the neglect of the po-
larization interaction. It is difftcult to compare our
results to those of Woods et al. due to the spherical
potential approximation employed by them which
does not correspond to any specific Si/Al ratio.
Fig. 1 shows the interaction-energy distribution
function, N(U). The curve shows a main peak near
- 12 kJ/mol and a shoulder near - 15 kJ/mol. The
shoulder arises from the xenon near the minimum
energy or the adsorption site. The xenon atoms which
are not near the adsorption site contribute to the
higher-energy region comprising the main peak and
the high-energy tail. This may be compared with the
adsorption of methane in faujasite which showed a
characteristic bimodal distribution. A similar bi-
modal distribution was also observed in the case of
benzene [ 51. In contrast to these, the present results
show an almost unimodal distribution with only a
barely visible shoulder which seems to suggest the
absence of two or more markedly distinct regions in
the supercage for the case of xenon. Therefore, it is
expected that a spherically averaged potential should
be more appropriate for xenon adsorbed in faujasite
than for methane and benzene for which there ap-
pear to exist several significantly different regions in
the supercage. The higher-energy region, namely the
region above - 8 kJ/mol, was initially thought to be
c
O.lO-
2
z
0.00
- 20.0 -12 0 -40
U.kJ/mol
Fig. 1. Energy distribution function for xenon in zeolite NaY at
a concentration of one atom per large cavity and a temperattire
of 375 K.
55
Volume177,number I CHEMICALPHYSICSLETTERS
due to xenon migrating from one large cavity to an-
other. Closer examination, however, revealed that
this is not so. The region with U> - 8 kJ/mol seems
to be due to xenon in the proximity of the cage centre.
The distribution of the methane in the supercage
is shown in fig. 2. Here, the centre-of-cage-centre-of-
mass (cot-corn) radial distribution function (rdf )
is plotted as a function of the distance of methane
from the centre of the supercage. The cot-corn rdf
shows a main peak near 4 A and a smaller one near
1 A. The main peak in the rdf suggests that the xenon
atoms spend a large fraction of their time near the
walls of the supercage. This is similar to the behav-
iour shown by methane and other molecules [ 5,141.
This type of cot-corn rdf seems to be a characteristic
feature of X,Y-type of zeolites. The shape of the coc-
corn rdf and the position of the peaks are strongly
influenced by two factors: One is the nature of the
interaction and the other is the geometry of the cage.
The comparison with the results of Rowlinson and
co-workers [ 21, who employed a spherically aver-
aged potential, is worthwhile. The present results
show a broader spread of the main peak extending
to much smaller r values and a small peak near 1 A
absent in the earlier study [2]. This means that the
molecules are, in fact, able to stray significantly more
often towards the centre of the cage than suggested
by a spherically averaged potential. This view is in
accordance with the fact that the sites in the large
cavity are localized regions near the cage wall, and
it is only in these regions that molecules spend a fairly
large amount of time, thus contributing to the main
6
/f-l
/ \
Fig. 2. Centre-of-cage-centre-of-mass radial distribution func-
tion for xenon in sodium-Y zeolite at a temperature of 375 K.
56
8 February1991
peak in the cot-corn rdf. Thus, if P(r, 0, 4) is the
probability of finding a xenon atom at a point given
by (r, 8, $), where r, 0, 9 are the polar coordinates
of points within the large cavity, then it is evident
that P( r, 19,4) varies as a function of i3and # as well
as of r. This suggests that the potential function has
strong angular dependence. It is not known if these
anisotropies are also tetrahedral in symmetry reflect-
ing the cage symmetry, since the potential felt by the
guest atom arises not only from just the atoms com-
prising the inner walls of the large cavity but also from
those beyond it. The tail near 6 A arises from the dif-
fusion of xenon from one large cavity to another. This
tail is likely to become increasingly prominent with
increase in temperature.
Fig. 3 shows the xenon-xenon radial distribution
function. The main peak near 4.5 A corresponding
to the minimum in the Xe-Xe interaction potential
(0=4.10 A) suggests the existence of a significant
population of dimer, even at this low concentration
of one xenon per supercage. Such dimer formation
has been observed for a one-site model of methane
adsorbed in ZSM-5 [ 31. For a noble gas fluid, the
second peak in the g(r) should appear at approxi-
mately $ r, where rl is the position of the first peak.
It is interesting to note the second peak in the xe-
non-xenon rdf appears only beyond I 1 A. It is there-
fore, apparent that the zeolite influences the fluid
structure strongly, at least at low loadings.
The cage distribution function is shown in fig. 4.
It is seen that the fraction of cages with zero-occu-
pancy is 0.33 which is less than the fraction of cages
with an occupancy of one. This is in contrast to a
value of 0.37 obtained by Rowlinson and co-workers
I
Fig. 3. Xenon-xenon radial distribution function for xenon ad-
sorbed in sodium-Y zeolite at 375 K.
Volume 177,number I CHEMICALPHYSICS LETTERS 8 February 1991

