Eur. Phys. J. Appl. Phys.

(2016) 74: 24605

DOI: 10.1051/epjap/2015150329
THE EUROPEAN
PHYSICAL JOURNAL
APPLIED PHYSICS
Regular Article

Mechanical coupled vibrations in an individual double-walled

carbon nanotube
Mourad Boutahir, Abdelhai Rahmani, Hassan Chadli, and Abdelali Rahmania
Laboratoire d’Etude des Matériaux Avancés et Applications (LEM2A), Université Moulay Ismail, FSM-FLSH-FPE, BP 11201,
Zitoune, 50000 Meknes, Morocco

Received: 29 June 2015 / Received in final form: 16 October 2015 / Accepted: 19 October 2015
Published online: 3 May 2016 – 
c EDP Sciences 2016

Abstract. In this paper we calculate the Raman spectra of different double-walled carbon nanotubes
(DWCNTs) by using the spectral moments method. Using a convenient Lennard-Jones expression of the
van der Waals intermolecular interaction between the inner and outer tubes, the optimized structures of
DWCNT are derived. We found that the C-C bond length in DWCNT is depending on the metallic (M)
or semiconducting (Sc) character of the inner and outer nanotubes. We show that the radial breathing-like
modes (RBLM) of DWCNT are characterized by concerted inner and outer wall motions. Comparison with
Raman spectra measurements is given.

1 Introduction RBLMs with respect to the radial breathing-mode (RBM)

of the corresponding SWCNT was calculated, (ii) for outer
Carbon nanotubes (CNTs) [1] can be classified into single- tube diameter larger than 2 nm, the RBLMs are collective
walled carbon nanotubes (SWCNTs) and multi-walled breathing vibrations of both layers.
carbon nanotubes (MWCNTs). Double-walled carbon In a previous papers, using the spectra moment’s
nanotubes (DWCNTs) are a limiting case between the method (SMM) [8,9], in the framework of the bond-
SWCNTs and MWCNTs, and are very important from polarization theory, one has calculated the polarized
both theoretical and experimental viewpoints [2]. Raman spectra for different DWCNTs of different sizes
DWCNTs provide the simplest systems for studying the upon their diameter, chirality and length. The dependence
interactions between layers. The structure of DWCNT of the Raman spectrum, upon these parameters, was
can be considered as consisting of two coaxial SWCNTs, clearly observed [8]. In other works using the combination
and fully defined by chiral indices (no , mo )@(ni , mi ) of of high resolution transmission microscopy (HRTEM),
the coaxial outer-/inner-wall [3–5]. Compared to single- electron diffraction (ED) and resonant Raman spectros-
walled carbon nanotubes, DWCNTs have higher mechan- copy (RRS) on DWCNTs, the effect of coupling between
ical strength and thermal stability and they also possess semiconducting (Sc) and/or metallic (M) nanotubes on
interesting electronic and optical properties [6]. the phonons was investigated [10].
In the low frequency range of the Raman spectrum In this work, we focus our study on the Sc@Sc and
of DWCNT, the RBLMs are dominant [7]. The mechan- M@Sc configurations. We investigate quantum coupled
ical coupling depends on the interlayer distance and the RBM oscillation in chirality-defined on Sc@Sc and M@Sc
tube diameters. Recently, it was experimentally found that DWCNTs by simultaneously determining structural, elec-
for an interlayer distance larger than 0.4 nm, interaction tronic and vibrational properties. We consider here the
between layers is weak independently of tube diameter [7]. low-frequency range of the Raman spectrum, where the
Theoretically, two coupling regimes are predicted as a breathing modes are detected, and the calculations have
function of the tube diameter [7]: (i) for outer tube diam- been performed in the framework of the bond-polarization
eters smaller than 2 nm, the vibrations of the inner and theory using the spectral moment’s method (SMM)
the outer tubes are independent. In this weak coupling [11,12].
regime, an upshift of the in-phase and the counterphase
a
e-mail: a.rahmani@fs-umi.ac.ma

Contribution to the topical issue “Materials for Energy
2 Models and computational method
Harvesting, Conversion and Storage (ICOME 2015) – Elected
submissions”, edited by Jean-Michel Nunzi, Rachid Bennacer In the DWCNTs, the inner and outer tubes are assumed to
and Mohammed El Ganaoui be at a distance d close to 0.34 ± 0.01 nm, and the relation

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 The European Physical Journal Applied Physics

