International Journal of Nanoscience

Vol. 10, No. 3 (2011) 391
396

#.c World Scienti¯c Publishing Company
DOI: 10.1142/S0219581X11008125

COMPUTATION OF INTERACTION
POTENTIAL OF ADSORBATES ON
ZIGZAG SWCNTs — APPLICATION
TO FUNCTIONALIZATION AND
HYDROGEN STORAGE

I. LAKSHMI
Department of Computer Science
Jothi Nivas College for Women
Bangalore — 560095, Karnataka, India
D. SILAMBARASAN, V. J. SURYA,
M. RAJARAJESWARI and K. IYAKUTTI*
School of Physics, Madurai Kamaraj University
Madurai — 625021, Tamil Nadu, India
*iyakutti@yahoo.co.in

H. MIZUSEKI and Y. KAWAZOE

Institute for Materials Research
Tohoku University, Sendai — 980-8577, Japan

Received 17 November 2009

Accepted 1 August 2010

Nature of the interaction potential of di®erent adsorbates on di®erent zigzag single-walled

carbon nanotubes is investigated. The intermolecular potentials for H2 absorbed in carbon
nanotubes (5, 0), (6, 0), (7, 0), (8, 0), (9, 0), and (10, 0) are computed and sketched. This study
is extended to N2 adsorbed on (4, 0) and BH3 adsorbed on (10, 0) tubes. The equilibrium
positions of the adsorbates obtained from the potential model serve as an initial guess in
designing the CNT þ adsorbate complex in the simulation cell and this process considerably
reduces the computation time. Further, the hydrogen storage capacity of CNTð10; 0Þ þ BH3
complex is calculated. The estimated storage capacity of this system is in the range 6
12 wt.%.

Keywords: Carbon nanotube; interaction potential; functionalization; hydrogen storage.

1. Introduction to hydrogen storage. Hydrogen would be an ideal

The discovery of carbon nanotubes (CNTs) has
generated tremendous interest in physicists, che-
mists, and the scientists in other ¯elds. Much e®ort
has been devoted for ¯nding the uses of these tubes
in applications ranging from nano electronic devices
* Corresponding author.
1 synthetic fuel because it is of light weight, highly
abundant, and its oxidation product is water.
Because of large surface area, capillarity and chemical
stability CNTs have been proposed as the promising
material for hydrogen storage. Lot of investigations

391
392 I. Lakshmi et al.

are done in the hydrogenation of single-walled 80

CNT (5,0)
carbon nanotubes2
5 (SWCNTs). Dillon et al.6 70
CNT (6,0)
CNT (7,0)
suggested the possibility of achieving hydrogen sto- CNT (8,0)
rage capacity of 5
10 wt.% in SWCNTs. In recent 60

years the chemical reactivity of the tube wall has been

Potential energy(eV)
50
investigated theoretically and experimentally.7
11 It
has been found that many kinds of atoms and mo- 40

lecules, such as F, K, O2 , H2 O, and NO2 , can be 30

adsorbed on the outer surface of SWCNTs. To
20
simulate the adsorption of various molecules on the
CNT, we have to model the interaction of the mo- 10
lecules with CNT. To start with we have used the
model potential of Yildirim et al.12 We have deduced 0
-0.4 -0.2 0 0.2 0.4
Distance r(A)
a similar potential expression and the empirical par-
ameters for N2 adsorbed on (4, 0) tube and BH3 Fig. 1. Potential energy curve for H2 adsorbed inside the
adsorbed on (10, 0) tube. From the potential plot tubes (5, 0), (6, 0), (7, 0), and (8, 0).
equilibrium position of the adsorbate on the CNT
can be determined. These positions are used in the
construction of the simulation cell in the Vienna 100
CNT (9,0)
Ab-initio Simulation Package (VASP),13,14 nonweb- CNT (10,0)
based versatile software used in computational 50

materials science.
Potential energy(meV)

-50
2. Model Potential
Yildirim et al.12 modeled the intermolecular poten- -100

tial for the adsorbate H2 trapped on a CNT as a sum

of atom
atom potentials: -150

V ðr; ­Þ ¼
i;H
j;C ½B expð
Crij Þ
A=r 6ij  ; ð1Þ -200

-0.3 -0.2 -0.1 0 0.1 0.2 0.3
Distance r(A)
where the summations are over the coordinates of
hydrogen and carbon atoms. The dependence of the Fig. 2. Potential energy curve for H2 adsorbed inside the
potential on the position (r) and orientation (­) tubes (9, 0) and (10, 0).
of H2 molecule is through the interatomic distances
rij . The empirical parameters are A ¼ 5:94 eV Å,
B ¼ 678:2 eV, and C ¼ 3:67  A
1 . The exponential 40
CNT (5,0)
term in the expression represents the interaction 30 CNT (6,0)
CNT (7,0)
between the ¯lled orbitals of H2 and CNT; it is CNT (8,0)
overall repulsive. The second term represents the 20 CNT (9,0)
CNT (10,0)
Potential energy(meV)

weak long-range van der Waals attraction which 10

decreases as 1/r 6ij . The interaction potentials are
computed for the adsorption of H2 on (5, 0), (6, 0), 0

