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Chemical Physics Letters 480 (2009) 203–209

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Chemical Physics Letters


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

First-principles determination of the ground-state structure of Mg(BH4)2


Riccarda Caputo a,*, Adem Tekin b,c, Wieslawa Sikora d, Andreas Züttel a
a
EMPA, Swiss Federal Laboratories for Materials Testing and Research, Division Hydrogen and Energy, Switzerland
b
Atomic-scale Materials Design (CAMD), Department of Physics, Technical University of Denmark, DK-2800 Lyngby, Denmark
c
National Laboratory for Sustainable Energy, Technical University of Denmark, DK-4000 Roskilde, Denmark
d
Faculty of Physics and Applied Computer Science, AGH University of Science and Technology, al. Mickiewicza 30, 30-059 Kraków, Poland

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

Article history: The ground-state structure of magnesium tetrahydroborate, Mg(BH4)2, is still under debate. The experi-
Received 6 April 2009 mentally and theoretically proposed structures mismatch, and even among the computationally deter-
In final form 4 September 2009 mined structures a disagreement still exists. The main debated question is related to the lattice
Available online 8 September 2009
stability of the proposed structures. We combined several computational methods to build and compute
the lowest energy structure. We found that the building motif of the crystalline structure of alkali and
earth-alkaline metal tetrahydroborates is dictated by the coordination of metal atom. We report here
the case of Mg(BH4)2.
Ó 2009 Elsevier B.V. All rights reserved.

1. Introduction work [8] in which they clearly stated that the structure of
Mg(BH4)2 is quite complex and that the previous [4,3] theoretically
Magnesium tetrahydroborate has been proposed as a promising predicted structures did not fit with the experimental crystal struc-
material for solid-state hydrogen storage due to its high hydrogen ture refinements. Although that, another DFT study [9] published
content, 14.9 wt% of atomic hydrogen. Even if the compound has last year reported about the systematic searching for the ground-
attracted interest since 1950, in particular as to the synthesis [1] state, and they showed that the structure Pmc21 proposed two
and later as regarding the structure determination [2], still today years before [3], in fact, is slightly unstable due to the presence
it is unclear which structure is exactly the ground-state. In [2], it of imaginary frequencies after phonon analysis. Furthermore, they
is reported the existence of two crystalline modifications: a- proposed, as the ground-state structure, the crystalline phase with
tetragonal lattice (a = 13.57 Å, c = 15.5 Å) and b-cubic face-centred a symmetry group I4m2  (IT 119). Another recent paper [10] argued
lattice (a = 15.5 Å). The polymorphic transition occurs at tempera- that the ground-state structure reported by Ozolins [9] is thermo-
ture T = 186°. Searching for the structural information on the ICSD dynamically unstable because of imaginary modes in the acoustic
returns with just the recent structure reported by Vajeeston et al. phonon branch. They found the structure with symmetry group
in 2006 [3]. Their results were published one month after another F222 (IT 22) as the true ground-state structure. Finally, another re-
paper on similar calculations [4]. They reported [3] the symmetry cent paper [11] reported the P6122 (IT 178) structure as the lowest
group Pmc21 (IT 26) as the lowest total energy structure that is energy structure, in agreement with the experimental structure re-
found among 28 potential structures. In [4], two phases were sug- ported by Cerny [8] in some respects. Actually, the P6122 symme-
gested: trigonal and monoclinic phases, of which the trigonal P3m 1 try is a super-group of the experimentally observed P61 symmetry.
(IT 164) was found to be the most stable structure. One year later How to explain and solve the discrepancies between theoretically
some experimental structure determination studies were reported proposed structures and experimentally resolved structures? Actu-
[5–8]. In [5], the polymorphic transition a-Mg(BH4)2 ? b- ally, since the first synthesis of Mg(BH4)2 reported by Wiberg and
Mg(BH4)2 in the temperature range (180, 190) °C is confirmed Bauer [1] several attempts and a lot of efforts have been directed
and at low temperature only the a-Mg(BH4)2 is present. In [7], towards new synthesis route and structure determination. At that
the low temperature phase is identified with the hexagonal sym- time huge interest was going on to develop in metal tetrahydrob-
metry group P61 (IT 169) and the high temperature phase is iden- orates, M(BH4)2, where M = Li, Na, K, Be, Mg, Ca thanks in particular
tified with orthorhombic symmetry group Fddd (IT 70). A to the work of Schlesinger and Brown started already a decade ear-
confirmation that the experimental structure at low temperature lier [13,12]. Since then they have been widely exploited as versatile
has hexagonal symmetry with a group P61 come from another nucleophilic reducing agents capable of attacking centre of low
electron density. Their large-scale industrial production was intro-
duced in the early 1960s with the Bayer process [14], which proves
* Corresponding author. Address: EMPA, Division Hydrogen and Energy Abt138,
Überlandstrasse 129, CH-8600 Dübendorf, Switzerland. Fax: +41 (0) 44 8234022. that such class of materials is not completely unknown and that
E-mail address: Riccarda.Caputo@empa.ch (R. Caputo). their chemical properties are already well recognized and used

