international journal of hydrogen energy xxx (xxxx) xxx

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Structures and hydrogen storage properties of

AeVH3 (Ae ¼ Be, Mg, Ca, Sr) perovskite hydrides by
DFT calculations

Areeba Siddique a, Adnan Khalil a,*, Badriah S. Almutairi b,

Muhammad Bilal Tahir a,c, Muhammad Sagir d, Zaka Ullah e,
Abdul Hannan a, H. Elhosiny Ali f,g, Hussein Alrobei h, Meshal Alzaid i
a
Institute of Physics, Khwaja Fareed University of Engineering and Information Technology, Rahim Yar Khan,
64200, Pakistan
b
Department of Physics, College of Science, Princess Nourah bint Abdulrahman University, P.O. Box 84428, Riyadh
11671, Saudi Arabia
c
Centre for Innovative Material Research, Khwaja Fareed University of Engineering and Information Technology,
Rahim Yar Khan, Punjab, Pakistan
d
Institute of Chemical and Environmental Engineering, Khwaja Fareed University of Engineering and Information
Technology, Rahim Yar Khan, 64200, Pakistan
e
Department of Physics, Division of Science and Technology, University of Education, Lahore, 54770, Pakistan
f
Research Center for Advanced Materials Science (RCAMS), King Khalid University, Abha 61413, P.O. Box 9004,
Saudi Arabia
g
Physics Department, Faculty of Science, Zagazig University, Zagazig, Egypt
h
Department of Mechanical Engineering, College of Engineering, Prince Sattam Bin Abdulaziz University, Al Kharj,
Saudi Arabia
i
Physics Department, College of Science, Jouf University, P.O. Box: 2014, Sakaka, Saudi Arabia

highlights

Four new hydride perovskites have been investigated for hydrogen storage.

The electronic analysis showed that these metal based hydride perovskites are metallic in nature.

These metal hydrides are found to be structurally and mechanically stable.

article info abstract

Article history: The capability of hydrogen to be an energy source has made the hydrogen storage as one of
Received 6 October 2022 the most investigated research fields during the recent years, and novel perovskite mate-
Received in revised form rials have become the current focus for hydrogen storage applications. Here we study the
3 March 2023 AeVH3 (Ae ¼ Be, Mg, Ca, Sr) perovskite-type hydrides to explorer their potential for
Accepted 11 March 2023 hydrogen storage applications using the density functional theory (DFT) implemented
Available online xxx CASTEP code along with exchange correlation potential. The study examines the electronic
structure, optical properties, elastic features and mechanical stability of the materials. The
Keywords: crystal structure of AeVH3 compounds is found to be cubic with lattice constant as 3.66,
Perovskite 3.48, 3.76 and 3.83 for Ae ¼ Be, Mg, Ca and Sr compounds, respectively. The calculated
Hydrides electronic structures of these compounds show ionic bonding and no energy bandgap. The

* Corresponding author.
E-mail address: [email protected] (A. Khalil).
https://doi.org/10.1016/j.ijhydene.2023.03.139
0360-3199/© 2023 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.

Please cite this article as: Siddique A et al., Structures and hydrogen storage properties of AeVH3 (Ae ¼ Be, Mg, Ca, Sr) perovskite hy-
drides by DFT calculations, International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2023.03.139
2 international journal of hydrogen energy xxx (xxxx) xxx

First principle calculations mechanical characteristics of compounds are also investigated as to meet the Born stability
Mechanical stability criterion, these compounds should be mechanically stable. The Cauchy pressure and Pugh
Hydrogen storage criteria revealed that these materials have a brittle character and rather hard. In low en-
ergy range, all optical properties are found to be suitable as needed for storing the
hydrogen. Furthermore, the gravimetric ratios suggested that all the compounds are
suitable for hydrogen storage as a fuel for a longer time and may provide remarkable
contributions in diversity of power and transportation applications.
© 2023 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.

