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Planar σ‑Aromaticity in Ga-Doped Au Clusters

Qiman Liu,* Manli Zhang, Xing Gao, and Longjiu Cheng*
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ABSTRACT: Recently, the first example of Au−Ga clusters is synthesized

and characterized, which can be described by the jellium model as a superatom
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with 8 valence electrons that come from the joint contribution of Au and Ga
atoms, opening a whole new field for further research. Here, the structure
features and stability of one Ga-doped Au cluster with magic number electrons
(6 and 8) are analyzed in detail. Moreover, the valence electron fillings and
chemical bonding of them are also further explored. It is found that Au3Ga and
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Au5Ga clusters present planar configurations, and they have higher stability
than that of neighbor clusters. The AIMD simulations show that these two
clusters still have a good thermal stability at 500 K. The molecular orbital
analyses show that the Au3Ga and Au5Ga have three and one typical
delocalization orbital throughout the whole planar spaces, respectively,
following the planar σ-aromaticity rule. The ELF and LOL analyses are
further performed, and the results are consistent with the molecular orbital
analyses. The NICSzz-scan curves confirm that the Au3Ga is more aromatic than the Au5Ga, and the reason is that the former has
more delocalized electrons than the latter. Our work opens up aromaticity studies in the Au−Ga clusters.

1. INTRODUCTION effect. Much of the interest centers on Au−Au, Au−Ga, and

Au−Ga alloys belong to the group of gold-based materials, Ga−Ga metal interactions. For instance, Yao et al. found that
whose phase diagrams that were first investigated by Weibke the GaAun (n = 1−4) clusters with n-Au terminals and Ga2Aun
and Hesse using X-ray and differential thermal analyses have (n = 1−4) clusters with bridged Au atoms possess geometric
been well established.1−6 There are five intermediate phases structures and bonding patterns similar to those of the
corresponding gallium hydrides GaHn and Ga2Hn.18 What is
that exist in the phase diagram of Au−Ga systems: a high-
more, the Ga−Au interaction is predicted to occur through
temperature phase; high- and low-temperature polymorphs; an
highly polar covalent bonds in monogallium aurides.
order−disorder transformation; one AuGa phase; and one
Subsequently, the equilibrium configurations and relative
AuGa2 phase.7−9 For example, the famous compound of
stabilities of anionic AunGa− clusters (n = 1−8) are also
AuGa2 crystallizes in the cubic fluorite (CaF2) structure and
investigated.19 Among them, the Ga atom attracts electrons
exhibits anomalous physicochemical properties in the magnetic
from Au atoms, except for the anionic AuGa− cluster. Most
susceptibility, Knight shifts, nuclear spin−lattice relaxation
notably, there has been additional interest in the field of the
rate, and thermoelectric power.10−12 The characteristics of
structures and electronic properties of gold clusters doped with
such alloys have been examined over the years by numerous
gallium, of which the semiconducting element Ga is greatly
research groups, and literature databases show that the Au−Ga
important in the microelectronics industry. However, we
systems are interesting investigation topics nowadays as
retrieved the relevant literature of the Au−Ga system, and it is
well.13−15 Understanding better the role of alloy elements
found that few researchers reported the chemical bonding and
and designing novel Au-based solids, structure descriptions and
electronic characteristics of their clusters before.
electronic properties of the related Au-based alloy systems
Recently, the first example of Au−Ga superatom clusters
containing gallium and gold are indispensable.
[Chem. Commun., 2021, 57, 3551−3554] is synthesized and
Since the first complex containing Au−Ga bonds was
characterized by using the low-valent gallium(I) compound
reported, which is also the first gold−gallium cluster complex
in which the gold atoms are bonded only to an electropositive
main-group metal, the Au−Ga clusters have attracted extensive Received: December 14, 2022
research interest.16,17 However, there are very few reports Revised: February 26, 2023
about the isolations and characterizations of Au complexes Published: March 20, 2023
with the lighter group metal Ga. This may be attributed to the
special characteristic of the Au element, which generally forms
stronger bonds with heavier elements due to the relativistic

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Figure 1. Optimized structures of AunGa (n = 1−9) at the PBE0/Def2-TZVP level. The notes are point energies (eV) relative to the GM one. Au,
yellow; Ga, brown.
