i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 7 ( 2 0 2 2 ) 4 2 0 e4 2 7

Available online at www.sciencedirect.com

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

Anionic LaH

8 : A nanocluster-based hydrogen
storage material

Shou Jun Huang, Hai Yan Wang*, Si Min Li, Guang Zhou Zhang, Yuan Su
School of Materials Science and Engineering, Henan Polytechnic University, Jiaozuo, 454000, China

highlights graphical abstract

 The geometrical structures of

LaH

n (n ¼ 2e20) clusters are deter-

mined by CALYPSO cluster struc-

tural search method.
 The maximum number of
hydrogen atoms adsorbed on
LaH

n (n ¼ 2e20) clusters is 14.

 The LaH

8 cluster with high stabil-

ity and hydrogen storage capacity

of 5.4 wt% is discovered.
 The high stability of LaH

8 cluster is

mainly due to the interaction of H

1s and La 5d orbital.

article info abstract

Article history: The geometric structures of anionic LaH

n ðn ¼ 2
20Þ clusters are predicted by CALYPSO
Received 8 July 2021 cluster structural search method and first-principles calculations. The low-lying isomers
Received in revised form for each size of LaH

n ðn ¼ 2
20Þ clusters are further reoptimized at B3LYP level by setting
30 September 2021 all-electron 6-311G þ þ (d, p) basis set for H atoms and SDD basis set for La atom,
Accepted 1 October 2021 respectively. The photoelectron spectroscopy (PES) of the ground-state structures are
Available online 23 October 2021 simulated by time-dependent DFT (TD-DFT) method. It is found that the anionic LaH

8
cluster with D2d symmetry is the most stable structure and its hydrogen storage capacity
Keywords: arrives at 5.4 wt%. The stability of anionic LaH

8 cluster is mainly affected by the strong
LaH

8 cluster interaction between H 1s orbital and La 5d orbital. The present results provide insights into
CALYPSO method the further exploration and discovery of novel rare-earth based hydrogen storage
Geometric structure nanomaterials.
Hydrogen storage capacity © 2021 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.

* Corresponding author.
E-mail address: wanghy@hpu.edu.cn (H.Y. Wang).
https://doi.org/10.1016/j.ijhydene.2021.10.015
0360-3199/© 2021 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 7 ( 2 0 2 2 ) 4 2 0 e4 2 7 421

