Chemical Physics Letters 380 (2003) 292–297

www.elsevier.com/locate/cplett

Theoretical study of the Ru + N2 molecular interaction

F. Colmenares *, S. Mel
endez
Departamento de F
ısica y Qu
ımica Te
orica, Facultad de Qu
ımica,
Universidad Nacional Aut

onoma de M
exico, M
exico DF 04510, M
exico
Received 14 July 2003; in final form 22 August 2003
Published online: 2 October 2003

Abstract

The results of Hartree–Fock (with relativistic effective core potentials) followed by variational and second order
multireference perturbational configuration interaction (CIPSI) calculations are reported for the linear (C1v ) and bent
(C2v ) electronic states of the RuN2 molecule which arise from the ground state Ru(5 F;d7 s1 ) + N2 and the first excited
state Ru(3 F;d7 s1 ) + N2 of the free fragments. For both coordination modes, the most important metal–ligand inter-
action channels are obtained for those states correlating with the low-multiplicity asymptotic limit. Due to the existence
of symmetry-avoided crossings involving the potential energy curves which evolve from the second-lying triplet state of
the separated fragments, Ru(3 F;d8 ) + N2 , the ability of ruthenium to capture the N2 molecule through these low-
multiplicity channels is strongly determined by the maximal d-shell occupancy metallic state.
Ó 2003 Elsevier B.V. All rights reserved.

1. Introduction
The interaction of the nitrogen molecule with
ruthenium containing systems has been the subject
of different theoretical and experimental studies.
Due mainly to its catalytic relevance, research
work has been done on the synthesis and charac-
terization of compounds involving this interaction
as well as in the study of the activation of the ni-
trogen molecule by clusters and surfaces of ru-
thenium [1–10]. In fact, a promoted catalyst of this
metallic element has been used commercially since
*
Corresponding author. Fax: +52-55-56-22-37-19.
E-mail address: colmen@servidor.unam.mx (F. Colmen-
ares).
the last decade for the N2 activation and the NH3
synthesis [7].
With regard to the interaction between the N2
molecule and a single ruthenium atom, just few
years ago there were identified by matrix infrared
spectroscopy at cryogenic temperatures the NRuN
and Ru(NN) complexes, as being formed among
the products of the reaction of laser-ablated ru-
thenium atoms with nitrogen [8].
Theoretically, results obtained from DFT cal-
culations have been reported for the interaction of
the N2 molecule with a naked ruthenium atom and
small ruthenium clusters [8–10]. Citra et al. [8]
investigated different electronic states of the RuN2
molecule involving an important N–N distance
elongation (more than twice the equilibrium value
of the isolated N2 molecule). Likewise, Dooling

