CHAPTER-I

INTRODUCTION TO VIBRATIONAL SPECTROSCOPY

ABSTRACT

In the introductory chapter, some of the very basic concepts of vibrational

spectroscopy and its applications to polyatomic molecules are discussed. As

molecular symmetry and group theory plays an important role in the structure and

characteristics of molecules, some of the concepts are discussed. Principles of UV–

VIS absorption spectroscopy and the types of electronic transitions are given

briefly. In addition, selection rules for IR, Raman, NMR and UV–VIS absorption

spectra are outlined. Various types of force filed with their relative merits and

limitations are dealt briefly. The concept of group frequency and the factors

influencing the vibrational frequencies of polyatomic molecules are discussed

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 CHAPTER-I

INTRODUCTION TO VIBRATIONAL SPECTROSCOPY

1.1 FUNDAMENTALS OF SPECTROSCOPY

Spectroscopy is the study of the interaction of electromagnetic radiation

with matter. When matter is energized (excited) by the application of thermal,

electrical, nuclear or radiant energy, electromagnetic radiation is often emitted as

the matter relaxes back to its original (ground) state. The spectrum of radiation

emitted by a substance that has absorbed energy is called an emission spectrum,

and the science is appropriately called emission spectroscopy [1].

Vibrational spectroscopy is the collective term used to describe two

analytical techniques: infrared (IR) and Raman spectroscopy. IR and Raman

spectroscopy are non-destructive, non-invasive tools that provide information

about the molecular composition, structure and interactions within a sample. These

techniques measure vibrational energy levels that are associated with the chemical

bonds in the sample. The sample spectrum is unique, like a fingerprint and

vibrational spectroscopy is used for identification, characterization, structure

elucidation, reaction monitoring, quality control and quality assurance [2].

1.2 INFRARED SPECTROSCOPY

Infrared spectroscopy is generally concerned with the absorption or

transmit of radiation incident upon a sample. IR technique when coupled with

intensity measurements may be used for qualitative and quantitative analysis.

Currently, this technique has become more popular when compared with other

physical techniques (X-ray diffraction, electron spin resonance, etc.) in the

elucidation of the structure of unknown compounds [2].

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1.2.1 INFRARED ACTIVITY

For a normal mode of vibration to be infrared active, there must be a

change in the dipole moment of the molecule during the course of vibration.

During the vibrational motion of a molecule, a regular fluctuation in the dipole

moment occurs, and a field which is established can interact with the electric field

associated with incident radiation. For this interaction or absorption to occur,

it is important that the dipole moment at one extreme of the vibration must be

different from the dipole moment at the other extreme of the vibration in a

molecule [1].

1.2.2 INFRARED SPECTROSCOPY

It has been noted that the covalent bonds of molecules are not rigid, but are

like stiff springs that can be stretched and bent. Transitions between vibrational

energy states may be induced by absorption of infrared radiation, whose photons

have the appropriate energy. The stretching vibrations appear at higher

wavenumbers than the bending vibrations, because more energy is required to

stretch (compress) a bond than to bend it. The transition probability of infrared

absorption is given by
1 2
a  k (t )a k (t )  2 m  k E0 2t.
ℏ (1.1)

The vibrations of a molecule result only in small deviations of the bond

from its equilibrium length [2]. Hence, the dipole moment can be expanded as a

power series in the displacement r around the equilibrium value r0

    
m  k     0    (r  r0 )  k dr 
m
  r r  r0  
r   m r k dr .
 (1.2)

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The zero order of the expansion makes the integral non-zero only for m = k, so no

transition is taking place. For the second term, due to the orthogonality of the wave

functions, the integral will only be ≠ 0 for k = m + 1, which corresponds to a

transition from a lower-energy level m to the next higher level (k = m + 1). In

addition, a change in the dipole moment connected with the vibration is necessary

to obtain a non-zero transition and, hence, absorption:


m  k  0 if  0 for k = m + 1. (1.3)
r

Hence, it is evident that not all molecular vibrations lead to observable infrared

absorption. In general, a vibration must cause a change in the electric dipole

moment within a molecule to absorb IR light. The greater this change, the stronger

will be the absorption [3].

