Table of Contents

Acknowledgments..................................................................................................1

Statement of Originality.........................................................................................2

Executive Summary...............................................................................................3

Introduction............................................................................................................4

4.1

Background....................................................................................................4

4.2

Project Aims..................................................................................................7

4.3

Analysis of Literature....................................................................................8

Research Methodology........................................................................................10
5.1

Dipole Interaction Energy...........................................................................10

5.2

Metallic Contribution to the vdW Interaction Energy................................17

5.3

Conventional Contribution to the vdW Interaction Energy........................20

Results.................................................................................................................22
6.1

Dipole Interaction Energy..........................................................................22

6.2

Metallic Contribution to the vdW Interaction Energy................................23

6.3

Conventional Contribution to the vdW Interaction Energy.......................27

Discussion..........................................................................................................28
7.1

Comparison of the Various Forces for Gold Nanowires...........................28

7.2

Comparison of the Various Forces for Carbon Nanotubes.......................29

Conclusions.......................................................................................................30

References.................................................................................................................31

1
1

1 Acknowledgments
I would like to acknowledge the following individuals and organisations for their assistance
during this project.

Professor John Dobson: For providing assistance with reading and gleaning information from
scientific papers, and many proofreads and corrections of the planning report and the current
report.

Dr Jim Webb: For the advice on the current report, as well as assessing the planning report
and the IAP seminar

Queensland Micro and Nanotechnology Centre: For providing a workspace and computer for
use during the project.

3 Executive Summary
As part of the Industrial Affiliates Program (IAP) in Semester 2, 2010, a research project was
undertaken with the Queensland Micro and Nanotechnology Centre (QMNC). The research
concerned the analysis of the feasibility of an experiment that was proposed to measure the
unusual contributions to the van der Waals (vdW) force that had been predicted for low
dimensional metallic nano-systems such as metallic nanowires and nanotubes.

The following were found regarding conditions required for a feasible experiment:

The experiment should be done with wires or tubes of unequal length, in order to
minimise the unwanted effects of the fixed end dipoles situated at the ends

The experiment should be done at low temperatures (~1 K), in ordr to minimise the
energy due to thermal noise

The separation distance of the wires or tubes should be chosen carefully for the
metallic contribution to be measurable but not dominated by other confounding
effects. This distance was found to be typically between 10-100 nm for nanowires
and 10-50 nm for nanotubes.

4 Introduction
4.1 Background
The van der Waals (vdW) attractive forces between molecules and atoms are relatively weak
compared to other forms of interatomic forces, such as covalent and ionic forces. For this
reason, the vdW force is usually the dominant mechanism for interatomic and intermolecular
bonding only in the absence of these other stronger forces. Various situations in which vdW
forces are important include rare-gas bonding and the cohesive interactions of soft matter,
such as proteins and polymers. Another situation is hydrogen intercalation in graphitic
systems, such as carbon nanotubes [1].

Probably the simplest qualitative argument for the origin of the vdW force is the correlatedfluctuation approach [2]. This is illustrated for the case of two rare gas atoms in figure 4.1.
Zero point quantal or thermal fluctuations can induce a temporary fluctuating dipole moment
d2 on atom #2, as in figure 4.1(a). The resulting dipole electric field acting on atom #1 is
proportional to R-3, where R is the distance separating the two atoms. This gives rise to a
correlated non-random dipole moment d1 on atom #1, which is also of order R-3. As figure
4.2(b) shows, d1 generates a backfield of order R-3.R-3 = R-6 back at atom #1, which interacts
with the original dipole d2. The potential energy of this interaction is also of order R-6. This
energy is of second order in the fluctuating dipole d2 and thus the time average of the
potential energy is non-zero. Therefore, the overall vdW attractive potential energy is of the
form:

E = C6 R 6

(4.1)

where C6 is the Hamaker constant for the particular system of atoms or molecules (not
considered in the present work).

4.1: The origin of vdW forces for the case of two rare-gas atoms [2]. Used with permission

Conventional methods of calculating vdW forces for systems made up of many atoms employ
a pairwise summation of R-6 atom-atom contributions, where R is taken to be the distance
between elements of the systems concerned. However, in low-dimensional metallic nanosystems such as metallic carbon nanotubes, recent theory has predicted another unusual
contribution to the vdW force [3], [4]. Dobson, Gould and Klich [4] note that this is the force
contributed by the conduction band electrons of the tubes. For parallel nanotubes separated by
distance D, the conventional energy contribution, obtained by a pairwise R-6 summation, is of
form Econv = K5D-5, where K5 is a constant, but the new theory notes that this only gives the
vdW force from the electrons in the insulating electronic Bloch bands [4]. The contribution to
the vdW force from the metallic bands is predicted in [3] to vary as Emet = K3D-2(ln(D/D0))3/2
where K3 and D0 are constants independent of D. Because it falls off more slowly with D, Emet
will dominate the conventional vdW contribution Econv when the distance of separation D
between the tubes is sufficiently large. Consequently, conventional means of calculating vdW
forces for these structures fail to give quantitatively correct results for widely separated tubes
in the metallic regime [4].
The unconventional energy Emet leads to an unconventional force Fmet = -dEmet/dD and also to
torques for non-parallel wires or tubes (see Fig 4.2). This project concerns design of a force
microscopy experiment to measure these unconventional forces and torques directly. The
metallic contribution Fmet to the force is predicted to be negligible compared with the
conventional force when the tubes are near to contact. At larger separations the new force
should dominate but the total force is then quite small, so that careful experimental design
will be required if the new predictions are to be verified experimentally. The experiment
could also be done with metallic nanowires, which also experience a metallic contribution to
the vdW force, with less of the conventional insulating component than for carbon
nanotubes.

