Journal of Physics and Chemistry of Solids 115 (2018) 84–91

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Journal of Physics and Chemistry of Solids

journal homepage: www.elsevier.com/locate/jpcs

The study of structures and properties of PdnHm(n¼1–10, m¼1,2) clusters by

density functional theory
Jun-Qing Wen a, *, Guo-Xiang Chen a, Jian-Min Zhang b, Hua Wu a
a
School of Science, Xi'an Shiyou University, Xi'an 710065, China
b
College of Physics and Information Technology, Shaanxi Normal University, Xi'an 710062, China

A R T I C L E I N F O A B S T R A C T

Keywords: The geometrical evolution, local relative stability, magnetism and charge transfer characteristics of
Density functional theory PdnHm(n ¼ 1–10, m ¼ 1,2) have been systematically calculated by using density functional theory. The studied
PdnHm clusters results show that the most stable geometries of PdnH and PdnH2 (n ¼ 1–10) can be got by doping one or two H
Structure atoms on the sides of Pdn clusters except Pd6H and Pd6H2. It is found that doping one or two H atoms on Pdn
Stability clusters cannot change the basic framework of Pdn. The analysis of stability shows that Pd2H, Pd4H, Pd7H, Pd2H2,
Pd4H2 and Pd7H2 clusters have higher local relative stability than neighboring clusters. The analysis of magnetic
properties demonstrates that absorption of hydrogen atoms decreases the average atomic magnetic moments
compared with pure Pdn clusters. More charges transfer from H atoms to Pd atoms for Pd6H and Pd6H2 clusters,
demonstrating the adsorption of hydrogen atoms change from side adsorption to surface adsorption.

1. Introduction catalytic activity, stability and selectivity, widely used in catalytic hy-
drogenation and dehydrogenation reaction. So the study about the
Hydrogen energy as a clean, efficiently renewable energy has broad adsorption, dynamics behavior of hydrogen in the Pd surface is one of the
application prospects in the future with depletion of the traditional fossil important contents [15–17]. Those studies can help people to understand
energy and environmental pollution becoming more and more serious the gas-solid catalytic mechanism on the surface [18–25]. Tripodi and
caused by the combustion. Today, new technology and new theory others [18] studied the effect of hydrogenation/dehydrogenation cycles
related to hydrogen energy has been listed as national key research to Pd samples, and found that the resistivity of Pd samples increased
content [1–3]. Because the metal has good catalytic activity, selectivity when hydrogen entered the lattice. Cao et al. [19] researched the
and stability, widely used in catalytic hydrogenation and dehydrogena- transport properties of H2 adsorption on Pd4-cluster-functionalized CNTs.
tion reaction, which can effectively improve the hydrogen storage Ni et al. [20] studied the interaction of H2 and Pdn(n ¼ 1–7) clusters using
properties. In the catalytic reaction, the adsorption and dissociation of density functional theory. Moc et al. [21] studied the activation and
hydrogen molecules from the surface is a critical step in the catalytic adsorption of several H2 molecules on Pd5 clusters, and described the
reaction [4,5]. Research by Christian et al. [6] about reactions of mechanism of H–H activation by the triangle bipyramid Pd5 clusters.
Pdn(n < 8) clusters and hydrogen shows that the electron structures of Genest et al. [22] studied the effect of the main group element impurities
hydrogen in the clusters is similar to that in the crystal. Clusters have on Pd4 cluster, and they found that the Pd4H cluster is most stable.
large surface area and numbers of active centers, which can raise effi- Barone [23] described two reactive pathways for the dissociative
ciency of utilization of the catalyst. So the study about the adsorption adsorption of hydrogen molecule on Pd4 pyramidal cluster using density
characteristics of hydrogen on metal clusters has important meaning functional theory methods.
[7–9]. Considering the rich application about Pd–H system and there is no
The geometric structure of atomic clusters' ground state is one of most systematic study about the adsorption properties of H on Pdn clusters, our
interesting properties [10–14]. The Ⅷ group element palladium as 4d research group will systematically study the adsorption properties of one
transition metal, because it has special d shell structure, fantastic physical H or two H on Pdn(n ¼ 1–10) clusters. More studies about Pdn clusters
and chemical properties, so Pd nanoparticles have very important have been reported by a lot of Ref. [26–32]. In the following the struc-
application in surface adsorption, chemical catalysis. Pd metal has good tures, stability, magnetic properties of PdnHm(n ¼ 1–10, m ¼ 1,2) clusters