0009-2614/$ - see front matter Ó 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.cplett.2009.09.019
204 R. Caputo et al. / Chemical Physics Letters 480 (2009) 203–209

for reducing organic functional groups. Nowadays, many different coordinates and lattice parameters were relaxed. A crystal struc-
new approaches have been developed to synthesize Mg(BH4)2. Sur- ture prediction method based on simulated annealing (SA) [24]
prisingly, it has been observed that the structure of metal tetrahyd- was also used. The number of Mg–H bonds in Mg(BH4)2 is impor-
roborates depends on the synthesis route [14]. That means that the tant to stabilize the crystal structure. This fact was exploited in the
same compound could show different structures depending on SA [24] search method to construct crystal structures by maximiz-
whether it has been synthesized using a solvent (wet chemistry ing the number of Mg–H bonds within (2  2  2) cut-through lat-
synthesis) or by the solid state synthesis methods, because the tice using only several bond length constraints. SA search is
presence of the solvent, even at very low concentration, could pro- exemplified for Mg(BH4)2 using a model system illustrated in
mote different crystallization processes that can end up with dif- Fig. 1: (i) two formula units of Mg(BH4)2 were used in the model;
ferent crystal structures. Therefore, the polymorphism of such a (ii) one of the Mg atom was set to the origin; (iii) a fixed tetrahe-
kind of compound is a direct consequence of the synthesis route, dral coordinate system was used for (BH4) with B–H distances to
as also recently pointed out [15]. However, the chemical and phys- be 1.24 Å; (iv) the positions of the other Mg atom and (BH4) groups
ical reasons why the metal tetrahydroborates can undergo to a were determined using three spherical coordinates (the centre of
wide range of polymorphic phases are not yet clear. One reason mass distance, H and U); (v) three euler angle parameters (a, b
could be that the (BH4) anion, despite it is iso-electronic with and c) were used to rotate each (BH4) group; (vi) the lattice vectors
methane, it acts as a versatile ligand capable of forming many coor- were used as parameters; (vii) the resulting 36 parameters were
dination compounds by 3-centre (B–H) ? M bonds to less electro- globally optimized to maximize the number of Mg–H bonds in
positive metals, as reported for transition and lanthanide metals Mg(BH4)2. In addition to this model, in the SA search, the type of
[16,17]. Moreover, most of the discrepancies between theoretical crystal system, e.g., triclinic and monoclinic, was also used as con-
and experimental structures could be attributed to the fact that straints to be able to reduce the parameter search space. Since the
the total energy calculations deal with perfect crystal lattice at current SA optimizations are only based on the geometrical fea-
temperature T = 0 K while the experimental structure determina- tures of the studied system (neither empirical potentials nor DFT
tion has to cope with the practical difficulty to obtain pure and energies are used), bond length constraints must be carefully intro-
crystalline compounds as possible. In both the cases, anyway a duced into the models discussed above to prevent resulting in an
scrupulous internal consistency should be achieved to enable com- unphysical crystal structure. In particular, if the Mg–B, Mg–Mg,
parison between different structures, independently on the specific B–B, and H–H distances in the (2  2  2) cut-through lattice is
method and refinement tool that have been used. longer than 2.44, 3.85, 2.0, and 1.8 Å, respectively, then the crystal
structure is accepted in these model systems. The fitness criteria in
SA optimizations, namely the total number of Mg–H bonds in the
2. Computational approach cut-through lattice, are determined by simply counting the num-
ber of Mg–H bonds, for the Mg–H bond in the range (2.6, 2.8) Å.
We approached the problem of searching for the ground-state All these constraints were adjusted with the help of some preli-
structures from ab initio and model calculations: we built the crys- minary DFT calculations and searching for data reported in the lit-
talline structure from the optimized molecular unit and then fully erature. These SA optimizations successfully yielded previously
relaxed the lattice. We found [18,19] that actually the local coordi- proposed I4m2 and F222 symmetry structures of Mg(BH4) as
nation of the metal cation is the key motif to build the crystal shown in Fig. 1. The symmetry analysis method, based on the the-
structure. We used both the wave function based approach and ory of groups and group representation, helped to search for possi-
density functional theory (DFT) method. In particular, we used ble relationships between different symmetry groups proposed. In
the all electron unrestricted Hartree–Fock self-consistent method particular, small displacements of atomic positions from the initial
(UHF-SCF) to optimize the geometry of the isolated building unit, ones in high symmetry, parent structure, or changes of sites occu-
which was modelled as molecular cluster. The atomic basis set pations, can be treated as structural elements to re-construct the
used for Mg, B, H was contracted from all electron Gaussian basis crystal. These relations were described by k-vectors, which charac-
sets (GTO) plus polarization functions as implemented in the SCF terized the relations between crystal lattices, and connected to gi-
code [20]. Furthermore, the DMol3 [21] method which is imple-
mented in Materials Studio 4.3 was used for cluster calculations.
For the periodic lattice calculations, we used plane-wave and pseu-
do-potential-based methods in the framework of density func-
tional theory (DFT). We used the Materials Studio CASTEP
version 4.3 [22] to optimize ionic positions and lattice parameters
for a-boron and magnesium (hexagonal phase) and for all the
structures reported in the present work. Norm-conserving pseu-
do-potentials are used for all atoms and a fine mesh of k-points,
with the energy conversion threshold of 0.01 meV/atom, maxi-
mum displacement of 0.001 Å and maximum force of 0.03 eV/Å,
yielding high accuracy for the energy and atomic displacements.
In addition, DFT calculations were performed with Car-Parrinello
molecular dynamics (CPMD) code version 3.11.1 [23]. The Per-
dew-Burke-Ernzerhof 96 and the Generalized Gradient form
(GGA-PBE) of the exchange-correlation functional was used. The
fully optimized structures calculated by CPMD and CASTEP were
also used as input geometry for accurate phonon calculations using
plane-wave self-consistent field, PWscf, which is a computer code
for electronic-structure calculations within density functional the-
Fig. 1. The model system used in SA optimizations. (See details in the text.)
ory and density functional perturbation theory, using pseudo- Representing colors: magnesium, green; boron, pink; hydrogen, white. (For
potentials and a plane-wave basis set. Full geometry optimization interpretation of the references to colour in this figure legend, the reader is
was run for all the structures investigated and both internal atomic referred to the web version of this article.)
R. Caputo et al. / Chemical Physics Letters 480 (2009) 203–209 205

