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 1 ( 2 0 1 6 ) 3 5 0 8 e3 5 1 6

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Site preference and diffusion of hydrogen during

hydrogenation of Mg: A first-principles study

Jinghua Xin a, Jianchuan Wang a,*, Yong Du a, Lixian Sun b,

Baiyun Huang a
a
State Key Laboratory of Powder Metallurgy, Central South University, Changsha, Hunan 410083, China
b
Guangxi Key Laboratory of Information Materials, Guilin University of Electronic Technology, Guilin 541004, China

article info abstract

Article history: First-principles calculations are used to investigate the site preference and diffusion of
Received 6 February 2015 hydrogen in the initial stage of hydrogenation of Mg. The fcc-hollow site and the tetra-
Received in revised form hedral site are found to be the energetically favorable sites for hydrogen atom on and
6 December 2015 below Mg(0001) surface, respectively. When a hydrogen atom diffuses into the bulk Mg, it
Accepted 22 December 2015 has to firstly overcome an energy barrier of 0.45 eV. There exist two different diffusion
Available online 19 January 2016 pathways with this energy barrier, which start from two possible surface adsorption sites.
While a lower barrier of 0.31 eV is necessary for hydrogen further diffusion into the bulk
Keywords: region. The effect of the subsurface vacancy on hydrogenation is also investigated in terms
Mg(0001) surface of hydrogen trapping and diffusion barrier. At most six hydrogen atoms can be trapped by a
First-principles calculation single Mg vacancy in the subsurface. It is required at least 0.40 eV for the trapped hydrogen
Hydrogenation to escape from the vacancy. This trapping property and relatively large diffusion barrier to
Diffusion escape from the vacancy would prevent further diffusion of hydrogen into Mg during the
Trapping initial stage of hydrogenation. The vacancy, however, has little influence on the diffusion
property of its neighboring hydrogen atom.
Copyright 2015, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights
reserved.

Although MgH2 has a high gravimetric hydrogen capacity

Introduction
As one of light metals with high strength and good mechanical
properties, Mg is traditionally considered to have wide appli-
cations in manufacturing and aircraft industry. However, with
the awareness of clean energy, more and more researchers
are now focusing on its application as a hydrogen storage
medium [1,2]. Hydrogen can be stored and released in Mg
according to the reversible reaction:
Mg H2 MgH2 :
of 7.6 wt% [3], its practical application is limited primarily by
the high hydrogenation reaction temperature and slow ki-
netics. It is reported that the hydrogenation of Mg occurs only
at high temperatures of an order of 350e400  C under a
hydrogen pressure of more than 3 MPa [4]. To improve the
performance of Mg as a hydrogen storage material, it is highly
desirable to know more about its hydrogenation process.
Basically, the hydrogenation process of Mg can be divided into
four steps. The first step is the dissociation of hydrogen mol-
(1) ecules on Mg(0001) surface, which is proved to be the rate-

* Corresponding author. Tel.: 86 0731 88877300; fax: 86 0731 88710855.

