Notes Bull. Korean Chem. Soc. 1999, Vol. 20, No.

2 247

A Comparative Study of the Bonding of N2 and CO to Ru(001) and the Role of

Department of Chemistry, Kyungsung University, Pusan 608-736, Korea

The adsorption of N2 and CO on transition metal surfaces slabs. The molecules are adsorbed with their molecular axes
has been the subject of many experimental and theoretical normal to the surface. CO is upright on the surface with the
studies over the past few decades.1~10 Their interactions with C end down. The molecular bond lengths for N2 and CO are
surfaces have been used to present prototypical systems of set to 1.11 Å and 1.15 Å, respectively. The Ru-N and Ru-C
molecular chemisorption for many years. The great activity distances are derived from the density functional theory cal-
in this area arose mainly because of the importance of these culations (Ru-N 2.00 Å and Ru-C 1.92 Å).23 For the average
systems to the understanding of catalytic surface processes property calculations a mesh of 66 k points was chosen in
such as the ammonia synthesis and the so-called Fischer- the irreducible part of the Brillouin zone, according to the
Tropsch process. Particular attention has been given to the Ramirez and Böhm method.24 Concerning the bonding of
chemisorptive behavior of N2 and CO, two isoelectronic the neutral isoelectronic molecules N2 and CO to the
molecules, on transition metal surfaces. It has been sug- Ru(001) surface, the four frontier orbitals (4σ, 5σ and 2π
gested that the bonding of the two molecules to transition pair) of the adsorbate molecules are important in the mole-
metal surfaces should be fundamentally different.11 We
investigate the differences in the surface-adsorbate bonding Table 1. Extended Hückel parameters
of these two molecules and the effect of 5σ donation on their orbital Hii, eV ζ1 orbital Hii, eV ζ1
molecular bond weakening upon adsorption on Ru(001). Rub 5s -7.78 2.08 Cd 2s -18.20 1.63
Concerning the latter, in particular, it appears that a decrease
5p -2.72 2.04 2p -9.50 1.63
in the stretching frequencies for N2 and CO upon adsorption
is mainly attributable to the degree of π back-donation, but 4da -9.57 5.38 Od 2s -29.60 2.27
there is also some effect due to donation. We find that the Nc 2s -23.95 1.95 2p -13.60 2.27
character of the 5σ HOMO shifts toward the antibonding 2p -10.95 1.95
nature as one goes from N2 to CO. Thus, the 5σ depletion aζ =2.30;
2 C1=0.5573, C2=0.6642. C=contraction coefficients used in
due to charge donation accounts for the change in N2 and CO double-ζ expansion. b From ref 26. c From ref 27. d From ref 10.
bond strength.
The simplest standard picture used to describe N2 chemi- Table 2. Calculated Results for (√3×√3)R30o overlayer structure of
sorption is an extension of the basic Blyholder model12 for N2 and CO adsorbed on Ru(001)
CO-transition metal bonding, which involves σ electron N2/Ru(001) CO/Ru(001)
donation from CO into metal orbitals and π back-donation
Overlap Populations
from metal orbitals into 2π orbitals of CO. Our results indi-
Ru-C - 0.78
cate that the surface chemical bonding is not qualitatively
different between the two molecules. The main difference is Ru-N 0.49 -
that the interaction of the antibonding 2π orbitals with the C-O - 1.09 (1.21 in free CO)
metal d states is considerably weaker for N2 than for CO. N-N 1.64 (1.70 in free N2) -
The analysis was carried out using the tight-binding calcula- Electron Densities
tions of the extended Hückel type13~18 with the atomic
4σ 1.91 1.89
parameters in Table 1. We used two conceptual tools,19 den-
1π 3.99 4.00
sity of states (DOS) and crystal orbital overlap population
(COOP), to identify the most important adsorbate-surface 5σ 1.62 1.63
interactions. 2π 0.26 0.60
Experimentally, a (√3×√3)R30o overlayer structure at a Binding Energies (eV)a
coverage of one-third was found to be formed in which both 2.01 2.61
N2 and CO molecules were located at the on-top site on the
Vibrational Frequencies (cm–1)b
Ru(001) surface.20~22 We used this unit cell model of the
2195 (2359)c 2015 (2170)c
unreconstructed Ru(001) surface to calculate the adsorption
a E (Ru slab and separated molecule) - E (Ru slab and adsorbed
energy and selected bonding information shown in Table 2.
molecule) for one unit cell. b The experimental data are taken from ref 11
The Ru substrate is modeled by a three-layer slab with the and the values in parentheses are for the gas-phase molecules. c From ref
adsorbate molecules on one side of the two-dimensional 25.
248 Bull. Korean Chem. Soc. 1999, Vol. 20, No. 2 Notes

