Chemical Physics Letters 543 (2012) 121–126

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Chemical Physics Letters

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Influence of Sn interaction on the structural evolution of Au clusters: A first

principles study
Suman Kalyan Sahoo a, Sandeep Nigam b, Pranab Sarkar a, Chiranjib Majumder b,⇑
a
Dept. of Chemistry, Visva-Bharati, Santiniketan 731 235, India
b
Chemistry Division, Bhabha Atomic Research Centre, Trombay, Mumbai 400 085, India

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

Article history: Here we report the structural and electronic properties of AunSn (n = 2–13) clusters by using pseudo-
Received 4 May 2012 potential and LCAO–MO method. A comparison between the structures of Aun and AunSn clusters reveals
In final form 25 June 2012 that while Aun clusters favor planar isomers up to n = 13, AunSn clusters follow a different trend; 3D
Available online 1 July 2012
structure for n = 3 and 4, quasi planar in the size range n = 5–11, and again 3D isomers from n = 12
onwards. Enhanced contribution of Au p-orbital and significant charge transfer from Sn to the gold atoms
is attributed for such interesting growth pattern of AunSn clusters.
Ó 2012 Elsevier B.V. All rights reserved.

1. Introduction stable isomers of AunZn (n = 2–10) clusters favor planar structures,

The structure and stability of small metal clusters are of great
interest. The size-dependent properties of metal clusters strongly
depend on the atomic arrangement and consequently, on their
electronic structure [1]. In recent years, an extensive research has
been carried out on gold clusters, mainly due to their wide use in
the catalysis, microelectronics and optical materials [2–42]. Small
gold clusters show unique behavior in terms of their ground state
geometries. In particular, it is interesting to note that gold clusters
remain planar even beyond n = 6. Moreover, it is observed that the
equilibrium geometries of charged gold clusters are often different
from the corresponding neutral cluster [19–26].
Doping of an impurity atom in pure clusters has been used to
underscore the variation of properties as a function of cluster size
and to tune the chemical reactivity of the host system more pre-
cisely [27–36]. Small clusters are agglomeration of few atoms,
and therefore, an impurity atom corresponds to extremely high
dopant concentration and affects the physico–chemical properties
significantly [2–5]. Wang and co-workers [29] reported that iso-
electronic substitution of Au atom by Cu or Ag shifts the onset of
2D–3D structural transition to a smaller size. Yuan et al. [30] stud-
ied the Ni, Pd, Pt doped Au clusters and found that for Ni, the host
cluster geometry does not change, but for Pd and Pt doped Au clus-
ters, the ground state geometries changes significantly. Dong et al.
[31–33] studied the Sc, V, Mn and Fe doped gold clusters and con-
cluded that, the ground state geometries of doped clusters favors
planar configuration with transition atom occupying the higher
co-ordination site. Li and co-workers [34] reported that the most
⇑ Corresponding author.
E-mail addresses: chimaju@barc.gov.in, chimaju@magnum.barc.ernet.in
(C. Majumder).
which resembles with pure gold cluster anions. Based on all-
electron scalar relativistic calculation Kuang et al. [35] reported
that the most stable isomers of AunPt (n = 1–12) clusters are
distorted slightly in comparison to pure gold Aun+1 clusters, but
still retains the planar motifs due to the strong scalar relativistic
effect.
Although a large number of studies are available on transition-
metal doped gold clusters [3,5,27–36], few are available using non
transition elements as dopants. One of the major differences is the
preference of non-planar geometries using S or P block elements as
dopants. Heiz et al. [37] reported that Na doping in gold clusters
leads to higher polarization and more directionality of the metal–
metal bonds. Previously we have reported the ground state geom-
etries of Au clusters doped with various P block elements [38–41].
For Si doped Au clusters, an early onset of non-planar geometries of
AunSi clusters (n = 3) has been observed, which is strikingly differ-
ent than what is reported for transition-metal doped Au clusters.
The reason for the preference of non-planar geometry of AunSi
clusters was attributed to the involvement of p-orbital electrons
into the bonding, which results in a strong directional covalent
bond. Recently Wang and co-workers [42] have carried out a com-
bined photoelectron spectroscopy and computational study on the
structural evolution of doped gold anion clusters MAun (M@Si, Ge,
Sn; n = 5–8). It was found that for n = 6 and 7, all three doped clus-
ters MAun (M@Si, Ge, Sn) exhibit similar quasi–planar structures.
Importantly, they proposed that 2D–3D transition for Si doped
clusters occurs at n = 8, and in contrast Ge and Sn doped clusters
have quasi–planar structure.
To the best of our knowledge, so far there is no theoretical study
on neutral gold–tin bimetallic clusters. In general, there is a funda-
mental difference between Si and Sn interactions. In bulk, Si is a
semiconductor and has stronger tendency to form covalent bonds.

