Computational and Theoretical Chemistry 1025 (2013) 67–73

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Computational and Theoretical Chemistry

journal homepage: www.elsevier.com/locate/comptc

Geometries, stabilities, and magnetic properties of AunTi (n = 1–9)

clusters: A density functional study
Die Dong a,b,⇑, Zheng Ben-Xia b, Wang Hui a,c, Du Quan b
a
Key Laboratory of Advanced Scientific Computation, Xihua University, Chengdu 610039, China
b
School of Physics and Chemistry, Xihua University, Chengdu 610039, China
c
School of Physical Science and Technology, Southwest Jiaotong University, Chengdu 610031, China

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

Article history: The geometrical structures, relative stabilities, and magnetic properties of AunTi (n = 1–9) clusters have
Received 14 August 2013 been studied by using density functional method PW91. An extensive structural search shows that the
Received in revised form 17 September 2013 Ti atom in low-energy AunTi isomers tends to occupy the most highly coordinated position. The ground
Accepted 19 September 2013
state structures of AunTi clusters are different from that of Aun+1 clusters. The relative stabilities of ground
Available online 28 September 2013
state AunTi clusters are analyzed based on the averaged binding energies, second-order difference of
energies, and HOMO–LUMO energy gaps. It is found that the substitution of a Ti atom for an Au atom
Keywords:
in gold cluster enhances the stability of the host cluster. The AunTi clusters with even n exhibit higher
Geometrical structure
Relative stability
stability over the clusters with odd n. The chemical activity of AunTi clusters is higher for odd n and lower
Magnetic property for even n than that of the corresponding Aun+1 clusters. The Au4Ti cluster, which corresponds to a large
AunTi cluster energy gap, has a large VIP. The magnetism calculations indicate that the magnetic moment of the Ti
atom in the ground-state AunTi (n = 3–9) clusters is reduced to 0.75–1.15 lB for odd n and is completely
quenched for even n.
Ó 2013 Elsevier B.V. All rights reserved.

1. Introduction
During the past few years, the doping of an impurity atom in
small pure clusters has been extensively used to change the prop-
erties of the host cluster [1–16]. Gold clusters doped with transi-
tion-metal atom have been actively pursued to tailor the desired
structural, catalytic, optical, electronic, and magnetic properties
for potential applications in solid state chemistry, materials sci-
ence, microelectronics, medical science, energy, biology, and nano-
technology [17–35]. For example, Zhang and Fa reported that the
ground state configurations of NaAu 
19 and Na2 Au18 clusters do
not favor the face-centered and two-face-centered doped struc-
tures based upon the pyramidal Au 20 [17]. Peng et al. [18] proved
that CO oxidation barrier on Au2Pd is found to be lower than that
on Au3 and Pd3. The VAu 12 cluster can bind a high number of oxy-
gen molecules over pure gold cluster [19]. These imply that Au–
Pd(V) bimetallic clusters could be an improved novel catalyst for
CO oxidation. Zhao et al. explored the optical properties of AumAgn
and found that Au4Ag4 might be used as a good molecular photo-
electric device in future [20]. Recently, the experimental and theo-
retical efforts have been devoted to the Ti@Auþ n and Ti@Au6
clusters due to their unique physical and chemical properties
⇑ Corresponding author at: School of Physics and Chemistry, Xihua University,
Chengdu 610039, China.
E-mail address: science_dd@163.com (D. Dong).
[36–42]. It was shown that the positive charge of cationic AunTi+
clusters is mostly localized in the Ti atom and decreases when
the size of the cluster increases [36]. For the Au5Ti+ system, the
number of delocalized electrons not only depends on the number
and kind of the constituent atoms but also on the shape of the clus-
ter [37]. The most stable structures of both Au6Ti- and Au6Ti+ clus-
ters are a two-dimensional (2D) structure with the Ti atom sitting
in the center of an Au6 ring [38]. At the same time, these studies
mostly concentrate on the ionic clusters. To the best of our knowl-
edge, there is no theoretical work on small neutral Ti-doped gold
clusters so far. On the other hand, it is well known that small metal
clusters usually exhibit remarkable size-dependent properties,
which should be different from those of the atom or the bulk,
due to a large fraction of surface atoms and a distinct electronic
structure. Therefore, in this paper, the geometries, stabilities, and
magnetic properties of the AunTi (n = 1–9) clusters will be investi-
gated systematically by density functional theory (DFT). It is hoped
that our work could provide powerful guidelines for future exper-
imental studies and would be helpful to understand the influence
of material structure on its properties.
2. Computational details
Geometry optimizations and harmonic frequency analyses of
AunTi clusters were performed using DFT with the PW91