GaCp as a reductant, opening a whole new field for further
research.20 Especially, the cluster [(PPh3)8Au9GaCl2]2+ can be
described by the jellium model as a superatom with 8 valence
electrons that come from joint contributions of Au and Ga
atoms. In previous work, the jellium model with its magic
numbers can also be extended to open-shell half-filled
systems.21 Hence, considering the open-shell jellium aroma-
ticity provides a new perspective for the analysis of structural
stability. In fact, a single dopant atom drastically changes the
structures and electronic properties of Au alloy clusters, which
are based on different numbers of electrons that can be
delocalized depending on the electronic configurations of the
dopant atoms. For example, Pyykkö and Runeberg suggested
that the icosahedral WAu12 cluster showed high chemical
stability and is an 18-electron superatom.22 Khanna’s group
found that ScAu6+ and TiAu5+ are magic species that are
revealed by the photo-fragmentation experiment, where the Sc
and Ti atoms delocalize 3 and 4 electrons, respectively.23
To the best of our knowledge, theoretical researches of
superatom characteristics of single gallium atom-doped gold
clusters have very few reports so far. Here, the structure
features and stability of one Ga-doped Au alloy cluster with
magic number electrons (6 and 8) are analyzed in detail. The
conformation behaviors of Au−Ga clusters on the finite
temperatures are also given. Moreover, the valence electron
fillings and chemical bonding of them are further explored.
2. COMPUTATIONAL METHODS AND DETAILS
The global minimum (GM) configurations and other isomers
of AunGa (n = 1−9) clusters are globally located on their
potential energy surfaces by using the global genetic algorithm
(GA) with different DFT functionals. The GA framework we
use here is one of the search heuristic strategies that imitates
processes of the natural evolution to produce successful
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schemes for treating optimization puzzles.24−27 Because the
GA search cannot guarantee that the GM structures are found
only through a calculation, three standalone GA runs were
implemented per case. For example, in the optimization of
(AuGa)5, the population size is set to 30, and the maximum
iteration number is 1000. After similarity checking, the isomers
in the structural library are sorted at the PBE0/Def2-SVP
level.28 Finally, the top 30 lowest energy isomers are fully
relaxed at the PBE0/Def2-TZVP level of theory, and spin
multiplicities are reset to (1, 3, and 5) or (2, 4, and 6) to find
the GM structures. The Def2-SVP/Def2-TZVP basis sets are
used for Au and Ga atoms that account for the relativistic
effective core potentials.29 The vibration frequencies are also
carried out to check that obtained structures belong to
veritable local minimums of the potential energy surfaces at the
same theory level. The first-principles computations are run in
the Gaussian 09 software package.30 The ab initio molecular
dynamics (AIMD) simulations are performed in the VASP
package, and the simulation temperatures during AIMD
processes conform to the Nosé−Hoover method.31,32
3. RESULTS AND DISCUSSION
3.1. Configuration Features and Growths of AunGa (n
= 1−9) Clusters. We determined the GM structures and
other isomers for neutral AunGa (n = 1−9) nano-alloys at the
PBE0/Def2-TZVP level employing the GA program with DFT
methods. In fact, such a strategy based on the functional and
basis set has been widely applied to nano-alloys and rigorously
confirmed to be authenticated.27,33 Earlier work has reported
configuration characters of anionic AunGa− (n = 1−8) clusters,
but they cannot guarantee that the optimized structures are
globally optimal because the initial geometries are limited.
Moreover, the connection of structure characteristics and
electronic properties of them is still not well established. The
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configurations in our results are compared with those reported
previously.18,19 Figure 1 plots the isomer structures of AunGa
(n = 1−9) clusters, only involving singlet and doublet states,
which are more stable by >1.0 eV than the corresponding high-
spin states. Their point groups of symmetry are also given, and
relative energies are arranged in order from low to high. Here,
we only give a part of isomers that are within 0.5 eV of the GM
structures in energies because there are quite a lot of isomers
per component. The GM structures and other isomers are all
demonstrated to be veritable local minimums of their potential
energy surfaces at the same theory level by frequency tests.
Spin multiplicities of the AunGa clusters are 1 (odd number
n) and 2 (even number n), respectively. Among them, the
AuGa dimer is a linear structure, and the distance between Au
and Ga atoms is 2.42 Å. The Au2Ga after structural
optimizations only converges to the four stable ones. Among
them, the GM 2a has a V-shape structure in the C2v symmetry,
where the distances between Au and Ga atoms are 2.40 Å. The
metastable 2b isomer with the C2v symmetry is only 0.08 eV
higher in energy. The GM 3a for Au3Ga is a planar
configuration in the D3h symmetry, and the spin multiplicity
of the cluster with 6 valence electrons is a singlet state, in
which the Au−Ga distances are all 2.38 Å. The Au4Ga after
optimizations only converges to four isomers, and the GM 4a
is in the D2d symmetry where the Au−Ga distances are within
the limits of 2.38−2.50 Å. The GM 5a with the Cs symmetry
for Au5Ga has a planar configuration in which the Au−Ga
distances are in the range of 2.41−2.51 Å, and other isomers
are compact configurations. The GM 6a with the C2v symmetry
is based on the growth of 5a, which can be obtained by adding
one Au atom. GM 7a with the Cs symmetry adopts an irregular
planar configuration. The top lowest energy isomers of Au8Ga
and Au9Ga are planar configurations. Furthermore, the
existences of the same structural skeletons but different kinds
of atom distributions in binary AunGa isomers further manifest
that the search project we used can well handle the
HOMOTOP puzzles in alloy clusters.34,35
Overall, the AunGa (n = 1−9) clusters show a diversity and
flexibility in geometric structures, and the global structures of
them are more inclined to two dimensions with cluster size n.