* Corresponding author.
E-mail address: [email protected] (J.-Q. Wen).

https://doi.org/10.1016/j.jpcs.2017.12.011
Received 17 June 2017; Received in revised form 11 October 2017; Accepted 8 December 2017
Available online 9 December 2017
0022-3697/© 2017 Elsevier Ltd. All rights reserved.
J.-Q. Wen et al. Journal of Physics and Chemistry of Solids 115 (2018) 84–91

Table 1 augmented wave (PAW) [35,36] is chosen as potential function to

Calculated and experimental values of bond length (R/Å), binding energy (Eb/eV) for Pd2, describe the interaction between ions and valence electrons and the
H2and PdH dimers.
generalized gradient approximation (GGA) [37] in the Per-
Method R Eb dew–Burke–Ernzerhof (PBE) [38] form is used as the
Pd2 H2 PdH Pd2 H2 PdH exchange-correlation potential. The kinetic energy cutoff of 400 eV is
This work 2.571 0.745 1.576 1.14 4.61 2.28
chosen for the plane-wave expansion. Geometrical structures are relaxed
(DMOL3) until the force on each atom less than 0.02 eV/Å, and the convergence
This work 2.472 0.732 1.536 0.66 4.44 2.60 criteria for energy of 1  105 eV is met.
(VASP) In order to verify the accuracy of the selected method, the bond length
Ref. [20] 2.615 0.747 1.555 0.72 4.68 2.25
(R/Å) and binding energy (Eb/eV) of Pd2, H2 and PdH are calculated, and
EXP. 2.480 0.730 1.534 0.74  0.26 4.48 2.39
[39] [41] [40] [42] the related theoretical and experimental data are presented in Table 1.
1.12  0.24 From the table we can find that the bond lengths of Pd2, H2 and PdH by
[40] VASP are closer to the experimental value, while Eb of Pd2 and PdH are
slightly far from the experimental value compared with DMOL3 and
Ref. [20]. For the DMOL3 package, the bond lengths of Pd2, H2 and PdH
will be investigated in detail by the first principles method. The rest of
and Eb of Pd2, H2, PdH are more closer to the experimental value than the
the article is arranged as follows: In the second part, the detailed calcu-
literature [20].
lation process and methods are discussed in brief. The structural evolu-
tion, stability and magnetic properties of PdnHm(n ¼ 1–10, m ¼ 1,2)
3. Theoretical results and discussion
clusters are presented in the third part and the conclusions of the article
are described in the fourth part.
In this section, the structure evolution of PdnHm(n ¼ 1–10, m ¼ 1, 2) is
analyzed based on DMOL3 package, the most stable structures and some
2. Computational methods
typical stable structures of PdnHm(n ¼ 1–10, m ¼ 1, 2) are listed in Figs. 1
and 2, where the blue sphere represents Pd atom, the white sphere rep-
Based on previous study of 4d metal clusters Pdn, we firstly get the
resents H atom, respectively, and those stable structures are marked with
stable structures of Pdn(n ¼ 1–10) clusters, and then use one and two H
(1), (2) and (3), which represent the stable order. The Related parameters
atoms to fill, cap and replace in the stable structures of Pdn(n ¼ 1–10). We
of the most stable structures of Pdn, PdnH and PdnH2 are displayed in
design many initial structures of PdnHm(n ¼ 1–10, m ¼ 1,2) clusters, then
Tables 1–4.
the initial structures are optimized at generalized gradient approxima-
tion (GGA) with exchange-correlation potential BP function [33,34] and
double numerical plus polarization basis set (DNP) with the spin- 3.1. Geometry
unrestricted treatment under DMOL3 package. An effective core poten-
tial (ECP) is used to describe the core electrons. Moreover, the VASP 3.1.1. PdH and PdH2
software is used to further optimize the stable structures and calculate the The bond length of PdH is 1.576 Å, the average binding energy (Eb/
magnetic properties of the most stable structures, and the projector- eV/atom) is 1.261 eV/atom (see Table 4). The most stable structure of

PdH PdH2(1) PdH2(2) PdH2(3)

Pd2 Pd2H(1) Pd2H(2) Pd2H2(1) Pd2H2(2) Pd2H2(3)

Pd3 Pd3H(1) Pd3H(2) Pd3H2(1) Pd3H2(2) Pd3H2(3)

Pd4 Pd4H(1) Pd4H(2) Pd4H(3) Pd4H2(1) Pd4H2(2) Pd4H2(3)

Pd5 Pd5H(1) Pd5H(2) Pd5H(3) Pd5H2(1) Pd5H2(2) Pd5H2(3)

Fig. 1. The most stable structures of Pdn(n ¼ 1–5), the most stable structures and two low-lying structures of PdnHm(n ¼ 1–5, m ¼ 1,2).