1.2.3 SELECTION RULE FOR IR

According to quantum mechanics, the selection rule for the infrared

spectrum is determined by the integral

  ' ''    ' *  Qa   ''  Qa  dQa , (1.4)

where  is the dipole moment in the electronic ground state,  is the vibrational

eigenfunction,  ' and  ' are the vibrational quantum numbers of the states before

and after transition, respectively, and Qa is the normal coordinate whose activity to

be determined. The dipole moment can be resolved into three components in the x,

y and z directions, as
  x  ' ''    '  Qa  x  ''  Qa  dQa , (1.5)

  y    '  Qa  y  ''  Qa  dQa ,

 ' '' (1.6)

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   z  ' ''    '  Qa  z  ''  Qa  dQa . (1.7)

For the vibrations to be infrared active, at least one of the components of the

derivative of the dipole moment with respect to the normal coordinate taken the

vibration is infrared inactive [1,2].

1.3 RAMAN SCATTERING

Raman spectroscopy is an important method for investigating molecular

vibrations. The Raman effect can be understood by considering the light scattering

process as collision of photons of the incident light with the molecules. The

incident light consists of photons of energy h 0 . On collision with molecules,

photons may be elastically scattered, where the photons neither gain nor lose

energy in their collision with the molecules. This gives rise to the phenomenon of

Rayleigh scattering. However, collision of photons with molecules may be

inelastic. They may induce the molecules to undergo a transition to a higher energy

level with a result that the photons lose energy and are scattered with a lower

frequency. However, if the molecules are already in a higher vibrational energy

state, on collision with photons, they may undergo a transition to a lower energy

level in which case the photons are scattered with increased frequency. The Raman

line on the low- and high-frequency sides of the Rayleigh line are called stokes and

anti-stokes line, respectively. The scattered phonons have frequency shifts (10–

4000 cm–1) characteristic of the vibrational or rotational energies of the molecule.

These weak lines of modified frequencies are generally referred to as the Raman

lines [3].

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1.3.1 QUANTUM THEORY OF RAMAN EFFECT

Quantum mechanics gives a qualitative description of the phenomenon of

Raman effect. The schematic energy level diagram is shown in Figure 1.1. The

interaction of a photon of the incident beam with the molecule in its ground

electronic and vibrational state (V = 0), may momentarily raise the molecule to a

time dependent quasi-excited electronic state (or a virtual state) whose height is

above the initial energy level. Virtual states are those in which the molecule has a

very short mean lifetime and, hence the uncertainty in energy is large according to

the Heisenberg uncertainty principle. In the case of stokes line, the molecule at the

ground electronic state (V = 0) is excited to the virtual electronic state and then

radiates light in all directions except along the direction of the incident light [5].

On return to the ground electronic state, quantum of vibrational energy may

remain with the scattering species and there will be a decrease in the frequency of

the scattered radiation.

Anti-stokes line arise when the molecule is already in an excited vibrational

state (say V = 1) and is raised to quasi-excited state and reverts to ground

electronic state (V = 0) on scattering of photon. The energy of the scattered photon

is equal to the sum of the energy of the incident photon and the energy difference

between the vibrational levels V = 1 and V = 0.

In another instance, a molecule in the ground state on interaction with a

photon and attaining the virtual state may leave the unstable electronic state and

return to the ground electronic state. In this case, scattered photon has the same

energy as the incident radiation and the result is Rayleigh scattering [1,2].

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 Figure 1.1 Energy levels involved in Rayleigh and Raman scattering.

1.3.2 RAMAN ACTIVITY

For a molecular vibration to be Raman active there must be a change in the

polarizability of the molecule during its vibration. This change can be considered

as being a change in the shape of the electron cloud surrounding the molecule

(polarization ellipsoid). In a molecule without any symmetry elements, all the

normal vibrations are accompanied by polarizability changes, and the

corresponding frequencies appear in the Raman spectrum. But in a symmetric

molecule, some of these vibrations may not produce any change in polarizability

and the corresponding normal frequencies are not observed. Such vibrations are

Raman inactive [3–14]. i.e., molecules with a center of symmetry have no

fundamental lines in common in the IR and Raman spectra.

Raman spectrum gives information about molecular symmetry, which can

then be used to determine the molecular configuration. There are various chemical

problems, which have been successfully solved with the help of Raman spectra.

The advent of laser has revolutionizes Raman spectroscopy. Today, with the

development of optical spectrometers and new detection techniques, Raman

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spectroscopy has been developed as an extremely useful tool for material

characterization.

1.3.3 SELECTION RULE FOR RAMAN SPECTRA

The selection rule for the Raman spectrum is determined by the integral:
 ' ''    ' *  Qa   ''  Qa  dQa . (1.8)

The polarizability of the molecule  consists of six components xx ,  yy ,  zz ,

 xy ,  yz and  xz . For the vibrational to be Raman active, at least one of these

integral should be non-zero. If all the integrals are zero, the vibration is said to be

Raman inactive [5].

