Computational Materials Science 54 (2012) 115–118

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Computational Materials Science

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

Theoretical study of hydrogen adsorption on the B12P12 fullerene-like nanocluster

Javad Beheshtian a, Mohammad Kamfiroozi b, Zargham Bagheri c, Ali Ahmadi d,⇑
a
Department of Chemistry, Shahid Rajaee Teacher Training University, P.O. Box 16875-163, Tehran, Iran
b
Department of Chemistry, Islamic Azad University, Shiraz Branch, Shiraz, Iran
c
Physics Group, Science Department, Islamic Azad University, Islamshahr Branch, P.O. Box 33135-369, Islamshahr, Tehran, Iran
d
Young Researchers Club, Islamic Azad University, Islamshahr Branch, Tehran, Iran

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

Article history: We investigate and discuss the interaction of a hydrogen atom with B12P12 nano-cluster based on the
Received 14 August 2011 density functional theory, calculating the adsorption energy and, change of enthalpy and Gibbs free
Received in revised form 27 September 2011 energy. Our results show that electron density of adsorbing atoms play an important role in the H adsorp-
Accepted 28 September 2011
tion on the B12P12 and it is thermodynamically feasible above on the top of both the B and P atoms of
Available online 13 December 2011
cluster with Gibbs free energies of 1.18 and 0.80 eV, respectively. We indicate that this process on
the B12P12 clusters is energetically more favorable than that on the B12N12 clusters or boron nitride nano-
Keywords:
tubes. The HOMO/LUMO energy gap of B12P12 cluster is dramatically reduced to one-half its initial value
B12P12 cluster
Density functional theory
upon H adsorption on the B atom.
Hydrogen Ó 2011 Elsevier B.V. All rights reserved.
Adsorption
B3LYP

1. Introduction Interaction of hydrogen with III–V compound semiconductors

Hydrogen, the third most abundant element on earth, has the
potential to meet the energy needs of the mobile industry. Its
economical use as an alternate energy has substantial difficulties
to overcome. Among these, the most difficult challenge is to find
materials that can store hydrogen with large gravimetric and
volumetric density and operate under ambient thermodynamic
conditions. Nanotubes and nanoclusters have attracted great inter-
est in recent years. Their high surface/volume ratio has significant
implications with respect to energy storage. Carbon nanotubes,
nano-magnesium based hydrides, complex hydride/carbon nano-
composites, boron nitride nanotubes (BNNTs), TiS2/MoS2 nanotubes,
etc. are considered to be potential candidates for storing large
quantities of hydrogen [1–4].
Exploring the interaction between atomic hydrogen and nano-
structures (nanotubes, graghene, nanoclusters, etc.) surfaces is
rather crucial in understanding these reactions and many impor-
tant technological processes such as hydrogen storage and trans-
port and fuel cell research. For example, Frances et al. have
recently studied the adsorption of H atoms on graphite sheets
showing an exothermic and favorable process [5]. Wu et al. have
indicated that H atoms prefer to adsorb on the top sites of adjacent
B and N atoms of BNNTs to form an armchair chain along the tube
axis [6].
⇑ Corresponding author. Tel.: +98 912 5061827.
E-mail address: ahmadi.iau@gmail.com (A. Ahmadi).
has attracted much attention over the past decades [6–8]. An early
study to understand hydrogen interaction with phosphorus-rich
indium phosphide and gallium-rich gallium arsenide has been per-
formed [9,10]. However, understanding its interaction with clus-
ters is still primitive even though experimental studies have
been available for quite some time.
Recently, research efforts have been devoted on the (XY)n nano-
structures such as nanocages, nanohorns, nanotubes, and nano-
wires [11,12]. In the theoretical studies on the several (XY)n
clusters, the fullerene-like cages (XY)12 were predicted to be the
most stable ones [13,14]. These facts indicate that the fullerene-
like cage (XY) may be a magic cluster and have inherent special
stability when n is equal to 12.
Atom interactions with nanoclusters are important for catalysis
as well as for the development of cluster-based materials. Consti-
tuting an integral part of several organic materials, hydrogen is
very special, that is technologically important with regard to cata-
lytic reactions and also studies of biological systems. Additionally,
there is great interest in hydrogen interaction with clusters that
could lead to novel hydrogen-absorbing nanomaterials [15].
Hydrogenation of a B12N12 and Al12N12 clusters was investigated
by using ab initio molecular orbital theory.
In this work, the stability and hydrogen adsorption behavior of
alternate fullerene-like cage structures of B12P12 cluster was inves-
tigated by using DFT theory. BP is a refractory semiconductor com-
pound with peculiar properties. It is a III–V material with a strong
covalent binding character, its zinc blende structural phase is the

