CHAPTER ONE

1. INTRODUCTION

1.1 Background of the study

Nanotechnology is science, engineering, and technology conducted at the nanoscale, which is

about 1 to 100 nanometers.Nanotechnology involves creating, manufacturing, and manipulating
materials. It is the study and application of small object which can be used across all fields such
as physics, material science, chemistry and engineering. Therefore nanotechnology is the general
name of the sciences that are interested in the study of materials on the nanometer-sized scale for
the purpose of developing practical applications. It is also being applied to issues involving the
environment and agriculture. The use of nanotechnology in both public and private sectors is
rapidly increasing and expected to continue increasing in the future[4]. Today silver is among the
most commonly used metals in the field of nanotechnology due to its unique optical, electrical,
medical, biological, physical and chemical characteristics.

Nano scale materials, also known as nanoparticles. Nanoparticles often have different
properties than those associated with the element at the macro scale. For example, silver, gold,
and copper interact with light differently at the nano scale which is turn affects the color.
Therefore silver nanoparticles are nanoparticles of silver of between 1nm and 100 nm in size
[4,56 ]
. It absorbs and scatters light with extraordinary efficiency[4,5,9]. Their strongly interaction
with light occurs because the conduction electrons on the metal surface undergo a collective
oscillation when they are excited by light at specific wavelengths. Due to the size of silver
nanoparticles dependent optical, electrical,magnetic and thermal properties, are being
incorporated into products that range from photovoltaic to biological and chemical sensors.
Silver nanoparticles are important disinfectant due to their antimicrobial property. The quantity
of nanoparticle based nanomaterial is increasing. Therefore, it is important to study of this
reaserch to determine the size of silver nanoparticles from UV-Vis spectra resonance peaks using
Mie’s scattering theory and Beer’s -lambert law. The Beer-Lambert law (or Beer's law) is used
to show the linear relationship between absorbance and concentration of an absorbing species
[51,52]
. Mie’s scattering is the straight forward application of Maxwell's equations to an isotropic,
homogeneous, dielectric sphere [34,77]. It is understanding how light interacts with small particles

1
is necessary for a description of a wide range of physical phenomenon. When light is incident on
a particle the charges in the material are set in motion. This coupling of the light wave to the
charged particles gives rise to absorption, via energy transfer to the surrounding medium, and
scattering, via re-radiation of the light wave.

1.2 Statement of the Problem

The mie's Method is one of the most widely accepted for finding the size of silver nanoparticle
(AgNPs). Due to the range of sizes, it may be difficult to determine the size of silver
nanoparticles. Although there are set system to obtain a certain average size extremely sensitive
which makes a characterization of the produced nanoparticles necessary.Another issue is that the
theoretical concentration of silver nanoparticles suspended in solution may not be accurately
depicted depending on whether the reaction is fully complete.A possible method to characterize
these silver nanoparticles is by observing their light scattering properties. According to the Mie
theory, different-sized silver nanoparticles exhibit unique light-scattering properties. By
observing these trends by collecting their absorption at their surface plasmon resonance (SPR)
and at the wavelength of λ (nm), the size of silver nanoparticles can be estimated. With Beer-
Lambert’s law, the concentration of silver nanoparticles in solution was calculated. Here we will
determine the size of silver nanoparticles using different several peaks. To do this take nine
different peaks of size silver nanoparticles, and compare the literature value with the size
determined at a given wave length by using Mie scattering theory and Beer’s lambert law.

2
1.3 Research Objectives

1.3.1 General Objective

The general objective of this study:

To determine the size of silver nanoparticles from UV-Vis spectra resonance peak using Mie’s
scattering theory and beers law.

1.3.2 Specific Objective

The specific objectives of this study were to:

 Collect several resonance peaks of silver nanoparticles from previously done research

 Tabulate the resonance wave length and size using Get Data Graph Digitizer

 Plot the wavelength against the size

 Fit the plot with appropriate equation

 Solve Mie equation at the resonance ω

 Find the relation between σ ext and Beers law

 Determine the size from the absorbance

 Determine the size of silver nanoparticles using Mie scattering theory and Beer’s lamert
law

 Compare the literature value with the size determined using Mie scattering theory and
Beer’s lambert law

3
1.4 Significance of the Study

The aim of this research was to determine the size of spherical silver nanoparticles from UV-
Vis spectra resonance peaks by using Mie’theory and Beer’s law. Particularly silver
nanoparticles studied on the size of the core areas of this research in which my studied would be
significant.AgNPs use largely considered as the one-on-one interaction of the individual with
technology. Silver nanoparticles such as silver have been studied extensively due to their unique
properties that are significantly different from those of bulk material. These unique properties
could be attributed to their small size and large surface area which is in many applications
including electronic, catalyst and photonic. The study of this reaserch is expected to have the
following significances:

 To determine the size of silver nanoparticles using Mie’s scattering theory

 To know the therelation ship between the size and the absorbance wavelength of silver
nanoparitcles
 To tabulate the resonance wave length and size
 To plot the graph of size against wavelength.
 It can also serve as an input for further researchers to investigate (try to understand)
more.
When the wavelengths for the concentration of reducing agents increase, the size of silver
nanoparticles is also increase.Furthermore, the document of the study is to encourage other
researchers to do more researches on related field of study and serving as input for other
researchers as a reference materials.