The isomer structures per cluster vary greatly in point energy.
In addition, we need to note that the Ga atom is invariably
inclined to stay inside the clusters, occupying the highly
coordinated positions. This may be attributed to the principle
of maximum overlap in molecular orbital theory. If the orbital
overlaps between Au and Ga atoms increase, the energy of
AunGa clusters will decrease.
3.2. Stability of AunGa (n = 1−9) Clusters. As is well
known, the relative stability of binary alloy clusters is usually
analyzed by the binding energy per atom (Eb) and the second
difference in energy (Δ2E), which can give direct information
about the stability versus cluster compositions at the different
sizes. These two quantities are respectively defined by the
following equations: Eb = [nE(Au) + E(Gd) − E(AunGa)]/(n
+ 1); Δ2E = E(Aun+1Ga) + E(Aun−1Ga) − 2E(AunGa), where
values of E(Au), E(Gd), and E(AunGa) are the total energy of
individual Au and Ga atoms, as well as AunGa clusters,
respectively.
Figure 2 plots the Eb curve with GM structures and the Δ2E
curve, where these quantities are two functions of the size
number n for the considered AunGa (n = 1−9) clusters. The Eb
curve as shown in Figure 2a of the AunGa clusters presents an
overall trend of slow rising with the size number n, and it has a
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Figure 2. (a) Binding energy per atom (Eb) and (b) second difference
in energy (Δ2E) for AunGa (n = 1−9) clusters.
steep upward change at n = 4. The curve appears two local
maximums at n = 3 and 5, respectively. According to the
definition of the Eb equation, we can conclude that the planar
Au3Ga and Au5Ga clusters have higher stability than that of
their neighbors. The reasons may be that these two clusters
have electronic shell closures. From the curve in Figure 2b, we
intuitionally find that the Δ2E curve of the AunGa clusters
shows even−odd oscillations common to other alloy clusters.
But distinct peaks of it also appear at n = 3 and 5. This result
also further verifies that the Au3Ga and Au5Ga clusters are very
salient on the Eb curve.
To further investigate the thermal stability of the planar
Au3Ga and Au5Ga clusters, we carry out the AIMD simulations
in different temperatures. During the modeling process, the 20
× 20 × 20 Å boxes are established for the structures to avert
interactions between any two clusters. The initial temperatures
300 and 500 K are selected for simulations, respectively. The
total simulation time per temperature was set to around 10 ps,
and the time step was set at 2.0 fs. During the simulations, the
trajectory information is taken every 20 fs to supervise the
structure change details, and the energy fluctuations are
extracted after 10 ps AIMD simulations. The AIMD simulation
curves are shown in Figure 3. It can be seen that the
configurations of both Au3Ga and Au5Ga clusters remain intact
at a temperature of 500 K and only appear metal atom slight
disturbances, suggesting that they have excellent thermal
stability at high temperatures.
3.3. Planar Aromaticity in the Au3Ga and Au5Ga
Clusters. The discovery for chemically stable structures of
clusters, e.g., superatom and aromaticity clusters, is one of the
fastest-growing fields in current nanomaterial researches.36,37 It
is generally recognized that the stabilities of alloy clusters are
synergistically decided by their geometries and electronic
characteristics. When electron shells of clusters appear closed,
size-dependent stability features will emerge in the cluster
sequences. Here, the Au3Ga and Au5Ga clusters have higher
stability than that of their neighbors from the results of Eb and
Δ2E curves, and they also have excellent thermal stabilities at
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Figure 3. AIMD simulations of the (a) Au3Ga and (b) Au5Ga cluster energy trajectories with the time step at 500 K.

Figure 4. (a, b) MO diagrams of the Au3Ga and Au5Ga clusters under top and side views. Their isosurface values are set to 0.02.

