Eur. Phys. J.

D (2013) 67: 11
DOI: 10.1140/epjd/e2012-30080-x THE EUROPEAN
PHYSICAL JOURNAL D
Regular Article

Structural stability and electronic properties of small gold

clusters induced by 3p electron atoms
Meng Zhanga , Su-Bin Yang, Xiao-Juan Feng, Li-Xia Zhao, Hong-Yu Zhang, and You-Hua Luob
Department of Physics, East China University of Science and Technology, Shanghai 200237, P.R. China

Received 30 January 2012 / Received in final form 22 September 2012

Published online 31 January 2013 – 
c EDP Sciences, Società Italiana di Fisica, Springer-Verlag 2013

Abstract. The geometries and electronic properties of gold clusters doped with atoms containing 3p valence
electrons (MAun ; M = Al, Si, P, S, Cl; n = 2−8) have been systematically investigated using density
functional theory (DFT) at the PBE/LANL2DZ level. A number of low-energy isomers are identified for
neutral MAun clusters. It is found that doping with different 3p impurity atoms can drastically influence
the geometrical structures, relative stabilities, electronic properties, and growth-pattern behaviors of gold
clusters, which is very different from the case of 3d transition-metal impurity doped Aun clusters. Partially
filled 3p electron impurities can stabilize Au clusters. In particular, SiAu4 cluster with Td symmetry have
been found to have highly stable geometries and electronic structures with binding energies of 2.43 eV
per atom (0.96 eV higher than pristine Au5 clusters), large HOMO-LUMO gaps (2.17 eV), and vertical
ionization potentials of 8.68 eV. Using scalar relativistic molecular dynamics at T = 300 K, we show that
the Td symmetry structure of SiAu4 is stable. The frontier molecular orbitals (HOMO and LUMO) and
the partial densities of states (PDOS) show that strong hybridization occurs between the atomic orbitals
of Si and Au atoms, resulting in strong Si-Au bonding. In addition, the vertical ionization potential, the
vertical electron affinity, and charge transfers of MAun clusters have also been analyzed. Our results are
in good agreement with available experimental data.

1 Introduction the finite temperature behavior of gas phase neutral Aun

Gold clusters constitute an interesting research field ow-
ing to their potential applications in nanoscience be-
cause of their unique catalytic, electronic, and optical
properties [1–4]. The strong relativistic effects of gold
cause the Aun clusters to exhibit unique geometrical struc-
tures that distinguish them from other metallic clusters.
Over the past two decades, pure gold clusters, Aun , in the
small-to-medium size range have been identified through
experimental [5–18] and theoretical studies [19–46]. In
2008, Gruene and co-workers determined the structures
of neutral Au7 , Au19 , and Au20 by comparing the ex-
perimental spectrum (Far-IR multiple-photon dissocia-
tion (FIR-MPD) spectroscopy in the gas phase) with the
calculated vibrational spectra for multiple isomers [18].
Huang and Wang probed the two-dimensional (2D) to
three-dimensional (3D) structural transition in gold clus-
ter anions using argon tagging [47]. Assadollahzadeh and
Schwerdtfeger performed a systematic search for minimum
energy structures of small gold clusters Aun (n = 2−20)
using density functional theory together with a relativis-
tic pseudopotential [48]. Recently, De et al. investigated
a
e-mail: mzhang@ecust.edu.cn
b
e-mail: yhluo@ecust.edu.cn
(n = 3−10) clusters using relativistic density functional
theory based molecular dynamical simulations [49].
In addition, a considerable amount of experimental
and theoretical work has been carried out on gold clusters
doped with an impurity atom to enhance the stability of
gold clusters and tailor the desired structural, magnetic,
and chemical properties for potential applications [50–69].
Most of these studies have focused on the interaction
of transition-metal (TM) atoms as impurity atoms. For
example, previous studies show that both WAu12 and
MoAu12 clusters, with perfect Ih symmetry, in which
the TM atom is located in the center of the Au12 cage,
are particularly stable in accordance with the 18-electron
rule [70,71]. These clusters are unique as they possess an
exceptionally high thermodynamic stability and a partic-
ularly large frontier orbital energy gap. Neukermans and
coworkers [72,73] have investigated the stability of cationic
gold clusters doped with a 3d TM atom, TMAu+ n , with
TM from Sc to Zn, and extended their investigations to
gold clusters doped with multiple TM atom Xm Aun clus-
ters (X = Sc, Ti, Cr, Fe; n = 1−40, m = 0−3) by means
of photo-fragmentation experiments [74]. Torres et al. in-
vestigated the atomic and electronic structure of MAu+ n
clusters (M = Sc, Ti, V, Cr, Mn, Fe, Au; n  9) using
first-principles density functional calculations in which the
Page 2 of 15 Eur. Phys. J. D (2013) 67: 11