4
 CHAPTER TWO
2.Literature Review
2.1 Optical properties of silver nanoparticles

In the case of noble metals, strong absorption in the visible - near ultraviolet (UV) occurs if
the size of the particle is below the electron mean free path. The mean free path is a measure of
the average distance between successive collisions of energy carriers. Michael Faraday was the
first to show that metal particles many times smaller than the wavelength of light scatter and
absorb light strongly such that even the dilute solution of the particles exhibit bright colors.
The resonance condition depends on the size and shape of the nanoparticles, the aggregation
state, as well as the dielectric function of the medium. Consequently, the nanoparticle optical
properties are highly dependent on material composition, size, and the medium in which the
particles are embedded[7]:

2.1.1 Effect of size on the optical properties of silver nanoparticles

Silver nanoparticles absorb and scatter light with extraordinary efficiency. Their strong
interaction with light occurs because the conduction electrons on the metal surface undergo a
collective oscillation when they are excited by light at specific wavelength. This oscillation is
known as surface plasmon resonance (SPR), and it causes the absorption and scattering
intensities of silver nanoparticles to be much higher than identically sized non-plasmonic
nanoparticles. In fact, silver nanoparticles can have effective extinction (scattering + absorption)
cross sections up to ten times larger than their physical cross section. The strong scattering cross
section allows for sub 100 nm nanoparticles to be easily visualized with a conventional
microscope. Figure(1a) is a schematic of the distortion of surface charge distributions of a silver
nanoparticle due to the impact of an electric field from the light source and figure(1b) is a dark
field optical microscopy image of 60 nm silver nanoparticle.

5
 Figure:(1a) schematic of surface plasmon resonance where the free electrons in the metal
nanoparticle are driven into oscillation due to a strong coupling with a specific wavelength of
incident light. b) Dark field microscopy image of 60 nm silver nanoparticles[5,6,9].

The characteristic SPR of silver nanoparticle is seen at wavelengths ranging from 390 nm to
450 nm depending on the size of the nanoparticle. Therefore, the absorption and scattering
properties of silver nanoparticlecles can be tuned by simply controlling the particle size. Figure 2
is the absorption versus wavelength plot of different size silver nanoparticles. As can be seen
from the figure, the absorption peak moves to longer wave length (red shifted) as the size of the
nanoparticle increases.

6
 Figure:2 Size-dependent absorption cross sectionc|¿|¿ ¿¿) per Ag NP of various diameters
d(nm) dispersed in hexane at room temperature. For clarity, each spectrum has been multiplied
by an arbitrary factor listed in the parentheses. The numbers out of the parentheses represent the
diameters of the Ag NPs. The inset plots the experimental (black squares) and theoretically
calculated (red line) absorption areas integrated from 320 to 600 nm.

2.1.2The effect of local refractive index on optical properties of silver nanoparticles

The optical properties silver nanoparticle also depends on the refractive index near the
nanoparticle surface. As the refractive index near the nanoparticle surface increases, the
nanoparticle extinction spectrum shifts to longer wavelengths (known as red-shifting). figure 3
displays the extinction spectrum of a 50 nm silver nanoparticles as the local refractive index is
increased. Increasing the refractive index from 1.00 to 1.60 resulted in an extinction peak shift of
over 90 nm, moving the peak from the ultraviolet to the visible region of the spectrum.

Figure:3 Extinction spectra of 50 nm silver nanoparticles in air, water, and Silica. As the
refractive index of the medium increases, the nanoparticle spectrum shifts to longer wavelengths
with the size[5] .

2.1.2The effect of aggregation on optical properties of spherical silver nanoparticles

The aggregation state of silver nanoparticles also has significant effect on their optical
properties[5]. Aggregation is a process where aggregates are formed from the association of
dispersed particles. The optical properties of silver nanoparticles change when particles
aggregate (combine) and the conduction electrons near each particle surface become delocalized
and are shared among neighboring particles. When this occurs, the surface Plasmon resonance

7
shifts to lower energies, causing the absorption and scattering peaks to red-shift to longer
wavelengths. The extinction peak will decrease in intensity (due to the depletion of stable
nanoparticles), and often the peak will broaden or a secondary peak will form at longer
wavelengths (due to the formation of aggregates). It is worth noting that the dependence of the
absorption peak position ( λ max) on the particle size is quite interesting. The absorption peak blue-
shifts as particle size decreases from d ∼ 20 nm to ∼12 nm (Fig:4). Such a blue-shift is well
known in the larger particle limit and arises from radiative depolarization effects that occur when
the particle size is not negligible compared to the size of the wavelength. However, as particle
size is further decreased, a strong red-shift takes over. So the figure is as shown below

Figure: 4(a) extinction (the sum of scattering and absorption) spectra of silver nanoparticles with
different diameters ranging from 10-100 nm . So the resonance wavelength depends on the size
of silver nanoparticles. Threfore silver nanoparticles size dependent surface plasmon resonance.
Note the red-shift of the absorption maximum as the silver nanoparticles size increase. (b) the
extinction spectra of silver nanoparticles after the addition of a destabilizing salt solution [5,6,19].

2.2 Characterization of silver nanoparticles

The size of silver nanoparticles are typically measured by analytical techniques such as
transmission Electron Microscopy (TEM), scanning electron microscopy (SEM) or atomic force
microscopy (AFM). Measuring the aggregation state of the particles requires a technique to
measure the effective size of silver nanoparticles in solution such as dynamic light scattering
(DLS) or analytical disc centrifugation (ADC). However, due to the unique optical properties of
silver nanoparticles, a great deal of information about the physical state of the nanoparticles can

8
be obtained by analyzing the spectral properties of silver nanoparticles in solution. The spectral
response of silver nanoparticles as a function of diameter was shown in figure 4a. As the
diameter increases, the peak plasmon resonance shifts to longer wavelengths and broadens. At
diameters greater than 80 nm, a second peak becomes visible at a shorter wavelength than the
primary peak. This secondary peak is due to a quadrupole resonance that has a different electron
oscillation pattern than the primary dipole resonance. The peak wavelength, the peak width, and
the effect of secondary resonances yield a unique spectral fingerprint for a plasmonic
nanoparticle with a specific size and shape. Additionally, UV-Visible spectroscopy provides a
mechanism to monitor how the nanoparticles change over time. When silver nanoparticles
aggregate, the metal particles become electronically coupled and this coupled system has a
different SPR than the individual particles. For the case of a multi-nanoparticle aggregate, the
plasmon resonance will be red-shifted to a longer wavelength than the resonance of an individual
nanoparticle, and aggregation is observable as an intensity increase in the red/infrared region of
the spectrum. This effect can be observed in figure 6, which displays the optical response of a
silver nanoparticle solution destabilized by the addition of saline. Carefully monitoring the UV-
Visible spectrum of the silver nanoparticles with time is a sensitive technique used in
determining if any nanoparticle aggregation has occurred [6].This effect can be observed in figure
6.

