Structural and electronic properties of

Aun−xPtx (n = 2–14; x ⩽ n) clusters: The density

functional theory investigation
Cite as: AIP Advances 4, 037107 (2014); https://doi.org/10.1063/1.4869019
Submitted: 17 November 2013 . Accepted: 06 March 2014 . Published Online: 17 March 2014

H. K. Yuan, A. L. Kuang, C. L. Tian, and H. Chen

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Paper published as part of the special topic on Chemical Physics, Energy, Fluids and Plasmas, Materials Science and
Mathematical Physics

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AIP Advances 4, 037107 (2014); https://doi.org/10.1063/1.4869019 4, 037107

© 2014 Author(s).
 AIP ADVANCES 4, 037107 (2014)

Structural and electronic properties of Aun−x Ptx (n = 2–14;

x ≤ n) clusters: The density functional theory investigation
H. K. Yuan, A. L. Kuang, C. L. Tian, and H. Chena
School of Physical Science and Technology, Southwest University, Chongqing,
400715, People’s Republic of China
(Received 17 November 2013; accepted 6 March 2014; published online 17 March 2014)

The structural evolutions and electronic properties of bimetallic Aun–x Ptx (n = 2–14;
x ≤ n) clusters are investigated by using the density functional theory (DFT) with the
generalized gradient approximation (GGA). The monatomic doping Aun–1 Pt clusters
are emphasized and compared with the corresponding pristine Aun clusters. The
results reveal that the planar configurations are favored for both Aun–1 Pt and Aun
clusters with size up to n = 13, and the former often employ the substitution patterns
based on the structures of the latter. The most stable clusters are Au6 and Au6 Pt,
which adopt regular planar triangle (D3h ) and hexagon-ring (D6h ) structures and can
be regarded as the preferential building units in designing large clusters. For Pt-rich
bimetallic clusters, their structures can be obtained from the substitution of Pt atoms
by Au atoms from the Ptn structures, where Pt atoms assemble together and occupy
the center yet Au atoms prefer the apex positions showing a segregation effect. With
respect to pristine Au clusters, Aun Pt clusters exhibit somewhat weaker and less
pronounced odd-even oscillations in the highest occupied and lowest unoccupied
molecular-orbital gaps (HOMO-LUMO gap), electron affinity (EA), and ionization
potential (IP) due to the partially released electron pairing effect. The analyses of
electronic structure indicate that Pt atoms in AuPt clusters would delocalize their
one 6s and one 5d electrons to contribute the electronic shell closure. The sp-d
hybridizations as well as the d-d interactions between the host Au and dopant Pt
atoms result in the enhanced stabilities of AuPt clusters.  C 2014 Author(s). All

article content, except where otherwise noted, is licensed under a Creative Commons
Attribution 3.0 Unported License. [http://dx.doi.org/10.1063/1.4869019]

I. INTRODUCTION
In the past few decades, small Au clusters have attracted considerable interests in the context of
scientific issues as well as the potential applications in biomedicine, catalytic industry, and colloidal
chemistry.1–3 The interests mainly stem from their specific electronic and structural characters:
they not only show the pronounced electronic shell effect which can indicate the applicability of
jellium model in metal clusters,4–6 but also adopt the planar structures which can provide large
surfaces for reactivity (or cage-like structures which can coat a center-target for biocompatibility,
functionality, and stability).7–10 Up to now, abundant experimental measurements in combination
with theoretical calculations have commonly confirmed that the crossover size from two dimensional
(2D) to three dimensional (3D) is around large sizes of n = 12–14 for Au clusters (or to cage-like
structures around n = 15–16).8–20 It has been determined that the stabilities of Au clusters are mainly
determined by their electronic shell closure, and the occurrence of 2D structure at such amazing large
size is correlated with the strong hybridizations of atomic 5d and 6s orbitals due to the relativistic
effects.21, 22

a Corresponding author E-mail: chenh@swu.edu.cn

2158-3226/2014/4(3)/037107/19 4, 037107-1 
C Author(s) 2014
037107-2 Yuan et al. AIP Advances 4, 037107 (2014)

Inspired by above intriguing findings, the alternative investigations focused on how the dopant
atoms improve the properties of small Au clusters, because the effect of impurity atoms would be
particularly pronounced as a cluster is composed of small number of atoms. What remained to be
determined is which dopant atoms would be better for imparting Au clusters within the desired
properties. Since the stabilities of pristine Au clusters are mainly determined by the electronic shell
closure that is contributed from the delocalization s electrons,4–6 on general grounds, the dopant
atoms within delocalization s or p electrons should be explored. On the one hand, different atoms
(e.g., alkali metal,23, 24 simple metal,23–25 transition metal,26–34 or nonmetal35–37 ) have been doped
into small Aun (n ≤ 10) clusters to tune their geometrical structures, electronic properties, and
magnetic magnetic moments. On the other hand, the endohedral doping Aun (n = 12–20) buckyballs
with different atoms (e.g., alkali metal,38 transition metal,34, 39–45 rare earth,46 or nonmetal47 ) have
been extensively investigated to obtain the highly stable cage-like structures with strong magnetism
or catalytic activity. Generally, above dopant atoms can actually stabilize some cage-like structures of
middle size Au clusters, however, they often badly distort the 2D structures of small Au clusters.23–36
Alternately, doping coinage-metal atoms Cu or Ag can be viewed as a prior venue to adjust the
electromagnetic properties of Au clusters without distorting their attractive 2D structures, owing to
their similar valence electronic configurations with Au atom (nd10 (n + 1)s1 , with n = 3, 4, and 5
for Cu, Ag, and Au atom). With the help of photoelectron spectroscopy measurements and DFT
calculations, it was revealed that the single substitution of Au atom by Ag or Cu atom does not
significantly change the electronic shell closures of Au clusters.48–57 Nevertheless, they often shift
the 2D → 3D structural transition to a smaller size (n < 11), mainly due to a weaker relativistic
effect of Ag and Cu atom compared with Au atom.56, 57
As gold’s neighbor, Pt atom (5d9 6s1 ) possesses not only one s valence electron as Au atom has
but also strong relativistic effect comparable to Au atom. More interestingly, appearance of 2D →
3D transition in Pt clusters has been predicted to be at large size comparable to Au clusters.58–62
Consequently, one assumes that the Pt dopants can enhance the s-d hybridization and d-d interaction
between Pt and Au atoms, which may enhance the structural stability and enlarge the transition size in
AuPt clusters. Moreover, if unfilled d orbitals of Pt atoms preserve their atomic character and maintain
localization in clusters, possible magnetic moments of AuPt clusters induced by Pt atoms would meet
the magnetization requirement of the applications.60 However, the accurate ab inital investigation
on small bimetallic AuPt clusters is relatively scarce, only limited in sizes not exceeding 7 atoms
that is not large enough to assess the transition size.63–71 A majority of these studies were focused
on the catalytic actions of CO or H2 rather than structural evolutions and electronic properties.66–71
From the side of applications, it has been observed that the catalytic activities of Au clusters can be
significantly improved by Pt dopants.66–72 Understanding the geometrical and electronic structures
of small AuPt clusters is of critical importance to provide insight into the mechanisms of their
catalytic effects.
With these views in mind, we carry out a systematic study on atomic and electronic structures
of Aun–x Ptx (n = 2–14; x ≤ n) clusters. One wonders whether bimetallic AuPt clusters adopt the
structures of pure Au clusters of the same size, or that of pure Pt clusters. If a distinctive structure
is preferred, then, what is the role of composition in determining the stable structures of AuPt
clusters of the same size? Also, relative stabilities, geometric and electronic properties, as well as
the magnetism are discussed. We predict that the overall size-dependent properties of AuPt clusters
are different from that of AuX (X = Ag, Cu, and Pd) clusters.