Carbon nanotubes can exist as free-standing entities, so a nanotube attached to an Atomic

Force Microscope (AFM) tip can sense forces without being dominated by large additional
vdW forces from a massive supporting structure. On the other hand, the metallic carbon
nanotube force is dominated by the conventional contributions from gapped (insulating)
electronic transitions at small to medium separations. Thus to see the metallic force as the
dominant component, one has to go to large separations where the total force is relatively
weak [J. F. Dobson, private communication].

In nanowires made of metal (Au, Bi etc) the electron response is dominated by the metallic
(gapless) transitions and so one expects to see the metallic form of force at relatively smaller

distances the gapless transitions are not so dominant (compared with carbon nanotubess).
Therefore, one can measure larger forces at smaller separations, and expect to see the unusual
metallic power laws. One disadvantage is that metal nanowires cannot usually be freestanding they have to be grown on a large substrate (e.g. surface of a macroscopic piece of
Si ). Consequently, both interacting wires would need to be attached to a substrate containing
much more matter than the wires themselves. Under these circumstances, there will be
relatively large vdW forces between these substrates. A possible solution is to work in a
cylindrical geometry where rotation of the supporting substrate does not produce any change
in the large force, and also no torque. Thus any torque will be due to interactions between the
symmetry-breaking wires laid down on the two substrates [J. F. Dobson, private
communication].

For these reasons it is good to do the theory both for the torque (via angular spring constant)
and the force between nanowires or nanotubes, corresponding to the supported and
freestanding experiments for wires or tubes respectively. The torque experiment would
require a new type of experimental setup that is not presently in common use. On the other
hand, experimental colleagues at QUT (Prof. N. Motta) have advised that an experiment for
force on a nanotube would be possible with existing equipment. A tube could be attached to
an AFM tip so that the tube is parallel to a fixed substrate on the stage The tip-tube
assembly of the AFM. could be moved (translated) across the subtstrate surface upon which a
nanotube or wire had been laid down. As long as the mobile carbon nanotube is nearly
parallel to the deposited tube/wire, a peak in the force should be seen when the mobile tube
crosses over the deposited tube/wire.

The proposed experiment will aim to measure the recently predicted metallic contribution to
the vdW force in metallic nanotubes and nanowires. It was originally intended that this would
be an experiment to deliberately measure the angular oscillations of one tube which feels the
force due to another nearby tube (see figure 4.2). This experiment would consist of two tubes
separated by a nanoscale distance D. One of these tubes would be fixed and the other free to
rotate about its centre in the x-y plane, making an angle with the orientation of the fixed
tube. Both of the tubes would have to be mounted on a kind of support structure such as a
silicon stage. The crossed configuration of the tubes would undoubtedly give rise to an
effective angular spring constant term. This term would be important in the experiment as it
would reduce the large attractive force due to the support structures.

z
y

Figure 4.2: Basic set-up of nanotubes.

However, recent advice from an experimental colleague [N. Motta, private communication]
suggests that a more practical approach than this angular oscillation experiment may be a
parallel linear motion experiment where one tube is made to move over the other fixed tube
in a linear fashion. The tubes would be oriented parallel to each other, although a crossed
configuration like that in figure 4.2 may occur due to inaccurate alignment of the tubes. In the
experiment, careful attention must be paid to confounding sources of force, such as the
inevitable fixed electric dipoles at the ends of the tubes and the thermal noise.

The nanotubes which will be used in the proposed experiment will of course be finite in
length and will thus have small fixed dipoles situated at both ends. When two of these tubes
are placed close to each other the electric fields generated by each of these dipole will interact
with the other three dipoles. The energy of these interactions will need to be considered in the
proposed experiment, as well as the contribution of these interactions to the effective angular
spring constant of the system. The energy due to thermal noise, which is equal to kBT, where
kB is Boltzmanns constant and T is the temperature of the surroundings, will also need to be
taken into consideration.

4.2 Project Aims

Through analytic and numerical simulations, the metallic and conventional contributions to
the vdW forces were modeled. This included an analysis of the various contributions to the
interaction energy and angular spring constant of two nanowires or nanotubes oriented as
shown in figure 4.2.

This investigation allowed an assessment to be made of the feasibility of this class of

experiment. The particular aims of the project were [5]:

Investigation of the contributions to the energy and angular spring constant due to the
interactions of the dipoles at the ends of two nanowires.

Investigation of the contributions to the energy and angular spring constant arising
from the force unique to the case of metallic nanowires and nanotubes.

Investigation of the the contributions to the energy and angular spring constant due to
the conventional vdW force that exists between carbon nanotubes.

Estimation of whether the effects of the metallic interaction are significant compared
with thermal noise at distances such that the metallic interaction dominates all other
interactions.

4.3 Analysis of Literature

The existing knowledge in this field includes theoretical predictions of the vdW energy for
distant metallic and semiconducting infinite tubes that are either parallel [3] or crossed at an
angle [4].