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J.-Q. Wen et al. Journal of Physics and Chemistry of Solids 115 (2018) 84–91

Pd6 Pd6H(1) Pd6H(2) Pd6H(3) Pd6H2(1) Pd6H2(2) Pd6H2(3)

Pd7 Pd7H(1) Pd7H(2) Pd7H(3) Pd7H2(1) Pd7H2(2) Pd7H2(3)

Pd8 Pd8H(1) Pd8H(2) Pd8H(3) Pd8H2(1) Pd8H2(2) Pd8H2(3)

Pd9 Pd9H(1) Pd9H(2) Pd9H(3) Pd9H2(1) Pd9H2(2) Pd9H2(3)

Pd10 Pd10H(1) Pd10H(2) Pd10H(3) Pd10H2(1) Pd10H2(2) Pd10H2(3)

Fig. 2. The most stable structures of Pdn(n ¼ 6–10), the most stable structures and two low-lying structures of PdnHm(n ¼ 6–10, m ¼ 1,2).

1.731 eV/atom. There are two linear structures PdH2(2) and PdH2(3),
Table 2
which are higher in energy than PdH2(1) by 0.244 eV and 1.224 eV.
The average value of the total bond length (ABL/Å), the shortest Pd–Pd bond length (R/Å),
the average binding energy(Eb/eV/atom), total energy (Et/-a.u.) and the energy of HOMO-
LUMO for Pdn(n ¼ 2–10) clusters at DMOL3 package. 3.1.2. Pd2H and Pd2H2
Clusters ABL/ R/Å Eb/eV/ Et/-a.u HOMO/ LUMO/ The bond length of linear Pd2 is 2.571 Å. For Pd2H, the most stable
Å atom eV eV structure is an isosceles triangle, the average value of the total bond
Pd2 2.571 2.571 0.722 255.966 3.571 1.348
length (ABL) is 2.014 Å and Eb is 1.526 eV/atom. The other isomer
Pd3 2.610 2.603 1.248 384.007 3.586 1.385 Pd2H(2) is linear structure, the ABL and Eb is 2.114 Å and 1.505 eV/atom,
Pd4 2.678 2.673 1.599 512.061 3.348 1.289 which is higher in energy above Pd2H(1) by 1.170 eV. For Pd2H2,
Pd5 2.704 2.670 1.735 640.101 3.412 2.357 rhombus (1) is the most stable structure, whose ABL and Eb are 1.889 Å
Pd6 2.711 2.710 1.879 768.153 3.164 2.110
and 1.846 eV/atom, respectively. The second and third isomers are “Y”
Pd7 2.723 2.688 1.971 896.202 3.563 2.846
Pd8 2.716 2.703 2.052 1024.255 3.256 2.584 structure Pd2H2(2) and distorted trapezoid Pd2H2(3), which are higher in
Pd9 2.729 2.708 2.125 1152.311 3.474 3.109 energy above Pd2H2(1) by 0.816 and 0.871 eV, respectively.
Pd10 2.737 2.684 2.194 1280.371 3.482 2.722
3.1.3. Pd3H and Pd3H2
PdH2 is an isosceles triangle, the Pd–H bond length is 1.773 Å, H–H The lowest energy structure of Pd3 is an isosceles triangle. One
bond length is 0.844 Å, the average bond length is 1.476 Å, the Eb is hydrogen atom locating on the side of triangle is the most stable structure

Table 3
The average value of the total bond length (ABL/Å), the shortest Pd–Pd bond length (R/Å), the shortest Pd–H bond length (R1/Å), the average binding energy(Eb/eV/atom), total energy
(Et/-a.u.) and HOMO-LUMO for PdnH(n ¼ 1–10) clusters at DMOL3 package.

