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A density functional study of chemical, magnetic and

thermodynamic properties of small palladium clusters
a a
Ngangbam Bedamani Singh & Utpal Sarkar
a
Department of Physics, Assam University, Silchar, 788011, India
Published online: 16 Jan 2014.

To cite this article: Ngangbam Bedamani Singh & Utpal Sarkar , Molecular Simulation (2014): A density functional
study of chemical, magnetic and thermodynamic properties of small palladium clusters, Molecular Simulation, DOI:
10.1080/08927022.2013.861903

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 Molecular Simulation, 2014
http://dx.doi.org/10.1080/08927022.2013.861903

A density functional study of chemical, magnetic and thermodynamic properties of small

palladium clusters
Ngangbam Bedamani Singh and Utpal Sarkar*
Department of Physics, Assam University, Silchar 788011, India
(Received 10 April 2013; final version received 30 October 2013)

Structural, chemical, magnetic and thermodynamic properties of palladium clusters Pdn with n ¼ 2– 11 are studied using
density functional methods. The average bond length, entropy, enthalpy and polarisability are observed to increase as the
cluster grows in size. The binding energy per atom also increases with cluster size. Stability function and atom addition
energy change predict that Pd4, Pd6 and Pd9 are relatively more stable than their neighbouring clusters. Electron affinity,
electronegativity and electrophilicity values suggest that larger clusters have stronger tendency to accept electrons, thereby
supporting the relative stability of Pd4 and Pd6. Chemical hardness is also seen to decrease with cluster size, which suggests
that large clusters are more prone to changes in their electronic structure. The magnetic properties of these clusters are
Downloaded by [Assam University, Silchar] at 23:25 16 January 2014

reported.
Keywords: palladium cluster; DFT; reactivity parameters; magnetic moment; thermodynamic property

1. Introduction their successful applications in the nanoscale devices and

Atomic cluster is an important class of material consisting
of a few to hundreds of atom, which is in fact, either large
to be considered as molecules or too small to be considered
as bulk material. Compared with their bulk counterparts,
cluster shows distinct physical and chemical properties
which arise due to the quantum size effects. High surface
to volume ratio and significant change in electronic
structures are the important features of the clusters. Their
study can bridge the gap between the atomic and the
macroscopic solid-state physics. They exhibit extraordi-
nary size-dependent physical,[1] chemical,[2 – 4] magnetic
[5 – 9] and electrical properties.[10 –12] One of the most
significant features of atomic clusters is drastic changes in
their structures even with the addition of a single atom.
Palladium is one of the most promising catalyst
materials for many applications, mainly in hydrogenation
and dehydrogenation reactions.[2] Their unusual closed-
shell 4d10 electronic structures make them interesting as
well as challenging. Earlier study shows that the
promotion of electrons to the 5s (and sometimes even
5p) orbital [5] shortens the bond lengths and increases the
binding energy (BE) thereby stabilising small Pd clusters.
The small Pd clusters Pdn (n # 30) not only open the
possibility of tuning a catalytic process by changing
cluster size but can also be used to catalyse chemical
reactions at low temperatures.[3] Pd also plays integral
roles in a number of nanoscale devices, e.g. Pd nanowire-
based hydrogen sensors and carbon nanotube field effect
transistors.[10] So a clear and in-depth understanding of
the electronic properties of metal clusters is essential for
catalytic uses. Generally, the catalytic activity is directly
proportional to the size of the catalytically active species,
and catalysed reactions also exhibit structural sensitivity to
the size of the active species. Thus small metal clusters
whose sizes are in the range of few nanometers emerge as
the most suitable candidate to serve as catalytic particles.
These further arises a need to study and understand the
chemical reactivity of these small clusters. In order to
understand the physical and chemical properties of these
clusters, the determination of atomic configurations is
essential. Hence, our primary interest is to find out the
equilibrium configurations of the small Pd clusters and
correlation of their electronic properties with cluster size.
This may lead to understand the catalytic activity of such
clusters thus designing more efficient catalysts. Based on
this, a detailed systematic study is necessary to design
more efficient catalysts, although there have been a
number of studies (both theoretical and experimental) on
the Pd clusters.
Experimental studies have been carried out for
investigating many of the cluster properties such as
ionisation potential (IP), electron affinity (EA), reactivity
and magnetic behaviour.[9,13,14] Clusters of particular
stability, i.e. magic number clusters, can be observed with
the help of mass spectrometroscopy measurements,[15]
but experimental determination of geometrical structure of
clusters, particularly in the gas phase, is very difficult.
Theoretical calculations can help in determining the
equilibrium geometries of these clusters and can
complement the experimental studies. Advancement of
computational techniques in these days has enabled to

