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Theoretical Studies on Hydrogen

Activation by Iridium Dimers

S. CASTILLO,1 V. BERTIN, 2 E. SOLANO-REYES,1

H. LUNA-GARCIA, ´ 1 A. CRUZ, 3 E. POULAIN 4
1
´
Area de Fısica, ´
CBI, UAM-A, Av. San Pablo 180, 02200, Mexico, ´
D.F., Mexico
2
´
Dep. de Quımica, ´
CBI, UAM-I, A.P. 55-534, 09340, Mexico, ´
D.F., Mexico
3
´ Industrial, IMP, A.P. 14-805, 07730, Mexico
Subdirec. de Transformacion ´ ´
D.F., Mexico
4
´ Mexico
Div. de Est. de Posgrado e Invest., ITTLA, A.P. 750, 54070 Tlalnepantla de Baz, Mex. ´

Received 23 February 1998; accepted 20 April 1998

ABSTRACT: The basic and fundamental mechanisms governing the catalytic reaction
of small iridium clusters with H 2 are presented here with the purpose to determine its
behavior in hydrogenation reactions. The iridium dimer’s lowest states in interaction
with H 2 potential energy surface were obtained using ab initio multiconfigurational
self-consistent-field calculations ŽMC᎐SCF., with relativististic pseudopotentials. The
electronic correlation contribution was included by configurations interaction ŽCI.
calculations, which considered a variational part plus a second-order perturbative part.
The Ir2 q H 2 reactions were developed in the C2 v symmetry. The Ir2 ’s five lowest
electronic states were determined, 5 ⌸ g , 3 ⌸ g , 1 ⌺q 3 q 5
g , ⌺ u , and ⌺ g , and studied when
reacted with H 2 . It was found that the iridium dimer, in these five states, might capture
and break the H H bond, spontaneously in certain cases and after surmounting
activation barriers in other cases. 䊚 1998 John Wiley & Sons, Inc. Int J Quant Chem 70:
1029᎐1035, 1998

in a dissociative way w 1x : in the last mode, in a

Introduction 1:1 H and Ir rate, with an adsorption heat of
18.40 kcalrmol in the Ž110. plane w 1x . But in in-
creasing the iridium dispersion over a support,

T hat metallic iridium adsorbs H 2 without acti-

vation is observed in many experiments. The
adsorption occurs both as a molecular reaction and
Correspondence to: E. Poulain.
Contract grant sponsor: CONACYT ŽMexico..
Contract grant number: 3494PE.
each Ir atom can adsorb two or three H atoms w 2x .
The dispersion is increased easily in iridium-sup-
ported catalysts, reaching almost a 100% value w 3x ,
by far different from other transition metals, as
platinum, where the atoms have the tendency to
sinter.

International Journal of Quantum Chemistry, Vol. 70, 1029᎐1035 (1998)