ven k-vector irreducible representations of high-symmetry space which is located at about the centre of a tetrahedron formed by
group. All possible subgroups of a given parent group, and corre- boron atoms. The differences between them are due to different
sponding structural changes can be predicted by this method. A orientation of the hydrogen atoms bound to boron in (BH4) groups.
close inspection of the symmetry analysis revealed relations be- One remarkable difference is shown by the structure with symme-
tween the symmetry of different phases of Mg(BH4)2.  1 (IT 164): there the first coordination shell of mag-
try group P3m
nesium atom is formed by a distorted square-bi-pyramid, where
the hydrogen atoms of the (BH4) groups are alternatively eclipsed
3. Results and discussion
and staggered to each other. In all the structures the preferred
coordination of magnesium atoms is bidentate, as already found
3.1. Structure
for the coordination of calcium in Ca(BH4)2 and in alkali metal tetr-
ahydroborates, so far investigated MBH4, with M = Li, Na, K [18,19].
The molecular unit represents the building motif of the crystal-
The magnesium–boron distance is in the range (2.413, 2.416) Å for
line structure and any deviation in the bond lengths and coordina-
the iso-energetic structures and (2.480, 2.396) Å for the Pmc21
tion can only be attributed to the periodicity effects of the crystal  1 structure has six magnesium–boron distances
structure. The P 3m
lattice. The stability of the crystalline structure depends on the lo-
to be 2.700 Å. The coordination of magnesium atom in all the opti-
cal coordination of the metal atom, Mg, which plays a key role in
mized structures reported in Table 1 is drawn in Figs. 2–5. We opti-
determining the symmetry group. Therefore, the geometric analy-
mized all the structures quoted in the remarks of Table 1, and
sis of the first coordination shell of magnesium atoms contributed
compared them with our structures obtained by combining the
to elucidate the relationship between phase stability and configu-
SA global optimizations with the DFT full geometry optimization.
ration of (BH)4 in the lattice. In fact, all the structures reported in
The orthorhombic structure obtained starting from the symmetry
Table 1 show the tetrahedral-like coordination of magnesium,

