CHAPTER-I

INTRODUCTION
 CHAPTER-I

INTRODUCTION

1.1 Introduction to Spectroscopy

Spectroscopy is the branch of Science dealing with the study of

interaction of electromagnetic radiation with matter. Spectroscopy and its

applications form a significant part of modern Physics and Chemistry. The

various branches of Spectroscopy generally involve measurements of two

important experimental parameters which are the energy of the radiation

absorbed or emitted by the system and the intensity of the spectral lines. In

most branches of Spectroscopy, the system interacts with the electric field.

However, in case of magnetic resonance spectroscopy it interacts with the

magnetic field [1-2].

Spectroscopy is one of the most powerful tools available for the

study of atomic and molecular structure and is used in the analysis of a wide

range of samples [1-2]. After interaction, there may occur variation in

intensity of electromagnetic radiation with frequency or wavelength. The

study of Spectroscopy can be carried out under the following heads:

(i). Atomic Spectroscopy which deals with the interaction of

electromagnetic radiation with atoms. Its importance has increased by the

development of Lasers. (ii). Molecular Spectroscopy which deals with the

1
interaction of electromagnetic radiation with molecules. This results in

transitions between rotational and vibrational energy levels in addition to

electronic transitions. The molecular spectra arise from three types of

transitions, viz., rotational, vibrational and electronic transitions.

Molecular Spectra extend from the visible through infrared into the

microwave region. All Spectroscopic techniques are more or less

dependent on the emission or absorption of electromagnetic radiation

characteristic of certain energy changes within an atomic or molecular

system. From molecular spectra, information may be obtained about

molecular vibrations and rotations that reveal a great deal about molecular

structure [3-5].

1.2 Vibrational Spectroscopy

The measurement and interpretation of vibrational spectra due to

polyatomic molecular systems constitutes the scope of Vibrational

Spectroscopy. The interpretation of the Vibrational Spectra (4000-200

ern") is made in terms of spectra-structure correlations, conformational

aspects, substitutional effects and hydrogen bonding all of which may very

well be correlated with physical, chemical and biological process [6].

A knowledge of molecular spectra enables us to study the nature if the

forces acting between the atoms of a molecule, the molecular

2
vibrations, molecular symmetry and the calculations of thermodynamic

quantities [7,8].

1.2.1 Infrared Spectra

Infrared Spectroscopy IS one of the most powerful analytical

techniques which offers the possibility of chemical identification. It

provides useful information about the structure of molecule quickly.

A molecule emits or absorbs infrared radiation in the 4000 - 200 ern",

known as pure vibrational spectra. The vibrational spectra arise from

transitions between vibrational energy levels, caused by the vibrational

motions of the molecule. The physical property of the molecule that

interacts with the incident infrared radiation is electronic dipole moment.

The change in electronic dipole moment during vibration leads to

vibrational spectra.

In a Polyatomic molecule, each atom is having three degrees of

freedom in three directions. A molecule of N atoms has 3N degrees of

freedom. For a non-linear molecule, three of the degrees of freedom

describe rotation and three describe translation; the remaining 3N-6

degrees are vibrational degrees of freedom or fundamental vibrations.

A linear molecule has 3N-5 vibrational degrees of freedom. Since we are

concerned with only the vibrational motions of the molecule, the number of

vibrational degrees of freedom or "normal modes of vibration" for an

N-atomic molecule is 3N-6 or 3N-5, depending whether the molecule is

3
non-linear or linear respectively. Thus the problem of molecular

vibration is made independent of rotational and translational motions.

From quantum mechanical view, the 3N-6 (or 3N-5) normal modes of

vibration correspond to as many harmonic oscillators with energies (eigen

values) given by (VI + 12) hVI , (V2+ 12) hv, , (V3N_6or 3N-S + 12) hv (3N-60r3N-S),

where v I,V2, V3N-6 or 3N-S are called "normal frequencies of vibration";

Vj,V2, V3N-6 or 3N-5 are vibrational quantum numbers. The vibrational

states are represented by the vibrational eigen functions, 'I'1(Qt),

\f'2(Q2), ··'I'(Q3N-6 or 3N-S) (Qj,Q2, Q3N-6 or 3N-S) are normal

coordinates one for each normal mode, which are the solutions to the

vibrational Schrodinger wave equation in the harmonic oscillator

approximation.