*Corresponding author. Email: utpalchemiitkgp@yahoo.com

q 2014 Taylor & Francis
 2 N.B. Singh and U. Sarkar

predict the structure and also properties of clusters with a
high degree of accuracy.
In the bulk form, Pd has no magnetic moment due to its
closed electronic configuration of 4d105s0. However, in the
cluster form, the delocalisation of electrons and depletion
of states because of sp-d hybridisation may give rise to
magnetism. The answer to the question ‘whether Pd
clusters have magnetic properties or not’ is still a
controversial issue. Experimental studies either find non-
magnetic or very weak magnetic moments. For example,
Pd clusters do not show any magnetic moment in Stern-
Gerlach deflection experiments,[9] whereas photoemis-
sion studies show Ni-like magnetic behaviour in Pdn
(n ¼ 3 –6) and non-magnetic behaviour in n . 15.[14]
Theoretical calculations predict very weak ferromagnetic
properties,[16] while in some cases, large magnetic
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electrophilicity (v),[31 – 33] and polarisability (a) [34]
are investigated for these clusters, and their dependence on
the cluster size is discussed thoroughly. The stability of the
clusters is also discussed with the help of these reactivity
parameters. The magnetic moments for each of the clusters
are also computed. Thermodynamic functions such as heat
capacity at constant volume, entropy and enthalpy are
calculated for small palladium clusters Pdn (n ¼ 2 –11) at
different temperatures. The knowledge of these properties
may be useful to understand how these small clusters work
as catalysts.
2. Theoretical background
DFT successfully provides the theoretical basis for many
chemical concepts, e.g. IP, EA, chemical potential (m),

moments.[5,7,8] In view of the present circumstances, it electronegativity (x), chemical hardness (h), electrophili-
seems reasonable to analyse the magnetic properties of the city index (v) and polarisability (a) to explain the stability
Pd clusters by using an appropriate exchange-correlation and chemical reactivity of atoms, molecules and clusters.
functional and basis set suitable for describing transition [21 – 39]
metals. IP and EA have been calculated using finite difference
The structural and electronic properties of neutral, approach [28]:
anionic and cationic Pd clusters atoms have been studied
[17] using density functional theory (DFT). Pd4, Pd6 and IP ¼ EðN 2 1Þ 2 EðNÞ; ð1Þ
Pd8 are observed to be relatively more stable compared
with others with relatively high value of stability function and
(DE2 ).[17] Pd4 (with 40 valence electrons) is found to be
the magic cluster with relatively high BE and stability EA ¼ EðNÞ 2 EðN þ 1Þ; ð2Þ
function (DE2 ). The second energy calculations of Pd
clusters using DFT have shown that Pdn (n ¼ 4, 6, 8, 10
where EðN 2 1Þ, E(N) and EðN þ 1Þ are the energies of the
and 13) clusters are relatively more stable.[18] Using DFT,
(N –1), N and (N þ 1) electron systems. Koopmans’
Zhang et al. [6] have studied the energetic, electronic and theorem [35] also provides an alternative way to predict IP
magnetic properties of Pd nanoparticles of up to 55 atoms and EA. It is also reported that IP may be calculated by
and showed that the stability of the nanoparticles increases using shape function.[36] With the help of IP and EA, we
with cluster size and dimensionality. have computed chemical potential, electronegativity and
Thermodynamic study is useful in understanding the chemical hardness [28]:
behaviour of clusters with change in temperature. In the
realm of small clusters, phase transitions are not sharp but IP þ EA
gradual,[19] and the thermodynamic properties are greatly m¼2 ; ð3Þ
2
dependent on size.[1] Theoretical study can predict the
structural transitions on increasing temperature for small
IP þ EA
clusters. For example, theoretical prediction of structural x¼ ; ð4Þ
change from fcc to decahedral and icosahedral structures 2
was made and observed in many systems.[20] The
stability, reactivity and aromaticity of metallic species IP – EA
h¼ : ð5Þ
can be successfully explained [21 – 39] using DFT-based 2
descriptors and occasionally augmented by the maximum
hardness principle (MHP).[23,24] In this paper, we have According to Parr’s prescription, electrophilicity index
studied the dependence of stability, chemical, magnetic (v) [33] is defined as
and thermodynamic properties on the structures of small
Pdn (n ¼ 2– 11) clusters. The stability of the clusters is m2
v¼ : ð6Þ
examined with BE per atom, atom addition energy change 2h
and the stability function. Chemical reactivity parameters
such as IP,[28] EA,[28] chemical potential (m),[28] The static electric dipole polarisability (a) is the
electronegativity (x),[29] chemical hardness (h),[30] second-order variation of energy (E) with respect to the

