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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
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 ,
Correspondence to: E. Poulain.
by far different from other transition metals, as
Contract grant sponsor: CONACYT ŽMexico.. platinum, where the atoms have the tendency to
Contract grant number: 3494PE. 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 Method of Calculation
bimetallic catalyst is not easily regenerated, so its
industrial application is difficult. Better applica- The potential energy states ŽPES. parameters’
tions have iridium catalysts in a variety of hydro- determination in each point is done and initiated
genation or dehydrogenation reactions, as, for ex- using ab initio Hartree᎐Fock self-consistent-field
ample, in cyclohexene, benzene w 4x , and linoleic ŽHF᎐SCF. calculations with the PSHONDO pro-
acid hydrogenation w 5x , with the purpose to obtain gram w 30x , with relativistic pseudopotentials, also
products with a large added value. Iridium cata- called relativistic effective core potentials ŽRECP..
lysts also have been employed in hydrogenolysis The Ir pseudopotential is a xenon core type w 31x .
reactions. Also, iridium complexes Žphosphynes, These calculations are followed by small multicon-
carbonyls. are currently employed w 4x . figurational ŽMC. SCF calculations, which gives
The Ir ground state is an 4F Ž5d 7 6 s 2 . configura- the initial energy value and the initial wave func-
tion. Ir reacts very quickly and easily with alkenes, tion. The electronic correlation is considered and
but does not react with methane and other al- added to the energy value previously described
kanes. This behavior has to be explained in terms throughout configuration interaction ŽCI. methods.
of the ground and excited states’ electronic config- This term is obtained by CI variational and pertur-
uration w 6x and topology. bative calculations, where an energy value is de-
It was suggested that the 6 s orbital lanthanide termined by making a variational calculation,
contraction modifies the 5d series atoms reactivity. modified by a perturbative calculation upon sec-
Also, the positive Ir ion is efficient, the most effi- ond order, using the CIPSI algorithm w 32x . The
cient among transition-metal ions. For instance, iridium atomic basis functions are Gaussians taken
among other characteristics, in gas-phase methane from w 31x , contracted to a triple zeta scheme
Ž3s3 p4 d .rw 111r21r211x . The hydrogen functions
dehydrogenation, the Ir ion easily changes its spin
value w 7x . Ir monomers have been studied theoreti- are of double-zeta quality w 33x plus two polariza-
tion functions w 34x .
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 Results and Discussion
H 2 reaction with many metals has been the object
IRIDIUM ATOM CALCULATIONS
of intense work in our laboratory. Due to, in par-
ticular, that the Ir q H 2 interaction is a prelimi- As the first step of the Ir2 q H 2 reaction study,
nary not yet well-determined catalytic reaction, the Ir atomic basis and the Ir pseudopotential were
many steps of these reactions are in process. More- tested. Here, we used the best set from the litera-
over, they are especially important in petrochemi- ture reproducing the experimental iridium atomic
cal processes w 25x , where in these reaction types, energy spectra; Table I presents the calculated and
the hydrogen is a reactant or a product and is the reported energies w 35x of the atomic iridium’s
employed to activate the catalysts. For instance, three low-lying F states. These results show that
the H 2 interaction with metal is a powerful reac-
tion test, which has produced the greatest number
of experimental reports w 26x . TABLE I
Pd and Pt are the most employed metals in Experimental and calculated splitting of the three
catalysis because of their electronic properties. The lowest F iridium atom states.
most important catalyzed reactions using them are ⌬ E (this work) ⌬ E (experimentala )
the CO, H 2 , and alkane activations w 27, 28x . But Atomic state (kcal / mol) (kcal / mol)
there are other metals also with important catalytic
4
properties. Iridium is one of these metals. Some F (5d 7 6 s 2 ) 0.0 0.0
4
iridium organometallic complexes may activate F (5d 8 6 s1) 13.6 9.2
2
and break the C H alkane bonds by inserting an F (5d 8 6 s1) 19.3 26.0
Ir atom in the bonds and forming a carbon᎐metal᎐ a
From [34], the J-averaged values over all spin᎐orbit com-
hydrogen complex w 29x . ponents.