II. COMPUTATIONS
A. Methods used
All calculations are based on the DFT method within the framework of generalized-gradient ap-
proximation (GGA) in the form of Perdew, Burke, and Ernzerhof (PBE)73 exchange-correlation
potential, which is provided by the DMol3 program.74 The DFT semi-core pseudo-potential
(DSPP)75 and the double numerical basis sets with the p-polarization function (DNP) are employed.
In the consideration of the relativistic effect, a combined scalar relativistic zeroth-order regular
037107-3 Yuan et al. AIP Advances 4, 037107 (2014)

iso -E low )/n of different isomeric structure with respect to the lowest energy configuration for
FIG. 1. The relative energy (E tot tot
Aun–x Ptx (n = 3–7, x = 0–2) clusters.

approximation is taken into account. The effects of core electrons and nuclei are replaced by an ef-
fective ionic potential, and the valence electrons that are 5s2 5p6 5d10 6s1 for Au and 5s2 5p6 5d9 6s1 for
Pt are involved in electronic structure calculations. The geometries are optimized without any symme-
try constraints and relaxed until the forces at each atom site vanish. In the geometrical optimizations,
the convergence thresholds are set to 5 × 10−4 Ha/Å for energy gradient and 2 × 10−4 Å for atomic
displacement. The self-consistent field (SCF) calculations are done with convergence criterions
1 × 10−5 Ha on total energy and 1 × 10−6 Ha on electron density, respectively.
There are a large number of geometrical structures accompanying with excessive homotops
(different atomic arrangements at a given geometry) for each bimetallic AuPt cluster. Typically, it
is difficult to optimize all possible topological isomers for clusters with large size and high doping
concentration, and an artificial structural construction is needed according to the bonding tendency
in small clusters. Thus, three preliminary methods are followed in the structural constructions: (1)
The designed structures of one component Au and Pt clusters, including the linear, planar, Y-like,
square-pyramid, pentagonal-pyramid, tetrahedral, octahedral, prism configurations, as well as their
capping configurations have been firstly optimized with the help of previous works.8–20, 58–62 In the
processes, exhaustive planar and compact 3D structures are emphasized for Aun and Ptn clusters,
respectively. (2) One expects that the structural shapes of AuPt binary cluster is in between pure
Au and Pt clusters. Consequently, the tentative structures for small Aun–x Ptx clusters (n = 2–7) are
mainly constructed at the additive and substitutive patterns based on the host Aun and Ptn structures
within distinctive features. In addition, the structures discussed in the literatures for the Au or Pt
based bimetallic clusters are also considered.23–36, 48–57 In the processes, each unsymmetrical site in
various low-lying Aun structures is tried for Pt atoms (vice versa for Au substitution of Pt atoms
in Ptn structures), yielding abundant isomeric structures. In Fig. 1, we plotted the energy spectra of
iso low
different Aun–x Ptx clusters, where the relative energy (E tot -E tot )/n is the total energy per atom of the
isomeric structures with respect to the corresponding lowest energy configurations. It is clear that
the total energies of the calculated AuPt structures are spread over a wide range of energies, which
indicates that a wide range of local environments and different configurations were calculated.
For particular Au5 Pt2 cluster, more than 90 isomeric structures are considered. A few different
configurations have the similar energies near the lowest energy structures, which we will discuss
below. More interestingly, we found that the Pt atoms often assemble together and occupy the center
037107-4 Yuan et al. AIP Advances 4, 037107 (2014)

TABLE I. Comparison of the calculated (GGA-PBE; HF-MP2; HF-CCSD) and experimental bond-lengths L (Å), vibrational
frequencies ω (cm−1 ), average binding energies Eb (eV/atom), ionization potential IP (eV), and electron affinity EA (eV) of
Au2 , AuPt, and Pt2 dimers.

Structure Method L Eb ω IP EA

Au2 GGA-PBE 2.55 1.06 172.50 9.31 1.63

MP2 2.59 0.91 167.16 8.45 1.38
CCSD 2.60 0.93 161.95 8.41 1.53
Exp. 2.4779, 80 1.1579–81 190.9080, 81 9.4582 1.9212
AuPt GGA-PBE 2.50 1.24 188.70 9.10 1.70
MP2 2.55 1.21 186.08 7.81 1.46
CCSD 2.59 1.32 161.44 7.76 1.53
Theor. 2.4764 1.2764
Pt2 GGA-PBE 2.37 1.75 229.70 8.81 1.53
MP2 2.43 1.76 180.93 9.16 1.35
CCSD 2.40 2.00 225.51 9.34 1.35
Exp. 2.3383 1.5783, 84 222.4685 8.6884

yet Au atoms prefer the apex positions in showing a segregation effect. Consequently, the approaches
for the constructions of large Pt-rich alloy clusters are typically based on above atomic arrangement
preferences. (3) For large Aun–x Ptx clusters (n = 8–14), as the Pt atoms successively substitute the
different Au positions in the several low-lying Aun−x Ptx structures, the other x Pt atoms are positioned
at the initial sites (vice versa for Au substitution of Pt). With the aim of overcoming the homotops
effect, the low-lying alloy structures are intensively built from the geometries by swapping positions
of Au atoms with Pt atoms. Ultimately, more than 800 various equilibrium geometries are achieved
for AuPt alloy clusters. The low-lying structures are obtained from the maximum in average binding
energy Eb , which is is defined as Eb (n)=([(n − x)EAu + xEPt − Et ])/n, where EAu and EPt are the
atomic energies and Et is the total energy of cluster.