hydrogen storage materials is limited to its microstructure

Introduction and hydrogen storage state. Thus, the related theoretical
research is insufficient. In particular, the lack of information
Hydrogen is recognized as the most promising clean fuel due about the RE-H clusters for hydrogen storage stimulates the
to its high calorific value (142 MJ/kg), small mass density, and study of the hydrogen storage potential of anionic LaH
n
huge environmental and economic benefits [1,2]. Although the clusters. The hydrogen storage properties of anionic
current hydrogen production technology is not perfect, it is LaH
n ðn ¼ 2/20Þ clusters were studied using the CALYPSO
still expected to be an alternative for fossil fuels [3]. Hydrogen
method and DFT calculation. In this work the geometric and
can be stored in three forms: gas, liquid, and solid. Hydrogen
electronic properties of rare-earth nanoclusters were
stored in solid form is considered the safest and most reliable enhanced. Further, we provide theoretical guidance for com-
[4]. Solid hydrogen storage materials include carbon nano- prehending the potential hydrogen storage capacity of anionic
tubes [5e7], metal-organic frameworks (MOFs) [8], metal hy- LaH
n clusters and how to prepare a new rare earth hydrogen
drides [9e11], and nanostructured clusters [12,13]. Although
storage material.
solid-state hydrogen storage is the most promising way of
hydrogen storage, the problems of high dehydrogenation
temperature, poor dynamic stability, and poor reversibility
Computational methods
have not been solved [14]. Therefore, the research and devel-
opment of low-cost, efficient, and safe hydrogen storage ma-
An unbiased structural search has been performed to deter-
terials is still the eternal theme of materials science. The rare
mine the ground-state structures of anionic LaH
n clusters in
earth elements can improve hydrogen storage performance
the size range of n ¼ 2
20 by the Particle Swarm Optimization
via doping and modifying hydrogen storage [15,16], which
(PSO) structure searching method. The outstanding feature of
have become a research hotspot because of their distinctive 4f
this method is that the most stable structure can be predicted
orbital and abundant electronic energy levels [17].
only by the knowledge of chemical composition. The ground
Despite the fact that, MgH2 is an excellent hydrogen stor-
state structures of various systems [36e41] have been suc-
age material, and the mass fraction of hydrogen is as high as
cessfully predicted by the CALYPSO method [42e47]. To pre-
7.6%, hydrogen is not conducive for decomposition at room
dict low-lying isomers for each cluster size, 50 generations of
temperature due to the poor thermodynamic stability and
structures are predicted, where each generation contains 30
reaction kinetics of MgH2 [18]. Since Philips laboratory in the
structures. Among all the isomers, the top fifty low-lying iso-
Netherlands found that LaNi5 has a good hydrogen storage
mers are selected as candidates for the lowest energy struc-
performance with a hydrogen storage capacity of 1.4 wt%,
ture. The selected low-lying isomers are then re-optimized at
further research on lanthanide hydrogen storage materials
the B3LYP [48] level in conjunction with the SDD [49,50] basis
has emerged in an endless stream [19e23]. In later studies,
set and all-electron 6-311þþG(d,p) [51] basis set for La and H
Reilly and Wiswall found that the hydrogen content of
atoms, respectively. The spin multiplicity and vibrational
La2Mg17 is 5.3%, and the dissociation pressure was similar to
frequencies from singlet to sextuple are considered to obtain
that of MgH2 [24]. In addition, it is found that Mg-based
the global minimum structure. All DFT calculations are per-
La2Mg17 alloy is a potential hydrogen storage material
formed using Gaussian 09 software package [52]. The theo-
[25,26]. Moreover, La2Mg17 alloy has higher hydrogen storage
retical photoelectron spectroscopy (PES) of anionic LaH
n
capacity and lower hydrogen storage temperature than mag-
clusters were simulated using the time-dependent density
nesium due to the catalysis of rare earth elements (RE).
functional theory [53]. Chemical bonding analysis depends on
However, the hydrogen absorption and desorption kinetics
the natural bond orbital (NBO) and adaptive natural density
performance of La2Mg17 at a lower temperature are still poor,
assignment (AdNDP) methods [54]. To confirm the accuracy
which limits its application [27e30]. In recent years, Hu et al.
and effectiveness of the selected basis sets and functions, the
found that the formation of the LaeH compound and the
calculated bond lengths of La2 and LaH are 2.66
A and 2.00

A,
synergistic effect of various elements led to the rapid
adsorption/desorption kinetics of La7.0Mg75.5Ni17.5 [31], which which is consistant with the experimental values of 2.70

A and
is also considered as a promising hydrogen storage material. 2.03

A for La2 and LaH, respectively [55,56].
Qi et al. found that addition La in as-spun alloys significantly
improved their hydriding rates, and the (Mg24Ni10Cu2)90La10
alloy with a spinning rate of 40 m/s holds the maximal Results and discussions
discharge capacity of 425.6 mAh/g [32]. Hou et al. further
demonstrated that the mechanism of the reduction of the Geometrical structures
stability of hydrides by the addition of La is the interaction
between the unsaturated d-electron shell of La and the The geometrical structures of anionic LaH
n ðn ¼ 2
20Þ clus-
valence electron of H, which weaken the MgeH bond [33]. In ters are obtained using CALYPSO cluster structure prediction
addition, rare earth metal hydrides YH10, LaH8, LaH10 have method combined with the first principles calculation. For
been found to be stable and can become superconductors at narrative convenience, we only show the structure of ground
high temperatures and pressures [34,35]. state and two metastable states. The size of each cluster of
Although rare earth hydrogen storage alloys have shown anionic LaH
n (n ¼ 2e15) clusters is expressed as m-ai, where m
excellent hydrogen storage properties, low hydrogen storage represents number of H atoms, a denotes anion, and i is the
capacity has not been solved. The research on rare earth number of isomers that increases with energy order. The
422 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 7 ( 2 0 2 2 ) 4 2 0 e4 2 7