0009-2614/$ - see front matter Ó 2012 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.cplett.2012.06.055
122 S.K. Sahoo et al. / Chemical Physics Letters 543 (2012) 121–126
On the other hand Sn is a semi-metal, i.e. semiconductor at lower
temperature and metallic at higher temperature, and moreover Si
is more electropositive than Si. Therefore, the mechanism of the
AunSn cluster growth could not be simply understood through pure
ionic or covalent type of bonding. Additionally, as reported earlier
that ground state structure of the charged and neutral gold clusters
are often not the same (as their transitions from 2D ? 3D structures
have been found at different sizes) thus it will be of interest to
know that how structures and properties of neutral AunSn differ
from the reported anionic ones. Further, dimensionality of any
cluster is an important aspect because (i) it is a leading benchmark
for energetic competition between open and compact structural
isomers (ii) it is intimately linked to catalytic activity. Therefore,
it is of significance to found out the dimensionality transition in
AunSn cluster and compare it with the dimensionality transition
of pure gold clusters. In view of above facts, it is worth to probe
the structural and electronic properties of AunSn cluster.
In the present work, we have calculated the equilibrium geom-
etries of AunSn clusters (n = 2–13). From previous reports it is
known that both neutral and anionic gold cluster (Aun) shows
2D ? 3D transition in n = 12–14 region [19–26]. The primary
objective of this study is two folds: (i) to find out the role of Sn
atom on the geometry and electronic structure of Au clusters and
(ii) to find out the size range where the quasi 2D structures of Au
clusters converts into 3D framework. With an intention to rational-
ize the similarities and differences in the structures and properties
of Aun and AunSn clusters, stability analysis was carried out using
various energy parameters: atomization energy, fragmentation
behavior, second order difference in energy, and the HOMO–LUMO
energy gap.
2. Computational details
The calculations are carried out in two steps. In the first step the
geometries and energetics of low lying isomers have been identi-
fied using the density functional theory formalism and plane wave
basis set as implemented in the Vienna ab initio Simulation Pack-
age [43] (VASP). The electron–ion interaction was described by
the all-electron projector augmented wave (PAW) method [44],
as implemented in VASP by Kresse and Joubert [45]. The spin
polarized Perdew, Burke and Ernzerhof (PBE) approximation [46]
has been used to calculate the exchange–correlation energy. It is
already known [19] that relativistic effects play key role in growth
pattern of gold cluster. The preference for planar structure by gold
clusters has been attributed to the strong relativistic effects, which
enhance the s–d hybridization by shrinking the size of the 6s orbi-
tal. Therefore, with an intent to get correct growth pattern of AunSn
cluster, the PAW pseudo-potential was generated taking scalar rel-
ativistic corrections into account and further all calculations were
carried out including the spin–orbit coupling effect as employed in
the VASP software [43,45]. The cut off energy for the plane wave
basis set was fixed at 230 eV for all calculations performed in this
study. The geometry optimization has been performed by ionic
relaxation, using a conjugate gradient method. The geometries
are considered to be converged when the forces on each ion
becomes 0.01 eV/Å or less. The total energy convergence was
tested with respect to the plane-wave basis set size and simulation
cell size, and the total energy was found to be accurate within
1 meV. Each configuration was placed inside a large cubic box of
15  15  15 Å to prevent interaction between clusters. The
Brillouin zone integration was carried out at the C point only.
In order to verify the stability of each isomer we have re-opti-
mized the geometries under the LCAO–MO scheme at the B3LYP/
lanl2dz level followed by frequency calculations. All these calcula-
tions were carried out using GAUSSIAN 03 program [47].
3. Result and discussion
3.1. Structure of Aun and AunSn cluster
