Computational and Theoretical Chemistry 979 (2012) 64–72

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Computational and Theoretical Chemistry

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Adsorption of thiophene on transition metal atoms (Co, Ni and Mo) modified

Al20O30 clusters: DFT approaches
Xiaozhen Zheng a, Yonghong Zhang b,⇑, Shiping Huang a,⇑, Hui Liu c, Peng Wang d, Huiping Tian d
a
Division of Molecule and Materials Simulation, State Key Laboratory of Organic–Inorganic Composites, Beijing University of Chemical Technology, Beijing 100029, China
b
Dept. of Physics, Tianjin Polytechnic University, Tianjin 300160, China
c
State Key Laboratory of Chemical Resource Engineering, Beijing University of Chemical Technology, Beijing 100029, China
d
Research Institute of Petroleum Processing, SINOPEC, Beijing 100083, China

a r t i c l e i n f o a b s t r a c t

Article history: Transition metal atoms (Co, Ni and Mo) modified alumina are of interest in hydrodesulfurization cataly-
Received 15 August 2011 sis. In this study, full geometry optimization, bonding characters, electronic structures and vibrational
Received in revised form 18 October 2011 analysis for thiophene adsorption on MAl20O30 (M = Co, Ni and Mo) clusters are carried out by density
Accepted 18 October 2011
functional theory method. The impurity of transition metal atoms promotes the activity of catalyst by
Available online 24 October 2011
an elongation of the SAC bond in all thiophene adsorption modes. The bonding characteristics analysis,
based on the values of charge transfer and molecular orbital pictures for different adsorption modes, indi-
Keywords:
cates that p-backdonation exists for g2 and g5 bonding modes. In addition, compared with the vibra-
Density functional theory
Thiophene
tional frequencies of free thiophene, the m(C@C)sym bands for g5 bonding mode are shifted to lower
Transition metal atoms modified alumina wavenumbers, which is consistent with experimental results.
clusters Ó 2011 Elsevier B.V. All rights reserved.
Electronic structure
Vibrational frequencies

1. Introduction presence of gas-phase hydrogen. Furthermore, thiophene

Hydrodesulfurization (HDS) is an important catalytic process in
the petroleum industry used to remove sulfur from petroleum frac-
tions. Thiophene adsorption on the surface of catalysts is consid-
ered as the first step of HDS reactions. Many experimental and
theoretical studies have been undertaken with regard to thiophene
adsorption on the HDS catalysts. Experimentally, Quigley et al.
have investigated thiophene adsorption on c-Al2O3 surface in
ultrahigh vacuum (UHV) using infrared (IR) spectroscopy and tem-
perature-programmed desorption (TPD) [1]. Thiophene is weakly
adsorbed on c-Al2O3 surface at saturation coverage. Thus, a series
of alumina-supported Co, Ni and Mo HDS catalysts have attracted
much attention in previously experimental studies. Pablo et al.
have determined that thiophene is coplanar to the surface of Ni/
Al2O3 catalyst by X-ray photoelectron spectroscopy and Fourier
transform infrared spectroscopy [2]. Adsorption and reaction of
thiophene on sulfided Mo/Al2O3 catalysts have been investigated
using IR and TPD methods [3,4]. Thiophene is coordinated via its
sulfur atom to coordinately unsaturated Mod+ sites on the surface
and becomes reactive on sulfided Mo/Al2O3 catalysts only in the
⇑ Corresponding authors. Fax: +86 10 64427616.
E-mail addresses: yonghongzhang@tjpu.edu.cn (Y. Zhang), huangsp@mail.buc-
t.edu.cn (S. Huang).
adsorption on the surface of alumina-supported bimetallic (CoMo
and NiMo) HDS catalysts has been focused on in previously exper-
imental studies [5–8]. Theoretically, the most widely applied cata-
lysts for thiophene adsorption are based on layered nickel and
disulfides. Thiophene adsorption on the Ni(1 0 0) surface brings
on the scission of one of the SAC bonds, while the sulfur atom is
located at most favorable adsorption position—the bridge site [9–
11]. In addition, the different adsorption possibilities of thiophene
on the Ni(1 1 0) surface have been studied, and three structures
with the thiophene molecule plane parallel to the surface have
comparatively large adsorption energies [12]. Raybaud et al. have
investigated thiophene adsorption on the catalytically active
MoS2(0 1 0) surface using ab initio local-density-functional molec-
ular dynamics [13]. The results indicate that thiophene adsorption
on the surface is with the molecular ring parallel to the surface (g5
bonding mode) and with the sulfur atom in a binding position be-
tween two Mo surface atoms. Moreover, thiophene adsorption on
the different surfaces of MoS2 has been investigated by density
functional theory (DFT) calculations [14,15]. The active site of dif-
ferent surfaces of MoS2 for thiophene HDS is the brim site of the
Mo edge. The hydrogenation (HYD) and direct desulfurization
(DDS) pathways of thiophene HDS over cobalt- or nickel-promoted
MoS2 have been studied by DFT calculations [16–18]. The net result
of Co or Ni promotion is of the relative importance of the DDS

