Surface Science 494 (2001) 111118

www.elsevier.com/locate/susc

Catalytic formation of ammonia: a lattice gas non-thermal

LangmuirHinshelwood mechanism
K.M. Khan a,*, N. Ahmad a, E.V. Albano b
a

Nuclear Physics Division, Pakistan Institute of Nuclear Science and Technology (PINSTECH), P.O. Nilore, Islamabad, Pakistan
b
Research Institute of Theoretical and Applied Physical Chemistry (INIFTA), CONICET, UNLP, CIC, Sucursal 4-Casilla de
Correo 16, 1900 La Plata, Argentina
Received 9 April 2001; accepted for publication 26 June 2001

Abstract
The catalytic formation of ammonia synthesis through dimers N2 and H2 has been studied through Monte-Carlo
simulation via a model based on lattice gas non-thermal LangmuirHinshelwood mechanism, which involves the
precursor motion of H2 molecule. The most interesting feature of this model is it yields a steady reactive window, which
is separated by continuous and discontinuous irreversible phase transitions. The phase diagram is qualitatively similar
to well-known ZGB model. The width of the window depends upon the mobility of precursors. The continuous
transition disappears when mobility of precursors is extended to third nearest neighbourhood. The dependence of
production rate on partial pressure of hydrogen is predicted by simple mathematical equations in our model. Some
more interesting results are observed when reaction between precursors and chemisorbed hydrogen atoms is considered. 2001 Published by Elsevier Science B.V.
Keywords: Monte Carlo simulations; Catalysis; Ammonia; Adsorption kinetics

1. Introduction
Ever since its discovery and technical realization, the catalytic synthesis of ammonia from
hydrogen and nitrogen over iron surface has been
the subject of fundamental investigation. The
commercial development of ammonia synthesis is
considered as one of the most signicant technological advances beneting all mankind. However,
the fact that the mechanism of this reaction is still

*
Corresponding author. Tel.: +92-51-207278; fax: +92-519290275.
E-mail address: kmkhan99@yahoo.com (K.M. Khan).

not easy to understand and many problems remain

to be solved may serve as a warning against too
optimistic a view concerning the progress that
will be made in the elucidation of the mechanism
of even more complicated catalytic reactions.
With the help of modern surface spectroscopic [1]
methods the reaction mechanism and some details
of the role of structural and energetic promoters
(such as Al2 O3 and K2 O) on the surface have been
claried but no clear understanding of the reaction has been obtained because it turns out to be
very complex. Stoltze and Norskov [2] took many
aspects of the reaction system into account and
introduced some complex kinetics and thermodynamic calculations. Their results are in very good

0039-6028/01/$ - see front matter 2001 Published by Elsevier Science B.V.

PII: S 0 0 3 9 - 6 0 2 8 ( 0 1 ) 0 1 4 4 4 - 3

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K.M. Khan et al. / Surface Science 494 (2001) 111118

agreement with experimental observations of the

reaction rate. But due to the use of various experimental data their model becomes involved and
one cannot understand the evolution of the reaction system in detail. The tool of computer simulations may be helpful for understanding certain
aspects of the behaviour of this complex system.
In recent years a number of computer models
have been proposed to study this reaction system.
Mai and von Niessen [3] studied this reaction by
cellular automation (CA) model. When the concentration of the promoted sites was taken to be
one, a kinetic phase transition point which separated the two poisoned states from each other was
obtained at yc yH 0:738 (where yH is partial
pressure of hydrogen in gas phase). For yH < yc the
surface is covered by a combination of N, NH and
NH2 whereas for yH > yc the surface was completely covered by H atoms alone. They claimed
that yc is very close to the stoichiometric ratio of
0.75. The small discrepancy arises due to absence
of diusion of H atoms. Later on Mai et al. [4]
studied this system by stochastic model with the
introduction of diusion of H. When all the surface sites are activated, they found a kinetic phase
transition at yH 0:77 and 0.79 for dierent diffusion rates. Below and above this point a similar
behaviour was obtained as discussed in CA model.
Khan et al. [5] have studied this reaction system through Monte-Carlo (MC) simulation. Their
model is based on LangmuirHinshelwood (LH)
mechanism. In this mechanism all reactants are
adsorbed on the surface and attain thermal equilibrium with the surface before reaction. This is
also called a thermal mechanism. With this model
the occurrence of a single transition point yc ,
which separates one poisoned state from another,
is observed at yH 0:75. For yH 6 yc and yH > yc a
similar behaviour as discussed in CA model was
observed. With introduction of diusion of H
atoms, the general features of the phase diagram
remain the same as discussed earlier. Therefore, no
steady reactive window (with continuous production of NH3 ) was obtained in all the three above
mentioned computer models. However, with the
introduction of desorption of H2 dimer in model
of Khan et al. [5], an interesting situation was
observed. A steady reactive state (SRS), which is

