CHAPTER II

EXPERIMENTAL
MATERIALS, METHODS AND SET UP
11.1 INTRODUCTORY REMARKS

Raman Scattering arises as a result of interaction of electromagnetic radiation with

matter resulting in some additional frequencies on the both sides of the incident radiation
which are characteristic of matter or molecule. With the advent of strong, monochromatic,
polarised and tunable lasers, the Raman spectroscopy has emerged as a sensitive technique for
probing structural details of complex molecules. In this chapter, the method of sample
preparation and purification, the experimental technique, instrumental details for Raman and

absorption spectroscopy have been discussed briefly.

ll.2 SAMPLE PREPARATION AND PURIFICATION

The samples chosen for the present investigation are procured from different reputed
manufactures, like Aldrich Chemical Co. (U.S.A.), Fluka (Buchs, Switzerland), B.D.H.
(London) with chemical purity 97% to 99%. Pyridine derivatives, which have been studied
presently, are purified by subjecting them to repeated distillation under vacuum in order to
remove impurities further. These distillates are then ready for use in the proper experiment.
Spectroscopic grade solvents CHCb and CC4 are supplied by S.R.L. (India) and have
been used as received. As ordinary Raman spectroscopy is not suitable for vibrational studies
at low concentration for weak scatterer, the concentration of the solution is maintained around
1M for recording the Raman spectra. Chloroform and carbon tetrachloride are chosen as the
solvents because of the following reasons. {i} All samples, studied in the present work, are
readily dissolved in both the solvents even at higher concentration. {ii} In order to test the
consistency of experimental observation, these weakly polar and non-polar solvents,
respectively, are preferred. {iii} No intense Raman line of CHCh and CC4 appears in the
frequency range of the fundamentals, whose REPs have been studied. {iv} The Raman
1
wavenumbers, 667 cm· of CHCh and 461 cm· 1 of CC4, have been conveniently used as
internal standards. {v} No strong Raman bands of samples overlap with these reference lines.
Otherwise, the intensities of the reference lines would have led to erroneous results in the
measurement of the REPs. Attempt has been made to measure the REPs in the polar solvent
methanol also. But the solvent band at 1032 cm" 1 (generally used as internal standard)
overlaps with the solute bands in this region so profoundly that the idea of measuring REPs in
this solvent is left undone.

AQ
ll.3 MEASUREMENT OF ABSORPTION SPECTRA

The electronic absorption spectra are recorded with the help of Shimadzu UV-Vis
21 OA spectrophotometer (shown in figure [11.1 ]). This model is capable of measuring light
from 900 to 190 nm range and employs a tungsten light source in the visible range of the
spectrum (900 to 340 nm) and a deuterium source in the ultra violet range of the spectrum
(360 to 190 nm). The resolution of the spectrophotometer is 0.2 nm and has wavelength
repeatability better than 0.2 nm.

Figure ll.l A schematic optical diagram ofShimadzu UV-Vis 210A Spectrometer.

The samples are taken in a quartz cells of path lengths 1 em or 1 mm for the
concentration range (10-5 to 10-3) M, whereas, the range (10-3 to 1) M is studied by making
thin films of the solutions between two quartz plates. The thickness (-0.002 em) of the thin
film is determined by calibrating with samples of known concentrations. Spectroscopic grade
ethanol, purchased from Aldrich Chemical Co. (U.S.A.) is used as solvent

ll.4 FOURIER TRANSFORM INFRARED ABSORPTION MEASUREMENT

Fourier transformed Infrared Absorption spectra are recorded on a Nicholet Magna

750 FTIR spectrophotometer. The schematic optical diagram of the spectrophotometer is
shown in figure [II .2].

AO
 Michelson
·----------.-..------------·--
1
I
.....
interferometer
1
. d
Fue
I

1 mirror I
I I
I I
I I
I I
I 0-J 0-2 D-1
I
I
I Source
I
I

;...,
'
~ 1!2A. l/4t.. ZPD
L-1----~---t------
plitter

-----..J I

.".:::!