0927-0256/$ - see front matter Ó 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.commatsci.2011.09.039
116 J. Beheshtian et al. / Computational Materials Science 54 (2012) 115–118
most stable one, and it is a promising material for use in optoelec-
tronic and microelectronic devices working under difficult condi-
tions such as high temperatures or aggressive environments [16].
2. Computational details
We used GAUSSIAN 98 package of programs [17] for the calcu-
lations. Spin-unrestricted B3LYP hybrid DFT method within 6-31G
all electron basis sets were used for the optimization, natural bond
orbital (NBO), molecular electrostatic potential (MEP), density of
states (DOS), frontier molecular orbitals (FMO) analyses, and en-
ergy calculations. The B3LYP/6-31G is a reliable and common used
level of theory in the study of different nanostructures [18–20].
Frequency analyses at the optimized structures are carried out at
the same theoretical level to calculate enthalpy and Gibbs free en-
ergy changes.
With the optimized structures, the adsorption energy (Ead) of H
atom on the pure cluster is obtained using the following equation
Ead ¼ EðB12 P12 HÞ  EðB12 P12 Þ  EðHÞ
where E (B12P12 H) is the total energy of the adsorbed form of B12P12
cluster and E(H) is referred to the energy of an isolated H atom. The
results are summarized in Table 1. The negative value of Ead indi-
cates that the adsorption is exothermic.
3. Results and discussion
3.1. The structure optimization
As shown in Fig. 1, generally, a B12P12 cage is formed from eight
6-membered rings (6-MR) and six 4-membered rings (4-MR) with
Th symmetry. There are two distinct B–P bonds in the optimized
structure of B12P12 cluster; one is shared by two 6-MRs and an-
other by a 4- and a 6-MR with lengths of 1.91 and 1.92 Å, respec-
tively. They are both shorter than the single bond in H3B–PH3
(1.96 Å), but longer than the double bond in H2B–PH2 (1.87 Å) at
spin-unrestricted B3LYP/6-31G (d). It indicates that B12P12 has aro-
matic nature stabilizing by the p electron conjugation.
Calculated NMR spectrum of cluster consists of two single
peaks, confirming its Th symmetry. The NBO analysis reveals that
the hybridization of P and B atoms is nearly sp3 and sp2, respec-
tively. The value of B–P–B angle in 6-MR and 4-MR is 101.8° and
76.0° and that of P–B–P is 129.5° and 99.0° respectively (Fig. 1).
Table 1
The adsorption energy (Ead), change of enthalpy (DH), change of Gibbs free energy
(DG), charge transferred (QT), the distance between cluster and H atom (d) and change
of Eg upon H adsorption on B12P12 cluster. All energies are in eV.
Tube Ead DH DG QT (e) d (Å)
B 1.59 1.45 1.18 0.016 1.19
P 1.19 1.05 0.80 0.036 1.43