applied electric field (F) and is defined as
 
›2 E
aa;b ¼2 ; a; b ¼ x; y; z:
›F a ›F b
The polarisability (a) is then given by
1
, a .¼ : ð8Þ
3ðaxx þ ayy þ azz Þ
The above-mentioned descriptors can be properly
understood in terms of their related electronic structure
principles such as the electronegativity equalisation
principle (EEP),[29,37] the MHP,[23,24] the minimum
polarisability principle (MPP),[34] and minimum electro-
philicity principle (MEP).[38 –40] The statement of EEP
[29,37] is
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during an electron-transfer process in a chemical reaction,
electrons flow from a species of lower electronegativity
(higher chemical potential) to one with higher
electronegativity (lower chemical potential) until the
electronegativities get equalized to a value equal to the
geometric mean of the electronegativities of the isolated
species.
The MEP [38 –40] is stated as ‘electrophilicity will be
a minimum (maximum) when both chemical potential and
hardness are maxima (minima)’.
The binding energy per atom (BE/atom) is calculated
as follows:
 
BE nEatom 2 Ecluster
¼ ; ð9Þ
atom n basis set are presented in Figure 1. The number of
where n is the number of atoms in the cluster, Eatom and
Ecluster are the energies corresponding to single atom, and
cluster, respectively.
The change in energy upon the addition of atom
[DE1(Pdn)] and the stability function [DE2(Pdn)] are
defined as
DE1 ðPdn Þ ¼ EðPdn Þ 2 EðPdn21 Þ 2 EðPdÞ; ð10Þ
and
DE2 ðPdn Þ ¼ EðPdnþ1 Þ 2 EðPdn21 Þ 2 2EðPdÞ; ð11Þ
respectively. A large negative change in DE1(Pdn) implies
that the cluster Pdn is more stable than the preceding Pdn – 1
structure.
3. Computational method
We performed an ab initio molecular dynamics run at a
temperature near the melting temperature of bulk palladium,
using SIESTA 3.1 software,[41] for each cluster. During the
simulation process, the cluster goes through various
Molecular Simulation 3
structural changes and we recorded the energy and
geometries of the cluster during simulation and choose
some (three structures for small cluster and five for large
ð7Þ
cluster) of those structures based on minimum energy
criterion with reasonably different geometry. These
minimum energy structures of molecular dynamics run are
considered as initial geometries (or conformers) of
palladium clusters Pdn (n ¼ 2–11) (given in Figure S1 and
Table S1, Supplementary material, available via the article
webpage). Then optimisation is performed on each
conformer to determine the geometry having the lowest
energy in each of the cluster sizes. The optimisation is
performed within the framework of DFT using the
GAUSSIAN 09 suite of program.[42] In this study, we
used B3LYP,[43,44] B3P86 [43,45] and B3PW91 [43,46]
functionals and LanL2DZ [47], LanL2MB [47–49] and
Stuttgart/Dresden basis sets (SDD) [50–52] to see the effects
of functionals and basis sets on the calculated properties.
Thermodynamic functions for the lowest energy
structures are calculated at the same level of theory and
also at different temperatures.
4. Results and discussions
A number of structural isomers of Pdn clusters (n ¼ 2 –11)
have been investigated using DFT methods. All the
clusters were fully optimised with three functionals and
three basis sets, and the most stable structures having the
lowest energy are determined. The optimised palladium
cluster geometries with B3LYP functional and LanL2DZ
imaginary frequency for the geometries shown here are
zero signifying that they correspond to minimum energy
structure on the potential energy surface.