1030 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 Considering the bond formation, the following
Approach of H 2 to Ir 2 reaction mechanism is proposed to explain the
In this reaction mode ŽTable IV., it was found Ir2 Ž5 ⌸ g . q H 2 interaction in the lowest state: At
that Ir2 activates the H 2 in its four low-lying the beginning, the H 2 ␴ * empty orbital started to
states, 5 ⌸ g , 3 ⌸ g , 1 ⌺q 3 q
⌺ u , where capture and populate from the singled occupied Ir2 ␴u w IrŽ s . q
g ,
dissociation of H 2 is obtained, but with barriers IrŽys .x orbital, later interacted with the double-
present, whereas in the highest state, 5 ⌺ g , the H 2 occupied ␲g w IrŽ dz 2 . q IrŽydz 2 .x , due to that at the
capture and dissociation occurs spontaneously. beginning the ␴u orbital has a higher energy than
But, this last state is a very high one, hardly has the ␲g orbital, but when the reaction pro-
important in catalyzed reactions. gresses, the ␲g becomes more important and both
From Table IV, we can see that all the well interactions contribute to generate the a 2 orbital.
depths Žadsorption heats. are larger than the ex- In the barrier zone, the a 2 orbital formation is in
perimental adsorption heat Ž18.40 kcalrmol.. All competition with a repulsive interaction of the
the capture distances are similar, and, in general, occupied IrŽ s . q IrŽ s . with the H 2 ␴ orbital and
the captures need to be activated. the bonding a1 orbital of the Ir2 H 2 in equilibrium
The Ir2 Ž5 ⌸ g . q H 2 PEs ground-state reaction system.
shows a well only surmounting a potential barrier
of 13 kcalrmol. This barrier is produced by an H 2 in C 2 v Perpendicular Approach to One of
avoided crossing of this PES with an attractive PES the Ir of the Ir Dimer
coming from a high quintuplet state, whose sepa-
rate fragments correlate with an iridium dimer in a In this approach, the metal and the hydrogen
quintuplet state and the hydrogen molecule is in are in a plane and Ir2 in its five 5 ⌸ g , 3 ⌸ g , 1 ⌺q
g ,
3 q
the ground state. Similar to this case, all the poten- ⌺ u , and 5 ⌺ g low-lying states captures and acti-
tial barriers in this reaction mode are produced by vates H 2 without need of activation Žsee Table V..
avoided crossings. In the two lowest states, 5 ⌸ g and 3 ⌸ g , the hydro-
Let us now analyze the molecular orbitals of the gen molecule is only relaxed, whereas in the next
system. The Ir2 H 2 in equilibrium resulting from three highest states of the metal, the hydrogen
the Ir2 Ž5 ⌸ g . q H 2 reaction present the following molecule is clearly dissociated. In addition, the
molecular orbital elements: a bonding a1 orbital, adsorption heat is lower in the lowest metal states,
due to the overlap of the IrŽ s q d z 2 q d y z . q being quite close to the reported values. The
IrŽ s q d z 2 y d y z . orbitals with the HŽ1 s . q HŽ1 s . Ir2 Ž5 ⌺ g . q H 2 PES depth of the potential well dif-
orbital; and a bonding a 2 orbital coming from the fers -2 kcalrmol with the Ir adsorption heat in
overlap of the orbital IrŽ s q d z 2 q d y z . orbital q the Ž110. plane. This is the minor adsorption heat
IrŽys y d z 2 q d y z . with the antibonding HŽ1 s . q found in the present study. The capture distances
HŽy1s . orbital. are smaller for the highest metal states.

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 % H—H Depth of well Barrier
state (au) (au) relax (kcal / mol) (kcal / mol)
5
⌸g 2.8 5.6 297 33.4 13.3
3
⌸g 2.8 4.6 226 49.2 16.7
1 +
⌺g 3.0 4.0 184 54.3 8.5
3 +
⌺u 3.0 4.6 226 66.0 13.0
5
⌺g 3.0 4.6 226 50.2 No
a
Mass center᎐mass center distance.
b
Compared with d (H—H) nonactivated = 1.41 au.