The infrared vibrational spectrum of a polyatomic molecule shows a

senes of bands as fundamentals, overtones and combinations.

A fundamental band is produced when a vibrational transition takes place,

for which v-=L, V2=V3= =0. Overtone bands are possible when v]=2,

V2=V3= =0. Combination levels arise when v.=I, v2=2, V3=0 .

E; - Ev"/h, where E, is
The frequency of vibration is given by Vv''v'=Vv'v''=

the vibrational energy of the upper vibrational state v' and Ev" is the

vibrational energy of the lower vibrational state v" [8].

4
 Experimentally, the infrared vibrational spectrum is more easily

measured in absorption than in emission. When infrared radiation from the

source is passed through a sample (the sample may be a gas or liquid or

solid) and then spectrometer, the absorbed radiation is measured as

vibrational spectrum. Most commonly the spectra of liquid or solid

samples are measured. Except for small frequency shifts and additional

bands due to intermolecular associations, the condensed phase spectra are

almost similar to gaseous phase spectra [9].

1.2.2 Raman Spectra

Raman Spectroscopy deals with the scattering of light and not with

its absorption. It gives information about molecular vibrations that are

inactive in the infrared region because of molecular symmetry.

Homonuclear diatomic molecules such as H2, N2, O2 etc., which do not

show IR Spectra do show Raman Spectra. Whenever monochromatic

visible light is incident on a transparent sample (a gas, liquid, solid), the

molecular scattering of light takes place. On examining the scattered light

we find that, it consist of a strong line with the same frequency as the

incident light (due to Rayleigh scattering) and symmetrically arranged faint

lines on either side of the Rayleigh line. The lines that appear on the longer

wavelength are called Stokes lines and the very weak lines on the shorter

wavelength side are called Anti-stokes lines. When the difference in

frequency between the Rayleigh line and Stokes lines (or Anti-stokes lines)

5
is measured, the difference, known as the Raman Shift, is equal to the

vibrational frequency of the molecule. A Vibrational Raman Spectrum is

the scattered intensity verses the Raman shifts corresponding to different

bands that arise, as in infrared absorption, due to vibrational transitions.

The quantum mechanical picture of the Raman scattering is as

follows: A photon of frequency v (=E/h) in the incident light is scattered

with no change in energy giving rise to the Rayleigh line; the photon either

gives up energy to the molecules in which case it has frequency v - L\E/h or

it can take energy from the molecules in which case it has frequency

v + L\E/h, where L\E = E; - E,» Thus the Stokes line has frequency

Vs = v-L\E/h, and anti-stokes line has the frequency Vas = V + L\E/h: Here the

molecular property that interacts with the incident light is the induced

electric dipole moment f.l = a E where E is the electric field of oscillation

with frequency v in the light and a the molecular polarizability [7,8]. In

order to account for the observed infrared and Raman Spectra, a certain

model is assumed for the molecule, the spectra are then deduced from the

model.

A simple model that is used in Vibrational Spectroscopy is one of a

model consisting of atoms held together by certain forces. As the atoms

vibrate, the electric dipole moment and polarizability vary giving rise to,

respectively, infrared and Raman Spectra. The vibrational spectra show

6
bands with characteristic features corresponding to different chemical

functional groups. Assignments of the bands to normal modes of the

functional groups constitute the main body of the work discussed in the

present thesis.

1.2.3 Normal Modes of Vibration

In a diatomic molecule the two nuclei are joined by a single bond

much like two mass points joined by a spring. Thus the molecule has a

single mode of vibration, that is to say, the two nuclei move back and forth

along the bond with a characteristic vibrational stretching frequency

determined by the stiffness of bond oscillator and masses.

A polyatomic molecule has a large number of normal modes, 3N-6

for nonlinear and 3N-5 for linear molecules as discussed in the preceding

section 1.2.1. They are often given descriptive names, such as stretching,

bending, scissoring, rocking and twisting. Assignment of the bands to

different normal modes forms an important spectroscopic study, which

involves, among others, the role of substituents in determining the

molecular structure [10]. The assignment of observed bands normally

proceeds on the basis of band positions and relative intensities. However,

knowledge of force fields, intensities, amplitudes of normal modes and

depolarization ratios (for Raman bands) would be on immense value in the

satisfactory assignment. The normal modes of vibration have certain

7
symmetry properties characterized by symmetry point group to which the

molecule belongs and hence the normal mode corresponds to symmetry

species. Each symmetry species describes symmetry character of a

particular normal mode.

