Chapter 3

Beryllium Hydride and its Oligomers

3.1 Introduction
The search for new potential compounds with desired properties for hydrogen storage has
been a continuous challenge among researchers for past few decades [1, 69]. Hydrogen storage
in the solid state is a better choice compared to the storage in gaseous or liquid state, because
storage in solid state is safer, less sensitive to flammability and compact. The Alkali and
Alkaline metal hydrides, amides, borates and alanates are hydrogen storage compounds with
promising applications [5, 12, 70, 71]. In this chapter, we present the electronic structure
and bonding nature of known simple light metal hydride, Beryllium hydride (BeH2 ) as a
solid and also as a molecular polymer (upto decamer). Beryllium hydride (BeH2 ) is a simple
light weight metal hydride well known for its hydrogen storage capability. The crystalline
BeH2 has been reported as a three dimensional array of tetrahedral BeH4 molecules and
not as BeH2 chains [72–74]. The beryllium hydride oligomers are obtained from the excited
beryllium (1 P𝑜 ) atom and hydrogen molecule [75]. These are very difficult to synthesize and
are easily hydrolyzed by dilute acids. Because of its high hydrogen storage capacity (18.2
wt%), it is of considerable interest especially for use in nuclear reactor and also as a rocket
fuel [12]. Therefore, a theoretical understanding of the geometry, stability and electronic

27
properties of beryllium hydride oligomers is essential for developing chemical methods of
hydrogen release and recovery of oligomers. Several theoretical studies emphasizing the
electron correlations [76], static dipole polarizabilities [77], and electronic structures [78]
have been reported. Chen et al. [79] have reported the geometry and binding energies of
possible beryllium hydride clusters (BeH2 )𝑛 (where, n = 1 to 4). However, the stability of
these oligomers towards hydrogen storage applications is not clearly understood. Hence, an
in-depth theoretical investigation is deemed necessary to explore the various properties such
as stability, reactivity, electronic structure and spectroscopic parameters of molecules. In this
chapter we describe, density functional theory calculations at HF/6-311++G**, B3LYP/6-
31+G**, B3LYP/6-311++G**, B3P86/6-31+G** and B3P86/6-311++G** levels have been
performed to investigate geometry, stability, reactivity, spectral parameters and electronic
structure properties of model molecules. The stabilities of beryllium hydride oligomers are
determined from the frontier molecular orbital energies and their gaps.

3.2 Computational details

Ab initio molecular orbital calculations have been performed for the molecules, BeH2 ,
Be2 H4 , Be3 H6 , Be4 H8 , Be5 H1 0, Be6 H12 , Be7 H14 , Be8 H16 , Be9 H18 and Be10 H20 using the Gaus-
sian 03 quantum chemical package [67]. Their structure optimizations have been performed
at the above mentioned levels. All the geometric parameters were allowed to be optimized
and no constraints were imposed on the molecular structure during the optimization process.
Vibrational frequencies were calculated for the optimized structures to enable us to charac-
terize the nature of the stationary points, zero-point vibrational energy (ZPVE) and thermal
correction (H𝑇 ). All stationary points have been positively identified as local minima with no
imaginary frequencies [68]. Total energy has been used to evaluate reactive descriptors such
as ionization potential (IP), electron affinity (EA), polarizability (𝛼), chemical potential (𝜇),
hardness (𝜂), softness (S) and △E(𝐿𝑈 𝑀 𝑂−𝐻𝑂𝑀 𝑂) of model molecules. The chemical potential

28
(𝜇) and the hardness (𝜂) of the molecules were calculated according to ref [80, 81].
Electronic structure calculations based on Kohn-Sham density functional theory are more
efficient and accurate, therefore the DFT version of Koopman’s theorem naturally becomes
an interesting topic [82, 83]. Koopman’s theorem has been used to calculate the ionization
potential and electron affinity of the beryllium hydride oligomers. The ionization potential
and electron affinity of the molecule are in general equal to the negative of the highest
occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO),
respectively [84, 85]. The first principle calculations of crystalline BeH2 were also carried out
by using the plane wave pseudopotential density functional method using CAmbridge Series
of Total Energy Package (CASTEP) [60, 86]. We have used ultra-soft pseudopotentials for
electron-nuclei interactions with local density approximation (LDA) and generalized gradient
approximation (GGA). A plane wave basis set with energy cut-off 480 eV has been applied.
For the Brillouin zone sampling, the 5 x 8 x 5 Monkhorst-Pack [87] mesh has been used.

