Theoretical Studies of Palladium-Gold Nanoclusters

J. Phys. Chem.
C 2009, 113, 91419152
9141
Theoretical Studies of Palladium-Gold Nanoclusters: Pd-Au Clusters with up to 50 Atoms

Faye Pittaway, Lauro Oliver Paz-Borbon, Roy L. Johnston,*, Haydar Arslan,
Riccardo Ferrando, Christine Mottet,| Giovanni Barcaro, and Alessandro Fortunelli
School of Chemistry, UniVersity of Birmingham, Edgbaston, Birmingham, B15 2TT, United Kingdom, Department of
Physics, Zonguldak Karaelmas UniVersity, Zonguldak 67100, Turkey, Dipartimento di Fisica, UniVersita di GenoVa,
and CNISM, Via Dodecaneso 33, 16146 GenoVa, Italy, CINaM-CNRS, Campus de Luminy, case 913,
13288 Cedex 09, Marseille, France, and Molecular Modeling Laboratory, Istituto per i Processi Chimico-Fisici del
Consiglio Nazionale delle Ricerche (IPCF-CNR), Via G. Moruzzi 1, I-56124 Pisa, Italy
ReceiVed: January 20, 2009; ReVised Manuscript ReceiVed: April 6, 2009
Global optimization of Pd-Au bimetallic clusters in the size range N ) 2-50 has been performed using a
genetic algorithm, coupled with the Gupta many-body empirical potential (EP) to model interatomic interactions.
Three sets of EP parameters have been examined in this work: (a) an average of pure Pd and Au parameters,
(b) experimental Pd-Au-fitted parameters, and (c) DFT-fitted parameters. Stability criteria, such as binding
energy and second difference in energy, have been used to determine the lowest energy structures, that is, the
global minima (GM). DFT local relaxations have been performed on all the putative GM structures for 1:1
compositions of (Pd-Au)N/2 up to N ) 50 for the three sets of EP parameters. It is found that the average
parameter set a leads to a PdcoreAushell segregation, whereas the fitted parameter sets b and c lead to more
Pd-Au mixing. DFT reoptimization of the structures produced by potentials a, b, and c shows small differences
in binding energies. In addition, 34- and 38-atom Pd-Au clusters were studied using these three Gupta potential
parametrizations as a function of composition and analyzed in terms of their mixing energies and chemical
order parameters. DFT relaxations were performed on the lowest mixing energy compositions, allowing us
to have a clearer description of the energy landscape for all three EP parameter sets at these cluster sizes. For
the compositions, Pd17Au17 and Pd19Au19, DFT calculations confirm that some degree of Au surface segregation
is energetically preferred, though it is not necessarily complete PdcoreAushell segregation, as predicted by the
average potential a.
TABLE 1: Some Elemental Properties of Pd and Au
1. Introduction
The desire to fabricate materials with well-defined, controllable properties and structures on the nanometer scale has
generated considerable interest in bimetallic clusters or nanoalloys.1 Much research on nanoalloys has been driven by their
actual and potential applications in a number of catalytic
processes. Pd-Au nanoparticles, in particular, have been found
to be efficient catalysts for a wide variety of chemical reactions,
such as acetylene cyclotrimerization, the hydrogenation of hex2-yne to cis-hex-2-ene, hydrodechlorination of trichloroethene
(TCE) in water, the low-temperature synthesis of hydrogen
peroxide, and the reduction of CO and alcohols.2-6 Previous
experimental studies of Pd-Au nanoalloys (e.g., see refs 3,
7-13) have shown that PdcoreAushell, AucorePdshell, 3-shell, and
solid solution configurations can be generated, whereas theoretical studies (e.g., see refs 14 and 15) have indicated that the
PdcoreAushell configuration is favored. Surface segregation in
nanoalloys may be simply predicted on the basis of simple
elemental properties, such as cohesive energy (Ecoh), surface
energy (Esurf), atomic radius (ra), and electronegativity ().1
These quantities are listed for Pd and Au in Table 1.
* Corresponding author. r.l.johnston@bham.ac.uk.
University of Birmingham.
Zonguldak Karaelmas University.
Universita di Genova, and CNISM.

|
CINaM-CNRS, Campus de Luminy.
Istituto per i Processi Chimico-Fisici del Consiglio Nazionale delle

Ricerche (IPCF-CNR).
Pd
Au
Ecoh/eV atom-1
Esurface/meV -2
ra/
3.89
3.81
131
96.8
1.38
1.44
2.2
2.4
Preferential segregation of Au atoms to the surface of

Pd-Au nanoalloys can be rationalized in terms of the
marginally larger cohesive energy of Pd (favoring a Pd core,
maximizing Pd-Pd bonds) and the smaller surface energy
of Au (atoms with lower surface energy forming a surface
shell lower in cluster surface energy). The smaller atomic
radius of Pd also leads to preferential core location of Pd
atoms as it helps to minimize bulk elastic strain. Finally, the
slightly higher electronegativity of Au compared with Pd will
lead to a certain degree of Pd to Au electron transfer, as
found in density functional theory (DFT) calculations by
Yuan et al.16 This ionic contribution may be expected to favor
Pd-Au mixing, although we have previously shown for
Ag-Au clusters that M-Au charge transfer (M ) metal)
can also favor surface enrichment by the more negatively
charged Au atoms.15,17 Of course, the arguments presented
above are rather simple, and the fine details of cluster
structure, chemical ordering (segregation or mixing), and
surface site preferences depend critically on electronic
structure. For example, recent DFT calculations on fcc-type
cuboctahedral Pd-Au nanoparticles have indicated that
surface Pd atoms occupy (111) rather than (100) facets,
thereby maximizing the number of relatively strong surface
Pd-Au bonds.18 In fact, the ionic contribution to Pd-Au
10.1021/jp9006075 CCC: $40.75 2009 American Chemical Society