separated from the poisoned states by two transition points y1 and y2 , is obtained when desorption
probability (P) is 0.55. Both the transitions (at y1
and y2 ) are continuous contrary to well-known
ZGB model [6], where transition at y2 is discontinuous. Between the two transition points the
system is in SRS with continuous production of
NH3 . The window width w y2 y1 , dening the
SRS, depends upon value of P. When w is plotted
versus P, a behaviour of the type W 0:0024
exp(6.87P) is observed. For P 1, a single transition point separates a poisoned state from a SRS.
Many research groups have given evidence that
non-thermal processes are also important to understand the catalytic reactions [712]. The transient non-thermal mobility caused by the inability
to instantaneously dissipate the energy gained by
a particle after formation of the surface bond
seems to be a common process in nature. Jackson
and Persson [13], have studied the dynamics of
`hot' hydrogen dimer in EleyRideal (ER) mechanism (direct reaction between a gas phase H atom
and an adsorbed H atom) using a fully threedimensional at surface model for Cu(1 1 1). Hot
dimers are molecules, which after adsorption
dissociate and each of the remaining hot atom
y apart up to a maximum distance R from the
original adsorption site. In a work Brune et al.
[14] have demonstrated (by means of scanning
tunneling microscopy observations) that oxygen
molecules striking the Al(1 1 1) surface not only
dissociate upon adsorption but also they dissipate
part of their excess energy in degrees of freedom
parallel to the surface. The resulting hot oxygen
atoms y apart, on the average, up to a distance of
 from the original impingement site,
at least 80 A
before being accommodated on their respective
adsorption sites. After this ballistic ight oxygen
atoms remain practically immobile at 300 K. By
taking into account this experimental fact, Pereyra
and Albano [15] have studied the inuence of the
hot dimer adsorption mechanism on the kinetics
of a monomerdimer (COO2 ) catalytic reaction.
Due to this hot dimer mechanism, they observed a
remarkable enhancement of the rate of production (of CO2 ). The catalytic reaction of H2 and
O2 on polycrystalline Pt has been studied with
quartz crystal micro-beam data in the early work

K.M. Khan et al. / Surface Science 494 (2001) 111118

of Harris et al. [12]. They have analysed the data

by means of a mean eld approach and have
shown that this particular reaction system is an
example of a precursor mechanism. Harris and
Kasemo [16] have given a detailed discussion on
precursor mechanism of surface reactions. This
mechanism involves direct collisions between chemisorbed species and molecules or atoms that are
trapped in the neighbourhood of the surface but
have not thermalized. The precursor kinetics are
generally dierent from those characteristics of LH
or ER mechanisms [8,12,16].
On the basis of the precursor mechanism,
Khan et al. [17] have recently studied the catalytic
production of water through MC simulations.
Through this model they have reproduced some
experimental results of the real system. Khan and
Ahmad [18] have also studied the catalytic formation of ammonia on the basis of a hot hydrogen
precursor along the lines envisaged by Harris and
Kasemo [16]. This model has led to a SRS, which
is limited by continuous and discontinuous irreversible phase transitions. They have also shown
that within SRS the average production rate P
increases with decrease in average nitrogen coverage (hN ). This shows a behaviour of the type:
P a bhN . The values of a and b have been
evaluated from the t of the data as a 0:294 
0:003 and b 0:525  0:007. hN has a maximum
critical value (hMax ) at hMax  0:54 and a minimum
critical value (hMin ) at hMin  0.275. For hN > hMax
(low region), the catalytic activity is not further
possible due to small supply of H2 gas whereas for
hN < hMin (high region), the catalytic activity again
stops due to large supply of H2 gas (and less
supply of N2 gas). We believe that the catalytic
activity can be initiated in the low and high regions
if we increase the supply of H2 and N2 gases respectively. We may increase this supply of H2 gas
in the low region through the increase in the mobility of the precursors into the second and third
nearest neighbourhood. The supply of N2 gas can
be increased in the high region if we also consider
reaction of the type HC HP ! H2 g S. In
fact, the reaction between HP and HC will create
more vacancy pairs and hence the supply of N2 gas
will increase. The above mentioned two possibilities will be considered in our present work. The

