CNT Nano Sensors Simulation in Drdo

Chapter 1
Introduction to Carbon Nanotubes

1.1
Introduction
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 (C 2 H 2 ), sp2 (Graphite)
or sp3 (CH 4 ) 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 sp2 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 Thess 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.
1
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.
Property
Comparison
Carrier mobility: 79000 cm2/Vs (at RT) [4]
> Hole mobility in Si
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: ~ 1 TPa [8]
> Diamond
Table 1.1 Properties of Carbon Nanotubes

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
2
sensors also as because of their high aspect ratio there is large field concentration induced
in them which ionizes gaseous molecules.
1.2
Structure 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 = |a 1 | = |a 2 | = 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.
3
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 C h and the armchair
line (sheet of graphene is folded at this line thus the two halves are thereby 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 C h = (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
C h = na 1 + ma 2
-
n and m are indices representing wrapping of sheet
a 1 and a 2 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 [25; nordheim].
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
Properties of Carbon Nanotubes
1.3.1 Mechanical properties

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 [11].
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 [12]. 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 [13, 14, 15, 16, 17, 18]
Material
Young's modulus
Tensile strength
Elongation at break
(TPa)
(GPa)
(%)
~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
0.186
0.38
1550
0.060.18
3.63.8
~2
SWNT
Stainless Steel
Kevlar29&149E
1.3.2 Electrical properties

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 [19] 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. Therefore it has been found according to
calculations that a (5,0) SWCNT is in fact metallic whereas by looking at its indices it can
be wrongly assumed that it should be semiconducting. Similarly it has been found that
zigzag and chiral SWCNTs with small diameters thus which should be metallic are not so
and have finite band gap present. Theoretical calculations performed has shown that electric
current density of around 4 109 A/cm2 can be successfully carried by metallic nanotubes
it is thus more than 1,000 times greater than copper [20] which is most widely used metal
in applications for electrical conduction therefore this is an astonishing property of carbon
nanotubes and can bring about a revolution by its highly useful electrical applications.
During conduction CNTs allow only a one-dimensional degree of freedom for the
movement of electrons due to the small nanometer wide cross-section. The movement of
electrons is thus termed as ballistic conductance through a quantum channel. The maximum
electrical conductance of a single-walled carbon nanotube is 2G 0 , where G 0 = 2e2/h is the
conductance of a single ballistic quantum channel [21].
1.3.3 Thermal properties

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
7
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 Wm1K1 [22] this conductivity
is very large as if we compare it to copper which transmits 385 Wm1K1 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 [23]
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 [24].
1.4
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 1.8 Synthesis methods for CNTs [25]
1.4.1 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:
Anode
(-)
Cathode
(+)
Carbon soot deposits

containing CNTs
Inert
atmosphere
+
DC
current
Figure 1.9 Schematic setup of arc discharge method.
1.4.2 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
1200C, 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).
Inert gas stream
Quartz tube
Water-cooled
Cu collector
Laser
Graphite
target
Figure 1.10 Schematic representation of laser ablation.

10
1.4.3 Chemical Vapour Deposition

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 1.11 CVD process inside quartz tube with heaters.
11
Chapter 2
Gas Sensing
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
12
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 [26]. 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 [27].
However recent research is focused more on modification/functionalization 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 sensors

Unmodified or pristine carbon nanotubes are highly stable because they have strong
sp2 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, NO2
and NH3 are detected to some extent.
13
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 [28]. 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. [29] 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
Functionalized carbon nanotubes as 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.
14
Such limitations need to be overcome for development of an effective gas sensor.

