Master's Thesis 2014

COMPUTATIONAL STUDIES ON THE
INTERACTIONS BETWEEN SARIN, DMMP & NO2

GAS MOLECULES WITH SINGLE WALLED
CARBON NANOTUBES
MAJOR PROJECT, UNN055
Submitted in partial fulfilment of the
requirements of
B.Tech + M.Tech (Dual Degree)
Nanotechnology
BY: HIMANSHU
A1223309017
UNDER THE GUIDANCE OF
NEERAJ JAIN DR. NEELAM KUSHWAHA
SCIENTIST G, ASSISTANT PROFESSOR II
SOLID STATE PHYSICS LAB (DRDO), AINT, AMITY UNIVERSITY,
MINISTRY OF DEFENCE, SECTOR-125 NOIDA,
LUCKNOW ROAD, TIMARPUR, UTTAR PRADESH-201313,
DELHI - 110054, INDIA. INDIA.
Amity Institute of Nanotechnology

AMITY UNIVERSITY
Noida, July 2014
Major Project by Rahul Sharma: RADIATION DETECTORS
DECLARATION
I, Himanshu, student of B.Tech. + M.Tech. (Dual Degree) Nanotechnology, hereby declare

that the project titled Computational studies on the interactions between Sarin, DMMP and NO 2
gas molecules with single walled carbon nanotubes which is submitted by me to Amity Institute
of Nanotechnology, Amity University Uttar Pradesh, Noida, in partial fulfilment of requirement for
the award of the degree of B.Tech. + M.Tech. (Dual Degree) in Nanotechnology, has not been
previously formed the basis for the award of any degree, diploma or other similar title or recognition.
The Author attests that permission has been obtained for the use of any copy righted material
appearing in the Project report other than brief excerpts requiring only proper acknowledgement in
scholarly writing and all such use is acknowledged.
HIMANSHU
A1223309017
CERTIFICATE- I
This is to certify that Himanshu, a student of B.Tech. + M.Tech. (Dual Degree) Nanotechnology has
successfully completed the dissertation project titled Computational studies on the interactions
between Sarin, DMMP and NO2 gas molecules with single walled carbon nanotubes in a period
of six months from Feb 2014 to Aug 2014 submitted to Amity Institute of Nanotechnology, Amity
University Uttar Pradesh, Noida, in partial fulfilment for the award of the degree. It is an original
contribution with existing knowledge and faithful record of work carried out by him under my
guidance and supervision.
work has not been submitted in part or full for any Degree or Diploma to this University or elsewhere.
NEERAJ JAIN
SCIENTIST G,
SOLID STATE PHYSICS LAB,
DEFENCE R&D ORGANISATION,
MINISTRY OF DEFENCE,
LUCKNOW ROAD, TIMARPUR,
DELHI-110054, INDIA.
CERTIFICATE- II
This is to certify that Himanshu, a student of B.Tech. + M.Tech. (Dual Degree) Nanotechnology has
successfully completed the dissertation project titled Computational studies on the interactions
between Sarin, DMMP and NO2 gas molecules with single walled carbon nanotubes which is
submitted to Amity Institute of Nanotechnology, Amity University Uttar Pradesh, Noida, in partial
fulfilment of the requirement for the award of the degree of B.Tech. + M.Tech. (Dual Degree) in
Nanotechnology in a period of six months from Feb 2014 to Aug 2014 and it is an original
contribution with existing knowledge and faithful record of work carried out by him under my
guidance and supervision.
To the best of my knowledge this work has not been submitted in part or full for any Degree or
Diploma to this University or elsewhere.
Dr. NEELAM KUSHWAHA

ASSISTANT PROFESSOR II
AINT, AMITY UNIVERSITY,
SECTOR-125, NOIDA,
UTTAR PRADESH - 201313,
INDIA.
ACKNOWLEDGMENTS
I am grateful to the authorities of Defence Research and Development Organization for having
permitted us to go ahead with the Training on Computational studies on the interactions between
Sarin, DMMP and NO2 gas molecules with single walled carbon nanotubes in partial fulfilment
of B.TECH +M.TECH. (dual degree) in nanotechnology from Amity University Noida.
My sincere thanks & gratitude also due to Sc. Neeraj Jain for her valuable guidance regarding
the study of Carbon Nanotubes. I am very thankful to Dr. L.M. Bhardwaj, Head of the department of
Nanotechnology for approving our Training, timely encouragement and supervision. I am thankful &
grateful to Dr. Neelam Kushwaha (faculty guide of AINT) for her valuable guidance on principles,
fundamentals, concepts and execution regarding the Training which have helped us in completion of
training & preparation of the report.
I would like to place our thankfulness to Mr. B. Sateesh and Mr. S.K. Luthra on record without
whose guidance and timely help the Training could not have been completed in time.
HIMANSHU
Date- 28-6-14
ABSTRACT
Carbon Nanotubes (CNTs) are carbon allotropes with a cylindrical nanostructure. Nanotubes
have high aspect ratio of range 132,000,000:1, significantly larger than for any other material. Due to
high aspect ratio and 1-dimensional structure these cylindrical carbon molecules have unusual
properties, which are valuable for nanotechnology, nanoelectronics, nanophotonics and other fields
of materials science and technology.
We can use CNTs as gas sensor because of its high aspect ratio, and dependence of electronic
band structure of CNTs on electron cloud of gas molecules that gets adsorbed on the surface of CNTs.
When charge transfer takes place between gas molecules and CNT, we observe a change in the
electrical resistance of CNTs. This becomes the sensing mechanism in CNT bases sensors. Pristine
CNTs are p-type semiconductors having holes as majority charge carriers. When a gas molecule of
electron withdrawing nature gets adsorbed on the surface of CNTs, it takes away electron from the
CNT surface resulting in increase the hole concentration and hence increase electrical conductivity of
CNTs.
In this project, we tried to verify the fact that CNTs can be used to detect different gases such as
nitrogen dioxide (NO2), Dimethyl methylphosphonate (DMMP) and Sarin (a chemical weapon) and so
has potential of being used as a gas sensor. For it, I used a software package named Atomistix Tool Kit
(ATK) developed by Quantum Wise and calculated the interactions of different gas molecules for
different positions and orientations with the surface of CNT and as a result of computation we find
most probable orientation and position which show remarkable interactions with CNTs. Then we study
functionalization of CNT with HFIPA to make it selective for Sarin gas, here we again shows
remarkable interaction of it with CNTs. Then we computed band diagram, DOS and I-V characteristics
of naked CNT and compare them with CNT after adsorption of different gas molecules to show how
change in electronic properties of CNT can be used to develop an efficient gas sensor.
TABLE OF CONTENTS
DECLARATION
I
CERTIFICATE- I
II
CERTIFICATE- II
III
ACKNOWLEDGMENTS
IV
ABSTRACT...........................................................................................
V
TABLE OF CONTENTS
VI
LIST OF FIGURES
VII
CH . 1 ..........................................INTRODUCTION TO CARBON NANOTUBES

10
1.1 Introduction
10
1.2 Structure of Carbon Nanotubes
12
1.3 Band structure and electron transport physics of 1D SWNTs
15
1.4 Mechanical properties of CNT
20
1.5 Thermal properties of CNT
21
1.6 Synthesis of CNT
23
CH . 2 ................................................CARBON NANOTUBES AS GAS SENSORS
24
2.1 .......................................................................................................... Introduction
24
2.2 ............................................................Pristine Carbon Nanotubes as gas sensor
25
2.3 Functionalised Carbon Nanotubes as gas sensor
26
2.4 .................................Advantages of SWNT gas sensor over existing gas sensors
27
2.5 Fabrication of CNT based gas sensors
29
2.6 Computational studies of CNT gas sensor
29
CH . 3 ..............................................................DENSITY FUNCTION THEORY
30
3.1 Introduction
30
3.2 Oerview of methodology used
30
3.3 Introduction to Atomistix Toolkit (ATK)
31
CH . 4 ...............................................................CNT AS NO2 GAS SENSOR
33
4.1 Findig the optimized position of NO 2 on CNT surface

33
4.2 Calculating DOS, Transmission, Conductance and I-V relation for CNT
34
4.3 Calculating DOS, Transmission, Conductance and I-V relation for CNT+NO 2
system 38
4.4 Results and discussions
40
CH . 5 ........STUDY OF INTERACTION OF DMMP, SARIN AND HFIPA MOLECULE ON
PRISTINE CNT 42
5.1 Finding optimized configuration of DMMP on Pristine
42
5.2 Finding optimized configuration of Sarin on Pristine CNT
53
5.3 Finding Binding Energy of HFIPA on Pristine CNT
61
FUTURE PROSPECTS
74
REFERENCES........................................................................................
75
List of figures
1.1 TEM image of a MWNT and its cross section below

1.2 A Single Walled CNT- Single sheet of graphene rolled to form CNT
1.3 A Multi Walled CNT- Multiple sheets of graphene rolled to form CNT
1.4 Armchair Carbon Nanotubes
1.5 Zigzag Carbon Nanotubes
1.6 Chiral Carbon Nanotubes
1.7 Unrolled hexagonal network of nanotube i.e.; a planar graphene sheet
1.8 Energy dispersion of graphene along high-symmetry points as indicated
1.9 (a) Surface plot and (b) contour plot of the energy dispersion in graphene
1.10 Representation of a SWNT by a chiral vector, C = n1a1+n2a2.
1.11 (a) A first Brillouin zone of graphene with conic energy dispersions at six K points.
(b) a metallic SWNT and (c) a semiconducting SWNT. Adapted from [10]
1.12 (a)(c) all are STS spectra. (a) and (b) are for semiconducting SWNTs.
(c) is for a metallic SWNT. (dI/dV)/(I/V) is proportional to DOS in SWNTs.
1.13 Synthesis methods for CNTs [25]
1.14 Schematic setup of arc discharge method.
1.15 CVD process inside quartz tube with heaters
2.1 Representing a possible sensing mechanism of DMMP using TFQ functionalized SWCNTs
2.2 Resistor based CNT gas sensor
2.3 FET based CNT gas sensor
4.1 Possible configurations for physisorption and chemisorption of one NO2 group on the exterior of a carbon nanotube.
4.2 SWNT as a device with self electrode
4.3 DOS and band diagram of SWNT
4.4 I-V curve for SWNT with its conductance
4.5 Transmission spectrum for SWNT with its band structure
4.6 SWNT device with 1 NO2 molecule adsorbed on its surface
4.7 DOS and band diagram of SWNT with adsorbed NO2 molecule
4.8 I-V curve for SWNT with adsorbed NO2.with its conductance.
4.9 Transmission for SWNT with adsorbed NO2 with band diagram.
5.1 Top view of DMMP molecule on CNT- where Oxygen atom of P=O bond of DMMP is directly above Carbon atom
of CNT
5.2 Axial Side view of DMMP molecule on CNT- where Oxygen atom of P=O bond of DMMP is directly above
Carbon atom of CNT