magnetic moment shows pronounced odd-even effects as a Table 1. Calculated bond distance d (Å), vibrational fre-
function of the cluster size and results in values very sen- quency ωe (cm−1 ), average binding energies per atom Eb (eV),
sitive to the geometrical environment [75]. Later, it was vertical electron detachment energies VDE (eV), and adia-
found that all the ground-state structures of the MAu6 batic electron detachment energies ADE (eV) of the Au2 , Au−
2 ,
clusters doped with an open d-shell TM atom are planar AlAu, Au7 , Au− −
7 and SiAun (n = 2−8) clusters, optimized
structures in which the TM atom is located in the cen- with PBE/ LANL2DZ (G03).
ter of a Au6 ring. The magnetic moment of MAu6 clusters Experimental
(M = Sc-Ni) can be tuned by the incorporation of different System Property This work
[5–13,18,37,88,93]
dopant atoms, which renders these clusters perfectly ap-
d 2.51 2.47
plicable in the design of nanomagnets [76–78]. Recently,
Au2 ωe 173 191
Nhat and Nguyen performed a systematic investigation
Eb 1.15 1.15,1.18
on the electronic, geometric and energetic properties of
d 2.63 2.58
bimetallic VAun clusters with the size n going up to 14 in Au−
2
both neutral and anionic states [79]. VDE 1.98 2.01
Although a number of experimental and theoreti- d 2.39 2.34
cal studies focused on the investigations of TM atom AuAl ωe 313 333
doped small gold clusters, there have been relatively Eb 1.66 1.67
few studies on gold clusters doped with non transi- ωe1 153 165
tion elements [80–87], in particular on the interaction Au7 ωe2 172 185
of p-block elements with Au clusters. In a photoelectron ωe3 185 203
spectroscopy (PES) study of mono-silicon gold alloy clus- VDE 3.39 3.46
Au−
7
ters (SiAun , n = 2−4), it was found that the Au atoms ADE 3.35 3.40
behave like H atoms in the mixed clusters, resulting in VDE 1.82 1.75
structures analogous to silicon hydrides SiHn [88], which SiAu−
2
ADE 1.79 1.71
is also confirmed in other small Si-doped gold clusters such VDE 3.46 3.48
as Si2 Au4 , Si2 Au2 , and Si3 Au3 clusters [89,90]. The atomic SiAu−
3
ADE 3.18 3.22
and electronic structure of MAu5 (M = Na, Mg, Al, Si, VDE 2.24 2.01
P, S, and Au) and SiAun (n = 1−8) clusters have been SiAu−
4
ADE 2.17 1.98
investigated by Majumder and Kandalam using the gen- VDE 4.34 4.21
eralized gradient approximation to density functional the- SiAu−
5
ADE 3.93 4.11
ory [91,92]. Recently, Pal et al. conducted a combined pho-
VDE 2.71 2.70
toelectron spectroscopy and computational study on the SiAu−
6
ADE 2.57 2.62
structural evolution of doped gold clusters MAu− x (M = Si,
VDE 3.26 3.40
Ge, Sn; x = 58) [93]. To the best of our knowledge, system- SiAu−
7
atic investigation of neutral Aun clusters doped with 3p ADE 3.42 3.35
VDE 3.24 3.23
atoms has not been reported. In this paper, we perform SiAu−
8
a first-principles study of the impurities with 3p electron ADE 3.03 3.14
doped gold clusters (MAun ; M = Al-Cl; n = 2−8) to ex-
plore their structural and electronic properties. These 3p
impurity atoms are from the same row of the periodic ta-
Gaussian03 program package [96]. Two “f-type” polariza-
ble and their principle quantum numbers remain same,
tion functions (exponents 0.498, 1.461) were used for the
but the number of valence electrons increases.
Au atoms. The generalized gradient approximation in the
The aim of our investigation is to evaluate two most
Perdue-Burke-Ernzerhof (PBEPBE key word) functional
important features: (1) How can these impurity atoms
form was chosen [97]. To search for the lowest-energy
with different numbers of 3p valence electrons influence
structures, we used the basin-hopping global optimiza-
the ground-state properties of gold clusters? (2) How do
tion method [98,99] to produce a large number of isomers,
the geometrical structures and electronic properties of 3p
which include one-, two-, and three-dimensional configura-
atom doped Aun clusters evolve with increasing cluster
tions for further DFT optimization. Harmonic vibrational
size and what is the size-dependent growth behavior? The
frequency analysis was also undertaken at the same level of
rest of our paper is organized as follows. In Section 2, our
theory to confirm that the low-energy isomers were true
computational method is described. In Section 3, the core
minima. There is no imaginary frequency for structures
of our work is displayed. Finally, a summary is given.
presented here.
The reliability of the current computational method
2 Computational methods has been tested by calculations on Au2 , Au−
2 , AlAu, Au7 ,
Geometrical structure optimizations and frequency anal- Au− −
7 , and SiAun (n = 2−8) clusters. The results are sum-
ysis of MAun (M = Al, Si, P, S, Cl) clusters in the size marized in Table 1. All of the properties of these clus-
rang of n = 2−8 have been performed using density func- ters computed at the PBE/LANL2DZ level in our work
tional theory (DFT) method and an effective core poten- are in good agreement with available experimental data.
tial LANL2DZ basis [94,95] set as implemented in the This indicates that our methods are reliable and accurate
Eur. Phys. J. D (2013) 67: 11
enough to describe the structures and properties of MAun
clusters.
3 Results and discussions
3.1 Geometrical structure
Using the computational scheme described in Section 2,
we have explored a number of low-lying isomers of Aun
clusters surrounding a 3p impurity atom and deter-
mined the lowest-energy structures. The obtained lowest-
energy structures and some low-lying isomers are shown
in Figure 1, ordered by energy (lowest to highest). The
lowest-energy geometries of pure Aun+1 clusters from our
optimized results are in accord with the previously re-