The normal modes that have the same frequencies are said to be

degenerate and which have different frequencies are said to be

non-degenerate modes. For example, benzene molecule has ten non-

degenerate modes and twenty degenerate modes. In the theory of molecular

vibrations, each normal mode is best described in terms of a normal

coordinate, which is a linear combination of internal coordinates

(i.e. coordinates referring to change in bond lengths, bond angles etc.,).

1.2.4 Symmetry Point Groups

The method of classification of molecules is easily stated in terms of

group theory. The geometrical configuration of the nuclei and the resultant

field of the electrons in any molecule is characterized by a certain set of

symmetry operations that leave at least one common point unchanged

which form a group in a mathematical sense, called the point group. Every

molecule belongs to a certain point group directly by what are called the

irreducible representations (symmetry species) of the point group describing

the molecule.

8
 The irreducible representations of the point group describing the

molecule have been worked out for all point groups with which the known

molecules may be identified. It is possible to determine, again a priori,

which of the normal modes are IR active and which are Raman active,

including the degeneracy of modes [7,8,10]. For a given molecule, the

symmetry properties of the normal modes of vibration can be known using

the character table of a symmetry point group of which the molecule

belongs. Further, the symmetry properties of the components of the electric

dipole moment, "u" the molecular polarizability, "a" and vibrational

eigen functions \f'1(QI), \f'2(Q2), \f'(Q3N-6) can be determined in the

same way.

1.2.5 Selection Rule

According to the theory of Infrared spectroscopy, the vibrational

transitions that produce a spectrum are governed by certain Selection

Rules [8].

1.2.6 Selection Rule for Infrared Transitions

For a fundamental transition to occur by absorption of infrared

radiation, say, v"~v' (where v" is the lower vibrational state and v' is the

higher vibrational state), the transition moment integrals of the form:

f'¥y"llx\!fy,d't,f\f'y"lly\f'y,d'tand f\f'y"llz\f'y,d't,where \f'y' is the wave function

for the higher vibrational state and \f' v" is the wave function for the lower

9
state involved in the transition, must be non-zero; the f.lx,f.lyand f.lz are the

components of the molecular electric dipole moment. If anyone of these

three components is nonzero, then the transition moment integral is

non-zero and the transition is allowed.

By the symmetry considerations, we can determine whether the

transition moment integral is zero or non-zero and hence whether the

transitions is allowed or forbidden. If one of the products say, 'l' v"f.lx

'l' v' in

the transition moment integral is not totally symmetry operation of the point

group to which the molecule belongs, then the integral will be zero. This

leads to a very simple rule for the activity of fundamentals in infrared

absorption.

"A fundamental transition will be infrared active (that is, gives rise

to an IR band) only when there is at least one components of the dipole

moment f.l that has the same symmetry species as the product

\fv"'l'v'" [7]

1.2.7 Selection Rule for Raman Transitions

For the fundamental transition to occur by Raman scattering of

radiation the transition moment integral must be nonzero as for IR

transitions. The transition moment integrals are of the form: J'l'v"a'l' v,d-t

where a represents the polarizability of the molecule and it is a tensor of

second rank having nine Cartesian components (am ayY' azz, axy ).

10
The symmetry species of these components are usually shown in the

character tables for different symmetry point groups. The selection rule for

Raman transition is similar as for IR transitions:

" A fundamental transition will be Raman active (that is, give rise

to a Raman Shift) if the product '¥ v"'¥ v' has the same species as at least

one of the components am axy, of the polarizability tensor a" [7].

For both IR and Raman transitions, the vibrational quantum numbers of the

vibrational states changes by ~v = v' - v" = ± 1. However, any observed

spectrum shows, in addition to bands corresponding to fundamentals, bands

due to overtones and combination as a result of anharmonicity of normal

modes. Thus the additional selection rules are: ~v = ±2,±3 ....

1.2.8 Group Frequency Correlations

Theoretical calculations of frequency and force constants are only

approximations of the observed. This led to the development of charts for

the analysis of the spectra, which correlate the frequencies and functional

groups. By studying a large number of particular classes of compounds,

Correlation Charts have been deduced with regard to intensities and band

positions of one class to another. Much has been published in terms of the

Group Frequencies over the years and is extensively used in the analysis of

normal modes of vibration of the simple to complex molecules, which are

11
the key to unlocking the structure-spectral relationships of the associated

molecular vibrations [7-11].

