Article

pubs.acs.org/JPCC

Linear Carbon Chains under High-Pressure Conditions

N. F. Andrade,† A. L. Aguiar,‡ Y. A. Kim,¶ M. Endo,§ P. T. C. Freire,† G. Brunetto,∥ D. S. Galvaõ ,∥
M. S. Dresselhaus,⊥ and A. G. Souza Filho*,†
†
Departamento de Física, Universidade Federal do Ceará, 60455-900 Fortaleza, Ceará, Brazil
‡
Departamento de Física, Universidade Federal do Piauí, 64049-550 Teresina, Piauí, Brazil
¶
School of Polymer Science and Engineering, Chonnam National University, 77 Yongbong-ro, Buk-gu, Gwangju 500-757, Korea
§
Faculty of Engineering, Shinshu University, 4-17-1 Wakasato, Nagano-shi 380-8553, Japan
∥
Instituto de Física Gleb Wataghin, Universidade Estadual de Campinas, 13083-859 Campinas, Sao Paulo, Brazil
⊥
Departments of Physics and Electrical Engineering & Computer Science, Massachusetts Institute of Technology, Cambridge,
Massachusetts 02139, United States

ABSTRACT: A high-pressure resonance Raman spectroscopy study of linear carbon chains encapsulated inside multiwalled
carbon nanotubes (MWCNTs) is reported. While the frequencies of the tangential modes of carbon nanotubes (G band) harden
as the pressure increases, the vibrational frequencies of the chain modes (around 1850 cm−1) decrease, thus indicating a softening
of the carbon−carbon bonds in this 1D solid. Pressure-induced irreversible structural changes in the linear carbon chains are
unveiled by the red shift in the vibrational modes when pressure is released. These results have been interpreted as being due to a
coalescence of carbon chains, and this hypothesis is supported by state-of-the-art atomistic reactive molecular dynamics
simulations.

■ INTRODUCTION
The study of linear carbon chains originated from interstellar
space research, and this early work is closely related to carbon
nanoscience because these early investigations by Kroto
historically led to the discovery of fullerenes.1 The discovery
of these fullerene carbon cages inspired conjectures about the
possible existence of tubular carbon structures,2 which were
proven true by the report of multiwall carbon nanotubes
(MWCNTs) by Iijima in 1991.3 Single-walled carbon nano-
tubes (SWCNTs) became known independently in 1993 after
Iijima and Ichihashi4 and Bethune et al.5 attempted to produce
MWCNTs filled with transition metals. Some years later, Smith
et al. found that the core of SWCNTs could host fullerenes,
thus leading to the discovery of the new hybrid carbon
structure called peapods. 6 Due to their capability of
encapsulating different species, the hollow cores of carbon
nanotubes (CNTs) have been used as templates for confining
different nanowires and molecule arrays within nanotube
cores.7,8 In this scenario, the inner space of CNTs is found
to be ideal for encapsulating and stabilizing 1D solids, such as
long linear carbon chains, which are not stable under ambient
conditions.9−14 We should mention that small-length carbon
chains have been investigated from both the experimental and
the theoretical points of view, including looking at different
phenomena and properties (electronic states, vibrational
modes, transport properties, and mechanical properties) and
proposing alternatives for designing and measuring a variety of
chain-based systems such as carbon chains terminated with Pt
atoms15 and with different aromatic end groups,16,17 bridging
graphene domains,18 and N-doped carbon chains.19 All these
studies pointed out relevant properties for these chains that are
very promising for nanoelectronics and spintronic devices.