ported results [36,42,45–49]. The calculated vibrational
frequency ωe of the bare Au7 cluster with a planar, edge-
capped triangle in our work is in good agreement with the
result of the experiment (see Tab. 1) [18].
For small clusters with less than five Au atoms, all pos-
sible structures were considered, including linear chains,
planer structures, and three-dimensional (3D) structures.
For the triatomic MAu2 cluster (M = Al, Si, P, S, Cl),
the angular isomer with C2v symmetry, i.e. where the im-
purity M atom occupies the apex position, is found to be
the most stable structure. This structure is related to the
lowest-energy structure of the Au3 cluster.
The tetraatomic AlAu3 cluster is characterized by a
highly symmetric (D3h ) planar structure with Al in the
central position. The rhombic structure is 0.55 eV higher
in energy than the Al-(3a) structure in Figure 1. SiAu3
and PAu3 clusters have the same ground-state structures
with C3v symmetry, in which the Si or P atom is on the
top of the Au3 equilateral triangle. A Y-shaped structure
is the lowest-energy structure for SAu3 . This configura-
tion is similar to the meta-stable structure of bare Au4 .
Finally, a C2v rhombic form is the most stable structures
for ClAu3 , which is similar to the lowest-energy structure
of Au4 .
For Au5 cluster, the most stable structure is an isosce-
les trapezoid. The lowest-energy configuration of the
AlAu4 with Cs symmetry can be obtained by adding one
Au atom to the Y-shaped structure. The planar, M-shaped
structure is 0.21 eV higher in energy than its lowest-energy
configuration. We find that the lowest-energy structure
of SiAu4 is a perfect Td tetrahedron. Interestingly, SiAu4
has the highest symmetry among all the MAun clusters.
The square pyramidal arrangement (Si-(4c) in Fig. 1) with
the Si atom at the top is 0.10 eV higher in energy. For
PAu4 clusters with a rhombic structure capped by one
Au atom, the isomer P-(4a) is the most stable structure.
Similar to the configuration of the ground-state Au5 clus-
ter, the trapezoidal isomer is the most-stable structure of
SAu4 and ClAu4 clusters, as long as the S or Cl atom is
substituted for a Au atom at the apex of the Au5 frame.
The ground-state structures of MAu5 clusters can all
be considered as arising from the addition of one gold
atom to the ground-state structures of MAu4 . The lowest-
energy isomer of the AlAu5 cluster can be viewed as
Page 3 of 15
adding the fifth Au atom connected to the Al at the top
of the AlAu4 square pyramid (see Fig. 1 Al-(4c)); this
isomer adopts the C4v point group symmetry. The next
isomer is 0.32 eV higher in energy than this structure.
For SiAu5 clusters, the lowest-energy isomer is a capped
tetrahedron with C3v symmetry, which can be obtained by
capping the fifth Au atom on the meta-stable SiAu4 clus-
ter. The side-capped square pyramid structure with Cs
symmetry and the top-capped square pyramid structure
with C4v symmetry are 0.01 eV and 0.08 eV higher in
energy than the lowest-energy isomer, respectively. In the
case of PAu5 clusters, the most stable structure is P-(5a)
in Figure 1, which can be obtained from P-(4a) by adding
one Au atom. As we can see from Figure 1, AlAu5 , SiAu5 ,
and PAu5 have a tendency to prefer 3D structural mo-
tifs over planar geometries. With regard to the SAu5 and
ClAu5 clusters, the lowest-energy isomers form the same
planar triangular structure. They can be obtained by re-
placing one Au atom with an impurity M atom at the apex
site of the triangle of the ground-state Au6 cluster. Our
results for the atomic structure of MAu5 (M=Al, Si, S)
clusters are in agreement with the results of Majumder
and Kandalam [92]. The ground-state structure of PAu5
in Majumder’s result, which is similar to the structure of
P-(5d) in Figure 1, is 0.53 eV higher in energy than the
P-(5a) in our optimization.
The ground-state structure of AlAu6 is a 3D quadri-
lateral bipyramid with C4v symmetry. This structure can
be directly obtained from AlAu5 . The meta-stable isomer
with Cs point group symmetry is found very close in en-
ergy (ΔE = 0.02 eV) to the ground-state structure. For
SiAu6 clusters, a nonplanar geometry with the Si atom
rising to an upright position above the six Au atoms is
the global minimum. This similar structure has been pre-
viously reported by Majumder using the generalized gra-
dient approximation to density functional theory imple-
mented in VASP [91]. The structure of SAu6 follows the
SAu5 growth motif by capping a Au atom as Figure 1
shows. For PAu6 and ClAu6 , the lowest-energy isomers
are a planar structure, which is an edge-bridged triangle
with the M atom located at one apex, a distortion away
from the ground-state geometric structure of pure Au7 .
It should be mentioned that previous experimental and
theoretical studies showed that the ground-state struc-
ture of MAu6 (M = transition-metal atoms) remains pla-
nar after doping with TM elements, which consists of a
six-membered ring of gold atoms with the dopant at its
center with high symmetry [76–78]. The structures of 3p
atom doped Au6 clusters form various disordered geome-
tries with low symmetry. From the above discussions, it is
obvious that the partially filled 3d shell of the TM atoms
and 3p shell of Al, Si, S, P, and Cl atoms play completely
different roles in determining the structures and properties
of MAun clusters.
The number of isomers for MAun increases as suc-
cessive Au atoms are added. The most stable struc-
ture for AlAu7 is a 3D configuration with Cs symme-
try, which can be obtained by directly adding one Au
atom to the most stable structure of the SiAu6 cluster.
Page 4 of 15 Eur. Phys. J. D (2013) 67: 11