To start with, we have optimized Au2, Sn2 and Au–Sn dimers.
The bond lengths of Au2, Sn2 and Au–Sn are found to be 2.52,
2.80, and 2.53 Å, respectively, and the corresponding bond energies
are 2.50, 2.59, and 3.17 eV. These values are found to be in good
agreement with the available experimental results [48]. Moreover,
the higher binding energy of the Au–Sn dimer than Au2 and Sn2 is
attributed to the iconicity of the Au–Sn bond. Further, our results
on pure Aun (n = 1–14) clusters are found to be in line with previ-
ously reported results [25,26], i.e. the lowest energy isomers of Aun
clusters are planar up to n = 13. The most stable geometries of Aun
clusters (n = 3–14) are presented in Figure S1 of the supporting
information.
Now let us turn to the ground state geometries of the AunSn
clusters. To obtain the ground state geometries of AunSn clusters,
the starting configurations were prepared in two ways: (i) by plac-
ing the Sn atom on each possible site of few low lying planar and
non-planar isomers of Aun host cluster, and (ii) by substituting
Au by Sn atom from the Aun+1 clusters. The lowest energy isomers
of AunSn clusters are shown in Figure 1. Other low lying isomers of
AunSn clusters, which are close to the ground state isomer, are pre-
sented in Figure S2 of the supporting information. The stability of
the ground state isomers has been verified by frequency analysis
and the details of this information are summarized in Table S1 of
the supporting information. In the following section we have dis-
cussed some details of the structural parameters for few low lying
isomers of AunSn clusters.
The Au2Sn trimer forms an open triangle (<Au–Sn–Au = 89°)
with interatomic separations of Au–Au and Au–Sn 3.57 and
2.55 Å, respectively. A linear chain of Au2Sn is significantly higher
in energy. The geometry of Au3Sn cluster is important as it is the
smallest size to show the onset of 3D configurations. For Au3Sn,
the lowest energy isomer is a bent rhombus with dihedral angle
of 100° and Sn atom occupies the tri coordination site. The second
higher energy isomer of Au3Sn cluster is planar rhombus
(DE = 0.44 eV). Another planar isomer of Au3Sn, where Sn atom is
placed at the center of a triangle formed by three Au atoms (D3h
symmetry), is 0.58 eV higher in energy. It is worth to mention here
that the addition of Al to Au3 cluster leads to planar D3h symmetry
[40], while addition of Si to Au3 shows capped triangle with C3v
point symmetry [41].
The interaction of Sn with four Au atoms needs special mention.
Wang and coworkers have shown that the ground state geometry
of SiAu4 is similar to SiH4, thus establishing the H-like behavior
of Au atoms [49]. In another interesting study Gagliardi et. al.
showed that in MAu4 clusters (M@Ti, Hf, etc.), Au atoms behave
like halogen atoms [50]. Therefore, it is of interest to investigate
whether the equilibrium structure of Au4Sn is a tetrahedron, sim-
ilar to SnH4 (or SnCl4). In sharp contrast, the lowest energy isomer
of the Au4Sn cluster forms square pyramidal structure with Sn
atom occupying the apex position. The Sn–Au and Au–Au bond dis-
tances are found to be 2.71 and 2.78 Å, respectively. However, a
tetrahedron configuration of Au4Sn cluster is found to be 0.77 eV
higher in energy as compared to the ground state isomer. A planar
isomer of Au4Sn cluster, which is formed by substituting one Au
from the ‘W’ shaped Au5 cluster, is 1.02 eV higher in energy.
For Au5Sn cluster, the lowest energy isomer is formed by edge
capping of the Au4Sn cluster as shown in Figure 1. A pentagonal
pyramid of Au5Sn, where Sn is placed at the fivefold coordination
site, is 0.18 eV higher in energy. The octahedral configuration of
Au5Sn cluster is 0.38 eV higher in energy. The planar isomer of
Au5Sn, obtained by substituting Au atom from the triangular Au6
 S.K. Sahoo et al. / Chemical Physics Letters 543 (2012) 121–126
Figure 1. Lowest energy structure of neutral AunSn clusters (n = 2–13) at B3LYP/lanl2dz level of theory.
cluster, is 0.69 eV higher in energy. The most stable geometry of
the Au6Sn cluster is formed by capping the pentagonal pyramidal
structure where Sn is capping the pentagon formed by five gold