113

paper is structured as follows: In the next section

the reaction mechanism and the simulation procedure is discussed. The results are presented and
discussed in Section 3. Finally the conclusions are
inferred in Section 4.

2. Model and simulation

We have divided this study into two parts. In
model A, we will neglect the interaction between
precursors and chemisorbed hydrogen atoms.
Through this model we will study the mobility of
precursors in second and third nearest neighbourhood i.e. enhancement of catalytic activity in
the low region. Then through model B we will be
able to understand that how the catalytic activity
in high region is enhanced by the consideration
of direct reaction between precursors and chemisorbed hydrogen atoms.
2.1. Model A
We may write the equations for this reaction
system, which incorporates the precursor mechanism, as follows:
N2 g 2S ! 2NC

H2 g S ! HP HP S

NC HP ! NHC

NHC HP ! NHC2

NHC2 HP ! NH3 g S

HP S ! HC

HC NC ! NHC S

HC NHC ! NHC2 S

HC NHC2 ! NH3 g 2S

HP HP ! H2 g

10

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K.M. Khan et al. / Surface Science 494 (2001) 111118

Here (g) indicates the species in the gas phase and

S is a vacant surface site. XP and XC represent the
precursor and chemisorbed adatoms respectively.
We consider an innite reservoir lled with dimers H2 and N2 with partial pressures yH and
1 yH respectively. This reservoir is in contact
with a surface which is simulated by means of a
square lattice of linear dimension L 128. It is observed that an increase in the lattice size changes
the critical pressures slightly but the overall qualitative nature of the phase diagram is not aected
[5,19]. Periodic boundary conditions are used in
order to avoid boundary eects. The simulation
starts with a clean surface. If the striking molecule
is H2 then it requires only one vacant site in order
to produce two precursors (Eq. (2)). If the striking
molecule is N2 then it requires two vacant sites in
order to produce two chemisorbed atoms (Eq. (1)).
We will study the motion of a precursor (and its
collision with chemisorbed species) upto the rst,
second and third nearest neighbourhood. However, the reaction between two chemisorbed species will only be restricted to the rst nearest
neighbourhood. Therefore, in our simulation there
are two variables yH and the range of neighbourhood visited by the precursor (R). We have conp
sidered three dierent values of R namely 1, 2
and 2 respectively. The equilibrium coverages
are measured as a function of yH . In order to locate
the critical points 10 independent runs each up to
50,000 MC cycles were carried out. If all the 10
runs proceed up to 50,000 MC cycles without the
lattice getting poisoned, the particular point is
considered to be within SRS. The poisoning of
even a single run is a sucient criterion for considering the point to belong to the poisoned state.
If the run does not end up in a poisoned state, then
in order to get the coverages corresponding to the
SRS, the initial 10,000 MC cycles are disregarded
and averages are taken over the subsequent 40,000
MC cycles. The values of coverages (production
rate) are obtained after every 10 MC cycles, so that
the nal coverage (production rate) is an average
taken over 4000 congurations. The steps involved
in the simulation are as follows: A site is picked
randomly. If the site is occupied the trial ends (the
molecule is backscattered) else collision of molecules H2 and N2 is considered with probability yH