B. Performance of the methods

In order to test the performance of the computational method, we compare these efficiently
calculated DFT results with the highly accurate but computationally expensive post-Hartree-Fock
approaches of Möler-Plesset second-order many body perturbation theory (MP2) and coupled cluster
[CCSD(T)] as well as experimental values. The calculations are carried out as implemented in
Gaussian 09 Package.76 The relativistic 19-electron for Au (18-electron for Pt) Los Alamos National
Laboratory (LANL2DZ) effective core pseudopotentials, together with the basis sets 3s2p5d for Au
atom77 (3s1p4d for Pt atom78 ), are employed in the studies partially accounting for the relativistic
effect.
The validations are firstly done on Au2 , AuPt, and Pt2 dimers for which the experimental gas-
phase data are available79–85 (Table I). It is clear that the calculated bond-lengths and average binding
energies at various methods differ by at most 0.09 Å and 0.15 eV/atom. The GGA-PBE method
generally yields the slightly shorter bond-lengths than the MP2 or CCSD method does (LPBE < LMP2
< LCCSD ), while a reverse behavior in average binding energy Eb can be discerned. In comparison
with the experimental values, GGA-PBE often does a better than MP2 or CCSD, but the accordance
is still rather good for three methods. Referring to IP and EA values, we find that the divergences
are not exceed to 15% within different methods, and GGA-PBE again gives the values more close
to experimental ones. Overall, GGA-PBE values are in good agreement with experimental and
more accurate ab initio results for different dimers. The average binding energy of Pt2 is larger
than that of Au2 , and the average binding energy of AuPt dimer is in between that of Pt2 and Au2
dimers. Reasonably, one may expect that the stabilities of AuPt binary clusters tend to increase with
the increasing numbers of Pt atom. The comparisons of three methods are further made on small
Aun–x Ptx clusters (n = 3, 4). The results for the lowest energy structures of each cluster are listed
037107-5 Yuan et al. AIP Advances 4, 037107 (2014)

TABLE II. The same as in Table I, but for the lowest energy structures of Aun–x Ptx (n = 3, 4) clusters. Corresponding
structures of these clusters are shown in Fig. 2. The bond-lengths L refer to the averaged Au-Au bonds (or Pt-Pt bonds) in
pure Au (or Pt) clusters but to the averaged Au-Pt bonds in bimetallic AuPt clusters.

Structure Method Symmetry L Eb IP EA

Au3 GGA-PBE C2v 2.59 1.11 7.20 3.36

MP2 C2v 2.63 0.95 9.11 2.05
CCSD C2v 2.65 0.97 9.18 2.09
Exp. 7.5082 3.8812
Au2 Pt1 GGA-PBE C2v 2.57 1.52 7.76 2.59
MP2 C2v 2.58 1.55 7.05 1.28
CCSD C2v 2.62 1.50 6.73 1.61
Au1 Pt2 GGA-PBE C2v 2.64 1.85 7.45 1.77
MP2 C2v 2.69 1.51 5.98 2.58
CCSD C2v 2.71 1.68 6.20 2.30
Pt3 GGA-PBE D3h 2.53 2.32 7.64 1.62
MP2 D3h 2.56 2.68 8.58 1.63
CCSD D3h 2.55 2.45 7.29 1.42
Au4 GGA-PBE D2h 2.70 1.42 7.86 2.25
MP2 D2h 2.75 1.32 7.34 2.09
Exp. 8.6082 2.7012
Au3 Pt1 GGA-PBE C2h 2.66 1.64 7.24 2.73
MP2 C2h 2.70 1.58 7.42 1.84
Au2 Pt2 GGA-PBE D2h 2.68 1.95 7.85 2.47
MP2 D2h 2.76 2.02 8.84 1.82
Pt4 GGA-PBE Td 2.61 2.60 6.51 1.61
MP2 Td 2.65 2.75 5.70 1.66

in Table II. Clearly, different methods always predict the same ground state structures within the
same structural symmetries. As is observed in dimers, little differences of bond-lengths and binding
energies among different methods appear again, but the deviations of GGA-PBE values from MP2
or CCSD values are still rather small. Despite the large differences in IP and EA, GGA-PBE method
reports the values for Au clusters more close to the experimental ones than MP2 or CCSD method
does.
By comparing the performance of three methods, we demonstrate that MP2 or CCSD offers
no advantage over GGA-PBE for predicting the structural stability and physical properties of AuPt
clusters, because GGA-PBE method always yields results very close to experimental values but
at a much reduction of the computational cost. Therefore, we will consistently use the GGA-PBE
method in this work.

III. RESULTS AND DISCUSSION

Although a large number of isomeric structures are obtained for each cluster, for the sake
of simplicity we only show the lowest energy structures in Fig. 2 and 3 (the atomic coordinates
are reported in the supporting information86 ). For pristine Au and Pt clusters, our lowest energy
structures are commonly consistent with previous reports.10–20, 58–62 Consequently, we would not
individually compare them with existing results but concern on the structures of bimetallic AuPt
clusters. The calculated results, including the average binding energies (Eb ), average bond lengths (L)
and coordination numbers (N) of Pt atoms, second energy difference (2 E), fragmentation energies
(Ef ), HOMO-LUMO gaps (Eg ), electron affinity (EA), ionization potential (IP), and magnetic
moments (MT ) are listed in Tables III–V and presented in Figs. 4–11.
037107-6 Yuan et al. AIP Advances 4, 037107 (2014)

FIG. 2. The lowest energy structures of Aun–x Ptx (n = 3–8; x ≤ n) clusters, where Au and Pt atoms are represented by
yellow and blue balls, respectively. The bond-lengths (Å) are shown in red on each structure, and the symmetry as well as
the averaged bond-lengths for Au-Au and Au-Pt bonds are listed orderly below each structure.