Table 1
Structural parameters and heat of formation of Mg(BH4)2 according to the following reaction: Mg(s) + 2B(a)(s) + 4H2(g) ? Mg(BH4)2. The input structures, taken from the
references reported in the column, remarks, were fully optimized and the corresponding optimized lattice parameters are reported in the second column of the table.

Symmetry group Lattice parameters DfH(T = 0 K) Remarks


a, b, c (Å)
a, b, c () (kJ/mol)
 1 (IT 164) trigonal
P 3m 4.272, 4.272, 6.510 237.16 4.279, 4.279, 5.761 [4]
90, 90, 120
Pmc21 (IT 26) orthorhombic 4.321, 8.131, 8.128 262.85 4.309, 6.088, 8.389 [3]
90, 90, 90

I4m2 (IT 119) tetragonal 8.186, 8,186, 9.980 282.50 8.18, 8.18, 9.965 [9]
90, 90, 90
F222 (IT 22) orthorhombic 11.931,11.234, 9.996 282.43 9.928, 11.183, 11.891 [10]
90, 90, 90

I4m2 (IT 119) tetragonal 8.176, 8.176, 10.080 282.51 Our result from the formula unit
90, 90, 90
P6122 (IT 178) hexagonal 10.478, 10.478, 37.057 277.72 10.354, 10.354, 37.055 [35]
90, 90, 120


Fig. 2. (Left) Coordination of Mg (in green) in the tetragonal structure I4m2. The molecular symmetry is D2d with the bond lengths boron–hydrogen in the range 1.219,
1.226 Å. Magnesium (in green) is coordinated by four (BH4) groups, where the boron (pink) atom forms a tetrahedron at which centre is located Mg. The projection of the
hydrogen positions along the boron–boron direction shows an eclipsed configuration. The boron–magnesium distances (in blue) are all equal to 2.416 Å and the boron–boron
 direction. The (BH4) units are drawn with polyhedra at which
distances are 4.022 and 3.786 Å (in red). (Right) The top view of the conventional cell projected along ½0 0 1
centre is boron. (For interpretation of the references to colour in this figure legend, the reader is referred to the web version of this article.)
206 R. Caputo et al. / Chemical Physics Letters 480 (2009) 203–209

as reported in Table 1. An accurate analysis of the symmetry rela-


tions revealed that the two structures, I4m2  and F222, are related
by a symmetry relation, being the F222 a subgroup of I4m2.  In fact,
the symmetry analysis calculations revealed that the tetragonal

I4m2 space group structure can be transformed into the F222 space
group by small displacements of atoms, which lead to small distor-
tion of tetrahedron, according to s4 (in Kovalev notation [25]) irre-
ducible representation of I4m2  group connected to k –
vector k = (0, 0, 0). That indicated that the lattice of the subgroup
was the same as the parent group, and only three twofold axis
stayed as the symmetry operations of the transformed structure
(in tetragonal setting they are 2(0, 0, z), 2(x, x, 0) and 2(x, x, 0) axis).
The last four tetragonal elements (two planes – m(0, y, z), m(x, 0, z)
and two fourfold inversion axis 4z and the reversed one) were
lost because of structure deformations. In order to compare the
description of this group with that described in the International
Tables for Crystallography, the tetragonal coordinate system
should be rotated on 45° round the z-axis. That symmetry opera-
tion led from I-type tetragonal lattice to F-type orthorhombic lat-
tice, and consequently the volume of orthorhombic elementary
cell became twice as large as tetragonal one. Accordingly, the num-
ber of the corresponding equivalent Wyckoff positions was re-
quired to be double. It means, that there is group–subgroup
relation between I4m2  and F222 groups.