E-mail address: jcw728@126.com (J. Wang).
http://dx.doi.org/10.1016/j.ijhydene.2015.12.157
0360-3199/Copyright 2015, 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 1 ( 2 0 1 6 ) 3 5 0 8 e3 5 1 6
controlling step for the hydrogenation of Mg [5]; the second is
the diffusion of hydrogen atom from surface into interstitial
sites to form H layers between adjacent Mg layers, which is
the essential step of hydride formation; the third is the
formation of a-phase at low hydrogen concentration; and the
last step is the nucleation of b-phase and the transformation
from a- to b-phase with the increasing of hydrogen concen-
tration [6].
In order to improve the hydrogenation process of Mg,
extensive investigations are carried out against the above four
steps. Most of the studies are focused on decreasing the
dissociation energy of hydrogen molecules [7e13]. One effec-
tive way is to add metal catalysts, such as Ti, Ni and Fe, to the
surface of Mg [7e10]. For example, the dissociation barrier of
molecule H2 is as high as ~1.0 eV on the pure Mg(0001) surface,
while it can be neglected with Ti and Ni added on the surface
[8]. Another well-known method is to produce vacancies on
the surface to activate Mg [11,12], which has been reported to
lower the dissociation energy by 0.12 eV [11]. Recent work by
Lei et al. [13] provides a third way to reduce the dissociation
energy by enforcing a tensile strain. They investigated biaxi-
ally strained Mg(0001) surface and found that the dissociation
energy of molecule H2 decreases linearly in the tensile strain
region. As for the second step of hydrogenation, i.e., the
diffusion of dissociated hydrogen atom into the bulk Mg,
experimental data on individual atomic diffusion processes is
scarce due to the complexity involved in isolating the indi-
vidual events. Thus theoretical calculations have drawn at-
tentions. Vegge [5] investigated the dissociation of molecule
H2 on Mg(0001) surface and the subsequent diffusion of
hydrogen atom into the bulk region using density functional
theory (DFT) [14,15]. He proved the diffusion barrier from the
on-surface fcc-hollow site to the subsurface fcc-like site to be
high as 0.53 eV, but the barrier is reduced to 0.18 eV when
hydrogen atom going further to the oct site of bulk Mg. Li et al.
[16] also studied the diffusion of hydrogen from the on-surface
fcc-hollow site into the octahedral site, while they reported
the diffusion barrier to be 0.45 eV. Studies on the third and
fourth steps of hydride formation are also productive. Jiang
et al. [17] examined the formation of HeMgeH trilayer, which
is the precursor of MgH2. Tao et al. [18] evaluated the hydrogen
diffusion property in three different MgH2 structures, which
gives a clue on altering the hydrogen kinetics by controlling
the structure of the hydride. Later on, the effects of biaxial
strain and hydrogen chemical potential on the structural
stabilities of the MgeH system is studied by Tang et al. [19]. It
is proved that the compressive strains facilitate the formation
of the HeMgeH trilayers and MgH2 is more energetically
favored under tensile strains.
As have mentioned above, the second step (hydrogen
diffusion) is essential and of vital importance during the initial
stage of hydrogenation. However, the above mentioned cal-
culations of hydrogen diffusion from surface to the bulk Mg
[5,16] are limited to the channel mechanism (from the on-
surface fcc-hollow site straightly down to oct sites in bulk
Mg). Since there is no geometric obstacle along the channel, it
is natural to expect that the adsorbed hydrogen on the surface
diffuse into bulk via the channel mechanism. Nevertheless,
little attention is paid on initial and final states of diffusion
based on investigation of site preference. As reported later in
3509
the present work, the real diffusion route between layers is
not a straight channel; furthermore, there exist two penetra-