A. The lowest energy structures

Figure 2 shows the lowest energy structures of Aun − x Ptx (n = 3–8; x ≤ n) clusters. The Au3 − x Ptx
clusters with x = 0–2 are isosceles triangles (C2v ) within the apex angles of 140◦ , 68x00B0;, and
57x00B0;, respectively, while Pt3 cluster is an equilateral triangle (D3h ). The linear configuration is
merely 0.08 eV less stable than the triangle for Au3 cluster, whereas the energy difference increases
to 0.93 eV for Pt3 cluster. As for Au2 Pt (Au1 Pt2 ) cluster, the linear configuration with central Pt
atom is 0.50 eV (0.35 eV) higher in energy than corresponding triangle. Considering the increased
energy differences between the linear and triangular structures with increasing Pt atoms, one could
deduce that Pt atom in bimetallic AuPt clusters tends to bond more neighboring atoms as much as
it likes, and the formations of Au-Pt or Pt-Pt bonds would improve the structural stability.
For Au4–x Ptx (x = 0–4) clusters, quadrilateral, rhombic, Y-shaped, and tetrahedral structures
with different symmetries are optimized. Except for Pt4 cluster (tetrahedron with Td symmetry),
other bimetallic clusters are planar rhombus, in which Pt atoms are located at the high-coordinated
sites. However, it should be mentioned that the optimal rhombic structures are nearly degenerate
in energy with the Y-shaped structures (they lie only 0.01–0.03 eV lower in energy). All Au5–x Ptx
(x=0-5) clusters are 2D configurations, where a trapezoidal shaped structure with Pt atom centered
in the middle of bottom lateral is adopted by clusters with x=1–2 while a side-capped square
structure is favored by clusters with x = 3–5. The geometrical evolutions reveal that bimetallic AuPt
clusters tend to adopt Au5 or Pt5 structures depending on the Pt compositions less or more than 50%.
Moreover, in these structures the high (low)-coordinated positions are often occupied by Pt (Au)
atoms, which indicates that Pt atoms in large AuPt clusters would occupy the center sites but Au
atoms would prefer the surrounding sites. Based on the DFT calculations, Yuan et al.64 and Song
et al.68 have reported the same planar structures as we obtained for Au5−x Ptx clusters with x = 0–3.
037107-7 Yuan et al. AIP Advances 4, 037107 (2014)

FIG. 3. The lowest energy structures of Aun–x Ptx (n = 9–14; x = 0–3) clusters.
037107-8 Yuan et al. AIP Advances 4, 037107 (2014)

TABLE III. The average binding energy Eb (eV/atom), HOMO-LUMO gap Eg (eV), ionization potential IP (eV), electron
affinity EA (eV), magnetic moment MT (μB ), and average Au-Pt bond length L (Å) of the most stable structures of Aun–x Ptx
(n = 2–10; x ≤ n) clusters.

Cluster Eb Eg IP EA MT L Cluster Eb Eg IP EA MT L

Au2 1.06 2.01 9.31 1.63 0 − Au7 1.74 0.24 7.07 3.18 1 −
AuPt 1.24 0.16 9.10 1.70 1 2.50 Au6 Pt 2.02 0.98 7.38 2.31 0 2.71
Pt2 1.75 0.53 8.81 1.53 2 − Au5 Pt2 2.15 0.45 7.49 2.95 1 2.71
Au3 1.11 0.32 7.20 3.36 1 − Au4 Pt3 2.34 0.33 7.17 2.61 0 2.70
Au2 Pt 1.52 0.61 7.76 2.59 0 2.57 Au3 Pt4 2.57 0.37 6.92 2.53 1 2.73
Au1 Pt2 1.85 0.27 7.45 1.77 1 2.64 Au2 Pt5 2.79 0.41 7.03 2.49 0 2.67
Pt3 2.32 0.33 7.64 1.62 0 − Au1 Pt6 2.94 0.23 7.19 2.78 1 2.63
Au4 1.42 1.04 7.86 2.25 0 − Pt7 3.19 0.31 6.86 2.40 4 −
Au3 Pt 1.64 0.28 7.24 2.73 1 2.66 Au8 1.85 1.51 7.74 2.66 0 −
Au2 Pt2 1.95 0.46 7.85 2.47 0 2.68 Au7 Pt 2.00 0.24 7.08 3.10 1 2.72
Au1 Pt3 2.25 0.31 7.05 2.59 1 2.70 Au6 Pt2 2.16 0.59 7.04 2.58 0 2.82
Pt4 2.60 0.14 6.51 1.61 2 − Au5 Pt3 2.35 0.34 7.15 2.85 1 2.72
Au5 1.55 0.31 7.39 2.84 1 − Au4 Pt4 2.54 0.12 7.19 2.89 2 2.73
Au4 Pt 1.80 0.40 7.67 2.69 0 2.67 Au3 Pt5 2.73 0.24 6.87 2.71 1 2.67
Au3 Pt2 2.00 0.49 7.54 2.72 1 2.68 Au2 Pt6 2.92 0.16 6.73 2.69 0 2.77
Au2 Pt3 2.28 0.26 7.47 2.50 2 2.64 Au1 Pt7 3.12 0.36 6.81 2.44 1 2.76
Au1 Pt4 2.60 0.27 7.66 2.44 1 2.67 Pt8 3.34 0.33 6.99 2.66 2 −
Pt5 2.84 0.32 7.61 2.56 2 − Au9 1.84 0.20 6.89 3.28 1 −
Au6 1.78 2.17 8.09 1.94 0 − Au8 Pt 2.02 0.51 6.99 2.83 0 2.74
Au5 Pt 1.92 0.21 7.62 2.73 1 2.69 Au7 Pt2 2.20 0.59 6.88 2.73 1 2.80
Au4 Pt2 2.13 0.27 7.35 2.72 0 2.70 Au6 Pt3 2.35 0.37 7.14 2.85 0 2.81
Au3 Pt3 2.34 0.13 7.55 2.76 1 2.76 Au10 1.92 1.37 7.41 2.72 0 −
Au2 Pt4 2.53 0.13 7.69 2.98 2 2.77 Au9 Pt 2.04 0.09 7.18 3.41 1 2.72
Au1 Pt5 2.76 0.22 7.56 2.90 1 2.62 Au8 Pt2 2.21 0.21 7.16 3.25 0 2.74
Pt6 3.00 0.12 7.46 2.87 2 − Au7 Pt3 2.38 0.52 6.79 2.54 1 2.75

TABLE IV. Similar to that of Table III, but for Aun–x Ptx clusters with n = 11–14 and x ≤ n.