1032 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 H 2 in C 2 v Approach to Ir 2 , Both Systems in
the direct reaction of a single Ir atom with the Perpendicular Planes
hydrogen molecule. Comparing the one and two Ir
Again, for Ir2 in the four lowest states, 5 ⌸ g ,
atoms’ reactions with H 2 and comparing with the 3
⌸ g , 1 ⌺q 3 q
g , and ⌺ u , for this reaction mode, activa-
platinum case, we can see that there are at least
tion is necessary to induce the dissociative capture
two differences: A ground-state single Ir atom can
activate H 2 , whereas a single Pt atom only can of H 2 , especially in the ground state ŽTable VI..
activate H 2 from an excited state. Also, the second But we have to remark that this approach is not a
Ir atom does not poison the reaction of one Ir atom comparable scheme with the experimental results,
and the Pt dimer is able to activate the H 2 , but in due to the following: This model does not consider
an excited state, with a lower angle Žalmost one- the Ir atoms of the subjacent plane.
half of a single Pt atom. because of the poisoning In the experimental situation, the hydrogen
of the second atom. molecule falls over the Ir crystal plane but not on a
The 100% dispersed Ir catalysts are easily pre- single isolated dimer. However, it is useful to
pared and adsorb H 2 w 3x , whereas it is very diffi- consider the characteristics of this approach over
cult to have Pt catalysts with this dispersion. In an isolated and naked cluster because the H 2 can
some experiments, by introducing Pt in small rotate.
porous zeolites, it is possible to get such a disper- From Table VI, we can observe, that in this
sion, but in any of these cases, Pt does not adsorb approach mode, the distances between the metal
H 2 w 37x . 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 quite probable, mainly because the ligands may
ruptured with a very different well depth, depend- modify the electronic structure of the metal’s lead-
ing on the electronic state, but all the five metal ing to many active states, giving the best catalyst
states show dissociative capture. In the 5 ⌺ g highest w 8, 20x .
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- From the Ir dimer study, we obtain the molecu-
tween the Ir atoms, forming a bridged structure lar configuration, the equilibrium interatomic dis-
ŽTable VI.. This structure is presented in tances, and the energies of the five lowest states,
organometallic compounds w 38x . Comparing the re-
5
⌸ g being the ground state, and 3 ⌸ g , 1 ⌺q 3 q
g , ⌺u ,
5
sults of Tables V and VI, there are some similar and ⌺ g , the four lowest excited states.
behaviors. This can be explained by considering Ir2 could capture and activate the hydrogen
that it is possible to change the reaction mode molecule in almost all the cases studied. In the
from the same plane to the perpendicular planes, perpendicular reaction mode, where H 2 and Ir2
with a simple rotation. are in the same plane, both the molecular and the
This reaction mode for the equilibrium Ir2 H 2 dissociative capture of H 2 is obtained. As experi-
system, the Ir2 Ž5 ⌸ g . —H 2 interaction, presents, mentally observed, no barriers are presented.
among others, the following orbitals: a bonding a1 The participation of some of the metal excited
orbital, resulting from the overlap of the ␴g w IrŽ s . q states must be considered because they also have a
IrŽ s .x orbital, with the H 2 Ž ␴g . orbital. Also, there is dissociative reaction with H 2 . Other modes of re-
a bonding b 1 orbital from the overlap ␲u w IrŽ d x y . q action may be considered as important because the
IrŽyd x y .x orbital with the ␴ *ŽH 2 . orbital. The bond excited states are also active, but the presence of
arises from the following proposed mechanism: avoided crossings generate high barriers which
The empty ␴ ⬘ŽH 2 . orbital may be populated and make it more difficult to reach these states.
form a bond with the Ir2 doubly occupied
␲u w IrŽ d x y . q IrŽyd x y .x orbital; nevertheless, at the ACKNOWLEDGMENTS
beginning of the reaction, this Ir2 orbital is much
deeper in energy than are the other Ir2 partially We wish to thank once again our colleagues at
occupied orbitals, so the ␴ *ŽH 2 . y␲u ŽIr2 . cannot the University of Toulouse, France, and at the
overlap completely. In advancing the reaction, the University of Barcelona, Spain, for the PSHF᎐
overlap is produced and the described equilibrium GMCP᎐CIPSI chain of programs. This work was
geometry is achieved. ´ . Pro-
partially supported from CONACYT ŽMexico
The interaction of both orbitals led to the Ir2 H 2 b 1 ject No. 3494PE. The calculations were done with
orbital formation. Also, at the beginning of the an Aspen Alpha Durango II 533 Mhz computer
reaction, the b 1 orbital formation is in competi- provided by the mentioned project.
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. References
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