Computational Condensed Matter 2 (2015) 11e15

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Computational Condensed Matter

journal homepage: http://ees.elsevier.com/cocom/default.asp

Regular article

Ab-initio structural and electronic properties of the intermetallic

compound TiFeH2
Lazhar Mohammedi*, B. Daoudi, A. Boukraa
Univ Ouargla, Fac. des Math

ematiques et des Sciences de la Mati
ere, Lab. D

eveloppement des

energies nouvelles et renouvelables dans les zones arides et
sahariennes, Ouargla 30 000, Algeria

a r t i c l e i n f o a b s t r a c t

Article history: Using the first principles “full-potential linearized augmented plane-wave method” based on density
Received 3 November 2014 functional theory, structural and electronic properties of the dihydride TiFeH2 was investigated. This
Received in revised form intermetallic hydride
65 Cmmm space group-with moderate hydrogen storage (1.8e1.9%Wt.) has an
1 December 2014
orthorhombic structure. The stability analysis and total energy were calculated using the general
Accepted 8 December 2014
Available online 9 December 2014
gradient approximation (GGA). We have investigated in the ground state the lattice parameters, bulk
modulus, electronic structure and formation energy of TiFeH2 hydride. Total and partial DOS analysis
show that the TiFeH2 hydride has a metallic character. Iron below the Fermi level is the main contributor
Keywords:
First principles
to bonding manifold whereas anti-bonding titanium states dominate above. The hybridization between
Density function theory iron 3d and hydrogen 1s states appear to be the strongest. Electron density reveals that a relatively high
TiFeH2 hydride electron density extends from the hydrogen atom site to the iron atom site, but not to the titanium atom
Formation energy site. Formation energy values indicate that the TiFeH2 system is more hydrogen reversible compared
DOS analysis with TiFeH.
© 2014 The Authors. Published by Elsevier B.V. This is an open access article under the CC BY-NC-ND
license (http://creativecommons.org/licenses/by-nc-nd/3.0/).

1. Introduction neighbors) and at 91% in Ti2Fe4 sites (2 Ti and 4 Fe nearest neigh-

bors). Hydrogen storage is well understood in terms of the nature of
The research about reversible hydrogen storage materials with the chemical bond between metal and hydrogen atoms. First
low risk and cost is an important key for future clean energy principles calculations based on quantum theory have successfully
development. Smithson et al. [1] showed that the early transition been used in predicting structural and electronic properties (lattice
metals (so-called type A elements) have higher tendencies for hy- constants, bulk modulus, band structure, etc.) of the systems at
dride formation and this trend decreases systematically towards their ground states. In addition to experimental studies, theoretical
the right of the periodic table (so-called type B elements). Ti has a modeling techniques became widely used following the de-
highly stable hydride phase but Fe has an unstable hydride phase, velopments in computer technology. Computational science can
necessitating respectively high temperatures and high pressures provide reliable and in-depth information about the system under
for the reversible insertion/removal of hydrogen. The intermediate consideration. In this work, the structural and electronic properties
or intermetallic compound TiFe, which crystallizes in the cubic of TiFeH2 intermetallic are systematically studied, by means of DFT
CsCl-type structure [2], was studied many times. It can absorb calculations, in order to gain knowledge on the comparatively
reversibly up to 1.9 wt% hydrogen, due to its moderate kinetics with stable TiFeH2 hydride. FP-LAPW energy states and electronic den-
relatively high equilibrium hydrogen pressure (z4.5 atm) at room sity reveal the contribution of each atom to the bonding properties
temperature. Many investigations about TiFe hydrides were carried in TiFeH2 hydride.
out in the past [3e12]. Fischer et al. [8] investigated FeTiD1.94
assuming an orthorhombic symmetry for the crystal structure.
They identified two types of deuterium-occupied octahedral 2. Computational details
framework sites, filled at 100% in Ti4Fe2 sites (4 Ti and 2 Fe nearest
Firstly, we define the structure of both TiFe and TiFeH com-
pounds. TiFe has a CsCl-like structure with a (221) space group
* Corresponding author. (Fig. 1), whereas TiFeH has an orthorhombic structure with a P2221
E-mail address: [email protected] (L. Mohammedi). (17) space group (Fig. 2) [13]. In TiFeH hydride, the hydrogen atoms

http://dx.doi.org/10.1016/j.cocom.2014.12.001
2352-2143/© 2014 The Authors. Published by Elsevier B.V. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/3.0/).
12 L. Mohammedi et al. / Computational Condensed Matter 2 (2015) 11e15

Fig. 3. TiFeH2 (Cmmm) orthorhombic structure.