3.2. Heat of formation and thermodynamic stability

The stability of different structures is ascertained by calculating


the enthalpy of formation for each of them and analyzing whether
the optimized structure is really in the electronic ground-state. For
this purpose phonon calculations are required once the structure is
fully optimized and all the forces acting on the atoms are usually
well below than 0.0001 eV/Å. The heat of formation reported in Ta-
ble 1 was calculated referring to the elements in their most stable
structure at T = 0 K; that means hexagonal Mg, the a-B and hydro-
gen gas, according to the following equation:

Mg(s) + 2BðaÞ (s) + 4H2 (g) ! Mg(BH4 )2 (s) ð1Þ

for which the enthalpy of formation is DfH(T = 0 K) =


[H(Mg(BH4)2)  (H(Mg) + 2H(B(a)) + 4H(H2))], expressed in energy
per mole of magnesium tetrahydroborate formed. The enthalpy,
 1 . The
H, is equal to the internal total energy at T = 0 K. We used the a-
Fig. 3. (Left) Coordination of Mg (in green) in the trigonal structure P 3m
molecular symmetry is D3d with the bond lengths boron–hydrogen in the range
rhombohedral modification of boron, which was studied and fully
1.222, 1.211 Å. All the boron–magnesium distances (in blue) are equal to 2.70 Å optimized [26] instead of the b-phase, for the following motiva-
while the boron–boron distances (in red) are equal to 3.301, 4.272 Å. A view along tions. Even if the most easily available modification of boron which
the boron–boron direction projects the hydrogen atoms alternatively in eclipsed is found commercially or made within the laboratory is the b-phase,
and staggered configuration. (Right) The top view of the conventional cell projected
 direction. The (BH4) units are drawn with polyhedra at which centre is the a-phase can be synthesized at low temperature [27]. The former
along ½0 0 1
boron. (For interpretation of the references to colour in this figure legend, the is considered to be the thermodynamically preferred phase [28],
reader is referred to the web version of this article.) while the latter the mechanically stable phase. The phase transition
a ? b rhombohedral boron occurs at 1400 K [29] and reference
Pmc21 reported by Vajeeston et al. [3] has the magnesium atom therein. Moreover, the a-rhombohedral boron is a low-temperature
coordinated by four (BH4) groups in bidentate and quasi-tridentate allotrope which transforms with heating into b-rhombohedral bor-
configuration. A view along the boron atoms shows that the (BH4) on near 1370 K through a series of intermediate (tetragonal) phases
groups are alternatively staggered and eclipsed. The two struc- [30,31]. Actually, up to the present moment the stable structure of

tures, orthorhombic, Pmc21, and tetragonal, I4m2, differ by only boron, even under normal conditions has not yet been established
20.68 kJ/mol, being the latter more stable than the former. In par- [28]. Therefore, it is correct to refer to a-phase and eventually, if

ticular the tetragonal I4m2 structure shows eclipsed hydrogen con- the reference is the b-phase, the quantity of heat of formation could
figuration: it is highly symmetric because all the boron–hydrogen, be shifted by a quantity equal to the energy difference between the
boron–boron and magnesium–boron bond lengths are equivalent. two boron phases. Nevertheless, that does not affect the relative
In the F222 structure, all the four magnesium–boron distances stability. The heat of formation reported in Table 1 does not include,
are equal, but the tetrahedron is distorted due to unequal B–B dis- for the moment, the zero-point energy contribution. In contrast to
tances, while the hydrogen atoms are slightly staggered to each 
reference [10], the I4m2 symmetry structure of Mg(BH4)2 is lower
other. This lowered the symmetry group. In terms of total energy, in energy by 0.08 kJ/mol of Mg(BH4)2 formed, compared to the
the two structures are degenerated in the limit of DFT-type calcu- structure with symmetry F222, as reported in Table 1. This small
lations (the energy difference is less than 1 meV, that is 0.08 kJ/mol energy difference can simply be explained by considering the coor-
R. Caputo et al. / Chemical Physics Letters 480 (2009) 203–209 207

Fig. 4. (Left) Coordination of Mg (in green) in the orthorhombic structure Pmc21. The molecular symmetry is Cs, with the bond lengths boron–hydrogen equal to 1.228, 1.233,
1.201, 1.225, 1.216, 1.221 Å. Magnesium (in green) is coordinated by four (BH4) groups, in a distorted tetrahedron at which centre is located magnesium. The boron atoms
distant each other by 4.011 and 4.303 Å (values reported in red). The magnesium–boron distances are all equal to 2.428 Å. The projection of the hydrogen atoms along the
boron–boron direction shows the eclipsed configuration. (Right) The top view of the conventional cell projected along ½0 0 1  direction. The (BH4) units are drawn with
polyhedra at which centre is boron. (For interpretation of the references to colour in this figure legend, the reader is referred to the web version of this article.)