MWCNTs are the category of carbon nanotubes with the
greatest potential for technological applications, such as energy
storage, electronic devices, and nanocomposites, among others,
due to their remarkable mechanical, thermal, and electrical
Received: January 28, 2015
Revised: April 10, 2015
Published: April 23, 2015

© 2015 American Chemical Society 10669 DOI: 10.1021/acs.jpcc.5b00902

J. Phys. Chem. C 2015, 119, 10669−10676
The Journal of Physical Chemistry C
properties.20 In this context, MWCNTs filled with carbon linear
chains (Cn@MWCNTs) are very attractive for searching for
new properties and for designing some novel applications. It is
hoped that under appropriate conditions, such hybrid
nanostructures as Cn@MWCNTs could have Young’s
modulus, strength, and toughness properties superior to those
of the carbon fibers, graphite whiskers, and bare MWCNTs,
which would make this system very appealing to materials
scientists.9
Many techniques have been used for characterizing carbon
nanostructures, and among optical spectroscopies, Raman
scattering has been very powerful for simultaneously studying
both the vibrational and the electronic properties of these
nanomaterials. In addition, the use of this technique can go
beyond studying the normal conditions of temperature and
pressure, being appropriate for studying nanocarbons under
extreme conditions such as high pressure and high temperature.
Pioneering work by Venkatesvaran21 in the late 90s showed
that high-pressure Raman studies could provide insights into
the properties of carbon nanotubes themselves, and since then,
many works using this technique have been published for
different nanotube samples (pristine and doped forms) such as
SWCNTs, DWCNTs, and MWCNTs.22−34
The study of carbon chains by experimental means is difficult
due to the fact that the chains are unstable under ambient
conditions because the unsaturated bonds are highly reactive,35
and once they are placed and stabilized in the core of a
MWCNTs, it is not easy to directly access them. In this
scenario, the use of the high-pressure Raman technique appears
as a suitable method for probing the carbon chains for three
main reasons: (i) the Raman signal of carbon chains is very
intense, (ii) high pressure is effective for tuning the degree of
interaction between the carbon chains and its adjacent carbon
nanotube wall, and (iii) the vibrational frequencies of the
carbon chains are sensitive to any structural changes that the
chain may experience.
The aim of this study is to investigate the behavior of 1D
linear carbon chains encapsulated into the innermost shells of
MWCNTs by evaluating their structural stability at high
pressure values using experimental and theoretical tools. The
Raman band close to 1800 cm−1, which is characteristic of the
1D carbon chain, has been used in the present work as a probe
for tracking the pressure-induced structural changes of this
system. We report here a softening of the C−C stretch mode of
the carbon chain as the pressure increases, and the results for
the subsequent decompression show that the carbon chains
experiences a pressure-induced irreversible process. This result
has been interpreted as being a pressure-induced coalescence
between the different carbon chains inside the carbon
nanotubes, which is supported by fully atomistic reactive
molecular dynamics simulations.
■
METHODOLOGIES
Sample Preparation. Linear carbon chains encapsulated
within the hollow core of multiwalled carbon nanotubes
(MWCNTs) were synthesized by the atmospheric arc discharge
method, as described in ref 36. A hollow graphite anode (outer
diameter of 10 mm, inner diameter of 4 mm) was moved with a
speed of 170 mm/min, and a rod-type carbon cathode
(diameter of 35 mm) with a high specific resistivity above
4000 mΩ·cm was rotated with a rate of 155 rpm. The cathode
and anode were made of pure graphite with a purity of 99.99%.
Then, by precisely controlling the gap between the electrodes
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(∼1 mm), applying a constant current of 10 A (voltage of 20
V), and using argon gas at a flow rate of 1 L/min along the
hollow tube of the graphite cathode, we obtained a gray tape
spiraling on the outer surface of the cathode (width of 3−5
mm, thickness of ∼175 mm). Finally, cooling gas was used to
detach the deposited thin tape from the cathode.
Experimental Techniques. We measured the Raman
spectra of the samples using different laser excitation energies
(2.54, 2.33, and 1.57 eV) at ambient pressure, aiming to find
the most sensitive resonant laser energy to probe pressure-
induced changes in the linear chains. Several Raman spectra
were collected at random points over the sample, and we
attempted to verify the homogeneity of the sample regarding
the observation of the vibrational modes associated with the
carbon chains. A LabRam HR Jobin Yvon spectrometer was
used for measuring the Raman spectra. This system contains a
microscope with an objective lens containing a plan chromatic
focal length of 20 mm and a numerical aperture (N.A.) of 0.35.