1.4 SELECTION RULE FOR IR AND RAMAN SPECTRA

A selection rule is a quantum mechanical rule that describes the type of

quantum mechanical transitions that are permitted. Transitions not permitted by

selection rules are said forbidden, which means they may occur, in practice, but

with low probabilities. All the transitions may not be active in both IR and Raman

spectra. Some may be active in IR while inactive in Raman or vice versa. Some of

the transitions may be inactive in IR and Raman spectra. In a molecule having a

centre of symmetry, Raman active transitions are IR inactive and IR active modes

inactive in Raman [6].

1.5 COMPARISON OF IR AND RAMAN SPECTROSCOPY

IR absorption spectroscopy together with Raman spectroscopy will give

almost complete information about the vibrational spectrum of a molecule in the

ground electronic state. The methods are complementary, which follows from the

nature of the phenomena on which they are based. The complementarity of infrared

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and Raman spectroscopy results from the different selection rules which determine

the presence of a band corresponding to a given vibration of the molecule in the

infrared and/or Raman spectrum. If the vibration causes a change in the dipole

moment, which occurs when the vibration changes the symmetry of the charge

density distribution, i.e. if (  / r) ≠ 0, it is active in the IR spectrum. If the

vibration is connected with a change of the molecular polarizability, i.e. if (α / r)

≠ 0, it is active in the Raman spectrum.

The fulfillment of one or both of these conditions is related to the symmetry

of the molecule (If the molecule has a centre of symmetry, a vibration which is

active in the infrared spectrum is inactive in the Raman spectrum and vice versa.

This rule is called the rule of mutual exclusion) If the molecule does not possess a

centre of symmetry, a number of vibrations appear in both spectra. The differences

between the selection rules of both effects are related to the behavior of an

anharmonic oscillator, used as a model for the vibrations of a molecule [7-9].

Band intensities in both types of spectra can be predicted with great

reliability from some general rules. Non-polar or slightly polar groups tend to have

strong Raman lines, whereas strongly polar groups show strong IR absorption.

Overtones and combinational bands are stronger in the IR than in the Raman

spectrum. In addition, there is a long list of relations for specific types of vibrations

of certain molecular groups [8].

1.6 MOLECULAR FORCE CONSTANTS AND ITS SIGNIFICANCE

Force constant is used as a basis for probing the nature of chemical bonds

and structural characteristics of molecules. The restoring force per unit

displacement of a bond is known as force constant. From the empirical relations of

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Badger, it is possible to calculate the inter-atomic distances by force constants

[15]. The other important molecular constants can be evaluated from force

constants.

The electrons are binding with nuclei together by electrostatic energy and

the energy changes thus gives the “force field”. The force constant depends on the

bond order and the mass of atoms. For the absolute intensity studies, force fields

are used to identify the normal coordinates associated with each vibrational

frequency. Infrared and Raman intensities have been used along with force

constants in order to obtain the dipole moments, polarizabilities and their

derivatives [16].

1.6.1 VIBRATIONS OF POLYATOMIC MOLECULES

In a polyatomic molecule, each atom is having three degrees of freedom in

three directions, which are perpendicular to one another. Thus, a molecule of n

atoms has 3n degrees of freedom. For a nonlinear 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. For linear

molecule, there is no rotation about the bond axis consequently two degrees of

freedom are required to describe the rotation. Hence a linear molecule has 3n–5

vibrational degrees of freedom [17].

The number of degrees of freedom possessed by the molecule is the

number of co-ordinates required to completely specify the positions of the nuclei.

The number of normal modes is equal to the number of vibrational degrees of

freedom possessed by the molecule. For each normal vibration, every atom

performs a simple harmonic motion with the same characteristic frequency. The

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(3n–6)/(3n–5) vibrations are called the internal vibrations or fundamental

vibrations or normal vibrations of the molecule. During a normal vibration, the

centre of gravity of the molecule remains unchanged. Because a molecule having n

atoms has n–1 bonds, out of the (3n–6)/(3n–5) vibrations, (n–1) would be the bond

stretching and (2n–5)/(2n–4) would be deformation vibrations. In large molecules

the number of deformation vibrations becomes more involved. The theoretical

number of fundamental vibrations or absorption frequencies given by (3n–6)/(3n–

5) will rarely be observed because overtones and combination tones increase the

number of bands [17].

The theoretical number of bands is reduced by following reasons:

1) Some fundamental bands are too weak to be observed.

2) Some of the fundamental frequencies fall beyond the range of the

instruments.

3) Fundamental vibrations that are very close may overlap.