2210-271X/$ - see front matter Ó 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.comptc.2011.10.016
 X. Zheng et al. / Computational and Theoretical Chemistry 979 (2012) 64–72
pathway and shows an increase in the HYD activity. Moreover, thi-
ophene adsorption on the MoP(0 0 1), Mo2N(1 0 0), Mo2C(0 0 1) and
Ni2P(0 0 1) surfaces has been investigated by DFT method [19,20].
Up to now, several studies have focused on thiophene adsorption
on the surface of Mo disulfides [21,22] and Co or Ni modified Mo
sulfides clusters [23,24]. It is worth noticing that even today there
are no published theoretical studies for thiophene adsorption on
the surface of the transition metal atoms modified alumina clus-
ters. Therefore, it would be interesting to know about the proper-
ties of the transition metal atoms modified alumina clusters after
thiophene adsorption. To investigate this question, we have per-
formed a systematic study on the geometries, stabilities and elec-
tronic structures of thiophene adsorption on MAl20O30 (M = Co, Ni
and Mo) clusters by DFT calculations.
In the present study, we firstly explore the different adsorption
modes of thiophene on the surface of MAl20O30 (M = Co, Ni and Mo)
clusters and compare the geometrical parameters of adsorbed thi-
ophene with these of free thiophene. Next, we study the bonding
characters between thiophene and transition metal atoms
(M = Co, Ni and Mo) in MAl20O30 clusters. Then, the electronic
properties of thiophene adsorption on MAl20O30 (M = Co, Ni and
Mo) clusters are systematically investigated. Finally, we analyze
the vibrational frequencies of the stretching modes of the adsorbed
thiophene molecule.
2. Models and methods
Before studying transition metal atoms (M = Co, Ni, and Mo)
modified Al20O30 cluster, we construct the Al20O30 fullerene-like
structure model proposed by Linnolahti et al. [25,26], in which
Al atoms are all threefold coordinated. In addition, Charkin
et al. [27] and Dabbagh et al. [28] have reported Al20O30 fullerene
shape nanoballs. In previous studies, Raybaud et al. have investi-
gated the much complex structure of c-Al2O3 [29–31] and single
Pd atoms doped c-Al2O3 [32]. However, the curvature of fuller-
enes helps to avoid the clustering problem [33] thereby helping
to keep the doped metal atoms isolated from one another. Conse-
quently, we choose the transition metal atoms doped Al20O30 ful-
lerene-like structure for the further study. Four possible sites for
transition metal atoms adsorption on Al20O30 cluster, including
the sites on the top of the aluminum (Al site) and oxygen atoms
(O site), the site at the center of a pentagon (P site), the bridge
site over the AlAO bond (B site), are considered as initial posi-
tions. We calculate adsorption energies of a single metal atom
at these sites, which are listed in Supporting Information Table
S1 along with relevant structural parameters. The adsorption en-
ergy of the transition metal atom modified Al20O30 cluster is de-
fined as:
Eads ¼ EðMAl20 O30 Þ  EðMÞ  EðAl20 O30 Þ
where E(M) is the energy of an isolated metal atom. E(Al20O30) is the
total energy of Al20O30 cluster and E(MAl20O30) is the total energy of
MAl20O30 cluster. Hence the negative adsorption energy indicates
the stability of the system. In the case of CoAl20O30 cluster, the
adsorption energy at the B site is 1.76 eV. The CoAAl and CoAO
bond lengths are 2.436 Å and 1.897 Å, respectively. The AlAO bond
length nearest to the Co atom elongates from 1.711 Å to 1.847 Å. For
Co atom starting at the O site, it moves to the B site after geometry
optimization. Although Co atom starting at the Al site remains there
after geometry optimization, the adsorption energy is only
1.22 eV, much smaller than that at the B site. In addition, the re-
sults in Supporting Information Table S1 indicate that the most sta-
ble site is the P site rather than the B site. For reasons described
below, we do not choose thiophene adsorption on the P site. Firstly,
65
Fig. 1. Modes of thiophene and thiophene adsorption observed in transition metal
complexes.
steric effects [20] are significant for the thiophene adsorption on
MAl20O30 (M = Co, Ni and Mo) clusters. Steric effects at the P site
are largest in all adsorption sites for thiophene adsorption as shown
in Supporting Information Fig. S1. Secondly, we attempt to consider
the g1(S), g2 and g5 bonding modes as the initial structures of thi-
ophene adsorption on CoAl20O30 cluster at P site. The most stable
structures after geometry optimizations are obtained as shown in
Supporting Information Fig. S2. Although the g1(S) bonding mode
as the initial structure remains there after geometry optimization,
the CoAl20O30 cluster at P site after thiophene adsorption presents
dramatic change and the cage of CoAl20O30 (P1) breaks. For g2 or
g5 bonding mode as the initial structure, thiophene molecule in
the corresponding structure (P2 and P3) is found to move away
from the CoAl20O30 cage, implying that thiophene adsorption on
the P site is very difficult. Our calculations show that the results