n=2

Al-(2a) ΔE = 0 eV Al-(2b) ΔE = 0.191 eV Si-(2a) ΔE = 0 eV Si-(2b) ΔE = 1.61 eV

P-(2a) ΔE = 0 eV P-(2b) ΔE = 1.365 eV S-(2a) ΔE = 0 eV

Cl-(2a) ΔE = 0 eV Cl-(2b) ΔE = 0.44 eV

n=3

Au-(3a) ΔE = 0 eV Au-(3b) ΔE = 0.01 eV

ΔE = 0 eV Al-(3b) ΔE = 0.55 eV Si-(3a) ΔE = 0 eV Si-(3b) ΔE = 0.11 eV

ΔE = 0 eV P-(3b) ΔE = 1.67 eV S-(3a) ΔE = 0 eV S-(3b) ΔE = 0.07 eV

ΔE = 0 eV Cl-(3b) ΔE = 0.34 eV

Fig. 1. (Color online) Lowest-energy structures and low-lying isomers with relative energies (in eV) of MAun (M = Al, Si, P,
S, Cl; n = 2−8) clusters, optimized with PBE/LANL2DZ (G03). M atom is represented by a colored sphere. See Table 2 for
corresponding energetic and structural information.
Eur. Phys. J. D (2013) 67: 11 Page 5 of 15

n=4

Al-(4a) ΔE = 0 eV Al-(4b) ΔE = 0.21 eV Al-(4c) ΔE = 0.25 eV Al-(4d) ΔE = 0.46 eV

Si-(4a) ΔE = 0 eV Si-(4b) ΔE = 0.09 eV Si-(4c) ΔE = 0.10 eV

P-(4a) ΔE = 0 eV P-(4b) ΔE = 0.18 eV P-(4c) ΔE = 0.26 eV

S-(4a) ΔE = 0 eV S-(4b) ΔE = 0.27 eV S-(4c) ΔE = 0.33 eV S-(4d) ΔE = 1.08 eV

Cl-(4a) ΔE = 0 eV Cl-(4b) ΔE = 0.23 eV

Fig. 1. Continued.

The second-lowest-energy isomer with 0.08 eV higher en-
ergy is a 2D geometry and has a large structural distor-
tion relative to the corresponding pure Au8 clusters. For
SiAu7 , our calculations predict a quasi-planar Cs struc-
ture as the global minimum, which can be viewed as built
upon an isomer of the C4v SiAu4 based structure Si-(4c)
in Figure 1. This Cs isomer of neutral SiAu7 is similar to
the anionic SiAu− 7 reported by Pal et al. [93] through a
joint experiment and higher-level MP4 (SDQ) calculation.
By comparing the structures of different charge states be-
tween the neutral SiAun clusters in this work and the
anionic SiAun clusters in Wang’s group [88,93], more in-
sight may be provided into the effect of the localized co-
valent bonding on the Si atom with small gold clusters.
The ground-state of PAu7 clusters is a Cs isomer obtained
by adding one Au atom to the meta-stable structure of
Page 6 of 15 Eur. Phys. J. D (2013) 67: 11

n=5

Al-(5a) ΔE = 0 eV Al-(5b) ΔE = 0.32 eV Al-(5c) ΔE = 0.48 eV Al-(5d) ΔE = 0.62 eV

Si-(5a) ΔE = 0 eV Si-(5b) ΔE = 0.01 eV Si-(5c) ΔE = 0.08 eV Si-(5d) ΔE = 0.09 eV

P-(5a) ΔE = 0 eV P-(5b) ΔE = 0.497 eV P-(5c) ΔE = 0.498 eV P-(5d) ΔE = 0.53 eV

S-(5a) ΔE = 0 eV S-(5b) ΔE = 0.89 eV S-(5c) ΔE = 0.92 eV S-(5d) ΔE = 1.58 eV

Cl-(5a) ΔE = 0 eV Cl-(5b) ΔE = 0.87 eV Cl-(5c) ΔE = 1.94 eV

Fig. 1. Continued.