0009-2614/$ - see front matter Ó 2003 Elsevier B.V. All rights reserved.
doi:10.1016/j.cplett.2003.08.117
 F. Colmenares, S. Mel
endez / Chemical Physics Letters 380 (2003) 292–297
and co-workers [9] have analyzed the effect of the
particle size and surface morphology on the in-
teraction of molecular nitrogen with ruthenium in
terms of the structural parameters calculated for
different Run –N2 clusters. In [10] the adsorption of
the N2 molecule on ruthenium is modeled by
comparison of two approaching modes of the di-
atomic molecule to a Ru6 cluster.
In this contribution, the low-lying linear and
bent electronic states of the RuN2 molecule were
investigated through the computation of the po-
tential energy curves which correlate with the
ground state, Ru(5 F;d7 s1 ) + N2 , and the first
excited triplet states, Ru(3 F;d7 s1 ) + N2 and
Ru(3 F;d8 ) + N2 , of the separated fragments. We
focused our attention particularly on the role
played by the second-lying excited state Ru(3 F;d8 )
in the capture of the nitrogen molecule. With the
aim of stressing the importance of this maximal
d-shell occupancy state, trends predicted for the
Ru + N2 interaction are compared with those
reported in [11] for Fe + N2 (as discussed later,
the equivalent electronic state is not energetically
accessible for iron).
As for other simple systems investigated before
[12,13], 1 it is expected that the picture attained in
this way for the Ru + N2 interaction could be a
useful guide for including the effect of additional
constituents on the ability of the ruthenium atom
toward the capture of the N2 molecule in more
complex models, as well as for providing some
insight into the way the electronic factors deter-
mining the existence of attractive channels in this
simple interaction could be involved in real reac-
tion systems. Interestingly, in the context of the
N2 ! NH3 conversion on ruthenium-based cata-
lysts it has been suggested that the rates of am-
monia synthesis depend on the electronic state of
the ruthenium [6].
2. Computational details
At the Hartree–Fock level, the calculations
were performed using the PSHF code [14], a
1
In [13] the effect of the copper atom on the ruthenium ability
to dissociate de H2 molecule is analyzed in terms of the results
previously reported in [12] for the simple interaction Ru + H2 .
293
pseudopotential adapted version of the HO N D O
program, with the core electrons being taken into
account through relativistic effective core poten-
tials, following the theory developed by Durand
and Barthelat [15–18].
For the ruthenium atom, the AREP (Averaged
relativistic effective potential) and gaussian basis
set as given by LaJohn et al. [19] were used. This
basis set is of triple-f quality for the 4d and 5s
shells. For consistency, the nitrogen atoms were
taken into account using the AREP and the triple-
f quality basis set for the 2s and 2p valence region
subshells developed by Pacios and co-workers
[20,21].
Electronic correlation effects were included via
variational and second order (M€ oller-Plesset)
perturbative multireference configuration interac-
tion (MRCI) schemes, using the CIPSI algorithm
[22,23]. Potential energy curves described below
were calculated using variational spaces including
roughly 300 determinants which generate more
than 12 000 000 configurations in the perturba-
tional space. Calculations at the energy minima
reported in Tables 1 and 3 were performed using
variational and perturbational spaces of nearly
1000 and 35 000 000 configurations, respectively.
A similar methodological approach such as that
followed in a previous contribution on the Zn + N2
interaction was used [24]. Potential energy curves
were calculated for all the linear and bent elec-
tronic states of the RuN2 molecule which evolve
from the ground state, Ru(5 F;d7 s1 ) + N2 , and
the first excited states, Ru(3 F;d7 s1 ) + N2 and
Ru(3 F;d8 ) + N2 , of the free fragments. At this
stage, calculations for each state were performed
keeping the N–N distance fixed at the equilibrium
value of the isolated molecule (1.095 A ). For the
attractive states detected in this way, the relaxation
of the N–N distance was allowed so that the en-
ergy minimum of the potential energy surface for
each one of the electronic states investigated could
be determined: for the linear states, optimization
of the N–N distance was carried out for each
Ru–N distance whereas for the attractive side-on
electronic states, the Ru–N distance was optimized
for each N–Ru–N angle.
The C2v electronic states of the RuN2 system
were calculated with the molecule oriented in the
294 F. Colmenares, S. Mel
endez / Chemical Physics Letters 380 (2003) 292–297

Table 1
Leading configurations and energies of the low-lying linear electronic states of the RuN2 molecule
State Energy (kcal/mol) CI coefficient Main configuration (valence part only)
5
R )9.6 0.945 11r2 12r2 13r2 5p4 6p4 2d2 14r1 15r1
5
P )2.6 0.945 11r2 12r2 13r2 5p4 6p3 2d3 14r1 15r1
3
R )13.3 0.933 11r2 12r2 13r2 5p4 6p4 2d2 14r2
3
D )11.4 0.939 11r2 12r2 13r2 5p4 6p4 2d3 14r1
3
P 2.4 0.928 11r2 12r2 13r2 5p4 6p3 2d3 14r2
Energies are relative to the ground state dissociation limit Ru (5 F;d7 s1 ) + N2 .

yz-plane with the z-axis bisecting the N–Ru–N 60

angle.
40

Energy (kcal/mol)
3 8
3. Results and discussion 3
Σ Ru( F;d ) + N2
20 3 7 1
Ru( F;d s ) + N2
In Fig. 1 are shown the potential energy curves
3
associated with the linear electronic states of the Σ
0 5 7 1
RuN2 molecule which arise from the ground state, 5
Ru( F;d s ) + N2
Σ
Ru(5 F;d7 s1 ) + N2 , and the first excited states,
2 3 4 5
Ru(3 F;d7 s1 ) + N2 and Ru(3 F;d8 ) + N2 , of the free Ru-N2 Distance (Å)
fragments. The energy (as calculated after allowing
the N–N distance relaxation; see Section 2 for 60
details) as well as the main configuration evolving
from the CI scheme for each one of the low-lying 40
Energy (kcal/mol)