3.3 Results and discussion

This section presents and discusses the results on the geometry, electronic properties, ion-
ization and chemical potentials, electron affinities, softness, hardness, polarizability infrared
and Raman spectra of model compounds.

3.3.1 Optimized structures

At the outset, we have performed geometry optimizations of molecules, the optimized

structures of model oligomers from the B3LYP/6-311++G** level are shown in figure 3.1.
The terminal and bridge Be-H lengths in all molecules are in agreement with the experimental
values of ∼1.33 and 1.44 ± 0.04 ˚
𝐴, respectively [75, 76]. The calculated Be-H-Be angles vary
from 84.54𝑜 to 85.91𝑜 with the method adopted and also with the size of basis set. The
molecules are asymmetric and are tetragonal with four Be-H bonds i.e., there are two H-

29
 Table 3.1: The total energy (E0 ), thermal correction to enthalpy (H𝑇 ) and zero-point vibrational energy (ZPVE) of
oligomers as computed from the various levels of theory arranged in different columns.(The total energy and
thermal correction is in atomic units and zero point vibrational energy are in kcal/mol)

Compound HF B3LYP B3P86

6-311++G** 6-31+G** 6-311++G** 6-31+G** 6-311++G**
E0 H𝑇 ZPVE E0 H𝑇 ZPVE E0 H𝑇 ZPVE E0 H𝑇 ZPVE E0 ZPVE H𝑇
30

BeH2 -15.770 0.016 8.375 -15.919 0.016 8.250 -15.922 0.016 8.254 -16.014 0.016 8.188 -16.017 0.016 8.181
Be2 H4 -31.580 0.037 20.794 -31.889 0.037 20.303 -31.896 0.037 20.393 -32.085 0.037 20.224 -32.091 0.037 20.298
Be3 H5 -47.400 0.060 33.805 -47.873 0.059 33.250 -47.883 0.059 33.230 -48.170 0.059 33.126 -48.178 0.059 33.077
Be4 H8 -63.219 0.082 46.607 -63.854 0.081 45.949 -63.867 0.081 45.874 -64.252 0.081 45.773 -64.263 0.080 45.663
Be5 H10 -79.039 0.104 59.352 -79.835 0.102 58.563 -79.852 0.102 58.451 -80.334 0.102 58.359 -80.349 0.102 58.194
Be6 H12 -94.858 0.126 72.024 -95.816 0.124 71.197 -95.836 0.124 70.994 -96.416 0.124 70.941 -96.434 0.124 70.517
Be7 H14 -110.67 0.148 84.882 -111.79 0.146 83.647 -111.82 0.146 83.685 -112.49 0.146 83.545 -112.51 0.146 83.199
Be8 H16 -126.49 0.170 97.590 -127.77 0.168 96.187 -127.80 0.168 96.191 -128.58 0.167 95.921 -128.60 0.167 95.803
Be9 H18 -142.31 0.192 110.38 -143.75 0.189 108.56 -143.79 0.189 108.60 -144.66 0.189 108.29 -144.68 0.189 108.10
Be10 H20 -158.09 0.212 121.74 -159.69 0.210 120.52 -159.77 0.211 121.21 -160.74 0.211 120.58 -160.77 0.211 120.73
Figure 3.1: Optimized structures of model molecules computed at the B3LYP/6-311++ G** level.
The bond lengths are in Angstrom and bond angles are in degree (Green spheres
represents Beryllium atoms and white spheres represents Hydrogen atoms).

Be-H-Be-H planes that are perpendicular to each other in the Be3 H6 to B10 H20 molecules.
With increase in the basis set as well as the size of the molecules the point group symmetries

31
change from D∞ h to Cl. The point groups of Be2 H4 , Be4 H8 , Be6 H12 , Be8 H16 and Be10 H20
molecules at the three levels (HF, B3LYP and B3P86) of calculations are D∞ℎ , C2 𝑣, C2 , C1
and C1 , respectively. The total energies (E0 ) and zero point vibrational energies (ZPVE) of
the oligomers computed from the HF, B3LYP and B3P86 methods with basis sets 6-31+G**
and 6-311++G** are presented in table 3.1. The total energies of the molecules calculated
from the basis set 6-311++G** with three methods are nearly same. The binding energies
(BE) of oligomers are apparently higher, revealing that the stability of model molecules
increases with increasing size. The binding energies calculated per unit and lowest harmonic
frequencies of molecules are summarized in table 3.2.