The paper, Asymptotics of the Dispersion Interaction: Analytic Benchmarks for van der
Waals Energy Functionals [3], provided an expression for the energy due to the interaction
force between parallel metallic nanotubes or nanowires of infinite length. The authors showed
that conventional methods of summing contributions of vdW forces from elements along the
nanotubes give qualitatively wrong results when the tubes are metallic. A new method was
used in order to gain an expression for the energy per unit length of parallel one dimensional
metallic nanostructures. The method involved using the correlation energy from the random
phase approximation (RPA). The authors found that this was equivalent to the zero-point
energies of the delocalized coupled one dimensional plasmons of the metallic structures. This
gave an energy per unit length that was proportional to D-2, up to logarithmic corrections
where D is the separation distance of the two tubes or wires. The conventional method of
summing vdW interactions gives a distance dependance of D-5 [3].

The paper, Dispersion Interaction Between Crossed Conducting Wires [4], concerns the
calculation of interaction forces between infinite nanotubes or wires that are not parallel, and
crossed at an angle . As in the previously discussed paper, the authors noted that
conventional methods for calculating vdW forces are not suitable for quasi-one-dimensional
objects, such as nanotubes or nanowires. The prescription used for obtaining an expression
for the interaction energies between crossed wires involves using second order perturbative
non-retarded theory to obtain the dispersion energy for two wires. The density response of a

single wire within the RPA was then calculated. This revealed that the dispersion energy of
two crossed metallic nanowires was proportional to D-1 and also to _VLQ_-1. This energy
decreases much more slowly with distance than the standard D-4 energy dependence predicted
by simply summing individual vdW force contributions [4].

The authors of [3] note that there are three conditions under which the standard models of
dispersion forces and energies can give incorrect results. One is when the system under
consideration is metallic or has a zero energy band gap. The other conditions are when the
system is spatially extended in at least one dimension, and is of nanoscale dimensions in
another, as is the case for a nanotube or nanowire. These last two conditions imply that long
wavelength charge fluctuations can occur along the spatially extended dimension.
Conventional methods for calculating dispersion forces and energies fail to produce the right
results as they do not consider these charges fluctuation in enough detail. By considering the
zero-point energies of one dimensional plasmons, the authors of [3] were able to perform
more thorough analysis of the nanowire interaction forces which include the microscopic
properties and charge densities of the nanowires. Analysis of the charge fluctuations has also
allowed for a more precise expression of the interaction energies for crossed nanowires in [4].

Some experimental work is required in order to verify the expressions given for the
interaction energies in these papers. The results of the papers can be verified by experiments
involving atomic force microscopy or measurement of the mechanical oscillations of the
metallic nanotubes or wires [4]. The authors of [4] have estimated the force Fmet due to the
conduction band electrons of two metallic nanotubes, as a function of their separation
distance. Fmet is estimated for non-parallel tubes of infinite length and oriented at an angle of
= 1DQGIRUSDUDOOHOWXEHVRIOHQJWKP7KLVZDVWKHQFRPSDUHGWRWKHYG:IRUFHFins
due to the remaining insulating electron bands estimated using the conventional model of
vdW interactions. This comparison shows that at small separations (~2nm), the pure metallic
force Fmet is dominated by the usual vdW force due to the insulating bands Fins. However, at
larger separations, (~5nm) Fmet begins to dominate Fins [4]. The metallic force should be easily
detected at micron separations by modern instruments [6].

The two main articles reviewed here both agreed that the conventional models of vdW forces
in materials do not give correct results for certain systems, particularly metallic nanotubes.
These methods sum vdW energy contributions from different elements of the tube, whilst
ignoring the metallic behavior of the nanotube and the surface electrons (plasmons). This is
important to consider when measuring the interaction forces between two nanotubes that are
either parallel or non-parallel and separated by a nanoscale distance.

5 Research Methodology

5.1 Dipole Interaction Energy

The energy and angular spring constant ontributed by the interactions of fixed electric dipoles
at the ends of two nanowires separated by a nanoscale distance was modeled as described
below.

L1
+ p2

-+

p1

R1

R2

z
y
x

-+

p4

+ p3

R4
R3

L2

Figure 5.1: Fixed dipoles at the end of the nanowires.

Figure 5.1 shows two nanowires of lengths L1 and L2 separated by a nanoscale distance D,
and oriented at an angle to each other. The electric dipoles at the ends of the wires were
specified as vectors labelled p1 through p4. A Cartesian coordinate system was set up, with
the origin, O, at the center of the lower wire. The dipole vectors p1 through p4 and the position
vectors R1 through R4 of the dipoles were also set up as:

p1 = ( p, 0, 0 )

(5.1)

p 2 = ( p, 0, 0 )

(5.2)

p 3 = ( p cos , p sin , 0 )

(5.3)

p 4 = ( p cos , p sin , 0 )

(5.4)

R 1 = L21 , 0, D

10

(5.5)

1
0

R2 =

L1
2

, 0, D

( cos ,
= ( cos ,

R3 =
R4

L2
2

L2
2

(5.6)

)
sin , 0 )
sin , 0

L2
2
L2
2

(5.7)
(5.8)

The energy of the interaction of two of the end dipoles was modeled based on the following
formula for the electric field F(x) at point x due to a dipole p at point x [7]:

F(x) =

3n (pn ) p
x x

(5.9)

where n is a unit vector pointing from x to x. The energy E of the interaction of a pair of
dipoles was obtained by taking the dot product of the result of (5.9) for the first dipole acting
with the second, with the second dipole. For example for the case of dipole p1 acting on p2,
the interaction energy is:

E12 = F12 (x)p 2

=

1 )(np
2)
p1 p 2 3(np
x2 x1

(R )
= 12

(5.10)

p1 p 2 3(R12 p1 )(R12 p 2 )

( R12 )

Here the vector R 12 = R 2 R 1 = ( L1 , 0, 0 ) points from p1 to p 2 , and R12 is the magnitude

of this vector. This expression, along with (5.1) and (5.2) was used to obtain an expression for
the energy of the interaction between dipoles p1 and p 2 . Using symmetry arguments, it was
also shown that E21 = E12 . Therefore:

E12 + E21

(R )
= 2 12

p1 p 2 3(R12 p1 )(R12 p 2 )

( R12 )

2 L12 p 2 + 6 L12 p 2
=
L15
=

(5.11)

4 p2
L13

11

1
1

Similar methods were used to obtain the energy of the interaction between dipoles p1 and p 3 .
Using symmetry arguments, it was also shown that E31 = E13 .