䊚 1998 John Wiley & Sons, Inc. CCC 0020-7608 / 98 / 041029-07
CASTILLO ET AL.
Iridium has been employed to improve the
PtrAl 2 O 3 reforming catalyst, but the resulting
bimetallic catalyst is not easily regenerated, so its
industrial application is difficult. Better applica-
tions have iridium catalysts in a variety of hydro-
genation or dehydrogenation reactions, as, for ex-
ample, in cyclohexene, benzene w 4x , and linoleic
acid hydrogenation w 5x , with the purpose to obtain
products with a large added value. Iridium cata-
lysts also have been employed in hydrogenolysis
reactions. Also, iridium complexes Žphosphynes,
carbonyls. are currently employed w 4x .
The Ir ground state is an 4F Ž5d 7 6 s 2 . configura-
tion. Ir reacts very quickly and easily with alkenes,
but does not react with methane and other al-
kanes. This behavior has to be explained in terms
of the ground and excited states’ electronic config-
uration w 6x and topology.
It was suggested that the 6 s orbital lanthanide
contraction modifies the 5d series atoms reactivity.
Also, the positive Ir ion is efficient, the most effi-
cient among transition-metal ions. For instance,
among other characteristics, in gas-phase methane
dehydrogenation, the Ir ion easily changes its spin
value w 7x . Ir monomers have been studied theoreti-
cally, where some characteristics were presented:
particularly, studies of the Ir q H 2 and Ir q CH 4
reactions are shown in w 8, 9x .
Theoretically and experimentally w 10᎐24x , the
H 2 reaction with many metals has been the object
of intense work in our laboratory. Due to, in par-
ticular, that the Ir q H 2 interaction is a prelimi-
nary not yet well-determined catalytic reaction,
many steps of these reactions are in process. More-
over, they are especially important in petrochemi-
cal processes w 25x , where in these reaction types,
the hydrogen is a reactant or a product and is
employed to activate the catalysts. For instance,
the H 2 interaction with metal is a powerful reac-
tion test, which has produced the greatest number
of experimental reports w 26x .
Pd and Pt are the most employed metals in
catalysis because of their electronic properties. The
most important catalyzed reactions using them are
the CO, H 2 , and alkane activations w 27, 28x . But
there are other metals also with important catalytic
properties. Iridium is one of these metals. Some
iridium organometallic complexes may activate
and break the C H alkane bonds by inserting an
Ir atom in the bonds and forming a carbon᎐metal᎐
hydrogen complex w 29x .
1030
Method of Calculation
The potential energy states ŽPES. parameters’
determination in each point is done and initiated
using ab initio Hartree᎐Fock self-consistent-field
ŽHF᎐SCF. calculations with the PSHONDO pro-
gram w 30x , with relativistic pseudopotentials, also
called relativistic effective core potentials ŽRECP..
The Ir pseudopotential is a xenon core type w 31x .
These calculations are followed by small multicon-
figurational ŽMC. SCF calculations, which gives
the initial energy value and the initial wave func-
tion. The electronic correlation is considered and
added to the energy value previously described
throughout configuration interaction ŽCI. methods.
This term is obtained by CI variational and pertur-
bative calculations, where an energy value is de-
termined by making a variational calculation,
modified by a perturbative calculation upon sec-
ond order, using the CIPSI algorithm w 32x . The
iridium atomic basis functions are Gaussians taken
from w 31x , contracted to a triple zeta scheme
Ž3s3 p4 d .rw 111r21r211x . The hydrogen functions
are of double-zeta quality w 33x plus two polariza-
tion functions w 34x .
Results and Discussion
IRIDIUM ATOM CALCULATIONS
As the first step of the Ir2 q H 2 reaction study,
the Ir atomic basis and the Ir pseudopotential were
tested. Here, we used the best set from the litera-
ture reproducing the experimental iridium atomic
energy spectra; Table I presents the calculated and
the reported energies w 35x of the atomic iridium’s
three low-lying F states. These results show that
TABLE I
Experimental and calculated splitting of the three
lowest F iridium atom states.
⌬ E (this work) ⌬ E (experimentala )
Atomic state (kcal / mol) (kcal / mol)
4
F (5d 7 6 s 2 ) 0.0 0.0
4
F (5d 8 6 s1) 13.6 9.2
2
F (5d 8 6 s1) 19.3 26.0
a
From [34], the J-averaged values over all spin᎐orbit com-
ponents.
VOL. 70, NO. 4 / 5
 HYDROGEN ACTIVATION BY IRIDIUM DIMERS

