Top Catal (2009) 52:431–443
DOI 10.1007/s11244-008-9178-9
ORIGINAL PAPER
Molecular-Level Characterization of Heterogeneous Catalytic
Systems by Algorithmic Time Dependent Monte Carlo
N. Armata Æ G. Baldissin Æ G. Barone Æ R. Cortese Æ
V. D’Anna Æ F. Ferrante Æ S. Giuffrida Æ G. Li Manni Æ
A. Prestianni Æ T. Rubino Æ Zs. Varga Æ D. Duca
Published online: 30 January 2009

Springer Science+Business Media, LLC 2009
Abstract Monte Carlo algorithms and codes, used to
study heterogeneous catalytic systems in the frame of the
computational section of the NANOCAT project, are pre-
sented along with some exemplifying applications and
results. In particular, time dependent Monte Carlo methods
supported by high level quantum chemical information
employed in the field of heterogeneous catalysis are
focused. Technical details of the present algorithmic Monte
Carlo development as well as possible evolution aimed at a
deeper interrelationship of quantum and stochastic methods
are discussed, pointing to two different aspects: the ther-
mal-effect involvement and the three-dimensional catalytic
matrix simulation. As topical applications, (i) the isother-
mal and isobaric adsorption of CO on Group 10 metal
surfaces, (ii) the hydrogenation on metal supported cata-
lysts of organic substrates in two-phase and three-phase
reactors, and (iii) the isomerization of but-2-ene species in
three-dimensional supported and unsupported zeolite
models are presented.
Keywords Algorithmic Monte Carlo
tdMC