In the high-pressure experiments, we used a diamond anvil
cell (DAC) in the 0−10 GPa pressure range. The gasket used
for mounting the sample chamber consists of a metal alloy foil
with a thickness of 200 μm. The sample chamber is a drilled
hole with a diameter of about 300 μm. The cell was loaded with
a tiny piece of sample and a ruby pressure sensor and then filled
with the pressure-transmitting fluid. We used Nujol mineral oil
as the pressure transmitting medium because this oil does not
react with the sample, and it maintains the hydrostatic behavior
over the entire pressure range investigated in this experiment.
To determine the pressure P within the cell, we used the
ruby luminescence technique, which is based on the fact that
the frequency of the two emission lines of ruby vary linearly as a
function of the hydrostatic pressure P (given here in units of
GPa), by using the expression
ωRi − ωR0i
P=
7.535 (1)
where ωRi is the wavenumber for any of the ruby’s two
luminescent lines (units of cm−1 relative to the laser line) and
ω0Ri is the relative wavenumber of the respective line at ambient
pressure.
Theoretical Methods. To investigate the structural
behavior of linear carbon chains inside a carbon nanotube
when the system is subjected to high external pressure values,
we created a model system that mimics the main features of the
experiments. The interactions in this model system are
described using a reactive force field (ReaxFF) based on the
bond energy−bond order (BEBO) method.37 The ReaxFF is
designed to incorporate chemical reactions so that bond
formation and bond breaking can be properly described.
During chemical reactions, the bonded neighbors and the
geometry both change and, consequently, the charge
distribution also changes.38 ReaxFF is parametrized against
DFT calculations and it is, in principle, able to describe the
change in the coordination number in the carbon atoms.39 The
methodology was employed successfully previously in different
cases, and the results obtained are in good agreement with
more accurate calculations and experimental evidence.40,41
ReaxFF uses the electronegativity equalization method
(EEM)42 to assign partial point charges to every atom.
Interatomic distances, computed as a sum of σ, π, and ππ
terms (eq 2), are used to calculate the bond order
contributions. The system energy is computed by a sum of
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different contribution terms (eq 3) 37 in which Ebond is the bond
energy, Eover and Eunder are, respectively, the over- and
undercoordination energy, Eval is the angle-dependent strain
energy, Epen is the energy penalty paid for introducing allene-
type molecules into the chains, Etors is the torsion energy, Econj
is the torsion conjugation energy, EvdW is the van der Waals
interaction energy, and ECoul is the Coulomb interaction
energy:
BOij = BOijσ + BOijπ + BOijππ
⎡ ⎛ rij ⎞ pbo2 ⎤ ⎡ ⎛ rij ⎞ pbo4 ⎤
= exp⎢pbo1 ⎜ σ ⎟ ⎥ + exp⎢pbo3 ⎜ π ⎟ ⎥
⎢⎣ ⎝ r0 ⎠ ⎥⎦ ⎢⎣ ⎝ r0 ⎠ ⎥⎦
⎡ ⎛ rij ⎞ pbo6 ⎤
+ exp⎢pbo5 ⎜ ππ ⎟ ⎥
⎢⎣ ⎝ r0 ⎠ ⎥⎦ (2)
Esystem = E bond + Eover + Eunder + Eval + Epen + Etors
+ Econj + EvdW + ECoul (3)
The structural changes in the carbon chains due to the
external pressure increase were studied dynamically through
molecular dynamics (MD) simulations. We used the ReaxFF
model system as implemented in the Large-Scale Atomic/
Molecular Massively Parallel Simulator (LAMMPS) code.43,44
We used CNTs that are periodic along the tube axial direction
and pairs of carbon chains of different sizes (two chains with 19
atoms (19−19), one chain with 19 and the other with 20 atoms
(19−20), and two chains with 20 atoms each (20−20)). We
used a (5,5) CNT with a diameter d = 6.8 Å and length l = 73.6
Å. The tube diameter was chosen to fit the carbon chains inside
the tube and to reproduce a typical configuration obtained
experimentally when the carbon chain is inside a MWCNT.