-5"'
~=

Sample
Detector signal
Moving mirror position
Detector

Figure II.2 A schematic optical diagram ofNicholet Magna 750 FTIR Spectrometer.

IR spectra of different organic compounds are studied in thin films and in the solutions
of CHCb and CC4. The solid samples have been studied in KBr pellet. About 1 mg of the
sample and 100-200 mg of potassium bromide are ground together finely, dried to remove
moisture, pressed at elevated temperature under high pressure into a small disc that measures
about 1 ClJl in diameter and 1-2 mm in thickness. The resolution of theIR band is about 2 em·
1
for sharp bands and slightly less for the broader ones.

ll.S RAMAN SPECTRAL MEASUREMENT

The necessary components for the observation of Raman spectra are : (a) source of
monochromatic radiation, (b) an appropriate device to mount the sample illuminated optimally
and efficient scattered light gathering mirrors, (c) a· dispersive system, (d) a detection device.
The factors governing· the intensity and resolution of the scattered radiation are primarily
guided by the Raman instrumentation. The Raman scattered intensity from a sample is
proportional to the forth power of the scattered frequency, the intensity of the excitation
radiation, amount of the samp]e (Le. number of scattering centers in the interaction radiation)
and most crucial among all, the scattering cross-section. Out of these factors, first two factors
are characteristic of exciting source, where£third and forth ones are basically determined by
the geometry of the illumination and r6t'ure of the sample, respectively. Ideally, for good
Raman spectra to be observed, opt~um concentrated sample should be illuminated by an.
intense monochromatic source with frequency as high as possible towards blue region. For
non-resonance Raman scattering, the exciting source should not have a frequency so as to
excite an electronic transition band of the sample being studied. In other words, hv of the
exciting source should be such that it does not match with an electronic transition of the
sample. Since, this may cause a very intense fluorenence from the sample and the Raman
signal may be buried in the background.
In the presence of the entire Rayleish scattered light, it is impossible to observe the
1
Raman shift below 50 cm- [1 ], even with the most efficient monochromatic systems in case of
liquid molecules. The well-defined polarised laser beam may be used to decrease Rayleijh
scattering light in the direction of observation. In fact, it can be decreased to an appreciably
low value by observing the scattered light in a direction perpendicular to the incident laser
beam and the plane of the polarisation of incident beam should be parallel to the plane of
observation. Further, a 90° scattering geometry should be used to record the Raman spectra
along with their polarisation measurements.
The advantage of using laser as an exciting source is many-fold, such as, availability of
several exciting lines, (usually having small bandwidth < 0.1 cm- 1), well-defined polarisation
properties and controllable high intensity. These factors together greatly facilitate the Raman
instrumentation. There are so many lasers, which are commonly used in the Raman
experiments. However, the Ar-ion laser is one of the most frequently used lasers for recording
the normal Raman spectra and has been used as excitation source in all the experiments in the
present work also. Under normal conditions, a given laser line consists of a number of
longitudinal cavity modes of slightly varying wavenumbers, which form .an envelop. By
appropriate mode selection optical device, very narrow laser line width can be achieved, which
is important for the high-resolution study. For example, the Ar+ laser at 514.5 nm normally
has a line width of~ 0.15 cm·I, whereas, by mode selection, a line width ofO.OOl cm·1 can be
achieved [2].
Raman scattering being an essentially weak process as one out of a million incident
photons, in normal case, is expected to be scattered, one needs an effective dispersive device
with high light gathering optics and a very sensitive detection device to record Raman