Surface processes
Heterogeneous catalysis

Catalytic reaction modelling
G. Baldissin
G. Barone
R. Cortese
V. D’Anna

S. Giuffrida
G. Li Manni
A. Prestianni
T. Rubino

Zs. Varga
D. Duca (&)
Dipartimento di Chimica Inorganica e Analitica ‘‘S.
Cannizzaro’’, Università degli Studi di Palermo viale delle
Scienze Ed. 17, 90128 Palermo, Italy
e-mail: dduca@cccp.unipa.it
N. Armata
F. Ferrante
Dipartimento di Chimica Fisica ‘‘F. Accascina’’, Università degli
Studi di Palermo viale delle Scienze Ed. 17, 90128 Palermo,
Italy
1 Introduction
The study of heterogeneous catalysis can be significantly
improved by modelling the catalytic reaction processes
through the consideration and rationalization of the simple
elementary events, taking place at molecular-level on the
catalyst surface and at the interface. In this aim, nowadays,
computational and simulation approaches, both in the
deterministic and stochastic paradigm frameworks, are
usually taken into consideration to support the explanation
of experimental results, to find simple representation of
microscopic aspects and to design material structure and
reaction mechanism to be employed in catalytic processes.
The recent and constant evolution of both hardware and
software has promoted the development of in silico (i.e.
computation and simulation of natural or laboratory)
chemical applications, hence molecular-level systems also
in catalysis and surface chemistry fields can be now simply
faced [1, 2].
Time dependent Monte Carlo (tdMC) algorithms [3, 4]
have been designed and employed, as many other equi-
librium and nonequilibrium Monte Carlo (MC) and
Cellular Automata approaches [5], to adequately simulate
kinetic details and reaction mechanisms of heterogeneous
catalytic systems, in the aim to obtain (i) dynamic results
fully comparable with those of corresponding experimental
systems and, when possible, (ii) hints on experimental
aspects not yet investigated [6, 7]. The catalysis oriented
tdMC algorithms, mainly employed in the simulation of
hydrogenation processes, have been derived from the Ziff–
Gulari–Barshad (ZGB) code [8], originally introduced to
study the CO oxidation on metal surfaces, by including
‘‘real-time’’ dynamic functions. The latter allowed us to
evaluate with the steady-state also the big-bang system
properties [9–12]. With respect to this, it has to be stressed
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that the tdMC algorithms are not based, as the kinetic MC
ones [13, 14], on the dynamic interpretation of equilibrium
results [15] but instead constitute non-equilibrium exam-
ples of algorithmic [16] and true-dynamic [17] MC
approaches. The present application fields concern the CO
adsorption/desorption processes on Group 10 metal sur-
faces [5], the hydrogenation of unsatured hydrocarbons and
hydrocarbon mixtures [6–10, 18] as well as the hydroge-
nation of nitro-derivatives [19] on metal surfaces and the
but-2-ene isomerization on unsupported or metal-supported
H-ZSM-5 zeolite catalysts. Each of these topics are dis-
cussed in Sect. 3.
The tdMC algorithms have been built by the consider-
ation of characteristic sets of simple elementary events, on
the whole defining the macroscopic processes by molecular
details. A primary role has been given to the local steric
hindrance that accounts for the lateral interactions of the
surface species. Noteworthy, the steric hindrance has
always shown to be able to drive the surface and interface
elementary events involved in the simulated catalytic
processes. In the tdMC simulations, adsorption/desorption
and diffusion phenomena of the single species have been
considered along with the proper reactive processes and the
null event [6, 7]. Each of these elementary steps, including
the null event, is characterized by an occurrence proba-
bility, which might be derived either from experimental or
from quantum chemical (qc) calculation findings. Like-
wise, also the interactions between the various species
adsorbed on the surface sites are characterized by adequate
residence probabilities [5, 9, 10], which account for the
steric hindrance of the adsorbed surface derivatives. Due to
local interaction-potential changes, the surface-event
occurrence probabilities are usually variable at the same
time as the system is evolving. The tdMC codes automat-
ically face the parameter adjustments while with the proper
evaluation of the occurrence and residence probabilities,
the surface populations and the energetics of the system are
continuously monitored, allowing one to modify the sur-
face characteristics, which can be easily related to the
modelled catalyst activity and selectivity.
However, the ‘‘experimental‘‘ probabilities are generally
derived from fitting procedures, performed through the
same tdMC codes, on connected experimental data.
Straightforwardly, this method might require the consider-
ation of a huge amount of fitting parameters with respect to
the number of the investigated catalytic properties. On the
contrary, the application of qc information, in determining
the occurrence probabilities, grants a substantial reduction
of the number of arbitrary parameters, allowing for (i) a
more self-consistent evaluation of the inferred catalytic
mechanisms and surface species properties and for (ii) the
study of systems whose experimental parameterization is
lacking [20, 21]. In this approach, the qc calculations
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Top Catal (2009) 52:431–443
provide structural and energetic information to be used in
setting the event probabilities, whilst the tdMC code pro-
vides the dynamic engine bringing forward the simulative
process hence mimicking the experimental processes.
The qc-based probabilities are often derived from a large
number of simple elementary systems, designed to better
encompass the whole set of possible events in the reactive
process. Therefore, specific local events are described with
a high level of accuracy, and the approach is developed on
a fully molecular-level base, revealing the inmost details of
the process and suggesting criticisms to results obtained by
more conventional modelling approaches [5, 19].
In fact, the algorithmic tdMC models have been applied
in energetics, thermodynamics, and kinetics studies. The
approach resulted very effective in reproducing and pre-
dicting experimental properties and at the same time in
suggesting molecular-level reaction mechanisms for the
corresponding macroscopic processes. It was also very
useful in studying complex phenomena as bifunctionality,
particle size effects, and different surface reaction condi-
tions, e.g. due to by-products and carbonaceous species
formation. In particular, as already mentioned, the side
interactions of the adsorbed molecules and the related
steric hindrance have been demonstrated to be of crucial
importance in the definition of the main properties of the
surface systems.
Summarizing, the tdMC codes were used both for ana-
lysing two-phase and three-phase systems, showing that the
catalyst properties strongly depend on: (i) the local char-
acteristics of the surface sites, (ii) the surface population
distribution, (iii) the formation of characteristic surface
decorations and (iv) the onset of surface temperature gra-
dients. In passing, it has to be recalled that the catalytic
properties shortly outlined by the points above could
dynamically change along the reaction that, as shown by
point (iv), also depends on the energy redistribution ability
of the system.
In particular, with respect to the latter point, the avail-
able surface energy (ASE) hypothesis, which has given a
new molecular-level information to two-phase and three-
phase reactions, was parameterized and used in the analysis
of surface and interface elementary events through the
tdMC models [9, 10, 22]. Within this hypothesis the dis-
tribution of events in the neighbourhood of a specific site
would determine variable ASE and consequently a differ-
ent behaviour for the various configurations found in the
different surface sites. The knowledge and control of the
ASE distributions could therefore give important feedbacks
for driving the surface energetics and the surface reactive
properties, and could result useful to develop real-time
models of surface events [5].
The algorithms are illustrated in the following Sect. 2,
dealing in Sect. 2.1 with the architecture of the tdMC codes
Top Catal (2009) 52:431–443
and the principles employed to build them. In this section
are also described (i) the physical laws, mostly character-
izing the thermal tdMC (T-tdMC) codes that have been
employed to simulate the local energy exchanges taking
place along the occurrence of surface and interface pro-
cesses, and (ii) the resulting energy gradients and
concurrent flows present in the system. The following two
Sects. 2.2 and 2.3, are focused on the modelling of three
dimensional structures and catalytic reaction mechanisms.
In details, in Sect. 2.2 the algorithms employed to build 3D
material structures are presented, whereas in Sect. 2.3 the
integration of the 3D building and managing procedures
into the tdMC algorithmics is discussed and the general
applications illustrated by a flow-chart. In Sect. 3 some
exemplifying tdMC simulations are presented, showing the
ability of such approaches in studying:
• the adsorption/desorption processes of carbon monox-
ide under variable thermal conditions—Sect. 3.1,
• the origin of well known exotic phenomena related to
the surface adsorption and catalytic oxidation of carbon
monoxide—Sect. 3.1,
• the two-phase hydrogenation of unsaturated hydrocar-
bons—Sect. 3.2,
• the three-phase hydrogenation of aromatic nitro-deriv-
atives—Sect. 3.3,
• the two-phase isomerization of but-2-ene on 3D
matrices—Sect. 3.4.
Developments of the tdMC codes are finally discussed in
the conclusive Sect. 4.
2 Methods and Algorithms
The deterministic modelling of heterogeneous catalytic
systems as well as of surface and interface transformations
requires preliminary information on the surface site prop-
erties and on the surface species configurations, related to
the attribution of starting boundary conditions. At variance,
the stochastic modelling approaches, as the MC ones,
applied to the same surface fields are able to overcome
some of these drawbacks, simply defining starting ele-
mentary events occurring on the surface or at the interface,
as the molecular hitting, sticking, desorption, diffusion and
reaction with the formation or removal of radicals, by-
products and polymeric species and carbonaceous deposits.
In any case the use of stochastic approaches preserves the
possibility to include deterministic events, when needed.
MC simulations have been performed by home-made
FORTRAN and/or ANSI C codes in the frame of the
NANOCAT project, running on Linux operative system on
x86 or ia64 cluster architectures. The codes have been
designed to minimise the number of the involved variable
433
parameters, by introducing qc information concerning the
elementary events, dealing with the whole macroscopic
processes. For the qc calculations the Gaussian03 suite of
programs [23] has been mainly utilised, by employing both
high level DFT methods and semi-empirical approaches
[24]. The main subroutines constituting the codes are
common to the various algorithms, although specific pro-
cedures have been employed for simulating peculiar
characteristics of the different real systems considered.
2.1 tdMC Codes
The tdMC codes have been employed in modelling surface
and interface processes in two-phase and three-phase sys-
tems. In details, isothermal and isobaric, two-phase
continuous-flow and two-phase or three-phase batch reac-
tors have been modelled. The catalytic phase was usually
modelled by two-dimensional matrices whose elements
represented surface sites. The two-phase continuous-flow
systems have also been modelled by four-dimensional
matrices with every matrix element representing a 3D unit-
cell of a metal crystallite, containing local energy
information.
In any case, the event occurrences and the simulation of
the surface reaction have been up to now restricted to a 2D
matrix, representing the crystallite surface. Despite that,
the consideration of 2D surface matrix allowed us to per-
form surface simulations involving 3D effects as those
related to the catalytic metal dispersion and to the geo-
metrical location of the active-sites (i.e. surface-, edge- and
corner-sites) and of the crystallite defects [10]. Although
very reliable, these approaches have some disadvantages,
needing non-physical and somehow obscure technical
treatments to introduce the 3D effects [10] hence pre-
cluding the simple use of the code to the ‘‘experimental-
minded’’ researcher interested in the application of simu-
lation methods. Moreover, the dynamic simulation on 2D
surface matrix is constrained in two dimensions without
considering either the bulk diffusion or the confinement
effects. In Sect. 2.3 the extension to simulated 3D systems
is discussed.
All the molecular events, and more generally any ele-
mentary act that needs stochastic choices, are driven by a
portable Random Number Generator, namely the ranN or
the ran0s subroutines taken from the Numerical Recipes
[25, 26]. Different starting seeds have always been
employed for each different event considered. The occur-
rence probability for a given event depends on many
variables: the system temperature and pressure, the number
of surface sites, the surface population and the distribution
of the reagents in the different phases, the activation energy
(Ea) of the simulated event, and the steric hindrance of the
species on the surface. The event frequencies and
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probabilities can also change following the energy gradi-
ents, evaluated through the thermal conductivity and the
thermal radiation laws [5]. The steric hindrance and the
lateral interactions of the surface species has recently been
evaluated in terms of interaction probability, PI, or resi-
dence probability, Pq : As an example, the latter was
calculated as:
 