5.3 Front view of DMMP molecule on CNT- where Oxygen atom of P=O bond of DMMP is directly above
Carbon atom of CNT
5.4 Top view of DMMP molecule on CNT- where Oxygen atom of P=O bond of DMMP is in middle of C-
C bond of CNT
5.5 Axial Side view of DMMP molecule on CNT- where Oxygen atom of P=O bond of DMMP is in
middle of C-C bond of CNT
5.6 Front view of DMMP molecule on CNT- where Oxygen atom of P=O bond of DMMP is in middle of C-C bond of
CNT
5.7 Top view of DMMP molecule on CNT- where Oxygen atom of P=O bond of DMMP is above mid of hexagon formed
by Carbon atoms of CNT
5.8 Axial Side view of DMMP molecule on CNT- where Oxygen atom of P=O bond of DMMP is above mid of hexagon
formed by Carbon atoms of CNT
5.9 Front view of DMMP molecule on CNT- where Oxygen atom of P=O bond of DMMP is above mid of hexagon
5.10Top view of DMMP molecule on CNT- where Oxygen atom of P=O bond of DMMP is above a Carbon atom
but tilted to keep methyl group away from CNT
5.11 Axial Side view of DMMP molecule on CNT- where Oxygen atom of P=O bond of DMMP is above a Carbon
atom but tilted to keep methyl group away from CNT
5.12 Front view of DMMP molecule on CNT- where Oxygen atom of P=O bond of DMMP is above a Carbon atom but
tilted to keep methyl group away from CNT
5.13 Top view of Sarin molecule on CNT- where Oxygen atom of P=O bond of Sarin is directly above Carbon atom of
CNT
5.14 Axial Side view of Sarin molecule on CNT- where Oxygen atom of P=O bond of Sarin is directly above Carbon
atom of CNT
5.15 Front view of Sarin molecule on CNT- where Oxygen atom of P=O bond of Sarin is directly above
Carbon atom of CNT
5.16 Top view of Sarin molecule on CNT- where Oxygen atom of P=O bond of Sarin is in middle of C-C
bond of CNT
5.17 Axial Side view of Sarin molecule on CNT- where Oxygen atom of P=O bond of Sarin is in middle
of C-C bond of CNT
5.18 Front view of Sarin molecule on CNT- where Oxygen atom of P=O bond of Sarin is in middle of C-C bond of
CNT
5.19 Top view of Sarin molecule on CNT- where Oxygen atom of P=O bond of Sarin is above mid of hexagon formed by
Carbon atoms of CNT
5.20 Axial Side view of Sarin molecule on CNT- where Oxygen atom of P=O bond of Sarin is above mid of hexagon
5.21Front view of Sarin molecule on CNT- where Oxygen atom of P=O bond of Sarin is above mid of hexagon
5.22Top view of HFIPA molecule on CNT where Benzene ring of HFIPA molecule is parallel displaced over hexagonal
ring of Carbon atoms of CNT and OH group facing towards the CNT
5.23 Axial Side view of HFIPA molecule on CNT where Benzene ring of HFIPA molecule is parallel displaced over
hexagonal ring of Carbon atoms of CNT and OH group facing towards the CNT
5.24 Front view of HFIPA molecule on CNT where Benzene ring of HFIPA molecule is parallel displaced over hexagonal
ring of Carbon atoms of CNT and OH group facing towards the CNT
5.25Top view of HFIPA molecule on CNT where Benzene ring of HFIPA molecule is directly over hexagonal ring of
Carbon atoms of CNT and OH group facing towards the CNT.
5.26 Axial Side view of HFIPA molecule on CNT where Benzene ring of HFIPA molecule is directly over hexagonal ring
of Carbon atoms of CNT and OH group facing towards the CNT
5.27 Front view of HFIPA molecule on CNT where Benzene ring of HFIPA molecule is directly over
hexagonal ring of Carbon atoms of CNT and OH group facing towards the CNT
5.28 Top view of HFIPA molecule on CNT where Benzene ring of HFIPA molecule is directly over
hexagonal ring of Carbon atoms of CNT and OH group facing away from CNT.
5.29 Axial Side view of HFIPA molecule on CNT where Benzene ring of HFIPA molecule is directly over hexagonal ring
of Carbon atoms of CNT and OH group facing away from CNT
5.30 Front view of HFIPA molecule on CNT where Benzene ring of HFIPA molecule is directly over hexagonal ring of
Carbon atoms of CNT and OH group facing away from CNT
5.31Top view of HFIPA molecule on CNT where Benzene ring of HFIPA molecule is placed in t-configuration above mid
of Carbon atoms of CNT but OH group facing down towards CNT
5.32Axial Side view of HFIPA molecule on CNT where Benzene ring of HFIPA molecule is placed in t-configuration
above mid of Carbon atoms of CNT but OH group facing down towards CNT
5.33Front view of HFIPA molecule on CNT where Benzene ring of HFIPA molecule is placed in t-
configuration above mid of Carbon atoms of CNT but OH group facing down towards CNT
Chapter 1
Introduction to Carbon
Nanotubes
1.1Introduction
Carbon is present in almost all material present around us; it is most important element and is a
major constituent of all organic matter. Because of its catenation property it can combine in various
ways and has large number of unique properties which has led to its large number of applications.
Carbon atoms can hybridize in sp (Ethyne), sp2 (Graphite) or sp3 (Methane) forms these different forms
of hybridisation govern most of the properties and this makes for interesting products with wide
applications.
CNTs are made up of carbon atoms alone which are sp 2 hybridized and bonded in a benzene-
ring shape to from a one-atom thick sheet called graphene which can be said as further rolled
symmetrically or asymmetrically to form a tubular structure which is a Carbon Nanotube. There has
been intense research done on Carbon Nanotube since its discovery in 1991 by Iijima [1], while
analysing an electrode deposit from arc chamber using Transmission Electron Microscopy (TEM) Fig.
1.1. Previously there has been discovery of cylindrical graphitic tubes but now in this discovery by
Iijima the tubes were found to be perfectly graphitised and had closed pentagons at its both ends [1].
Using TEM it was possible to estimate the diameter of nanotubes and it was found to be almost
similar to that of fullerenes but clearly their lengths were around micrometer range. Iijima had
discovered carbon nanotubes which had many walls thus it was termed to be multiwalled carbon
nanotubes (MWNT). But later in 1993 Iijima was successful in isolating single-walled carbon
nanotubes (SWNT) [2] but it was only in 1996 that Thesis et al. [3] were successful in production of
good quantity of CNTs using laser vaporisation techniques. It led to commercial availability of carbon
nanotubes which resulted in direct generation of increase in both commercial and academic research
interests.
Figure 1.1 TEM image of a MWNT and its cross section below [1]
Carbon nanotubes can be said as unique one dimensional nano scale materials. They have been
widely studied globally because of their extraordinary mechanical, structural and electronic properties
which is unrivalled across any material present in nature. Also research in carbon nanotube has been
partly due to the theoretical interest in 1D-materials. Table 1.1
Table 1.1 Properties of Carbon Nanotubes
Properties Comparison
Carrier mobility :79000cm2 /Vs (at RT) [4] > Hole mobility in silicon
Maximum electrical current density > 109 A/cm2 [5] 100 times > than copper wires
Thermal conductivity 6600 W m-1 K-1 [6] > Diamond
Tensile strength: 150 GPa [7] 100 times the strength of steel
Youngs modulus: 1TPa [8] > Diamond
In the context of this thesis we will focus mainly on carbon nanotubes for purpose of
sensing gases so our focus will be on those properties which will be useful for this purpose. CNTs are
ideal for sensing of gases as they have high adsorbing surface area, excellent electrical properties and
facile charge transfer characteristics thus making it an ideal material for this purpose. Carbon
nanotubes can be used as ionisation based gas sensors also as because of their high aspect ratio there is
large field concentration induced in them which ionizes gaseous molecules.
1.2Structure of Carbon Nanotubes
We can assume a carbon nanotube as rolled up sheet of graphene. Hence similar to Graphene
the carbon atoms are arranged hexagonally in a Carbon Nanotube and its lattice can be defined by two
lattice vectors-
where a = |a1 | = |a2| = 1.42 3 = 2.46 is the lattice constant of the graphene sheet as a result of the
C-C bond length of 1.42 in graphene.
CNTs can be classified into various types based on the multiplicity of graphene sheets that
compose their wall(s) or the rolling pattern of sheet(s):
Based on multiplicity:
Single Walled Carbon Nanotubes (SWCNT)
Multi Walled Carbon Nanotubes (MWCNT)
Figure 1.2 A Single Walled CNT- Single sheet of graphene rolled to form CNT
sensors also as because of their high aspect ratio there is large field concentration induced in them
which ionizes gaseous molecules.
Figure 1.3 A Multi Walled CNT- Multiple sheets of graphene rolled to form CNT
Based on rolling pattern:
Armchair
Zigzag
Chiral
Figure 1.4 Armchair Figure 1.5 Zigzag Figure 1.6 Chiral

nanotube [9] nanotube [9] nanotube [9]
A wrapping angle say is formed between the chiral vector Ch and the armchair line (sheet
of graphene is folded at this line thus the two halves are there by mirror-images of each other) this
wrapping angle decides the rolling pattern that is being formed.
Figure 1.7 Unrolled hexagonal network of nanotube i.e a planar graphene sheet. As seen in figure if O
is connected to A and B connected to B' a tube of chiral vector Ch= (4,2) is formed. Here chiral angle
is marked by and the translational vector T is perpendicular to to the tube axis [10].
Chiral vector can be easily defined by this equation
Ch = na1 + ma2
- n and m are indices representing wrapping of sheet

- a1 and a2 are respective unit vectors
If = 0 => Armchair nanotube; n=m

If = 30 => Zigzag nanotube; m=0
If 0 < < 30 => Chiral nanotube; wrapping about C h
The Structure of nanotube formed and thereby its electronic properties are hence dependent
entirely on the axis along which the graphene sheet is rolled to form the cylindrical Carbon
nanotube. However its to be kept in mind that in practicality there is no such rolling up of
graphene sheet taking place during the synthesis of CNT the usage of Chiral vector is in
understanding the electronic properties of various different CNTs.
1.3 Band structure and electron transport physics of one-dimensional SWNTs
The structure of the carbon nanotubes gives characteristic electronic structure, this strongly
affects the electrical properties of CNTs. Band gap of CNTs is governed by the indices (n,m) that
represent the wrapping of graphene as seen earlier. Values of (n,m) decides the electrical properties of
CNTs
n = m, then the nanotube is metallic;

n m is a multiple of 3, then the nanotube is semiconducting having small band gap,
otherwise the nanotube is a moderate semiconductor.
It can thus be concluded safely that all armchair (n = m) nanotubes are metallic, and nanotubes
like (8,6), (11,1) etc. are semiconducting [11] but there is an exception to this rule as the curvature
effects have been found to interfere in electrical properties of nanotubes which are small in diameter.
The electronic band structures of single-walled carbon nanotubes (SWNTs) along with their small size
and low dimension are responsible for their unique electrical transport properties.
1.3.1 Electronic band structure of graphene [12]