tion paths with the same energy barrier. Therefore it is a
worth topic to exam the diffusion behavior of hydrogen under
the consideration of site preference, in order to deeply un-
derstand the hydrogenation of Mg. Vacancies can not only
reduce the dissociation energy of hydrogen molecule as
mentioned above, but also improve the kinetics of hydroge-
nation [20,21]. It is clear that surface vacancies can affect the
interaction and bonding of surface atoms with the adsorbate
by changing the electronic structure and atomic surrounding,
but the role of subsurface vacancy in the hydrogenation of Mg
has not yet been considered to our knowledge. The subsurface
vacancy is chosen as a target due to its different character
compared with the surface vacancies: transition metals
located in the vacancy of subsurface Mg are more stable than
that in the first Mg layer [22,23]. Moreover, vast investigations
on the strong interaction between vacancy in metal and
hydrogen are carried out [24e26]. For example, vacancy in
bulk Mg is reported to have the capacity to trap as many as
nine hydrogen atoms by Ismer et al. [25], which implies the
possibility of trapping behavior during hydrogenation.
Therefore, further investigation on the effect of the subsur-
face vacancy on the hydrogenation of Mg including the
hydrogen trapping property is necessary.
In this paper, hydrogenation properties of Mg are investi-
gated via first-principles calculations based on DFT calcula-
tion. Site preference and possible hydrogen diffusion routes
from surface to the bulk region are investigated, and the most
likely diffusion route as well as according barrier is provided.
Meanwhile, the present work also focuses on hydrogen trap-
ping property by the vacancy in subsurface Mg and its effect
on hydrogen diffusion behavior.
Methodology
Computational details
In this work, DFT calculations are performed by means of
Vienna ab initio simulation package (VASP) [27,28]. The
generalized gradient approximation (GGA) [29] calculation is a
quantitatively accurate predictor of hydride formation en-
ergies, diffusion, binding energy and basic physical property
of Mg according to previous studies [30,31]. Therefore GGA
with Perdew, Burke and Ernzerh (PBE) [32] functional is
adopted to describe the electron exchangeecorrelation inter-
action. Electron wave functions are expanded in plane waves
with a kinetic energy cutoff of 350 eV. The Mg(0001) surface is
modeled using a (4  4) surface unit cells with six atomic
layers and a vacuum distance of 12 . The thickness of vac-
uum is tested until the work function is converged to 3.71 eV,
which is in line with 3.66 eV from experimental data [33] and
3.72 eV from theoretical result [17]. Hydrogen and Mg atoms in
the top three layers are fully relaxed until the forces on the
atoms are less than 0.01 eV/
A. However, atoms in the lower
three layers are fixed in the theoretical bulk position to
represent the semi-infinite bulk crystal beneath the surface. A
4  4  1 Monkhorst and Pack k-point [34] is adopted for the
integration of Brillouin zone. Convergence tests indicate that
3510 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 1 ( 2 0 1 6 ) 3 5 0 8 e3 5 1 6
the cutoff energy and k-point sampling are sufficient to limit
the energy uncertainty to 1 meV/atom. The minimum energy
path (MEP) and the corresponding diffusion barrier are
determined by the nudged elastic band (NEB) [35] method. The
path is represented by a discrete set of images, i.e., configu-
rations of all the atoms in the system, between the initial and
final states. At least nine-image calculations are performed to
get the minimum energy pathway and migration barrier for all
designed diffusion routes. The spring constant of 5.0 eV/
A2 is
used for all the calculations, and the total force convergence
criteria for all the atoms of images is set to 0.03 eV/