Eaq ðxÞ
Pq ðxÞ ¼ exp m ¼ ½pq ðxÞm ð1Þ
kB T
in the hypothesis that only species of x type were on the
surface. In Eq. 1, Eaq ðxÞ is the activation energy needed
to bring in contact two neighboring species, m is the
number of the neighboring couples while pq ðxÞ is the
probability that two molecules are neighboring-neighbors.
The dependence of the residence probability from the
temperature allows to infer that the local surface popu-
lation could increase with the increasing of the local
surface temperature, in agreement with the Thon and
Taylor equation [27]. Moreover, an explicit dependence
on the coverage and the temperature could be formally
employed to modulate the activation energy of the above
equation, to take in account the eventual compensation
effects arising at high coverage, which could modify the
Eaq value [28–31].
The kinetic theory of gases has been utilised to calculate
the hitting frequencies of gas-phase reagents in the two-
phase systems. It has to be stressed that the hit event
occurrence is used to start the internal clock, to account for
the simulated dynamic properties and to monitor the
elapsed simulation time. In the case of molecular hitting
from the liquid phase on solid surfaces, characterizing the
three-phase systems, the Stokes–Einstein theory has been
considered [19] for the same purposes. When three-phase
batch reaction systems have been taken into consideration,
the concentration changes occurring in the different phases
have been mandatory whereas in the two-phase continuous-
flow systems the update of the number of molecules in the
gas-phase was not necessary.
The Maxwell–Boltzmann distribution law has been
employed in computing the energetics of the surface hits
and to calculate the variable sticking probabilities, which
also depend on the surface population and energy distri-
butions—see Eq. 2. Desorption, surface diffusion and
reactive event frequencies, hence the corresponding prob-
abilities, were calculated through the modified transition
state theory (TST) equation:
 
