Langmuir 1997, 13, 903-908

903

Monte Carlo Simulation Study for Adsorption of Dimers on

Random Heterogeneous Surfaces
Tomoshige Nitta,* Hideki Kiriyama, and Takeshiro Shigeta
Department of Chemical Engineering, Faculty of Engineering Science, Osaka University,
Toyonaka, Osaka, 560, Japan
Received October 30, 1995. In Final Form: February 27, 1996X
Adsorption isotherms of dimers on random heterogeneous surfaces, based on the lattice gas model, are
calculated by the grand canonical ensemble Monte Carlo simulation method. Random heterogeneous
surfaces are presumed to consist of two active sites with different energies a and b which are randomly
distributed on a simple square lattice, on which dimer molecules composed of the identical segments
occupy two adjacent sites without lateral interactions. Calculated adsorption isotherms are used to test
the applicability of two versions of the multisite occupancy model originally proposed by Nitta et al. (1984);
one is characterized by the quasi-chemical approximation for segment-site pairs and another is by moleculebond pairs. The two model equations are found to be good only when the difference in rb ) exp{(b - a)/kT}
is smaller than 10. For rb values greater than 50, some discrepancies are observed in such a way that
the first model overestimates the energetically more stable states while the second model underestimates
them.

1. Introduction
Surface heterogeneity, which comes from different
atoms, different slit width, and surface edges and cracks,
is known to affect the adsorption equilibrium and catalysis
on solid surfaces.1,2 The adsorption energy distribution
function is an important property used to describe the
surface heterogeneity; however, the surface topography
is also an important factor used to characterize the surface
heterogeneity. The patchwise heterogeneous surface3 and
the random heterogeneous surface4 are two extreme
models representing the surface topography, while the
correlated energy surface proposed by Zgrablich et al.5-7
is an intermediate topography model. Although the size
of adsorbate molecules is an important factor influencing
the adsorption isotherms,1 there have been very few
theories on multisite occupancy adsorption on heterogeneous surfaces.1,8-11 One significant problem for the
adsorption of oligomers on heterogeneous surfaces is how
to take into account the entropic defect due to the
preferential adsorption of molecular segments on energetically more stable sites. The multisite occupancy model
proposed by Nitta et al.9 used the quasi-chemical approximation (QCA) theory which was first introduced by
Guggenheim12 for treating the local compositions occurring
* To whom correspondence should be addressed: Tel and Fax:
+81-6-850-6265. E-mail: nitta@cheng.es.osaka-u.ac.jp.
Presented at the Second International Symposium on Effects
of Surface Heterogeneity in Adsorption and Catalysis on Solids,
held in Poland/Slovakia, September 4-10, 1995.
X Abstract published in Advance ACS Abstracts, September 15,
1996.
(1) Rudzinski, W.; Everett, D. H. Adsorption of Gases on Heterogeneous
Surfaces; Academic Press: London, 1992.
(2) Jaroniec, M.; Madey, R. Physical Adsorption on Heterogeneous
Solids; Elsevier: Amsterdam, 1988.
(3) Ross, S.; Olivier, J. P. On Physical Adsorption; Interscience: New
York, 1964.
(4) Hill, T. L. J. Chem. Phys. 1949, 17, 762.
(5) Ripa, P.; Zgrablich, G. J. Phys. Chem. 1975, 79, 2118.
(6) Riccardo, J. L.; Chade, M. A.; Pereyra, V.; Zgrablich, G. Langmuir
1992, 8, 1518.
(7) Riccardo, J. L.; Pereyra, V.; Zgrablich, G.; Rojas, F.; Mayagoita,
V.; Kornhauser, I. Langmuir 1993, 9, 2730.
(8) Marczewski, A. W.; Derylo-Marczewska, M.; Jaroniec, M. J.
Colloid Interface Sci. 1986, 109, 310.
(9) Nitta, T.; Kuro-oka, M.; Katayama, T. J. Chem. Eng. Jpn. 1984,
17, 45.
(10) Nitta, T.; Yamaguchi, A. J. Chem. Eng. Jpn. 1992, 25, 420.
(11) Nitta, T.; Yamaguchi, A. Langmuir 1993, 9, 2618.