operating temperature range. Conventional hydrogen stor-

Introduction age methods such as gas pressure and liquefaction are pro-
hibitively expensive and possess serious safety concerns
Global energy consumption has expanded dramatically in [15,16].
parallel with population growth. This is due to the fact that the The hydrogen storage through gas compression and
energy demands have been increased with the development liquefaction is not effective for longer time, hence novel ma-
of research and technology for provision of advanced facilities terials are being developed to achieve this feature [17]. A
to humankinds. The major portion of energy is obtained from possible candidate for future hydrogen storage materials in
fossil fuels which are non-renewable and take longer time to solid state is the perovskite-type hydride. Detailed studies on
recover or change back to their initial capacity [1,2]. Sustain- potential uses of ABH3 perovskite-type hydrides have been
able energy research development, and innovation tactics are conducted using the experimental and theoretical approaches
also being upgraded with rise in global energy requirements during the recent years [18]. To achieve the long-term efficient
[3]. As carbon combustion and use of less efficient fossil fuels hydrogen storage, the methodologies must meet various
have been blamed for a 35% rise in CO2 emissions, the criteria including the reversibility and fruitful kinetics [19].
hydrogen popularity as an alternative energy source is The ABH3 compounds can be divided into two categories
continuously being increased owing to its abundance, non- based on the elements they contain: either an A element from
toxicity, efficiency and sustainability [4]. Because of its group I or II, and B from transition metals group of the periodic
adaptability and environmental-friendliness, hydrogen out- table [20,21].
performs among all other fuels proposed so far [5]. After the The literature shows that the hydrogen stability and its
worldwide oil crisis that began in 1970, hydrogen-based en- restricted combinations of cations have led to the develop-
ergy systems were developed that may revolutionize the ment of oxides rather than hydrides. However, the notable
transportation and power engineering [6]. thermal stability and absorption/desorption capabilities of
Hydrogen has emerged as a promising choice for energy lightweight hydrides have received substantial attentions.
source owing to its ability to provide cost-effective and clean Owing to their high gravimetric densities, light metal hy-
energy [7]. The first manned mission to the moon was the first drides offer great promise for hydrogen storage applications
project to use the hydrogen fuel as reserve fuel. Currently, [22,23]. The researchers have also reported the investigations
many countries around the world are using it for transport. on alkali metal hydrides as hydrogen storage materials. The
For both fixed and portable applications, hydrogen is a safe, metal hydrides which can be used to absorb the hydrogen,
environmentally-friendly and cost-effective energy source [8]. are considered as functional materials [24]. Hydrogen is
When it comes to powering our planet, fossil fuels are still the stored in huge quantities in inter-metallic phases of several
only option [9]. Materials that can store hydrogen at ambient metals through chemical bonding. A reaction takes place
pressure and temperature with high volumetric and gravi- between the hydrogen, metal and alloy phase, resulting in
metric hydrogen densities, are the current focus of the re- substantial absorption of hydrogen. Metal hydrides,
searchers [10]. It has been realized that for a big interstice to compared to compressed gas and liquid hydrogen, are a safer
store a significant quantity of hydrogen and the ability to fuel source, and these have become commercially accessible
absorb it more effectively through a catalyst, the proposed during the recent years [25].
materials/nanostructures must have a strong hydrogen bond In ideal case, hydrogen should be extracted at ambient
[11]. temperature and pressure. Among the simple metal hydrides,
To industrialize the hydrogen as a sustainable energy magnesium hydrides have long been the subject of many
source, numerous technical challenges have to overcome scientific researchers [26]. However, some features make this
[12]. The use of hydrogen as an alternate clean fuel has material difficult to use in applications i.e. high enthalpy of
widely been observed throughout the world since it produces formation or high thermodynamic stability, slow (de)hydro-
energy without emitting carbon dioxide. The only product it genation process (reaction kinetics of absorption/desorption),
delivers is water which is free of any pollutants, ozone- and high oxidability in air. The addition of small amount of
damaging chemicals or harmful synthetics [13,14]. Exten- lightweight transition metals (TMs) to MgH2, such as V, Ti and
sive research attempts are being employed to find the novel Sc elements, is the best known way to improve the (de)hy-
materials with higher hydrogen contents and a suitable drogenation kinetics of H2 diffusitivity in MgH2 [27]. The

Please cite this article as: Siddique A et al., Structures and hydrogen storage properties of AeVH3 (Ae ¼ Be, Mg, Ca, Sr) perovskite hy-
drides by DFT calculations, International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2023.03.139
 international journal of hydrogen energy xxx (xxxx) xxx 3