kB T Eag ðxÞ
feg ðxÞ ¼ exp  FðH; Pq ðxÞÞ ð2Þ
h kB T
where Eag ðxÞ is the activation energy of the considered, g,
event for the generic, x, species while F is a function of the
occupied surface site molar ratio (i.e. the surface coverage),
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H, and of the residence probability, Pq ðxÞ: F is dinamically
updated by the tdMC code and has not a constant form,
because of the different dependence of the molecular
surface diffusion and desorption on H. This equation has
been obtained by setting in the TST expression the
partition-function ratio and the transmission coefficient to
1 [5]. The effect of the diffusion, on otherwise highly
activated surface processes, is almost null while it could
be considered as a molecular surface population mixing,
not changing the average population distributions on
the surface. In these cases, pseudo-steady-state surface
populations are often observed. The sticking probability of
given species could be calculated as:
rx ¼ Px ðEÞFðH; Pq ðxÞÞ ð3Þ
where Px(E) is the probability that a hitting, x, molecule
owns an energy amount, E, having a value in-between the
adsorption and the desorption energies for the same mol-
ecule on the surface. The E values are Maxwell–Boltzmann
distributed energies, depending on the temperature. The E
values have been evaluated by using the qtrap subroutine,
taken from the Numerical Recipes [25, 26].
The time step, Dt, is a driving factor in the tdMC sim-
ulations, which in the title codes is anchored to the
frequency of the fastest event, fE, determined automatically
during the simulations. In the latter, Dt ¼ CfE1 ; where C is
a term calculated so that the sum of the event occurrence
probabilities, including the null event, is normalised to 1.
Consequently, the Dt values change as the considered
physical process is changed and along the mimicking of a
given system.
The total probability of the system, constituting the
whole events sample-space (wss), is determined by the
whole set of mutually independent events. Reduced sam-
ple-spaces (rss) [32] have been also introduced in the tdMC
algorithmics, considering only selections of events, having
physical meaning within a given part of the simulation. In
the various rss the simulation fastest event, and conse-
quently its frequency value, is different and always smaller
with respect to the fastest events of the unreduced space,
thus determining larger simulation time steps that allow
one to increase the range of simulated time and/or to
reduce the simulation length.
The Fourier thermal-conductivity law, the Kirchhoff–
Stefan–Boltzmann thermal-radiation law, the Drude–
Sommerfield model, and the equipartition theorem have
been used for the simulation of the catalytic systems
involving the thermal treatment [5]. The corresponding
T-tdMC codes, in the following considered to illustrate
other rss details of the tdMC algorithmics, have included
three rss to manage the physical models. The first rss is
constituted by the sample-space of hit, diffusion and null
events, occurring the other events only after a hit of the
Top Catal (2009) 52:431–443
surface. This is the case of sticking that could actually be
tried in a second rss, just after the molecular hitting
occurrence. If sticking occurs, a third level rss is invoked.
In the third level rss the adsorption activated processes, i.e.
diffusion and desorption, are considered. In the second and
third rss all the occurrence probabilities are conditional to
the generating event, i.e. hit and sticking following hit,
respectively. If the generating event does not occur and
only diffusion or null events take place, or after any event
following the second and third rss, the code rearranges the
surface energy distribution, modulating the energy content
of each crystallite unit-cell through an ordinary differential
equation system (ODEs) approach, using the rk4 subrou-
tine of the Numerical Recipes [25, 26], up to reach a
situation in which either the energy gradients are close to
zero or a previously set time interval is elapsed. This delay
depends on the starting parameters and on the energy
gradients of the neighboring cells. The time contributions
of the different parts of the code are kept synchronised by
appropriate subroutines, which deal also with the correct
updating of the simulation time. Further details about the
rss are reported in previous articles [5, 19] and in Sect. 3.1.
All the tdMC simulations run up to reach steady-state
conditions, in which the surface characteristics, although
dynamically variable, maintain homogeneous properties.
Straightforwardly, selectivity, activity or other discrete
chemical and physical features can be evaluated both along
the transient (big-bang-state) period needed to reach the
steady-state and in the same steady-state conditions. For
this reason, the code monitors systematically the occur-
rence of true steady-state conditions, ending the simulation
when they are achieved. During the simulations the system
always reaches locally oscillating situations that in real
steady-state are mostly caused by hitting and sticking
immediately followed by desorption. This phenomenon,
studying the carbon monoxide adsorption on Group 10
metal crystallites has suggested a molecular explanation for
the adsorption-assisted-desorption (AAD) effects [33–36],
discussed in Sect. 3.1.
The codes can also identify the occurrence of a pseudo-
steady-state in which only diffusion events are occurring,
even in conditions quite far from the real dynamic surface
equilibrium, i.e. at the real steady-state of the system, and
lead just to molecular surface population mixing, intrinsic
of the diffusion events [5, 19]. The surface properties thus
become uniformly monotonic and, in agreement with the
random parking model [37], the only visible effect is the
reaching of a homogeneous molecular surface redistribu-
tion, clearly determined by the relative molecular residence
probabilities of the different surface species.
This temporary state could be ruled out by forcing a
redistribution of the surface species, usually originating less
hindered surface configurations. In these new conditions,
435
less probable surface or interface events are opportunely
managed into parallel rss, producing a jump of the simu-
lated time [5, 19]. The time-jump procedure activated by
new event-chains can greatly improve the efficiency of the
code, without altering the final simulated results, by
reducing the large quantity of simulated time actually
wasted along with the pseudo-steady-state occurrence.
2.2 PMB and MCAE Codes
The simulation of real 3D material structures represents an
improvement in the tdMC algorithmics. Indeed, the use of
large 3D model framework allows one to take explicitly into
consideration surface defects and/or confinement effects,
characterizing as an example space-embedding porous
material, which are common in the surface-science and
heterogeneous catalysis field analysis. The subroutines and
codes described here, useful to generate 3D matrices sim-
ulating heterogeneous catalytic material, have been
implemented in ANSI C89 language and specifically
designed for the NANOCAT project. They have been tested
in the but-2-ene isomerization process on H-ZSM-5 zeolite
catalysts, either bare or embedding small Pd clusters.
In modelling large 3D systems, issues concerning the
regularity of the corresponding structures have been faced.
In fact, large porous structures cannot be considered com-
pletely uniform and also in the very regular H-ZSM-5
aluminated matrices, a certain degree of randomness has to
be taken into account. As an example, the Si $ Al substi-
tution, although mainly occurring on given sites within the
structure [38], could in principle take place in very different
locations. Moreover, when metal clusters are embedded in a
porous matrix, their distribution is not always regular, and
the metal deposition processes yield more or less randomly
distributed supported materials, although also in this case
some sites are preferred (e.g. those nearby the acidic sites in
aluminosilicate systems) [39].
This lack of regularity could be bypassed when small
fragments of the whole structure are mimicked. In fact, the
model could be considered as a particular of a possible
structure or rather as the most stable among a possible set
of structures. However, the models needed for the large
scale 3D-tdMC simulation, e.g. to be used in mimicking
confinement effects, should span thousands of atoms. In
these conditions the assumption of structural regularities
could introduce errors on the evaluation of the macroscopic
properties, e.g. considering the most stable surface sites
among a whole distribution of sites or considering periodic
boundary conditions (PBC) that clearly introduce a certain
degree of regularity in modelling amorphous structures.
Therefore, a new code was designed to overcome these
drawbacks, with the specific task to build 3D regular, and
even non regular, porous structures. The code is able to
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shape whatever material matrix is necessary in the tdMC
simulations, on the basis of the information provided by the
users on the composition hence on the structure and mor-
phology of a given material, either real or just
hypothesized. The Porous Matrix Builder (PMB) algorithm
was for this purpose implemented as a stand-alone code
and also as a subroutine of the 3D-tdMC package.
In our opinion, the speed-up of the tdMC simulative
approaches with an algorithm providing the starting space-
embedded material model matrices, without the manual
modifications of each simulated system, already justifies
the efforts for the algorithm design and the code develop-
ment. In the PMB algorithm the three-dimensional systems
are reduced to 3D matrices in which every element repre-
sents an ‘‘elementary-site’’, that can be occupied by void or
filled space, in the latter case by one of the different con-
stituents of the system (reagents, intermediates, products,
catalyst sites, inerts, promoters or poisons). These 3D
matrices are mathematical objects directly usable in any
implemented algorithmic MC code designed for studying
either surface-science or heterogeneous catalytic systems.
Of course, they represent the starting systems treated by
following tdMC simulations—see next section.
It has to be underlined that the matrix builder is oriented
toward a molecular-level approach. The sizes of the ele-
mentary-site pointed out by a matrix element are kept
variable, so the generated models can be tuned on the
specific MC simulation needs, and an elementary-site could
represent one atom or a specific assembly of larger atomic
groups. In the presented H-ZSM-5 zeolite case, the grain
unit of the material has been chosen to correspond to the
radius of gyration [40] of the 1T unit, i.e. the tetrahedral
silicate or aluminate building block of the zeolite material
[41]. In Fig. 1 examples of H-Y and H-ZSM-5 zeolite
structures are shown.
The PMB code reads experimental and/or computational
structural information and builds the material model by
arranging the basic information above. This is used by the
Fig. 1 Examples of zeolite
structures built by the PMB
code: on the left a 1536T H-Y
model, with a grain (i.e.
elementary-site) resolution
(diameter) equal to 243 pm; on
the right a 96T H-ZSM-5 model,
with a grain resolution equal to
81 pm. The representation of
the two models are clearly not
in scale
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Top Catal (2009) 52:431–443
code up to reach the selected size of the simulated model.
Along this procedure, structural irregularities can be
introduced by stochastic or deterministic procedures. The
radius of gyration of the involved chemical group has been
usually taken as the main parameter for the characterization
of the material and its defects, giving the structure reso-
lution. The code can thus model from extremely regular
systems to true amorphous material at a very limited
computational cost. In order to perform the stochastic
changes in the regular structure matrices, the PMB
algorithm has been linked to a Monte Carlo subroutine,
able to change either the composition or the structure of
the considered material—MC atom exchanger (MCAE)
subroutine. Examples of PMB-MCAE applications on
different material representations are shown in Fig. 2.
MCAE code modifies at a very low computational cost,
an already built 3D material matrix by a stochastic engine
using the ranN subroutines [25, 26]. Since MCAE has to
deal with the same grain produced by PMB, it has been
implemented only as a subroutine of the former code. As
the tdMC codes described in this paper, MCAE is driven by
occurrence probabilities managing elementary events that
could be calculated referring to growth potentials, charac-
terizing metal deposition and by-product or poison and/or
promoter formation [18]. MCAE has been used also to
modulate the number of the Al-substituted sites in the H-
ZSM-5 zeolite matrices, used to model the but-2-ene
isomerization described in the next section, and to drive the
growth of the metal clusters inside or outside given mate-
rial cavities. Figure 3, as an example, shows a Pdn/H-ZSM-
5 fragment obtained by the PMB-MCAE code, the linear
size of a single site being comparable with the radius of
gyration of the zeolite T unit [41].
2.3 3D-tdMC Codes
The 3D simulation has been performed, without thermal
treatment, using a code similar to those discussed in Sect.
Top Catal (2009) 52:431–443 437