4) Occurrence of degenerate bands from several absorptions of the same

frequency in symmetrical molecule.

5) Certain vibrational bands do not appear in the infrared region due to lack of

required change in dipole character of the molecule.

1.6.2 GROUP THEORY AND MOLECULAR VIBRATIONS

Knowledge of point group symmetry of a molecule and application of

group theory concept is useful in the determination of their normal vibrations and

spectral activity. Molecule of different symmetries has qualitatively different

spectra [18–21]. A very important property of the normal vibrations is that they

transform according to the irreducible representations of the molecular point group.

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The normal coordinates and the vibrational wave functions can be classified

according to their symmetry properties.

1.6.3 NORMAL MODES OF VIBRATIONS

Normal modes (or fundamental modes) of vibrations of any molecule are

internal atomic motions in which all the atoms move in phase and with the same

frequency but different amplitudes. The amplitude and direction of each atom may

be represented by a displacement vector. The various displacements of the atoms in

a given normal mode of vibration may be represented by a linear combination of

atomic displacements known as normal coordinates which are functions of angles

and distance [22].

A very important property of these vibrations is that for non-degenerate

normal modes of vibration, the normal coordinates and the vibrational wave

functions are either symmetric or antisymmetric with respect to the symmetry

operations of the point group symmetry of the molecule in its mean position. For

degenerate normal mode of vibration, the symmetry operation will transform the

degenerate set of vibrations into a linear combination of mutually degenerate

normal coordinates. A normal mode in a molecule is equivalent to a simple

harmonic motion of certain mass and force constant, and can vibrate independently

without exciting any other mode for small amplitude motion. The number of

molecular vibrations of a chemical compound depends upon the number of atoms

in its molecular composition, and the molecular vibration allowed in the IR or

Raman depends upon its molecular symmetry. Thus, the number of vibrational

modes is 3n–6 or 3n–5 for nonlinear or linear molecule, respectively [23].

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1.6.4 MOLECULAR SYMMETRY AND POINT GROUPS

Molecular symmetry plays an important role in the structure determination

and characteristics of the molecules. Symmetry is a visual concept as reflected by

the geometrical shapes of molecules such as benzene, methane, etc. Symmetry

defines the mutual relationship of parts of something with respect to magnitude

and position. Its importance in many theoretical problems in chemistry and physics

arises from the reflection, exchange or inversion of equivalent features of the

system [22].

In spectroscopy, the symmetry possessed by a molecule may be used with

advantage to simplify the calculation of energy levels of the system and to

determine the allowed and forbidden transitions. The symmetry of a rigid system is

easily defined in geometrical terms. The molecular symmetry is systematized

quantitatively by introducing the concept of symmetry operation. It is an action,

which moves the nuclear framework into a position equivalent to the original one.

The symmetry element is a geometrical entity such as a point, or an axis or a plane

about which a symmetry operation may be performed. The symmetry operation is

applied on the molecule, thus the molecule is physically indistinguishable.

All the axes and planes of symmetry of a molecule must intersect at least at

one common point [23]. Thus, the symmetry operation performed on molecule

must leave at least one point unaffected. Such groups of operations are called point

groups. In a point group, the symmetry of space about a point is uniquely described

by a collection of symmetry elements about that point. Point groups are used to

describe the symmetry of isolated molecules.

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1.6.5 VIBRATIONAL ASSIGNMENT AND GROUP FREQUENCIES

The observed vibrational spectrum of any molecule consists of a large

number of bands. The normal vibrations of a molecule are associated with

appropriate Raman and infrared frequencies and this process is referred to as

vibrational assignment. The assignment of the infrared and Raman spectra is

generally made on the basis of the group frequency concept.

By comparing the spectra of large number of compounds, it has been

observed that the presence of certain groups, for example C–H, O–H, N–H, C=O,

C=N, etc., in various molecules may be correlated with a constant occurrence of

absorption bands in the infrared spectra whose positions are only slightly altered

on going from one compound to another. The atomic group vibrates independent of

the other groups in the molecule and has its own frequency. These frequencies are

called characteristic group frequencies [24]. The vibration of the group is assumed

to occur independently of the rest of the molecule. A number of characteristic

group absorptions have been established. The group frequency concept is

extremely useful in the interpretation of vibrational spectra. The force constant of a

bond changes with its electronic structure, consequently small shifts in the

vibrational frequency and this enable us to gather more information about the

respective bond. A number of characteristic group absorptions have been

established. The general technique of assigning new group frequencies begins with

the vibrational assignments of small molecules and proceeds to the assignments of

large molecules. If certain vibrations retain fairly constant spectral positions, they

can be considered as good group frequencies.