of Ni and Mo adsorption on Al20O30 cluster are similar to that of
Co adsorption. Therefore, we investigate thiophene adsorption on
the B sites for transition metal atoms modified Al20O30 cluster. An
isolated thiophene molecule can be identified: four corresponding
to CAH bonds, one to a CAC single bond, two to CAC double bonds,
two SAC bonds and one for the lone electron pair at the sulfur atom
as shown in Fig. 1. Based upon the previous studies of IR spectra
[34,35], the most commonly cited bonding modes are presented
in Fig. 1. The g1(S), g2 and g5 bonding modes represent S-bonding
to a metal site, p-binding of two carbons and p-binding of all five
atoms in the thiophene ring to a metal atom, respectively [36]. Then
we consider these three different bonding modes as the initial
structures of thiophene adsorption on the MAl20O30 (M = Co, Ni
and Mo) clusters. For geometry optimization of each isomer, the
spin multiplicity (SM) is considered at least 1, 3, 5 for even-electron
clusters (Ni, Mo) and 2, 4, 6 for odd-electron clusters (Co). Full
geometry optimizations are carried out by DMol3 package [37–
39] based on DFT. The exchange–correlation interaction is treated
within the generalized gradient approximation (GGA) using the Per-
dew, Burke, and Ernzerhof correlation functional (PBE) [40]. Full
structural optimizations are obtained by using a convergence crite-
rion of self-consistent field SCF of 1.0  106 Hartree, a convergence
ð1Þ
tolerance of energy of 1.0  105 Hartree, a maximum force of
2.0  103 Hartree/Å and a maximum displacement of
5.0  103 Å. In addition, the density functional semi-core pseudo-
potentials (DSPP) and the double numerical basis set (DNP) are em-
ployed. Finally, the stable structures of (g1(S)-C4H4S)M(Al20O30)
(M = Co, Ni and Mo), (g2-C4H4S)M(Al20O30) (M = Co and Ni) and
(g5-C4H4S)M(Al20O30) (M = Ni and Mo) are obtained after geometry
optimizations. For the MAl20O30 (M = Co, Ni and Mo) clusters with
thiophene adsorption, the values (negative values) of total energy
increase with increasing of SM as shown in Supporting Information
Table S2. In other words, the stability decreases with increasing of
SM. In our study, we investigate the most stable structures of thio-
phene adsorption on MAl20O30 (M = Co, Ni and Mo) clusters with
the lowest-energy. The partial density of states (PDOS) is calculated
with a k-point of (4  4  4).
66 X. Zheng et al. / Computational and Theoretical Chemistry 979 (2012) 64–72
3. Results and discussion
3.1. Thiophene adsorption on MAl20O30 (M = Co, Ni and Mo) clusters
The optimized structures of MAl20O30 (M = Co, Ni and Mo) clus-
ters and thiophene adsorption on MAl20O30 (M = Co, Ni and Mo)
clusters are shown in Fig. 2, and the geometrical parameters of free
and adsorbed thiophene are listed in Table 1. To determine the
most possible adsorption site of thiophene, we calculate the
adsorption energies of different adsorption sites shown in Table
1. The adsorption energy for thiophene adsorption on MAl20O30
clusters is defined as:
Eads ¼ EðC4 H4 S þ MAl20 O30 Þ  EðC4 H4 SÞ  EðMAl20 O30 Þ
where E(C4H4S) is the energy of an isolated thiophene molecule.
E(MAl20O30) is the total energy of MAl20O30 cluster and
E(C4H4S + MAl20O30) is the total energy of MAl20O30 cluster with
thiophene. By definition, negative adsorption energy corresponds
to stable adsorption on the clusters.
In the case of thiophene adsorption on CoAl20O30 cluster (a),
three different adsorption modes are shown in Fig. 2. In the
(g1(S)-C4H4S)Co(Al20O30) cluster (a1), the CoAS bond length is
2.059 Å, while the SAC bond lengths are 1.734 Å. The (g1(S)-
C4H4S)Co(Al20O30) cluster has the adsorption energy of 1.34 eV.
In the (g2-C4H4S)Co(Al20O30) cluster (a2), the two carbons are p-
bonding to the Co atom. The CACo bond length (C3ACo) is
1.965 Å for the carbon atom forming SAC bond, and a value of
2.013 Å for the other carbon atom. In addition, the SAC bond
length (C3AS) becomes longer to 1.784 Å for the carbon atom
forming CACo bond. The (g2-C4H4S)Co(Al20O30) cluster has the
largest adsorption energy of 1.82 eV among three different
adsorption modes. The second stable adsorption mode is (g5-
C4H4S)Co(Al20O30) cluster (a3) with the adsorption energy of
1.64 eV. In this g5 bonding mode, the distance between S atom
and its neighbor Co is 2.472 Å, and the CACo distances (C3ACo
and C4ACo) have the values of 2.111 Å and 2.113 Å for the carbon
atoms forming CAS bonds, and the values of 2.065 Å and 2.063 Å
for the other two carbon atoms. In fact, there are no remarkable
changes for the structures between free and corresponding thio-
phene adsorption on MAl20O30 (M = Co, Ni and Mo) clusters. For
example, the CoAAl and CoAO bond lengths in CoAl20O30 cluster
with thiophene adsorption are in the range of 2.442–2.463 Å and
1.866–1.900 Å which are close to their corresponding bond lengths
(2.436 Å and 1.897 Å) in CoAl20O30 cluster. Interestingly, the
adsorption energy of (g2-C4H4S)Ni(Al20O30) cluster (b2) is
2.21 eV, which is very close to that (2.23 eV) of hollow B site