atoms and the additional Au atom is at the basal plane capping
one of the edges of the pentagon as shown in Figure 1. The next
higher energy isomer (DE = 0.09 eV) follows the trend of Au5Sn
cluster, with additional Au atom connected with another edge of
the rhombus. The planar isomer of Au6Sn obtained by substituting
one Au from the Au7 cluster is 0.89 eV higher in energy. Similar to
Au5Sn and Au6Sn, larger size clusters (Au7Sn, Au8Sn, Au9Sn, Au10Sn
and Au11Sn) also favor the growth pattern via quasi–planar struc-
ture, where Sn occupies the centre position with tetra or penta
coordination. The lowest energy isomers of Au7Sn and Au8Sn form
by edge capping the square pyramidal Au5Sn unit with additional
Au atoms. The ground state geometries of the Au9Sn, Au10Sn and
Au11Sn clusters show edge capped pentagonal pyramid. It is impor-
tant to mention that for Au10Sn and Au11Sn clusters, the third and
second higher energy isomers, respectively, favor three dimen-
sional moiety.
The exception to the quasi–planar growth pattern occurs at
n = 12, where the ground state geometry adopts very different
structural moiety, suggesting a major structural change in this ser-
ies of doped clusters. The Au12Sn cluster favors flat cage like 3D
structure as the ground state isomer. Importantly, the second high-
er energy isomer also shows 3D arrangement. Both these isomers
are obtained by adding Sn atom to the second higher energy iso-
mer of Au12. For Au12Sn cluster, the quasi–planar isomer is found
to 0.45 eV higher in energy. It is worth to mention that gold anion
clusters also shows the 2D–3D transition at n = 12. In line with the
growth motif of Au12Sn, Au13Sn also prefers 3D arrangement of
atoms in the ground state. In fact, first three low lying isomers of
Au13Sn favor 3D configuration. The quasi–planar isomer is
0.63 eV higher in energy. The lowest energy isomer of the Au13Sn
can be viewed as a substitution of Au atom in the Au14 cluster. In
123
order to verify the stability and possibility of a structural transition
between quasi-2D and 3D isomers we have performed a dynamical
simulated annealing of the Au12Sn cluster, which showed the tran-
sition at 0 K. For this purpose we have heated the different initial
configurations of Au12Sn cluster at different higher temperatures
(from 300 to 1000 K), equilibrated for a long time (15 ps) and
thereafter cooled at 0 K. The results reconfirmed the higher stabil-
ity of the 3D isomer over the quasi-2D isomer as shown in Figure 2.
On the basis of the above results it is inferred that the ground
state geometries of AunSn clusters follow the pattern: for n = 3
and 4, it shows 3D arrangement, for n = 5–11, it favors quasi–
planar structures, and thereafter from n = 12 onwards 3D atomic
arrangements are favorable. To have an insight analysis of the
structural evolution of these AunSn clusters, the extent of dimen-
sionality has been measured through average dihedral angle of
the Sn atom with respect to connected Au atoms. These values
are summarized in Table 1. It is found that for small size clusters,
where the doping concentration is relatively more, and show high-
er dihedral angle. However, for larger cluster, the relative concen-
tration of Au increases, and therefore, the degree of dimensionality
reduces. This is evident from the dihedral angles presented in Table
1. In particular, for these mid-sized clusters, Sn doping induces
localized non-planarity, and the rest of the structure continues to
grow in planar mode resulting in an over-all quasi planar structure.
Now for Au12Sn, due to transition from quasi–planar to 3D config-
uration occurs, the dihedral angle of Sn increases sharply.
From our analysis of the ground state geometry of AunSn cluster
it is found that there is interplay between the strength of Au–Sn
and Au–Au interaction, which primarily decides the co-ordination
number of the Sn atom (viz. Table 1). The lowest energy structures
reorient in such a way that it can maximize the number of strong
interactions. When Sn atom is in fivefold coordination site, it forms
three strong Au–Sn bonds (within 2.9 Å bond distance) and two
relatively weak Au–Sn bonds (bond distances between 2.9 and
124 S.K. Sahoo et al. / Chemical Physics Letters 543 (2012) 121–126

