Atomistic modeling of the AlH and NiH systems

Won-Seok Ko
Department of Materials Science and Engineering, Pohang University of Science and Technology (POSTECH),
Pohang 790-784, Republic of Korea

Jae-Hyeok Shim
Materials/Devices Division, Korea Institute of Science and Technology, Seoul 136-791, Republic of Korea

Byeong-Joo Leea)
Department of Materials Science and Engineering, Pohang University of Science and Technology (POSTECH),
Pohang 790-784, Republic of Korea; and Division of Advanced Nuclear Engineering, Pohang University of Science
and Technology (POSTECH), Pohang 790-784, Republic of Korea
(Received 6 December 2010; accepted 17 March 2011)

Second nearest-neighbor modied embedded-atom method (MEAM) interatomic potentials for the
AlH and NiH binary systems have been developed on the basis of previously developed MEAM
potentials of pure Al, Ni, and H. The potentials can describe various fundamental physical properties
of the relevant binary alloys (structural, thermodynamic, defect, and dynamic properties of
metastable hydrides or hydrogen in face-centered cubic solid solutions) in good agreement with
experiments or rst-principles calculations. The applicability of the present potentials to atomic level
investigations of dynamic behavior of hydrogen atoms in metal membranes is also discussed.

I. INTRODUCTION

Hydrogen has been known to form micropores in aluminum alloys and cause the formation of microcracks,
which signicantly reduces mechanical properties of
alloys.16 An atomic scale analysis of the local diffusion
of hydrogen in the liquid and solid aluminum is necessary
for a prediction and control of the pore formation behavior.
Many metallic alloys including the nickel alloys suffer from
hydrogen embrittlement in the usage as structural materials, 710 but the exact mechanism of hydrogen embrittlement
in nickel alloys has not yet been discovered. It is expected
that atomistic simulations can be a good approach to clarify
the mechanism of hydrogen embrittlement.11,12
Use of hydrogen as an energy source is the most efcient
way, and improving methods of hydrogen manufacturing,
separation and purication of pure hydrogen has grown in
recent years.13 Although H2 gases are manufactured by
various processes, membrane separation method has received a great attention owing to its ultimate cost effectiveness and ease of operation.14 Among many possible choices
of materials, metallic membranes are of interest for its high
hydrogen selectivity and cost effectiveness.15,16 Even
though palladium and its alloys are most appropriate for
membrane use, the extremely high cost is dragging down its
practical applications, and recent researches have been
focused on the development of non-palladiumbased membranes using economically feasible metals.17 As a possible
a)

Address all correspondence to this author.

e-mail: calphad@postech.ac.kr
DOI: 10.1557/jmr.2011.95
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alternative, vanadium is a promising candidate because of

not only its relatively low cost but also its higher permeability than palladium.18 In spite of these advantages, the
membranes based on vanadium usually suffer from severe
hydrogen embrittlement. One approach to solve this problem is to add the above-mentioned elements, Al or Ni, in
hopes of preventing the formation of brittle hydrides by
decreasing the solubility of hydrogen.1924 However, the
effects of Al or Ni addition on the diffusivity (or permeability) of hydrogen and the mechanical properties of bodycentered cubic (bcc) solid solutions are not clearly known
and hard to analyze quantitatively because it is still impossible to experimentally observe the atomistic behavior of
hydrogen atoms in metallic alloys. On the other hand,
atomic scale simulation/calculation techniques can be an
effective alternative.
First-principles calculations provide the most accurate
results in the atomic scale. However, this method is not
appropriate to investigate large-scale materials behavior
because of its size (or number of atoms) limit. As another
alternative, one can consider molecular dynamics (MD)
simulations that can handle more than a million atoms
using (semi)empirical interatomic potentials. In this case,
accurate descriptions of various fundamental physical
properties (structural properties, elastic properties, defect
properties, thermal properties, etc.) by interatomic potentials are important. Among various semiempirical interatomic potentials, the embedded-atom method (EAM)
proposed by Daw and coworkers25,26 has been widely
used for metallic alloys. To the knowledge of the present
authors, an EAM potential was developed by Ruda et al.27
for the AlH binary system and by Daw and Baskes,25