hydrogen storage capacity and different catalytic effects on space utilizing ideal crystal geometries. The elastic modulus
the hydrogenation process of TM-doped magnesium hydride of a single crystal was utilized to compute the elastic modulus
nanocomposite powders are investigated [28]. of polycrystalline materials. The calculations were driven by
A report in literature shows the study on CaXH3 (X ¼ Mn, Fe the VRH approximation. Voight and Reuss' bulk and shear
and Co) hydride-type perovskites to investigate their potential modulus values were also determined. After optimizing the
for hydrogen storage. The structural, mechanical, electrical geometry of the unit cell, all the properties were investigated.
and hydrogen storage properties of these materials were
examined and discussed in details [29,30]. Several similar re-
ports have been published in literature which show first- Results and discussion
principle/computational study of structural, optical, elec-
tronic and thermodynamic properties of hydride-type perov- Structural stability Properties
skites at low temperatures [31,32]. Gencer A. et al. Investigated
hydrogen storage properties of MgTiH3 and hydrogen doped Alkaline earth metals-based perovskites (AeVH3 with Ae ¼ Be,
MgTiH3þx (x ¼ 3, 6, 8) compounds using VASP in his work [33]. Mg, Ca, Sr) depict face centred cubic structure with space
In addition to the gravimetric storage capacity, the hydrogen group Pm-3m (221) at room temperature. This structure has 4
desorption temperatures have been enhanced with the atoms per unit cell with Wyckoff positions as Ae ¼ Be, Ca, Mg,
hydrogen doping. T. Sato et al. prepared CaNiH3 experimen- Sr atoms at corners (0, 0, 0), V atoms in centre of body (0.5, 0.5,
tally and showed the hydrogenation reaction, which is per- 0.5) and three hydrogen atoms on centre of face (0, 0.5, 0.5).
formed at rather low temperatures, a major rearrangement of Fig. 1 shows the schematic representation for crystal structure
the metal atoms takes place, e.g., CaNi3 þ 3/2H2 ¼ CaNiH3þNi. of AeVH3 (Ae ¼ Be, Mg, Ca, Sr). The lattice parameters,
The decomposition reaction CaNiH3 ¼ CaH2þNi occurs at bandgap and volume of AeVH3 (Ae ¼ Be, Mg, Ca, Sr) are
748 K in an H2 atmosphere which prevents the employment of recorded (Table 1) after optimization of geometry.
heat treatments for use in hydrogen storage systems [34]. Table 2 summarizes the free energy F (eV), bulk modulus B
In present work, we employ DFT computations imple- (GPa), enthalpy H (eV) and formation energy E (eV) for ternary
mented in CASTEP to investigate structural, electronic, opti- hydride perovskite AeVH3 calculated by GGA-PBE functional.
cal, mechanical and hydrogen storage properties of AeVH3 The values of bulk moduli increases as i.e. BeVH3 > MgVH3 >-
(Ae ¼ Be, Mg, Ca, Sr) perovskite hydrides. The obtained results CaVH3 > SrVH3 and enlisted in Table 2. From previous litera-
have been discussed in details to deeply understand the ture [18], we know that superhard compounds have bulk
behaviour of these materials for the proposed applications. moduli greater than 40 GPa. Thus, the condition of rigidity is
The study is a significant addition to present knowledge of fulfilling by all our materials. Due to the largest value of B,
these materials which will be fruitful for the development of BeVH3 is the hardest one among all compounds. The cohesive
hydrogen storage devices. energy is found to have negative value which depicts that the
compounds have stable structure. Moreover, their mechanical

Computational details

To optimize the geometry of metal-based hydride perovskites

AeVH3, Cambridge serial total energy package (CASTEP) algo-
rithm [35] and material studio (version 2017) were used.
Whereas, the first principle approach based on density func-
tional theory (DFT) was employed to compute all the physical
properties these compounds. To approximate the exchange-
correlation potential, Perdew, Burke and Ernzerhof (PBE)
type pseudo-potentials were studied in the framework of
generalized gradient approximation (GGA) for all atoms of
investigated compositions [36]. The periodic boundary condi-
tion was implemented and extended as per set of plane waves
using Bloch's theorem [37,38]. In crystalline materials, the
electronic wave functions and charge densities were calcu-
lated using the Broyden, Fletcher, Goldfarb & Shanno (BFGS)
energy minimization methodology which has been preferred
and extensively used in the reported literature [39]. For k point
sampling, the Monkhorst Pack scheme was used in first Bril-
louin zone. For reliable results, an ultrafine k points (8  8  8)
mesh was selected and the energy cutoff value was taken as
630 eV with a smearing value of 0.5 eV. In terms of energy, the
maximum ionic force per atom was 5  102 eV and the energy
convergence was 2  106 eV/atom. The highest displacement
was 2  104  A and the maximum stress was 0.1 G Pa. Elec- Fig. 1 e Crystal structure of AeVH3 where Ae could be Be,
tronic and optical properties were calculated in reciprocal Mg, Ca or Sr.