of thiophene adsorption on the Ni(1 0 0) surface [9]. In addition,
the adsorption energy of (g1(S)-C4H4S)Mo(Al20O30) cluster (c1) is
0.04 eV, which is far smaller than that (0.89 eV) of perpendicu-
lar adsorption mode on the perfect molybdenum edge of MoS2
[14]. However, (g5-C4H4S)Mo(Al20O30) cluster (c2) with large
adsorption energy of 2.40 eV is most stable in all thiophene
adsorption modes.
3.2. Mayer bond orders
Mayer bond orders for thiophene adsorption on MAl20O30
(M = Co, Ni and Mo) clusters are exhibited in Table 2. It is well
known that the SAC bonds in free thiophene are covalent. Mayer
bond orders of SAC bond in free thiophene are 1.29. One can see
that the bonding characters between S and C atoms in all bonding
modes of thiophene adsorption are mainly covalent, which could
be confirmed by the large Mayer bond orders (1.02–1.23) of SAC
bond. However, Mayer bond orders of SAC bond in free thiophene
are larger than these in adsorbed thiophene. To our knowledge, a
large positive value of bond order signifies the strong bonding be-
tween the atoms. Moreover, there is a trend of decreasing bond
lengths with increasing bonding ability for thiophene adsorption
on MAl20O30 (M = Co, Ni and Mo) clusters. The length of SAC bond
is 1.732 Å in free thiophene which is very close to the previously
published data (1.733 Å) [41,42]. For g1(S), g2 and g5 bonding
modes, the SAC bond lengths are in the range of 1.734–1.755 Å,
1.744–1.784 Å and 1.776–1.806 Å, respectively. In other words,
Mayer bond orders between the S atom and C atom in adsorbed
thiophene decrease, while the lengths of SAC bond increase com-
pared with those in free thiophene. It is clear that the SAC bonds
are all stretched in some degrees after thiophene adsorption on
MAl20O30 (M = Co, Ni and Mo) clusters. This result indicates that
ð2Þ the SAC bonds in adsorbed thiophene are active by the transition
metal atom in MAl20O30 (M = Co, Ni and Mo) clusters.
3.3. Charge transfer and molecular orbitals
The values of charge transfer from thiophene to MAl20O30
(M = Co, Ni and Mo) clusters are shown in Table 2. For g1(S),
g2 and g5 bonding modes of thiophene adsorption on CoAl20O30
cluster, the values of charge transfer from thiophene to CoAl20O30
are 0.25 |e|, 0.13 |e| and 0.27 |e|, respectively. For g1(S) bonding
mode of thiophene adsorption on the NiAl20O30 and MoAl20O30
clusters, the values of charge transfer (0.19 |e| and 0.16 |e|) are
smaller than that (0.25 |e|) for (g1(S)-C4H4S)Co(Al20O30) cluster.
The values of charge transfer are only 0.05 |e| for (g2-C4H4S)Ni(A-
l20O30) and (g5-C4H4S)Mo(Al20O30) clusters. The values of charge
transfer from thiophene to MAl20O30 (M = Co, Ni and Mo) clusters
are all positive. Thus, charge transfer occurs in the same direction,
namely, from the thiophene to metal atoms. In general, a large
value of charge transfer signifies strong interaction between the
adsorbent and the adsorbate. However, for g2 and g5 bonding
modes, the trend is just opposite. It indicates that additional elec-
tronic effects are commonly invoked, i.e., the most important
being p-backdonation for g2 and g5 bonding modes. In other
words, the transition metal atom (Co, Ni or Mo) acts now as elec-
tron donor. Interestingly, g1(S) bonding mode is not favored in
these cases since it would possess a positive charge on an already
electron-deficient thiophene ring.
To further investigate bonding characteristic, we investigate
the orbital contour plots of the p-donation and p-backdonation
molecular orbitals for g2 and g5 bonding modes in Fig. 3. In de-
tail, for g2 bonding mode the transition metal atoms (Co and Ni)
have the vacant d orbitals which accept the p electron of the con-
jugated double bond (C@C) resulting in the formation of the
strong p-bonding modes (p-donation). Meanwhile, the vacant p
orbital of C@C accepts the electrons from the occupied d orbitals
of the transition metal atoms, which should be described as p-
backdonation. Similarly, for g5 bonding mode of thiophene
adsorption on MAl20O30 (M = Co and Mo) clusters, the Co or Mo
atom has the vacant d orbitals which accept the p electron of
the thiophene ring. It should be noted that the p orbital of thio-
phene ring accepts the electron of the occupied d orbitals of tran-
sition metal atoms (Co and Mo) due to p-backdonation. In
addition, the valence electronic configurations of Co element in
the (g1(S)-C4H4S)Co(Al20O30), (g2-C4H4S)Co(Al20O30) and (g5-
C4H4S)Co(Al20O30) cluster are 3d7.944(sp)1.29, 3d7.844(sp)1.26 and
3d7.934(sp)1.26, respectively. Mulliken charges of the metal center
occupied d orbitals in thiophene adsorption on CoAl20O30 cluster
decrease with increasing adsorption energies. It also confirms that
the backdonation exists and makes the binding ability between
the transition metal atom and thiophene strengthened. For thio-
phene adsorption on MAl20O30 (M = Ni and Mo) clusters, a similar
tendency can be also observed.
 X. Zheng et al. / Computational and Theoretical Chemistry 979 (2012) 64–72 67