PAu6 as shown in Figure 1. The SAu7 and ClAu7 have
the same ground-state C2v structure, which can be ob-
tained as replacing one Au atom by a S or Cl atom at one
apex of the Au8 cluster.
With regard to AlAu8 clusters, many isomers have
been found and the lowest-energy structure is a quasi-
planar structure with a Al atom replacing the Au atom in
the centre of the hexagon in the corresponding pure Au9
isomer. The 2D planar structure is 0.05 eV higher in en-
ergy. SiAu8 evidently favors 3D structures, and the isomer
with C1 symmetry is found to be the ground state. The
second-lowest-energy structure, obtained by attaching one
more Au atom to the ground-state isomer of SiAu7 , is
found to be 0.02 eV higher in energy. The most stable
structure of the PAu8 cluster we obtained is P-(8a) in
Figure 1, which is related to PAu7 by adding one more
Eur. Phys. J. D (2013) 67: 11 Page 7 of 15

n=6

Al-(6a) ΔE = 0eV Al-(6b) ΔE = 0.02 eV Al-(6c) ΔE = 0.18 eV Al-(6d) ΔE = 0.29 eV

Si-(6a) ΔE = 0 eV Si-(6b) ΔE = 0.03 eV Si-(6c) ΔE = 0.32 eV Si-(6d) ΔE = 0.35 eV

P-(6a) ΔE = 0 eV P-(6b) ΔE = 0.18 eV P-(6c) ΔE = 0.61 eV P-(6d) ΔE = 0.68 eV

S-(6a) ΔE = 0 eV S-(6b) ΔE = 0.27 eV S-(6c) ΔE = 0.72 eV S-(6d) ΔE = 1.23 eV

Cl-(6a) ΔE = 0 eV Cl-(6b) ΔE = 0.08 eV Cl-(6c) ΔE = 0.21 eV Cl-(6d) ΔE = 0.32 eV

Fig. 1. Continued.
Page 8 of 15 Eur. Phys. J. D (2013) 67: 11

n=7

Al-(7a) ΔE = 0 eV Al-(7b) ΔE = 0.08 eV Al-(7c) ΔE = 0.11 eV Al-(7d) ΔE = 0.4eV

Si-(7a) ΔE = 0 eV Si-(7b) ΔE = 0.30 eV Si-(7c) ΔE = 0.36 eV Si-(7d) ΔE = 0.39 eV

P-(7a) ΔE = 0 eV P-(7b) ΔE = 0.28eV P-(7c) ΔE = 0.40eV P-(7d) ΔE = 0.64 eV

S-(7a) ΔE = 0 eV S-(7b) ΔE = 0.28 eV S-(7c) ΔE = 0.38 eV S-(7d) ΔE = 0.66 eV

Cl-(7a) ΔE = 0 eV Cl-(7b) ΔE = 0.25 eV Cl-(7c) ΔE = 0.62 eV Cl-(7d) ΔE = 0.71 eV

Fig. 1. Continued.
Eur. Phys. J. D (2013) 67: 11 Page 9 of 15

n=8

Al-(8a) ΔE = 0 eV Al-(8b) ΔE = 0.05 eV Al-(8c) ΔE = 0.06eV Al-(8d) E=0.07eV Al-(8e) E=0.22eV

Si-(8a) ΔE = 0 eV Si-(8b) ΔE = 0.02 eV Si-(8c) ΔE = 0.36 eV Si-(8d) ΔE = 0.50 eV Si-(8e) ΔE = 0.57 eV

P-(8a) ΔE = 0 eV P-(8b) ΔE = 0.05 eV P-(8c) ΔE = 0.13 eV P-(8d) ΔE = 0.16 eV P-(8e) ΔE = 0.20 eV

S-(8a) ΔE = 0 eV S-(8b) ΔE = 035 eV S-(8c) ΔE = 0.46 eV S-(8d) ΔE = 0.62 eV S-(8e) ΔE = 1.13 eV

Cl-(8a) ΔE = 0 eV Cl-(8b) ΔE = 0.11 eV Cl-(8c) ΔE = 0.11 eV Cl-(8d) ΔE = 0.25 eV Cl-(8e) ΔE = 0.29 eV

Fig. 1. Continued.