Research is thus focussed 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 [30]. 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 [30].
15
2.4
Computational Studies
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 Cl 2 , CO, NO and H 2
[31, 32]. 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, H 2 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 H 2 gas molecules effectively while O-doped CNTs can sense H 2 , Cl 2 and CO also Ndoped interacts and detects CO, NO and Cl 2 [32].
Hamadanian et al. have reported theoretical study of Al-substituted SWCNTs (10,0)
for use as CO gas sensor [33]. 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.
16
Chapter 3
Density Functional 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 [34, 35, 36, 37].
3.2
Overview of Method
Conceptual roots of DFT are in the Thomas Fermi Model but it received a
phenomenal development by the two theorems of Hohenberg and Kohn [38] 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 [39].
17
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
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
18
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
19
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.
20
Chapter 4
Simulations Performed and Results
4.1
Finding Binding Energy 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
21
calculated using DFT. This procedure has been performed similarly on HFIPA and Sarin
molecules with every possible configuration.
4.1.1 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 4.1 Top view of DMMP molecule on CNT- where Oxygen atom of P=O bond of
DMMP is directly above Carbon atom of CNT
Figure 4.2 Axial Side view of DMMP molecule on CNT- where Oxygen atom of P=O
bond of DMMP is directly above Carbon atom of CNT
22
Figure 4.3 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 slowlycloser 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 formulaE b (CNT+ DMMP) = E T (CNT+DMMP) E T (CNT) E T (DMMP)
- where E T (CNT+DMMP) and E T (CNT) are the total energies of the CNT with
and without a DMMP molecule attached respectively.
E T (DMMP) is the total energy of an isolated DMMP molecule.
E b (CNT+ DMMP) is the binding energy of DMMP molecule on CNT.
Table 4.1 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
-27296.72902
-25109.28319
-2187.17416
-0.27167
23
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
E b (CNT+ DMMP) = -0.30758 eV
-in Configuration-1

P=O bond of DMMP above mid of C-C bond of CNT
DMMP is in middle of C-C bond of CNT
24
bond of DMMP is in middle of C-C bond of CNT
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 slowlycloser 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.
25

Distance
From Oxygen
Total Energy (eV)
Total Energy(eV)
Total Energy (eV)
Binding
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
E b (CNT+ DMMP) = -0.30023 eV
-in Configuration-2
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.
26
P=O bond of DMMP above mid of hexagon formed by Carbon atoms

of CNT
DMMP is above mid of hexagon formed by Carbon atoms of CNT
bond of DMMP is above mid of hexagon formed by Carbon atoms of CNT
27
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 slowlycloser 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
From Oxygen to
Total Energy (eV)
Total Energy(eV)
Total Energy (eV)
Binding
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
28
2.5
-30443.88805
-28256.38182
-2187.17416
-0.33207
2.4
-30443.87194
-28256.38182
-2187.17416
-0.31596
E b (CNT+ DMMP) = -0.34016 eV
-in Configuration-3

P=O bond of DMMP directly 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
29
bond of DMMP is above a Carbon atom but tilted to keep methyl group away from CNT
Figure 4.12 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
30
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
From Oxygen to
Total Energy (eV)
Total
Total Energy (eV)
Binding
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
-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
E b (CNT+ DMMP) = -0.25226 eV
-in Configuration-4
31
4.1.5 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.
E b (CNT+ DMMP) = -0.30758 eV -in Configuration-1
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
E b (CNT+ DMMP) in Configuration-4 is -0.25226 eV whereas E b (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.
32
4.2
Finding Binding Energy 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
give values very close to experimental ones and thus highly relaxed geometry of Sarin
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.
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.
33
4.2.1 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 4.13 Top view of Sarin molecule on CNT- where Oxygen atom of P=O bond of
Sarin is directly above Carbon atom of CNT
Figure 4.14 Axial Side view of Sarin molecule on CNT- where Oxygen atom of P=O
bond of Sarin is directly above Carbon atom of CNT
34
Figure 4.15 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 slowlycloser 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 formulaE b (CNT+ Sarin) = E T (CNT+Sarin) E T (CNT) E T (Sarin)
- where E T (CNT+Sarin) and E T (CNT) are the total energies of the CNT with and
without a Sarin molecule attached respectively.
E T (Sarin) is the total energy of an isolated Sarin molecule.
E b (CNT+ Sarin) is the binding energy of Sarin molecule on CNT.
Table 4.5 Energy of Sarin molecule in Configuration-1
Distance
Total Energy (eV)
Total Energy(eV)
Total Energy (eV)
Binding Energy
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
35
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
E b (CNT+ Sarin) = -0.25964 eV
-in Configuration-1
4.2.2 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
Sarin is in middle of C-C bond of CNT
bond of Sarin is in middle of C-C bond of CNT
36
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 slowlycloser
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.
Distance
From Oxygen
Total Energy (eV)
Total Energy(eV)
Total Energy (eV)
Binding
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
-in Configuration-2
37
4.2.3 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
Sarin is above mid of hexagon formed by Carbon atoms of CNT
bond of Sarin is above mid of hexagon formed by Carbon atoms of CNT
38
Sarin 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 Sarin is above mid
of hexagon formed by Carbon atoms of CNT and from this position moving in both
system was calculated at every step then Binding Energy of Sarin molecule was calculated.
Distance
From Oxygen to
Total Energy (eV)
Total Energy(eV)
Total Energy (eV)
Binding
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
-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
-in Configuration-3
39
4.2.4 Conclusion on Configurations of Sarin on CNT