E13 + E31

(R )
= 2 13

p1 p 3 3(R 13 p1 )(R 13 p 3 )

( R13 )

( L L cos +
=
1 2

1
2

1
2

L12 + 12 L22 + 2 D 2 ) ( p 2 cos ) 6( 12 L2 p cos + 12 L1 p) ( 12 L1 p cos 12 L2 p )

1
2

L1 L2 cos + 14 L12 + 14 L22 + D 2 ) 2

p 2 L1 L2 cos 2 + ( L12 + L22 2 D 2 ) p 2 cos + 32 p 2 L1 L2

1
2

L1 L2 cos + 14 L12 + 14 L22 + D 2 ) 2

(5.12)

Similar methods were used to obtain the energy of the interaction between dipoles p1 and p 4 .
Using symmetry arguments, it was also shown that E41 = E14 .

E14 + E41

(R )
= 2 14
=

p1 p 4 3(R14 p1 )(R14 p 4 )

( R14 )

( L L cos +
2 1

1
2

L12 + 12 L22 + 2 D 2 )( p 2 cos ) 6 ( 12 pL2 cos + 12 pL1 )( 12 pL1 cos 12 pL2 )

(
1
2

1
2

L1 L2 cos + L + L + D
1
4

2
1

1
4

2
2

5
2 2

p 2 L1 L2 cos 2 + ( 2 D 2 L12 L22 ) p 2 cos + 32 p 2 L1 L2

1
2

L1 L2 cos + L + L + D
1
4

2
1

1
4

2
2

5
2 2

(5.13)

Similar methods were used to obtain the energy of the interaction between dipoles p 2 and p 3 .
Using symmetry arguments, it was also shown that E32 = E23 .

12

1
2

E23 + E32

(R )
= 2 23

p 2 p 3 3(R 23 p 2 )( R 23 p 3 )

( R23 )

( L L cos +
=

1
2

2 1

1
2

L12 + 12 L22 + 2 D 2 )( p 2 cos ) 6 ( 12 pL2 cos + 12 pL1 )( 12 pL1 cos 12 pL2 )

1
2

L1 L2 cos + L + L + D
1
4

2
1

1
4

2
2

5
2 2

p 2 L1 L2 cos 2 + ( 2 D 2 L12 L22 ) p 2 cos + 32 p 2 L1 L2

5

( 12 L1L2 cos + 14 L12 + 14 L22 + D 2 ) 2

(5.14)

Similar methods were used to obtain the energy of the interaction between dipoles p 2 and p 4 .
Using symmetry arguments, it was also shown that E42 = E24 .

E24 + E42

(R )
= 2 24

p 2 p 4 3(R 24 p 2 )(R 24 p 4 )

( R24 )

( L L cos +
=
1 2

1
2

1
2

L12 + 12 L22 + 2 D 2 ) ( p 2 cos ) 6( 12 L2 p cos + 12 L1 p ) ( 12 L1 p cos 12 L2 p

1
2

L1 L2 cos + 14 L12 + 14 L22 + D 2 ) 2

p 2 L1 L2 cos 2 + ( L12 + L22 2 D 2 ) p 2 cos + 23 p 2 L1 L2

1
2

L1 L2 cos + L + L + D
2
1

1
4

1
4

2
2

5
2 2

(5.15)

Similar methods were used to obtain the energy of the interaction between dipoles p 3 and p 4 .
Using symmetry arguments, it was also shown that E43 = E34 .

E34 + E43

(R )
= 2 34

p 3 p 4 3(R 34 p 3 )(R 34 p 4 )

( R34 )

2 L22 p 2 + 6 L22 p 2
=
L52

(5.16)

4 p2
= 3
L2

13

1
3

An expression for the total energy Edip of the dipole interactions was obtained by adding
equations (5.11), (5.12), (5.13), (5.14), (5.15) and (5.16). This was also multiplied by (40)-1
in order to ensure SI units:

E dip

4 p 2 4 p 2 p 2 L1 L2 cos 2 + 2 cos ( 2 p 2 D 2 p 2 L12 p 2 L22 ) + 3 p 2 L1 L2

3 + 3 +

5
L2
L1

2
1 2 1 2
1
2

L1 L2 cos + L1 + L2 + D
4
4
1
2

2
2
2 2
2 2
2 2
2
4 0
+ p L2 L1 cos + 2 cos ( p L1 + p L2 2 p D ) + 3 p L1 L2

2
1 2 1 2
1

2
L2 L1 cos + L + L2 + D

4
4
2

(5.17)

In order to find the angular spring constant dip=2d2E/dD2|=0 for the torque experiment,
expression (5.17) was simplified and expanded to second order in for two cases. In the first
case, both of the wires in figure 5.1 were assumed to be one micron long:

E dip = 2

p2
D2
1 8 p 2 L2 4 p 2 D 2
2
p
+
+
5
0 L3
0 D 5 4
2
2
L
D
+
0

5 p2

1 p 2 L2 2 p 2 D 2
2
L
+

5
4
0 D 5
8 0 D
2
2
2 2
2 2
+ 5 8 p 2 L2 4 p 2 D 2
L
1 3 p L + 2 p D
+
+
5
5
2
2
4
L
4
D
4
+
2
2
2
2
8

L +D
0 L + D
0

(5.18)

In the second case, one wire was assumed to be one micron long, while the other was
assumed to be two microns long. The assumed configuration of the wires here is depicted in
figure 5.2, where the end dipoles are not near each other.