Pd2 dimer shown in Figure 1 is found to have inter-
atomic Pd – Pd bond length of 2.53 Å which is in
conformity with the results found by other researchers.
[53,54] Optimised structure of Pd3 is an isosceles triangle
with bond lengths 2.55 and 2.76 Å and the symmetric point
group is C2v. Our obtained geometry is in agreement with
those reported by Zanti et al. [55]. The lowest energy
structure for Pd4 is tetrahedron with C3v symmetry and an
average bond length of 2.66 Å, whereas Pd5 isomer is
square pyramidal with C4v point group symmetry and
average bond length 2.67 Å. Pd6 is regular octahedron with
D4 h symmetry. Both Pd7 and Pd8 have C2 symmetry, but
the structure of the former is pentagonal bipyramid and the
latter is bicapped octahedron. The average bond lengths of
Pd6, Pd7 and Pd8 are 2.72, 2.75 and 2.74 Å, respectively.
Our observed bond lengths are in good agreement with the
previously reported values.[17] Pd9 has the ground-state
structure of double trigonal antiprism with C3h symmetry.
Two octahedrons sharing one common edge is found to be
the most stable structure for Pd10, which has C2h
 4 N.B. Singh and U. Sarkar
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Figure 1. Most stable structures of Pdn clusters (n ¼ 2 – 11).
symmetry. We have found average bond lengths of 2.74
and 2.76 Å for Pd9 and Pd10 clusters, respectively. The
average bond length of Pd11 is observed as 2.79 Å. In
general, the average bond length shows increasing
behaviour as the cluster grows in size.
The variation in BE per Pd atom with cluster size is
plotted in Figure 2(a). It is clear from Figure 2(a) that as the
cluster becomes larger in size, the BE per atom increases
due to the increased number of bonds in the larger cluster.
However, this increment is not homogeneous. For cluster
containing 2 – 4 atoms, the BE per atom increases rapidly
compared with cluster containing more than 4 atoms. Since
the experimental BE for the bulk is 3.91 eV/atom,[56]
much higher than the BE of our studied clusters, we infer
that large numbers of atoms are required in the cluster to
obtain the bulk behaviour. In this work, the BE of Pd2 is
calculated as 0.96 eV at B3LYP/LanL2DZ level, which is
very close to the experimental value of 0.73 ^ 0.26 eV.
[57] For Pd3, our calculated BE per atom (0.853 eV/atom)
is close to the results depicted by other researchers [4,58]
using DFT calculation. For Pd4 and Pd5, this study shows
that BE per atom is 1.249 and 1.301 eV/atom, respectively,
which is higher than that observed by Qui et al. [4], which
is 1.020 and 1.148 eV/atom, respectively, and lower than
that calculated by Kalita et al. [17], which is 1.41 and
1.48 eV/atom, respectively. In the case of Pd6, Pd7, Pd8,
Pd9 and Pd10, we found BE per atom as 1.411, 1.439,
1.467, 1.528 and 1.555 eV/atom, respectively, which are
greater than 1.295, 1.321, 1.372, 1.407 and 1.449 eV/atom
[4] and less than 1.878, 1.903, 1.982, 2.037 and 2.095
eV/atom [12], respectively. Pd11 has a BE per atom of
1.745 eV/atom.
The change in energy upon the addition of an atom and
the stability functions of the Pdn clusters are presented in
Figure 2(b),(c), respectively. The change in energy upon
the addition of atom shows that at n ¼ 4, 6 and 9, the
change is more negative as compared to their neighbouring
clusters, indicating that Pd4, Pd6 and Pd9 are more stable.
The stability function ðDE2 Þ has relatively high value for
n ¼ 4, 6 and 9 (Figure 2(c)), which clearly implies that
these clusters are relatively more stable than their
neighbouring clusters. The change in IP with respect to