Published on Web 05/01/2009
9142
J. Phys. Chem. C, Vol. 113, No. 21, 2009
Pittaway et al.
TABLE 2: Gupta Potential Parameters Used in This Study

(a) average parameters (average)
(b) experimental-fitted parameters (exp-fit)
(c) DFT-fitted parameters (DFT-fit)
parameter
Pd-Pd
Au-Au
Pd-Au
Pd-Pd
Au-Au
Pd-Au
Pd-Pd
Au-Au
Pd-Au
A/eV
/eV
p
q
ro/
0.1746
1.7180
10.867
3.7420
2.7485
0.2061
1.7900
10.229
4.0360
2.8840
0.1900
1.7500
10.540
3.8900
2.8160
0.1715
1.7019
11.000
3.7940
2.7485
0.2096
1.8153
10.139
4.0330
2.8840
0.2764
2.0820
10.569
3.9130
2.8160
0.1653
1.6805
10.8535
3.7516
2.7485
0.2091
1.8097
10.2437
4.0445
2.8840
0.1843
1.7867
10.5420
3.8826
2.8160
bonding has been used to predict that Pd-Au bonds are

stronger than both Pd-Pd and Au-Au bonds.16 These
findings are consistent with earlier studies by Goodman and
co-workers9 and by Jose-Yacaman and colleagues,10 who have
also combined TEM and HAADF-STEM measurements with
image simulation and classical molecular dynamics simulations to study shell structure and defects in Pd-Au
nanoalloys.11-13
In the present study, global optimizations are performed
for Pd-Au bimetallic clusters in the size range of N ) 2-50
with the interatomic interactions modeled by the Gupta manybody empirical potential (with three different potential
parametrizations investigated). Furthermore, DFT local relaxations are performed on all the putative GM structures
for 1:1 Pd/Au compositions up to 50 atoms for all sets of
EP parameters. For specific nuclearities (N ) 34 and 38),
the structures and chemical ordering are investigated as a
function of composition at both the Gupta and DFT levels.
2. Methodology
2.1. Genetic Algorithm. Global optimizations were performed using a genetic algorithm (GA), as encoded in the
Birmingham Cluster Genetic Algorithm (BCGA) program,19
with interatomic interactions modeled by the Gupta many-body
empirical potential.20 The GA parameters used in the BCGA
were population size ) 40; crossover rate ) 0.8 (i.e., 32
offspring are produced per generation); crossover type ) 1-point
weighted (the splice position is calculated on the basis of the
fitness values of the parents); selection ) roulette wheel;
mutation rate ) 0.1; mutation type ) mutate_move; and number
of generations ) 400. The number of GA runs for each
composition was 100. The high number of GA runs is made
necessary by the relatively large size of the clusters and the
presence of homotops.
2.2. Homotops. The term homotop was introduced by
Jellinek et al. to describe AaBb nanoalloy isomers with a fixed
number of atoms (N ) a + b) and composition (a/b ratio) and
the same geometrical structure, but which differ in the way the
different atom types are arranged.21 The number of homotops
rises combinatorially with cluster size, which makes global
optimization an extremely demanding task. A single geometrical
isomer of an N-atom AB binary cluster gives rise to NPA,B
homotops
PA,B )
N!
N!
)
NA!NB !
NA!(N - NA)!
(1)
where N is the total number of atoms and NA and NB are the

number of atoms of type A and B, respectively.
2.3. Gupta Many-Body Potential. Empirical potentials have
been developed to allow relatively rapid searching of large areas
of configuration space. We use the Gupta potential, formulated
by Cleri and Rosato,20 to model the interatomic interactions in
nanoalloys. The Gupta potential is based on the second moment
approximation to tight-binding theory and comprises an attrac-
tive many-body (V m) term and a repulsive pair (V r) term,

obtained by summing over all N atoms
N
Vclus )
[V r(i) - V m(i)]
(2)
where V r(i) and V m(i) are defined as
Vr(i) )
j*i
and
[
N
Vm(i) )
)]
A(a, b)exp -p(a, b) r0(a,ij b) - 1
j*i
2(a, b)exp -2q(a, b)
(3)
))]
rij
-1
r0(a, b)
1/2
(4)
where a and b refer to the element type. In eqs 3 and 4, rij

represents the distance between atoms i and j in the cluster.
The parameters A, r0, , p, and q are fitted to experimental values
of the cohesive energy, lattice parameters, and independent
elastic constants for the reference bulk crystal structure at
absolute zero. The parameter is the many-body energy scaling
parametersalso known as the hopping integral.
2.4. Pd-Au Parameters. Three sets of potential parameters
have been adopted in this work (see Table 2): (a) one in which
the heteronuclear Pd-Au parameters were obtained as averages
of the pure Pd-Pd and Au-Au parameters, hereafter referred
to as average;15 (b) one in which Pd-Pd, Pd-Au, and Au-Au
parameters were simultaneously fitted to experimental properties
of bulk Pd, Au, and Pd-Au alloys, hereafter referred to as expfit; and (c) one in which the parameters for Pd-Au heteronuclear interactions were fitted to DFT calculations, hereafter
referred to as DFT-fit. The choice of set a, in which the
Pd-Au parameters have been rounded to the precision where
the arithmetic and geometric means are the same, was based
on our earlier work on Pd-Pt nanoalloys, where averaged
parameters were found to qualitatively reproduce the experimental Pd surface segregation.22 Recently, we have shown that
the average Pd-Pt Gupta potential also gives results that are
in reasonable agreement with DFT calculations.23,24
In parameter set b, the mixed parameters A and have been
fitted to the dissolution energies of one impurity Au atom
substituted into bulk Pd and vice versa. These values are derived
from the enthalpy curves in the Pd-Au phase diagram.25 The
dissolution energies are taken as the slope of the mixing enthalpy
curve on each side of the phase diagramsthat is, the Pd-rich
phase for the dissolution energy of Au and the Au-rich phase
for the dissolution energy of Pd. As the difference in size
between the two elements is not negligible, we took into account
possible relaxations around the impurity in our fitting procedure.
The Pd-Au bulk phase diagram presents a complete series of
solid solutions with some possible ordered L12 AuCu3-type
phases near the composition, Au60Pd40. This means that there
is a strong tendency to mix the two elements in the bulk. It is
Theoretical Studies of Palladium-Gold Nanoclusters
J. Phys. Chem. C, Vol. 113, No. 21, 2009 9143
interesting to note that the exp-fit parameter set b has a pair