S0743-7463(95)00957-7 CCC: $14.00

in liquid mixtures due to the difference in intermolecular

interactions. They applied the QCA theory to segmentsite pairs and derived an analytical expression for the
isotherm equation. However, the validity or the applicability of the approximation has not been demonstrated
so far.
Very recently, Zgrablich and his co-workers13 reported
the comparison of the multisite occupancy model with
adsorption data generated by Monte Carlo (MC) simulations for a model system of dimers on the random
heterogeneous surface. They concluded that the validity
of the multisite occupancy model is limited in the case
where the difference in the adsorption energies of active
sites is small and claimed that the Fermi-Dirac (F-D)
approach, which treats each energy level of the adsorbed
dimers to be independent, is able to qualitatively represent
the simulated isotherms of the dimers. However, their
comparisons of the F-D theory are made primarily with
the experimental data of gases on zeolites, instead of
simulated data.
The present work is a study to explore the applicability
of the multisite occupancy model based on the lattice gas
model by using the grand canonical ensemble MC simulation method for the model system of homogeneous dimers
on the random heterogeneous surface. In section 2, we
describe how we have made random heterogeneous
surfaces and their characteristics in terms of bond
correlations. Section 3 outlines the interaction model and
the MC simulation method. In section 4, we will describe
two theoretical models based on the quasi-chemical
approximation, whose data will be compared with the
simulation data. Comparisons of adsorption isotherms
and internal energies are reported in section 5, while those
of site coverages and bond coverages are given in section
6. Some concluding remarks will be given in the last
section.
2. Random Heterogeneous Surfaces
We use a surface of simple square lattices composed of site a
and site b. The algorithm we used for making a random
heterogeneous surface is briefly outlined, as follows. At first, all
(12) Guggenheim, E. A. Mixtures; Clarendon Press: Oxford, 1952;
Chapter 11.
(13) Ramirez-Pastor, A. J.; Nazzarro, M. S.; Riccardo, J. L.; Zgrablich,
G. Surf. Sci. 1995, 341, 249.

1997 American Chemical Society

904

Langmuir, Vol. 13, No. 5, 1997

Nitta et al.

Figure 1. Illustrative diagrams of two random surfaces: (a) fb ) 0.1; (b) fb ) 0.3.
that have already been occupied. When a dimer occupies sites
R and , the interaction energy is given by -ab ) -a - b. The
total energy of N molecules adsorbed is therefore expressed as

Table 1. Number of Bonds for the Random Surface

theory

simulation

Maa
Mab
Mbb

fb ) 0.1
16200
3600
200

16190
3620
190

Maa
Mab
Mbb

fb ) 0.2
12800
6400
800

12790
6420
790

Maa
Mab
Mbb

fb ) 0.3
9800
8400
1800

9760
8480
1760

U ) -(Naaaa + Nabab + Nbbbb)

where Naa, Nab, and Nbb are the number of bonds occupied by
dimer molecules.
We used the standard Metropolis algorithm for three different
steps: molecular creation, destruction, and rotation. The
transition probability Pmn from state m to state n is given14,15 as

Mab ) Mfafb,

Mbb ) Mf 2b/2

Fn
Fm

Pmn ) min 1,

of the lattices are set as site a and the number of site b lattices
Mb is set at zero. Then we choose one site randomly; if it is the
site a, then we change it to site b and add one to Mb. If it is not
site a, then we again choose one site randomly and repeat the
process until Mb g M fb, where M is the total number of sites and
fb is the fraction of site b among M sites. Figure 1 shows two
computer-generated random surfaces for fb ) 0.1 and 0.3 where
black squares represent site b. The size of a surface is 100 100
lattices making M ) 10 000.
When the surfaces are perfectly random, the theoretical
numbers of bonds per site are given by the following equation:

Maa ) Mf 2a/2,

(2)

(1)

The numbers of bonds for the three surfaces for fb ) 0.1, 0.2, and
0.3 were calculated and divided by 4 (the coordination number)
to get the MR value comparable to that in eq 1. Table 1 shows
the numbers of bonds Maa, Mab, and Mbb for the three surfaces
along with the numbers calculated from eq 1. They are not
identical but almost the same as to consider the surfaces to be
almost energetically random.