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Figure 2. (a) Variation in BE per atom with cluster size, n. (b)
Variation in atom addition energy with cluster size, n. (c)
Variation in stability function with cluster size, n.
the cluster size is depicted in Figure 3(a). The variation in IP
(with the size of the cluster) is more prominent up to Pd5. IP
for Pd2 is 8.70 eV, which is higher than the result (7.69 eV)
of Kalita et al. [17]. In the case of Pd3, Pd4, Pd5, Pd6 and
Pd7, we found IPs as 7.86, 7.00, 6.67, 6.70 and 6.44 eV,
respectively, which are greater than 7.56, 6.86, 6.60, 6.33
and 6.30 eV, respectively, of Kalita et al. [17]. It may be
noted that IP calculated using B3P86 functional (see
Figure 3(a) and Table S2(i)–(viii)) is higher than the other
two functionals considered here.
The EA values for Pd2, Pd3 and Pd4 at B3LYP/
LanL2DZ level of calculation are observed to be 0.630,
0.837 and 0.726 eV, respectively, which are lower than the
values observed by Kalita et al. [17] using BLYP
functional and DNP basis set where they have found EA
values of 1.5809, 1.486 and 1.2388 eV, respectively. Our
Molecular Simulation 5
Figure 3. (a) Variation in IP with number of atoms in palladium
clusters. (b) Variation in EA with number of atoms in palladium
clusters.
calculation with B3P86 functional and SDD basis set
shows EA values 1.257, 1.418 and 1.342 eV for Pd2, Pd3
and Pd4, respectively. Therefore, EA value depends on the
functional and basis set used in the calculation. Our
calculated EA value, using B3LYP functional and
LanL2DZ basis set, for Pd5, Pd6, Pd7, Pd8, Pd9, Pd10 and
Pd11 clusters are 1.243, 1.215, 1.754, 1.865, 1.869, 2.207
and 2.204 eV, respectively, which are close to the
experimental results of 1.45 ^ 0.10, 1.65 ^ 0.10,
1.70 ^ 0.15, 1.85 ^ 0.25, 1.95 ^ 0.25, 2.00 ^ 0.25 and
1.95 ^ 0.25 eV, respectively.[59] Among the functionals
and basis sets considered here, B3P86 functional gives the
highest EA, and LanL2DZ basis set gives the lowest EA
(see Table S2(i)–(viii), Supplementary material, available
via the article webpage). The overall trend of EA with the
variation in cluster size, with three functionals and three
basis sets, is depicted in Figure 3(b). EA increases with
increasing number of atoms in the cluster. Such close
agreement of the observed EA with the experimental
results implies the validity of our calculation methods.
 6 N.B. Singh and U. Sarkar
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Figure 4. (a) Size dependence of chemical hardness in
palladium clusters. (b) Size dependence of electronegativity in
palladium clusters.
Thus, the larger clusters have higher tendency to gain
electrons and become negatively charged species com-
pared with the smaller clusters. Pd4 and Pd6 are seen to
have lower EA values than their neighbouring clusters,
which support the higher stability of these two clusters as
suggested by the atom addition energy change and the
stability function.
The variation in chemical hardness with respect to the
number of atoms is plotted in Figure 4(a). The hardness
value is seen to decrease with increasing cluster size
except for a small shoulder at n ¼ 6, 8 and 11. The
observed trend is expected since in larger clusters the
electrons are more loosely bound, and the clusters are
more prone to change their electronic structure.[60] The
chemical potential measures the escaping tendency of
electrons, and electrons tend to flow from a region of high
chemical potential to a region of low chemical potential.
The difference in chemical potential causes electron
transfer and the flow of the electrons is linearly
proportional to the difference of chemical potential.
Among the clusters in our study, Pd4 has the highest value
of 2 3.865 eV of chemical potential and Pd2 has the lowest
chemical potential of 2 4.670 eV using B3LYP/LanL2DZ
level of calculation. In DFT, chemical potential measures
the escaping tendency of an electron cloud.[28] So higher
chemical potential implies higher escaping tendency of the
electron cloud from the system. Hence when Pd2 or Pd4
clusters interact with any other cluster, Pd4 shows the
highest electron donating power, whereas Pd2 shows the
highest electron accepting power, since the chemical
potential of Pd4 is the highest and Pd2 is the lowest among
the other clusters. This result is also in conformity with the
EEP.[29,37]
The electronegativity (x) as defined above is the
measure of attracting electrons towards itself and is equal
to the negative of chemical potential. In interacting
systems, electrons flow from a region of low electro-
negativity to a region of high electronegativity until the
electronegativity values of the constituent systems
equalise. The behaviour of electronegativity (x) as a
function of the cluster size is shown in Figure 4(b). It is
clear from Figure 4(b) that in general the electronegativity
of the cluster increases as the size of the cluster increases
albeit after a sudden decrease from Pd2 to Pd4. In other
words, the larger clusters have stronger tendency to attract
electrons. The observed trend is consistent with the
behaviour shown by EA. It is clear from Figure 4(b) that the
electronegativity (x) of Pd4, Pd6 and Pd9 clusters is lower
compared with that of their neighbouring clusters. The
B3P86 functional shows similar trend and similar value for
chemical hardness with the other two functionals due to the
mutual cancellation of the differences shown by IP and EA
ðh ¼ ðIP 2 EAÞ=2Þ; however, for electronegativity, it
shows similar trend but a comparatively large value due
to the addition of the differences shown by IP and EA
ðx ¼ ðIP þ EAÞ=2Þ. The electrophilicity (v) is a measure
of the stabilisation in energy when the cluster acquires an
additional electronic charge from the surroundings. It is
closely related to EA and shows same variation with
changing cluster size. In Figure 5(a), we present the
variation in electrophilicity with respect to the number of
atoms in the cluster. In the case of B3P86 functional, the
electrophilicity values are higher compared with those of
the other two functionals. We observed that in general v
increases as the cluster grows in size, i.e. the larger cluster
has stronger tendency to accept electrons. It is consistent
with what we observed from EA and electronegativity. The
electrophilicity for Pd10 is the highest (4.532 eV at B3LYP/
LanL2DZ level of calculation) as expected as Pd10 was
found to have the highest value of EA among the clusters in
this study. Pd4 has the lowest value of electrophilicity
(2.379 eV at B3LYP/LanL2DZ level of calculation) and is
least prone to gain electrons from its surrounding. The
electrophilicity value of Pd4, Pd6 and Pd9 is found to be
lower than their neighbouring clusters, which supports the
 Molecular Simulation 7