Please cite this article as: Siddique A et al., Structures and hydrogen storage properties of AeVH3 (Ae ¼ Be, Mg, Ca, Sr) perovskite hy-
drides by DFT calculations, International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2023.03.139
4 international journal of hydrogen energy xxx (xxxx) xxx

studied materials. These measurements help us to observe

Table 1 e Calculated values of lattice parameters, volume
the contribution of each cation in the band structure. The
and bandgap energy of AeVH3 (Ae ¼ Be, Mg, Ca, Sr)
compounds. TDOS at fermi level are noted as 2.51, 3.24, 4.61 and 5.47
electrons/eV respectively for AeVH3 with Ae ¼ Be, Mg, Ca, and
Compound Lattice parameters Volume Bandgap
Sr. Moreover, another peak is observed at 5.26, 4.03, 5.77, 5.63
(
A) (
A3) (eV)
electrons/eV in BeVH3, MgVH3, CaVH3 and SrVH3, respectively.
BeVH3 3.48 42.21 0
The study of PDOS informs about the dominated states in
MgVH3 3.66 49.22 0
CaVH3 3.76 53.28 0
conduction and valence bands of the materials. Fig. 4 shows
SrVH3 3.83 56.22 0 that for BeVH3, the contribution of s state is dominated in
valence band (from 10 to 0 eV) and p state is dominated in
conduction band (from 0 to 10 eV). Similarly, MgVH3 shows
similar dominated states in valence and conduction bands.
Table 2 e Bulk modulus B (GPa), free energy F, enthalpy H Beside these two hydride-perovskites, CaVH3 and SrVH3 show
and cohesive energy E (eV) for AeVH3 (Ae ¼ Be, Mg, Ca, Sr)
slightly different dominated states in conduction band where
perovskite hydride.
the d state contributes more than the p state. The metallic
Parameters BeVH3 MgVH3 CaVH3 SrVH3
behaviour is confirmed by the fact that the Fermi level is
B (GPa) 133.2 102.21 67.713 64.605 contributed by s, p and d states. Owing to this inter-metallic
E (eV) 3.24 3.45 3.86 4.06 behaviour, these compounds possess the ability to store
F (eV) 2389.64 3004.32 3689.48 3876.60
notably higher amount of hydrogen.
H (eV) 2.389 3.004 3.689 3.876

Optical analysis

stability has been determined by computing the elastic con- The optical characteristics of the materials which are associ-
stants of these compounds. ated with different optical parameters including complex
refractive index, dielectric constant, energy-loss function,
Electronic band structure and density of states optical conductivity, absorption and reflection, were also
investigated to elaborate the optical response of AeVH3
To evaluate the electronic behaviour of AeVH3 compounds, (Ae ¼ Be, Mg, Ca, Sr). The obtained results are shown in Figs. 5
their electronic band structure and density of states (DOS) and 6 which were used to inspect the suitability of these
were studied. The energy bands are the energy states that materials for hydrogen storage applications.
electrons can occupy and those which the electrons cannot The optical characteristics of a medium can be described
occupy between the conduction and valence bands, are by complex dielectric function, as given below:
referred as bandgap. A periodic band structure is the spectrum
εðuÞ ¼ ε1 ðuÞ þ i ε2 ðuÞ (1)
of energy eigen values [40]. One may get insight into the ge-
ometry of Fermi surface by calculating the band structure. The When an electron is excited, the peak value of real component
understanding of electrical and optical characteristics is of dielectric constant is increased. In Kramers-Kronig relation,
directly associated with energy bands structure and Fermi ε1 (u) is used to deduce the real part of dielectric constant
level. The bandgap is one of the most important parameters of which depicts the dispersion and polarization of incident
band structure as it has a notable influence on optoelectronic electromagnetic radiation [43]. Due to dipole creation upon
properties of the material [41,42]. application of electric field, the magnitude of polarization can
Researchers have conducted the computational studies on be determined using the real part of dielectric function ε1 (u).
versatile electronic transitions from valence band maxima The imaginary component of dielectric constant ε2 (u) can be
(VBM) to conduction band minima (CBM) using the electronic calculated using the momentum matrix elements between
band structure information. Fig. 2 shows the band structures the unoccupied and occupied states which describes the
of AeVH3 (Ae ¼ Be, Mg, Ca, Sr) perovskites computed using the absorptive nature of the incident radiation.
GGA-PBE approach in Brillouin zone. It is obvious from the Fig. 5 (a, b) shows the real ε1 (u) and imaginary ε2 (u)
figure that the VBM and CBM meet each other and materials components of complex dielectric constant against varying
did not show any bandgap. Hence, the demonstrated mate- photon energy. For real component of complex dielectric
rials are metallic in nature. constant, the static values are recorded as 19.06, 19.05, 3.95,
Electronic DOS is the measure of electrons that occupy the and 2.91 for BeVH3, MgVH3, CaVH3 and SrVH3, respectively.
certain number of electronic energy states in unit volume. The peak values for BeVH3, MgVH3, CaVH3 and SrVH3 are
Figs. 3 and 4 depict the electronic structure of AeVH3 at zero observed as 8.51 at 4.95 eV, 7.17 at 3.39 eV, 4.36 at 5.41 eV and
pressure in terms of its total and partial electronic density of 4.03 at 3.06 eV. Till minimum energy up to 6.34 eV, the
states. The vertical line indicates the Fermi level (Ef). The dielectric function decreases gradually and attains the nega-
contributions of s, p and d orbitals of Ae (whereas, Ae ¼ Be, Mg, tive values as 0.98 at 8.27 eV, 2.5 at 8.01 eV, 0.75 at 15.2 eV
Ca, Sr) and H have been studied. The valence and conduction and 0.1 at 27.2 eV for respectively BeVH3, MgVH3, CaVH3 and
bands consist of 2s2 in Be, 2s2 2p6 3s2 in Mg, 3s2 3p6 4s2 in Ca, SrVH3. The negative values suggest the poor reflectivity,
4s2 4p6 5s2 in Sr, 3s2 3p6 3d3 4s2 in V and 1s1 in H. Figs. 3 and 4 transmission and optical losses. After decreasing, the dielec-
show the graphical representation of TDOS and PDOS of tric function regains its positive value in maximum energy