E dip =

9 p2
18 p 2 L2 4 p 2 D 2
2 p 2 L2 + 4 p 2 D 2
8
8
+
+
5
5
8 0 L3
0 L2 + 4 D 2
0 9 L2 + 4 D 2

3 p 2 L2 2 p 2 D 2
2 p 2 L2 + 4 p 2 D 2 2
40
L
8

+
+

7
5

0 L2 + 4 D 2
0 L2 + 4 D 2

2
+
2
2
2
2
2
2
2
2

18 p L 4 p D
7 p L + 2 p D
L2 + 8
40
7
5
2
2
0 9 L2 + 4 D 2

0 9 L + 4 D

14

(5.19)

1
4

In expressions (5.18) and (5.19), L = 1 micron. By analogy with Hookes law for a spring, the
coefficients of 2 in these expressions were taken to equal

1
2

dip for the two cases, where

dip is the contribution to the effective angular spring constant of the wires from the dipole
interactions.
L1
+ p
2

p1 - +

R1

R2

y
x

-+

p4

+ p3

R4

L2

R3

Figure 5.2: Fixed dipole at the ends of nanowires of unequal length.

In order to evaluate E dip and dip for gold nanowires, an estimate of the relevant dipole
moment p was obtained. The end of the nanowire was treated as a circular surface with the
same properties (e.g. dipole moment per unit area, work function) as an infinite gold surface.
In the following the dipole moment per unit area is estimated via a jellium model for an
infinite clean gold surface, using the experimental gold work function as input data. This was
done by considering Q] , the number density of electrons minus the number density of the
positive background as a function of z, the distance into the vacuum (i.e. the distance outside
the end of a metallic nanowire in the present case). This is illustrated in figure 5.3.
Gauss law was applied in order to obtain p , the dipole moment at the ends of a gold
nanowire.

EdS = A ( E ( z ) E ( ) ) =

Q( z )
0

(5.20)

Here A is the cross sectional area of the nanowires and, E ( z ) E ( ) is the difference in
electric field through the wire. Q ( z ) is the charge contained in the nanowire and is given by

15

1
5

Q ( z ) = Ae n( z )dz

(5.21)

where the integral is over a cylindrical volume straddling the end of the nanowire, with one
end insidethe metal and one end in the vacuum. Substituting (5.21) into (5.20) and noting that

E ( ) = 0 since the electric field inside a metal is zero, gives

E ( z) =

e
0

n( z ) dz

(5.22)

n(z)

Figure 5.3: Number density of electrons minus positive background at the end of a metallic nanowire

The change in electrostatic potential across the end of the wire is then

= ( ) ( ) = E ( z ) dz
=

e
0

dz n( z )dz

(5.23)

Integration by parts was used to solve (5.23), with the dummy variables

dv
=1
dz
z

u ( z ) = n( z ) dz

(5.24)

v=z
du
= n( z )

dz

Therefore, the change in potential is

16

1
6

e
=
0

z =

n
(
z
)
dz

z n( z ) dz

z =

The first term in (5.25) goes to zero because

(5.25)

n( z )dz 0 exponentially as z .

Therefore:

e
0

z n( z ) dz

P
=
0

(5.26)

Where P is the dipole moment per unit area of the metal. For a metal with work function W
and Fermi energy [8]:

W =

(5.27)

Therefore, the magnitude of the dipole moment per unit area of a fixed dipole at the end of a
metallic nanowire is approximately,

P = 0 [W + ]

(5.28)

For gold, = 5.5 V and W = 5.1 V [9] (in units of volts since the above treatment used
electrostatic potential). Substituting these values into (5.28) gave P = 9.410-11 C/m.
Multiplying by the cross sectional area of a wire with a radius of 1nm gave the dipole
moment at the end of a gold nanowire as p = 3.0 10-28 C-m.

5.2 Metallic Contribution to the vdW Interaction Energy

Another aspect of the proposed experiment that was analysed was the metallic interaction
force that was predicted in [3] and [4] to exist between two metallic nanowires or tubes.