Figure:5 UV-visible Spectrum of silver nanoparticles at different time duration [64,65,66,67 ]

9
 Size distribution of silver nanoparticles measured by the DLS techniques.At diameters greater
a second peak becomes visible at a shorter wavelength than the primary peak. This secondary
peak is due to a quadruple resonance that has a different electron oscillation pattern than the
primary dipole resonance. The peak wavelength, the peak width, and the effect of secondary
resonances yield a unique spectral fingerprint for a plasmonic nanoparticle with a specific size
and shape. Additionally, UV-Visible spectroscopy provides a mechanism to monitor how the
nanoparticles change over time. Therefore UV-Spectra of silver nanoparticles at different sizes
from the literature suggests that, given the absorption spectrum, one can quantitatively derive the
nanoparticle size using a special subset of Mie's scattering theory.These are
d/nm (size) 424.9 (peaks)
8 392
10 392.1
12 395.2
14 397.2
16 398.5
18 399.7
20 400.8
22 401.6
24 402.5
26 403.5
28 404.5
30 405.6
32 406.8
34 408.1
36 409.4
38 410.8
40 412.3
42 413.9
44 415.5
46 417.3
48 419.1
50 420.9
52 422.9
54
56 427
58 429.2
60 431.5
62 433.8
64 436.2
66 438.7

10
 68 441.3
70 443.8
72 446.7
74 449.5
76 452.3
78 455.3
80 458.3
82 461.4
84 464.6

86 467.9
88 471.2
90 474.6

92 478.1

94 481.6
96 485.3

98 489.0

100 492.8

Table:1 The particle size increases from 8nm to 100 nm, the absorbance peak (lambda max)
increases from 392nm to 492.8nm, and broadens (increase in scope, range or area) in
width[1,58,59,60,61,62,63].

Figure 7 showns the graph of sizeVs the position of the surface plasmon resonance peak ( λ spr ¿ in
the spectrum of each suspension. This one can be fitted to the fifth order polynomial function for
wavelength in nm( R2=¿0.99989).

The equation which is fitted from the graph is as shown below:

2 3 4 5
d=BO + B1 λ+ B2 λ + B3 λ + B4 λ +B 5 λ …………………………………………....(2.1)

Where λ is the position of the SPR peak, R2 is regression or statistics this means the relation
between selected values of x and observed values of y (from which the most probable value of y
can be predicted for any value of x)and BO=¿380.8, B1=¿1.7, B2=¿-0.058, B3=¿ 0.00124, B4 =¿
-1.04×10−5 and B5=¿ 3.5×10−8 are the fit parameters. So when we substitute each values we get
the folloing formula[41].

d=¿ 380.8+¿ 1.7 λ+ ¿(-0.058) λ 2+ 0.00124 λ3 +¿ (-1.04×10−5 ¿ λ 4 +3.5 ×10−8 λ5

¿380.8+¿ 1.7 λ−¿0.058 λ 2+ 0.00124 λ3 −¿1.04×10−5 λ4 +3.5 ×10−8 λ5

11
∴ d=¿ 380.8+¿ 1.7 λ−¿0.058 λ 2+ 0.00124 λ3 −¿1.04×10−5 λ4 +3.5 ×10−8 λ5………………(2.2)

Figure:7 is a plot of particle size Vs resonance wavelength i.e a plot of table 1. The plot was
fitted with a fifth order polynomial function, for equation 2.1.
2.3 Parameters influencing of size of silver nanoparticle
There are many factors that affect the size and shape of silver nanoparticles[54].
These are:
 Type of reducing agent used during synthesis,
 Reaction mixture composition,
 Temperature of the reaction,
 stirring time,
 Stabilization with a stabilizing agent,
 PH-value.
In this part, we will address the impact of the pH on the size of Ag NPs by monitoring size
variations as a result of changing the pH of the solution. A general trend is that the surface

12
plasmon resonance peak shifts toward the short wavelength region as well as becomes narrower
when the Ph value increases[6,7,10].
The shift in the surface plasmon resonance peak indicates the change in the size of AgNPs and
hence any shift of the peak toward the shorter wavelength is accompanied by a decrease in the
size of AgNPs.we conclude that raising the pH of the solution results in the formation of
nanoparticles with smaller size and vice versa. On the other hand, the broadening of the surface
plasmon resonance peak indicates the existence of a wider range of sizes in the
solution.Thereforethe relationship between the size of AgNPs and the pH value is inversely
proportional.On the other hand is temperature.
The effect of temperature on resonance wavelength (UV spectra indicated that wavelength was
higher at lower temperature. This indicated that the wavelength was higher at lower temperature,
but the wavelength shifted to a lower value at higher temperature resulting in the formation of
smaller silver nanoparticles at higher temperature, whereas at higher wavelength the size of
silver nanoparticles increased[21,39].

This result agrees well with the Mie theory for the surface plasmon peak of nanoparticles in UV-
Vis absorption spectra. According to the Mie theory, silver nanoparticles of diameters ranging
from 1 to 10 nm have the plasmon peak width increasing linearly with the reciprocal of the
particle diameter[25,33]. The surface plasmon peak of a lager nanoparticle is more narrowed
(intrinsic size effect). However, when the particle diameter increases further (> 20 nm) the peak
width increases with the particle diameter (extrinsic size effect. Therefore temperature is the
main factor that affecting the size and the wavelength of silver nanoparticles.

13
 3. METHODOLOGY

Mie scattering equation was solved to relate the size of the nanoparticle with the resonance
frequency and the absorbance at that point. The resonance frequency and the absorbance can be
taken from UV vis measurements. This approach may provid a rapid means to estimate the size,
absorption , extinction and scattering cross section of silver nanoparticles.