A.
Judgment of site preference of hydrogen
There are four high symmetry sites for hydrogen atom on
Mg(0001) surface to be adsorbed, as pictured in Fig. 1(a). The hcp-
and fcc-hollow sites are both on the top of the center of three
adjacent Mg atoms, while the former site is right on the top of a
subsurface Mg atom. As mentioned above, there is a channel
direct bellow the fcc-hollow site. The bridge site is located in the
middle of the line connecting two adjacent Mg atoms, and the
on-top site is right on the top of a Mg atom on the surface. Site
preference of hydrogen atom on Mg(0001) surface is confirmed
by adsorption energy, which is defined by equation

stitial hydrogen is determined by the formation energy Eint
Ead EH=Mg0001  EMg0001 1=2  EH2 ;
where EH=Mg0001 , EMg0001 and EH2 stand for the total energy of
adsorbed Mg(0001) surface, pure Mg(0001) surface and isolate
molecule H2, respectively. According to this definition, a
negative value of Ead indicates that the adsorption is
Fig. 1 e High symmetry sites on and below Mg(0001)
surface. (a) Different adsorption sites for hydrogen atom on
Mg(0001) surface; (b) Three different interstitial sites (tet-1,
tet-2, and oct) under the top layer of Mg(0001) surface. Large
red balls are Mg, while small green balls are high
symmetry sites for hydrogen to occupy.
exothermic, while a positive one is endothermic and hence
unstable.
It is also necessary to find out the stable high symmetry site
near surface for the accommodated hydrogen atom in order to
study the hydrogenation of Mg. As for hydrogen atom being
placed in interstitial site near Mg(0001) surface, there are three
inequivalent high symmetry sites, as illustrated in Fig. 1(b).
Due to surface effect, two types of tetrahedral (denoted as tet)
sites between the top two layers are considered. The first type
is located in the tetrahedron formed by one Mg atom from the
upper layer and three Mg atoms from the lower layer, which
will be denoted as the tetrahedral site-1 (tet-1) in this work.
The tet-1 site is directly below the surface Mg atoms. The
second type consists of three Mg atoms from the upper layer
and one Mg atom from the lower layer. It is right below the on-
surface hcp-hollow site, denoted as the tetrahedral site-2 (tet-
2). These two tetrahedral sites would become equivalent if
they are located below the second Mg layer, thus will be
denoted as the deeper and the shallow tet sites in that case.
The third type is the octahedral site (oct), which has six
nearest-neighbor Mg atoms formed by both three Mg atoms in
the upper and lower layers. Previous DFT calculations are
done to investigate hydrogen diffusion from the on-surface
fcc-hollow site to this oct site [16]. Site preference for inter-
f
(2) defined similar to equation (2), only for that EH=Mg0001 in this
situation represents the corresponding surface containing
interstitial hydrogen.
Hydrogen trapping by subsurface Mg vacancy
Vacancy in the subsurface of Mg is constructed by taking one
Mg atom away from the second layer of the slab model.
Interaction between this vacancy and hydrogen atom is dis-
cussed in term of trapping property. The trapping energy is
related to the energy gained by the system when n interstitial
hydrogen atoms are added to the vacancy, which is defined by
Etrap n 1=nfEV nH  EV nmHTd g; (3)
where EV nH, EV represent the total energy of defective
surface with and without trapping n hydrogen atoms,
respectively. mHTd stands for the chemical potential of
hydrogen atom in the tet site, which is given by:
mHTd m0 Ef Td; (4)
where m0 stands for chemical potential of free hydrogen,
which is equal to half of the total energy of molecule H2 at 0 K.
Ef Td represents the formation energy of isolated hydrogen
placed in the tet-1 site, as found later in the present work that
interstitial hydrogen is energetically more favorable in the tet-
1 site. According to this definition, a negative trapping energy
implies that the vacancy have the ability to trap n hydrogen
atoms, while a positive one reveals disability.
Results and discussions
In order to verify the accuracy and validity of our surface
model and calculation method, the bulk properties of Mg are
calculated firstly. For bulk hcp Mg, the calculated lattice
 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 1 ( 2 0 1 6 ) 3 5 0 8 e3 5 1 6
parameters are a 3.19
A and c/a 1.62, which agree well
with theoretical result (a 3.21 and c/a 1.62) [17] as well as
experimental data (a 3.21
A, c/a 1.624) [36]. Cohesive en-
ergy of the bulk Mg is calculated to be 1.50 eV, which
matches very well with experimental measurement of
1.51 eV [36]. For isolated molecule H2 in a cubic cell of 15
A between the first and second Mg layers is favorable for
with single k point, the calculated binding energy, bond length
and vibrational frequency are 4.52 eV, 0.75
A and 4446 cm1
(corresponding to a zero point energy of 0.276 eV), respec-
tively. These data agree well with previous calculations [5,17],