Fig. 2 Examples of amorphous

and defected crystalline
structures built by the PMB-
MCAE code; up and left: low
density porous polymeric
aggregate (number of
elementary-site 1004); up and
right: high density porous
polymeric aggregate (number of
elementary-site 2001); down:
simple-cubic-cell metal surface
obtained by randomly
removing, starting from the
ideal surface of the
corresponding cubic metal
crystallite, 498 of the initially
present 3375 elementary-sites

isothermal and isobaric cis/trans but-2-ene isomerization,

Fig. 3 Zeolite structure built by the PMB-MCAE code: 768T
H-ZSM-5 (dark grey), containing 9% w/w Al sites (black), and 8%
w/w Pdn (light grey), the grain units of the different material components
almost correspond to the radius of gyration of the T zeolite unit
2.1 that included the application of the 3D system matrix.
A flow-chart of the 3D-tdMC code is shown in Fig. 4. This
code has been preliminary tested on the chemical-regime
simulating a continuous-flow reactor. Details of the flow-
chart are given in the following, to show the main char-
acteristics of the first 3D-tdMC algorithm employed to
analyse catalytic processes.
The stochastic choices, represented by the subunit boxes
2 and 6 in Fig. 4, have been performed with the ran2
subroutine code [25, 26]. In the INPUT box the tempera-
ture and the hydrocarbon partial pressures are defined
together with the total time of the simulation (simulated
time), the activation energies, useful to calculate the event
occurrence probabilities, and the metal content. The
material characteristics, e.g. the room-surface organization
and the metal dispersion, are determined by the applica-
tions of the PMB-MCAE code, which is implemented as a
subroutine of the 3D-tdMC code (boxes 0). Subroutines in
box 1 calculate, from the INPUT information addressed by
the DRIVER, the maximum occurrence probability values
of the events on clean surface and state the optimized time
unit. This is the largest allowed starting time value for
given simulated conditions, characterizes the starting wss
of the system and is used to fix the initial sum of the event