Cluster Eb Eg IP EA MT L Cluster Eb Eg IP EA MT L

Au11 1.92 0.16 6.90 3.61 1 − Au11 Pt2 2.24 0.30 6.53 2.96 1 2.77
Au10 Pt 2.06 0.42 7.08 3.20 0 2.72 Au10 Pt3 2.36 0.56 6.60 2.84 0 2.82
Au9 Pt2 2.21 0.26 6.75 3.16 1 2.72 Au9 Pt4 2.51 0.12 6.28 2.81 1 2.82
Au8 Pt3 2.35 0.14 6.05 2.96 0 2.76 Au8 Pt5 2.64 0.60 6.75 2.78 0 2.82
Au12 1.98 0.96 7.23 3.11 0 − Au1 Pt12 3.55 0.08 6.32 2.77 1 2.76
Au11 Pt 2.09 0.10 7.19 3.73 1 2.73 Pt13 3.69 0.13 6.40 2.83 2 −
Au10 Pt2 2.21 0.60 6.51 2.71 0 2.77 Au14 2.03 1.66 7.18 2.46 0 −
Au9 Pt3 2.33 0.53 6.55 2.74 1 2.75 Au13 Pt 2.12 0.17 6.99 3.45 1 2.78
Au13 1.97 0.14 6.58 3.41 1 − Au12 Pt2 2.25 0.62 6.66 2.95 0 2.79
Au12 Pt 2.11 0.41 6.91 3.32 0 2.73 Au11 Pt3 2.37 0.27 6.34 3.29 1 2.79

For Au6–x Ptx (x = 0–6) clusters, all their structures are a planar triangle owing to the resembling
triangular structures of Au6 and Pt6 clusters. The tendency to form a planar structure is so strong for
Pt-poor clusters that the initially designed 3D structures are often relaxed to a quasi-planar structure.
By calculating the energy differences between the most stable 2D structures and the most stable 3D
structures of bimetallic Au6–x Ptx (x = 0–5) clusters, we find that the energy differences decrease
gradually from 0.48, 0.45, 0.41, 0.35, 0.20 to 0.05 eV, which indicates that the priority of 2D structure
over 3D structure decreases gradually with the increase of Pt composition. This speculation can be
supported in the calculations of Au7–x Ptx (x = 0–7) clusters, where Pt-poor clusters with x = 0–2
are planar structures while Pt-rich clusters with x = 3–7 are 3D structures. Except for Au6 Pt cluster
037107-9 Yuan et al. AIP Advances 4, 037107 (2014)

TABLE V. The electronic configurations and local magnetic moments (μB ) of dopant Pt atom in Aun Pt (n = 1−13) clusters.
The last column lists the total moment of Pt atom.

Cluster Configuration 5d 6s 6p MT

AuPt 5d9.093 6s0.853 6p0.045 0.72 0.25 0.00 0.97

Au3 Pt 5d9.071 6s0.713 6p0.185 0.61 0.01 0.03 0.65
Au5 Pt 5d8.950 6s0.784 6p0.254 0.58 0.14 0.01 0.73
Au7 Pt 5d8.865 6s0.757 6p0.348 0.32 0.01 0.01 0.34
Au9 Pt 5d8.851 6s0.770 6p0.353 0.41 0.00 0.01 0.42
Au11 Pt 5d8.806 6s0.786 6p0.369 0.34 0.09 0.01 0.45
Au13 Pt 5d8.767 6s0.783 6p0.414 0.55 0.05 0.01 0.61

FIG. 4. The average binding energies and the second energy differences (insert chart) of pristine Aun and monatomic doping
Aun Pt clusters with cluster size n = 1–14.

that is a planar hexagon-ring with a centered Pt atom (D6h ) and Au5 Pt2 cluster that is a capped
planar triangle (Cs ), other bimetallic Au7–x Ptx clusters favor 3D structures. They can be obtained by
successively substituting Pt atoms by Au atoms from Pt7 structure and then relaxing Au atoms to
occupy the apex positions. Owing to the high symmetry and stability of Au6 and Au6 Pt structures,
they can act as the basic units to construct larger Aun or Aun Pt clusters (n < 14).
For the series of Au8–x Ptx (x = 0–8) clusters, the transition from 2D to 3D occurs at x = 3. The
pristine Au8 cluster is a tetracapped square (D4h ), which is 0.25 eV and 0.31 eV more favorable than
the optimal capped hexagon-ring and bicapped triangle, respectively. Bimetallic Au8–x Ptx clusters
with x = 1–3 are capped hexagon-ring structures, while clusters with x = 4–7 are 3D structures that
can be derived from the corresponding structures of Au7–x Ptx clusters by adding one Au atom (from
another side of view, they also obey structural substitutive pattern from Pt8 structure as Au7–x Ptx
clusters do). The lowest energy structures of Aun–x Ptx (n = 9–14; x = 0–3) clusters are illustrated
in Fig. 3. It is clear that pure Aun and monatomic doping Aun–1 Pt clusters present the similar planar
037107-10 Yuan et al. AIP Advances 4, 037107 (2014)

FIG. 5. The average binding energies as variation of impurity Pt atoms for Aun–x Ptx (n = 6, 7, 8, 13; x ≤ n) clusters.

FIG. 6. The average Au-Pt bond length and coordination number of Pt atom (insert chart) for monatomic doping Aun Pt
(n = 1–13) clusters.
037107-11 Yuan et al. AIP Advances 4, 037107 (2014)

FIG. 7. The fragmentation energies of Aun → Aua +Aun–a (up panel), Aun Pt → Aua +Aun–a Pt (middle panel), and Aun Pt2
→ Aua +Aun–a Pt2 (bottom panel) clusters as a function of cluster size n (n = 2–14).

configurations, which consist of a planar triangle Au6 and hexagon-ring Au6 Pt units. The critical
composition from 2D to 3D transition is down to x = 1 except for Au10 Pt2 cluster (2D structure is
merely 0.01 eV lower in energy than 3D structure). The segregation effect becomes clear in Pt-rich
large clusters, i.e, Pt atoms always assemble together forming more Pt-Pt bonds. Being from n =
14, 3D configurations become the most stable structure in all cases, even for pristine Au14 cluster.
One should mention that abundant plausible planar structures are examined and finally found to be
metastable.
Overall, the planar configurations are favored for both pristine Aun and bimetallic Aun–1 Pt
cluster with sizes up to n = 13, and Aun–1 Pt clusters often employ the substitutive pattern of structural
evolution based on the structures of Aun clusters. For large Aun (or monatomic doping Aun–1 Pt)
clusters, their structures can be viewed as the D3h planar triangle unit (or the central D6h hexagonal-
ring unit) with additional Au atoms arranged on different edge sides. Our structural searches do
not find any most stable 3D configurations for Aun clusters (n = 2–13), which is consistent with
that of previous works.8–20 For Pt-rich Aun − x Ptx clusters, their structures can be derived from the
substitution of Pt atoms by Au atoms from Ptn structures, exhibiting the segregation effect that Pt
atoms assemble together and occupy the center sites yet Au atoms occupy the apex positions. With
037107-12 Yuan et al. AIP Advances 4, 037107 (2014)

FIG. 8. The HOMO-LUMO gaps of Aun–x Ptx (n = 6, 7, 8, 13; x ≤ n) clusters, together with that of Aun and Aun Pt
(n = 1–14) clusters (insert chart).

