7 September 2001

Chemical Physics Letters 345 (2001) 111±117

www.elsevier.com/locate/cplett

Theoretical study of the CuRu ‡ H2 molecular interaction

F. Colmenares a,1, A. Ramõrez-Solõs b, O. Novaro c,*,2
a
Centro de Investigaciones Te oricas, Facultad de Estudios Superiores-Cuautitl
an, Universidad Nacional Aut
onoma de M exico,
Apartado Postal 142, Cuautitlan-Izcalli, Estado de Mexico 54700, Mexico
b
Departamento de Fõsica, Facultad de Ciencias, Universidad Aut onoma del Estado de Morelos, Av. Universidad 1001,
Cuernavaca, Morelos 62210, M exico
c
Instituto de Fõsica, Universidad Nacional Autonoma de M exico, Apartado Postal 20-364, M exico D.F. 01000, Mexico
Received 16 May 2001; in ®nal form 10 July 2001

Abstract
The results of Hartree±Fock (with relativistic e€ective core potentials) followed by variational and second-order
multireference perturbational con®guration interaction (CIPSI) calculations are reported for the nine lowest-lying
electronic states of the CuRu molecule and the eight low-lying states of the CuRuH2 molecule belonging to the C2v
symmetry group which evolve from the H2 side-on interaction with the ruthenium atom. The e€ect of the copper atom
on the ability of the ruthenium atom toward the capture and dissociation of the H2 molecule is analyzed through
comparison with the results previously reported for the simpler systems RuH2 and RuH‡ 2 . For all the reaction channels
investigated here, the copper atom depresses the ability of ruthenium to dissociate the H2 molecule. Ó 2001 Published
by Elsevier Science B.V.