(repulsive) energy scaling parameter (A) that is larger for Pd-Au
than for either Pd-Pd or Au-Au: in our previous work, a high
heteronuclear A value was found to lead to layerlike segregation.22 However, set b also has a many-body (attractive) energy
scaling parameter () that is greatest for Pd-Au: in our previous
work, this was found to favor ordered heteronuclear mixing.22
As will be shown below, for set b, the many-body term wins
out so that, overall, the fitted potential favors Pd-Au mixing,
as expected from the fitting procedure detailed above. The pair
and many-body range exponents (p and q) for Pd-Au interactions (and the atomic radii, ra) were taken as arithmetic means
of the pure metal values.
In parameter set c, the parameters have been fitted to the
results of first-principles DFT calculations. This consists of
taking the DFT cohesive energy curves of the pure systems and
rescaling these to fit the experimental ones (to obtain the exact
values of the cohesive energy, lattice parameter, and stickiness).
The obtained rescaling factors are used to rescale the cohesive
energy curves of the systems given by ordered intermetallic
phases, which are then used to fit the parameters of the
heteronuclear Pd-Au interaction. For the metals A and B (i.e.,
Pd and Au), the chosen ordered alloys are of the type AnBm,
with m + n ) 4: in the case where m ) n ) 2, we chose the
L10 ordering of the alloy, whereas in the case where m ) 1 and
n ) 3 and vice versa, we chose the L12 ordering.
2.5. DFT Calculations. DFT calculations on finite Pd-Au
clusters were performed using the NWChem 5.1 quantum
chemistry package26 and the Perdew-Wang (PW91) exchangecorrelation functional.27 Spherical Gaussian-type orbital basis
sets of double- quality28,29 were used for Pd (7s6p5d)/[5s3p2d]
and Au (7s5p5d)/[6s3p2d], combined with effective core
potentials (ECP).30 Charge density fitting basis sets were used
to speed the evaluation of Coulombic contributions:31 Pd
(8s7p6d5f4g)/[8s6p6d3f2g] and Au (9s4p4d3f4g)/[8s4p3d3f2g].
All the calculations were performed spin-unrestricted, using a
Gaussian smearing technique (with a smearing parameter of 1.36
eV) for the fractional occupation of the one-electron energy
levels. For the fitting of the DFT-fit parameters, DFT calculations on the solid phases were performed using the PWscf
(plane-wave self-consistent field) computational code32 employing ultrasoft pseudopotentials.33 A total of 10 and 11 electrons
is explicitly considered for Pd and Au, respectively. The PBE
exchange-correlation functional, which is a gradient-corrected
functional, was used. Values of 40 Ry on the energy cutoff of
the wave function and of 160 Ry on the energy cutoff of the
electronic density have been shown to provide accurate results
(1 Ry ) 13.606 eV) and have, thus, been employed. All the
calculations have been performed by applying a smearing
procedure of the energy levels with a Gaussian broadening of
0.002 Ry. The Brillouin zone has been described by choosing
a (10,10,10) grid.
2.6. Energetic Analysis. The average binding energy of an
N-atom cluster at the Gupta level is defined as
EGupta
)
b
-Vclus
N
(5)
where Vclus is the total cluster potential energy (eq 2). At the
DFT level, the average binding energy per atom is obtained as
the difference in total energy between the N-atom cluster and
its constituent atoms, divided by N.
When studying fixed-size bimetallic clusters as a function of
composition, the mixing energy NGupta is a useful quantity34
NGupta
Gupta
Etotal
(PdnAum)
Gupta
Gupta
Etotal
(PdN)
(AuN)
Etotal
-n
-m
N
N
(6)
where EGupta
total (PdnAum) is the Gupta total energy (Vclus) for a given
Gupta
cluster and ( EGupta
total (PdN))/(N) and ( Etotal (AuN))/(N) are the Gupta
energies per atom calculated for the pure PdN and AuN clusters,
respectively. Negative values of the mixing energy indicate
favorable mixing and, thus, more stable clusters. NDFT can be
similarly defined at the DFT level.34 A final indicator of the
relative stabilities of clusters is the second difference in energy,
2E, which is defined as follows at the Gupta level
2EGupta
) EGupta
(Pd/Au)N+1 + EGupta
(Pd/Au)N-1 b
b
b
(Pd/Au)N
2EGupta
b
(7)
for clusters of increasing size and fixed composition (e.g., for

a 1:1 composition). Intense peaks in 2EbGupta can be related to
relatively stable clusters. To analyze trends in chemical order
as a function of size and composition, it is convenient to define
an order parameter with the following characteristics: positive
when phase separation (segregation) takes place, close to zero
when disordered mixing occurs, and negative when mixing and
layerlike structures coexist. The chemical order parameter, ,
is defined as
NPd-Pd + NAu-Au - NPd-Au