(7, 0), (8, 0), (9, 0), and (10, 0) CNTs. With this the -10
potential energy curves are plotted. The H2 mo-
-20
lecule is perpendicular to the nanotube axis and its
position is varied along the radial direction of the -30
CNT. The shapes of the potential curves are para-
-40
bolic and Mexican hat like when the adsorbate 2 3 4 5 6 7 8 9 10
Distance r(angstrom)
is inside and outside of the tube, respectively.
In Figs. 1
5 the distance along the x-axis refers to Fig. 3. Potential energy curve for H2 adsorbed outside the
the distance between carbon atom and hydrogen/ tubes (5, 0), (6, 0), (7, 0), (8, 0), (9, 0), and (10, 0).
 Computation of Interaction Potential of Adsorbates on Zigzag SWCNTs 393

0.012 Table 1. The equilibrium positions of H2 on zig-

zag tubes.
0.01
CNT Radius Potential minimum of H2 from
0.008 (n; 0) (Å) the surface of the CNT (Å)
Potential energy(eV)

0.006
(5, 0) 1.98 3.29
(6, 0) 2.38 3.27
(7, 0) 2.78 3.22
0.004
(8, 0) 3.17 3.28
(9, 0) 3.57 3.25
0.002
(10, 0) 3.96 3.28
0

5.1 5.2 5.3 5.4 5.5 5.6 5.7 5.8 5.9 6

Distance r(A) the distance of the adsorbate from the surface of
Fig. 4. The potential energy curve for N2 molecule adsorbed the CNT using density functional theory as
outside the CNT (4, 0). implemented in the VASP.13,14 In the case N2
adsorbed on (4, 0) tube and BH3 on (10, 0) tube we
vary the position of the adsorbate from the surface
of the tube. The potential energy curves obtained for
0.008
N2 adsorbed on CNT (4, 0) and BH3 adsorbed on
0.007 CNT (10, 0) are given in Figs. 4 and 5, respectively.
0.006
The solid curve is drawn for the data obtained
from the density functional theory calculation. The
Potential energy(eV)

0.005
0.004
0.003
0.002
0.001
0 of correction term Drij: Both N2 and BH3 are
6.6 6.65 6.7
Distance r(A)
Fig. 5. The potential energy curve for BH3 molecule adsorbed
outside the CNT (10, 0).
nitrogen/boron atoms in their respective molecules.
Figures 1 and 2 show the potential energy curves for
H2 adsorbate inside the CNTs (5, 0), (6, 0), (7, 0), (8,
0), and (9, 0), (10, 0) respectively. Figure 3 shows the
potential energy curves for H2 adsorbed outside the
CNTs, (5, 0), (6, 0), (7, 0), (8, 0), (9, 0), and (10, 0).
The possible equilibrium positions of the adsorbate
on the di®erent CNTs are read from the minimum of
the curves. The values are given in Table 1.
From Table 1 it is clear that the energetically
preferred adsorption positions of H2 molecule on
the tubes (5, 0) to (10, 0) occur nearby 3.3 Å from
the surface of the tubes. The applicability of this
model potential to other molecules N2 and BH3 are
analyzed by computing the potential energy curves
from the total energy calculated as a function of
dotted curve corresponds to the potential energy
expression. The curves obtained from the new
potential expressions are ¯tted with the above
curve obtained using density functional theory cal-
culation. The modi¯ed potential energy expressions
are obtained for N2 and BH3 with the inclusion
parallel to the tube axis and their positions are varied
6.75 6.8
similar to that of H2 . For N2 the deduced potential
expression is
V ðr; Þ ¼
i;N2
j;C ½B expð
Crij Þ
A=r 6ij þ Drij  :
ð2Þ
The ¯tting parameters are A ¼ 5:94 eV Å, B ¼
A
1 , D ¼ 0:4 
678:2 eV, C ¼ 3:67  A
1 .
The corresponding expression for BH3 is
V ðr; Þ ¼
i;BH3
j;C ½B expð
Crij Þ
ð3Þ

A=r 6ij þ Drij  :
The ¯tting parameters are A ¼ 5:94 eV Å, B ¼
678:2 eV, C ¼
1:67  A
1 , D ¼ 0:001 
A
1 .
The potential minimum for N2 occurs at 3.9 Å
from the surface of the (4, 0) tube. For BH3 ,
potential minimum occurs at 2.74 Å from the sur-
face of the (10, 0) tube. The position of the mini-
mum in the potential energy curve gives the
equilibrium position of the adsorbate on the CNT.
This information can be used in constructing the
394 I. Lakshmi et al.

simulation cell which is used in VASP. This process

considerably reduces the computation time.