1. Introduction reactions, such as the hydrogenolysis of alkanes

Copper±ruthenium-containing systems have
been used as catalysts in di€erent reaction pro-
cesses of industrial interest [1,2]. Likewise, they
have also been considered as model systems for
analyzing aspects concerning the metal±metal in-
teraction in catalytic processes [3]. In particular,
several experimental groups have studied the na-
ture of this interaction and its catalytic properties
in regard with the activity and selectivity patterns
observed for pure ruthenium catalysts in di€erent
*
Corresponding author. Fax:+52-56-22-5015.
E-mail address: novaro@®sica.unam.mx (O. Novaro).
1
Permanent address: Departamento de Fõsica y Quõmica
Te
orica, Facultad de Quõmica, Universidad Nacional
Autonoma de Mexico, Mexico DF 04510, Mexico.
2
Member of El Colegio Nacional.
0009-2614/01/$ - see front matter Ó 2001 Published by Elsevier Science B.V.
PII: S 0 0 0 9 - 2 6 1 4 ( 0 1 ) 0 0 8 2 9 - 6
[4]. Although copper and ruthenium are immis-
cible in the bulk state, it has been proposed that
bimetallic aggregates can be formed by chemi-
sorption of the inactive metal (copper) on the
ruthenium surface [5]. Experimental data support
the fact that even a small percentage of atomic
copper enriching or coating ruthenium surfaces
depresses signi®cantly the hydrogen chemisorp-
tion process [1]. Likewise, it has been reported
that the presence of copper in these bimetallic
systems also decreases the catalytic activity
towards hydrogenolysis reactions, a€ecting the
selectivity patterns presented by ruthenium cata-
lysts [3].
The mechanism by which the inactive metal
a€ects the activity and selectivity patterns charac-
teristic of ruthenium catalysts in these kinds of
reactions has not been well established. In this
112 F. Colmenares et al. / Chemical Physics Letters 345 (2001) 111±117
sense, although the catalytic chemistry of these
bimetallic systems depends on the composition of
their surfaces and other chemical factors, the the-
oretical modeling of the Cu ‡ Ru and CuRu ‡ H2
simple interactions could give some insight into the
electronic aspects involved in hydrogen chemi-
sorption by this bimetallic catalyst.
Previously, theoretical results on the interaction
of the hydrogen molecule with copper and ruthe-
nium atoms have been published [6±8]. In these
papers di€erent aspects concerning the capture
and dissociation of the diatomic molecule by these
metal atoms are discussed. As pointed out in [6],
the H2 molecule interacts only weakly with the
copper atom, mainly through the side-on elec-
tronic state 2 B2 which correlates with the
Cu…2 P; d10 p1 † ‡ H2 excited asymptote. For the
Ru ‡ H2 interaction, on the other hand, reaction
channels which involve an important H±H elon-
gation were found for the electronic states of the
RuH2 molecule in the C2v symmetry that correlate
with the lowest-lying triplet state Ru…3 F; d7 s1 †‡ H2
[7,8].
The main goal of the present contribution is to
analyze the e€ect of the copper atom on the ability
of the ruthenium one towards the capture and
dissociation of the hydrogen molecule. The inter-
action of the H2 molecule with the CuRu fragment
is analyzed through the potential energy curves
corresponding to those electronic states of the
molecule CuRuH2 associated with the previously
determined low-lying electronic states of the bi-
metallic fragment. Particularly, we focused our
attention only on those electronic states of the
CuRuH2 molecule belonging to the side-on coor-
dination geometry for which the ruthenium atom
is approached by the hydrogen molecule. This re-
striction was imposed since it is known, from
previous studies on the simpler interaction M ‡ H2
for atoms belonging to the middle and second-half
transition metal series [9,10], that no signi®cant H2
elongation has been determined among the low-
lying electronic states corresponding to the col-
linear approach. The main features associated with
the CuRuH2 electronic states are discussed com-
paring them with the results previously reported
for the simpler Ru ‡ H2 [7,8] and Ru‡ ‡ H2 [11]
interactions.
2. Computational details
At the Hartree±Fock level, the calculations
were performed using the PSHF code [12], a
pseudopotential adapted version of the HO N D O
program, with the core electrons being taken into
account through relativistic e€ective core poten-
tials (RECP) following the theory developed by
Durand and Barthelat [13±16].
The RECP for the copper atom was taken from
[17] along with the copper gaussian basis set which
is of triple-f quality for the 3d and 4s shells and of
double-f quality for the 4p polarization function.
For the ruthenium atom, the RECP and gaussian
basis set as given by LaJohn et al. [18] were used.
This basis set is of triple-f quality for the 4d and 5s
shells. The gaussian basis set for the hydrogen
atom was taken from [19] and augmented with a
p-type polarization function (exponent ˆ 0.68).
Electronic correlation e€ects were taken into
account via variational and second-order (M oller±
Plesset) perturbative multireference con®guration
interaction (MRCI) schemes, using the CIPSI al-
gorithm [20,21]. For all the studied states, MCSCF
calculations [12] were performed to obtain the
optimal molecular orbital set and integrals to be
used in the MRCI treatment. For each electronic
state of the CuRu molecule, the variational refer-
ence space S included nearly 500 con®gurations,
which generate more than 1:8  107 con®gurations
in the perturbational space P , whereas for the
CuRuH2 electronic states the calculations were
performed including variational and perturba-
tional spaces of roughly 200 and 1  107 con®gu-
rations, respectively.
The C2v electronic states of the CuRuH2 system
were calculated with the molecule oriented in the
yz-plane with the z-axis bisecting the H±Ru±H
angle.
3. Results and discussion
3.1. The Cu ‡ Ru interaction
In Table 1 are shown the calculated relative
energies corresponding to the low-lying electronic
states of the CuRu molecule. Likewise, in this ta-
 F. Colmenares et al. / Chemical Physics Letters 345 (2001) 111±117 113

ble are reported the optimized distance and the
leading con®guration for each one of these states,
as well as the coecients associated with these
dominant con®gurations in the CI scheme. The
calculated spectroscopic constants of these states
are shown in Table 2.
Although local energy minima were detected for
the sextuplet states which evolve from the ground
state dissociation limit Cu…2 S; d10 s1 †‡Ru…5 F; d7 s1 †,
a more interesting picture is obtained for the
quadruplet states, for which deep minima were
obtained near the Cu±Ru distance of 4.9 a.u.. In-
terestingly, this value is in very good agreement
with the experimental one of 5.0 a.u. obtained
through EXAFS studies on the bimetallic cluster
[22]. The lowest energy level involves the nearly
degenerate 4 D and 4 R‡ electronic states, although
the 4 D is slightly more stable and we think it is the
best candidate for the ground state of the CuRu
molecule, whereas the 4 P excited state lies roughly
5 kcal/mol above this energy level. As shown in
Table 1, doublet states lie well above the 4 D
ground state energy, so they do not represent vi-
able channels for the metal±metal bonding inter-
action.
In accordance with the leading con®gurations in
Table 1, the most important di€erence between the
sextuplet and quadruplet states involves the elec-
tron occupancy of the molecular orbitals 16r and
17r, which contain in each case the bonding and
antibonding combinations of the 3s and 4s atomic
orbitals of the copper and ruthenium atoms, re-
spectively. For the high-multiplicity states both of
these orbitals have a single occupancy, whereas for
the con®gurations corresponding to the more sta-
ble quadruplet states the antibonding orbital is
empty while the low-lying orbital 16r is doubly
occupied. As only small interactions between the
d-shell-type orbitals of the metallic atoms were
detected for the electronic states investigated
(mainly among the dz2 orbitals), the r…Cu…3s† ‡
Ru…4s† † bonding interaction seems to be the most
important stabilizing factor for the attractive
states of this bimetallic molecule. As discussed