ground state structure of LaH
2 can be marked with 2-a1 for

Table 1 e Electronic states, Eb(eV), Egap(eV), and charges
clarity. The symmetry and relative energy difference of the
on the La atom Q(La), as well as the calculated vertical
size of 2e15 cluster structures are displayed in Fig. 1. The size detachment energies and adsorption energies of the
of 16e20 cluster structures can be seen in Fig. S1 (where the anionic LaH
n clusters (n ¼ 2 ¡ 20).
energy of the ground state structure is set to 0 eV). The elec-
n State Eb Egap Q(La) VDE Eads
tronic states of each size cluster are listed in Table 1. It is 1
2 A1 2.19 2.06
0.84 0.80 3.28
interesting to note that all ground states structures are singlet 2
3 A1 2.41 2.42
0.62 0.87 3.21
or doublet resting with the electron number of a species. No 4 1
A1 2.60 5.30 0.86 3.95 3.25
imaginary frequencies are found in all of the reported ground 5 2
A 2.42 2.36 0.21 0.92 2.90
state and metastable structures except for 2-a2 (metastable 6 1
A1 2.55 5.18 0.80 3.48 2.97
state) with frequency of 369.98i cm
1. 7 2
A 2.42 2.30 0.09 0.84 2.77
1
Furthermore, all the optimized structures are three 8 A1 2.52 5.26 0.73 3.40 2.83
1 0
9 A 2.41 2.34 0.61 1.13 2.69
dimensional configurations, except for the smallest cluster 1
10 A1 2.49 4.97 0.62 3.56 2.74
(n ¼ 2), which forms a planar structure. When n  14, all 2 0
11 A 2.42 2.30 0.53 1.12 2.64
ground-state structures have high symmetry, and there is no 12 1
A1 2.48 5.01 0.85 4.12 2.68
hydrogen molecular detachment, except that the symmetry of 13 2
A 2.42 2.26 0.27 1.13 2.60
12-a1 and 13-a1 is C1. When n  15, the ground-state structure 14 1
A 2.47 5.01 0.52 4.06 2.65
2
begins to appear hydrogen molecule separation phenomenon, 15 A 2.41 2.22 0.35 1.14 2.57
1
and all of them possess low symmetry, except that 20-a1 is C2. 16 A 2.46 4.94 0.45 3.95 2.61
2
17 A 2.41 2.10 0.28 1.01 2.55
The ground-state structure 3-a1 has C2v symmetry in the 1
18 A 2.45 4.99 0.49 4.07 2.59
singlet state, where three H atoms form an equilateral triangle 2
19 A 2.41 2.10 0.28 1.03 2.24
at the bottom. The La atom is located above the centre of the 20 1
A 2.45 5.00 0.46 4.06 2.27
triangle to form a regular triangular pyramid. The energies of
the metastable structures 3-a2 and 3-a3 are 1.313 eV and
1.414 eV, respectively, which are higher than that of 3-a1. The
Td in a doublet state. The four H atoms are arranged in four
structure with the lowest energy of 4-a1 has perfect symmetry
different directions of the La atom to form a regular tetrahe-
dron structure. The energies of metastable structures are
1.592 eV and 1.674 eV, which are higher than that of 4-a1.
Furthermore, the lowest-energy geometric structure of 5-a1
with CS symmetry in the singlet state is observed. Its geometry
is similar to that of 3-a1, and one hydrogen molecule is bonded
to the La atom. The energies of isomers 5-a2 and 5-a3 are
0.052 eV and 1.107 eV, respectively, which are higher than that
of 5-a1. The structure of 6-a1 has C2v symmetry in a doublet
state, while its structure is formed by adding a hydrogen atom
to the 4-a1. The energies of the two low-lying isomers, 6-a2
and 6-a3, in which the detachment of hydrogen molecule
takes place, are 0.003 eV and 0.028 eV respectively, which are
higher than that of 6-a1. The symmetry of the ground-state
isomer of the anionic LaH
7 cluster is CS. Note that two
Hydrogen molecules are bonded to the adjacent La atoms.
Furthermore, the energies of the two metastable structures
are 0.009 eV and 0.034 eV, higher than that of 7-a1. The sym-
metry of the ground-state structure of the anionic LaH
8
cluster is D2d in a doublet state, while its structure is formed by
adding a hydrogen molecule to that of 4-a1. The hydrogen
molecule firstly detaches in metastable structures 8-a2 and 8-
a3, of which the energies are 0.003eV and 0.022eV higher than
that of 8-a1. Moreover, 9-a1 has CS symmetry in the singlet
state, and three pairs hydrogen molecules bond with the La
atom. The energies of two metastable structures 9-a2 and 9-a3
are 0.021 eV and 0.077 eV, respectively, which are higher than
that of 9-a1. The symmetry of the ground-state structure of
the anionic LaH
10 cluster is C2v in a doublet state. Its geometry
is adding a hydrogen molecule to the geometry of 8-a1. The
energies of two metastable structures 10-a2 and 10-a3 are
Fig. 1 e Geometrical structures of LaH
0.015 eV and 0.019 eV higher than that of 10-a1. Also, the
n ðn ¼ 2
15Þ clusters,
as well as the relative energy (in eV) and point group ground-state structure of the anionic LaH
11 cluster with C2v