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J. Phys. Chem. A 2023, 127, 2697−2704
The Journal of Physical Chemistry A
high temperatures. Since the 6/8 valence electrons have
already followed the magic number rules of electron shell
closures in cluster models, are the fillings of these valence
electrons also satisfied as well?
As the transition metal, 6s1 electrons of Au atoms are
generally delocalized on the whole clusters, and the Ga atom as
the main-group metal has 4s24P1 valence electrons. What are
the electronic structures of the mixing clusters formed by
them? To explore the 6/8 valence electron filling details of
Au3Ga and Au5Ga clusters, their molecular orbitals (MOs) at
the PBE0/Def2-TZVP level are calculated. The isosurface
values are set to 0.02. From Figure 4a, the HOMO, HOMO-1,
and HOMO-2 orbitals are typical superatomic 1Px, 1Py, and 1S
orbitals from their shapes, respectively. Moreover, we can see
the 5d-type lone pairs in the Au atoms, involving the HOMO-
3, HOMO-4, HOMO-5, HOMO-6, and HOMO-7 orbitals.
Hence, the 6 valence electrons of the Au3Ga occupy three
delocalized orbitals, which come from joint contributions of
Au and Ga atoms, having σ-aromaticity following the (4n + 2)
rule. We present the example of aromatic bimetallic cluster
involving only σ orbitals. In fact, the same situations can be
seen in previous reports. For example, the enhanced stability of
the Au5Zn+ and Au9Zn− is ascribed to their σ-aromaticity.38,39
In the PtZnH5− cluster anion, the σ-aromaticity is found in the
H5-cycle supported by the 5d orbitals on the Pt atom, where
the σ-aromaticity is assigned to the five-membered ring formed
by the five H atoms, although the distance between two Au
atoms is also too long.40 From Figure 4b, only 2 valence
electrons of the HOMO orbital delocalize over the whole
structure of the Au5Ga, also following planar σ-aromaticity.
The electron localization function (ELF) and localized
orbital locator (LOL) analyses are implemented by the
Multiwfn 3.8 software, and they provide quantitative standards
to investigate the electronic characters in alloy clusters.41−43
The values of ELF and LOL range from 0.0 to 1.0, where the
relatively large values (0.5 to 1.0) indicate regions containing
localized electrons, whereas smaller values (<0.5) describe
regions where electrons are expected to be delocalized. As
shown in the color-filled ELF and LOL maps in Figure 5, the
valence electrons of the Au3Ga and Au5Ga clusters have very
obvious delocalization characteristics throughout the whole
planar spaces, whereas the bonding localized electrons between
two metal atoms are almost impossible to see. The ELF and
LOL results are consistent with the results of MO analysis.
MO, ELF, and LOL analyses have been verified that 6 and 2
valence electrons delocalize over the entire structures of Au3Ga
and Au5Ga, respectively. Since delocalization is always
associated with aromaticity, we focus on the aromaticity of
those systems. The nucleus-independent chemical shift
(NICS) values are often used for quantitative measurements
of aromaticity.44 Negative NICS values indicate that systems
are aromatic, and positive NICS values imply anti-aromaticity.
Here, we further analyze the aromaticity of planar Au3Ga and
Au5Ga clusters employing the NICSzz-scan method. The
NICSzz-scan analysis is similar to the aromatic ring current
shielding method and can clearly delineate the type of the ring
current in aromatic and anti-aromatic systems.45,46 Figure 6
plots the curves of NICSzz-scan values for the Au3Ga and
Au5Ga clusters in the range of −5.0 to 5.0 Å above the
structural centers. It is found that NICSzz-scan values of
Au3Ga are all negative, while those of the Au5Ga are only
negative in the range of −2.0 to 2.0 Å. The center of the
geometry is a Ga atom, whereas in Au5Ga, we have a four-
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Figure 5. ELF and LOL of (a) Au3Ga and (b) Au5Ga clusters. Notes
are the color scale of the values.
membered ring. The curve magnitudes of NICSzz scans are
incredibly different in the range of −0.5 to 0.5 Å and cannot be
compared. But we can select NICS values above the molecular
plane and >1 Å to the center atom for comparisons. For
example, the NICS(1) values of Au3Ga (−2.9 ppm) are more
negative than those of the Au5Ga (−1.9 ppm), suggesting that
the former has more delocalized electrons than the latter,
which also are consistent with the results of MO analysis. Such
a situation that the NICS is ring size dependent has been
reported by other authors as well. For example, Foroutan-
Nejad et al. assess the complex pattern of aromaticity in all-
metal species and concluded that the single-point NICS are
highly dependent on the ring size.45 At the centers of the plane
configurations, the NICSzz-scan curves display descending
peaks. We think the reason may be that the Au3Ga and Au5Ga
clusters have six and two delocalized electrons, respectively,
which all satisfy Hückel’s 4n + 2 rule for σ-aromaticity.