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W-S. Ko et al.: Atomistic modeling of the AlH and NiH systems

Ruda et al.,27 and Angelo et al.28 for the NiH binary

system. These EAM potentials can describe some physical
properties of the face-centered cubic (fcc) structure well but
have a limitation in dealing with other crystal-structured
metals such as bcc vanadium and cannot be extended to
multicomponent systems including those elements.
For simulations of multicomponent systems composed
of elements with different structures, one needs an interatomic potential model that can deal with all constituent
elements simultaneously. From this point of view, the modied embedded-atom method (MEAM) interatomic potential, proposed by Baskes,29 is highly applicable because it
can describe a wide range of crystallographic structures [fcc,
bcc, hexagonal close-packed (hcp), diamond structure, and
even gaseous elements] using a common mathematical
formalism. Recently, the MEAM was modied again by
Lee and Baskes30 [second nearest-neighbor modied embedded-atom method (2NN MEAM)] to partially consider
second nearest-neighbor interactions overcoming some
critical shortcomings of the original MEAM31.
The eventual purpose of the present work is to investigate the dynamics of hydrogen atoms (hydrogen diffusion and effect of defects, e.g., grain boundaries or
alloying elements) and mechanical properties (the mechanism of hydrogen embrittlement) in aluminum and nickel
alloys, in an atomic scale. Those studies need interatomic
potentials for the relevant metal alloyshydrogen systems.
The most essential system would be the AlH and NiH
binary systems and the development of potentials for those
systems has the highest priority. However, since the
atomistic investigation for vanadium membrane alloys is
also of high impact, the potentials for the AlH and NiH
systems should be the one that can be easily extended to
multicomponent systems including bcc vanadium. As such
extensible potential formalism, the present authors select
the 2NN MEAM. Therefore, the purpose of the present
work is to develop 2NN MEAM interatomic potentials for
the AlH and NiH binary systems.
This article presents a brief description of the 2NN
MEAM formalism and the procedure for the determination of potential parameters. The reliability of the developed potentials is then examined by comparing
calculated fundamental physical properties with available
experimental or rst-principles data.
II. INTERATOMIC POTENTIAL
A. Potential formalism

In the 2NN MEAM, the total energy of a system is

approximated as
"
#
1
E 5 + Fi qi + Sij uij Rij
;
1
2 j6i
i

where Fi is the embedding energy as a function of

background electron density qi . Sij and uij (Rij) are the
screening function and the pair interaction between atoms
i and j separated by a distance Rij. For the calculation of the
embedding energy, functional form of the background
electron density should be dened rst. Although EAM
potentials concern only spherically averaged atomic electron densities, MEAM potentials introduce additional
angular terms to account for directional character of
bonding. The background electron density is computed
by combining several partial electron density terms
for different angular contributions with weight factors
t(h) (h 5 13). Each partial electron density is a function of
atomic conguration and atomic electron density. The
atomic electron densities qa(h) (h 5 04) are given as
qah R 5 qo expbh R=re  1 ;

where qo the atomic electron density scaling factor and b(h)

the decay lengths are adjustable parameters; re is the
nearest-neighbor distance in the equilibrium reference
structure.
To compute the total energy in Eq. (1), a functional
form of the pair interaction uij (Rij) is also necessary.
However, in the MEAM, the value of pair interaction
uij (Rij) is computed not from a specic functional form
but from a known value of the total energy and the
embedding function for an atom in an equilibrium reference
structure. Here, the equilibrium reference structure is dened as a structure where individual atoms are on exact
lattice points. The total energy per atom for the equilibrium
reference structure is obtained from the zero-temperature
universal equation of state by Rose et al.32 as a function of
nearest-neighbor distance R.
E u R 5  Ec 1 a da ea
3