The simulation box has dimensions of 32 × 32 × 73.6 Å3. In
the nonperiodic directions, the box edges are constrained to
deflect the atoms once the atoms are going to pass through the
edges of the box. The atoms are elastically scattered and have
no box wall in the periodic direction. Water molecules fill the
space between the outside of the CNT and the inside of the
box limits. A typical cross section view of the system is
presented in Figure 1, in which the linear carbon chains
(colored yellow) are in the middle, the CNT is colored gray
Figure 1. Carbon nanotube immersed in a water environment. A cross
section of the simulation box showing the linear carbon chain
(indicated in yellow) placed inside the (5,5) CNT (colored in gray)
and immersed in water (colored in red and blue).
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and red, and the water molecules are depicted as blue-colored
balls surrounding the nanotube.
To increase the external pressure experienced by the CNT,
we decreased the box dimensions x and y with a constant rate
of vwall = 2 × 10−5 Å/ps. The box dimension along the tube
axial direction (periodic dimension) was kept constant to keep
the tube length unchanged. The simulations were carried out
with a Nosé−Hoover thermostat coupled to both the water and
the CNT atoms with a target temperature of T = 300 K. The
time constant considered in the temperature relaxation was τ =
10 fs. In all simulations, we used Δt = 0.025 fs for the time step
size.
To calculate the vibrational density of states (VDOS) Φ(ω)
(eq 4) for the linear carbon chain, we use the relationship
⎡ 1 ∞ ⎤2
Φ(ω) = ⎢
⎣ 2 ∫−∞ dt eiωt Z(t )⎥⎦ (4)
The system was first thermalized during a time of 20 ps. After
the system reached thermal equilibrium, the thermostat was
removed and the system was placed in an adiabatic box, where
it was allowed to evolve during a time of 500 ps with a constant
energy (microcanonical or NVE ensemble where the system is
isolated and preserves its number of moles (N), volume (V),
and energy (E)) and where the atom velocities in the carbon
chain were recorded every 10−3 ps.
The function Z(t) in eq 4 is the autocorrelation of the
velocities recorded while the system evolves within a constant
energy (NVE) scheme and is described by
⟨v(0) ·v(t )⟩
Z (t ) =
⟨v(0) ·v(0)⟩ (5)
The vibrational density of states was calculated for carbon
chains with different lengths, ranging from 19 to 40 atoms.
■
RESULTS AND DISCUSSION
The Raman spectra of linear carbon chains encapsulated in the
innermost shell of MWCNTs are shown in Figure 2 using the
laser excitation energies 1.58, 1.96, 2.33, and 2.54 eV. All
measured points (more than 20 different spots) over the
sample using this laser energy showed the band at about 1850
cm−1 (labeled as Cn in Figure 2) associated with the carbon
chain. This Cn band always appears with the same line shape
Figure 2. Average Raman spectra at ambient pressure obtained at
different points of a sample showing linear carbon chains (Cn band)
inside carbon nanotubes excited with different laser energies. All of the
spectra are normalized to the peak intensity of the G band.
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for Elaser = 1.96 eV. The Cn mode from the chain is more
intense than the G band from the MWCNTs, thus indicating a
strong resonance process when the chain and MWCNTs are
excited with Elaser = 1.96 eV. The peaks characteristic of carbon
nanotubes (D and G bands) are also shown in Figure 2. In fact,
the band associated with the carbon chain is actually formed by
four peaks according to the line shape analysis (discussed in the
high-pressure experiments in the next paragraphs).
By using only Raman spectroscopy, it is not possible to
address the geometry of the carbon chain confined in the
central hollow part of the nanotubes and the determination of
what length that particular carbon chain actually has. However,
some studies reported in the literature have attempted to
characterize similar systems by means of Raman spectroscopy.
Kurti et al.45 performed theoretical calculations of the Raman
spectra of molecules containing linear carbon chain segments to Figure 3. Observed Raman spectra measured with Elaser = 1.96 eV as a
model cumulene (···CCC···) and polyyne (···CC function of the pressure applied to linear carbon chains encapsulated
C···) structures. As a result, they predicted the presence of an in MWCNTs.
intense peak at about 2000 cm−1, which corresponds to the
stretching mode of the linear carbon chain. This result was
confirmed by the experimental data recorded in nanostructured
carbon films,46 which showed the presence of modes in this
frequency range by using the Elaser = 2.33 eV excitation and
observing contributions from different polyyne and cumulene
species. Our experimental data described here do not show
Raman modes around 2000 cm−1 for the 2.33 eV laser energy.