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 Frequency shifts generally result from mechanical or electronic effects.

Mechanical effects arise from changes in mass or from coupling of the vibrations.

They do not affect the force constant of the bond. Electronic effects such as

inductive, conjugative, and other effects probably control the vibrations by altering

the force constants. The electronic effects are generally transmitted through

chemical bonds. In some instances, steric effects may occur, resulting in either

the hindrance to electronic effects or to dipolar effects transmitted through space

(field effect).

1.6.6 FACTORS INFLUENCING VIBRATIONAL FREQUENCIES

Many factors influence the precise frequency of a molecular vibrations and

it is usually impossible to isolate one effect from another. Each molecular group is

influenced by the structure of the molecule of different electronic environments

[25,26]. Some of the important factors which are responsible for shifting the

vibrational frequencies of certain groups from their normal value are discussed

below:

(a) Coupled Interactions

The energy of a vibration and thus the wavelength of its absorption peak

may be influenced by other vibrations in the molecule [27]. The degree of coupling

is influenced by the following important factors:

1. When the vibrations contain a common atom strong coupling occurs

between stretching vibrations.

2. Interaction between bending vibrations occurs only when the common

bond is present between the vibrating groups.

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 3. Interaction is at the peak when the coupled groups have individual

energies that are approximately equal.

4. If groups are separated by two or more bonds, little or no interaction

occurs.

5. Coupling occurs when the vibrations are of the same symmetric species.

(b) Hydrogen bonding

Hydrogen bonding can occur in any system containing a proton donor (X–

H) and a proton acceptor (Y), if the s-orbital of the proton can effectively overlap

the p- or π-orbital of the acceptor group. Atoms X and Y are electronegative with

Y possessing lone pair of electrons. In organic molecules, the common proton

donor groups are hydroxyl amine or amide group and common proton acceptor

atoms are oxygen, nitrogen and halogens. The strength of the hydrogen bond is at

its maximum, if the proton donor group and the axis of the lone pair orbital are

collinear. The force constant of both the groups X and Y is altered as a result of

hydrogen bonding [28]. Hence, frequencies of both stretching as well as bending

vibrations are altered because of hydrogen bonding.

The X–H stretching bands move to lower frequencies usually with

increased intensity and band widening. The X–H bending vibration usually shifts

to higher frequencies or shorter wavelength when bending occurs. Thus hydrogen

bonding changes the position and shape of an infrared absorption band.

Intermolecular hydrogen bonding involves association of two or more molecules of

same or different compound, and it may results in dimmer. While intramolecular

hydrogen bonds are formed by the interaction of proton donor and acceptor, which

is present in a single molecule. In general, intramolecular hydrogen bonds give rise

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to sharp and well-defined bonds, whereas intermolecular hydrogen results in a

broadband. Hydrogen bonding also involves in an interaction between functional

groups of the molecule and solvent.

(c) Fermi resonance

When interactions take place between fundamental vibration and overtones

or combination tones vibrations, such interactions are known as Fermi resonance.

This phenomenon may occur when two vibrational transitions have same energy

and both belong to the same symmetry [28].

(d) Electronic effects

Apart from external factors such as hydrogen bonding and molecular

association, various internal factors like electronic structure of the carbonyl group,

etc., may influence the vibrational frequency. The nature of the substituent group X

in carbonyl compounds of the formula R–C=O–X may influence the frequency of

C=O stretching by inductive and mesomeric effects. Inductive effect arises due to

the different electronegativities of the carbonyl carbon and of the substituent group

X in RCOX compounds. In addition, it involves the electrons in the sigma bonds.

The mesomeric effect includes electrons in the π and non-bonding orbitals and it

operates, in general, opposite to that of inductive effect [28]. These effects cannot

be isolated from one another and the contribution of one of them can only be

estimated approximately.

1.7 UV–VISIBLE OR ELECTRONIC SPECTROSCOPY

Electronic spectroscopy provides vital information about molecular

structure such as nature of chemical bonds, functional groups, isomerism,

tautomerism and extent of conjugation in organic compounds. Electronic spectra

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arise due to the absorption of energy by the molecule in the ultraviolet region and

make transitions between the electronic energy levels (Figure 1.2).

Figure 1.2 Regions of the electronic spectrum and corresponding types of transitions.

These transitions are quantized and depend on the electronic structure of

the molecule. The energy differences between electronic energy levels in most

molecules vary from 125 to 650 kJ/mol. When a molecule absorbs energy an

electron is promoted from an occupied orbital to an unoccupied orbital of greater

potential energy. Generally, the most probable transition is from the Highest

Occupied Molecular Orbital (HOMO) to the Lowest Unoccupied Molecular

Orbital (LUMO) [29–32].