Fig. 1. Geometrical parameters of the optimized B12P12 nano-cluster. Distances are
in angstrom and the angles are in degree.
The ranges of calculated IR frequencies are from 152 to
909 cm1, indicating that this structure is a true stationary point
on the potential energy surface. The calculated HOMO/LUMO en-
ergy gap (Eg) for B12N12 cluster is 3.71 eV, suggesting that it is a
semiconductor material.
To assess the stability of B12P12 cage, we calculated the binding
energy (Eb) using the following expression, as this trend has previ-
ously been used by Wang et al. [21].
Eb ¼ ½Etot  12ðEB þ EP Þ=24 ð1Þ
where Etot is the total energy of the B12P12 cluster, 12 is the number
of P and N atoms involved, and EB and EP are the energies of an iso-
lated B and P atom, respectively. The calculated value is about
95.2 kcal/mol, suggesting that the B12P12 may be a stable
substance.
3.2. Hydrogen adsorption
As mentioned above on the basis of NMR results and Th symme-
try of the cluster, there are two distinct sites for an H atom adsorp-
tion; the top of P atom and that of B one. Thus, to find the
adsorption behavior of an H atom on the B12P12 cluster, H atom
is put on the top site of B or N atom (Fig. 2). The results (Table 1)
show that this adsorption is site selective and H atom prefers to ad-
sorb on the top site of the B atom (B configuration, Fig. 2) with Ead
of 1.59 eV. In this configuration the length of newly formed H–B
is 1.19, indicating that the interaction is very strong and a covalent
bond is formed. The NBO analysis shows that the hybridization of
adsorbing B atom changes from sp2 in free cluster to sp3 in B12P12H
form, confirming the strong nature of interaction.
The adsorption of H on P atom (P configuration) is also possible.
It induces a locally structural deformation to adsorbing site of
B12P12 cluster. The B–P–B angles of 6-MR and 4-MR are signifi-
cantly changed from 101.8° and 76.0° in free cluster to 108.5°
and 77.6° in the adsorbed form, respectively (Fig. 2). Nevertheless,
its Ead is smaller than that of B configuration by 0.40 eV (Table 1)
and the length of newly formed P–H bond is about 1.43 Å. Previ-
ously, Yang and Yang [5] have shown that the Ead of H on B and
N atom of BNNTs is about 0.32 and +0.30 eV, respectively.
However, our result show that in contrast to BNNTs, the elec-
tron rich P atom of B12P12 cluster can effectively capture the H
atoms. As we will show in the following this is due to the LUMO
DEg
1.85
0.66
Fig. 2. Geometrical parameters of the optimized B12P12H nano-cluster. (a) The H
adsorption on the B atom of B12P12 and (b) the H adsorption on the B atom of B12P12.
Distances are in angstrom and the angles are in degree.
 J. Beheshtian et al. / Computational Materials Science 54 (2012) 115–118 117