It is known that the polyyne configuration is less stable than
the cumulene, because the latter has a degenerate pair of half-
filled energy bands that experience a Peirels distortion.47,48
Also, the polyyne structure is unstable under ambient
conditions.49 However, when these structures are encapsulated
into a carbon nanotube core, these carbon chains become
considerably more stable, even when subjected to high
Figure 4. Comparison between the behavior of the G band of the
temperatures.13 This is due to the more favorable nanoscale sample under study and of the G band of a graphite sample when both
confinement provided by the carbon nanotube cage.12 The are subjected to high pressure. The data for graphite were taken from
observation of intense Raman modes at around 1850 cm−1 has ref 53.
been reported in the literature for linear chains (cumulene or
polyyne structures) encapsulated into carbon nanotubes.9,13,50
These modes were attributed to the vibrations of one- In the case of the band around 1850 cm−1 after the line shape
dimensional carbon chains. It is difficult to distinguish between analysis, it is possible to construct the frequency versus pressure
cumulene and polyyne structures on the basis of Raman spectra plots for the three peaks assigned to the chains during the
because the frequencies also depend on the chain lengths.45 compression (Figure 5).
We can observe in Figure 2 that the mean frequency of the In Figure 6 we show the behavior of the sample during the
vibrational bands from the carbon chains increases as the laser decompression processes at pressure values of 9, 6, 3, and 0
excitation energy increases. This upshift can be associated with GPa and outside the cell after decompression. We can clearly
shorter chains whose carbon−carbon bond strength (assuming see from Figure 6 that the sample exhibits a tendency to return
the same bonding type) is expected to be weaker than for to its original conformation, thus increasing the intensity of the
longer chain lengths. To understand the behavior of the chains G band and recovering the line shape of the band at about 1850
inside MWCNTs when they are subjected to pressure cm−1. Just one pressure cycle was run due to difficulties in the
variations, we show in Figure 3 the Raman spectrum obtained experiments. First, the metal piece used for placing the sample
for different pressure values. Because this mode was observed lost its elasticity and became plastic, which did not allow us to
along the entire sample, and its intensity was the highest at 1.96 run the hydrostatic pressure experiment again. Second, to run
eV for all tested lasers, we used this laser excitation energy for the experiment on the same sample, it is necessary to recover
studying the carbon chains under high-pressure conditions in the sample from the pressure cell after one pressure cycle and
which the limited sample volume leads to a low-intensity to prepare another sample for loading. This is difficult to do
Raman signal. We notice here that as the pressure increases, the because the sample is tiny and we have no guarantee that we
G band frequency value increases (hardens) whereas the band are going to measure in the new cycle the same part of the
at 1850 cm−1 downshifts (softens). sample that was previously measured. This point is important
The pressure dependence observed for the G band frequency because the sample is not homogeneous (as we discussed
is well documented in the literature for different sp2 carbon above).
structures.31,51,52 The pressure coefficients (∂ωG)/(∂P) re- However, by comparing the Raman spectra of the sample
ported for the multiwall carbon nanotubes measured here are before and after the high-pressure experiments, we can observe
almost the same as those obtained for graphite (see Figure 4).53 that the overall spectrum is not completely recovered, thus
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Figure 5. Frequency dependence of the Raman peaks around 1850
cm−1 with the pressure applied to the linear carbon chains inside the
MWCNTs. Solid (compression) and open (decompression) symbols
stand for data taken during the compression and decompression
processes, respectively. The dotted lines are intended to guide the eye.
Figure 6. Raman spectra measured with Elaser = 1.96 eV, recorded at 9,
6, 3, and 0 GPa and outside the cell before compression.
suggesting that the pressure cycle has induced some irreversible
changes, and also that the linear carbon chains have possibly
undergone some modification in their structure at high pressure
values. This assumption is based on the downshift (about 13
cm−1 for the highest intense peak of the chain) associated with
the chain band after the pressure loading in comparison to the
spectrum obtained before the pressure loading.