However the characteristic frequencies, functional group frequencies

and intensities may change depending upon molecular environment. The

application of this principle is effective as long as normal modes are pure,

that is to say, each normal mode corresponds to a single vibrational

frequency of a chemical group, which is valid for small to moderate sized

symmetrical molecules. However, as molecules become large and their

symmetry is lowered, this picture often becomes more complex with

coupling of normal modes showing contributions from more than one bond

oscillators, where we have to depend on potential energy distributions

[PEDs] for analysis of major contributions from different modes [12].

1.3 Background for FT-IR

Fourier Transform Infrared (FT-IR) Spectroscopy is an interference

technique through which recent advances in digital computer technology

has demonstrated in superiority to dispersive IR techniques. Fourier

transform Spectroscopy uses the Michelson Interferometer as the multiplex

optical device [13]. The building blocks of all FT-IR instruments have the

following chain.

I I--~·I
Source Interferometer 1---..1 Sample ~I Detector 1
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1.3.1 Source

The most commonly used radiation source is globar operating on the

basis of the block body radiation. It consists of a SiC (silicon carbide)

dimensions 2 cm in length and 0.5 em in diameter heated to about 1450 K.

The globar is generally used in the spectral range up to 100 urn. The globar

is operated in vacuum only. It is self-starting. Nernst Glower (sintered

mixtures of the oxides of Zr, Tm, Ce, Y, and Er) is also used as source in

some spectrometers depending upon the spectral range. For more

sophisticated applications, gas plasmas must be used as radiation sources.

Besides thermic Microwave generators like Klystrons or Magnetrons are

also used for wide frequency range.

1.3.2 Interferometer

The interferometer IS the heart of the FT-IR instrument. The

interferometer is the bit that analyses the infrared or near infrared and hence

enable us to generate the spectrum. The classic Michelson Interferometer

is shown in Fig.1.1 contains a source, detector, stationary and moving

mirrors and a beam splitter.

The beam splitter is the crystal of potassium bromide coated with

germanium [14], splits the incident light equally reflecting half to the

stationary mirror while transmitting the other half to the moving mirror.

The white light from the source located at the focus of lens L I is separated

13
into two parts by the beam splitter. The reflected part is focused into the

detector D after reflection from the stationary mirror MJ and after a second

split by the beam splitter.

M1
M2
L\X

~ •
LS
L1 BS

L2

Fig. 1.1 Optical path in Michelson Interferometer

(LS - Light Source, LI, L2 - Lenses, MI, M2 - Mirrors,
D - Detector, BS - Beam Splitter)

The transmitted part of the light is also focused onto the detector

after it was reflected from the moving mirror M2 is movable, which produce

the path difference between the two beams thereby develop interference

pattern at the detector. Their intensity I(x) depends on the position x of the

mirror M 2. I(x) is termed as interferogram function.

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 If the incident beam IS monochromatic of the form

E(x,t) = Eocos (kx-rot), the field Eo at the detector is

where 2~x is the optical path difference between the two beams. The

intensity at the detector is given by the following expression

(1.2)

In terms of the spectral intensity l(v)=coEoE028(v- vo)/2, the above equation

can be written as

1 co
I(x) = - fl(v)[l + cost 47n-x}tv (1.3)
20

Generalising this equation to an arbitrary intensity spectrum I (v) yields the

basic relationship for Fourier Spectroscopy.

1 co 1 co
I' (x) = I(x) - - fl(v)dv = - fl(v) cas( 47n-x)dv (1.4)
20 20

The interferogram function I(x) or I'(x) contains the whole

information about the spectrum I(v). In fact, I'(x) is the Fourier transform

of I(v) performed with a cosine function. The observed intensity I(x)

oscillates around an average intensity fl(v) dv/2 =10/2 which is exactly half

of the original total intensity of the beam.

For x=O it reaches its maximum value of 10. This position

corresponds to zero optical path differences. It is called the white light

15
position. For x~oo, the coherence of the radiation is lost, and therefore the

intensity at the detector becomes 10/2.

A Fourier transformation ofI'(x) yields for x = y/2,

I'"
fI'(yl2) cos(2mJ y)dy=- fI(v)dv fcos(2A ljl)cos(2mJ y)dy= I(v')/2 (1.5)
20

Since the integration over y gives o(v - v'). This equation shows that the

spectral components of the light are obtained directly from the inteferogram

by Fourier transformation, without any spectral dispersion [15]. This

Fourier Spectroscopy has many basic advantages when compared to

dispersive spectroscopy.