by using the selected functions we obtained a IRIDIUM DIMER CALCULATIONS

satisfactory description of the Ir states.
The electronic configurations of the iridium
dimer’s lowest most important states were calcu-
H 2 in C 2 v Approach to the Ir(4 F:5d 76s 2 ) and lated. The energies and interatomic distance for
Ir(4 F:5d 8 6s1 ) Atoms these configurations are presented in Table III. As
The hydrogen molecule activation by a single we can see from this table, the Ir2 ground state is a
iridium atom was studied previously w 36x and quintuplet, where the excited-state energy gap dif-
recently by Gropen et al. w 8x . In both calculations, ference is similar and the metal᎐metal distance
it was found that the iridium atom in its 4F ground presents a very interesting behavior. The electronic
state captures H 2 after surmounting a small bar- configuration of the Ir2 5 ⌸ g ground state as well as
rier. In addition, the former authors found that the the first 3 ⌸ g excited state have the same four
iridium atom in its lowest 2 F excited state sponta- single-occupied molecular orbitals: ␴u ŽIrŽs. q
neously inserts between the H atoms. These con- IrŽys.., ␲g ŽIrŽ d y z . q IrŽ d y z .., ␦ g ŽIrŽ d x y . q IrŽ d x y ..,
figurations were calculated by us and the results and ␦u ŽIrŽ d x y . q IrŽyd x y ...
presented in the mentioned work were repro-
duced. It seems not relevant to include them here.
Table II shows that the iridium atom, in its POTENTIAL ENERGY SURFACES FOR THE
ground state 4F:5d 7 6 s 2 , captures and breaks the Ir 2 + H 2 INTERACTION
hydrogen molecule. These PES reactions are 4A 2 The PES reactions of the five Ir2 lowest states in
and 4B1 excited states. The 4A1 and 4B2 PES of the the reaction with H 2 were determined. The hydro-
first iridium excited state present, first, an attrac- gen molecule approached the iridium dimer in the
tive character, arriving at an avoided crossing re- C2 v symmetry in two ways: one in which both
gion with the 4A 2 and 4B1 PES. After that, they systems are in the same plane, and in the other,
change to a repulsive character. The 4A 2 and 4B1 where the two systems are in perpendicular planes.
states of the 4F:5d 7 6 s 2 q H 2 reaction are initially
repulsive curves. After the avoided crossing, these
PES became attractive, showing potential wells,
where the H 2 is captured and the H—H rupture TABLE III
occurs. The potential barriers presented in these The five lowest Ir 2 states.
interactions are in all cases a consequence of
Relative Ir—Ir
avoided crossings. energy distance
Molecular electronic state (kcal / mol) (au)
H 2 C 2 v Approach to the Ir(2 F:5d 8 6s1 ) Atom 5
⌸ g : ␲u2␲u2␦u2␴g2␦u2␲g2␴g2␲g1␦ g1␴u1␦u1 0.0 4.6
For the iridium in the doublet state, we found 3
⌸ g : ␲u2␲u2␦u2␴g2␦u2␲g2␴g2␲g1 ␦ g1 ␴u1␦u1 15.9 4.4
that in the 2 F:5d 8 6 s 1 q H 2 reaction the 2A1 , 2A 2 , ⌺ g : ␲u2␲u2␴g2␦ g2␦u2␲g2␲g2␦ g2␴u2
1 +
21.6 4.4
and 2 B1 states spontaneously occur, capturing and ⌺ u : ␲u2␲u2␦ g2␴g2␦u2␲g2␲g2␦ g2␴g1␴u1
3 +
29.6 4.6
breaking the hydrogen molecule. Our results are in 5
⌺ g : ␲u2␲u2␴g2␦ g2␦u2␲g2␲g2␴g1␦ g1 ␴u1␦u1 35.3 4.8
very good agreement with those of w 36x .

TABLE II
H 2 C 2v approach to an Ir atom.

Ir electronic d (Ir—mcH 2 ) d (H—H) a % H—H Depth of well Barrier

state (au) (au) relax (kcal / mol) (kcal / mol)
4
A1 No capture for this state
4
A2 2.5 3.0 113 11.2 15.0
4
B1 2.1 4.0 184 11.8 4.5
4
B2 No capture for this state
a
d (H—H) nonactivated = 1.41 au.

INTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY 1031

CASTILLO ET AL.
Both Systems in the Same Plane: Side on C 2 v
Approach of H 2 to Ir 2
In this reaction mode ŽTable IV., it was found
that Ir2 activates the H 2 in its four low-lying
states, 5 ⌸ g , 3 ⌸ g , 1 ⌺q 3 q
⌺ u , where capture and
g ,
dissociation of H 2 is obtained, but with barriers
present, whereas in the highest state, 5 ⌺ g , the H 2
capture and dissociation occurs spontaneously.
But, this last state is a very high one, hardly
important in catalyzed reactions.
From Table IV, we can see that all the well
depths Žadsorption heats. are larger than the ex-
perimental adsorption heat Ž18.40 kcalrmol.. All
the capture distances are similar, and, in general,
the captures need to be activated.
The Ir2 Ž5 ⌸ g . q H 2 PEs ground-state reaction
shows a well only surmounting a potential barrier
of 13 kcalrmol. This barrier is produced by an
avoided crossing of this PES with an attractive PES
coming from a high quintuplet state, whose sepa-
rate fragments correlate with an iridium dimer in a
quintuplet state and the hydrogen molecule is in
the ground state. Similar to this case, all the poten-
tial barriers in this reaction mode are produced by
avoided crossings.
Let us now analyze the molecular orbitals of the
system. The Ir2 H 2 in equilibrium resulting from
the Ir2 Ž5 ⌸ g . q H 2 reaction present the following
molecular orbital elements: a bonding a1 orbital,
due to the overlap of the IrŽ s q d z 2 q d y z . q
IrŽ s q d z 2 y d y z . orbitals with the HŽ1 s . q HŽ1 s .
orbital; and a bonding a 2 orbital coming from the
overlap of the orbital IrŽ s q d z 2 q d y z . orbital q
IrŽys y d z 2 q d y z . with the antibonding HŽ1 s . q
HŽy1s . orbital.
TABLE IV
H 2 C 2v lateral approach to Ir 2 reaction parameters.
Ir 2
electronic d (Ir 2 —H 2 ) a d (H—H)b
state (au) (au)
5
⌸g 2.8
3
⌸g 2.8
1 +
⌺g 3.0
3 +
⌺u 3.0
5
⌺g 3.0
a
Mass center᎐mass center distance.
b
Compared with d (H—H) nonactivated = 1.41 au.
1032
Considering the bond formation, the following
reaction mechanism is proposed to explain the
Ir2 Ž5 ⌸ g . q H 2 interaction in the lowest state: At
the beginning, the H 2 ␴ * empty orbital started to
populate from the singled occupied Ir2 ␴u w IrŽ s . q
IrŽys .x orbital, later interacted with the double-
occupied ␲g w IrŽ dz 2 . q IrŽydz 2 .x , due to that at the
beginning the ␴u orbital has a higher energy than
has the ␲g orbital, but when the reaction pro-
gresses, the ␲g becomes more important and both
interactions contribute to generate the a 2 orbital.
In the barrier zone, the a 2 orbital formation is in
competition with a repulsive interaction of the
occupied IrŽ s . q IrŽ s . with the H 2 ␴ orbital and
the bonding a1 orbital of the Ir2 H 2 in equilibrium
system.
H 2 in C 2 v Perpendicular Approach to One of
the Ir of the Ir Dimer
In this approach, the metal and the hydrogen
are in a plane and Ir2 in its five 5 ⌸ g , 3 ⌸ g , 1 ⌺q
g ,
3 q
⌺ u , and 5 ⌺ g low-lying states captures and acti-
vates H 2 without need of activation Žsee Table V..
In the two lowest states, 5 ⌸ g and 3 ⌸ g , the hydro-
gen molecule is only relaxed, whereas in the next
three highest states of the metal, the hydrogen
molecule is clearly dissociated. In addition, the
adsorption heat is lower in the lowest metal states,
being quite close to the reported values. The
Ir2 Ž5 ⌺ g . q H 2 PES depth of the potential well dif-
fers -2 kcalrmol with the Ir adsorption heat in
the Ž110. plane. This is the minor adsorption heat
found in the present study. The capture distances
are smaller for the highest metal states.
% H—H Depth of well Barrier
relax (kcal / mol) (kcal / mol)
5.6 297 33.4 13.3
4.6 226 49.2 16.7
4.0 184 54.3 8.5
4.6 226 66.0 13.0
4.6 226 50.2 No
VOL. 70, NO. 4 / 5
 HYDROGEN ACTIVATION BY IRIDIUM DIMERS