which indicate that the present set of parameters and model
can provide reliable description for the MgeH system.
Site preference
Before investigating the hydrogenation of Mg, the first step is
to find the most stable site near surface to accommodate
hydrogen atom. Hydrogen adsorption energies at the four
surface adsorption sites on pure Mg(0001) surface, i.e., the
bridge site, on-top site, fcc- and hcp-hollow sites are calcu-
lated. Our calculated result shows that the fcc-hollow site is
the most favorable adsorption site among the four locations.
The adsorption energy of hydrogen at the fcc-hollow site is
0.05 eV, which is only 0.02 eV lower than that of the hcp-
hollow site. This finding is consistent with previous theoret-
ical results [5,37]. However, the adsorbing of hydrogen atom at
the other two sites is predicted to be endothermic with respect
to gaseous molecule H2 and a pure Mg surface. The calculated
hydrogen adsorption energies at the bridge and on-top sites
are 0.13 and 0.74 eV, respectively, which match well with the
work from Lei et al. [13]. This implies that the dissociated
hydrogen atom will not be adsorbed at the two sites. However,
it can either be adsorbed at the fcc- or hcp-hollow site due to
the tiny difference in the adsorption energy. Therefore, two
possible start positions (fcc- and hcp-hollow sites) should be
considered for hydrogen diffusion from Mg(0001) surface into
the bulk region in the following investigation.
Formation energies of interstitial hydrogen at high sym-
metry sites between the top three Mg layers in pure and
defective systems are listed in Table 1, where dash lines imply
that hydrogen atoms primarily located in those sites are un-
stable. Formation energy of hydrogen in the tet-1 site between
the first and second Mg layers of pure system is predict to be
0.05 eV, which is 0.22 eV lower than in the oct site. Hydrogen
atom in the tet-2 site is unstable, since it is pushed up to the
on-surface hcp-hollow site after relaxation. Hence the tet-2
site might be a saddle point of the potential energy surface of
the system. When hydrogen atom is located between the
Table 1 e Formation energies (in eV) of hydrogen
interstitial at high symmetry sites between the top three
Mg layers in pure and defective systems. Dash lines
imply that hydrogen atoms primarily located in those
sites are unstable.
Pure surface Defective surface
Layer 1&2 Layer 2&3 Layer 1&2 Layer 2&3
tet site tet-1 0.05 0.13 tet-1 0.07 0.15
tet-2 e tet-2 e between the first and second layers. All the values are
oct site 0.27 0.25 e e
3511
second and third Mg layers, the tet site is still superior to the
oct site by 0.12 eV. For investigating site preference in the
defective Mg(0001) surface, the adjacent high symmetry sites
of the vacancy are chosen as the accommodation sites for
hydrogen atom. Like the case of pure system, the tet-1 site
hydrogen atom to occupy, while neither the tet-2 nor the oct
site is the stable site. Hydrogen atom in the tet-2 site near the
Mg vacancy is still found to move up to the on-surface hcp-
hollow site spontaneously, indicating that there is no local
minimum in the vicinity of the tet-2 site. When it comes below
the second Mg layer, the tet site is the only stable site for
hydrogen atom to occupy.
Two characteristics could be drawn by evaluating the
calculated results in Table 1. Firstly, the tet site is always
proved to be the most energetically favorable site for hydrogen
atom to occupy. Generally speaking, a neutral interstitial atom
should occupy the site with bigger space in order to minimize
the repulsion forces from the nearby lattice atoms. The space
of oct site in the hcp lattice is obviously larger than that of tet
site. Thus one would speculate that hydrogen atom might
occupy the oct site, but the present result is in contrast with
this intuitive expectation. In order to clarify this abnormal
phenomenon, the electron density of both the tet-1 and oct
sites between the first and second Mg layers is calculated. A
1013 plane which crosses the above two positions is sliced in
the pure system to display charge density. As indicated in
Fig. 2, charge density at the tet-1 site (in red) is larger than that
at the oct site (in green). It is obvious that hydrogen atom
prefers to occupy the site where charge density is larger. A
possible reason for this is that hydrogen atom in Mg looks like
a proton with positive charge, hence the electron-proton
attractive interaction decreases the energy of the system.
Secondly, the oct site in the defective system is no longer
stable between the top three Mg layers. Nevertheless, the
existence of subsurface vacancy does not change the site
preference for hydrogen between adjacent layers.
Fig. 2 e Electron charge density contours for pure Mg1013
surface. Red colored area indicates larger electron density,
while blue colored area indicates smaller electron density.
The arrows indicate the positions of the oct and tet-1 sites