FIG. 9. The energy levels (in eV, the red and black lines represent the unoccupied and occupied orbitals, respectively),
together with the electron densities of the HOMO and LUMO states (isodensity surfaces correspond to ±e/0.02 a.u.3 ), are
show for Au12 and Au12 Pt clusters. The energy levels of free Pt atom are compared.
037107-13 Yuan et al. AIP Advances 4, 037107 (2014)

FIG. 10. The electron affinity (EA; a) and ionization potential (IP; b) of pristine Aun and monatomic Pt-doping Aun Pt
clusters with cluster size n = 1–14.

the increase of cluster size, the critical composition from 2D to 3D structural transition is gradually
down to low Pt-compositions. The presences of d electrons from the unfilled d shell of Pt atoms
give rise to more directional bonds, which may result in a more compact structure with enhanced
stability.
Importantly, the appearance of segregation effect in small AuPt clusters is in line with previous
investigations on larger AuPt clusters, where the preference for thermal stability of Ptcore Aushell mor-
phologies has been experimentally detected87–90 and theoretically determined with genetic algorithm
methods or molecular dynamics or Monte Carlo simulations.91–97 Recently, the favorable Ptcore Aushell
growth pattern has been found also in the DFT calculations by Leppert and Hu et al.,98–100 who con-
sidered some selected sizes of n = 20, 40, 85 within various compositions. Here, our systemic DFT
study on further small AuPt clusters can provide an electronic structural insight into microstruc-
tural evolution and thermal stability of core-shell AuPt nanoclusters, contributing to the design and
engineering of a wide variety of larger AuPt nanostructures. There may be three reasons for the
037107-14 Yuan et al. AIP Advances 4, 037107 (2014)

FIG. 11. The PDOS of Au13 and Au12 Pt clusters. Fermi energy is shifted to zero and denoted by the vertical dotted line.

Pt(core)-Au(shell) segregation effect: (1) the straining effects are optimal since the Wigner-Seitz
radius for Au (1.44 Å) is larger than that for Pt (1.39 Å) (the surface bond-lengths are about 3–8%
longer than the inside ones for a spherical structure). (2) the Pt-Pt bonds are stronger than the Pt-Au
and Au-Au ones. (3) the surface energy of Au is larger than the Pt one.101

B. Binding energies and relative stabilities

To understand the relative stabilities of Aun–x Ptx clusters, the average binding energies (Eb ) as
well as the second order energy differences (2 E) are analyzed (Fig. 4). The values of corresponding
pure Aun clusters are shown for comparison. The 2 E is defined as: 2 E(n) = Et (n + 1) + Et (n − 1)
−2Et (n). For simplicity, the figure 4 only shows the values of pure Aun clusters and monatomic
doping Aun Pt (n = 2–14) clusters. The average binding energies of Aun–1 Pt clusters are larger
than corresponding values of pure Aun clusters, suggesting that the introduction of one Pt atom
can stabilize Aun clusters. In the inset of Fig. 4, a significant odd-even oscillation as the result of
electron pairing effect can be clearly discerned for Aun clusters, however, this tendency vanishes
when intruding one Pt atom. As indicated in previous theoretical works,27, 35 Au6 is the most stable
cluster among the considered gold clusters. In the series of Aun Pt clusters, a pronounced peak at
n = 6 followed by small values in the range of n = 8–13 reveals that, the gradual addition of Au
atoms does not change the relative stabilities of the following clusters. Thus, Au6 and Au6 Pt can be
regarded as the magic number clusters.
037107-15 Yuan et al. AIP Advances 4, 037107 (2014)

For polyatomic Pt-doping Aun–x Ptx (n = 6–8, 14; x=0–8) clusters, their average binding ener-
gies are plotted as the number of Pt atom in Fig. 5. Concerning the values with fixed n yet increased
x (increasing Pt concentration), one notes that Eb increases linearly with the increase of substitu-
tional Pt atoms (e.g., the increasing stabilities Au13 → Au12 Pt1 · · ·Au9 Pt4 → Au8 Pt5 ). These linear
relationships were not expected a priori. The similar studies of clusters composed of silver and gold,
which are also next to each other in the same group of the periodic table, shows a rather nonlinear
trend.48–57 Such enhancements of stabilities are attributed to the progressive formations of Pt-Pt and
Pt-Au bonds with the successive substitutions of Au atoms by Pt atoms. By analyzing the values
with fixed x yet increased n (decreasing Pt concentration), on the other hand, one observes that
the stabilities increase gradually with the increasing size for clusters containing Pt atoms less than
three, while the case is reversal for clusters containing Pt atoms more than three (e.g., the increasing
stabilities of Au5 Pt1 → Au7 Pt1 → Au12 Pt1 with increasing Au atoms vs the decreasing stabilities of
Au1 Pt5 → Au3 Pt5 → Au8 Pt5 with increasing Au atoms). The latter decreasing trend may originate
from the competitions between the increasing tendency as the function of increasing cluster size and
the decreasing tendency as the function of decreasing Pt-concentration. It is rather interesting to see
all the curves crossing each other through a common point at x = 3.5 independent of cluster size,
showing the decreasing slops as the increasing size n. Thus, one expects that the slop ratios of the
binding energy curves tend to be 0 for extremely large alloy clusters and their curves would also
cross the binding energy point at x = 3.5. This indicates that the maximum average binding energy
is about 2.45 eV/atom for large alloy AuPt clusters.
The bond length is an important quality to reflect the growth pattern of clusters. The aver-
age Au-Pt bond lengths as well as the coordination numbers of Pt atom are analyzed for Aun Pt
(n = 1–13) clusters. Two curves in Fig. 6 represent a similar sharp increasing tendency in the range
of n = 1–6, followed by a flat region in the range of n = 7–12, and then represent an ascending trend
at n = 13. Three different ranges can be related to the diverse environments of Pt atom in different
Aun Pt clusters. The local circumstance of Pt atom varies significantly in the first range owning to
the successively increasing of Au-Pt bonds, while the surrounding of Pt atom maintains the same
(Pt atom is located in the center of Au6 planar hexagon-ring) and results in a faint change of bond
lengths in the second range, and the occurrence of 3D structure changes the local circumstance of
Pt again in the third range. The similar behaviors of two curves can be interpreted from the stability
of structural growth: the clusters try to stabilize their structures by gradually forming sufficient
coordinations for Pt atom as a result of the gradually extending of Au-Pt bond lengths.
To further confirm the magic number clusters, we compute all possible fragmentation channels,
and show the lowest energy channels of Aun–x Ptx (n = 2–14; x = 0–2) clusters in Fig. 7, where
the fragmentation energy Ef is defined as the energy differences between the parent cluster and
the daughter fragments. The lowest energy channel is regarded as the most favorable dissociation
channel in experiment which is labeled by (a, n − x − a). For pure Aun clusters, the sizes with
odd (even) atoms prefer a monomer (dimer) dissociation fragment, which is just the reverse of the
observed behavior on cationic Au+ n clusters.
102
It implies that the stabilities of Aun clusters are
mainly determined by their electronic closure. The largest Ef of Au6 cluster together with the most
favorable channel (6, 6) of Au12 cluster supports our findings that Au6 cluster is the most stable
size and can be regarded as the building unit in constructing large Au clusters. However, the (6, 6)
channel is only 0.07 eV lower in energy than the (2, 10) channel, indicating that the superior stability
of Au6 cluster over other clusters is rather weak. There is no dissociation measurement on neutral
Aun clusters, however, their Ef can be determined by combining the experimental fragmentation
energies of cationic Au+ n clusters
102
with the experimental values for their ionization potentials:82
Ef (n) = E f (n) + IP(n) − IP(n − 1) for monomer dissociation; Ef (n) = E f+ (n) + IP(n) − IP(n − 2)
+