Please cite this article as: Siddique A et al., Structures and hydrogen storage properties of AeVH3 (Ae ¼ Be, Mg, Ca, Sr) perovskite hy-
drides by DFT calculations, International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2023.03.139
 international journal of hydrogen energy xxx (xxxx) xxx 5

Fig. 2 e Band structure of metal-based perovskite hydrides (a) BeVH3, (b) MgVH3, (c) CaVH3 and (d) SrVH3.

Fig. 3 e TDOS of perovskite hydrides: (a) BeVH3, (b) MgVH3, (c) CaVH3 and (D) SrVH3.

Please cite this article as: Siddique A et al., Structures and hydrogen storage properties of AeVH3 (Ae ¼ Be, Mg, Ca, Sr) perovskite hy-
drides by DFT calculations, International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2023.03.139
6 international journal of hydrogen energy xxx (xxxx) xxx

Fig. 4 e PDOS of hydride perovskites: (a) BeVH3, (b) MgVH3, (c) CaVH3 and (d) SrVH3.

Fig. 5 e (a, b) Variation in real and imaginary parts of complex dielectric function, (c) absorption and (d) reflectivity of AeVH3
(Ae ¼ Be, Mg, Ca, Sr).

Please cite this article as: Siddique A et al., Structures and hydrogen storage properties of AeVH3 (Ae ¼ Be, Mg, Ca, Sr) perovskite hy-
drides by DFT calculations, International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2023.03.139
 international journal of hydrogen energy xxx (xxxx) xxx 7

Fig. 6 e Optical parameters of AeVH3 (Ae ¼ Be, Mg, Ca, Sr): (a, b) refractive index, (cee) optical conductivity and (f) loss
function.

range. In all cases, the dielectric function behaves in a similar 3.91 eV for SrVH3. Due to the inter-metallic nature of these
fashion and spread parallel against the energy beyond 30.7 eV, materials, an intraband transition is expected to be dominant
indicating the least dispersion and polarization of incident for electronic transitions. In maximum energy range, the
electromagnetic radiations. The highest polarization is found values of imaginary component decrease and become parallel
in BeVH3 owing to its maximum value of static dielectric to the energy change beyond 31.2 eV. Owing to the large value
function (real) as compared to MgVH3, CaVH3 and SrVH3, of ε2 (u), BeVH3 is regarded as an efficient candidate for
which shows its notable ability of energy storage in hydrogen hydrogen storage devices.
storage appliances. The absorption coefficient measures how much incident
The imaginary component of dielectric functions ε2 (u) light of a certain energy (frequency) is absorbed by the mate-
Fig. 5 (b) shows the peak values as 9.77 at 6.76 eV for BeVH3, rial before it can be converted into energy. Higher absorption
8.62 at 5.73 eV for MgVH3, 3.43 at 6.37 eV for CaVH3 and 2.56 at coefficient signifies the ability of a material to absorb more

Please cite this article as: Siddique A et al., Structures and hydrogen storage properties of AeVH3 (Ae ¼ Be, Mg, Ca, Sr) perovskite hy-
drides by DFT calculations, International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2023.03.139
8 international journal of hydrogen energy xxx (xxxx) xxx