To understand band structure of CNT, we need to understand band structure of grapheme after
which on applying boundary conditions we can get band structure of CNT. Graphene has a hexagonal
arrangement of carbon atoms in its lattice as shown in figure 1.8. Each carbon atom has 6 electrons out
of it 4 valence electrons of carbon are filled in 2s, 2px, 2py, and 2pzatomic orbitals Formation of
grapheme occurs 2s, 2px, and 2py, are hybridized into three sp2 orbitals with remaining 2pzorbital
perpendicular to the plane of three sp2 orbitals. These 2pzorbitals are responsible for formation of -
bonds between different grapheme layers. As we are interested in electrons near Fermi level , since
only these electrons have ability to access unoccupied states and help in conduction. Therefore we only
consider the electrons in -bonds, which lie near Fermi level, and hence are responsible for the
electronic properties by forming delocalized state.
The band structure of graphene derived from -orbitals can be calculated by the tight-binding
approximations [13]. To find band structure of graphene, we need to solve of the Schrodinger equation.
H= E ....1
where H is the Hamiltonian, is the total wave function, and E is the energy of electrons in the
orbitals of graphene. On solving Schrodinger equation for grapheme we will get energy dispersion
relation
E = E0 0(1 + 4 cos(3kxa/2) cos(kya/2)+ 4 cos2(kya/2))1/2 ............2
In Eq. (2), negative sign denotes valence bands of graphene formed by bonding -orbitals, while
positive sign represents conduction bands formed by antibonding -orbitals.The dispersion relation in
Eq. (2) is plotted in Fig.1.8 alonghigh-symmetry points in the reciprocal space with E0= 0. The surface
and contour plots of the energy dispersion are also shown in Fig.1.9 (a) and fig.1.9 (b) respectively.
The density of states (DOS) in graphene can be derived from the energy dispersion relation and it is
found to be zero at the Fermi level [14]. Along with the zero bandgap, this is why graphene is a zero
bandgap semiconductor.
The main point to be noted in the energy dispersion of graphene is the six K points at the corners
of the BZ, these points signifies that the conduction and valence bands are meeting which leads to zero
bandgap only at these points.
Figure 1.8 Energy dispersion of graphene along high-symmetry points as

indicated
Figure 1.9 (a) Surface plot and (b) contour plot of the energy dispersion in graphene as given by Eq.
(2). Note that there are six K points where the band gap becomes zero. Of the six K points, only two
are nonequivalent, denoted by K1 and K2
1.3.2 Band structure of SWNT from graphene

A SWNT can be uniquely defined by a chiral vector, C = n1a1 + n2a2, where n1 and n2 are
integers and a1 and a2 are the unit vectors of the graphene lattice as shown in Fig. 1.10. We can treat a
SWNT as a rolled graphene sheet. With wrapping indices, n1 and n2, SWNTs can be uniquely defined
and classified as armchair and zigzag SWNTs for indices (n, n) and (n, 0) respectively. Since a SWNT
is a rolled-up sheet of graphene, the band structure can be constructed from that of graphene by
imposing an appropriate boundary condition around the SWNT. A SWNT is an infinitely long cylinder,
so there are two wave vectors associated with it. One is the wave vector k||, which is parallel to the
SWNT axis, it is continuous along the infinitely long SWNT, while the wave vector k, which is along
the circumference of SWNT, it should satisfy a periodic boundary condition,
kC = dk= 2m .........(3)
transport properties is the band structure near the Fermi level which is given by allowed k
states that are closest to the K points. Depending on position of allowed k states CNTs can be
semiconducting or metallic. If k lines pass directly through the K points as in Fig. 1.11(b), then the
energy dispersion shows two linear bands crossing at the Fermi level without a bandgap, it will leads
to metallic SWNTs. However, if the allowed k does not intersect the K points as in Fig. 1.11(c), then
there are two parabolic 1D bands with an energy bandgap and it leads to semiconducting SWNTs [15-
17].
Figure 1.10 Representation of a SWNT by a chiral vector, C = n1a1+n2a2. In this figure, the wrapping
index of the SWNT described by C is (7, 1). a1 and a2 are unit vectors of the underlying graphene
lattice
Figure 1.11 (a) A first Brillouin zone of graphene with conic energy dispersions at six K points. The
allowed k states in a SWNT are presented by dashed lines. The band structure of SWNT is obtained
by cross-sections as indicated. Zoom-ups of the energy dispersion near one of the K points are
schematically shown along with the cross-sections by allowed k states and resulting 1D energy
dispersions for (b) a metallic SWNT and (c) a semiconducting SWNT. Adapted from [18]
1.3.3 Density of states in SWNTS

The DOS is an actual physical quantity measured in many measurements. The DOS, n(E), with
1D subband (k), can be calculated as [19]
n(E) = N(E)/E = 2/L dk (k ki) /k1 (4)
kiare the roots of the equation E (ki) = 0 and L is the length of the 1D BZ, and N(E) is the number of
energy states of electrons for given energy E. For parabolic 1D subbands such as those of SWNTs the
resulting DOS in Eq. (4) is proportional to 1/E1/2 for each subband and diverges for each onset of a
subband, giving rise to the so-called van Hove singularity in 1D systems.
Figure 1.12 (a)(c) all are STS spectra. (a) and (b) are for semiconducting SWNTs. (c) is for a
metallic SWNT. (dI/dV)/(I/V) is proportional to DOS in SWNTs. Note that DOS is zero for
semiconducting SWNTs and finite for metallic SWNTs. Also, the van Hove singularities are evident in
the STS spectra [20, 21].
1.4 Mechanical properties of CNT
Carbon nanotube is said to be the strongest existing material, its in fact ten times harder than
diamond. But Carbon nanotubes by geometry possess different properties in different directions i.e.
mechanical properties are not found to be same along its axial and radial directions. It has been shown
that CNTs are very strong in the axial direction. Young's modulus on the order of 270-950 GPa and
tensile strength of 11-63 GPa were obtained [22].
In radial direction it has been observed that carbon nanotubes are very soft. It was observed
with the help of transmission electron microscope that even weak van der Waals forces are sufficient
enough to deform nanotubes radially hence clearly they have high radial elasticity [23]. This radial
elasticity is useful as when in CNT composites the embedded tubes experience deformation
transversely when load is applied on the composite structure.
CNTs are preferred for their unique mechanical properties especially their high yield strength
and aspect ratio. It has been reported that CNTs are ten times harder than diamond and lighter than
steel. Also, very high length to diameter ratios have been reported. By virtue of the high strength,
CNTs have been used in varied industries that require stronger and lighter materials, such as aviation,
automotive, etc.
Table 1.2 Comparison of mechanical properties [24, 25, 26, 27, 28]
Material Young's modulus Tensile strength Elongation at break

(TPa) (GPa) (%)
SWNT ~1 (from 1 to 5) 1353 16
Armchair SWNT 0.94 126.2 23.1
Zigzag SWNT 0.94 94.5 15.617.5
Chiral SWNT 0.92 - -
MWNT 0.8 150 -
Stainless Steel 0.186 0.38 1550
Kevlar29&149E 0.060.18 3.63.8 ~2
1.5 Thermal properties of CNT
As seen earlier electron conductance is ballistic in nature owing to the narrow tube cross-
section of the CNTs, similarly carbon nanotubes show very good thermal properties
along the tube axis only and thus thermal properties of these tubes also arise from phenomenon of
Ballistic conduction in CNTs. This property allows for ballistic transportation of phonons with a one-
dimensional degree of freedom movement.
SWNT has been measured successful at room-temperature and its thermal conductivity along
axis has been found out to be about 3500 Wm 1K1 [29] this conductivity is very large as if we
compare it to copper which transmits 385 Wm 1K1 but even then it is used widely for its good thermal
conductivity. Whereas in radial direction i.e. across the axis SWNT has room-temperature thermal
conduction of about 1.52 Wm1K1 [30]
The temperature stability of pristine carbon nanotubes have been estimated to be about 2800C
in vacuum and even in air it is sufficiently higher at about 750C [31].
1.6 Synthesis of CNTs
CNTs can be fabricated through physical and chemical routes and for each there are various
methods formulated. Intense research worldwide have focused on developing a technique that is easy
to repeat with low production cost and most importantly yielding lot of CNTs with minimal defects.
There is also need to control other parameters like diameter, purity, chirality, shell numbers (MWCNT)
because they affect the various properties.
There are several methods as seen in the figure. But in general there are said to be these three
methods which are widely known and these are-
Electric-arc discharge
Laser ablation
Chemical Vapour Deposition
Figure 1.13 Synthesis methods for CNTs [32]
1.6.1 Electric arc discharge
It is typically a low-voltage discharge between two electrodes caused by electric breakdown of

a gas. DC current is passed through non-conductive medium such as air maintained between the
electrodes, subsequently thermionic emission of electrons causes the arc discharge phenomenon to
occur.
In case of CNT fabrication, arc discharge is created between two graphite electrodes in an
ambient gas environment. Electric arc formed henceforth vaporizes graphite into carbon soot which is
mainly composed fullerenes, SWCNTs and MWCNTs. Desired CNTs are obtained through a
purification process that involves oxidation of soot depositions on the cathode. A schematic diagram
representing arc discharge is shown below:
Cathode Anode
(+) (-)
Carbon soot deposits
containing CNTs
Inert
atmosphere
+
Figure 1.14 Schematic setup of arc discharge method.