51
spectrum. Single; double; double-pass tandem and triple monochromators are now available
as good dispersing system. Both photographic and p~otoelectric technique are used, PMT
(photomultiplier tube) is still in common use. Another technique using photo diode arrays
(PDAs), which is in a new electronic version of the photographic technique, has also been
used in the last five to ten years. Another very sensitive detection device, which has come up
in last five years, is the CCD (charge coupled device). The PMT detection is used in scarming
mode, whereas, PDAs and CCDs are used in multi-channel mode. Combining the advantages
of both multi-channel. technique (using PDAs & CCDs) and scarming technique, namely,
scarming multi-channel (SMT) technique has been introduced most recently in the field of
Raman Spectroscopy by Kiefer and co-workers [3, 4].
In the present work, however we have used a Spex double monochromator (Model
1401) equipped with a cooled photomultplier tube (Model R 928/7, Hamamatsu Photonics,
Japan) and photon counting system. Samples were taken in a quartz cell and were illuminated
by different laser radiation available from a Spectra Physics Ar+ laser (Model 165-06). PC 32
GB was used for monochromator control, data acquisition and analysis. A schematic diagram
of the Raman set up is shown in figure [11.3]. Brief description of the instrument used is given
below.

U.S.A General Experimental Set Up

The Raman spectra are recorded on a Spex Ramalog spectrometer, whose details are
given below. A 2 watt Spectra Physics Ar-ion laser model 165-2 was used as excitation
source. The Spex Ramalog spectrometer consists a UVSIR sample mounting compartment, a
1401 double monochromator system, thennoelectrically chilled photomultiplier tube and a PC
(32 GB) for performing the spectrometer control, data acquisition and analysis.
As illustrated in figures [IIJ] and [11.4], the plane polarized light of appropriate
intensity from the Ar-ion laser enters the monochromator where self emission of unwanted
components (such as plasma lines) from the incident laser beam are eliminated. The beam
deflector deflects the beam by 90° and sends it to the laser ate. The laser beam is then
focused, into the sample placed in sample holder in UVSIR compartment from below as
shown in the figure [II.4]. The beam is reflected in vertical direction with the help of a mirror
(M5). During the entire process, the power of the laser incident at the sample reduces
approximately to one third of initial laser power. The light is then collimated at the samples

52
with the help of lens L1• L1 is a fused silica condensing lens of small focal length which can
focus a laser beam of diameter 1.5 mm to a spot of about 10 ~m diameter. The scattered
beam from samples is collected using a usual 90° scattering geometry and is made to fall on
the entire slit of the double monochromator with the help of an elliptical mirror (Ms) and a
plane mirror (M9 ). After passing through a optical path shown in the figure [II.4] in the
monochromator, the dispersed light reaches the PMT for detection. As the monochromator is
scanned, the scattered light of signal frequency (with same line width) falls into the PMT and a
signal proportional to the intensity at that particular frequency is produced and detected.

Sample

Focu11sing
Lens

m
Argon Laser

Figure U.3 The general layout of the experimental set up of Laser Raman Spectrometer.

The resolution of the spectrometer, in the first place is a linear function of the width of
the grating. Thus for better resolution, as much width of the grating as possible should be
illuminated. The entrance slit (S4) to some extent and the exit slit (S1) to very large extent
govern the resolution of the spectrometer, whereas two middle slits (Ss & S6) are meant to
reduce the stray radiations which helps in reducing the back ground intensity and hence
improving the quality of the spectrum.

53
 rfiSIDE EXIT OPTIONAL
I

SJ
I
I
I
J.'af
I
SIDE ENTRANCE OPTIONAL

LASERMATE ILLUMINATOR MONOCHROMATOR

Figure 11.4 A schematic optical diagram of Spex 1403 Double Monochromator with Sample
llluminator.

II.S.B Spectra Physics Ar+ Laser (Model 165-02)

The Ar+ laser (model 165-02) from Spectra Physics, used in the present set of
experiment, is a 2-watt (all wavelength) CW laser. This whole system consists of the laser
head and an exciter (model 265) from Spex, connected by 8 ft long umbilical. The head
contains plasma tube, solenoid and optical resonator. The plasma tube is made up of beryllium
oxide (BeO) which provides a number of advantages; such as :- high terminal conductivity,
strength, structural stability etc. The tube is terminated at each end by fused silica Brewster's
angle windows. The necessary magnetic field generated by a solenoid surrounding the plasma
tube keeps the electrons away from the walls of the tube and ultimately helps to achieve a
stronger population inversion. The magnetic field also caused Zeeman splitting of the laser
lines. However the split lines are elliptically polarised and Brewster's angle windows take care
of them by allowing the laser oscillation only of such lines which are polarised very near to the
vertical direction and discarding those polarised in the other directions. The whole plasma