TABLE V
H 2 C 2v perpendicular approach to one Ir of the Ir 2 , both species in the same plane.

Ir 2
electronic d (Ir 2 —H 2 ) a d (H—H)b % H—H Depth of well Barrier
state (au) (au) relax (kcal / mol) (kcal / mol)
5
⌸g 3.0 1.8 28 17.0 No
3
⌸g 3.0 1.8 28 29.2 No
1 +
⌺g 3.0 4.7 233 34.8 No
3 +
⌺u 1.5 5.0 255 52.2 No
5
⌺g 2.5 4.6 226 42.7 No
a
Ir—Ir bond bisecting the H—H bond.
b
As in Table IV.

This reaction mode is the most similar one to
the direct reaction of a single Ir atom with the
hydrogen molecule. Comparing the one and two Ir
atoms’ reactions with H 2 and comparing with the
platinum case, we can see that there are at least
two differences: A ground-state single Ir atom can
activate H 2 , whereas a single Pt atom only can
activate H 2 from an excited state. Also, the second
Ir atom does not poison the reaction of one Ir atom
and the Pt dimer is able to activate the H 2 , but in
an excited state, with a lower angle Žalmost one-
half of a single Pt atom. because of the poisoning
of the second atom.
The 100% dispersed Ir catalysts are easily pre-
pared and adsorb H 2 w 3x , whereas it is very diffi-
cult to have Pt catalysts with this dispersion. In
some experiments, by introducing Pt in small
porous zeolites, it is possible to get such a disper-
sion, but in any of these cases, Pt does not adsorb
H 2 w 37x .
H 2 in C 2 v Approach to Ir 2 , Both Systems in
Perpendicular Planes
Again, for Ir2 in the four lowest states, 5 ⌸ g ,
3
⌸ g , 1 ⌺q 3 q
g , and ⌺ u , for this reaction mode, activa-
tion is necessary to induce the dissociative capture
of H 2 , especially in the ground state ŽTable VI..
But we have to remark that this approach is not a
comparable scheme with the experimental results,
due to the following: This model does not consider
the Ir atoms of the subjacent plane.
In the experimental situation, the hydrogen
molecule falls over the Ir crystal plane but not on a
single isolated dimer. However, it is useful to
consider the characteristics of this approach over
an isolated and naked cluster because the H 2 can
rotate.
From Table VI, we can observe, that in this
approach mode, the distances between the metal
dimer and the hydrogen are the smallest. In all the

TABLE VI
C 2v approach of H 2 to Ir 2 , both dimers in perpendicular planes.

Ir 2
electronic d (Ir 2 —H 2 ) a d (H—H)b % H—H Depth of well Barrier
state (au) (au) relaxation (kcal / mol) (kcal / mol)
5
⌸g 0.8 3.8 170 22.1 39.8
3
⌸g 0.0 3.8 170 32.5 9.1
1 +
⌺g 0.0 4.4 212 48.7 13.7
3 +
⌺u 0.8 4.2 198 35.1 27.5
5
⌺g 1.5 3.4 141 24.0 No
a, b
See footnotes a and b to Table IV.

INTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY 1033

CASTILLO ET AL.
cases presented, the H H bond is completely
ruptured with a very different well depth, depend-
ing on the electronic state, but all the five metal
states show dissociative capture. In the 5 ⌺ g highest
state, the dissociative H 2 adsorption is sponta-
neous, that is, it does not present a barrier.
For the Ir2 Ž3 ⌸ g . —H 2 and Ir2 Ž1 ⌺q g —H 2 interac-
. Conclusions
tions, it was found that the metal᎐hydrogen dis-
tance is null, that is, the hydrogen atoms are be-
tween the Ir atoms, forming a bridged structure
ŽTable VI.. This structure is presented in
organometallic compounds w 38x . Comparing the re-
sults of Tables V and VI, there are some similar
behaviors. This can be explained by considering
that it is possible to change the reaction mode
from the same plane to the perpendicular planes,
with a simple rotation.
This reaction mode for the equilibrium Ir2 H 2
system, the Ir2 Ž5 ⌸ g . —H 2 interaction, presents,
among others, the following orbitals: a bonding a1
orbital, resulting from the overlap of the ␴g w IrŽ s . q
IrŽ s .x orbital, with the H 2 Ž ␴g . orbital. Also, there is
a bonding b 1 orbital from the overlap ␲u w IrŽ d x y . q
IrŽyd x y .x orbital with the ␴ *ŽH 2 . orbital. The bond
arises from the following proposed mechanism:
The empty ␴ ⬘ŽH 2 . orbital may be populated and
form a bond with the Ir2 doubly occupied
␲u w IrŽ d x y . q IrŽyd x y .x orbital; nevertheless, at the
beginning of the reaction, this Ir2 orbital is much
deeper in energy than are the other Ir2 partially
occupied orbitals, so the ␴ *ŽH 2 . y␲u ŽIr2 . cannot
overlap completely. In advancing the reaction, the
overlap is produced and the described equilibrium
geometry is achieved.
The interaction of both orbitals led to the Ir2 H 2 b 1
orbital formation. Also, at the beginning of the
reaction, the b 1 orbital formation is in competi-
tion with the repulsive interaction of the occupied
IrŽ s . q IrŽ s . with the ␴ ŽH 2 . orbital. This last
interaction produces the bonding a1 Ir2 H 2 orbital.
As a consequence, in this approach mode, a high
barrier appears in the Ir2 Ž5 ⌸ g . —H 2 interaction.
When the reactants are in the same plane, they
show from the beginning an attractive interaction
compared with the high barrier existence in this
approach and is in agreement with a less favorable
directional character of the molecular orbitals in
the reaction with the metal dimer and the hydro-
gen in perpendicular planes.
The present study shows that the iridium dimer,
in the ground state, as in its four low-lying excited
states, can activate the hydrogen molecule. In cat-
alytic processes, the excited states’ contribution is
1034
quite probable, mainly because the ligands may
modify the electronic structure of the metal’s lead-
ing to many active states, giving the best catalyst
w 8, 20x .
From the Ir dimer study, we obtain the molecu-
lar configuration, the equilibrium interatomic dis-
tances, and the energies of the five lowest states,
5
⌸ g being the ground state, and 3 ⌸ g , 1 ⌺q 3 q
g , ⌺u ,
5
and ⌺ g , the four lowest excited states.
Ir2 could capture and activate the hydrogen
molecule in almost all the cases studied. In the
perpendicular reaction mode, where H 2 and Ir2
are in the same plane, both the molecular and the
dissociative capture of H 2 is obtained. As experi-
mentally observed, no barriers are presented.
The participation of some of the metal excited
states must be considered because they also have a
dissociative reaction with H 2 . Other modes of re-
action may be considered as important because the
excited states are also active, but the presence of
avoided crossings generate high barriers which
make it more difficult to reach these states.
ACKNOWLEDGMENTS
We wish to thank once again our colleagues at
the University of Toulouse, France, and at the
University of Barcelona, Spain, for the PSHF᎐
GMCP᎐CIPSI chain of programs. This work was
´ . Pro-
partially supported from CONACYT ŽMexico
ject No. 3494PE. The calculations were done with
an Aspen Alpha Durango II 533 Mhz computer
provided by the mentioned project.
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