1.6.2 Laser ablation
A physical method of synthesis using high-energy laser beam is common for the production of
SWCNT. This method involves focusing a converging beam of laser such as continuous CO 2 laser on a
graphite target pellet maintained at a high temperature inside a quartz tube. A furnace surrounds the
tube heating the inert gas stream inside to about 1200 C, this is done to promote sublimation rather
than transformation into liquid phase. The ablated particles from the target swept away by the stream
onto a water-cooled copper collector, some particles also get deposited on the rear end of target pellet.
As this method favours the growth of SWCNT, the catalyst mixed in target pellet need to be
removed to obtain MWCNT. The standard catalytic method delivers purest quality of SWCNT as
compared to other synthesis methods. However, the efficiency of the method is low as compared to
other methods and this translates into high cost of CNTs (until 2012 it cost 1000$ per gram).
1.6.3 Chemical Vapour Deposition (CVD)
CVD uses a chemical route of CNT synthesis as the name suggests, and it is most preferred for
mass production of CNTs. This method employs the reaction between two or more precursor gases
over a substrate using a catalyst and therefore deposition of particles in a conformal fashion.
Sometimes the reaction is between a single gas and the substrate itself. The resulting product is a
mixture of SWCNT and MWCNT however, conditions can be set for specifically producing either one.
Figure 1.15 CVD process inside quartz tube with heaters
Chapter 2
Carbon Nanotubes as gas
sensors
2.1 Introduction
A gas sensor is a device which on exposure to gaseous species, brings about a change in one or
more of its-
Physical properties i.e. it changes the physical characteristics of the material concerned
and as these changes are detectable it serves indirectly a way to sense the concerned
analyte.
Electrical properties
Optical properties,
Chemical properties- binding energies between molecules changes
All the changes are thus clearly measurable through various methods either directly or indirectly. The
applications of these devices are immense and affects the lives of almost each and every human being
in everyday life. They are used extensively in homeland security, environmental pollution, medical
diagnosis, industrial emission, agriculture, food processing, aerospace and aeronautics, etc.
The most sought after characteristics in a gas sensor are sensitivity at low concentrations,
operation at room temperature, energy efficiency, low cost, fast response, low maintenance and
portability.
Traditional techniques are fast becoming obsolete like gas chromatography (GC), GC coupled
to mass spectrometry (GC-MS), Fourier transmission infrared spectroscopy (FTIR) and atomic
emission detection (AED) because they are bulky, provide slow responses, operates at high
temperature, energy consuming and there is also other factors like high maintenance costs and
requirement of trained technicians. Clearly there is need to overcome these disadvantages, and sensors
developed using nanoparticles and Carbon nanotubes (CNTs) are very promising.
Carbon nanotubes (CNTs) are now studied all over world and under intense research as sensing
material because they possess some extraordinary characteristics like chemical, thermal and
mechanical stability, high surface area, metallic and semi-metallic conductive properties and
functionalization capability [33]. CNTs are basically graphene sheets rolled into a tube. As discussed
earlier there are different types of CNTs: single walled carbon nanotubes (SWCNT), double wall
carbon nanotubes (DWCNTs) and multi walled carbon nanotubes (MWCNT).
Research in CNT-based gas sensor received impetus after publication of first CNT sensor for
NH3 and NO2 detection using an individual semiconducting SWCNT [34]. However recent research is
focused more on modification/functionalisation of CNT for increasing selectivity and sensitivity of
devices which can detect variety of gases at room temperature.
Theoretical studies based on computational science are gaining importance for development of
sensing devices due to their cost efficiency, easy data collection and analysis, and mainly because of
their safety- as dealing with harmful gases practically requires lot of protection. Various methods of
calculations and simulations are used extensively to design new structures and then to study them.
Moreover so as to predict interactions and adsorption energies between those materials and gaseous
molecules. Most common form of sensing method is through measuring changes of electrical
conductivity. Gas molecules when adsorbed on surface of the sensor brings about the change in
electrical characteristics.
2.2 Pristine Carbon Nanotubes as gas sensors
Unmodified or pristine carbon nanotubes are highly stable because they have strong sp 2
hybridised carbon-carbon bonds thus they are to a large extent insensitive to most gases. However
because of high surface area and lots of sites of adsorption, gases like NO, NO 2 and NH3 are detected
to some extent.
A basic problem encountered in using CNT as gas sensors is that CNTs remains mostly in
bundles or as agglomerates due to high van der walls attraction between them thus this results in
presence of less adsorption sites where the gaseous molecules can bind, resulting in less sensitivity.
Mechanism of detection of NO gas on CNT is not yet fully understood but it is believed that
NO is an electron acceptor species and thus is attracted to the zones which are electron rich in nature.
Thereby negative potential is applied to the CNT and thus there is enhancement of movement of NO
molecules towards the CNT surface which translates into increase in sensitivity. Recovery of the
sensor is also readily possible by application of reverse potential on CNT that is applying a positive
potential which leads to movement of NO molecules away from the CNT surface [35]. Therefore there
is a very quick recovery time of the gas sensor.
Detection of Chemical Warfare Agents (CWA) like DMMP is shown successfully by Horrillo et
al. [36] by using SWCNTs. Chemical Warfare Agents (CWA) like DMMP was exposed to CNT grid
and there was a remarkable change in resistance observed. The greatest advantage is that the sensors
showed higher sensitivity at room temperature than when tested at other different temperatures.
Sensing mechanism can be attributed to the fact that DMMP has a P=O group in it and it acts as a
hydrogen bond acceptor because there is development of slight negative charge on Oxygen and thus
when a positive potential is applied on CNT the negative charge on Oxygen is attracted to it thus there
is enhancement of DMMP molecules on surface of CNTs.
2.3 Functionalised Carbon Nanotubes as gas sensors

CNTs are modified with different functional groups as they have drawbacks in pristine form. A
Pristine CNT has low sensitivity towards gas molecules in general as it has low adsorption energy.
CNT interacts with a whole lots of gaseous molecules thus there is lack of selectivity towards a
particular gaseous species. Moreover gas molecules once adsorbed on CNT dont readily detach from
the CNT automatically and tend to bind for long time thus there is clearly a problem of irreversibility
or long recovery time.
Such limitations need to be overcome for development of an effective gas sensor. Research is
thus focused on finding out various molecules which possess the capability of selective detection of a
particular gaseous species by interacting only with it. But most of the molecules were found out to be
extremely poor in electronic properties thereby there direct usage for sensing purpose is not possible.
To overcome these limitations, functionalization of CNTs with these different materials is carried out
and CNT imparts its extraordinary electronic properties to them and gets in return their special nature
of selectivity towards certain analyte/gas moreover increase in sensitivity is also observed.
Functionalization in basic layman terms can be said as a technique of attaching a molecule group on to
CNT. This attachment can take place by two different types of interactions i.e. by covalent
functionalization and non-covalent functionalization.
For detection of DMMP there has been reported a sensor for its detection at parts per trillion
(ppt) levels at room temperature [37]. This breakthrough was possible only by functionalization of
SWCNTs with tetrafluorohydroquinone (TFQ). The sensors displayed a very fast response and ultra-
high sensitivity when compared with un-modified SWCNTs sensor. This increase in sensitivity was
possible because the molecule TFQ provides for binding of DMMP molecule through the hydrogen
bond between the hydroxyl group in TFQ and P=O group in DMMP.
Figure 2.1 Representing a possible sensing mechanism of DMMP using TFQ functionalized
SWCNTs [37].
2.4 Advantages of SWNT gas sensor over existing gas sensors

1. High sensitivity can be achieved by using SWNT gas sensor as it can detect gas up to ppb
concentration.
2. High sensitivity even at room temperature operation due to high surface area.
3. Low response time of SWNT because of higher adsorption energy of NO2 gas.
4. High reusability can be achieved with SWNT by using UV-desorption of gas.
5. Less power consumption, this is strict requirement for military applications.
6. Smaller size and light weight makes it handy for use.
2.5 Fabrication of CNT based gas sensor

A) Resistor based CNT gas sensor (passive sensor)
The most simple and efficient system that can be used to detect an analyte is a resistor based
gas sensor in it a single or few networks of CNT bridging two metal contact pads (which acts as
electrodes). In it current changes due to change in resistance of SWNT on adsorption of NO 2 gas
molecule. This change in current is direct measurement of change in resistance of SWNT.
Figure 2.2 Resistor based CNT gas sensor
B) FET based CNT sensor (active sensor)
FET based configuration is similar to resistive based sensors configuration except that
conductance of CNT between source and drain is controlled by third electrode (gate) separated by a
thin layer of insulating layer usually of SiO 2 layer. It is even more sensitive than resistive gas sensor
because of the ability to tune the conductance of CNTs by controlling the gate voltage, and can be
simply used in electronic circuits for signal amplification and signal conditioning, although the
fabrication techniques require for realizing such sensors is more complicated and so the electronics
required for measuring the change in the electrical resistance, than the resistor based sensors.
Figure 2.3 FET based CNT gas sensor
2.6 Computational Studies of CNT gas sensor
There have been new efforts in field of theoretical studies to better understand the interactions
of molecules with CNTs. Ab initio (ABINIT) simulations of CNTs have been reported in which CNTs
were doped with heteroatoms of oxygen, nitrogen and boron so as to predict their behaviour and also
use them as sensors for gases like Cl2, CO, NO and H2 [38, 39]. The calculations were found to be
consistent with general predictions like doping of CNTs with O, N and B resulted in a shift of
conduction band of CNTs. O and B causes a downward shift creating p-type semiconductor whereas N
caused an upward shift thereby creating a n-type semiconductor. For these results Density functional
Theory (DFT) was applied into the ABINIT code and Generalized Gradient Approximation (GGA)
used for calculations. It is also reported through calculations that gas molecules Cl 2, NO, H2 and CO
affected the Density of States (DOS) and Fermi level of the Nanotubes as they come closer to the
surface. It was found that B-doped CNTs can be used for sensing of CO, NO and H2 gas molecules
effectively while O-doped CNTs can sense H2, Cl2 and CO also N-doped interacts and detects CO, NO
and Cl2 [39].
Hamadanian et al. have reported theoretical study of Al-substituted SWCNTs (10,0) for use as
CO gas sensor [40]. DFT calculations were used but with local density approximation (LDA) to study
various properties of Al-substituted SWCNTs and particularly focus was on electronic properties.
Thus clearly there is growth of research in the field of computational studies recently because
of the various improvements in theoretical calculations which are fast accurately estimating the
practical values. There are many advantages associated with computational studies particularly in
sensing of gases which make it an attractive means for studying of various mechanisms involved in
adsorption of gas molecules on CNTs. Therefore this study also focused on determination of various
Energies associated with Binding of molecules on CNT and thus there subsequent sensing could be
possible by further practical development of sensor based on theoretical study.
Chapter 3
Density function theory
3.1 Introduction
Density Functional Theory is a modelling method in Quantum mechanics and is the most
advanced theoretical formalism till date. It is widely used in physics and chemistry for calculation of
ground state electronic structure of many-body systems i.e. comprising of atoms, molecules, etc. This
theory uses functionals (functions of another function) to determine properties of many-electron
systems. Therefore in electron density calculations functionals are the spatially dependent electron
density. Hence this use of functionals of electron density gave the name Density Functional Theory
(DFT).
DFT is very popular in solid state physics calculations but in field of quantum chemistry
breakthrough was achieved only in 1990s when better approximations were developed and they
provide an increased accuracy in exchange and correlation interactions. Then onwards research
conducted showed results generated using DFT were very satisfactory compared to experimental data.
But despite phenomenal achievements there is still required to be done lots of work on approximations
of different interactions to properly get highly accurate results. This development of DFT methods so
as to achieve desired accuracy is also a widely researched topic [41, 42, 43, 44].
3.2 Overview of methodology used
Conceptual roots of DFT are in the Thomas Fermi Model but it received a phenomenal
development by the two theorems of Hohenberg and Kohn [45] in 1964. But credit for the popularity
of DFT today can be safely given to ingenious approach of Kohn and Sham who together put this
theory into various practices [46].
3.2.1 First Hohenberg and Kohn theorem
The First Hohenberg and Kohn Theorem demonstrates it is possible to uniquely determine the
ground state properties of many-electron system by using an electron density that depends just on 3
spatial coordinates. It therefore has tremendously reduced the work load by reduction of the many-
body problem of N electrons having 3N spatial coordinates to just 3 spatial coordinates. This was
possible by using the functionals of electron density.
3.2.2 Second Hohenberg and Kohn theorem
This theorem actually defines the energy functional of the system and gives proof that on
substitution of correct ground state electron density this energy functional is minimized. Thereby vice
versa if minimum energy functional value is determined then corresponding to it we can get accurate
ground state electron density of the system.
3.3 Introduction to Atomistix Toolkit (ATK)
Atomistix Toolkit is a software package developed by QuantumWise. It has the capability to