This shift in peak position may be associated with some
structural changes experienced by the linear chain resulting
from the pressure loading experiment. It is expected that longer
carbon chains will show a lower frequency in the vibrational
peaks as discussed above, and our hypothesis is that after the
pressure loading, the average length of the carbon chains has
increased. This is possibly due to a pressure-induced
coalescence of the individual chains forming longer individual
chains. In addition to this shift, we also observed that the profile
of the band is slightly different for samples exposed to high
pressure cycles, which confirms the structural changes in the
carbon chain. To validate our hypothesis and get further
insights into the pressure effects in the carbon chain structure,
we performed atomistic modeling using reactive molecular
dynamics simulations, which is discussed in the next section.
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■ ATOMISTIC MODELING
To understand the pressure-induced red shifts in the vibrational
bands of the chain after the pressure cycle, we ran atomistic
simulations. Because longer chains have lower frequencies, we
propose that the observed red shifts come from the coalescence
between two or more chains that are confined within the
nanotube core. This hypothesis was tested and validated by the
atomistic MD simulations. However, the observed changes
were not phase-transition-like because in the experiment we
have a distribution of chain lengths, and the coalescence can
occur over a range of pressure values. These aspects were taken
into account in the atomistic simulations considering two
chains of different lengths inside a single-walled nanotube. To
study the chain coalescence, we considered two carbon chains
within a given tube, each having even (20−20 atoms), odd
(19−19 atoms), and mixed (19−20 atoms) numbers of carbon
atoms confined inside an infinite tube with periodic boundary
conditions along the main tube axis. Figure 7a shows the two
Figure 7. Representation of the linear carbon chain (in yellow)
confined inside the carbon nanotubes. Some atoms belonging to the
tubes were made transparent to facilitate the visualization. (a) The red
double arrow indicates the chain separation before the increase of the
external pressure value. (b) Pressure induces the coalescence of the
two chains.
chains (colored in yellow) confined inside a (5,5) carbon
nanotube; some atoms were made transparent to facilitate the
visualization. The red arrow indicates that initially there was a
distance between the two chains (the distance between the C
ending atoms of adjacent chains shown by a red double arrow),
which are kept separated before the compression process starts.
Although the external pressure is increased, the reaction
between the two chains can be identified by an abrupt decrease
in the chain potential energy, as shown in Figure 8 at 60 ps.
The atomic structure of the new chain is shown in Figure 7b.
We observed that the coalescence of the two chain pairs
composed of 19−20 (red) atoms occurs at a much lower
pressure (0.6 GPa) in comparison to that of the 19−19 (green)
and 20−20 (blue) atom chain pairs (10.2 and 11.4 GPa,
respectively). Also, the energy variation for the chain pair
composed of 19−20 atoms is about 1.4 times larger than that
for the other chain pairs (19−19 and 20−20), thus leading to a
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Figure 8. Evolution of the chain potential energy during the
hydrostatic compression. Red, green, and blue curves show the chain
potential energy during the coalescence process for pair chain lengths
of 19−20, 19−19, and 20−20 atoms, respectively. The yellow filled
curve represents the system pressure evolution with time.
more stable configuration when the two chains are joined. The
coalescence procedure causes the chain energy to drop by
around 3.5 kcal/mol/atom (around 136 kcal/mol for the
considered chain lengths). The obtained value is in good
agreement with a previous value reported by Kertesz et al.35
and points out that the aggregation reaction is not reversible
under the investigated conditions. In the atomistic simulations
we did not observe any reaction between the chain and the tube
walls for pressure values up to 50 GPa.
Besides the energy drop (shown in Figure 8), the coalescence
between two adjacent chains can be identified by measuring the
distance between the two chains (the red double arrow in
Figure 7a). By measuring the distance between the terminating
atoms of the chains while the external hydrostatic pressure is
increased, we observed that the two chains executed a large
back and forth movement, as indicated in Figure 9. This implies
that the natural chain movement inside the CNT due to the
thermal energy is not enough to overcome the reaction barrier
to the coalescence between two chains. The back and forth
movements continuously exist until the external pressure value
is high enough and the conditions become favorable for the
reaction that joins the two chains to occur. The energy barrier
for merging the two linear chains is estimated to be around 40
kcal/mol.35 This energy is provided to the chains by the
external pressure applied to the system. Once the reaction
occurs, the distance between the two former outermost carbon
atoms reaches a constant value of 1.2 Å, which is characteristic
of a CC bond. Larger chains have lower vibrational
frequency energies, which is consistent with the experimental
observations (Figure 6).
