Effects of Mechanical Deformation on Outer Surface Reactivity of Carbon Nanotubes
Xiaohui Song1, Sheng Liu1,2*, Han Yan2, Zhiyin Gan2
1
Research Institute of Micro/Nano Science and Technology, Shanghai Jiao Tong University, Shanghai, P. R. China, 20030
2
Wuhan National Lab for Optoelectronics, Huazhong University of Science & Technology, Wuhan, P. R. China, 430074
*Corresponding author: Sheng Liu, Telephone: 86-13871251668, Fax number: 86-27-87557074, Email:
shengliu63@yahoo.com
Abstract
An ab initio approach of Car-Parrinello molecular
dynamics is used to study the chemisorption of a single
oxygen atom on outer surface of zigzag single-wall carbon
nanotubes under various uniaxial strains and bending
deformation. The effect of mechanical deformation on
adsorption of oxygen atom on CNT is demonstrated by
linking the chemical reactivity and structural deformation.
The adsorption energy Eb and pyramidalization angle θP are
obtained by structural relaxation calculations, and ground-
state electronic structures are described according to density
functional theory (DFT) within a plane-wave pseudopotential
framework. Our results show that the surface reactivity of
CNT is mostly determined by its pyramidalization angle of
carbon atom. For bending SWCNT, both Eb and θP vary with
adsorption sites, the Eb is higher at sites with larger
pyramidalization angle. An approximate linear relation of
strain and adsorption energy can be obtained. It is indicated
that the structure of CNT is crucial for its surface reactivity,
and the mechanical deformation can be a method for
controlling the surface reactivity of CNT and offering
adsorption site selectivity as the adsorption is facilitated on
the sites with higher pyramidalization angle.
Introduction
Carbon nanotubes (CNTs), discovered in 1991 [1], have
been identified to be one class of the novel candidate
materials to continue the miniaturization of microelectronics
to a new level [2]. It is expected to produce a variety of novel
nanodevices by using foreign atoms and molecules for
functionalization of CNTs [3]. In this context, the adsorption
of oxygen on CNTs is of particular interest. Both simulation
[4] and experimental data [5] have shown that the electron
transport properties of singe-wall carbon nanotubes (SWNT)
change dramatically upon exposure to gas molecules of
oxygen at ambient temperature. Such process offers the
opportunity for the chemical modification of nanotubes to
produce distinct structural and electronic properties.
Therefore, the CNTs can be used as sensitive material of gas
sensors. On the other hand, the change of electron transport
properties should be avoided when the CNTs to be used as
interconnect materials, where the reactivity should be reduced
to guarantee the reliability of interconnects.
So far most theoretical studies of the interaction of
molecular or atomic oxygen with carbon nanotube focused on
physisorption [6-9] and chemisorption [9, 10] mechanism.
They suggest that oxygen is predominantly physisorbed on
CNTs. Most of these studies have concluded that the
reactivity of the CNTs is correlated with strains produced by
the curved surface which induces transformation of carbon
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atoms from sp2 to sp3 hybridization, and the physisorbed
molecular oxygen get chemisorbed at some special sites with
high local strain such as various defects. For perfect CNTs,
the side-wall of a carbon nanotube is considerably less
reactive when the tube diameter is over 1 nm, furthermore, the
reactivity decreases as the tube diameter increases due to the
reduction in curvature. Therefore, in order to produce a
variety of novel nanodevices by using foreign atoms and
molecules for functionalization of CNTs, the surface
reactivity of CNTs should be tuned. Some studies have
reported that tuning the atom adsorption on CNTs by radial
deformation [11-13], which can be a method to control
surface reactivity of the CNTs via bringing out local strains
that induce change of the hybridization of carbon atoms in
CNTs. It indicated that the mechanical deformation not only
radical deformation, but also other types of deformation such
as tension and bending which can produce local strain could
tune the surface reactivity of CNTs.
The mechanical deformation can be a very useful tool to
control the interaction of atomic oxygen with CNTs. The
advantage of this method is the extent of the deformation can
be easily controlled by macroscopic variable of force and
pressure, and such modification is more extensive than the
localized groups at the end caps and offers a natural way to
change the properties of the carbon nanotube. Furthermore,
the adsorption sites can be controlled by mechanical
deformation that induces local structural change of an