2210-271X/$ - see front matter Ó 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.comptc.2013.09.022
68 D. Dong et al. / Computational and Theoretical Chemistry 1025 (2013) 67–73
exchange–correlation functional, implemented in the Gaussian09
package [43]. The def2-TZVPP and LANL2DZ basis sets were,
respectively, used for Au and Sc atoms [44–46]. To search the glo-
bal minimum, lots of possible initial isomers, which include one-,
two- and three-dimensional (3D) structures, had been taken into
account in geometry optimizations. Owing to the spin polarization,
every initial configuration was optimized at possible spin sate. In
all calculation, the convergence thresholds were set to 1.5  105 -
Hartree/Bohr for the forces, 6.0  105 Å for the displacement, and
106 Hartree for the energy change. The validity of current compu-
tational method has been verified by calculations on gold dimer
and titanium dimer. The results, which were summarized in
Table 1, show the reliability of current computational scheme to
describe small AunTi clusters.
3. Results and discussion
3.1. Geometrical structures
The optimized results for AuTi manifest that the quartet spin
state is energetically lower than the doublet and sextet spin states
by 0.56 and 2.56 eV, respectively. Hence, the quartet AuTi dimer is
the ground state structure. The bond length of AuTi dimer (2.47 Å)
is shorter than that of Au2 (2.51 Å). This may be ascribed to the fact
that the ionic radius of Ti is smaller than the covalent radius of Au.
For the AunTi (n = 2–9) clusters, the ground-state structure and
three low-lying isomers for each AunTi cluster are depicted in
Fig. 1. According to the energies from low to high, these isomers
are designated by na, nb, nc, and nd, where n represents the num-
ber of Au atoms in the AunTi clusters. Their symmetry, spin multi-
plicity and energy difference compared to each of ground state
structures are also indicated in the figure. Meanwhile, the most
stable structures of Aun (n = 2–10) clusters, as shown in Fig. 1, have
been obtained at the same level of theory in order to discuss the
effects of the dopant atom on the host clusters. These structures
are also in accord with the results of foregone research [29,47].
The angular 2a isomer with C2V symmetry, which resembles the
lowest energy structure of Au3 cluster, is found to be the ground
state structure of Au2Ti cluster. The Au–Ti bond lengths are
2.45 Å and the corresponding electronic state is 3B1. The linear 2b
and 2d isomers are two low-lying structures. Their energy is higher
than that of 2a isomer by 1.24 and 1.76 eV, respectively. The trian-
gular 2c isomer with an apex angle of 60.8° is another metastable
isomer.
The doublet 3a isomer in the electronic state of 2A1 is the
ground-state structure of Au3Ti cluster and has D3h symmetry.
The configuration of 3b isomer is very similar to that of 3a, but it
belongs to C2V point group symmetry. The rhombus 3c isomer lies
0.89 eV above 3b isomer. The Y-like 3d isomer can be regarded as a
substitution of Ti atom for an Au atom in the lowest energy Au4
cluster. Both 3c and 3d isomers have the same spin multiplicity.
Table 1
The geometries and electronic properties of Au2 and Ti2 dimers.
Dimer Functional/basis set r (Å)
Calc. Expt.
Au2 PW91/TZVPP 2.51 2.47a
LSDA/LanL2DZ 2.49
B3LYP/LanL2DZ 2.57
PW91/LanL2DZ 2.55
Ti2 PW91/LanL2DZ 1.933 1.942c
a
Ref. [51].
b
Ref. [52].
c
Ref. [53].
The 4a isomer, which is the first 3D structure of all clusters, is
found to be global minimum in Td symmetry in the electronic state