and 1 yH , respectively. (a) If the colliding molecule is N2 then its four neighbouring sites are also
scanned for the presence of a vacancy. The trial
ends if no vacancy is found in the neighbourhood.
In case a second vacant site is available then step
(1) takes place to produce two chemisorbed atoms
NC . (b) If the colliding molecule is H2 then after
collision with this randomly chosen site two precursor HP are produced via step (2), which move
into the ``environment'' with a range R. We have
considered three dierent ranges of this environment: (i) rst nearest neighbourhoodpR
1 (ii)
second nearest neighbourhood (R 2) and (iii)
third nearest neighbourhood R 2. Each environment consists of a specic pattern for the set
of sites around the striking site. For example, rst
environment consists of four nearest neighbouring sites. The second environment contains four
nearest and four second nearest neighbouring sites
whereas third environment contains all eight sites
of the second environment and additional four
third nearest neighbouring sites. (c) If during its
motion in a particular environment a precursor HP
strikes a chemisorbed atom NC then reaction step
(3) takes place and the precursor ends its life. In a
similar way if a precursor HP strikes the chemisorbed species NHC or NHC2 then reaction step (4)
or (5) takes place and the precursor ends its life. In
the rst case NHC2 is formed whereas in the second
case NH3 (g) is formed which desorbs from the
surface and the site occupied by NHC2 is vacated.
The collision of this precursor atom is taken at
random so that the collision of HP with NHC ,
NHC2 and NC is equally probable. In case the
precursor does not nd any chemisorbed reacting
species within the range R then it takes one vacant
site (randomly chosen) from the environment to
become chemisorbed (step (6)) and the precursor
ends its life. This chemisorbed atom scans its
four neighbouring sites for the presence of NC or
intermediate species (NHC or NHC2 ) in order to
complete reaction steps (7), (8) or (9) as the case
may be. If NC is found then NHC is formed and
the site occupied by HC is vacated. If NHC is found
then NHC2 is formed and the site occupied by HC is
vacated. In case NHC2 is found then NH3 (g) is
formed, which desorbs and the sites occupied by
HC and NHC2 are vacated. It should be noted that

K.M. Khan et al. / Surface Science 494 (2001) 111118

115

after adsorption the NC atoms also scan their rst

nearest neighbourhood in order to complete possible reaction step (7). (d) If both precursors of the
H2 molecule do not end their life through any of
the above mentioned ways, then they return to gas
phase via step (10) and hence the trial ends. If one
of the two precursors does not end its life through
any of above mentioned ways, then it is adsorbed
on the surface through step (5).
2.2. Model B
In this model we will add one more equation to
the set of equations of model A, that is
HP HC ! H2 g S

11

In order to incorporate this equation, the simulation step (c) of model A is slightly modied. If
precursor HP strikes with a chemisorbed atom HC
then reaction step (11) takes place. This collision
brings the two H atoms into gas phase. As a result
the precursor HP ends its life and the site occupied
by HC is vacated. All other simulation procedures
are the same as discussed in model A. It should be
noted that in this model the consideration of Eq.
(11) is dierent from that used in our earlier work
[5]. Here, we are not considering the re-association
and consequent desorption of two HC atoms,
which leaves two vacant sites on the surface.
3. Results and discussion
The numerical results of this reaction system for
the case when a precursor moves in the rst environment are already well known [18]. We get two
transition points y1 and y2 (see Fig. 1 in Ref. [18]),
between which the system has a SRS with continuous production of NH3 . The nature of these
transitions is second order (continuous) and rst
order (discontinuous), respectively. The values of
y1 and y2 are 0:445  0:005 and 0:585  0:005, respectively, showing a window width of the order
of 0.14.
Here, Fig. 1 shows the phase diagram for the
case when the precursor mobility is increased up to
the second environment. This situation is qualitatively similar to that observed by Khan and

Fig. 1. Coverages of N ( ), H , NH , NH2 j and

production rate of NH3 N versus H2 partial pressure for the
second environment of model A.

Ahmad [18] where the mobility was restricted to

rst environment only. However, here due to increase in mobility of the precursors the values of y1
and y2 are 0:390  0:005 and 0:620  0:005 respectively. This shows a window width of the order
of 0.23, which is considerably larger than that in
the previous case [18]. For yH > y2 , a poisoning of
the lattice with HC and isolated vacancies is observed. The isolated vacancies cannot be successfully used by H2 molecules because of the
unavailability of NC and intermediate species on
the surface. In this region each striking attempt of
H2 molecule results in either their chemisorption,
adsorption or their return to gas phase. This increases the H coverage because the probability for
a reaction event becomes very small. This situation
is not only in good agreement with our previous
work of thermal LH model [5] but such a strong
inhibition of the reaction by H2 is also observed in
real systems [20]. For yH < y1 , the situation is
similar to that observed in the case when mobility
of the precursor is restricted to rst environment
only [18] but this situation is dierent from that
observed in our earlier thermal LH model [5]. In
this region the surface is completely covered by a
combination of NC , NHC and NHC2 . The isolated
vacancies are successfully used by H2 molecules. In
this region the coverage of N decreases whereas

