Chapter- IV

RESULTS AND DISCUSSIONS

58

In this work reviewed herein and in theoretical researchby other

workers[1-21], a consensus has beenreached that anomalous
properties (compared tographite and normal graphitic nanotubes)
can beobtained with graphitic nanotubes with diameters ofthe order of
a nanometer. In terms of electronic properties,the nanotubes are
expected to fall into two majorclasses: on one hand the moderate band
gap nanotubesthat do not satisfy the

n1n2

= 3 m condition in the

graphene sheet, and on the other hand the small bandgap and truly
metallic serpentine conformation nanotubesthat do satisfy this
condition. We have earlierdemonstrated[1-3] for the serpentine
nanotubesthat, for diameters under a nanometer, we expect thatthe
density of states at the Fermi level is comparableto metallic densities
and that the

nanotubes should

notPeierls-distort at normal

temperatures.
Independentof helicity, we find that the larger-diameter
moderateband gap members of the family of moderate bandgap
n1n2

3 m) have bandgaps givenapproximately by

r cc {R
V pp ( T )

and hence donot have bandgaps approaching

nanotubes (
Eg

kBT at room temperatureuntil their diameters exceed approximately

about30 nm[l]. We have also examined the energetics and
elasticproperties of small-diameter graphitic nanotubes usingboth
first-principles and empirical potentials[14]. Wefind that the strain
energy per carbon relative to an unstrainedgraphite sheet goes as l
2

RT

(where

RT

is thenanotube radius) and is insensitive to other

59

aspects

ofthe

lattice

structure,

indicating

that

relationships

derivablefrom continuum elastic theory persist well intothe small

radius limit. In general, we find that the elasticproperties are those
expected by directly extrapolatingthe behavior of larger graphitic
fibers to a smallcross-section. The recent advances in synthesis of
single-shellnanotubes

should

stimulate

wealth

of

new

experimentaland theoretical studies of these promising materialsaimed

at determining their structural, electronic,and mechanical properties.
Many questions remain tobe further investigated. How can they be
terminated[20,22] and can they be connected[21]? What aretheir
electrical properties? For those that are semiconductors,can they be
successfully doped[14]? What arethe mechanical properties of these
nanotubes? Howwill they respond under compression and stress[1419]? Do they have the high strengths and rigidity thattheir graphitic
and

tubular

structure

implies?

How

these

nanotubes

are

formed[22,24,25]? Can techniques bedevised that optimize the growth

and allow the extractionof macroscopic amounts of selected
nanotubes[26,27]? These questions all deserve immediateattention,
and the promises of these novel all-carbon materials justify this as a
major research area for thecurrent decade.

Conculusion
The potential energy surface characterizing the interaction
between the individual tubes in the (5,5)@(10,10) double-wall
nanotube as a function of the interaxis distance and the mutual tube
orientation. We found that the weak intertube interaction periodically
opens and closes four pseudogaps near EF due to symmetry lowering
during the low-frequency librational motion about and vibrational
60

motion normal to the double-tube axis. The soft librational motion is

expected

to

occur

at

&30

cm21

below

theorientational

meltingtemperature, which marks the onset ofrelatively free rotations

of

theindividual

tubes,

probably

via

axial

displacement

of

orientational dislocations that were frozen in during the tube

formation. The strong coupling between the libration mode and the
electronic states at the Fermi level, which is apparently absent in
nanotube and fullerene crystals, may cause superconductivity in
systems containing multiwall nanotubes.

Results
A graphene sheet is a more structural properties to MWCNT
(Multi walled carbon nanotube). Reduction in ultimate energy and
pseudogaps, band gap due to the structure is comparatively small.

61

Table 4.1 Relaxation energy per carbon (eV) obtained b) geometry

optimization of nanotubes relative to extrapolated value for graphene

Nanotube

Radiu5 (nm)

Unrelaxed energy Relaxed energy

(eV)
(eV)

[12,5]

0.6050

0.067

0.064

[13,2]

0.5630

0.071

0.068

[11,4]

0.5370

0.076

0.073

[7,5]

0.4170

0.133

0.130

[9,2]

0.4060

0.140

0.137

[4,3]

0.2460

0.366

0.354

62

Table 4.2.The band gaps of the [n, 0] tubes.

Our
sp3sTB
model
Tube

Bottom of
the
conductio
n band
(eV)

Top of
the
valence
band
(eV)

Energy
gap
(eV)

The sp3
TB
model
[12]
Energy
gap
(eV)

[6, 0]

0.0558

0.1133

0.1791

0.05

0.83

[7, 0]

0.4656

0.5808

1.0463

1.04

0.09

[8, 0]

0.5643

0.5723

1.1866

1.19

0.62

[9, 0]

0.0249

0.0505

0.0754

0.07

0.17

63

The LDA
[12]

Energy
gap
(eV)

Table4.3

Calculate

SWNT

strain

[Loading,Unloading].

64

and

Graphene

strain

Table4.4 Calculate strain (%) result [Loading, Unloading] in effective

modulus (TPa).

65

66

Fig.4.1 Strain energy as a function of tube radius.

67

Fig.4.2 Band structure of aligned nanotubepairs, along the tube axis.