3.
shown in e/A
3512 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 1 ( 2 0 1 6 ) 3 5 0 8 e3 5 1 6
Diffusion of hydrogen in the bare system
Based on the above investigated site preference, diffusion of
hydrogen should obey the following rules. Firstly, hydrogen
adsorbed at fcc- or hcp-hollow site should be considered as
possible initial state of diffusion due to the comparable
adsorption energies. Secondly, hydrogen locating in tetrahe-
dral sites should always be considered as final states of indi-
vidual hydrogen diffusion due to its energetically favorable
property. This is different from the channel mechanism [5,16],
in which the oct sites at the bottom of channel are considered
as final state. Choosing the tetrahedral sites as the final
diffusion configuration is obviously more reasonable, because
hydrogen will spontaneously occupy interstitial site with a
lower formation energy. Four different diffusion routes, which
are illustrated in Fig. 3, for hydrogen atom crossing the first
layer of Mg are chosen in order to find out the energetic
favorable migration pathway for injecting hydrogen in Mg
matrix.
Fig. 4 shows the optimized MEP for hydrogen diffusion
from surface to the tet-1 site. For dissociated hydrogen atom
initially adsorbed at the fcc-hollow site on Mg(0001) surface,
the most probably pathway might be route 1: fcc-
hollow / oct / tet-1, since little lattice distortion occurs for
hydrogen going straight into the oct site. Note that the initial
step of this diffusion route (fcc-hollow / oct) is just the same
as the channel diffusion in previous literatures. As shown in
route 1, it gives an energy barrier of 0.45 eV, which is the same
as that reported by Li et al. [16]. By checking in detail the
structures of the NEB images, the transition state of route 1
emerges when hydrogen is going through the center of the
first layer. Therefore the energy barrier is mainly attributed to
hydrogen breaking MgeMg bonds in the basal plane. Actually,
an extra NEB calculation in which the hydrogen atom diffuses
directly from the fcc-hollow into tet-1 site is also conducted in
the present work, but it converges to the same MEP as route 1.
As mentioned above, hydrogen atom may also permeate
bulk from the on-surface hcp-hollow site. For hydrogen atom
initially adsorbed at the hcp-hollow site, we designed three
potential diffusion paths: route 2, hcp-hollow / tet-2 / tet-1;
route 3, hcp-hollow / tet-2 / oct / tet-1; route 4, hcp-
hollow / oct / tet-1. Though the tet-2 site is unstable as
mentioned above, it is still included in routes 2 and 3 because
Fig. 3 e Side view of possible diffusion routes for hydrogen
atom migrating from Mg(0001) surface into the tet-1 site. 1
fcc-hollow / oct / tet-1; 2 hcp-hollow / tet-2 / tet-1; 3
hcp-hollow / tet-2 / oct / tet-1; 4 hcp-
hollow / oct / tet-1.
Route 1
Route 2
Route 3
Route 4
Fig. 4 e Diffusion routes and barriers of hydrogen atom
from Mg(0001) surface into the tet-1 site.
this site is straight below the hcp-hollow site. As shown in
Fig. 3, the only difference between route 3 and 4 is whether
hydrogen diffuses through the tet-2 site before going through
the oct site or not. It is obvious from Fig. 4 that route 2, which
corresponds to the diffusion of hydrogen atom from the hcp-
hollow site to the tet-1 site via the tet-2 site, gives the highest
diffusion barrier of ~0.6 eV among all the three possible
routes. However, routes 3 and 4 seem to reveal the same
diffusion barrier of ~0.45 eV, even though an unstable site (tet-
2) is related in route 3. Actually, the two paths converged to
the same MEP and provide the same transition state after a
more deep analysis on atomic configuration in every image.
This reveals that hydrogen adsorbed at the hcp-hollow site
will always migrate into the tet-2 site before further diffusion.
The hydrogen diffusion barrier from the oct site to the tet-1 site
is rather small (0.03 eV). It is also found from the diffusion
profile in Fig. 4 that the tet-2 site is not an energy local mini-
mum for hydrogen atom.
Concerning the two possible initial states for hydrogen
diffusion, an energy barrier of ~0.45 eV is needed for adsorbed
hydrogen to go through the first Mg layer, regardless of
migrating from the fcc- or hcp-hollow site. Hence adsorbed
hydrogen at fcc- or hcp-hollow site has an equal opportunity
to go through the surface at the initial state of hydrogenation.
Moreover, the calculated on-surface diffusion (from the fcc- to
hcp-hollow site) provides a relatively small barrier of 0.17 eV.
The value is in consistent with 0.14 eV reported by Vegge [5],
which is smaller than that of any designed diffusion route
mentioned above. This implies that if one of the two diffusion
routes is blocked by some reason, hydrogen can still migrate
alternatively through the other route by firstly carrying out a
surface migration.
For hydrogen atom further going into interior of Mg,
namely, hydrogen diffusion from the tet-1 site to the deeper tet
site between the second and third Mg layers, two migration
paths are considered, as shown in Fig. 5. If the hydrogen atom
in the tet-1 site migrates to the deeper tet site via its nearest-
neighbor tet site (the shallower one), route 1 provides an en-
ergy of 0.45 eV. Another possibility shown in route 2 is that
interstitial hydrogen will migrate to the final state via the oct
 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 1 ( 2 0 1 6 ) 3 5 0 8 e3 5 1 6
site. It is obvious that hydrogen atom tends to go through this
oct site, as it provides a lower energy barrier of 0.31 eV. The
value is smaller than that of hydrogen diffusion from surface
into the tet-1 site. It implies that diffusion under surface is
easier than one guest hydrogen atom going through the sur-