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where d is an adjustable parameter,

a 5 aR=re  1

and

a5

9BX
Ec

1=2
:

re is the equilibrium nearest-neighbor distance, Ec is the

cohesive energy, B is the bulk modulus, and X is the
equilibrium atomic volume of the reference structure.
Although the original MEAM considers only rst nearestneighbor interactions by using a strong many-body screening function,33 the 2NN MEAM considers also second
nearest-neighbor interactions by adjusting the screening
parameters, Cmin, so that the many-body screening becomes
less severe.

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W-S. Ko et al.: Atomistic modeling of the AlH and NiH systems

Cmin and Cmax. Cmin and Cmax determine the extent of

screening of an atom (k) to the interaction between two
neighboring atoms (i and j). For pure elements, the three
atoms are all the same type (i-k-j 5 A-A-A or B-B-B).
However, in case of binary alloys, one of the interacting
atoms and/or the screening atoms can be of different type
(there are four cases: i-k-j 5 A-B-A, B-A-B, A-A-B, and
A-B-B). Different Cmin and Cmax values may have to be
given in each case. Another model parameter is the atomic
electron density scaling factor qo. As shown in Eq. (2), the
values of all atomic electron densities become qo for an
equilibrium reference structure (R 5 re). This parameter is
often omitted when describing the potential model for pure
elements because it does not have effect on calculations.
However, for alloy systems, especially for systems where
the constituent elements have different coordination numbers, the ratio of scaling factors has a great effect on
calculations.
The above 13 parameters are determined by tting
physical properties of the alloy system obtained from
experiments or rst-principles calculations. After investigating the relationship between parameters and physical
properties by a systematic trial and error approach, an
optimized set of parameters is determined. Some parameters have a negligible effect on the properties considered, and those parameters are given a default assumed
value.
Although the AlH binary phase diagram36 shows no
intermediate phase, some experimental and rst-principles
information are available for the metastable a-AlH3.3744
The structure of the metastable phase a-AlH3 is too complicated to be used as a reference structure, and the NaCl
type AlH hydride was chosen as the reference structure.
Since no experimental or higher level calculation data
were available for the NaCl type AlH reference structure,
the potential parameters re and B were optimized to
reproduce lattice parameters and bulk modulus of the
a-AlH3 phase. The parameter Ec of the reference structure
was determined to reproduce simultaneously the heat of
formation of the a-AlH3 phase and the dilute heat of
solution of hydrogen in fcc Al. The parameter d was given
a default assumed value (the average of those for pure
elements) because the necessary information to determine
the value of this parameter (@B/@P of AlH) was not

To describe an alloy system, pair interaction between

different elements needs to be determined. For this, a
similar technique that is used to determine pair interaction
for pure elements is applied to binary alloy systems.
A binary reference structure, where one type of atom has
only the same type of atoms as second-nearest neighbors,
is chosen. The total energy per atom of the reference
structure is computed again using the universal equation
of state. Then, the pair interaction between different
elements is obtained from the known values of the total
energy per atom and the embedding energy of the reference structure. Detailed formulation for binary MEAM
formalism is available in literature.2931,33,34
B. Determination of binary potential parameters