Near degenerate bandswith no gap characterize the (5,5)@(10,10)
double-wall nanotube without intertube interaction (a) Intertube
sinteraction opens a gap in apair of ~individually metallic
(10,10)Nanotubes

(b)

In

presence

of

intertube

interaction,

dependingon the mutual tube orientation, the (5,5)@(10,10) system

may show zero gap in themost symmetric, stable configuration at
win50 (c) or four pseudogaps in a less symmetric andstable
configuration at win53 (d) The Fermilevel is shown by the dashed
line.

68

Fig. 4.3 (a) Schematic view of the (5,5)@(10,10) double-wall tube.

The relative radial, axial, and rotational displacement of the inner with
respect to the outer tube are described by Dr, Dz,

and w out ,

respectively. Energy dependence on (b) the separation of the tube axes

Dr (for Dz50, win50, wout50), and (c) the orientationof the inner tube
win (for Dr50, Dz 50, wout50). All energies are given per atom.

69

Fig 4.4 Density of states of aligned nanotubepairs, corresponding to

the band structures in Fig. 4.2: The (5,5)@(10,10) double-wall tube
with no intertube interaction (a) pair of interacting (10,10) nanotubes
(b); the (5,5)@(10,10)Doublewalltube as a function of mutual tube
orientation, for win50 (c) and win53 (d) The Fermi levelis shown by
the dashed line. The densities of states of (5,5)@(10,10) tubes near
EF are comparedon an expanded energy scale in (e) Appearanceof
pseudogaps, shown by the solid linefor win53, is in stark contrast
with the flat densityof states for win50 and win59, shown bythe
long-dashed line. The dotted line indicates thedensity of states of
noninteracting (5,5)And (10,10) tubes.

70

References
[1]

J. W. Mintmire, B. I. Dunlap, and C. T. White, Phys. Rev. Lett.

[2]

68, 631 (1992).

C. T. White, J. W. Mintmire, R. C. Mowrey, D. W. Brenner, D.
H. Robertson, J. A. Harrison, and B. I. Dunlap, In

[3]

Buckminsterfullerenes (1993).
J. W. Mintmire, D. H. Robertson, B. I. Dunlap, R. C. Mowrey,

[4]

D. W. Brenner, and C. T. (1992).

C. T. White, D. H. Robertson, and J. W. Mintmire, Phys. Rev. B

[5]

47, 5485 (1993).

J. W. Mintmire, D. H. Robertson, and C. T. White, J. Phys.

[6]

Chem. Solids 54, 1835 (1993).

N. Hamada, S. Sawada, and A. Oshiyamu, Phys. Rev. Lett. 68,

[7]

1579 (1992).
R. Saito, M. Fujita, G. Dresselhaus, M. S. Dresselhaus, Phys.
Rev. B 46, 1804 (1992). Mater. Rex Sot. Sym. Proc. 247, 333

[8]

(1992); Appl. Phys. Lett. 60, 2204 (1992).

R. Saito, O. Dresselhaus, and M. S. Dresselhaus, J. Appl. Phys.

[9]

73, 494 (1993).

H. Ajiki and T. Ando, J. Phys. Sot. Japan 62, 1255 (1993). J.

[10]

Phvs. Sot. Ju~an 62. 2470 (1993).

P.-J. Lin-Chuhg and A. i. Rajagopal, j Phyi. C6, 3697 (1994).

[11]
[12]
[13]
[14]

Phys. Rev. B 49, 8454 (1994).

X. Blase, L. X. Benedict. Phys. Rev. Lett. 72, 1878 (1994).
D. J. Klein, W. A. Seitz, J. Pnys. Chem. 97, 1231 (1993).
K. Harigaya, Phys. Rev. B 45, 12071 (1992).
D. H. Robertson, D. W. Brenner, and J. W. Mintmire, Phys. Rev.

[15]
[16]

B 45, 12592 (1992).

A. Lucas, P. H. Lambin, J. Phys. Chem. Solids 54, 587 (1993).
J.-C. Charlier and J.-P. Michenaud, Phys. Rev. Lett. 70, 1858

[17]
[18]

(1993).
G. Overney, W. Zhong. Phys. D 27, 93 (1993).
R. S. Ruoff, J. Tersoff, D. C. Lorents, Nature 364, 514 (1993).
71

[19]
[20]

J. Tersoff and R. S. Ruoff, Phys. Rev. Lett. 73, 676 (1994).

M. Fujita, R. Saito, G. Dresselhaus, M. S. Dresselhaus, Phys.

[21]
[22]
[23]
[24]
[25]
[26]

Rev. B 45, 13834 (1992).

B. I. Dunlap, Phys. Rev. B 46, 1933 (1992).
S. Iijima, Muter. Sci. Eng. B19, 172 (1993).
J.-Y. Yi and J. Bernholc, Phys. Rev. B 47, 1703 (1993).
M. Endo and H. W. Kroto, J. Phys. Chem. 96, 6941 (1992).
S. Iijima, P. M. Ajayan, Phys. Rev. Lett. 69, 3100 (1992).
S. Iijima and T. Ichihashi, Nature (London) 363, 603 (1993).
D. S. Bethune, C. H. Klang, Nature (London) 363, 605 (1993).

[27]

72