Table 1
Leading con®gurations and relative energies of the low-lying states of the CuRu molecule
State dCu±Ru Energy CI coecient Con®guration
(a.u.) (kcal/mol) (valence part only)
X4 D 4.9 0 0.9581 14r2 7p4 2d4 15r2 3d3 16r2 8p2
4
R‡ 5.0 1.61 0.9669 14r2 7p4 2d4 15r1 3d2 16r2 8p4
4
P 4.9 4.95 0.9569 14r2 7p4 2d4 15r2 3d2 16r2 8p3
6
P 5.0 17.82 0.9609 14r2 7p4 2d4 15r2 3d2 16r1 8p3 17r1
6
D 5.0 18.82 0.9658 14r2 7p4 2d4 15r2 3d3 16r1 8p2 17r1
6 ‡
R 5.1 30.68 0.9690 14r2 7p4 2d4 15r1 3d2 16r1 8p4 17r1
2
D 5.0 41.91 0.9329 14r2 7p4 2d4 15r2 3d3 16r2 8p2
2
P 4.9 45.11 0.9324 14r2 7p4 2d4 15r2 3d2 16r2 8p3
2 ‡
R 5.0 53.58 0.9112 14r2 7p4 2d4 15r2 3d4 16r1 8p2

Table 2
Calculated spectroscopic constants for the electronic states of the CuRu molecule
State xe xe X e Be ae …10 4 † De …10 8 †
X4 D 342 2.635 0.062 3.89 0.82
4 ‡
R 327 0.077 0.063 1.34 0.96
4
P 382 5.270 0.062 4.77 0.68
6
P 309 0.810 0.061 2.65 0.95
6
D 293 0.305 0.062 0.49 1.14
6 ‡
R 199 1.800 0.056 3.00 1.82
2
D 334 1.682 0.062 3.35 0.87
2
P 306 2.238 0.063 4.16 1.07
All energies in cm 1 .
114 F. Colmenares et al. / Chemical Physics Letters 345 (2001) 111±117
later, the comparison of the potential energy
curves obtained for the CuRu ‡ H2 reaction
channels with those previously reported for the
RuH2 [7,8] and RuH‡ 2 [11] systems suggests that as
a consequence of this interaction there is an ionic
character in the metallic fragment, Cu Ru‡ , which
could be important in determining the ability of
the ruthenium atom in the bimetallic compound
towards the dissociation of the hydrogen molecule.
3.2. The CuRu ‡ H2 interaction
Once the low-lying electronic states of the
CuRu molecule were determined, the interaction
of the bimetallic system with the hydrogen mole-
cule was investigated. In this study we considered
only the sextuplet and quadruplet electronic states
of the molecule CuRuH2 belonging to the C2v
symmetry group for which the hydrogen molecule
nearest neighbor is the ruthenium atom.
In Fig. 1 are shown the potential energy curves
corresponding to the electronic states of the
Fig. 1. Plot of the potential energy vs. the Ru±H2 distance for
the low-lying quadruplet and sextuplet electronic states of the
CuRuH2 molecule. The Cu±Ru and H±H distances are kept
®xed at 4.9 and 1.41 a.u., respectively.
CuRuH2 molecule which evolve from the elec-
tronic states of the free fragments involving the
previously determined low-lying electronic states
of the metallic fragment. For each distance ru-
thenium±center of mass of the hydrogen molecule,
the H±H distance was kept ®xed at the equilibrium
value of the isolated molecule (1.41 a.u.) whereas
the metal±metal distance was ®xed at the equilib-
rium geometry (4.9 a.u.) previously calculated for
the CuRu…4 D† ground state.
For the attractive states detected in this way,
the relaxation of the H±H distance was allowed
through the optimization of the Ru±H distance in
the H±Ru±H angle interval 0±50°. The bending
potential energy surfaces corresponding to the
low-lying attractive states are shown in Fig. 2. For
these states, reoptimization of the Cu±Ru distance
at the energy minima practically did not produce
additional energy shifts. In Tables 3 and 4 are
reported the relative energies, the geometrical
parameters and the leading con®guration corre-
sponding to these bent states.
Fig. 2. Potential energy surfaces for the attractive quadruplet
electronic states of the CuRuH2 molecule.
 F. Colmenares et al. / Chemical Physics Letters 345 (2001) 111±117 115