Au atom. For SAu8 , the V-shaped structure with Cs sym-
metry is most stable among all the 3D structures. As in
the previous cases, the ground state of ClAu8 is found to
have similar structure to Au9 by replacing one Au atom
with a Cl atom in the Au9 cluster. From the above dis-
cussion, it is obvious that the ground-state structures of
ClAun clusters follow the same pattern: a Au atom in pure
Aun+1 clusters is substituted with a Cl atom.
3.2 Relative stabilities
To further analyze the stability of clusters, we calculated
the average binding energy (Eb ) per atom of MAun and
Aun+1 clusters, which is defined as the difference between
the energy sum of all the free atoms constituting the clus-
ter and the total energy of the cluster using the following
Page 10 of 15 Eur. Phys. J. D (2013) 67: 11

Table 2. Symmetry type, shortest M-Au bond length RAu−M (Å), average binding energy per atom Eb (eV), HOMO-LUMO
gaps Egap (eV), vertical ionization potential VIP (eV), vertical electron affinity VEA (eV) and atomic charges (eV) at the
M atom of MAun (M = Al, Si, P, S, Cl; n = 2−8) clusters for the lowest-energy structures, optimized with PBE/LANL2DZ
(G03).
Cluster Symmetry RAu−M Eb VIPs VEAs Egap Charges
Au3 C2v 1.12 8.62 3.51 0.31
Au4 D2h 1.43 8.07 2.56 1.01
Au5 Cs 1.57 7.62 3.14 0.30
Au6 C3v 1.80 8.52 2.16 1.72
Au7 Cs 1.75 7.29 3.30 0.24
Au8 D4h 1.87 8.03 2.82 1.61
Au9 C2v 1.85 7.15 3.49 0.20
AlAu2 C2v 2.43 1.75 7.33 2.09 0.80 0.44
SiAu2 C2v 2.37 2.41 8.55 1.95 1.72 0.17
PAu2 C2v 2.36 2.21 8.49 1.94 1.21 –0.17
SAu2 C2v 2.36 2.14 8.52 2.00 1.22 –0.52
ClAu2 C2v 2.66 1.21 8.58 2.63 0.55 –0.41
AlAu3 D3h 2.41 2.03 8.99 1.81 2.52 0.29
SiAu3 C3v 2.44 2.31 7.82 2.80 0.37 –0.13
PAu3 C3v 2.37 2.30 8.85 1.60 2.46 –0.32
SAu3 C2v 2.34 1.99 9.63 2.98 0.37 –0.30
ClAu3 C2v 2.67 1.55 8.89 2.36 1.69 –0.50
AlAu4 Cs 2.40 1.92 7.28 2.70 0.34 –0.06
SiAu4 Td 2.34 2.43 8.68 2.01 2.17 –0.32
PAu4 Cs 2.37 2.10 7.42 2.65 0.37 –0.35
SAu4 Cs 2.40 2.12 8.05 2.99 0.35 –0.58
ClAu4 Cs 2.52 1.63 8.09 3.31 0.33 –0.46
AlAu5 C4v 2.39 2.05 8.04 1.72 1.93 –0.42
SiAu5 C3v 2.37 2.24 7.07 2.87 0.26 –0.54
PAu5 C1 2.37 2.14 7.88 2.62 1.12 –0.37
SAu5 C2v 2.45 2.11 10.0 3.47 0.36 –0.37
ClAu5 C2v 2.57 1.87 8.80 2.27 2.20 –0.47
AlAu6 C4v 2.43 1.97 7.08 2.98 0.25 –0.46
SiAu6 Cs 2.51 2.28 7.74 2.20 1.71 –0.32
PAu6 Cs 2.41 2.15 7.82 3.31 0.45 –0.34
SAu6 C1 2.40 2.19 8.10 2.47 1.44 –0.58
ClAu6 Cs 2.55 1.82 7.77 3.52 0.25 –0.46
AlAu7 Cs 2.40 2.07 7.43 2.18 1.41 –0.46
SiAu7 Cs 2.51 2.25 7.15 3.24 0.24 –0.26
PAu7 Cs 2.41 2.21 7.88 2.35 1.80 –0.37
SAu7 C2v 2.41 2.18 9.28 3.61 0.51 –0.38
ClAu7 C2v 2.52 1.94 8.39 2.81 1.77 –0.46
AlAu8 Cs 2.55 2.04 6.78 3.09 0.30 –0.27
SiAu8 C1 2.41 2.28 7.66 2.40 1.76 –0.37
PAu8 C1 2.40 2.16 7.03 3.02 0.30 –0.40
SAu8 Cs 2.49 2.25 8.15 2.52 1.72 –0.65
ClAu8 Cs 2.54 1.90 7.35 3.56 0.20 –0.46

formula: than those for the corresponding pure Aun+1 clusters.