The 2NN MEAM potential for a binary system is

based on the 2NN MEAM potentials for individual
constituent elements. In the present work, potentials for
pure Al and Ni from Lee et al.34 were taken without any
modication. For H, the potential originally developed by
Baskes29 and slightly modied by Lee was used to better
describe the FeH binary system35. The 2NN MEAM
potential parameters for pure elements, Al, Ni, and H, are
listed in Table I.
The parameterization of binary 2NN MEAM potential
parameters starts by determining the four parameters in the
universal equation of state as shown in the Eqs. (3)(5).
Ec, re, and B are material properties if the reference structure
is a stable phase structure that exists under specic equilibrium conditions of the relevant system. Experimental data
for that phase can be used directly. Otherwise, the parameter
values should be optimized so that experimental information
for other phases or high-level calculation results can be reproduced, if available, or assumptions should be made. The
parameter d is a model parameter related with the (@B/@P)
value of the binary reference structure. When the reference
structure is not a stable phase, it is difcult to estimate
a reasonable value of d for the alloy system. For such alloy
systems, d is given an average value of those for pure
elements.
In addition to the parameters for the universal equation
of state, model parameters Cmin and Cmax are determined.
As shown in Table I, each element has its own value of
TABLE I. 2NN MEAM potential parameter sets for Al, Ni, and H.

34

Al
Ni34
H35

Ec

re

b(0)

b(1)

b(2)

b(3)

t(1)

t(2)

t(3)

Cmin

Cmax

3.36
4.45
2.37

2.860
2.490
0.741

0.794
1.876
2.960a

1.16
0.94
2.50

3.20
2.56
2.96

2.60
1.50
3.00

6.00
6.00
3.00

2.60
1.50
2.50

3.05
3.10
0.20

0.51
1.80
0.10

7.75
4.36
0.00

0.49
0.81
2.00

2.80
2.80
2.80

0.05
0.05
0.00

The units of the cohesive energy Ec, equilibrium nearest-neighbor distance re, and bulk modulus B are eV, , and 1012dyne/cm2, respectively. The reference
structures of Al, Ni, and H are fcc, fcc, and dimer respectively.
a
This is an a value as dened in Eq. (5). Bulk modulus B is not dened for a gaseous element.
2NN MEAM, second nearest-neighbor modied embedded-atom method; fcc, face-centered cubic.
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W-S. Ko et al.: Atomistic modeling of the AlH and NiH systems

available. Remaining parameters, Cmin, Cmax, and the

atomic electron density scaling factor qo, were optimized
so that given experimental information on physical properties of hydrogen atoms in fcc phase are closely reproduced. The available physical properties in the literature
are dilute heat of solution, vacancyhydrogen binding
energy, and migration energy barrier of hydrogen. The
knowledge that tetrahedral site is the preferred interstitial
site for hydrogen atoms in fcc Al was also used for the
parameter optimization.
In the case of the NiH system, experimental reports4548
were available for the existence of the NaCl type NiH
hydride as an equilibrium phase under high pressures of
H2, and this phase was chosen as a reference structure. The
Ec, re, and B parameter values were directly determined from
corresponding experimental or rst-principles values for
NiH with some adjustment to better describe the migration
energy barrier of hydrogen in fcc Ni. The parameter d was
given a default assumed value. The dilute heat of solution,
vacancyhydrogen binding energy, migration energy barrier
of hydrogen, and the information that octahedral interstitial
site is preferred for hydrogen atoms in fcc Ni were also
available in the literature. The Cmin, Cmax, and qo values
were optimized so that experimental information on those
properties are closely reproduced.
Table II shows the nally determined MEAM potential
parameter sets for the AlH and NiH binary systems.
III. CALCULATION OF PHYSICAL PROPERTIES

In this section, fundamental physical properties of

individual binary systems are calculated and compared
with experimental data and/or other calculations. Because
the 2NN MEAM formalism includes up to second

TABLE II. 2NN MEAM potential parameter sets for the binary MH
(M 5 Al, Ni) systems.
AlH
NiH
Reference state
FCC_B1
FCC_B1
Ec
0.5 EcAl + 0.5 EcH + 0.680 0.5 EcNi + 0.5 EcH + 0.040
re
1.875
1.865
B
1.122
1.730
d
0.5 dAl + 0.5 dH
0.5 dNi + 0.5 dH
H
qM
1:18
1:18
0 : q0
Cmin (M-H-M)
0.64
0.04
Cmin (H-M-H)
0.09
0.49
0.49
1.80
Cmin (M-M-H)
Cmin (H-H-M)
0.49
[0.5 (CminNi)1/2 + 0.5 (CminH)1/2]2
Cmax (M-H-M)
2.80
2.00
2.80
2.80
Cmax (H-M-H)
Cmax (M-M-H)
2.80
2.80
Cmax (H-H-M)
1.44
2.80
The units of the cohesive energy Ec, equilibrium nearest-neighbor distance
re, and bulk modulus B are eV, , and 1012dyne/cm2, respectively. The
reference structure is NaCl type metastable hydride for both systems.