individual SWCNT.
In this paper, the effects of unaxial tension and bending
deformation on the reactivity of the CNT are examined by
first principles calculations. Various unaxial tensions and a
bending angle are applied to a zigzag single wall carbon
nanotube and oxygen atom adsorptions on different sites of
CNT are calculated respectively. In order to illustrate this
coupling effect, the relation between chemical reactivity and
structure deformation will be studied from point of view of
pyramidalization angle.
Method
In this work, the Car-Parrinello molecular dynamics [14]
simulation package was used for structural relaxation
calculations. Ground-state electronic structures were
described according to density functional theory (DFT) within
a plane-wave pseudopotential framework [15].
We used a periodically repeated supercell approach and
sample the Brillonin Zone with a single k-point, and our
supercell was large enough to avoid spurious interaction
between periodic replicas of an oxygen atom. For atoms in
simulation, the electron-ion interaction was described by
Tronullier-Martins nonlocal norm-conserving
pseudopotentials. The generalized gradient corrected
exchange functional Becke-Lee-Yang-Par (BLYP) was
adopted, and the plane wave basis set had a kinetic energy
cutoff of 60 Ry.
In order to illustrate the interaction of atomic oxygen with
deformed SWCNT, a semiconducting (10, 0) single wall
carbon nanotube (SWCNT) with 140 atoms was modeled. A
oxygen atom is placed at a distance of 1.5A above the center
of a hexagon on each adsorption sites, as shown in Fig.1.
(a)
(b)
Fig. 1. Schematic for computational model: (a) axial tension; (b) bending
deformation.
. The uniaxial strains was obtained by axial tension [16,
17] which was applied by shifting the end atoms along the
axis by small steps, and then relaxing the model via the
conjugate-gradient method, while keeping each end
constrained as shown in Fig.1(a). The strains of 2.5%, 5%,
7.5%, 10%, 12.5%, and 15% were applied and computed
respectively with the same pseudopotentials and generalized
gradient corrected exchange function.
The bending angle of 30° is applied and six different
adsorption sites that denote different strains were considered.
To obtain relax structures under bending and calculate atomic
adsorption properties, the atoms of two rings at each ends
were fixed, as shown in Fig.1(b), and then relaxing the model
via the conjugate-gradient method. The binding energy of
atomic oxygen on different system was calculated as:
Eb =E (oxygen) + E (CNT) - E (oxygen + CNT)
where E (oxygen) was the energy of oxygen atom, E (CNT)
was the energy of isolated CNT system and E (oxygen +
CNT) was the energy of the whole system including the
adsorbed oxygen atom, all calculation of total energy at
certain strain used the same supercell and k-points. A positive
Eb corresponded to an adsorption process.
Results and Discussion
First we study the adsorption of atomic oxygen on a
pristine SWCNT, the results show that the atomic oxygen is
very reactive and adsorption takes place with no barrier to
form epoxide-like structure, as shown in Fig.2, the adsorption
energy is 2.12eV, the bond length of C-C and C-O are 1.573
Å and 1.465 Å respectively, and the oxygen atom
preferentially attacks “twisted C-C bonds” shown in Fig.2,
because they are of a larger curvature and more reactive. The
results are in agreement with previous study [10].
Fig. 2. The structure of epoxide-like product after adsorption of atomic
oxygen.
Next, the structure is considered under various uniaxial
strains, with the adsorption energy Eb and epoxide-like
structure parameters for the optimized structures listed in
Table 1. It is shown that the adsorption energy increases with
increasing uniaxial strain, the C-C bonds elongate and are apt
to break with the adsorption of oxygen atom, and the change
of C-O distance has a general trend towards more stable
equilibrium under larger strains. All these changes of
adsorption energy and CNT structure parameters indicate that
the uniaxial strains enhance the reactivity of CNT surface to
adsorb oxygen atom, an approximate linear relation between
strain and adsorption energy can be obtained form the
calculation, as plotted in Fig. 3.
（1）
Fig. 3. The variation of Eb and θP against strain.
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Table 1. The calculated adsorption energy Eb and optimized epoxide-like
structure parameters
Strain Eb (eV) C-C (Å) C-O (Å) θP (°) Parallel C-C (Å) Twisted C-C
(Å)
0.000 2.12 1.573 1.465 5.11 1.434 1.422
0.025 2.25 1.666 1.442 5.36 1.456 1.435
0.050 2.55 2.101 1.398 5.59 1.485 1.440
0.075 2.76 2.112 1.399 5.75 1.518 1.442
0.100 3.03 2.174 1.403 5.91 1.566 1.443
0.125 3.29 2.179 1.405 6.11 1.642 1.444
0.150 3.57 2.185 1.408 6.29 1.676 1.445