3. Interaction Model and Simulation Method

The dimer molecule is composed of two identical segments
which occupy two neighboring sites. The interaction energies
between one segment and sites a and b are denoted by -a and
-b, respectively, where a and b are positive. No lateral
interaction energy is assumed; therefore, one molecule is like a
hard dimer expelling other molecules to occupy the two sites

(3)

The ratio of the probability densities Fn/Fm of state n and state

m is given for the three steps as follows.

(a) The molecular creation step

Fn
s Un - Um
M
)
exp
Fm (N + 1)
kT
kT

(4)

where M is the total number of sites on the surface, N is the

number of dimer molecules existing on the lattice, s is the
chemical potential difference on the surface, and Um - Um is the
difference of internal energies between the trial state n and the
present state m.

(b) The molecular destruction step

Fn N
s Un - Um
) exp Fm M
kT
kT

(5)

(c) The molecular rotation pivoting at one end

Un - Um
Fn
) exp Fm
kT

(6)

(14) Nicholson, D.; Parsonagee, N. G. Computer Simulation and

Statistical Mechanics of Adsorption; Academic Press: London, 1982.
(15) Allen, M. P.; Tildesley, D. J. Computer Simulation of Liquids;
Clarendon Press: Oxford, 1987.

Monte Carlo Study for Adsorption of Dimers

Langmuir, Vol. 13, No. 5, 1997 905

Details of the simulation are as follows: After one trial of

rotation, 10 trials of creation or destruction were executed. For
equilibration of the system, 440 MMCSs (mega Monte Carlo steps)
were discarded and 1100 MMCSs were normally used for
ensemble averages. The minimum value of success we set for
creation and destruction trials was 20 000; all runs exceeded
this criterion.
The quantities calculated in the present MC simulations are
summarized as follows

The new variables Na and Nb are solved by using the free

energy minimization principle subject to the constraint
eq 14. The expression of eq 13 for g with eq 14 is equivalent
to an intuitive expression for site coverages a and b, the
Langmuir type equation given by

b/(1 - b)

) exp

a/(1 - a)

b - a
rb
kT

(15)

surface coverage
) 2N/M

(7)

site coverages
a ) Na/Ma;

b ) Nb/Mb

The parameter rb represents the relative strength of

adsorption on site b compared to that on site a. From the
above relations, the adsorption isotherm equation for a
random heterogeneous surface is derived as

(8)

( )

ln Kaf ) - ln 2 + 2 ln

bond coverages
R ) NR/Mab

internal energy
(10)

where Na and Nb are the number of sites a and b, respectively,

occupied by dimers.

where f is the fugacity of a dimer molecule in gas phase

and Ka is the adsorption equilibrium coefficient for a
hypothetical homogeneous surface composed of only site
a. For the derivation of eq 16, the reader should refer to
the previous paper of Nitta et al.9 or the textbook of
Rudzinski and Everett.1 The relation between Kaf and
s is given as Kaf ) exp(s/kT). The site coverage a is
calculated by solving eq 17 with respect to Y,

4. Theoretical Models

fa

The canonical partition function Q composed of N

molecules distributing over M sites is expressed by

Q ) jsNg exp(-E/kT)

M!
1
N!(M - 2N)! MN

Y a/(1 - a)

ln g ) ln g0 -

N*ij!(Mij - N*ij)!

i j ln

(19)

Nij!(Mij - Nij)!

subject to

Naa + Nab + Nbb ) N

(20)

The above assumptions yield almost the same expressions

as the first version of QCA; they are summarized as follows:

the Langmuir type assumption

R/(1 - R)

(13)

(18)

Equation 17 is a variant of constraint eq 14.