Figure 2. Molecular dynamics simulation starting with the (a) SnAu12@3D (b) SnAu12@quasi-2D structure as an initial configuration: 2 ps [300 K] 15 ps [1000 K] 2 ps
[300 K].

Table 1
Structural parameters of AunSn clusters (n = 2–13) at the B3LYP/lanl2dz level. The Eb(Aun) = [(n)E(Au)  E(Aun)]/n
bond lengths are divided into two parts: (i) bond lengths within 2.9 Å (15% stretching DESn(AunSn) = [E(Aun) + E(Sn)  E(AunSn)]
w.r.t. the dimers of Sn–Au/Au–Au), and (ii) bond lengths in between 2.9 to 3.2 Å
DEAu(AunSn) = [E(Aun1Sn) + E(Au)  E(AunSn)]
(more than 15% large w.r.t. the Sn–Au/Au–Au bond lengths).
DEAu(Aun) = [E(Aun1) + E(Au)  E(Aun)]
Cluster Sn Co- No. of No. of No. of No. of Dihedral D2E(AunSn) = [E(Aun+1Sn) + E(Aun1Sn)  2E(AunSn)]
ordination Sn–Au Sn–Au Au–Au Au–Au angle
D2E(Aun) = [E(Aun+1) + E(Aun1)  2E(Aun)]
bond bond bond bond
under between under between
2.90 2.90 and 2.90 2.90 and In general the trend in the binding energy is to increase sharply
3.20 3.20 for very small clusters and then follow a plateau as the cluster size
(Å) (Å) (Å) (Å) (Å) grows with small humps or dips for specific size of clusters reflect-
SnAu3 3 3 0 2 0 49.37 ing their relative stabilities. Based on the trend in binding energy, it
SnAu4 4 4 0 0 4 52.51 is found that Sn doped Au clusters are more stable than Aun clus-
SnAu5 4 4 0 4 2 53.10 ters. This is due to higher bond strength of Au–Sn in comparison
SnAu6 5 3 2 5 2 45.43 to the Au–Au bond. An odd–even alteration in the stability pattern
SnAu7 4 4 0 6 3 50.86
is observed, which is a typical signature of monovalent clusters.
SnAu8 5 3 2 6 4 49.39
SnAu9 5 3 2 11 3 46.12 Further, it is found that the trend in the binding energy of Aun
SnAu10 5 3 2 15 2 44.46 and AunSn clusters are similar, suggesting the predominant role
SnAu11 5 3 2 14 5 47.47 of Au atoms. This is more prominent in the variation of Au attach-
SnAu12 3 3 0 11 15 59.60
ment energy and second order difference in energy (D2E) pattern.
SnAu13 4 3 1 13 16 58.87
The attachment energy of Au or Sn atom to a specific size cluster
represents its stability towards spontaneous unimolecular dissoci-
ation. The variation in the attachment energy of Au and Sn atoms
3.2 Å). On the other hand, while Sn is in tetra-co-ordination site, it with Aun clusters is shown in Figure 3b. It is clear from this figure
forms four strong Au–Sn bond of 2.9 Å and in the process it that the binding of Sn is stronger than Au. We have also compared
strengthens one of the nearby Au–Au bonds. the Au attachment energy (DEAu) between Aun and AunSn clusters.
The results show that the trend is similar in both cases. However,
3.2. Energetics and electronic structure an interesting difference in the Au attachment energy between Aun
and AunSn clusters is observed. For n < 5, it is found that the disso-
The relative stability of Aunand AunSn clusters has been verified ciation of Au from AunSn requires more energy than that from Aun
based on various energy parameters viz. average binding energies, clusters. However, this trend is reversed for n = 5 and 6. The reason
atom attachment energy, and second order difference in energy for such difference is attributed to the strong Sn–Au bond, which
(D2E) as shown in Figure 3. The above mentioned energy parame- saturates at n = 4 or 5 coordination. For n < 5, all Au atoms are in-
ters are calculated as following volved in Au–Sn bond, while in larger size clusters, this is not the
case. From the total energy calculations it is possible to identify
Eb(AunSn) = [nE(Au) + E(Sn)  E(AunSn)]/(n + 1) few stable clusters by plotting the second order difference in en-
 S.K. Sahoo et al. / Chemical Physics Letters 543 (2012) 121–126 125