model electronic properties of quantum systems by density-functional theory. It can calculate density
matrix of open quantum systems using non-equilibrium Greens functions whereas for closed or
periodic systems calculation is done by diagonalizing the Kohn-Sham Hamiltonian. It therefore serves
as a complete all in one package. In this present study therefore Atomistix Toolkit was solely relied
upon and no other software was used.
3.3.1 Features
ATK has numerous features in a single package there is integration of many different methods
together in ATK. For graphene, one can perform quantum-mechanical calculations using
DFT
Tight-binding Model
Extended Hckel
Classical Brenner potential is used to perform fast geometry optimizations or molecular

dynamics simulations.
Even very simple and fast methods alone can predict accurately many normal properties
associated with structures of CNT, graphene, etc. Whereas for applications like gas sensing it is
required a bit of detailed quantum-chemical calculations of the interactions between molecules and
CNT. Thus by having access to a wide variety of methods working with ATK is efficient and flexible,
for simple calculations faster methods can be used and for detailed applications there are powerful
tools present as well. It is possible to perform calculations on structures with several hundred to tens of
thousands of atoms.
It is possible to calculate wide range of properties like-
Electronic structure properties
Band structure, density of states, real-space density, Bloch states, and other quantities.
Transport properties at finite bias via non-equilibrium Green's functions
Current-voltage (I-V) curve
Transmission spectrum
Conductance
Voltage drop
Transmission Eigen-states and pathways
Thermoelectric properties
See-back coefficient
Thermionic emission current
Optical properties
Absorption spectrum
Dielectric constant
Refractive index
Mechanical properties
Moreover it is possible to calculate all of the above properties with added collinear spin-
polarization, thus computation spin currents and magneto-resistance is also easily possible.
Chapter 4
Carbon Nanotubes as NO2 gas
sensor
4.1 Finding the optimized position of NO2 on CNT surface [47, 28]
We are using SWNT (10,0) unit cell in builder in ATK and repeat it 2 times so that length of
CNT becomes 0.85 nm having 40 C-atoms. Then the interaction between NO2 and an (10, 0) carbon
nanotube is studied by density functional theory. This method has been applied to a variety of chemical
problems in recent years [49]. The Generalized Gradient Approximation (GGA)[50] is used to study
some of the physisorption configurations, so that they could be compared with previous GGA results.
For a complete understanding of NO 2 adsorption on the exterior of a carbon nanotube we have to
consider orientation of the triangular shaped NO2 relative to the nanotube surface, as schematically
illustrated in Figure 4.1. In the nitro configuration, the NO2 molecule is bonded to the tube surface with
the nitrogen end. In nitrite configuration NO2 bonds with one oxygen end, while bonding with both
oxygen ends produces the cycloaddition configuration. These configurations are important for
physisorption of NO2.
Figure 4.1 Possible configurations for physisorption and chemisorption of one NO2 group on the
exterior of a carbon nanotube.
To find the binding configuration, we calculated the binding energy as a function of the distance
between the N and C atoms in the CNT. The binding energy, Eb(CNT+NO2), was calculated using
Eb(CNT+ NO2) = Et(CNT+ NO2) Et(CNT) Et(NO2) .3.1
,where Et(CNT+NO2) and Et(CNT) are the total energies of the CNT with and without a NO 2
molecule attached, respectively. Et(NO2) is the total energy of an isolated NO2molecule. The structure
of NO2was then reoptimized, allowing the atoms of the NO 2 to relax while the C atoms in the CNT
were constrained to their initial positions. There is no noticeable change in binding energy on
optimization.
4.1.1 Results
We obtained total energy of CNT+NO2 system and CNT and NO2 molecules in DFT under GGA
with PBE exchange correlation functional. Then by using equation (3.1) we obtained binding energy of
NO2 with CNT in different configurations. Out of all these configuration we obtained maximum
binding energy in case of nitro configuration.
Binding energy of NO 2 gas molecule on CNT = -0.28 eV which is near to the binding energy as
calculated in reference [18].
Distance of NO2 gas molecule from C-atom of CNT = 2.4 angstrom.
4.2 Calculating dos, transmission, conductance and I-V relation for CNT
Take 1 unit cell of CNT in builder and repeat it 10 times to make its length 4.2 nm. Then we
make its device by using self electrodes. And then we calculate its DOS, transmission, conductance
and I-V relation in DFT with 100 k points with The Generalized Gradient Approximation (GGA) and
PBE as exchange correlation functional. It takes approximately 6 days to complete calculations.
Figure 4.2 SWNT as a device with self electrode

Figure 4.3 DOS and band diagram of SWNT
Figure 4.4 I-V curve for SWNT with its conductance

Fig
Figure 4.5 transmission spectrum for SWNT with its band structure
4.2.1 Interpretation and discussion of data

1. DOS of CNT
In DOS of CNT we take Fermi level of CNT as our reference level so we assigned it energy of 0
eV. Now as we know only those electrons and holes take part in conduction in any system which are
near Fermi level hence we are taking DOS only in energy range of -2 eV to +2 eV. Now we can see
that there is no energy level in energy range of -0.5 eV to +0.5 eV, this shows that pristine CNT taken
is showing semiconducting nature having band gap of 1 eV.
2. band diagram
In band diagram of CNT we can easily see the band gap of 1 eV in CNT. Also by observing
position of Fermi level which is in middle of valence band and conduction band, we can say that
pristine CNT is a intrinsic semiconductor in nature, ie; number of electrons in conduction band in CNT
is equals to number of holes in CNT in valence band.
3. I-V curve
I-V curve of CNT represents no conductivity in region of 1 V, due to band gap of CNT. After 1
eV, it shows sudden nonlinear increase in current with voltage. And as voltage applied is increasing,
we can see the increase in conductivity of CNT.
4. Conductivity curve
Conductivity of CNT can be easily observed by dI/dV curve. In case of pristine CNT this shows
increase in conductance with voltage above 1 V.
5. Transmission curve
It represents the probability of transfer of charge carriers in CNT at a given voltage. As in
transmission curve we can see that there is no transfer of chare for voltage less than 1 V and after it
there is increase in transmission with increase in voltage, it supports the fact of increase in
conductivity of CNT with voltage.
4.3 Calculating dos, transmission, conductance and I-V relation for CNT + NO 2
system
Take 1 unit cell of CNT in builder and repeat it 10 times to make its length 4.2 nm, then add NO 2
on middle of CNT in optimized configuration. Then we make its device by using self-electrodes. And
then we calculate its DOS, transmission, conductance and I-V relation in DFT with 100 k points with
The Generalized Gradient Approximation (GGA).it takes approximately 8 days to complete
calculations.
Figure 4.6 SWNT device with 1 NO2 molecule adsorbed on its surface
Figure 4.7 DOS and band diagram of SWNT with adsorbed NO2 molecule
Figure 4.8 I-V curve for SWNT with adsorbed NO2.with its conductance.
Figure 4.9 transmission for SWNT with adsorbed NO2 with band diagram.
4.3.1 INTERPRETATION AND DISCUSSION OF DATA
1. DOS OF CNT WITH NO2

In DOS of CNT + NO 2 system we can see shift in Fermi level towards valence band, this shows
that now CNT acts as p-type semiconductor. When we compare this DOS with DOS of bare CNT we
can see new energy levels exist near Fermi levels it is due to presence of NO 2 molecule which have
energy levels near Fermi level of CNT.
2. BAND DIAGRAM
In band diagram again we can see the shift in Fermi level towards valence band which makes it
p-type semiconductor. This is due to the electron withdrawing nature of NO 2 molecule, when it come
near CNT in minimum energy configuration it attracts electrons towards it. This decreases electron
concentration in CNT which results in increases hole concentration in CNT and finally makes it to
behave as p-type extrinsic semiconductor.
3. I-V curve
I-V curve of CNT with NO2 represents no conductivity in region of 1 V, due to band gap of CNT.
After 1 eV it shows sudden nonlinear increase in current with voltage. And as voltage applied is
increasing, we can see the increase in conductivity of CNT. Also by comparing it with I-V of pristine
CNT we can see increase in conductivity is more in this case than pristine CNT.
4. Conductivity curve
Conductivity of CNT with NO 2 is more than conductivity of bare CNT. Hence we can say that
on adsorption of NO2 molecule conductivity of CNT increases, this fact is used in sensing mechanism
of CNT gas sensor.
4.4 Results and discussions

Here we observe the change in conductance of CNT on adsorption of NO 2 molecule due to
increase in holes concentration. This will lead to us in new direction of developing a CNT based gas
sensor for NO2 gas with high sensitivity.
Now to increase selectivity of CNT based gas sensor, we will use functionalisation of CNT with
different organic molecules.
Chapter 5
Study of interaction of DMMP, Sarin
and HFIPA molecule on pristine
CNT
5.1 Finding optimized configuration of DMMP on pristine CNT