incident radiation. Fig. 5 (c) depicts the frequency dependent radiations, only BeVH3 could achieve a static value and high-
a(u) for AeVH3 (Ae ¼ Be, Mg, Ca, Sr) hydride-perovskites est extinction coefficient of 2.22 at 7.4 eV, owing to which it
against the incident photon energy (ranging from 0 to 35 eV). can be a fruitful choice for hydrogen storage applications.
The increasing and decreasing trends of a(u) are shown in Fig. 6(cee) shows the real and imaginary components of
figure, where the maximum absorption peaks are observed as: optical conductivity which informs about conduction mech-
4.1  105 cm1 at 27.7 eV for BeVH3, 2.8  105 cm1 at 11.7 eV for anism and bond breaking process in the material. When no
MgVH3, 2.7  105 at 7.8 eV for CaVH3 and 2.8  105 cm1 at light is incident on AeVH3 (Ae ¼ Be, Mg, Ca and Sr) hydride-
23.4 eV for SrVH3. In a higher energy (frequency) range, the perovskites, all the materials show zero conductivity. In low
absorption coefficient decreases and becomes almost zero energy range, BeVH3 shows maximum value of real compo-
beyond 32.6 eV. For hydrogen storage applications, a material nent of optical conductivity as 8.16 fs1 at 6.7 eV. The
with greatest absorption coefficient is desired and BeVH3 maximum negative values of optical conductivity are
among the studied materials, offers notable potential for this observed as 4.31 fs1 at 5.0 eV, 2.28 fs1 at 4.1 eV,
application. 3.66 fs1 at 5.3 eV and 3.18 fs1 at 4.9 eV for BeVH3, MgVH3,
The reflectivity of a material gives its ability to bounce back CaVH3 and SrVH3, respectively. The probability of scattering of
the incident light. Fig. 5 (d) shows the reflectivity R(u) of AeVH3 photoelectrons is proportional to the loss function of the
(Ae ¼ Be, Mg, Ca, Sr) compounds plotted against the varying material. The results for energy loss function for AeVH3
incident light energy. The peak values of R(u) are observed as (Ae ¼ Be, Mg, Ca, Sr) hydride-perovskites are shown in Fig. 6 (f).
0.51 at 13.2 eV, 0.34 at 6.1 eV, 0.84 at 1.4 eV and 0.92 at 1.74 eV The peak value of loss function is observed as 5.74 at 19.3 eV
for BeVH3, MgVH3, CaVH3 and SrVH3, respectively. The value for BeVH3, 3.89 at 28.8 eV for MgVH3, 3.4 at 27.2 eV for CaVH3
of reflectivity decreases with small ups and downs, and be- and 3.24 at 20.7 eV for SrVH3. The largest value is observed for
comes zero beyond 35.20 eV. As compared to other perovskite BeVH3. Beyond 35 eV, the loss function approaches to zero.
hydrides, MgVH3 and BeVH3 show minimum degree of
reflection from its surface. Mechanical stability and debye temperature
The extinction coefficient k(u) estimates the material ca-
pacity to absorb a certain wavelength of incident radiation, The elastic constants tell about the mechanical stability of a
and the refractive index n(u) gives information about material material, and these can be calculated using the stress strain
transparency for incident radiation. Following dielectric method. Table 2 shows the values of elastic constants C11, C12,
function relations are used to determine the n(u) and k(u) [44]: and C44 for AeVH3 (Ae ¼ Be, Mg, Ca, Sr). The accuracy of these
values is further confirmed when these meet the Born elastic
1  pffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi 12
stiffness stability requirements [45]. These relations are used
nðuÞ ¼ pffiffiffi ε1 ðuÞ þ ε1 2 þ ε2 2 (2)
2 for the determination of mechanical stability:
8
1 hpffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi i12 >
> C11  C12 > 0;
kðuÞ ¼ pffiffiffi ε1 2 þ ε2 2  ε1 ðuÞ (3) <
2 C11 > 0;
(4)
>
> C44 > 0;
:
The real component of refractive index is never zero. C11 þ 2 C12 > 0
However, its imaginary component also known as extinction
The calculated values of elastic constants are used to
coefficient could be zero. The phase velocity of electromag-
determine the physical properties (including shear modulus
netic wave in a medium is determined by real-part of refrac-
and bulk modulus) of a material. The values of Bulk and shear
tive index, whereas attenuation of electromagnetic wave in a
moduli have been estimated using the Voigt Reuss Hill (VHR)
material is associated with imaginary-part of the refractive
approximations. The Voigt approximation provides the high-
index. Fig. 6 (a, b) shows the dependence of complex refractive
est limit for modulus, while the Reuss approximation provides
index and extinction coefficient on incident light energy. The
the lowest limit. However, the Hill approximation is more
n(u) is determined as 4.63 for BeVH3 and 4.82 for MgVH3. The
accurate [46]. The data given in Table 3 was obtained using the
peak values of n(u) are found to be 3.02 at 4.9 eV, 2.83 at 3.4 eV,
Hill approximation. It resists the volume change upon appli-
2.68 at 5.2 eV and 2.19 at 5.6 eV for respectively BeVH3, MgVH3,
cation of a force. The bulk modulus B and shear modulus G are
CaVH3 and SrVH3. The highest magnitude of refractive index
determined from BV, R and GV, R in simple forms as:
was observed for BeVH3 among the others perovskites, as
illustrated in Fig. 6 (a). This depicts that the incident radiations 1
B ¼ BR ¼ BV ¼ ðC11 þ 2C12 Þ (5)
are linked with large amount of valence electrons during the 3
transmission of photons which induces more polarization in
the material. In this scenario, BeVH3 becomes the promising 1 5C44 ðC11  C12 Þ
Gv ¼ ðC11 þ 3C44  C12 Þ & GR ¼ (6)
and noteworthy new hydride perovskite for hydrogen storage 5 4C44 þ 3ðC11  C12 Þ
systems.
Fig. 6 (b) shows the variations in extinction coefficient with 1
G ¼ ðGV þ GR Þ (7)
varying incident photon energy. At critical point, the value of 2
extinction coefficient is noted as 0.54 for BeVH3 and 0.30 for The bulk modulus of BeVH3 is far higher than that of other
MgVH3. The peak values are found to be 2.22 at 7.4 eV for compounds. Where, the shear modulus (G) is the measure of
BeVH3, 1.78 at 6.2 eV for MgVH3, 2.31 at 7.2 eV for CaVH3 and ratio of stress to strain, and its value is lowest for SrVH3
2.59 at 6.4 eV for SrVH3. Due to effective interaction of incident among the studied materials, as tabulated in Table 3.