3.1 Solving mie scattering theory

The general solution for mie scattering theory is given by equation 3.1,3. 2 and 3.3 for extinction
, scattering and absorption crossections, respectively by metal spheres.

∞
2π
σ ext =¿ 2 ∑ ( 2 L+1 ) ℜ {aL +b L}…………………………………………………….3.1
|k| L=1

∞
2π
2∑
( 2 L+1 ) (|a L| +|b L| )……………………..…………………………..3.2
2 2
σ sca=¿
|k| L=1

14
σ|¿|=σ ext −σ sca ¿ …………………………………………………………………………3.3

For small metal spheres ( small compared to the wavelength  of the exciting light, >2R) only
the dipole absorption of the Mie equation contributes to the extinction cross section σ ext of the
nanoparticles. The Mie theory then reduces to the following relationship (quasi-static or dipole
approximation), see equ.(3.4). [2, 3, 11, 78 and 34].

ω 3/ 2 ϵ 2 ( λ)
σ ext =¿9 ℇm V 2 ………………………..………………………… 3.4
C [ϵ ¿ ¿ 1 ( λ ) +2 ε m ] + ϵ 2 ¿ ¿ ¿

Where V is the volume of spherical silver nanoparticles (V ¿ ( 43π ) R ¿, cis the speed of light (
3

2 πc
C=3 ×10 m/s ) , ω is the angular frequency of the exciting light ( ω=
8
¿were taken from [44,
λ
45],
λ is the wavelength of the light in media, ε m is dielectric constant of the medium and ϵ 1 and
ϵ 2 (ε m=ϵ 1 ( λ ) +i ϵ 2 ( λ )), are the real and the imaginary parts of dielectric constant of the metal [2, 3, 44,
45, and 55]
: Since our objective is to determine the size of the nanoparticle from the peak(resonance)
frequency, we considered the resonce condition. In scattering of light by small metal
nanopparticles the condition for resonace is when
1. the real part of the dielectric constant is equal to the negative of twice the dielectric
constant of the sourunding medium that is the solvent

ϵ 1 ( λ )=−2 ε m……………….………………………….…………..…………. 3.5

2. And the imaginary of the dielectric constant of the metal sphere is nearly constant at
the resonance that is the first derivative of the imaginary part of the dielectric constant
at the resonance is small or nearly zero[76]. This means that
∂ ϵ2
¿ =0 …………………………………………….………………………...3.6 For
∂ω ω s

metals, like silver, where there is a substantial bound electron component the dielectric
function can be decomposed into two terms. These are free-electron term and inter-band
or bound-electron term [35]. Consequently, the size dependent dielectric constant of metals
is given by equation 3.7 and 3.8 for the real and imaginary part respectively.
ϵ
1 ,¿ ( ω , r ) =1− 2
ω 2p
2
+ ϵ1bound −electron ¿ …………………..……………………...….. 3.7
ω + γ (r )

15
ϵ
2 ,¿ ( ω , r) =
ω2p γ (r )
¿ +ϵ 2bound — electron …………………….………….………............. 3.8
( ω +γ 2(r )) ω
2

And inter band or bound-electron term dielectric constants can be calculated using equation 3.9
and the data given for bulk dierlectric constant by Johnson and Christi.

2
+ω p
ϵ bound — electron (ω)¿ ε bulk ( ω )−¿ 1 2 …………………………………………..3.9
ω +iω γ bulk

After normalizing equation 3.9, we get equation 3.10 for the imaginary part of the
bound electron contribution to the dielectric constant
2
−ω p γ bulk
ϵ 2bound −electron= 3 2 ……………..……………………….……...3.10
ω + ω γ bulk

After substituting equation 3.10 in to equation 3.8 we get equation 3.11

ϵ
2 ,¿ ( ω , r) =
ω2p γ (r )
3
−
2
ω2p γ b
=¿¿ ……………….……………………3.11
( ω2+γ 2(r )) ω ω + ω γb

Where ω pis the plasma frequency with the density of conduction electrons (for silver ω p=¿1.36
× 1016 Hz[47]), γ ( r ) is the damping constant for the electron oscillations and it is given by equation
3.12 [48,49,50,69]
R γ b+ C V F
γ ( r )= ……………………………………..………………………………….3.12
R
where V F is the velocity of the electrons at the Fermi energy(for silver V F=1.39 ×10 6 m/ s ),γ bulk
is the velocity of bulk scattering or damping parameter of the bulk metal (for silver ¿ ¿5×10 12 s−1
) and C is a theory-dependent parameter which is dependent on the details of the scattering
process (e.g. isotropic or diffuse scattering). For isotropic electron scattering C = 1; for diffuse
3
scattering its value is reduced to 0.75 (for silver C= ) [36, 70]. After substituting equation (3.12)
4
in to equation (3.11), we get equation (3.13)

ϵ R ω2p ω2 C V F − R ω2p γ2b C V F −C 2 V 2F ω2p γ b

2 ,¿ ( ω , r) = .…..3.13
¿
R (ω +2 γ ω +γ b ω) +R ( 2 γ b CV F ω +2 γ b C V F ω )+C V F ω +C V F γ b ω
2 5 2 3 4 3 3 2 2 3 2 2 2
b

16
And substituting equation 3.13 in to equation 3.4, we obtain equation 3.14 for the extinction
cross section (or absorption)

[( ) (
3 3 2 3
278.4
5 5
9 32 π c 16 π c γ b 4 8 24 c γ b V F 3
σ ext = 2 2 2 2 2 2 2 2 2 2
R 4
+ 2
+2 γ b πc + R 2
+3 γ b V F
(3 R ω p π c V F −R ω p γ b λ C V F −C V F ω p λ γ b) λ λ λ

…………………3.14
Equation 3.14 is an expersion of the extinction crossection of a single nanoparticle with radius R
embedded in a medium with dielectric constant m. In a spectrophotometer, monochromatic
plane-parallel light enters a sample at right angles to the plane-surface of the sample. In these
conditions, the absorbance (A) of a sample depends on the light path length in centimeters (L),
and extinction coffiecient (ϵ ext ) for the dissolved substance at the specified wavelength (λ).
ϵ ext L
A=log 10 (e ) …………………………………………………………………………..3.15
The extinction crossection is not usually measurable, therefore, it is related to the extinction
cofficient by equation 3.15(see Experimental Determination of the Absorption Cross-Section and
Molar Extinction)
ϵ ext = N [σ ext ¿ ………………………..……..………………………………….3.16

Where N is the number of particles in the solution (concentration).