1.7.1 PRINCIPLES OF UV-ABSORPTION SPECTROSCOPY

When electromagnetic radiations of ultraviolet and visible wavelengths are

passed through the compound with multiple bonds, a portion of radiation is

normally absorbed. Amount of absorption depends on the wavelength of radiation

and the structure of the compound. The amount of light absorbed by the sample is

explained by the following empirical expression, known as the Beer–Lambert law,

A = log (I0/I) = εcl, (1.9)

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where A is the absorbance, I0 is the intensity of light incident upon the sample cell,

I is the intensity of light leaving the sample cell, c is the molar concentration of

solute, l is the length of the sample cell and ε the molar absorptivity. The term log

(I0/I) is also known as absorbance and may be represented by A. The molar

absorptivity ε (molar extinction coefficient) is a property of the molecule

undergoing an electronic transition. The size of the absorbing system and the

probability of electronic transition will control the absorptivity, which ranges from

0 to 106 [33].

The Beer–Lambert law is strictly obeyed when a single species give rise to

the observed absorption. The law may not be obeyed, due to the molecular

properties of the sample such as complex formation or sample aggregation.

1.7.2 SELECTION RULES FOR UV SPECTRA

The conditions for occurrence of transitions between the energy levels are

called selection rules. The most important requirement is that the electron must be

promoted without change in spin orientation, i.e., ∆S = 0. The transitions that

involve a change in the spin quantum number are not allowed to take place, they

are forbidden transitions. One more condition is, the transition of electron occurs if

the symmetry of the molecular orbitals (MOs) must change from g → u or u → g

and change in symmetry g → g or u → u are not allowed (Laporte forbidden) [33].

1.7.3 TYPES OF ELECTRONIC TRANSITIONS

The ultraviolet absorption bands are associated with the chemical bonds

containing the organic molecules. Ultraviolet absorption occurs due to the

transitions of valence electrons in the molecule, i.e., the excitation of an electron

from the occupied orbital (bonding orbital) to an unoccupied orbital (anti-bonding

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orbital). The lowest energy occupied molecular orbitals are the σ-orbitals, which

corresponds to σ-bonds. The π-orbitals have quite higher energy levels and holds

unshared pairs. The non-bonding (n) orbitals are very higher energy levels. The

unoccupied (anti-bonding) orbital of π* and σ* are the orbitals of highest energy.

Electronic energy levels and transitions are shown in Figure 1.3. Thus, the

promotion of an electron from a π-bonding orbital to an anti-bonding (π*) orbital is

designated as π → π*.

σ* Unoccupied levels

π*

n→σ* n→π*

π→π* σ→π* σ→σ* Occupied levels

Figure 1.3 Electronic energy levels and transitions.

As shown in Figure 1.3., it is clear that n → π* transition requires less

energy compared with π → π* or σ → σ* transition. For many applications, the

transition of lowest energy is the most essential. Saturated organic compounds

such as alkanes provides σ → σ* transitions with λmax around 190 nm. The

saturated compounds with one heteroatom with unshared pair of electrons such as

saturated halides, alcohols, ketones and amines may undergo n → σ* transition.

The compounds with unsaturated centers such as alkenes, aromatics, carbonyl

compounds gives π → π* transition. Unsaturated molecules that contain atoms

such as oxygen or nitrogen may also undergo n → π* transition. These perhaps the

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most interesting, particularly among carbonyl compounds. These transitions are

quite sensitive to the substitution on the chromophore structure. Most n → π*

transitions are forbidden and hence are of low intensity [34–36].

1.7.4. FACTORS AFFECTING THE POSITION OF λmax

The position of λmax depends on number of factors, including conjugation of

chromophores, auxochromes and solvent. A covalently unsaturated group such as

C=C, C=O and NO2 is responsible for electronic absorption in chromophore.

Auxochromes are saturated groups with non-bonding electrons. Furthermore,

auxochromes alter the wavelength and intensity of absorption while attached to

chromophores. The bathochromic shift (a shift to longer wavelength) occurs due to

the conjugation of chromophores, auxochromes and hyperconjugative effects. In

auxochromes, the resonance interaction of lone pair with the double bond increases

the length of the conjugated system. The exact position and intensity of the

absorption band of the conjugated system can be correlated with the extent of

conjugation in the system. Furthermore the hyperconjugative interaction takes

place due to the overlap of C–H bonding orbitals with the π system [37].