From our simulation results we can see that there is close

relation between surface reactivity and CNT structure, any
effects that alter the structure may induce change of surface
reactivity. So we can explain the effect of uniaxial strain on
surface reactivity of CNTs from point of view of structure
deformation. It is known that a carbon nanotube is made by
rolling up a graphene sheet into a cylinder [1], and the strains
produced by the curved surface induces σ-л hybridization.
An addition reaction can take place with carbon atoms
transformed from sp2 to sp3 hybridization. The reactivity is
correlated with the extent of this hybridization transformation
denoted by pyramidalization angle θP [11], as shown in Fig. 4.
For θP=0°, there is the sp2 hybridization as a flat graphene
which exhibits lower surface reactivity [5], and for θP=19.5°,
there is the sp3 hybridization as CH4. The θP value for carbon
atom on a carbon nanotube falls between these two values,
and both the curvature and the reactivity increase with the θP
value [18]. For the (n, 0) tubes in our calculation, the
pyramidalization angle θP can be calculated by the formula:
Fig. 4. Schematics for the θP angle.
In previous report [20], an approximate linear relation
between adsorption energy and pyramidalization angle has
been fitted by calculating various pristine carbon nanotubes of
different diameter to illustrate the crucial effect of
pyramidalization angle on surface reactivity of pristine CNT.
However, in our study, an approximate linear relation
between adsorption energy and pyramidalization angle can
only be obtained in strains that are below 10%, as the strain
increases, the pyramidalization angle alters little but the
adsorption energy alters a lot, as plotted in Fig. 5. It is clear
that the pyramidalization angle is not the only factor affects
the surface reactivity of CNT.

⎡ x1 ⎤ ⎡ −1⎤
⎢y ⎥ = ⎢ 0 ⎥ (2)
⎢ 1⎥ ⎢ ⎥
⎢⎣ z1 ⎥⎦ ⎢⎣ 0 ⎥⎦

⎡ x2 ⎤ ⎡ − cos θ12 ⎤
⎢ y ⎥ = ⎢ sin θ ⎥ (3)
⎢ 2⎥ ⎢ 12 ⎥

⎢⎣ z2 ⎥⎦ ⎢⎣ 0 ⎥⎦
Fig. 5. The Eb plotted versus θP.

⎡ ⎤ It has been reported that it costs less energy to change

⎢ ⎥ bond angle than bond length of CNT under small
⎢ − cos θ 31 ⎥ deformation, as evidenced from MD simulation [21] and
⎡ x3 ⎤ ⎢ ⎥ finite element method [22]. Therefore, the CNT structure is
⎢y ⎥ = ⎢ cos θ 23 − cos θ12 cos θ 31 ⎥
(4) apt to deform by changing bond angle shown in Fig. 4 rather
⎢ 3⎥ ⎢ sin θ12 ⎥
⎢⎣ z3 ⎥⎦ ⎢ ⎥ than bond length under low strains, and the uniaxial strain
⎢ 2 ⎥ makes the diameter that determines pyramidalization angle of
⎢ 1 − cos 2 θ − ⎡ cos θ 23 − cos θ12 cos θ 31 ⎤ ⎥ the CNT structure decrease with increasing of uniaxial strain,
⎢ ⎢ ⎥ ⎥
sin θ12
31
⎣ ⎣ ⎦ ⎦ nevertheless hexagon structure of CNT under strains is close
to that of pristine CNT for little change of bond length. So the
and approximate linear relation between adsorption energy and
pyramidalization angle is obtained in low uniaxial strains as
cos (θ p + 90o ) =
plotted in Fig. 5, and pyramidalization angle plays a crucial
x1 y2 z3 (5) role in surface reactivity of CNT in which the hexagon
structure is close to that of pristine CNT. Furthermore, there
( y 2 z3 ) + ⎡⎣ z3 ( x2 − x1 ) ⎤⎦ + [ y3 ( x2 − x1 ) − y2 ( x3 − x1 )]
2 2 2
is an approximate linear relation between strain and
as reported by Haddon [19]. The results of pyramidalization angle in low strains as plotted in Fig. 3.
pyramidalization angle θP at different adsorption sites are
shown in Table 1.