Table 3
1.8 Variations in the orbital (s, p, and d) charge contributions of Au atoms in AunSn/Aun
clusters.

Clusters n AnnSn Aun

Eb (eV)

Au [a] %s %p %d p/s ratio %s %p %d p/s ratio

n
1.2 Au Sn
n 2 8.01 0.50 91.49 0.06 5.94 0.52 93.55 0.09
3 7.01 1.05 91.93 0.15 6.65 0.87 92.48 0.13
4 6.61 1.28 92.11 0.19 6.09 1.25 92.65 0.21
5 6.62 1.48 91.91 0.22 6.20 1.38 92.42 0.22
6 6.70 1.53 91.77 0.23 6.31 1.44 92.25 0.23
Sn attachement energy on Au n 7 6.67 1.59 91.73 0.24 6.33 1.55 92.12 0.24
4 8 6.78 1.65 91.56 0.24 6.38 1.52 92.10 0.24
9 6.51 1.79 91.70 0.27 6.31 1.72 91.97 0.27
3 10 6.40 1.84 91.76 0.29 6.21 1.81 91.98 0.29
Δ E(eV)

11 6.47 1.89 91.63 0.29 6.29 1.84 91.87 0.29

[b] 12 6.23 1.97 91.81 0.32 6.25 1.92 91.83 0.31
2
13 6.13 2.10 91.77 0.34 6.33 1.95 91.72 0.31

1 parameter in understanding its chemical stability. In order to

Δ E (eV)

[c] understand the relative stability of the AunSn clusters, we have

0 calculated the vertical ionization potential (VIP) and adiabatic ion-
2

-1
ization potential (AIP). The results are presented in Table 2.