Fig. 5. (Left) Coordination of Mg (in green) in the orthorhombic structure F222. The molecular symmetry is D2, with the hydrogen–boron bond lengths equal to 1.226, 1.220,
1.219 Å. Magnesium (in green) is coordinated by four (BH4) groups. The boron–magnesium distances (in blue) are equal to those found for the tetragonal symmetry. The
boron atoms are arranged in a distorted tetrahedron at which centre is the magnesium atom. The boron–boron distances are alternatively 4.129 and 3.919 Å. A view along the
boron–boron direction projects the hydrogen atoms in a staggered configuration. (Right) The top view of the conventional cell projected along ½0 0 1  direction. The (BH4) units
are drawn with polyhedra at which centre is boron. (For interpretation of the references to colour in this figure legend, the reader is referred to the web version of this article.)

dination arguments. The I4m2 symmetry brings the hydrogen required to bring a couple of (BH4) groups slightly staggered to each
atoms in eclipsed configuration to each other, while in F222 they other. It is clear that a slight molecular rearrangement can deter-
are slightly staggered. The eclipsed configuration is found to be mine symmetry changes at a very low cost of energy: the two struc-
the lowest energy one for the single formula unit. Furthermore, tures orthorhombic (F222) and tetragonal (I4m2)  are almost

for the I4m2 symmetry the tetrahedron formed by the nearest degenerate. Interesting is on the other side the comparison between
neighbor boron atom to magnesium is more symmetric than in the reported tetragonal structure and the same symmetry structure
F222 symmetry. Therefore, the comparison between the two opti- we calculated. Even if they are isomorphic and almost iso-energetic,
mized structures clearly shows that an small amount of energy is our tetragonal structure showed slightly different lattice parame-
208 R. Caputo et al. / Chemical Physics Letters 480 (2009) 203–209

ters. They are shorter by 0.12% along ~ ^ and ~


a ^ directions and by 0.92%
b
larger along ~ ^c direction. The tolerance used in searching for the
symmetry group was 0.001 Å. We also optimized the experimen-
tally reported structure: the hexagonal low temperature phase.
Actually, there is not yet a full agreement between the reported
structures, as we have already mentioned. The recently reported
structures confirm that the low temperature phase, the a-phase,
has hexagonal symmetry P61 [8,32,7,33], but it is not yet clear
whether the P61 (IT 169) or the P6122 (IT 178) symmetry group is
the right one to describe and resolve the low temperature phase.
On the basis of symmetry considerations, the P61 symmetry group
is a sub-group of the parent group P6122. Furthermore, as already
reported [10], it also showed lattice instability by the presence of
imaginary modes in the phonon calculations. We optimized the re-
ported experimental structure with symmetry group P6122 and 330
atoms per unit cell, which means 30 formula units per unit cell. The
optimized lattice parameters and the corresponding heat of forma-
tion are reported in Table 1. A close inspection of the coordination
of magnesium, as reported in Fig. 6, highlighted once again the
importance of the local molecular arrangement, which turns to af-
fect the lattice stability and determine the lattice symmetry. To
ascertain the lattice stability, we performed the vibrational analysis,
even if at first approach within the harmonic approximation. We
performed the phonon calculations using CASTEP code and the
vibrational analysis by finite differences method in CPMD. As a fur-
ther check we also used the phonon calculation tool available in
Pwscf code. It has been noted that CASTEP phonon calculations
yielded imaginary modes for all considered structures. However,