of 1A1. The calculated Au–Ti bond distance is 2.38 Å. The results are
in agreement with the conclusion of Laura [42]. The 4b and 4c isomers
are two planar structures. The 4d isomer is obtained by optimizing
the geometry from Td to C2V symmetry. The 4b, 4c, and 4d isomers
in the singlet state all turn into the most stable structure (4a).
Among the Au5Ti cluster, the 5a isomer in 2A1 state is the lowest
energy structure. The 5b isomer is almost degenerate with the 5a
isomer and only 0.002 eV less stable than the lowest energy struc-
ture. The 5c isomer is got by optimizing a face-capped square pyr-
amid. The 5d isomer with a funnel shape is more stable than the
octahedral configuration with C4V symmetry. In addition, the trian-
gular Au5Ti structure, which relates to the ground state structure of
Au6 cluster, is substantially higher in energy than the 5d isomer.
The 6a and 6b isomers are obtained by distorting the geometry
from D6h to Cs and D2 symmetry, respectively. The former in 1A0
state is the most stable structure of Au6Ti cluster and two dihedral
angles are 162.5° for \1234 and 166.2° for \2435. The latter has a
slight deviation from C2V symmetry duo to the Jahn–Teller effect.
The dihedral angles in the 6b isomer are 152.2° for \3124. The
6c isomer is 0.42 eV higher in energy than the 6b isomer. The 6d
isomer in triplet sate is more stable than in other states. Other
2D and 3D isomers are less stable than the four isomers.
In the case of Au7Ti clusters, five isomers, such as 7a in Fig. 1,
show a similar structure to that of the second isomer of Au8 cluster
[47] and their energies increase as the coordinated number of Ti
atom decreases. The 7a isomer in 2A1 state is the ground state
structure in all configurations. Other four isomers, which are not
plotted in Fig. 1, are higher in energy than the 7d isomer. The 7b
isomer is above the ground state by 0.84 eV. The 7c isomer is a but-
terfly-like planar structure with C2V symmetry. The 7d isomer can
be achieved by optimizing the 7b with CS symmetry.
With regard to the Au8Ti cluster, over 20 isomers were attained
by optimizing various structures. The lowest energy structure is
the 8a isomer with an electronic state of 1A1. The 8a isomer in triplet
state is optimized and becomes the 8c isomer with D3h symmetry.
The 8b isomer can be viewed as intermediate between 8a and 8c iso-
mers. Consequently, the conversion of 8b into 8c will cause a spin
transform from singlet to triplet. The 8d isomer is the most stable
planar structure and energetically higher than the 8c by 0.01 eV.
As for the Au9Ti cluster, many 2D and 3D configurations have
been considered in geometry optimizations. The low-lying isomers
evidently favor 3D structures. The 9a isomer in 2A00 state is the
ground state structure. The 9b isomer is higher by 0.04 eV in en-
ergy than the 9a. The initial configurations of 9a and 9b isomers
are constructed by adding one Au atom to the 8a and 8b isomers.
The 9c and 9d isomers, which have a deviation from C3V symmetry,
are two alike degenerate structures. For other planar and solid iso-
mers, their energy is higher than that of the 9d isomer.
From the above discussions, it is obvious that the ground-state
structures of AunTi (n = 2, 3, 5 and 7) clusters favor the planar
De (eV) VIP (eV) EA (eV)
Calc. Expt. Calc. Expt. Calc. Expt.
2.30 2.30a 9.51 9.50a 1.88 1.92b
2.78 10.07 2.26
1.87 7.26 4.42
2.20 9.64 2.04
1.36 1.54 ± 0.19c
 D. Dong et al. / Computational and Theoretical Chemistry 1025 (2013) 67–73 69