For strictly parallel one dimensional conductors of infinite length , Reference [3] predicted a
finite energy per unit length met (D, = 0) equal to

17

1
7

 met ( D, = 0) = (16 ) hc1D D 2 ln ( 2.39 D / b )

1

3
2

(5.29)

and hence an infinite total energy. Here, b is the radius of the nanotubes, D is their separation
distance and c1D is a characteristic velocity. By contrast, in [4] , for infinitely long one
dimensional conductors inclined at an angle the prediction was for a finite absolute energy
Emet() equal to

E met ( ) = (16 D )

( sin )

hc1D ln ( D / b )

3
2

(5.30)

In the experiments proposed here the length L of the wires will be finite but large compared
with their separation i.e. L >> D, and the angle will be as small as possible but not exactly
zero because of experimental considerations. It is therefore necessary extend the two theories
given in [3] and [4] to the case of finite L, and to interpolate between the = 0 and 0
cases. The simplest assumption to allow for finite length is to assume that for strictly parallel
wires ( = 0) the absolute energy is

E met ( L, D, = 0) L0 met ( D )

(5.31)

where L0 is the overlap length (see Figure 5.2), It will be further assumed that for long wires
(L>>D) and angles that are not too small,

E met ( L, D, 0) E met ( L , D, ) = F / sin F /

(5.32)

where F is given in [4]:

F = (16 D ) hc1D ln ( D / b )
1

3
2

(5.33)

To analyse a realistic experimental situation it is necessary to interpolate between (5.31) and

(5.32) for small but finite angles . The basis of this is that the attractive vdW force will cause
the energy to be a minimum at = 0, so that for a finite wire and very small angles up to
some angle 0 we have a quadratic behaviour,

E met ( L, D, ) = L met ( D) + 12 met 2

(5.34)

where met will be determined below by a matching procedure

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The matching procedure is illustrated in figure 5.4, which depicts the expected form of the
metallic contribution to the energy as a function of , the angle of orientation of the two
wires. At = 0WKHYDOXHRIWKHHQHUJ\LV L0 met ( D ) , which is the energy per unit length of
two infinite parallel wires from (5.29) multiplied by the length that they overlap each other.

Angle

Energy

L0 met
Fgure 5.4: Metallic contribution to vdW energy of two crossed wires

Up to some angle 0, the energy in figure 4 is quadratically dependent on angle as in equation

(5.34). However, after this point, the energy is inversely dependent on angle:

E=

F
0

(5.35)

where F is a constant, given by equation (5.33).

This allowed two conditions to be set up so that the metallic contribution to the spring
constant of the wires, met, could be obtained:
Condition (i): The quadratic and linear dependence agree at some angle 0:

E ( 0 ) = L0 Emet + 12 met 0 2 =

F
0

(5.36)

Condition (ii): The first derivatives with respect to also agree at 0 :

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9

d
F
E ( 0 ) = met 0 = 2
d 0
0

met

F
= 3
0

(5.37)

Substituting (5.38) into (5.37) yields

L0 Emet

F
F
=
2 0 0

L0 EvdW =

0 =

3F
2 0

(5.38)

3F
2 L0 EvdW

Substituting (5.39) into (5.38) yields

met =

3
8
L vdW ( D) )
2 ( 0
27 F

(5.39)

5.3 Conventional Contribution to the vdW Interaction Energy

Girifalco, Hodak and Lee proposed a continuum version of the pairwise summation model for
the computation of the energy of interaction of two parallel, infinite carbon nanotubes using a
carbon-carbon Lennard-Jones potential [10]. They used their result to find the conventional
vdW contribution to the potential energy of interaction per unit length between two parallel
carbon nanotubes:

conv

3 n 2
21B
IB
=
AI A +
3
8b
32b6

(5.40)

where b is the radius of the nanotubes, R D is the perpendicular distance between tube
centres. and n = 0.381910-20 m-2 [11] is the mean surface density of carbon atoms. The
second, repulsive contact term in (5.40) is dominated by the first term for the D values of
interest here and was therefore neglected.

The consant A = 15.2 eV A 6 in (5.40) is the attractive Lennard-Jones constant for graphenegraphene [10] and IA is given by [10]:

20

2
0

I A = ( cos 2 cos 1 ) + ( sin 2 sin 1 + R ')

0

5
2

d1d 2

(5.41)

Here, R = D/b is a reduced distance. For large values of R (ie. D>>b), (5.42) may be
simplified to:
2
2
4 2

IA =
d =
5
5
( R ') 0 ( R ')

(5.42)

Therefore, (5.41) becomes:

conv =

12 3 n 2 A
8b3 ( R ')

(5.43)

This energy was multiplied by an overlap length L0 of 1 micron to obtain the energy
experienced by two carbon nanotubes of overlap length L0 due to the conventional vdW force.

21

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6 Results
6.1 Dipole Interaction Energy
Tables 6.1 and 6.2 show the potential energy Edip and the contribution to the angular spring
constant dip for two gold nanowires due to the interactions of the fixed end-dipoles from the
present theory. Table 6.1 shows this energy for nanowires of equal length (one micron each),
which was calculated using equation (5.18). Table 6.2 shows the energy for nanowires of
unequal length (one and two microns), which was calculated using equation (5.19). The
energy was also compared for different values of D, the separation distance of the nanowires.

D (nm)

Edip(eV)

dip(eV/rad2)

10

2.010-2 - 75 2

-4.210-6

20

2.510-3 - 2.8 2

-4.210-6

50

1.610-4 - 2.410-2 2

-4.010-6

100

2.010-5 - 7.510-4 2

-3.610-6

Table 6.1: Dipole interaction energy for wires of equal length

D (nm)

Edip(eV)

dip(eV/rad2)

10

-2.910-7 + 2.110-6 2

4.210-6

20

-2.910-7 + 2.110-6 2

4.210-6

50

-2.810-7 + 2.010-6 2

4.010-6

100

-2.510-7 + 1.810-6 2

3.610-6

Table 6.2: Dipole interaction energy for wires of unequal length

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6.2 Metallic Contribution to the vdW Interaction Energy

Plots similar to figure 5.4 of the metallic contribution to the vdW energy vs. angle for two
gold nanowires of length L one micron separated by various distances D were created and
used to obtain values of E(1), the energy of two wires oriented at an angle of one degree to
each other. The metallic energy of parallel wires with an overlap length L0 of one micron, was
obtained using (5.29), multiplied by L0 . The value of c1D used for gold nanowires was:

c1D

k F3 e 2b 2 2
= 3

6 0 me

(6.1)

where k F = 1.21010 m-1 is the Fermi wavenumber of gold [9].