Substituting equation 3.14 in to 3.16 we get equation 3.17

[( ) (
3 3 2 3
278.4 N
5 5
9 32 π c 16 π c γ b 4 8 24 c γ b V F 3
ϵ ext = 2 2 2 2 2 2 2 2 2 2
R 4
+ 2
+2 γ b πc + R 2
+3 γ b V F
(3 R ω p π c V F −R ω p γ b λ C V F −C V F ω p λ γ b ) λ λ λ
………………….3.17
To determine number of particles in the solution (concentration), first the extinction coffiecient
will be calculated using equation 3.15 and then using equation 3.18, we can determine the
concentration.
3
π d ρANA
C NP = ……………………………………………………………………
6 Lε
3.18

So from equation 3.15

ϵ ext L
A=log 10 (e )

Let x=ϵ ext L

17
 x
A=log 10 e

¿ x log 10 e

Where log 10 e ¿0.434

¿ 0.434 x

But x=ϵ ext L

Therefore

A=(0.434 )(ϵ ext L)

A
ϵ ext =
0.434 L

ϵ ext ¿ 2.303 AL−1 …………………………………………………………………….3.19

And the consentration is given by using equation 3.18 we get equation 3.20
3
π d ρA N A
C NP = −1
(6 L)(2.303 AL )

3
πd ρ NA
¿
(6)(2.303)
3
πd ρ NA
C NP ¿ ……………………………………………………………….3.20
13.818

But C NP =¿NmNp
π 3
mNP =V NP ρ (Mass of a single nanoparticle)¿ d ρ
6

π
C NP =¿N D3 ρ………………………….………………………….…………………………3.21
6
Equate equation 3.20and 3.21 we get equation 3.22
NA
N¿ ………………………………….……………………….…………………………..3.22
2.303

In another alternative
A¿ C . ε ext . L (Beer-Lambert law):

18
 A
C=
ε ext . L

L−¿ Is Path length of light through the sample (usually 1cm for a cuvette)

C −¿ Molar concentration of nanoparticles

ε ext −¿ Is extinction coefficient

A
ε ext =
C .L

N
C= (Nanoparticle molar concentration)
NA

N=C . N A

A
N= . N A ………………………………………………………………………………3.23
ε ext . L

Substituting equation 3.20 in to equation 3.23 we gt quation 3.24

NA
N= . ……………………………………………………………..…………………3.24
2.303

Where ρ is density silver( 10.5 g/cm3 ¿, D is diameter of silver nanoparticles ( D=2 R ¿, M is

g
atomic mass of silver(108 ) and N A is Avogadro’s number (6.022x1023 atoms/mol)[34].
mol
Substitute equation 3.22 in to equation quation 3.17 we get equation 3.25

[( ) (
3 3 2 3
120.89 N A 9 32 π c 16 π c γ b
5 5
4 8 24 c γ b V F 3
ϵ ext = 2 2 2 2 2 2 2 2 2 2
R 4
+ 2
+2 γ b πc + R 2
+3 γ b V F
(3 R ω p π c V F −R ω p γ b λ C V F −C V F ω p λ γ b ) λ λ λ
……………………………………………………..3.25

The absorption coefficient α and the extinction coefficient ϵ ext are related by the following
formula [9,40,61].
1
α¿ ln
x ( II )= 4 πλϵ
o ext
…………………………….…………….…………. 3.26

And in an experiment that involves UV visible spectroscopy, we usually measure the light that
passes through a sample. And, in a typical experimental setup, the light which is transmitted
through a sample composed of nanoparticles dispersed in a homogeneous matrix is given by [1].
−αx
I =I O e …………………………………………...……….……………………… 3.27

19
Where α is absorption coefficient, I o is the initial intensity of the light, I is the intensity after
2 πR
passing through at distance x of material with an absorption coefficient α. Here x= is the
λ
dimensionless optical particle size parameter. Therefore equation 3.27 becomes

ϵ ext =
λ2
2
8π R
I
I( )
ln o ………………………………………………………………………..3.28

And from the Beer-Lambert law the relationship between the absorption at specific wavelength
[42, 43, ]
Absorbance=0.434 ln¿
ln ¿ Absorbance……………………………………….……………………. 3.29
Equating equation 3.25 and 3.28 we get equation 3.30

( ) ( ) ( )
5 5 3 3 2 4 3 3 3 3 2 2 2
10 32 π c 16 π c γ b 2 γ b πc 9 24 c γ b V F 3 γ b V F πc 8 4.5 π c V F 1.13 πc V F γ b 1
R + + + R + + R + − absorbance
λ 6
λ 4
λ 2
λ 4
λ 2
λ 4
λ 2
N A

……3.30

1
[ A R10 +B R 9+C R8 ]− absorbance [ DR −E ] ¿0................................................................3.31
NA

5 5 3 3 2 4
32 π c 16 π c γ b 2 γ b πc
Where A= 6
+ 4
+ 2
λ λ λ
3 3
24 c γ b V F 3 γ b V F πc
B¿ 4
+ 2
λ λ
3 3 2 2 2
4.5 π c V F 1.13 πc V F γ b
C= 4
+ 2
λ λ

D=( 7.26 x 10−7 ω 2p π 2 c 2 V F −2.42× 10−4 ω 2p γ 2b λ 2 C V F )

−4 2 2 2 2
E=2.42× 10 C V F ω p λ γ b

3.2 size of nanoparticle from surface effects

The second alternative of determining the nanoparticle size if using the following equation which
is taken from [76]