Fig. 1. The ground-state structures of Aun+1 and AunTi (n = 2–9) clusters, and three low-lying isomers for the AunTi clusters. Bond lengths are in Å. The point group, spin
multiplicity, and energy difference compared to each of the ground state structures are given below them. The yellow and black balls represent Au and Ti atoms, respectively.
(For interpretation of the references to color in this figure legend, the reader is referred to the web version of this article.)

structures. The Ti atom in the ground sate AunTi clusters tend to
occupy the most highly coordinated position. This may be attrib-
uted to the fact that the Ti atom has a partially filled d shell. The
ground state structure of AunTi (n = 3–9) clusters is different from
that of Aun+1 clusters. The Ti atom alters the geometric properties
of gold clusters.
3.2. Relative stability
In this part, the relative stability of the ground state AunTi
(n = 1–9) clusters are discussed on the basis of the atomic averaged
binding energy, second-order energy difference, the vertical ioni-
zation potential (VIP), the electron affinity (EA) and energy gap
70 D. Dong et al. / Computational and Theoretical Chemistry 1025 (2013) 67–73

between the highest occupied molecular orbital (HOMO) and low-

est unoccupied molecular orbital (LUMO).
The atomic averaged binding energy (Eb) is useful for stability
comparison of clusters [48,49]. The Eb of the AunTi and Aun+1 clus-
ters can be calculated as follows:

Eb ½Aun Ti ¼ ðnE½Au þ E½Ti  E½Aun TiÞ=ðn þ 1Þ ð1Þ

Eb ½Aunþ1  ¼ fðn þ 1ÞE½Au  E½Aunþ1 g=ðn þ 1Þ ð2Þ

where E[AunTi], E[Au], E[Ti] and E[Aun+1] are the energy of the AunTi
cluster, an Au atom, a Ti atom and the Aun+1 cluster. The calculated
binding energies per atom for the most stable AunTi and Aun+1 clus-
ters are plotted in Fig. 2. As can be seen from this figure, the replace-
ment of an Au atom by a Ti atom increases the stability of the host
clusters. For the AunTi clusters, the averaged binding energy of AuTi
dimer is much smaller than that of AunTi (n = 2–9) clusters. From
Fig. 3. Size dependence of the second-order energy differences for the ground state
n > 2, the Eb of AunTi clusters stay nearly constant.
AunTi and Aun+1 (n = 1–8) clusters.
In cluster physics, the second-order difference of energies (D2E)
is a quite sensitive quantity that reflects the relative stability of
clusters and can be compared with the relative abundances deter-
mined in mass spectroscopy experiment. For the lowest energy
AunTi and Aun+1 clusters, it can be estimated as follows