The 'energy advantage' originates from the fact that during the

whole period of measurement nearly always the total beam intensity is

captured by the detector. This means the detection operates on a high signal

level which improves the signal-to-noise ratio, particularly for weak

radiation sources.

The 'Fellgett' or the 'multiplex advantage' originate from the

simultaneous measurement of full spectrum. To obtain spectra from

radiation of very low intensity such as from astronomical sources, all the

frequencies are recorded simultaneously during spectroscopy as in

dispersive spectroscopy, they are said to be 'multiplexed'. In dispersive

spectroscopy N parts of the widths t..v of the spectrum will be measured

16
successively so that for each part only the time T' =TIN is available. The

signal-to-noise ratio would be smaller by ~.

v'4N

Interferometer also has greater 'throughput' than dispersive IR

methods. 'Throughput', a measure of the optical efficiency of the system, is

defined as the product of the area and solid angle of the beam passing from

the source to the detector. Since there is no slit in FT-IR Spectrometer, the

cross section of the beam of radiation in an interferometer can be much

larger than that of a dispersive spectrometer, which leads to considerable

improvements in signal-to-noise ratio. But in much chemical and analytical

application the sample size limits the energy advantage. The optimum

resolution is obtained by using the theoretical relationship r ~ F ~ 2 where

Ro

r is the radius of the entrance pinhole and Ro is the resolution. This yields

for the brightness of the interferometer.

(1.6)

where A is the beam diameter in the spectrometer. For dispersive

spectrometer the brightness is given by

E = (ARoHoA) / F (1.7)

where Hand F are the height of the slit and the focal length of the grating

spectrometer respectively. By comparing these two equations 1.6 and 1.7 it

17
is found that for Fourier Spectrometer the enhancement of the brightness is

of the order of 500 times greater than the grating and prism spectrometer

known as the 'Jacquinot advantage' .

The dispersive spe~trometer suffer from greater wavenumber

errors, of a less predictable form owing to their general mechanical and

thermal instability and can also be affected by non-uniform illumination

across the monochromator entrance slit [16]. FT Spectrometer typically

uses the He-Ne lasers as a reference beam to monitor the displacement of

the moving optical element, so providing an active internal absolute

wavelength calibration [17]. This feature of FT Spectrometers is known as

the 'Cannes advantage'.

1.3.3 Detector

There are two detector commonly used depending upon the energy

reaching the detector. A normal detector for routine work function is based

on pyroelectric effect. Crystals such as deuterium triglycine sulphate in

temperature resistant alkali halide window, with a permanent electric dipole

moment respond to a sudden change in the dipolar order with the generation

of compensating surface charges. IR or heat pulses can be origin if such

induced disorder. The voltage accompanying the compensation charges can

be used to detect the IR to the heat pulse.

18
 The commonly used system is the Golay detector which works

under a pneumatic principle. A thin film absorbs the incident IR light. The

generated heat increases the pressure in the gas chamber which drives a

mirror. The mirror is a part of an optical system that images a grating onto

itself. Any small motion of the mirror leads to change in the overlap

between grating and the image and thus gives a signal to the detector.

1.3.4 Sampling Methods in IR Spectroscopy

A wide range of sampling technique is available for mounting of

the sample. The technique depends on whether the sample is a gas, liquid,

solid or polymer. Sampling techniques play an important role in recording

IR Spectrum. A choice of sampling technique is available for all states of

matter depending on the applications.

Solids are usually examined as a mull, a pressed disc or as

.deposited glassy films. Mulls are prepared by grinding the solid and then

suspending with 1-2 drops of mulling agent followed by grinding until the

suspended particles are less than 2 urn. The mull is then examined as a thin

film between flat salt plates. This technique has the advantage of speed but

suffers many disadvantages. If the sample concentration is too low, the

spectrum is due to mulling agent. On the other hand, if too much sample is

used the mull will not transmit radiation. The commonly used mulling

19
agents are nujol, hexachlorobutadiene and avoltof 3s oil (halogenated

hydrocarbon) depending upon the spectral region.