Fig. 1. Cubic structure of TiFe.

convergence energy of 10
4 Ry, the RMTkmax and the number of k-
points for TiFe, TiFeH and TiFeH2 were optimized to be 9 and 3000,
respectively. All the calculations were performed in the non-spin
polarized approximation.

3. Results and discussion

3.1. Structural analysis

To determine at ground state the values of a, b and c, the lattice

constants of orthorhombic TiFeH and TiFeH2, we have optimized
the volume according to the optimization procedure of L. D Marks
[18]. By fitting the total energy versus volume data to the non-
linear Murnaghan equation of state [20], as shown in Fig. 4 for
TiFeH2, we obtained the lattice parameters, the value of the bulk
modulus and its pressure derivative for TiFe, TiFeH and TiFeH2
(Table 1). The calculated equilibrium lattice parameters in all
structures are in the range of available experimental data and
previous theoretical calculations, as shown in Table 1. We focus our
Fig. 2. TiFeH (P2221) orthorhombic structure. attention on TiFeH2. For this compound the shortest interatomic
distance in the structure (see Table 2) is that involving the iron
atoms FeeH1 ¼ 1.761 Å, in good agreement with the experimental
occupy Ti4Fe2-type octahedral framework sites, and the atomic distance of 1.774 Å [8]. We also observed that the FeeH distances
coordinates are: titanium in 2d (0.5, 0.757, 0.25), iron in 2c (0, are smaller than TieH distances whatever the types of octahedral
0.2941, 0.25), and H in 2a (0, 0, 0). framework sites for hydrogen. The low bond length between iron
According to the experimental structure given by ref. [8], TiFeH2 and hydrogen atoms shows that the FeeH interaction (in particular
has an orthorhombic structure and a Cmmm (65) space group, as
shown in Fig. 3. The structure is characterized by three types of
octahedral framework sites; two of type Ti4Fe2, occupied by H1 and
H3 atoms and one of type Ti2Fe4, occupied by H2 atoms. The atomic
coordinates are: titanium in equipoint 4h (0.223, 0, 0.5), iron in 4i
(0, 0.2887, 0), H1 in 4e (0.25, 0.25, 0); H2 in 2c (0.5, 0, 0.5) and H3 in
2a (0, 0, 0).
In this work, first-principles calculations are performed by
employing the FP-LAPW approach [14,15] based on DFT [16],
approximated by the generalized gradient approximation (GGA 96)
as proposed by PerdeweBroukeeErnzerhof [17], and implemented
in the WIEN2k [18] code. The KohneSham equations are solved
self-consistently by choosing the muffin-tin radii (MT) to be 1.8, 1.8
and 1.4 a.u for Ti, Fe and H, respectively. The fully relativistic
treatment was used for the core states [19], whereas the sca-
larerelativistic calculations included not only the (3d and 4s)
valence bands but also the 3s and 3p states. These states should be
taken into account because they are located sufficiently close to the
valence bands. Thus, we have chosen a separation energy of
7 eV
Fig. 4. Total energy versus volume for TiFeH2 structure after the optimization of the
to separate core states from valence band states. Taking a internal parameters.
 L. Mohammedi et al. / Computational Condensed Matter 2 (2015) 11e15 13

Table 1
Calculated lattice constants, bulk modulus, pressure derivative B0 compared to experimental data and other works of TiFeH2 structure when available.

Compounds Reference Method Approximation Calculated cell parameters (Å) B (GPa) B0

A B C

TiFe Present FP-LAPW GGA-96 2.959 2.959 2.959 361.3996
22.6742

[21] Experimental Experimental 2.972 2.972 2.972 / /
[22] PAW GGA-96 2.945 2.945 2.945 / /
TiFeH Present FP-LAPW GGA-96 2.932 4.515 4.276 178.8451
0.2786
[13] Experimental experimental 2.966 4.522 4.370 / /
[22] PAW GGA-96 2.889 4.529 4.264 / /
TiFeH2 Present FP-LAPW GGA-96 6.980 6.115 2.813 201.0409 1.7448
[8] Experimental Experimental 7029 6233 2835 / /
[6] Experimental Experimental 7.041 6.234 2.828 / /
[22] PAW GGA-96 6957 6071 2769 / /
[23] PP-PW GGA-99 7123 6302 2819 / /

Table 2 3.2. Electron density analysis

Interatomic distances of TiFeH2 structure for Cmmm space group.