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 On the other hand, with the increase of strain, elongation
of “parallel C-C bond” will be more obvious，as shown in
Table 1, and the CNT structure is not approximate hexagon
structure as pristine CNT, the results are in agreement with
the theoretical study on structural mechanics of zigzag carbon
nanotubes [22].. It is clear that elongation of “parallel C-C
bonds” shown in Table 1 will change the electron structure
greatly under larger strains, and the electron structure has
been reported as an important factor affects surface reactivity
[20]. In this case, the hybridization is complex and can not be
denoted by pyramidalization angle, and the elongation of C-C
bonds induces high surface potential energy that increase the
surface reactivity of CNT. That is why we can also obtain
approximate linear relation between strain and adsorption
energy in high strains.
At last, the structure was considered under bending angle
of 30°, with the adsorption energy Eb at each site for the
optimized structures listed in Table 2. The structure of an
epoxide-like product after adsorption of atomic oxygen is
shown in Fig. 6. It is shown that the application of bending
angle to a carbon nanotube produces bond elongation or
shortening at different location, and the adsorption energy at
each site is different. The adsorption energy levels at site_1,
site_2 and site_3 which are under tension strains are larger
than those on a pristine SWCNT, while the adsorption energy
levels at site_4, site_5 and site_6 which are under
compression strain is smaller than those on a pristine
SWCNT.
Table 2. The calculated adsorption energy Eb and pyramddalization angle θP
Sites Eb (eV) θP (°)
1 3.59 5.6141
2 3.51 5.5294
3 2.65 5.2780
4 2.09 5.0307
5 1.89 4.8861
6 1.81 4.8023
Fig. 6. The structure of epoxide-like product after adsorption of atomic
oxygen.
The bending deformation of SWCNT which can be
illustrated as classic elastic beam by generalized Hooke’s law
and elastic models theory produces different strains on the
surface of SWCNT, for sites 1-3, the tension strains induce
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larger pyramidalization angles than pristine SWCNT, the
pyramidalization angle increases with the strain increasing, as
a result, the site 1 has the largest pyramidalization angle. In
contrast, for sites 4-6, the compression strain induces smaller
pyramidalization angles, and the pyramidalization angle
decreases with the compression strain increasing, so that the
site_6 has the smallest pyramidalization angle. Since the
pyramidalization angle is directly related to the reactivity, it
indicates that the six sites in our study has different surface
reactivity, and the oxygen atom will be tend to be adsorbed on
site_1 which has the highest surface reactivity. Therefore, the
bending deformation of CNT offers a method to control the
pattern of adsorption.
Conclusions
In our study, the effort of mechanical deformation on
adsorption of oxygen atom on CNTs is demonstrated by
linking the chemical reactivity and structural deformation.
The results indicate that CNT surface is very reactive and
oxygen atom adsorption takes place without barrier to form
epoxide-like structures, for a certain type of CNT, its
reactivity is mostly determined by its pyramidalization angle
of carbon atom. Although we have considered only a limited
set of structures with axial tension and bending angle, our
calculations show that the surface reactivity of CNT can be
tuned by structural deformation which produce different
strains on the surface of CNTs that induce different
pyramidalization angle at various adsorption sites, and an
approximate linear relation between adsorption energy and
pyramidalization angle has been obtained form our
calculation.
Therefore, the effect should be fully considered in the
application of CNTs. We can tune the surface reactivity of
CNT by mechanical method, which can be determined by
macroscopic variables of force or pressure; for another thing,
the method offers site selectivity, as the adsorption is