√ ( )
2
RO
ω s ( R )=¿ ⍵ S
Cl
1+ ( 1+2 ϵ m )
R

20
 ⍵p
Where ws is resonance frequency, wscl is ⍵SCl ¿ √1+2 Ԑ m and R0 is
2
3π ℏ
2
RO =¿ 2
4 m e kF
ωs were taken from[76]

√
ω s ( R )=¿ ⍵sCl 1+ ( 1+2 ϵ m )
R2o
R
2

¿⍵sCl
√ R 2+ R 2o +2 R 2o ϵ m
R
2

√
2
⍵p 2 3 π ℏ2 6 ℏ ϵ m π
¿ R+ 2
+ 2
√1+2 Ԑm 4 me k F 4 m e k F
2
R

¿
⍵p
√1+2 Ԑm √ 4 R2 me 2 k F +3 ℏ2 π +6 ℏ 2 ϵ m π
4 R2 me 2 k F

( )
2 2 2 2
2 ⍵p
2
4 R m e k F +3 ℏ π +6 ℏ ϵ m π
⍵ (R)=
s
1+2 Ԑm 4 R 2 m e2 k F

R2 [ 8 m e2 k F ϵ m ⍵ 2s ( R )+ 4 m e 2 k F ⍵2s ( R )−4 ⍵2p m e2 k F ] −( 3 ⍵2p ℏ2 π + 6 ⍵2p ℏ2 ϵ m π ) =¿0

R { 4 m e k F [ 2 ϵ m ⍵ s ( R )+⍵ s ( R )−⍵ p ] }−3 ⍵ p ℏ π [1+2 ϵ m ] =0

2 2 2 2 2 2 2

A R2−B=¿0…………………………………………..………………………………..3.23
Where A¿ 8 m e2 k F ϵ m ⍵2s ( R )+ 4 m e 2 k F ⍵2s ( R )−4 ⍵ 2p m e 2 k F

B¿ ( 3 ⍵ p ℏ π +6 ⍵ p ℏ ϵ m π )
2 2 2 2

Where ⍵p = 1.38x1016 S-1, γ0 = 2.7 x1012 s-1, Vf = 1.39x106 m/s,һ=62606957 x 10−34 Js(Plank’s

=¿ 1.055x10-34Js, e=¿ 1.602176565×10−19C , me =9.12 ×10−22g,ω s ( R )=? ,

һ
constant) , ℏ=¿
2π
2π
k F =¿ and A=0.8 (taken from Influence of size-corrected bound-electroncontribution on
λ

nanometric silver dielectric function. Sizing through optical extinction spectroscopy )

3.3 Size dependence of the band width

21
For small metal nanoparticles, radius less than the mean free path, the band width is linearly
dependent on the inverse of the particle size , equation 3.24 were taken from [71, 72, 73, 74,75]
o AVF
γ ( r )=γ +
R
AV F
R= ………………………………………………………………………….3.24
γ ( r )−γ o
Where V F is the Fermi velocity (for silver 1. 39× 106 m/s) , γ is width of the peak , γ o is the
velocity of bulk scattering (for silver 5× 1012 s−1[71]) and A is attributed to scattering process (3/4
for silver)[ 72].

3. Result and discussion

Therefore UV-Spectra of silver nanoparticles at different sizes from the literature and finding
suggests that, given the absorption spectrum, one can quantitatively derive the nanoparticle size
using a special subset of Mie's scattering theory.These are
d/nm (size) (peaks) Full width at half Peak frequency Calculated by equation Calculated by Calculated by equation
maximum 3.22 equation 3.23 3.24
8 392
10 392.1
12 395.2
14 397.2
16 398.5
18 399.7
20 400.8
22 401.6
24 402.5
26 403.5
28 404.5
30 405.6
32 406.8
34 408.1
36 409.4
38 410.8
40 412.3
42 413.9
44 415.5
46 417.3
48 419.1
50 420.9
52 422.9

22
 54 424.9
56 427
58 429.2
60 431.5
62 433.8
64 436.2
66 438.7
68 441.3
70 443.8
72 446.7
74 449.5
76 452.3
78 455.3
80 458.3
82 461.4
84 464.6

86 467.9
88 471.2
90 474.6

92 478.1

94 481.6
96 485.3

98 489.0

100 492.8

Table:1 The particle size increases from 8nm to 100 nm, the absorbance peak (lambda max)
increases from 392nm to 492.8nm, and broadens (increase in scope, range or area) in
width[1,58,59,60,61,62,63].

Figure 7 showns the graph of sizeVs the position of the surface plasmon resonance peak ( λ spr ¿ in
the spectrum of each suspension. This one can be fitted to the fifth order polynomial function for
wavelength in nm( R2=¿0.99989).

23
24
 CHAPTER FOUR

Result & Discussion

To determine the size of spherical silver nanoparticles was obtained from Mie’s scattering theory
and beer’s lambert law.Using equation (3.32) I can determine the size of silver nanoparticles by
using colletedsveral peaks from published journals. Using figure 6to tabulate absorption against
resonance wavelength by using getdata digitize. After tabulating the absorption and the
resonanewavelength,tosubstituting in to equation (3.32)and inorder to find the size of silver
nanoparticlesby using matlab program and finally tabulate resonance wavelength against
size.Therefore the value of each peak was calculated as shown the table. So from the appendix
table:2-11 shows data table from AgNPs relating nanoparticles absorption and peak absorbance
wavelength. This data was plotted against a scatter plot graph of average peak SPR wavelength
to absorption. And in addition from figure: 9-17 shows UV–Vis absorption spectra of silver
nanoparticles. The curve indicates the typical peak 395nm, 405nm, 411nm, 419nm, 426nm,
443nm, 452nm, 463nm, and 490nm corresponds to the characteristic of resonance wavelength of
silver nanoparticles respectively.From such figures are shows with decreasing the concentration
of nanoparticles, decreases the intensity of the characteristic energy band and also be the
plasmon peak tends to shorter wavelengths resulting in smaller particle sizes. It has been
represent that as the absorbance wavelength is shifted toward longer when particle sizes are
larger. Thereore the graph is as shown below.