123
438
Fig. 4 Simplified flow-chart of a 3D-tdMC code
occurrence probabilities, including the null event, to the
value of one.
Along the simulation, knowing the details on the surface
population and the actual time unit, the code randomly
chooses one event from a comb of predefined events (hit-
ting, reaction, desorption, diffusion and null event) in
boxes 2 and 3. If adsorption (hit plus the conditional
sticking), reaction, desorption or diffusion occurred, the
code determines in which position of the surface the event
has happened and records the new surface population (box
4). Of course, reaction, diffusion and desorption just occurs
for species already present on the surface and, conse-
quently, the surface population must be modified every
time they take place. On the contrary, the hit of a given
species leads to surface changes only if some room is
present on the surface to give the following adsorption.
Timing procedures, as seen above, are characterized by
routines which allow to switch among different rss, fol-
lowing the specific events occurring in the system, as
exemplified in Sect. 2.1. In the implementation of the
present 3D-tdMC two rss have been included. Indeed, once
pseudo-steady-state conditions have been reached (i.e.
when at least 103  104 diffusion or hitting events per
102  103 surface sites have serially occurred) the code
skipped hitting and diffusion, restricting the choice only to
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Top Catal (2009) 52:431–443
desorption or reactive but-2-ene isomerization events
(boxes 5 and 7), in this way going from the wss to the first
rss. The second rss is conversely reached if just hitting
diffusion and desorption take place, in going forward and
back from the wss to the first rss, for a previously fixed
number of times ð102  103 Þ: In the second rss just reac-
tive events are considered (boxes 5 and 7). Before facing
the first and second rss the surface molecules are always
adequately shuffled (box 6).
Following the occurrence of one of the events of the first
or the second rss, the simulated time is incremented as the
inverse of its occurrence frequency value, normalized to
the size of the mimicked surface, and the occurred event
book-kept, like for the wss, in boxes 8 and 9, respectively.
After the time jump, characterizing both the first and the
second rss, the time calculation procedure is restored to the
standard time. By this procedure, no information is lost
while the simulation time can be shortened of several
orders of magnitude and the simulated reaction time easily
gets values comparable to those of the experimental reac-
tion time. In any case, following the occurrence of each
event the system upgrades the simulated time, registers the
information regarding the involved events, boxes 8 and 9,
and returns to the DRIVER box, which monitors the
elapsed simulation time and stops the code when the
steady-state or the total time to be simulated is reached.
Finally, the code goes in sequence to the boxes OUTPUT
and END, hence collects the simulated results. The results
of the simulations, for example expressed as turnover fre-
quency (TOF) [6] taken at different simulation times, are
sent to the OUTPUT box. In Sect. 3.4 the results obtained
with this algorithm are discussed.
3 Applications
In the following sections a summary of the main applica-
tions of the algorithmic tdMC approaches is given.
Technical details are omitted while the main simulation
findings are shortly recalled. The simulated systems have
been chosen following (i) academic and technological
significance, (ii) difficulty in the interpretation of experi-
mental results and (iii) achievable hints in the investigation
of undisclosed surface properties.
3.1 CO Adsorption on Group 10 Metal Surface
The capability of the tdMC codes to model the adsorption
of simple molecules on the metal surface and to calculate
the corresponding system properties under variable thermal
conditions has been tested by modelling the adsorption of
the CO molecules on the surface of Group 10 metal crys-
tallites. The study has been in particular focused on the
Top Catal (2009) 52:431–443
steric hindrance effects, whose interest arises both from
experimental findings and qc calculations [42–44]. The
IDEA code, presented as the first T-tdMC code, has been
specifically developed for this purpose [5].
IDEA have correctly reproduced the experimental
results. In the performed simulations the steric hindrance
values have been used as fitting variables, whereas the
other parameters have been derived from qc calculations or
from the literature. This allowed us to modulate the event
occurrence probabilities by the steric hindrance of the
surface species configurations, using a reduced number of
fit parameters.
The steric hindrance effect has been evidenced by the
dependence of the sticking probability from the surface
population ratio, decreasing the CO residence probability
values with increasing the same surface population. This
behaviour resulted dependent on the metal surface char-
acteristics, pointing out the lowest CO steric hindrance on
Pd, and the highest on Pt, being this order confirmed by
potential energy surface (PES) calculations [5, 44]. The
tdMC simulations have thus explained the mechanistic
basis involved in the surface steric hindrance effects, being
also able to clarify related surface phenomena—see below.
In passing, it has also to be stressed that the T-tdMC IDEA
code allowed us to point out that the molecular steric
hindrance induces on populated metal surfaces an activa-
tion energy also on adsorption processes, which usually are
considered as inactivated.
Finally, mechanistic microscopic aspects related to the
carbon monoxide adsorption on Group 10 metal surfaces
have been elucidated by the analysis of the tdMC findings.
In particular special consideration deserves the hints given
on the interpretation of the hot-atom (HA) [45, 46] and the
AAD phenomena, using the ASE concept [5, 9, 10, 22].
ASE seems to play a fundamental role in regulating the
carbon monoxide adsorption–desorption processes and on
the whole in regulating surface and interface events, taking
place in catalysis and in surface-science.
In particular, mimicking the CO on metal crystallite
adsorption, IDEA has shown that the surface can not loose
energy in-between two hitting events, when the pressure
increases, raising both the bulk and the average metal
crystallite temperature. In this case, adsorption immedi-
ately followed by desorption is observed. This behaviour
straightforwardly illustrates the microscopic origin of the
AAD phenomenon on the metal surfaces [33–36]. The HA
phenomenon seems instead to be related to the existence of
surface temperature spots, locally produced by occurring
surface-events. Neither the crystallite sizes nor the crys-
tallite shapes play a critical role, but the opposite is true for
the metal crystallite properties (e.g. the extension of metal/
gas-phase interface) able to dissipate energy and to deter-
mine local surface temperature spots [5].
439
3.2 Hydrogenation of Ethylene and Acetylene/ethylene
Mixtures
Hydrogenation of ethylene and ethylene–acetylene mix-
tures on Group 10 metal catalysts is largely studied both for
the intrinsic experimental simplicity and for the large
industrial applicability [47]. In particular, removal of
alkynes from alkene-based feedstock by selective hydro-
genation is useful to prevent catalyst poisoning in
polymerization reactions [48], involving the same alkenes.
Different catalytic conditions have been taken into con-
sideration in the simulations of the ethylene hydrogenation
[6, 7, 9], performed employing probabilities, referring to
experimental and/or calculated information, both for the
event occurrence and for the residence of the surface
species.
Ethylene hydrogenation results, obtained through
2D-tdMC simulations on progressively more hindered
surfaces, have pointed out the fundamental role of the
steric hindrance parameters, which have been able to
explain the increasing catalyst activity along its use. This
occurrence can be ascribed to the reduction of available
surface sites caused by the carbonaceous deposit buildup
[9, 10, 28]. The explanation rests upon the different
reaction order (r.o.) characterizing the main reagents
(r.o. [1 for hydrogen, r.o. *0 for ethylene) and the
evidence that, on a hindered surface, ethylene population
decreases while hydrogen population slightly increases
[18]. The tdMC simulations have given also an explain-
ation of the existence of two reactive regimes in the
ethylene hydrogenation on Pt/silica catalysts, switching at
a critical temperature. In fact, taking into account the
ASE concept, the activity jump was attributed to coherent
order–disorder transition promoted by a surface energiz-
ing effect, that causes reorganization of the spatial
distribution of the H atoms [9, 49].
These are simple examples of the use of the tdMC codes
in producing molecular-level explanation of seemingly
complex processes. Other tdMC applications of industrial
chemistry interest can be exemplified by the study per-
formed on the selective hydrogenation of front-end and
tail-end feedstocks in isothermal and isobaric continuous-
flow fixed bed reactor. Also in this case the steric hindrance
plays a fundamental role. Indeed, the tdMC simulations
have shown that the same surface species behave either as
promoters or as poisons, depending on the surface deposit
amount and configuration [18]. The employed model was
designed to mimic the acetylene TOF and the selectivity to
ethane [28, 48].
In this catalytic system, different amounts of carbona-
ceous deposits, characterized by different steric hindrance,
have been progressively incorporated on the simulated
metal supported catalyst, in this way modelling surface
123
440
ageing phenomena. The simulated and experimental find-
ings have resulted in agreement both for the front-end and
tail-end mixtures, hypothesizing that given amounts of
surface sites were occupied by characteristically hindered
surface carbonaceous deposits. Interestingly, the acetylene
TOF value increased, if compared to that of ethylene, by
decreasing the number of active catalytic sites. This is not
surprising and can be explained considering that the local
steric hindrance of the acetylene carbon atoms is smaller
than that of the ethylene carbon atoms.
The geometrical effects related to a specific activity of
the catalyst sites, depending on the relative position of the
same sites in the catalyst particles, have also been studied.
However, the influence of the geometrical effects above
has been found less significant in explaining the connec-
tions between the catalyst behaviour, toward activity and
selectivity, and the catalyst particle dispersion character-
istics, confirming that the surface decoration effects plays a
fundamental role in driving the unsaturated hydrocarbon
hydrogenation on Group 10 metal surfaces [10, 18].
3.3 Hydrogenation of Aromatic Nitro-Derivatives
The catalytic hydrogenation of 2,4-dinitrotoluene to
2,4-diaminotoluene is an important industrial process,
fundamental for the toluene diisocyanate synthesis. This
reaction is characterized by a complex mechanism, leading
to different products. From results obtained at a laboratory
scale in ethanol at a constant temperature and H2 pressure,
a dependence from the surface structure has been proposed
for this mechanism, based on the presence of two different
kinds of adsorption: parallel and perpendicular to the sur-
face [50]. The 2,4-dinitrotoluene hydrogenation was
modelled by a dedicated tdMC code, designed for studying
three-phase batch reaction on Pd/C catalysts at isobaric and
isothermal conditions [12, 19, 20].
It was possible to define the role of all the molecular
species both in solution and on the surface, taking into
consideration three different types of adsorption, one par-
allel and two perpendicular to the catalyst surface. Each of
these types of adsorption has been assumed to hinder a
specific number of sites, allowing for mimicking the steric
hindrance of every population distribution and configura-
tion on the catalyst surface. The hitting probability of the
solvated species has been calculated by the Stokes–Ein-
stein theory, considering the radius of gyration of the
different species in water/ethanol solution. The remaining
probabilities have been evaluated as explained in Sect. 2.1.
The production of water during the reaction did not affect
the timing procedures [12, 19, 20].
The simulations, based on preliminary qc information,
fully reproduced the macroscopic properties of the con-
sidered system, giving a reliable evaluation of the
123
Top Catal (2009) 52:431–443
activation energy of the whole nitro-derivative hydroge-
nation processes. Moreover, it showed that the parallel
adsorption of the reactant molecules, with respect to the
surface, has a negligible influence on the product distri-
bution, being the activity and selectivity patterns mainly
controlled by the ratio between the two perpendicularly
adsorbed molecular configurations. Moreover, the catalyst
morphology, namely the metal dispersion related to the
single surface species configurations, had a minor role with
respect to the determination of the whole molecular dis-
tributions. Hence, the determination of the catalyst activity
and selectivity were explained [12, 19, 20] taking into
consideration, besides the system temperature and pressure,
the whole set of species involved in the different phases,
the size of the catalysts particles and the surface random
parking model [37].
3.4 But-2-ene Isomerization on H-ZSM-5 Systems
PMB and MCAE routines have been employed to simulate
a H-ZSM-5 zeolite matrix in 3D-tdMC studies. The reli-
ability of the 3D-tdMC code has been tested in the but-2-
ene cis/trans isomerization processes. The zeolite models
were matrices containing up to 5000 alumino-silicate units.
However the results here presented have been obtained by
2304T H-ZSM-5 system models. Along the simulation we
have not considered the formation of surface by-products,
like polymer or carbonaceous deposits, or the formation of
multi-layers of adsorbed species. Nevertheless, these sur-
face modifications can easily be introduced in the
simulation model and their effects evaluated to test their
influence on the whole process.
The value of the activation energy of the cis/trans
isomerization and the related probabilities have been
obtained by qc calculations on a 22T model of Pd sup-
ported and unsupported H-ZSM-5 fragments [51]. The but-
2-ene adsorption/desorption activation energies and prob-
abilities have been also obtained by qc calculations on the
same models and for the unsupported systems were inte-
grated by information obtained on 52T H-ZSM-5 models
[38]. The activation energy for the diffusion processes has
been calculated as a fraction, namely 20%, of the corre-
sponding desorption Ea value. The occurrence probabilities
of hitting and sticking have been calculated as explained in
Sect. 2.1.
The event occurrence probabilities when needed have
been tuned with the residence probabilities, accounting of
the corresponding steric hindrance terms and referring to
values already used for similar hydrocarbon species [10].
The physical surface properties of the catalytic systems has
been mimicked by normalizing to the number of active-
sites the values of the extensive variables and leaving
unchanged those of the intensive ones. The tdMC
Top Catal (2009) 52:431–443 441