The choice of solvent can shift the peaks to longer or shorter wavelengths.

This will depend on the nature of the interaction of the particular solvent with the

environment of the chromophore. Additionally, solvent effect influences the fine

structure of the absorption spectrum. A non-polar solvent does not affect the fine

structure of the spectrum as it does not make hydrogen bond with chromophore.

Whereas polar solvents definitely influence the fine structure of the spectrum due

to the hydrogen bonding of solvents with chromophore, consequently solute–

solvent complex [38,39].

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1.7.5 INTERACTION OF MOLECULES WITH ELECTROMAGNETIC
RADIATION
Using the Born–Oppenheimer approximation, the energy of a molecule in

one of its eigenstates can be written as the sum of four terms which correspond to

different motions of the molecule:

E = Etransl + Eelec + Evib + Erot, (1.10)

where Etransl is the energy of the translation of the molecule, Eelec the

electronic energy, Evib the contribution of the vibrations of the atoms or atomic

groups and Erot that of the rotation of the complete molecule. Because the

translational motion is not of interest, the Etransl term can be neglected. In addition,

Erot can be disregarded, because rotational transitions are not resolved in condensed

matter.

Molecular spectroscopy is the study of the interaction of light with matter.

The photons can interact with the molecules in three different ways: by absorption,

emission and scattering. Absorption takes place if the photon energy corresponds

to the difference between two energy eigenlevels of the molecule. The molecules

are excited to a higher energy level when they absorb light. The type of excitation

depends on the wavelength of this light (λ) [38]. For example, with UV and visible

light (200–700 nm) electrons are promoted to higher orbitals, with infrared light

(1000 nm–2.5 µm) vibrations are excited, and with far-IR and microwaves (25

µm–2.5 cm) rotations are excited. An absorption spectrum represents the

absorption as a function of wavelength.

Emission occurs when the excited molecules decay to lower energy levels

emitting a photon whose energy corresponds to the difference between two energy

levels of the molecule. If the transition is between states with the same spin, the

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emission is called fluorescence, if they have different spin, the emission is called

phosphorescence. Also scattering of the irradiated light can occur but with less

probability. The energy of the scattered photon does not correspond to the

difference between two energy levels of the molecule. If the interaction is elastic, it

is called Rayleigh scattering, if inelastic, Raman scattering [39]. This process takes

place instantaneously (<10−12s). The different interactions of molecules with

light: (a) UV–VIS absorption/emission, (b) IR absorption and (c) Raman scattering

are shown in Figure 1.4.

Figure 1.4 Comparisons of the different interactions of molecules with light: (a)
UV–VIS absorption/emission, (b) IR absorption and (c) Raman scattering.

Transitions between energy levels of the molecular system can occur with

absorption or emission of radiation, if the transition dipole moment between the

initial and the final molecular state is non-zero. For light scattering, the

polarizability of the molecule is the important quantity.

The Bouguer–Lambert–Beer law forms the mathematical–physical basis of

light absorption measurements in the UV–VIS and IR region. This law relates the

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decrease in the intensity of the radiation as it penetrates a distance dl in an
absorbing sample, and reads

dI   ( ) IXdl , (1.11)

where X is the molar concentration and α(ω) the absorption coefficient.

The absorption band for a given transition usually extends over a range of

frequencies. The total intensity of the band is obtained by measuring and

integrating α (ω) in the region of the absorption [39].

    ( )d  .
bond (1.12)

The integrated form of Beer’s law is given by

I0 1 I0 1
ln  ln   ( ) Xl  log  log   ' ( ) Xl 
(1.13)
A,
I T I T

where I0 is the intensity of the radiation before and I after passing through the

sample, T = I/I0 is the transmittance, and A the absorbance, which is given in units

of the optical density (OD = log (I0/I)).

1.8. NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY

Nuclear magnetic resonance spectroscopy (NMR) is a non-invasive and robust

tool for chemical structure determination [40]. In NMR, the local environment and

properties of atomic nuclei are probed by inducing transitions between nuclear spin

energy levels whose separation is determined by the Zeeman interaction.

Subsequently, molecular structure is assigned by the energy spectrum of nuclear

spins in a molecule, and by interpreting the symmetry and position of the

resonance lines in the spectrum. Several parameters associated with NMR helps in

the chemical structure determination, such as chemical shifts give information

about the different chemical environments in a molecule. In addition, coupling

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constants helps to establish connectivity between the different chemical

environments in a molecule [41].