NPd-Pd + NAu-Au + NPd-Au
(8)
where Nij (with i, j ) Pd, Au) is the number of nearest-neighbor

i-j bonds. An order parameter of this type has proven to be
useful in the description of short-range order in binary bulk
alloys and surfaces.35
3. Results and Discussion
3.1. Gupta Potential Calculations on (Pd-Au)N/2 Clusters
(N ) 2-50). Some of the putative GM for (Pd-Au)N/2 clusters
(with N ) 2-50) are compared in Figure 1 for the average,
exp-fit, and DFT-fit parameters. The symmetries and total
energies of all the GM at the Gupta level (in this size range)
are listed in Tables 1-3 in the Supporting Information (for the
average, exp-fit, and DFT-fit parameters, respectively). The
geometrical structures found for the three sets of parameters
are often the same but generally exhibit different chemical
ordering. From the structures shown in Figure 1, it is clear that
the average parameters favor PdcoreAushell segregation (as found
in our previous study15), whereas the exp-fit parameters favor
more mixed configurations, with more Pd-Au bonds. The DFTfit parameters predict a degree of Au/Pd mixing between the
two other potentials. A wide range of structural motifs are found
after performing GA global optimizations for the three sets of
parameters. Structural families include icosahedra (e.g., N )
54), Marks decahedra (e.g., N ) 98), and fcc-type structures
(e.g., the truncated octahedron, N ) 38).1,15,36-40
Figure 2a shows the calculated Gupta potential binding
energies (EbGupta) for 1:1 Pd-Au nanoalloys with 2-50 atoms
for the three sets of parameters. In each case, the binding energy
is reported for the putative GM found by the BCGA. The
binding energies (EbGupta) of the GM obtained for the exp-fit
parameters are higher than those obtained for the average
parameters but slightly higher than for the DFT-fit parameters,
indicating that Pd-Au mixing is preferred (at the empirical
potential level) in this size regime. Figure 2b shows plots of
the corresponding second differences in binding energy
(2EbGupta). Large positive peaks in 2EbGupta correspond to
9144
Pittaway et al.
Figure 1. Comparison of selected GM found for (Pd-Au)N/2 clusters with N ) 2-50 for the average, exp-fit, and DFT-fit parameters. Au and Pd
atoms are denoted by yellow and gray colors, respectively.
Figure 2. Plots of (a) binding energies (EGupta

) and (b) second differences in binding energy (2EGupta
) for (Pd-Au)N/2 clusters with N ) 2-50 at
b
b
the Gupta level, calculated using the average (black line), exp-fit (red line), and DFT-fit (blue line) parameters.
structures that have high stability relative to their neighbors.

However, for Pd-Au nanoalloys, the 2EbGupta values are quite
small (for the three sets of parameters) because of the small
difference in the cohesive energies of Pd and Au (see Table 1).
The 2EbGupta plots are similar for the three sets of potentials
(which tend to find the same structure as GM, with different
chemical order), where the discrepancies are due to the different
structures and homotops stabilized by these potentials.
3.2. DFT Calculations. DFT local relaxations have been
performed on all the putative GM structures for 1:1 Pd-Au
clusters with up to 50 atoms for the three sets of parameters.
Figure 3a shows a plot of the DFT binding energies (EbDFT)
versus N. Here, one can see that there is not much difference at
the DFT level between the GM isomers found for the average,
exp-fit, and DFT-fit parameters. Figure 3b shows the differences
in DFT binding energies between the fitted and average
parameters (i.e., EbDFT ) EbDFT(average) - EbDFT(fitted)), highlighting that, for some specific sizes, one or both fitted potentials
may give rise to more stable structures (indicated by negative
EbDFT values) than the average parameters.
Structural Analysis. In Figure 4, the total number of bonds

(nearest-neighbor contacts) of each type and the chemical
ordering parameter (, see eq 8) for the three parameter sets
are plotted as a function of cluster size (N) for 1:1 Pd-Au
clusters. For the average potential, one can see that the numbers
of Pd-Pd and Pd-Au bonds increase monotonically (quasilinearly) with N and are nearly equal (see Figure 4a). The
number of Au-Au bonds also increases with N, but less steeply
than for NPd-Pd and NPd-Au. For both fitted parameters (Figure
4b,c), the rate of increase in the number of bonds is in the order
Pd-Au . Pd-Pd > Au-Au, indicating the greater Pd-Au
mixing favored by the fitted potentials. The corresponding
values for all three sets of parameters are plotted in Figure 4d.
We find that, for the average parameters (Figure 4d), is
positive for cluster sizes N > 10, corresponding to PdcoreAushell
segregation. In contrast, for both fitted parameters, the values
are negative for all cluster sizes, indicating that the clusters have
significant Pd-Au mixing (NPd-Au > NPd-Pd + NAu-Au).
3.3. 34-Atom Pd-Au Clusters. Figure 5 shows the mixing
Gupta
) calculated at the Gupta level (for the three sets
energy (34
Figure 3. (a) DFT binding energies (EDFT