0.25

0.20

0.15

θ
0.10

0.05

0.00
0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5
-5
10 t / s
Fig. 5 A snapshot of a 768T fragment of the unsupported 2304T H-
ZSM-5 model, during the 3D-tdMC simulation of the but-2-ene cis/ Fig. 6 First-instants partial surface coverage as a function of the
trans interconversion—gas-phase starting parameters: ptot bar, T = simulated time for cis-but-2-ene (filled circle) and trans-but-2-ene
360 K, vcis ¼ vtrans ¼ 0:5: Silicate sites are in dark grey, aluminate (open circle), occurring on a 2304T H-ZSM-5 model—gas-phase
sites in black, some but-2-ene molecules are evident in white, the starting parameters: ptot bar, T = 360 K, vcis ¼ vtrans ¼ 0:5
grain units of the alumino-silicate and of the hydrocarbon molecules
are about corresponding to the radii of gyration of the 1T and the
C2H4 groups, respectively 10.0

8.0
simulation has been carried out for even more than 10-3 s
of real-time (t), producing reliable results. A snapshot of a 6.0
ln(TOF)

reacting fragment of the system during the simulation of

the isobaric and isothermal process performed at a tem-
perature (T) equal to 360 K and a total pressure ptot equal
to 1 bar, with cis and trans gas-phase molar ratio (v) equal
to 0.5, is reported in Fig. 5.
The calculated values of TOF and Ea are in good
agreement with our chemical-regime experimental results
obtained at 1  2 bar and different starting reagent (but-1-
ene, cis-but-2-ene and trans-but-2-ene) partial pressure, in
the temperature range 303  363K; obtained in a continu-
ous-flow reactor.
In Fig. 6 the ‘‘first-instants’’ (order of magnitude 105 s)
surface population ratio, got by a simulation performed at
T = 360 K, ptot bar and vcis ¼ vtrans ¼ 0:5; is reported as a
function of the simulated time, the latter corresponding to
the real experimental time. Figure 6 shows just the first-
instants’ surface readjustments, in order to outline the
population ratio transient behaviour. Steady-state condi-
tions have as expected been reached already within 10 ls
of simulation. The limiting value for the partial (i.e.
depending on a given species) surface coverage (h) has
been found at h [ 0.20 both for the cis-but-2-ene and
trans-but-2-ene surface species.
In Fig. 7 the Arrhenius plot, ln(TOF) vs. 1/T, of the cis/
trans and trans/cis isomerization, corresponding to a
2304T unsupported H-ZSM-5 system with a 7% of alu-
minated sites, under cis-but-2-ene and trans-but-2-ene
partial pressure equal to 0.5 bar, is shown. The covered
temperature values range in-between 285–420 K. Figure 8
4.0
2.0
0.0
-2.0
2.2 2.4 2.6 2.8 3.0 3.2 3.4 3.6
-3
10 K / T
Fig. 7 Arrhenius plot, ln(TOF) vs. 1/T, for the but-2-ene isomeriza-
tion occurring on a 2304T H-ZSM-5 unsupported system: cis ? trans
(filled circle) and trans ? cis (open circle) processes—gas-phase
starting parameters: ptot bar, T = 360 K, vcis ¼ vtrans ¼ 0:5
shows the Arrhenius plot for the same system when 90% of
the aluminated (acidic) sites are neighboring small (3  5
atoms) palladium clusters. The covered temperature values
range in-between 330–390 K.
The Arrhenius plots of both Figs. 7 and 8 show a correct
linear trend both in the presence and in the absence of the
metal. To check this behaviour we extended to the, less
time-consuming, unsupported simulation systems the
temperature spectrum analysis and always the linear trend
has been found.
The Ea values calculated for the isomerization processes
are reported in Table 1. Noteworthy, the activation ener-
gies calculated from these plots are quite different from
those of the qc evaluations and systematically higher. This
behaviour is related to the involvement, in the tdMC