The plots were created by noting the quadratic dependence of the metallic energy on angle up
to a certain point, which becomes an inverse linear dependence after that point, as described
by equations (5.31) and (5.32). 0, the point at which the quadratic dependence switches over
to a linear dependence, was calculated using equation (5.39). met, the contribution to the
angular spring constant of the wires, was calculated using equation (5.40), and the constant F
was calculated using equation (5.33). These parameters are shown in table 6.3 and the plots
are shown in figures 6.1 - 6.4.

D (nm)

L0 met (eV)

E(1) (eV)

met (eV/rad2)

0 (rad)

F (eV)

10

-0.13

-0.12

14.4

0.0763

-6.810-3

20

-2.3310-2

-2.3210-2

0.82

0.1382

-2.210-3

50

-2.7110-3

-2.7110-3

1.7810-2

0.3185

-5.810-4

100

-5.5310-4

-5.5310-4

9.8810-4

0.6111

-2.310-4

Table 6.3: Metallic energy parameters for gold nanowires

23

2
3

0.00

Energy (eV)

0.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

-0.05

-0.10

-0.15
Angle (rad)

Figure 6.1: Metallic contribution to the vdW energy of crossed gold nanowires at 10nm separation
distance

0.00
0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

Energy (eV)

-0.01
-0.01
-0.02
-0.02
-0.03
Angle (rad)

Figure 6.2: Metallic contribution to the vdW energy of crossed gold nanowires at 20nm separation
distance

0.000

Energy (eV)

-0.001

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

-0.001
-0.002
-0.002
-0.003
-0.003
Angle (rad)

Figure 6.3: Metallic contribution to the vdW energy of crossed gold nanowires at 50nm separation
distance

24

2
4

0.0000

Energy (eV)

-0.0001

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

-0.0002
-0.0003
-0.0004
-0.0005
-0.0006
Angle (rad)

Figure 6.4: Metallic contribution to the vdW energy of crossed gold nanowires at 100nm separation
distance

The plots were recreated for the metallic contribution to the vdW energy and angular spring
constant of carbon nanotubes. The value of c1D used here was:

2e 2 vF 2
c1D =

4 0 h

(6.2)

where vF = 1.0106 is the Fermi velocity of carbon [9]. The parameters used to obtain the
plots a shown in table 6.4 and the plots themselves are shown in figures 6.5 - 6.8

D (nm)

L0 met (eV)

E(1) (eV)

met (eV/rad2)

0 (rad)

F (eV)

10

-2.7310-2

-2.6810-2

3.14

0.0763

-1.410-3

20

-5.0710-3

-5.0410-3

0.18

0.1382

-4.710-4

50

-5.9010-4

-5.8910-4

3.8810-3

0.3185

-1.310-4

100

-1.2010-4

-1.2010-4

-2.1410-4

0.6111

-4.910-5

Table 6.4: Metallic energy parameters for carbon nanotubes

25

2
5

0.00

Energy (eV)

0.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

-0.01

-0.02

-0.03

Angle (rad)

Figure 6.5: Metallic contribution to the vdW energy of crossed carbon nanotubes at 10nm separation
distance

0.000

Energy (eV)

-0.001

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

-0.002
-0.003
-0.004
-0.005
-0.006
Angle (rad)

Figure 6.6: Metallic contribution to the vdW energy of crossed carbon nanotubes at 20nm separation
distance

0.0000

Energy (eV)

-0.0001 0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

-0.0002
-0.0003
-0.0004
-0.0005
-0.0006
-0.0007
Angle (rad)

Figure 6.7: Metallic contribution to the vdW energy of crossed carbon nanotubes at 50nm separation
distance

26

2
6

0.00000

Energy (eV)

-0.00002 0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

-0.00004
-0.00006
-0.00008
-0.00010
-0.00012
-0.00014
Angle (rad)

Figure 6.8: Metallic contribution to the vdW energy of crossed carbon nanotubes at 100nm separation
distance

6.3 Conventional Contribution to the vdW Interaction Energy

The conventional contribution to the vdW energy of two carbon nanotubes with an overlap
length L0 of one micron was calculated for various separation distances D of the tubes by
using equation (5.44) and multiplying the result by L0. These energies are shown in table 6.5.

D (nm)

L0 conv (eV)

10

-1.0310-2

20

-3.2210-4

50

-3.3010-6

100

-1.0310-7

Table 6.5: Conventional contribution to vdW energy of carbon nanotubes

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7

7 Discussion
7.1 Comparison of the Various Forces for Gold Nanowires
From comparison of the values of Edip and dip for different separation distances in tables 6.1
and 6.2, it was seen that that both the energy and the contribution to the overall angular spring
constant due to the end dipoles of two nanowires are minimised when the wires are not of
equal length, and are set up as in figure 5.2. When the wires are set up like this, the end
dipoles are not near each other and so do not interact as strongly as when the wires are of the
same length as in figures 5.1.

It would therefore be advantageous for an experiment which is designed to measure the

metallic contribution to the vdW energy and spring constant of two nanowires if wires of
unequal length were used.