1.3.5 Alkali Halide Disc

The solid is mixed with suitable dry alkali halide (l00-200 mg)

grounded in a mortar or ball mill and subjected to a pressure of about 10

ton/sq.inch in an evacuated dye. This sinters the mixture and produces a

clear transparent disc of diameter 10-15 mm. The advantage of this method

over mull technique is that it eliminates the problem of bands, which appear

due to mulling agent. The most commonly used alkali halide is KBr, which

is transparent in the commonly scanning region. The commonly used other

alkali halides are NaCI, CsCI and CsBr.

1.3.6 Solutions

The sample can be dissolved in a solvent and the spectrum of this

solution can be recorded. The solution (usually 5%) is placed in a solution

cell, which has length of usually 0.1-1.0 mm. The solvent chosen must

satisfy certain criteria: (i) it has to dissolve the compound (ii) it should be

non-polar as possible, to minimize solute solvent interactions (iii) it should

not react with the sample (iv) it should not absorb IR radiation (v) it should

be volatile and not viscous and (vi) it should be pure and dry CS2, CCI4,

CHCh and C2H2Cl4 are some of the solvents commonly used.

20
1.3.7 Reflectance Method

Reflectance technique is used for samples with low transmission

which cannot be analysed by the normal transmittance method [18]. This

method depends on the total internal reflectance of light. The refractive

index of the prism used for this purpose should be greater than refractive

index of the sample and the angle of incidence of IR radiation is greater

than the critical angle.

1.3.8 Limitation of Infrared Spectroscopy

Materials such as KBr, NaCI, LiF and the like do not yield

characteristic infrared absorption spectra. Hence it is fortunate that they are

useful as prisms, window materials and other optical components [19].

Molecules such as H2, O2, N2 etc., will not yield any useful infrared spectra

because no change in dipole moment occurs during their lone stretching

vibrations. The detectability limits of the usual infrared quantitative

procedure are not very great except for analytical methods relaying on

absorption arising from vibration involving very highly polar bonds

between atoms. The inability to transfer quantitative analytical methods

from one instrument to another, even of the same make and model is

another limitation.

Optical isomers yield identical absorption spectra and therefore

infrared studies cannot distinguish between them. By IR Spectroscopy, it

•

21
is not possible to know molecular weight of a substance. Generally, the IR

Spectroscopy does not provide information of the relative positions of

different functional groups on a molecule.

1.3.9 Background for Raman Spectroscopy

All substance to be analysed by Raman Spectroscopy should be

free from impurities likely to absorb in the range of the Raman Spectrum.

FT-Raman Spectrophotometer is designed to eliminate the fluorescence

problem encountered in conventional Raman Spectroscopy [20]. The

FT-Raman instrument has the following components: i) ANIR laser

excitation source, generally an Nd:YAG laser working at 1.06f.lm, ii) an

interferometer equipped with an appropriate beam splitter, made of glass,

and a detector for the NIR region. The detector is usually InGaAs or Ge

semiconductor detector, iii) a sample chamber with scattering optical that

match the input port of the FT instrument, iv) An optical filter rejection of

the Rayleigh-scattering light.

Fluorescence is eliminated by utilizing an excitation frequency well

below the threshold for any fluorescence process. To focus and align the

invisible Nd: YAG laser beam a visible He:Ne laser beam is co-aligned

with the Nd: YAG beam. Another method of optical alignment can be

realized by using fiber optics [21]. With fiber optic components, optical

22
alignment is virtually eliminated which allows rapid switching from one

sample to another.

One of the advantages of FT instrument is that it can collect all the

scattered radiation over the entire range of frequencies simultaneously

during the whole period of the detection and it is called multiplexing. This

becomes a disadvantage as the intense Ray leigh line is the primary source

of noise. Multiplexing redistributes the noise associated with Rayleigh line

across the entire spectrum by the FT process and this is called as

multiplexing disadvantage [22]. Interferometer can be combined with

Rayleigh line filters (notch filters) in order to prevent the consequences of

the multiplex disadvantage. The Rayleigh line filter minimizes the amount

of Rayleigh scattered light entering the interferometer [23] and is essential

for FT-Raman Spectroscopy.

1.4 Dual Instruments

Due to the rapid development in the instrumentation techniques,

nowadays both IR and Raman Spectrophotometer are incorporated into a

single instrument assembly and available commercially as a single package.