Distance Ref [8] (Å) Present calculations (Å) The intermetallic hydride TiFeH2 is an intermediate hydride
FeeH1 1.774 1.7610
which is constituted from two elements, titanium (type A element)
FeeH2 1.935 1.9099 forming stable hydrides and iron (type B element) forming unstable
FeeH3 1.800 1.7654 hydrides. A contour map of electron densities on the (001), (010),
TieH1 2.115 20.859 (100) and (002) reveal that relatively high electron density regions
TieH2 1.951 1.9335
extend from the hydrogen atom site to the iron atom site, but not to
TieH3 2.111 2.0979
H1eH3 2.349 2.3199 the titanium atom site, as shown in Fig. 5. This result shows that the
hydrogen atom exhibits a larger affinity with iron atoms (type B
element) rather than titanium atoms (type A element) in TiFeH2
structure, despite the larger affinity of titanium atoms for hydrogen
FeeH1) is the strongest in this structure. Solid hydrogen storage
than iron atoms in the binary metal-hydrogen system. The same
compounds are classified into two categories according to the
result, not mentioned here, was found on (100) and (011) atomic
structural change between the compound and its hydride. The first
planes of TiFeH. The FeeH bond seems to be an important char-
category is for those hydrides which conserve the structure of the
acteristic of hydrogen storage applications. Similar results are also
parent compound (such as ZrTi2, ZrMn2 and NaB), and the second
found in other hydrogen storage compounds [24e27].
one is for those hydrides having a completely different structure
from the initial structure (such as ErNi3, Mg2Ni and Mg2Co). Most
researchers classify TiFeH2 in the second category. 3.3. Band structure and density of states analyses

Fig. 6 shows energy band structure of TiFeH2. The hydride has a

Fig. 5. Contour maps of the electron density distributions on the a) (001), b) (010), c) (100) and d) (002) atomic planes of the TiFeH2 structure.
14 L. Mohammedi et al. / Computational Condensed Matter 2 (2015) 11e15

150
a) Ef (TiFeH2) = 0.87047 Ryd
125 TiFeH2 tot
100 Ti tot
Fe tot
75 H1 tot
H2 tot
50
H3 tot
25
100
0
b)
Ti tot
75 Ti s
Ti p
50 Ti d

25

100
0
c)

DOS (States/Ryd)
Fe tot
75 Fe s
Fe p
50 Fe d

25

100
0
d)
Ti tot
75 H1 tot
H2 tot
50 H3 tot

Fig. 6. Band structure of TiFeH2. 25

100
0
e)
Fe tot
metallic character because there is no gap and the orbitals can 75 H1 tot
move through the Fermi level. The Density of states of both TiFeH H2 tot
50 H3 tot
and TiFeH2 shows that the DOS structure moves towards anti-
bonding states at higher energies with increasing hydrogen den- 25
sity (Fig. 7). Therefore, The TiFeH2 dihydride is less stable than the
0
TiFeH monohydride. The DOS of TiFeH2 is shown in Fig. 8. We note 0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6 1.8 2.0
Energy (Ryd)

Fig. 8. Total and partial density of states of a) TiFeH2 tot, Ti tot, Fe tot, H1 tot, H2 tot
10 and H3 tot, b) Ti (tot, s, p, and d), c) Fe (tot, s, p, and d), d) Ti tot, H1 tot, H2 tot and H3
a) Ef
tot, and e) Fe tot, H1 tot, H2 tot and H3 tot.

TiFeH-total
8
that there are two separate sets starting at 0.04 Ry which corre-
spond to the structures of the bands (Fig. 6). To study the hybrid-
6 ization interaction of TiFeH2, the total and partial DOS of the Ti (tot,
s, p and d) and Fe (tot, s, p, and d) are shown in Fig. 8b) and Fig. 8c).
The valence band below the Fermi level in the energy range of
4
(0.6e0 Ry) is highly dominated by the Fe 3d orbitals, while the
contribution of Ti 3d orbitals is small (Fig. 8a)). The orbital contri-
butions Fe (s and p), Ti (s and p), and H 1s are almost zero in this
2
range. The low energy range (0.04e0.47 Ry) shows a strong hy-
DOS (States/eV)

bridization interaction between Fe 3d and H 1s orbitals, while the

10
0 interactions between Ti 3d-H 1s and Ti 3d-Fe 3d are low (Fig. 8d)
b) and Fig. 8e)). Thus iron is the main bonding manifold as shown in
the study of Papaconstantopoulos for TiFeH [28]. The main
TiFeH2-total
8 contribution to the conduction bands above the Fermi level is from
Ti orbitals. The latter are Ti non-bonding orbitals, not participating
in the bonding. There are also non-bonding orbitals from iron but
6
less than bonding orbitals.

Table 3
Formation energy of TiFeH and TiFeH2 compounds.
0
-15 -10 -5 0 5 10 15 Compounds Formation energy (kJ/mol H2)
Energy (eV)
TiFeH
45.0964
TiFeH2
42.7075
Fig. 7. Total density of states of a) TiFeH and b) TiFeH2.
 L. Mohammedi et al. / Computational Condensed Matter 2 (2015) 11e15 15

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