nearest-neighbor interactions, a radial cut off distance

should be at least larger than the second nearest-neighbor
distance in structures under consideration. All calculations were performed with a radial cut-off distance of
4.7 for AlH and 4.0 for NiH, which are between the
second and third nearest-neighbor distances of fcc Al and
fcc Ni, respectively. Moreover, if not designated, all
MEAM values presented in this section are those calculated at 0 K. The calculations were performed using
a homemade MD (and statics) code, KISSMD, which is
based on the Velocity Verlet algorithm and is available
online.49
The properties calculated in this study can be divided
into two groups. The rst group is the fundamental
physical properties: lattice parameters, bulk modulus,
and heat of formation of metastable hydrides, and dilute
heat of solution, vacancyhydrogen binding energy, and
migration energy barrier of hydrogen in fcc solid solutions.
Those are the properties used for parameter optimization.
The comparison between calculation and experimental or
rst-principles values will show the quality of tting. The
second group is those properties with experimental information or higher level calculation values not used for
parameter optimization. The diffusivity of hydrogen atoms
in fcc solution phases and the adsorption energy of a
hydrogen atom on Ni surfaces are selected because experimental information is available for those properties in one
hand and reproducing diffusivity correctly is thought to be
important for the present purpose on the other hand.
No stable hydride exists on the AlH binary phase
diagram36; however, several experimental works have
reported the formation of metastable hydrides at high
pressures.3740 The most stable aluminum hydride, a-AlH3
(space group R-3c), was relatively selected for calculation
and comparison in this study. The calculated lattice parameters, bulk modulus, and heat of formation of a-AlH3 are
compared with experimental data and/or other calculations
in Table III. The calculated variation of molar volume of
a-AlH3 with respect to pressure is also compared with
experimental data in Fig. 1. In the case of the NiH binary
system, NaCl type NiH was selected for the same type of
comparison as shown in Table III. The two experimental
values for the heat of formation are of the opposite sign from
each other even though the absolute values are small. It
should be noted here that the measurement was made for
nonstoichiometric nickel hydrides (NiHx) with different
H/Ni ratios, whereas the present MEAM calculation was
carried out for the stoichiometric NiH.
Table IV shows calculated interstitial solid solution
behaviors of hydrogen in fcc Al and Ni, in comparison
with experimental data and/or other calculations. The main
difference between Al and Ni is that the tetrahedral (Td)
site is the preferred interstitial site for hydrogen atoms in
Al, whereas the octahedral (Oh) interstitial site is preferred
in Ni. First-principles calculations reporting the Oh site

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W-S. Ko et al.: Atomistic modeling of the AlH and NiH systems

TABLE III. Physical properties of metal hydrides calculated using the present 2NN MEAM potentials, in comparison with experimental data or other
calculations.
Compound

a-AlH3 (R-3c)

NiH (NaCl type)

Property

MEAM

Experimental

Lattice parameter ()
a
c
Bulk modulus (1012 dyne/cm2)
Heat of formation (eV/atom)
Lattice parameter ()
Bulk modulus (1012 dyne/cm2)
Heat of formation (eV/atom)

4.40
11.25
0.537
0.017
3.73
1.73
0.040

4.4537, 4.4638
11.8037, 11.8338
0.47939
0.03040
3.7245, 3.7346
0.046a,47, 0.026b,48