The main advantages of such instruments are: i) Switching over from one

technique to other is simple; ii) They are compact and iii) Comparatively

cheaper. Bruker's FT-IR Spectrophotometer IFS 66/S filter with

FRA 106/S. ThermoNicolet's Nexus/Magna FT-IR and FT-Raman

systems, ABB Bomen MB 157 series these are some of the commercially

23
available dual instrument package. The comparison of IR (absorption) and

Raman (scattering) Spectroscopy is shown in Fig.l.2.

l••Sl*Ctroscop¥

- lo(v) ---1,. _.Sa ••m.PIe

__ 1- 1(., -

-'0(\1') Sample

Raman Scattering
Vo •. vm or Vo - vm

Rayleigh Scattering Vo

Fig. 1.2 Comparison ofIR (absorption) and

Raman(scattering) Spectroscopy

1.4.1 Sampling Methods in Raman Spectroscopy

Gases, liquids and solids can be studied by Raman Spectrometer

but the important thing to be taken care of while preparing sample is that

they should be dust free. Glass is almost transparent in the Raman

24
frequency region and thus samples in different phases can be measured in

glass or silica containers or capillaries [24].

1.4.2 Solids

Solids as poly crystalline material or as a single crystal can be

studied with the help of Raman technique. Solvents or alkyl halides or mull

are not required for recording the spectra. Solids in the form of fine powder

enclosed in a glass or silica fiber can be used. When the measurement is

made as a single crystal, depending on the orientation of the crystal axis and

polarization of the incident radiation the spectra may vary. Raman Spectra

can also be recorded for absorbed species. Samples can also be studied

using the Raman technique various pressures and temperatures [24].

1.4.3 Liquids

Liquids may be examined neat or in solution and normally liquids

of about 0.3 ml enclosed in glass or silica containers of capillaries may be

required for obtaining good spectrum. Even though water can not be used

as solvent in IR studies, in the Raman studies water is one of a good

solvent. Thus spectra of aqueous solutions can be easily studied and also

spectra of water soluble biological material can be easily recorded [25].

1.4.4 Uses of Raman Spectroscopy

Raman Spectroscopy is useful for analyzing molecules without a

permanent dipole moment which would not show up on an IR Spectrum.

A useful 'exclusion rule' states that for molecules with an inversion centre,

25
no modes can be both IR and Raman active. It can be used to determine

bond lengths in non-polar molecules. It is useful for determining the

identity of organic and inorganic species in solution, as the Raman

transitions for these species are more characteristic than for IR, where the

transitions are much more affected by the other species present in the

solution. Raman Spectra can be used to study materials in aqueous

solutions, a medium that transmits infrared very poorly. Sample preparation

for Raman is generally considerably simpler than for the infrared. Raman

Spectroscopy has a distinct advantage in the detection of low-frequency

vibrations.

1.5 Computational Details

Modeling molecular properties is an important aspect of the quantum

mechanical based electronic structure theory calculations [25-28]. The

electronic structure methods broadly fall into two methods:

semi-empherical methods and ab initio & DFT methods. Semi-empirical

methods use parameters derived from experimental data to simplify the

computation. They solve an approximate form of the Schrodinger equation

that depends on having appropriate parameters available for the type of

chemical system under investigation. Ab initio methods use no experimental

parameters in their computations and are based solely on the laws of

quantum mechanics and use only physical constants like speed of light (c),

masses (m) and charges of the electrons and nuclei (e) and Planck's

26
constant (h). They compute solutions to the Schrodinger equation using a

series of rigorous mathematical approximations.

Ab initio computations provide high quality and quantitative

prediction for a broad range of system and are not limited to a class of

molecules. The simplest type of ab initio electronic structure calculation in

the Hartree-Fock (HF) scheme, in which the Coulombic electron-electron

repulsion is not specifically taken into account; only its average effect is

included in the calculation.

Density functional theory (DFT) is a quantum mechanical method

used in physics and chemistry to investigate the electronic structure of

many-body systems. Traditional methods in electronic structure theory, in

particular Hartree- Fock theory and its descendants, are based on the

complicated many-electron wave functions. The main objective of density

functional theory is to replace the many-body electronic wave function with

the electronic density as the basic quantity [29], whereas the many-body

wave function is dependent on 3N variables, three spatial variables for each

of the N electrons, the electronic density is only a function of three

variables and is a simpler quantity to deal with body conceptually and

practically [26-32].