54
tube is mounted in an optical cavity resonator, which is formed by a spherical reflector at the
output end and a prism assisted by a flat mirror at the high reflector end. The flat mirror is
used to select the wavelength. The resonator assembly is strongly held against quartz rods
with springs. Aperture adjusting wheel is provided for changing the intra cavity aperture,
which results in change in wavelength.
The Spectra Phy~ics model 265 exciter is fully equipped with the necessary electronic
circuits to create, to sustain and to regulate the ion discharge in the plasma tube and to control
the output power from the laser by simultaneously regulating the solenoid current. An
arrangement is provided to have a desired constant output optical power when operated in
'light control' mode. The 265 exciter is fed with a stabilized three phases 380 V (phase to
phase) power line. This unit requires cooling of the transistor pass bank in the exciter, the
solenoid and the BeO plasma tube, which is achieved by circulating distilled and deionized
water at 15°C at 40 PSI from water chiller plant from Neslab model HX-500.
As mentioned earlier the laser operates at a number of wavelengths. Excitation is
effected with some prominent radiation at 514.5, 501.7, 496.5, 488.0, 476.5 and 457.9 nm. at
the blue green region of the electromagnetic spectrum. The atomic transitions [5] in an Ar-ion
laser are given in figure [II.S]. Three different excitation process, as shown below, may take
place:-

(a) Ar + e(.fast)-+ Ar + + e(slow)

(b) Ar + + e(.fast)-+ Ar +* + e( slow)

(c) Ar + e(fasl)-+ Ar +* + e(slow)

With the addition of an etalon accessory, extremely stable single frequency output power is
available, what is desired for recording the Raman spectra.

55
 -----......-----------112 4p2so

-----112

Argon II

Wavelength in Angstroms

Figure II. 5 The energy level diagram of Ar+ laser showing the blue, green laser line
in 4p - 4s super multiplate.

56
II.S.C Sample Chamber (Illuminator)

Schematic diagram of the sample chamber is shown in figure [11.4]. The laser line is
focused at the center ofthe 1-cm quartz cell (containing the samples) through its bottom face.
The laser beam is focused to produce a beam of much smaller diameter, which extends over a
short length before beginning to diverge again. The region in which the beam is concentrated
is called the focal cylinder. As the area of the focused beam is about 10'3 times the area of the
3
unfocused beam the irradiance at the sample is increased by a factor of about I 0 • If high
irradiance is harmful to the sample, focused beam,, is not used. The sample is placed in such a
way that it is illuminated well and the scattered radiations are collected effectively. A lens is
used to collect the scattered radiation for further dispensation. Additional concave mirrors,
M6 and M1 placed opposite to the monochromator side and on the top of the cell respectively
are used to increase the observed intensity of the scattered light by 8 to 10 times. Filters and
optical devices such as polarisor and analyzer may be inserted in the path of incident and
scattered laser beam respectively. Moreover, the elliptical mirror Ms and the plane mirror M9
send the collected scattered light into the monochromator.

II.S.D Spex Double Monochromator (Model 1401)

Since Raman scattered intensities are too low compared to the excitation radiation,
utmost care must be taken to minimize the stray radiation. The use of double monochromator
equipped with two intermediate middle slits (see figure [11.4]) reduces the stray radiation
considerably. For historical reasons, the instrument for Raman spectroscopy may be divided
into the two classes depending upon the final method of recording spectra. Prisms are
generally used in photographic instruments in earlier days (like 50's and 60's), whereas,
grating are used as dispersing system in modem photoelectric instruments mostly after the
advent of lasers. The speed of an instrument based on photoelectric detection depends upon
the total energy incident on the detector [I].