Polarisability as a function of cluster size is presented in

Figure 5(b). It is to be noted that the polarisability of the
Pdn clusters depends almost linearly on the cluster size, and
it is revealed that smaller clusters have lower polarisability
and higher value of chemical hardness, while larger
clusters have higher polarisability and lower value of
chemical hardness (see Tables S3(i) –(viii)). The observed
trend is expected from the principles of minimum
polarisability [34] and maximum hardness.[23,24]
In this study, we observed that magnetism is
associated with the Pd clusters. In Table 1, we present
the magnetic moment per atom for the lowest energy
structures of Pd clusters with B3LYP functional and
LanL2DZ basis set and are compared with the results of
other DFT calculations. The other two functionals and
basis sets also give the same values (see Table S4). Our
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calculated magnetic moments for Pdn clusters up to

Figure 5. (a) Change in electrophilicity with number of atoms
in Pdn (n ¼ 2 – 11) clusters. (b) Change in polarisability with
number of atoms in Pdn (n ¼ 2 – 11) clusters.
result of their higher stability as predicted from high
stability function and low atom addition energy. The
relative stability of these clusters also mimics the validity
of MEP since the electrophilicity of these clusters is
relatively less than that of its neighbouring counterparts.
n ¼ 11 are exactly same with the results of Granja et al.
[7], with the only exception of Pd10 for which they have
obtained 0.60 mB per atom, greater than our result of
0.40 mB per atom. The magnetic moments for Pdn clusters
up to n ¼ 7 are same with Futschek et al. [8], with the
only exception that Futschek et al. [8] observed zero
magnetic moment for Pd3. The observed magnetic
moments also agree with the results of Kumar et al. [5]
up to Pd7, except for Pd6, which they found to be non-
magnetic. In the case of Pd8, our magnetic moment is
similar to Granja et al. [7] but differ from Kumar et al. [5]
and Futschek et al. [8]. In the case of Pd9 and Pd11, our
calculated magnetic moments are in agreement with the
results of Kumar et al. [5] and Granja et al. [7]. For Pd10,
our calculated magnetic moment 0.40 mB per atom is in
agreement with the results reported by Futschek et al. [8].
Therefore, in general, our calculated magnetic moments
for Pdn clusters are in good agreement with other DFT
study.[5,7,8] It is to be noted that clusters studied here are
very floppy and so many isomeric structures with very
close in energy exist. These isomers are not only
structural but also magnetic. Researchers have found very
small difference in total energy [61] due to the presence

Table 1. The variation in magnetic moments (mB per atom) with cluster size calculated in this work at B3LYP/LanL2DZ level, and by
Kumar et al. [5], Granja et al. [7] and Futschek et al. [8], is presented.