Figure 3.2: Optimized crystalline structure of BeH2 with local density approximation (LDA).
Blue spheres represents Beryllium atoms and red spheres represents Hydrogen atoms.

Furthermore, we have optimized the crystalline BeH2 within LDA and GGA, the opti-
mized crystalline structure of BeH2 is shown in figure 3.2. The crystalline beryllium hydride
contains twelve BeH2 units with network of BeH4 tetrahedral molecules in the unit cell. The
structural parameters such as lattice constants, atomic positions and the band gap with
experimental values are listed in table 3.3 except for band gap for which there is yet no
experiment result. The calculated properties have been found to be in good agreement with
the experimental values [73]. We have also calculated the electronic band structure as well

32
 Table 3.2: The calculated binding energy (BE) and lowest harmonic frequencies (𝜔 𝐿 ) of oligomers computed from the
various levels of theory (The binding energies are in atomic units and lowest harmonic frequencies are in cm−1 ).

Compound HF B3LYP B3P86

6-311++G** 6-31+G** 6-311++G** 6-31+G** 6-311++G**
BE 𝜔𝐿 BE 𝜔𝐿 BE 𝜔𝐿 BE 𝜔𝐿 BE 𝜔𝐿
BeH2 -15.770 750.427 -15.919 736.106 -15.922 739.186 -16.014 722.029 -16.017 723.669
Be2 H4 -15.790 344.529 -15.944 325.674 -15.948 326.455 -16.042 317.452 -16.045 323.105
33

Be3 H5 -15.800 159.258 -15.957 162.252 -15.961 147.876 -16.056 154.450 -16.059 141.750
Be4 H8 -15.804 89.936 -15.963 97.993 -15.966 88.427 -16.063 93.771 -16.065 85.113
Be5 H10 -15.807 64.528 -15.967 67.322 -15.970 61.670 -16.066 67.822 -16.069 58.648
Be6 H12 -15.809 45.785 -15.969 48.427 -15.972 45.403 -16.069 45.953 -16.072 41.597
Be7 H14 -15.811 34.355 -15.971 35.254 -15.974 34.792 -16.071 32.499 -16.074 33.276
Be8 H16 -15.812 26.422 -15.972 26.734 -15.975 26.383 -16.072 24.389 -16.075 25.372
Be9 H18 -15.812 21.135 -15.973 21.658 -15.976 20.230 -16.073 18.574 -16.076 18.481
Be10 H20 -15.809 5.138 -15.969 15.748 -15.977 17.129 -16.074 15.036 -16.077 16.551
as the total and partial density of states of BeH2 . The density of states and band structure
of the compound are shown in figure 3.3. The direct band gap along Γ- Γ direction of the
crystalline BeH2 has been calculated to be 5.51eV with LDA and 5.58 eV with GGA. The
valence band consists of Be-2p states and H-1s states and the conduction band is dominated
by the Be-2s states. The overlap of Be-2p states and H-1s states at Fermi level indicates the
presence of sp hybridization in the molecule with covalent character.

Table 3.3: The Optimized lattice parameters, atomic positions and the calculated band gap of
the crystalline BeH2 along with experimental values.

Property LDA GGA Expt𝑎

a(˚
𝐴) 8.700 8.964 9.082
b(˚
𝐴) 3.939 4.147 4.160
c(˚
𝐴) 7.477 7.633 7.707
Atomic Positions
Be1(x) 0.000 0.000 0.000
Be1(y) 0.000 0.000 0.000
Be1(z) 0.250 0.250 0.250
Be2(x) 0.168 0.167 0.169
Be2(y) 0.121 0.118 0.125
Be2(z) 0.000 0.000 0.000
H1(x) 0.089 0.088 0.089
H1(y) 0.248 0.225 0.194
H1(z) 0.154 0.152 0.151
H2(x) 0.321 0.310 0.305
H2(y) 0.256 0.274 0.282
H2(z) 0.000 0.000 0.000
E𝑔 (eV) 5.51 5.58 -

𝑎
Ref[74];

3.3.2 Electron affinity, ionization and chemical potentials

The ionization potential (IP) and electron affinities (EA) provide the information about
the reactivity and stability of the compounds. The compounds with higher IP and lower EA

34
 (a) (b)

Figure 3.3: (a) The density of states and (b) band structure of crystalline BeH2 within local
density approximation (LDA).