First-principles
4.4241, 4.4942
11.8041,11.8242
0.40043
0.03941, 0.03044
1.9850
0.07841

EAM

3.6027
0.06227

X(H/Ni) 5 0.5.
X(H/Ni) 5 0.7.
MEAM, modied; EAM, embedded-atom method.
a

FIG. 1. Molar volume change of AlH3 for pressures 035 GPa, calculated
using the present second nearest-neighbor modied embedded-atom
method (2NN MEAM) potential, in comparison with experimental
data.39,43

preference in Al are also available in literatures.7981

However, an experiment devoted to clarify this issue82
and a recent rst-principles calculation41 support the Td
site preference. The agreement with the experimental
dilute heat of solution obtained for a H2(g) saturation of
1 atm is good, and the small preference for hydrogen
atoms in Td site is also correctly reproduced. The same
calculations were performed for fcc Ni. The experimentally observed Oh site preference for hydrogen atoms is
correctly reproduced. Also, the calculated dilute heat of
solution of hydrogen in Oh site, 0.18 eV, is reasonably
consistent with scattered experimental data (0.12
0.24 eV), also obtained for a H2(g) saturation of 1 atm.
It should be mentioned here that the values for the
dilute heat of solution of hydrogen in Td and Oh sites of Al
are similar to each other (0.64 versus 0.73 eV), whereas
those in Ni show a large difference (0.79 versus 0.18 eV).
Further, the value for the Oh site in Ni is much lower than
the other quantities. To nd probable explanations for
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those, the local strains on surrounding atoms of an

interstitial hydrogen atom were examined. According to
the present calculation, the distance between a hydrogen
atom in Td and four rst nearest-neighboring Al atoms
increases by 1.3% compared to the hydrogen-free lattice
structure, whereas that between a hydrogen atom in Oh and
six rst nearest-neighboring Al atoms decreases by 1.9%.
In the case of Ni, the distance between a Td hydrogen atom
and rst nearest-neighboring Ni atoms increases by 9.2%
and that for an Oh hydrogen atom increases by 3.2%. The
amount of the local strain due to the interstitial hydrogen
atom would contribute to the increase in dilute heat of
solution. The large difference between the dilute heat of
solution in Td site and Oh site of Ni can be explained by the
large difference in the amount of local strain in surrounding Ni atoms (9.2 versus 3.2%). On the other hand, the
strain effect should not be the only factor that contributes
to the dilute heat of solution. Chemical effect which
implies the interaction between hydrogen and metal atoms
would also be an important factor, and those can be
explained qualitatively in terms of heat of formation of
intermediate compounds. Table II shows that the heat of
formation of NaCl type AlH (0.68 eV) is much higher than
that of the same type NiH phase (0.04 eV), and this
difference can be used to explain the difference between
dilute heat of solution in stable interstitial sites in both
elements (0.64 eV in Td of Al versus 0.18 eV in Oh of Ni).
The binding energy of two defects is dened as energy
difference between when the two defects are adjacent to
each other and when they are separated and noninteracting. The calculated vacancyhydrogen binding energy in
fcc Al by the present potential is 0.35 eV, which is
somewhat smaller than experimental data (0.430.53 eV)
but slightly larger than a rst-principles calculation
(0.33 eV). The binding energy in fcc Ni is 0.61 eV, which
is overestimated compared to the experimental value
(0.430.44 eV).
All the above defect properties show a sample size
dependence because of relatively long-range strains

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TABLE IV. Physical properties of hydrogen in fcc AlH and NiH alloys calculated using the present 2NN MEAM potential, in comparison with
experimental data or other calculations.
Property
AlH

NiH

MEAM

Experimental

First-principles

Dilute heat of solution of hydrogen (eV/atom)

Tetrahedral site
Octahedral site
Vacancyhydrogen binding energy (eV)
Migration energy barrier of hydrogen (eV)