Table 3
Leading con®gurations and relative energies of the low-lying states of the CuRuH2 molecule
State Energy CI coecient Main con®guration
(kcal/mol) (valence part only)
4
A2 0 0.9699 15a21 16a21 2a22 17a21 7b21 7b22 3a12 18a11 8b21 8b22 19a21 20a11
4
B2 10.02 0.9726 15a21 16a21 2a22 17a21 7b21 7b22 3a12 18a21 8b11 8b22 19a21 20a11
4
B1 21.58 0.9721 15a21 16a21 2a22 17a21 7b21 7b22 3a12 18a21 8b21 8b12 19a21 20a11
6
A2 58.43 0.9782 15a21 16a21 2a22 17a21 7b21 7b22 3a12 18a11 8b21 8b22 19a11 20a11 21a11
4
A1 ± ± 15a21 16a21 2a22 17a21 7b21 7b22 3a12 18a21 8b11 8b12 19a21 20a11

Table 4
Geometrical parameters corresponding to the low-lying states of the CuRuH2 molecule
State Cu±Ru distance Ru±H distance H±H distance H±Ru±H angle
(a.u.) (a.u.) (a.u.) (degrees)
4
A2 5.0 3.18 1.75 32
4
B2 5.0 3.18 1.65 30
4
B1 5.0 3.57 1.54 25

The ground state of the CuRuH2 molecule
corresponds with the 4 A2 state evolving from the
dissociation limit CuRu…4 R‡ † ‡ H2 . For this state,
there is a potential well of 26 kcal/mol below the
energy of the ground state of the free fragments,
for an H±Ru±H equilibrium angle of 32° and a
Ru±H distance of 3.18 a.u., which suggests the
formation of a stable CuRu±H2 complex. The
leading con®gurations associated with the most
stable states, 4 A2 and 4 B2 , have a double electron
occupancy of the 8b2 molecular orbital, which
contains the molecular interaction Ru…dyz † ‡
H2 …r †. Interestingly, this molecular orbital is only
singly occupied in the less stable 4 B1 state and in
the 4 A1 repulsive one.
The matching between the results evolving from
this investigation for the CuRuH2 molecule and
those previously reported for the simpler interac-
tions Ru ‡ H2 [7,8] and Ru ‡ H2 [11] could be a
useful tool for understanding the e€ect of the
copper atom on the ruthenium ability towards the
capture and dissociation of the hydrogen molecule.
As mentioned before, for the triplet states of the
RuH2 molecule, potential energy surfaces with
energy minima lying below the energy of the
ground state Ru…5 F; d7 s1 † ‡ H2 dissociation limit
have been reported [7,8]. These energy surfaces
show a ¯at-shaped behavior in the region of the
energy minima for a wide interval of H±Ru±H
angle values, which allows the possibility of an
important H±H elongation without a signi®cant
additional energy cost. On the other hand, for the
equivalent attractive quadruplet states belonging
to the cationic system RuH‡ 2 , acute potential en-
ergy wells de®ned for lower values of the H±Ru±H
angle (and hence also a lower H±H distance
elongation) have been reported in [11].
In accordance with the geometrical parameters
shown in Table 4, the copper atom in the CuRu
molecule depresses the ability of the ruthenium
atom towards the dissociation of the H2 molecule,
as the energy minima corresponding to the low-
lying states of the CuRuH2 molecule states are
located at smaller H±Ru±H angle values than
those reported for the analogous low-multiplicity
reaction channels belonging to the simpler inter-
action Ru ‡ H2 . In fact, the H±Ru±H angle and
the Ru±H distance shown in Table 4 for the 4 A2
ground state of the CuRuH2 molecule are closer to
those reported in [11] for the 4 A2 ground state of
the cationic system, a Ru±H distance of 3.17 a.u.
and an H±Ru±H angle of 28.2°, than to the cor-
responding values calculated for the 3 A2 ground
state of the RuH2 molecule (2.83 a.u and 60.4°,
respectively) [7]. In general, the geometrical pa-
rameters determined for the low-lying states of the
116 F. Colmenares et al. / Chemical Physics Letters 345 (2001) 111±117