Fig. 2. Geometry optimized structures of the MAl20O30 (M = Co, Ni and Mo) clusters and the clusters with thiophene adsorption. Purple ball for Al, red ball for O, blue ball for
Co, green ball for Ni, black ball for Mo, yellow ball for S, gray ball for C, and white ball for H. (a) CoAl20O30, (a1) (g1(S)-C4H4S)Co(Al20O30), (a2) (g2-C4H4S)Co(Al20O30), (a3) (g5-
C4H4S)Co(Al20O30), (b) NiAl20O30, (b1) (g1(S)-C4H4S)Ni(Al20O30), (b2) (g2-C4H4S)Ni(Al20O30), (c) MoAl20O30, (c1) (g1(S)-C4H4S)Mo(Al20O30), (c2) (g5-C4H4S)Mo(Al20O30). (For
interpretation of the references to color in this figure legend, the reader is referred to the web version of this article.)
68 X. Zheng et al. / Computational and Theoretical Chemistry 979 (2012) 64–72

Table 1 change tendency of chemical hardness of thiophene adsorption

Bond lengths (Å), bond angles (°) for free and adsorbed thiophene and adsorption on MAl20O30 (M = Ni and Mo) clusters is similar to that of thio-
energies (Eads/eV) for thiophene adsorption on MAl20O30 (M = Co, Ni and Mo) clusters.
phene adsorption on CoAl20O30 cluster. That is to say, the chemical
Adsorption SAC3 SAC4 C2AC3 C1AC4 C1AC2 h(C3ASAC4) Eads hardness increases with increasing adsorption energies when thio-
mode phene is adsorbed on one of the MAl20O30 (M = Co, Ni and Mo)
Freea 1.732 1.732 1.378 1.378 1.423 91.7 – clusters.
a1 1.734 1.734 1.376 1.375 1.427 93.1 1.34
a2 1.784 1.746 1.435 1.375 1.443 91.2 1.82
a3 1.777 1.776 1.413 1.412 1.432 89.2 1.64
3.4.2. HOMO–LUMO gaps
b1 1.755 1.755 1.371 1.371 1.431 92.0 1.71 The energy gaps (Eg) between the highest occupied molecular
b2 1.781 1.744 1.434 1.374 1.440 91.3 2.21 orbital (HOMO) and the lowest unoccupied molecular orbital
c1 1.747 1.745 1.374 1.374 1.430 92.1 0.04 (LUMO) of thiophene adsorption on MAl20O30 (M = Co, Ni and
c2 1.806 1.803 1.438 1.428 1.428 88.5 2.40
Mo) clusters are shown in Table 3. Free thiophene has a big energy
a
Free represents an isolated thiophene. gap (4.49 eV), which is close to previously published data (5.07 eV)
[42]. It can be seen that all the clusters with adsorbed thiophene
show smaller gaps than free thiophene. It is well known that a
large gap indicates high stability and a small gap shows low stabil-
Table 2
Mayer bond orders, Mulliken charge transfer (QT/|e|), ionization potential (IP/eV), ity. In turn, the high stability is associated with low chemical reac-
electron affinity (EA/eV) and chemical hardness (g/eV) for free thiophene and tivity and the small stability with high chemical reactivity [47–49].
thiophene adsorption on MAl20O30 (M = Co, Ni and Mo) clusters. The HOMO–LUMO gap (0.63 eV) of NiAl20O30 cluster is consistently
Adsorption Bond length QT Mayer bond IP EA g narrower than those (0.84 and 1.31 eV) of CoAl20O30 and MoA-
mode orders l20O30 clusters. This fact is illustrated that nickel performs better
SAM CAM SAC SAM
in promoting the reactivity of Al20O30 cluster than cobalt and
molybdenum do. By comparison of calculated HOMO–LUMO gaps
Free – – 0.00 1.29 – 8.81 1.63 5.22
a1 2.059 – 0.25 1.20 1.20 6.24 2.24 2.00
between thiophene adsorption on one of the MAl20O30 (M = Co,
a2 – 1.965/ 0.13 1.13/ – 6.32 2.16 2.08 Ni and Mo) clusters, it is yet valuable in order to recognize ten-
2.013 1.21 dency. For g1(S), g2 and g5 bonding modes of thiophene adsorp-
a3 2.472 2.063– 0.27 1.11 0.42 6.00 2.31 1.85 tion on CoAl20O30 clusters, the values of energy gaps are 1.15 eV,
2.113
1.33 eV and 1.27 eV, respectively. We find that the values of
b1 2.093 – 0.19 1.16 1.03 6.25 2.09 2.08
b2 – 1.957/ 0.05 1.13/ 6.50 2.12 2.19 HOMO–LUMO gaps become larger with increasing adsorption
2.012 1.23 energies when thiophene is adsorbed on CoAl20O30 clusters. For
c1 2.309 – 0.16 1.12 1.39 5.47 2.30 1.59 thiophene adsorption on MAl20O30 (M = Ni and Mo) clusters, a sim-
c2 2.528 2.167– 0.05 1.02 0.72 5.81 2.10 1.86 ilar tendency can be observed.
2.273