(II.I)

Where, B~.. is source brightness, TA is a function of optical system, A is area of the limiting
aparture, .1.A is the spectral slit width, D is the angular dispertion and f is the focal length of
collimeters. The position is governed by the fundamental grating equation
mA = d(Sina + Sin{3) (II.2)

57
where, m is spectral order number, A. is wavelength, d is grating spacing, a is angle of

incidence and f3 is angle of diffraction. For simplicity, equation (II.2) may be expressed as,
mA. =2d Sine Coscp (II.3)

Such that a = (e + cp) and f3 = (e - cp). Again 8 is grating rotation angle measured from zero

and rp is 10°. [ Cosrp =11.984 (manufacturer's supplied values)]. sJ6t'-f C

There are tw@comings, which are generally associated with the grating
spectrometers. One of them is the overlapping of different orders of diffraction patterns and

the other one is that only a fraction of radiation is concentrated in any particular diffraction
order. ln a Raman spectrometer, however, this problem is avoided due to the fact thatthe<::
...
entire Raman spectrum is spread about 3500 cm- on the~side of the exciting frequency
1

and hence the question of overlap of different orders does not exit.
The transmission factor or the efficiency of a grating varies with the polarisation of the
incident radiation [6, 7]. This effect causes problems in obtaining Raman polarisation data. A
polarisation scrambler consists of a quartz or calcite wedge, which rotates the plane
polarisation of a given wavelength by different amounts for each point on the slit. Thus the
net effect is the change of the incident light with definite polarisation into the light of mixed
po larisations.
Spectral purity is the most important factor of any monochromator system used in

Raman spectroscopy. It is basically its ability to distinguish a narrow wavenumber band v +

8v, to which it is set, from the other wavenumbers. The ability of a monochromator to
distinguish between the lines at comparable intensity depends essentially upon the factors like
resolution power, dispersion power and slit width. The optical ray diagram and schematics of
the spex 1403 double monochromator has been shown in the figure [11.4]. It covers a spectral

range from, 3I 000 cm- 1 to II 000 cm- 1 with an accuracy of± 1 cm- 1 in 10000 cm-1 range. The

spectral repeatability is± 0.2 cm- 1 and the aperture is f /7.8. The holographic type grating in
this instrument has 1800 grooves/mm and it is mounted on a modified Czemy-Turner mount.

II.S.E Photomultiplier Tube (Model 928-7)

In a Raman spectrometer, the photoelectric detection is achieved with a special kind of

photocell called photomultiplier tube (PMT). The essential components of the PMT are a
photosensitive cathode of low work function, and dynodes with the property to emit more
secondary electrons that received in the incident electron bombardment. Photons falling on

58
the photocathode, depending upon its quantum efficiency, get the electrons released from the
cathode and these electrons are accelerated to different dynodes one after another, which
results in the multiplication of number of electrons at every dynode. The total gain of a PMT
may be represented as b", where b is the secondary gain and n is the number of dynodes. The
electron multiplying process makes the PMT a suitable device for the detection of the low-
level light signal. A schematic diagram of the PMT is given in figure [11.6].

+200V +400V +600V +SOOV

DYNODES
PATH OF
I '
I \ ELECTRON
I \
I \
I \
I

+100 v +300 v +500V +700V +900V

Figure ll.6 A schematic diagram ofthe PMT.

Along with the signal electrons, there may be additional electrons randomly (thermally)
emitted from the photo-cathode and dynodes. These electrons will also be multiplied and will
contribute as a noise to the main signal. Even with no signal, due to these thermally emitted
electrons in the PMT, the value of current or voltage developed is not insignificant and
constitutes the dark noise of the detecting device. The photomultiplier tube (model 928-7
Hamamatsu Photonics, Japan) that responds to Raman scattered radiation over the full scan
range, has been used in the experiments of the present work. The PMT is cooled by
thermoelectric cryostat. Circulation of cold water at 15°C cools the PMT housing. The dark
current of a properly cooled PMT is quite small and therefore allows the observation of even a
very weak Raman band. The PMT associated with the photon counting system in conjunction
with a computer drive and linear (in wave number) chart recorder facilitates the recording of
the Raman spectra. The tube has a high quantum efficiency and uniform sensitivity over the
range 400- 800 nm, which is the usual range for detection of scattered Raman radiation. By
properly cooling the PMT, selecting an appropriate time constant (1 sec), and using a slow

59
scan speed (0.5 cm- 1/sec), the Raman spectra with a reasonably good signal to noise ratio were

recorded in the present work.