symmetry. symmetry in a singlet state is formed by adding three

 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 7 ( 2 0 2 2 ) 4 2 0 e4 2 7 423

hydrogen molecules to the geometry of 5-a1. In this case the

energies of two metastable structures 11-a2 and 11-a3 are
0.002 eV and 0.021 eV, respectively, which are higher than that
of 11-a1. The symmetry of the ground-state structure of the
anionic LaH
12 cluster is C1 in the doublet state, while the main
structure is slightly different from 7-a1, and three pairs of
hydrogen molecules bond with the La atom. In the case of 12-
a2 and 12-a3, the energies of the two isomers 12-a2 and 12-a3
are 0.017 eV and 0.058 eV higher than that of 12-a1. For 13-a1,
there is a low symmetry C1 in the singlet state. Five pairs of
hydrogen molecules bond with La atom, and the energies of
isomers 13-a2 and 13-a3 are 0.004 eV and 0.008 eV higher than
that of 13-a1. As for 14-a1, the geometry has C1 symmetry with
three mutually symmetric hydrogen molecule pairs bonded to
the La atom. The symmetry of the ground-state structure of
the anionic LaH
15 cluster is C1 in the singlet state, while its
geometry is formed by adding a detachment hydrogen mole-
cule to the geometry of 13-a1. From the above analysis of the
geometric structure, it can be seen that dehydrogenation
phenomenon of the anionic clusters occurs at n ¼ 15 and can
not absorb more hydrogen atoms effectively. It means that the
maximum coordination number of the La atom is 14.

PES of the LaH

n clusters

To confirm the validity of the electronic structure of anions,

the PES of the global minima arrangements of
LaH
n ðn ¼ 2
20Þ has been computed by the time-dependent
density function theory method. The PES calculation results
are shown in Fig. 2. The first peak of each spectrum is inter-
preted as the vertical detachment energy (VDE), which de-
notes the separation and transition of electrons from the
anion ground state to the corresponding neutral ground state
or excited state under the optimized anion geometry. The Fig. 2 e Theoretical PES for the ground states of LaH

n

theoretical VDE values are listed in Table 1. clusters.

As shown in Fig. 2, the VDE values of LaH
n ðn ¼ 2; 3; …; 20Þ
are in the binding energy range of 0.80 eVe4.12 eV. The
LaH
n ðn ¼ 2; 3; …; 20Þ clusters with n ¼ 2, 3, 5 appear crowded
spectra with theoretical VDE values of 0.80 eV, 0.87 eV, and
0.92 eV, respectively. For LaH
4 , there are two prominent peaks,
and the first peak appears at 3.95 eV. Also, three distinct peaks
are observed in the spectra of LaH


6 and LaH8 , and the first peak
appears at 3.48 eV and 3.40 eV, respectively. Furthermore, two
prominent peaks were identified in LaH

7 spectrum, but the first
one appears at 0.84 eV and that with a shoulder at 3.84 eV.
Similarly, two significant peaks are identified in the LaH
11
spectra. Its first peak is recorded at 1.12 eV and another peak
with a shoulder at 3.74 eV in the spectrum. On contrary to what
are obtained above, the simulated spectra of LaH
9 and LaH13


contain a weak peak, and a double-peak at 1.13 eV, 3.90 eV,
4.30 eV, 1.12 eV, 3.71 eV, and 4.15 eV, respectively. As for LaH
10 ,
there are two significant peaks at 3.56 eV, and 4.15 eV. But for
LaH
12 , there is only one significant peak at 4.11 eV. In the
theoretical PES of LaH
n clusters with n ¼ 14
20, two distinct
peaks are observed except for LaH