b ) after local re-minimization of the putative GM for the average (black line), exp-fit (red line), and
DFT-fit (blue line) Gupta parameters for (Pd-Au)N/2 clusters with N ) 2-50. (b) Differences in DFT binding energies (EDFT
b ): exp-fit and DFT-fit
vs average parameters, where negative values indicate more stable structures than those found using the average parameters.
Figure 4. (a-c) Numbers of Pd-Pd (black), Au-Au (red), and Pd-Au (green) nearest-neighbor bonds as a function of nuclearity (N ) 2-50)
for the 1:1 composition of Pd-Au clusters for GM obtained using the average, exp-fit, and DFT-fit parameters. (d) Comparison of the chemical
order parameter () for the three sets of parameters: average (red), exp-fit (black), and DFT-fit (green).
of potentials) for all compositions of 34-atom Pd-Au clusters

plotted against the number of Au atoms (m). We selected 34atom clusters to allow comparisons to be made with the results
of our previous in-depth study of 34-atom Pd-Pt clusters.23,24
The tendency of the exp-fit and DFT-fit parameters to favor
Pd-Au mixing is emphasized by the significantly more negative
mixing energies obtained for these potentials. These large
negative mixing energies (i.e., representing highly exothermic
mixing) are reminiscent of the mixing energy curves obtained
for 34-atom Pd-Pt clusters when weighting the heteronuclear
Pd-Pt interactions toward the strongest (Pt-Pt) homonuclear
interactions.24
The mixing energies (DFT
34 ) calculated at the DFT level (based
on the GM found for the three sets of potentials) are shown in
Figure 6 for the composition range, Pd24Au10-Pd6Au29, which

corresponds to the region of most negative mixing energies for
these potentials at the Gupta potential level; see Figure 6 and
Table 4 in the Supporting Information for a comparative analysis
of GM structures for the three sets of potentials at the DFT
Gupta
curves, the
level. Compared with the relatively smooth 34
plots
are
rather
jagged,
especially
for
both
exp-fit
and DFTDFT
34
fit parameter curves. It is not clear what the preference is at the
DFT level for structures based on these potentials, though the
exp-fit potential gives marginally lower mixing energy structures
compared to the average and DFT-fit parameter GM. The jagged
DFT
34 plots are reminiscent of those obtained for 34-atom Pd-Pt
clusters and may (as in the Pd-Pt case) indicate that there are
differences between the energy ordering of structural motifs at
9146
Pittaway et al.
Figure 5. Bottom: Gupta potential mixing energies (Gupta

34 ) for 34-atom Pd-Au nanoalloys as a function of the number of Au atoms (m), over the
entire composition range, for the average (black line), exp-fit (red line), and DFT-fit (blue line) parameters. Top: Dark blue squares indicate distorted
icosahedral or poly-icosahedral structures; red squares, pIh-6 (pancake-type) structures; white squares denote incomplete decahedral structures.
Figure 6. DFT mixing energies (DFT

34 ) after local minimization of the putative GM for the average (black line), exp-fit (red line), and DFT-fit (blue
line) Gupta parameters for 34-atom Pd-Au nanoalloys in the range of m ) 10-29 (m ) number of Au atoms).
the Gupta and DFT levels.23 The reason is that some of the
motifs that are energetically close and crossing at the Gupta
DFT
curve obtained by
level are disfavored by DFT so that the 34
reoptimizing the Gupta GM at the DFT level becomes irregular
whenever such motifs are predicted as the Gupta GM. Further
research in this area will include DFT re-minimization of other
low-lying structural isomers, not just the Gupta global minima.
The structures of the average, exp-fit, and DFT-fit GM (after
DFT re-minimization) are shown in Figure 7 for the composition
range, Pd17Au17-Pd10Au24. This composition range includes the
most negative DFT
34 values, as shown in Figure 6. In this region,
all of the putative GM for the average parameters have
incomplete decahedral structures (but no Dh-cp(DT) structures
as found previously for 34-atom Pd-Pt clusters). This probably
explains the rather smooth curve for the average parameters
DFT
minimum at the
(black line) in Figure 6, with the 34
composition, Pd10Au24. On the other hand, the structures derived
from both fitted parameters tend to maximize the number of
Pd-Au bonds; hence, they tend to form incomplete icosahedral
or poly-icosahedral (here we classify as poly-icosahedral those
clusters containing at least two elementary 13-atom icosahedra)
arrangements in this composition range. It is interesting to note
that the lowest DFT
34 compositions correspond to two incomplete
icosahedral structures obtained using exp-fit parameters (i.e.,
compositions of Pd13Au21 and Pd15Au19). When comparing these
two structures with those found using the DFT-fit parameters,
we notice that they have a distorted five-fold shape compared
to the more asymmetric (amorphous) structures found using the
DFT-fit parameters. It remains to be seen whether the Dh-cp
(DT) motif (found as GM for 34-atom Pd-Pt clusters) will be
Figure 7. GM structures obtained after DFT optimization (for the three sets of Gupta parameters) for 34-atom Pd-Au clusters in the composition
range, Pd17Au17-Pd10Au24.
Figure 8. Bottom: Gupta potential mixing energies (Gupta