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K.M. Khan et al. / Surface Science 494 (2001) 111118

coverages of NH and NH2 increase with the increase of yH . This is because with the increase of yH
there are enough H atoms for the production of
NH and NH2 which ultimately decreases the N
coverage. However, most of the surface sites are
covered by N atoms which is in agreement with the
experiment [2].
The qualitative nature of Fig. 1 also resembles
to that observed in ZGB model for the CO oxidation despite the fact that reaction scheme and
adsorption rules are dierent in the two models. In
our present model the adsorption of N2 takes place
on pair of nearest neighbouring sites (like O2 in
ZGB model) whereas adsorption (striking) of H2
molecules takes place on single vacant site. At high
N2 partial pressure, as the clean surface starts
lling with N atoms, the pair of nearest neighbouring sites will decrease due to occupation of
NHC and NHC2 molecules on single sites. On the
other hand, a single vacant site can accommodate
H2 molecule in order to produce two precursors
and this single site can be easily available as a result of the NHC2 HP reaction. So, the supply of H2
gas will continue until the availability of even a
single site (like ZGB model where supply of CO
will continue until the availability of even a single
site). Therefore, this is a case of a pseudo-monomerdimer type reaction. That is why the phase
diagram as shown in Fig. 1 is qualitatively very
similar to that of ZGB model.
It was seen that N atoms formed ordered islands
at high partial pressure of nitrogen [18]. The
occupation of NHC and NHC2 on a single site decreases the number of pair of vacancies and ultimately the single vacancies are trapped between
N-islands and intermediate species. In our previous model [18] such trapped single vacancies were
picked by H2 molecules to create two precursors
HP . Since the mobility of HP was restricted to rst
environment in that model, so precursor starts
burning NC , NHC and NHC2 in the perimeter of the
islands, since edge atoms experience more encounters with H atoms than N atoms inside of the
islands. In our present model not only the single
vacancies, which are trapped between N-islands
and intermediate species, are being picked by H2
molecules but also, due to the precursor motion of
HP into the second environment, more sites are

being created inside the islands. Therefore, for

yH < y1 , the hoping of HP atoms into second environment indirectly increases the supply of H2
gas, which will require more N2 gas to burn and
hence y1 should be shifted towards lower value of
yB . That is why here y1 has been shifted from yH
0:445 (in our previous model) to yH 0:395. For
yH > y2 , in the present case less HP precursors are
ending their life as HC atoms (due to increase in
HP reactivity) as compared to rst environment in
our previous model [18] and hence N2 molecules
can nd more vacancy pairs for adsorption.
Therefore, y2 should be increased towards higher
values of yH . That is why here y2 has been shifted
from yH 0:585 (in our previous model) to yH
0:620. Therefore, in the present case the reactive
window width is considerably larger than that in
the previous case where the mobility of the precursors was restricted to rst environment.
A rather more interesting situation is observed
when the third environment is considered, because
here the second-order transition disappears. For
yH 0, surface is covered with 90% nitrogen
atoms and 10% isolated vacancies. The moment yH
is non-zero (say yH 0:01 coverage of N drops
sharply to 0.43 with coverage of NH2  0:30 and
that of NH  0:1. This means that almost 17%
vacancies are still available to carry out the productive activity. With further increase in yH , these
values of coverages remain almost stationary till
yH  0:40. Then these values decreases to zero at
y2 yH  0:65, where coverages of H shoots close
to unity and thus the catalytic activity is stopped
by a rst-order transition. Therefore, the width of
the reactive window is quite large of the order of
0.65. This situation has been shown in Fig. 2.
The dependence of the reaction rate on yH (or
yN 1 yH ) cannot be understood from the thermal gas phase kinetics (and CA model) because of
the formation of cluster structures which consist
of one type of adsorbed molecules. Therefore, the
simple prediction of the reaction rate via a lattice
gas thermal LH mechanism fails [3]. However, our
model can present a simple prediction of the reaction rate on yH (or yN ) for this reaction system.
Fig. 3 shows production rate (R) of NH3 (within
SRS) as a function of yH for the cases when mobility of the precursors is extended to second (top)

K.M. Khan et al. / Surface Science 494 (2001) 111118

Fig. 2. Same as in Fig. 1 for the third environment of model A.