for dimer dissociation. According to this approach, the experimental Ef (n) agree well with the DFT
values for neutral Aun clusters (up panel).
For monatomic doping Aun Pt or diatomic doping Aun Pt2 clusters (middle and bottom panels),
there is no lowest energy channel containing a daughter of pure Pt component (n > 2), and the
dissociations of Au-monomer are often more favorable. The largest Ef of Au6 Pt → Au + Au5 Pt1
channel (1, 5) and Au4 Pt2 → Au + Au3 Pt2 channel (1, 3) suggest that Au6 Pt and Au4 Pt2 clusters
are more stable than their neighboring sizes in Aun Pt and Aun Pt2 series, respectively. In fact, as
037107-16 Yuan et al. AIP Advances 4, 037107 (2014)

the dangling bonds of Pt atom (or Pt atoms) are almost saturated in Au6 Pt (or Au4 Pt2 ) clusters,
additive Au atoms in forming successive Aun Pt (or Aun Pt2 ) clusters would joint with Pt atoms
faintly, resulting in a nearly invariable Ef that approximately equals to the value of Au2 dissociation.
The dissociation of Au monomer is the most possible fragmentation pathway can be readily extended
to polyatomic Pt doping Aun–x Ptx clusters.

C. Electronic and magnetic properties

Fig. 8 presents the HOMO-LUMO gaps Eg of Aun–x Ptx (n = 6–8,13; x = 0–8) clusters.
Introducing one Pt atom would significantly reduce the values of the even-sized Aun clusters,
however, odd-even alternation is still preserved in Aun Pt clusters (inset chart). High Eg of Aun and
Aun Pt clusters with even-Au atom reflect that these clusters are closed electronic shells, which also
indicates that Pt dopant delocalizes even number of their valence electrons. Assuming that one 6s
electron and one 5d electron of Pt atoms are delocalized, Au6 Pt and Au4 Pt2 clusters can contain 8
itinerant electrons that equals to the electronic magic number. Although the closure effect is partially
released in Aun Pt clusters, the d-d interaction between Pt and Au atoms would overcompensate
this reduced contribution and result in an increased stabilities of Aun Pt clusters. For each series of
polyatomic doping Aun–x Ptx clusters with fixed n, it is found that Eg decreases with the increasing x
and the oscillating trend nearly dies down at large Pt concentrations.
To underline the mechanism behind the findings, we perform an analysis of the molecular
orbitals by examining the energy levels and electron density of HOMO and LUMO states for Au12 ,
Au12 Pt, and free Pt atom, which are displayed in Fig. 9. From the energy spectrum, the HOMO-level
of free Pt atom is higher in energy than that of Au12 cluster but an opposite case can be clearly found
for the LUMO-level. Once Pt atom is doped in Au12 cluster, the electrons from HOMO state of Pt
atom would form a new occupied-orbital (being the HOMO of Au12 Pt cluster) and LUMO state of
Pt atom would form a new unoccupied-orbital (being the LUMO of Au12 Pt cluster), resulting in
decreased Eg of Au12 Pt cluster with respect to that of Au12 cluster. Our assumption that the HOMO
and LUMO of Au12 Pt cluster are mostly contributed from the Pt atom can be easily evidenced by the
electron density, where the accumulated charges are mainly around the Pt atom in Au12 Pt cluster.
Further verifying via the partial densities of states shows that the HOMOs of all bimetallic AuPt
clusters mainly consist of 5d orbitals of Pt atom. This manifests that Pt atoms donate their d electrons
to the frontier orbital in Aun–x Ptx clusters and the chemical activities of bimetallic AuPt clusters are
strongly correlated with the Pt concentration.
The adiabatic electron affinity (EAa ) and ionization potential (IPa ) can be directly measured
and are good properties in identifying the size dependent evolutions of geometrical and electronic
structures. They are calculated from the energy differences between neutral and charged species at
the neutral geometries within structural relaxations. Fig. 10 shows our calculated values for pure Aun
and Aun Pt (n = 1–14) clusters, compared with the experimental measurements on Aun clusters.12, 82
For Aun clusters, our EAa and IPa are in good agreement with experimental measurements but
show a somewhat weaker and less pronounced odd-even oscillation. Due to the electron-pairing
effect, even-sized clusters exhibit smaller EAa and larger IPa . Clearly, the low (high) value of EAa
(IPa ) is identified as a signature of closed-shell pattern of electronic configuration with large Eg .
However, the agreement between theory and experiment seems to be little worse for the IP (about
0.5 eV divergence).82 This may be due to the fact that our calculations are based on the structures
of neutral Aun clusters, i.e, it may not be a simple substitution of Au+ n structure by Aun structure.
In previous theoretical works, they also underestimate about 0.5 eV with respect to experimental
values.19, 49, 54
For Aun Pt clusters, they present a prominent odd-even alternative behavior for EAa yet a
faintness one for IPa . There is the anomaly for clusters with sizes n = 1–5. In this size range, Au
atoms prefer saturating the dangling bonds of Pt atom and leave out less s valence electrons in
presenting electron-pairing effect, thus disappearing odd-even oscillation in EAa and IPa . Although
there is no EAa measurement on Aun Pt clusters, the experiment on Aun Pd clusters (n = 2–7) can give
some clues,103 because Pd atom in solid mainly takes the 4d10 5s0 configuration similarly to a free Pd
atom, however, the configuration 4d9 5s1 of Pd atom in small Aun Pd clusters is theoretically predicted
037107-17 Yuan et al. AIP Advances 4, 037107 (2014)