Furthermore, we find the positive NICS region above the ring
planes that is an indirect sign of local currents. Any point-wise
comparison based on the NICS, whether it is in the center or
an arbitrary point above the center, is meaningless because it
cannot provide any information regarding the ring cur-
rent.47−50
The ring current analysis is further performed in the ACID
software.51 The ACID plot (Figure S1) shows that the
molecule sustains extremely strong paramagnetic currents
around the atoms. Certainly, many magnetic criteria can also
be helpful to further assess the presence of σ-aromaticity in
novel clusters and molecules, but some precautions should be
taken into account. Referring to the reference, Boldyrev et al.
in the review present examples of metal clusters, for which the
use of σ-aromaticity concepts is essential for understanding
chemical bonding and electron delocalization.52 For example,
the stability and planarity of the high-symmetry BeM5+ (M =
Cu, Ag, and Au) with the D5h symmetry are mainly reinforced
by σ-aromaticity.53 Therefore, the σ-aromaticity in this paper is
characterized by delocalized σ-bonding, after all MO, ELF,
LOL, and NICS-scan results have been verified that the
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Figure 6. NICSzz-scan curves for the Au3Ga and Au5Ga clusters within the range of −5.0 to 5.0 Å above the geometric centers of the systems.
valence electrons delocalize over the entire structures of Au3Ga
and Au5Ga.
4. CONCLUSIONS
In summary, the structures and stability of neutral AunGa (n =
1−9) clusters are analyzed in detail using the GA-DFT
methods. The global structures of them are more inclined to
two dimensions with cluster size n, where the Ga atom tends to
stay inside the clusters, occupying the highly coordinated
positions. Moreover, the valence electron fillings and chemical
bonding of the clusters with magic number electrons (6 and 8)
are further explored. It is found that the Au3Ga and Au5Ga
clusters present planar configurations, and they have higher
stability than that of neighbor clusters by Eb and Δ2E analyses.
The AIMD simulations show that these two clusters still have a
good thermal stability at 500 K. MO analysis shows that the
Au3Ga and Au5Ga clusters have three and one typical
delocalization orbital throughout the whole planar spaces,
respectively, as well as localized 5d-type lone pairs of the Au
atoms, following σ-aromaticity with the (4n + 2) rule. ELF and
LOL analyses are further performed, and the results are
consistent with the results of MO analysis. The NICSzz-scan
curves confirm that the Au3Ga is more aromatic than the
Au5Ga, and the reason is that the former has more delocalized
electrons than the latter. The work opens up aromaticity
studies in the Au−Ga clusters.
■ ASSOCIATED CONTENT
* Supporting Information
sı
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acs.jpca.2c08741.
The ring current density plots for the Au3Ga on the ring
plane of the molecule and the Cartesian coordinates of
AunGa (n = 1−9) clusters (PDF)
■ AUTHOR INFORMATION
Corresponding Authors
Qiman Liu − School of Chemistry and Materials Engineering,
Huainan Normal University, Huainan 232038, P. R. China;
Anhui Provincial Institute of Modern Coal Processing
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pubs.acs.org/JPCA Article
Technology, Anhui University of Science and Technology,
Huainan 232038, P. R. China; orcid.org/0000-0002-
9213-7009; Email: qimliu@ustc.edu.cn
Longjiu Cheng − Key Laboratory of Structure and Functional
Regulation of Hybrid Materials, Ministry of Education, Anhui
University, Hefei, Anhui 230601, P. R. China; orcid.org/
0000-0001-7086-6190; Email: clj@ustc.edu.cn
Authors
Manli Zhang − School of Chemistry and Materials
Engineering, Huainan Normal University, Huainan 232038,
P. R. China
Xing Gao − School of Chemistry and Materials Engineering,
Huainan Normal University, Huainan 232038, P. R. China
Complete contact information is available at:
https://pubs.acs.org/10.1021/acs.jpca.2c08741
Notes
The authors declare no competing financial interest.
■ ACKNOWLEDGMENTS
This work is supported by the Open Research Fund Program
of Anhui Provincial Institute of Modern Coal Processing
Technology (MTY202204), the Horizontal Cooperation
Project of Huainan Normal University (2022HX47), and the
Key Project of Scientific Research Foundation of Anhui
Province Education Department (KJ2021A0961 and
KJ2021A0962). The calculations were carried out at the
High-Performance Computing Center of Anhui University.
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