0.64
0.73
0.35
0.39c

0.60a,51, 0.65a,52, 0.66a,53, 0.67a,54,

0.83a,55, 1.90 (60.6)a,56
0.4357, 0.4858, 0.5259, 0.5360
0.1761, 0.3862, 0.4163, 0.4251,
0.4964, 0.5765, 0.6166

0.6941
0.8241
0.3341
0.18d,41

Dilute heat of solution of hydrogen (eV/atom)

Tetrahedral site
Octahedral site
Vacancyhydrogen binding energy (eV)
Migration energy barrier of hydrogen (eV)

0.79
0.18
0.61
0.56c

0.120.246773
0.4374, 0.4475
0.4076, 0.4277

EAM

0.58b,27

0.1625, 0.1827
0.47d,78

0.35d,27, 0.45d,25

Site preference is unknown.

Octahedral site is preferred.
c
Obtained from a temperature dependence of calculated diffusivity.
d
Obtained from an assumed diffusion path.
b

atoms (7  7  7 unit cells) was used and it was conrmed

that the order of magnitude of numerical errors were
105 eV when compared with a larger sample with 4000
atoms (10  10  10 unit cells).
So far, it has been shown that the present potentials
describe the fundamental physical properties of metastable hydrides and fcc solid solutions in both binary
hydride systems mostly well. The developed interatomic
potentials were further utilized in calculating hydrogen
diffusivity to examine the applicability of the present
potentials to atomistic investigations for dynamic behavior of hydrogen atoms in fcc Al and Ni solid solutions.
The adsorption energy of a hydrogen atom on Ni surfaces
was also calculated since experimental information was
available and the surface property could be a good test
bed to examine the transferability of the present potential.
The diffusivity and the migration energy barrier of
interstitial atoms in solid solutions are calculated by
a series of isobarisotherm ensemble MD simulations.
The directly obtainable quantity from the MD simulation
is the time dependence of the mean square displacement
(MSD), and diffusivity can be calculated using the
following Einstein relation
D5

FIG. 2. Arrhenius plot of the diffusivity of hydrogen in (a) face-centered

cubic (fcc) Al and (b) fcc Ni, calculated using the present 2NN MEAM
potentials, in comparison with experimental data.51,6166,77,8388

around the defect. However, the calculated values converge to certain values as the sample size (number of
atoms) increases. In this study, a sample containing 1372

R2 t
6t

where D is the diffusivity, R2(t) is the MSD of atoms,

and t is the time. This relation only involves true random
walks of the interstitial species, and thus we considered a
dilute system (0.1 at.%H) where the probability of
interactions among hydrogen atoms is negligible. To
diminish the statistical error, six independent MD simulations were carried out for fcc crystalline sample with
16,384 solvent atoms (16  16  16 unit cells) and
averaged. The total simulation time was 50 ps with a time

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TABLE V. Adsorption energies (eV) of a hydrogen atom for several possible adsorption sites on the (100), (110), and (111) surfaces of nickel,
calculated using the present 2NN MEAM potential, in comparison with experimental data or other calculations.
Surface
(100)

(110)

(111)

Site

MEAM

Hollow
Bridge
Top
Hollow
Pseudo-threefold
Long bridge
Short bridge
Top
Hollow (fcc)
Hollow (hcp)
Bridge
Top

Experimental
89

0.50
0.08
0.91
0.41
0.29
0.47
0.11
0.90
0.28
0.26
Unstable
0.89

0.50

0.4789

0.4791

First-principles
90

0.58
0.3990
0.1790
0.1990
0.4490
0.4190
0.4290
0.2190
0.5790
0.5590
0.3590
0.2090

EAM
0.2625, 0.5128
0.1425, 0.4028
0.1425, 0.3528
0.1325
0.3125, 0.4628
0.2825, 0.3228
0.2325, 0.4928
0.0625, 0.4328
0.1625, 0.4528
0.1625
Unstable25, unstable28
0.1925, 0.3428

hcp, hexagonal close-packed.