Fig. 3. Average production rate in the SRS of second environment (top) and third environment (bottom) of model A
versus partial pressure of H2 . Fits of the data are also shown.

and third (bottom) environments. A nice second

degree polynomial t of the type: R 0:245
1:492yH 2:238yH 2 (with standard deviation of
the data equal to 0.00256) satises the data of
second environment whereas data of third environment is well satised by an exponential relation
of the type: R 0:0054 exp(5.783yH ). The reactivity of H2 dimer in third environment is higher
than that of in second environment, which changes

117

Fig. 4. Same as in Fig 1 for the rst environment of model B.

the behaviour of production rate from polynomial

to exponential.
The reaction between HP and HC creates more
pair of vacancies and hence the supply of N2 gas
is increased. Fig. 4 corresponds to the situation of
model B when considered for the rst environment. The reaction stops only when the partial
pressure of N2 gas is exactly zero. Even a very
small N2 pressure is sucient to continue the reaction for an innite time period. For low values
of yH the surface becomes poisoned by a mixture of
NC , NHC and NHC2 but the reaction starts close
to yH  0:445 where a second-order irreversible
transition is observed. The location of the critical
point is the same (within error bars) than that of in
model A when only rst environment was considered (Fig. 1 of Ref. [18]) pointing out that the
additional mechanism introduced in model B (Eq.
(11)) is irrelevant for lower H2 pressures. A similar
observations are seen when model B was studied
for second and third environments. Subsequently,
the production rate shows an increase with yH , gets
a maximum value at yH  0:7 and then decreases
slowly to zero at yH 1.
4. Conclusions
The introduction of a lattice gas non-thermal LH
(precursor) mechanism along the lines envisaged

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K.M. Khan et al. / Surface Science 494 (2001) 111118

by Harris and Kasemo [16] adds some interesting

features in the phase diagram of this catalytic dimerdimer reaction system which were not seen by
considering lattice gas thermal LH mechanism. On
the basis of the proposed models, some important
aspects of this reaction system can clearly be understood. We have studied two variants of this
mechanism. Model A, which does not take into
account the reaction between precursor and chemisorbed H atoms and model B where reaction between precursor and chemisorbed H atoms is also
taken into account along with reactions of model
A. The most striking feature of model A is occurrence of a steady reactive region with continuous
production of NH3 . The LH mechanism (ZGB like
model), CA model and stochastic model were unable to predict any steady reactive region for this
reaction system. The reactive region is limited by
continuous and discontinuous irreversible transitions. The phase diagram is qualitatively similar to
that of ZGB model, which shows that our model
can lead the behaviour of usual dimerdimer reaction to a behaviour like monomerdimer reaction. The width of the reactive region increases if
the mobility of the precursor is extended to longer
neighbourhood. The continuous transition disappears when precursor motion is extended to the
third nearest neighbourhood. Remarkably, in our
model the dependence of reaction rate on yH can be
predicted through simple mathematical relations
(second-order polynomial and exponential growth)
whereas previously the thermal LH mechanism
(ZGB like model), CA model and stochastic model
were unable to predict any such relation. Therefore, this is also one key factor of our study. When
the reaction between a precursor and a chemisorbed H atom is taken into account (model B), the
situation is also very interesting. Once the reaction
starts, it continues even for a very small amount of
N2 available in the gas phase. The productive activity is only terminated when the partial pressure
of N2 gas is zero. However, it is observed that
this additional mechanism introduced in model B
(Eq. (11)) is irrelevant for lower H2 pressures i.e.
it does not have any signicant eect on the value
of continuous transition for a particular environment.

In our opinion the inclusion of precursors to

single lattice gas non-thermal LH models leads to
a better and more realistic description of heterogeneous catalysed reactions. Consequently, further
numerical and theoretical activity in this eld will
be very useful for the understanding of complex
heterogeneous reactions.
Acknowledgements
K.M. Khan is deeply indebted to TWAS for
award of Associate Membership, due to which this
collaborative work was possible. E.V. Albano acknowledges the nancial support of CONICET,
UNLP and ANPCyT.
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