3. Results and Discussion

3.1. Functionalization
The information derived from the potential energy
curve is used in the functionalization of CNT with
BH3 . The total energy calculations are carried out
using VASP.13,14 Ultrasoft pseudopotentials are
used with C: 2s 2 , 2p 2 ; B: 2s 2 , 2p 1 , and H: 1s 1 as
valence states. The LDA is adopted for exchange-
correlation functional. Two unit cells are taken
along the tube axis and are considered for our study.
The calculations are performed in the simulation
cell of geometry 28  A  28  A  7:92  A. The simu-
lation cell has 80 carbon atoms. It has 20 full Fig. 7. The relaxed structure of CNT20BH3 .
hexagons. The structures are optimized using con-
jugate gradient algorithm. The convergence is
achieved when the energy is less than 1  10
5 eV/ 3.2. Hydrogenation
atom and the force is less than
0:5  10
5 eV/Å.
In bare CNT the adsorption of H2 is very weak.
The energy cuto® for the plane wave basis set is
One way of enhancing the hydrogen adsorption on
287 eV. The Brillouin zone is sampled by 1  1  8
CNT is to functionalize of CNT the CNT with suit-
mesh points with Monkhorst
Pack k-point scheme.
able molecule. Recently Iyakutti et al.15 reported
Initially the system CNT (10, 0) is relaxed. Figure 6
that the functionalization of CNT with metal
shows the front view of CNT (10, 0). Then we have
hydrides enhances the storage capacity. Functiona-
attached BH3 on the center of each hexagon at a
lization of CNT (5, 5) with BH3 enhances the binding
distance of 2.74 Å (obtained from the potential
energy of hydrogen molecules as well as increases the
energy curve) from the surface of the tube. Twenty
storage capacity.16 To have an idea about the e®ect
BH3 molecules are attached on 20 full hexagons
of chirality on the binding energy of BH3 with CNT,
around the CNT and it corresponds to full coverage
we have functionalized CNT (10, 0) with BH3 . To
case. It is denoted as CNT20BH3 (Fig. 7). The
simulate hydrogenation, a single H2 molecule is
binding energy per BH3 is 3.98 eV and thus it is
added to each BH3 in the relaxed structure of
chemisorbed on the CNT.
CNT20-BH3 . The system CNT20(BH3 þ H2 ) was
allowed to relax further. After relaxation the binding
energy per H2 , desorption temperature, and storage
capacity are calculated (Table 2). Desorption tem-
perature is calculated by using the van't-Ho®
equation.17 Similarly, the second, third, and fourth
H2 molecules are attached. The systems are relaxed
to achieve the required energy convergence. After
relaxation an increase in bond length is noted in all
H2 molecules. The average H
H bond length of the
H2 in all the systems namely CNT20(BH3 þ H2 ),
CNT20(BH3 þ 2H2 ), CNT20(BH3 þ 3H2 ), and
CNT20(BH3 þ 4H2 ) are 0.9 Å, 0.78 Å, 0.83 Å, and
0.83 Å, respectively. All H2 are molecularly physi-
sorbed through BH3 and oriented randomly on CNT.
The binding energy of H2 , desorption temperature,
and storage capacity of all the systems are given in
Fig. 6. Front view of CNT (10, 0). Table 2. Since the BH3 binding energy is more
 Computation of Interaction Potential of Adsorbates on Zigzag SWCNTs 395

Table 2. Binding energy, desorption temperature, and 3.98 eV and it is at a distance of 2.74 Å from the
storage capacities for system CNT20(BH3 þ nH2 ) (n ¼ 1
4). surface of the tube. Even though the curvature of
Binding Desorption Storage
the tubes are comparable, because of the chirality of
energy/H2 temperature capacity the tube the interaction between BH3 with CNT
System (eV) (K) wt.% (10, 0) is strong which results in higher binding
energy. From this we conclude that a zigzag CNT
CNT20(BH3 þ H2 ) 0.86 1100 3.16
has higher binding energy than the armchair
CNT20(BH3 þ 2H2 ) 0.38 486 6.12
CNT20(BH3 þ 3H2 ) 0.24 307 8.90 nanotube having almost the same radius.
CNT20(BH3 þ 4H2 ) 0.16 208 11.5

4. Conclusion
The interaction of di®erent adsorbates on zigzag
SWCNTs is studied and the equilibrium positions of
the adsorbates are found. The hydrogen storage
capacity of the system CNT20(BH3 þ 3H2 ) lies in
the range recommended by DOE (US). This system
is capable of releasing H2 at ambient temperature
(307 K). Thus, the single-walled zigzag CNT (10, 0)
coated with BH3 is identi¯ed as one of the practic-
able and suitable hydrogen storage medium.
Between two nanotubes of same radii of di®erent
chiralities the zigzag CNT turns out to be a better
candidate for hydrogen storage.

Acknowledgments
The authors K. I., M. R., and V. J. S. acknowledge
the ¯nancial assistance by UPE and CSIR (ES).
They thank the crew of Centre for Computational
Materials Science at IMR for making the Hitachi
SR11000 supercomputer available for computational
Fig. 8. Relaxed structure of CNT20(BH3 þ 3H2 ).
work.

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