Pristine SWCNT (10,0) was used because of its semiconducting properties thus its unit cell was
built in ATK which was repeated 4 times resulting in formation of CNT having length 1.56295 nm and
comprising of 159 Carbon atoms in it.
DMMP molecule was also constructed in builder and geometry optimisation was performed on
it by Density Functional Theory (DFT) with Exchange correlation as GGA (Generalized Gradient
Approximation) and Functional as PBE. These set of parameters give values very close to
experimental ones and thus highly relaxed geometry of DMMP molecule was obtained.
To study DMMP molecule interactions with CNT first there is need to find the lowest energy
configuration of the molecule over CNT. It is well known fact that the P=O bond present in DMMP is
the one responsible for various interactions thus focus was on this bond only and its various possible
geometrical positions over CNT were tried out. For every configuration minimum energy position was
derived by finding the least Total Energy of the system at a set distance r from CNT to DMMP
molecule. Thereby most stable configuration was at the minima of Energy v/s Distance curve. At that
position Binding Energy of the molecule was also determined.
Any molecule which is getting adsorbed on CNT and thereby getting detected can be visualized
practically as first approaching the CNT with help of some of its Kinetic Energy and as it approaches it
continuously gets relaxed by losing its Energy and then when its sufficiently close to CNT it interacts
and gets physiorbed or chemisorbed thereby finding a position which has least Total Energy of the
system. In our simulation study same procedure has been applied as Total Energy of the system has
been computed by slowly bringing DMMP molecule closer to CNT i.e. at every 0.1 distance Total
Energy has been calculated using DFT. This procedure has been performed similarly on HFIPA and
Sarin molecules with every possible configuration.
5.1.1 Configuration-1: DMMP on Pristine CNT (10,0) with Oxygen atom of P=O
bond of DMMP directly above a Carbon atom in CNT
Figure 5.1 Top view of DMMP molecule on CNT- where Oxygen atom of P=O bond of DMMP is
directly above Carbon atom of CNT
Figure 5.2 Axial Side view of DMMP molecule on CNT- where Oxygen atom of P=O bond of
DMMP is directly above Carbon atom of CNT
Figure 5.3 Front view of DMMP molecule on CNT- where Oxygen atom of P=O bond of
DMMP is directly above Carbon atom of CNT
As clearly seen in the above figures the Oxygen atom of P=O bond of DMMP is
directly placed above Carbon atom of CNT and from this position moving in both
directions of Y-axis slowly- closer and farther to CNT by 0.1 the Total energy of the
system was calculated at every step. Then Binding Energy of DMMP molecule was
calculated using the simple formula-
Eb (CNT+ DMMP) = ET (CNT+DMMP) ET (CNT) ET (DMMP)
- where ET (CNT+DMMP) and ET (CNT) are the total energies of the CNT with and
without a DMMP molecule attached respectively.
ET (DMMP) is the total energy of an isolated DMMP molecule.
Eb (CNT+ DMMP) is the binding energy of DMMP molecule on CNT.
Table 5.1 Energy of DMMP molecule in Configuration-1
Distance Total Energy (eV) Total Energy(eV) Total Energy (eV) Binding Energy
From Oxygen to CNT+ DMMP CNT DMMP (eV) CNT +
Carbon atom (in DMMP
angstrom)
3.1 -27296.70903 -25109.28319 -2187.17416 -0.25168
3.0 -27296.72902 -25109.28319 -2187.17416 -0.27167
2.9 -27296.74884 -25109.28319 -2187.17416 -0.29149

2.8 -27296.76182 -25109.28319 -2187.17416 -0.30447
2.7 -27296.76493 -25109.28319 -2187.17416 -0.30758

2.6 -27296.75437 -25109.28319 -2187.17416 -0.29702
2.5 -27296.74347 -25109.28319 -2187.17416 -0.28612
Eb (CNT+ DMMP) = -0.30758 eV -in Configuration-1
5.1.2 Configuration-2: DMMP on Pristine CNT (10,0) with Oxygen

atom of P=O bond of DMMP above mid of C-C bond of CNT
Figure 5.4 Top view of DMMP molecule on CNT- where Oxygen atom of P=O bond of
DMMP is in middle of C-C bond of CNT
DMMP is in middle of C-C bond of CNT
Figure 5.6 Front view of DMMP molecule on CNT- where Oxygen atom of P=O bond of DMMP is in
middle of C-C bond of CNT
As seen in the above figures the Oxygen atom of P=O bond of DMMP is in middle of C-C
bond of CNT and from this position moving in both directions of Y-axis slowly-closer and farther to
CNT by 0.1 the Total energy of the system was calculated at every step. Then Binding Energy of
DMMP molecule was calculated.
Distance Total Energy (eV) Total Energy(eV) Total Energy (eV) Binding
From Oxygen CNT+ DMMP CNT DMMP Energy (eV)
to mid of C-C CNT +
bond (in DMMP
angstrom)
3.1 -27296.70989 -25109.28319 -2187.17416 -0.25254
3.0 -27296.72692 -25109.28319 -2187.17416 -0.26957
2.9 -27296.74531 -25109.28319 -2187.17416 -0.28796
2.8 -27296.75659 -25109.28319 -2187.17416 -0.29924
2.7 -27296.75758 -25109.28319 -2187.17416 -0.30023
2.6 -27296.74408 -25109.28319 -2187.17416 -0.28673

2.5 -27296.71062 -25109.28319 -2187.17416 -0.25327
As visible in the results the Binding energy of Configuration-2 here is less than that of
Configuration-1 (-0.30023 eV is less than -0.30758 eV) thus we can conclude that there is higher
probability of DMMP molecule attaching to CNT in Configuration-1 than in Configuration-2 but
we are not arriving at conclusion here as there are more possible configurations of DMMP on
CNT which are more stable as shown in following results of Configuration-3 and Configuration-4.
5.1.3 Configuration-3: DMMP on Pristine CNT (10,0) with Oxygen atom of P=O
bond of DMMP above mid of hexagon formed by Carbon atoms of CNT
Figure 5.7 Top view of DMMP molecule on CNT- where Oxygen atom of P=O bond of DMMP is
above mid of hexagon formed by Carbon atoms of CNT
DMMP is above mid of hexagon formed by Carbon atoms of CNT
Figure 5.9 Front view of DMMP molecule on CNT- where Oxygen atom of P=O bond of
DMMP is above mid of hexagon formed by Carbon atoms of CNT
As seen in the above figures the Oxygen atom of P=O bond of DMMP is above mid of
hexagon formed by Carbon atoms of CNT and from this position moving in both directions of Y-
axis slowly- closer and farther to CNT by 0.1 the Total energy of the system was calculated at
every step. Then Binding Energy of DMMP molecule was calculated.
From Oxygen to CNT+ DMMP CNT DMMP Energy (eV)
mid of hexagon CNT +
formed by Carbon DMMP
atoms (in angstrom)
2.9 -30443.85367 -28256.38182 -2187.17416 -0.29769
2.8 -30443.87579 -28256.38182 -2187.17416 -0.31981
2.7 -30443.89086 -28256.38182 -2187.17416 -0.33488
2.6 -30443.89614 -28256.38182 -2187.17416 -0.34016
2.5 -30443.88805 -28256.38182 -2187.17416 -0.33207

2.4 -30443.87194 -28256.38182 -2187.17416 -0.31596
5.1.4 Configuration-4: DMMP on Pristine CNT (10,0) with Oxygen atom of

P=O bond of DMMP directly above a Carbon atom but tilted to keep methyl
group away from CNT
Figure 5.10 Top view of DMMP molecule on CNT- where Oxygen atom of P=O bond of DMMP
is above a Carbon atom but tilted to keep methyl group away from CNT
DMMP is above a Carbon atom but tilted to keep methyl group away from CNT
Figure 5.12 Front view of DMMP molecule on CNT- where Oxygen atom of P=O bond of DMMP is
above a Carbon atom but tilted to keep methyl group away from CNT
As seen in the above figures the Oxygen atom of P=O bond of DMMP is above a Carbon atom
but tilted to keep methyl group away from CNT, this position can be said as analogous to
Configuration-1 but the difference is that the methyl groups are tilted away from CNT. Thereby from
this configuration we can see the role of methyl groups and their effect on binding energy. As done
previously here also same procedure is followed and
thus from this position moving in both directions of Y-axis slowly closer and farther to CNT by 0.1
the Total energy of the system was calculated at every step. Then Binding Energy of DMMP molecule
was calculated.
Distance Total Energy (eV) Total Total Energy (eV) Binding

From Oxygen to CNT+ DMMP Energy(eV) DMMP Energy (eV)
Carbon atom (in CNT CNT +
angstrom) DMMP
11.5 -27296.45401 -25109.28319 -2187.17416 0.00334
3.5 -27296.5645 -25109.28319 -2187.17416 -0.10715
3.4 -27296.58463 -25109.28319 -2187.17416 -0.12728
3.3 -27296.60641 -25109.28319 -2187.17416 -0.14906

3.2 -27296.62926 -25109.28319 -2187.17416 -0.17191
3.1 -27296.65211 -25109.28319 -2187.17416 -0.19476
3.0 -27296.67528 -25109.28319 -2187.17416 -0.21793
2.9 -27296.69345 -25109.28319 -2187.17416 -0.2361
2.8 -27296.70605 -25109.28319 -2187.17416 -0.2487
2.7 -27296.70961 -25109.28319 -2187.17416 -0.25226
2.6 -27296.69982 -25109.28319 -2187.17416 -0.24247
2.5 -27296.67074 -25109.28319 -2187.17416 -0.21339
2.3 -27296.52612 -25109.28319 -2187.17416 -0.06877
2.1 -27296.19299 -25109.28319 -2187.17416 0.26436
1.9 -27295.56417 -25109.28319 -2187.17416 0.89318
1.7 -27294.52913 -25109.28319 -2187.17416 1.92822
1.6 -27293.84345 -25109.28319 -2187.17416 2.6139
Eb (CNT+ DMMP) = -0.25226 eV-in Configuration-4
5.1.5 Conclusion on configurations of DMMP on CNT
As visible clearly in the results the Binding energy of Configuration-3 i.e. where Oxygen atom
of P=O bond of DMMP is above mid of hexagon formed by Carbon atoms of CNT is greater than all
the other 3 configuration analysed.
It can thereby be said that it is the most stable configuration, also by looking at the geometry
of the configuration we can conclude that the stability is due to the interaction of all 6 carbon atoms of
hexagon with oxygen atom of DMMP which stabilizes the molecule greatly as in configuration-1 and
configuration-2 there is interaction with just 1 and 2 carbon atoms respectively.
There is another fact to be noticed that the methyl group if tilted away from CNT as done in
configuration-4 and keeping other parameters same as was in configuration-1 reduces the stability of
the interaction as the binding energy decreases significantly ( Eb(CNT+ DMMP) in Configuration-4 is
-0.25226 eV whereas Eb(CNT+ DMMP) in Configuration-1 is -0.30758 eV ). This finding thus shows
that there is interaction of methyl groups of DMMP with CNT backbone which affects the stability of
the interaction and thereby its binding energy.
5.2 Finding optimized configuration of Sarin on Pristine CNT
For finding the binding energy of Sarin on CNT same procedure was performed as done on
DMMP. Pristine SWCNT (10,0) was used because of its semiconducting properties thus its unit cell
was built in ATK which was repeated 4 times resulting in formation of CNT having length 1.56295 nm
and comprising of 159 Carbon atoms in it.
Sarin molecule was also constructed in builder and geometry optimisation was performed on it
by Density Functional Theory (DFT) with Exchange correlation as GGA (Generalized Gradient
experimental ones and thus highly relaxed geometry of Sarin molecule was obtained.
To study Sarin molecule interactions with CNT first there is need to find the lowest energy
configuration of the molecule over CNT. It is well known fact that the P=O bond present in Sarin is the
one responsible for various interactions thus focus was on this bond only and its various possible
geometrical positions over CNT were tried out. For every configuration minimum energy position was
derived by finding the least Total Energy of the system at a set distance r from CNT to Sarin
molecule. Thereby most stable configuration was at the minima of Energy v/s Distance curve. At that
position Binding Energy of the molecule was also determined.
continuously gets relaxed by losing its Energy and then when its sufficiently close to CNT it interacts
and gets physiorbed or chemisorbed thereby finding a position which has least Total Energy of the
system. In our simulation study same procedure has been applied as Total Energy of the system has
been computed by slowly bringing Sarin molecule closer to CNT i.e. at every 0.1 distance Total
Energy has been calculated using DFT. This procedure has been performed similarly on HFIPA
molecule with every possible configuration.
5.2.1 Configuration-1: Sarin on Pristine CNT (10,0) with Oxygen atom of P=O
bond of Sarin directly above a Carbon atom in CNT
Figure 5.13 Top view of Sarin molecule on CNT- where Oxygen atom of P=O bond of Sarin is
directly above Carbon atom of CNT
Figure 5.14 Axial Side view of Sarin molecule on CNT- where Oxygen atom of P=O bond of Sarin
is directly above Carbon atom of CNT
Figure 5.15 Front view of Sarin molecule on CNT- where Oxygen atom of P=O bond of
Sarin is directly above Carbon atom of CNT
As clearly seen in the above figures the Oxygen atom of P=O bond of Sarin is
directly placed above Carbon atom of CNT and from this position moving in both
directions of Y-axis slowly- closer and farther to CNT by 0.1 the Total energy of the
system was calculated at every step. Then Binding Energy of Sarin molecule was
calculated using the simple formula-
Eb (CNT+ Sarin) = ET (CNT+Sarin) ET (CNT) ET (Sarin)
- where ET (CNT+Sarin) and ET (CNT) are the total energies of the CNT with and without
a Sarin molecule attached respectively.
ET (Sarin) is the total energy of an isolated Sarin molecule.
Eb (CNT+ Sarin) is the binding energy of Sarin molecule on CNT.
Table 5.5 Energy of Sarin molecule in Configuration-1