linear states are shown in Table 1. As seen from 3 8

Ru( F;d ) + N2
3
this table, CI coefficients lying above 0.9 were Π
20 3 7 1
obtained for all the states investigated. Geometri- Ru( F;d s ) + N2
cal parameters for these states are provided in 3
Π
Table 2. 0
5 7 1
5
Π
Ru( F;d s ) + N2
Although energy minima were determined for
the 5 R and 5 P states correlating with the ground 2 3 4 5
state dissociation limit (the 5 D state being repul- Ru-N2 Distance (Å)
sive) slightly deeper potential wells are associated
60
with the 3 R and 3 D electronic states which evolve
from the first low-lying triplet asymptote
Ru(3 F;d7 s1 ) + N2 . In fact, the lowest energy level 40
Energy (kcal/mol)

3
∆ 3 8
Ru( F;d ) + N2
predicted for the RuN2 molecule involves these
nearly degenerate states. As seen from Table 1, the 20 5
3 7 1
Ru( F;d s ) + N2
3 ∆
R is slightly more stable and is then proposed as
the best candidate for the ground state of the 0 5 7 1
RuN2 molecule. 3
∆ Ru( F;d s ) + N2
The potential energy curves for the RuN2 side-
2 3 4 5
on electronic states are shown in Fig. 2. A repul-
Ru-N2 Distance (Å)
sive character is obtained for all the bent states
which evolve from the ground state of the free Fig. 1. Potential energy curves for the low-lying linear elec-
fragments. In fact, no stable states were detected tronic states of the RuN2 molecule. The N–N distance is kept
for this coordination mode. Nevertheless, poten- ).
fixed at the equilibrium value of the isolated molecule (1.095 A
 F. Colmenares, S. Mel
endez / Chemical Physics Letters 380 (2003) 292–297 295

Table 2 Ru(3 F;d7 s1 ) + N2 dissociation limit and the at-

Geometrical parameters corresponding to the low-lying linear tractive one correlating with the Ru(3 F;d8 ) + N2
electronic states of the RuN2 molecule
asymptote. In fact, the leading configurations at
State )
Ru–N distance (A )
N–N distance (A the energy minima for the lowest-lying RuN2
5
R 2.01 1.15 triplet states (Tables 1 and 3) correspond to the
5
P 2.11 1.14 maximal d-shell occupancy of the second excited
3
R 1.79 1.14
3
triplet state of the free fragments, as in these
D 1.74 1.20
3
P 1.85 1.17 configurations the molecular orbital containing the
most important 5s-type metallic contribution is
not occupied, i.e., the 15r orbital in Table 1 and
tial energy wells lying below the energy of their the 16a1 orbital for the side-on electronic states
corresponding dissociation limits were determined (not appearing in the main configurations shown
for all the low-multiplicity channels (Fig. 2). The in Table 3). In this sense, the reactivity of the ru-
energy and the geometrical parameters for the thenium atom toward the nitrogen molecule cap-
triplet states correlating with the Ru(3 F;d7 s1 ) + N2 ture seems to be strongly determined by the
asymptote are provided in Tables 3 and 4. Ru(3 F;d8 ) + N2 asymptote.
As seen from Figs. 1 and 2, for each one of the Interestingly, the capture and dissociation of
different low-multiplicity symmetry channels (both the H2 molecule by the ruthenium atom [12] follow
coordination modes) there exists an avoided a similar reactivity pattern as that discussed here
crossing between the curve evolving from the for the Ru + N2 interaction. As a consequence of

Fig. 2. Plot of the potential-energy vs. the Ru–N2 distance for the low-lying bent electronic states of the RuN2 molecule. The N–N
).
distance is kept fixed at the equilibrium value of the isolated molecule (1.095 A
296 F. Colmenares, S. Mel
endez / Chemical Physics Letters 380 (2003) 292–297

Table 3
Leading configurations and energies of the low-lying bent electronic states of the RuN2 molecule
State Energy (kcal/mol) CI coefficient Main configuration (valence part only)
3
A1 3.86 0.942 11a21 6b22 12a21 13a21 5b21 6b21 7b22 14a11 2a22 15a11
3
A2 6.49 0.941 11a21 6b22 12a21 13a21 5b21 6b21 7b22 14a21 2a12 15a11
3
B1 4.64 0.939 11a21 6b22 12a21 13a21 5b21 6b11 7b22 14a21 2a22 15a11
3
B2 8.56 0.938 11a21 6b22 12a21 13a21 5b21 6b11 7b22 14a21 2a12 15a21
Energies are relative to the ground state dissociation limit Ru (5 F;d7 s1 ) + N2 .