face. Moreover, it is observed that the diffusion barrier is
decreased gradually along with hydrogen penetrating into Mg.
The calculated hydrogen diffusion barrier in bulk Mg is
0.22 eV, which in accord with other DFT calculation (0.22 eV)
[25] and experimental value of 0.24 eV [38].
Hydrogen trapping property of subsurface Mg vacancy
Vacancy may have impact on the hydrogenation of Mg in
terms of two aspects: trapping hydrogen and affecting
hydrogen diffusion. In order to investigate hydrogen trapping
property by the vacancy, all the possible trapping sites in the
vacancy region are firstly analyzed. The center of subsurface
vacancy is considered to be the most possible site for
hydrogen atom to occupy due to its large space. Another
assumed trapping site should be the high symmetry sites
next to the vacant Mg lattice. Two kinds of sites inside the
vacancy denoted as the vac-tet and vac-oct sites are
considered, corresponding to the original tet and oct sites, as
illustrated in the insert graph of the right panel of Fig. 6.
There exist eight vac-tet and six vac-oct sites in the vacancy
region. According to our definition of the trapping energy,
hydrogen atom is added to these sites one by one until the
trapping energy turns to positive or the vacancyeH complex
becomes unstable.
All the above mentioned trapping sites have been searched
for hydrogen atoms and the corresponding trapping energies
are compared. The trapping energies and the corresponding
configurations by subsurface vacancy versus the number of
trapped hydrogen atoms are illustrated in Fig. 6. As shown in
Fig. 6, the first trapped hydrogen atom cannot stay in the
center of the vacancy; in contrast, it tends to stay in the vac-tet
site upon the second Mg layer with a trapping energy of
0.11 eV. Hence trapping one hydrogen atom in an initially
empty vacancy is an exothermic process. The trapping energy
tet (the shallower) tet (the deeper)
tet-1
Fig. 5 e Diffusion routes and barriers of hydrogen atom
from the tet-1 site to the deeper tet site between the second
and third layers of Mg(0001) surface.
3513
is still negative (0.13 eV and 0.14 eV) when the following
two hydrogen atoms are added into the vacancy. Those two
hydrogen atoms stay in the other two vac-tet sites upon the
second Mg layer, instead of being stored in molecular form or
in the center of vacancy. The fourth hydrogen atom also
prefers to stay in vac-tet site with a trapping energy of
0.11 eV, but it occupies the vac-tet site right above the third
Mg layer. After this, the fifth hydrogen being trapped into vac-
tet sites become unfavorable: three of the unoccupied vac-tet
sites are very close to the occupied vac-tet sites, thus become
less favorable due to the repulsive force between hydrogen
atoms; the last vac-tet site is right below surface, which is
unfavorable for trapping hydrogen due to surface effect.
When the 5th and 6th hydrogen atoms are added to subsur-
face vacancy, they occupy two of the vac-oct sites between the
second and third Mg layers with a trapping energy of 0.07 eV
and 0.05 eV, respectively. If we add the 7th hydrogen to va-
cancy region, the vacancyeH complex becomes unstable, as
we find one of the seven H atoms escapes from the vacancy
region. Therefore, at most six hydrogen atoms can be trapped
by one Mg vacancy in the subsurface.
The effect of this hydrogen trapping by subsurface vacancy
can be analyzed from two aspects. On one hand, this trapping
property will drag hydrogen atoms into vacancy before
hydrogen diffusion and formation of H layers upon Mg layers,
which is disadvantageous to the initial stage of hydrogenation
process. On the other hand, trapping hydrogen into the va-
cancy may also enhance the process of hydride formation, by
reducing the block effect of HeMgeH trilayer. This blocking
phenomenon is observed from experiments, in which the
hydrogenation reaction is stopped abruptly at a critical
thickness [39,40]. This is due to the very slow diffusion prop-
erty in HeMgeH trilayer, so that the dissociated H atom on the
surface is prevented by this trilayer from further migrating
into Mg. However, hydrogen in the trilayer can be dragged into
the subsurface vacancy according to the present study and
results in a looser structure of the HeMgeH trilayer, which
may accelerate the mobility of hydrogen going through the
trilayer and thus enhance hydride formation. But the verifi-
cation of such assumption is beyond our investigation of
initial stage of hydrogenation.
Comparing hydrogen trapping property by subsurface Mg
vacancy with that by bulk Mg vacancy from Ismer et al. [25], a
similar trend is found in Fig. 6. Trapped hydrogen atoms do
not locate in the substitutional lattice site, but they prefer to
occupy certain sites such as the vac-tet and vac-oct sites. To
explain the preference of trapping site (take the first three
trapped hydrogen atoms as an example, they prefer the vac-
tet sites), the charge density contours for surfaces in both pure
and defective systems are shown in Fig. 7(a) and (b), respec-
tively. The two plots are all centered on the position of the
vacancy, i.e., the second Mg layer of the slab model, and is
observed parallel to Mg(0001) surface. Charge density in the
center of the vacancy is calculated to be near to zero, and
remarkable electron accumulation is observed around the
vacancy, at the bridge site, formed a shell. This is the same as
reported by Carling et al. [41]. Comparing Fig. 7(a) and (b), it is
found that the charge density of some areas among triangle
positions (illustrated by dashed boxes) increases, while that of
others around the vacancy decreases. It is very interesting
3514 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 1 ( 2 0 1 6 ) 3 5 0 8 e3 5 1 6