3.4.3. Partial densities of states

3.4. Electronic structures
3.4.1. Ionization potential, electron affinity and chemical hardness
Ionization potential (IP) and electron affinity (EA) can be calcu-
lated using the formulas given below:
IP ¼ EðN  1Þ  EðNÞ
EA ¼ EðNÞ  EðN þ 1Þ
where IP and EA are obtained from total electronic energy calcula-
tions on the N  1, N, and N + 1 electron systems at the neutral
geometry [43–45]. The natural way to approximate the chemical
hardness (g) is to evaluate it directly from the calculated IP and
EA as:
IP  EA
g¼
2 C 2sp states and S 3sp states give contribution to three sharp peaks
The IP, EA and g for thiophene adsorption on MAl20O30 (M = Co,
Ni and Mo) clusters are presented in Table 2. For free thiophene the
IP value is 8.81 eV, which is in good agreement with the previously
calculated value (8.75 eV) [42]. The EA value is negative, implying
that thiophene does not prefer to accept electrons any more as the
electron–electron repulsion becomes stronger than the electron-
nuclear attraction. Therefore, the values of charge transfer from
thiophene to MAl20O30 (M = Co, Ni and Mo) clusters are all positive.
In principle, a chemically inert cluster has high IP and low EA [46].
For g1(S), g2 and g5 bonding modes of thiophene adsorption on
CoAl20O30 clusters, the values of the chemical hardness are
2.00 eV, 2.08 eV and 1.85 eV, respectively. The g2 bonding mode
of thiophene adsorption on CoAl20O30 cluster has the larger chem-
ical hardness and the stronger adsorption energy (1.82 eV). The
In order to further understand electronic structures of thio-
phene adsorption on MAl20O30 (M = Co, Ni and Mo) clusters, we
analyze partial densities of states (PDOS) between 24 eV and
6 eV from the contributions of different orbital components pre-
sented in Fig. 4 and Supporting Information Fig. S3. Obviously,
PDOS of the same bonding mode for thiophene adsorption on
ð3Þ MAl20O30 (M = Co, Ni and Mo) clusters very much resemble each
other. Therefore, we only focus on the PDOS of thiophene adsorp-
ð4Þ tion on CoAl20O30 cluster. In the case of (g1(S)-C4H4S)Co(Al20O30)
clusters, C 2sp and S 3sp states are hybridized in a lower energy
range between 19 eV and 8 eV, making CAS bond to be a strong
directional covalent bonding. The peaks located between 6 eV
and 2 eV originate from the hybridized C 2p and S 3p states with
a small contribution of Co 3d states. The peaks in the vicinity of
Fermi level are from the hybridized Co 3d and S 3p states with a
small contribution of Co 4s states and S 3d states, making CoAS
ð5Þ bond to be a covalent bonding. For (g2-C4H4S) Co(Al20O30) clusters,
around 17.5 eV, 14 eV and 10 eV which slightly are shifted to
higher energy than those of (g1(S)-C4H4S) Co(Al20O30) cluster. The
peaks in the vicinity of Fermi level are mainly consisted of the
hybridized Co 3d and C 2p states with a small contribution of Co
4s states and S 3p states. For (g5-C4H4S)Co(Al20O30) clusters, these
peaks far below the Fermi level slightly are shifted to lower energy
and originate from the hybridized Co 3d and C 2p states. The peaks
in the vicinity of Fermi level are mainly composed of the hybrid-
ized Co 3d states, S 3p states and C 2p states.
3.5. Vibrational frequency
In order to obtain the global minima for the structures of
thiophene adsorption on MAl20O30 (M = Co, Ni and Mo) clusters,
 X. Zheng et al. / Computational and Theoretical Chemistry 979 (2012) 64–72 69