16 and LaH18 . The same to
LaH12 , there is only one prominent peak for LaH




16 and LaH18 ,
which appears at 3.95 eV, 4.07 eV, respectively. The simulated
PES provide a guide for experimental PES measurements of rare
earth hydrides.
Relative stabilities
The average binding energy (Eb) is used to determine the
intrinsic stability of clusters. For anionic LaH

n ðn ¼ 2
20Þ
clusters, the Eb values can be calculated according to the
formula (1)

Eb ðLaH



n Þ ¼ ½nEðHÞ þ EðLa Þ
EðLaHn Þ ðn þ 1Þ (1)
where E is the energy of the corresponding cluster or atom.
The variation trend of Eb value of the ground state anionic
LaH
n cluster with the cluster size is shown in Fig. 3a. The odd-
even oscillation of the average binding energy (Eb) can be seen
in Fig. 3a, which demonstrates that the clusters with the
closed-shell electronic structure are more stable than those
with open shell geometry. Noted that the theoretical values of
average binding energy are larger at n ¼ 4, 6, 8. Thus, LaH
4,
LaH


6 , and LaH8 are relatively stable structures.
To further explore the most stable structure of anionic
LaH
n ðn ¼ 2
20Þ clusters, the values of the second-order en-
ergy difference (D2E) are calculated using the formula (2), and
the curve with the increase of cluster size is plotted in Fig. 3b.
D2 EðLaH




n Þ ¼ EðLaHnþ1 Þ þ EðLaHn
1 Þ
2EðLaHn Þ (2)
424 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 7 ( 2 0 2 2 ) 4 2 0 e4 2 7
Fig. 3 e (a) The binding energy Eb, (b) the second-order
energy difference D2E and (c) the energy difference Egap for
the LaH
n with H atom n from 2 to 20.
It is evident from Fig. 3b that the second-order energy
difference (D2E) shows odd-even oscillation behavior. The
maximum point occurs at n ¼ 4, 6, 8, which indicates that
these even clusters are more stable than the odd clusters
adjacent to them. The energy difference (Egap) between the
highest occupied molecular orbital (HOMO) and the lowest
unoccupied orbital (LUMO) reflects the ability of extra-nuclear
electrons to move from occupied to unoccupied orbits. The
larger the Egap, the better the chemical stability of the clusters,
and it is difficult to gain or lose electrons cv g [57]. As shown in
Fig. 3c, the HOMO-LUMO difference value of the ground state
structure of anionic LaH

n ðn ¼ 2
20Þ cluster shows odd-even
oscillation again. The maximum values are 5.29 eV and
5.26 eV at n ¼ 4, 8, respectively. Considering the previous
relative stability analysis of Eb and D2E, the most stable
structures of anionic LaH


n ðn ¼ 2
20Þ clusters are LaH4 and


LaH8 . They are considered as “magic” clusters with enhanced
structural stability.
Adsorption and charge transfer analysis
In order to determine the interaction between the H atoms
and the La cluster, the adsorption energies are calculated
using the formula (3)

Ead ðLaH



n Þ ¼ ½EðLa Þ þ nEðHÞ
EðLaHn Þ n
The calculated values of adsorption energy are shown in
Table 1. All Eads values are positive, which indicates that the
average adsorption of the H atom is energetically stable. It is
found that the average adsorption energies of anionic
LaH
n ðn ¼ 2
20Þ clusters ranged from 2.57 eV to 3.28 eV. These
values indicate that the hydrogen atom on the surface of the
anionic La cluster belongs to chemisorption. In addition, the
Eads values of LaH
n ðn ¼ 2
20Þ clusters exhibit odd-even os-
cillations. The Eads values of even clusters are larger than
those of odd clusters adjacent to them. The Eads values
decrease gradually with the increase of H atoms, which in-
dicates that the interaction between H atoms and anionic La
clusters decreases gradually. The natural population analysis
method is employed to investigate the charge transfer of La
atom in the ground state structure of anionic LaH
n ðn ¼ 2
20Þ
clusters. The charge number of the La atom is shown in Table
1. It is found that the charge number of La atom also shows
odd-even oscillation behavior in the same direction as Eads
values, and the charge amount of La atom in even cluster is
always more than that of the adjacent odd cluster, which
confirms the fact that even size LaH
n clusters have large Eads
values. Additionally, the charge on the La atom is positive
except for LaH