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.
-in Configuration-1
-in Configuration-2
-in Configuration-3
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.
40
4.3
Finding Binding Energy 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
give values very close to experimental ones and thus highly relaxed geometry of HFIPA
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.
41
bringing HFIPA molecule closer to CNT i.e. at every 0.1 distance Total Energy has been
calculated using DFT.
4.3.1 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 4.22 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
42
Figure 4.23 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 4.24 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
43
system was calculated at every step. Then Binding Energy of HFIPA molecule was
calculated using the simple formulaE b (CNT+ HFIPA) = E T (CNT+HFIPA) E T (CNT) E T (HFIPA)
- where E T (CNT+HFIPA) and E T (CNT) are the total energies of the CNT with and
without a HFIPA molecule attached respectively.
E T (HFIPA) is the total energy of an isolated HFIPA molecule.
E b (CNT+ HFIPA) is the binding energy of HFIPA molecule on CNT.
Table 4.8 Energy of HFIPA molecule in Configuration-1
Distance
Total Energy (eV)
Total Energy(eV)
Total Energy (eV)
Binding Energy
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
-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
E b (CNT+ HFIPA) = -0.22006 eV
-in Configuration-1
44

HFIPA molecule directly over hexagonal ring of Carbon atoms of CNT
is directly over hexagonal ring of Carbon atoms of CNT and OH group facing towards the
CNT
molecule is directly over hexagonal ring of Carbon atoms of CNT and OH group facing
towards the CNT
45
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
calculated.
Distance
Total Energy (eV)
Total Energy(eV)
Total Energy (eV)
Binding Energy
From Oxygen to
CNT+ HFIPA
CNT
HFIPA
(eV) CNT +
Carbon atom (in
HFIPA
angstrom)
5.1
-31210.36081
-25109.28319
-6100.93216
-0.14546
-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
46
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
-in Configuration-2

HFIPA molecule directly over hexagonal ring of Carbon atoms of CNT
but OH group facing away from CNT
is directly over hexagonal ring of Carbon atoms of CNT and OH group facing away from
CNT
47
away from CNT
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
48
calculated.
Distance
Total Energy (eV)
Total Energy(eV)
Total Energy (eV)
Binding Energy
From Oxygen to
CNT+ HFIPA
CNT
HFIPA
(eV) CNT +
Carbon atom (in
HFIPA
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
-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
-in Configuration-3
49

HFIPA placed in t-configuration above mid of Carbon atoms of CNT but
OH group facing down towards CNT
is placed in t-configuration above mid of Carbon atoms of CNT but OH group facing
down towards CNT
molecule is placed in t-configuration above mid of Carbon atoms of CNT but OH group
facing down towards CNT
50
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
slowlycloser 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.
Distance
Total Energy (eV)
Total Energy(eV)
Total Energy (eV)
Binding Energy
From Oxygen to
CNT+ HFIPA
CNT
HFIPA
(eV) CNT +
Carbon atom (in
HFIPA
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
51
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
-31210.64412
-25109.28319
-6100.93216
-0.42877
3.9
-31210.62206
-25109.28319
-6100.93216
-0.40671
-in Configuration-4
4.3.5 Conclusion on Configurations of HFIPA on CNT