ment with the energy distribution function shown in

o.4, fig. I. The calculated diffusion coefficient was also

found to be much smaller than that of methane in
Nay.

-03r
I I
Fig. 5 shows the velocity autocorrelation function
5 for the motion of xenon in Nay. The striking feature
IL 0.2
of the velocity autocorrelation function here is the
slow decay of the correlation as compared with those
reported in the literature for other atoms or mole-
0.1
cules such as methane adsorbed in faujasite [ 3,5,14].
This is primarily due to the exceptionally high mass
-1:,:
012345 of xenon, We have also calculated the velocity au-
N tocorrelation function for the velocity component
Fig. 4. Distribution of occupancies, F(N), for the large cavity at parallel and perpendicular to the surface of the zeo-
a temperature of 375 K. lite cage,

for both zero- and one-occupancy. However, the dif-

ference is not surprising in view of the relatively large
size of the supercage as a consequence of using the
spherically averaged potential. The distribution
function shows that there exist cages with a high oc- c,(~)=(~,(O)~fi,(t)) 3 (3)
cupancy of rive, even at the low loading of one xe-
where i(t) is the unit vector from the centre of the
non/cage.
cage to the centre-of-mass of the xenon atom. Thus,
ii,,(t) is the velocity component parallel to the sur-
face whereas z?*(t) is the velocity component per-
4. Dynamics
pendicular to the surface. The behaviour of the C,,(I)
and C, ( f ) is shown in the inset of fig. 5. We are not
The cage residence time, site residence time and
aware of any experimental studies related to the dy-
the site-site migration time have been calculated. The
cage residence time, z,, was determined using a dis-
tance criterion to decide whether a given molecule
belonged to a specific cage. A molecule within a dis-
tance of 5.9 A of a cage is said to reside in the cage
in question. The value reported here, 9.9 ps, is found
to be about an order of magnitude larger than that
found for methane near 300 K [ 14 1. The difference
can be attributed to the large mass of xenon com-
pared to that of methane. This decreases the mobil-

_o.toO
ity of xenon significantly compared to that of meth-
ane. This is also supported by the velocity
autocorrelation function discussed below. In the cal-
culation of the site residence time (r$), an energy cut-
0.0 2 4 6 8
off of - 13 kJ/mol has been employed. The calcu-
t,ps
lated site residence time is 0.59 ps, which is again
Fig. 5. Xenon velocity autocorrelation function for xenonin zeo-
significantly greater than the value obtained for
lite NaY at 375 K. The inset shows (a) thevelocity autocorrela-
methane. The site-site migration time (r,) is the tion function for the velocity component perpendicular to the
average time the particle spends between two visits zeolite surface, and (b) the velocity component parallel to the
to a site. It is found to be 1.3 ps, which is in agree- zeolite surface.

57
Volume 177,number I CHEMICALPHYSICSLETTERS
namics of xenon in faujasite. The velocity autocor-
relation function, C, (l), crosses the x-axis below 1
ps, thereby indicating the high-frequency motion
being performed by the xenon atom in the direction
perpendicular to the surface. In contrast, along the
direction parallel to the surface the motion is of rel-
atively lower frequency, as indicated by C,,(t). The
calculated diffusion coefficient at this loading and
temperature was found to be 2.4~ low8 m2 s-‘. It
should be possible to measure the diffusion coeffl-
cient by ‘29Xe pulsed-field-gradient NMR.
We have described a molecular dynamics calcu-
lation of a realistic model of xenon adsorbed in zeo-
lite NaY. The results are generally in good agreement
with the grand canonical and partition function cal-
culations of Rowlinson and co-workers using a
spherical potential but differ in some details. The de-
cay of the correlation is slow as compared to other
organic molecules adsorbed in faujasite. We are pres-
ently investigating several other small molecules ad-
sorbed in faujasite.
8 February 1991
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