Please cite this article as: Siddique A et al., Structures and hydrogen storage properties of AeVH3 (Ae ¼ Be, Mg, Ca, Sr) perovskite hy-
drides by DFT calculations, International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2023.03.139
 international journal of hydrogen energy xxx (xxxx) xxx 9

Table 3 e The calculated values of elastic constants (Cij in GPa), bulk modulus (B in GPa), shear modulus (G in GPa), Young's
modulus (E in GPa), Poisson's ratio (n), G/B ratio, and B/G ratio for AeVH3 (Ae ¼ Be, Mg, Ca, Sr) compounds.
Compound C11 C12 C44 B G E n G/B B/G
BeVH3 297.06 78.53 14.10 151.38 86.53 102.41 0.31 0.24 1.73
MgVH3 142.32 54.52 51.82 83.79 53.49 121.94 0.25 0.56 1.71
CaVH3 91.96 28.32 44.49 77.12 48.89 131.14 0.22 0.69 1.46
SrVH3 128.53 40.08 49.92 69.56 47.56 116.21 0.21 0.68 1.43

Young's modulus (E) is the measure of ratio of uniaxial formulated through the averaged elastic wave velocity (vm). As
stress to uniaxial strain. It anticipates the stiffness and mea- proposed by Anderson, Debye temperature (qD) of LiAH3
sures the stress resistance of the materials. It was calculated (A ¼ Sc, Ti & V) are calculated by Vogit Reuss approximation
for all the studied materials and its value was largest for as:
CaVH3. The bonding strength of a material can be measured
  13 =
by determining its Poisson ratio (n). When a material is com- h 3n NA r
qD ¼ vm (9)
pressed or stretched, it measures the expansion or contrac- kB 4p M
tion of the material in perpendicular direction. When Here, kB is the Boltzmann's constant (1.381  1023 J/K), h is
Poisson's ratio is around 0.25, the ionic bonding is dominant in the Plank's constant (6.626  1034 Js), n is the number of
the materials. The studied compounds are predominantly atoms in the molecule, M is the molecular weight, NA is the
ionic. According to the charge density distributions of these Avogadro's number (6.022  1023), r is the density and vm is the
materials, this is a fair conclusion [47]. average sound velocity of the solid can also be described in
There are numerous approaches to analyse the type of terms of transverse and longitudinal wave velocities by using
bonding in a material including the G/B ratio (also known as the following formula:
Pugh's modulus). It was calculated for all the studied materials
  1=3
and its values can be found in Table 3. The prevailing bonding 1 1 1
vm ¼ þ 3 (10)
is ionic if the G/B ratio is roughly ~0.6, and covalent if it is ~1.1. 3 vl 3 vt
The materials having G/B ratio in the range 0.2e0.6, are
where, vl and vt are the longitudinal and transverse sound
dominated by ionic bonding. The B/G ratio (Pugh's ratio) can
velocities in solids which can be calculated by using G and B
also be employed to know whether the studied materials are
values as:
brittle or ductile. When B/G > 1.75 or n > 0.26, the material is
refereed to be ductile [11]. As deformation is not expected in sffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
3B þ 4G
brittle materials, yet it is feasible in ductile materials before vl ¼ (11)
r
fracture. However, the B/G ratio of the investigated materials
is less than 1.75, which suggests these to be brittle. sffiffiffiffi
Some physical features like phonon modes, anisotropic G
vt ¼ (12)
plastic deformation and fracture behaviour of the material r
could be influenced by crystal anisotropy. For instance, the
The results of understudy perovskite hydrides AeVH3
shear anisotropic factors and crystal orientation may affect
(Ae ¼ Be, Mg, Ca, Sr) is enlisted in Table 4. From the calcula-
the elastic anisotropy of the material. The anisotropy of atom-
tions, it is clear that the trend of Debye temperature is qD
to-atom bonding in different planes of motion can be found
(BeVH3) > qD (MgVH3) > qD (CaVH3) > qD (SrVH3), which in-
using the elastic-anisotropy ratio (A). When symmetry exists
dicates that their interatomic forces, elastic moduli and
in the crystal structure, the cubic crystal anisotropic indices
thermal conductivities are also consistent with that order.