values are more stable compared to the compounds with lower IP and higher EA values. The
chemical potential (𝜇) characterizes the tendency of electron to escape from the molecule in
the equilibrium state. Koopman’s theorem has been used to calculate IP, EA and 𝜇 of the
molecules [84]. Electron affinity, ionization and chemical potentials of the model molecules
are shown in figure 3.4. In our case, it has been observed that the IP and EA values of
oligomers vary with the method and the basis set. The IP values decreased with the size
of the oligomers. However, the IP of Be2 H4 is less compared to that of Be3 H6 molecule. A
maximum EA value (∼0.095 a.u) for the Be2 H4 has been noticed. However, we have found
that the EA values of Be2 H4 , Be4 H8 , Be6 H12 , Be8 H16 and Be10 H20 molecules (even series)
are higher compared to BeH2 , Be3 H5 , Be5 H10 , Be7 H14 and Be9 H18 molecules (odd series).

35
The higher EA values of even series indicate that these could be less stable or highly reactive
compared to odd series. The variation in the EA values of the molecules is probably due
to the charge transfer among the atoms within the molecule. The chemical potentials (𝜇)
values of even series are also higher than those of the odd series.

3.3.3 Hardness, softness and polarizability

The hardness (𝜂) and softness (S) are the important factors for the charge transfer re-
sistance and these are inversely proportional to each other [88]. The calculated hardness
and softness of the model oligomers in the present case are shown in figure 3.5. It is found
that the hardness and softness values are independent of the method and choice of basis set.
According to the principle of maximum hardness (PMH), it is expected that the molecule
in the equilibrium state possess maximum hardness and in the transition state possess min-
imum hardness [89, 90]. It has been found that the odd series are more stable than the even
series. The dipole polarizability (𝛼) measures the distortion of electron density of molecules
and the response of the molecule to external electric field. The polarizability, like for the
other polymers, increases rapidly with size of the oligomers i.e., distortion of the electronic
density of oligomer is linear with external electric field and it is in good agreement with the
previous studies [78].

3.3.4 Frontier molecular orbital energies

The stability of the compounds is usually measured by the total energy (for isomers),
bond length, bond dissociation energy, frontier orbital highest occupied molecular orbital
(HOMO) and lowest unoccupied molecular orbital (LUMO) energy and their gaps. We
have used frontier orbital energies to evaluate the stability of the BeH2 oligomers. Fukui
et al [91] noticed the prominent role played by HOMO and LUMO in governing chemical
reactions. It has been revealed in several investigations that the band gap (△E(𝐿𝑈 𝑀 𝑂−𝐻𝑂𝑀 𝑂))
in energy between the HOMO and LUMO is an important stability index of the molecules

36
 (a) (b)

(c)

Figure 3.4: (a) Electron affinity, (b) ionization and (c) chemical potential of the model molecules
computed from various levels of the theory.

[92–95]. A large band gap implies high stability and small gap implies low stability. The high
stability in turn indicates low chemical reactivity and small band gap indicates high chemical

37
 (a) (b)

Figure 3.5: (a) The calculated hardness and (b) softness of model oligomers computed from var-
ious levels of the theory.

reactivity. In other words, smaller the gap between HOMO and LUMO, the easier the
electron transition and lesser the stability of the compound will be. The frontier molecular
orbitals of model molecules obtained from the B3LYP/6-311++G** level are shown in figure
3.6. With increase of the monomer units of the BeH2 oligomer, the HOMO has been observed
to correspond to that of a finite-graphene-like-structure [96] and is prominent in the molecules
Be4 H8 to Be10 H20 . With increase of the basis set, the frontier molecular orbital energies and
their gaps have increased. In the model compounds BeH2 is found to be most stable and
Be10 H20 is found to be least stable, which is reflected in the band gap values. The frontier
molecular orbital energies of odd series have higher values compared to even series. The
frontier molecular orbital energies of the model molecules are shown in figure 3.7. BeH2
oligomer structures are like the zig zag edge states of finite graphene [96]. The edge states in
non metallic graphene ribbons are located on length confined zig zag edge have been discussed
by Shemella et al [96]. We also observe a similar zig zag edge in the present oligomers.
Therefore one can expect the similar HOMOs in BeH2 oligomers like finite graphene or

38
nanotubes where they are located at the edges. In finite graphene ribbons this typical
behavior is observed only for non metallic ribbons, which is not the case for metallic graphene
ribbons. In the present case we observe the HOMO energy levels located at the length
confined edge of the oligomers. Since HOMOs are localized at the edges, it may be possible
to control the band gaps using different functionalized groups.

