Introduction

spectroscopy is the study of properties of the matter its interaction with various
type of radiation (mostly electromagnetic radiation) of the electromagnetic
spectrum.
The UV-VIS spectroscopy is one of the oldest instrumental techniques of analysis
and is the basis for number of ideal methods for the determination of micro and
semi micro quantities of analytes in a sample. It concern with the measurement of
the consequence of interaction of electromagnetic radiation in the UV or VISIBLE
region in the absorbing species like atoms, molecules or ions.
 Origin of uv-visible spectra

In some molecules and atoms, photons of UV and VISIBLE light have enough energy to cause the
transitions between different electronic energy levels. The wavelength of light absorbed is that
having the energy required to move an electron from lower energy level to higher energy level. UV-
VISIBLE spectrum results from the interaction of electromagnetic radiation in the UV-VISIBLE region
with the molecules, ions or complexes.
Ultraviolet visible spectroscopy

 UV-VISIBLE is absorption spectroscopy is the measurement of the attenuation of a beam

of light after it passes through the sample or after reflection from the sample.

 The visible spectrum ranges from 400 nm to about 800 nm. The color which we see it
depends on the wavelength of light. The color of the matter is related to its absorptivity or
reflectivity. The human eye sees the complementary color to that which is absorbed.
Instrumentation for uv-visible spectroscopy

 The five essential components of UV-VISIBLE instruments are as follows.

1) A stable radiation source
2) Wavelength selector
3) Sample holder
4) Radiation detector or transducer
5) Signal processing output device
Review work

 1) Determination of force constant and refractive index of

semiconducting polymer composite using UV-Visible
spectroscopy: a new approach

 Materials and methods

 Preparation of polymer composites

 Polymer composites of various NiCl2 concentrations were prepared by employing

solution casting method. Stock solution of 5% HPMC was prepared and NiCl 2 of required
weight percentage was doped to prepare 1,2,3 and 4% NiCl 2-HPMC polymer composites.
The dried polymer membranes were then peeled out carefully by avoiding any
mechanical distortions; these films were stored in zip-lock covers to avoid interaction
with other contaminations and moisture. The films were dried using hot air oven to
remove the residual water molecules and moisture.
UV-visible spectroscopy

 UV-Visible spectroscopy of the samples, denoting a macrostructural aspect of the

polymer composites are measured using a Labtronics LT- 2800 double beam UV-
Visible spectrometer to verify the characteristics absorption of the polymer composites
with respect to dopant concentration for a wavelength range from 190 to 900 nm. UV-
Visible absorption spectrum obtained for pure HPMC and NiCl 2 doped HPMC polymer
composites as show in fig.1

Theory

 The differential equation describing the motion of an elastically bound polymer part
with a negative charge ‘e’ and mass ‘m’ in an alternating field is
 m. d2x/dt2 + m. ʋ dx/dt + mω2x = eE0 eoωt
 ʋ is the damping factor, x is the displacement of electron from its mean position.
 The solution is
 X(t) = e E0 eiωt / (m . ω02 – ω2 + iʋω)
 ω0 =( f/m)1/2
 where ω0 is the resonance frequency from which force constant can be determined and
also ‘x’ .
 α = ex / |E| = 3 / 4πN.( n2 – 1 /n2 + 1 )
 N is number of polymer parts per unit volume,
 N = NA ρ / Mol. Wt

 As the EM absorption in these polymer composites varies, it results in defining several

optical parameters. We have considered both the density and molecular weights of host
polymer and dopant and have made the necessary calculations accordingly, based on
the concentration of particular composite.

Result and discussion
 Force constant between the polymeric chains in these polymer composites are
calculated and are shown in fig.2. From the fig., it can be seen that force constant
values determined for each sample lie on the same exponentially decreasing slope
which varies with wavelength. The result show depict that there is no change in the
force constant among the chains of these polymer composites which is an important
finding of the study.
 From the plot of refractive index as a function of wavelength is shown in fig.3 it can be
seen that refractive index of these polymer composites, increases with the wavelength
that is shows its resistance towards the incident wave. The addition of NiCl 2 makes the
polymer matrix denser in nature and thus makes it exhibit a higher refractive
index.There are many methods to determine to find refractive index from UV-Visible
results, we have defined this by considering the absorption region wavelength and not
the absorption coefficient. An attempt is made to depict the variation of refractive index
and force constant as a function of wavelength and is shown in fig.4.
Conclusion

Refractive index can be used to determine the reflectivity, transmittance,

absorbance, etc of material. In the same way forced constant also gives
information about the structural changes in a material. Thus the method proposed
here will be a very useful contrivance in determining these physical parameters
from UV-Visible spectroscopic results.
2) Size and concentration analysis of gold nano- particles
with UV-Visible spectroscopy
Problem statement
Due to the range of sizes, it may be difficult to determine the average size of these
synthesized nanoparticles. Another issue is that the theoretical concentration of gold
nanoparticles suspended in solution may not be accurately depicted depending on whether
the reaction is fully complete.
Discussion

 By using Beer’s Law, the concentration of the solution fell into the range of theoretical
values presented in Sigma-Aldrich. As presented in the SEM scan in Figure 3, different
size GNPs exist in the solution which would cause some discrepancy between the actual
and theoretical calculation. Another issue presented is if the reducing agent, trisodium
citrate dihydrate, was not fully used up in the reaction. If so, then floating particles of
trisodium citrate dihydrate would exist in the solution, therefore, Equation (6) would be
appropriate to use.
In Figure 4, a logical correlation between wavelength peak and concentration exists
showing validity in using Beer-Lambert’s law. If the particle size increases, then the
concentration of GNP should decrease since the GNPs will be taking up a larger volume of
the solution.

By using the data collected from the UV-VIS spectrophotometer in Figure 1, the λ, Aspr,
and A450 were calculated. When using Equation (1), both theoretical that were developed
in the literature (B1 = 3.55 and B2 = 3.11) and experimental values (B1 = 2.01 and B2 =
3.11) of B1 and B2 was used. The diameters that were received were then compared to the
average diameter recorded by Sigma Aldrich.
 Conclusion and recomondation

By utilizing Beer-Lambert’s law to determine the concentration of GNP in solution a fairly

accurate estimate can be drawn if one assumes that no excess trisodium citrate dihydrate
remains in the solution and that the size is monodispersed. To improve the accuracy of the
data, one should use a DLS instrument to determine the average diameter of the GNP and
use the corresponding extinction coefficient. Another improvement that could be made is to
filter out any particles of trisodium citrate dihydrate which would allow one to use Equation
(4) with high precision.
By using the ratio of the absorbance of the SPR peak to the absorbance at 450 nanometers,
a fair approximation obtained if one uses their own fit parameters based on their previous
GNP samples. Therefore, the equation does not consider the polydispersity of the GNPs
which will result in error. An improvement that can be made is to use a wider set of values
when plotting the best fit line. Having a larger spread of data points can allow one to use
their own experimental values for a wider range of GNP sizes. Using the absorbance peak
should not be used as the main determinant of finding the average diameter of the GNPs.
The best accuracy may be obtained by using an SEM, TEM, or DLS instrument.