From Oxygen to CNT+ Sarin CNT Sarin (eV) CNT +
Carbon atom (in Sarin
angstrom)
3 -27680.85203 -25109.28319 -2571.34198 -0.22686
2.9 -27680.86907 -25109.28319 -2571.34198 -0.2439
2.8 -27680.88022 -25109.28319 -2571.34198 -0.25505
2.7 -27680.88481 -25109.28319 -2571.34198 -0.25964
2.6 -27680.87483 -25109.28319 -2571.34198 -0.24966

2.5 -27680.84704 -25109.28319 -2571.34198 -0.22187
2.4 -27680.79449 -25109.28319 -2571.34198 -0.16932
Eb (CNT+ Sarin) = -0.25964 eV -in Configuration-1
5.2.2 Configuration-2: Sarin on Pristine CNT (10,0) with Oxygen atom

of P=O bond of Sarin above mid of C-C bond of CNT
Figure 5.16 Top view of Sarin molecule on CNT- where Oxygen atom of P=O bond of
Sarin is in middle of C-C bond of CNT
Figure 5.17 Axial Side view of Sarin molecule on CNT- where Oxygen atom of P=O
bond of Sarin is in middle of C-C bond of CNT
Figure 5.18 Front view of Sarin molecule on CNT- where Oxygen atom of P=O bond of Sarin is
in middle of C-C bond of CNT
As seen in the above figures the Oxygen atom of P=O bond of Sarin is in middle of C-C
bond of CNT and from this position moving in both directions of Y-axis slowly- closer and farther
to CNT by 0.1 the Total energy of the system was calculated at every step.
Then Binding Energy of Sarin molecule was calculated.
From Oxygen CNT+ Sarin CNT Sarin Energy (eV)
to mid of C-C CNT + Sarin

bond (in
angstrom)
3.1 -27680.84081 -25109.28319 -2571.34198 -0.21564
3.0 -27680.85320 -25109.28319 -2571.34198 -0.22803
2.9 -27680.86480 -25109.28319 -2571.34198 -0.23963
2.8 -27680.87458 -25109.28319 -2571.34198 -0.24941
2.7 -27680.87724 -25109.28319 -2571.34198 -0.25207
2.6 -27680.86450 -25109.28319 -2571.34198 -0.23933
2.5 -27680.83316 -25109.28319 -2571.34198 -0.20799

5.2.3 Configuration-3: Sarin on Pristine CNT (10,0) with Oxygen atom of P=O
bond of Sarin above mid of hexagon formed by Carbon atoms of CNT
Figure 5.19 Top view of Sarin molecule on CNT- where Oxygen atom of P=O bond of Sarin is
Figure 5.20 Axial Side view of Sarin molecule on CNT- where Oxygen atom of P=O bond of Sarin
is above mid of hexagon formed by Carbon atoms of CNT
Figure 5.21 Front view of Sarin molecule on CNT- where Oxygen atom of P=O bond of Sarin is
As seen in the above figures the Oxygen atom of P=O bond of Sarin is above mid of
hexagon formed by Carbon atoms of CNT and from this position moving in both directions of Y-
axis slowly- closer and farther to CNT by 0.1 the Total energy of the system was calculated at
every step then Binding Energy of Sarin molecule was calculated.

From Oxygen to CNT+ Sarin CNT Sarin Energy (eV)
mid of hexagon CNT +
formed by Carbon Sarin
atoms (in angstrom)
3.1 -30827.93461 -28256.38182 -2571.34198 -0.21081
3 -30827.95531 -28256.38182 -2571.34198 -0.23151
2.9 -30827.98289 -28256.38182 -2571.34198 -0.25909
2.8 -30828.00382 -28256.38182 -2571.34198 -0.28002
2.7 -30828.02107 -28256.38182 -2571.34198 -0.29727
2.6 -30828.02766 -28256.38182 -2571.34198 -0.30386
2.5 -30828.02214 -28256.38182 -2571.34198 -0.29834
5.2.4 Conclusion on Configurations of Sarin on CNT
As visible clearly in the results the Binding energy of Configuration-3 i.e. where Oxygen atom
of P=O bond of Sarin is above mid of hexagon formed by Carbon atoms of CNT is greater than all the
other configuration analysed.
It can thereby be said that it is the most stable configuration, also by looking at the geometry of
the configuration we can conclude that the stability is due to the interaction of all 6 carbon atoms of
hexagon with oxygen atom of Sarin which stabilizes the molecule greatly as in configuration-1 and
configuration-2 there is interaction with just 1 and 2 carbon atoms respectively. In this study of Sarin
interactions the study of methyl group on interaction with CNT was omitted as while studying DMMP
configuration-4 we observed a clear case of methyl group affecting the binding energy and thus Sarin
sharing a very similar geometry to DMMP will show similar results.
Comparing results of DMMP and Sarin we can see that binding of DMMP is stronger than that
of Sarin this happens due to the presence of Fluorine molecule on Sarin which is highly
electronegative and destabilizes the molecules interaction with that of CNT. After this study of binding
energy, IV characteristics (using CNT as self-electrode) of the most stable configuration of DMMP and
Sarin were simulated using DFT.
5.3 Finding optimized configuration of HFIPA on Pristine CNT
For finding the binding energy of HFIPA on CNT same procedure was performed as done on
DMMP and Sarin. It is necessary to find whether the interaction of HFIPA molecule with CNT is
sufficient enough to form the composite. Again similar Pristine SWCNT (10,0) was used because of its
semiconducting properties thus its unit cell was built in ATK which was repeated 4 times resulting in
formation of CNT having length 1.56295 nm and comprising of 159 Carbon atoms in it.
HFIPA molecule was also constructed in builder and geometry optimisation was performed on
it by Density Functional Theory (DFT) with Exchange correlation as GGA (Generalized Gradient
experimental ones and thus highly relaxed geometry of HFIPA molecule was obtained.
HFIPA molecule has benzene ring in its structure and with this benzene ring there is p -p
interactions taking place with the benzene like hexagonal ring of CNT. This stacking of one Benzene
ring leads to formation of stable composite with CNT. But HFIPA molecule though having benzene
ring cant be said as showing interaction properties purely because of the benzene ring as there is this
Hexafluoro-isopropanol structure which will surely affect the interaction mechanism. Therefore this
simulation study on HFIPA was performed to check the feasibility of using the HFIPA molecule for
selective sensing purpose by calculating its Binding energy with CNT for formation of CNT composite
and then looking for hydrogen bonding between OH group of HFIPA and Oxygen atom of P=O bond
of DMMP and Sarin.
It is thus required to find the lowest energy configuration of the molecule over CNT. Thus for
almost every configuration minimum energy position was derived by finding the least Total Energy of
the system at a set distance r from CNT to HFIPA molecule. Thereby most stable configuration was
at the minima of Energy v/s Distance curve. At that position Binding Energy of the molecule was also
determined.
continuously gets relaxed by losing its Energy and then when
its sufficiently close to CNT it interacts and gets physiorbed or chemisorbed thereby finding a position
which has least Total Energy of the system. In our simulation study same procedure has been applied
as Total Energy of the system has been computed by slowly bringing HFIPA molecule closer to CNT
i.e. at every 0.1 distance Total Energy has been calculated using DFT.
5.3.1 Configuration-1: HFIPA on Pristine CNT (10,0) with Benzene ring of HFIPA
molecule parallel displaced over hexagonal ring of Carbon atoms of CNT
Figure 5.22 Top view of HFIPA molecule on CNT where Benzene ring of HFIPA molecule is parallel
displaced over hexagonal ring of Carbon atoms of CNT and OH group facing towards the CNT
Figure 5.23 Axial Side view of HFIPA molecule on CNT where Benzene ring of HFIPA molecule is
parallel displaced over hexagonal ring of Carbon atoms of CNT and OH group facing towards the
CNT
Figure 5.24 Front view of HFIPA molecule on CNT where Benzene ring of HFIPA molecule is
parallel displaced over hexagonal ring of Carbon atoms of CNT and OH group facing towards the
CNT
As clearly seen in the above figures the Benzene ring of HFIPA molecule is not directly above
the hexagonal ring of CNT whereas its parallel displaced such that the 3 carbon atoms of benzene ring
in HFIPA in top view are seen in mid of hexagons of CNT and other 3 carbon atoms of HFIPA is
directly above 3 carbon atoms of CNT. This position allows for maximum interaction of their electron
clouds. From this position moving in both directions of Y-axis slowly- closer and farther to CNT by
0.1 the Total energy of the system was calculated at every step. Then Binding Energy of HFIPA
molecule was calculated using the simple formula-
Eb (CNT+ HFIPA) = ET (CNT+HFIPA) ET (CNT) ET (HFIPA)
- where ET (CNT+HFIPA) and ET (CNT) are the total energies of the CNT with and
without a HFIPA molecule attached respectively.
ET (HFIPA) is the total energy of an isolated HFIPA molecule.
Eb (CNT+ HFIPA) is the binding energy of HFIPA molecule on CNT.
Table 5.8 Energy of HFIPA molecule in Configuration-1
From Oxygen to CNT+ HFIPA CNT HFIPA (eV) CNT +
Carbon atom (in HFIPA
angstrom)
5.2 -31210.33129 -25109.28319 -6100.93216 -0.11594
5.1 -31210.35143 -25109.28319 -6100.93216 -0.13608
5 -31210.37189 -25109.28319 -6100.93216 -0.15654
4.9 -31210.39396 -25109.28319 -6100.93216 -0.17861
4.8 -31210.41198 -25109.28319 -6100.93216 -0.19663
4.7 -31210.42658 -25109.28319 -6100.93216 -0.21123
4.6 -31210.43541 -25109.28319 -6100.93216 -0.22006
4.5 -31210.43493 -25109.28319 -6100.93216 -0.21958
4.4 -31210.41981 -25109.28319 -6100.93216 -0.20446
4.3 -31210.38527 -25109.28319 -6100.93216 -0.16992
Eb (CNT+ HFIPA) = -0.22006 eV -in Configuration-1
molecule directly over hexagonal ring of Carbon atoms of CNT
Figure 5.25 Top view of HFIPA molecule on CNT where Benzene ring of HFIPA molecule is directly
over hexagonal ring of Carbon atoms of CNT and OH group facing towards the CNT.
directly over hexagonal ring of Carbon atoms of CNT and OH group facing towards the CNT
Figure 5.27 Front view of HFIPA molecule on CNT where Benzene ring of HFIPA
molecule is directly over hexagonal ring of Carbon atoms of CNT and OH group facing
towards the CNT
As clearly seen in the above figures the Benzene ring of HFIPA molecule is
directly above the hexagonal ring of CNT such that all the 6 carbon atoms of benzene ring
in HFIPA are above the 6 carbon atoms of hexagon of CNT. From this position moving in
both directions of Y-axis slowly- closer and farther to CNT by 0.1 the Total energy of
the system was calculated at every step. Then Binding Energy of HFIPA molecule was
calculated.
angstrom)
5.1 -31210.36081 -25109.28319 -6100.93216 -0.14546
5 -31210.38009 -25109.28319 -6100.93216 -0.16474
4.9 -31210.40146 -25109.28319 -6100.93216 -0.18611
4.8 -31210.41865 -25109.28319 -6100.93216 -0.2033
4.7 -31210.43214 -25109.28319 -6100.93216 -0.21679
4.6 -31210.43901 -25109.28319 -6100.93216 -0.22366
4.5 -31210.43534 -25109.28319 -6100.93216 -0.21999