Another version of quasi-chemical approximation is
considered. Instead of the number of adsorbed sites, the
number of bonds Nij adsorbed on site i and adjacent site
j could be a variable for taking into account the entropic
effect of preferential adsorption; that is

(12)

N*R!(MR - N*R)!
ln

(17)

where Y is defined as

When the surface is heterogeneous, more active sites are

preferentially adsorbed for the system to be energetically
more stable, which results in the decrease in the number
of configurations for distributing molecules on lattice sites.
This entropic effect due to the preferential adsorption on
more active sites has not been solved exactly; however,
one approach for this problem is the quasi-chemical
approximation (QCA) originally proposed by Guggenheim12 for treating lateral interactions between unlike
molecules and later applied to segment-site interactions
by Nitta et al.9 The expression for g by using QCA is
given as

ln g ) ln g0 -

rbY
Y
+ fb
)1
1 + Y
1 + rbY

(11)

where jsN is the molecular partition function for a molecule

vibrating in three directions on lattice sites, g is the
combinatory factor representing the number of ways to
distribute N dimer molecules over M heterogeneous sites,
and E is the total energy. In the case where the surface
is homogeneous, the Flory-Huggins equation for dimers
is used for the combinatory factor, which is denoted by g0.

g0 )

(16)

(9)

where R ) aa, ab, bb, and

U ) -Naaaa - Nabab - Nbbbb

a
1 - a

aa/(1 - aa)

) exp

R - aa
) rRr
kT

(21)

NR!(MR - NR)!
the adsorption isotherm

where NR denotes the number of occupied sites R and the

asterisk represents the random distribution for the
homogeneous surface. This term has been introduced for
normalzing the g factor. The constraint equation for NR
is

Na + Nb ) 2N

(14)

ln Kaf ) -ln 2(1 - ) + ln

aa
1 - aa

(22)

the definition of a variable Y

Y aa/(1 - aa)

(23)

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Langmuir, Vol. 13, No. 5, 1997

Nitta et al.

and the determining equation for Y

rabY
rbbY
Y
f 2a
+ 2fafb
+ f 2b
)1
1 + Y
1 + rabY
1 + rbbY

(24)

Equation 24 is solved with respect to Y; then bond coverage

aa is calculated through eq 21. Therefore, the right-hand
side of eq 22 is evaluated from surface coverage , giving
the relation between the fugacity f and . It is noted that
the set of equations from 21 to 24 resembles the isotherm
equation of the F-D approach proposed by Ramirez-Pastor
et al.13
5. Adsorption Isotherms and Internal Energies
Figure 2 shows adsorption isotherms for three random
heterogeneous surfaces with fb ) 0.1, 0.2, and 0.3 The
ordinate is the surface coverage, and the abscissa is the
logarithm of Kaf. The keys represent the simulation data
points; the dotted and the solid lines represent the
theoretical isotherms of the first and the second versions
of the QCA theory, respectively. The parameter rb, defined
by eq 15, represents the relative strength of adsorption
on site b compared to that of site a. When rb equals unity,
which implies that the surface is homogeneous, the FloryHuggins equation is a good expression for representing
the dimer adsorption on the homogeneous surface.
When the parameter rb is smaller than approximately
10, the two theories give almost the same curves and are
good approximations for representing the simulation data
of surface coverage against the fugacity. However, when
rb is greater than 100, the first version of the theory (shown
by the dotted lines) predicts a lager than the simulation
data in the low surface coverage region and a smaller
in the middle region. The crossing point (in ) is
approximately the surface fraction fb. On the other hand,
the second version of the theory (solid lines) predicts a
smaller in the low surface coverage region and a larger
in the middle region. It is interesting to see that the
simulation points would be well represented if we mixed
the two theoretical isotherms.
Figure 3 shows the negative internal energy of the
system against the surface coverage for the surface of
fb ) 0.3. When parameter rb is large, the values obtained
for the first version of QCA theory (dotted lines) are larger
than the simulation data points, while the values
obtained for model 2 (solid lines) are usually smaller.
Figure 4 shows the results for the surface of fb ) 0.1. The
predictions of the two approximations deviate from the
simulations in the region of lower surface coverage, and
the discrepancy seems to be magnified compared to the
previous case, fb ) 0.3.

Figure 2. Adsorption isotherms of dimer on three random

heterogeneous surfaces: (...) model 1; (s) model 2.