Fig. 3. The p-donation and p-backdonation molecular orbitals of thiophene adsorption on MAl20O30 (M = Co, Ni and Mo) clusters. (a2) (g2-C4H4S)Co(Al20O30), (b2) (g2-
C4H4S)Ni(Al20O30), (a3) (g5-C4H4S)Co(Al20O30), (c2) (g5-C4H4S)Mo(Al20O30).
70 X. Zheng et al. / Computational and Theoretical Chemistry 979 (2012) 64–72

Table 3
Energy gaps (Eg/eV) between the highest occupied molecular orbital (HOMO) and the
lowest unoccupied molecular orbital (LUMO) for free thiophene, MAl20O30 clusters
and thiophene adsorption on MAl20O30 (M = Co, Ni and Mo) clusters.

Adsorption mode HOMO LUMO Ega

Free 5.77 1.28 4.49
a 4.43 3.59 0.84
a1 4.31 3.16 1.15
a2 4.46 3.13 1.33
a3 4.76 3.49 1.27
b 4.24 3.61 0.63
b1 4.08 3.10 0.98
b2 4.39 3.14 1.25
c 4.49 3.18 1.31
c1 4.19 3.50 0.69
c2 3.90 3.12 0.78
a
Eg is calculated by Eg ¼ ELUMO  EHOMO (unit in eV).

vibrational frequencies are calculated in our study. All vibrational

frequencies are positive, indicating that the optimized structures
indeed correspond to the minima on the potential energy surface.
Vibrational frequencies of free and adsorbed thiophene are
presented in Table 4. We restrict our analysis to frequencies above
1000 cm1, because below this value the mixing of the various
normal modes occurs and is difficult to analyze, hindering a
comparison of free and adsorbed thiophene.
For free thiophene molecule, the calculated vibrational frequen-
cies are in good agreement with the experimental data [50,51]. In
previous studies [3,52], the m(C@C)sym band is shifted to higher
wavenumber when thiophene is g1(S)-bonding to a metal center
(or surface). Moreover, the m(C@C)sym band is shifted to lower
wavenumber when thiophene is p-bonding (g4 or g5 bonding
mode) to a metal center (or surface). Compared with the m(C@C)sym
band of free thiophene molecule, the m(C@C)sym band of (g1(S)-
C4H4S)Ni(Al20O30) is shifted by +3 cm1, whereas the m(C@C)sym
bonds of (g1(S)-C4H4S)Co(Al20O30) and (g1(S)-C4H4S)Mo(Al20O30)
are shifted by 35 cm1 and 22 cm1, respectively (i.e., in the
opposite direction). It should be noted that m(C@C)sym bands of
(g1(S)-C4H4S)Co(Al20O30) and (g1(S)-C4H4S)Mo(Al20O30) are
shifted to lower wavenumbers, which should be attributed to the
special cluster structures of adsorbent. The m(C@C)sym band of
(g5-C4H4S)Co(Al20O30) is shifted by 46 cm1 in comparison with
that of free thiophene, which is shifted to lower wavenumber. A
similar tendency is observed from the vibrational frequencies of
(g5-C4H4S)Mo(Al20O30). It indicates that the direction of the shifts,
with respect to gas-phase thiophene, depends on the bonding
mode of the thiophene ligand rather than the chemical identity
of the metal species in MAl20O30 clusters. These decreased stretch-
ing frequencies for g5 bonding mode can be attributed to the dona-
tion of the electrons of the p system of the molecule and to the
bonds formed between the atoms of thiophene ring and the metal
atom of the MAl20O30 clusters. In addition, we calculate the
m(C@C)sym bands of (g2-C4H4S) M(Al20O30) (M = Co and Ni) which
are shifted to lower wavenumbers (76 cm1 and 69 cm1).
The reason of these decreased stretching frequencies for g2 bond- Fig. 4. Partial densities of states of thiophene adsorption on the CoAl20O30 cluster.
Broken line is the Fermi level (EF). (a1) (g1(S)-C4H4S)Co(Al20O30), (a2) (g2-
ing mode is consistent with that for g5 bonding mode.
C4H4S)Co(Al20O30), (a3) (g5-C4H4S)Co(Al20O30).