Before submitting the system to an external hydrostatic
pressure, the CNT is filled by chains of small length (around 10
atoms), on average. Calculating the vibrational spectra for a
carbon chain with a length of 9 atoms, we observed an intense
peak around 1870 cm−1 (Figure 10). The applied external
pressure induces the coalescence between neighbor chains, as
shown before, and increases the chain length in general. Yang et
al.54 showed that longer chains have a characteristic frequency
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Figure 9. Distance values between the two carbon atoms that
participate directly in the coalescence process (19−19 atom carbon
chain). During the pressure increase stages (t = 0 until 1200 ps), the
two chains show a bouncing movement until the pressure reaches a
value that is high enough to induce the coalescence between the chains
(t > 1200 ps).
Figure 10. Vibrational density of the states for linear carbon chains
(LCC) of different lengths. Increasing the carbon chain length from 9
(black trace) to 40 (blue trace) atoms red-shifts the strongest peak
from 1870 to around 1850 cm−1.
around 1850 cm‑1 (red shifted in comparison with the
frequency of the 9 atoms length chain). The peak around
1660 cm−1 could be an artifact of the force field used and
should not be considered in the analysis.
The red shift in the most intense peak in the initial
vibrational spectrum, when the carbon chain length is
increased, indicates that the C−C bonds become softer when
the chain size increases.
■
CONCLUSIONS
In this work, we studied the behavior of linear carbon chains
encapsulated inside of carbon nanotubes under high-pressure
conditions (up to 10 GPa). We investigated the vibrational
properties of this hybrid Cn@MWCNT material as well as the
structural changes occurring under externally applied hydro-
static pressure. The enclosed chains are protected by the
surrounding carbon nanotube layers in the MWCNT, which
makes it difficult to directly access the chains by several
experimental techniques. We showed that high-pressure Raman
spectroscopy can provide a sensitive experimental probe for
studying these systems because the Raman signal is very strong
due to resonance conditions, and the vibrational frequencies
ωCn are very sensitive to any structural and electronic changes
induced in the chains. Upon applying external pressure, we
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observed that the carbon−carbon bond in the sp2 lattice
(carbon nanotube) becomes stronger, while the carbon−carbon
bond in the sp lattice (1D chain) softens. Furthermore,
pressure can induce irreversible structural changes in the linear
carbon chains, as revealed by the red shift in the vibrational
modes when the pressure is released. These results have been
interpreted as being due to the coalescence of different carbon
chains, and this hypothesis is supported by the results obtained
by fully atomistic reactive molecular dynamics simulations.
■
AUTHOR INFORMATION
Corresponding Author
*A.G.S.F. E-mail: agsf@fisica.ufc.br.
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
N.F.A., P.T.C.F., A.G.S.F., A.L.A., G.B., and D.S.G. acknowl-
edge funding from the Brazilian agencies CNPq, CAPES, and
FAPESP. A.G.S.F. acknowledges CNPq (grant no. 307317/
2010-2 and INCT NanoBioSimes) and Fundaçaõ Cearense de
Apoio ao Desenvolvimento Cientifico ́ e Tecnológico (FUN-
CAP) through PRONEX (grant no. PR2-0054-00022.01.00/
11). G.B. and D.S.G. thank the Center for Computational
Engineering and Sciences at Unicamp for financial support
through the FAPESP/CEPID, grant no. 2013/08293-7. M.S.D.
acknowledges financial support from NSF grant DMR-
1004147. Y.A.K. acknowledges NRF-2014R1A2A1A10050585.
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10676 DOI: 10.1021/acs.jpcc.5b00902

J. Phys. Chem. C 2015, 119, 10669−10676