2 and LaH3 , which indicates that the charge is
more easily to transfer from La atom to hydrogen molecule.
Based on the molar mass of lanthanum and hydrogen, the
hydrogen storage density of LaH
8 is calculated as percentage.
The result shows that LaH
8 has a high hydrogen storage ca-
pacity of 5.4 wt%.
Chemical bonding analysis
Based on the aforementioned analysis, it is found that the
anionic LaH
8 cluster possesses excellent stability, a closed-
shell electronic structure with 12 valence electrons, and the
HOMO-LUMO gap, with adsorption energy 5.26 eV and 2.83 eV.
To further understand the bonding mechanism of the anionic
LaH
8 cluster, the HOMO-LUMO frontier orbitals of anionic
LaH
8 cluster are calculated. The calculated results are shown
in Fig. 4. It is evident from Fig. 4 that the molecular orbitals of
anion LaH
8 cluster are primarily composed of the H 1s orbital
and the La 5d orbital. The contribution of H 1s orbital to LUMO
is 86.27%. HOMO is mainly composed of La 5d orbital and H 1s
orbital, with contribution rates of 24.41% and 71.56%, respec-
tively. The contribution of the La 5d orbital to LUMOþ1,
HOMO-1, and their corresponding merger orbitals LUMOþ1',
(3)
Fig. 4 e Molecular orbitals of the LaH

8 cluster.
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 7 ( 2 0 2 2 ) 4 2 0 e4 2 7
Fig. 5 e The bonding molecular orbitals obtained from
AdNDP analysis for the LaH

8 cluster. ON stands for
occupation number.
HOMO-1' are 44.56% and 18.37%, respectively. For HOMO-3
and HOMO-4, the H 1s orbital contributes 95.19% and 93.34%,
respectively. The orbital of HOMO-2 is mainly contributed by
H 1s orbital and La 6s orbital. HOMO-5 and its merger orbit
HOMO-5' are almost entirely composed of La 5p orbit. In gen-
eral, the analysis of molecular orbitals composition shows
that there is a strong interaction between H 1s orbital and La
5d orbital, which is mainly responsible for the stability of the
anionic LaH
8 cluster.
To further study the binding pattern of the ground state
structure of anion LaH
8 cluster, the adaptive natural density
partitioning (AdNDP) method is applied. The calculation re-
sults are shown in Fig. 5. All the occupation values are more
than 1.97 because the H 1s orbital and the La 5d orbital can
only form localized s bond. Also, 2c-2e has a relatively low
occupancy value of 1.97 |e|. Whereas 3c-2e, 4c-2e, and 7c-2e
possess the same occupancy value with ON ¼ 1.99 |e|. Our
results also show that 5c-2e, and 9c-2e have an ideal occu-
pancy value ON ¼ 2.00 |e|, which indicate that the interaction
between the H 1s orbital and the La 5d orbital is responsible for
the structural stability of the anionic LaH
8 cluster.
Conclusions
In conclusion, we have determined the ground state struc-
tures of anionic LaH
n ðn ¼ 2
20Þ clusters by CALYPSO struc-
ture searching method and density functional theory
calculations. The calculated results show that the adsorption
energy of the clusters is in the range of 2.57 eVe3.27 eV, and H
atoms prefer chemisorption on La atom. Interestingly, the
anionic LaH
8 cluster with D2d symmetry is extremely stable
with large HOMO-LUMO gap of 5.26 eV. And its hydrogen
storage capacity arrives at 5.4 wt%. This results enrich the
geometrical structures and electronic properties of rare-earth
425
based nanoclusters, which provide crucial insights for explo-
ration and discovery of new-style hydrogen storage nano-
materials. The simulated theoretical PES provides guidance
for the experimental measurement of rare earth hydrogen
storage material.
Declaration of competing interest
The authors declare that they have no known competing
financial interests or personal relationships that could have
appeared to influence the work reported in this paper.
Acknowledgements
This work was supported by the Higher Levels of Young
Teachers Funding Scheme of Henan Province (Grant No.
2019GGJS057), the Key Scientific Research Projects of Colleges
and Universities in Henan Province (Grant No. 2019GGJS057)
and the Postdoctoral Science Foundation of Henan Province.
Appendix A. Supplementary data
Supplementary data to this article can be found online at
https://doi.org/10.1016/j.ijhydene.2021.10.015.
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