D2 E½Aun Ti ¼ E½Aunþ1 Ti þ E½Aun1 Ti  2E½Aun Ti ð3Þ

D2 E½Aun  ¼ E½Aunþ1  þ E½Aun1   2E½Aun  ð4Þ

where E is the energy of the ground state clusters. Fig. 3 reveals the
size dependence of the second-order energy differences for the
ground state AunTi and Aun+1 clusters. It is clear from the figure that
the even-numbered gold clusters are more stable than the odd-
numbered ones. The AunTi clusters have the opposite behavior be-
cause of the doping of a Ti atom. However, there is a consistency
with respect to the number of gold atoms in the cluster. Namely,
the AunTi clusters with even-numbered gold atoms are still more
stable than its two nearest neighbors. Fig. 4. Size dependence of the HOMO–LUMO energy gaps of the ground state AunTi
The HOMO–LUMO gap (Eg), which depends on the HOMO and and Aun+1 (n = 1–9) clusters.
LUMO energy levels, is always considered to be an important
parameter that characterizes chemical stability of small metal
clusters. A small energy gap usually corresponds to a high chemical even number for even n. The energy gap of AunTi clusters is smaller
activity. For the ground state AunTi and Aun+1 clusters, the energy for odd n and larger for even n than that of the corresponding Aun+1
gaps as a function of the cluster size are displayed in Fig. 4. The cluster. The inference is in accord with the calculated results. The
gold clusters show an odd–even oscillation in their HOMO–LUMO changes of HOMO–LUMO gap also appear an odd–even alteration.
gap spectrum. The primary cause should be that the chemical The Au4Ti cluster with eight valence-electrons and Td symmetry
activity of the cluster with even-numbered electrons, which corre- has the biggest energy gap (1.84 eV) in all doped clusters. This
sponds to a closed shell structure, is weaker than that of cluster means that the Au4Ti cluster is less reactive and should be useful
with odd-numbered electrons. When an Au atom ([Xe]4f145d106s1) as building block for constructing the cluster-assembled materials.
in Aun+1 cluster is replaced by a Ti atom ([Ar]3d24s2), The electron The VIP and EA, which are two significant quantities to gain an
amount of host cluster will become an odd number for odd n and a elementary insight into the electronic structures, and are defined
as

þ
VIP ¼ EðAun Ti Þ  EðAun TiÞ ð5Þ


EA ¼ EðAun Ti Þ  EðAun TiÞ ð6Þ

Fig. 2. Size dependence of the averaged binding energies for the ground state AunTi
and Aun+1 (n = 1–9) clusters.
where E(AunTi+) and E(AunTi) are the energy of the cationic and
anionic clusters with the same geometry as the neutral cluster.
For the ground state AunTi clusters, the calculated VIP and EA are
given in Table 2 and no experimental finding is available. Although
the VIP does not correlated directly with the HOMO–LUMO gap, the
Au4Ti cluster which corresponds to a large energy gap still has a
large VIP. This is understandable in terms of the closed shell and
high symmetry. The EA of the most stable AunTi clusters tends to in-
creases in the mass with the growth of the clusters. In other words,
the big AunTi clusters will release more energy relative to the small
ones when they capture an electron.
 D. Dong et al. / Computational and Theoretical Chemistry 1025 (2013) 67–73 71

Table 2
VIP and EA of the ground state AunTi clusters, and the charge (Q) and local magnetic moment (M) of 3d, 4s, 4p, and 5p states for the Ti atom in the ground state AunTi clusters.

Clusters VIP (eV) EA (eV) Ti-4s Ti-3d Ti-4p Ti-5p

Q(e) M (lB) Q(e) M (lB) Q(e) M (lB) Q(e) M (lB)
AuTi 7.09 0.91 0.86 0.56 2.65 2.41 0.02 0 0.04 0.04
Au2Ti 7.54 1.32 0.52 0.06 2.54 1.98 0.03 0.01 0.18 0
Au3Ti 7.97 1.85 0.70 0.06 2.44 1.06 0.02 0 0.50 0
Au4Ti 8.45 2.26 0.73 0 2.6 0 0.01 0 0.99 0
Au5Ti 7.69 2.50 0.48 0.04 2.77 1.09 0.04 0 0.74 0
Au6Ti 7.95 2.02 0.59 0 2.90 0 1.40 0 0.01 0
Au7Ti 7.48 2.59 0.38 0.02 2.90 1.12 0.04 0 0.75 0.01
Au8Ti 7.25 3.06 0.41 0 3.40 0 0 0 1.5 0
Au9Ti 6.82 2.75 0.41 0.01 3.34 0.74 0 0 1.48 0