are identical [11,48]. It is possible to calculate the elastic-
anisotropy ratio for AeVH3 (Ae ¼ Be, Mg, Ca, Sr) compounds
Hydrogen storage Properties
by comparing the three independent elastic constants of these
materials. The computed values for all compounds are given
Physisorption and chemisorption are the two types of solid-
in Table 3. The determination of an anisotropic component
state hydrogen storage mechanisms. The physisorption
may restore the elastic properties of perovskite hydrides. The
mechanism is based on weak dispersive interaction between
values of A are calculated as 1.13, 1.14, 1.12 and 1.13 for BeVH3,
hydrogen molecules and host materials whereas
MgVH3, CaVH3, and SrVH3, respectively. The material is
considered to be isotropic if its value of A is equal to 1. In this
scenario, all the studied compounds are referred to aniso-
tropic as their values of A are greater than 1. The relation Table 4 e Calculated longitudinal vl, transverse vt,
between the elastic constants and elastic-anisotropy ratio can averaged vm sound velocities (km/s) and Debye
be given as: temperature qD (K) for AeVH3 (Ae ¼ Be, Mg, Ca, Sr).
Compounds vl vt vm qD
2 C44
A¼ (8) BeVH3 7.891 4.786 4.786 665.3
ðC11  C12 Þ
MgVH3 7.342 4.532 4.412 644.4
Debye temperature is a parameter which is related to the CaVH3 7.213 4.032 4.006 542.2
natural frequency of the elastic lattice vibrations and SrVH3 6.452 3.876 3.731 495.7

Please cite this article as: Siddique A et al., Structures and hydrogen storage properties of AeVH3 (Ae ¼ Be, Mg, Ca, Sr) perovskite hy-
drides by DFT calculations, International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2023.03.139
10 international journal of hydrogen energy xxx (xxxx) xxx

chemisorption usually involves the chemical reaction be- the auspicious and fruitful choices of materials for future
tween hydrogen and condensed matters (mostly metals) hydrogen storage applications.
which results in the formation of a hydride phase. Recently,
novel fabricated perovskite-hydrides with a higher hydrogen
gravimetric density have received extensive attentions in Declaration of competing interest
addition to metal hydrides that have already been widely
studied. The authors declare that they have no known competing
To promote the hydrogen and fuel energy cell automation financial interests or personal relationships that could have
for their use in stationary power sources, portable power and appeared to influence the work reported in this paper.
transportation, hydrogen storage devices are a key accommo-
dating technology. The major hurdles in using the hydrogen as
a fuel includes lack of materials with suitable gravimetric
Acknowledgment
density. To overcome this hurdle, an interactive approach is
needed through which we can synthesize such material having
This research was supported by Princess Nourah bint Abdul-
sufficient storage capacity at higher densities. Molecular
rahman University Researchers Supporting Project number
hydrogen absorbing material gravimetric storage capacity (Cwt.
(PNURSP2023R327), Princess Nourah bint Abdulrahman Uni-
%) is typically calculated from the ratio of molar mass of stored
versity, Riyadh, Saudi Arabia. In addition, the authors extend
hydrogen and molar mass of host compound [45,48]:
their appreciation to the Research Centre for Advanced Mate-
  rials Science (RCAMS), King Khalid University, Saudi Arabia, for
nMH
Cwt: % ¼  100% (13) funding this work under grant number RCAMS/KKU/014-22.
nMH þ Mhost

In this equation, n is the hydrogen to host compound atomic

ratio (H/M), MH is the molar mass of hydrogen and Mhost is the
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drides by DFT calculations, International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2023.03.139
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Please cite this article as: Siddique A et al., Structures and hydrogen storage properties of AeVH3 (Ae ¼ Be, Mg, Ca, Sr) perovskite hy-
drides by DFT calculations, International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2023.03.139