Eb (MAun ) = [nE (Au) + E (M) − E (MAun )] / (n + 1) .
(1)
    
Eb Aun+1 = (n + 1) E (Au) − E Aun+1 / (n + 1).
(2)
Table 2 gives various structural and energetic character-
istics for the lowest-energy structures of MAun clusters
and the corresponding bare Aun+1 clusters (n = 2−8). It
can be seen from Table 2 that the binding energies per
atom for the ground-state of MAun clusters are higher
This indicates that Aun clusters doped with a partially
filled p shell atom are more stable than the pure Aun+1
cluster. Figure 2 shows that the binding energies of differ-
ent 3p impurity atom doped Aun clusters can be widely
different due to the different nature of the bonding be-
tween the dopant atom and the gold clusters. SiAun clus-
ters always have the largest binding energies among those
MAun clusters of the same size. Consequently, the doping
with Si atoms obviously improves the stability of Aun+1
clusters. In particular, the SiAu4 cluster is found to have
the largest Eb (2.43 eV) among all the clusters, which
is 0.86 eV higher than that of the pure Au5 .
Eur. Phys. J. D (2013) 67: 11
Fig. 2. Average binding energy (Eb ) per atom of MAun
(M = Al, Si, P, S, Cl) and bare Aun+1 clusters (n = 2−8)
for the lowest-energy structures.
Fig. 3. Second-order differences in binding energy (Δ2 E ) of
MAun (M = Al, Si, P, S, Cl) and bare Aun+1 clusters (n =
2−8) for the lowest-energy structures.
The second-order difference of the cluster’s binding en-
ergy is a sensitive quantity, reflecting the relative stability
of a cluster compared to its neighbors. It can be defined
as follows:
Δ2 En = [Eb (n + 1) + Eb (n − 1) − 2Eb (n)] . (3)
Figure 3 shows the second-order differences in binding en-
ergy (Δ2 E) of the MAun and bare Aun+1 clusters for the
lowest-energy structures as a function of the number of
Au atoms. The Δ2 E of these clusters exhibit obvious odd-
even oscillations. We can clearly find the same tendency of
odd-even oscillations of AlAun , PAun , ClAun , and Aun+1
clusters. It is interesting to see that the MAun (M=Al, P,
Cl) clusters with odd numbers of gold atoms are relatively
stable compared to the neighboring even-numbered gold
atom clusters. Also, the Δ2 E oscillations of SiAun and
SAun clusters are out of step with other clusters. In these
two clusters, the impurity atoms Si and S have even num-
bers of 3p electrons. The odd-even electron pairing effect
Page 11 of 15
in the relative stability of 3p atom doped Aun clusters are
reflected in the sharp oscillations of the Δ2 E values.
The energy gap (Egap ) between the highest occupied
molecular orbital (HOMO) and the lowest unoccupied
molecular orbital (LUMO), the vertical ionization poten-
tial (VIP) and vertical electron affinity (VEA) are useful
and important characteristics which reflect the electronic
properties of small clusters. The calculated results of Egap ,
VIPs, and VEAs of the most stable MAun and Aun+1
clusters are also given in Table 2 and plotted in Figure 4.
There are clear odd-even oscillations in Figure 4. It can
be seen from Figure 4 that Egap for MAun (M = Al, P,
Cl) clusters with odd numbers of gold atoms is larger
than that of the neighbors with even numbers of gold
atoms, while Egap for SiAun and SAun clusters with
even numbers of gold atoms is larger than for their odd-
numbered neighbors. It is currently believed that large
gaps and high VIPs are good indicators of the stabil-
ity of clusters. As seen from Figure 4, AlAu3 , SiAu2 ,
SiAu4 , PAu3 , ClAu3 , and ClAu5 have large Egap and high
VIPs, so these clusters possess higher kinetic stability than
other clusters. It should be mentioned that the study
of PES spectra of SiAu− n (n = 2−4) clusters by Kiran
et al. suggested that neutral SiAu4 has a large HOMO–
LUMO gap (2.36 eV), thus indicating an extremely chem-
ically stable molecule [88]. Our calculated result show that
the gap for SiAu4 has the largest value (2.17 eV) among
the series of Si doped Aun clusters, which is in accor-
dance with the experimental results of Kiran et al. [88].
The large HOMO–LUMO gap of the SiAu4 cluster may
be attributed to the closed eight-electron shell and highly
symmetrical geometry.
Previous studies have shown that some interac-
tions correlate with the electronegativity of the main
atom [100,101]. Figure 5 gives the natural bond orbital
NBO charge (a.u.) of the M atom in the ground-state
MAun clusters calculated at the PBE/LANL2DZ level.
As seen from Figure 5, for SiAu2 , AlAu2 , and AlAu3 clus-
ters, a small amount of charge is transferred from Si and
Al atoms to the host Au atoms, suggesting that the Au
atom has a larger electronegativity than Si and Al in these
clusters. On the other hand, for other clusters the charge
transfer occurs in the reverse direction. Au is likely to lose
its valence electrons and the 3p impurity atom has a nega-
tive charge. The charge transfer has odd-even oscillations
as the SAun cluster size increases.
Based on the above discussion, we note that SiAu4 is
prominent as an isolated compound with a high binding
energy per atom of 2.43 eV, a big energy gap of 2.17 eV,
and a large vertical ionization potential of 8.68 eV, thus
indicating that SiAu4 is an extremely structurally and
chemically stable molecule. The thermodynamic stability
of the ground state structure of SiAu4 is also confirmed
by using molecular dynamics simulation at T = 300 K.
Our molecular dynamics simulation lasted for 4 ps and the
structure was monitored during this time. Each step in the
molecular dynamics simulation was 0.4 fs long. We show
that the Td symmetry structure of SiAu4 is stable. It can
be clearly seen from Figure 6 that the relative potential
Page 12 of 15 Eur. Phys. J. D (2013) 67: 11

Fig. 4. HOMO-LUMO gaps Egap (eV), vertical ionization potential VIPs (eV), and vertical electron affinity VEAs (eV) of
MAun (M = Al, Si, P, S, Cl) and bare Aun+1 clusters (n = 2−8) for the lowest-energy structures.