3.3.5 Mulliken atomic charges

One of the most important properties of a molecule is its charge or spin density distri-
bution. Although there is no unique definition of how many electrons are attached to an
atom in a molecule it has nevertheless proven useful in many cases to perform such popula-
tion analysis. Due to its simplicity the Mulliken population analysis has become the most
familiar method to count electrons to be associated with an atom. It has been found that
the hydrogen and beryllium atoms have negative and positive Mulliken atomic charges, re-
spectively. However, beryllium atoms in Be4 H8 , Be5 H10 and Be6 H12 molecule have negative
charges of two, one and four, respectively. We have noticed only two negative charges in
Be7 H14 , Be8 H16 , Be9 H18 and Be10 H20 molecules. In general, if more electrons are shared by
the hydrogen atom, higher is the negative charge. The higher negative charges have been ob-
served for the beryllium atoms in Be4 H8 to Be10 H20 molecules and thus there is a possibility
of covalent bonding among beryllium and hydrogen atoms.
The Mulliken population on the charge density distribution of crystalline BeH2 is shown
in figure 3.8. The charges of beryllium and hydrogen atoms of crystalline BeH2 have been
calculated to be -0.23, -0.24, +0.50 and +0.45 e for H(1), H(2), Be(1) and Be(2) atoms,
respectively. The negative charge of hydrogen atoms implies the electronegative nature
towards beryllium atoms. R. S. Mulliken [97] states that “If the total overlap population
between two atoms is positive, they are bonded; if negative, they are anti-bonded”. The
high positive population indicates the possibility of having high degree of covalent character
of bond [97, 98]. All Be-H bonds have bond population about 0.55 indicating the equal ionic

39
Figure 3.6: Frontier molecular orbitals of the model molecules computed at B3LYP/6-311++G**
level. Green spheres represents Beryllium atoms and white spheres represents Hydro-
gen atoms.

and covalent character. Figure 3.8 shows the charge density distribution of crystalline BeH2 .
The charge density around H atom has been found to be higher compared to beryllium atom.

40
Figure 3.7: The HOMO-LUMO gap of the model molecules computed at B3LYP/6-311++G**
level.

Figure 3.8: The charge density distribution of the crystalline BeH2 within local density approxi-
mation (LDA)

The shape of charge density around hydrogen atoms is slightly deformed towards beryllium
atoms. Therefore, there is possibility of equal covalent and ionic character of Be-H bonds in

41
BeH2 .

3.3.6 Infrared and Raman spectra

The infrared (IR) and Raman spectra of molecules are obtained from the computed struc-
tures at B3LYP/6-31++G** levels and are presented in figures 3.9 & 3.10. The calculated
wave numbers of BeH2 and Be2 H4 molecules are in good agreement with experimental val-
ues [72–74]. It was observed that the stretching vibration (1510 cm−1 ) of Be3 H6 molecule is
splitting and the same has been found sin all oligomers. The splitting of vibrational line of
1510 cm−1 has been observed in Be3 H6 to Be10 H20 molecules. However, the wave numbers
corresponding to 1900, 1910, 1920 and 1930 cm−1 in Raman spectra of Be10 H20 are probably
due to the splitting of the line corresponding to 1810 cm−1 .

Figure 3.9: The infrared (IR) spectra of the molecule are obtained from the computed structures
at B3LYP/6-31++G** level.

42
Figure 3.10: Raman spectra of the molecule are obtained from the computed structures at
B3LYP/6-31++G** level.

3.4 Conclusions
The electronic structure properties of beryllium hydride oligomers have been carried out
at HF, B3LYP and B3P86 methods with 6-31+G** and 6-311++G** basis sets. The band
gap △E(𝐿𝑈 𝑀 𝑂−𝐻𝑂𝑀 𝑂), ionization potential (IP), electron affinity (EA), chemical potential
(𝜇), hardness (𝜂), softness (S) and polarizabilities (𝛼) of beryllium hydride oligomers have
been calculated. From the band gap, chemical potential, hardness and softness of molecules,
BeH2 , Be3 H5 , Be5 H10 , Be7 H14 and Be9 H18 molecules have been found to be more stable
compared to Be2 H4 , Be4 H8 , Be6 H12 , Be8 H16 and Be10 H20 molecules. The IR spectra of BeH2
and Be2 H4 molecules were found to be in good agreement with the experimental values. The
IR spectra of molecules have five fundamental bands (475 to 575, 840 to 890, 1410 to 1520,
1610 and 2150 cm−1 ) that are prominent.
The next chapter discusses complex hydride ammonia borane (AB).

43