Table 4 state has practically no contribution from the d8

Geometrical parameters corresponding to the low-lying bent state of Fe [11].
electronic states of the RuN2 molecule
In accord with the results discussed here for
State Ru–N distance N–N distance N–Ru–N angle Ru + N2 , the lack of stable states associated with
)
(A )
(A (deg)
the Fe + N2 interaction could be related to the
3
A1 2.05 1.20 34 poor contribution of the Fe(3 F,d8 ) state, which in
3
A2 1.98 1.21 34
3
turn is a consequence of the significant energy
B1 2.03 1.22 35
3
B2 2.05 1.20 34 difference (approximately 95 kcal/mol) between
this excited state and the Fe(5 D,d6 s2 ) ground state
[25] (for the ruthenium atom, the equivalent state
symmetry-avoided crossings between the potential lies only 25 kcal/mol above the ground state energy
energy curves correlating with the Ru(3 F;d7 s1 ) + [25]). Interestingly, in a related investigation on the
H2 and Ru(3 F;d8 ) + H2 dissociation limits, the Fe2 N2 model system [26], an electronic state of this
dominant electronic configuration at the energy molecule with a significant d8 metallic contribution
minimum for each one of the attractive triplet and a relatively important N–N distance elonga-
states of the RuH2 molecule corresponds with the tion is predicted.
maximal d-shell occupancy configuration of the In this sense, the different behavior of ruthe-
Ru(3 F;d8 ) + H2 asymptotic limit [12]. nium and iron atoms with regard to the M + N2
With the aim of approaching slightly more the molecular interaction seems to be related to the
role played by the excited states of the metallic fact that the electronic state determining the ability
center in the N2 capture, matching is attempted of the metallic atom toward the N2 capture is en-
between trends obtained for Ru + N2 and those ergetically accessible for ruthenium but not for
previously reported by Siegbahn et al. [11] for the iron.
Fe + N2 interaction (Table 5). As discussed by
these authors, no stable molecular states are pre-
dicted for the interaction of the N2 molecule with a 4. Conclusions
naked iron atom. Likewise, just as in the case of
the RuN2 molecule, the linear 3 R is proposed as In this contribution, aspects concerning the
the lowest-lying FeN2 electronic state. As far as the capture of the nitrogen molecule by a ruthenium
present contribution is concerned, it is important atom were investigated. The most important me-
to point out that, as suggested by the authors, this tal–ligand interactions are obtained for the low-

Table 5
Energies and geometrical parameters corresponding to the low-lying linear and bent electronic states of FeN2
State Energy (kcal/mol) )
Fe–N distance (A )
N–N distance (A N–Fe–N angle (deg)
3
R(C1v ) 31 1.84 1.09 –
3
B1 (C2v ) 64 1.94 1.19 35.8
All values were taken from [11] or calculated from data in that reference. Energies are relative to the ground state dissociation limit
Fe(5 D;d6 s2 ) + N2 .
 F. Colmenares, S. Mel
endez / Chemical Physics Letters 380 (2003) 292–297
multiplicity RuN2 electronic states arising from
the linear approach of the N2 molecule toward the
ruthenium atom, the 3 R being the best candidate
for the RuN2 ground state.
As a consequence of symmetry-avoided cross-
ings between the potential energy curves evolving
from the two lowest-lying triplet states of the free
fragments, the ability of the ruthenium atom to
capture the N2 molecule is strongly determined
by the maximal d-shell occupancy triplet state
Ru(3 F;d8 ).
Acknowledgements
This research was partially supported by the
Universidad Nacional Aut
onoma de M
exico
(Proyecto DGAPA-IN101293). The PSHF-CIPSI
package was kindly furnished by the Laboratoire
de Physique Quantique de Toulouse.
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