CuRuH2 molecule are closely related to those account in this model reaction, there is a nice
corresponding to the cationic system RuH‡ 2 . This parallelism among the theoretical results and the
matching suggests the existence of an ionic char- experimental ones: for all the states investigated
acter Cu Ru‡ associated with the low-lying states for the CuRuH2 molecule the presence of copper
of the metallic fragment, which determines the atom inhibits the dissociation of the H2 molecule
e€ect of the copper on the H2 dissociation poten- by ruthenium, favoring the formation of a stable
tial of the ruthenium atom. complex without a signi®cant elongation of the H±
The electronic states of the ruthenium atom H distance.
with a maximal d-shell occupancy electron con-
®guration play an important role in determining
the ability of the metallic center towards the dis-
4. Conclusions
sociation of the H2 molecule [7]. Thus, leading
con®gurations at the energy minima regions for
In this investigation, we have studied the nine
the attractive states associated with the Ru ‡ H2
lowest-lying electronic states of the CuRu mole-
interaction have d8 -type electron con®gurations
cule and the eight low-lying electronic states of the
(similarly, the leading electron con®gurations of
CuRuH2 molecule in C2v symmetry. For the di-
the corresponding binding states of the cationic
7 atomic molecule the ground state corresponds to a
system RuH‡ 2 have a d character). The signi®cant 4
D electronic state whereas for the CuRuH2 mol-
H±H distance elongation associated with these
ecule the electronic state 4 A2 is the lowest energy
reaction channels involves the interaction among
state detected for the geometry in which the ru-
the d-type shell of the metallic atom with the hy-
thenium is the nearest neighbor of the hydrogen
drogen molecule, mainly through the Ru…dyz †
atoms. This state is adiabatically correlated to the
atomic orbital and the originally empty r orbital
CuRu…4 R‡ † ‡ H2 fragments.
of the H2 molecule. The ionic character detected
For all the electronic states of CuRuH2 inves-
for the low-lying states of the CuRu metallic
tigated, the copper atom decreases the ability of
fragment, which implies the withdrawal of elec-
the ruthenium towards the capture and dissocia-
tronic charge on the ruthenium atom, decreases
tion of the hydrogen molecule. An ionic character
the e€ect of this molecular interaction, depressing
associated with the low-lying states of the CuRu
the ability of the metallic center toward H2 disso-
metallic fragment, which implies the withdrawal of
ciation.
electronic charge on the ruthenium atom, explains
In regard with the high-multiplicity reaction
the smaller H±H elongation determined for the
channels (Fig. 1), only for the 6 A2 state is a shallow
attractive states of the CuRuH2 molecule, as
potential well found lying 10.7 kcal/mol above the
compared with the Ru±H2 interaction that clearly
energy of the CuRu…6 D† ‡ H2 fragments, after
promotes H2 dissociation.
surmounting an energy barrier of more than 17
kcal/mol. The equivalent electronic state 5 A2 be-
longing to the RuH2 molecule [7] presents a rela-
tive energy minimum as deep as the potential well Acknowledgements
found for the 6 A2 electronic state of the CuRuH2
molecule. However, for the electronic state be- This research was partially supported by the
longing to the Ru ‡ H2 reaction the minimum lies Universidad Nacional Aut onoma de Mexico
below the ground state dissociation limit energy (Proyecto DGAPA-IN101293). A.R.S. acknowl-
and no potential barrier exists. edges partial support from CONACYT project
Thus, although the simple molecular interaction number 34673-E and ECOS-CONACYT-ANU-
CuRu ‡ H2 analyzed in this contribution could be IES project number M98-P01. The PSHF-
only a very crude model of any real catalytic sys- MCSCF-CIPSI package was kindly furnished by
tem, since important factors concerning the role the Laboratoire de Physique Quantique de Tou-
played by the surface e€ects are not taken into louse.
 F. Colmenares et al. / Chemical Physics Letters 345 (2001) 111±117
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