123
442 Top Catal (2009) 52:431–443

planned, and new simulation with true qc-based diffusion

10.0
Ea values carried on.
8.0 Finally, the 3D-tdMC code simulations show its ability
to model the test process while the correction of the fun-
6.0 damental qc information employed should improve the
ln(TOF)

mimicked results. The code can be used to study a wide

4.0 range of reactions by changing the process basis input and
it should allow to obtain a very large output spectra, ade-
2.0
quately modulating the parameters of the system. In fact,
0.0 the here 3D-tdMC code is at present mainly targeted to
two-phase continuous-flow systems but extension of this
-2.0 approach to the study of two-phase and three-phase batch
2.5 2.6 2.7 2.8 2.9 3.0 3.1
-3 reactor processes is actually planned.
10 K / T

Fig. 8 Arrhenius plot, ln(TOF) vs. 1/T, for the but-2-ene isomeriza-
tion occurring on a 2304T H-ZSM-5 system embedding small Pd 4 Conclusion and Future Developments
(3  5 atoms) clusters (90% of the aluminated sites is interacting with
the metal clusters): cis ? trans (filled circle) and trans ? cis (open
circle) processes—gas-phase starting parameters: ptot bar, T = 360 K, The heterogeneous catalytic simulations by the tdMC
vcis ¼ vtrans ¼ 0:5 codes can be employed to analyse large sets of different
surface species and molecular-level events, occurring on
two-phase and three-phase systems in different reaction
Table 1 Activation energies characterizing the isomerization pro- conditions on 2D and 3D matrices, mimicking the physical
cesses of supported and unsupported palladium H-ZSM-5 fragments
properties of the involved catalytic materials. In addition,
Pdn/Al ratioa qc Eab MC Eac qc Eab MC Eac the use of T-tdMC approaches could help in explaining
cis ? trans trans ? cis
microscopic properties related to surface energy gradients.
The use of qc-tdMC simulations allows one to obtain
0.00 35.2 78.2 30.0 75.8
fully computational models taking into account local
0.10 – 82.0 – 78.2
information, regarding simple molecular events, and sys-
0.50 – 88.8 – 86.8
tem-wide information, regarding the whole reaction that
0.75 – 89.9 – 87.7
self-consistently emerge from the complex set of the
0.90 – 112.0 – 108.5
same molecular events. Through the use of qc calculations,
1.00 76.0 – 70.6 –
reliable results can be obtained without referring to
a
Palladium clusters (2  5 atoms) per aluminated (acidic) sites experimental approaches.
present in the modelled H-ZSM-5 fragments In any case, the algorithmic tdMC methods can be tested
b
The in vacuo qc Ea values, obtained by 22T H-ZSM-5 models, by the analysis of simulated and experimental results that,
must be considered as preliminary and refer, excluding the adsorp-
tion/desorption and diffusion steps, to the highest activation energy due to the characteristics of the described tdMC models are
values involved in the elementary surface processes of the cis/trans easily comparable.
isomerization paths, characterizing the supported and unsupported Future improvements of T-tdMC and/or 3D-tdMC
zeolite system algorithms are currently pursued for more realistic simu-
c
The 3D-tdMC simulation results are obtained on 2304T H-ZSM-5 lations of the experimental processes. The deepening of the
fragments at ptot = 1 bar and cis/trans isomer ratio equal to 1
mechanism of diffusive processes in the nano-structured
3D matrices is considered essential because the diffusion
simulations, of the diffusion and desorption events that are plays a basic role in explaining the apparent discrepancies
not taken into consideration in the qc approach. Interest- occurring among simulated and experimental findings. In
ingly, desorption and diffusion become more and more particular, onsets of diffusion, influenced by the steric
significant decreasing the size of the zeolite rooms for the hindrance of the surface derivatives, strongly affect the
presence of embedded metal atoms, as it is clearly shown reagent availability in local reactive surface environments,
by the cis/trans isomerization 3D-tdMC Ea values reported which could be also modified by molecular concentration
in Table 1. In any case, the evaluation of the diffusion and energy gradient effects.
contribution considered as a constant fraction of the Finally, Molecular Dynamics (MD) is at present con-
desorption Ea has to be refined in order to reproduce more sidered to mimic in details the gas-phase phenomena
realistically the experimental findings. Quantum chemical occurring above the interface, characterizing two-phase
calculations of surface molecular diffusion events are qc-3D-T-tdMC surface simulations. This would allow one

123
Top Catal (2009) 52:431–443
to follow by the deterministic MD treatment the gas-phase
processes and by the three dimensional thermal quantum
stochastic treatment the surface-event and the energy
readjustment processes, in this way realizing a surface-
science and catalysis process virtual laboratory able to face
macroscopic processes by molecular-level in silico meth-
ods. The but-2-ene isomerization, taking also into account
parallel processes, as the double-bond migration, and dis-
tinguishing between the catalyst activity inside and outside
the zeolite cavity, could represent a suitable test reaction
for the proposed developments.
Acknowledgements This work was supported by the NANOCAT
Project, funded in the frame of the 6th Framework Programme of the
European Community—Contract No. NMP3-CT-2005-506621, by
the University of Palermo and by the Italian Ministero dell’Università
e della Ricerca.
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