Table 7.1 compares the dipole interaction energy and contribution to the angular spring
constant with the metallic contributions to the vdW energy and spring constant of parallel
gold nanowires with lengths of one and two microns. When the orientation of the wires is not
strictly parallel, but offset by one or two degrees, there is only a negligible change in the
dipole interaction energy. This is because the angle is measured in radians, and so the 2 term
in Edip would only represent a very small contribution to the dipole interaction energy for a
non-zero angle. The metallic contribution to the vdW energy also only changes by a
negligible amount for small angles, as shown in table 6.3.

Edip (eV) = 0

dip (eV/rad2)

L0 met (eV)

met(eV/rad2)

10

-2.910-7

4.210-6

-0.13

14.4

20

-2.910-7

4.210-6

-2.3310-2

0.82

50

-2.810-7

4.010-6

-2.7110-3

1.7810-2

100

-2.510-7

3.610-6

-5.5310-4

9.8810-4

D (nm)

Table 7.1: Dipole and metallic energies for gold nanowires of unequal length

As table 7.1 shows, the metallic contribution to the vdW energy and angular spring constant
of the wires was found to dominate the energy due to the dipole interactions at all separation

28

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8

distances shown here. At room temperature (~102 K), the energy due to thermal noise is of the
order of 10-2eV, which is comparable to the metallic contribution for a separation distance of
20 nm, and dominates the metallic contribution for separation distances of 50 and 100 nm.
However, at cold temperatures (~1K), the energy due to thermal noise is only of the order 10-4
eV, which is only comparable to the metallic contribution at a separation distance of 100nm.

7.2 Comparison of the Various Forces for Carbon Nanotubes

Table 7.2 shows comparison data for parallel carbon nanotubes. The dipole interaction energy
Edip for nanotubes with lengths of one and two microns was estimated using equation (5.19)
assuming that the dipole moment at the ends of a nanotube was five times larger than the
dipole moment for a gold nanowire..

D (nm)

Edip (eV) = 0

L0 met (eV)

L0 conv (eV)

10

-7.2110-6

-2.7310-2

-1.0310-2

20

-7.1810-6

-5.0710-3

-3.2210-4

50

-6.9810-6

-5.9010-4

-3.3010-6

100

-6.3210-6

-1.2010-4

-1.0310-7

Table 7.2: Metallic and conventional contributions to the vdW energy for carbon nanotubes

As table 7.2 shows, the metallic contribution to the vdW energy of the tubes was found to
dominate the conventional contribution for separation distances of 20, 50 and 100 nm. The
two contributions were found to be comparable at a separation distance of 10 nm. Both of
these contributions were found to dominate the dipole interaction energy at all separation
distances.

As discussed before, the energy due to thermal noise at room temperature is of the order of
10-2 eV, which is comparable to the metallic contribution at a separation distance of 10 nm,
but dominates the metallic contribution for all other separation distances. At cold
temperatures, the energy due to thermal noise is comparable to the metallic contribution for
separation distances of 50 and 100 nm.

29

2
9

8 Conclusions
The investigation outlined in this report considered an experiment which will attempt to
measure the metallic contribution to the van der Waals (vdW) energy and force of metallic
nanotubes or nanowires. The findings suggest three conditions for to the experiment to be a
success. The first one is that it should be done with wires of unequal length, so that there is
only a very small energy contribution from the end-dipoles. The experiment should also be
done at cold temperatures (~1 K), to minimise the energy due to thermal noise. Furthermore,
the separation distance of the wires or tubes should be such that the metallic contribution to
the vdW energy is not dominated by the dipole and thermal noise energies. This distance was
found to be typically between 10-100 nm for nanowires and 10-50 nm for nanotubes.

One of the main aspects of the proposed experiment that was investigated was the effective
angular torque that would be experienced by two crossed wires or tubes. This was done by
estimating the various contributions the angular spring constant of the system from the
interactions of the end dipoles, and the metallic and conventional contributions to the vdW
energy. Estimation of the force contributed by each of these factors, as well as by thermal
noise, may yield a more accurate value for the angular spring constant in the future. This
would also prove to be a useful result considering the initial aim of the proposed experiment.

30

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References
[1] J. F. Dobson, K. McLennan, A. Rubio, J. Wang, T. Gould, H. M. Le and B. P. Dinte,
Aust. J. Chem. 54, 513 (2001)
[2] J. F. Dobson, J. Wang, B. P. Dinte, K. Mclennan and H. M. Le, International Journal of
Quantum Chemistry. 101 579 (2005)
[3] J. F. Dobson, A. White, and A. Rubio, Phys. Rev. Lett. 96, 073201 (2006)
[4] J. F. Dobson, T. Gould and I. Klich, Phys. Rev. A 80, 012506 (2009)
[5] O. Dancewicz, Analysis and Planning for a fundamental Nano-science Experiment Project Planning Report (2010)
[6] J. F. Dobson, ICONN '06. 669. (2006)
[7] J. D. Jackson, Classical Electrodynamics, 2nd ed. Wiley (1975)
[8] N. D. Lang and W. Kohn, Phys. Rev. B. 3 1215 (1971)
[9] C. Kittel, Introduction to Solid State Physics (3rd ed. John Wiley and Sons Inc., 1972)
[10] L. A. Girifalco, M. Hodak and R. S. Lee, Phys. Rev. B 62 13 104 (2000)
[11] J. F. Dobson (unpublished)

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