Fig. 6 e Hydrogen trapping energies and corresponding configurations by subsurface Mg vacancy versus the number of
trapped hydrogen atoms, compared with hydrogen trapping energies by vacancy in bulk Mg from Ismer et al. [25]. The
insert graph in the right panel shows the possible trapping positions in the vacancy region. The vac-tet and vac-oct sites (see
text) are denoted by small gray and green balls, respectively.

that these sites in dashed boxes happen to be the first three
trapping site for hydrogen atoms. It is again proved that
hydrogen atom tends to be trapped in the location with larger
charge density. This is in consistent with the conclusion from
the site preference of interstitial hydrogen in Sec. Site
preference.
The effect of subsurface Mg vacancy on diffusion of
hydrogen
Vacancy can not only trap hydrogen atoms, but also affect the
kinetic behavior of hydrogen atom in the vicinity of the va-
cancy. Two different circumstances are considered in the
present work to evaluate the effect of vacancy in subsurface
on hydrogen diffusion. On one hand, vacancy in subsurface
can trap hydrogen atoms, thus diffusion routes and barriers of
the first trapped hydrogen atom migrating down to the tet site
below the third Mg layer are investigated. On the other hand,
the diffusion property of hydrogen atom in the vicinity of (but
not trapped by) the vacancy is investigated.
Due to the existence of the subsurface vacancy, hydrogen
atom may diffuse via the hcp-like site on the third Mg layer,
which is denoted as route 1. Another possible route should be
the above mentioned channel mechanism via the vac-oct site,
denoted as route 2. The two diffusion routes and corre-
sponding barriers are calculated and shown in Fig. 8. As can be
seen from Fig. 8, route 1 requires a relatively large energy
barrier of 0.53 eV for hydrogen migrating to the hcp-like site.
However, there is almost no energy barrier for the hydrogen
atom at the hcp-like site to further move to the shallower tet
site, according to Fig. 8. If hydrogen atom goes along route 2,
two energy barriers of 0.40 eV and 0.19 eV have to be gone over
to reach the final state. The diffusion barrier along route 2
(0.40 eV) is relative large, and comparable to that for the
adsorbed hydrogen to penetrate the top layer of Mg(0001)
surface (0.45 eV). Such trapping property is therefore disad-
vantageous to hydrogen diffusion into Mg, which is essential
to the formation of HeMgeH trilayer during the initial stage of
hydrogenation.
For hydrogen diffusion near the vacancy in the subsurface,
the diffusion routes and barriers for hydrogen atom
migrating from the tet-1 site to the deeper tet site below the
second Mg layer are considered. Same as the pure system,
two possible diffusion routes are considered, as shown in
Fig. 9. It is clear that hydrogen atom in the vicinity of the
vacancy tends to diffuse via the oct site along route 2, with an
energy barrier of 0.31 eV. The value is the same as that of the
same step in the pure system. The other considered pathway
(migration via the shallow tet site in route 1) gives a higher
energy barrier of 0.43 eV. It seems that the vacancy in the
subsurface have little effect on diffusion barrier of its neigh-
boring hydrogen atom.
Conclusions
In summary, density functional theory calculations in com-
bination with NEB method are utilized to study the site
 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 1 ( 2 0 1 6 ) 3 5 0 8 e3 5 1 6
Fig. 7 e Electron charge density contours for (a) pure
Mg(0001) surface and (b) defective Mg(0001) surface. Red
colored area indicates larger density, while blue colored
area indicates smaller electron density. Dashed boxes
indicate the region of the vac-tet sites between the first and
second layers of Mg(0001) surface. The contour value is
shown in e/A
3.
vac-oct
tet (the shallower)
Fig. 8 e Diffusion routes and barriers of hydrogen atom
from the first trapped site to the tet site below the third
layer of Mg(0001) surface.
3515
tet-1 tet (the shallower) tet (the deeper)
Fig. 9 e Diffusion routes and barriers for the hydrogen
atom adjacent to the subsurface Mg vacancy from the tet-1
site to the deeper tet site between the second and third
layers of Mg(0001) surface.
preference and diffusion behavior of hydrogen atom from
Mg(0001) surface into bulk. The fcc-hollow site is calculated to
be energetically favorable on the surface, while the tetrahe-
dral site is always the most stable interstitial site between Mg
layers. From the energetic point of view, there are two equal
diffusion pathways for hydrogen atom to go through surface.
Both the two favorable pathways provide a diffusion barrier of
0.45 eV, and these two equal-opportunity routes for hydrogen
penetration are found for the first time. As for hydrogen atom
further migrating into the deeper tet site below the second Mg
layer, it prefers to diffuse via the oct site with an energy barrier
of 0.31 eV. Furthermore, the effect of subsurface vacancy on
the hydrogenation of Mg is studied in terms of hydrogen
trapping and diffusion behavior. At most six hydrogen atoms
are found to be trapped by the subsurface vacancy. An energy
barrier of 0.40 eV is required for the trapped hydrogen atom to
escape from the vacancy. This trapping property and rela-
tively large escape barrier will prevent hydrogen diffusion into
Mg during the initial step of hydrogenation. However, such
kind of vacancy has weak influence on diffusion route and
barrier of neighboring hydrogen atom.
Acknowledgments
This research was supported by the National Natural Science
Foundation of China (Grant No. 11404409), and was jointly
sponsored by Guangxi Key Laboratory of Information Mate-
rials (Guilin University of Electronic Technology), P.R. China
(Project No. 131003-K) as well as Guangxi Collaborative Inno-
vation Center of Structure and Property for New Energy and
Materials. The research was also supported as part of the
Hunan Provincial Natural Science Foundation (12JJ5018) and
the outstanding graduate project of Advanced Non-ferrous
Metal Structural Materials and Manufacturing Collaborative
Innovation Center. We also gratefully acknowledge the sup-
port by the High Performance Computing Center of Central
South University.
3516 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 1 ( 2 0 1 6 ) 3 5 0 8 e3 5 1 6

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