Clusters ABL/Å R/Å R1/Å Eb/eV/atom Et/-a.u. HOMO/eV LUMO/eV

PdH(1) 1.576 1.576 1.261 128.549 3.967 0.816

Pd2H(1) 2.014 2.612 1.715 1.526 256.581 4.099 1.504
Pd3H(1) 2.279 2.601 1.676 1.638 384.610 3.678 2.032
Pd4H(1) 2.449 2.637 1.715 1.797 512.656 3.350 2.282
Pd5H(1) 2.533 2.674 1.726 1.886 640.698 3.533 3.008
Pd6H(1) 2.546 2.701 1.793 1.976 768.747 3.323 2.644
Pd7H(1) 2.610 2.705 1.760 2.071 896.804 3.407 3.026
Pd8H(1) 2.621 2.695 1.738 2.127 1024.855 3.548 3.215
Pd9H(1) 2.657 2.684 1.729 2.187 1152.912 3.445 2.553
Pd10H(1) 2.661 2.686 1.761 2.237 1280.969 3.514 2.847

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Table 4
The average value of the total bond length (ABL/Å), the shortest Pd–Pd bond length (R/Å), the shortest Pd–H bond length (R1/Å), the average binding energy(Eb/eV/atom), total energy
(Et/-a.u.) and HOMO-LUMO for PdnH2(n ¼ 1–10) clusters at DMOL3 package.

Clusters ABL/Å R/Å R1/Å Eb/eV/atom Et/-a.u. HOMO/eV LUMO/eV

PdH2(1) 1.476 1.773 1.731 129.147 3.856 1.413

Pd2H2(1) 1.889 2.662 1.696 1.846 257.184 4.125 1.670
Pd3H2(1) 2.137 2.620 1.683 1.834 385.206 4.060 2.937
Pd4H2(1) 2.325 2.660 1.704 1.921 513.249 3.554 2.826
Pd5H2(1) 2.419 2.674 1.736 1.986 641.293 3.395 3.057
Pd6H2(1) 2.442 2.678 1.724 2.053 769.342 3.502 2.855
Pd7H2(1) 2.524 2.714 1.739 2.159 897.409 3.574 2.590
Pd8H2(1) 2.550 2.677 1.74 2.192 1025.457 3.550 2.713
Pd9H2(1) 2.553 2.711 1.833 2.234 1153.511 3.425 2.686
Pd10H2(1) 2.615 2.654 1.748 2.294 1281.576 3.790 3.241