(similar to 5d9 6s1 of Pt atom in Aun Pt clusters).104–106 In addition to that, the structures of Aun Pd (n
= 2–7) clusters are same to that of Aun Pt clusters.64 If this analogy is feasible, our EAa calculations
on Aun Pt clusters can reproduce the experimental observations that there are obscuring even-odd
alternation in the size range n = 4–7 as well as a higher value of 3 eV at n = 7.103 For polyatomic
Pt-doping Aun–x Ptx clusters(n = 2–14; 2 ≤ x ≤ n), EAa and IPa are also calculated and listed in
Tables III and IV.
The partial density of state (PDOS) of Au13 and Au12 Pt clusters is plotted in Fig. 11 as an
illustration to understand the bonding characters from the electronic structures. There is strong
sp-d hybridization in Au13 cluster, which plays a decisive role in favoring planar structure up to a
surprisingly large size.21 The presence of 6p electrons indicates the occurrence of charge transfer
from 6s and 5d states to 6p states, however, the Mulliken population analyses show that the 6p
electrons are small and around 0.4 e at large sizes (Table V). As one Au atom is substituted by Pt
atom in forming Au12 Pt cluster (Fig. 11), the bandwidth and shape of the DOS of the Au12 component
are very similar to that of Au13 cluster. The d states (dz 2 , dx 2 −y 2 ) of Pt atom are largely localized
around the fermi level being the HOMO, indicating the enhancement of reactivities of AuPt clusters
toward O2 , NO, and CO, etc.72 Below the fermi level, the d states of Pt and Au are overlapped and
come into being the d-d hybridization, which would impact the geometrical structures and stabilities
of AuPt clusters. Moreover, the s and p states of Au or Pt atoms spread over the d band, forming
additional sp-d hybridization between the Au and Pt atoms. Thus, strong d-d interactions as well as
unique sp-d hybridizations between Pt and Au atoms that have not been found in AuAg and AuCu
clusters48–57, 64 give rise to the planar structures of large Aun Pt clusters.
The magnetic moments of Aun–x Ptx (n = 2–14; x ≤ n) clusters are collected in Tables III and
IV. For each cluster, the reliability of spin state is further examined by calculating the allowed
spin moments above and below the ground state spin moment. The calculations show that the total
magnetic moments are 1 μB for Aun Pt clusters with odd n yet zero for Aun Pt clusters with even n.
Due to the close electronic shells, the local moments as well as the total moments are completely
quenched in Aun Pt clusters with even Au atoms. For the unpaired spin clusters, the electronic
configuration as well as the local magnetic moment of the dopant Pt atom are given in Table V. One
notes that Pt atom contains a substantial amount of spin magnetic moment compared to any one
Au atom, and the value decreases with an increasing of neighboring Au atoms from n = 1–6. The
enhanced s-d and d-d hybridizations stemming from host Au and impurity Pt increase the tendency
of Pt-d electrons toward itinerant behavior and decrease the local magnetic moment of Pt atom.
Beyond n = 6, additive Au atoms interact with Au atoms of the hexagon-ring of Au6 Pt unit, which in
turn would decrease the d-d hybridizations between the centered Pt and the surrounded Au atoms of
the hexagon-ring. Thus, the decreased interactions would localize the Pt-d electrons and increase the
local magnetic moment of Pt atom. For polyatomic Aun–x Ptx , the same conclusions can be generally
achieved, i.e, the spin singlet (doublet) states are favored for clusters with even (odd) Au atoms,
except for Au2 Ptx (x = 3–4) and Au4 Pt4 clusters which show a spin triplet state.

IV. CONCLUSION
Based on the DFT method, we carry out a comparative study on pristine Aun and bimetallic
Aun–x Ptx clusters (n = 2–14; x ≤ n), concerning their structural evolutions and electronic properties
at the variations of cluster size and composition. In general, the favorable structures of Pt-poor
(rich) bimetallic Aun–x Ptx clusters can be derived from that of one-component Aun (Ptn ) clusters by
partially substituting the high (low)-coordinated Au (Pt) atoms by Pt (Au) atoms, in which the Pt
components assemble together and occupy the structural center yet the Au components occupy the
apex positions. One Pt atom substitution of Au atom can further stabilize the planar Aun clusters up
to n = 13, but does not improve the crucial size of 2D → 3D structural transition to a large value.
However, the polyatomic-Pt doping often yields the early appearance of the 3D structures. Although
the electronic closure effect is partially released in stabilizing Aun Pt cluster, which is reflected by
the less pronounced odd-even oscillations in HOMO-LUMO gap, IP, and EA, as well as the Au-
monomer dissociation, the d-d interactions between Pt and Au atoms would overcompensate this
037107-18 Yuan et al. AIP Advances 4, 037107 (2014)

decreasing behavior and result in the enhanced stabilities of Aun–x Ptx clusters. The frontier orbitals
of Aun–x Ptx clusters mainly contributed from the d electrons of Pt atoms validate that the chemical
activities are strongly correlated with the impurity Pt component.

ACKNOWLEDGMENTS
This work was supported by the National Natural Science Foundation of China (Project
Nos. 10904125 and 91121013), the Chongqing’s Natural Science Foundation of China (Project
Nos. CSTC-2012JJA50006 and CSTC-2011BA6004), and the Fundamental Research Funds for the
Central Universities (Project No. XDJK2012B008).
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