Fig. 5. NBO charge (a.u.) of the M atom in the lowest-energy Fig. 6. Relative potential energy of the SiAu4 structure dur-
MAun clusters (M = Al, Si, P, S, Cl; n = 2−8). ing 4 ps of molecular dynamics simulation.
Eur. Phys. J. D (2013) 67: 11 Page 13 of 15

HOMO LUMO

Fig. 7. HOMO and LUMO orbitals for the lowest-energy

SiAu4 clusters. Red indicates that the wave function has a
positive sign, while green indicates a negative sign.

energy remains unchanged within the time of the dynamic

simulation. To perform a detailed analysis of molecular
orbitals of SiAu4 , we depict the HOMO and LUMO of
SiAu4 in Figure 7. There are obvious hybridizations be-
tween the s − d orbitals in Au atoms and the p orbitals
of the impurity Si in SiAu4 clusters. The LUMO shows
four similar Si-Au bonding orbitals in SiAu4 and brings
out sp 3 hybridization in silicon and s − d hybridization in
gold. Molecular orbital analyses show that Si and Au form
strong single covalent bonds in the closed eight-electron
shell SiAu4 , which is responsible for the high stability of
the SiAu4 molecules. This conclusion is consistent with
the previous investigation for a series of SiAun (n = 2−4)
clusters by Kiran et al. [88]. They revealed that the chem-
ical bonding in these SiAun are similar to the correspond-
ing SiHn molecules, suggesting that Au behaves like a H
in the auride clusters. To further explore the hybridiza-
tion between Si and Au atoms in SiAu4 clusters, we plot
the partial densities of states (PDOS) of SiAu4 cluster in
Figure 8. The PDOS is obtained by Gaussian extension
applied to the eigenvalues and the broadening width pa- Fig. 8. Partial density of states (PDOS) of s, p, and d or-
rameter is chosen to be 0.1 eV. Figure 7 shows that gold bital for (a) Si atom in SiAu4 clusters, (b) Au atoms in SiAu4
atoms have strong s − d hybridization due to the strong clusters, (c) SiAu4 clusters. Spin up (positive) and spin-down
relativistic effect, and there is obviously strong hybridiza- (negative) densities are given in each case. The dashed lines
tion between the atomic orbitals of the Si atom and Au indicate the location of the HOMO level.
atom. That is the reason why the SiAu4 cluster is more
stable than other clusters.
from transition-metal atom doped Aun clusters, in which
the gold cluster retains its two-dimensional geometrical
4 Conclusion shape up to size n = 8. Al and Si prefer to occupy
the center position in the most stable MAun clusters,
We have carried out a first-principles investigation with while P and S favor the side position. ClAun clusters can
density functional theory at the PBE/LANL2DZ level to be viewed as a Cl atom replacing the apex Au atom of the
systematically study the geometrical structures, growth- Aun+1 clusters. The results indicate that the geometries of
pattern behaviors, relative stabilities, and electronic prop- impurity-atom-doped Aun clusters can be widely different
erties of the gold clusters doped with 3p electron atoms: because of the nature of the bonding between the different
MAun clusters (M = Al, Si, P, S, Cl; n = 2−8). In con- dopant atoms and the gold cluster. The relative stabili-
trast to the pure gold clusters, M-atom-substituted Aun+1 ties of MAun clusters for the ground-state structures have
clusters, as well as Au-capped MAun−1 clusters, are dom- been analysed based on the binding energies per atom and
inant growth patterns for the equilibrium structures of second-order difference in binding energy, which shows os-
MAun clusters. As the number of Au atoms increases, cillations due to the odd-even electron pairing effect. It
the clusters doped by impurities with different num- is found that partially filled 3p electron impurities can
bers of p electrons have various planar, quasi-planar, and enhance the stabilities of gold clusters. In particular, the
three-dimensional geometries. This is strikingly different SiAu4 cluster with Td symmetry has been found to show
Page 14 of 15
extraordinary stability. Moreover, SiAu4 also exhibits ki-
netic stability with a big HOMO–LUMO gap of 2.17 eV
and a large VIP of 8.68 eV, which is in agreement with
the available experiment. SiAu4 can be seen as a build-
ing block for the novel material in microelectronics due
to its high relative stability and strong chemical stabil-
ity. The high stability of SiAu4 may be attributed to the
closed eight-electron shell and obviously strong hybridiza-
tion between the atomic orbitals of the Si and Au atoms.
This work is financially supported partly by the National
Natural Science Foundation of China (Grant No. 11204079)
and by the Natural Science Foundation of Shanghai (Grant
No. 12ZR1407000).
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