4.4 -31210.41562 -25109.28319 -6100.93216 -0.20027
4.3 -31210.37472 -25109.28319 -6100.93216 -0.15937
5.3.3 Configuration-3: HFIPA on Pristine CNT (10,0) with Benzene ring

of HFIPA molecule directly over hexagonal ring of Carbon atoms of CNT
but OH group facing away from CNT
Figure 5.28 Top view of HFIPA molecule on CNT where Benzene ring of HFIPA
molecule is directly over hexagonal ring of Carbon atoms of CNT and OH group facing
away from CNT.
directly over hexagonal ring of Carbon atoms of CNT and OH group facing away from CNT
Figure 5.30 Front view of HFIPA molecule on CNT where Benzene ring of HFIPA molecule is
directly over hexagonal ring of Carbon atoms of CNT and OH group facing away from CNT
As clearly seen in the above figures the Benzene ring of HFIPA molecule is directly above the
hexagonal ring of CNT such that all the 6 carbon atoms of benzene ring in HFIPA are above the 6
carbon atoms of hexagon of CNT but the OH group is facing away from CNT thereby its interaction
with CNT is minimised. From this position moving in both directions of Y-axis slowly- closer and
farther to CNT by 0.1 the Total energy of the system was calculated at every step. Then Binding
Energy of HFIPA molecule was calculated.

angstrom)
5.3 -31210.44596 -25109.28319 -6100.93216 -0.23061
5.2 -31210.4726 -25109.28319 -6100.93216 -0.25725
5.1 -31210.4947 -25109.28319 -6100.93216 -0.27935
5 -31210.51254 -25109.28319 -6100.93216 -0.29719
4.9 -31210.51763 -25109.28319 -6100.93216 -0.30228
4.8 -31210.50845 -25109.28319 -6100.93216 -0.2931
4.7 -31210.47898 -25109.28319 -6100.93216 -0.26363
4.6 -31210.42066 -25109.28319 -6100.93216 -0.20531
4.5 -31210.32181 -25109.28319 -6100.93216 -0.10646
4.4 -31210.16644 -25109.28319 -6100.93216 0.04891
4.3 -31209.93576 -25109.28319 -6100.93216 0.27959
4.2 -31209.59553 -25109.28319 -6100.93216 0.61982
placed in t-configuration above mid of Carbon atoms of CNT but OH group
facing down towards CNT
Figure 5.31 Top view of HFIPA molecule on CNT where Benzene ring of HFIPA molecule is placed in
t-configuration above mid of Carbon atoms of CNT but OH group facing down towards CNT
placed in t-configuration above mid of Carbon atoms of CNT but OH group facing down towards
CNT
Figure 5.33 Front view of HFIPA molecule on CNT where Benzene ring of HFIPA
molecule is placed in t-configuration above mid of Carbon atoms of CNT but OH group
facing down towards CNT
As clearly seen in the above figures the Benzene ring of HFIPA molecule is placed
in t-configuration above mid of Carbon atoms of CNT with OH group facing down
towards CNT. In this configuration the benzene ring is far away from CNT and thereby its
interaction with CNT is minimised. From this position moving in both directions of Y-axis
slowly- closer and farther to CNT by 0.1 the Total energy of the system was calculated
at every step. Then Binding Energy of HFIPA molecule was calculated.
angstrom)
5 -31210.34224 -25109.28319 -6100.93216 -0.12689
4.9 -31210.37099 -25109.28319 -6100.93216 -0.15564
4.8 -31210.40365 -25109.28319 -6100.93216 -0.1883
4.7 -31210.44167 -25109.28319 -6100.93216 -0.22632
4.6 -31210.48011 -25109.28319 -6100.93216 -0.26476
4.5 -31210.51962 -25109.28319 -6100.93216 -0.30427

4.4 -31210.55848 -25109.28319 -6100.93216 -0.34313
4.3 -31210.59395 -25109.28319 -6100.93216 -0.3786
4.2 -31210.62275 -25109.28319 -6100.93216 -0.4074
4.1 -31210.64268 -25109.28319 -6100.93216 -0.42733
4 -31210.64412 -25109.28319 -6100.93216 -0.42877
3.9 -31210.62206 -25109.28319 -6100.93216 -0.40671
5.3.5 Conclusion on configurations of HFIPA on CNT
As visible clearly in the results the Binding energy of Configuration-4 i.e. where
Benzene ring of HFIPA molecule is placed in t-configuration above mid of Carbon atoms
of CNT with OH group facing down towards CNT is greater than all the other
configuration analysed.

It can thereby be said that it is the most stable configuration, also by looking at the
geometry of the configuration we can conclude that the stability is due to the least
interaction between the benzene ring of HFIPA molecule and the carbon atoms of CNT.
After this study of binding energy, I-V characteristics (using CNT as self-
electrode) of the most stable configuration of HFIPA was simulated using DFT.
Future prospects
In future we want to increase selectivity and sensitivity of CNT based gas sensor. For it we are
exploring different functionalization groups which can enhance working of CNT as gas sensor. Besides
this we are also searching for effect of combination of CNT and Graphene, combination of these two
can enhance properties of CNT gas sensors. We are also trying to find out possibilities of
Nanoparticles attached with CNT to increase sensitivity and convert physisorption into chemisorption
with easy desorption.
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Master&#39;s Thesis 2014

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COMPUTATIONAL STUDIES ON THE

INTERACTIONS BETWEEN SARIN, DMMP & NO2

Amity Institute of Nanotechnology

I, Himanshu, student of B.Tech. + M.Tech. (Dual Degree) Nanotechnology, hereby declare

Dr. NEELAM KUSHWAHA

CH . 1 ..........................................INTRODUCTION TO CARBON NANOTUBES

4.1 Findig the optimized position of NO 2 on CNT surface

1.1 TEM image of a MWNT and its cross section below

Carbon atom of CNT

Table 1.1 Properties of Carbon Nanotubes

1.2Structure of Carbon Nanotubes

Based on rolling pattern:

Figure 1.4 Armchair Figure 1.5 Zigzag Figure 1.6 Chiral

Chiral vector can be easily defined by this equation

- n and m are indices representing wrapping of sheet

If = 0 => Armchair nanotube; n=m

1.3 Band structure and electron transport physics of one-dimensional SWNTs

n = m, then the nanotube is metallic;

1.3.1 Electronic band structure of graphene [12]

E = E0 0(1 + 4 cos(3kxa/2) cos(kya/2)+ 4 cos2(kya/2))1/2 ............2

Figure 1.8 Energy dispersion of graphene along high-symmetry points as

1.3.2 Band structure of SWNT from graphene

1.3.3 Density of states in SWNTS

n(E) = N(E)/E = 2/L dk (k ki) /k1 (4)

1.4 Mechanical properties of CNT

Material Young's modulus Tensile strength Elongation at break

1.5 Thermal properties of CNT

1.6 Synthesis of CNTs

Figure 1.13 Synthesis methods for CNTs [32]

1.6.1 Electric arc discharge

It is typically a low-voltage discharge between two electrodes caused by electric breakdown of

Figure 1.14 Schematic setup of arc discharge method.

1.6.3 Chemical Vapour Deposition (CVD)

Figure 1.15 CVD process inside quartz tube with heaters

Chemical properties- binding energies between molecules changes

2.2 Pristine Carbon Nanotubes as gas sensors

2.3 Functionalised Carbon Nanotubes as gas sensors

2.4 Advantages of SWNT gas sensor over existing gas sensors

2.5 Fabrication of CNT based gas sensor

Figure 2.2 Resistor based CNT gas sensor

B) FET based CNT sensor (active sensor)

Figure 2.3 FET based CNT gas sensor

2.6 Computational Studies of CNT gas sensor

3.2 Overview of methodology used

3.2.1 First Hohenberg and Kohn theorem

3.2.2 Second Hohenberg and Kohn theorem

3.3 Introduction to Atomistix Toolkit (ATK)

Atomistix Toolkit is a software package developed by QuantumWise. It has the capability to

Classical Brenner potential is used to perform fast geometry optimizations or molecular

It is possible to calculate wide range of properties like-

Electronic structure properties

Transport properties at finite bias via non-equilibrium Green's functions

Current-voltage (I-V) curve

Transmission Eigen-states and pathways

Thermionic emission current

Eb(CNT+ NO2) = Et(CNT+ NO2) Et(CNT) Et(NO2) .3.1

Figure 4.2 SWNT as a device with self electrode

Figure 4.3 DOS and band diagram of SWNT

Figure 4.4 I-V curve for SWNT with its conductance

4.2.1 Interpretation and discussion of data

4.3.1 INTERPRETATION AND DISCUSSION OF DATA

1. DOS OF CNT WITH NO2

4.4 Results and discussions

Master's Thesis 2014

Master's Thesis 2014