Fig. 3. The calculated lower unoccupied molecular orbital (LUMO, a) and molecular electrostatic potential surface (MEP, b) of the B12P12 cluster. The red and blue colors are
referred to the higher and lower electron density, respectively.

X X
localization on both the P and B atoms of these clusters. Using DHrxn ¼ ðe0 þ HÞ  ðe0 þ HÞ ð2Þ
B3LYP/6-31G⁄ approach, Wu et al. have reported that the H products reactants

adsorption on either B or N atom of B12N12 nano-cluster is endo-

dermic process with Ead of +7.61 and +11.73 kcal/mol, respectively. where e0 and H are electronic energy and enthalpy, respectively (Eq.
It suggests that the H atom adsorption on the B12P12 clusters is (2)). The same short cut can be used to calculate Gibbs free energies
energetically more favorable than that on the B12N12 ones or of the reaction, DGrxn (Eq. (3)).
BNNTs. X X
DGrxn ¼ ðe0 þ GÞ  ðe0 þ GÞ ð3Þ
products reactants
3.3. FMOs and MEP analyses
The computed values of DHrxn for configurations B and P are about
To explain the nature of difference between H adsorption on P 1.45 and 1.05 eV and those of DGrxn are 1.18 and 0.08 eV,
and B sites, we performed FMO analysis on the B12P12 cluster and respectively. However, the less value of DGrxn in comparison to that
H atom. Our results indicate that the LUMO energy of H atom is of DHrxn is due to the entropic effect. It shows that adsorption of H
too high (+19.34 eV) to interact with the LUMO of cluster and this atom on both its B and P atoms is thermodynamically feasible and
reaction is energetically forbidden based on the FMO theory. Thus,
H atom has to interact with the LUMO of cluster with its frontier
HOMO. As depicted in Fig. 3 the distribution of LUMO are partly
equal on both the B and P atoms of cluster, indicating that both
sites are active to interact with HOMO of H atom. Thus the FMO
analysis cannot further help us to explain the nature of this differ-
ence. That is we performed MEP analysis on the B12P12 cluster
showing that the electron density (red1 color in Fig. 3) is less local-
ized on the B atoms of cluster.
We think that the electron rich HOMO of H atom should be pref-
erably interacted with the electron poor atom of cluster and this
process is energetically more favorable than the interaction of H
atom with P one. The charge is transferred from the H atom to clus-
ter is 0.016 and 0.036 e in the B and P configurations, respectively.
It seems that the more charge transfer in the B configuration is due
to the more electronegativity of P atom in comparison that of B
one.

3.4. Thermochemistry

To further examine the thermodynamic feasibility of H adsorp-

tion on B12P12 we calculated free energies and enthalpy changes in-
volved at 298.14 K and 1 atmosphere. Since Gaussian program
provides the sum of electronic and thermal enthalpies, we simply
took the difference of the sums of these values for the reactants
and product. This works since the number of atoms is the same
on both sides of the chemical equation. Therefore all atomic infor-
mation cancels out, and we need only the molecular data,
Fig. 4. Calculated density of states (DOS) for the bare B12P12 cluster (A) and (B)
configuration (B, the H atom adsorbed on the B atom of cluster) Energies are in eV.
1
For interpretation of color in Figs. 1–4, the reader is referred to the web version of (For interpretation of the references to color in this figure legend, the reader is
this article. referred to the web version of this article.)
118 J. Beheshtian et al. / Computational Materials Science 54 (2012) 115–118
the H atom prefers to adsorb at B site of cluster in comparison to the P
site. The main IR active frequencies of the B–H and P–H stretching
modes of B12P12H are at 2626 and 2258 cm1, respectively. These
frequencies were not scaled.
3.5. HOMO/LUMO energy gap
As shown in Table 1, the Eg of P and B configuration are about
3.05 and 1.86 eV, respectively. Interestingly, comparing these val-
ues with that of clean cluster, we found that the H adsorption on
the B atom of B12P12 significantly affects the electrical properties
of cluster. As shown in Fig. 4, the DOSs of this configuration near
the valence band has a distinct change compared to that of the
pristine cluster, so that local energy levels appear after the adsorp-
tion of H atom which would result in an electrical conductivity
change of the cluster. The Eg decreases from 3.71 eV in free cluster
to 1.86 eV in this configuration. It shows a considerable change of
Eg about 1.85 eV (50%), indicating that the electronic properties of
B12P12 are very sensitive toward the H adsorption. However, there
is a little change in Eg of cluster upon H adsorption on P atom that
is not comparable with that of B configuration.
4. Conclusion
We performed a DFT study on the interaction of a hydrogen atom
with B12P12 nano-cluster, calculating the adsorption energy, change
of enthalpy and Gibbs free energy. Our results indicated that electron
density of adsorbing atoms play an important role in the H
adsorption. We showed that the H adsorption is thermodynamically
feasible atop both the B and P atoms of cluster with Gibbs free ener-
gies of 1.18 and 0.80 eV, respectively. It suggested that this pro-
cess on the B12P12 clusters is energetically more favorable than
that on the B12N12 clusters and BNNTs. The HOMO/LUMO energy
gap of B12P12 cluster is dramatically reduced to one-half its initial va-
lue upon H adsorption on its B atom.
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