the I4m2 structure shows less imaginary modes than the other
structures. A refinement of the geometry optimization using CPMD
and hence running the vibrational analysis gave only rotational
imaginary modes: all the vibrational modes were positive. In fact,
the visualization of the normal modes confirmed that rotational
modes bring into the system lattice instability because the rotation
of [BH4] group relatively to Mg changes its local coordination and
makes the system move from the global minimum, which is the
ground-state, to a local minimum of the potential energy surface.
Clearly, those modes can be identified as fictitious imaginary modes
due to instability induced by slight rotation of[BH4] groups. To Fig. 6. (Left) Coordination of Mg (in green) in the hexagonal structure P6122. The
prove that, we performed the vibrational analysis using a larger molecular symmetry is C1, with the hydrogen–boron bond lengths equal to 1.217,
super-cell. In fact, given that enlarging the super-cell does not affect 1.223, 1.220 Å. Magnesium (in green) is coordinated by four (BH4) groups. The
the eigenvalues of the dynamical matrix, any changes of the eigen- boron–magnesium distances (in blue) are shorter than in the tetragonal symmetry.
The boron atoms are arranged in a distorted tetrahedron at which centre is the
modes frequencies could only be attributed to a locally modified
magnesium atom. Of the six boron–boron distances three are larger (4.421, 4.210,
coordination of the rotating group, [BH4]. In principle, the supercell 3.958 Å) and three are shorter (3.458, 3.771, 3.753 Å) than in the tetragonal
size does not affect the eigenvalues of the dynamical matrix. This is symmetry. A view along the boron–boron direction projects the hydrogen atoms in
why we can use a unit cell to perform phonon calculations and re- a staggered configuration. (Right) The top view of the conventional cell projected
 direction. The (BH4) units are drawn with polyhedra at which centre is
along ½0 0 1
duce the amount of CPU time taking advantage of the symmetry.
boron. (For interpretation of the references to colour in this figure legend, the
However, when even a slight rotation of one particular molecular reader is referred to the web version of this article.)
unit in the lattice can locally affect the molecular configuration,
then it is crucial, for discriminating between proper and fictitious E, which are the translational and rotational modes, have negative
lattice instabilities, to enlarge the supercell and to re-run the pho- frequency of 30.8 cm1. As expected, because the F222 and I4m2 
non calculations. Doing that, the negative vibrational frequencies structures are related by symmetry, being the former a subgroup
are released and the still resultant imaginary modes reveal the of the latter, the accurate refinement of the geometry optimization
instability induced by rotation, which obviously, changing the local and then the phonon calculations using PWscf, gave for F222 sym-
molecular configuration move the system from the minimum en- metry one imaginary modes out of 66 modes (here the super-cell
ergy point of the potential energy surface. Therefore, the rotation was modelled by 22 atoms) with frequency 30.4 cm1 and sym-
of one molecular group, as it is the case of [BH4] in Mg(BH4)2, metry A. The other symmetries investigated show lattice instability
changes the local configuration and brings the [BH4] groups in stag- due to rotational imaginary modes as well. In particular, the ortho-
gered or eclipsed positions relatively to each other. That in turn rhombic structure with the symmetry group Pmc21 has two rota-
moves the system from the ground-state geometry. In addition, tional modes at 95.5, symmetry A00 and 33.1 cm1, symmetry
increasing the size of the supercell allows to directly treat the  1 also has neg-
A0 . Instead the trigonal structure with symmetry P 3m
geometry optimization of a number of formula units sufficient to ative rotational frequencies at 60.5 and 40.9 cm1, with symme-
describe the coordination of the metal atoms and the relative con- try Eu and A2u, respectively. As shown in Table 1, the tetragonal
figuration of the [BH4] groups. In fact, using PWscf code with a large structure with the symmetry group I4m2  is the ground-state struc-
super-cell (44 atoms instead of 22 atoms as in CPMD) among the ture of Mg(BH4)2. The lattice stability depends on the local coordi-
132 normal modes of vibration only the first two with symmetry nation of the metal atom and on the relative configuration of the
R. Caputo et al. / Chemical Physics Letters 480 (2009) 203–209 209

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[19] R. Caputo, A. Züttel, Poster presentation at Swiss Impulse Day, PSI, Villigen,
models is possible. In this study, this strategy was successful to lo- Switzerland, 30 November 2007.

cate the lowest energy crystal structure (I4m2) of Mg(BH4)2. [20] V. Stämmler and alt. SCF-UHF-code.
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[23] Car-Parrinello Molecular Dynamics, CPMD version 3.11.1, IBM Research
The project was supported by European Commission DG Re- Division and MPI Festkoerperforschung Stuttgart, 2007.
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