for Pd3H, the ABL is 2.279 Å, Eb is 1.638 eV/atom. A hydrogen atom on 3.1.7. Pd7H and Pd7H2
the vertex of triangle is the second isomer for Pd3H, the ABL and Eb are The pentagonal bipyramid structure is the most stable structure for
2.377 Å and 1.475 eV/atom, which is higher in energy above Pd3H(1) by Pd7 cluster. Adding one H atom to Pd7 cluster, we obtain three stable
0.871eV. For Pd3H2 cluster, the most stable structure is two H atoms structures, and which are one H atom on side, surface and vertex of
locating on the two sides of Pd3 structure, whose ABL and Eb are 2.137 Å pentagonal bipyramid. The Pd7H(2) and Pd7H(3) are higher in energy
and 1.834 eV/atom. One vertex of Pd3 structure connecting to two H than Pd7H(1) by 0.136 and 0.707 eV. The three stable structures of Pd7H2
atoms is the second isomer, and two vertex of Pd3 structure connecting to can be got from Pd7H by adding one H atom. The structure with two H
two H atoms is the third isomer, which are higher in energy than atom locating on the adjacent sides of pentagonal face is the most stable
Pd3H2(1) by 0.381 and 1.551 eV, respectively. structure for Pd7H2, whose ABL and Eb are 2.524 Å and 2.159 eV/atom.
The other two isomers are two H atoms locating on two surfaces and
3.1.4. Pd4H and Pd4H2 connecting vertex of Pd7 cluster, which are higher in energy above
The tetrahedron is the most stable structure for Pd4 cluster. Adding Pd7H2(1) by 0.245 and 0.544 eV.
one hydrogen atom to Pd4 structure, the most stable structure is one
hydrogen atom on the side of tetrahedron, whose ABL and Eb are 2.449 Å 3.1.8. Pd8H and Pd8H2
and 1.797 eV/tom. The other two isomers are one hydrogen atom on the The most stable structure of Pd8 cluster is two capped octahedron
triangular surface and the vertex of tetrahedron. Pd4H(2) and Pd4H(3) structure. Adding one H atom to Pd8 cluster, we get the same calculation
are higher in energy than Pd4H(1) by 0.054 and 0.463eV. The three result as above, the most stable structure of Pd8H is one H atom on the
stable structures of Pd4H2 cluster are two H atoms locating on the two side of Pd8 cluster. ABL and Eb are 2.621 Å and 2.127 eV/atom. The other
sides of Pd4, one vertex of Pd4 structure connecting to two H atoms and two structures are one H atom locating on the surface and vertex of Pd8
two H atoms locating on the two triangular surfaces of Pd4, respectively. cluster, and they are higher in energy above Pd8H(1) by 0.027 and
ABL and Eb of Pd4H2(1) are 2.325 Å and 1.921 eV/atom. Pd4H2(2) and 0.108 eV. Like Pd7H2, the three stable structures of Pd8H2 can be got from
Pd4H2(3) are higher in energy than Pd4H2(1) by 0.027 eV and 1.108 eV, Pd8H. The structure of two H atoms locating on the adjacent sides of
respectively. quadrangle is the most stable structure for Pd8H2, whose ABL and Eb are
2.550 Å and 2.192 eV/tom. Two H atoms locating on the up and down
3.1.5. Pd5H and Pd5H2 surface of Pd8 and two H atoms connecting to vertex of Pd8 are other two
The most stable structure of Pd5 cluster is triangle bipyramid. Adding stable structures for Pd8H2. Moreover, the two isomers are higher in
one hydrogen atom to Pd5 structure, we obtain the most stable structure, energy above Pd8H2(1) by 0.191 and 0.381 eV.
which is one hydrogen atom on the side of triangle bipyramid, whose
ABL and Eb are 2.533 Å and 1.886 eV/atom. The second and third stable 3.1.9. Pd9H and Pd9H2
structures are one hydrogen atom on the vertex and surface of trigonal For Pd9 cluster, the most stable structure is two capped pentagonal
bipyramid. Pd5H(2) and Pd5H(3) are higher in energy than Pd5H(1) by bipyramid structure. We present three stable structures of Pd9H, one H
0.299 and 0.353 eV. The three stable structures of Pd5H2 are same to atom on the pentagonal side of Pd9 cluster is the most stable structure,
Pd4H2, the first stable structure is two H atoms locating on the two sides whose ABL and Eb are 2.657 Å and 2.187 eV/atom. The structure of H
of Pd5, and ABL and Eb are 2.419 Å and 1.986 eV/atom. The other two atom on surface and vertex of Pd9 cluster are second and third isomers,
isomers are one vertex of Pd5 connecting to two hydrogen atoms and two which are higher in energy above Pd9H(1) by 0.054 and 0.435 eV. For
H atoms locating on the two surfaces of Pd5, which are higher in energy Pd9H2 cluster, the most stable structure is two H atoms locating on the
than Pd5H2(1) by 0.027 and 0.163 eV. adjacent sides of pentagonal face, ABL and Eb are 2.553 Å and 2.234 eV/
atom. The geometries of two H atoms on two surfaces and two H atoms
3.1.6. Pd6H and Pd6H2 connecting to vertex are the other two stable isomers, which are higher in
We find that the most stable structure of Pd6 is an octahedron struc- energy above Pd9H2(1) by 0.081 and 0.108 eV.
ture, and Eb is 1.879 eV/atom. For Pd6H clusters, H atom on the surface of
octahedron is the most stable structure, whose ABL and Eb are 2.546 Å 3.1.10. Pd10H and Pd10H2
and 1.976 eV/atom. The second stable isomer is one H atom on the side Three capped pentagonal bipyramid structure is the most stable
of Pd6, and the third isomer is the H atom on the vertex of Pd6. The two structure for Pd10 cluster. Adding one H atom to Pd10 cluster, the most
isomers are higher in energy than Pd6H(1) by 0.027 and 0.245 eV. For stable structure is one H atom locating on triangle surface, whose ABL
Pd6H2, the most stable structure Pd6H2(1) can be obtained from Pd6H(1) and Eb are 2.661 Å and 2.237 eV/atom. The other two isomers are H atom
by adding one H atom on the surface of Pd6H(1), whose ABL and Eb are locating on side of Pd10 cluster, and only the location of H atom is
2.442 Å and 2.053 eV. The second structure is one vertex of Pd6 con- different. The two isomers are higher in energy above Pd10H by 0.027
necting to two H atoms, the third isomer is two H atoms locating on two and 0.054 eV. We find the most stable structure of Pd10H2 is two H atoms
sides of Pd6, and the two structures are higher in energy than Pd6H(1) by on the two sides of pentagon, and the other two isomers are two H atoms
0.027 and 0.082 eV. locating on the surface of Pd10 cluster, which are higher in energy than
Pd10H2(1) by 0.191 and 0.272 eV.