4. Conclusions
In this study, (g5-C4H4S)Mo(Al20O30) cluster is the most stable
adsorption among all thiophene adsorption modes. In addition,
transition metal atoms (Co, Ni and Mo) in MAl20O30 cluster are
responsible for an elongation of the SAC bonds after thiophene
adsorption. The values of charge transfer and the molecular orbital
pictures explain that p-backdonation exists for g2 and g5 bonding
modes. The values of the chemical hardness and the HOMO–LUMO
gaps become large with increasing adsorption energies when thio-
phene is adsorbed on one of the MAl20O30 (M = Co, Ni and Mo) clus-
ters. The m(C@C)sym band of (g1(S)-C4H4S)Ni(Al20O30) is shifted to
higher wavenumber, whereas these bonds of (g1(S)-C4H4S)M(A-
l20O30) (M = Co and Mo) are shifted to lower wavenumbers in com-
parison with that of free thiophene. Especially, the m(C@C)sym
bands for g5 bonding mode are shifted to lower wavenumbers,
which is in good agreement with experimental results.
 X. Zheng et al. / Computational and Theoretical Chemistry 979 (2012) 64–72 71

Table 4
Vibrational frequencies (cm1) for free and adsorbed thiophene.a

Adsorption mode m(CAH) m(CAH) m(CAH) m(CAH) m(C@C)as m(C@C)sym m ring d(CAH) d (CAH) d (CAH)
Expt. 3126 3125 3098 3098 1507 1409 1360 1256 1085 1083
Free 3217 3176 3151 3121 1499 1418 1362 1237 1070 1063
a1 3231(+14) 3212(+36) 3149(2) 3131(+10) 1498(1) 1383(35) 1343(19) 1225(12) 1071(+1) 1063(0)
a2 3160(57) 3125(51) 3118(33) 3100(21) 1453(46) 1342(76) 1284(78) 1186(51) 1054(16) 1037(26)
a3 3194(23) 3190(+14) 3164(+13) 3142(+21) 1396(103) 1372(46) 1291(71) 1217(20) 1078(+8) 1040(23)
b1 3187(30) 3183(+7) 3166(+15) 3141(+20) 1521(+22) 1421(+3) 1339(23) 1229(8) 1075(+5) 1054(9)
b2 3173(44) 3142(34) 3121(30) 3114(7) 1459(40) 1349(69) 1299(63) 1191(46) 1078(+8) 1036(27)
c1 3227(+10) 3207(+31) 3152(+1) 3115(6) 1518(+19) 1396(22) 1342(20) 1227(10) 1077(+7) 1062(1)
c2 3200(17) 3181(+5) 3157(+6) 3122(+1) 1382(117) 1345(73) 1241(121) 1176(61) 1059(11) 1035(28)
a
Values in parentheses indicate the relative shifts with respect to the calculated frequencies for free thiophene molecule.

Acknowledgments
This study is supported by the National Natural Science Founda-
tion of China (Grant 20876005 and 21076007) and the National Ba-
sic Research Program of China (Grant No. 2010CB732301). This
project or paper is supported by ‘‘Chemical Grid Project’’ of Beijing
University of Chemical Technology.
Appendix A. Supplementary material
Supplementary data associated with this article can be found, in
the online version, at doi:10.1016/j.comptc.2011.10.016.
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