II.S.F Data Acquisition System

J\ J2-GB PC perf(mns the spectrometer control and data acquisition. The inbuih
software facilities one to do frequency and intensity range expansion or reduction. Microcal
origin 16 bit program is also employed to analysis the spectrum. The background-corrected
spectra are presented without any smoothing. Spectral data can be stored in a floppy disk.

II.S.G Scanning Of Raman Spectra

There are number of difficulties associated with recording Raman spectra of coloured
samples under resonance conditions. The prominent includes: (a) the optimization of the
sample to minimize reabsorption of the scattered light by the sample and at the same time
allowing the scattering to be maximum; (b) the local heating of the sample due to absorption
of exciting light which may give rise to thermal lens effect and also lead to thermal
decomposition of the sample and (c) the strong background due to fluorescence. from
impurities in the compound or in the solvents or intrinsic fluorescence from the sample itself.
The first point can be taken care by using samples of different concentrations until a
good quality spectrum is obtained. To avoid local heating effect Kiefer and Bernstein [8, 9]
had developed a technique, which involves continuous rotation of the sample with respect to
the laser beam. In this case, as the sample rotates continuously, the small portion of the
sample from which light scattering take place due to laser irradiation remains in the laser beam
only for a short period of time. Again a fresh sample replaces previous place due to
continuous movement of the solution. Thereby this process reduces the ·local heating and
thermal decomposition. To reduce the fluorescence background, Raman spectra can be
measured in solid form in KBr pellet. However to obtain vibrational information from
solution, it is always better to get rid of impurities from compounds and solvents that are in
use by usual purification method.
To record Raman spectra of liquid solution, 1-2 ml solution of respective sample at the
appropriate concentration is taken in a cylindrical quartz cell and positioned in a proper
mount. The laser beam of selected wavelength is then made to strike the bottom of the cell
very near to its perimeter. In this way self-absorption in the scattered light is minimized. The

60
spectra are routinely calibrated with known Raman lines of solvents (CHCb & CCLt). To
minimize any damage of the sample and degradation of the solute due to its prolonged
exposure to laser radiation, the laser power is kept at a low value (20 mW) for all excitations.
The slit widths of the monochromators are adjusted to obtain reasonably good spectra. Other
1
spectral parameters such as integration time (1 sec), wavenumber increment (0.5 cm- ),

scanning speed etc. are adjusted from time to time to optimize signal to noise ratio. For weak
Raman signals, the spectra are averaged (4-5) times with help of Datamate.

11.6 POLARISATION MEASUREMENT

The different techniques, which are used for polarisation measurement [1] in the
Raman spectrum, may be divided into the three categories. In the first one, natural
unpolarised incident radiation is used and the scattered radiation is analysed in term of its
polarisation. In the second one, polarised incident radiation is used but no analysis of
scattered is made in terms of polarisation. In the third and final one, both the polarised
incident radiation and analysis of scattered radiation in terms of polarisation are employed.
Out of the above three techniques, it is the last one that is commonly employed
nowadays. However, this technique has also two variants. In the first one, the analyser for
analysis of the scattered radiation is rotated through 90° using a polariser. In the second
technique, incident polarisation is kept fixed and it is the analyser that is rotated by 90° after
one scan is complete and whole spectrum is scanned once again. Since the At laser that was
used in the present work, already gives a radiation that is polarised in the vertical direction the

later arrangement is used in the polarisation measurements in order to record In and I1

components. Thus in order to study the character of polarisation of Raman lines of a
compound in the liquid state, the arrangement is slightly modified by introducing an analyser in
the path of scattered radiation.
Bringing the instrumental set up in an appropriate condition for the polarisation
measurements, test run are taken with CC4 by scanning the (150 - 550) cm· 1 range for both
the parallel (In) and perpendicular (I1) components of Raman intensity. During the test runs,
the Raman spectra are recorded with a data step size 0.5 cm- 1, integration time of 0.5 sec and
slit setting 400:200:200:400 IJ.. The polarisation of the incident laser line was carefully
adjusted to produce the depolarisation ratio [1 1 I (Iu x %)] for the bands of CCLt, which are
recorded to adjust the proper polarisation in 90° scattering geometry.