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Fig. 3. The average Pd–Pd bond length and the average value of the total bond length (ABL) of PdnHm(n ¼ 2–10, m ¼ 1, 2) (left chart), and the shortest Pd–Pd bond length (R) and the
shortest Pd–H bond length (R1) of PdnHm(n ¼ 2–10, m ¼ 1,2) (right chart).

from n ¼ 2–6, and it is nearly equal from n ¼ 7–10 compared with that of
Pdn. The results show that the influence on the pd-pd bond is small by
adding one or two H atoms. Because the Pd–H bond is shorter, so the
ABL of PdnHm(n ¼ 1–10, m ¼ 1,2) is smaller than the average Pd–Pd
bond length, which increases with the increase of the cluster size and the
amplitude decreases gradually.
The shortest Pd–Pd bond lengths (R/Å) of PdnHm(n ¼ 1–10, m ¼ 1,2)
clusters are almost equal except n ¼ 2, and which are more and more
close to the shortest Pd–Pd bond lengths of Pdn(n ¼ 1–10) clusters as
shown in Fig. 3. At the same time, the shortest Pd–H bonds (R1/Å) in
PdnHm(n ¼ 1–10, m ¼ 1,2) is approximately equal, except for a slight
oscillation of n ¼ 6 and 9. The ranges of the shortest Pd–H bonds (R1/Å)
are from 1.576 Å to 1.793 Å in PdnH, and from 1.683 to 1.833 in PdnH2,
which is an important physical parameter in physical adsorption of
hydrogen by Pdn cluster.

3.3. Relative stability

In order to analyze the relative stability of PdnHm(n ¼ 1–10, m ¼ 1,2)

clusters, the average binding energy (Eb), the second difference in energy
(△2E) have been calculated. Eb and △2E are calculated according to the
following formulas: Eb (PdnH) ¼ nE(Pd) þ E(H)  E(PdnH)

Eb (PdnH2) ¼ nE(Pd) þ 2E(H)  E(PdnH2)

Δ2E (PdnH) ¼ E(Pdnþ1H) þ E(Pdn-1H)  2E(PdnH)

Δ2E (PdnH2) ¼ E(Pdnþ1H2) þ E(Pdn-1H2)  2E(PdnH2)

Fig. 4. The Eb, △2E of Pdn and PdnHm(n ¼ 1–10, m ¼ 1,2).
where, E represents the energy of the clusters or the energy of single atom
in a system. The Eb shows the average gain in energy per atom during the
From above analysis, we can find that the hydrogen atoms are easily formation of cluster from individual atom, while, the △2E means the
isolated and adsorbed on the sides and surface of Pdn clusters and doping difference of the energy of a cluster surrounding to its neighbor. Eb and
H atoms cannot change the geometrical framework of Pdn cluster. Next, △2E of Pdn and PdnHm(n ¼ 1–10, m ¼ 1,2) clusters with number of Pd
the bond length, local stability, magnetism and charge transfer of atoms are listed in Fig. 4 (a) and (b). The Eb of Pdn, PdnH and PdnH2
PdnHm(n ¼ 1–10, m ¼ 1,2) clusters will be investigated. increases monotonically with the increase of cluster size, and the rate of
increase gradually decreases and tends to flatten. The initial faster in-
3.2. Bond lengths analysis crease in Eb is an indication of thermodynamic instability of the clusters.
Moreover, the values of PdnH and PdnH2 are obviously larger than those
In this section, we studied the average Pd–Pd bond length of Pdn and of pure Pdn from n ¼ 2–7, and with the size increase, the values are
PdnHm(n ¼ 1–10, m ¼ 1,2), and the average value of the total bond length getting closer.
(ABL) of PdnHm(n ¼ 1–10, m ¼ 1,2), the shortest Pd–Pd bond length (R/ From Fig. 4 (b), the △2E of Pdn clusters appears local peaks at n ¼ 2,
Å) and the shortest Pd–H bond length (R1/Å) of PdnHm(n ¼ 1–10, 4, 6, which show that Pd2, Pd4 and Pd6 clusters have higher local relative
m ¼ 1,2), and related bond lengths are shown in Fig. 3. From Fig. 3, the stability than neighboring clusters, the calculated results are same to
average Pd–Pd bond length has same variation tendency, and the Reference [43]. For PdnH and PdnH2 clusters, the local peaks appear at
addition of H leads to a slight increase in the average Pd–Pd bond length n ¼ 2, 4, 7, the results also indicate that the corresponding clusters have