25
Figure:9 at resonance wavelength =395nm Figure:10 at resonance wavelength =405nm

With absorption =4.17 with absorption = 3.73

Figure:11 at resonance wavelength =411nm Figure:12 at resonance wavelength= 419nm

With absorption =3.34 with absorption =3.15

26
 Figure:13 at resonance wavelength =426nm Figure:14at resonance wavelength= 443nm

With absorption=2.56 with absorption=2.23

Figure:15 at resonance wavelength =452nm Figure:16 at resonance wavelength =463nm

With absorption= 1.86 with absorption =1.45

Figure: 17 at resonance wavelength =493nm with absorption =1.15

27
Then when we substitute the value of resonance wavelength and absorption in to equation(3.32)
and using matlab program we get the size of silver nanoparticles . Therefore
d 1=¿ 14.3nm (at λ max=¿395nm and absorption=4.17)

d 2=¿ 35.7nm(at λ max=¿405nm and absorption=3.73)

d 3=¿44.6nm(at λ max=¿411nm and absorption=3.34)

d 4 =¿53.5nm(at λ max=¿419nm and absorption=3.15)

d 5=¿62.3nm(at λ max=¿426nm and absorption=2.56.)

d 6 =¿71.6nm(at λ max=¿443nm and absorption=2.23)

d 7=¿80.3nm(at λ max=¿452nm and absorption=1.86.)

d 8 =¿88.7nm(at λ max=¿463nm and absorption=1.45)

d 9 =¿98.7nm(at λ max=¿490nm and absorption=1.13)

Therefore the value of d 1,d 2,d 3,d 4 ,d 5,d 6 ,d 7,d 8 and d 9 indicates the size (diameter ) of each UV–
Vis absorption spectra of silver nanoparticles which is takes from figure(6).
We observed from this value the absorbance wavelength of a nanoparticle is large with large of
size of silver nanoparticles. This indicates wavelength is one of the key influence factors in the
size of silver nanoparticles . The shift in the strongest absorption peak to longer wavelengths
means the size of nanoparticle is increases. When we plot the size against the resonance
wavelength from appendix for table 11is as shown in figure 18.

28
Figure:18 Shows the relationship between nanoparticle diameter and highest peak absorbance
wavelength of silver nanoparticles.This indicates different size nanoparticles will absorb
different wavelengths of light. A large variance in particle size will result in a wider absorbance
peak.Therefore the strongest absorption peak to longer wavelengths means the longer of the size
of nanoparticles.

DISCUSSION

When we solve the size of silver nanoparticles using different several peaks (using fig 6) , as
the resonane wavelength increases with the increases of the size of silver nanoparticles.
Therefore resonance wavelength is the main fator which affecting of the size. When we
compered the value of the size of Ag NPs from the calculation value to the literature values, the
size of silver nanoparticles have the same value for the whole case.

29
 CHAPTER FIVE

CONCLUSIONS AND RECOMMENDATIONS

5.1: conclusion
The objective of this study was to determine the size of silver nanoparticles from UV –Vis
spectra resonance peak using Mie’s scattering and Beer’s Lambert law. Based on the result
shown in Table 11, we can conclude from this result resonance peaks in different wavelength
yielding different values of size of silver nanoparticles. According to the Mie theory, silver
nanoparticles of diameters ranging from 1 to 100 nm have the Plasmon peak width increasing
linearly.To compare these theoretical results to mathematical calculation data, silver
nanoparticles in the size range of 1 to100 nm were characterized with TEM and UV−Vis. It is
shown that the data produced here can be used to determine size of silver nanoparticles directly
from UV−Vis spectra. In general we observed that the peak shift for the peak in range from 395-
490nm is higher indicating a higher sensitivity to the higher absorption of the nanoparticles and
the higher of the wavelength the higher of the size of silver nanoparticles. This may be due to the
fact that silver nanoparticles have a larger negative dielectric function at high wavelengths. For
noble metal nanoparticles ε 1 is negative and decreases with increasing wavelength so that as ε m
increases, the resonance condition is fulfilled at higher wavelengths. Additionally the peak shifts
to higher wavelengths with increases in the refractive index of the surrounding medium. As the
size of spherical silver nanoparticles get larger, the peaks broaden and shift to longer
wavelengths.
5.2: Recommendation

The work presented in this thesis has shown promising results which can be used to
understand the size of silver nanoparticles from different literature data collection. Literature
data collection have been used as resource assessment by different researchers as alternative
means to direct measured data. It can be shown for instance that the nine different peaks obtained
from the literature for the present study was estimated the size of silver nanoparticles. This study
was focused basically on the size and the wavelength based models to estimate the size of silver
nanoparticles. Thus it could be recommended that in the future work,I will doing especial
element of equations will be the most suitable to estimate the size of silver nanoparticles using
experiment equipment.

30
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36
5.4 appendix
Resonane wavelength (nm) Absorption (a.u)
Table:
300 2 shows data table from AgNPs
0.419 relating nanoparticles absorption and peak absorbance
wavelength
310 is 395nm. 0.291
4.07
319 0.217

329 0.234

341 0.415

350 0.67

357 0.906

362 1.12

366 1.4

370 1.69

372 1.98

375 2.25

377 2.54

379 2.83

381 3.16

384 3.49

386 3.75 37
388 3.93

391 4.09

395 4.17
 399
401 3.93

403 3.74

406 3.47

408 3.18

410 2.87

412 2.61

414 2.29

416 1.98

419 1.68

422 1.32
426 1.05

430 0.753

437 0.552

449 0.314
461 0.186

482 0.111
501 0.0728
529 0.052

554 0.0315

584 0.0288
601 0.0455

Table :3 data table from AgNPs relating nanoparticles absorption and peak absorbance wavelength
405nm.
Resonane wavelength (nm) 2.88 Absorption (a.u)
300 0.294