6. Site Coverages and Bond Coverages

Figure 5 shows the comparisons of the site coverages
of model 1 (ordinate) with those of the simulations
(abscissa) for fb ) 0.3. The site coverages a and b in the
ordinate are calculated from eqs 15, 17, and 18 by
specifying the surface coverage , which is obtained from
a simulation run, and the corresponding site coverages a
and b are given for the abscissa; these points should be
on the straight line if the theory is satisfactory.
In the case of large rb, b values calculated by model 1
are always larger than the simulation values, while a
values calculated by model 1 are smaller. This is
attributable to the fact that model 1 treats each site
independently; therefore, a larger number of the active
site b is favorable for each segment even when two sites
of b are not bonded. In the case where fb ) 0.1, the

Figure 3. Internal energy vs surface coverage for fb ) 0.3: (...)

model 1; (s) model 2.

discrepancies for b between the simulation and model 1

become larger than in the case where fb ) 0.3.
Figure 6 shows similar comparisons of bond coverages
of model 2 (ordinate) with those of simulations (abscissa)
for fb ) 0.3. The ordinate bond coverages aa, ab, and bb
are calculated from eqs 21, 23, and 24 by specifying the
surface coverage . At first glance, we see that the values

Monte Carlo Study for Adsorption of Dimers

Langmuir, Vol. 13, No. 5, 1997 907

Figure 4. Internal energy vs surface coverage for fb ) 0.1: (...)

model 1; (s) model 2.

Figure 6. Comparisons of the bond coverages aa, ab, and bb

between simulations and model 2 for fb ) 0.3.

Figure 7. Two types of active bonds b-b: (O) site a, (b) site
b; (a) one effective bond b-b, (b) two effective bonds b-b.

Figure 5. Comparisons of the site coverages a and b between

simulations and model 1 for fb ) 0.3.

of bb, bond coverages on more active sites, exceed unity

in the abscissa and approach unity as the surface coverage
approaches unity. Since the values of bb obtained from
the simulation are evaluated by Nbb/Mbb, the value of
Mbb should be responsible for the strange result of the
values of bb exceeding unity.
The theoretical value of Mbb defined by eq 1 is the
number of bonds b-b per active site since the number of
bonds b-b evaluated on the model surface was divided by
4 (the coordination number) as stated in section 2.

However, the effective number of bonds b-b available for

dimer adsorption on adjacent active sites b-b is not as
simple as presumed in eq 1. Figure 7 shows two types of
bonds b-b which have two bonds b-b but differ in the
effective number for dimer adsorption; that is, the effective
number of bonds b-b is 1 for type a while it is 2 for type
b. This is because the occupation of one site inevitably
excludes the other three bonds issued from the site from
being occupied. The value of Mbb defined by eq 1 has
presumed that all bonds b-b were type a even though the
simulated random surface had many bonds of type b.
Therefore, we will need to have some measure for
characterizing all bonds on the surface, which may be
called the bond correlation or the lattice connectivity. At
present it is open to question. It is noted here that the
theoretical number of bonds, Maa, Mab, and Mbb defined by
eq 1, is the limiting value, which is appropriate when
approaches unity. This is because the state of the
maximum entropy is realized at full surface coverage since
the total energy of the system does not change with
changes in the configurations of the dimers when they
cover the whole surface.
7. Concluding Remarks
Monte Carlo simulations were performed to obtain
adsorption isotherms of dimers on random heterogeneous

908

Langmuir, Vol. 13, No. 5, 1997

surfaces consisting of two different energy sites. When

the surface is homogeneous, the Flory-Huggins equation
is found to be a good expression for representing the
adsorption isotherms of dimer molecules. The data
obtained with two versions of the quasi-chemical approximation (QCA) approaches to represent the combinatory factor for distributing dimer molecules on heterogeneous lattices are compared to the simulation data. The
first version of QCA, which treats each active site

Nitta et al.

independently, is found to overestimate the occupancy of

more energetically stable sites, while the second version
of QCA, which treates each bond independently, underestimates them. It is noteworthy that the simulated
adsorption isotherms might be well represented if we could
mix the isotherms predicted from the two versions of QCA.
More theoretical work is needed to represent the adsorption isotherms calculated by computer simulations.
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