38 ) for 38-atom Pd-Au nanoalloys as a function of the number of Au atoms (m) over the
entire composition range for the average (black line), exp-fit (red line), and DFT-fit (blue line) parameters. Top: Light blue squares denote compositions
at which TO structures were found, yellow denotes Oh-Ih (close-packed) structure, green denotes Ih-Mackay (pseudo-five-fold structures), and
orange denotes pIh5 (five-fold pancakes), white denotes incomplete decahedral structures.
found as a GM for Pd-Au as this structure was not found during

our GA global optimization procedure.
3.3. 38-Atom Pd-Au Clusters. Figure 8 shows the mixing
Gupta
) calculated at the Gupta level (for the three sets
energy (38
of parameters) for all compositions of 38-atom Pd-Au clusters
plotted against the number of Au atoms, m. We selected 38atom clusters because size 38 is a magic number for the
truncated octahedral (TO) structure, which has fcc packing (the
bulk crystalline structure for both Pd and Au), and also for
the poly-icosahedral, pIh-6 six-fold pancake structure. These
structures, along with other structural motifs, have been studied
in our previous work on 38-atom nanoalloy clusters.15,38,39 The
tendency of the exp-fit parameters to favor Pd-Au mixing is
again manifested in the much more negative mixing energies
Gupta
) obtained for this potential, which is also found for the
(38
values (see Figure 8). Less negative Gupta

values
DFT-fit Gupta
38
38
are found for the average parameters, for which the lowest Gupta
38
value corresponds to the Au-rich composition, Pd14Au24. As
shown in Figure 9 (which reproduces the GM structures found
as the putative GM for the average, exp-fit, and DFT-fit
parameters in the composition range, Pd19Au19-Pd13Au25 at the
DFT level), this structure has regular Oh symmetry, consisting
of an fcc-like truncated octahedron (TO) with an octahedral Pd6
core surrounded by a shell of 24 Au atoms, with 8 Pd atoms
occupying the centers of the (111) facets.
Gupta
The corresponding minimum in 38
for the exp-fit and
DFT-fit parameters is at Pd18Au20, which is consistent with these
parameters favoring Pd-Au mixingswhich should be maximized around the 1:1 composition (although we still see a
preference of Pd atoms to occupy core positions in the cluster
9148
Pittaway et al.
Figure 9. GM structures (for the three sets of Gupta parameters) for 38-atom Pd-Au clusters in the composition range, Pd18Au20-Pd13Au25.
for the three sets of potentials, i.e., PdcoreAushell segregation).

The preferred sites for occupation by Pd and Au atoms are
Gupta
curves. Specifically, for
evident from the shapes of the 38
Gupta
38 (average), there are straight sections corresponding to the
first 24 Au atoms occupying surface (100) TO sites (square
faces), the next 8 atoms occupying the centers of the surface
(111) facets (hexagonal faces), and the final 6 atoms occupying
Gupta
(exp-fit), however,
the octahedral core of the cluster. For 38
the shape of the curve is different: the first 12 Au atoms occupy
half of the (100) sites, the next 8 occupy the (111) sites, the
next 12 occupy the remainder of the (100) sites, and the final 6
occupy the octahedral core.
For the average parameters (see Figure 9), the GM structures
obtained for all compositions are TO with surface Au enrichment
(i.e., idealized PdcoreAushell configurations), in agreement with
our previous studies.15 In agreement with the DFT calculations16
and as discussed above for Pd14Au24, surface Pd atoms
preferentially occupy (111) facets. TO structures are also found
as GM structures for the DFT-fit parameters. For the exp-fit
parameters (see Figure 9), the GM for most compositions are
also TO, though there is a five-fold symmetry structure found
as GM at the composition of Pd13Au25 (an icosahedral Mackaytype structure, previously described in ref 15). Again, the expfit parameters show significantly more Pd-Au mixing, though
they tend to favor surface Pd atoms occupying (100) rather than
(111) sites, in contrast to the findings of Yuan et al.16 This is
probably due to an incorrect interplay between binding and
equilibrium distance.
The mixing energies (DFT
38 ) calculated at the DFT level (based
on the GM found for all three parameter sets) are shown in
Figure 10 for the composition range, Pd18Au20-Pd13Au25 (the
DFT
energies are
point-group symmetries, structure types, and 38
listed in Table 5 in the Supporting Information). In contrast to
DFT
DFT
shown in Figure 6, the 38
plots are quite
the plots of 34
smooth, and it is also clear that, in this composition range, the
isomers predicted to be the GM by the average parameters have
consistently more negative mixing energies after DFT reminimization than those from the exp-fit and DFT-fit parameters.
The smoothness of the plots and lack of fluctuations are probably
because all of the structures (with the above-mentioned exception of Pd13Au25 (exp-fit)) have the same geometric structure
(TO), as shown in Figure 9.
Figure 10. DFT mixing energies (DFT

38 ) after local re-minimization
of the putative GM for the average (black line), exp-fit (red line), and
DFT-fit (blue line) Gupta potentials for 38-atom Pd-Au nanoalloys,
in the range of m ) 19-25 (m ) number of Au atoms).
DFT
plots for
It should be noted that the minimum in the 38
the average and exp-fit parameters occurs at the composition,
Pd15Au23-that is, one less Au atom than the minimum of Gupta
38
(average) and three more Au atoms than the minimum of Gupta
38
(exp-fit). Thus, for 38-atom Pd-Au clusters in this composition
range, we can say that the average parameters produce TO
homotops that are closer to the true DFT GM (for this structure
type) than those found using the exp-fit parameters. It is
interesting to note that the DFT-fit parameters also predict TO
structures as GM, with a higher mixing of Pd-Au bonds
compared to that of the GM structures predicted by the average
parameters. The DFT-fit parameter DFT
38 curve is rather smooth,
DFT
curves, with a minimum at the
similar to the other two 38
composition, Pd14Au24 (a highly symmetrical Oh structure),
though it also has a maximum at Pd18Au20.
The increased mixing on going from the average to the expfit parameters has been confirmed by a detailed analysis (for
38-atom Pd-Au clusters) of the number of homo- and heteronuclear bonds and other mixing parameters as a function of
composition. Figures 11 and 12 show the average nearestneighbor distance (ANND); the number of Pd-Pd, Pd-Au, and
Figure 11. Variation of average nearest-neighbor distance (ANND)