3.3. Magnetic properties
Small metal clusters offer an especial medium to probe the
magnetism. The total magnetic moment of the ground state AunTi
clusters has been analyzed and their spin density of states (SDOS)
[37] is presented in Fig 5. The AuTi dimer has a total magnetic mo-
ment of 3 lB, which is the largest in all clusters. Its linear structure
may be responsible for the large magnetic moment. For the Au3Ti,
Au5Ti, Au7Ti and Au9Ti clusters, the number of valence electrons is
an odd number and the total magnetic moments are 1 lB. The
AunTi clusters with even n is not magnetic except that the Au2Ti
clusters has a total magnetic moment of 2 lB. Meanwhile, it is also
evident from Fig. 5 that all ground state clusters have an intense
band between 0 eV and 5 eV, which is composed principally of
the valence s and d orbitals of the constituent atoms. The electrons
near the HOMO play a key role in the generation of magnetic
behavior of the AunTi clusters.
In order to interpret the magnetic properties further, we have
carried out the natural bond orbital analysis for the ground state
AunTi (n = 1–9) clusters [50]. The local magnetic moments on the
Ti atoms are 3.01 lB for AuTi, 2.05 lB for Au2Ti, 1.12 lB for Au3Ti,
1.13 lB for Au5Ti, 1.15 lB for Au7Ti, 0.75 lB for Au9Ti and are
completely quenched for the Au4Ti, Au6Ti and Au8Ti clusters.
For the AuTi and Au2Ti clusters, the local magnetic moment on
Ti atom exceeds that the magnetic moment of free Ti atom.
The Ti atom in the doped clusters for n = 3, 5, 7 and 9 carry most
of the total magnetic moments. The Au atoms exhibit an antifer-
romagnetic alignment for n = 1, 2, 3, 5, 7 and ferromagnetic
alignment for n = 9 with respect to the magnetic moment of Ti
atom. The charge and magnetic moment on 3d, 4s, and 4p states
of the Ti atom in the ground state AunTi clusters were listed in
Table 2. It can be seen from Table 2 that the magnetic moment
of Ti atom in magnetic clusters mainly originates from the par-
tially filled 3d orbital. Compared with the free Ti atom, the 3d
and 5p orbitals gain 0.04–1.48 electrons and the 4s orbital loses
1.14–1.62 electrons. Meanwhile, there is also the charge transfer
from Ti atom to Au atoms for n = 1–3 and from Au atoms to Ti
atom for n = 4–9. The charge transfer and orbital hybridization
should be the major reasons for the magnetic moment changes
of Ti atom.

Fig. 5. The SDOS of ground state AunTi clusters. A broadening factor d = 0.1 eV is used. Spin up (positive) and spin down (negative) densities are given in each case. The dashed
line indicates the location of the HOMO level.
72 D. Dong et al. / Computational and Theoretical Chemistry 1025 (2013) 67–73
4. Conclusions
The geometries, stabilities, and magnetic properties of AunTi
(n = 1–9) clusters have been investigated by first-principles density
functional calculations. The structural optimizations indicate that
the Ti atom in low-energy AunTi isomers tends to occupy the most
highly coordinated position. The most stable structures of AunTi
clusters are different from that of Aun+1 clusters. The replacement
of an Au atom in gold cluster by a Ti atom enhances the stability
of the host cluster. The AunTi clusters with even n are more stable
than the clusters with odd n. The chemical activity of AunTi clusters
is higher for odd n and lower for even n than that of the corre-
sponding Aun+1 clusters. The ground state Au4Ti cluster has a large
VIP and corresponds to a large energy gap. The magnetism analyses
show that the magnetic moment of the Ti atom in the ground-state
AunTi (n = 3–9) clusters is reduced to 0.75–1.15 lB for odd n and is
completely quenched for even n.
Acknowledgements
This project was supported by the open research fund of key
laboratory of advanced scientific Computation, Xihua University
(Grant No: szjj2012-035), the key scientific research fund of Xihua
University (Grant No: Z1213320) and the Fundamental Research
Funds for the Central Universities (Grant No: SWJTU12CX084).
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