-2 VIP = E(cation at optimized neutral geometry)  E(optimized

1 2 3 4 5 6 7 8 9 10 11 12 13 14
neutral)
Number of Au atom in clusters
AIP = E(optimized cation)  E(optimized neutral),
Figure 3. Energetics of Aun and AunSn clusters (n = 2–13) at B3LYP/lanl2dz level of
theory. (a) Average binding energy of Aun and AunSn clusters. (b) Au attachment Further, the extent of geometrical changes between the neutral
energy of Aun and AunSn clusters (Sn attachment energy of Aun cluster by filled and cationic AunSn clusters are estimated by the relaxation energy
triangles). (c) Second order difference D2E of Aun and AunSn clusters.
(DR = VIPAIP). While large relaxation energy of any particular
cluster indicates a significant structural change, small relaxation
energy suggests higher stability of neutral cluster. In general, small
Table 2
clusters (having 3D configuration) show relatively larger relaxation
Point group symmetry, adiabatic ionization potential (AIP), Vertical ionization energy and medium size cluster (having quasi–planar configura-
potential (VIP), relaxation energy (VIP–AIP), HOMO–LUMO gap, Mullikan charge on tion) shows small relaxation energy. In contrast to this trend,
Sn atom of AunSn clusters at B3LYP/lanl2dz level. Au12Sn and Au13Sn clusters relax more on removal of an electron.
n Symmetry AIP VIP D HLG Charge on Sn atom In this context it should be mentioned that both these clusters
have 3D atomic arrangement. The relaxed geometries of all AunSn
(eV) (eV) (R) (eV)
clusters after removal of one electronic charge have been pre-
2 C1v 8.03 8.33 0.30 2.96 +0.72
sented in Figure S3 of supporting information.
3 C2v 8.33a 7.35 – 2.82 +0.72
4 Cs 7.80 8.10 0.30 3.10 +0.78 In Table 2 we have presented the Mullikan population on Sn
5 C4v 6.48 6.65 0.17 1.65 +0.75 atom calculated at the B3LYP/lanl2dz level. It is found that charge
6 Cs 7.38 7.52 0.14 2.50 +0.87 is transferred from Sn atom to the Au atoms leading to positive
7 Cs 6.69 6.84 0.15 2.17 +0.77 charge on the Sn atom. This is due to electro-negativity difference
8 C1 7.56 7.70 0.14 2.82 +0.87
9 Cs 6.61 6.76 0.15 1.82 +0.86
between Sn (1.96) and Au (2.54) atoms. Further, it is noticed that
10 C1 7.23 7.30 0.07 2.01 +0.86 positive charge on Sn atom increases as the cluster size increases
11 C1 6.65 6.80 0.15 1.63 +0.90 and in case of Au12Sn and Au13Sn, the Sn atom has one positive
12 C1 7.07 7.28 0.21 2.45 +0.90 charge. This fact can also be inferred that in Au12Sn and Au13Sn,
13 C1 6.20 6.65 0.45 1.82 +0.92
Au12 and Au13 gold units are in anionic chemical state (i.e. Au12,
a
The higher AIP value is due to spin crossover from singlet to triplet state. Au13). Therefore, for Au12Sn and Au13Sn clusters, the Au atoms
show atomic arrangements similar to that of anionic gold clusters
[13–14,24]. In order to get further insight about the bonding nature
in these clusters, we have analyzed the electronic charge distribu-
ergy as a function of cluster size. From the expressions mentioned tion in s, p and d-orbitals and the results are listed in Table 3. The
before, it is clear that the clusters with positive D2E values are orbital distribution is obtained by expanding the wave function
more stable than their nearest neighbors. Figure 3c shows a pro- into angular momentum components within spheres of given
nounced odd–even oscillation in the D2E pattern. From this figure radius. As significant charge lies outside the spheres, this decom-
it is also clear that, both AunSn and Aun, clusters with even number position is only representative and is expected to give a qualitative
of Au atoms are more stable than odd clusters. picture of the charge distribution. From Table 3 it is clear that
It is known that the removal of electronic charge from a neutral p-orbital contribution increases with cluster size. In particular,
cluster can lead to reordering of the energy levels and thereby for the larger cluster the p-contribution was much higher. The
altering the structural symmetry and chemical stability. Thus, the HOMO–LUMO energy gap reflects the chemical stability of clusters.
extent geometrical changes on charge removal can give an account Although there are variations in the energy gap for doped and
about the stability of the parent system (viz. Table 2). Further, we undoped clusters, in general they follow similar trend with few
know that the ionization potential of a cluster is an important exceptions. For small doped clusters while Au2Sn and Au4Sn show
126 S.K. Sahoo et al. / Chemical Physics Letters 543 (2012) 121–126

higher HOMO–LUMO gap, for undoped clusters, Au6 shows the Appendix A. Supplementary data
largest gap. Interestingly, it is noticed that in the Sn doped Au clus-
ters, Au12Sn and Au13Sn have higher HOMO–LUMO gap than the Supplementary data associated with this article can be found, in
bare Au12 and Au13 clusters. the online version, at http://dx.doi.org/10.1016/j.cplett.2012.06.
055.
4. Conclusions
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Computer Division, BARC, for their kind cooperation during this
work.