61
 The I11 and IJ_ components of Raman scattered intensity for our bands of interest are

subsequently recorded without altering the slit settings.

II. 7 RELATIVE INTENSITY CALCULATION

For the measurement of the REPs, the Raman intensity of the each band is normalized
relative to that for the excitation wavelength at 514.5 run and also the excitation frequency
dependence of the intensity of the solvent band, used as internal standard, is taken into

consideration. The relative intensity of a Raman line of wavenumber Va corresponding to a

excitation radiation of wavenumber Vexc is given by,

Ire! (va,Vexc) = I(va,Vexc) I I(Vrs,V5J45)

= [ I(va,Vexc) I I(vrs,Vcxc)] X [ l(Vrs,Vexc) I I(Vrs, Vsr4.s)]
3
= [ l(va,Vexc) I I(Vrs,Vexc)] X [ (Vexc- Vrs) I (Vsi4.5- Vrs)] (11.4)
where, all the intensities (i.e. I' s) are measured in terms of the number of photons per sec per
4
scan. Thus v3 dependence is taken instead of v . v 51 4.s is the wavenumber of the excitation

radiation of wavelength 514.5 run and Vrs is the wavenumber of the solvent band used as
internal standard.

11.8 MOPAC COMPUTATIONAL PACKAGE

MOPAC is a general-purpose semi-empirical molecular orbital package used for study

of chemical structures and reactions [10-12]. The semi-empirical Hamiltonians MNDO,
MIND0/3, AMI and PM3 are used in the electronic part of the calculation to obtain molecular
orbital, the heat of formation and its derivative with respect to molecular geometry. Using
these results MOP AC computational program can calculate the vibrational spectra,
thermodynamic quantities, isotopic substitution effects and force constants for molecules,
radicals, ions, and polymers. For studying chemical reactions, a transition-state location
routine and two transition states optimizing routines are available in this package.
In our work, MOPAC package having NLLSQ gradient minimization routine with
AM 1 Hamiltonian has been utilized in order to have a proper understanding of the ground
state property of the molecule. With this computational help, the ground and lowest excited
state geometry of molecule under consideration has been calculated.

62
11.9 REFERENCES

[I] C. E. Hathway, in "The Raman Effect", (ed. Anderson), Marcel Dekker, Inc., New
York, Vol. 2, (1971).
[2] D. A. Long, in "Raman Spectroscopy", Mcgrew-Hill International Book Company,
New York, (1977).
[3] P. Knoll, R. Singer and W. Kiefer, Applied Spectrosc., 44, 776, (1990).
[4] Y. Deckert and W. Kiefer, Applied Spectrosc., 46,332, (1992).
[5] J. U. White, N. L. Albert and A. G. Debell,.! Opt. Soc. Am., 45, 154, (1955).
(6] W. Demtroder, in "Laser Spectroscopy", Springier series in Chemical Physics,
Springier-Verlag, Berlin, Heidelberg, New York, ( 1981 ).
[7] J. R. Lascnrna, 'Modern Technique in Raman Spectroscopy', John Wiley and Sons,
New York, ( 1996).
[8] W. Kiefer and H. J. Bernstein, Applied Spectrosc., 25, 500, (1971 ).
[9] W. Kiefer and H. J. Bernstein, Applied Spectrosc., 25, 609, (1971).
[10] J. Stewart, in "MOPAC Program 455; Quantum Chemistry Program Exchange",
University oflndiana, Bloomington, IN.
[II] M. J. S. Dewar, E. G. Zoebish, E. F. Healy and J. J. Stewart, J. Am. Chem. Soc., 107,
3902, ( 1985).

[12] M. 1. S. Dewar and W. Thiel, .f. Am. Chern. Soc., 99, 4899, (1977).

63