Figure 1. Total DOS for on-top CO/Ru(001). Major peaks are Figure 2. Total DOS for on-top N2/Ru(001). Major peaks are
labeled. The corresponding molecular orbital energies of free CO labeled. The corresponding molecular orbital energies of free N2
are indicated by vertical bars. The dashed line refers to the Fermi are indicated by vertical bars. The dashed line refers to the Fermi
level. level.

cules' interactions with the metal surface. For simplicity, we is originated from the strong mixing between 5σ and metal d
refer to 2σu, πu, 3σg, and πg of N2 as 4σ, 1π, 5σ, and 2π, orbitals. The 4σ bands are shifted down ~0.3 eV after
respectively, according to the CO orbital labeling scheme. adsorption. This indicates that the strength of the 4σ-surface
The 5σ orbital of N2 lies slightly higher in energy than 1π as interaction is considerably weak compared with the 5σ case.
a result of substantial mixing of 3σg with 2σg and represents Since there are no significant interactions between the adsor-
the HOMO, as in CO. bate 1π and the metal d states, as seen in the electron density
The electron density shift between bare Ru(001) and and the DOS curves of the 1π in Table 2 and Figures 1 and 2,
molecular adsorbate in the chemisorbed system is shown in these interactions are essentially not involved in surface-
Table 2. The major surface chemical bonding is described by adsorbate bonding. There seems to be little doubt that the 5σ
the interactions of the 5σ and 2π molecular states with the and 2π are responsible for most of the surface-adsorbate
metal d states in a donation and back-bonding picture bonding. The most significant factor in the difference
because the 5σ and 2π levels have a good energy match with between the bonding of N2 and CO to Ru(001) is the cou-
the d band of the Ru slab (see Figures 1 and 2). Since the pling of the metal dπ to the 2π states. Table 2 and Figures 1
degree of the depopulation of 4σ and 5σ and the population and 2 show that the population of CO 2π, 0.60 electrons, and
of 2π provides a rough measure of their interactions with the also the shift of the antibonding 2π DOS peak after adsorp-
surface, we can use their electron occupancies to compare tion, ~0.5 eV, are larger than the corresponding values (0.26
the relative strength of the bonding of these orbitals to the electrons and ~0.2 eV) for N2. This explains the stronger
metal surface. We analyzed the on-top CO situation first. binding of CO to the metal surface compared with N2 (2.61
Both 4σ and 5σ orbitals donate 0.11 and 0.37 electrons, eV vs. 2.01 eV in binding energies). The stronger π back-
respectively, on interaction with the Ru slab. The 2π set bonding in CO is largely a result of the fact that the 2π orbit-
receives 0.60 electrons upon chemisorption. The adsorbed als have a higher amplitude on the atom closer to the surface.
CO thus fits nicely with the Blyholder picture. One conse- We finally consider the shifts of the N2 and CO vibrational
quence of the strong metal to CO back-donation is a signifi- frequencies upon adsorption. From the increased occupan-
cant weakening of the C-O bond. The overlap population is cies of the antibonding 2π molecular orbitals for both
reduced from 1.21 for the free CO molecule to 1.09 for the adsorbed N2 and CO shown in Table 2 one would expect
adsorbed CO (see Table 2). These interactions form a strong decreased vibrational frequencies for the N2 and CO upon
Ru-C bond; the corresponding overlap population is 0.78. adsorption. The stronger coupling of the CO 2π to the Ru dπ
The on-top N2 case follows closely the CO situation. The 5σ states and the consequent increased population of the 2π
orbital of N2 interacts efficiently with the d band of the Ru states should give rise to a greater lowering of the frequency
slab; 0.38 electrons are donated. We see in Table 2 that the for CO than for N2. From Table 2, however, a comparison of
2π set is populated by 0.26 electrons. This metal to 2π back- the stretching frequencies for chemisorbed CO and N2 with
donation is not as strong as in CO, resulting in a weaker Ru- those for the gas phase CO and N2 molecules shows about
N bond. The result is a relatively small Ru-N overlap popu- the same magnitude in the ratio of frequency shifts. The rea-
lation, 0.49. To illustrate our point, the total and projected son is that there is also some effect due to donation from 5σ.
DOS curves are depicted in Figures 1 and 2 for on-top CO Exploring this, it is interesting to examine the bonding or
and N2. In both cases, the 5σ is the most important bonding antibonding character for the 5σ orbitals of N2 and CO. The
orbital. Note its large downshift of ~1.2 eV in energy, which Mulliken overlap populations calculated for these molecular
Notes Bull. Korean Chem. Soc. 1999, Vol. 20, No. 2 249

orbitals in gas-phase are 0.11 (N2) and -0.01 (CO). Judging 5. Sung, S.-S.; Hoffmann, R. J. Am. Chem. Soc. 1985, 107,
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