between diameters of the inner (Dinner ) and outer (Douter ) number of carbon in the sample under consideration.
tubes is: In our calculations, the common axis of the two tubes
Douter = Dinner + 2d. (1) is along the Z axis.
The diameter of a (n, m) SWCNT is given by:
3 Results and discussion
D = a0 [3(m2 + mn + n2 )]1/2 /π, (2)
First, to compare our calculations to DWNT samples
with a0 = 0.142 nm (C-C length). synthetized by Wang et al. [16], we have generated DWNT
Among all the models used to describe the phonon structures by considering bond length C-C variations
bands, the force constants model (FCM) has the low- under van der Waals interactions. The optimized struc-
est computation time requirements. In this model, the tures are obtained for interatomic bond length between
dynamic of the systems is described by a few force springs 0.139 and 0.1420 nm for the outer (resp. inner) tubes and
connecting an atom to its surroundings up to given num- between 0.1422 and 0.1424 nm for inner (resp. outer) tubes
bers of neighbors. Despite its simplicity, this model can in the Sc@Sc (resp. M@Sc) configuration. A contraction
provide accurate and robust method to investigate (dilatation) of the outer tube and a dilatation (contrac-
dynamics and thermal properties of crystals and in par- tion) of the inner tube are obtained for the Sc@Sc (M@Sc)
ticular carbon nanotubes [13]. DWCNT configuration.
In the present study, the intratube interactions are In order to reproduce the experimental positions of the
restricted only to the first-, second-, third- and fourth- RBLM measured by Wang et al. [16], the first-nearest-
nearest neighbors and the C-C interactions in SWCNT neighbor radial force constant (φr ) of the Saito et al.
are described by the force constants model introduced by model is slightly modified (±10%). To compare our results
Saito et al. [13]. The values of the force constants used in with respect to the experimental data, we present in the
this model are given in Table 1. Table 2 the RBLMs of relaxed (expansion or contraction of
A Lennard-Jones potential: the tubes) and un-relaxed DWCNTs. One can see that the
   frequency values of the RBLMs obtained for relaxed struc-
σ 12  σ 6 tures are in agreement with the experimental values [16].
ULJ (r) = 4ε − , (3) We found that the structure and the RBLMs positions are
r r
controlled by the electronic properties of DWCNTs.
is used to describe the van der Waals intertube interac- We present in Figure 1, the Raman spectra of two
tions between the inner and outer tubes, with parameters Sc@Sc DWCNTs ((16,14)@(12,8) and (27,5)@(18,5))
 = 2.964 meV and σ = 0.3407 nm. with diameters close to those of Wang et al. synthe-
In our calculations, inner and outer super-cells of more sized samples. One observes two strong components at
than 10 000 atoms are considered and the electronic 128 cm−1 and 192 cm−1 (resp. 108 cm−1 and 158 cm−1 )
exchange effects between relaxed tubes are represented by for (16,14)@(12,8) (resp. (27,5)@(18,5)) DWCNT. The fre-
van der Waals mechanical interactions. We suppose that quency of the counterphase RBLM calculated for the
inter-tube electronic coupling is negligible between the (16,14)@(12,8) DWCNT, located at 192 cm−1 , can be
incommensurate inner- and outer-wall carbon nanotubes compared to that of the RBM calculated at 164 cm−1
because coupling at different carbon atom sites oscillate for the (12,8) SWCNT. The RBM frequency of the (12,8)
with random phases and could cancel each other [15]. SWCNT upshifted by about 28 cm−1 with respect to the
We calculated the Raman spectra of DWCNTs using counterphase RBLM of the DWCNT. The in-phase RBLM
the SMM (for more detail see Ref. [11]). Raman inten- calculated at 128 cm−1 downshifted of about 18 cm−1 with
sity of each vibrational mode is calculated in the frame- respect to the RBM frequency 110 cm−1 of the (16,14)
work of non-resonant bond-polarizability model [14]. The SWCNT. The calculated upshifts are in agreement with
frequencies of Raman-active modes are derived from the the experimental values for these systems.
position of the peaks in the calculated Raman spectra. Next, we consider the second configuration where the
The Raman intensity is normalized with respect to the outer nanotube is metallic and the inner one is semicon-
ductor. In Figure 2, we present the Raman spectra of
(31,4)@(15,13) and (40,1)@(22,14) M@Sc DWCNTs. For
example, for (31,4)@(15,13) DWCNT, two strong compo-
Table 1. Force constant parameters for SWCNT in units nents are observed at 97 cm−1 and 142 cm−1 . We found
of N/m. Here the subscripts φr , φi , and φo refer to radial, an upshift by 28 cm−1 (18 cm−1 ) of couterphase (in phase)
transverse in plane, and transverse out of plane, respec- with respect to the RBM frequency of the isolated
tively [13]. SWCNTs.
Raman spectra of DWCNTs, for Sc@Sc and M@Sc
N φr φti φto
configurations, show many coupling modes originate from
1 365.0 245.0 98.2
interactions between inner and outer nanotubes. The pro-
2 88.0 −32.3 −4.0
files of the RBLM bands associated to inner and outer
3 30.0 −52.5 1.5
4 −19.2 22.9 −5.8
tubes are depending on their metallic or semiconducting
character.

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 M. Boutahir et al.: Mechanical coupled vibrations in an individual double-walled carbon nanotube

Table 2. Comparison the radial-breathing modes for double-walled carbon nanotubes calculated in this paper with those
obtained with a0 = 0.142 nm (any change in the structure of the tubes).

Our work Experimental results [16] Results with a0 = 0.142 nm

−1 −1 −1 −1
Systems ωLF (cm ) ωHF (cm ) ωLF (cm ) ωHF (cm ) ωLF (cm−1 ) ωHF (cm−1 )
(27,5)@(18,5) 108 158 108 154 107 160
(23,13)@(14,12) 103 144 103 143 100 147
(19,15)@(19,3) 110 158 110 156 108 162
(20,19)@(24,1) 93 129 93 129 92 132
(24,7)@(13,9) 116 168 123 169 112 166
(16,14)@(12,8) 128 192 133 186 116 194
(27,6)@(15,10) 105 163 105 155 103 165
(27,12)@(20,9) 93 138 93 133 91 145
(26,17)@(27,2) 83 114 84 114 85 118
(32,11)@(23,10) 82 113 83 112 80 116
(31,4)@(15,13) 97 142 98 137 96 143
(40,1)@(22,14) 79 117 79 115 78 118

tubes. A contraction (expansion) of the outer tube and an

ωL = 108 expansion (contraction) of the inner tube are obtained for
Raman Intensity (unit,arb)

the Sc@Sc DWCNT (M@Sc DWCNT) configuration. Our

results are compared to the experimental data.
90 115
130 ωH = 158
(27,5)@(18,5) * *
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