The most common implementation of density functional theory is

through the Kohn-Sham [32] method. Within the framework of

27
Kohn-Sham DFT, the intractable many-body problem of interacting

electrons in a static external potential is reduced to a tractable problem of

non-interacting electrons moving in an effective potential. The effective

potential includes the external potential and the effects of the Coulomb

interactions between the electronic, e.g. the exchange and correlation

interactions.

Since from the electronic density is not known explicitly, many

functionals have been defined to calculate electronic density of the system.

They are broadly classified into Local Density Approximations (LDA)

methods (e.g. SVWN which takes into account a local spin density

exchange by Slater, combined with the correlations function of Vosko, Wilk

and Nusair); Generalized Gradient Approximation (GGA) methods

(e.g. BL yP Slater exchange along with corrections involving the gradient

of the density combined with the correction function of Lee-Yang and

Parr); PW91 (with the non-local correlation provided by Perdew/Wang 91

correction functional); PW86 (the Perdew 86 correction functional) etc., ;

Hybrid methods (e.g. B3L YP Becke's three parameter hybrid functional

combined with Lee- Yang-Parr correlation functional); BP86 (Becke's 1988

exchange functional combined with the gradient-corrected correction

function of Perdew); B3P86 (Becke's three parameter hybrid method with

the non-local correlation provided by Perdew/Wang 91 expression) etc.,

[26-32]. The acronyms like GGA, VWN etc., are generic names in practice.

28
 The most popular method to calculate electronic density is the hybrid

method and B3L yP is one of the most popular hybrid methods. In B3L yP

method, three parameter have been used to give satisfied theoretical results

compared to the experimental results in many cases. In all of these

approaches, in addition to the choice of method, it is necessary to choose a

basis set.

1.5.1 Basis Sets

A basis set is a mathematical representation of the molecular orbitals

within a molecule. Expression of the molecular orbitals as linear

combinations of a pre-defined set of one-electron functions are known as

basis functions. If the basis functions are the atomic orbitals for the atoms

making up the molecule, then they are often described as the 'linear

combination of atomic orbitals (LeAD) approximation' and frequently

used in qualitative descriptions of electronic structures. To provide a basis

set for any given nuclear configuration, a particular set of basis functions

associated with each molecules is defined depending only on the charge on

that nucleus. Such functions may have the symmetry properties of atomic

orbitals and may be classified as s, p, d, f. .. type according to their angular

properties.

There are mainly two types of atomic basis functions, namely, Slater

type atomic orbitals (STO) and Gaussian type atomic orbitals (GTO) [27].

Having decided on the type of basis functions, the most important factor is

29
the number of functions to be used. The smallest number of functions

possible is a minimal basis set. To increase the accuracy we can increase

the number of basis functions per atom; such basis sets are known as split

valence basis set. The basis set formed by doubling all the functions of a

minimal representation is called double zeta basis set.

For example a 6-31 G basis set is a set where the inner .shell of each

atom is written in terms of a linear combination of six Gaussian functions,

two valence orbitals represented by the linear combination of three and one

Gaussian functions. Similarly, triple zeta basis set (6-311 G) can be

constructed. Split valance basis set allows orbital to change size but not

shape. Hence to split valence basis set additional functions are added in

order to incorporate functions of higher angular momentum that are needed

by the atom in its electronic ground state, they are called Polarized basis set

and are indicated by the presence of "*,, as for example 6-311G*. All

electronic structure calculations can be performed using Gaussian 03 W

suite of programs [33].

We have performed geometry optimizations and computed harmonic

vibrational frequencies, IR intensities and Raman activities, force constants,

and depolarization ratios for the ground electronic state at HF and B3L yP

levels of theory for the substituted phenol and for the derivatives of benzoic

acid are discussed in the thesis. The equilibrium geometry obtained

30
corresponds to the lowest minimum on the potential energy surface and the

analytic second derivatives of the energy lead to the vibrational frequencies.

Evaluation of the related second derivatives allows the prediction of

vibrational frequencies if harmonic motion is assumed. In some ways more

importantly it allows the characterization of stationary points. The

frequencies are related to the eigen values of the matrix of second

derivatives (the Hessian matrix). If the eigen values are all positive, then

the frequencies are all real and the stationary point is a local minimum, if

one eigen values is negative (an imaginary frequency), the stationary point

is a transition structure. If more than one eigen value is negative the

stationary point is a more complex one, and usually of little interest. To

rectify the systematic errors due to finite basis sets and neglect of

anharmonicity we scaled all the computed frequencies.

31
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