increment of 0.0005 ps, and the time evolution of MSD

was counted at every 0.125 ps. The migration energy
barrier was obtained from the temperature-dependence of
diffusivity
D 5 D0 exp

Em

RT

where Em is the migration energy barrier, R is the gas

constant, T is the absolute temperature, and D0 is the
preexponential factor.
The calculated diffusivities of hydrogen in fcc Al and
Ni are shown in Fig. 2. The migration energy barriers of
hydrogen obtained by linearly tting the Arrhenius plots
are shown in Table IV. Figure 2(a) shows that the
diffusivity of hydrogen in fcc Al is reproduced well within
the scattering range of experimental values over many
orders of magnitude. The migration energy barrier coincides with most of the experimental works as shown in
Fig. 2(a) and also in Table IV. However, it should be
mentioned here that the most recent experimental work61
and a recent rst-principles calculation41 report relatively
small migration energy values compared to the previous
works. In the case of Ni, many experimental data sets
for the diffusivity of hydrogen are generally consistent.
Figure 2(b) shows that the calculated diffusivity is in a
fairly good agreement with experiments even though the
migration energy barrier is slightly overestimated as
shown also in Table IV.
Adsorption energy is dened as the energy gained
when a hydrogen atom is attached on surfaces compared
to the state where the hydrogen exists as gaseous H2
molecules far from the surfaces outside the sample. The
calculated and experimentally observed adsorption energies and binding sites of hydrogen for the (100), (110), and
(111) surfaces of fcc Ni are presented in Table V and
Fig. 3. The calculated adsorption energies are fairly good
on the (100) and (110) surfaces but underestimated on the
(111) surface. The adsorption site preference is correctly
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FIG. 3. The possible sites considered for hydrogen adsorption on the

(100), (110), and (111) surfaces of an fcc crystal. The large circles are
metal atoms and the small circles are hydrogen atoms in various possible
sites, HL (hollow), TP (top), BR (bridge), LB (long bridge), SB (short
bridge), and PT (pseudo-threefold).

reproduced on the (100) and (111) surfaces but not on the

(110) surface. It should be mentioned here that the EAM
by Ref. 28 is a modied version of that by Ref. 25 with
a special attention to the surface property, but this potential
has a limitation in extension to bcc-structured materials.
The reasonable agreement between the present calculations and literature information on the diffusivity of hydrogen and adsorption energy on surfaces indicate the
applicability of the present potential to atomistic investigations of hydrogen diffusion and effect of defects in relevant
materials. The applicability of the present potentials is not
conned to the present binary systems. The most signicant
advantage of the present 2NN MEAM formalism is that one
can easily extend binary potentials into higher-order systems including the V(Al,Ni)H ternary and many other
related multicomponent alloy systems.
IV. CONCLUSIONS

Empirical interatomic potentials for the AlH and

NiH binary systems are now available on the basis of
the 2NN MEAM formalism. The potentials can reproduce
various physical properties such as the interstitial site
preference, dilute heat of solution, vacancyhydrogen
binding energy, and migration energy barrier of hydrogen
atoms in fcc phase and lattice parameters, bulk modulus,

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W-S. Ko et al.: Atomistic modeling of the AlH and NiH systems

and heat of formation of metastable hydrides. The potentials also reproduce the diffusivity of hydrogen in fcc Al or
Ni solid solution phases in good agreement with experiments, which indicates the suitability of the potentials for
atomistic investigations of dynamic behavior of hydrogen
atoms and effect of point defects on it in relevant materials.
Being combined with already developed 2NN MEAM
potentials for other alloy systems (e.g., the VH binary
system), the present potentials can be easily extended to
higher order multicomponent alloys systems, e.g., the
V(Al,Ni)H ternary systems.
ACKNOWLEDGMENT

This work has been supported by Korea Institute of

Science and Technology (2E21652).
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