as a function of the number of Au atoms (m) for 38-atom Pd-Au
clusters, for GM obtained using the (a) average, (b) exp-fit, and (c)
DFT-fit parameters.
Au-Au bonds; and chemical order parameter () as a function

of the Au content (m) for the GM found for the average, expfit, and DFT-fit parameters, at the Gupta level of theory. The
average nearest-neighbor distance (ANND) plots (Figure 11)
show a steady increase with increasing Au content due to the
larger atomic radius of Au (see Table 1). For the average
parameters, there is an increase in the slope at m ) 24; as for
higher Au content, the additional Au atoms start to occupy the
(111) facets and the core of the cluster-causing a greater rate
of cluster expansion per added Au atom. For the exp-fit
parameters, however, there is a steeper initial slope (as there
are more Pd-Au bonds, the effect of adding Au atoms is
initially greater), but the plot flattens out at m ) 20. The points
at which the slope changes-that is, Pd14Au24 (average) and
Pd18Au20 (exp-fit)-correspond to the maxima in the Pd-Au
bond plot (Figure 12). For the case of the average nearestneighbor distance (ANND) plot for the DFT-fit parameters, we
see a rather jagged behavior as this set of parameters leads to

a high degree of mixing (Pd-Au bonds), but not as much as
for the exp-fit parameters.
Figure 12 shows that, for the average potential, NPd-Pd
decreases monotonically, whereas NAu-Au increases with increasing Au content, m. NPd-Au increases to a maximum at
Gupta
(average)
Pd14Au24, corresponding to the minimum in 38
observed in Figure 8. For the exp-fit parameters, NPd-Pd
decreases monotonically until m ) 20, after which there are
some fluctuations. In contrast to the average parameters, there
are no Au-Au bonds up to Pd26Au12 as the Au atoms are
dispersed on the surface of the cluster. The number of Pd-Au
bonds is maximized at the composition, Pd18Au20, corresponding
Gupta
(exp-fit) observed in Figure 8. A
to the minimum in 38
substantially analogous (even though slightly more irregular)
behavior is observed for the DFT-fit parameters, confirming the
qualitative similarity between exp-fit and DFT-fit parameters.
Finally, Figure 12 shows plots of the chemical order
parameter () for the three sets of potentials. For the average
parameters, is positive for all compositions, falling to a
minimum value of 0 for Pd15Au23 and Pd14Au24. Positive
values correspond to core-shell segregation. The fact that the
plot goes through a minimum is inevitable because, even for
core-shell segregation, there are a high number of Pd-Au
bonds (which lead to a reduction of , see eq 8) for comparable
numbers of Pd and Au atoms.24 The minimum at around m )
24 is because of the extra Pd-Au mixing due to the Pd atoms
occupying the (111) facets (correlating with the maximum in
NPd-Au shown in Figure 12). For the exp-fit parameters, is
negative in the region of m ) 13-27 (being 0 for m ) 12),
indicating a high degree of Pd-Au mixing. Similar behavior is
found for the DFT-fit parameters. The minimum in for the
exp-fit and DFT-fit parameters occurs at Pd18Au20, corresponding
to the maximum in NPd-Au, as shown in Figure 12. It is
interesting to note that the minima in the mixing energy plots
for both the average and fitted parameters correspond to the
maximum number of Pd-Au bonds (and minima in ) for
different homotopic configurations. Thus, Pd14Au24 (average)
has the maximum number of Pd-Au bonds, consistent with
the PdcoreAushell ordering favored (energetically) by the average
potential; whereas Pd18Au20 (fitted) maximizes Pd-Au bonding
according to the tendency of the fitted parameters to favor more
mixed homotops. In principle, the maximum possible number
of Pd-Au bonds should be realized for the 1:1 composition,
that is, for Pd19Au19, but it is possible that to achieve this
maximum Pd-Au bonding would require a structure that is not
energetically competitive.
3.4. DFT Investigation of Segregation in 34- and 38-Atom
Pd-Au Clusters. Due to the vast combinatorial problem of
systematically evaluating all possible homotops for a given
nanoalloy structure and composition (see eq 1) and the impossibility of carrying out a reasonably rigorous homotop search
at the DFT level, we have chosen to carry out a DFT analysis
of normal and inverted homotops for the 1:1 composition
of 34- and 38-atom Pd-Au nanoalloys, Pd17Au17 and Pd19Au19
(this approach has previously been used to study a range of
nanoalloy clusters15,23). For the three sets of Gupta parameters
(i.e., average, exp-fit, and DFT-fit), the normal homotop is
the putative GM found (using the BCGA) for Pd17Au17 or
Pd19Au19. In each case, an inverted homotop is generated by
exchanging the positions of all Pd and Au atoms. All of the
normal and inverted homotops are then energy-minimized at
the DFT level.
The normal and inverted homotops for Pd17Au17 and Pd19Au19
are shown in Figure 13 (for the three sets of parameters), along
9150
Pittaway et al.
Figure 12. Variation of the number of bonds (black ) Pd-Pd, red ) Au-Au, green ) Pd-Au) and chemical order parameter () as a function
of composition (number of Au atoms ) m) for 38-atom Pd-Au clusters, for GM obtained using the (a) average, (b) exp-fit, and (c) DFT-fit
parameters.
with the total DFT cluster energies (in electronvolts) relative

to the lowest energy isomer found for each nuclearity. For
Pd17Au17, the isomer derived from the exp-fit potential (a quite
distorted fragment of a 55-atom icosahedron structure, with a
high number of Pd-Au bonds) is lower in energy (by 0.29 eV)
than the average structure (an incomplete decahedron with more
defined PdcoreAushell segregation) after DFT re-minimization,
which is consistent with its more negative DFT
34 value (see Figure
6). The DFT-fit parameters predicted a GM poly-icosahedral
structure; but this structure is not energetically favorable as it
is found to be approximately 0.40 eV higher in energy. DFT
optimizations on the three inverted homotops reveal that they
are higher in energy (ranging from 1.85 eV for the DFT-fit
inverted to 4.08 eV for the average inverted structures). For
Pd19Au19, the GM structures for these potentials are truncated
octahedra (TO). In this case, the lowest energy structure
corresponds to that derived from the average parameters (welldefined PdcoreAushell), which is lower in energy than the exp-fit
and DFT-fit parameter-predicted structures by 0.74 and 0.81
eV, respectively. This is consistent with the more negative DFT
38
value (see Figure 7b) of the Pd19Au19 average potential structure.