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J.-Q. Wen et al. Journal of Physics and Chemistry of Solids 115 (2018) 84–91

Fig. 5. The adsorption energy Eads of PdnHm(n ¼ 1–10, m ¼ 1,2).

higher local relative stability compared with neighboring clusters. △2E Fig. 6. Magnetic moment/atom of Pdn and PdnHm(n ¼ 1–10, m ¼ 1,2).
of Pd4, Pd4H and Pd4H2 have highly local relative stability, which show
that addition one or two H atoms do not change the relative stability of charge density distribution of PdnH and PdnH2 (n ¼ 7–10) in Fig. 7. It can
Pd4 cluster. be seen that the total magnetic moments mainly originate from the spin
The adsorption energy Eads (eV) of hydrogen is calculated according polarization of Pd atoms, and the adsorbed hydrogen atom is essentially
to the following equation: not polarized.
Eads ¼ E(Pdn) þ E(H)  E(PdnH), Eads ¼ E(Pdn) þ 2E(H)  E(PdnH2)
3.5. Charge analysis
where, Eads is the adsorption energy, E represents the energy of the
clusters or the energy of single atom in a system. In Fig. 5, the Eads at In order to understand how the structural transition and physical
DMOL3 and VASP package are plotted with the number of Pd atoms as properties of PdnHm(n ¼ 1–10, m ¼ 1,2) clusters change as the size of the
horizontal ordinate. If the calculated Eads is smaller, meaning that the cluster increasing, the Mulliken population and the charge distribution of
structure is more stable and more favorable in experiment. It can be PdnH and PdnH2 clusters are presented in Tables 6 and 7. At the same
found that the change rule of Eads is the same by the two methods, and all time, Fig. 8 draws the charges of H atoms in PdnH and PdnH2 clusters. For
Eads are negative, meaning that all structures are energetically stable. Eads PdH, Pd2H, Pd6H, Pd10H, PdH2, Pd2H2, Pd6H2, Pd9H2 clusters, the H
of Pd2H and Pd2H2 is the smallest, implying that the corresponding atoms carry positive charges, which mean that the charges are trans-
structure has higher relative stability and is easier to obtain ferred from H atoms to Pd atoms and H atoms act as electron donor. For
experimentally. other clusters, the H atoms carry negative charges, which indicate that
the charges are transferred from Pd atoms to H atoms and Pd atoms act as
3.4. Magnetic analysis electron donor. From Fig. 8, it can be seen that the peaks appear at n ¼ 6,
which imply that more charges transfer from H atom to Pd atoms, which
The magnetic properties of H adsorption on Pdn(n ¼ 1–10) have been
studied by the VASP [31] program under the spin polarized
density-functional theory (DFT) formwork. The total magnetic moments
Mtot and average atomic magnetic moments Matom of system are pre-
sented in Table 5 and Fig. 6. The Mtot increase with the increase of the
size except PdnH2(n ¼ 1–6) with zero magnetic moment, and the Mtot
decreases after hydrogen absorption except for Pd9H. For the average
atomic magnetic moments, Matom of Pdn clusters decrease from n ¼ 2 to 7,
then increase from n ¼ 8 to 10, and the Matom obtained by Ref. [43] are in
good agreement with our results by VASP package except for n ¼ 2, 3, 8,
9. After adsorption one or two H, Matom of PdnH clusters decrease from
0.319μB to 0.127μB at n ¼ 1–7, then increase from 0.127μB to 0.444μB at
n ¼ 7–9, and Matom is 0.411μB for Pd10H. Matom of PdnH2 clusters is zero
from n ¼ 1–6, then increase from n ¼ 6–8, and decrease from n ¼ 8–10 as
shown in Fig. 6.
Fig. 7. The spin charge density distribution of PdnHm(n ¼ 7–10, m ¼ 1,2).
For a better understanding of magnetic properties, we plot the spin

Table 5
The total magnetic moments Mtot(μB) and average atomic magnetic moments Matom(μB/atom) of PdnHm(n ¼ 1–10, m ¼ 1,2) clusters at VASP package.