314 0.146

339 0.31

349 0.512

357 0.75

370 1.26

373 1.54

381 2.15

384 2.42

394 3.21

397 3.45

405 3.71

409 3.61

411 3.41

417
421 2.36

427 1.81

429 1.56

38
 442 0.673

449 0.434

460 0.268
521 0.0266

547 0.0254
570 0.0243

618 0.00375
644 0.00258

656 0.0204

677 0.0378
691 0.0188

Table :4 data table from AgNPs relating nanoparticles absorption and peak absorbance wavelength
411nm
Resonane wavelength (nm) 2.85 Absorption (a.u)
300 0.364

310 0.236

321 0.144

330 0.198

341 0.324

352 0.487

360 0.687

366 0.887

372 1.1

376 1.34

381 1.6

385 1.87

388 2.14

391 2.41

393 2.6

396 2.8

400 3.02

403 3.22

411 3.34

414 3.27

416 3.09

419
422 2.59

426 2.32

428 2.01

432 1.74

435 1.43

39
 438 1.12

441 0.953

447 0.734

454 0.496

464 0.331
478 0.202

495 0.128

517 0.0896

536 0.0332
559 0.0128

581 0.0291
601 0.0273
625 0.025

646 0.00489

668 0.0335
687 0.0012

Resonane wavelength (nm) Absorption (a.u)

300 0.313

Table :5 data table from AgNPs relating

312 0.165 nanoparticles absorption and peak absorbance
wavelength 419nm.
327 0.146

339 0.275
2.83
348 0.422

359 0.643

368 0.864

374 1.08

382 1.34

386 1.58

392 1.88

397 2.15

401 2.47

404 2.71

408 2.89 40
413 3.06

419 3.15

424 3.04
 429
432 2.58

436 2.34

438 2.11

441 1.82

446 1.58

450 1.23

455 1.01

462 0.712

472 0.472

484 0.305
498 0.194

519 0.119

540 0.0627

562 0.0248
584 0.00536

611 0.0328
634 0.0338
657 0.0165

684 0.0192

Table :6data table from AgNPs relating nanoparticles absorption and peak absorbance
wavelength 426nm.
Resonane wavelength (nm) 1.69 Absorption (a.u)

300 0.311

314 0.163

329 0.162

339 0.289

349 0.435

361 0.635

372 0.853

381 1.07

389 1.33

396 1.56

412 2.29

419 2.48

426 2.56

440 2.29

445 2.13

449 1.89

453
458 1.45

464 1.21

470 1.01

41
 486 0.605

496 0.476

518 0.273

548 0.16
563 0.122

578 0.0844

595 0.0646

609 0.045
642 0.042
663 0.04
676 0.0206

691 0.0192

700 0.0367

Table :7data table from AgNPs relating nanoparticles absorption and peak absorbance
wavelength 443nm.
Resonane wavelength (nm) 2.04 Absorption (a.u)

300 0.382

311 0.217

323 0.179

336 0.268

345 0.413

355 0.557

364 0.72

372 0.865

379 1.08

393 1.32

402 1.5

410 1.68

417 1.88

424 2.08

431 2.2

437 2.22

443 2.23

449 2.16

455 2.15

461
465 1.89

471 1.74

477 1.56

483 1.36

490 1.14

497 0.993

504 0.847

42
 516 0.681

528 0.497

542 0.386
554 0.33

567 0.273

577 0.235

590 0.179
608 0.14

627 0.119
643 0.0989
662 0.078

678 0.0577

695 0.0189

Table :8 data table from AgNPs relating nanoparticles absorption and peak absorbance
wavelength. This data was plotted against a scatter plot graph of average peak SPR wavelength
to absorption.
Resonane wavelength (nm) 1.86 Absorption (a.u)

300 0.347

310 0.237

317 0.2

326 0.217

348 0.38

359 0.507

369 0.634

382 0.925

391 1.09

399 1.2

414 1.47

421 1.6

435 1.84

452
460 1.78

467 1.67

486 1.28

494 1.08

504 0.859

544 0.38

560 0.287
580 0.212

602 0.137

619 0.117

643 0.0967
659 0.0952

689 0.0559

43
 699 0.055

Table: 9 data table from AgNPs relating nanoparticles absorption and peak absorbance
wavelength 463nm.
Resonane wavelength (nm)1.41 Absorption (a.u)

300 0.294

313 0.146

325 0.127

338 0.237

349 0.384

361 0.512

373 0.658

384 0.823

394 0.933

403 1.01

410 1.06

417 1.12

425 1.19

437 1.3

453
463 1.45

473 1.39

485 1.28

502 1.09

515 0.945

526 0.798

541 0.65

573 0.41

590 0.317
610 0.243

628 0.169

648 0.149

666 0.112
692 0.055
Resonane wavelength (nm) Absorption (a.u)

300 0.24

Table: 10 data table from AgNPs relating

312 0.148 nanoparticles absorption and peak absorbance
wavelength
322 of 490nm. 0.0922

334 0.148
1.15
350 0.295

366 0.443

379 0.572

391 0.701

403 0.793

418 0.904

434 0.977 44
452 1.07

463 1.11

476 1.14
 490
504 1.09

515 0.996

527 0.904

544 0.775

559 0.645

572 0.553

585 0.48

599 0.406

609 0.35

623 0.277

638 0.221
654 0.166

669 0.129

684 0.111

699 0.0738

Table: 11Calculation value on size of silver nanoparticles for varying concentration in UV-vis
using Mie’ scattering theory and Beer’s lambert law.this shows the size of silver nanoparticles
for varying concentration in UV-visible spectra.

( )
Resonance wavelength of silver IO Diameter(size) of silver
nanoparticles(nm) ( λ max) Absorbance ¿ log =ϵ nanoparticles(nm)
I
bc

395 4.17
d 1=¿ 14.3
405 3.73
d 2=¿ 35.7
411 3.34
d 3=¿44.6
419 3.15
d 4 =¿53.5
426 2.56
d 5=¿62.3
443 2.23
d 6 =¿71.6
452 1.86
d 7=¿80.3
463 1.45
d 8 =¿88.7
490 1.13
d 9 =¿98.3

45