As the normal and inverted isomers all have TO structures and
because homotop inversion forces Pd and Au atoms to adopt
unfavorable sites, it is not surprising that the inverted homotops
have higher energies.
It should be noted that, because of the size of the homotop
search space, we cannot be sure that we have found the lowest
energy homotop at the Gupta potential level, let alone at the
DFT level. A possible way forward would be to couple DFT
calculations with low-temperature basin-hopping Monte Carlo
searching41 to perform a partial homotop optimization by
permuting unlike atoms, an approach that has previously been
applied to Gupta potential calculations for 34-, 38-, and 98atom nanoalloys.15,23,36-40
4. Conclusions
Three parametrizations of the many-body Gupta empirical
potential have been compared with regard to the geometrical
structures and homotops that they stabilize for Pd-Au
Figure 13. DFT investigation of segregation effects in 34- and 38-atom Pd-Au clusters for compositions 17-17 and 19-19, respectively. The
normal homotop is the lowest energy homotop found using the average or fitted Gupta parameters. In each case, the inverted homotop is
generated by swapping the positions of all the Pd and Au atoms. The energies quoted are the total DFT cluster energies relative to the lowest energy
isomer found for each nuclearity.
nanoalloy clusters with up to 50 atoms. The average

parameters (where the Pd-Au parameters are obtained by
averaging those for Pd-Pd and Au-Au interactions) are
found to favor PdcoreAushell segregationsas these maximize
the number of the stronger Pd-Pd bonds and expose the most
Au atoms (which have lower surface energies). The fitted
experimental (exp-fit) and DFT (DFT-fit) parameterssobtained
by fitting Pd/Au dissolution energies and the three ordered
phases of Pd-Au, respectivelysfavor Pd-Au mixing, generally leading to mixed Pd-Au nanocluster surfaces. Analysis
of the 1:1 Pd-Au clusters with up to 50 atoms shows that
there is no clear preference for any one set of parameters
over the whole size range. Hence, we decided to compare
the three potentials for fixed size (i.e., 34- and 38-atom
Pd-Au clusters) with variable composition.
From our DFT analysis of 34-atomPd-Au clusters, mixing
DFT
) curves for the fitted parameters showed a rather
energy (34
jagged behavior compared with those of the average parameters.
This can be interpreted in the sense that global optimizations
(at the EP level) using the fitted parameters tend to find
incomplete icosahedra or distorted poly-icosahedral structures,
whereas when using average parameters, incomplete decahedral
motifs are found as the lowest energy structures. It is not clear
what the preference is at the DFT level for structures based on
these potentials, though the exp-fit potential gives marginally
lower mixing energy structures compared to the average and
DFT-fit potentials.
For 38-atom nanoalloys, whose structures and chemical
ordering have been studied as a function of composition, the
average parameters have been found to yield isomers with lower
energies at the DFT level than those of both fitted parameters
(i.e., a preference for more PdcoreAushell-type structures at this
specific cluster size). A more extensive homotop search
(incorporating a limited BHMC search and DFT re-minimization) would be helpful to establish whether the average
homotops are, in fact, the GM or if there are lower energy
homotops at the DFT level. This would involve the DFT reminimization of low-lying Gupta isomers as well as the Gupta
GM, as previously performed for a number of 38-atom nanoalloys.15 This is currently being investigated, along with a detailed
analysis of the effect of systematically varying the Gupta
parameters on the structures and chemical ordering of 34- and

38-atom Pd-Au nanoalloys.
Acknowledgment. L.O.P.-B. and R.L.J. acknowledge the
National Service for Computational Chemistry Software (http://
www.nsccs.ac.uk) for the award of a CPU grant. Calculations
were also performed on the University of Birminghams
e-Science cluster and the BlueBEAR 1500+ processor highperformance computer cluster (http://www.bear.bham.ac.uk/).
H.A. acknowledges the HPC-EUROPA project for a travel grant
and CPU time on HPCx at EPCC (Edinburgh). Computer
resources on the HPCx service were provided to L.O.P.-B. and
R.L.J. via their membership of the UKs HPC Materials
Chemistry consortium and funded by EPSRC (portfolio grant
EP/D504872). F.P. is grateful to the EPSRC for financial
support, and L.O.P.-B. is grateful to CONACYT (Mexico) for
the award of a Ph.D. scholarship. We acknowledge support from
ESF for the Workshop on Computational Nanoalloys within the
Simbioma Programme.
Supporting Information Available: Tables 1-5 list the
energies of (PdAu)N/2 clusters with a 1:1 composition (N )
2-50) and 34- and 38-atom Pd-Au clusters with variable
composition, for both Gupta potential and DFT calculations,
as well as their corresponding point-group symmetries. This
material is available free of charge via the Internet at http://
pubs.acs.org.
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Theoretical Studies of Palladium-Gold Nanoclusters - Pd-Au Clusters With Up To 50 Atoms

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