1.8.1 Quantum mechanical description of NMR

Atomic nucleus has an intrinsic property called spin which is a measure

of the angular momentum of the nucleus. The spin angular momentum P, of a

nucleus is

1 ħ, (1.14)

where I = 0, 1/2, 1, 3/2, 2…. are spin quantum numbers and ћ is reduced Plank’s

constant. All nuclei with I > 0 have magnetic dipole moment µ, which is collinear

with angular momentum vector P,

µ = γP, (1.15)

where γ is the gyromagnetic ratio of the observed nucleus. When the nuclei is

placed in magnetic field (B0) the nuclei makes precessional motion about the

applied field (B0). The frequency of precession is known as the Larmor or resonant

frequency (ω0) and depends on the type of nuclei and strength of applied magnetic

field B0. The equation is

ω0 = γ B0. (1.16)

For a nucleus with I = 1/2, such as 1H and 13

C there are two allowed state in the

presence of an applied external magnetic field. One with its magnetic moment

along the field direction and other opposite the field direction. The two orientations

have corresponding energies ± 1/2ν ћB0 which results in an energy difference of

νћB0 as shown in Figure 1.5.

It is possible to make the nuclear transitions between two levels by injecting a

photon with correct frequency.

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 ∆E = E2–E1 = νћB0 = ћω0. (1.17)

At room temperature, there are a slightly greater number of aligned nuclei than the

anti-aligned and the difference is given as

N↑–N↓ = (1.18)

E2 = -1/2νħB0

B0 = 0 ∆E = νħB0

E1 = +1/2νħB0

Figure 1.5 Energy levels for protons.

In NMR spectroscopic method, a transition will be induced between

two energy states when an electromagnetic wave is applied to the nuclei in the

sample, provided the resonance condition ∆E = hν is satisfied. An additional

oscillating exciting field (B1) will be generated by irradiating the sample with a

short pulse of radio frequency (RF) perpendicular to the main field (B0). As a

result, the nuclei will be subjected to a processional motion about a new effective

field Beff, which is the sum of B0 and B1. Thus, Larmor precession of the transverse

magnetization vector will produce a detectable signal by inducing an oscillating

current in the receiver coil. When the RF pulse is removed, the precessions tend

to decay back to the equilibrium state by relaxation process T1 and T2. This is

known as free induction decay (FID) which is recorded as a function of time. By

a mathematical treatment using Fourier transform (FT) function, the FID data

are converted into standard NMR spectrum presented in the frequency-varying

method [42].

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1.8.2. Chemical shift

Nuclear magnetic resonance has great utility, because not all the protons in

a molecule have resonance at the same frequency. This variability is due to

diamagnetic shielding or diamagnetic anisotropy. As a result of diamagnetic

anisotropy, each proton in a molecule is shielded from the applied magnetic field

to an extent that depends on the electron density surrounding it. Each proton in a

molecule is in a slightly different amount of electronic shielding, which results in a

slightly different resonance frequency [42]. The position of the resonance signal

for a molecule is shifted relative to the reference signal is termed as chemical shift

and is expressed in parts per million.

1.8.3. Causes of Chemical shift

The variation in chemical shifts may arise due to the following factors:

The secondary fields produced by the circulating electrons about a nucleus

in a molecule can oppose or reinforce the applied field. As a result, the resonance

position in NMR spectrum moves up field or downfield, respectively. This is

known as positive shielding and negative shielding.

The field experienced by a nucleus may be modified by field due to

induced circulation of electrons localized on the nucleus. This is known as the

local shielding. In aromatic compounds, the secondary field set up the induced

circulation of π electrons which often influence the fields experienced by nuclei

not directly associated with the π electrons. Due to this, additional shielding or

deshielding effects may be included within the molecule [43, 44].

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1.8.4 Spin–spin Coupling

The interaction between the spins of the neighboring nuclei in a molecule

may cause the splitting of the lines in the NMR spectrum. This is known as spin–

spin coupling that occurs through bonds by means of a marginal unpairing of the

bonding electrons [44].

1.9 APPLICATIONS OF VIBRATIONAL SPECTROSCOPY

The applications of vibrational spectroscopy are extremely diverse and the

techniques are making a contribution to many areas of science. Perhaps the most

interesting areas are in materials science and in biomedical research where the

early detection of cancer in human tissues is the primary goal. Industrial

applications, both on- and offline are also receiving attention [45]. The use of

chemometrics (statistical data processing techniques) has become a standard

method for extracting maximum information from vibrational spectroscopic data.

Various spectroscopic techniques were used for the present work, the

instrumentation of FT–IR, FT–Raman, UV-VIS and FT–NMR are discussed in the

next chapter.

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