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.
E b (CNT+ HFIPA) = -0.22066 eV -in Configuration-1
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, IV characteristics (using CNT as self-electrode)
of the most stable configuration of HFIPA was simulated using DFT.
52
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S. Iijima and T. Ichihashi. Single-shell carbon nanotubes of 1-nm diameter. Nature,

361:603, 1993.
[3]
A. Thess et al. Crystalline ropes of metallic carbon nanotubes. Science, 273:483

487, 1996.
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T. Durkop, S. A. Getty, E. Cobas, and M. S. Fuhrer. Extraordinary mobility in

semiconducting carbon nanotubes. Nano Letters, 4(1):35-39, January 2004.
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B. Q. Wei, R. Vajtai, and P. M. Ajayan. Reliability and current carrying capacity

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CNT Nano Sensors Simulation in Drdo

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Chapter 1

Introduction to Carbon Nanotubes

Carrier mobility: 79000 cm2/Vs (at RT) [4]

> Hole mobility in Si

Tensile strength: 150 GPa [7]

100 times the strength of steel

Youngs modulus: ~ 1 TPa [8]

Table 1.1 Properties of Carbon Nanotubes

Structure of Carbon Nanotubes

where a = |a 1 | = |a 2 | = 1.42 3 = 2.46 is the lattice constant of the graphene sheet as a

Figure 1.4 Armchair

Figure 1.5 Zigzag

Figure 1.6 Chiral

n and m are indices representing wrapping of sheet

a 1 and a 2 are respective unit vectors

If = 0 => Armchair nanotube; n=m

Properties of Carbon Nanotubes

1.3.1 Mechanical properties

1.3.2 Electrical properties

1.3.3 Thermal properties

various methods formulated. Intense research worldwide have focused on developing a

Figure 1.8 Synthesis methods for CNTs [25]

1.4.1 Electric arc discharge

Carbon soot deposits

Figure 1.9 Schematic setup of arc discharge method.

1.4.2 Laser ablation

Inert gas stream

Figure 1.10 Schematic representation of laser ablation.

1.4.3 Chemical Vapour Deposition

Figure 1.11 CVD process inside quartz tube with heaters.

Pristine carbon nanotubes as sensors

Functionalized carbon nanotubes as sensors

Such limitations need to be overcome for development of an effective gas sensor.

Figure 2.1 Representing a possible sensing mechanism of DMMP using TFQ

3.2.1 First Hohenberg and Kohn Theorem

3.2.2 Second Hohenberg and Kohn Theorem

Atomistix Toolkit (ATK)

capability to model electronic properties of quantum systems by density-functional theory.

Classical Brenner potential is used to perform fast geometry optimizations or

Moreover it is possible to calculate all of the above properties with added

Finding Binding Energy of DMMP on Pristine CNT

4.1.1 Configuration-1: DMMP on Pristine CNT (10,0) with Oxygen atom of

Total Energy (eV)

Total Energy (eV)

Carbon atom (in

E b (CNT+ DMMP) = -0.30758 eV

4.1.2 Configuration-2: DMMP on Pristine CNT (10,0) with Oxygen atom of

Table 4.2 Energy of DMMP molecule in Configuration-2

Total Energy (eV)

Total Energy (eV)

E b (CNT+ DMMP) = -0.30023 eV

4.1.3 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

Total Energy (eV)

Total Energy (eV)

atoms (in angstrom)

E b (CNT+ DMMP) = -0.34016 eV

4.1.4 Configuration-4: DMMP on Pristine CNT (10,0) with Oxygen atom of

Total Energy (eV)

Total Energy (eV)

Carbon atom (in

E b (CNT+ DMMP) = -0.25226 eV

4.1.5 Conclusion on Configurations of DMMP on CNT