Clusters Mtot Matom Clusters Mtot Matom Clusters Mtot Matom

Pd 0 0 PdH(1) 0.639 0.319 PdH2(1) 0 0

Pd2 1.408 0.704 Pd2H(1) 0.952 0.317 Pd2H2(1) 0 0
Pd3 1.914 0.638 Pd3H(1) 0.959 0.239 Pd3H2(1) 0 0
Pd4 1.904 0.476 Pd4H(1) 0.961 0.192 Pd4H2(1) 0 0
Pd5 1.931 0.386 Pd5H(1) 0.978 0.163 Pd5H2(1) 0 0
Pd6 1.961 0.327 Pd6H(1) 1.014 0.145 Pd6H2(1) 0 0
Pd7 1.935 0.276 Pd7H(1) 1.013 0.127 Pd7H2(1) 1.713 0.191
Pd8 3.621 0.453 Pd8H(1) 2.747 0.305 Pd8H2(1) 3.578 0.358
Pd9 3.688 0.409 Pd9H(1) 4.439 0.444 Pd9H2(1) 3.535 0.321
Pd10 5.364 0.536 Pd10H(1) 4.514 0.411 Pd10H2(1) 3.659 0.305

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J.-Q. Wen et al. Journal of Physics and Chemistry of Solids 115 (2018) 84–91

Table 6
Atomic charge (Q/e) of the ground state structures of PdnH(n ¼ 1–10), Q(n) for Pd atoms and Q(H) for H atoms.

Clusters Q(1) Q(2) Q(3) Q(4) Q(5) Q(6) Q(7) Q(8) Q(9) Q(10) Q(H)

PdH(1) 0.012 0.012

Pd2H(1) 0.085 0.084 0.169
Pd3H(1) 0.042 0.026 0.027 0.010
Pd4H(1) 0.109 0.028 0.032 0.115 0.165
Pd5H(1) 0.093 0.009 0.092 0.059 0.033 0.085
Pd6H(1) 0.127 0.166 0.125 0.167 0.136 0.177 0.899
Pd7H(1) 0.020 0.005 0.018 0.009 0.017 0.056 0.048 0.053
Pd8H(1) 0.096 0.057 0.111 0.031 0.027 0.040 0.086 0.083 0.019
Pd9H(1) 0.010 0.049 0.060 0.003 0.061 0.153 0.040 0.051 0.088 0.011
Pd10H(1) 0.189 0.064 0.126 0.031 0.010 0.083 0.023 0.075 0.057 0.120 0.593

Table 7
Atomic charge (Q/e) of the ground state structures of PdnH2(n ¼ 1–10), Q(n) for Pd atoms and Q(H) for H atoms.

Clusters Q(1) Q(2) Q(3) Pd(4) Q(5) Q(6) Q(7) Q(8) Q(9) Q(10) Q(H1) Q(H2)

PdH2(1) 0.218 0.110 0.109

Pd2H2(1) 0.239 0.239 0.239 0.239
Pd3H2(1) 0.159 0.006 0.006 0.074 0.072
Pd4H2(1) 0.032 0.063 0.037 0.123 0.066 0.063
Pd5H2(1) 0.058 0.170 0.049 0.019 0.189 0.053 0.054
Pd6H2(1) 0.154 0.223 0.233 0.213 0.142 0.195 0.573 0.588
Pd7H(1) 0.013 0.051 0.053 0.005 0.039 0.071 0.069 0.014 0.017
Pd8H2(1) 0.078 0.067 0.109 0.043 0.064 0.073 0.072 0.080 0.020 0.041
Pd9H2(1) 0.050 0.005 0.046 0.002 0.074 0.099 0.017 0.055 0.056 0.023 0.024
Pd10H2(1) 0.047 0.028 0.029 0.029 0.023 0.176 0.066 0.070 0.032 0.076 0.006 0.006

from H atoms to Pd atoms for Pd2H, Pd6H, Pd2H2 and Pd6H2 clusters.

Acknowledgements

Thanks to the help provided by the High Performance Computing

Center of Northwestern Polytechnical University. The project was sup-
ported by the National Natural Science Foundation of China No.
11247229, 11104175 and 11304246, the Scientific Research Program
Fund by Shaanxi Provincial Education Department under Grant No.
2013JK0629, the Natural Science Foundation of Shaanxi Province of
China No. 2014JQ6206, 2016JQ1027.

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