Magnetic moment Magnetic moment Magnetic moment Magnetic moment

Cluster size in this study by Kumar et al. by Granja et al. by Futschek et al.
Pd2 1.000 1.000 1.000 1.000
Pd3 0.666 0.666 0.666 0.000
Pd4 0.500 0.500 0.500 0.500
Pd5 0.400 0.400 0.400 0.400
Pd6 0.333 0.000 0.333 0.333
Pd7 0.290 0.290 0.290 0.290
Pd8 0.500 0.250 0.500 0.250
Pd9 0.444 0.444 0.444 0.222
Pd10 0.400 0.600 0.600 0.400
Pd11 0.550 0.550 0.550
 8 N.B. Singh and U. Sarkar
Figure 6. (a) Heat capacity (Cv) as function of temperature (at B3LYP/LanL2DZ method). (b) Entropy as function of temperature and
Downloaded by [Assam University, Silchar] at 23:25 16 January 2014
cluster size (at B3LYP/LanL2DZ method). (c) Enthalpy as function of temperature and cluster size (at B3LYP/LanL2DZ method).
of different magnetic moments in cluster and the low-
lying spin states are basically controlling the electronic
and magnetic properties of the cluster. Due to the closed
shell electronic configuration, palladium atom shows no
magnetic moment. This closed shell results weak bonding
in the small cluster. However, in cluster, the aggregation
of atoms leads to delocalisation of electrons. Upon
bonding, sp-d hybridisation develops with the depletion
of 4d states in each atom. This depletion may be the
reason for magnetism in the small palladium cluster.
Thermodynamic properties, such as heat capacity at
constant volume (Cv), entropy (S) and enthalpy (H), for
these Pdn clusters at different temperatures are computed
and analysed. The vibrational zero-point energies for the
clusters Pd2, Pd3, Pd4, Pd5, Pd6, Pd7, Pd8, Pd9, Pd10 and
Pd11 are 1.220, 2.790, 4.970, 8.510, 8.130, 9.890, 12.240,
14.400, 16.180 and 17.600 kJ/mol, respectively, in the
B3LYP/LanL2DZ level of calculation. Increasing the
number of atoms in the cluster resulted in increase in its
vibrational zero-point energy due to increase in vibrational
modes. As the cluster size becomes larger, the heat
capacity (Cv) of these clusters also becomes higher. The
variation in the heat capacity (Cv) with temperature for Pdn
is presented in Figure 6(a). It is clear from Figure 6(a) that
(Cv) is a monotonically increasing function of temperature
and ultimately levels off for high temperatures. Entropy (S)
and enthalpy (H) of Pdn at different temperatures are
presented in Figure 6(b),(c), respectively. Heat capacity,
entropy and enthalpy for other two functional and basis
sets are presented in Figures S2– S4, Supplementary
material, available via the article webpage. Both entropy
and enthalpy increases linearly with the increase in cluster
size. The same effect was also observed by increasing the
temperature, and this is expected since an increase in
temperature is associated with an increase in internal
energy and volume of the cluster.
5. Conclusion
Palladium clusters Pdn containing up to 11 atoms are
studied using DFT and analysed in terms of various
reactivity parameters such as IP, EA, chemical potential,
electronegativity, electrophilicity, chemical hardness and
polarisability. As the cluster grows in size, the average
bond length, BE per atom of the clusters, entropy and
enthalpy are found to increase, whereas chemical hardness
decreases. Larger clusters have higher polarisability and
lower chemical hardness value, which are consistent with
the MPP and MHP. Stability function and atom addition
energy change predict that Pd4, Pd6 and Pd9 are relatively
more stable than their neighbouring clusters. Chemical
reactivity parameters such as EA, electronegativity and
electrophilicity suggest that larger clusters have stronger
tendency to accept electrons. The trend of reactivity
parameters mimics the result of the change in energy upon
the addition of atom and stability function. All the Pd
clusters are found to be magnetic.
Acknowledgement
Dr U. Sarkar acknowledges the support from SHARCNET
Canada for providing computational facilities for this research.
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