facilitated on the sites with higher pyramidalization angle. On
the other hand, when the CNTs are used as interconnections
material, the effect should be avoided to reduce the reactivity
that may induce molecules adsorption. It suggests that the
application of the mechanical deformation will be a promising
method to control the functionalization of CNTs by using
foreign atoms and molecules.
Acknowledgments
This work is supported by National High Technology
Research Program (863) of China (No. 2007AA04Z348).
References
1. Iijima, S., “Helical of Graphitic Carbon”, Nature, Vol.
354, (1991), pp. 56–58.
2. Sun, YP., Fu, KF., Lin, Y., Huang, WJ.. “Functionalized
Carbon Nanotubes Properties and Applications”, Acc
Chem Res., Vol. 35, No. 12 (2002), pp. 1096-104.
3. Burghard, M., “Electric and Vibrational Properties of
Chemically Modified Single Walled Carbon Nanotubes”,
Surf. Sci. Rep., Vol. 58, No. 1 (2005) , pp. 1-109.
4. Noejung, P., Suklyun. H., “Electronic Structure
Calculations of Metal-nanotube Contacts with or without
 Oxygen Adsorption”, PHYSICAL REVIEW B, Vol. 72, 21. Jian, W., Feng, L., et al., “Computational Design of
(2005), pp. 045408-1-5. Carbon Nanotube Electromechanical Pressure Sensors”,
5. Philip, G., et al., “Extreme Oxygen Sensitivity of PHYSICAL REVIEW B, Vol. 69, (2004), pp. 153406-1-5.
`Electronic Properties of Carbon Nanotubes”, Science, 22. Najib, A., Kasti, “Zigzag Carbon Nanotubes—
Vol. 287, (2000), pp. 1801-1804. Molecular/structural Mechanics and the Finite Element
6. Giannozzi, P., Car, R., Scoles, G., “Oxygen Adsorption on Method”, International Journal of Solids and Structures,
Graphite and Nanotubes”, J. Chem. Phys., Vol. 118, Vol. 44, (2007), pp. 6914–6929.
(2003), pp. 1003-1006.
7. Ulbricht, H., Moos, G., Hertel, T., “Physisorption of
molecular oxygen on single-wall carbon nanotube bundles
and graphite”, Phys. Rev. B, Vol. 66, (2002), pp. 075404-
1-7.
8. Liu, H. J., Chan C. T., “Density Functional Study of
Oxygen Adsorption on 4-Å Carbon Nanotubes”, Phys.
Rev. B, Vol. 72, (2005), pp. 075437-1-6.
9. Liu, H. J., Zhai, J, P., Chan, C. T., Tang, Z. K.,
“Adsorption of O2 n a (4, 2) Carbon Nanotube”,
Nanotechnology, Vol. 18, No. 6 (2007), pp. 065704-1-5.
10. Margulis, Vl. A., Muryumin, E. E., “Atomic Oxygen
Chemisorption on the Sidewall of Zigzag Single-Walled
Carbon Nanotubes”, PHYSICAL REVIEW B, Vol. 75,
(2007), pp. 035429-1-12.
11. Da Silva, L. B., Fagan, S.B., Mota, R., “Ab Initio Study of
Deformed Carbon Nanotube Sensors for Carbon
Monoxide Molecules”, Nano Lett, Vol. 4, No. 1 (2004),
pp. 65-67.
12. Park, S., Srivastava, D., Cho, K., “Generalized Chemical
Reactivity of Curved Surfaces: Carbon Nanotubes”, Nano
Lett, Vol. 3, No. 9 (2003), pp. 1273-1277.
13. Gulseren, O., Yildirim, T,, Ciraci, S,, “Tunable
Adsorption on Carbon Nanotubes”, Phys Rev Lett., Vol.
87, (2001), pp. 116802-1-4.
14. Car, R., Parrinello, M., “Unified Approach for Molecular
Dynamics and Density-Functional Theory”, Phys. Rev.
Lett., Vol. 55, (1985), pp. 2471-2474.
15. Kühne, T. D., Krack, M., Mohamed, F. R., Parrinello, M.,
“Efficient and Accurate Car-Parrinello-like Approach to
Born-Oppenheimer Molecular Dynamics”, Phys Rev Lett.,
Vol. 98, No. 6 (2007), pp. 066401-1-5.
16. Buongiorno, N. M., Yakobson, B. I., Bernholc, J.,
“Mechanism of Strain Release in Carbon Nanotubes”,
Phys. Rev. B, Vol. 57, (1998), pp. 4277 -4280.
17. Takanori, I., Kazume, N., “First Principles Calculations
for Electronic Band Structure of Single-Walled Carbon
Nanotube under Uniaxial Strain”, Surface Science, Vol.
514, No. 3 (2002), pp. 222-226.
18. Niyogi, S., Hamon, M. A., Hu, H. et al., “Chemistry of
Single- Walled Carbon Nanotubes”, Acc. Chem. Res., Vol.
35, No. 12, (2002), pp. 1105-1113
19. Haddon, R. C., “Comment on the Relationship of the
Pyramidalization Angle at a Conjugated Carbon Atom to
the Sigma Bond Angles”, J Phys Chem A, Vol. 105,
(2001), pp. 4164-4165.
20. Zhang, Y. F., Liu, Z. F., “Oxidation of Zigzag Carbon
Nanotubes by Singlet O2: Dependence on the Tube
Diameter and the Electronic Structure”. J Phys Chem B,
Vol. 108, (2004), pp. 11435-11441.

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